High-efficiency inverted polymer solar cells via dual effects of introducing the high boiling point solvent and the high conductive PEDOT:PSS layer

Polymer solar cells (PSCs) are of great interest in the past decade owing to their potentially low-cost in the manufacturing by the solution-based roll to roll method. In this paper, a novel inverted device structure was introduced by inserting a high conductive PEDOT:PSS (hcPEDOT:PSS) layer between the Au nanoparticles (NPs)-embedded hole transport layer (PEDOT:PSS) and the top electrode layer. Power conversion efficiency (PCE) initially reached up to 4.51%, illustrating ∼10% higher compared with the device similarly enhanced by Au NPs plasmonics where only one PEDOT:PSS layer with the embedded Au NPs was used in single bulk heterojunction inverted PSCs based on the poly(3-hexylthiophene):[6,6]-phenyl C61-butyric acid methylester (P3HT:PCBM). The PCE was further improved from 4.51% to 5.01% by adding the high-boiling point solvent of 1,8-diiodooctane (DD) into the active layer, presenting ∼20% enhancement in PCE through dual effects of introducing the high boiling point solvent and the high conductive PEDOT:PSS layer. Morphologies of the active layers were characterised by SEM and AFM separately in the paper.     

Directional dependence of electron blocking in PEDOT:PSS

The directional dependence of electron blocking by poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) is investigated in organic photovoltaic devices. In a conventional OPV architecture we find that a doped interlayer forms between poly(3-hexylthiophene) (P3HT) and the PSS-rich top layer of spin-coated PEDOT:PSS films. In an inverted OPV architecture, we find no mixing between PEDOT:PSS and P3HT, which is due to the lower concentration of PSS in bulk PEDOT:PSS than is found in the PSS-rich top layer. Through electrical measurements of conventional and inverted photovoltaic devices we show that the interlayer is necessary for PEDOT:PSS to be electron blocking. This result implies that PEDOT:PSS is not intrinsically electron blocking and that its directional anisotropy must be considered when comparing the advantages and disadvantages of conventional and inverted architecture photovoltaic devices.     

Isopropanol-treated PEDOT:PSS as electron transport layer in polymer solar cells

Isopropanol (IPA)-treated poly(3,4-ethylenedioxithiophene):poly(styrene sulfonate) (PEDOT:PSS) was applied as a new electron transport layer (ETL) in P3HT:PCBM bulk heterojunction polymer solar cell (BHJ-PSC) devices for the first time, revealing the electron transport property of IPA-treated PEDOT:PSS in sharp contrast to the well known hole transport property of the untreated PEDOT:PSS. Under the optimized condition for incorporating PEDOT:PSS ETL, the power conversion efficiency (PCE) of the ITO/untreated PEDOT:PSS (HTL)/P3HT:PCBM/IPA-treated PEDOT:PSS (ETL)/Al device (3.09%) is quite comparable to that of the reference ITO/untreated PEDOT:PSS (HTL)/P3HT:PCBM/Al device without any ETL (3.06%), and an annealing treatment of PEDOT:PSS ETL at 120 °C for 10 min led to a PCE of 3.25%, which even slightly surpasses that of the reference device, revealing the electron transport property of IPA-treated PEDOT:PSS. The electron transport property of IPA-treated PEDOT:PSS is interpreted by the lowering of the work function of PEDOT:PSS upon IPA treatment and incorporation as ETL as probed by scanning Kelvin probe microscopy (SKPM).     

Influence of PEDOT:PSS buffer layer on the performance of organic photocoupler

We have fabricated an organic photocoupler with organic light-emitting diodes （OLEDs） with 520 nm emissive wavelength as the input light source and a photodiode （PD） based on poly（3-hexylthiophene） （P3HT）：1-（3-methoxycarbonyl）propyl- 1-phenyl-（6,6）-C61 （PCBM） as the detector. The influences of buffer layer （PEDOT：PSS） on output current （Iout）, current transfer ratio （CTR） and time response characteristics of the photocoupler device were studied. Through our experiments, It is found that the output current linearly increases with the input current, the max output current and CTR of the devices with PEDOT：PSS buffer layer are 2 times and 7 times than that of the devices without buffer layer respectively, which show that the existence of buffer layer can enhance the output photocurrent efficiently. Moreover, the existence of PEDOT：PSS eliminates the time delay of the devices.     

A review of recent plasmonic nanoparticles incorporated P3HT: PCBM organic thin film solar cells

An optimum thickness of organic active layer of 100 nm or possibly less results in poor optical absorption in organic photovoltaic cells (OPV). The optical absorption can be improved by using a thick organic active layer, but the charge carrier collection efficiency will decrease due to low charge carrier mobility for most of the polymeric organic semiconductor. This phenomenon imposes a trade-off between optical absorption and charge carriers transport inside OPV. Recently, metallic nanostructures such as gold (Au) and silver (Ag) with various sizes and morphologies have been identified as an alternative route to boost the performance of OPV at this specific limited thickness (ie. ≤100 nm). Multiple plasmonic effects such as optical and electrical effects are induced upon introducing metallic nanoparticle(s), NP(s) into OPV. This review highlights recent progress in plasmonic-enhanced poly(3-hexylthiophene-2,5-diyl): phenyl-C61-butyric acid methyl ester (P3HT: PCBM)-based OPV with NP(s) located either inside organic active layer or carrier transport layer (CTL) or at various interfaces within the OPV cell architecture. With understanding of the physical plasmonic effects for Au and Ag in OPV, such plasmonic NP(s) act as a new class of strategy for performance optimization.     

Decahedral-shaped Au nanoparticles as plasmonic centers for high performance polymer solar cells

The photon harvesting of the photoactive layer within a multilayered polymer solar cells (PSCs) greatly affects the output electric power of the devices. For PSCs, the device performance is very sensitive to the photoactive layer thickness. Therefore, how to enhance the light absorption of the photoactive film with fixed thickness is still a big challenge. Plasmonic enhancement induced by noble metal nanoparticles has been proved to be an effective way to enhance light trapping inside the photoactive film without increasing the thickness of film. By incorporating Au decahedra into the poly(3,4-ethylenedioxythiophene): poly(4-styrenesulfonate) (PEDOT:PSS) anode buffer layer, high performance plasmonic PSCs based on P3HT:PC₆₀BM and PBDT-TS1:PC₇₀BM were fabricated and the light response of the PSCs are greatly improved in a broadband wavelength, resulting in a remarkable enhancement in short-circuit current density. The calculation results of finite difference time domain (FDTD) confirm that the plasmonic effects induce enhancement in device performance. Upon optimization, the best power conversion efficiency (PCE) of the device based on P3HT:PC₆₀BM and PBDT-TS1:PC₇₀BM reaches 4.14% and 10.29%, respectively, among the best values reported in literature. These results can provide valuable guidelines for the design of metal nanostructures for organic photovoltaic applications.     

Comparison of dimethyl sulfoxide treated highly conductive poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) electrodes for use in indium tin oxide-free organic electronic photovoltaic devices

Indium tin oxide (ITO)-free organic photovoltaic (OPV) devices were fabricated using highly conductive poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) as the transparent conductive electrode (TCE). The intrinsic conductivity of the PEDOT:PSS films was improved by two different dimethyl sulfoxide (DMSO) treatments – (i) DMSO was added directly to the PEDOT:PSS solution (PEDOT:PSS_ADD) and (ii) a pre-formed PEDOT:PSS film was immersed in DMSO (PEDOT:PSS_IMM). X-ray photoelectron spectroscopy (XPS) and conductive atomic force microscopy (CAFM) studies showed a large amount of PSS was removed from the PEDOT:PSS_IMM electrode surface. OPV devices based on a poly(3-hexylthiophene):[6,6]-phenyl-C₆₁-butyric acid methyl ester (P3HT:PCBM) bulk hetrojunction showed that the PEDOT:PSS_IMM electrode out-performed the PEDOT:PSS_ADD electrode, primarily due to an increase in short circuit current density from 6.62 mA cm⁻² to 7.15 mA cm⁻². The results highlight the importance of optimising the treatment of PEDOT:PSS electrodes and demonstrate their potential as an alternative TCE for rapid processing and low-cost OPV and other organic electronic devices.     

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.     

Broad-band plasmonic Cu-Au bimetallic nanoparticles for organic bulk heterojunction solar cells

In this work, a facile preparation of Cu-Au bimetallic nanoparticles (NPs) with core-shell nanostructures is reported. Importantly, as-prepared Cu-Au NPs are highly stable, solution-processable and exhibit a broad localized surface plasmon resonance (LSPR) band at long wavelengths of 550–850 nm. Highly efficient plasmonic organic solar cells (OSCs) were fabricated by embedding Cu-Au NPs in an anodic poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) layer. The average power conversion efficiency (PCE) was enhanced from 3.21% to 3.63% for poly(3-hexylthiophene) (P3HT):phenyl-C₆₁-butyric acid methyl ester (PC₆₁BM) based devices, from 6.51% to 7.13% for poly[(ethylhexyl-thiophenyl)-benzodithiophene -(ethylhexyl)-thienothiophene](PTB7-th):PC₆₁BM based devices and from 7.53% to 8.48% for PTB7-th:PC₇₁BM based devices, corresponding to 9.5–13.4% PCE improvement. Such an improvement is very comparable to that (12.5%) obtained in those with plasmonic Au NPs but achieved at lower cost. This study thus demonstrates a novel and cost-effective approach to enhance the photovoltaic performance of OSCs, in combination with the broad-band plasmonic Cu-Au bimetallic nanostructures.     

Phase separation-driven stratification in conventional and inverted P3HT:PCBM organic solar cells

We have used neutron reflectivity to investigate the stratification of poly(3-hexylthiophene) (P3HT) and phenyl-C₆₁-butyric acid methyl ester (PCBM) blend films. Films were spun-cast on poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) and titanium oxide (TiOx) layers to mimic the procedures followed for the fabrication of conventional and inverted organic photovoltaics respectively. The resultant scattering length density profiles reveal a PCBM-rich layer is formed in the vicinity of PEDOT:PSS or TiOx, while PCBM is depleted at the free surface of the film. PCBM segregation close to the substrate is further enhanced by annealing. This stratification is considered to be favorable only for inverted devices.     

Influence of aluminium electrode preparation on PCE values of polymeric solar cells based on P3HT and PCBM

The main goal of the paper was investigation of influence of aluminum electrode preparation via thermal evaporation (TE) and the magnetron sputtering (MS) on power conversion efficiency (PCE) of polymeric solar cells. The photovoltaic properties of such three kinds devices based on poly(3-hexylthiophene-2,5-diyl) (P3HT) as ITO/P3HT/Al, ITO/P3HT:PCBM (1:1, w/w)/Al and ITO/PEDOT:PSS/P3HT:PCBM (1:1, w/w)/Al were investigated. For the constructed devices impedance spectroscopy were analyzed. For devices lack of PEDOT:PSS layer or lack of PCBM, photovoltaic parameters were very low and similar to the parameters obtained for device with Al electrode prepared by magnetron sputtering. The devices comprising PEDOT:PSS with P3HT:PCBM showed the best photovoltaic parameters such as a V_OC of 0.60 V, J_SC of 4.61 mA/cm², FF of 0.21, and PCE of 5.7 × 10^?1%.     

The dual localized surface plasmonic effects of gold nanodots and gold nanoparticles enhance the performance of bulk heterojunction polymer solar cells

In this study, we investigated the effects of plasmonic resonances induced by gold nanodots (Au NDs), thermally deposited on the active layer, and octahedral gold nanoparticles (Au NPs), incorporated within the hole transport layer, on the performance of bulk heterojunction polymer solar cells (PSCs) based on poly(3-hexyl thiophene) (P3HT) and [6,6]-phenyl-C₆₁butyric acid methyl ester (PC₆₁BM). Thermal deposition of 5.3-nm Au NDs between the active layer and the cathode in a P3HT:PC₆₁BM device resulted in the power conversion efficiency (PCE) of 4.6%—that is 15% greater than that (4.0%) for the P3HT:PC₆₁BM device without Au NDs. The Au NDs provided near-field enhancement through excitation of the localized surface plasmon resonance (LSPR), thereby enhancing the degree of light absorption.     

Influence of oxygen on semi-transparent organic solar cells with gas permeable electrodes

Semi-transparent P3HT:PCBM (poly(3-hexylthiophene):[6,6]-phenyl C61 butyric acid methyl ester) solar cells with high conductivity PEDOT:PSS (poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate)) top electrodes are used to study degradation. Due to the gas permeability of this type of electrode, the simultaneous exposure to oxygen and light leads to a strong decrease of the short circuit current on the timescale of minutes. The losses are not due to a change in the conductivity of the PEDOT:PSS layer, and the short circuit current can be partially recovered by a heating step, indicating that the observed degradation is taking place in the photo-active layer of the cell.     

Plasmon-enhanced polymer bulk heterojunction solar cells with solution-processable Ag nanoparticles

We report the plasmon-enhanced polymer bulk-heterojunction solar cells with Ag nanoparticles (AgNPs) obtained via chemical method. Here, the AgNPs films with different particle densities are introduced between the poly (3,4-ethylene dioxythiophene) poly (styrenesulfonate) (PEDOT: PSS) buffer layer and the poly (3-hexythiophene):[6,6]-phenyl-c61 butyric acid methyl ester (P3HT: PCBM) layer. By improving the optical absorption of the active layer owing to the localized surface plasmons, the power conversion efficiency of the solar cells is increased compared with the control device. It is shown that the efficiency of the device increases with the density of AgNPs. For the device employing higher density, the resulted power conversion efficiency is found to increase from 2.89% to 3.38%, enhanced by 16.96%.     

Organic solar cells using plasmonics of Ag nanoprisms

We demonstrate plasmonic effects in bulk heterojunction organic solar cells (OSCs) consisting of poly(3-hexylthiophene) (P3HT) and [6,6]-phenyl-C₆₁-butyric acid methyl ester (PCBM) by incorporating silver (Ag) triangular shaped nanoparticles (nanoprisms; NPSs) into a poly(3,4-ethylenedioxythiophene) buffer layer. The optical absorption and geometric characteristics of the Ag NPSs were investigated in terms of their tunable in-plane dipole local surface plasmon resonance (LSPR) bands. The photovoltaic characteristics showed that the power conversion efficiency (PCE) of the plasmonic OSCs was enhanced by an increase of short circuit current (J_sc) compared to that of the reference cells without any variation in electrical properties. The enhanced J_sc is directly related to the enhancement of optical absorption efficiency by the LSPR of the Ag NPSs. We measured the photovoltaic characteristics of the plasmonic OSCs with various distances between the Ag NPSs and the P3HT:PCBM active layer, in which the PCEs of the plasmonic OSCs decreased with increasing distance. This suggests that the increase of photocurrent and optical absorption was due to near field enhancement (i.e., intensified incident light on the active layer) by the LSPR of the Ag NPSs.     

超薄PCBM层提高有机太阳电池效率

为研究超薄PCBM层对有机太阳电池的影响,制备了含和不含超薄PCBM层的两种不同结构的体相异质结太阳电池,电池结构分别为:ITO/PEDOT:PSS/P3HT+PCBM/PCBM/AI,ITO/PEDOT:PSS/P3HT+PCBM/Al.测试结果表明:所制备电池的开路电压分别为0.599 2V和0.572 7 V,能量转换效率分别为2.24％、1.21％,超薄PCBM层起到了电子传输的作用.     

Solution processed WO3 layer for the replacement of PEDOT:PSS layer in organic photovoltaic cells

Tungsten oxide layer is formed uniformly by a sol–gel technique on top of indium tin oxide as a neutral and photo-stable hole extraction layer (HEL). The solution processed tungsten oxide layer (sWO₃) is fully characterized by UV–Vis, XPS, UPS, XRD, AFM, and TEM. Optical transmission of ITO/sWO₃ substrates is nearly identical to ITOs. In addition, the sWO₃ layer induces nearly ohmic contact to P3HT as PEDOT:PSS layer does, which is determined by UPS measurement. In case that an optimized thickness (～10 nm) of the sWO₃ layer is incorporated in the organic photovoltaic devices (OPVs) with a structure of ITO/sWO₃/P3HT:PCBM/Al, the power conversion efficiency (PCE) is 3.4%, comparable to that of devices utilizing PEDOT:PSS as HEL. Furthermore, the stability of OPV utilizing sWO₃ is significantly enhanced due to the air- and photo-stability of the sWO₃ layer itself. PCEs are decreased to 40% and 0% of initial values, when PEDOT:PSS layers are exposed to air and light for 192 h, respectively. In contrast, PCEs are maintained to 90% and 87% of initial PCEs respectively, when sWO₃ layers are exposed to the same conditions. Conclusively, we find that solution processed tungsten oxide layers can be prepared easily, act as an efficient hole extraction layer, and afford a much higher stability than PEDOT:PSS layers.     

Enhancement of organic solar cell efficiency by patterning the PEDOT:PSS hole transport layer using nanoimprint lithography

In order to improve the conversion efficiency of organic photovoltaic (OPV) cells, nano-patterned poly (3,4-ethylenedioxythiophene) poly (styrenesulfonate) (PEDOT:PSS) was used as a hole transfer layer (HTL). Using nanoimprint lithography, a process that is easily applied to large-area substrates, a spherical array of PEDOT:PSS droplets was formed. The effect of the PEDOT:PSS nanostructure was characterized by optical and electrical measurements. Because the hemispherical array of PEDOT:PSS scatters light efficiently, absorption of the incident light increases when the nanostructured layer is employed. The conversion efficiency of the nano-patterned OPV cells is 25% larger than that of non-patterned OPV cells, due to the increase in short-circuit current (J_sc).     

Performance of ITO-free inverted organic bulk heterojunction photodetectors: Comparison with standard device architecture

We report on the fabrication of Indium Tin Oxide (ITO)-free inverted organic bulk heterojunction (BHJ) photodetectors of poly(3-hexylthiophene) (P3HT): 1-(3-methoxycarbonyl)-propyl-1-1-phenyl-(6,6) C61 (PCBM). The final inverted device structure is Cr/Al/Cr/P3HT:PCBM/poly-3,4-ethylenedioxythiophene:poly-styrenesulfonate (PEDOT:PSS)/Ag (Zimmermann et al., 2009) [1]. The device is top-absorbing with the light entering through the hole contact grid. We have fabricated standard devices with structure ITO/PEDOT:PSS/P3HT:PCBM/LiF/Al in order to carry out a comparison study. Inverted photodetectors show slightly higher quantum efficiency and responsivity compared to standard devices. Frequency responses at different bias voltages were measured showing a maximum −3 dB cut-off frequency of 780 kHz and 700 kHz at −3 V for the standard and inverted structures respectively. Parameters extracted from the fit of a circuital model to the impedance spectroscopy measurements were used to estimate the photodiode cut-off frequency as function of bias.