Monolayer Hexagonal Boron Nitride: An Efficient Electron Blocking Layer in Organic Photovoltaics

In this study, monolayer hexagonal boron nitride (h-BN) grown via chemical vapor deposition (CVD) as an effective electron blocking layer (EBL) for the organic photovoltaics (OPVs) is proposed. Unexpectedly, it is found that h-BN can replace the commonly used hole transport layers (HTLs), i.e., molybdenum trioxide (MoO₃) and poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS) in an inverted device architecture. Here, a wet-transfer technique is employed and a single layer of h-BN on top of the PV2000:PC₆₀BM blend is successfully placed. Analysis of the bandgap diagram shows that the monolayer h-BN makes smaller barrier for holes but significantly larger barrier for electrons. This makes the h-BN effective in blocking electrons while creating a possible path for the holes through tunneling to the electrode, due to the low energy barrier at the PV2000/h-BN interface. Using h-BN as an EBL, efficient inverted OPVs are achieved with an average solar-to-power conversion efficiency of 6.13%, which is comparable with that of reference devices based on MoO₃ (7.3%) and PEDOT:PSS (7.6%) as HTLs. Interestingly, the devices with h-BN shows great light-soak stability. The study reveals that the monolayer h-BN grown by CVD could be an effective alternative EBL for the fabrication of efficient, lightweight, and stable OPVs.     

Plasticization of PEDOT:PSS by Common Additives for Mechanically Robust Organic Solar Cells and Wearable Sensors

Despite the ubiquity of poly(3,4‐ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) in applications demanding mechanical flexibility, the effect on the mechanical properties of common additives—i.e., dimethylsulfoxide (DMSO), Zonyl fluorosurfactant (Zonyl), and poly(ethyleneimine) (PEI)—has not been reported. This paper describes these effects and uses plasticized films in solar cells and mechanical sensors for the detection of human motion. The tensile moduli of films spin‐coated from solutions containing 0%, 5%, and 10% DMSO and 0.1%, 1%, and 10% Zonyl (nine samples total) are measured using the buckling technique, and the ductility is inferred from measurements of the strain at which cracks form on elastic substrates. Elasticity and ductility are maximized in films deposited from solutions containing 5% DMSO and 10% Zonyl, but the conductivity is greatest for samples containing 0.1% Zonyl. These experiments reveal enlargement of presumably PEDOT‐rich grains, visible by atomic force microscopy, when the amount of DMSO is increased from 0% to 5%. PEI—which is used to lower the work function of PEDOT:PSS—has a detrimental effect on the mechanical properties of the PEDOT:PSS/PEI bilayer films. Wearable electronic sensors employing PEDOT:PSS films containing 5% DMSO and 10% Zonyl are ­fabricated, which exhibit detectable responses at 20% strain and high mechanical robustness through elastic deformation.     

Efficient and Stable Perovskite Solar Cells via Dual Functionalization of Dopamine Semiquinone Radical with Improved Trap Passivation Capabilities

Highly efficient planar heterojunction perovskite solar cells (PVSCs) with dopamine (DA) semiquinone radical modified poly(3,4‐ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS) (DA‐PEDOT:PSS) as a hole transporting layer (HTL) were fabricated. A combination of characterization techniques were employed to investigate the effects of DA doping on the electron donating capability of DA‐PEDOT:PSS, perovskite film quality and charge recombination kinetics in the solar cells. Our study shows that DA doping endows the DA‐PEDOT:PSS‐modified PVSCs with a higher radical content and greater perovskite to HTL charge extraction capability. In addition, the DA doping also improves work function of the HTL, increases perovskite film crystallinity, and the amino and hydroxyl groups in DA can interact with the undercoordinated Pb atoms on the perovskite crystal, reducing charge‐recombination rate and increasing charge‐extraction efficiency. Therefore, the DA‐PEDOT:PSS‐modified solar cells outperform those based on PEDOT:PSS, increasing open‐circuit voltage (V _oc) and power conversion efficiency (PCE) to 1.08 V and 18.5%, respectively. Even more importantly, the efficiency of the unencapsulated DA‐PEDOT:PSS‐based PVSCs are well retained with only 20% PCE loss after exposure to air for 250 hours. These in‐depth insights into structure and performance provide clear and novel guidelines for the design of effective HTLs to facilitate the practical application of inverted planar heterojunction PVSCs.     

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.     

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.     

Stretchable and Transparent Conductive PEDOT:PSS‐Based Electrodes for Organic Photovoltaics and Strain Sensors Applications

The development of transparent, conducting, and stretchable poly(3,4‐ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS)‐based electrodes using a combination of a polyethylene oxide (PEO) polymer network and the surfactant Zonyl is reported. The latter improves the ductility of PEDOT:PSS and enables its deposition on hydrophobic surfaces such as polydimethylsiloxane (PDMS) elastomers, while the presence of a 3D matrix offers high electrical conductivity, elasticity, and mechanical recoverability. The resulting electrode exhibits attractive properties such as high electrical conductivity of up to 1230 S cm^?1 while maintaining high transparency of 95% at 550 nm. The potential of the electrode technology is demonstrated in indium‐tin‐oxide (ITO)‐free solar cells using the PBDB‐T‐2F:IT‐4F blend with a power conversion efficiency of 12.5%. The impact of repeated stretch‐and‐release cycles on the electrical resistance is also examined in the effort to evaluate the properties of the electrodes. The interpenetrated morphology of the PEDOT:PSS and polyethylene oxide network is found to exhibit beneficial synergetic effects resulting in excellent mechanical stretchability and high electrical conductivity. By carefully tuning the amount of additives, the ability to detect small changes in electrical resistance as a function of mechanical deformation is demonstrated, which enables the demonstration of stretchable and resilient on‐skin strain sensors capable of detecting small motions of the finger.     

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.     

Electron‐Enhanced Hole Injection in Blue Polyfluorene‐Based Polymer Light‐Emitting Diodes

It has recently been reported that, after electrical conditioning, an ohmic hole contact is formed in poly(9,9‐dioctylfluorene) (PFO)‐based polymer light‐emitting diodes (PLED), despite the large hole‐injection barrier obtained with a poly(styrene sulfonic acid)‐doped poly(3,4‐ethylenedioxythiophene) (PEDOT:PSS) anode. We demonstrate that the initial current at low voltages in a PEDOT:PSS/PFO‐based PLED is electron dominated. The voltage at which the hole injection is enhanced strongly depends on the electron‐transport properties of the device, which can be modified by the replacement of reactive end groups by monomers in the synthesis. Our measurements reveal that the switching voltage of the PLED is governed by the electron concentration at the PEDOT:PSS/PFO contact. The switching effect in PFO is only observed for a PEDOT:PSS hole contact and not for other anodes such as indium tin oxide or Ag.     

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.     

Fluorinated alkyl phosphonic acid SAMs replace PEDOT:PSS in polymer semiconductor devices

Fluorinated phosphonic acids were self-assembled to form monolayers (SAMs) on indium tin oxide anodes, resulting in work functions that are 0.15-0.4 eV larger than PEDOT:PSS by Kelvin probe. X-ray photoelectron spectroscopy and water contact angle measurements were used to study monolayer growth kinetics and to verify the degree of coverage. Hole-only devices and white polymer light emitting diodes were constructed using unmodified ITO, SAM-modified ITO, and PEDOT:PSS on ITO to investigate the influence of the fluorinated SAMs on hole injection. Hole-only devices indicate improved hole injection compared to PEDOT:PSS. Compared with light-emitting diodes using pure ITO anodes, the SAM-modified devices show improved charge injection and ten times higher luminous efficiency. Compared to devices using PEDOT:PSS, SAM-modified devices show improved brightness and luminous efficiency, although with a slightly larger turn-on voltage. These materials are therefore suitable candidates to replace PEDOT:PSS as a hole injection layer in PLEDs.     

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.     

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.     

PEDOT:PSS‐Assisted Exfoliation and Functionalization of 2D Nanosheets for High‐Performance Organic Solar Cells

Here, a facial and scalable method for efficient exfoliation of bulk transition metal dichalcogenides (TMD) and graphite in aqueous solution with poly(3,4‐ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) to prepare single‐ and few‐layer nanosheets is demonstrated. Importantly, these TMD nanosheets retain the single crystalline characteristic, which is essential for application in organic solar cells (OSCs). The hybrid PEDOT:PSS/WS₂ ink prepared by a simple centrifugation is directly integrated as a hole extraction layer for high‐performance OSCs. Compared with PEDOT:PSS, the PEDOT:PSS/WS₂‐based devices provide a remarkable power conversion efficiency due to the “island” morphology and benzoid–quinoid transition. This study not only demonstrates a novel method for preparing single‐ and few‐layer TMD and graphene nanosheets but also paves a way for their applications without further complicated processing.     

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).     

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.     

Improving Performance and Stability of Flexible Planar‐Heterojunction Perovskite Solar Cells Using Polymeric Hole‐Transport Material

For realizing flexible perovskite solar cells (PSCs), it is important to develop low‐temperature processable interlayer materials with excellent charge transporting properties. Herein, a novel polymeric hole‐transport material based on 1,4‐bis(4‐sulfonatobutoxy)benzene and thiophene moieties (PhNa‐1T) and its application as a hole‐transport layer (HTL) material of high‐performance inverted‐type flexible PSCs are introduced. Compared with the conventionally used poly(3,4‐ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS), the incorporation of PhNa‐1T into HTL of the PSC device is demonstrated to be more effective for improving charge extraction from the perovskite absorber to the HTL and suppressing charge recombination in the bulk perovskite and HTL/perovskite interface. As a result, the flexible PSC using PhNa‐1T achieves high photovoltaic performances with an impressive power conversion efficiency of 14.7%. This is, to the best of our knowledge, among the highest performances reported to date for inverted‐type flexible PSCs. Moreover, the PhNa‐1T‐based flexible PSC shows much improved stability under an ambient condition than PEDOT:PSS‐based PSC. It is believed that PhNa‐1T is a promising candidate as an HTL material for high‐performance flexible PSCs.     

Stable photovoltaic cells based on graphene oxide/indium zinc oxide bilayer anode buffer

We report a solution-processed graphene oxide (GO) functioned as an anode buffer layer in organic photovoltaic cells (OPVs). The OPVs using indium zinc oxide (IZO), IZO/GO, GO/IZO, and poly(3,4-thylenedioxythiophene) doped poly(styrene sulfonate) (PEDOT:PSS) as a control device, exhibited the conversion efficiency of 3.4%, 3.5%, 3.9% and 3.4%, respectively. No obvious degradation was discovered for the OPVs with incorporating GO as one of the anode buffer layers after 1 h continuous illumination under AM1.5. On the other hand, after only 1 h continuous illumination, a momentous degradation was observed for the OPVs without the presence of GO. All these results demonstrate that the GO layer plays an important role in the improvement of the stability with conventional device architecture.     

Structural Stability and Optical Studies of Poly(3-hexylthiophene) in an ITO/PEDOT:PSS/P3HT Interface

An interface between poly(3-hexylthiophene) (P3HT) and poly(3,4-ethylenedioxythiophene) doped with poly(4-styrenesulfonate) (PEDOT:PSS) was prepared in LiClO_4-–acetonitrile (ACN) over indium-doped tin oxide (ITO), known as the ITO/PEDOT:PSS/P3HT system. This system was compared with ITO/P3HT with the aim of studying the stability of aromatic, quinone, and semiquinone segments in the polymer matrix and also elucidating the influence of the structure on the efficiency of organic photovoltaic cells (OPVs). Initially, Raman spectroscopy was used, varying the laser power to verify the destabilization of radical cation segments to dication segments in the ITO/P3HT system. Electrochemical impedance spectroscopy (EIS) was used to show the behavior of the charged species and the charge-transfer processes of the different P3HT segments as a function of time since preparation of the studied systems. In addition, photoluminescence (PL) and time-resolved PL spectroscopy showed the optical properties of the interfaces formed, based on the different quantities of segments present. It was possible to conclude that the modification introduced into the interface by PEDOT:PSS favors stabilization of the P3HT radical cation segment, which remains stable in this interface for lengthy periods (240 h). This should in turn boost hole extraction, increasing OPV efficiency.     

Over 16.7% Efficiency Organic‐Silicon Heterojunction Solar Cells with Solution‐Processed Dopant‐Free Contacts for Both Polarities

Realization of synchronous improvement in optical management and electrical engineering is necessary to achieve high‐performance photovoltaic device. However, inherent challenges are faced in organic‐silicon heterojunction solar cells (HSCs) due to the poor contact property of polymer on structured silicon surface. Herein, a remarkable efficiency boost from 12.6% to over 16.7% in poly(3,4‐ethylenedioxythiophene):poly(styrenesulfonate)/n‐silicon (PEDOT:PSS/n‐Si) HSCs by independent optimization of hole‐/electron‐selective contacts only relying on solution‐based processes is realized. A bilayer PEDOT:PSS film with different functionalizations is utilized to synchronously realize conformal contact and effective carrier collection on textured Si surface, making the photogenerated carriers be well separated at heterojunction interface. Meanwhile, fullerene derivative is used as electron‐transporting layer at the rear n‐Si/Al interface to reduce the contact barrier. The study of carriers' transport and independent optimization on separately contacted layers may lead to an effective and simplified path to fabricate high‐performance organic‐silicon heterojunction devices.