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.

Over 19% Efficient Inverted Organic Photovoltaics Featuring a Molecularly Doped Metal Oxide Electron-Transporting Layer.

Molecular doping is commonly utilized to tune the charge transport properties of organic semiconductors. However, applying this technique to electrically dope inorganic materials like metal oxide semiconductors is challenging due to the limited availability of molecules with suitable energy levels and processing characteristics. Herein, n-type doping of zinc oxide (ZnO) films is demonstrated using 1,3-dimethylimidazolium-2-carboxylate (CO2-DMI), a thermally activated organic n-type dopant. Adding CO2-DMI into the ZnO precursor solution and processing it atop a predeposited indium oxide (InOx) layer yield InOx/n-ZnO heterojunctions with increased electron field-effect mobility of 32.6 cm2 V-1 s-1 compared to 18.5 cm2 V-1 s-1 for the pristine InOx/ZnO bilayer. The improved electron transport originates from the ZnO's enhanced crystallinity, reduced hydroxyl concentrations, and fewer oxygen vacancy groups upon doping. Applying the optimally doped InOx/n-ZnO heterojunctions as the electron-transporting layers (ETLs) in organic photovoltaics (OPVs) yields cells with improved power conversion efficiency of 19.06%, up from 18.3% for devices with pristine ZnO, and 18.2% for devices featuring the undoped InOx/ZnO ETL. It is shown that the all-around improved OPV performance originates from synergistic effects associated with CO2-DMI doping of the thermally grown ZnO, highlighting its potential as an electronic dopant for ZnO and potentially other metal oxides.

Enhancing the Electrical Conductivity and Long-Term Stability of PEDOT:PSS Electrodes through Sequential Treatment with Nitric Acid and Cesium Chloride.

Solution-processable poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) is an important polymeric conductor used extensively in organic flexible, wearable, and stretchable optoelectronics. However, further enhancing its conductivity and long-term stability while maintaining its superb mechanical properties remains challenging. Here, a novel post-treatment approach to enhance the electrical properties and stability of sub-20-nm-thin PEDOT:PSS films processed from solution is introduced. The approach involves a sequential post-treatment with HNO3 and CsCl, resulting in a remarkable enhancement of the electrical conductivity of PEDOT:PSS films to over 5500 S cm-1, along with improved carrier mobility. The post-treated films exhibit remarkable air stability, retaining over 85% of their initial conductivity even after 270 days of storage. Various characterization techniques, including X-ray photoelectron spectroscopy, atomic force microscopy, Raman spectroscopy, Hall effect measurements, and grazing incidence wide angle X-ray scattering, coupled with density functional theory calculations, provide insights into the structural changes and interactions responsible for these improvements. To demonstrate the potential for practical applications, the ultrathin PEDOT:PSS films are connected to an inorganic light-emitting diode with a battery, showcasing their suitability as transparent electrodes. This work presents a promising approach for enhancing the electrical conductivity of PEDOT:PSS while offering a comprehensive understanding of the underlying mechanisms that can guide further advances.

Recent Progress in Colloidal Quantum Dot Thermoelectrics.

Semiconducting colloidal quantum dots (CQDs) represent an emerging class of thermoelectric materials for use in a wide range of future applications. CQDs combine solution processability at low temperatures with the potential for upscalable manufacturing via printing techniques. Moreover, due to their low dimensionality, CQDs exhibit quantum confinement and a high density of grain boundaries, which can be independently exploited to tune the Seebeck coefficient and thermal conductivity, respectively. This unique combination of attractive attributes makes CQDs very promising for application in emerging thermoelectric generator (TEG) technologies operating near room temperature. Herein, recent progress in CQDs for application in emerging thin-film thermoelectrics is reviewed. First, the fundamental concepts of thermoelectricity in nanostructured materials are outlined, followed by an overview of the popular synthetic methods used to produce CQDs with controllable sizes and shapes. Recent strides in CQD-based thermoelectrics are then discussed with emphasis on their application in thin-film TEGs. Finally, the current challenges and future perspectives for further enhancing the performance of CQD-based thermoelectric materials for future applications are discussed.

Dopant-Assisted Matrix Stabilization Enables Thermoelectric Performance Enhancement in n-Type Quantum Dot Films.

Efficient thermoelectric generators require further progress in developing n-type semiconductors that combine low thermal conductivity with high electrical conductivity. By embedding colloidal quantum dots (CQDs) in a metal halide matrix (QDMH), the metal halide matrix can enhance phonon scattering, thus suppressing thermal transport; however, simultaneously achieving high electrical conductivity in such systems has previously been limited by the deleterious impact of a large density of interfaces on charge transport. Therefore, new strategies are needed to improve charge carrier transport without sacrificing matrix-enabled low thermal transport. Here, we report the use of chemical doping in the solution state to improve electron transport while maintaining low thermal transport in QDMH films. By incorporating cesium carbonate (Cs2CO3) salts as a dopant prior to matrix formation, we find that the dopant stabilizes the matrix in colloidal inks and enables efficient n-type doping in QDMH films. As a result, this strategy leads to an enhanced n-type thermoelectric behavior in solution-processed QDMH films near room temperature, with a thermal conductivity of 0.25 W m-1 K-1-significantly lower than in prior films based on organic-ligand-cross-linked CQD films (>0.6 W m-1 K-1) and spark-plasma-sintered CQD systems (>1 W m-1 K-1). This study provides a pathway to developing efficient n-type thermoelectric materials with low thermal conductivity using single-step deposition and low-temperature processing.

Amphipathic Side Chain of a Conjugated Polymer Optimizes Dopant Location toward Efficient N-Type Organic Thermoelectrics.

There is no molecular strategy for selectively increasing the Seebeck coefficient without reducing the electrical conductivity for organic thermoelectrics. Here, it is reported that the use of amphipathic side chains in an n-type donor-acceptor copolymer can selectively increase the Seebeck coefficient and thus increase the power factor by a factor of ≈5. The amphipathic side chain contains an alkyl chain segment as a spacer between the polymer backbone and an ethylene glycol type chain segment. The use of this alkyl spacer does not only reduce the energetic disorder in the conjugated polymer film but can also properly control the dopant sites away from the backbone, which minimizes the adverse influence of counterions. As confirmed by kinetic Monte Carlo simulations with the host-dopant distance as the only variable, a reduced Coulombic interaction resulting from a larger host-dopant distance contributes to a higher Seebeck coefficient for a given electrical conductivity. Finally, an optimized power factor of 18 µW m-1 K-2 is achieved in the doped polymer film. This work provides a facile molecular strategy for selectively improving the Seebeck coefficient and opens up a new route for optimizing the dopant location toward realizing better n-type polymeric thermoelectrics.

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.

Enabling Ambipolar to Heavy n-Type Transport in PbS Quantum Dot Solids through Doping with Organic Molecules.

PbS quantum dots (QDs) are remarkable semiconducting materials, which are compatible with low-cost solution-processed electronic device fabrication. Understanding the doping of these materials is one of the great research interests, as it is a necessary step to improve the device performance as well as to enhance the applicability of this system for diverse optoelectronic applications. Here, we report the efficient doping of the PbS QD films with the use of solution-processable organic molecules. By engineering the energy levels of the donor molecules and the PbS QDs through the use of different cross-linking ligands, we are able to control the characteristics of PbS field-effect transistors (FETs) from ambipolar to strongly n-type. Because the doping promotes trap filling, the charge carrier mobility is improved up to 0.64 cm2 V-1 s-1, which is the highest mobility reported for low-temperature processed PbS FETs employing SiO2 as the gate dielectric. The doping also reduces the contact resistance of the devices, which can also explain the origin of the increased mobility.

High mobility and low density of trap states in dual-solid-gated PbS nanocrystal field-effect transistors.

Dual-gated PbS nanocrystal field-effect transistors employing SiO2 and Cytop as gate dielectrics are fabricated. The obtained electron mobility (0.2 cm(2) V(-1) s(-1) ) and the high on/off ratio (10(5) -10(6) ), show that the controlled nanocrystal assembly (obtained with self-assembled monolayers), as well as the trap density reduction (using Cytop as dielectric), are crucial steps for the future application of nanocrystals.