Non-peripheral octahexylphthalocyanine doping effects in bulk heterojunction polymer solar cells

The improvement of long-wavelength sensitivity in bulk heterojunction organic thin-film solar cells based on poly(3-hexylthiophene) (P3HT) by the addition of the soluble phthalocyanine derivative, 1,4,8,11,15,18,22,25-octahexylphthalocyanine (C6PcH₂) is reported. C6PcH₂ possesses near-infrared absorption and can be mixed with a P3HT:1-(3-methoxy-carbonyl)-propyl-1-1-phenyl-(6,6)C61 (PCBM) bulk heterojunction active layer. By doping C6PcH₂, the photosensitivity in the long-wavelength region was improved, and the energy conversion efficiency reached 3.0% at a composition ratio of P3HT:C6PcH₂:PCBM = 10:3:10. We discuss the principle of photoconversion in the bulk heterojunction solar cell based on the P3HT:C6PcH₂:PCBM active layer by taking into consideration the existence of both highly ordered P3HT domains and hexagonal columnar structures of C6PcH₂, and the microphase separation of P3HT and C6PcH₂ in the active layer.     

Magnetoconductance of polymer–fullerene bulk heterojunction solar cells

The organic magnetoconductance (MC) effects in poly(3-hexylthiophene): [6,6]-phenyl-C61-butyricacid methylester based bulk heterojunction solar cells were studied in dark and under illumination. The correlations between the MC and current character were revealed in this study. Results show that the dark current always exhibits a negative MC whereas a sign change in MC under illumination occurs at the bias around the open circuit voltage V_oc. We suggest that the positive MC in photocurrent is due to the field dependent conversion of singlet electron–hole pairs to triplet states and the negative MC is associated with space charge limited current with traps. Other possible mechanisms about the magnetoconductance effects are also discussed.     

Effect of bulk and planar heterojunctions based charge generation layers on the performance of tandem organic light-emitting diodes

Tandem organic light-emitting diodes (OLEDs) were fabricated using organic planar and bulk heterojunctions based charge generation layers (CGLs), which were composed of cobalt phthalocyanine (CoPc) and fullerene (C₆₀). The electroluminescent (EL) characteristics of these two kinds of devices were systematically studied. The results showed that, compared to the corresponding devices with planar heterojunction (PHJ) based CGL, the tandem OLEDs with bulk heterojunction (BHJ) based CGL exhibited a dramatic improvement of performance. By investigating the electrical characteristics of CGLs, it was found that more hetero-interfaces introduced in the BHJ blend were beneficial for generating more interfacial dipoles and charge carriers, and the optimized charge transport pathways were favorable to promote both electron and hole mobilities. As a result, the improved charge carrier balance led to the efficiency enhancement of device performance. The results demonstrated the advantageous effect of BHJ blend film for the rational design of CGLs on the realization of high OLEDs performance.     

Highly efficient organic tandem solar cell based on SubPc:C70 bulk heterojunction

Highly efficient organic tandem solar cell with peak power conversion efficiency (PCE) of 7.66% has been demonstrated by simply stacking two same boron subphthalocyanine (SubPc):C₇₀ bulk heterojunction devices, with a high active inter-connecting layer composed of bathophenanthroline (Bphen)/Silver/hexadecafluoro-copper-phthalocyanine (F₁₆CuPc)/MoO₃. We find that F₁₆CuPc plays an important role which extends the recombination zone, facilitates the extraction of hole and the carrier recombination. The measured PCE of the tandem solar cell corresponds to a 38% increase compared to that the optimal single cell.     

Tuning the viscosity of halogen free bulk heterojunction inks for inkjet printed organic solar cells

For the solution processing of organic photovoltaics on an industrial scale, the exclusion of halogenated solvents is a necessity. However, the limited solubility of most semiconducting polymer/fullerene blends in non-halogenated solvents results in ink formulations with low viscosities which poses limitations to the use of roll-to-roll compatible deposition processes, such as inkjet printing. We propose to add polystyrene as a rheological modifier to increase the viscosity of bulk heterojunction (BHJ) non-halogenated inks. The printing and performance of P3HT/PCBM photoactive layer inks are characterized as a function of polystyrene concentration and three different molecular weights. Addition of 1 wt% polystyrene provided a near two-fold gain in viscosity, with the largest viscosity gains coming from the polymer with the highest molecular weight. However, this coincided with greater viscoelastic behavior, which reduced the jetting performance of the inks. Differences in solvent compatibility of the polystyrene/P3HT/PCBM ternary blend resulted in phase separation upon layer drying, whereby polystyrene segregated to the layer-air interface to form an isolated domain or network like topology. Nevertheless, a 1.7-fold increase in dynamic viscosity was obtained for devices with printed BHJ layers containing polystyrene at the expense of a 20% reduction in OPV performance. The improved viscosity and good printing behavior achieved with small additions of polystyrene demonstrates its potential to overcome the limited viscosity resulting from typical non-halogenated ink formulations for semiconducting polymers. These results offer a step forward to the industrialization of inkjet printing as an effective deposition technique for functional layers of organic electronics.     

Improved efficiency of solution processed small molecules organic solar cells using thermal annealing

A solution processable A-D-A-D-A structure small molecule DCAEH5TBT using a BT unit as the core has been designed and synthesized for application in BHJ solar cells. The device employing DCAEH5TBT/PC₆₁BM as active layer shows PCE of 2.43% without any post treatment. After thermal annealing (150 °C, 10 min), the PCE of this molecule based device increased to 3.07%, with J_sc of 7.10 mA/cm², V_oc of 0.78 V and FF of 55.4%, which indicates that high performance of solution processed small molecule based solar cells can be achieved using thermal annealing by carefully design molecule structure.     

Ternary organic solar cells based on non-fullerene acceptors: A review

Organic solar cells (OSCs) have reached their second golden age in recent two years with a boosted number of publications. Non-fullerene acceptor (NFA) materials have become a rising star in the field which are widely applied in organic solar cells because of their excellent optoelectronic properties, such as strong light-harvesting ability and tunable energy level. Unlike the low synthetic flexibility and high production cost of fullerene materials, NFAs exhibit flexible structures, and relatively low fabrication costs. Recently, the ternary strategy has become another hot research topic in the field, which introduces a third component into the binary host system for OSCs. The application of a ternary strategy can break the limits of light absorption brought by the host system, improve the morphology and energy level alignment for the active layer and thus improved the efficiency of organic solar cell devices. Benefiting from the advancement in both NFA and ternary strategy, the power conversion efficiency (PCE) of organic solar cell has exceeded over 17.5% to date. A comprehensive review of the recent progress in NFA based ternary OSCs (TOSCs) is needed in the field. Herein, this review mainly focuses on recent research on ternary organic solar cells using NFA materials during the last two years. Firstly, device physics and frequently used active materials in NFA based TOSCs are summarized and discussed. Then, the recent reported high-performance NFA based TOSCs are reviewed. Finally, the outlook and future research direction in the field are proposed. This review aims to provide an insight into NFA based TOSCs and help researchers to explore the full potential of OSCs.     

Determination of the optical constants of bulk heterojunction active layers from standard solar cell measurements

The determination of the optical constants n(λ) and k(λ) for organic bulk heterojunction (BHJ) active layers from standard solar cell measurements is presented. We show for a small molecule based as well as for polymer solar cells that the complex refractive index can be derived from the external quantum efficiency (EQE) in combination with current–voltage curves obtained from a series of devices with different active layer thicknesses. The results are compared to those obtained via established techniques and the impact of differences in n(λ) and k(λ) on the solar cells is shown by simulation of the current density using a transfer matrix model.     

Small molecules based on bithiazole for solution-processed organic solar cells

A series of donor-acceptor-donor small molecules (1-3) with bithiazole as acceptor unit, triphenylamine as donor unit and thiophene with different number (0, 1, 2) as bridge were synthesized by palladium(0)-catalyzed Suzuki or Stille coupling reactions. The thermal, optical, electrochemical, charge transport, and photovoltaic properties of these small molecules were examined. All compounds exhibit excellent thermal stability with decomposition temperatures (5% weight loss) over 390 °C in nitrogen atmosphere. As increasing the number of thiophene and π-conjugation length of molecule, the absorption maximum in film red shifts from 406 to 498 nm, the extinction coefficient increases from 1.35 × 10⁴ to 7.66 × 10⁴ M⁻¹ cm⁻¹, and the optical band gap decreases from 2.6 to 2.0 eV. The electron-donating thiophene and bithiophene in compounds 2 and 3 up-shift HOMO energy level from −5.42 (1) to −5.24 eV (2) or −5.22 eV (3), and down-shift LUMO energy level from −2.48 (1) to −2.84 eV (2) or −2.81 eV (3). The hole mobility of compound 3 is up to 3.6 × 10⁻⁴ cm² V⁻¹ s⁻¹, which is one order of magnitude higher than that of compound 2, but compound 1 shows no field-effect transistor performance. Solution-processed bulk heterojunction organic solar cells based on 1-3:PC₇₁BM (1:4, w/w) blend films exhibit increasing power conversion efficiency (up to 2.61%) as increasing thiophene unit number.     

D-A-D-A-D push pull organic small molecules based on 5,10-dihydroindolo[3,2-b]indole (DINI) central core donor for solution processed bulk heterojunction solar cells

Two D-A-D-A-D small molecules based on same 5,10-dihydroindolo [3,2-b]indole central donor core and different benzothiadiazole (BT) and fluorine substituted BT (FBT) acceptor units, denoted as p-DINI-(BTTh₃)₂ (1) and p-DINI-(FBTTTh₃)₂ (2), respectively were synthesized and their optical and electrochemical properties were investigated. These molecules were applied as donor along with PC₇₁BM as electron acceptor for the fabrication of solution processed bulk heterojunction organic solar cells. The solar cells prepared from the optimized active blended layer (1:2) cast from dichlorobenzene (DCB) showed overall power conversion efficiency (PCE) of 2.02% and 2.70% for 1 and 2, respectively as donor. The higher PCE of 2 as compared to 1 is attributed to the higher hole mobility and broader IPCE spectra. In order to improve the PCE we have employed a two step treatment of active layer i.e. solvent vapor annealing after thermal annealing (SVA-TA) and the PCE has been enhanced up to 4.14% and 5.27% for optimized 1:PC₇₁BM and 2:PC₇₁BM active layers, respectively. The improvement in the PCE has been resulted from the improvement in the balanced charge transport and better crystallinity of the donor in the blended active layer.     

Power conversion efficiency enhancement of organic solar cells by addition of gold nanostars,nanorods, and nanospheres

The effects of gold (Au) nanoparticles (NPs) with different morphologies (star, rod, sphere) incorporated into buffer layer, poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS), of polymer-based organic solar cells (OSCs) were investigated. Solar cells having gold nanoparticles exhibited significant improvement in device efficiency relative to the reference device. The observed improvement is most likely due to the surface plasmon and enhanced light reflection and scattering properties of the Au NPs. The power conversion efficiency (PCE) is increased ca. 29% with Au nanostars, ca. 14% with Au nanorods and 11% with Au nanospheres compared to the device with no Au NP (reference device). Au nanostars provide the strongest contribution to the efficiency among all NP morphologies studied as they have large size, sharp features, and strongest localized surface plasmon resonance effect associate with their morphology.     

Tail states recombination limit of the open circuit voltage in bulk heterojunction organic solar cells

An analytical theory is presented for bimolecular recombination through tail states and open circuit voltage in bulk heterojunction organic solar cells. It is developed rigorously using the hopping transport and the drift diffusion theory. Based on the proposed model, a variety of temperature, energy disorders of the material and illumination intensity dependencies of the open circuit voltage can be well described. Good agreement between the calculation and recent experimental data is found.     

Analytical modeling of organic solar cells including monomolecular recombination and carrier generation calculated by optical transfer matrix method

An analytical model of organic solar cell has been developed including the effect of monomolecular recombination and charge carrier generation rate, simultaneously. The charge carrier generation rate, depending on position and wavelength, obtained from optical transfer matrix method, has been incorporated into electrical transport equation of carriers; this has led to combining optical and electrical phenomena into this model. Charge carrier generation rate profile has been investigated and included to develop the model. The proposed model addresses the propagation of light and the effects of optical phenomena like reflection and interference inside the device. Compared to previous models, this model is an improved version because of considering recombination mechanism and position and wavelength dependent generation rate simultaneously. This analytical model is useful for finding the performance of the organic solar cell device such as current-voltage relation, power-voltage relation, efficiency, etc. avoiding the complexities of numerical calculations. The proposed model has been validated by comparing the results obtained from the model with that of published experimental works. This model may help to analyse organic solar cells and optimize their parameters for improving the performance.     

Effects of processing additives on nanoscale phase separation,crystallization and photovoltaic performance of solar cells based on mesogenic phthalocyanine

A study on the effects of processing additives on the nanoscale phase separation, crystallization, and photovoltaic performance of bulk heterojunction (BHJ) thin films made of 1,4,8,11,15,18,22,25-octahexylphthalocyanine (C6PcH₂) and [6,6]-phenyl-C61 butyric acid methyl ester (PCBM) via spin-casting for photovoltaic applications is reported. By incorporating various solvents as processing additives to a volume of a few percent, the separation of donor and acceptor phases in C6PcH₂:PCBM thin films, which discussed by taking the photoluminescence quenching, Davydov splitting at the Q-band of the absorbance spectra and the surface nanomorphology into consideration, is improved, and the crystallinity of the discotic C6PcH₂ molecules with hexagonal structures is reinforced. Photovoltaic cells with the optimum phase-separated BHJ materials and high crystallinity of the discotic C6PcH₂ molecules are demonstrated to have a power conversion efficiency of 4.2%.     

Controlling the morphology of nanofiber-P3HT:PCBM blends for organic bulk heterojunction solar cells

Within the field of organic bulk heterojunction solar cells, the morphology of the active layer has a key role in obtaining high power conversion efficiencies. P3HT nanofibers, obtained in highly concentrated solutions, are able to give controlled morphologies directly upon deposition. Since the solar cell efficiency of fiber solar cells depends on the fiber content of the casting solution, it is important to control this parameter. Here, we demonstrate an easy way to control the fiber content in the casting solution, i.e. changing the solution temperature. By using solution heating, the overall molecular weight of the polymer in the blend is kept constant, fiber isolation is not needed and the use of solvent mixtures is avoided. The obtained optimal power conversion efficiency is shown to be linked to the morphology of the active layer, which is studied with Transmission Electron Microscopy (TEM).     

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.     

Influence of molar mass ratio,annealing temperature and cathode buffer layer on power conversion efficiency of P3HT:PC71BM based organic bulk heterojunction solar cell

In bulk heterojunction (BHJ) solar cells, the molar mass ratio of donor-acceptor polymers, the annealing temperature (T_an) and the cathode buffer layer plays very consequential role in improving the power conversion efficiency (PCE) by tuning the film morphology and enhancing the charge carrier dynamics. A comprehensive understanding of each of these factors is essential in order to optimize the performance of organic solar cells (OSCs). Albeit there are several fundamental reports regarding these factors, an altogether meticulous correlation of these physical processes with experimental evidence of the photo active layer are required. In this work, we systematically analyzed the influence of different molar mass ratio, the annealing temperature (T_an) and the cathode buffer layer of rrP3HT:PC₇₁BM based BHJ solar cells and their corresponding photovoltaic performances were correlated carefully with their thin film growth structure and energy level diagram. The device having 1:0.8 molar mass ratio of rrP3HT:PC₇₁BM and T_an = 150 °C annealing temperature with Bathocuproine (BCP) as the cathode buffer layer having ITO/PEDOT:PSS/rrP3HT:PC₇₁BM (molar mass ratio = 1:0.8; (T_an = 150 °C)/BCP/Al) configuration showed the best device performance with PCE, ɳ = 4.79%, Jsc = 14.21 mA/cm², V_oc = 0.58 V and FF = 57.8%. This drastic variation in PCE of the device having BCP/Al as the cathode contact compared to the other device configurations is due to the coalesced effects of better hole-blocking capacity of BCP along with Al and better phase separation of the active blend layer at 150 °C annealing temperature. These results explicate the cumulate role of all these physical parameters and their combined contribution to the PCE amendment and overall device performance with rrP3HT:PC₇₁BM based organic BHJ solar cell.     

An equivalent circuit approach to organic solar cell modelling

In this paper, we present a simulation study for a newly prepared organic solar cell, based on a composite of poly (2-methoxy-5-(2′-ethylhexyloxy)-1, 4-phenylenevinylene (MEH-PPV) with [6, 6]-phenyl C₆₀ butyric acid methyl ester (PCBM). Photo-current density vs. voltage (J–V) characteristics, for the cell, which were experimentally studied earlier, have been revisited here. The results indicated that the conduction mechanism in the organic solar cell is strongly influenced by the excitonic diffusion. Sound correlation, between theoretical and experimental photo-current density vs. voltage (J–V) plots, has been achieved. Moreover, the simulation clearly demonstrates that the performance of the tested device can be described, with sound accuracy, by a two-diode-equivalent model.     

The effect of processing solvent dependent film aggregation on the photovoltaic performance of squaraine:PC71BM bulk heterojunction solar cells

In this work, we systemically investigated the processing solvent-dependent aggregation behavior of a squaraine dye, 2,4-bis[4-(N,N-dibutylamino)-2,6- dihydroxyphenyl] squaraine (DBSQ), in a DBSQ: [6,6]-phenyl-C71-butyric acid methyl ester (PC₇₁BM) blend film, as well as the aggregation effect on the photovoltaic performance of DBSQ:PC₇₁BM bulk heterojunctions (BHJs). Our finding shows that the aggregation behavior of DBSQ dye in the blend film can be controlled via the proper selection of the processing solvents. For a J-aggregate (head-to-tail molecule alignment) DBSQ:PC₇₁BM active layer based BHJ cells, a power conversion efficiency (PCE) of over 5% can be obtained, which is 75% higher than that of the H-aggregate (parallel molecule packing) active layer based BHJ cells. Our results indicate that the processing solvent controlled J-aggregation formation shall be considered as effective approach to tune the optical and electrical properties of thin films for high-performance BHJ solar cells.     

Effect of side chains on the electronic and photovoltaic properties of diketopyrrolopyrrole-based molecular acceptors

Four molecular electron acceptors based on a common phthalimide end-capped diketopyrrolopyrrole π-conjugated backbone, solubilized by different alkyl groups, have been synthesized. The influence of the nature and position of the solubilizing alkyl chains attached at the three constitutive blocks has been investigated. Results collected from UV–Vis absorption spectroscopy, cyclic voltammetry, solar cells fabrication and testing as well as atomic force microscopy show that the mode of substitution has negligible effect at the molecular level but strongly affects the material self-assembling properties, charge carrier transport and in turn, devices performances.