High-lying Energy Research Articles

Benzothiadiazole-Fused Cyanoindone: A Superior Building Block for Designing Ultra-Narrow Bandgap Electron Acceptor with Long-Range Ordered Stacking.

There are great demands of developing ultra-narrow bandgap electron acceptors for multifunctional electronic devices, particularly semi-transparent organic photovoltaics (OPVs) for building-integrated applications. However, current ultra-narrow bandgap materials applied in OPVs, primarily based on electron-rich cores, exhibit defects of high-lying energy levels and inferior performance. We herein proposed a novel strategy by designing the benzothiazole-fused cyanoindone (BTC) unit with ultra-strong electron-withdrawing ability as the terminal to synthesize the acceptor BTC-2. The BTC unit imparts red-shifted absorption up to 1000 nm to BTC-2, attributed to enhanced intramolecular charge transfer and the quinoid resonance effect. Additionally, BTC-2 features deep-lying energy levels with the highest occupied molecular orbital level of -5.81 eV, due to the ultra-strong electron-withdrawing ability of BTC. Furthermore, BTC-2 exhibits long-range ordering in both molecular packing and macroscopic blend morphology, resulting from shoulder-to-shoulder packing of two BTC units, leading to an ultra-long exciton lifetime over 1.1 ns. These superiorities facilitated a 17.17 % efficiency in the binary OPV device with an extremely high photocurrent of 30.34 mA cm-2, representing the best performance for ultra-narrow bandgap electron acceptors, and a record light utilization efficiency of 4.88 % in binary semi-transparent systems. Overall, BTC is a superior building block for designing ultra-narrow bandgap electron acceptors.

Ligand-mediate exciton allocation enables efficient cluster-based white light-emitting diodes via single and heavy doping

Despite potential in high-resolution and low-cost displays and lighting, multi-doping structures and low concentrations (<1%) limit repeatability and stability of single-emissive-layer white light-emitting devices. Herein, we report a singly doped white-emitting system of blue thermally activated delayed fluorescence host matrix (CzAcSF) doped by yellow Cu4I4 cluster ([tBCzDppy]2Cu4I4). CzAcSF:x% [tBCzDppy]2Cu4I4 films realize photo- and electro-luminescence colors from cool white to warm white at x = 20–40. The external quantum efficiency of 23.5% was achieved at x = 30, indicating the record-high efficiency among solution-processed analogs and the largest doping concentration among efficient white light-emitting devices. It shows that di(tert-butyl)carbazole moieties in [tBCzDppy]2Cu4I4 provide high-lying excited energy levels at~2.6 eV to mediate energy transfer from CzAcSF (2.9 eV) to coordinated Cu4I4 (2.2 eV). Our results demonstrate the antenna effect of ligands on optimizing charge and energy transfer in organic-cluster systems and superiority of white cluster light-emitting diodes in practical applications.

Acceptor molecules with Carbon–Carbon singly bonded central and terminal units for efficient P3HT-based organic solar cells

Herein, we synthesized two small molecules named as 4TBTCN and 6TBTCN with strongly electron-rich 4,4,9,9-tetrakis(4-hexylphenyl)-4,9-dihydrothieno[3′,2′:4,5]cyclopenta[1,2-b]thieno[2″,3′′:3′,4′]cyclopenta[1′,2′:4,5]thieno[2,3-d]thiophene or 6,6,12,12-tetrakis(4-hexylphenyl)-6,12-dihydrothieno[2″,3′′:4′,5′]thieno[3′,2′:4,5]cyclopenta[1,2-b]thieno[2‴,3‴:4″,5′′]thieno[2″,3′′:3′,4′]cyclopenta[1′,2′:4,5]thieno[2,3-d]thiophene as central unit and weak electron-withdrawing benzo[c] [1,2,5] thiadiazole-4-carbonitrile as termini, which were connected by C–C single bond. Both molecules exhibited medium optical bandgap and high-lying frontier molecular orbital energy levels, which were matched with those of the representative low-cost polymer donor P3HT. Moreover, 4TBTCN and 6TBTCN showed high stability under continuous illumination and base condition, owing to a lack of exocyclic vinyl group between the central unit and end group. Compared to P3HT:6TBTCN, P3HT:4TBTCN blend system displayed lower miscibility and thus more distinct phase separation, leading to more efficient charge transport and collection. Although the LUMO energy level of 4TBTCN was 0.15 eV deeper than that of 6TBTCN, the energy loss for P3HT:4TBTCN based device was similar to that of P3HT:6TBTCN based device. As a result, P3HT:4TBTCN based device displayed a similar open-circuit voltage but higher fill factor and short-circuit current density, yielding a superior power conversion efficiency, in comparison to P3HT:6TBTCN based device. This work provides a new strategy for design of efficient and stable acceptor molecules.

High Open-Circuit Voltage Organic Solar Cells with 19.2% Efficiency Enabled by Synergistic Side-Chain Engineering.

Restricted by the energy-gap law, state-of-the-art organic solar cells (OSCs) exhibit relatively low open-circuit voltage (VOC) because of large nonradiative energy losses (ΔEnonrad). Moreover, the trade-off between VOC and external quantum efficiency (EQE) of OSCs is more distinctive; the power conversion efficiencies (PCEs) of OSCs are still <15% with VOCs of >1.0V. Herein, the electronic properties and aggregation behaviors of non-fullerene acceptors (NFAs) are carefully considered and then a new NFA (Z19) is delicately designed by simultaneously introducing alkoxy and phenyl-substituted alkyl chains to the conjugated backbone. Z19 exhibits a hypochromatic-shifted absorption spectrum, high-lying lowest unoccupied molecular orbital energy level and ordered 2D packing mode. The D18:Z19-based blend film exhibits favorable phase separation with face-on dominated molecular orientation, facilitating charge transport properties. Consequently, D18:Z19 binary devices afford an exciting PCE of 19.2% with a high VOC of 1.002V, surpassing Y6-2O-based devices. The former is the highest PCE reported to date for OSCs with VOCs of >1.0V. Moreover, theΔEnonrad of Z19- (0.200eV) and Y6-2O-based (0.155eV) devices are lower than that of Y6-based (0.239eV) devices. Indications are that the design of such NFA, considering the energy-gap law, could promote a new breakthrough in OSCs.

A Novel N-Type Molecular Dopant With a Closed-Shell Electronic Structure Applicable to the Vacuum-Deposition Process.

Rational design, synthesis, and characterization of a new efficient versatile n-type dopant with a closed-shell electronic structure are described. By employing the tetraphenyl-dipyranylidene (DP0) framework with two 7π-electron systems modified with N,N-dimethylamino groups as the strong electron-donating substituent, 2,2',6,6'-tetrakis[4-(dimethylamino)phenyl]-4,4'-dipyranylidene (DP7), a closed-shell molecule with an extremely high-lying energy level of the highest occupied molecular orbital, close to 4.0eV below the vacuum level, is successfully developed. Thanks to its thermal stability, DP7 is applicable to vacuum deposition, which allows utilization of DP7 in bulk doping for the development of n-type organic thermoelectric materials and contact doping for reducing contact resistance in n-type organic field-effect transistors. As vacuum-deposition processable n-type dopants are very limited, DP7 stands out as a useful n-type dopant, particularly for the latter purpose.

Quantum defect and Rydberg energy level calculations for 85Rb and 87Rb by Weakest Bound Electron Potential Model

The Weakest Bound Electron Potential Model (WBEPM) is an effective emerging method for atomic structure calculations that gives results compatible with the experimental observations. In this paper, we have done theoretical calculations of quantum defects and Rydberg energies of high-lying Rydberg energy levels for 85Rb and 87Rb of nS1/2 (n= 14 – 85, 87Rb), nP3/2 (n= 31 – 100, 85Rb), nD3/2 (n= 14 – 85, 87Rb) and nD5/2 (n= 14 – 85, 87Rb) series, through WBEPM. The spectral coefficients for each Rydberg energy level series are determined from Martin's formula and are used to calculate the quantum defects and energy values of the Rydberg energy levels. The obtained results are compared with the available experimental data and show a minimum deviation of the theoretically calculated values from the experimental data. For more insight into the results, values of the Rydberg energy levels and the quantum defects are plotted as a function of the principal quantum number, respectively.

Promoting multiexciton interactions in singlet fission and triplet fusion upconversion dendrimers

Singlet fission and triplet-triplet annihilation upconversion are two multiexciton processes intimately related to the dynamic interaction between one high-lying energy singlet and two low-lying energy triplet excitons. Here, we introduce a series of dendritic macromolecules that serve as platform to study the effect of interchromophore interactions on the dynamics of multiexciton generation and decay as a function of dendrimer generation. The dendrimers (generations 1–4) consist of trimethylolpropane core and 2,2-bis(methylol)propionic acid (bis-MPA) dendrons that provide exponential growth of the branches, leading to a corona decorated with pentacenes for SF or anthracenes for TTA-UC. The findings reveal a trend where a few highly ordered sites emerge as the dendrimer generation grows, dominating the multiexciton dynamics, as deduced from optical spectra, and transient absorption spectroscopy. While the dendritic structures enhance TTA-UC at low annihilator concentrations in the largest dendrimers, the paired chromophore interactions induce a broadened and red-shifted excimer emission. In SF dendrimers of higher generations, the triplet dynamics become increasingly dominated by pairwise sites exhibiting strong coupling (Type II), which can be readily distinguished from sites with weaker coupling (Type I) by their spectral dynamics and decay kinetics.

New Medium-Bandgap Nonfused Ring Guest Acceptor with a Higher-Lying LUMO Level Enables High-Performance Ternary Organic Solar Cells.

Adding another constituent into a binary system, known as a ternary strategy, represents a simple and effective approach to boosting the power conversion efficiency (PCE) of organic solar cells (OSCs). Herein, we have prepared a new nonfused ring small-molecule acceptor with a medium bandgap, named DFTQA-2FIC, which possesses a high-lying lowest unoccupied molecular orbital energy level and a strong intramolecular charge-transfer effect. We elaborately utilized it as a third component in a typical PM6:Y6 blend to obtain high-performance ternary OSCs. The resulting ternary blend film exhibited superior and balanced hole/electron mobility, enhanced favorable aggregation morphology, and reduced charge carrier recombination. Consequently, an optimized ternary OSC presented a distinctly increased PCE of 17.29%, accompanied by synchronous enhancements in crucial parameters, representing a 7.46% improvement over the binary OSC based on PM6:Y6 with a PCE of 16.09%. This study highlights that incorporating DFTQA-2FIC as a third component in a binary system is suitable for optimizing photovoltaic performance.

Ultra-Small-Bandgap Conjugated Polymers Based on an N-B←N Unit.

Since the breakthrough of conductive polymers in 1977, scientists have made great efforts to create small band gap (Eg ) conjugated polymers. Two general strategies to design small Eg conjugated polymers are quinoid structure and donor-acceptor structure. Ultrasmall Eg conjugated polymers (Eg <1.0 eV) always suffer from poor air stability because of high-lying HOMO energy levels. In this work, we report a new strategy to design ultrasmall Eg conjugated polymers by N-B←N unit, i.e. balanced resonant boron-nitrogen covalent bond (B-N) and boron-nitrogen coordination bond (B←N). The resulting polymer exhibits an Eg of 0.82 eV and an onset absorption wavelength of >1500 nm. Moreover, the polymer exhibits excellent air stability because of its low-lying LUMO/HOMO energy levels. An unprecedented property of this polymer is the selective light absorption in the infrared range (800-1500 nm) and high transparency in the visible range (400-780 nm). Using this property, for the first time, we demonstrate the application of conjugated polymers as transparent thermal-shielding coating layer on glass, which reduces indoor solar irradiation through window and consequently reduces power consumption for cooling of buildings and cars in summer.

Anthracene derivatives with hot exciton and TTA process for high-efficiency organic light-emitting diodes

Organic fluorophores with unique photophysical properties that converting the triplet excitons to singlet excitons, are desired to improve the efficiencies of organic light-emitting diodes (OLEDs). Here, two new anthracene-based emitters pipdAnCz and pipdAnTPA, with proper donor and acceptor substituents are designed and synthesized. The theoretical calculation and experimental results demonstrate that both pipdAnCz and pipdAnTPA possess hot exciton and triplet-triplet annihilation (TTA) characteristics, which can convert the triplet excitons to singlet excitons from the high-lying triplet energy levels (Tn) and the lowest triplet energy level (T1) respectively. Due to its relative higher photoluminescence quantum yields (PLQYs), the pipdAnTPA based non-doped device achieved a maximum external quantum efficiency (EQEmax) of 6.43% with an exciton utilization efficiency (EUE) of 72%. Further device physics study reveal that the hot exciton process is the dominant mechanism, assisted by TTA process, to convert the triplet excitons, especially for the pipdAnTPA based device.

Simultaneously enhancing the photovoltaic parameters of ternary organic solar cells by incorporating a fused ring electron acceptor.

The ternary strategy has been recognized as an effective method to improve the photovoltaic performance of organic solar cells (OSCs). In ternary OSCs, the complementary or broadened absorption spectrum, optimized morphology, and enhanced photovoltaic performance could be obtained by selecting a third rational component for the host system. In this work, a fused ring electron acceptor named BTMe-C8-2F, which possesses a high-lying lowest unoccupied molecular orbital (LUMO) energy level and a complementary absorption spectrum to PM6:Y6, was introduced to a PM6:Y6 binary system. The ternary blend film PM6:Y6:BTMe-C8-2F showed high and more balanced charge mobilities, and low charge recombination. Therefore, the OSC based on the PM6:Y6:BTMe-C8-2F (1 : 1.2 : 0.3, w/w/w) blend film achieved the highest power conversion efficiency (PCE) of 17.68%, with an open-circuit voltage (VOC) of 0.87 V, a short-circuit current (JSC) of 27.32 mA cm-2, and a fill factor (FF) of 74.05%, which are much higher than the binary devices of PM6:Y6 (PCE = 15.86%) and PM6:BTMe-C8-2F (PCE = 11.98%). This work provides more insight into the role of introducing a fused ring electron acceptor with a high-lying LUMO energy level and complementary spectrum for simultaneously enhancing the VOC and JSC to promote the performance of ternary OSCs.

Screening Constant per Unit Nuclear Charge Studies of Rydberg Resonances Due to the 4p → nd and ns Transitions in Se+ Ions

Calculations of high-lying energy resonances of 12 Rydberg series due to the 4p → nd and 4p → ns transitions from the 4s24p3 3S°3/2 ground-state and the 4s24p3 2P°3/2,1/2 and 4s24p3 2D°5/2,3/2 metastable states of the Se+ ion are reported. The calculations believed to be the first theoretical ones are performed using the Screening Constant per Unit Nuclear Charge (SCUNC) method up to n = 40. Analysis of the present results is achieved in the framework of the standard quantum-defect theory and of the SCUNC-procedure by calculating the effective nuclear charge. For many resonances, the SCUNC-method reproduces the ALS measurements excellently [Esteves et al., Phys. Rev. A, 84 013406 (2011)] up to n = 25. However, for some resonances belonging to the 4s24p2 (1D2)nd (2D) and 4s24p2 (1D2)ns (2D) and to the 4s24p2 (1D2)nd (2S) and 4s24p2 (1D2)nd (2P1/2) Rydberg series, the ALS data overlap at high n values. In addition, negative quantum-defect values were determined where positive values are allowable. In the present work, positive quantum defect values almost constants are obtained along all the series investigated up to n = 40, and the narrow resonances are clearly separated. Overall, the present theoretical study provides confidence in the ALS data on Se+ ions for astrophysical interest as far as the understanding of the chemical evolution of Se in the universe is concerned.

Spectroscopic properties of lithium like ions: Prospective elements for quantum computation

Rydberg physics is the most exquisite playground for the exploration of quantum technologies. Therefore, in this spectral investigation based on weakest bound electron potential model theory (WBEPMT). The quantum defects and Rydberg energies of low-lying and high-lying spectral Rydberg energy sequence in the following configurations: 1s2ns2Se1/2 and 1s2np2Po1/2 in Lithium-like ions (Z=4-6) Beryllium (Be II), Boron (B III) and Carbon (C IV) are computed with their radial expected values. Total 43 low-lying energies and quantum defects are computed and compared with 25 low lying radial expected values. The results are in good agreement with the previously published experimental / theoretical results. Based on the good agreement of low-lying data, total 257 new values of high-lying Rydberg energies and quantum defects are computed with 575 radial expected values currently not listed at NIST. The deviation in both sets of data doesn’t exceed 1 cm-1 .

IR laser oscillation on caesium and rubidium atomic transitions upon pumping to high-lying energy levels

Laser oscillation is obtained in caesium and rubidium atoms with wavelengths in the range of 2 – 5.5 μm under pumping to high-lying energy levels. Longitudinal resonant pumping is implemented using the second harmonic of radiation from an optical parametric oscillator. The pump wavelength is tuned over discrete levels from 8P to 10P in caesium atoms and from 6P to 8P in rubidium atoms. The width of the pump radiation spectrum is 12 cm−1. When caesium atoms are pumped, the pump pulse energy is no more than 10 mJ; when rubidium atoms are pumped, it does not exceed 3 mJ. The pulse repetition rate is 10 Hz. The maximum output energy of IR laser radiation upon pumping the 9P3/2 level of caesium atoms is about 100 μJ at a cell temperature of ∼170°C, while the efficiency of pump conversion into radiation energy with a wavelength λ ∼ 3.1 μm turns out to be ∼1 %. For rubidium atoms, an estimate of the output energy of IR radiation gives a value of ∼80 μJ at a cell temperature of 180 °C, which corresponds to an energy efficiency of ∼2.7 %.

Referential tuning strategy for high-lying triplet energy level setting in OLED emitter with hot-exciton characteristics

A tuning strategy for high-lying triplet energy level to design hot exciton emitters.

Rationally regulating the terminal unit and copolymerization spacer of polymerized small-molecule acceptors for all-polymer solar cells with high open-circuit voltage over 1.10 V

Two polymerized small molecule acceptors with wide bandgaps of ∼1.65 eV and high-lying LUMO energy levels above −3.70 eV were designed by introducing a novel terminal unit. Efficient all-PSCs with high VOC over 1.10 V were achieved.

Ladder-like energy-relaying exciplex enables 100% internal quantum efficiency of white TADF-based diodes in a single emissive layer

Development of white organic light-emitting diodes based on purely thermally activated delayed fluorescence with a single-emissive-layer configuration has been a formidable challenge. Here, we report the rational design of a donor-acceptor energy-relaying exciplex and its utility in fabricating single-emissive-layer, thermally activated delayed fluorescence-based white organic light-emitting diodes that exhibit 100% internal quantum efficiency, 108.2 lm W−1 power efficiency, and 32.7% external quantum efficiency. This strategy enables thin-film fabrication of an 8 cm × 8 cm thermally activated delayed fluorescence white organic light-emitting diodes (10 inch2) prototype with 82.7 lm W−1 power efficiency and 25.0% external quantum efficiency. Introduction of a phosphine oxide-based acceptor with a steric group to the exciplex limits donor-acceptor triplet coupling, providing dual levels of high-lying and low-lying triplet energy. Transient spectroscopic characterizations confirm that a ladder-like energy relaying occurs from the high-lying triplet level of the exciplex to a blue emitter, then to the low-lying triplet level of the phosphine oxide acceptor, and ultimately to the yellow emitter. Our results demonstrate the broad applicability of energy relaying in multicomponent systems for exciton harvesting, providing opportunities for the development of third-generation white organic light-emitting diode light sources.

Mid-infrared imaging through up-conversion luminescence in trivalent lanthanide ion-doped self-organizing optical fiber array crystal.

We propose a scheme for imaging mid-infrared (MIR) wavelengths via pre-excitation-assisted up-conversion luminescence in lanthanide ion (Ln3+)-doped Self-organizing Optical FIber Array (SOFIA) crystal. First, near-infrared pre-excitation wavelength excites an electron from the ground state to an excited state of Ln3+. Next, the MIR wavelength to be imaged promotes this excited electron to a higher-lying energy state. Finally, relaxation of the electron from the higher-lying energy state to the ground state emits the up-conversion luminescence in the visible region, completing the MIR-to-visible wavelength conversion. An analysis of the 4f to 4f intra-configurational energy level transitions in Ln3+, together with an appropriate selection of the pre-excitation wavelength and the visible luminescence constrained within the 500-700 nm wavelength range, reveals that trivalent erbium (Er3+), thulium (Tm3+), holmium (Ho3+), and neodymium (Nd3+) can be used to image MIR wavelengths. Our proposed scheme, called MIR imAging through up-Conversion LuminEscence in a SOFIA crystal, will enable the imaging of MIR wavelengths using low-cost optics and readily available silicon-based detectors in the visible spectral region and will open up new possibilities for MIR wavelength detection and imaging.

The Effects of Molecular Packing Behavior of Small-Molecule Acceptors in Ternary Organic Solar Cells

Herein, two diketopyrrolopyrrole (DPP)-based, small-molecule isomers, o- and p-DPP-PhCN, were introduced as acceptors in ternary organic solar cells (OSCs). The isomers have the same molecular backbone but differ in the positions of the cyanide (CN) substituents (ortho and para), which greatly affects their packing behavior. Ternary solar cells composed of poly(3-hexylthiophene) (P3HT):DPP-PhCN:phenyl-C61-butyric acid methyl ester (PCBM) were fabricated, and the effects of the different packing behaviors of the third component on the device performance and the working mechanism of the ternary cells were investigated. The addition of o-DPP-PhCN with a relatively high-lying lowest unoccupied molecular orbital energy level resulted in an increase in the open-circuit voltage (VOC) in the ternary devices, demonstrating the alloy-like structure of the two acceptors (o-DPP-PhCN and PCBM) in the ternary system. However, the p-DPP-PhCN-based ternary cells exhibited VOC values similar to that of a P3HT:PCBM binary cell, irrespective of the addition of p-DPP-PhCN, indicating a cascade energy-level structure in the ternary system and an effective charge transfer from the P3HT to the PCBM. Importantly, by increasing the addition of p-DPP-PhCN, the short-circuit current density increased substantially, resulting in pronounced shoulder peaks in the external quantum efficiency responses in the long-wavelength region, corresponding to the contribution of the photocurrent generated by the light absorption of p-DPP-PhCN. Despite sharing the same molecular backbone, the two DPP-PhCNs exhibited substantially different packing behaviors according to the position of their CN substituents, which also greatly affected the working mechanism of the ternary devices fabricated using the DPP-PhCNs as the third component.

Approximate non-relativistic energy expression and the rotational–vibrational constants of the Tietz–Hua potential: a semiclassical approach

The low- and high-lying rovibrational energy levels of the Schrodinger equation with the molecular Tietz–Hua potential are obtained via the Wentzel–Kramers–Brilluoin (WKB) quantization approach. The Pekeris-type approximation scheme is applied to deal with the orbital centrifugal term of the effective potential function. The obtained energy spectra and the rotational–vibrational (rovibrational) coefficients for [Formula: see text], [Formula: see text], [Formula: see text], and [Formula: see text] diatomic molecules were compared with the ones obtained by other analytical methods and available experimental data in the literature. The results revealed that the accuracy of the energy spectra for the high-lying rovibrational quantum states may depend on the rotational-vibrational constants.