Influence of Blend Morphology and Energetics on Charge Separation and Recombination Dynamics in Organic Solar Cells Incorporating a Nonfullerene Acceptor

Nonfullerene acceptors (NFAs) in blends with highly crystalline donor polymers have been shown to yield particularly high device voltage outputs, but typically more modest quantum yields for photocurrent generation as well as often lower fill factors (FF). In this study, we employ transient optical and optoelectronic analysis to elucidate the factors determining device photocurrent and FF in blends of the highly crystalline donor polymer PffBT4T‐2OD with the promising NFA FBR or the more widely studied fullerene acceptor PC₇₁BM. Geminate recombination losses, as measured by ultrafast transient absorption spectroscopy, are observed to be significantly higher for PffBT4T‐2OD:FBR blends. This is assigned to the smaller LUMO‐LUMO offset of the PffBT4T‐2OD:FBR blends relative to PffBT4T‐2OD:PC₇₁BM, resulting in the lower photocurrent generation efficiency obtained with FBR. Employing time delayed charge extraction measurements, these geminate recombination losses are observed to be field dependent, resulting in the lower FF observed with PffBT4T‐2OD:FBR devices. These data therefore provide a detailed understanding of the impact of acceptor design, and particularly acceptor energetics, on organic solar cell performance. Our study concludes with a discussion of the implications of these results for the design of NFAs in organic solar cells.     

Contrasting Effects of Energy Transfer in Determining Efficiency Improvements in Ternary Polymer Solar Cells

Crystallizable, high‐mobility conjugated polymers have been employed as secondary donor materials in ternary polymer solar cells in order to improve device efficiency by broadening their spectral response range and enhancing charge dissociation and transport. Here, contrasting effects of two crystallizable polymers, namely, PffBT4T‐2OD and PDPP2TBT, in determining the efficiency improvements in PTB7‐Th:PC₇₁BM host blends are demonstrated. A notable power conversion efficiency of 11% can be obtained by introducing 10% PffBT4T‐2OD (relative to PTB7‐Th), while the efficiency of PDPP2TBT‐incorporated ternary devices decreases dramatically despite an enhancement in hole mobility and light absorption. Blend morphology studies suggest that both PffBT4T‐2OD and PDPP2TBT are well dissolved within the host PTB7‐Th phase and facilitate an increased degree of phase separation between polymer and fullerene domains. While negligible charge transfer is determined in binary blends of each polymer mixture, effective energy transfer is identified from PffBT4T‐2OD to PTB7‐Th that contributes to an improvement in ternary blend device efficiency. In contrast, energy transfer from PTB7‐Th to PDPP2TBT worsens the efficiency of the ternary device due to inefficient charge dissociation between PDPP2TBT and PC₇₁BM.     

Efficient semitransparent organic solar cells with good color perception and good color rendering by blade coating

This paper proposes high efficiency semitransparent organic solar cells (OSCs) with good color perception and good color rendering using blade coating technique. We investigate four different polymer blends and first fabricate small area devices with active area of 0.04 cm², followed by large area devices with active area of 10.8 cm². Two of the polymer blends, 2,6-Bis(trimethyltin)-4,8-bis(5-(2-ethylhexyl)thiophen-2-yl)benzo[1,2-b:4,5-b']dithiophene:6,6-phenyl C71-butyric acid methyl ester (PBDTTT-CT:PC₇₁BM) and poly[4,8-bis(5-(2-ethylhexyl)thiophen-2-yl)benzo[1,2-b;4,5-b′] dithiophene-2,6-diyl-alt-(4-(2-ethylhexyl)-3-fluorothieno[3,4-b]thiophene-)-2-carboxylate-2-6-diyl)]:PC₇₁BM (PBDTTT-EFT:PC₇₁BM) show promising results. For small area devices, semitransparent PBDTTT-CT:PC₇₁BM and semitransparent PBDTTT-EFT:PC₇₁BM achieve a power conversion efficiency (PCE) of 5.2% (opaque PCE = 7.5%) and 5.6% (opaque PCE = 9.4%) respectively. For large area devices, they are found to produce a PCE of 3.8% (opaque PCE = 4.2%) and 5.3% (opaque PCE = 5.9%) respectively. Based on the CIE 1931 chromaticity diagram, semitransparent PBDTTT-CT:PC₇₁BM and semitransparent PBDTTT-EFT:PC₇₁BM are located very close to the standard illuminant D65, indicating good color perception. As for color rendering, they demonstrate high color rendering index (CRI) of 95.4 and 87.1 respectively. These combined high performances indicate high-quality transmitted light, which is suitable for window application.     

Energy levels in dilute-donor organic solar cell photocurrent generation: A thienothiophene donor molecule study

To investigate photocurrent generation mechanisms in these organic solar cells (OSCs), we design and synthesize four thienothiophene (TT)-based small-molecule donors with the highest occupied molecular orbital (HOMO) levels varying from −6.4 eV to −5.1 eV, which span across the HOMO value of the [6,6]-phenyl-C70-butyric acid methyl ester (PC₇₁BM) acceptor. We measure TT-based donor:PC₇₁BM films’ electronic and optical properties, OSC current density-voltage characteristic, and external quantum efficiency, and perform density functional theory (DFT) calculations. Our results show that photocurrent generation depends strongly on the substitutions of the center TT groups, cyano (-CN) versus hexyloxy (-OHex). With 1 wt% donor, TTOHex:PC₇₁BM devices produce seven times, increasing to twelve times for 5 wt % donor, higher photocurrent than neat PC₇₁BM devices. In contrast, TTCN:PC₇₁BM devices do not generate additional photocurrent even with 10 wt% donor. The photocurrent generation in TT-based donor:PC₇₁BM devices depends critically on the HOMO value of the donor molecule with respect to that of PC₇₁BM, indicating the importance of type II energy level alignment to facilitate exciton dissociation at the donor-acceptor interface. The photovoltage of all TT:PC₇₁BM devices are comparable to neat PC₇₁BM devices, 0.85–0.90 V, with a low voltage loss due to non-radiative recombination. The fill factor of TTOHex:PC₇₁BM devices are low due to the low hole mobility, ~10⁻⁸ cm²/V. Following exciton dissociation, hole transport is analyzed according to three possible mechanisms: tunneling, percolation pathways, and hole back transfer. We find that the hole back transfer mechanism can explain all experimental results and therefore is the primary hole transport mechanism for photocurrent generation in TT-based donor:PC₇₁BM dilute-donor OSCs.     

Polyacetylene-based polyelectrolyte as a universal interfacial layer for efficient inverted polymer solar cells

Here we report that poly(N-dodecyl-2-ethynylpyridiniumbromide) (PDEPB) interlayers between electron-collecting zinc oxide (ZnO) layers and bulk heterojunction (BHJ) layers act as a universal interfacial layer for improving the performances of inverted-type polymer:fullerene solar cells. Three different BHJ layers, poly(3-hexylthiophene) (P3HT):[6,6]-phenyl-C₆₁-butyric acid methyl ester (PC₆₁BM), poly[(4,8-bis(2-ethylhexyloxy)-benzo[1,2-b:4,5-b']dithiophene)-2,6-diyl-alt-(N-2-ethylhexylthieno[3,4-c]pyrrole-4,6-dione)-2,6-diyl]] (PBDTTPD):PC₆₁BM, and poly[4,8-bis[(2-ethylhexyl)oxy]benzo[1,2-b:4,5-b']dithiophene-2,6-diyl][3-fluoro-2-[(2-ethylhexyl)carbonyl]thieno[3,4-b]-thiophenediyl] (PTB7) and [6,6]-phenyl-C₇₁-butyric acid methyl ester (PC₇₁BM), were employed so as to prove the role of the PDEPB interlayers. Results showed that the power conversion efficiency (PCE) of polymer:fullerene solar cells with the three different BHJ layers increased in the presence of the PDEPB interlayers prepared from 0.5 mg/ml solutions. The improved PCE was attributed to the conformal coating of the PDEPB layers on the ZnO layers (by atomic force microscopy measurement), lowered work functions of ZnO induced by the PDEPB layers (by Kelvin probe measurement), and reduced interface resistance (by impedance spectroscopy measurement), as supported by the noticeable change in the atom environments of both the ZnO and PDEPB layers (by X-ray photoelectron spectroscopy measurement).     

A low-cost and low-temperature processable zinc oxide-polyethylenimine (ZnO:PEI) nano-composite as cathode buffer layer for organic and perovskite solar cells

Nanocomposite buffer layer based on metal oxide and polymer is merging as a novel buffer layer for organic solar cells, which combines the high charge carrier mobility of metal oxide and good film formation properties of polymer. In this work, a nanocomposite of zinc oxide and a commercialized available polyethylenimine (PEI) was developed and used as the cathode buffer layer (CBL) for the inverted organic solar cells and p-i-n heterojunction perovskite solar cells. The cooperation of PEI in nano ZnO offers a good film forming ability of the composite material, which is an advantage in device fabrication. In addition, power conversion efficiency (PCE) of the ZnO:PEI CBL based device was also improved when compared to that of ZnO-only and PEI-only devices. The highest PCE of P3HT:PC₆₁BM and PTB7-Th:PC₆₁BM devices reached to 3.57% and 8.16%, respectively. More importantly, there is no obvious device performance loss with the increase of the layer thickness of ZnO:PEI CBL to 60 nm in organic solar cells, which is in contrast to the PEI based devices, whose device performance decreases dramatically when the PEI layer thickness is higher than 6 nm. Such a nano composite material is also applicable in inverted heterojunction perovskite solar cells. A PCE of 11.76% was achieved for the perovskite solar cell with a thick ZnO:PEI CBL (150 nm) CBL, which is around 1.71% higher than that of the reference cell without CBL, or with ZnO CBL. In addition, stability of the organic and perovskite solar cells having ZnO:PEI CBL was also found to be improved in comparison with that of PEI based device.     

Synthesis and characterization of a wide bandgap polymer based on a weak donor-weak acceptor structure for dual applications in organic solar cells and organic photodetectors

We synthesized a novel wide bandgap polymer, PDTFBT, forming a weak donor (WD)-weak acceptor (WA) structure for use in organic photodetectors (OPDs) and organic solar cells (OSCs). The fluorination in the D unit and the alkoxy substitution in the A unit induced WD and WA properties, respectively. The WD-WA structure of PDTFBT effectively broadened the bandgap compared to typical D-A structures, and the S-F and S-O dipole-dipole interactions induces a highly planar backbone structure with excellent π-π stacking in the vertical direction. In OPDs, conformationally less disordered PDTFBT polymer retained the constant responsivity and significantly improved the detectivity of PDTFBT:PC₇₁BM devices even with a thick active layer of 470 nm, contrary to the variation in the responsivity of P3HT:PC₆₁BM devices depending on the thickness. In OSCs, the deep HOMO energy level (−5.57 eV) of PDTFBT led to high Voc of 0.92 V in PDTFBT:PC₇₁BM devices, which was 0.3 eV higher than that of P3HT:PC₆₁BM devices (0.62 V), resulting in 1.8-fold enhanced power conversion efficiency. We demonstrated that the WD-WA structure with S-F and S-O interactions is highly promising strategy to make wide bandgap polymers for organic photodetectors and for the bottom cell of tandem architecture.     

Effect of thermal annealing on the electrical properties of P3HT:PC70BM nanocomposites

We studied the electrical properties of organic photovoltaic (OPV) devices based on poly (3-hexylthiophene) and fullerene derivative [6, 6]-Phenyl-C₇₀-butyric acid methyl ester nanocomposite (P3HT:PC₇₀BM) as a function of the annealing temperature. Thermal annealing enables crystallization of the polymer and diffusion of the PC₇₀BM molecules. Diode parameters, such as the barrier height ϕ_b and the ideality factor n were calculated. They were found to be depend strongly on the annealing temperature. This dependence is attributed to surface states, inhomogeneity in the material and series resistance. Best OPV devices had a short circuit current density of 3.35 mA/cm², an open circuit voltage of 0.68 V, a fill factor of 0.45, and a power conversion efficiency of 2.2%, by applying a thermal annealing temperature of 150 °C for 10 min.     

Active layer thickness effect on the recombination process of PCDTBT:PC71BM organic solar cells

We investigated the effect of active layer thickness on recombination kinetics of poly[N-9″-hepta-decanyl-2,7-carbazole-alt-5,5-(4′,7′-di-2-thienyl-2′,1′,3′-benzothiadiazole)] (PCDTBT) and [6,6]-phenyl C71-butyric acid methyl ester (PC₇₁BM) based solar cells. Analysis of the fitted Lambert W-function of illuminated current density–voltage (J–V) characteristics revealed increased recombination processes with increased active layer thicknesses. The ideality factor extracted from PCDTBT:PCBM solar cells continuously increased from 1.89 to 3.88 when photoactive layer thickness was increased from 70 to 150 nm. We found that such increase in ideality factor is closely related to the defect density which is increased with increased photoactive layer thickness beyond 110 nm. Therefore, the different density of defect states in PCDTBT:PCBM solar cells causes the different recombination paths where solar cells with a thicker active layer (?110 nm) are considered to undergo coupled trap-assisted recombination processes while single-defect trap-assisted recombination is dominant for thinner (70–90 nm) PCDTBT:PCBM solar cells. As a result, we found that the optimal efficiencies of PCDTBT:PC₇₁BM solar cells were limited to the active layers between 70 and 90 nm. Particularly, when PCDTBT:PC₇₁BM solar cells were optimized with an active layer thickness of 70 nm, energy conversion efficiency reached 6.5% while an increase in thickness led to the reduction of efficiency to 4.7% at 133 nm but then an increase to 5.02% at 150 nm.     

New ultra low bandgap thiadiazolequinoxaline-based D-A copolymers for photovoltaic applications

In this communication, we designed two low bandgap D-A copolymers with same fluorinated thiadiazoloquinoxaline (TDQ) as acceptor and different donor units benzo[2,1-b;3,4-b′]dithiophene (P1) and benzo[1,2-b:4,5-b′]dithiophene (P2). P1 and P2 exhibit broad absorption profiles covering from 350 nm to 1150 nm and 350–950 nm, respectively with optical bandgaps of 1.06 eV and 1.18 eV, respectively. Both copolymers showed deep highest occupied molecular orbitals (HOMO), i.e. −5.38 eV and −5.26 eV, for P1 and P2. Their photovoltaic properties were evaluated using conventional devices with a structure of ITO/PEDOT:PSS/copolymer:PC₇₁BM/Al. After the optimizations of the copolymer to PC₇₁BM weight ratios, and concentration of the solvent additive (DIO), the devices showed overall power conversion efficiencies of 4.03% and 5.42% for the P1 and P2 based devices, respectively. The higher value of PCE of the P2 based device is attributed to the higher values of J_sc and FF, that is related to the higher hole mobility and better exciton dissociation efficiency. Although the PCEs of these devices are moderate, these ultra low band gap copolymers can be used for their potential application in tandem polymers solar cells. Finally, methanol treatment of the active layer was adopted to increase the PCE of the P2:PC₇₁BM based polymer solar cells that resulted in an improved PCE up to 6.93%.     

A star-shaped oligothiophene with triphenylamine as core and octyl cyanoacetate as end groups for solution-processed organic solar cells

A new star-shaped D–π–A molecule with triphenylamine (TPA) as core and donor unit, octyl cyanoacetate (CA) as end group and acceptor unit, and 2,2′-bithiophene vinylene (bTV) as π bridge, S(TPA-bTV-CA) was designed and synthesized for the application as donor materials in solution-processed bulk-heterojunction organic solar cells (OSCs). The compound is soluble in common organic solvents. The thermal, optical and electrochemical properties of the star molecule were studied. The OSC devices were fabricated by spin-coating the blend solution of the molecule as donor and PC₇₀BM as acceptor (1:3, w/w). The OSC device based on S(TPA-bTV-CA)/PC₇₀BM demonstrated a high open circuit voltage of 0.91 V, a short circuit current density of 4.64 mA/cm², a fill factor (FF) of 50%, corresponding to a power conversion efficiency of 2.1%, under the illumination of AM 1.5, 100 mW/cm².     

A plasmonically enhanced polymer solar cell with gold–silica core–shell nanorods

We report the use of chemically synthesized gold (Au)–silica core–shell nanorods with the length of 92.5 ± 8.0 nm and diameter of 34.3 ± 4.0 nm for the efficiency enhancement of bulk heterojunction (BHJ) polymer solar cells. Silica coated Au nanorods were randomly blended into the BHJ layers of these solar cells. This architecture inhibits the carrier recombination at the metal/polymer interface and effectively exploits light absorption at the surface plasmon resonance wavelengths of the Au–silica nanorods. To match the two plasmon resonant peaks of the Au–silica nanorods, we employed 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) to construct a solar cell. The absorption spectrum of PCPDTBT:[6,6]-phenyl-C₇₁-butyric acid methyl ester (PC₇₀BM) is relatively wide and matches the two plasmon resonance peaks of Au–silica nanorods, which leads to greater plasmonic effects. We also constructed the poly(3-hexylthiophene):[6,6]-phenyl-C₆₁-butyric acid methyl ester (P3HT:PC₆₀BM) cells for comparison. The absorption spectrum of P3HT:PC₆₀BM only overlaps one of the plasmon resonance peak of Au–silica nanorods. The efficiency of the P3HT:PC₆₀BM device incorporating optimized Au–silica nanorods is enhanced by 12.9% from 3.17% to 3.58%, which is due to the enhanced light absorption. Compared with the P3HT:PC₆₀BM device with Au–silica nanorods, the PCPDTBT:PC₇₀BM device with 1 wt% Au–silica nanorods concentration has a higher efficiency of 4.4% with an increase of 26%.     

Bulk Heterojunction Solar Cells: Impact of Minor Structural Modifications to the Polymer Backbone on the Polymer–Fullerene Mixing and Packing and on the Fullerene–Fullerene Connecting Network

The morphology of the active layer of a bulk heterojunction solar cell, made of a blend of an electron‐donating polymer and an electron‐accepting fullerene derivative, is known to play a determining role in device performance. Here, a combination of molecular dynamics simulations and long‐range corrected density functional theory calculations is used to elucidate the molecular‐scale effects that even minor structural changes to the polymer backbone can have on the “local” morphology; this study focuses on the extent of polymer–fullerene mixing, on their packing, and on the characteristics of the fullerene–fullerene connecting network in the mixed regions, aspects that are difficult to access experimentally. Three representative polymer donors are investigated: (i) poly[(5,6‐difluoro‐2,1,3‐benzothiadiazol‐4,7‐diyl)‐alt‐(3,3′″‐di(2‐octyldodecyl)‐2,2′;5′,2″;5″,2′″‐quaterthiophen‐5,5′″‐diyl)] (PffBT4T‐2OD); (ii) poly[(2,1,3‐benzothiadiazol‐4,7‐diyl)‐alt‐(3,3′″‐di(2‐octyldodecyl)‐2,2′;5′,2″;5″,2′″‐quaterthiophen‐5,5′″‐diyl)] (PBT4T‐2OD), where the fluorine atoms in the benzothiadiazole moieties of PffBT4T‐2OD are replaced with hydrogen atoms; and (iii) poly[(2,2′‐bithiophene)‐alt‐(4,7‐bis((2‐decyltetradecyl)thiophen‐2‐yl)‐5,6‐difluoro‐2‐propyl‐2H‐benzo[d][1,2,3]triazole)] (PT2‐FTAZ), where the sulfur atoms in the benzothiadiazole moieties of PffBT4T‐2OD are replaced with nitrogen atoms carrying a linear C₃H₇ side‐chain; these polymers are mixed with the phenyl‐C₇₁‐butyric acid methyl ester (PC₇₁BM) acceptor. This study also discusses the nature of the charge‐transfer electronic states appearing at the donor–acceptor interfaces, the electronic couplings relevant for the charge‐recombination process, and the electron‐transfer features between neighboring PC₇₁BM molecules.     

Efficient bulk heterojunction solar cells from regio-regular- poly(3,3‴-didodecyl quaterthiophene)/PC70BM blends

Blends of regio-regular poly(3,3‴-didodecyl quaterthiophene) (PQT-12) with (6,6)-phenyl-C₇₀-butyric acid methyl ester (PC₇₀BM) were investigated as active layers for application in organic photovoltaics (OPV). By optimizing the PQT-12:PC₇₀BM composition ratio and annealing conditions, power conversion efficiencies (η) of 1.4% could be obtained. Effects of different preparation parameters on the incident photon conversion efficiency (IPCE), short-circuit (J_sc), fill factor (FF), open-circuit voltage (V_oc) and η are discussed.     

Enhanced carrier dynamics of PTB7:PC71BM based bulk heterojunction organic solar cells by the incorporation of formic acid

Formic acid (FA) was used as a novel additive in bulk heterojunction (BHJ) solar cells, which contains blends of poly[[4,8-bis[(2-ethylhexyl)oxy]benzo[1,2-b:4,5-b']dithiophene-2,6-diyl][3-fluoro-2-[(2-ethylhexyl)carbonyl]thieno[3,4-b]thiophene-4,6-diyl]] (PTB7) and [6,6]-phenyl-C71-butyric acid methyl ester (PC₇₁BM). The effect of FA on the performance of PTB7:PC₇₁BM based BHJ solar cells is investigated. By the incorporation of FA, the device with the ratio of 6 vol % shows the best power conversion efficiency (PCE) of 9.04%, along with the short-circuit current density (J_sc), open-circuit voltage (V_oc), and fill factor (FF) being 24.11 mA/cm², 0.72 V, and 52.11%, respectively. Experimental results suggest that FA has a strong influence on charge carrier dynamics with a significant increase in J_sc by ∼65% and the dramatically enhanced PCE is mainly due to the increase of absorption and exciton generation of the active layers and the improved charge-carrier mobility of the devices.     

Luminescent cathode buffer layer for enhanced power conversion efficiency and stability of bulk-heterojunction solar cells

We report high photovoltaic efficiency of over 9% in solution-processed, small-molecule (SPSM) 7,7′-(4,4-bis(2-ethylhexyl)-4H-silolo[3,2-b:4,5-b′]dithiophene-2,6-diyl)bis(6-fluoro-4(5′-hexyl-[2,2′-bithiophen]-5-yl)benzo[c]1,2,5]thiadiazole) p-DTS(FBTTh₂)₂:[6-6]-phenyl C70 butyric acid methyl ester (PC₇₀BM) blend based inverted BHJ solar cell by incorporating luminescent zinc oxide doped with sodium (ZnO:Na) quantum dots (QD) (l-ZnO) as a cathode buffer layer (CBL) in inverted bulk-heterojunction (BHJ) solar cells for the first time. The l-ZnO absorbs ultraviolet (UV) light and down-converts it to visible light. The l-ZnO layer's emission overlaps significantly with the absorption of p-DTS(FBTTh₂)₂, leading to an enhanced absorption by p-DTS(FBTTh₂)₂. This resulted in a significant enhancement of photo-current from 15.4 to 17.27 mA/cm² and efficiency from 8% to 9.2% for ZnO and l-ZnO based devices, respectively. This is among one of the highest efficiency values reported so far in the case of SPSM based single junction BHJ solar cells. The luminescent ZnO layer also protects the active layer from UV-induced degradation as solar cells show high stability under constant solar light illumination retaining more than 90% (∼28 h) of its initial efficiency, whereas BHJ solar cells without the luminescent ZnO layer degraded to ∼50% of its initial value under same conditions. Since ZnO is an essential part of inverted organic solar cells, the luminescent l-ZnO CBL has great potential in inverted organic solar cells.     

Large-area organic solar cells by accelerated blade coating

Large-area photovoltaic devices have been fabricated using the blade coating technique. In this study, the use of accelerated blade motion in this technique significantly improved the thickness uniformity of blade-coated layers of polymer solar cells on an A4 glass substrate. Two types of active layers, P3HT:PC₆₁BM and POD2T-DTBT:PC₇₁BM, were studied. For the P3HT:PC₆₁BM film, a thickness of 221 ± 14 nm was realised in a 12 × 15 cm² active region with a coating blade acceleration of 8 mm/s². For the POD2T-DTBT:PC₇₁BM film, a thickness of 98 ± 6 nm was realised with a coating blade acceleration of 10 mm/s². Ten cells, each measuring 0.9 cm × 12 cm and monolithically fabricated, were connected in series, yielding a total active area of 108 cm². The power conversion efficiency of the resulting 10-cell module was 2.66% and 3.64% for P3HT:PC₆₁BM and POD2T-DTBT:PC₇₁BM, respectively. The blade coating technique involving the accelerated blade motion is therefore useful for fabricating low-cost large-area organic solar cells, and it may be a promising alternative for the commercialisation of organic solar cells.     

Synthesis of a Modified PC70BM and Its Application as an Electron Acceptor with Poly(3‐hexylthiophene) as an Electron Donor for Efficient Bulk Heterojunction Solar Cells

A simple and effective modification of phenyl‐C₇₀‐butyric acid methyl ester (PC₇₀BM) is carried out in a single step after which the material is used as electron acceptor for bulk heterojunction polymer solar cells (PSCs). The modified PC₇₀BM, namely CN‐PC₇₀BM, showed broader and stronger absorption in the visible region (350–550 nm) of the solar spectrum than PC₇₀BM because of the presence of a cyanovinylene 4‐nitrophenyl segment. The lowest unoccupied molecular energy level (LUMO) of CN‐PC₇₀BM is higher than that of PC₇₀BM by 0.15 eV. The PSC based on the blend (cast from tetrahydrofuran (THF) solution) consists of P3HT as the electron donor and CN‐PC₇₀BM as the electron acceptor and shows a power conversion efficiency (PCE) of 4.88%, which is higher than that of devices based on PC₇₀BM as the electron acceptor (3.23%). The higher PCE of the solar cell based on P3HT:CN‐PC₇₀BM is related to the increase in both the short circuit current (J_sc) and the open circuit voltage (V_oc). The increase in J_sc is related to the stronger light absorption of CN‐PC₇₀BM in the visible region of the solar spectrum as compared to that of PC₇₀BM. In other words, more excitons are generated in the bulk heterojunction (BHJ) active layer. On the other hand, the higher difference between the LUMO of CN‐PC₇₀BM and the HOMO of P3HT causes an enhancement in the V_oc. The addition of 2% (v/v) 1‐chloronapthalene (CN) to the THF solvent during film deposition results in an overall improvement of the PCE up to 5.83%. This improvement in PCE can be attributed to the enhanced crystallinity of the blend (particularly of P3HT) and more balanced charge transport in the device.     

Filter-Free Narrowband Photomultiplication-Type Planar Heterojunction Organic Photodetectors

Filter-free narrowband photomultiplication-type planar heterojunction (PHJ) organic photodetectors (PM-PHOPDs) are first realized by employing a thick front donor layer and an ultrathin PC₇₁BM layer. The thick front donor layer is employed as an optical field adjusting (OFA) layer. The sequentially coated PC₇₁BM will diffuse slightly into OFA layer, which works as interfacial electron traps to capture photogenerated electrons for assisting hole tunneling injection. The P3HT/PC₇₁BM-based PM-PHOPDs exhibit narrowband response with full-width of half-maximum of 32 nm and external quantum efficiency (EQE) of 1700% at 650 nm under −20 V bias. Due to the enhanced hole transport and reduced charge recombination in PHJ compared to those in bulk heterojunction (BHJ), the EQE of P3HT/PC₇₁BM-based narrowband PM-PHOPDs is twice as P3HT:PC₇₁BM BHJ-based narrowband PM-OPDs under the same bias. The response peak of PM-PHOPDs is adjusted from 650 to 695 or 745 nm by incorporating SMPV1 or DRCN5T in OFA layers due to the red-shifted absorption edge. The EQEs of 3600% at 695 nm and 870% at 745 nm are obtained for P3HT:SMPV1 and P3HT:DRCN5T-based PM-PHOPDs under −20 V bias, respectively. This work provides a smart strategy to achieve narrowband PM-OPDs by designing different OFA layers.