Electron–hole(e–h)recombination is a fundamental process that governs energy dissipation and device efficiency in semiconductors.In two-dimensional(2D)materials,the formation of tightly bound excitons makes exciton-...Electron–hole(e–h)recombination is a fundamental process that governs energy dissipation and device efficiency in semiconductors.In two-dimensional(2D)materials,the formation of tightly bound excitons makes exciton-mediated e–h recombination the dominant decay pathway.In this work,nonradiative e–h recombination within excitons in monolayer MoS2 is investigated using first-principles simulations that combine nonadiabatic molecular dynamics with𝐺𝑊and real-time Bethe–Salpeter equation(BSE)propagation.A two-step process is identified:rapid intervalley redistribution induced by exchange interaction,followed by slower phonon-assisted recombination facilitated by exciton binding.By selectively removing the screened Coulomb and exchange terms from the BSE Hamiltonian,their respective contributions are disentangled—exchange interaction is found to increase the number of accessible recombination pathways,while binding reduces the excitation energy and enhances nonradiative decay.A reduction in recombination lifetime by over an order of magnitude is observed due to the excitonic many-body effects.These findings provide microscopic insights for understanding and tuning exciton lifetimes in 2D transition-metal dichalcogenides.展开更多
The excitonic insulator(EI)is a more than 60-year-old theoretical proposal that is still elusive.It is a purely quantum phenomenon involving the spontaneous generation of excitons in quantum mechanics and the spontane...The excitonic insulator(EI)is a more than 60-year-old theoretical proposal that is still elusive.It is a purely quantum phenomenon involving the spontaneous generation of excitons in quantum mechanics and the spontaneous condensation of excitons in quantum statistics.At this point,the excitons represent the ground state rather than the conventional excited state.Thus,the scarcity of candidate materials is a key factor contributing to the lack of recognized EI to date.In this review,we begin with the birth of EI,presenting the current state of the field and the main challenges it faces.We then focus on recent advances in the discovery and design of EIs based on the first-principles Bethe-Salpeter scheme,in particular the dark-exciton rule guided screening of materials.It not only opens up new avenues for realizing excitonic instability in direct-gap and wide-gap semiconductors,but also leads to the discovery of novel quantum states of matter such as half-EIs and spin-triplet EIs.Finally,we will look ahead to possible research pathways leading to the first recognized EI,both theoretically and computationally.展开更多
Carbon dots(CDs),due to their low cost,high stability,and high luminous efficiency,have emerged as an excellent material for the emissive layer in next-generation electroluminescent light-emitting diodes(ELEDs).Howeve...Carbon dots(CDs),due to their low cost,high stability,and high luminous efficiency,have emerged as an excellent material for the emissive layer in next-generation electroluminescent light-emitting diodes(ELEDs).However,improving the efficiency of fluorescent CDs-based ELEDs remains challenging,primarily because it is difficult to utilize triplet excitons in the electroluminescence process.Therefore,enhancing the exciton utilization efficiency of CDs during electroluminescence is crucial.Based on this,we exploited the characteristic large exciton binding energy commonly found in CDs to develop exciton-emitting CDs.These CDs facilitate the radiative recombination of excitons during electroluminescence,thereby improving the electroluminescent efficiency.By rationally selecting precursors,we developed high quantum efficiency CDs and subsequently constructed CDs-based ELEDs.The blue-light device exhibited an external quantum efficiency of over 4%.This study introduces a novel design concept for CDs,providing a new strategy for developing high-performance blue ELEDs based on CDs.展开更多
We investigate electronic structures and excitonic properties of monolayer SiP_(2)within the framework of firstprinciples GW plus Bethe-Salpeter equation(GW-BSE)calculations.Within the G_(0)W_(0)approximation,monolaye...We investigate electronic structures and excitonic properties of monolayer SiP_(2)within the framework of firstprinciples GW plus Bethe-Salpeter equation(GW-BSE)calculations.Within the G_(0)W_(0)approximation,monolayer SiP_(2)is identified as a direct-gap semiconductor with an electronic gap of 3.14 e V,and the excitons exhibit a hybrid-dimensional character similar to that of the bulk counterpart.The optical absorption spectra reveal pronounced excitonic effects with strong anisotropy:the first bright exciton has a binding energy of 840 meV under x-polarized light,compared with 450 meV under y-polarized light.We further analyze the symmetry origins of the polarization-dependent optical selection rules through group theory.This binding energy difference arises from the intrinsic nature of the excitons:flat-band excitons under x-polarized light and conventional excitons localized at a single k point under y-polarized light.Our work enhances the understanding of excitonic behavior in monolayer SiP_(2)and highlights its potential for polarization-sensitive and directionally tunable optoelectronic applications.展开更多
Efficient generation of singlet oxygen(1 O_(2)) by an excitonic ene rgy transfer process is highly desired on a semiconductor photocatalyst for selective oxidation of methyl phenyl sulfide(MPS).Herein,it is demonstrat...Efficient generation of singlet oxygen(1 O_(2)) by an excitonic ene rgy transfer process is highly desired on a semiconductor photocatalyst for selective oxidation of methyl phenyl sulfide(MPS).Herein,it is demonstrated that a large amount of 1 O_(2) is produced on pristine graphitic carbon nitride(CN) nanosheet compared with bismuth oxybromide(BiOBr) and comme rcial P25 titanium dioxide(TiO_(2)).This leads to a certain photoactivity of CN for MPS oxidation.The observed ~77% selectivity for CN depends on the competitive results of excitonic energy transfer for 1 O_(2) formation and charge carrier separation for superoxide radical(O_(2)·) production,which are based on the phosphorescence spectra and electron paramagnetic resonance signals,respectively.Moreover,ultrathin CN nanosheets are synthesized by thermal treatment with the cyanuric acid-melamine hydrogen bonded aggregates as precursors.It is confirmed that the amount of produced 1 O_(2) could be increased by decreasing the thickness of resultant CN nanosheets.The optimized ultrathin CN nanosheet(~4 nm) exhibits excellent photoactivity with high selectivity(~99%).It is suggested that the excitonic energy transfer for 1 O_(2) formation is close related to the intrinsic exciton binding energy and the two-dimensional quantum confinement effect.This work establishes a basic mechanistic understanding on the excitonic processes in CN,and develops a feasible route to design CN-based photocatalysts for efficient 1 O_(2) generation.展开更多
Two-dimensional(2D) layered organic-inorganic hybrid perovskites have attracted much more attention for some applications than their three-dimensional(3D) perovskite counterparts due to their promising thermal and moi...Two-dimensional(2D) layered organic-inorganic hybrid perovskites have attracted much more attention for some applications than their three-dimensional(3D) perovskite counterparts due to their promising thermal and moisture stabilities.In particular, the 2D perovskite devices have shown better promise for optoelectronic applications.However, tunability of optoelectronic properties is often demanded to improve the device performance.Herein, we adopt a newly method to tune the electronic properties of 2D perovskite by introducing pseudohalide into the structure.In this work, we designed a pseudohalidesubstituted 2D perovskite by substituting the out-of-plane halide with pseudohalide and studied the electronic and excitonic properties of 2D-BA2MX4 and 2D-BA2MX2Ps2(M=Ge^(2+), Sn^(2+), and Pb^(2+);X=I;Ps=NCO, NCS, OCN, SCN, Se CN).We revealed the dependence of electronic properties including band gaps, composition of band edges, bonding characteristics, work functions, effective masses, and exciton binding energies on different pseudohalides substituted in 2D perovskite.Our results indicate that the substitution of pseudohalide in 2D perovskites is energetically favorable and can significantly affect the bonding characteristics as well as the CBM and VBM that often play major role in determining their performance in optoelectronic devices.It is expected that the pseudohalide substitution will be helpful in developing more advanced optoelectronic device based on 2D perovskite by optimizing band alignment and promoting charge extraction.展开更多
Two thin-film 2 D organic-inorganic hybrid perovskites,i.e.,2-phenylethylammonium lead iodide(PEPI)and 4-phenyl-1-butylammonium lead iodide(PBPI)were synthesized and investigated by steady-state absorption,temperature...Two thin-film 2 D organic-inorganic hybrid perovskites,i.e.,2-phenylethylammonium lead iodide(PEPI)and 4-phenyl-1-butylammonium lead iodide(PBPI)were synthesized and investigated by steady-state absorption,temperature-dependent photoluminescence,and temperature-dependent ultrafast transient absorption spectroscopy.PBPI has a longer organic chain(via introducing extra ethyl groups)than PEPI,thus its inorganic skeleton can be distorted,bringing on structural disorder.The comparative analyses of spectral profiles and temporal dynamics revealed that the greater structural disorder in PBPI results in more defect states serving as trap states to promote exciton dynamics.In addition,the fine-structuring of excitonic resonances was unveiled by temperature-dependent ultrafast spectroscopy,suggesting its correlation with inorganic skeleton rather than organic chain.Moreover,the photoexcited coherent phonons were observed in both PEPI and PBPI,pointing to a subtle impact of structural disorder on the low-frequency Raman-active vibrations of inorganic skeleton.This work provides valuable insights into the optical properties,excitonic behaviors and dynamics,as well as coherent phonon effects in 2 D hybrid perovskites.展开更多
Using the Lindemann criterion,we analyzed the quantum and thermal melting of electronic/excitonic crystals recently discovered in two-dimensional(2D)semiconductor moirépatterns.We show that the finite 2D screenin...Using the Lindemann criterion,we analyzed the quantum and thermal melting of electronic/excitonic crystals recently discovered in two-dimensional(2D)semiconductor moirépatterns.We show that the finite 2D screening of the atomically thin material can suppress(enhance)the inter-site Coulomb(dipolar)interaction strength,thus inhibits(facilitates)the formation of the electronic(excitonic)crystal.Meanwhile,a strong enough moiréconfinement is found to be essential for realizing the crystal phase with a wavelength near 10 nm or shorter.From the calculated Lindemann ratio which quantifies the fluctuation of the site displacement,we estimate that the crystal will melt into a liquid above a critical temperature ranging from several tens Kelvin to above 100 K(depending on the system parameters).展开更多
The intermolecular interaction determines the photophysical properties of the organic aggregates,which are critical to the performance of organic photovoltaics.Here,excitonic coupling,an important intermolecular inter...The intermolecular interaction determines the photophysical properties of the organic aggregates,which are critical to the performance of organic photovoltaics.Here,excitonic coupling,an important intermolecular interaction in organic aggregates,between theπ-stacking graphene quantum dots is studied by using transient absorption spectroscopy.We find that the spectral evolution of the ground state bleach arises from the dynamic variation of the excitonic coupling in the excitedπ-stacks.According to the spectral simulations,we demonstrate that the kinetics of the vibronic peak can be exploited as a probe to measure the dynamics of excitonic coupling in the excitedπ-stacks.展开更多
The influence of the pressure transmission medium（PTM）on the excitonic interband transitions in monolayer tungsten diselenide（WSe2）is investigated using photoluminescence（PL）spectra under hydrostatic pressure up...The influence of the pressure transmission medium（PTM）on the excitonic interband transitions in monolayer tungsten diselenide（WSe2）is investigated using photoluminescence（PL）spectra under hydrostatic pressure up to 5GPa.Three kinds of PTMs,condensed argon（Ar）,1：1 n-pentane and isopentane mixture（PM）,and4：1 methanol and ethanol mixture（MEM,a PTM with polarity）,are used.It is found that when either Ar or PM is used as the PTM,the PL peak of exciton related to the direct K-K interband transition shows a pressure-induced blue-shift at a rate of 32±4 or 32±1 meV/GPa,while it turns to be 50±9meV/GPa when MEM is used as the PTM.The indirect A-K interband transition presents almost no shift with increasing pressure up to approximatel.y 5 GPa when Ar and PM are used as the PTM,while it shows a red-shift at the rate of-17±7meV/GPa by using MEM as the PTM.These results reveal that the optical interband transitions of monolayer WSe2 are very sensitive to the polarity of the PTM.The anomalous pressure coefficient obtained using the polar PTM of MEM is ascribed to the existence of hydrogen-like bonds between hydroxyl in MEM and Se atoms under hydrostatic pressure.展开更多
We explore the excitonic effects in chiral graphene nanoribbons (cGNRs), whose edges are composed alternatively of armchair-edged and zigzag-edged segments. For cGNRs dominated by armchair edges, their energy gaps and...We explore the excitonic effects in chiral graphene nanoribbons (cGNRs), whose edges are composed alternatively of armchair-edged and zigzag-edged segments. For cGNRs dominated by armchair edges, their energy gaps and exciton energies decrease with increasing chirality angles, and they, as functions of widths, oscillate with the period of three, while the exciton binding energies do not have such distinct oscillation. On the other hand, for cGNRs dominated by zigzag edges, all the energy gaps, exciton energies, and exciton binding energies show oscillation properties with their widths, due to the interactions between the edge states localized at the opposite zigzag edges. In addition, the triplet excitons are energy degenerate when the electrons are spin-unpolarized, while the degeneracy split when the electrons are spin-polarized. All the studied cGNRs show strong excitonic effects with the exciton binding energies of hundreds of meV.展开更多
Two-dimensional(2D)2H-MoTe2 is a promising semiconductor because of its small bandgap,strong absorption,and low thermal conductivity.In this paper,we systematically study the optical and excitonic properties of atomic...Two-dimensional(2D)2H-MoTe2 is a promising semiconductor because of its small bandgap,strong absorption,and low thermal conductivity.In this paper,we systematically study the optical and excitonic properties of atomically thin 2H-MoTe2(1–5 layers).Due to the fact that the optical contrast and Raman spectra of 2H-MoTe2 with different thicknesses exhibit distinctly different behaviors,we establish a quantitative method by using optical images and Raman spectra to directly identify the layers of 2H-MoTe2 thin films.Besides,excitonic states and binding energy in monolayer/bilayer 2H-MoTe2 are measured by temperature-dependent photoluminescence(PL)spectroscopy.At temperature T=3.3 K,we can observe an exciton emission at^1.19 eV and trion emission at^1.16 eV for monolayer 2H-MoTe2.While at room temperature,the exciton emission and trion emission both disappear for their small binding energy.We determine the exciton binding energy to be 185 meV(179 meV),trion binding energy to be 20 meV(18 me V)for the monolayer(bilayer)2H-MoTe2.The thoroughly studies of the excitonic states in atomically thin 2H-MoTe2 will provide guidance for future practical applications.展开更多
Multiphoton excitations and nonlinear optical properties of exciton states in GaAs/AlxGa1-xAs coupled quantum well structure have been theoretically investigated under the influence of a time-varying high-intensity te...Multiphoton excitations and nonlinear optical properties of exciton states in GaAs/AlxGa1-xAs coupled quantum well structure have been theoretically investigated under the influence of a time-varying high-intensity terahertz(THz)laser field.Non-perturbative Floquet theory is employed to solve the time-dependent equation of motion for the laser-driven excitonic quantum well system.The response to the field parameters,such as intensity and frequency of the laser electric field on the state populations,can be used in various optical semiconductor device applications,such as photodetectors,sensors,all-optical switches,and terahertz emitters.展开更多
The excitonic optical absorption of GaAs bulk semiconductors under intense terahertz （THz） radiation is investigated numerically. The method of solving initial-value problems, combined with the perfect matched layer...The excitonic optical absorption of GaAs bulk semiconductors under intense terahertz （THz） radiation is investigated numerically. The method of solving initial-value problems, combined with the perfect matched layer technique, is used to calculate the optical susceptibility. In the presence of a driving THz field, in addition to the usual exciton peaks, 2p replica of the dark 2p exciton and even-THz-photon-sidebands of the main exciton resonance emerge in the continuum above the band edge and below the main exciton resonance. Moreover, to understand the shift of the position of the main exciton peak under intense THz radiation, it is necessary to take into consideration both the dynamical Franz-Keldysh effect and ac Stark effect simultaneously. For moderate frequency fields, the main exciton peak decreases and broadens due to the field-induced ionization of the excitons with THz field increasing. However, for high frequency THz fields, the characteristics of the exciton recur even under very strong THz fields, which accords with the recent experimental results qualitatively.展开更多
In the past few years,the renormalized excitonic model(REM)approach was developed as an efficient low-scaling ab initio excited state method,which assumes the low-lying excited states of the whole system are a linear ...In the past few years,the renormalized excitonic model(REM)approach was developed as an efficient low-scaling ab initio excited state method,which assumes the low-lying excited states of the whole system are a linear combination of various single monomer excitations and utilizes the effective Hamiltonian theory to derive their couplings.In this work,we further extend the REM calculations for the evaluations of first-order molecular properties(e.g.charge population and transition dipole moment)of delocalized ionic or excited states in molecular aggregates,through generalizing the effective Hamiltonian theory to effective operator representation.Results from the test calculations for four different kinds of one dimensional(1D)molecular aggregates(ammonia,formaldehyde,ethylene and pyrrole)indicate that our new scheme can efficiently describe not only the energies but also wavefunction properties of the low-lying delocalized electronic states in large systems.展开更多
Monolayer transition-metal dichalcogenides possess rich excitonic physics and unique valley-contrasting optical selection rule,and offer a great platform for long spin/valley lifetime engineering and the associated sp...Monolayer transition-metal dichalcogenides possess rich excitonic physics and unique valley-contrasting optical selection rule,and offer a great platform for long spin/valley lifetime engineering and the associated spin/valleytronics exploration.Using two-color time-resolved Kerr rotation and time-resolved reflectivity spectroscopy,we investigate the spin/valley dynamics of different excitonic states in monolayer WSe_(2)grown by molecular beam epitaxy.With fine tuning of the photon energy of both pump and probe beams,the valley relaxation process for the neutral excitons and trions is found to be remarkably different-their characteristic spin/valley lifetimes vary from picoseconds to nanoseconds,respectively.The observed long trion spin lifetime of>2.0 ns is discussed to be associated with the dark trion states,which is evidenced by the photon-energy dependent valley polarization relaxation.Our results also reveal that valley depolarization for these different excitonic states is intimately connected with the strong Coulomb interaction when the optical excitation energy is above the exciton resonance.展开更多
Two-dimensional(2D)Ga_(2)O_(3)has been confirmed to be a stable structure with five atomic layer thickness configuration.In this work,we study the quasi-particle electronic band structures and then access the excitoni...Two-dimensional(2D)Ga_(2)O_(3)has been confirmed to be a stable structure with five atomic layer thickness configuration.In this work,we study the quasi-particle electronic band structures and then access the excitonic optical properties through solving the Bethe-Salpeter equation(BSE).The results reveal that the exciton dominates the optical absorption in the visible light region with the binding energy as large as~1.0 eV,which is highly stable at room temperature.Importantly,both the dominant absorption P_(1)and P_(2)peaks are optically bright without dark exciton between them,and thus is favorable for luminescence process.The calculated radiative lifetime of the lowest-energy exciton is 2.0×10^(-11)s at 0 K.Furthermore,the radiative lifetime under+4%tensile strain is one order of magnitude shorter than that of the strainfree case,while it is less insensitive under the compressive strain.Our findings set the stage for future theoretical and experimental investigation on monolayer Ga_(2)O_(3).展开更多
It is theoretically shown that excitonic Doppler-Rabi oscillations can occur in an organic slab moving along the axis of a high-Q cavity. Due to the N enhancement of the vacuum Rabi frequency, this effect can be more ...It is theoretically shown that excitonic Doppler-Rabi oscillations can occur in an organic slab moving along the axis of a high-Q cavity. Due to the N enhancement of the vacuum Rabi frequency, this effect can be more eas ily observed than that in a moving two-level atom.展开更多
Quantum confinement effect and reduced dielectric screening in two-dimensional(2D)dramatically enhance theelectron-hole interactions.In this work,we use many-body perturbation theory and Bethe-Salpeter equation(BSE)to...Quantum confinement effect and reduced dielectric screening in two-dimensional(2D)dramatically enhance theelectron-hole interactions.In this work,we use many-body perturbation theory and Bethe-Salpeter equation(BSE)toinvestigate the electronic and excitonic optical properties of monolayer SnP_(2)S_(6).Our findings reveal that the excitoniceffect dominates the optical absorption spectra in the visible light range,and the lowest-energy exciton X0 in monolayerSnP_(2)S_(6)is optically bright with the binding energy of 0.87 eV and the radiative lifetime of~10^(-11)s,which is highly advantageousto the photo-luminescence.Most importantly,the absence of optically forbidden states below the bright statesX0 would give rise to a high quantum efficiency of 2D SnP_(2)S_(6).We also find that applied biaxial strain can further shortenthe radiative lifetime of the bright states.These results imply that 2D SnP_(2)S_(6)is a promising candidate for the optoelectronicdevices.展开更多
A series of GaAs/A1As multiple-quantum wells doped with Be is grown by molecular beam epitaxy. The photolu- minescence spectra are measured at 4, 20, 40, 80, 120, and 200 K, respectively. The recombination transition ...A series of GaAs/A1As multiple-quantum wells doped with Be is grown by molecular beam epitaxy. The photolu- minescence spectra are measured at 4, 20, 40, 80, 120, and 200 K, respectively. The recombination transition emission of heavy-hole and light-hole free excitons is clearly observed and the transition energies are measured with different quantum well widths. In addition, a theoretical model of excitonic states in the quantum wells is used, in which the symmetry of the component of the exciton wave function representing the relative motion is allowed to vary between the two- and three- dimensional limits. Then, within the effective mass and envelope function approximation, the recombination transition energies of the heavy- and light-hole excitons in GaAs/A1As multiple-quantum wells are calculated each as a function of quantum well width by the shooting method and variational principle with two variational parameters. The results show that the excitons are neither 2D nor 3D like, but are in between in character and that the theoretical calculation is in good agreement with the experimental results.展开更多
基金supported by the National Key Research and Development Program of China (Grant Nos.2024YFA1409800 for J.Z.and2024YFA1408603 for Q.Z.)the National Natural Science Foundation of China (Grant Nos.12125408,12334004for J.Z.,and 12174363 for Q.Z.)+1 种基金the Innovation Program for Quantum Science and Technology (Grant No.2021ZD0303306 for J.Z.)the Strategic Priority Research Program of the Chinese Academy of Sciences(Grant No.XDB0450101 for J.Z.)。
文摘Electron–hole(e–h)recombination is a fundamental process that governs energy dissipation and device efficiency in semiconductors.In two-dimensional(2D)materials,the formation of tightly bound excitons makes exciton-mediated e–h recombination the dominant decay pathway.In this work,nonradiative e–h recombination within excitons in monolayer MoS2 is investigated using first-principles simulations that combine nonadiabatic molecular dynamics with𝐺𝑊and real-time Bethe–Salpeter equation(BSE)propagation.A two-step process is identified:rapid intervalley redistribution induced by exchange interaction,followed by slower phonon-assisted recombination facilitated by exciton binding.By selectively removing the screened Coulomb and exchange terms from the BSE Hamiltonian,their respective contributions are disentangled—exchange interaction is found to increase the number of accessible recombination pathways,while binding reduces the excitation energy and enhances nonradiative decay.A reduction in recombination lifetime by over an order of magnitude is observed due to the excitonic many-body effects.These findings provide microscopic insights for understanding and tuning exciton lifetimes in 2D transition-metal dichalcogenides.
基金Project supported by the National Key Research and Development Program of China(Grant Nos.2023YFA1406400 and 2020YFA0308800)the National Natural Science Foundation of China(Grant No.12474064)。
文摘The excitonic insulator(EI)is a more than 60-year-old theoretical proposal that is still elusive.It is a purely quantum phenomenon involving the spontaneous generation of excitons in quantum mechanics and the spontaneous condensation of excitons in quantum statistics.At this point,the excitons represent the ground state rather than the conventional excited state.Thus,the scarcity of candidate materials is a key factor contributing to the lack of recognized EI to date.In this review,we begin with the birth of EI,presenting the current state of the field and the main challenges it faces.We then focus on recent advances in the discovery and design of EIs based on the first-principles Bethe-Salpeter scheme,in particular the dark-exciton rule guided screening of materials.It not only opens up new avenues for realizing excitonic instability in direct-gap and wide-gap semiconductors,but also leads to the discovery of novel quantum states of matter such as half-EIs and spin-triplet EIs.Finally,we will look ahead to possible research pathways leading to the first recognized EI,both theoretically and computationally.
基金supported by the National Natural Science Foundation of China(Nos.22205058,22105064,52122308)the Funding Plan of Key Scientific Research Projects in Colleges and Universities of Henan Province(No.23A150001)+2 种基金Doctoral Scientific Research Start-up Foundation from Henan University of Technology(No.2021BS024)the Project of Youth Backbone Teachers of Henan University of Technology(No.21421250)the Innovative Funds Plan of Henan University of Technology(No.2022ZKCJ01)。
文摘Carbon dots(CDs),due to their low cost,high stability,and high luminous efficiency,have emerged as an excellent material for the emissive layer in next-generation electroluminescent light-emitting diodes(ELEDs).However,improving the efficiency of fluorescent CDs-based ELEDs remains challenging,primarily because it is difficult to utilize triplet excitons in the electroluminescence process.Therefore,enhancing the exciton utilization efficiency of CDs during electroluminescence is crucial.Based on this,we exploited the characteristic large exciton binding energy commonly found in CDs to develop exciton-emitting CDs.These CDs facilitate the radiative recombination of excitons during electroluminescence,thereby improving the electroluminescent efficiency.By rationally selecting precursors,we developed high quantum efficiency CDs and subsequently constructed CDs-based ELEDs.The blue-light device exhibited an external quantum efficiency of over 4%.This study introduces a novel design concept for CDs,providing a new strategy for developing high-performance blue ELEDs based on CDs.
基金supported by the National Natural Science Foundation of China(Grant Nos.12234011 and 12374053)the National Key Research and Development Program of China(Grant No.2024YFA1409100)。
文摘We investigate electronic structures and excitonic properties of monolayer SiP_(2)within the framework of firstprinciples GW plus Bethe-Salpeter equation(GW-BSE)calculations.Within the G_(0)W_(0)approximation,monolayer SiP_(2)is identified as a direct-gap semiconductor with an electronic gap of 3.14 e V,and the excitons exhibit a hybrid-dimensional character similar to that of the bulk counterpart.The optical absorption spectra reveal pronounced excitonic effects with strong anisotropy:the first bright exciton has a binding energy of 840 meV under x-polarized light,compared with 450 meV under y-polarized light.We further analyze the symmetry origins of the polarization-dependent optical selection rules through group theory.This binding energy difference arises from the intrinsic nature of the excitons:flat-band excitons under x-polarized light and conventional excitons localized at a single k point under y-polarized light.Our work enhances the understanding of excitonic behavior in monolayer SiP_(2)and highlights its potential for polarization-sensitive and directionally tunable optoelectronic applications.
基金NSFC(Nos.U1805255,11804086,21706044,21971057)General Financial Grant from the China Postdoctoral Science Foundation(No.2017M621316)+2 种基金the Natural Science Foundation of Heilongjiang Province,China(No.B2017006)the General Financial Grant from the Postdoctoral Science Foundation of Heilongjiang Province,China(No.LBHZ17187)the General Financial Grant from Heilongjiang Province for returned students from overseas in 2018。
文摘Efficient generation of singlet oxygen(1 O_(2)) by an excitonic ene rgy transfer process is highly desired on a semiconductor photocatalyst for selective oxidation of methyl phenyl sulfide(MPS).Herein,it is demonstrated that a large amount of 1 O_(2) is produced on pristine graphitic carbon nitride(CN) nanosheet compared with bismuth oxybromide(BiOBr) and comme rcial P25 titanium dioxide(TiO_(2)).This leads to a certain photoactivity of CN for MPS oxidation.The observed ~77% selectivity for CN depends on the competitive results of excitonic energy transfer for 1 O_(2) formation and charge carrier separation for superoxide radical(O_(2)·) production,which are based on the phosphorescence spectra and electron paramagnetic resonance signals,respectively.Moreover,ultrathin CN nanosheets are synthesized by thermal treatment with the cyanuric acid-melamine hydrogen bonded aggregates as precursors.It is confirmed that the amount of produced 1 O_(2) could be increased by decreasing the thickness of resultant CN nanosheets.The optimized ultrathin CN nanosheet(~4 nm) exhibits excellent photoactivity with high selectivity(~99%).It is suggested that the excitonic energy transfer for 1 O_(2) formation is close related to the intrinsic exciton binding energy and the two-dimensional quantum confinement effect.This work establishes a basic mechanistic understanding on the excitonic processes in CN,and develops a feasible route to design CN-based photocatalysts for efficient 1 O_(2) generation.
基金funded by the National Key Research and Development Program of China (2017YFA0204800/2016YFA0202403)the Fundamental Research Funds for the Central Universities (2018CBLZ006)+5 种基金the National Natural Science Foundation of China (61604091 and 61674098)the 111 Project (B14041)the Changjiang Scholar and Innovative Research Team (IRT_14R33)the Chinese National 1000 Talents Plan program (1110010341)the China Postdoctoral Science foundation (2018M633455)the Fundamental Research Funds for the Central Universities (GK201903055)
文摘Two-dimensional(2D) layered organic-inorganic hybrid perovskites have attracted much more attention for some applications than their three-dimensional(3D) perovskite counterparts due to their promising thermal and moisture stabilities.In particular, the 2D perovskite devices have shown better promise for optoelectronic applications.However, tunability of optoelectronic properties is often demanded to improve the device performance.Herein, we adopt a newly method to tune the electronic properties of 2D perovskite by introducing pseudohalide into the structure.In this work, we designed a pseudohalidesubstituted 2D perovskite by substituting the out-of-plane halide with pseudohalide and studied the electronic and excitonic properties of 2D-BA2MX4 and 2D-BA2MX2Ps2(M=Ge^(2+), Sn^(2+), and Pb^(2+);X=I;Ps=NCO, NCS, OCN, SCN, Se CN).We revealed the dependence of electronic properties including band gaps, composition of band edges, bonding characteristics, work functions, effective masses, and exciton binding energies on different pseudohalides substituted in 2D perovskite.Our results indicate that the substitution of pseudohalide in 2D perovskites is energetically favorable and can significantly affect the bonding characteristics as well as the CBM and VBM that often play major role in determining their performance in optoelectronic devices.It is expected that the pseudohalide substitution will be helpful in developing more advanced optoelectronic device based on 2D perovskite by optimizing band alignment and promoting charge extraction.
基金supported by the National Key Research and Development Program on Nano Science and Technology of the Ministry of Science and Technology of China(No.2016YFA0200602 and No.2018YFA0208702)the National Natural Science Foundation of China(No.21573211 and No.21633007)the Anhui Initiative in Quantum Information Technologies(No.AHY090200)。
文摘Two thin-film 2 D organic-inorganic hybrid perovskites,i.e.,2-phenylethylammonium lead iodide(PEPI)and 4-phenyl-1-butylammonium lead iodide(PBPI)were synthesized and investigated by steady-state absorption,temperature-dependent photoluminescence,and temperature-dependent ultrafast transient absorption spectroscopy.PBPI has a longer organic chain(via introducing extra ethyl groups)than PEPI,thus its inorganic skeleton can be distorted,bringing on structural disorder.The comparative analyses of spectral profiles and temporal dynamics revealed that the greater structural disorder in PBPI results in more defect states serving as trap states to promote exciton dynamics.In addition,the fine-structuring of excitonic resonances was unveiled by temperature-dependent ultrafast spectroscopy,suggesting its correlation with inorganic skeleton rather than organic chain.Moreover,the photoexcited coherent phonons were observed in both PEPI and PBPI,pointing to a subtle impact of structural disorder on the low-frequency Raman-active vibrations of inorganic skeleton.This work provides valuable insights into the optical properties,excitonic behaviors and dynamics,as well as coherent phonon effects in 2 D hybrid perovskites.
基金support by the National Natural Science Foundation of China(Grant No.12274477)the Department of Science and Technology of Guangdong Province of China(Grant No.2019QN01X061)。
文摘Using the Lindemann criterion,we analyzed the quantum and thermal melting of electronic/excitonic crystals recently discovered in two-dimensional(2D)semiconductor moirépatterns.We show that the finite 2D screening of the atomically thin material can suppress(enhance)the inter-site Coulomb(dipolar)interaction strength,thus inhibits(facilitates)the formation of the electronic(excitonic)crystal.Meanwhile,a strong enough moiréconfinement is found to be essential for realizing the crystal phase with a wavelength near 10 nm or shorter.From the calculated Lindemann ratio which quantifies the fluctuation of the site displacement,we estimate that the crystal will melt into a liquid above a critical temperature ranging from several tens Kelvin to above 100 K(depending on the system parameters).
基金supported by the National Natural Science Foundation of China (No.22175145 and No.21771155)
文摘The intermolecular interaction determines the photophysical properties of the organic aggregates,which are critical to the performance of organic photovoltaics.Here,excitonic coupling,an important intermolecular interaction in organic aggregates,between theπ-stacking graphene quantum dots is studied by using transient absorption spectroscopy.We find that the spectral evolution of the ground state bleach arises from the dynamic variation of the excitonic coupling in the excitedπ-stacks.According to the spectral simulations,we demonstrate that the kinetics of the vibronic peak can be exploited as a probe to measure the dynamics of excitonic coupling in the excitedπ-stacks.
基金Supported by the National Key Research and Development Program of China under Grant No 2016YFA0301202the National Natural Science Foundation of China under Grant Nos 11474275,61674135 and 91536101+1 种基金the Strategic Priority Research Program of the Chinese Academy of Sciences under Grant No XDPB0603the China Postdoctoral Science Foundation under Grant No 2017M622400
文摘The influence of the pressure transmission medium（PTM）on the excitonic interband transitions in monolayer tungsten diselenide（WSe2）is investigated using photoluminescence（PL）spectra under hydrostatic pressure up to 5GPa.Three kinds of PTMs,condensed argon（Ar）,1：1 n-pentane and isopentane mixture（PM）,and4：1 methanol and ethanol mixture（MEM,a PTM with polarity）,are used.It is found that when either Ar or PM is used as the PTM,the PL peak of exciton related to the direct K-K interband transition shows a pressure-induced blue-shift at a rate of 32±4 or 32±1 meV/GPa,while it turns to be 50±9meV/GPa when MEM is used as the PTM.The indirect A-K interband transition presents almost no shift with increasing pressure up to approximatel.y 5 GPa when Ar and PM are used as the PTM,while it shows a red-shift at the rate of-17±7meV/GPa by using MEM as the PTM.These results reveal that the optical interband transitions of monolayer WSe2 are very sensitive to the polarity of the PTM.The anomalous pressure coefficient obtained using the polar PTM of MEM is ascribed to the existence of hydrogen-like bonds between hydroxyl in MEM and Se atoms under hydrostatic pressure.
基金Supported by the National Key Scientific Research Projects of China under Grant No 2015CB932400the National Natural Science Foundation of China under Grant Nos 11504158,61474059,and U1432129+1 种基金the Program for New Century Excellent Talents in University of Ministry of Education of China under Grant No NCET-11-1003the Jiangxi Provincial'Ganpo Talentes 555Projects'
文摘We explore the excitonic effects in chiral graphene nanoribbons (cGNRs), whose edges are composed alternatively of armchair-edged and zigzag-edged segments. For cGNRs dominated by armchair edges, their energy gaps and exciton energies decrease with increasing chirality angles, and they, as functions of widths, oscillate with the period of three, while the exciton binding energies do not have such distinct oscillation. On the other hand, for cGNRs dominated by zigzag edges, all the energy gaps, exciton energies, and exciton binding energies show oscillation properties with their widths, due to the interactions between the edge states localized at the opposite zigzag edges. In addition, the triplet excitons are energy degenerate when the electrons are spin-unpolarized, while the degeneracy split when the electrons are spin-polarized. All the studied cGNRs show strong excitonic effects with the exciton binding energies of hundreds of meV.
基金Project supported by the Natural Science Research Projects in Colleges and Universities of Jiangsu Province,China(Grant No.18KJD140003)
文摘Two-dimensional(2D)2H-MoTe2 is a promising semiconductor because of its small bandgap,strong absorption,and low thermal conductivity.In this paper,we systematically study the optical and excitonic properties of atomically thin 2H-MoTe2(1–5 layers).Due to the fact that the optical contrast and Raman spectra of 2H-MoTe2 with different thicknesses exhibit distinctly different behaviors,we establish a quantitative method by using optical images and Raman spectra to directly identify the layers of 2H-MoTe2 thin films.Besides,excitonic states and binding energy in monolayer/bilayer 2H-MoTe2 are measured by temperature-dependent photoluminescence(PL)spectroscopy.At temperature T=3.3 K,we can observe an exciton emission at^1.19 eV and trion emission at^1.16 eV for monolayer 2H-MoTe2.While at room temperature,the exciton emission and trion emission both disappear for their small binding energy.We determine the exciton binding energy to be 185 meV(179 meV),trion binding energy to be 20 meV(18 me V)for the monolayer(bilayer)2H-MoTe2.The thoroughly studies of the excitonic states in atomically thin 2H-MoTe2 will provide guidance for future practical applications.
文摘Multiphoton excitations and nonlinear optical properties of exciton states in GaAs/AlxGa1-xAs coupled quantum well structure have been theoretically investigated under the influence of a time-varying high-intensity terahertz(THz)laser field.Non-perturbative Floquet theory is employed to solve the time-dependent equation of motion for the laser-driven excitonic quantum well system.The response to the field parameters,such as intensity and frequency of the laser electric field on the state populations,can be used in various optical semiconductor device applications,such as photodetectors,sensors,all-optical switches,and terahertz emitters.
基金Project supported by the National Natural Science Foundation of China (Grant No 60777017)the National Basic Research Program of China (Grant No 2007CB310405)+1 种基金China Postdoctoral Scientists Foundation (Grant No 20060390323)K. C.Wong Education Foundation, Hong Kong, China
文摘The excitonic optical absorption of GaAs bulk semiconductors under intense terahertz （THz） radiation is investigated numerically. The method of solving initial-value problems, combined with the perfect matched layer technique, is used to calculate the optical susceptibility. In the presence of a driving THz field, in addition to the usual exciton peaks, 2p replica of the dark 2p exciton and even-THz-photon-sidebands of the main exciton resonance emerge in the continuum above the band edge and below the main exciton resonance. Moreover, to understand the shift of the position of the main exciton peak under intense THz radiation, it is necessary to take into consideration both the dynamical Franz-Keldysh effect and ac Stark effect simultaneously. For moderate frequency fields, the main exciton peak decreases and broadens due to the field-induced ionization of the excitons with THz field increasing. However, for high frequency THz fields, the characteristics of the exciton recur even under very strong THz fields, which accords with the recent experimental results qualitatively.
基金supported by the National Natural Science Foundation of China(No.22073045)the Fundamental Research Funds for the Central Universities。
文摘In the past few years,the renormalized excitonic model(REM)approach was developed as an efficient low-scaling ab initio excited state method,which assumes the low-lying excited states of the whole system are a linear combination of various single monomer excitations and utilizes the effective Hamiltonian theory to derive their couplings.In this work,we further extend the REM calculations for the evaluations of first-order molecular properties(e.g.charge population and transition dipole moment)of delocalized ionic or excited states in molecular aggregates,through generalizing the effective Hamiltonian theory to effective operator representation.Results from the test calculations for four different kinds of one dimensional(1D)molecular aggregates(ammonia,formaldehyde,ethylene and pyrrole)indicate that our new scheme can efficiently describe not only the energies but also wavefunction properties of the low-lying delocalized electronic states in large systems.
基金supported by the Strategic Priority Research Program of Chinese Academy of Sciences(No.XDB43000000).
文摘Monolayer transition-metal dichalcogenides possess rich excitonic physics and unique valley-contrasting optical selection rule,and offer a great platform for long spin/valley lifetime engineering and the associated spin/valleytronics exploration.Using two-color time-resolved Kerr rotation and time-resolved reflectivity spectroscopy,we investigate the spin/valley dynamics of different excitonic states in monolayer WSe_(2)grown by molecular beam epitaxy.With fine tuning of the photon energy of both pump and probe beams,the valley relaxation process for the neutral excitons and trions is found to be remarkably different-their characteristic spin/valley lifetimes vary from picoseconds to nanoseconds,respectively.The observed long trion spin lifetime of>2.0 ns is discussed to be associated with the dark trion states,which is evidenced by the photon-energy dependent valley polarization relaxation.Our results also reveal that valley depolarization for these different excitonic states is intimately connected with the strong Coulomb interaction when the optical excitation energy is above the exciton resonance.
基金supported by the National Natural Science Foundation of China(Grant No.12064032).
文摘Two-dimensional(2D)Ga_(2)O_(3)has been confirmed to be a stable structure with five atomic layer thickness configuration.In this work,we study the quasi-particle electronic band structures and then access the excitonic optical properties through solving the Bethe-Salpeter equation(BSE).The results reveal that the exciton dominates the optical absorption in the visible light region with the binding energy as large as~1.0 eV,which is highly stable at room temperature.Importantly,both the dominant absorption P_(1)and P_(2)peaks are optically bright without dark exciton between them,and thus is favorable for luminescence process.The calculated radiative lifetime of the lowest-energy exciton is 2.0×10^(-11)s at 0 K.Furthermore,the radiative lifetime under+4%tensile strain is one order of magnitude shorter than that of the strainfree case,while it is less insensitive under the compressive strain.Our findings set the stage for future theoretical and experimental investigation on monolayer Ga_(2)O_(3).
基金National Natural Science Foundation ofChina (No.10274051) and Shanghai Nat-ural Science Foundation(No.03ZR14060)
文摘It is theoretically shown that excitonic Doppler-Rabi oscillations can occur in an organic slab moving along the axis of a high-Q cavity. Due to the N enhancement of the vacuum Rabi frequency, this effect can be more eas ily observed than that in a moving two-level atom.
基金support by the National Natural Science Foundation of China(Grant No.12064032).
文摘Quantum confinement effect and reduced dielectric screening in two-dimensional(2D)dramatically enhance theelectron-hole interactions.In this work,we use many-body perturbation theory and Bethe-Salpeter equation(BSE)toinvestigate the electronic and excitonic optical properties of monolayer SnP_(2)S_(6).Our findings reveal that the excitoniceffect dominates the optical absorption spectra in the visible light range,and the lowest-energy exciton X0 in monolayerSnP_(2)S_(6)is optically bright with the binding energy of 0.87 eV and the radiative lifetime of~10^(-11)s,which is highly advantageousto the photo-luminescence.Most importantly,the absence of optically forbidden states below the bright statesX0 would give rise to a high quantum efficiency of 2D SnP_(2)S_(6).We also find that applied biaxial strain can further shortenthe radiative lifetime of the bright states.These results imply that 2D SnP_(2)S_(6)is a promising candidate for the optoelectronicdevices.
基金supported by the National Natural Science Foundation of China(Grant No.61178039)the Natural Science Foundation of Shandong ProvinceChina(Grant No.ZR2012FM028)
文摘A series of GaAs/A1As multiple-quantum wells doped with Be is grown by molecular beam epitaxy. The photolu- minescence spectra are measured at 4, 20, 40, 80, 120, and 200 K, respectively. The recombination transition emission of heavy-hole and light-hole free excitons is clearly observed and the transition energies are measured with different quantum well widths. In addition, a theoretical model of excitonic states in the quantum wells is used, in which the symmetry of the component of the exciton wave function representing the relative motion is allowed to vary between the two- and three- dimensional limits. Then, within the effective mass and envelope function approximation, the recombination transition energies of the heavy- and light-hole excitons in GaAs/A1As multiple-quantum wells are calculated each as a function of quantum well width by the shooting method and variational principle with two variational parameters. The results show that the excitons are neither 2D nor 3D like, but are in between in character and that the theoretical calculation is in good agreement with the experimental results.
