PCBM Blend Research Articles

Orienting the Microstructure Evolution of Copper Phthalocyanine as an Anode Interlayer in Inverted Polymer Solar Cells for High Performance.

Recent advances in the interfacial modification of inverted-type polymer solar cells (PSCs) have resulted from controlling the surface energy of the cathode-modified layer (TiO2 or ZnO) to enhance the short-circuit current (Jsc) or optimizing the contact morphology of the cathode (indium tin oxide or fluorine-doped tin oxide) and active layer to increase the fill factor. Herein, we report that the performance enhancement of PSCs is achieved by incorporating a donor macromolecule copper phthalocyanine (CuPc) as an anode modification layer. Using the approach based on orienting the microstructure evolution, uniformly dispersed island-shaped CuPc spot accumulations are built on the top of PTB7:PC71BM blend film, leading to an efficient spectral absorption and photogenerated exciton splitting. The best power conversion efficiency of PSCs is increased up to 9.726%. In addition to the enhanced light absorption, the tailored anode energy level alignment and optimized boundary morphology by incorporating the CuPc interlayer boost charge extraction efficiency and suppress the interfacial molecular recombination. These results demonstrate that surface morphology induction through molecular deposition is an effective method to improve the performance of PSCs, which reveals the potential implications of the interlayer between the organic active layer and the electrode buffer layer.

Dynamics of Additive Migration to Form Cathodic Interlayers in Organic Solar Cells

Migration of additives to organic/metal interfaces can be used to self-generate interlayers in organic electronic devices. To generalize this approach for various additives, metals, and organic electronic devices it is first necessary to study the dynamics of additive migration from the bulk to the top organic/metal interface. In this study, we focus on a known cathode interlayer material, polyethylene glycol (PEG), as additive in P3HT:PC71BM blends and study its migration to the blend/Al interface during metal deposition and its effect on organic solar cell (OSC) performance. Using dynamic secondary ion mass spectroscopy (DSIMS) depth profiles and X-ray photoelectron spectroscopy surface analysis (XPS), we quantitatively correlate the initial concentration of PEG in the blend and sequence of thermal annealing/metal deposition processes with the organic/Al interfacial composition. We find that PEG is initially distributed within the film according to the kinetics of the spin coating process, i.e., the majority of PEG accumulates at the bottom substrate, while the minority resides in the film. During electrode evaporation, PEG molecules kinetically "trapped" near the film surface migrate to the organic/Al interface to reduce the interfacial energy. This diffusion-limited process is enhanced with the initial concentration of PEG in the solution and with thermal annealing after metal deposition. In contrast, annealing the film before metal deposition stalls PEG migration. This mechanism is supported by corresponding OSC devices showing that Voc increases with PEG content at the interface, up to a saturation value associated with the formation of a continuous PEG interlayer. Presence of a continuous interlayer excludes the driving force for further migration of PEG to the interface. Revealing this mechanism provides practical insight for judicious selection of additives and processing conditions for interfacial engineering of spontaneously generated interlayers.

Morphological studies of small-molecule solar cells: nanostructural engineering via solvent vapor annealing treatments

Fine-tuning nano/micro-structural morphologies and their depth studies in small-molecule solar cells are key parameters in elevating device performances. In the current work, we focused on controlling the morphology of a small-molecule organic photovoltaic by treating its active layer film with solvent vapor annealing (SVA). For this project, the devices were made of all-small-molecule p-DTS(FBTTh2)2:PC71BM heterojunction films processed using different solvents for the vapor annealing. The different solvents resulted in different nano-domain packing structures and segregated phase separation as evidenced by detailed two-dimensional grazing-incidence wide-angle X-ray scattering (2D-GIWAXS) and atomic force microscopy (AFM) analyses. From the data, we demonstrated a correlation between the nanostructural morphology of the active layer film and the performance of the device and found an SVA condition that produced a p-DTS(FBTTh2)2:PC71BM blend system yielding an improved device performance.

Improved efficiency and stability in polymer solar cells using a Tetra-nuclear Zinc(II) complex interfacial layer

Abstract Tetra-nuclear Zinc(II) complex Zn 4 O(AID) 6 [AID = 7-azaindolate] is a wide band gap luminescent material that exhibits efficient emission matching the absorption spectra of organic donor materials such as polythiophene (P3HT). This work demonstrates polymer solar cells (PSC) based on P3HT:PCBM (phenyl-C 61 -butyric acid methyl ester) blend active layer with a Zn 4 O(AID) 6 cathode interfacial layer achieving a power conversion efficiency (PCE) significantly higher than that of the reference devices. The energy level and impedance spectroscopy analysis show that the Zn 4 O(AID) 6 cathode interfacial layer acts as an efficient exciton/hole blocking layer, and reduces charge recombination rate with more efficient electron extraction. The Zn 4 O(AID) 6 interfacial layer also helps achieve longer lifetime of PSC devices. The improved efficiency and stability combined with low cost and nontoxicity of Zn 4 O(AID) 6 make it a promising cathode interfacial material for high-performance and stable PSC devices.

Graphene Oxide by UV-Ozone Treatment as an Efficient Hole Extraction Layer for Highly Efficient and Stable Polymer Solar Cells.

The hole extraction layer has a significant impact on the achievement of high-efficiency polymer solar cells (PSCs). Here, we report an efficient approach to direct UV-ozone treatment by larger device performance enhancement employing graphene oxide (GO). The dramatic performance enhancement of PSCs with the P3HT:PCBM blend as an active layer was demonstrated by the UV-ozone treatment of GO for 30 min: best power conversion efficiency (PCE) of 4.18%, fill factor of 0.63, Jsc of 10.94 mA cm-2, and Voc of 0.61 V, which are significantly higher than those of the untreated GO (1.82%) and highly comparable PEDOT:PSS-based PSCs (3.73%). In addition, PSCs with UV-ozone-treated GO showed a longer stability than PSCs with PEDOT:PSS. The significant enhancement of PCEs of PSCs can be attributed to the fact that ozone molecules can oxidize GO into CO2 and leave highly conductive graphene particles. We suggest that this simple UV-ozone treatment can provide an efficient method for highly efficient GO hole extraction in high-performance PSCs.

Enhancing the Efficiency of Polymer Solar Cells by Incorporation of 2,5-Difluorobenzene Units into the Polymer Backbone via Random Copolymerization.

A series of conjugated polymers P0, P5, and P7 containing 0, 5, and 7 mol % 2,5-difluorobenzene units, respectively, were prepared and utilized as electron donors in polymer solar cells. Incorporation of a small amount of 2,5-difluorobenzene unit into the backbone of donor polymers can significantly increase their planarity and crystallinity as well as decrease their solubility. The improved molecular conformation can markedly affect the morphology of polymer:PC71BM blend films. After incorporation of 5 mol % 2,5-difluorobenzene unit into the backbone of donor polymers, the domain size of blend films became smaller and the hole mobility increased. Increasing the content of 2,5-difluorobenzene to 7 mol % can further decrease the solubility of resulting polymers and resulted in poor solution processability. As a result, P5-based devices achieved a power conversion efficiency (PCE) of 8.5%, whereas P0 based devices gave a PCE of 7.8%.

Impact of Aggregation on the Photochemistry of Fullerene Films: Correlating Stability to Triplet Exciton Kinetics.

The photochemistry and stability of fullerene films is found to be strongly dependent upon film nanomorphology. In particular, PC61BM blend films, dispersed with polystyrene, are found to be more susceptible to photobleaching in air than the more aggregated neat films. This enhanced photobleaching correlated with increased oxygen quenching of PC61BM triplet states and the appearance of a carbonyl FTIR absorption band indicative of fullerene oxidation, suggesting PC61BM photo-oxidation is primarily due to triplet-mediated singlet oxygen generation. PC61BM films were observed to undergo photo-oxidation in air for even modest (≤40 min) irradiation times, degrading electron mobility substantially, indicative of electron trap formation. This conclusion is supported by observation of red shifts in photo- and electro-luminescence with photo-oxidation, shown to be in agreement with time-dependent density functional theory calculations of defect generation. These results provide important implications on the environmental stability of PC61BM-based films and devices.

Laser-induced crystallization and conformation control of poly(3-hexylthiophene) for improving the performance of organic solar cells

Abstract Femto-second laser irradiation on P3HT:PCBM solutions have been demonstrated to have a significant impact on the conformational structures and photovoltaic performance of the resultant thin films. The crystallinity and edge-on/face-on conformations of P3HT and the aggregation of PCBM can be manipulated by controlling the wavelength (400–800 nm) and illumination duration (1–3 h) of the lasers. Grazing incidence wide- and small-angle X-ray scattering (GIWAXS and GISAXS) have been simultaneously utilized to characterize the nanostructures of the P3HT:PCBM blend films spin-cast from pristine and laser-irradiated solutions. The results show that the crystallinity, π-π* stacking and face-on conformations of P3HT can be enhanced as a result of the laser irradiation at 500 nm for 3 h. Furthermore, the diffusion and aggregation of PCBM molecules are suppressed by the photo-induced dimerization, as evidenced by the Raman spectra of the films cast from laser-irradiated PCBM solutions. The time-resolved fluorescence decay profiles show the charge transfer efficiency is improved, which may correlate to the supramolecular ordering of the polythiophene chains and the optimized phase separation in P3HT:PCBM composite. In the P3HT:PCBM active layer of the organic solar cells, more efficient charge transport and fine interpenetrating networks can be achieved due to the improved conformational microstructures. Consequently, the short-circuit current densities and power conversion efficiencies can be enhanced in organic solar cells based on the laser-irradiation processed P3HT:PCBM solutions.

Cross‐Linkable and Dual Functional Hybrid Polymeric Electron Transporting Layer for High‐Performance Inverted Polymer Solar Cells

A cross-linkable dual functional polymer hybrid electron transport layer (ETL) is developed by simply adding an amino-functionalized polymer dopant (PN4N) and a light crosslinker into a commercialized n-type semiconductor (N2200) matrix. It is found that the resulting hybrid ETL not only has a good solvent resistance, facilitating multilayers device fabrication but also exhibits much improved electron transporting/extraction properties due to the doping between PN4N and N2200. As a result, by using PTB7-Th:PC71 BM blend as an active layer, the inverted device based on the hybrid ETL can yield a prominent power conversion efficiency of around 10.07%. More interestingly, photovoltaic property studies of bilayer devices suggest that the absorption of the hybrid ETL contributes to photocurrent and hence the hybrid ETL simultaneously acts as both cathode interlayer material and an electron acceptor. The resulting inverted polymer solar cells function like a novel device architectures with a combination of a bulk heterojunction device and miniature bilayer devices. This work provides new insights on function of ETLs and may be open up a new direction for the design of new ETL materials and novel device architectures to further improve device performance.

Toward Long-Term Stable and Efficient Large-Area Organic Solar Cells.

Here, we report that long-term stable and efficient organic solar cells (OSCs) can be obtained through the following strategies: i) combination of rapid-drying blade-coating deposition with an appropriate thermal annealing treatment to obtain an optimized morphology of the active layer; ii) insertion of interfacial layers to optimize the interfacial properties. The resulting devices based on 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)] (PBDTTT-EFT):[6,6]-phenyl C71 butyric acid methyl ester (PC71 BM) blend as the active layer exhibits a power conversion efficiency (PCE) up to 9.57 %, which represents the highest efficiency ever reported for blade-coated OSCs. Importantly, the conventional structure devices based on poly(3-hexylthiophene) (P3HT):phenyl-C61 -butyric acid methyl ester (PCBM) blend can retain approximately 65 % of their initial PCE for almost 2 years under operating conditions, which is the best result ever reported for long-term stable OSCs under operational conditions. More encouragingly, long-term stable large-area OSCs (active area=216 cm2 ) based on P3HT:PCBM blend are also demonstrated. Our findings represent an important step toward the development of large-area OSCs with high performance and long-term stability.

Applying Thienyl Side Chains and Different π-Bridge to Aromatic Side-Chain Substituted Indacenodithiophene-Based Small Molecule Donors for High-Performance Organic Solar Cells.

A pair of linear tetrafluorinated small molecular donors, named as ThIDTTh4F and ThIDTSe4F, which are with tetrathienyl-substituted IDT as electron-rich central core, electron-deficient difluorobenzothiadiazole as acceptor units, and donor end-capping groups, but having differences in the π-bridge (thiophene and selenophene), were successfully synthesized and evaluated as donor materials in organic solar cells. Such π-bridge and core units in these small molecules play a decisive role in the formation of the nanoscale separation of the blend films, which were systematically investigated through absorption spectra, grazing incidence X-ray diffraction pattern, transmission electron microscopy images, resonant soft X-ray scattering profiles, and charge mobility measurement. The ThIDTSe4F (with selenophene π-bridge)-based device exhibited superior performance than devices based on ThIDTh4F (with thiophene π-bridge) after post annealing treatment owing to optimized film morphology and improved charge transport. Power conversion efficiency of 7.31% and fill factor of ∼0.70 were obtained by using a blend of ThIDTSe4F and PC71BM with thermal annealing and solvent vapor annealing treatments, which is the highest PCE from aromatic side-chain substituted IDT-based small molecular solar cells. The scope of this study is to reveal the structure-property relationship of the aromatic side-chain substituted IDT-based donor materials as a function of π-bridge and the post annealing conditions.

Interface engineering on phenanthrocarbazole/thienopyrroledione-based conjugated polymer for efficient organic photovoltaic devices with ideal nano-morphology and improved charge carrier dynamics

We synthesized PP-TPD, based on a phenanthro[1,10,9,8-cdefg]carbazole unit as a donor and a thieno [3,4-c]pyrrole-4,6-dione (TPD) unit as an acceptor for efficient bulk heterojunction photovoltaic cells. The copolymer achieves a relatively low bandgap (1.6 eV) by its internal charge-transfer, which concurs with the results of density functional theory (DFT) calculation for the distribution of HOMO and LUMO levels. In addition, we fabricated the bulk-heterojunction (BHJ) photovoltaic cells as a function of the blend ratio of the donor (PP-TPD) and acceptor (PC70BM), and applied a solvent additive and an interlayer to the device, with the optimized ratio used in this study. To comprehend the relationships between the device performance and the synergetic effects of 1,8-diiodooctane (DIO) and titanium oxide (TiOx) within the PP-TPD: PC70BM blends, we investigated the hole mobility related to the charge carrier transport, the charge generation, and the charge transport resistance using space-charge limited current (SCLC) measurement, photocurrent analysis, and impedance spectroscopy, respectively. Especially, we implemented fluorescence imaging by Raman spectroscopy, which related to the charge generation and recombination dynamics within the surface of photoactive areas.

Optical and electronic property tailoring by MoS2-polymer hybrid solar cell

The ternary blend system such as binary donor and an acceptor or binary acceptor and a donor offers a way to improve the power conversion efficiency of the polymer solar cells (PSCs) by enhancing optical properties and electrical properties. In this work, PTB7, PC71BM and Molybdenum disulfide nano-sheet (MoS2NS) ternary blend system were investigated as an active material for OPV. The optimized ternary blend system showed increment of 17% power conversion efficiency (PCE) from 6.98% to 8.18%. The origin of improved PCE mainly arises from the significant increment in JSC and marginal change in VOC and FF. This improved PCE is due to increased light harvesting and improved charge carrier mobility in the active matrix. The marginal enhancement in VOC and FF was correlated with the density of trap states (DOS) obtained from capacitance measurement of the device. The optical absorption and energy transfer mechanism of the ternary blend film is explained by absorption and photoluminescence measurement respectively. Further, the conversion efficiency due to improved charge carrier transport was described by modified SCLC mobility measurements for electron and hole only devices. The obtained result suggests that presence of MoS2NS along with PTB7:PC71BM binary system play dual role like an improved charge transport layer as well as light harvesting.

Increasing the fill factor of inverted polymer bulk heterojunction solar cells by doping PVP modified NaYF4 nanoparticles

ABSTRACTNaYF4 nanoparticles (NPs), synthesized by a facile solvothermal approach using polyvinylpyrrolidone (PVP) as a surfactant, were doped into P3HT:PCBM blend to fabricate inverted polymer bulk heterojunction solar cells. The results showed that the fill factor (FF) of the device was greatly enhanced by doping NaYF4 NPs/PVP composites into the active layer. There were evidences that PVP can form charge transfer (CT) complexes with PCBM. And the CT complexes, formed by PCBM and PVP carried by NaYF4 NPs, might make contributions to the phase separation of the active layer (P3HT:PCBM blend), which is vital to the FF of the devices.

π-Conjugation Effects of Oligo(thienylenevinylene) Side Chains in Semiconducting Polymers on Photovoltaic Performance

Semiconducting copolymers based on benzo[1,2-b:4,5-b′]dithiophene and thieno[3,4-c]pyrole-4,6-dione containing oligo(thienylenevinylene) side chains with different lengths were synthesized to examine the effect of the π-conjugated side chains on the performance of polymer solar cells (PSCs). Using the copolymers that had π-conjugated side chains as the PSC electron donor resulted in a higher short circuit current and fill factor compared with the reference copolymers, which had no side chain or an analogous side chain with no π-conjugation, resulting in an increase of power conversion efficiency of 10–22%. Measurements of hole mobility by space-charge-limited current and internal quantum efficiency indicated that introducing the π-conjugated side-chain units can facilitate both charge transport and charge separation in the polymer:PC71BM blend films.

Excitation Intensity Dependent Carrier Dynamics of Chalcogen Heteroatoms in Medium-Bandgap Polymer Solar Cells

The excitation intensity dependent carrier dynamics of blends with PC[70]BM of three new medium-band gap conjugated polymers with central chalcogen heteroatoms, PBDTfDTBX (X = O, T(Sulphur), Se) were studied. The PBDTfDTBX polymers (Poly[4,8-bis(5-(2-butyloctyl)thiophene-2-yl)benzo[1,2-b;4,5-b′]dithiophene-alt-4,7-bis(4-(2-ethylhexyl)-2-thienyl)-dithieno[3′,2′:3,4;2″,3″:5,6]benzo[1,2-c][1,2,5] furazan or thiadiazole or selenadiazole]) have symmetrical structures but exhibit different solar cell performances. In this study, we determined how the photogenerated charge carrrier dynamics of the PBDTfDTBX:PC[70]BM blends varies with the heteroatom by performing transient absorption measurements at various excitation intensities. It was found that the charge carrier dynamics of the PBDTfDTBX blends with X = T or Se heteroatoms are dependent on the excitation intensity whereas that of the PBDTfDTBO blend is independent of the intensity. The photogenerated charge carrier dynamics of the PBDTfDTBO:PCBM, PBDTfDTBT:PCBM, and PBDTfDTBSe:PCBM blends were all modeled globally and rates were estimated for different photophysical processes occurring on different time scales.

Electron-transporting small molecule/o-xylene hybrid additives to boost the performance of simplified inverted polymer solar cells

Electron-transporting small molecule bathophenanthroline (Bphen) together with o-xylene has been used as hybrid additives to improve the performance of simplified inverted polymer solar cells employing ITO alone as cathode and photoactive layer based on polymer [[2,6′-4,8-di(5-ethylhexylthienyl)benzo[1,2-b;3,3-b] dithiophene] [3-fluoro-2[(2-ethylhexyl)carbonyl]thieno[3,4-b]thiophenediyl]] (PTB7-Th) and (He et al., Nat. Photon. 9:174, 2015)-phenyl C71-butyric acid methyl ester (PC71BM). Because the Bphen additive could spontaneously aggregate onto the indium tin oxide (ITO) cathode during spin coating, the mixed solution containing PTB7-Th, PC71BM, and Bphen, thereby forming a thin cathode-modifying layer, the ternary blend PTB7-Th:PC71BM:Bphen functioned similar to a layered polyethylenimine ethoxylated (PEIE, a conventional cathode-modifying material)/binary blend PTB7-Th:PC71BM combination. The o-xylene additive was confirmed to enrich the distribution of PTB7-Th donor towards the bottom area of photoactive layer, thereby benefiting the charge collection in inverted structure. With the o-xylene optimization, the PTB7-Th:PC71BM:Bphen blend thin film showed a power conversion efficiency (PCE) of 5.87% in simplified inverted structure of ITO/photoactive layer/MoO3/Ag, much higher than that (4.21%) of the PTB7-Th:PC71BM blend thin film. The current research can be considered as a useful attempt towards fabricating low-cost photovoltaic devices without marked loss in PCE.

Unravelling the Thermomechanical Properties of Bulk Heterojunction Blends in Polymer Solar Cells

Glass transition temperature is a critical parameter for achieving favorable and thermally stable bulk heterojunction morphology as it determines the kinetics of molecular organization of polymeric semiconducting materials. This study presents a sensitive method of precisely determining the glass transition temperature (Tg) of conjugated polymers and polymer–PCBM blends using dynamic mechanical thermal analysis (DMTA). The method presented here is very versatile in which polymer or polymer–molecule films are reinforced using a woven glass fiber and utilizes only 5–10 mg of the material. This makes the method superior to differential scanning calorimetry (DSC) for determining the thermal properties of conjugated polymers. The effects of PCBM loading, solvents, and additive on the Tg of polymer–PCBM blends and on the miscibility of different phases are investigated using the novel DMTA method. For the P3HT:PC61BM system, two different thermal transitions were found corresponding to P3HT-rich and PCBM-rich p...

Generation of Photoexcitations and Trap-Assisted Recombination in TQ1:PC71BM Blends

The generation and recombination of long-lived photoexcitations is clarified in TQ1 films and TQ1:PC71BM 1:1 and 1:3, by weight, blends using photoinduced absorption measurements. At 80 K triplets are formed in TQ1 films, while both triplets and polarons are formed in the 1:1 and 1:3 blends. We suggest that the triplet state acts as a loss mechanism for generation of free charges in these blends and suggest an energy diagram for the photoexcitations in the blends. We estimate the triplet polaron annihilation (γTPA) constant to be 1.12 × 10–14 and 3.10 × 10–13 cm3 s–1 for the TQ1:PC71BM 1:1 and 1:3 blends, respectively. At 300 K triplets are mainly formed in the TQ1 films, while only polarons are present in the TQ1:PC71BM blends. Using frequency measurements we show that the TQ1:PC71BM 1:1 blend shows nondispersive kinetics (ζ = 1), while the 1:3 blend exhibits dispersive kinetics (ζ = 0.87). Using intensity-dependent measurements, we show that trap-assisted recombination is the dominating recombination me...

Structure-property relationship of D-A type copolymers based on thienylenevinylene for organic electronics

A series of D-A type conjugated polymers based on (E)-1,2-bis(3-dodecyllthiophen-2-yl)ethene (TV) as electron donor unit and with different repeating subunits, PTVBO8, PTVBT8, PTVTBO12, and PTVTBT12 were synthesized for use in organic field effect transistors and bulk heterojunction organic photovoltaics. Upon incorporation of alkoxy substituents in acceptor units, benzooxadiazole (BO) and benzothiadiazole (BT), polymer solubility improved and higher molecular weight polymers were obtained. In addition, all copolymers showed favorable thermal stability (Td > 300 °C), and low band gap properties (1.49–1.67 eV). The thiophene-flanked TV-TBX copolymers, PTVTBO12 and PTVTBT12, exhibited higher molecular weight and superior device performance in both OFETs and OPVs compared with the TV-BX copolymers. The electronic energy levels of copolymers were strongly influenced by the nature of acceptor units, while optical band gaps and shape of molecular orientation of polymer chains were affected by the presence or absence of thiophene spacer. Charge carrier mobilities in TV-TBX copolymers were 1 order of magnitude greater than in TV-BX copolymers. OFETs based on a PTVTBT12 with TG/BC configuration displayed the highest hole mobility of 0.48 cm2 V−1 s−1. The photovoltaic device containing a PTVTBO12:PC71BM (1:2 w/w) blend system exhibited best performance with a Voc of 0.56 V, a short-circuit current density (Jsc) of 13.1 mA cm−2, a fill factor (FF) of 69%, and a power conversion efficiency (PCE) of 5.0%.