Energy Splitting Research Articles

High-performance fully solution-processed OLEDs based on carbazole-benzonitrile TADF emitter with long alkyl chains

The introduction of alkyl chains into the luminescent molecules will increase solubility and film-forming performance for fabricating solution-processed organic semiconductor devices. In this work, 5CzBN-9CSP and 5CzBN-12CSP with long alkyl chains were synthesized based on the typical thermally activated delayed fluorescence (TADF) molecule 5CzBN as core, and bipolar 9,9′-spirobi[fluorene] (SP) groups as peripheral dendrons. Not only the excellent solution processability is invested, but also the uniform photophysical property is sustained, including small singlet-triplet splitting energy (ΔEST) and high reverse intersystem crossing (RISC) rate. However, excessive length of alkyl chains degrading thermodynamic stability and carrier transport and balance, results in a maximum external quantum efficiency (EQEmax) of 17.6% for 5CzBN-12CSP-based fully solution-processed non-doped device, which is lower than that for 5CzBN-9CSP counterpart. Furthermore, TADF sensitized (TSF) solution-processed device obtains a high EQEmax of 25.9% within 5CzBN-12CSP host and multiple-resonance (MR) final emitter thanks to an efficient energy transfer.

Phonon‐Bottleneck Enhanced Exciton Emission in 2D Perovskites

AbstractLayered halide perovskites exhibit remarkable optoelectronic properties and technological promise, driven by strongly bound excitons. The interplay of spin‐orbit and exchange coupling creates a rich excitonic landscape, determining their optical signatures and exciton dynamics. Despite the dark excitonic ground state, surprisingly efficient emission from higher‐energy bright states has puzzled the scientific community, sparking debates on relaxation mechanisms. Combining low‐temperature magneto‐optical measurements with sophisticated many‐particle theory, the origin of the bright exciton emission in perovskites is elucidated by tracking the thermalization of dark and bright excitons under a magnetic field. The unexpectedly high emission is clearly attributed to a pronounced phonon‐bottleneck effect, considerably slowing down the relaxation toward the energetically lowest dark states. It is demonstrated that this bottleneck can be tuned by manipulating the bright‐dark energy splitting and optical phonon energies, offering valuable insights and strategies for controlling exciton emission in layered perovskite materials that is crucial for optoelectronics applications.

Derivatives of Phenyl Pyrimidine and of the Different Donor Moieties as Emitters for OLEDs.

Two derivatives of phenyl pyrimidine as acceptor unit and triphenylamino or 4,4'-dimethoxytriphenylamino donor groups were designed and synthesized as emitters for organic light-emitting diodes (OLEDs) aiming to utilize triplet excitons in the electroluminescence. Thermogravimetric analysis revealed high thermal stability of the compounds with 5% weight loss temperatures of 397 and 438 °C. The theoretical estimations and photophysical data show the contributions of local excited and charge transfer states into emission. The addition of the methoxy groups led to the significant improvement of hole-transporting properties and the bathochromic shift of the emission from blue to green-blue spectral diapason. It is shown that mixing of the compounds with the organic host results in facilitation of the delayed emission. The singlet-triplet energy splitting was found to be too big for the thermally activated delayed fluorescence. No thermal activation of the long-lived emission was detected. No experimental evidence for triplet-triplet annihilation and room temperature phosphorescence were detected making the hot exciton mechanism the most probable one. The OLEDs based on the compounds reached the maximum external quantum efficiency of up to 10.6%.

Thermally Activated Delayed Fluorescent Binuclear Copper(I) Alkynyl Complexes with Cuprophilic Interactions.

Copper(I)-based thermally activated delayed fluorescence (TADF) emitters have been conceived to be promising candidates for display and lighting applications because of their multifarious structures and strong photoluminescence. Herein a string of binuclear Cu(I) complexes bearing pronounced cuprophilic interactions have been designed and synthesized. [Cu2(dppb)2(μ2-η1-C≡C-Ph)2] (1 a) and [Cu2(dppb)2(μ2-η1-C≡C-PPXZ)2] (1 b) display photoluminescence quantum yields of up to 67 % in doped films and solid states via TADF and exhibit reversible bicolor luminescence switching upon mechanical stimuli. Computational studies manifest that the metal-to-ligand charge transfer predominant transitions ensure a small energy splitting (ΔEST) between the lowest singlet (S1) and triplet (T1) excited states and cuprophilic interactions promote the spin-orbit coupling (SOC), favoring the reverse intersystem crossing (RISC) process. This study provides a new strategy for the construction of stimuli-responsive metal-based TADF materials.

Low disorder and high valley splitting in silicon

The electrical characterisation of classical and quantum devices is a critical step in the development cycle of heterogeneous material stacks for semiconductor spin qubits. In the case of silicon, properties such as disorder and energy separation of conduction band valleys are commonly investigated individually upon modifications in selected parameters of the material stack. However, this reductionist approach fails to consider the interdependence between different structural and electronic properties at the danger of optimising one metric at the expense of the others. Here, we achieve a significant improvement in both disorder and valley splitting by taking a co-design approach to the material stack. We demonstrate isotopically purified, strained quantum wells with high mobility of 3.14(8) × 105 cm2 V−1 s−1 and low percolation density of 6.9(1) × 1010 cm−2. These low disorder quantum wells support quantum dots with low charge noise of 0.9(3) μeV Hz−1/2 and large mean valley splitting energy of 0.24(7) meV, measured in qubit devices. By striking the delicate balance between disorder, charge noise, and valley splitting, these findings provide a benchmark for silicon as a host semiconductor for quantum dot qubits. We foresee the application of these heterostructures in larger, high-performance quantum processors.

Modeling Fe(II) Complexes Using Neural Networks.

We report a Fe(II) data set of more than 23000 conformers in both low-spin (LS) and high-spin (HS) states. This data set was generated to develop a neural network model that is capable of predicting the energy and the energy splitting as a function of the conformation of a Fe(II) organometallic complex. In order to achieve this, we propose a type of scaled electronic embedding to cover the long-range interactions implicitly in our neural network describing the Fe(II) organometallic complexes. For the total energy prediction, the lowest MAE is 0.037 eV, while the lowest MAE of the splitting energy is 0.030 eV. Compared to baseline models, which only incorporate short-range interactions, our scaled electronic embeddings improve the accuracy by over 70% for the prediction of the total energy and the splitting energy. With regard to semiempirical methods, our proposed models reduce the MAE, with respect to these methods, by 2 orders of magnitude.

DC to GHz measurements of a near-ideal 2D material: P+ monolayers

P+ monolayers in Si are of great scientific and technological interest, both intrinsically as a material in the “ideal vacuum” of crystalline Si and because they are showing great promise as qubits of electron and nuclear spin. The GHz complex conductivity σ(ω) can allow one to elucidate basic physical properties and is also important for fast devices, but measuring σ(ω) in 2D materials has not been easy. We report on such measurements, including showing (i) qualitatively a lack of any resonances up to 5 GHz (indicating no energy splittings below about 0.02 meV); and (ii) the quantitatively ideal Drude behavior of this novel material up to 5 GHz, showing a lower bound on the scattering rate of about 2 × 1010 s−1. We also discuss deconvolving the confounding effect of the distributed resistance and capacitance of the monolayer.

Interface engineering of BiVO4/Zn3V2O8 heterocatalysts for escalating the synergism: Impact of Cu electron mediator for overall water splitting

The risk of global warming is increasing due to excessive consumption of fossil fuels. To fill the gap between production and consumption of conventional energy sources, modern societies are searching green and renewable alternatives. In this work, BiVO4/Zn3V2O8 heterocatalysts were synthesized and interfacially engineered for overall water splitting reactions. To obtain the structural and interfacial morphologies, catalysts were characterized by XRD, FTIR, Raman spectroscopy, SEM and AFM techniques. The optical and chemical characteristics of as-synthesized catalysts were evaluated using UV–Vis/DRS, PL, EIS, EDX, XPS and BET analysis. The role of Cu metal, synergism between BiVO4/Zn3V2O8 and mechanistic approaches were further revealed. The results depict that Cu metal exceptionally compete to sustain the synergism as an electron mediator source. The synergistic effect and electron mediator were found as key factors to boost the overall water splitting efficiencies. Due to interfacial engineering of BiVO4/Zn3V2O8 system, charge transfer becomes more feasible for the redox reactions (i.e. water splitting). It was examined that due to presence of Cu metal, rate of overall water splitting reaction was higher than the catalysts having no mediator (i.e. absence of Cu). During photoreaction, two successive rates for H2 and O2 evolution were speculated 17.66 and 8.96 mmol g−1 h−1, respectively which delivers approximately 5.04 kJ g−1 h−1 energy. On the basis of results and activities, it could be concluded that, this research will exhibit exceptional potential and hold promise of an ultimate transition to the water splitting and green energy technologies.

Oscillating photonic Bell state from a semiconductor quantum dot for quantum key distribution

An on-demand source of bright entangled photon pairs is desirable for quantum key distribution (QKD) and quantum repeaters. The leading candidate to generate such pairs is based on spontaneous parametric down-conversion (SPDC) in non-linear crystals. However, its pair extraction efficiency is limited to 0.1% when operating at near-unity fidelity due to multiphoton emission at high brightness. Quantum dots in photonic nanostructures can in principle overcome this limit, but the devices with high entanglement fidelity (99%) have low pair extraction efficiency (0.01%). Here, we show a measured peak entanglement fidelity of 97.5% ± 0.8% and pair extraction efficiency of 0.65% from an InAsP quantum dot in an InP photonic nanowire waveguide. We show that the generated oscillating two-photon Bell state can establish a secure key for peer-to-peer QKD. Using our time-resolved QKD scheme alleviates the need to remove the quantum dot energy splitting of the intermediate exciton states in the biexciton-exciton cascade.

Tailored absorption/emission and ultrastrong coupling from heavily doped germanium plasmonic antennas

We evaluate the performance of heavily doped germanium (Ge) on silicon as a mid-infrared plasmonic material using experimental data and benchmark it against noble metals such as Au. Thanks to the strong confinement provided by the high refractive index of the spacer layer (undoped Ge) in our material system, along with the tunable plasma frequency and low scattering rate of heavily doped Ge, we demonstrate an ultrastrong coupling regime between the localized surface plasmon (LSP) resonance and the optical modes associated with the Fabry-Perot resonance in metal-dielectric-metal (MDM) cylindrical periodic arrayed antennas. These MDM antennas made up of heavily doped Ge exhibit multispectral perfect absorption. The spectral profile and absorption intensity of the resonances can be controlled by altering the lateral and vertical device geometry of the MDM antennas. The anti-crossing behavior implying ultrastrong coupling is investigated. A Rabi splitting energy (of 451 cm−1 in unit of wavenumber) is achieved in the cylindrical periodic arrayed antennas, which is ∼20 % larger than that in 1D gratings reported in a recently published work [42]. As a key application, the MDM antennas provide tailored emission spectrum. Based on the heavily doped Ge material platform, we demonstrate a wavelength-adjustable, Si-CMOS compatible plasmonic architecture, with potential for enhanced mid-infrared radiation.

Impact of Polarity Mismatch in Infinite-Layer Nickelates.

The recent discovery of superconductivity in infinite-layer Sr-doped NdNiO2 grown on SrTiO3(001) provides a new platform to explore the conducting mechanism of unconventional superconductors. However, the electronic structure of infinite-layer nickelates remains controversial. In this paper, we systematically compare the structural and electronic properties of NdNiO2 films grown on SrTiO3 and LaAlO3 substrates using first-principles calculations. Our results show that the lattice reconstruction accompanied by electronic reconstruction occurs in nickelate films on both substrates. Although both heterostructures (HSs) are conducting at the interface, the SrTiO3-based HS shows distinct atomic displacement in the interfacial TiO2 layer and significant electron accumulation deep into three SrTiO3 layers below the interface, while the LaAlO3-based HS shows negligible atomic displacement and electron localization in the interfacial AlO2 layer, reflecting the impact of polarity mismatch on the electronic structure. Further, Wannier function calculations reveal that the interface stress has no obvious effect on the splitting energy and hopping integral between Ni 3d and Nd-layer orbitals. Although the hybridization between Ni 3dx2-y2 and Nd 5d orbitals is tiny, the hybridization between the Ni 3dx2-y2 orbital and an itinerant interstitial s (IIS) orbital is significantly strong in both cases, suggesting that the IIS orbital may play a critical role in the superconductivity of nickelates.

Rational molecular design of efficient yellow-red dendrimer TADF for solution-processed OLEDs: a combined effect of substitution position and strength of the donors

AbstractThe development of high-performance solution-processed red organic light-emitting diodes (OLEDs) remains a challenge, particularly in terms of maintaining efficiency at high luminance. Here, we designed and synthesized four novel orange-red thermally activated delayed fluorescence (TADF) dendrimers that are solution-processable: 2GCzBP, 2DPACzBP, 2FBP2GCz and 2FBP2DPACz. We systematically investigated the effect of substitution position and strength of donors on the optoelectronic properties. The reverse intersystem crossing rate constant (kRISC) of the emitters having donors substituted at positions 11 and 12 of the dibenzo[a,c]phenazine (BP) is more than 10-times faster than that of compounds substituted having donors substituted at positions 3 and 6. Compound 2DPACzBP, containing stronger donors than 2GCzBP, exhibits a red-shifted emission and smaller singlet-triplet energy splitting, ΔEST, of 0.01 eV. The solution-processed OLED with 10 wt% 2DPACzBP doped in mCP emitted at 640 nm and showed a maximum external quantum efficiency (EQEmax) of 7.8%, which was effectively maintained out to a luminance of 1,000 cd m−2. Such a device∙s performance at relevant display luminance is among the highest for solution-processed red TADF OLEDs. The efficiency of the devices was improved significantly by using 4CzIPN as an assistant dopant in a hyperfluorescence (HF) configuration, where the 2DPACzBP HF device shows an EQEmax of 20.0% at λEL of 605 nm and remains high at 11.8% at a luminance of 1,000 cd m−2, which makes this device one of the highest efficiency orange-to-red HF SP-OLEDs to date.

Coulomb-assisted nonlocal electron transport between two pairs of Majorana bound states in a superconducting island

We investigate the nonlocal transport modulated by Coulomb interactions in devices comprising two interacting Majorana wires, where both nanowires are in proximity to a mesoscopic superconducting (SC) island. Each Majorana bound state (MBS) is coupled to one lead via a quantum dot with resonant levels. In this device, the nonlocal correlations can be induced in the absence of Majorana energy splitting. We find that the negative differential conductance and giant current noise cross correlation could be induced, due to the interplay between nonlocality of MBSs and dynamical Coulomb blockade effect. This feature may provide a signature for the existence of the MBSs.

Achieving Visible-Light-Excitable Blue TADF-Type Afterglow via Delicate Control of Excited States in Difluoroboron β-Diketonate Systems.

Blue afterglow constitutes of one of the primary afterglow colors and can convert into other afterglow colors through energy transfer. The reported studies show the fabrication of blue afterglow emitters, but most of them are formed by room-temperature phosphorescence mechanism and require UVB lights as excitation source (these high-energy lights may damage organic systems). Here we report visible-light-excitable blue thermally activated delayed fluorescence type (TADF-type) afterglow materials via delicate control of excited states in difluoroboron β-diketonate (BF2bdk) systems. Tiny change of the substituents in BF2bdk system has been found to pose significant influence on excited state energy levels and consequently narrow the singlet-triplet splitting energy of the system. As a result, both forward and reverse intersystem crossing have been accelerated, leading to the emergence of BF2bdk's TADF-type organic afterglow in rigid crystalline matrices. The resultant TADF-type afterglow materials exhibit emission lifetimes of several hundred milliseconds, photoluminescence quantum yield (PLQY) of 24.7 % and display temperature responsive property.

Pseudospin symmetry: Microscopic origin of the ground-state inversion in neutron-rich odd-A Cu isotopes

The role of the pseudospin symmetry in the inversion of the ground-state spin in Cu isotopes is investigated within the covariant density functional theory (CDFT). The density functional PC-PK1 gives a good agreement with the observed ground-state properties of the odd-A 69−79Cu. In particular, the inversion of the ground-state spin at A=75 is reproduced nicely, which can be explained by the level crossing between the proton pseudospin partners π2p3/2 and π1f5/2. It is found that the pseudospin symmetry plays a dominant role in the evolution of the energy splittings between the pseudospin partners. By comparing with the results of the nonrelativistic DFTs, our studies suggest that the pseudospin symmetry is essential to the shell evolution around this region.

The Substitution of Rare-Earth Gd in BaScCuTe3 Realizing the Band Degeneracy and the Point-Defect Scattering toward Enhanced Thermoelectric Performance.

Zintl compounds have continuously received significant attention, primarily due to their structural characteristics that align with the properties of the electron crystal and phonon glass. In this study, the crystal structure and thermoelectric properties of the quaternary Zintl chalcogenide BaScCuTe3 are investigated. The band structure calculations for BaScCuTe3 reveal a slight energy split of 0.08 eV between the second valence band and the valence band maximum, suggesting the presence of multiband-transport behaviors. Substitution of rare earth Gd for Sc is conducted, which significantly increases the hole concentration from 4.1 × 1019 cm-3 to 8.2 × 1019 cm-3 at room temperature. Meanwhile, the Seebeck coefficient increases because of the participation of the second valence band. A maximum power factor of 6.56 μW/cm·K2 at 773 K is obtained, which is 72% higher than that of the pristine sample. Moreover, the lattice thermal conductivity decreases from 0.57 W/m·K for BaScCuTe3 to 0.48 W/m·K for BaSc0.97Gd0.03CuTe3 at 773 K, owing to the introduction of point-defect scattering. As a result, there is a noteworthy improvement in the thermoelectric figure of merit zT, increasing from 0.44 for the undoped sample to 0.85 for BaSc0.98Gd0.02CuTe3. Considering these findings, BaScCuTe3 exhibits great potential and holds promise for further investigation in the field of thermoelectric materials.

Exploration of underlap induced high-k spacer with gate stack on strain channel cylindrical nanowire FET for enriched performance

This research explores a comprehensive examination of gate underlap incorporated strained channel Cylindrical Gate All Around Nanowire FET having enriched performances above the requirement of the 2 nm technology node of IRDS 2025. The device installs a combination of strain engineering based quantum well barrier system in the channel region with high-k spacers sandwiching the device underlaps and stack high-k gate-oxide. The underlaps are prone to parasitic resistance and various short channel effects (SCEs) hence, are sandwiched by HfO2 based high-k. This SCE degradations and a strong electric field in the drain-channel region is rendered controlling the leakages. The strain based Nanosystem engineering is incorporated with Type-II heterostructure band alignment inducing quantum well barrier mechanism in the ultra-thin cylindrical channel region creating an electrostatic charge centroid leading to energy band bending and splitting among the two-fold and four-fold valleys of the strained Silicon layer. This provides stupendous electron mobility instigating high current density and electron velocity in the channel. Thereby, the device is susceptible to on-current enhancement via ballistic transport of carriers and carrier confinement via succumbing of quantum charge carriers. The device transconductance, Ion, Ioff, Ion/Ioff ratio are measured and the output performance (ID-VDS) characteristics is determined providing emphatic enrichments in contrast to the existing gate all-around FETs as well as the 2 nm technology node data of IRDS 2025. Hence, the strained channel Nanowire FET device developed here is presented here as the device of the future for various digital applications, RF applications and faster switching speed.

Parallel Diffractive Multi‐Beam Pulsed‐Laser Ablation in Liquids Toward Cost‐Effective Gram Per Hour Nanoparticle Productivity

Nanoparticles (NPs) generated by pulsed‐laser ablation in liquids (PLAL) have benefited many key applications due to their versatility, enlarged surface area, and high purity. However, scaling up NPs production represents one of the main requisites to commercialize this technology. The established upscaling strategy demands high power and repetition rate laser source with fast scanning systems, which are not widely available and costly. Herein, a cost‐effective alternative is proposed, the addition of static diffractive optical elements to achieve parallel processing through the multi‐beam PLAL (MB‐PLAL). In MB‐PLAL, the optimum repetition rate is reduced to compensate laser energy splitting, hence achieving a higher interpulse distance, reducing pulse shielding, and increasing NPs productivity. MB‐PLAL with 11 beams reached a factor 4 productivity increase for iron–nickel alloy (Fe50Ni50) NPs compared to the single‐beam setup (0.4–1.6 g h−1), and a factor 3 increase for gold (Au) NPs (0.32–0.94 g h−1). The scalability of the proposed MB‐PLAL technique setup is confirmed by Au and Fe50Ni50 NPs productivity experiments using 1, 6, and 11 beams, showing a linear increase in productivity.

Pseudospin symmetry in resonant states in deformed nucleus 154Dy

It is known that pseudospin symmetry plays a crucial role in formation of many physical phenomena. By combining the relativistic mean field theory with the complex momentum representation method, the pseudospin symmetry in the single particle resonant states in the deformed nucleus [Formula: see text]Dy is investigated through the energy and width splittings, the quadrupole deformation parameter, the radial density distributions and occupation probabilities of the pseudospin doublets. Near the continuum threshold, the pseudospin symmetry is well reserved in both bound and resonant states. The energy and width splittings of pseudospin doublets in resonant states exhibit correlations with the deformation and quantum numbers. The good pseudospin symmetry is expected with lower pseudo-orbital angular momentum projection [Formula: see text] and the main quantum number N. In general, an increase in deformation tends to weaken the quality of the pseudospin symmetry. The understanding of the evolution of the pseudospin doublets in the resonant states has been deepened by studying the pseudospin symmetry in the deformed nuclei.

Searching for Dark Matter Axions via Atomic Excitations

Axions can be considered as good dark matter candidates. The detection of such light particles can be achieved by observing axion-induced atomic excitations. The target is in a magnetic field so that the m-degeneracy is removed, and the energy levels can be suitably adjusted. Using an axion-electron coupling indicated by the limit obtained by the Borexino experiment, which is quite stringent, reasonable axion absorption rates have been obtained for various atomic targets The obtained results depend, of course, on the atom considered through the parameters ϵ (the spin−orbit splitting) as well as δ ( the energy splitting due to the magnetic moment interaction). This assumption allows axion masses in the tens of μeV if the transition occurs between members of the same multiplet, i.e., |J1,M1=−J1⟩→|J1,M1=−J+1⟩,J1≠0, and axion masses in the range 1 meV–1 eV for transitions of the spin−orbit splitting type |J1,M=−J1⟩→|J2,M2=−J1+q⟩,q=−1,0,1, i.e., three types of transition. The axion mass that can be detected is very close to the excitation energy involved, which can vary by adjusting the magnetic field. Furthermore, since the axion is absorbed by the atom, the calculated cross-section exhibits the behavior of a resonance, which can be exploited by experiments to minimize any background events.