An Amidine‐Type n‐Dopant for Solution‐Processed Field‐Effect Transistors and Perovskite Solar Cells

This study reports an effective amidine‐type n‐dopant of 1,8‐Diazabicyclo[5.4.0]undec‐7‐ene (DBU) that can universally dope electron acceptors, including PC₆₁BM, N2200, and ITIC, by mixing the dopant with the acceptors in organic solvents or exposing the acceptor films in the dopant vapor. The doping mechanism is due to its strong electron‐donating property that is also confirmed via the chemical reduction of PEDOT:PSS (yielding color change). The DBU doping considerably increases the electrical conductivity and shifts the Fermi levels up of the PC₆₁BM films. When the DBU‐doped PC₆₁BM is used as an electron‐transporting layer in perovskite solar cells, the n‐doping removes the “S‐shape” of J–V characteristics, which leads to the fill factor enhancement from 0.54 to 0.76. Furthermore, the DBU doping can effectively lower the threshold voltage and enhance the electron mobility of PC₆₁BM‐based n‐channel field‐effect transistors. These results show that the DBU can be a promising n‐dopant for solution‐processed electronics.     

In‐Situ Switching from Barrier‐Limited to Ohmic Anodes for Efficient Organic Optoelectronics

Injection and extraction of charges through ohmic contacts are required for efficient operation of semiconductor devices. Treatment using polar non‐solvents switches polar anode surfaces, including PEDOT:PSS and ITO, from barrier‐limited hole injection and extraction to ohmic behaviour. This is caused by an in‐situ modification of the anode surface that is buried under a layer of organic semiconductor. The exposure to methanol removes polar hydroxyl groups from the buried anode interface, and permanently increases the work function by 0.2–0.3 eV. In the case of ITO/PEDOT:PSS/PBDTTT‐CT:PC71BM/Al photovoltaic devices, the higher work function promotes charge transfer, leading to p‐doping of the organic semiconductor at the interface. This results in a two‐fold increase in hole extraction rates which raises both the fill factor and the open‐circuit voltage, leading to high power conversion efficiency of 7.4%. In ITO/PEDOT:PSS/F8BT/Al polymer light‐emitting diodes, where the organic semiconductor's HOMO level lies deeper than the anode Fermi level, the increased work function enhances hole injection efficiency and luminance intensity by 3 orders of magnitude. In particular, hole injection rates from PEDOT:PSS anodes are equivalent to those achievable using MoO₃. These findings exemplify the importance of work function control as a tool for improved electrode design, and open new routes to device interfacial optimization using facile solvent processing techniques. Such simple, persistent, treatments pave the way towards low cost manufacturing of efficient organic optoelectronic devices.     

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.     

Improved lifetimes of organic solar cells with solution‐processed molybdenum oxide anode‐modifying layers

We report on the use and stability of solution‐processed molybdenum oxide (sMoO_x) thin films as anode‐modifying layers to replace conventionally used poly(3,4‐ethyldioxythiophene)/poly(styrenesulfonate) (PEDOT/PSS) layers in poly(3‐hexylthiophene):[6,6]‐phenyl C₆₁ butyric acid methyl ester (P3HT/PC₆₁BM) bulk heterojunction organic solar cells. Our results show that while as prepared devices using the two anode‐modifying layers possess similar performances, the sMoO_x devices exhibit a staggering 20‐fold stability improvement in its performance half‐life compared with PEDOT/PSS devices, ~3400 h versus ~150 h, respectively. A further comparison of the stability between encapsulated and unencapsulated devices demonstrates the necessity for protection from atmospheric moisture and oxygen but again highlights the lucrative nature of sMoO_x as a protective anode‐modifying layer compared with PEDOT/PSS even under ambient conditions. Copyright © 2014 John Wiley & Sons, Ltd.     

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.     

Efficient Polymer Solar Cells Based on Poly(3‐hexylthiophene):Indene‐C70 Bisadduct with a MoO3 Buffer Layer

Polymer solar cells (PSCs) with poly(3‐hexylthiophene) (P3HT) as a donor, an indene‐C₇₀ bisadduct (IC₇₀BA) as an acceptor, a layer of indium tin oxide modified by MoO₃ as a positive electrode, and Ca/Al as a negative electrode are presented. The photovoltaic performance of the PSCs was optimized by controlling spin‐coating time (solvent annealing time) and thermal annealing, and the effect of the spin‐coating times on absorption spectra, X‐ray diffraction patterns, and transmission electron microscopy images of P3HT/IC₇₀BA blend films were systematically investigated. Optimized PSCs were obtained from P3HT/IC₇₀BA (1:1, w/w), which exhibited a high power conversion efficiency of 6.68%. The excellent performance of the PSCs is attributed to the higher crystallinity of P3HT and better a donor–acceptor interpenetrating network of the active layer prepared under the optimized conditions. In addition, PSCs with a poly(3,4‐ethylenedioxy‐thiophene):poly(styrenesulfonate) (PEDOT:PSS) buffer layer under the same optimized conditions showed a PCE of 6.20%. The results indicate that the MoO₃ buffer layer in the PSCs based on P3HT/IC₇₀BA is superior to that of the PEDOT:PSS buffer layer, not only showing a higher device stability but also resulting in a better photovoltaic performance of the PSCs.     

银纳米颗粒界面层对有机太阳能电池光敏层相分离的影响

通过原子力显微镜(AFM)和X射线光电子能谱(XP S)表征,研究了在光敏层与阳极缓冲层界面引入银(Ag)纳米颗粒界面层后对PTB7:PC70BM光 敏层相分离的影响,并通过接触角测试对其影响机理进行了分的,结果表明,当引入Ag纳米 颗粒界面层后,光敏层的表面形貌并没有发生 明显的改变,但是光敏层在横向与纵向方向有了更好的相分离;并发现,引入Ag纳米颗粒引 起 的光敏层优化的相分离,本质上源于其底部PEDOT:PSS层表面能的减小,其中起关键作用的 是乙醇溶剂;通过紫外-可见吸收光谱以及相关电池性能测试确认,乙醇溶剂处理PEDOT:P SS表面有助于提高电池的电性能。 本文研究表明,在有机太阳能电池(OSCs)中引入金属纳米颗粒,不仅要考虑其 光学效应,还要考虑由于光敏层相分离的变化引起的电学效应。     

Improved conductive atomic force microscopy measurements on organic photovoltaic materials via mitigation of contact area uncertainty

Physical processes that lead to conversion of light into electrical energy inside photovoltaic devices happen at the nanoscale. Therefore, understanding of electrical properties of photovoltaic materials at this length scale is of paramount importance for improvement of device performance. In this paper, we describe and validate a new framework for high‐resolution quantitative measurements of electrical and mechanical properties of compliant materials with sub‐100‐nm resolution. Previous approaches have generally suffered from uncertainty in the quantitative level of contact between the probe and the material being measured; the methodology presented here overcomes this obstacle. We use the broadly studied ITO/PEDOT:PSS/P3HT:PC₆₁BM system as an example to illustrate variability of chemical composition and electrical properties of the active layer at hundred‐nanometers and micrometer length scales. Copyright © 2012 John Wiley & Sons, Ltd.     

Solution‐Processed Nickel Oxide Hole Transport Layers in High Efficiency Polymer Photovoltaic Cells

The detailed characterization of solution‐derived nickel (II) oxide (NiO) hole‐transporting layer (HTL) films and their application in high efficiency organic photovoltaic (OPV) cells is reported. The NiO precursor solution is examined in situ to determine the chemical species present. Coordination complexes of monoethanolamine (MEA) with Ni in ethanol thermally decompose to form non‐stoichiometric NiO. Specifically, the [Ni(MEA)₂(OAc)]⁺ ion is found to be the most prevalent species in the precursor solution. The defect‐induced Ni³⁺ ion, which is present in non‐stoichiometric NiO and signifies the p‐type conduction of NiO, as well as the dipolar nickel oxyhydroxide (NiOOH) species are confirmed using X‐ray photoelectron spectroscopy. Bulk heterojunction (BHJ) solar cells with a polymer/fullerene photoactive layer blend composed of poly‐dithienogermole‐thienopyrrolodione (pDTG‐TPD) and [6,6]‐phenyl‐C71‐butyric acid methyl ester (PC₇₁BM) are fabricated using these solution‐processed NiO films. The resulting devices show an average power conversion efficiency (PCE) of 7.8%, which is a 15% improvement over devices utilizing a poly(3,4‐ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) HTL. The enhancement is due to the optical resonance in the solar cell and the hydrophobicity of NiO, which promotes a more homogeneous donor/acceptor morphology in the active layer at the NiO/BHJ interface. Finally, devices incorporating NiO as a HTL are more stable in air than devices using PEDOT:PSS.     

Enhanced Performance of Fullerene n‐Channel Field‐Effect Transistors with Titanium Sub‐Oxide Injection Layer

Enhanced performance of n‐channel organic field‐effect transistors (OFETs) is demonstrated by introducing a titanium sub‐oxide (TiO_x) injection layer. The n‐channel OFETs utilize [6,6]‐phenyl‐C₆₁ butyric acid methyl ester (PC₆₁BM) or [6,6]‐phenyl‐C₇₁ butyric acid methyl ester (PC₇₁BM) as the semiconductor in the channel. With the TiO_x injection layer, the electron mobilities of PC₆₁BM and PC₇₁BM FET using Al as source/drain electrodes are comparable to those obtained from OFETs using Ca as the source/drain electrodes. Direct measurement of contact resistance (R_c) shows significantly decreased R_c values for FETs with the TiO_x layer. Ultraviolet photoelectron spectroscopy (UPS) studies demonstrate that the TiO_x layer reduces the electron injection barrier because of the relatively strong interfacial dipole of TiO_x. In addition to functioning as an electron injection layer that eliminates the contact resistance, the TiO_x layer acts as a passivation layer that prevents penetration of O₂ and H₂O; devices with the TiO_x injection layer exhibit a significant improvement in lifetime when exposed to air.     

Simple synthesis of solution-processable oxygen-enriched graphene as anode buffer layer for efficient organic solar cells

Interface material is a must for highly efficient and stable organic solar cells (OSCs) and has become a significant part of OSC research today. Here, low-cost and oxygen functionalized graphene (FG) was synthesized via a simple two-step method for applications in OSCs as anode buffer layer. The FG shows excellent dispersion in aqueous solution and great process compatibility with spin coating process. The introduction of work-function-tunable FG can effectively improve short current density of the devices. The power conversion efficiency of FG-based devices (4.13%, 4.49%, and 7.11% for P3HT:PC₆₁BM, P3HT:PC₇₁BM and PBDTTT-C:PC₇₁BM, respectively) outperforms PEDOT:PSS-based devices (3.67%, 4.17%, and 6.46%, respectively). Moreover, the stability of the devices was improved with FG as anode buffer layer compared to PEDOT:PSS. The results indicate that simple synthesized FG is a promising solution-processed anode buffer layer material for high-efficiency and stable OSCs.     

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

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

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.     

Stable Inverted Polymer/Fullerene Solar Cells Using a Cationic Polythiophene Modified PEDOT:PSS Cathodic Interface

A cationic and water‐soluble polythiophene [poly[3‐(6‐pyridiniumylhexyl)thiophene bromide] (P3PHT⁺Br^?)] is synthesized and used in combination with anionic poly(3,4‐ethylenedioxythiophene):poly(p‐styrenesulfonate) (PEDOT:PSS)^? to produce hybrid coatings on indium tin oxide (ITO). Two coating strategies are established: i) electrostatic layer‐by‐layer assembly with colloidal suspensions of (PEDOT:PSS)^?, and ii) modification of an electrochemically prepared (PEDOT:PSS)^? film on ITO. The coatings are found to modify the work function of ITO such that it could act as a cathode in inverted 2,5‐diyl‐poly(3‐hexylthiophene) (P3HT)/[6,6]‐phenyl‐C₆₁‐butyric acid methyl ester (PCBM) polymer photovoltaic cells. The interfacial modifier created from the layer‐by‐layer assembly route is used to produce efficient inverted organic photovoltaic devices (power conversion efficiency ～2%) with significant long‐term stability in excess of 500 h.     

In‐Situ Compositional and Structural Analysis of Plastic Solar Cells

Bulk‐heterojunction photovoltaic cells consisting of a photoactive layer of poly[2‐methoxy‐5‐(3′,7′‐dimethyloctyloxy)‐1,4‐phenylenevinylene] (MDMO‐PPV) and a C₆₀ derivative, (1‐(3‐methoxycarbonyl)propyl‐1‐phenyl‐[6,6]‐methanofullerene), (PCBM), sandwiched between an indium tin oxide (ITO) anode covered with poly(ethylene dioxythiophene):poly(styrene sulfonate) (PEDOT:PSS), and an aluminum cathode have been analyzed using transmission electron microscopy (TEM) and cryogenic Rutherford backscattering spectrometry (RBS) to assess the structural and elemental composition of these devices. TEM of cross sections of fully processed photovoltaic cells, prepared using a focused ion beam, provide a clear view of the individual layers and their interfaces. RBS shows that during preparation diffusion of indium into the PEDOT:PSS occurs while the diffusion of aluminum into the polymer layers is negligible. An iodinated C₆₀ derivative (I‐PCBM) was used to determine the concentration profile of this derivative in the vertical direction of a 100 nm active layer.     

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.     

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.     

The Curious Out‐of‐Plane Conductivity of PEDOT:PSS

For its application as transparent conductor in light‐emitting diodes and photovoltaic cells, both the in‐plane and out‐of‐plane conductivity of PEDOT:PSS are important. However, studies into the conductivity of PEDOT:PSS rarely address the out‐of‐plane conductivity and those that do, report widely varying results. Here a systematic study of the out‐of‐plane charge transport in thin films of PEDOT:PSS with varying PSS content is presented. To this end, the PEDOT:PSS is enclosed in small interconnects between metallic contacts. An unexpected, but strong dependence of the conductivity on interconnect diameter is observed for PEDOT:PSS formulations without high boiling solvent. The change in conductivity correlates with a diameter dependent change in PEDOT:PSS layer thickness. It is suggested that the order of magnitude variation in out‐of‐plane conductivity with only a 3‐4‐fold layer thickness variation can quantitatively be explained on basis of a percolating cluster model.     

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.     

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

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