Understanding Antiferromagnetic Coupling in Lead-Free Halide Double Perovskite Semiconductors.

Solution-processable semiconductors with antiferromagnetic (AFM) order are attractive for future spintronics and information storage technology. Halide perovskites containing magnetic ions have emerged as multifunctional materials, demonstrating a cross-link between structural, optical, electrical, and magnetic properties. However, stable optoelectronic halide perovskites that are antiferromagnetic remain sparse, and the critical design rules to optimize magnetic coupling still must be developed. Here, we combine the complementary magnetometry and electron-spin-resonance experiments, together with first-principles calculations to study the antiferromagnetic coupling in stable Cs2(Ag:Na)FeCl6 bulk semiconductor alloys grown by the hydrothermal method. We show the importance of nonmagnetic monovalence ions at the BI site (Na/Ag) in facilitating the superexchange interaction via orbital hybridization, offering the tunability of the Curie-Weiss parameters between -27 and -210 K, with a potential to promote magnetic frustration via alloying the nonmagnetic BI site (Ag:Na ratio). Combining our experimental evidence with first-principles calculations, we draw a cohesive picture of the material design for B-site-ordered antiferromagnetic halide double perovskites.

Ground-state electron transfer in all-polymer donor:acceptor blends enables aqueous processing of water-insoluble conjugated polymers.

Water-based conductive inks are vital for the sustainable manufacturing and widespread adoption of organic electronic devices. Traditional methods to produce waterborne conductive polymers involve modifying their backbone with hydrophilic side chains or using surfactants to form and stabilize aqueous nanoparticle dispersions. However, these chemical approaches are not always feasible and can lead to poor material/device performance. Here, we demonstrate that ground-state electron transfer (GSET) between donor and acceptor polymers allows the processing of water-insoluble polymers from water. This approach enables macromolecular charge-transfer salts with 10,000× higher electrical conductivities than pristine polymers, low work function, and excellent thermal/solvent stability. These waterborne conductive films have technological implications for realizing high-performance organic solar cells, with efficiency and stability superior to conventional metal oxide electron transport layers, and organic electrochemical neurons with biorealistic firing frequency. Our findings demonstrate that GSET offers a promising avenue to develop water-based conductive inks for various applications in organic electronics.

Ion-modulated radical doping of spiro-OMeTAD for more efficient and stable perovskite solar cells.

Record power conversion efficiencies (PCEs) of perovskite solar cells (PSCs) have been obtained with the organic hole transporter 2,2',7,7'-tetrakis(N,N-di-p-methoxyphenyl-amine)9,9'-spirobifluorene (spiro-OMeTAD). Conventional doping of spiro-OMeTAD with hygroscopic lithium salts and volatile 4-tert-butylpyridine is a time-consuming process and also leads to poor device stability. We developed a new doping strategy for spiro-OMeTAD that avoids post-oxidation by using stable organic radicals as the dopant and ionic salts as the doping modulator (referred to as ion-modulated radical doping). We achieved PCEs of >25% and much-improved device stability under harsh conditions. The radicals provide hole polarons that instantly increase the conductivity and work function (WF), and ionic salts further modulate the WF by affecting the energetics of the hole polarons. This organic semiconductor doping strategy, which decouples conductivity and WF tunability, could inspire further optimization in other optoelectronic devices.

Lactone Backbone Density in Rigid Electron-Deficient Semiconducting Polymers Enabling High n-type Organic Thermoelectric Performance.

Three lactone-based rigid semiconducting polymers were designed to overcome major limitations in the development of n-type organic thermoelectrics, namely electrical conductivity and air stability. Experimental and theoretical investigations demonstrated that increasing the lactone group density by increasing the benzene content from 0 % benzene (P-0), to 50 % (P-50), and 75 % (P-75) resulted in progressively larger electron affinities (up to 4.37 eV), suggesting a more favorable doping process, when employing (N-DMBI) as the dopant. Larger polaron delocalization was also evident, due to the more planarized conformation, which is proposed to lead to a lower hopping energy barrier. As a consequence, the electrical conductivity increased by three orders of magnitude, to achieve values of up to 12 S cm and Power factors of 13.2 µWm-1  K-2 were thereby enabled. These findings present new insights into material design guidelines for the future development of air stable n-type organic thermoelectrics.

Spontaneous exciton dissociation enables spin state interconversion in delayed fluorescence organic semiconductors.

Engineering a low singlet-triplet energy gap (ΔEST) is necessary for efficient reverse intersystem crossing (rISC) in delayed fluorescence (DF) organic semiconductors but results in a small radiative rate that limits performance in LEDs. Here, we study a model DF material, BF2, that exhibits a strong optical absorption (absorption coefficient = 3.8 × 105 cm-1) and a relatively large ΔEST of 0.2 eV. In isolated BF2 molecules, intramolecular rISC is slow (delayed lifetime = 260 µs), but in aggregated films, BF2 generates intermolecular charge transfer (inter-CT) states on picosecond timescales. In contrast to the microsecond intramolecular rISC that is promoted by spin-orbit interactions in most isolated DF molecules, photoluminescence-detected magnetic resonance shows that these inter-CT states undergo rISC mediated by hyperfine interactions on a ~24 ns timescale and have an average electron-hole separation of ≥1.5 nm. Transfer back to the emissive singlet exciton then enables efficient DF and LED operation. Thus, access to these inter-CT states, which is possible even at low BF2 doping concentrations of 4 wt%, resolves the conflicting requirements of fast radiative emission and low ΔEST in organic DF emitters.

A high-conductivity n-type polymeric ink for printed electronics.

Conducting polymers, such as the p-doped poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS), have enabled the development of an array of opto- and bio-electronics devices. However, to make these technologies truly pervasive, stable and easily processable, n-doped conducting polymers are also needed. Despite major efforts, no n-type equivalents to the benchmark PEDOT:PSS exist to date. Here, we report on the development of poly(benzimidazobenzophenanthroline):poly(ethyleneimine) (BBL:PEI) as an ethanol-based n-type conductive ink. BBL:PEI thin films yield an n-type electrical conductivity reaching 8 S cm-1, along with excellent thermal, ambient, and solvent stability. This printable n-type mixed ion-electron conductor has several technological implications for realizing high-performance organic electronic devices, as demonstrated for organic thermoelectric generators with record high power output and n-type organic electrochemical transistors with a unique depletion mode of operation. BBL:PEI inks hold promise for the development of next-generation bioelectronics and wearable devices, in particular targeting novel functionality, efficiency, and power performance.

Sequential Doping of Ladder-Type Conjugated Polymers for Thermally Stable n-Type Organic Conductors.

Doping of organic semiconductors is a powerful tool to optimize the performance of various organic (opto)electronic and bioelectronic devices. Despite recent advances, the low thermal stability of the electronic properties of doped polymers still represents a significant obstacle to implementing these materials into practical applications. Hence, the development of conducting doped polymers with excellent long-term stability at elevated temperatures is highly desirable. Here, we report on the sequential doping of the ladder-type polymer poly(benzimidazobenzophenanthroline) (BBL) with a benzimidazole-based dopant (i.e., N-DMBI). By combining electrical, UV-vis/infrared, X-ray diffraction, and electron paramagnetic resonance measurements, we quantitatively characterized the conductivity, Seebeck coefficient, spin density, and microstructure of the sequentially doped polymer films as a function of the thermal annealing temperature. Importantly, we observed that the electrical conductivity of N-DMBI-doped BBL remains unchanged even after 20 h of heating at 190 °C. This finding is remarkable and of particular interest for organic thermoelectrics.

Magnetizing lead-free halide double perovskites.

Spintronics holds great potential for next-generation high-speed and low-power consumption information technology. Recently, lead halide perovskites (LHPs), which have gained great success in optoelectronics, also show interesting magnetic properties. However, the spin-related properties in LHPs originate from the spin-orbit coupling of Pb, limiting further development of these materials in spintronics. Here, we demonstrate a new generation of halide perovskites, by alloying magnetic elements into optoelectronic double perovskites, which provide rich chemical and structural diversities to host different magnetic elements. In our iron-alloyed double perovskite, Cs2Ag(Bi:Fe)Br6, Fe3+ replaces Bi3+ and forms FeBr6 clusters that homogenously distribute throughout the double perovskite crystals. We observe a strong temperature-dependent magnetic response at temperatures below 30 K, which is tentatively attributed to a weak ferromagnetic or antiferromagnetic response from localized regions. We anticipate that this work will stimulate future efforts in exploring this simple yet efficient approach to develop new spintronic materials based on lead-free double perovskites.

Ground-state electron transfer in all-polymer donor-acceptor heterojunctions.

Doping of organic semiconductors is crucial for the operation of organic (opto)electronic and electrochemical devices. Typically, this is achieved by adding heterogeneous dopant molecules to the polymer bulk, often resulting in poor stability and performance due to dopant sublimation or aggregation. In small-molecule donor-acceptor systems, charge transfer can yield high and stable electrical conductivities, an approach not yet explored in all-conjugated polymer systems. Here, we report ground-state electron transfer in all-polymer donor-acceptor heterojunctions. Combining low-ionization-energy polymers with high-electron-affinity counterparts yields conducting interfaces with resistivity values five to six orders of magnitude lower than the separate single-layer polymers. The large decrease in resistivity originates from two parallel quasi-two-dimensional electron and hole distributions reaching a concentration of ∼1013 cm-2. Furthermore, we transfer the concept to three-dimensional bulk heterojunctions, displaying exceptional thermal stability due to the absence of molecular dopants. Our findings hold promise for electro-active composites of potential use in, for example, thermoelectrics and wearable electronics.

Nonequilibrium site distribution governs charge-transfer electroluminescence at disordered organic heterointerfaces.

The interface between electron-donating (D) and electron-accepting (A) materials in organic photovoltaic (OPV) devices is commonly probed by charge-transfer (CT) electroluminescence (EL) measurements to estimate the CT energy, which critically relates to device open-circuit voltage. It is generally assumed that during CT-EL injected charges recombine at close-to-equilibrium energies in their respective density of states (DOS). Here, we explicitly quantify that CT-EL instead originates from higher-energy DOS site distributions significantly above DOS equilibrium energies. To demonstrate this, we have developed a quantitative and experimentally calibrated model for CT-EL at organic D/A heterointerfaces, which simultaneously accounts for the charge transport physics in an energetically disordered DOS and the Franck-Condon broadening. The 0-0 CT-EL transition lineshape is numerically calculated using measured energetic disorder values as input to 3-dimensional kinetic Monte Carlo simulations. We account for vibrational CT-EL overtones by selectively measuring the dominant vibrational phonon-mode energy governing CT luminescence at the D/A interface using fluorescence line-narrowing spectroscopy. Our model numerically reproduces the measured CT-EL spectra and their bias dependence and reveals the higher-lying manifold of DOS sites responsible for CT-EL. Lowest-energy CT states are situated ∼180 to 570 meV below the 0-0 CT-EL transition, enabling photogenerated carrier thermalization to these low-lying DOS sites when the OPV device is operated as a solar cell rather than as a light-emitting diode. Nonequilibrium site distribution rationalizes the experimentally observed weak current-density dependence of CT-EL and poses fundamental questions on reciprocity relations relating light emission to photovoltaic action and regarding minimal attainable photovoltaic energy conversion losses in OPV devices.

Impact of Singly Occupied Molecular Orbital Energy on the n-Doping Efficiency of Benzimidazole Derivatives.

We investigated the impact of singly occupied molecular orbital (SOMO) energy on the n-doping efficiency of benzimidazole derivatives. By designing and synthesizing a series of new air-stable benzimidazole-based dopants with different SOMO energy levels, we demonstrated that an increase of the dopant SOMO energy by only ∼0.3 eV enhances the electrical conductivity of a benchmark electron-transporting naphthalenediimide-bithiophene polymer by more than 1 order of magnitude. By combining electrical, X-ray diffraction, and electron paramagnetic resonance measurements with density functional theory calculations and analytical transport simulations, we quantitatively characterized the conductivity, Seebeck coefficient, spin density, and crystallinity of the doped polymer as a function of the dopant SOMO energy. Our findings strongly indicate that charge and energy transport are dominated by the (relative) position of the SOMO level, whereas morphological differences appear to play a lesser role. These results set molecular-design guidelines for next-generation n-type dopants.

Fine Structure and Spin Dynamics of Linearly Polarized Indirect Excitons in Two-Dimensional CdSe/CdTe Colloidal Heterostructures.

Heterostructured two-dimensional colloidal nanoplatelets are a class of material that has attracted great interest for optoelectronic applications due to their high photoluminescence yield, atomically tunable thickness, and ultralow lasing thresholds. Of particular interest are laterally heterostructured core-crown nanoplatelets with a type-II band alignment, where the in-plane spatial separation of carriers leads to indirect (or charge transfer) excitons with long lifetimes and bright, highly Stokes shifted emission. Despite this, little is known about the nature of the lowest energy exciton states responsible for emission in these materials. Here, using polarization-controlled, steady-state, and time-resolved photoluminescence measurements, at temperatures down to 1.6 K and magnetic fields up to 30 T, we study the exciton fine structure and spin dynamics of archetypal type-II CdSe/CdTe core-crown nanoplatelets. Complemented by theoretical modeling and zero-field quantum beat measurements, we find the bright-exciton fine structure consists of two linearly polarized states with a fine structure splitting ∼50 µeV and an indirect exciton Landé g-factor of 0.7. In addition, we show the exciton spin lifetime to be in the microsecond range with an unusual B-3 magnetic field dependence. The discovery of linearly polarized exciton states and emission highlights the potential for use of such materials in display and imaging applications without polarization filters. Furthermore, the small exciton fine structure splitting and a long spin lifetime are fundamental advantages when envisaging CdSe/CdTe nanoplatelets as elementary bricks for the next generation of quantum devices, particularly given their ease of fabrication.

Effect of Backbone Regiochemistry on Conductivity, Charge Density, and Polaron Structure of n-Doped Donor-Acceptor Polymers.

We investigated the influence of backbone regiochemistry on the conductivity, charge density, and polaron structure in the widely studied n-doped donor-acceptor polymer poly[N,N'-bis(2-octyldodecyl)-1,4,5,8-naphthalenediimide-2,6-diyl]-alt-5,5'-(2,2'-bithiophene) [P(NDI2OD-T2)]. In contrast to classic semicrystalline polymers such as poly(3-hexylthiophene) (P3HT), the regioirregular (RI) structure of the naphthalenediimide (NDI)-bithiophene (T2) backbone does not alter the intramolecular steric demand of the chain versus the regioregular (RR) polymer, yielding RI-P(NDI2OD-T2) with similar energetics and optical features as its RR counterpart. By combining the electrical, UV-vis/infrared, X-ray diffraction, and electron paramagnetic resonance data and density functional theory calculations, we quantitatively characterized the conductivity, aggregation, crystallinity, and charge density, and simulated the polaron structures, molecular vibrations, and spin density distribution of RR-/RI-P(NDI2OD-T2). Importantly, we observed that RI-P(NDI2OD-T2) can be doped to a greater extent compared to its RR counterpart. This finding is remarkable and contrasts benchmark P3HT, allowing us to uniquely study the role of regiochemistry on the charge-transport properties of n-doped donor-acceptor polymers.

Effect of Side Groups on the Photovoltaic Performance Based on Porphyrin-Perylene Bisimide Electron Acceptors.

In this work, we developed four porphyrin-based small molecular electron acceptors for non-fullerene organic solar cells, in which different side groups attached to the porphyrin core were selected in order to achieve optimized performance. The molecules contain porphyrin as the core, perylene bisimides as end groups, and the ethynyl unit as the linker. Four side groups, from 2,6-di(dodecyloxy)phenyl to (2-ethylhexyl)thiophen-2-yl, pentadecan-7-yl, and 3,5-di(dodecyloxy)phenyl unit, were applied into the electron acceptors. The new molecules exhibit broad absorption spectra from 300 to 900 nm and high molar extinction coefficients. The molecules as electron acceptors were applied into organic solar cells, showing increased power conversion efficiencies from 1.84 to 5.34%. We employed several techniques, including photoluminescence spectra, electroluminescence spectra, atomic force microscopy, and grazing-incidence wide-angle X-ray to probe the blends to find the effects of the side groups on the photovoltaic properties. We found that the electron acceptors with 2,6-di(dodecyloxy)phenyl units show high-lying frontier energy levels, good crystalline properties, and low nonradiative recombination loss, resulting in possible large phase separation and low energy loss, which is responsible for the low performance. Our results provide a detailed study about the side groups of non-fullerene materials, demonstrating that porphyrin can be used to design electron acceptors toward near-infrared absorption.

Vibrationally Assisted Intersystem Crossing in Benchmark Thermally Activated Delayed Fluorescence Molecules.

Electrically injected charge carriers in organic light-emitting devices (OLEDs) undergo recombination events to form singlet and triplet states in a 1:3 ratio, representing a fundamental hurdle for achieving high quantum efficiency. Dopants based on thermally activated delayed fluorescence (TADF) have emerged as promising candidates for addressing the spin statistics issue in OLEDs. In these materials, reverse singlet-triplet intersystem crossing (rISC) becomes efficient, thereby activating luminescence pathways for weakly emissive triplet states. However, despite a growing consensus that torsional vibrations facilitate spin-orbit-coupling- (SOC-) driven ISC in these molecules, there is a shortage of experimental evidence. We use transient electron spin resonance and theory to show unambiguously that SOC interactions drive spin conversion and that ISC is a dynamic process gated by conformational fluctuations for benchmark carbazolyl-dicyanobenzene TADF emitters.

A Chemically Doped Naphthalenediimide-Bithiazole Polymer for n-Type Organic Thermoelectrics.

The synthesis of a novel naphthalenediimide (NDI)-bithiazole (Tz2)-based polymer [P(NDI2OD-Tz2)] is reported, and structural, thin-film morphological, as well as charge transport and thermoelectric properties are compared to the parent and widely investigated NDI-bithiophene (T2) polymer [P(NDI2OD-T2)]. Since the steric repulsions in Tz2 are far lower than in T2, P(NDI2OD-Tz2) exhibits a more planar and rigid backbone, enhancing π-π chain stacking and intermolecular interactions. In addition, the electron-deficient nature of Tz2 enhances the polymer electron affinity, thus reducing the polymer donor-acceptor character. When n-doped with amines, P(NDI2OD-Tz2) achieves electrical conductivity (≈0.1 S cm-1 ) and a power factor (1.5 µW m-1 K-2 ) far greater than those of P(NDI2OD-T2) (0.003 S cm-1 and 0.012 µW m-1 K-2 , respectively). These results demonstrate that planarized NDI-based polymers with reduced donor-acceptor character can achieve substantial electrical conductivity and thermoelectric response.

High Open-Circuit Voltages in Tin-Rich Low-Bandgap Perovskite-Based Planar Heterojunction Photovoltaics.

Low-bandgap CH3 NH3 (Pbx Sn1-x )I3 (0 ≤ x ≤ 1) hybrid perovskites (e.g., ≈1.5-1.1 eV) demonstrating high surface coverage and superior optoelectronic properties are fabricated. State-of-the-art photovoltaic (PV) performance is reported with power conversion efficiencies approaching 10% in planar heterojunction architecture with small (<450 meV) energy loss compared to the bandgap and high (>100 cm2 V-1 s-1 ) intrinsic carrier mobilities.

Exciton Fine-Structure Splitting in Self-Assembled Lateral InAs/GaAs Quantum-Dot Molecular Structures.

Fine-structure splitting (FSS) of excitons in semiconductor nanostructures is a key parameter that has significant implications in photon entanglement and polarization conversion between electron spins and photons, relevant to quantum information technology and spintronics. Here, we investigate exciton FSS in self-organized lateral InAs/GaAs quantum-dot molecular structures (QMSs) including laterally aligned double quantum dots (DQDs), quantum-dot clusters (QCs), and quantum rings (QRs), by employing polarization-resolved microphotoluminescence (µPL) spectroscopy. We find a clear trend in FSS between the studied QMSs depending on their geometric arrangements, from a large FSS in the DQDs to a smaller FSS in the QCs and QRs. This trend is accompanied by a corresponding difference in the optical polarization directions of the excitons between these QMSs, namely, the bright-exciton lines are linearly polarized preferably along or perpendicular to the [11̅0] crystallographic axis in the DQDs that also defines the alignment direction of the two constituting QDs, whereas in the QCs and QRs, the polarization directions are randomly oriented. We attribute the observed trend in the FSS to a significant reduction of the asymmetry in the lateral confinement potential of the excitons in the QRs and QCs as compared with the DQDs, as a result of a compensation between the effects of lateral shape anisotropy and piezoelectric field. Our work demonstrates that FSS strongly depends on the geometric arrangements of the QMSs, which effectively tune the degree of the compensation effects and are capable of reducing FSS even in a strained QD system to a limit similar to strain-free QDs. This approach provides a pathway in obtaining high-symmetry quantum emitters desirable for realizing photon entanglement and spintronic devices based on such nanostructures, utilizing an uninterrupted epitaxial growth procedure without special requirements for lattice-matched materials combinations, specific substrate orientations, and nanolithography.

Room-temperature electron spin amplifier based on Ga(In)NAs alloys.

The first experimental demonstration of a spin amplifier at room temperature is presented. An efficient, defect-enabled spin amplifier based on a non-magnetic semiconductor, Ga(In)NAs, is proposed and demonstrated, with a large spin gain (up to 2700% at zero field) for conduction electrons and a high cut-off frequency of up to 1 GHz.