Metal salt modified PEDOT:PSS as anode buffer layer and its effect on power conversion efficiency of organic solar cells

The effects of metal chlorides such as LiCl, NaCl, CdCl₂ and CuCl₂ on optical transmittance, electrical conductivity as well as morphology of PEDOT:PSS films have been investigated. Transmittance spectra of spun PEDOT:PSS layers were improved by more than 6% to a maximum of 94% in LiCl doped PEDOT:PSS film. The surface of the PEDOT:PSS films has exhibited higher roughness associated with an increase in the electrical conductivity after doping with metal salts. The improvement in the physical properties of PEDOT:PSS as the hole transport layer proved to be key factors towards enhancing the P3HT:PCBM bulk heterojunction (BHJ) solar cells. These improvements include significantly improved power conversion efficiency with values as high as 6.82% associated with high fill factor (61%) and larger short circuit current density (∼18 mA cm⁻²).     

Aging process of PEDOT:PSS dispersion and robust recovery of aged PEDOT:PSS as a hole transport layer for organic solar cells

Conducting p-type polymer of poly(3,4-ethylene dioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) has been widely used for organic optoelectronics, particularly as a hole transport layer for organic solar cells. While the aged PEDOT:PSS dispersion impacts device performance, the aging of PEDOT:PSS dispersion have not been well investigated. Moreover, the recovery process of aged (two-year-old) PEDOT:PSS dispersion has not been demonstrated yet. Herein, it is found that aqueous PEDOT:PSS dispersion undergoes extensive phase separation during the aging process, resulting in both nanoscale and macroscale hydrophobic PEDOT-rich agglomerates. When the aged PEDOT:PSS thin film is integrated into P3HT:PCBM organic solar cells, the PEDOT-rich agglomerates trap the photogenerated holes at the PEDOT:PSS/P3HT interface, resulting in poor extraction efficiency in organic solar cells. To recover a hole transport functionality from aged PEDOT:PSS, three different solvents such as isopropyl alcohol (C₃H₇OH), ethanol (C₂H₅OH) and methanol (CH₃OH) are investigated. Among them, it is found that isopropyl alcohol (IPA) yielded very uniform PEDOT:PSS thin film layer. This is because hydrophobic functional groups of IPA solvent facilitated the preferential solvation of phase separated hydrophobic PEDOT-rich agglomerates. However, when non-optimal concentration of IPA solvents was added into the aged PEDOT:PSS dispersion, the size of PEDOT-rich agglomerates was adversely enlarged. When organic solar cells were fabricated using more than a two-year-old PEDOT:PSS that was treated with IPA solvent, the resulting device performance of organic solar cells was fully recovered and became comparable or better than that of organic solar cells fabricated with fresh PEDOT:PSS.     

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).     

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).     

ITO-free organic solar cells using highly conductive phenol-treated PEDOT:PSS anodes

Phenol as one of the most polar solvent was used to enhance the conductivity of poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) films. The conductivity of PEDOT:PSS films improved to 1193 S/cm after treatment with phenol vapor and 1054 S/cm after treatment with phenol drop. The treated films also showed high transmittance in the visible region which is one of the crucial factors for optoelectronic devices such as organic solar cells and light emitting diodes. The mechanism of conductivity enhancement of treated thin PEDOT:PSS films was investigated by atomic force microscopy (AFM) and UV/Vis spectrophotometer. The AFM images showed that the ratio of PEDOT to PSS at top most of the surface was increased for treated film. Rearrangement of PEDOT segment throughout the film and hence conformational changes are the reasons for enhancement of conductivity. The modified PEDOT:PSS films were used as electrode for ITO-free organic solar cells (OSCs). These ITO-free OSCs showed almost equal operation to those for ITO electrodes.     

In-situ modification of PEDOT:PSS work function using alkyl alcohols as secondary processing solvents and their impact on merocyanine based bulk heterojunction solar cells

The influence of a series of alkyl alcohols on the work function of PEDOT:PSS thin films is systematically investigated by Kelvin probe measurements. We show that the PEDOT:PSS work function can be increased stepwise from 5.2 eV for pristine PEDOT:PSS to 5.61 eV using either alcohols with different alkyl chain length or varying the amount of alcohol in mixtures with chlorobenzene. Moreover, we demonstrate the effect of work function modification on merocyanine based bulk heterojunction solar cells, resulting in improved values for the open-circuit voltage comparable to those obtained with high work function MoO₃. Thus, the processing method presented herein can potentially serve as a simple, alternative route to adjustable and high work function electrodes while maintaining processability from solution.     

Optical properties and conductivity of PEDOT:PSS films treated by polyethylenimine solution for organic solar cells

We report on conductivity and optical property of three different types of poly(3,4-ethylenedioxythiophene):polystyrene sulfonate (PEDOT:PSS) films [pristine PH1000 film (PH1000-p), with 5 wt.% ethylene glycol additive (PH1000-EG) and with sulfuric acid post-treatment (PH1000-SA)] before and after polyethylenimine (PEI) treatment. The PEI is found to decrease the conductivity of all the PEDOT:PSS films. The processing solvent of 2-methoxyethanol is found to significantly enhance the conductivity of PH1000-p from 1.1 up to 744 S/cm while the processing solvent of isopropanol or water does not change the conductivity of PH1000-p much. As for the optical properties, the PEI treatment slightly changes the transmittance and reflectance of PH1000-p and PH1000-EG films, while the PEI leads to an substantial increase of the absorptance in the spectral region of 400–1100 nm of the PH1000-SA films. Though the optical property and conductivity of the three different types of PEDOT:PSS films vary with the PEI treatment, the treated PEDOT:PSS films exhibit similar low work function. We demonstrate solar cells with a simple device structure of glass/low-WF PEDOT:PSS/P3HT:ICBA/high-WF PEDOT:PSS cells that exhibit good performance with open-circuit voltage of 0.82 V and fill factor up to 0.62 under 100 mW/cm² white light illumination.     

Enhanced performance in inverted polymer solar cells via solution process: Morphology controlling of PEDOT:PSS as anode buffer layer by adding surfactants

Inverted polymer solar cells were fabricated by adding the amphiphilic surfactant ‘Surfynol 104 series’ to Poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) as a anode buffer layer by solution process. With the introduction of Surfynol 104 series-added PEDOT:PSS, it was able to form a homogeneous film by adjusting the wettability of a hydrophobic poly(3-hexylthiophene) (P3HT):[6,6]-phenyl C₆₁-butyric acid methyl ester (PCBM) film. With decrease in series resistance (R_S) and increase in shunt resistance (R_SH), as a result, the short circuit current density (J_SC), open circuit voltage (V_OC) and fill factor (FF) of the optimized device were 10.2 mA/cm², 0.63 V and 61.3%, respectively, calculated the power conversion efficiency (PCE) was 4.0%. In addition, the air stability of the fabricated device was improved.     

Stable organic photovoltaic with PEDOT:PSS and MoOX mixture anode interfacial layer without encapsulation

Herein, we report about an efficient and stable organic photovoltaic that uses a poly(3,4-ethylenedioxythiophene):poly(styrene-sulfonate) (PEDOT:PSS) and molybdenum oxide (MoO_X) mixture for the anode interfacial layer, and that can reach 4.43% power conversion efficiency (PCE) under AM1.5 conditions. Utilizing PEDOT:PSS:MoO_X (1:1), the shelf lifetime of poly(3-hexylthiophene) (P3HT), and indene-C₆₀ bisadduct (ICBA)-based solar cells without encapsulation, can be realized with only a 25% deterioration after 672 h of storage in air. Furthermore, we compare the photovoltaic performance of the P3HT:ICBA-based organic photovoltaic with PEDOT:PSS, and PEDOT:PSS:MoO_X, in which PEDOT:PSS:MoO_X has outperformed the others. In addition, the water vapor transmission rate of PEDOT:PSS:MoO_X is 0.17 gm/(m² day), which is much less than that of PEDOT:PSS.     

Improved efficiency of indium-tin-oxide-free organic light-emitting devices using PEDOT:PSS/graphene oxide composite anode

We have demonstrated an indium-tin-oxide free organic light-emitting device (OLED) with improved efficiency by doping poly (3,4-ethylene dioxythiophene):poly (styrene sulfonate) (PEDOT:PSS) with graphene oxide (GO) as a composite anode. In comparison with a pure PEDOT:PSS anode, 55% enhancement in efficiency has been obtained for the OLEDs based on the PEDOT:PSS/GO composite anode at an optimal condition. The PEDOT:PSS/GO composite anode shows a lower hole-injection barrier, which contributes to the improved device efficiency. Moreover, both high transmittance and good surface morphology similar to that of the pure PEDOT:PSS film also contribute to the enhanced efficiency. It is obvious that composite anode will generally be applicable in organic optoelectronic devices which require smooth and transparent anode.     

High performance inverted perovskite solar cells using PEDOT:PSS/KCl hybrid hole transporting layer

PEDOT:PSS is one of the most widely used hole transporting layer for inverted perovskite solar cells. Yet the performances of the corresponding perovskite solar cells are not satisfactory. Here, we demonstrate that KCl modified PEDOT:PSS film can promote the crystallization of perovskite film and enlarge the perovskite crystals. At the same time, KCl can diffuse into the perovskite film and effectively passivate the defects. As a result, inverted perovskite solar cells fabricated on 10 mg mL⁻¹ PEDOT:PSS/KCl films exhibit an average power conversion efficiency of 16.24 %, which is enhanced by 17.77 % compared with the reference perovskite solar cells. Open circuit voltage of 1.009 V and power conversion efficiency of 17.09 % have also been demonstrated using the optimized 10 mg mL⁻¹ PEDOT:PSS/KCl films.     

An ammonia modified PEDOT: PSS for interfacial engineering in inverted planar perovskite solar cells

Poly(3,4-ethylenedioxythiophene)-poly(styrene sulfonate) (PEDOT:PSS) is one of the most widely used hole transport layers (HTL) in inverted perovskite solar cells (PSCs) due to its simple solution-processed ability, high transparency, and conductivity. However, PEDOT:PSS-based devices suffer a lower open-circuit voltage (V_oc) than devices with the conventional structure. To address this issue, we fabricated ammonia-modified PEDOT:PSS films by simply doping PEDOT:PSS solution with different ratio of ammonia. The acidity of PEDOT:PSS can be neutralized by the doped ammonia, which inhibits the ion-exchange reaction between PSS-H and CH₃NH₃I, thus retarding the reduction of the work function for PEDOT:PSS to some extent. As a result, a superior power conversion efficiency (PCE) of 15.5% was obtained for the device based on the ammonia-doped PEDOT:PSS HTL than that of the pristine PEDOT:PSS-based device. We ascribe the PCE enhancement to the increased V_oc and fill factor (FF), which is attributed not only to the better energy-level alignment between the ammonia-modified PEDOT:PSS film and perovskite layer but also to the increased grain size and crystallinity of perovskite film.     

The effect of solvent treatment on the buried PEDOT:PSS layer

Solvent treatment has been widely used to improve the device performance of both Organic Light Emitting Diodes (OLEDs) and Polymer Solar Cells (PSCs). One of the proposed mechanisms is the modification of the buried PEDOT:PSS layer underneath the organic active layer by the permeating solvent. By measuring the lateral electric conductivity of the PEDOT:PSS layer, the 3 orders of magnitude's enhancement on the conductivity after solvent treatment confirms that the solvent permeates through the top organic active layer and modifies the PEDOT:PSS layer. Using a “peel-off” method, the buried PEDOT:PSS layer is fully exposed and studied by UV–vis spectra, XPS spectra, and c-AFM images. The data suggest that the permeating solvent dissolves PSS, changes PEDOT:PSS′ core-shell structure into a linear/coiled structure, and moves PSS from the bulk to the surface. As a result, PEDOT becomes more continuous in the bulk. The continuous conducting PEDOT-rich domains create percolating pathways for the current which significantly improve electric conductivity.     

Photolithographic patterning of PEDOT:PSS with a silver interlayer and its application in organic light emitting diodes

A patterning scheme for poly(3,4-ethylenedioxythio-phene):poly(styrenesulfonate) (PEDOT:PSS) is reported. With a silver interlayer, the conductive PEDOT:PSS film can be patterned down to micrometer scales by traditional photolithography, and this patterning scheme can be applied on large-area flexible substrates. Through systematical investigations, the patterning processes have no obvious influence on both the bulk and surface properties of PEDOT:PSS films. Efficient organic light emitting diodes (OLEDs) are realized based on this patterned PEDOT:PSS anode, and they show comparable performance to those devices with an indium tin oxide (ITO) anode. High-resolution OLED pixel arrays are also demonstrated. Our interlayer approach here has an advantage of patterning PEDOT:PSS with high resolution and large scale, and it is also compatible with traditional photolithographic processes which substantially save the capital cost. Results indicate that the photographically patterned conductive PEDOT:PSS film becomes a promising candidate for eletrical eletrode material in organic electronic applications.     

Neutral-pH PEDOT:PSS as over-coating layer for stable silver nanowire flexible transparent conductive films

The silver nanowire (AgNW) mesh film with poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) as the over-coating layer is a promising flexible transparent conductive film technology. In this work, experimental studies show that the hygroscopic and acid properties of the common PEDOT:PSS lead to poor stabilities of the composite films, due to the conductivity degradation of PEDOT:PSS by the water absorption and the acid corrosion of AgNWs by PEDOT:PSS. By using the modified PEDOT:PSS of neutral pH as the over-coating layer, the long term shelf-life time, thermal and current stressing stabilities are all significantly improved without sacrifice of transparency, electrical conductivity and mechanical flexibility. Under both cases of thermal aging test at 210 °C for 20 min and 12 h continuous current stressing at a current density of 30 mA/cm², no obvious change of the conductivity is observed. The results clearly demonstrate that using the neutral-pH PEDOT:PSS as an over-coating layer can help to achieve flexible AgNW transparent conductive films with superior stability for flexible optoelectronic devices.     

Influence of the surface treatment of PEDOT:PSS layer with high boiling point solvent on the performance of inverted planar perovskite solar cells

Since perovskite precursor solution is typically prepared from high boiling point solvents, understanding the effect of high boiling point solvent treatment of the PEDOT:PSS layer on the performance of perovskite solar cells is important for device processing optimization. In this paper, influence of the surface treatment of the PEDOT:PSS layer with high boiling point solvent, including N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), and ethylene glycol (EG), on the device performance of the perovskite solar cells was investigated. Increased conductivity was measured for the PEDOT:PSS film after solvent treatments, which was ascribed to the partial removal of PSS component from the PEDOT:PSS layer, as evidenced by the UV–vis absorption spectroscopy and XPS spectroscopy. In comparison with the reference cell, poorer device performance was obtained for the perovskite solar cells directly deposited on the solvent washed PEDOT:PSS film, which was ascribed to the increased pin hole density of the perovskite films. However, insertion of a thin PSSNa layer between the PEDOT:PSS layer and the perovskite layer greatly improved device performance, demonstrating that PSS-rich surface is favorite for the crystal growth of the perovskite film. Increased external quantum efficiency over 600–750 nm was measured for the cells based on solvent treated PEDOT:PSS layer, leading to a short circuit current and the consequent performance enhancement.     

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.     

High-performance hole transport layer based on WS2 doped PEDOT:PSS for organic solar cells

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An inverted,organic WORM device based on PEDOT:PSS with very low turn-on voltage

An organic Write-Once-Read-Many (WORM) device based on poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate) (PEDOT:PSS) as the active layer was fabricated with an inverted architecture. Insertion of an ultrathin layer of poly(methylmethacrylate) (PMMA) between the bottom electrode and the PEDOT:PSS resulted in a systematic and substantial decrease in turn-on voltage, from 7.0 V to less than 1.0 V. An optimal thickness of the PMMA layer was found to yield the lowest consistent turn-on voltage of ∼0.8 V, with 0.5 V being the lowest value of all fabricated devices. The switching mechanism was attributed to filamentary doping of the PEDOT:PSS. Insertion of the PMMA acted to protect the underlying ZnO from being etched by the acidic PEDOT:PSS as well as to improve its wetting properties. Devices were demonstrated on both ITO and aluminum bottom electrodes, with aluminum yielding the highest ON/OFF ratios in the study. Owing to their inverted architecture, the devices demonstrated good stability, and the retention time of the ON-state was determined to be greater than twenty months while stored in air for devices with ITO bottom electrodes. In addition to deposition via spin-coating, blade-coating was demonstrated as a viable processing technique for applications requiring rapid or large-area manufacturing.