Boosting Performance of Non‐Fullerene Organic Solar Cells by 2D g‐C3N4 Doped PEDOT:PSS

The power‐conversion efficiency (PCE) of single‐junction organic solar cells (OSCs) has exceeded 16% thanks to the development of non‐fullerene acceptor materials and morphological optimization of active layer. In addition, interfacial engineering always plays a crucial role in further improving the performance of OSCs based on a well‐established active‐layer system. Doping of graphitic carbon nitride (g‐C₃N₄) into poly(3,4‐ethylene‐dioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) as a hole transport layer (HTL) for PM6:Y6‐based OSCs is reported, boosting the PCE to almost 16.4%. After being added into the PEDOT:PSS, the g‐C₃N₄ as a Bronsted base can be protonated, weakening the shield effect of insulating PSS on conductive PEDOT, which enables exposures of more PEDOT chains on the surface of PEDOT:PSS core‐shell structure, and thus increasing the conductivity. Therefore, at the interface between g‐C₃N₄ doped HTL and PM6:Y6 layer, the charge transport is improved and the charge recombination is suppressed, leading to the increases of fill factor and short‐circuit current density of devices. This work demonstrates that doping g‐C₃N₄ into PEDOT:PSS is an efficient strategy to increase the conductivity of HTL, resulting in higher OSC performance.     

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.     

Tuning Hole Transport Layer Using Urea for High‐Performance Perovskite Solar Cells

Interface engineering is critical to the development of highly efficient perovskite solar cells. Here, urea treatment of hole transport layer (e.g., poly(3,4‐ethylene dioxythiophene):polystyrene sulfonate (PEDOT:PSS)) is reported to effectively tune its morphology, conductivity, and work function for improving the efficiency and stability of inverted MAPbI₃ perovskite solar cells (PSCs). This treatment has significantly increased MAPbI₃ photovoltaic performance to 18.8% for the urea treated PEDOT:PSS PSCs from 14.4% for pristine PEDOT:PSS devices. The use of urea controls phase separation between PEDOT and PSS segments, leading to the formation of a unique fiber‐shaped PEDOT:PSS film morphology with well‐organized charge transport pathways for improved conductivity from 0.2 S cm^?1 for pristine PEDOT:PSS to 12.75 S cm^?1 for 5 wt% urea treated PEDOT:PSS. The urea‐treatment also addresses a general challenge associated with the acidic nature of PEDOT:PSS, leading to a much improved ambient stability of PSCs. In addition, the device hysteresis is significantly minimized by optimizing the urea content in the treatment.     

Interface Modification to Improve Hole‐Injection Properties in Organic Electronic Devices

The performance of organic electronic devices is often limited by injection. In this paper, improvement of hole injection in organic electronic devices by conditioning of the interface between the hole‐conducting layer (buffer layer) and the active organic semiconductor layer is demonstrated. The conditioning is performed by spin‐coating poly(9,9‐dioctyl‐fluorene‐co‐N‐ (4‐butylphenyl)‐diphenylamine) (TFB) on top of the poly(3,4‐ethylene dioxythiophene): poly(styrene sulfonate) (PEDOT:PSS) buffer layer, followed by an organic solvent wash, which results in a TFB residue on the surface of the PEDOT:PSS. Changes in the hole‐injection energy barriers, bulk charge‐transport properties, and current–voltage characteristics observed in a representative PFO‐based (PFO: poly(9,9‐dioctylfluorene)) diode suggest that conditioning of PEDOT:PSS surface with TFB creates a stepped electronic profile that dramatically improves the hole‐injection properties of organic electronic devices.     

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.     

A Simple Cu(II) Polyelectrolyte as a Method to Increase the Work Function of Electrodes and Form Effective p-Type Contacts in Perovskite Solar Cells

One effective strategy to improve the performance of perovskite solar cells (PSCs) is to develop new hole transport layers (HTLs). In this work, a simple polyelectrolyte HTL, copper (II) poly(styrene sulfonate) (Cu:PSS), which comprises easily reduced Cu²⁺ counter-ions with an anionic PSS polyelectrolyte backbone is investigated. Photoelectron spectroscopy reveals an increase in the work function of the anode and upward band bending effect upon incorporation of Cu:PSS in PSC devices. Cu:PSS shows a synergistic effect when mixed with polyethylenedioxythiophene: polystyrenesulfonate (PEDOT:PSS) in various proportions and results in a decrease in the acidity of PEDOT:PSS as well as reduced hysteresis in completed devices. Cu:PSS functions effectively as a HTL in PSCs, with device parameters comparable to PEDOT:PSS, while mixtures of Cu:PSS with PEDOT:PSS shows greatly improved performance compared to PEDOT:PSS alone. Optimized devices incorporating Cu:PSS/PEDOT:PSS mixtures show an improvement in efficiency from 14.35 to 19.44% using a simple CH₃NH₃PbI₃ active layer in an inverted (P-I-N) geometry, which is one of the highest values yet reported for this type of device. It is expected that this type of HTL can be employed to create p-type contacts and improve performance in other types of semiconducting devices as well.     

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.     

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.     

High‐Performance Planar Solar Cells Based On CH3NH3PbI3‐xClx Perovskites with Determined Chlorine Mole Fraction

Solution‐processable hybrid perovskite solar cells are a new member of next generation photovoltaics. In the present work, a low‐temperature two‐step dipping method is proposed for the fabrication of CH₃NH₃PbI_3‐xCl_x perovskite films on the indium tin oxide glass/poly(3,4‐ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) substrate. The bandgaps of the CH₃NH₃PbI_3‐xCl_x perovskite films are tuned in the range between 1.54 and 1.59 eV by adjusting the PbCl₂ mole fraction (n_Cl/(n_Cl + n_I)) in the initial mixed precursor solution from 0.10 to 0.40. The maximum chlorine mole fraction measured by a unique potentiometric titration method in the produced CH₃NH₃PbI_3‐xCl_x films can be up to 0.220 ± 0.020 (x = 0.660 ± 0.060), which is much higher than that produced by a one‐step spin‐coating method (0.056 ± 0.015, x = 0.17 ± 0.04). The corresponding solar cell with the CH₃NH₃PbI_2.34±0.06Cl_0.66±0.06 perovskite film sandwiched between PEDOT:PSS and C₆₀ layers exhibits a power conversion efficiency as high as 14.5%. Meanwhile, the open‐circuit potential (V_oc) of the device reaches 1.11 V, which is the highest V_oc reported in the perovskite solar cells fabricated on PEDOT:PSS so far.     

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.     

Anode Interfacial Tuning via Electron‐Blocking/Hole‐Transport Layers and Indium Tin Oxide Surface Treatment in Bulk‐Heterojunction Organic Photovoltaic Cells

The effects of anode/active layer interface modification in bulk‐heterojunction organic photovoltaic (OPV) cells is investigated using poly(3,4‐ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) and/or a hole‐transporting/electron‐blocking blend of 4,4′‐bis[(p‐trichlorosilylpropylphenyl)‐phenylamino]biphenyl (TPDSi₂) and poly[9,9‐dioctylfluorene‐co‐N‐[4‐(3‐methylpropyl)]‐diphenylamine] (TFB) as interfacial layers (IFLs). Current–voltage data in the dark and AM1.5G light show that the TPDSi₂:TFB IFL yields MDMO‐PPV:PCBM OPVs with substantially increased open‐circuit voltage (V_oc), power conversion efficiency, and thermal stability versus devices having no IFL or PEDOT:PSS. Using PEDOT:PSS and TPDSi₂:TFB together in the same cell greatly reduces dark current and produces the highest V_oc (0.91 V) by combining the electron‐blocking effects of both layers. ITO anode pre‐treatment was investigated by X‐ray photoelectron spectroscopy to understand why oxygen plasma, UV ozone, and solvent cleaning markedly affect cell response in combination with each IFL. O₂ plasma and UV ozone treatment most effectively clean the ITO surface and are found most effective in preparing the surface for PEDOT:PSS deposition; UV ozone produces optimum solar cells with the TPDSi₂:TFB IFL. Solvent cleaning leaves significant residual carbon contamination on the ITO and is best followed by O₂ plasma or UV ozone treatment.     

Enhanced Hole Transportation for Inverted Tin‐Based Perovskite Solar Cells with High Performance and Stability

High electronic quality perovskite films with a balanced charge transportation is critical for satisfying high‐performance for perovskite solar cells (PVSCs). However, the inferior band alignment of tin‐based perovskite films with an adjacent hole‐transport layer (HTL) leads to a poor hole transportation and collection. In this work, the semiconducting molecule poly[tetraphenylethene 3,3′‐(((2,2‐diphenylethene‐1,1‐diyl)bis(4,1‐phenylene))bis(oxy))bis(N,N‐dimethylpropan‐1‐amine)tetraphenylethene] (PTN‐Br) is introduced into a lead‐free perovskite precursor to form a bulk heterojunction film. In addition, the PTN‐Br molecule with the suitable highest occupied molecular orbital energy level (?5.41 eV) can fill into the grain boundaries of the perovskite film, serving as a hole‐transport medium between grains. The gradient band alignment of the perovskite film with poly(3,4‐ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) HTL ensures excellent hole transportation and higher open‐circuit voltage. In addition, the π‐conjugated polymer PTN‐Br can passivate trap states within the perovskite film due to the formation of Lewis adducts between uncoordinated Sn atoms and the dimethylamino of PTN‐Br. Consequently, a champion efficiency of 7.94% is achieved with significant enhancements in the open‐circuit voltage and fill factor. Furthermore, the PTN‐Br incorporated device shows better ultra violet (UV) stability because of the UV barrier and passivating effect of PTN‐Br, retaining about 66% of its initial efficiency after 5 h of continuous UV light irradiation.     

Efficient 4,4′,4″‐tris(3‐methylphenylphenylamino)triphenylamine (m‐MTDATA) Hole Transport Layer in Perovskite Solar Cells Enabled by Using the Nonstoichiometric Precursors

To overcome the drawbacks of the acidic and hygroscopic nature of the poly(3,4‐ethylenedio‐xythiophene):poly(styrenesulfonate) hole transport layer (HTL), the p‐type polymeric hole transport materials have attracted great attention and have been applied into perovskite solar cells. Here, a starburst amine molecule 4,4′,4″‐tris(3‐methylphenylphenylamino)triphenylamine (m‐MTDATA) without any additive is demonstrated as an effective hole transport material in perovskite solar cells. Meanwhile, considering the different surface affinity of precursor's composition on m‐MTDATA, the influence of the molar ratios between lead iodine (PbI₂) and methylammonium iodide in precursor solution on the perovskite characteristics and device performance is investigated in‐depth. Ultimately, an enhanced efficiency of 17.73% and a high fill factor of 79.6% are achieved, which attribute to the strong passivation effect of traps and small resistance loss from appropriate unreacted PbI₂ left in the perovskite layer. This work not only provides a remarkable HTL, but also reveals that the adjustment of precursor ratio is necessary for the one‐step solution approach, because the affinities of precursor's composition may be different with the underlying transport layers.     

Flexible,hole transporting layer-free and stable CH3NH3PbI3/PC61BM planar heterojunction perovskite solar cells

Hole transporting layer (HTL)-free CH₃NH₃PbI₃/PC₆₁BM planar heterojunction perovskite solar cells were fabricated with the configuration of ITO/CH₃NH₃PbI₃/PC₆₁BM/Al. The devices present a remarkable power conversion efficiency (PCE) of 11.7% (12.5% best) under AM 1.5G 100 mW cm⁻² illumination. Moreover, the HTL-free perovskite solar cells on flexible PET substrates are first demonstrated, achieving a power conversion efficiency of 9.7%. The element distribution in the HTL-free perovskite solar cell was further investigated. The results indicated that the PbI₂ enriched near the PC₆₁BM side for chlorobenzene treatment via the fast deposition crystallization method. Without using HTL on the ITO, the device is stable with comparison to that with poly(3,4-ethylenedioxylenethiophene): poly(styrene sulfonate) (PEDOT:PSS) as HTL. In addition, the fabricating time of the whole procedure from ITO substrate cleaning to device finishing fabrication only cost about 3 h for our mentioned devices, which is much more rapid than other structure devices containing other transporting layer. The high efficient and stable HTL-free CH₃NH₃PbI₃/PC₆₁BM planar heterojunction perovskite solar cells with the advantage of saving time and cost provide the potential for commercialization printing electronic devices.     

Unraveling the Reasons for Efficiency Loss in Perovskite Solar Cells

The effect of the presence of unreacted PbI₂ on the perovskite solar cells efficiency is reported. N,N‐Dimethylformamide vapor treatment is introduced to study the influence of complete conversion to a power conversion efficiency of the device. It is discovered that the optimized morphology of the PbI₂ under layer is essential to form a dense perovskite layer preventing recombination by direct contact between TiO₂ and a hole transporting layer, and to increase the charge collection efficiency. The present findings provide an insight into the morphology and growth mechanism of perovskite layer, the correlation between the device performance, and the film deposition process.     

High efficiency arrays of polymer solar cells fabricated by spray‐coating in air

We present bulk heterojunction organic solar cells fabricated by spray‐casting both the PEDOT:PSS hole‐transport layer (HTL) and active PBDTTT‐EFT:PC₇₁BM layers in air. Devices were fabricated in a (6 × 6) array across a large‐area substrate (25 cm²) with each pixel having an active area of 6.45 mm². We show that the film uniformity and operational homogeneity of the devices are excellent. The champion device with spray cast active layer on spin cast PEDOT:PSS had an power conversion efficiency (PCE) of 8.75%, and the best device with spray cast active layer and PEDOT:PSS had a PCE of 8.06%. The impacts of air and light exposure of the active layer on device performance are investigated and found to be detrimental. Copyright © 2015 John Wiley & Sons, Ltd.     

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.     

Interface Molecular Engineering for Laminated Monolithic Perovskite/Silicon Tandem Solar Cells with 80.4% Fill Factor

A multipurpose interconnection layer based on poly(3,4‐ethylenedioxythiophene) doped with poly(styrene sulfonate) (PEDOT:PSS), and d ‐sorbitol for monolithic perovskite/silicon tandem solar cells is introduced. The interconnection of independently processed silicon and perovskite subcells is a simple add‐on lamination step, alleviating common fabrication complexities of tandem devices. It is demonstrated experimentally and theoretically that PEDOT:PSS is an ideal building block for manipulating the mechanical and electrical functionality of the charge recombination layer by controlling the microstructure on the nano‐ and mesoscale. It is elucidated that the optimal functionality of the recombination layer relies on a gradient in the d ‐sorbitol dopant distribution that modulates the orientation of PEDOT across the PEDOT:PSS film. Using this modified PEDOT:PSS composite, a monolithic two‐terminal perovskite/silicon tandem solar cell with a steady‐state efficiency of 21.0%, a fill factor of 80.4%, and negligible open circuit voltage losses compared to single‐junction devices is shown. The versatility of this approach is further validated by presenting a laminated two‐terminal monolithic perovskite/organic tandem solar cell with 11.7% power conversion efficiency. It is envisioned that this lamination concept can be applied for the pairing of multiple photovoltaic and other thin film technologies, creating a universal platform that facilitates mass production of tandem devices with high efficiency.     

High Efficiency Planar p‐i‐n Perovskite Solar Cells Using Low‐Cost Fluorene‐Based Hole Transporting Material

For commercial applications, it is a challenge to find suitable and low‐cost hole‐transporting material (HTM) in perovskite solar cells (PSCs), where high efficiency spiro‐OMeTAD and PTAA are expensive. A HTM based on 9,9‐dihexyl‐9H‐fluorene and N,N‐di‐p‐methylthiophenylamine (denoted as FMT) is designed and synthesized. High‐yield FMT with a linear structure is synthesized in two steps. The dopant‐free FMT‐based planar p‐i‐n perovskite solar cells (pp‐PSCs) exhibit a high power conversion efficiency (PCE) of 19.06%, which is among the highest PCEs reported for the pp‐PSCs based on organic HTM. For comparison, a PEDOT:PSS HTM‐based pp‐PSC is fabricated under the same conditions, and its PCE is found to be 13.9%.     

Improved performance of perovskite solar cells with a TiO2/MoO3 core/shell nanoparticles doped PEDOT:PSS hole-transporter

We demonstrate improved performance of inverted planar heterojunction CH₃NH₃PbI_3-xCl_x perovskite solar cells with a TiO₂/MoO₃ core/shell nanoparticles (NPs) doped poly(3,4-ethylene dioxythiophene):poly(4-styrenesulfonate) (PEDOT:PSS) hole-transporting layer (HTL). TiO₂/MoO₃ Core/shell NPs with size of approximately 40 nm are successfully prepared with a simple wet solution method and are interspersed into PEDOT: PSS layer to construct the HTL. The optimized device shows a high power conversion efficiency of 13.63%, which is dramatically improved compared with the reference device with a pristine PEDOT:PSS HTL. The improvement is mainly attributed to the increased crystalline of the CH₃NH₃PbI_3-xCl_x film with large-scale domains and a compact morphology. More interesting, the cells exhibit superior stability in ambient conditions, which is attributed to the inhibited penetration of moisture due to the compact morphology of the CH₃NH₃PbI_3-xCl_x film and the reduced hygroscopicity of the PEDOT:PSS film.