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.     

Vacuum-deposited interconnection layers for tandem solar cells

Two different types of vacuum-deposited interconnection layers (ICLs) were investigated for tandem solar cells: (1) a pure metal oxide and (2) an organic matrix doped with conductive dopants. The optical and electrical properties of these ICLs were systematically studied and compared. Taking the characteristics of ICLs into consideration, optical design methodology for balancing the photocurrent of each sub-cell in the tandem cell is presented. According to the design, highly efficient small-molecule tandem solar cells with power conversion efficiencies up to 7.3%–7.4% were experimentally demonstrated in both devices utilizing pure metal oxide and organic matrix ICLs.     

Influences of using a high mobility donor polymer on solar cell performance

We report a p-type polymer semiconductor, PDBFBT, which exhibits very high space charge limited current (SCLC) mobilities of up to 2.3 × 10⁻² cm² V⁻¹ s⁻¹, which are among the highest reported so far. When the polymer is employed as a donor material in solution coated bulk heterojunction organic solar cells (OSCs), with PC₆₁BM as the acceptor, an efficiency of 4.53% and very high fill factors (>70% in some cases) are achieved. Furthermore, in the inverted device configuration, consistent power conversion efficiencies are demonstrated throughout a wide range of active layer thicknesses (∼100 nm to ∼800 nm). Our results demonstrate the benefits of using very high mobility donor polymers in solar cell applications and will be very useful for the development of new semiconductor materials, as well as the design of device structures for more feasible manufacturing of high efficiency, large area photovoltaic devices via high speed roll-to-roll printing processes.     

Cyanine tandem and triple-junction solar cells

Ultrathin bilayer heterojunction solar cells using cyanine electron donors and electron acceptor C₆₀ are used to fabricate monolithically stacked tandem and triple junction devices. Sub-cell stack sequences as well as C₆₀ layer thicknesses are optimized by optical modeling and maximum efficiency is corroborated experimentally. The highest power conversion efficiency of 4.3% under full sun irradiation is achieved with a tandem cell where heptamethine and trimethine cyanine dyes are used in the front and back cell, respectively. The open circuit voltage matches the sum of the two respective open circuit voltages of the individual single junction solar cells within 3%. Triple junction cells using an additional sub-cell with a pentamethine cyanine suffer from electrical series resistance. At low light irradiation intensity, however, both triple and tandem solar cells reach power conversion efficiencies above 5% in agreement with the performance increase predicted from numerical simulation.     

High performance organic solar cells enabled by an iodinated additive

Additive engineering is a simple and effective strategy to enhance the efficiency of organic solar cells (OSCs). However, traditional additives such as 1,8-diiodooctane (DIO) or 1-chloronaphthalene (CN), suffer from inferior stability, concentration sensitivity, and need additional thermal treatments, which are not desirable for industrial application. Here we introduce a simple, effective and versatile solid additive 1,3-diiodobenzene (1,3-DIB) into the OSCs. In comparison to the control devices, the 1,3-DIB treated OSCs exhibit significantly improved performance with a power conversion efficiency (PCE) of 16.90% for polymer OSCs and a PCE of 14.35% for binary all-small-molecule OSCs. Mechanism studies reveal that 1,3-DIB can improve charge transport and extraction, decrease charge recombination, enhance crystallinity and improve the phase separation. Furthermore, no thermal annealing is needed in PM6:Y6 based OSCs and the 1,3-DIB treated devices show excellent stability and reproducibility in both polymer and small molecule OSCs. Our results demonstrated that additive engineering is a powerful method to enhance the OSC performance.     

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).     

An efficient merocyanine/zinc phthalocyanine tandem solar cell

We present a merocyanine:C₆₀/zinc phthalocyanine:C₆₀ tandem solar cell, comprising two complementary absorbing bulk heterojunction subcells connected in series. High-efficiency devices were realized in a rather simple tandem setup, consisting of only three organic layers that were successively deposited in an ultrahigh-vacuum chamber. The optimized tandem solar cell features an efficiency of 4.5%, demonstrating a performance improvement by ca. 50% compared to the individual optimized single-junction solar cells. The experimental data are in excellent agreement with optical simulations, assuming an internal quantum efficiency near unity in the optimized tandem device.     

Optically-enhanced performance of polymer solar cells with low concentration of gold nanorods in the anodic buffer layer

In this work, the effect of gold nanorods on the performance of poly(3-hexylthiophene-2,5-diyl):[6,6]-phenyl-C₆₁-butyric-acid-methyl-ester bulk heterojunction solar cells was investigated. Gold nanorods were introduced into the anodic buffer layer by simply blending them with the solution of poly(3,4-ethyl-enedioxythiophene):poly(styrenesulfonate). Even with a fairly low density of the nanorods, the resulting devices showed a remarkable 21.3% enhancement in the power conversion efficiency and a 13% enlargement in the short circuit current. By examining the absorbance profiles of active films made with different conditions, such enhancements can be related to the localized transverse and longitudinal plasmon resonance modes in the metallic nanoparticles. Gold nanorods helped as well in reducing the device series resistance by up to 36%, which also contributed to the global enhancement in the efficiency.     

光诱导镀改善太阳电池填充因子的研究

本文采用常规的太阳电池工艺制备了一批单晶硅电池片,退火后得到了填充因子迥异的结果。比较了光诱导镀前后电池参数尤其是串联电阻,并分析了光诱导镀提升填充因子的机理。利用扫描电镜（SEM）观察了去除体银后的微观结构,证明了差填充因子太阳电池在光诱导镀后填充因子的提高得益于烧结中形成的银晶粒的充分利用。文中还提出了将光诱导镀应用于接触电阻较大的电池,如纳米柱电池和径向结电池的可能性。     

Enhanced efficiency in GaInP/GaAs tandem solar cells using carbon doped GaAs in tunnel junction

Carbon doping of GaAs using CBr₄ (carbon tetrabromide) in metal-organic chemical vapor deposition (MOCVD) was investigated to obtain very high and sharp doping profiles required for tunnel junction in tandem solar cells. It was found that the hole concentration increased with decreasing growth temperature and V/III ratio. Hole doping profiles versus distance from the sample surface showed that the hole concentration near the surface was very low in comparison with that far below the surface. As a post-growth treatment, CBr₄ was supplied during the cool down process and produced almost constant hole concentration of 1 × 10²⁰ cm⁻³ regardless of the depth, when CBr₄ flow rate was 9.53 μmol/min. Based on these results, solar cells were fabricated using both carbon (C) and zinc (Zn) as a p-type dopant. It was shown that C doping exhibits higher efficiency and lower series resistance than those of Zn doping in GaInP/GaAs tandem solar cells.     

High efficiency polymer solar cells based on alkylthio substituted benzothiadiazole-quaterthiophene alternating conjugated polymers

We have designed and synthesized two alkylthio substituted benzothiadiazole-quaterthiophene based conjugated polymers (P1 and P2) and investigated their photovoltaic performances. Theoretical simulation has demonstrated that the introduction of alkylthio substituents can increase the planarity of the resulted conjugated polymers. The fluorinated polymer P1 possesses a deeper HOMO energy level than the non-fluorinated polymer P2 and can form well-developed fibril networks when blended with PC₇₁BM. PSCs based on P1:PC₇₁BM (1:1.2, by weight) gave a PCE of 7.76% with a V_oc of 0.69 V, a J_sc of 16.30 mA cm⁻² and an FF of 0.69. Our results have demonstrated that alkylthiothiophene could be a useful building block for the construction of high efficiency polymer donor materials used for PSCs.     

Solution-processed small molecules based on indacenodithiophene for high performance thin-film transistors and organic solar cells

Solution-processed indacenodithiophene (IDT)-based small molecules with 1,3-indanedione (ID) as terminal acceptor units and 3,3′-hexyl-terthiophene (IDT-3Th-ID(I)) or 4,4′-hexyl-terthiophene (IDT-3Th-ID(II)) as π-bridges, have been designed and synthesized for the application in organic field-effect transistors (OFETs) and organic solar cells (OSCs). These molecules exhibited excellent solubility in common organic solvents, good film-forming ability, reasonable thermal stability, and low HOMO energy levels. For the OFETs devices, high hole motilities of 0.52 cm² V⁻¹ s⁻¹ for IDT-3Th-ID(I) and 0.61 cm² V⁻¹ s⁻¹ for IDT-3Th-ID(II) were achieved, with corresponding high I_ON/I_OFF of ca. 10⁷ and ∼10⁹ respectively. The OSCs based on IDT-3Th-ID(I)/PC₇₀BM (2:1, w/w) and IDT-3Th-ID(II)/PC₇₀BM (2:1, w/w) without using any treatment of solvent additive or thermal annealing, showed power conversion efficiencies (PCEs) of 3.07% for IDT-3Th-ID(I) and 2.83% for IDT-3Th-ID(II), under the illumination of AM 1.5G, 100 mW/cm². The results demonstrate that the small molecules constructed with the highly π-conjugated IDT as donor unit, 3Th as π-bridges and ID as acceptor units, could be promising organic semiconductors for high-performance OFETs and OSCs applications.     

Semitransparent,thin metal grid-based hybrid electrodes for polymer solar cells

A conducting polymer/thin Au grid hybrid electrode was investigated to replace an indium tin oxide (ITO) electrode in polymer solar cells (PSCs). Semitransparent, thin Au films were combined with transparent conducting PEDOT:PTS films (70 nm thickness, ~90% of transmission), to form Au grid/conducting polymer hybrid electrodes. The mixed self-assembled monolayers coated on the Au grids and glass substrate provided uniform and adherent coating of conducting polymer on the monolayer, achieving a low contact resistance of 0.6 Ω mm. This resulted in a robust PEDOT:PTS/Au grid hybrid structure.Theoretical calculation showed the dependence of figure of merits (FM) on the filling ratio (=grid width/(grid spacing+grid width)) and Au thickness. In addition, grid spacing had an effect on the surface morphology of the conducting polymer; decreasing the grid spacing produced more flat surface of the overlayers, leading to enhanced performance of PSCs. The fabricated PSCs based on these hybrid electrodes showed that the best efficiency of 3.54%, comparable to that of devices based on an ITO electrode, was obtained at the filling ratio of 0.5 for 15 nm-thick Au electrodes, which was different from that predicted from the theoretical calculation, probably due to the grid spacing effects on the charge collection efficiency.     

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.     

New m-alkoxy-p-fluorophenyl difluoroquinoxaline based polymers in efficient fullerene solar cells with high fill factor

Two new donor (D) - acceptor (A) copolymers, named m-O-p-F-DFQx-BDT (OFQx-T) and m-EH-p-F-DFQx-BDT (EHFQx-T), which were based on meta-octyloxy-para-fluorophenyl and meta-ethylhexyloxy-para-fluorophenyl difluoroquinoxaline as acceptor units (O-DFQx/EH-DFQx) and alkylthienyl substituted benzodithiophene (BDT) as a donor unit, were designed and synthesized. EHFQx-T had higher absorption coefficient than OFQx-T which contributed to larger short-circuit current density (J_sc). EHFQx-T showed a lower the highest occupied molecular orbital (HOMO) which is beneficial for the voltage open-circuit (V_oc). The polymer solar cells (PSCs) based OFQx-T:PC₇₁BM and EHFQx-T:PC₇₁BM blended film as active layer showed high power conversion efficiency (PCE) of 7.60% and 8.44%, respectively, with 1,8-diiodooctane (DIO) solvent additive treatment. More importantly, OFQx-T:PC₇₁BM and EHFQx-T:PC₇₁BM had good fill factor (FF), especially the FF of OFQx-T:PC₇₁BM was over 70%. The high FF contributed to obtain high PCEs for OFQx-T and EHFQx-T. The more balanced and higher charge mobility, smaller geminate recombination and suitable nanoscale phase separation size of EHFQx-T demonstrate that changing octyl chain to ethylhexyl chain in DFQx acceptor unit is efficient to improve photovoltaic properties in fullerene solar cells.     

Alternating dithienobenzoxadiazole-based conjugated polymers for field-effect transistors and polymer solar cells

Three new alternating copolymers derived from dithienobenzoxadizole (DTfBO) and different thiophene-based π-spacers, including terthiophene, quarterthiophene, and dithienyl flanked thienothiophene, were successfully synthesized. The DTfBO-based polymers possess optical band-gaps in the range of 1.84–1.89 eV and exhibit relatively deep HOMO levels between −5.36 eV and −5.50 eV. Due to strong interchain aggregation, DTfBO-based polymers could not be well dissolved in chlorobenzene at room temperature, but they could be processed with hot chlorobenzene solutions of ∼100 °C. Evolutions of UV absorption spectra of polymer solutions during heating process could differentiate their different aggregation ability, among which a repeating unit based on a DTfBO and a terthiophene could supply the strongest inter-chain interaction. Notably, the three DTfBO-based polymers displayed high field-effect hole mobilities between 0.21 and 0.54 cm²/(V s). In polymer solar cells (PSCs) with the three polymers as the donors, high open-circuit voltages between 0.87 and 0.93 V could be realized. For active layer thickness of 80 nm, the PSCs displayed power conversion efficiency (PCE) between 2.85% and 5.07%. A very high fill factor of 75.4% was achieved for the polymer comprising dithienyl flanked thienothiophene. With thicker ative layers of 250 nm, the three DTfBO-based polymers exhibited comparable PCEs of ∼5.61% due to obviously increased short-circuit currents. Our results suggest that DTfBO, a big coplanar heterocycle, is a promising building block to construct high mobility conjugated polymers for efficient thick-film PSCs.     

Zwitterionic ammonium and neutral amino molecules as cathode interlayer for inverted polymer solar cells

Cathode interlayer is essential to inverted bulk heterojunction polymer solar cells (PSCs). A series of zwitterionic ammonium and neutral amino organic molecules are introduced into inverted PSCs as cathode interlayer and power conversion efficiency (PCE) as high as 8.07% is demonstrated. Compared to the devices without interlayer, all the devices exhibit significant improvements of the device parameters by reducing the work function of indium tin oxide (ITO) cathode. It is striking that the devices with neutral amino molecules as interlayer exhibit remarkably higher PCEs than the devices with zwitterionic ammonium molecules as interlayer. We attribute the improved performance to the better photoactive morphology induced by the hydrophobic properties of the neutral amino derivatives through research of ultraviolet photoelectron spectroscopy, atomic force microscopy, and contact angle measurements. Interestingly, the PCEs of the inverted PSCs with cathode interlayer are positively correlated with the hydrophobic properties of the interlayer materials, since devices with neutral amino molecules or molecules with a more hydrophobic alkyl pendant (piperidine) as interlayer exhibit higher PCEs. These results pave the way to the design of effective cathode interlayer materials.     

Thermally stable high performance non-fullerene polymer solar cells with low energy loss by using ladder-type small molecule acceptors

Two ladder-type small molecule acceptors IDT-BT-R and IDT-BT-R-CN are utilized in non-fullerene polymer solar cells by pairing with PTB7-Th as donor polymer, in which PTB7-Th:IDT-BT-R solar cells achieve high performance up to 8.3% with high voltage of 1.02 V and low energy loss of 0.59 eV. Thermal annealing triggered local rearrangement of ladder-type molecules in n-type phases of bulk heterojunction films, increased their absorption abilities and electron transport properties, therefore resulting in improved short-circuit current densities (Jscs) and fill factors (FFs), in contrast to fullerene-based solar cells which suffered from extensive aggregation of fullerenes upon annealing. The outstanding thermal stability, high performance and low energy loss demonstrated here show great potential of non-fullerene polymer solar cells.     

Poly(3-hexylthiophene) coated graphene oxide for improved performance of bulk heterojunction polymer solar cells

An effective method for preparing poly(3-hexylthiophene) (P3HT) coated graphene oxide (GO), (P-GO), based on an ethanol mediated mixing and solvent evaporation method is described. P-GO exhibits good dispersibility in the non-polar solvent o-dichlorobenzene (DCB) allowing the preparation of polymer blend composites. P-GO was doped into P3HT: PCBM blends by solution mixing and shown to facilitate phase separation of P3HT and PCBM in P3HT: PCBM blend films to achieve a more optimum morphology for polymer photovoltaic cells. Bulk heterojunction P3HT: PCBM solar cells exhibit ∼18% power conversion efficiency enhancement in the presence of P-GO.     

Facile embedding of SiO2 nanoparticles in organic solar cells for performance improvement

In this paper, performance improvement of organic solar cells (OSCs) via facile embedding of SiO₂ nanoparticles is reported. Both experimental and theoretical studies indicate that the improved performance is mainly owed to the increased short circuit current density (J_sc), which can be further attributed to elongated optical path length and thus to enhanced light confinement caused by light scattering of SiO₂ nanoparticles. Compared to the planar reference device with a structure of ITO/PEDOT:PSS/P3HT:PC₆₁BM/Al, the optimized one embedded with 160-nm-diameter SiO₂ nanoparticles exhibits ∼17.5% increase in J_sc, i.e., from 10.30 to 12.10 mA/cm², leading to the resultant performance improvement. Owing to the unique advantages of SiO₂ nanoparticles including electrical insulation, low cost and easy fabrication, valuable guidelines for fabricating the related high performance-to-cost OSCs can be provided by this study.