Improved performance of inverted polymer solar cells by utilizing alcohol-soluble oligofluorenes as efficient cathode interlayers

Two star-shaped oligofluorenes with hexakis(fluoren-2-yl)benzene as core are designed and synthesized, namely Tn0 and Tn1. Diethylamino groups are attached to the side chain of fluorene units of Tn0 and Tn1 and enable them alcohol solubility, additional hydrophobic nhexyl chains are grafted on the π-extended fluorene arms of Tn1. Power conversion efficiency (PCE) as high as 8.62% and 8.80% are achieved when utilizing Tn0 and Tn1 as cathode interlayers in inverted polymer solar cells, respectively. The work function of ITO effectively decreased by introducing interlayer, resulting in high Voc of the device, besides, the wetting properties of the interlayers can be tuned by modifying the oligofluorenes with π-extended structure, and the more hydrophobic interlayer will benefit the device performance with enhanced Jsc and FF.     

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).     

Ionic liquids with variable cations as cathode interlayer for conventional polymer solar cells

Interfacial layer materials have been demonstrated to be crucial for high-efficiency polymer solar cells (PSCs). In this work, we use ionic liquid (IL) as cathode interfacial layer (CIL) for highly efficient conventional PSCs (c-PSCs) and investigate functions of ILs with different cations and substituents. Employing IL as the CIL, PBDTTT-C:PC₇₁BM-based c-PSC affords a power conversion efficiency (PCE) of 7.29%, much higher than that without the CIL (2.78%) and that with Ca/Al electrode (6.18%). When the photoactive layer is a PTB7-Th:PC₇₁BM blend, a higher PCE of 8.67% can be obtained. The ILs reduce the energy barrier due to the existence of interfacial dipole in c-PSCs, leading to increased electron and hole mobilities, reduced series resistance and enhanced contact at the cathode interface. Meanwhile, alkyl chain-substituted ILs offer higher fill factor and PCE than aromatic groups-substituted analogue, which is mainly contributed to more balanced electron and hole mobilities. This work suggests that the ILs are qualified candidates as the CIL for c-PSCs and that one should take the substitution effect into account when choosing a CIL from a large library of materials.     

Rubrene-based interfacial engineering toward enhanced performance in inverted polymer solar cells

Rubrene, an organic semiconductor having stable fused-ring molecular structure was used as a double interfacial layer in inverted organic solar cells. When a thin, 3 nm-thick layer of rubrene was introduced between a MoO₃-based hole-collecting layer and a bulk-heterojunction (BHJ) photo-active layer consisting of poly{4,8-bis[(2-ethylhexyl)oxy]benzo[1,2-b:4,5-b']dithiophene-2,6-diyl-alt-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 power conversion efficiency was improved over 12% (from 7.2% to 8.1%). It was demonstrated that the insertion of thin rubrene layer showed suppressed exciton quenching and improved exciton dissociation, resulting in more efficient charge carrier collection and weaker charge recombination, thus improving the device performance.     

Influence of flexible substrates on inverted organic solar cells using sputtered ZnO as cathode interfacial layer

Zinc oxide (ZnO) has recently shown to be of considerable interest for the development of interfacial buffer layers in inverted organic solar cells (OSCs). High quality ZnO thin films can indeed be prepared on large-area ITO-coated flexible substrates, using low temperature deposition techniques such as sputtering, a compatible technique with roll-to-roll process. However, further studies are still needed for a better understanding of the influence of the flexible substrate properties on the photovoltaic performances of those devices. In this work, ZnO films have been sputtered on ITO-coated flexible (PEN) substrates and annealed at different temperatures. The role of the surface morphology and the crystalline quality of ZnO films has been investigated. In the window of flexible compatible process, we found that moderate annealing temperatures of ZnO (?180 °C) lead to improved structural properties and performances. Interestingly, we achieve optimal performances for an annealing temperature of 160 °C, resulting in power conversion efficiency (PCE) equivalent to the highest performances usually achieved on rigid cells.     

Influences of charge of conjugated polymer electrolytes cathode interlayer for bulk-heterojunction polymer solar cells

Two fluorene-based conjugated polymer electrolyte (CPE) poly[(9,9-bis(6′-(N,N,N-trimethylammonium)hexyl)-2,7-fluorene)-alt-2,7-(9,9-dioctylfluorene)] (PFNBr) and poly[9,9-bis(4′-sulfonatobutyl)fluorene-alt-2,7-(9,9-dioctylfluorene)] sodium salt (PFSO₃Na), bearing amine groups and anionic sulfonate groups on side chains respectively, are synthesized and applied as cathode interlayer in polymer solar cells. Both of the hydrophilic CPEs can well modify the interfacial properties and allow ohomic contact between the activelayer and cathode. The opposite charges exert great influence on the effective work function of cathode and interfacial interaction through the orientation of the interfacial dipole at the active layer/metal electrode interface, subsequently influence the resulting device performance. Compared with the cationic PFNBr, PFSO₃Na with anionic sulfonate groups can dramatically reduce the work function of Al by accumulation of the polar groups at the PFSO₃Na/Al interface to induce more favorable the interfacial dipole. The better energy alignment for electron extraction and transportation at active layer/Al interface is confirmed by a significant enhancement of V_OC. The better wettability and morphology of PFSO₃Na on the active layer and the more effective motion of sodium counterion further modify the barrier to facilitate electron extraction and transportation. Moreover, 14% and 22% performance enhancement can also be achieved respectively, when PFNBr and PFSO₃Na are used as interlayers for low bandgap poly[N-9″-heptadecanyl-2,7-carbazole-alt-5,5-(4′,7′-di-2-thienyl-2′,1′,3′-benzothiadiazole)] (PCDTBT)-based solar cells.     

Acid-functionalized fullerenes used as interfacial layer materials in inverted polymer solar cells

Two types of carboxylic acid functionalized fullerence derivatives, 4-(2-ethylhexyloxy)-[6,6]-phenyl C₆₁-butyric acid (p-EHO-PCBA) and bis-4-(2-ethylhexyloxy)-[6,6]-phenyl C₆₁-butyric acid (bis-p-EHO-PCBA), were synthesized and investigated as an interfacial layer for inverted polymer solar cells (iPSCs). The –COOH groups on the PCBAs chemisorb to inorganic metal oxide (TiO_X), generating fullerene-based self-assembled monolayers (FSAMs). The devices with the mono- and bis-FSAMs exhibited substantially lower series resistance (R_S) values of 2.10 Ω cm² and 1.46 Ω cm², compared to that (4.15 Ω cm²) of the unmodified device. The TiO_X films modified with mono- and bis-FSAMs showed higher contact angles of 50° and 91°, respectively, than that of the pristine TiO_X film (33°). The increased contact angles were attributed to the enhanced hydrophobicity, improving the wetting properties with the organic photoactive layer. In addition, a comparison of device characteristics with electroactive FSAMs and non-electroactive benzoic acid SAMs clearly indicates that the FSAMs may suggest an additional pathway for photo-induced charge transfer and charge collection to ITO. After surface modification with FSAMs, the short-circuit current density (J_SC) and fill factor (FF) values increased substantially. The iPSCs based on poly(5,6-bis(octyloxy)-4-(thiophen-2-l)benzo[c][1,2,5]thiadiazole) (PTBT) and [6,6]phenyl-C₆₁-butyric acid methyl ester (PCBM) as an active layer showed remarkably improved power conversion efficiency up to 5.13% through incorporation of the FSAMs-based interfacial layer.     

Solution-processed vanadium oxide as an anode interlayer for inverted polymer solar cells hybridized with ZnO nanorods

Solution-processed vanadium oxide (V₂O₅) as an anode interlayer is introduced between the organic layer and the Ag electrode for improving the performance of the low-cost inverted polymer solar cells hybridized with ZnO nanorods. Our investigations indicate that the solution-processed V₂O₅ interlayer as an electron-blocking layer can effectively prevent the leakage current at the organic/Ag interface. The power conversion efficiency is improved from 2.5% to 3.56% by the introduction of the V₂O₅ interlayer. The V₂O₅ interlayer also serves as an optical spacer to enhance light absorption, and thereby increases the photocurrent. Compared to the vacuum-deposited techniques, the fabrication of the solution-processed V₂O₅ interlayer is simple and effective. The solution-based approach makes it attractive for applications to mass production and potentially printed organic electronics.     

High-performance inverted polymer solar cells with lead monoxide-modified indium tin oxides as the cathode

The photovoltaic stability of polymer solar cells (PSCs) can be greatly improved by adopting an inverted device structure. This paper reports high-performance inverted PSCs with lead monoxide (PbO)-modified indium tin oxide (ITO) as the cathodes. A thin PbO layer can effectively lower the work function of ITO from 4.5 to 3.8 eV. The optimal inverted PSCs with poly(3-hexylthiophene) (P3HT) as the donor and [6,6]-phenyl-C₆₁-butyric acid methyl ester (PCBM) as the acceptor exhibited high photovoltaic performance: open-circuit voltage of 0.59 V, short-circuit current density of 10.8 mA cm⁻², fill factor of 0.632, and power conversion efficiency of 4.00% under simulated AM1.5G illumination (100 mW cm⁻²). The photovoltaic efficiency is significantly higher than that of the control inverted PSCs with unmodified ITO as the cathode. It is even better than that of the control PSCs with normal architecture, which have an optimal efficiency of 3.5%. The lowering in the work function by the PbO modification is attributed to the charge transfer between PbO and ITO, as evidenced by the X-ray photoelectron spectra.     

Effect of PEI cathode interlayer on work function and interface resistance of ITO electrode in the inverted polymer solar cells

In this paper, we investigated the effect of PEI cathode interlayer on the work function and the interface resistance of ITO electrode in the inverted polymer solar cells (PSCs) based on PBDTTT-C-T:PC₇₀BM. It is found that a very thin layer of PEI (⩽5.5 nm), either linear PEI (l-PEI) or branched PEI (b-PEI) with different molecular weights, is enough to lower the work function of the ITO electrode and to enhance the photovoltaic performance of the devices. The champion power conversion efficiency (PCE) of the devices with the PEI cathode interlayer is 7.84%, more than doubled of that without the interlayer. However, a thicker PEI interlayer (⩾10 nm) results in abrupt decrease of the PCEs due to the increase of the resistance. Interestingly, for the thicker interlayers, the l-PEI shows high photovoltaic performance than that of b-PEI, which can also be explained by their difference in the resistances. This work supplies an insight into the function of PEI cathode interlayer on improving the work function and resistance of ITO electrode in the inverted PSCs, and provides some instructions on the future design of interlayer materials in PSCs.     

Amphiphilic fullerene derivative as effective interfacial layer for inverted polymer solar cells

Amphiphilic fullerene derivative with poly(ethylene glycol) chain (C60-PEG) was applied as effective interfacial layer to improve the performance of inverted polymer solar cells. C60-PEG could not only be used as cathode buffer layer alone by replacing ZnO, but also be used as a self-assembled monolayer to modify ZnO. C60-PEG can tune energy level alignment and improve the interfacial compatibility between active layer and ITO or ZnO. Moreover, due to the strong interaction between ZnO nanoparticles and PEG chain, C60-PEG can passivate the surface defects and traps of ZnO, and facilitate the charge selective and dissociation. Consequently, inverted polymer solar cells based on thieno[3,4-b]thiophene/benzodithiophene (PTB7):[6,6]- phenyl C₇₁-butyric acid methyl ester (PC₇₁BM) present a PCE of 6.6% by incorporating C60-PEG into as cathode buffer layer. Moreover, an improved PCE of 7.4% with good long-term stability in air were further achieved by using C60-PEG/ZnO interlayer. In this work, C60-PEG could be prepared by solution process at room temperature without additional annealing, which shows the potential in large-scale printed polymer solar cells.     

Performance enhancement in inverted polymer solar cells incorporating ultrathin Au and LiF modified ZnO electron transporting interlayer

The performance enhancement of inverted polymer solar cells (PSCs), based on the blend system of regioregular poly(3-hexylthiophene) and [6,6]-phenyl C₆₁-butyric acid methylester, due to incorporating ultrathin Au and LiF interlayer between the front transparent indium tin oxide and a ZnO electron transporting layer was analyzed. The results reveal that a 40% increase in PCE, e.g., from 2.62% to 3.67%, was observed for PSCs made with an optimal Au/LiF interlayer as compared to the one having a bare ZnO electron transporting layer. The presence of Au/LiF-modified ZnO interlayer between ITO and the organic layer helps to improve the charge collection. The absorption enhancement arising from the plasmon resonance of Au nanostructures also contributed to the improvement in PCE. It is shown that PSCs with LiF incorporated ZnO electron transporting layer allow improving cell lifetime, demonstrating <50% decrease in PCE compared to that of the ones with a bare ZnO interlayer after 240 day aging test for cells without encapsulation in air.     

Enhanced performance of inverted perovskite solar cells using solution-processed carboxylic potassium salt as cathode buffer layer

Using a novel solution-processed carboxylic potassium salt (F-R-COOK) as cathode buffer layer (CBL), a power conversion efficiency (PCE) of 14.37% is obtained, which is more than 51% increase compared with that of the Ag-only device under similar fabrication conditions. The test result of single electron devices and Electrochemical impedance spectroscopy (EIS) measurements demonstrate that the interlayer decreases charge transport resistance. Ultraviolet photoelectron spectroscopy (UPS) measurements are used to study the interfacial effects induced by the new CBL. It is found that F-R-COOK can reduce the work function of the Ag electrode by forming desired interfacial dipoles. Our work indicates the promising applications of F-R-COOK based CBL in perovskite solar cells and may provide some insights into the design and synthesis of new interfacial materials to further improve the device performance.     

Prolonged lifetime of polymer solar cells with amphiphilic monolayers modified cathodes

The short lifetime and low stability of polymer solar cells (PSCs) devices limit their feasibility for commercial use. Modification of the interfacial electron-transport layers (ETL) has been demonstrated as an effective way to enhance power conversion efficiency (PCE) and device stability. In this work, two types of monolayers consisting of amphiphilic molecules (sodium stearate or sodium oleate - a major constituent of “soap”) are introduced as novel ETLs in polymer: PCBM based PSCs. Significant improvement of PCE was demonstrated and an extended operational lifetime by 5–25 times was achieved. We attributed the improved performance to the interface modification by the amphiphilic molecular layers. The amphiphilic interfacial layers established a better contact between the active layer and the cathode by reducing the roughness and forming a compact dipole at the interface, which facilitates charge generation, charge transport to, and charge collection at the electrodes, thereby enhancing the device efficiency and stability. This versatile interface modification approach has shown to be an immediate and promising means to improve the performance of PSCs.     

Improved efficiency and stability of inverted polymer solar cells with a solution-processed BPhen interlayer and polystyrene beads

We demonstrate improved power conversion efficiency (PCE) and strongly enhanced stability of inverted organic solar cells (OSCs) with Cs halides by solution casting BPhen (4,7-di(phenyl)-1,10-phenanthroline) on the halide layer and ∼100 nm polystyrene beads (PSB) on the blank side of the OSC’s substrate. The PCE of ITO/CsCl/P3HT:PCBM/MoO₃/Al (where P3HT is poly 3-hexylthiophene and PCBM is [6,6]-phenyl-C₆₀-butyric acid methyl ester) improves by up to 46%, from 2.5% to ∼3.7%, by adding a solution-processed BPhen layer between the CsCl and the active layer. For such cells with CsI (PCE ∼3.3–3.4%) the increase was only 6–9%, to 3.5–3.7%. The PCE of cells devoid of the halides but with BPhen was ∼3.3%. The cells were optimized by varying the BPhen concentration in a chlorobenzene solution. The results are consistent with reduced charge recombination at the ITO interface in the presence of the hole blocking BPhen interlayer. The use of hole blocking BCP (2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline), as a substitute for BPhen, also showed an enhancement (though lower due to its lower electron mobility), verifying the effect of these materials as hole blocking interlayers. Interestingly, the stability of such non-encapsulated devices with CsCl/BPhen or CsI/BPhen improved significantly. For example, the PCE of unencapsulated cells with CsCl/BPhen kept in the dark under ambient conditions dropped by less than 2% after more than 3 weeks; the PCE of similar cells devoid of the BPhen layer dropped by ∼60% during the same period. The PCE of the cell with CsCl/BPhen dropped by ∼16% after 2 months. High humidity, as expected, resulted in faster deterioration in cell performance. The PCE, however, was restored to within ∼10% of the original value for 2 week old cells by solution–application of a PSB layer on the blank side of the cell’s glass substrate. These beads direct and scatter the light to enhance absorption in the active layer. The results demonstrate that a simple approach such as casting a film of ∼100 nm diameter PSB from an aqueous suspension on the blank side of the OSC substrate can improve long-term performance, and that spin coating BPhen is a low-cost and easy approach to reduce charge recombination at the cathode in inverted structures for increased PCE and stability.     

Solvent-resistant ITO work function tuning by an acridine derivative enables high performance inverted polymer solar cells

In order to avoid an interpenetration of the buffer and the photoactive layers during preparation of polymer solar cells (PSCs), solvent-resistant buffer films were chemically modified on indium tin oxide (ITO) surface. The conjugated aromatics acridine orange base (AOB) was introduced into the films using 3-bromopropyltrimethoxysilane (BrTMS) as coupling agent. Upon ITO surface modification, the respective work functions show a significant decrease. The modified ITO substrates were implemented in inverted PSCs based on PBDTTT-C-T:PC₇₁BM. With the modification, the power conversion efficiency (PCE) was improved significantly from 4.10% (for the inverted PSC without this buffer layer) to 7.56%. The PCE enhancement is mainly caused by the increase of the open-circuit voltage (43%). These results indicate that the solvent-resistant film is able to facilitate electron collection and transportation, thus providing a novel route to high efficient PSCs by surface engineering.     

Highly conductive Zinc-Tin-Oxide buffer layer for inverted polymer solar cells

Thin-films of Zinc Tin Oxide (ZTO) with an extremely high charge carrier mobility and superior optical transmittance are synthesized using a simple solution method. These ZTO films have been systematically studied for the application in inverted polymer solar cells (PSCs). The Hall effects measurements show that the charge mobility of the ZTO semiconductor is over 16.5 cm².V⁻¹.S⁻¹, which is the highest mobility value ever reported for oxide buffer made by using solution process. By applying the ZTO buffer layer in the inverted PSCs of P3HT:PC₆₁BM, the power conversion efficiency of the device is 30% higher than that of the devices made with other common buffer layers such as ZnO and TiO₂. Light intensity-dependent JV studies and PL measurements also indicate that ZTO buffer layer reduces surface recombination. This work demonstrates that the solution-synthesized ZTO is a promising new buffer layer with superior electron extraction capability for the solar cells.     

Properties of inverted polymer solar cells based on novel small molecular electrolytes as the cathode buffer layer

Novel small-molecule electrolytes were designed and synthesized for use in the cathode interlayer in bulk-heterojunction polymer solar cells (PSCs). The synthesized materials consist of polar quaternary ammonium bromide with the addition of multiple hydroxyl groups, which are N,N,N,N,N,N-hexakis(2-hydroxyethyl)butane-1,4-diaminium bromide (C4) and N,N,N,N,N,N-hexakis(2-hydroxyethyl)hexane-1,6-diaminium bromide (C6). The materials generate a favorable interface dipole through the quaternary ammonium bromide. In addition, the multiple polar hydroxyl groups increased the interface dipole magnitude. The power conversion efficiency of the devices with the interlayer was up to 9.20% with a J_sc of 17.22 mA/cm², a V_oc of 0.75 V, and an FF of 71.3%. The PCE of devices with an interlayer show better long-term stability than a device without an interlayer. Our strategy shows that it is possible to enhance the efficiency of PSCs by simple approaches without complicated syntheses.     

Solvent extraction induced nano-porous zinc oxide as an electron transport layer for inverted polymer solar cells

A facile and cost-effective method is demonstrated to prepare a nano-porous rugged zinc oxide (ZnO) film without complicated processes and strict condition. A sol–gel derived ZnO is simply coated onto the substrate and subsequently removed the unreacted precursor and residual matters by solvent extraction. Thus, the precursor and residuals provide the vacancy to form a highly rugged surface. Compared with the flat ZnO film, the rugged ZnO is not only performs better purity than the flat film, but also increases the interfacial contact between the ZnO and bulk-heterojunction layer. By using the rugged ZnO as an electron transport layer, an enhancement of 20% in photocurrent generation could be achieved in an inverted poly(3-hexylthiophene):[6,6]-phenyl C₆₁ butyric acid methyl ester solar cell together with highly air stability.     

Efficient inverted polymer solar cells incorporating doped organic electron transporting layer

An efficient inverted polymer solar cell is enabled by incorporating an n-type doped wide-gap organic electron transporting layer (ETL) between the indium tin oxide cathode and the photoactive layer for electron extraction. The ETL is formed by a thermal-deposited cesium carbonate-doped 4,7-diphenyl-1,10-phenanthroline (Cs₂CO₃:BPhen) layer. The cell response parameters critically depended on the doping concentration and film thickness of the Cs₂CO₃:BPhen ETL. Inverted polymer solar cell with an optimized Cs₂CO₃:BPhen ETL exhibits a power conversion efficiency of 4.12% as compared to 1.34% for the device with a pristine BPhen ETL. The enhanced performance in the inverted device is associated with the favorable energy level alignment between Cs₂CO₃:BPhen and the electron-acceptor material, as well as increased conductivity in the doped organic ETL for electron extraction. The method reported here provides a facile approach to optimize the performance of inverted polymer solar cells in terms of easy control of film morphology, chemical composition, conductivity at low processing temperature, as well as compatibility with fabrication on flexible substrates.