Effect of blend layer thickness on the dielectric response of PCDTBT:PC71BM-based bulk heterojunction solar cells

Bulk heterojunction solar cells based on a blend of poly[N-9′-heptadecanyl-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), were studied. The organic photoactive layers were spin coated onto a poly(3,4-ethylenedioxythiophene)/poly(4-styrenesulfonate) (PEDOT-PSS) interfacial layer at speeds of 600 and 2000 rpm. The molecular structure of PCDTBT, PC₇₁BM, and the PCDTBT:PC₇₁BM blend was investigated using Fourier-transform IR (FTIR) spectroscopy, which confirmed the absence of interactions between the individual components of the composite. The dielectric properties of PCDTBT:PC₇₁BM-based solar cells were studied under illumination by means of impedance analysis. The dielectric constant, impedance, and ac conductance were analyzed as a function of frequency at different bias voltages close to the open circuit voltage (Voc). We found that the dielectric constant, dielectric loss, and conductance increased with increasing PCDTBT:PC₇₁BM thickness. Impedance spectroscopy analysis revealed decreases in charge recombination and the resistance of the whole device with increasing spin coating speed for the active layer. Moreover, an increase in recombination resistance for the solar cells was observed close to V_OC.     

Solvent–vapor induced morphology reconstruction for efficient PCDTBT based polymer solar cells

This paper reports polymer solar cells with a 7% power conversion efficiency (PCE) based on bulk heterojunction (BHJ) composites of the alternating co-polymer, poly[N-9′′-hepta-decanyl-2,7-carbazole-alt-5,5-(4′,7′-di-2-thienyl-2′,1′,3′-benzothiadiazole) (PCDTBT), and the fullerene derivative [6,6]-phenyl C₇₁-butyric acid methyl ester (PC₇₁BM). As confirmed by transmission electron microscopy, solvent–vapor annealing (SVA) of the thin (70 nm) BHJ photoactive layer by exposure to chloroform vapor, for a short period of time (30 s) after deposition, leads to reconstructed nanoscale morphology of donor/acceptor domains, well-dispersed fullerene phase and effective photo-absorption of BHJ. Consequently, SVA-reconstructed devices with a PCDTBT:PC₇₁BM blend ratio of 1:5 (wt%) exhibit ～50% improvement in PCE, with short-circuit current J_sc = 15.65 mA/cm², open-circuit voltage V_oc = 0.87 V, and PCE = 7.03%, in comparison to those of the 1:4 (wt%) blends with SVA treatment.     

Optimising the efficiency of carbazole co-polymer solar-cells by control over the metal cathode electrode

We have explored the effect of a range of different cathode materials on the power conversion efficiency of organic (polymer) solar cells based on a blend of the conjugated polymer poly[N-9′-heptadecanyl-2,7-carbazole-alt-5,5-(4′,7′-di-2-thienyl-2′,1′,3′-benzothiadiazole)] (PCDTBT) with the fullerene acceptor PC₇₀BM. We use a transfer matrix reflectivity model to quantify the optical properties of the cathode and the device structure on its operational efficiency and compare this with the results of experimental measurements. We show that both optical and electrical effects play a role in determining overall device efficiency through their impact on short-circuit current, open circuit voltage and fill-factor. We use our model to demonstrate that devices composed of a thin (60–70 nm) active semiconductor layer and a composite cathode composed of a 5 nm thick layer of calcium capped by aluminium combine low optical loss and improved charge extraction and optimised power conversion efficiency.     

Energy level alignment in PCDTBT:PC70BM solar cells: Solution processed NiOx for improved hole collection and efficiency

Solution-based NiO_x outperforms PEDOT:PSS in device performance and stability when used as a hole-collection layer in bulk-heterojunction (BHJ) solar cells formed with poly[N-9′-heptadecanyl-2,7-carbazole-alt-5,5-(4′,7′-di-2-thienyl-2′,1′,3′-benzothiadiazole) (PCDTBT) and PC₇₀BM. The origin of the enhancement is clarified by studying the interfacial energy level alignment between PCDTBT or the 1:4 blended heterojunctions and PEDOT:PSS or NiO_x using ultraviolet and inverse photoemission spectroscopies. The 1.6 eV electronic gap of PEDOT:PSS and energy level alignment with the BHJ result in poor hole selectivity of PEDOT:PSS and allows electron recombination at the PEDOT:PSS/BHJ interface. Conversely, the large band gap (3.7 eV) of NiO_x and interfacial dipole (?0.6 eV) with the organic active layer leads to a hole-selective interface. This interfacial dipole yields enhanced electron blocking properties by increasing the barrier to electron injection. The presence of such a strong dipole is predicted to further promote hole collection from the organic layer into the oxide, resulting in increased fill factor and short circuit current. An overall decrease in recombination is manifested in an increase in open circuit voltage and power conversion efficiency of the device on NiO_x versus PEDOT:PSS interlayers.     

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.     

Solution-processed annealing-free ZnO nanoparticles for stable inverted organic solar cells

We report the development and application of high-quality zinc oxide nanoparticles (ZnO NPs) processed in air for stable inverted bulk heterojunction solar cells as an electron extraction layer (EEL). The ZnO NPs (average size ∼11 nm) were dispersed in chloroform and stabilized by propylamine (PA). We demonstrated that the ZnO NP dispersion with 4 vol.% of PA as stabilizer can be used in air directly and remains clear up to one month after preparation. Our inverted solar cells consisted of a blade-coated poly(N-9′-heptadecanyl-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) (1: 4 by weight) active layer sandwiched between a ZnO electron extraction layer and a MoO₃/Ag anode. All solar cells with ZnO films fabricated in air using PA-stabilized ZnO dispersions prepared within a time window of one month exhibited power conversion efficiencies (PCE) above 4%. In contrast, if the ZnO film was prepared in air using regular un-stabilized ZnO NP dispersion, the PCE would drop to 0.2% due to poor film quality. More interestingly, X-ray photoelectron spectroscopy and nuclear magnetic resonance measurements indicated that the PA ligands were not covalently bonded to ZnO NPs and did not exist in the deposited ZnO films. The spin-cast ZnO thin films (without any thermal treatment) are insoluble in organic solvents and can be directly used as an EEL in solar cells. This feature is beneficial for fabricating organic solar cells on flexible polymer substrates. More importantly, our non-encapsulated inverted solar cells are highly stable with their PCEs remaining unchanged after being stored in air for 50 days.     

Highly efficient ITO-free polymer solar cells based on metal resonant microcavity using WO3/Au/WO3 as transparent electrodes

Indium tin oxide (ITO)-free polymer solar cells (PSCs) with the structure of Glass/tungsten trioxide (WO₃)/Au/WO₃/PCDTBT: PC₇₀BM/LiF/Al was fabricated and studied. The multilayer structure of WO₃/Au/WO₃ is used as the potential transparent electrode to replace ITO. Metal resonant microcavity, which can enhance light harvesting of active layers, was constructed between Au and Al electrodes. According to the J–V and IPCE characterization with 70 nm active layer, power conversion efficiency (PCE) of the ITO-free microcavity device is approaching 4.55%, which is higher than that of the ITO-based device. However, PCE of the ITO-free device is much lower than that of the ITO-based device when the thickness of active layer increases to 130 nm. The opposite experimental tendency leads to theoretical research toward the simulation of light absorption and optical electric field and the calculation of maximum short circuit current density (J_{sc max}) as a function of active layer thickness based on ITO-free and ITO-based devices. The research results show that microcavity effect is closely linked to intrinsic absorption of active layers.     

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%.     

Cathodic multilayer transparent electrodes for ITO-free inverted organic solar cells

We demonstrate cathodic multilayer transparent electrodes based on a ZnS/Ag/TiO_x (ZAT) structure for ITO-free inverted organic solar cells. A quality solution-based TiO_x layer is adopted as an inner dielectric layer to modify the effective work function of Ag, ensuring the ZAT electrode works as a cathode. The effect of the TiO_x layer is seen on the open-circuit voltage of a solar cell incorporating this layer, increasing to 900 mV from 600 mV in the case of a cell with a bare Ag layer for a bulk-heterojunction 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 C₇₀-butyric acid methyl ester (PCBM70). The results of a joint theoretical and experimental study indicate that the photocurrent of a ZAT-based solar cell can be significantly enhanced by carefully balancing the optical-spacer and cavity-resonance effects, both of which are modulated by the thickness of the WO₃ layer used as a hole-collection layer at the top anode side. ZAT-based inverted solar cells with an optimized structure exhibit a power conversion efficiency as high as 5.1%, which is comparable to that of the ITO-based equivalent.     

Improving the nanoscale morphology and processibility for PCDTBT-based polymer solar cells via solvent mixtures

The effect of solvent mixtures on the morphologies of poly[N-9′-hepta-decanyl-2,7-carbazole-alt-5,5-(4′,7′-di-2-thienyl-2′,1′,3′-benzothiadiazole)] (PCDTBT):[6,6]-phenyl C₇₁-butyric acid methyl ester (PC₇₁BM) blend films is investigated. 1,2,4-Trichlorobenzene (TCB) which is a good solvent for PCDTBT is selected to mix with chloroform (CF), chlorobenzene (CB) and o-dichlorobenzene (oDCB) for tuning the morphology of the PCDTBT:PC₇₁BM blend. It is found that formation of nanoscale phase separation with a fibrillar PCDTBT nanostructure of PCDTBT:PC₇₁BM blend which is favorable for exciton separation and charge carrier transport is strongly dependent on the solubility parameters of the solvent mixtures. A clearly defined nanoscale phase separation of the PCDTBT:PC₇₁BM blend can be obtained with TCB:CF mixture. The resulted morphology is similar to that produced with sole DCB solvent that is currently the best solvent for PCDTBT:PC₇₁BM blend solar cells. Moreover, the TCB:CF mixture demonstrates better solubility and processibility for PCDTBT:PC₇₁BM blend and allows us to prepare thick active layer that is required in large-area roll-to-roll process. The polymer solar cells with 250 nm- thick active layer are fabricated by using TCB:CF solvent mixture and the power conversion efficiency of the devices reaches 6.45%. A highest short-circuit current of 13.6 mA/cm² is achieved due to enhanced optical absorption of thick active layer.     

Solution processable,precursor based zinc oxide buffer layers for 4.5% efficient organic tandem solar cells

In this work we present regular and inverted organic tandem solar cells from poly[N-9′-hepta-decanyl-2,7-carbazole-alt-5,5-(4′,7′-di-2-thienyl-2′,1′,3′-benzothiadiazole): [6,6]-phenyl C₇₀-butyric acid methyl ester (PCDTBT:PC₇₁BM) with power conversion efficiencies of up to 4.5%. The recombination zone comprises an electron conducting, precursor based zinc oxide buffer layer that was applied from solution under ambient conditions and at moderate processing temperatures. Optimized active layer thicknesses in both subcells were derived from optical Transfer Matrix simulations. The short circuit current density of the tandem cell exceeds half the short circuit current density of the single absorber cells indicating a real gain in quantum yield when utilizing the tandem architecture.     

Origin of high fill factor in polymer solar cells from semiconducting polymer with moderate charge carrier mobility

The fill factor of polymer bulk heterojunction solar cells (PSCs), which is mainly governed by the processes of charge carrier generation, recombination, transport and extraction, and the competition between them in the device, is one of the most important parameters that determine the power conversion efficiency of the device. We show that the fill factor of PSCs based on thieno[3,4-b]-thiophene/benzodithiophene (PTB7):[6,6]-phenyl C₇₁-butyric acid methylester (PC₇₁BM) blend that only have moderate carrier mobilities for hole and electron transport, can be enhanced to 76% by reducing the thickness of the photoactive layer. A drift–diffusion simulation study showed that reduced charge recombination loss is mainly responsible for the improvement of FF, as a result of manipulating spatial distribution of charge carrier in the photoactive layer. Furthermore, the reduction of the active layer thickness also leads to enhanced built-in electric field across the active layer, therefore can facilitate efficient charge carrier transport and extraction. Finally, the dependence of FF on charge carrier mobility and transport balance is also investigated theoretically, revealing that an ultrahigh FF of 80–82% is feasible if the charge mobility is high enough (∼10⁻³–10⁻¹ cm²/V s).     

Layer by layer characterisation of the degradation process in PCDTBT:PC71BM based normal architecture polymer solar cells

This work demonstrates the stability and degradation of OSCs based on poly[N-9′-heptadecanyl-2,7-carbazole-alt-5,5-(4′,7′-di-2-thienyl-2′,1′,3′ benzothiadiazole)] (PCDTBT): (6,6)-Phenyl C₇₁ butyric acid methyl ester (PC₇₁BM) photoactive blend layers as a function of ageing time in air. Analysis of the stability and degradation process for the OSCs was conducted under ambient air by using current-voltage (I-V) measurements and x-ray photoelectron spectroscopy (XPS). The interface between photoactive layer and HTL (PEDOT:PSS) was also investigated. Device stability was investigated by calculating decay in power conversion efficiency (PCE) as a function of ageing time in the air. The PCE of devices decrease from 5.17 to 3.61% in one week of fabrication, which is attributed to indium and oxygen migration into the PEDOT:PSS and PCDTBT:PC₇₁BM layer. Further, after aging for 1000 h, XPS spectra confirm the significant diffusion of oxygen into the HTL and photoactive layer which increased from 3.0 and 23.3% to 20.4 and 35.7% in photoactive layer and HTL, respectively. Similarly, the indium content reached to 17.9% on PEDOT:PSS surface and 0.4% on PCDTBT:PC₇₁BM surface in 1000 h. Core-level spectra of active layer indicate the oxidation of carbon atoms in the fullerene cage, oxidation of nitrogen present in the polymer matrix and formation of In₂O₃ due to indium diffusion. We also observed a steady fall in the optical absorption of the active layer during ageing in ambient air and it reduced to 76.5% of initial value in 1000 h. On the basis of these experimental results, we discussed key parameters that account for the degradation process and stability of OSCs in order to improve the device performance.     

Effects of exciton blocking layer and cathode electrode work function on the performance of polymer solar cells

In this study the effects of some important processing and post-processing treatments on the performance of poly(3-hexylthiophene-2,5-diyl) (P3HT):[6,6]-phenyl-C₆₁-butyric acid methyl ester ([60]PCBM) solar cells were investigated. These parameters included the active layer film formation period, thermal annealing, electrical treatment, cathode work function modification, and exciton blocking layer type and thickness. Polymer bulk heterojunction solar cells having a glass/indium tin oxide (ITO)/poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS)/P3HT:PCBM/(Ca or LiF)/Al structure were fabricated. The morphology of the active layer was investigated using atomic force microscopy. The results showed that the morphology state of the active layer exactly after spin coating process was very important parameter, which could dictate different responses of solar cells to a certain treatment. Using solvent additives to prolong the film formation period and storing in small dish could reach the morphology of the active layer near its best state in which there was no need to apply common post-treatment processes. A thickness at about 20 nm was required for Ca layer to effectively act as exciton blocking layer while LiF with 1 nm thickness worked better.     

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

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

Stability enhancement of normal-geometry organic solar cells in a highly damp condition: A study on the effect of top electrodes

We present our efforts to enhance the stability of normal-geometry organic solar cells (n-OSCs), which are generally considered inferior to their inverted-geometry counterparts in terms of stability. Upon the identification of the vulnerability of top electrode/buffer layer interfaces under a humid environment, various top electrode combinations are assessed under an extremely damp condition (27 °C, 90%) for n-OSCs based on a bulk-heterojunction 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 C70-butyric acid methylester (PCBM70). Based on the experimental results, we propose an Al/Cu bilayer top electrode and demonstrate a 30-fold enhancement in the T₈₀-lifetime values. Our study reveals that the enhanced lifetime with an Al/Cu bilayer electrode can be attributed to its water vapor transmission rate (WVTR), which is significantly lower than that of the Al electrodes typically used in conventional organic solar cells. The enhanced normal OSCs yielded stability comparable to that of the previously reported inverted OSCs.     

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.     

Enhancing the short-circuit current,efficiency of inverted organic solar cells using tetra sulfonic copper phthalocyanine (TS-CuPc) as electron transporting layer

Efficient bulk-heterojunction polymer solar cells based on poly(3-hexylthiophene) (P3HT) blended with a fullerene derivative, [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) were fabricated in inverted configuration by using copper phthalocyanine-3,4′,4′′,4′′′tetra-sulfonated acid tetrasodium salt (TS-CuPc) as the electron collecting layer and MoO₃ as hole collecting layer. TS-CuPc is observed to be critical for the device performance, significantly enhancing the Jsc and the PCE compared to devices based on TiOx. The optimal thicknesses of MoO₃ and TS-CuPc were 10 nm and 15 nm, respectively. Based on these optimal parameters, the PCE of 3.6% was obtained compared to 3.4% for the reference TiOx/P3HT:PCBM/MoO₃/Ag.     

Adhesion properties of inverted polymer solarcells: Processing and film structure parameters

We report on the adhesion of weak interfaces in inverted P3HT:PCBM-based polymer solar cells (OPV) with either a conductive polymer, PEDOT:PSS, or a metal oxide, molybdenum trioxide (MoO₃), as the hole transport layer. The PEDOT:PSS OPVs were prepared by spin or spray coating on glass substrates, or slot-die coating on flexible PET substrates. In all cases, we observed adhesive failure at the interface between the P3HT:PCBM with PEDOT:PSS layer. The adhesion energy measured for the solar cells made on glass substrates was about 1.8 J/m², but only 0.5 J/m² for the roll-to-roll processed flexible solar cells. The adhesion energy was insensitive to the PEDOT:PSS layer thickness in the range of 10–40 nm. A marginal increase in adhesion energy was measured with increased O₂ plasma power. Compared to solution processed PEDOT:PSS, we found that thermally evaporated MoO₃ adheres less to the P3HT:PCBM layer, which we attributed to the reduced mixing at the MoO₃/P3HT:PCBM interface during the thermal evaporation process. Insights into the mechanisms of delamination and the effect of different material properties and processing parameters yield general guidelines for the design of more reliable organic photovoltaic devices.     

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.