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.     

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.     

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.     

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.     

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.     

Moderately reduced graphene oxide/PEDOT:PSS as hole transport layer to fabricate efficient perovskite hybrid solar cells

Graphene oxide (GO) with single layer was moderately reduced at 200 °C for 4 h under N₂. Then the moderately reduced graphene oxide (rGO) water solution was employed as an additive to tune the properties of conventional poly(ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) solution. It's found that the incorporation of rGO into PEDOT:PSS nearly did not change its transparency, hydrophilic property, or the surface roughness. So, the rGO/PEDOT:PSS composite was used as a hole transport layer (HTL) to fabricate perovskite solar cells (PSCs). As a result, PSCs with rGO/PEDOT:PSS as HTL exhibit improved power conversion efficiency than that of PSCs with PEDOT:PSS as HTL. Our findings show that moderately reduced rGO/PEDOT:PSS could be an efficient HTL to improve power conversion efficiency of PSCs.     

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).     

Graphene-oxide doped PEDOT:PSS as a superior hole transport material for high-efficiency perovskite solar cell

Inverted perovskite solar cells have attracted a great deal of attention due to its high power conversion efficiency, simple configuration, and low-cost processing. The hole transport material (HTM) is a crucial factor in high performance inverted perovskite solar cell. However, the hole mobility for most common of HTM is too low to matching perovskite materials. Herein, we report a superior HTM with high hole mobility to significantly improve solar cell efficiency. Upon doing the commonly used PEDOT:PSS HTM by graphene oxide (GO), its hole mobility is increased from 5.55 × 10⁻⁵ to 1.57 × 10⁻⁴ cm² V⁻¹ s⁻¹, leading to efficient hole extraction and low current leakage, therefore 20% higher power conversion efficiency comparing to the control device without the GO doping. The development open the opportunities for efficient HTMs based on the two-dimensional materials in the perovskite solar cells.     

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.     

Simultaneous enhancement of the efficiency and stability of organic solar cells using PEDOT:PSS grafted with a PEGME buffer layer

We report a simple processing method to simultaneously improve the efficiency and stability of organic solar cells (OSCs). Poly(4-styrene sulfonate)-doped poly(3,4-ethylenedioxy-thiophene (PEDOT:PSS), widely used as hole transport layer (HTL) in OSCs, tends to accelerate the degradation of devices because of its hygroscopic and acidic properties. In this regard, we have modified PEDOT:PSS to reduce its hygroscopic and acidic properties through a condensation reaction between PEDOT:PSS and poly(ethylene glycol) methyl ether (PEGME) in order to improve the efficiency and stability of OSCs. As a result, the power conversion efficiency (PCE) increased by 21%, from 2.57% up to 3.11%. A better energy level alignment by the reduced work function of the modified PEDOT:PSS with a highest occupied molecular orbital (HOMO) level of poly(3-hexylthiophene-2,5-diyl) (P3HT) is considered the origin of the improved the efficiency. The half-life of OSCs with PEDOT:PSS modified with PEGME buffer layer also increased up to 3.5 times compared to that of devices with pristine PEDOT:PSS buffer layer.     

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.     

Indium tin oxide-free semi-transparent inverted polymer solar cells using conducting polymer as both bottom and top electrodes

Poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) is investigated as a transparent cathode to replace indium tin oxide (ITO) in inverted polymer solar cells. Increasing the thickness of the PEDOT:PSS electrode leads to a reduction in transparency and sheet resistance which lowers the photocurrent but increases the fill factor of the solar cells. The offset of photocurrent and fill factor as the thickness is increased leads to a saturation of the power conversion efficiency to 3%. These electrodes were applied to flexible substrates showing similar device performance to glass based devices. Cyclic bending test of these flexible polymer electrodes show improved conversion efficiency retention (92%) when compared to flexible ITO based electrodes (50%) after 300 bend cycles. In addition to using PEDOT:PSS as a cathode replacement for ITO in inverted solar cells, its use as a semi-transparent anode replacement to Ag is also examined. Semi-transparent inverted solar cells fabricated with ITO as the cathode and PEDOT:PSS as the top anode electrode were demonstrated showing efficiencies of 2.51% while replacement of both ITO and Ag with PEDOT:PSS as both the cathode and anode show efficiencies of 0.47%.     

Hybrid photovoltaic structures based on amorphous silicon and P3HT:PCBM/PEDOT:PSS polymer semiconductors

Hybrid thin film photovoltaic structures, based on hydrogenated silicon (Si:H), organic poly(3-hexythiophene):methano-fullerenephenyl-C61-butyric-acid-methyl-ester (P3HT:PCBM) and poly(3,4ethylenedioxythiophene):poly(4-styrenesulfonate) (PEDOT:PSS) films, have been fabricated. Organic semiconductor thin films were deposited by spin-coating technique and were exposed to radio frequency plasma enhanced chemical vapor deposition (RF PECVD) of Si:H films at deposition temperature T_d = 160 °C. Different types of structures have been investigated: H1) ITO/(p)SiC:H /P3HT:PCBM/(n) Si:H, H2) ITO/PEDOT:PSS/(i)Si:H/(n) Si:H and H3) ITO/PEDOT:PSS/P3HT:PCBM/(i)Si:H/(n)Si:H. Short circuit current density spectral response and current-voltage characteristics were measured for diagnostic of the photovoltaic performance. The current density spectral dependence of hybrid structures which contains organic layers showed improved response (50–80%) in high photon energy range (hν ≈ 3.1–3.5 eV) in comparison with Si:H reference structure. An adjustment in the absorbing layer thickness and in the contact material for ITO/PEDOT:PSS/(i)Si:H/(n)Si:H structure, resulted in a remarkably high short circuit current density (as large as 17.74 mA/cm²), an open circuit voltage of 640 mV and an efficiency of 3.75%.     

Poly(3,4-ethylenedioxythiophene):polystyrene sulfonate films with low conductivity and low acidity through a treatment of their solutions with probe ultrasonication and their application as hole transport layer in polymer solar cells and perovskite solar cells

Poly(3,4-ethylenedioxythiophene):polystyrene sulfonate (PEDOT:PSS) has been widely used as the hole transport material in optoelectronic devices. To avoid the cross talk among different crossbars, PEDOT:PSS with low conductivity is required. It thus has a high loading of the non-conductive PSSH. The PSSH-to-PEDOT weight ratio is 6 for Clevios P VP Al 4083 that is the most popular polymer as the hole transport layer. However, the acidic PSSH brings severe problems to the device stability and performance. Here, PEDOT:PSS solutions with low acidity can be prepared through a facile treatment of PEDOT:PSS solution by probe ultrasonication. Two grades of PEDOT:PSS, Clevios PH1000 and Clevios P, with a PSSH-to-PEDOT weight ratio of 2.5 were treated by probe ultrasonication. The ultrasonication can lower the viscosity and the colloidal sizes of PEDOT:PSS solutions and conductivity of PEDOT:PSS films. The pH value of probe-ultrasonicated Clevios P was 2.12, higher than that (1.77) of pristine Clevios P VP Al 4083. The ultrasonication-treated PEDOT:PSS solutions were used as hole transport layer in polymer solar cells and perovskite solar cells. The photovoltaic performances of these solar cells are comparable to that of control devices employing Clevios P VP Al 4083 PEDOT:PSS as the hole transport layer.     

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.     

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.     

Cooperative Effect of GO and Glucose on PEDOT:PSS for High VOC and Hysteresis‐Free Solution‐Processed Perovskite Solar Cells

Hybrid organic–inorganic halide perovskites have emerged at the forefront of solution‐processable photovoltaic devices. Being the perovskite precursor mixture a complex equilibrium of species, it is very difficult to predict/control their interactions with different substrates, thus the final film properties and device performances. Here the wettability of CH₃NH₃PbI₃ (MAPbI₃) onto poly(3,4‐ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) hole transporting layer is improved by exploiting the cooperative effect of graphene oxide (GO) and glucose inclusion. The glucose, in addition, triggers the reduction of GO, enhancing the conductivity of the PEDOT:PSS+GO+glucose based nanocomposite. The relevance of this approach toward photovoltaic applications is demonstrated by fabricating a hysteresis‐free MAPbI₃ solar cells displaying a ≈37% improvement in power conversion efficiency if compared to a device grown onto pristine PEDOT:PSS. Most importantly, V_OC reaches values over 1.05 V that are among the highest ever reported for PEDOT:PSS p‐i‐n device architecture, suggesting minimal recombination losses, high hole‐selectivity, and reduced trap density at the PEDOT:PSS along with optimized MAPbI₃ coverage.     

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).