Doping Approaches for Organic Semiconductors.

Electronic doping in organic materials has remained an elusive concept for several decades. It drew considerable attention in the early days in the quest for organic materials with high electrical conductivity, paving the way for the pioneering work on pristine organic semiconductors (OSCs) and their eventual use in a plethora of applications. Despite this early trend, however, recent strides in the field of organic electronics have been made hand in hand with the development and use of dopants to the point that are now ubiquitous. Here, we give an overview of all important advances in the area of doping of organic semiconductors and their applications. We first review the relevant literature with particular focus on the physical processes involved, discussing established mechanisms but also newly proposed theories. We then continue with a comprehensive summary of the most widely studied dopants to date, placing particular emphasis on the chemical strategies toward the synthesis of molecules with improved functionality. The processing routes toward doped organic films and the important doping-processing-nanostructure relationships, are also discussed. We conclude the review by highlighting how doping can enhance the operating characteristics of various organic devices.

Intrinsic efficiency limits in low-bandgap non-fullerene acceptor organic solar cells.

In bulk heterojunction (BHJ) organic solar cells (OSCs) both the electron affinity (EA) and ionization energy (IE) offsets at the donor-acceptor interface should equally control exciton dissociation. Here, we demonstrate that in low-bandgap non-fullerene acceptor (NFA) BHJs ultrafast donor-to-acceptor energy transfer precedes hole transfer from the acceptor to the donor and thus renders the EA offset virtually unimportant. Moreover, sizeable bulk IE offsets of about 0.5 eV are needed for efficient charge transfer and high internal quantum efficiencies, since energy level bending at the donor-NFA interface caused by the acceptors' quadrupole moments prevents efficient exciton-to-charge-transfer state conversion at low IE offsets. The same bending, however, is the origin of the barrier-less charge transfer state to free charge conversion. Our results provide a comprehensive picture of the photophysics of NFA-based blends, and show that sizeable bulk IE offsets are essential to design efficient BHJ OSCs based on low-bandgap NFAs.

Isoindigo-3,4-Difluorothiophene Polymer Acceptors Yield "All-Polymer" Bulk-Heterojunction Solar Cells with over 7 % Efficiency.

Poly(isoindigo-alt-3,4-difluorothiophene) (PIID[2F]T) analogues used as "polymer acceptors" in bulk-heterojunction (BHJ) solar cells achieve >7 % efficiency when used in conjunction with the polymer donor PBFTAZ (model system; copolymer of benzo[1,2-b:4,5-b']dithiophene and 5,6-difluorobenzotriazole). Considering that most efficient polymer-acceptor alternatives to fullerenes (e.g. PC61 BM or its C71 derivative) are based on perylenediimide or naphthalenediimide motifs thus far, branched alkyl-substituted PIID[2F]T polymers are particularly promising non-fullerene candidates for "all-polymer" BHJ solar cells.

p-Type Conjugated Polymers Containing Electron-Deficient Pentacyclic Azepinedione.

Bisthienoazepinedione (BTA) has been reported for constructing high-performing p-type conjugated polymers in organic electronics, but the ring extended version of BTA is not well explored. In this work, we report a new synthesis of a key building block to the ring expanded electron-deficient pentacyclic azepinedione (BTTA). Three copolymers of BTAA with benzodithiophene substituted by different side chains are prepared. These polymers exhibit similar energy levels and optical absorption in solution and solid state, while significant differences are revealed in their film morphologies and behavior in transistor and photovoltaic devices. The best-performing polymers in transistor devices contained alkylthienyl side chains on the BDT unit (pBDT-BTTA-2 and pBDT-BTTA-3) and demonstrated maximum saturation hole mobilities of 0.027 and 0.017 cm2 V-1 s-1. Blends of these polymers with PC71BM exhibited a best photovoltaic efficiency of 6.78% for pBDT-BTTA-3-based devices. Changing to a low band gap non-fullerene acceptor (BTP-eC9) resulted in improved efficiency of up to 13.5%. Our results are among the best device performances for BTA and BTTA-based p-type polymers and highlight the versatile applications of this electron-deficient BTTA unit.

Emissive Charge-Transfer States at Hybrid Inorganic/Organic Heterojunctions Enable Low Non-Radiative Recombination and High-Performance Photodetectors.

Hybrid devices based on a heterojunction between inorganic and organic semiconductors have offered a means to combine the advantages of both classes of materials in optoelectronic devices, but, in practice, the performance of such devices has often been disappointing. Here, it is demonstrated that charge generation in hybrid inorganic-organic heterojunctions consisting of copper thiocyanate (CuSCN) and a variety of molecular acceptors (ITIC, IT-4F, Y6, PC70 BM, C70 , C60 ) proceeds via emissive charge-transfer (CT) states analogous to those found at all-organic heterojunctions. Importantly, contrary to what has been observed at previous organic-inorganic heterojunctions, the dissociation of the CT-exciton and subsequent charge separation is efficient, allowing the fabrication of planar photovoltaic devices with very low non-radiative voltage losses (0.21 ±  0.02 V). It is shown that such low non-radiative recombination enables the fabrication of simple and cost-effective near-IR (NIR) detectors with extremely low dark current (4 pA cm-2 ) and noise spectral density (3 fA Hz-1/2 ) at no external bias, leading to specific detectivities at NIR wavelengths of just under 1013 Jones, close to the performance of commercial silicon photodetectors. It is believed that this work demonstrates the possibility for hybrid heterojunctions to exploit the unique properties of both inorganic and organic semiconductors for high-performance opto-electronic devices.

Chlorine-Infused Wide-Band Gap p-CuSCN/n-GaN Heterojunction Ultraviolet-Light Photodetectors.

Copper thiocyanate (CuSCN) is a p-type semiconductor that exhibits hole-transport and wide-band gap (∼3.9 eV) characteristics. However, the conductivity of CuSCN is not sufficiently high, which limits its potential application in optoelectronic devices. Herein, CuSCN thin films were exposed to chlorine using a dry etching system to enhance their electrical properties, yielding a maximum hole concentration of 3 × 1018 cm-3. The p-type CuSCN layer was then deposited onto an n-type gallium nitride (GaN) layer to form a prototypical ultraviolet-based photodetector. X-ray photoelectron spectroscopy further demonstrated the interface electronic structures of the heterojunction, confirming a favorable alignment for holes and electrons transport. The ensuing p-CuSCN/n-GaN heterojunction photodetector exhibited a turn-on voltage of 2.3 V, a responsivity of 1.35 A/W at -1 V, and an external quantum efficiency of 5.14 × 102% under illumination with ultraviolet light (peak wavelength of 330 nm). The work opens a new pathway for making a plethora of hybrid optoelectronic devices of inorganic and organic nature by using p-type CuSCN as the hole injection layer.

18.4 % Organic Solar Cells Using a High Ionization Energy Self-Assembled Monolayer as Hole-Extraction Interlayer.

Self-assembled monolayers (SAMs) based on Br-2PACz ([2-(3,6-dibromo-9H-carbazol-9-yl)ethyl]phosphonic acid) 2PACz ([2-(9H-Carbazol-9-yl)ethyl]phosphonic acid) and MeO-2PACz ([2-(3,6-dimethoxy-9H-carbazol-9-yl)ethyl]phosphonic acid) molecules were investigated as hole-extracting interlayers in organic photovoltaics (OPVs). The highest occupied molecular orbital (HOMO) energies of these SAMs were measured at -6.01 and -5.30 eV for Br-2PACz and MeO-2PACz, respectively, and found to induce significant changes in the work function (WF) of indium-tin-oxide (ITO) electrodes upon chemical functionalization. OPV cells based on PM6 (poly[(2,6-(4,8-bis(5-(2-ethylhexyl-3-fluoro)thiophen-2-yl)-benzo[1,2-b:4,5-b']dithiophene))-alt-(5,5-(1',3'-di-2-thienyl-5',7'-bis(2-ethylhexyl)benzo[1',2'-c:4',5'-c']dithiophene-4,8-dione)]) : BTP-eC9 : PC71 BM ([6,6]-phenyl-C71-butyric acid methyl ester) using ITO/Br-2PACz anodes exhibited a maximum power conversion efficiency (PCE) of 18.4 %, outperforming devices with ITO/MeO-2PACz (14.5 %) and ITO/poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT : PSS) (17.5 %). The higher PCE was found to originate from the much higher WF of ITO/Br-2PACz (-5.81 eV) compared to ITO/MeO-2PACz (4.58 eV) and ITO/PEDOT : PSS (4.9 eV), resulting in lower interface resistance, improved hole transport/extraction, lower trap-assisted recombination, and longer carrier lifetimes. Importantly, the ITO/Br-2PACz electrode was chemically stable, and after removal of the SAM it could be recycled and reused to construct fresh OPVs with equally impressive performance.

Two-Step Dopamine-to-Polydopamine Modification of Polyethersulfone Ultrafiltration Membrane for Enhancing Anti-Fouling and Ultraviolet Resistant Properties.

Polydopamine has been widely used as an additive to enhance membrane fouling resistance. This study reports the effects of two-step dopamine-to-polydopamine modification on the permeation, antifouling, and potential anti-UV properties of polyethersulfone (PES)-based ultrafiltration membranes. The modification was performed through a two-step mechanism: adding the dopamine additive followed by immersion into Tris-HCl solution to allow polymerization of dopamine into polydopamine (PDA). The results reveal that the step of treatment, the concentration of dopamine in the first step, and the duration of dipping in the Tris solution in the second step affect the properties of the resulting membranes. Higher dopamine loadings improve the pure water flux (PWF) by more than threefold (15 vs. 50 L/m2·h). The extended dipping period in the Tris alkaline buffer leads to an overgrowth of the PDA layer that partly covers the surface pores which lowers the PWF. The presence of dopamine or polydopamine enhances the hydrophilicity due to the enrichment of hydrophilic catechol moieties which leads to better anti-fouling. Moreover, the polydopamine film also improves the membrane resistance to UV irradiation by minimizing photodegradation's occurrence.

17.1% Efficient Single-Junction Organic Solar Cells Enabled by n-Type Doping of the Bulk-Heterojunction.

Molecular doping is often used in organic semiconductors to tune their (opto)electronic properties. Despite its versatility, however, its application in organic photovoltaics (OPVs) remains limited and restricted to p-type dopants. In an effort to control the charge transport within the bulk-heterojunction (BHJ) of OPVs, the n-type dopant benzyl viologen (BV) is incorporated in a BHJ composed of the donor polymer PM6 and the small-molecule acceptor IT-4F. The power conversion efficiency (PCE) of the cells is found to increase from 13.2% to 14.4% upon addition of 0.004 wt% BV. Analysis of the photoactive materials and devices reveals that BV acts simultaneously as n-type dopant and microstructure modifier for the BHJ. Under optimal BV concentrations, these synergistic effects result in balanced hole and electron mobilities, higher absorption coefficients and increased charge-carrier density within the BHJ, while significantly extending the cells' shelf-lifetime. The n-type doping strategy is applied to five additional BHJ systems, for which similarly remarkable performance improvements are obtained. OPVs of particular interest are based on the ternary PM6:Y6:PC71BM:BV(0.004 wt%) blend for which a maximum PCE of 17.1%, is obtained. The effectiveness of the n-doping strategy highlights electron transport in NFA-based OPVs as being a key issue.

Solution-Processed Mixed-Dimensional Hybrid Perovskite/Carbon Nanotube Electronics.

Benefiting from their extraordinary physical properties, methylammonium lead halide perovskites (PVKs) have attracted significant attention in optoelectronics. However, the PVK-based devices suffer from low carrier mobility and high operation voltage. Here, we utilize sorted semiconducting single-walled carbon nanotubes (95% s-SWCNTs) to enhance the performance of thin-film transistors (TFTs) based on the mixed-cation perovskite (MA1-xFAx)Pb(I1-xBrx)3, enabling mixed-dimensional solution-processed electronics with high mobility (32.25 cm2/(V s)) and low voltage (∼3 V) operation. The resulting mixed-dimensional PVK/SWCNT TFTs possess ON/OFF ratios on the order of 107, enabling the fabrication of high-gain inverters.

Rapid Photonic Processing of High-Electron-Mobility PbS Colloidal Quantum Dot Transistors.

Recent advances in solution-processable semiconducting colloidal quantum dots (CQDs) have enabled their use in a range of (opto)electronic devices. In most of these studies, device fabrication relied almost exclusively on thermal annealing to remove organic residues and enhance inter-CQD electronic coupling. Despite its widespread use, however, thermal annealing is a lengthy process, while its effectiveness to eliminate organic residues remains limited. Here, we exploit the use of xenon flash lamp sintering to post-treat solution-deposited layers of lead sulfide (PbS) CQDs and their application in n-channel thin-film transistors (TFTs). The process is simple, fast, and highly scalable and allows for efficient removal of organic residues while preserving both quantum confinement and high channel current modulation. Bottom-gate, top-contact PbS CQD TFTs incorporating SiO2 as the gate dielectric exhibit a maximum electron mobility of 0.2 cm2 V-1 s-1, a value higher than that of control transistors (≈10-2 cm2 V-1 s-1) processed via thermal annealing for 30 min at 120 °C. Replacing SiO2 with a polymeric dielectric improves the transistor's channel interface, leading to a significant increase in electron mobility to 3.7 cm2 V-1 s-1. The present work highlights the potential of flash lamp annealing as a promising method for the rapid manufacture of PbS CQD-based (opto)electronic devices and circuits.

Long-range exciton diffusion in molecular non-fullerene acceptors.

The short exciton diffusion length associated with most classical organic semiconductors used in organic photovoltaics (5-20 nm) imposes severe limits on the maximum size of the donor and acceptor domains within the photoactive layer of the cell. Identifying materials that are able to transport excitons over longer distances can help advancing our understanding and lead to solar cells with higher efficiency. Here, we measure the exciton diffusion length in a wide range of nonfullerene acceptor molecules using two different experimental techniques based on photocurrent and ultrafast spectroscopy measurements. The acceptors exhibit balanced ambipolar charge transport and surprisingly long exciton diffusion lengths in the range of 20 to 47 nm. With the aid of quantum-chemical calculations, we are able to rationalize the exciton dynamics and draw basic chemical design rules, particularly on the importance of the end-group substituent on the crystal packing of nonfullerene acceptors.

Key Parameters Requirements for Non-Fullerene-Based Organic Solar Cells with Power Conversion Efficiency >20.

The reported power conversion efficiencies (PCEs) of nonfullerene acceptor (NFA) based organic photovoltaics (OPVs) now exceed 14% and 17% for single-junction and two-terminal tandem cells, respectively. However, increasing the PCE further requires an improved understanding of the factors limiting the device efficiency. Here, the efficiency limits of single-junction and two-terminal tandem NFA-based OPV cells are examined with the aid of a numerical device simulator that takes into account the optical properties of the active material(s), charge recombination effects, and the hole and electron mobilities in the active layer of the device. The simulations reveal that single-junction NFA OPVs can potentially reach PCE values in excess of 18% with mobility values readily achievable in existing material systems. Furthermore, it is found that balanced electron and hole mobilities of >10-3 cm2 V-1 s-1 in combination with low nongeminate recombination rate constants of 10-12 cm3 s-1 could lead to PCE values in excess of 20% and 25% for single-junction and two-terminal tandem OPV cells, respectively. This analysis provides the first tangible description of the practical performance targets and useful design rules for single-junction and tandem OPVs based on NFA materials, emphasizing the need for developing new material systems that combine these desired characteristics.

17% Efficient Organic Solar Cells Based on Liquid Exfoliated WS2 as a Replacement for PEDOT:PSS.

The application of liquid-exfoliated 2D transition metal disulfides (TMDs) as the hole transport layers (HTLs) in nonfullerene-based organic solar cells is reported. It is shown that solution processing of few-layer WS2 or MoS2 suspensions directly onto transparent indium tin oxide (ITO) electrodes changes their work function without the need for any further treatment. HTLs comprising WS2 are found to exhibit higher uniformity on ITO than those of MoS2 and consistently yield solar cells with superior power conversion efficiency (PCE), improved fill factor (FF), enhanced short-circuit current (JSC ), and lower series resistance than devices based on poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) and MoS2 . Cells based on the ternary bulk-heterojunction PBDB-T-2F:Y6:PC71 BM with WS2 as the HTL exhibit the highest PCE of 17%, with an FF of 78%, open-circuit voltage of 0.84 V, and a JSC of 26 mA cm-2 . Analysis of the cells' optical and carrier recombination characteristics indicates that the enhanced performance is most likely attributed to a combination of favorable photonic structure and reduced bimolecular recombination losses in WS2 -based cells. The achieved PCE is the highest reported to date for organic solar cells comprised of 2D charge transport interlayers and highlights the potential of TMDs as inexpensive HTLs for high-efficiency organic photovoltaics.

High-Efficiency Fullerene Solar Cells Enabled by a Spontaneously Formed Mesostructured CuSCN-Nanowire Heterointerface.

Fullerenes and their derivatives are widely used as electron acceptors in bulk-heterojunction organic solar cells as they combine high electron mobility with good solubility and miscibility with relevant semiconducting polymers. However, studies on the use of fullerenes as the sole photogeneration and charge-carrier material are scarce. Here, a new type of solution-processed small-molecule solar cell based on the two most commonly used methanofullerenes, namely [6,6]-phenyl-C61-butyric acid methyl ester (PC60BM) and [6,6]-phenyl-C71-butyric acid methyl ester (PC70BM), as the light absorbing materials, is reported. First, it is shown that both fullerene derivatives exhibit excellent ambipolar charge transport with balanced hole and electron mobilities. When the two derivatives are spin-coated over the wide bandgap p-type semiconductor copper (I) thiocyanate (CuSCN), cells with power conversion efficiency (PCE) of ≈1%, are obtained. Blending the CuSCN with PC70BM is shown to increase the performance further yielding cells with an open-circuit voltage of ≈0.93 V and a PCE of 5.4%. Microstructural analysis reveals that the key to this success is the spontaneous formation of a unique mesostructured p-n-like heterointerface between CuSCN and PC70BM. The findings pave the way to an exciting new class of single photoactive material based solar cells.

Hybrid tandem quantum dot/organic photovoltaic cells with complementary near infrared absorption.

Monolithically integrated hybrid tandem solar cells that effectively combine solution-processed colloidal quantum dot (CQD) and organic bulk heterojunction subcells to achieve tandem performance that surpasses the individual subcell efficiencies have not been demonstrated to date. In this work, we demonstrate hybrid tandem cells with a low bandgap PbS CQD subcell harvesting the visible and near-infrared photons and a polymer:fullerene-poly (diketopyrrolopyrrole-terthiophene) (PDPP3T):[6,6]-phenyl-C60-butyric acid methyl ester (PC61BM)-top cell absorbing effectively the red and near-infrared photons of the solar spectrum in a complementary fashion. The two subcells are connected in series via an interconnecting layer (ICL) composed of a metal oxide layer, a conjugated polyelectrolyte, and an ultrathin layer of Au. The ultrathin layer of Au forms nano-islands in the ICL, reducing the series resistance, increasing the shunt resistance, and enhancing the device fill-factor. The hybrid tandems reach a power conversion efficiency (PCE) of 7.9%, significantly higher than the PCE of the corresponding individual single cells, representing one of the highest efficiencies reported to date for hybrid tandem solar cells based on CQD and polymer subcells.

Improved Spectral Coverage and Fluorescence Quenching in Donor-acceptor Systems Involving Indolo[3-2-b]carbazole and Boron-dipyrromethene or Diketopyrrolopyrrole.

A novel π-conjugated triad and a polymer incorporating indolo[3,2-b]-carbazole (ICZ) and 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (BODIPY) were synthesized via a Sonogashira coupling. Compared to the parent BODIPY the absorption and fluorescence spectrum were for both compounds broader and redshifted. The redshift of the fluorescence and the decrease of the fluorescence quantum yield and decay time upon increasing solvent polarity were attributed to the formation of a partial charge-transfer state. Upon excitation in the ICZ absorption band the ICZ fluorescence was quenched in both compounds mainly due to energy transfer to the BODIPY moiety. In a similar ICZ-π-DPP polymer (where DPP is diketopyrrolopyrrole), a smaller redshift of the absorption and fluorescence spectra compared to the parent DPP was observed. A less efficient quenching of the ICZ fluorescence in the ICZ-π-DPP polymer could be related to the unfavorable orientation of the transition dipoles of ICZ and DPP. The rate constant for energy transfer was for all compounds an order of magnitude smaller than predicted by Förster theory. While in a solid film of the triad a further redshift of the absorption maximum of nearly 100 nm was observed, no such shift was observed for the ICZ-π-BODIPY polymer.