Efficient energy transfer from self-trapped excitons to Mn^(2+) dopants in CsCdCl_(3):Mn^(2+) perovskite nanocrystals

Mn^(2+)doping has been adopted as an efficient approach to regulating the luminescence properties of halide perovskite nano-crystals(NCs).However,it is still difficult to understand the interplay of Mn^(2+)luminescence and the matrix self-trapped exciton(STE)emission therein.In this study,Mn^(2+)-doped CsCdCl_(3) NCs are prepared by hot injection,in which CsCdCl_(3) is selected because of its unique crystal structure suitable for STE emission.The blue emission at 441 nm of undoped CsCdCl_(3) NCs originates from the defect states in the NCs.Mn^(2+)doping promotes lattice distortion of CsCdCl_(3) and generates bright orange-red light emission at 656 nm.The en-ergy transfer from the STEs of CsCdCl_(3) to the excited levels of the Mn^(2+)ion is confirmed to be a significant factor in achieving efficient luminescence in CsCdCl_(3):Mn^(2+)NCs.This work highlights the crucial role of energy transfer from STEs to Mn^(2+)dopants in Mn^(2+)-doped halide NCs and lays the groundwork for modifying the luminescence of other metal halide perovskite NCs.

Size dependence of biexciton binding energy in single InAs/GaAs quantum dots

This paper studies the size dependence of biexciton binding energy in single quantum dots （QDs） by using atomic force microscopy and micro-photoluminescence measurements. It finds that the biexciton binding energies in the QDs show ＂binding＂ and ＂antibinding＂ properties which correspond to the large and small sizes of QDs, respectively. The experimental results can be well interpreted by the biexciton potential curve, calculated from the exciton molecular model and the Heitler London method.

Exciton Energy Transfer in Hybrid Organics—Semiconductor Nanostructure

We consider a hybrid heterostructure containing an inorganic quantum well in close proximity with organic material as overlayer. The resonant optical pumping of Frenkel exciton can lead to an efficient indirect pumping of Wannier excitons. As organic material in such a hybrid structure, we consider crystalline tetracene. In tetracene, the singlet exciton energy is close to twice the one of triplet exciton state and singlet exciton fission into two triplets can be efficient. This process in tetracene is thermally activated and we investigate here how the temperature-dependent exciton energy transfer affects the functional properties of hybrid organic-inorganic nanostructures. We have obtained the exact analytical solution of diffusion equation for organics at different temperatures defining different diffusion lengths of excitons. The effectiveness of energy transfer in hybrid with tetracene was calculated by definite method for two selected temperatures that open possibility to operate in full region of temperatures. Temperature dependence of energy transfer opens a new possibility to turn on and off the indirect pumping due to energy transfer from the organic subsystem to the inorganic subsystem.

Steric hindrance induced low exciton binding energy enables low-driving-force organic solar cells

Exciton binding energy(E_(b))has been regarded as a critical parameter in charge separation during photovoltaic conversion.Minimizing the E_(b) of the photovoltaic materials can facilitate the exciton dissociation in low-driving force organic solar cells(OSCs)and thus improve the power conversion efficiency(PCE);nevertheless,diminishing the E_(b) with deliberate design principles remains a significant challenge.Herein,bulky side chain as steric hindrance structure was inserted into Y-series acceptors to minimize the E_(b) by modulating the intra-and intermolecular interaction.Theoretical and experimental results indicate that steric hindrance-induced optimal intra-and intermolecular interaction can enhance molecular polarizability,promote electronic orbital overlap between molecules,and facilitate delocalized charge trans-fer pathways,thereby resulting in a low E_(b).The conspicuously reduced E_(b) obtained in Y-ChC5 with pinpoint steric hindrance modulation can minimize the detrimental effects on exciton dissociation in low-driving-force OSCs,achieving a remarkable PCE of 19.1%with over 95%internal quantum efficiency.Our study provides a new molecular design rationale to reduce the E_(b).

Simultaneously optimizing exciton diffusion length and nonradiative energy loss in organic solar cells via ternary strategy

Significant nonradiative energy loss and short exciton diffusion length in organic solar cells(OSCs)are two major obstacles to achieving state-of-the-art efficiencies.It is crucial to conduct a study on the intensive mechanism and improvement strategies for future breakthroughs in the efficiency of OSCs.In this work,nonradiative energy loss and exciton diffusion length are optimized simultaneously by incorporating a guest acceptor(LA15)to construct ternary OSC(D18:L8-BO:LA15).Firstly,LA15 exhibits excellent compatibility with the host acceptor L8-BO,and effectively improves the fluorescence quantum efficiency(FLQY),resulting in suppressed non-radiative energy loss.Moreover,LA15 effectively prolongs the fluorescent lifetime of the acceptor phase from 0.85 to 1.12 ns,leading to larger exciton diffusion length,which is beneficial for reducing geminate recombination.Besides,the addition of LA15 optimizes the crystallinity of the active layer with amplified charge transport capacity.As a result,the optimized D18:L8-BO:LA15 device achieves ultralow nonradiative energy loss of 0.18 e V and improved fill factor(FF)with high efficiency up to 19.13%.These results highlight the crucial roles of regulating FLQYand exciton lifetime in achieving highefficiency OSCs.

Tuning the exciton binding energy of covalent organic frameworks for efficient photocatalysis

Owing to the large exciton binding energy(>100 meV)of most organic materials,the process of exciton dissociation into free electrons and holes is seriously hindered,which plays a key role in the photocatalytic system.In this study,a series of chalcogen(S,Se)-substituted mesoporous covalent organic frameworks(COFs)have been synthesized for enhanced photocatalytic organic transformations.Photoelectrochemical measurements indicate that the introduction of semi-metallic Se atom and the enlargement of conjugation degree can not only reduce the exciton binding energy accelerating the charge separation,but also reduce the band gap of COFs.As a result,the COF-NUST-36 with the lowest exciton binding energy(39.5 meV)shows the highest photocatalytic performance for selective oxidation of amines(up to 98%Conv.and 97.5%Sel.).This work provides a feasible method for designing COFs with high photocatalytic activity by adjusting exciton binding energy.

Reduced exciton binding energy and diverse molecular stacking enable high-performance organic solar cells with V_(OC)over 1.1 V

High-voltage organic solar cells(OSCs)have received increasing attention because of their promising applications in tandem devices and indoor photovoltaics,but the trade-off between energy loss and charge generation induced by exciton binding energy(E_(b))has become one of the biggest bottlenecks limiting the development of this field.Here,a wide bandgap(WBG)nonfullerene acceptor BTA503 with reduced E_(b) is designed by changing the phenyl side chain on the central core of Cl-BTA5 to an alkyl chain.The diverseπ-πinteractions and enhanced molecular stacking of BTA503 are responsible for its reduced E_(b).Furthermore,both the diminished charge recombination and the fast exciton dissociation caused by the small E_(b) favor the generation of more charge carriers for the PTQ10:BTA503 combination.The efficient Forster resonance energy transfer(FRET)and multiple π-π stacking patterns provide additional charge transfer and transport pathways.Ultimately,the PTQ10:BTA503-based OSC device achieves a V_(OC)of 1.112 V and a PCE of 12.70%,which is higher than that of PTQ10:Cl-BTA5(PCE=10.92%).Simultaneously,the thick film(~300 nm)binary device of PTQ10:BTA503 achieves a PCE of 10.13% with a V_(OC)of 1.102 V,which is the best result for thick film high-voltage OSCs.More importantly,the ternary device of PTQ10:BTA503:Cl-BTA5(1:0.9:0.1)realizes a champion PCE of 13.12% with a V_(OC)of 1.126 V.Our study demonstrates that it is an effective strategy to reduce E_(b) of A_(2)-A_(1)-D-A_(1)-A_(2) type WBG acceptors by modulating the side chains on D unit,which further favors the corresponding devices to obtain world-record PCE and improves their potential for commercial applications.

Impact of exciton fine structure on the energy transfer in magicsized(CdSe)13 clusters

Magic-sized(CdSe)13 clusters(MSCs)represent a material class at the boundary between molecules and quantum dots that exhibit a pronounced and well separated excitonic fine structure.The characteristic photoluminescence is composed of exciton bandgap emission and a spectrally broad mid-gap emission related to surface defects.Here,we report on a thermally activated energy transfer from fine-structure split exciton states to surface states by using temperature dependent photoluminescence excitation spectroscopy.We demonstrate that the broad mid-gap emission can be suppressed by a targeted Mn-doping of the MSC leading to the characteristic orange luminescence of the^(4)T_(1)→^(6)A_(1)Mn^(2+)transition.The energy transfer to the Mn^(2+)states is found to be significantly different than the transfer to the surface defect states,as the activation of the dopant emission requires a spin-conserving charge carrier transfer that only dark excitons can provide.

Dielectric confinement on exciton binding energy and nonlinear optical properties in a strained Zn_(1-x_(in))Mg_(x(in))Se/Zn_(1-x(out))Mg_(x(out))Se quantum well

The band offsets for a Zn1-xin Mgxin Se/Zn1-xout Mgxout Se quantum well heterostructure are determined using the model solid theory. The heavy hole exciton binding energies are investigated with various Mg alloy contents. The effect of mismatch between the dielectric constants between the well and the barrier is taken into account. The dependence of the excitonic transition energies on the geometrical confinement and the Mg alloy is discussed. Non-linear optical properties are determined using the compact density matrix approach. The linear, third order non-linear optical absorption coefficient values and the refractive index changes of the exciton are calculated for different concentrations of magnesium. The results show that the occurred blue shifts of the resonant peak due to the Mg incorporation give the information about the variation of two energy levels in the quantum well width.

Thermally-enhanced photo-electric response of an organic semiconductor with low exciton binding energy for simultaneous and distinguishable detection of light and temperature

Simultaneous and distinguishable detection of external stimuli such as light and temperature is of great interest for a variety of scientific and industrial applications.Theoretically,an organic semiconductor with low exciton binding energy,low thermal activation energy and good charge transporting property produces thermally enhanced photo-electric response in organic phototransistors(OPTs),which thus provides an ideal and effective way to realize the simultaneous and distinguishable detection of temperature and light.However,there is no report on such a kind of organic semiconductor until now.Herein,we designed and synthesized a narrow band gap organic small molecule semiconductor 2,5-bis(2-butyloctyl)-3,6-bis(5-(4-(diphenylamino)phenyl)thiophen-2-yl)-2,5-dihydropyrrolo[3,4-c]pyrrole-1,4-dione(DPP-T-TPA)with low exciton binding energy(about 37 meV)and small activation energy(about 61 meV)for distinct thermal-dependence of charge carrier and exciton.The low exciton binding energy enables the semiconductor to exhibit strong thermal dependence of exciton dissociation,which contributes to the thermally-enhanced photo-electric response.Furthermore,the low thermal activation energy produces the weak thermal dependence of charge transport,which avoids the disturbance of thermally-modulated charge transport on photo-electric response.Benefiting from these two features,phototransistors based on DPP-T-TPA show great potential in simultaneous and distinguishable detection of light and temperature,which represents a novel and efficient way for bifunctional detection.

Long-lived Single Excitons, Trions, and Biexcitons in CdSe/CdTe Type-II Colloidal Quantum Wells

Light-harvesters with long-lived excited states are desired for efficient solar energy conversion systems. Many solar-to-fuel conversion reactions, such as H2 evolution and CO2 reduction, require multiple sequential electron transfer processes, which leads to a complicated situation that excited states involves not only excitons （electron-hole pairs） but also multi-excitons and charged excitons. While long-lived excitons can be obtained in various systems （e.g., semiconductor nanocrystals）, multi-excitons and charged excitons are typically shorted-lived due to nonradiative Auger recombination pathways whereby the recombination energy of an exciton is quickly transferred to the third carrier on a few to hundreds of picoseconds timescale. In this work, we report a study of excitons, trions （an exciton plus an additional charge）, and biexcitons in CdSe/CdTe colloidal quantum wells or nanoplatelets. The type- II band alignment effectively separates electrons and holes in space, leading to a single exciton lifetime of 340 ns which is -2 order of magnitudes longer than that in plane CdSe nanoplatelets. More importantly, the electron-hole separation also dramatically slows down Auger decay, giving rise to a trion lifetime of 70 ns and a biexciton lifetime of 11 ns, among the longest values ever reported for colloidal nanocrystals. The long-lived exciton, trion, and biexciton states, combined with the intrinsically strong light-absorption capability of two-dimensional systems, enable the CdSe/CdTe type-II nanoplatelets as promising light harvesters for efficient solar-to-fuel conversion reactions.

Efficient singlet oxygen generation by excitonic energy transfer on ultrathin g-C_(3)N_(4) for selective photocatalytic oxidation of methyl-phenyl-sulfide with O_(2)

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.

Polaronic Effects of an Exciton in a Cylindrical Quantum Wire

The effects of exciton-optical phonon interaction on the binding energy and the total and reduced effective masses of an exciton in a cylindrical quantum wire have been investigated. We adopt a perturbative-PLL [T.D. Lee,F. Low, and D. Pines, Phys. Rev. B90 (1953) 297] technique to construct an effective Hamiltonian and then use a variational solution to deal with the exciton-phonon system. The interactions of exciton with the longitudinal-optical phonon and the surface-optical phonon have been taken into consideration. The numerical calculations for GaAs show that the influences of phonon modes on the exciton in a quasi-one-dimensional quantum wire are considerable and should not be neglected. Moreover the numerical results for heavy- and light-hole exciton are obtained, which show that the polaronic effects on two types of excitons are very different but both depend heavily on the sizes of the wire.

Fractional-dimensional approach for excitons in Ga As films on AlxGa(1-x)As substrates

Binding energies of excitons in GaAs films on AlxGal-xAs substrates are studied theoretically with the fractional- dimensional approach. In this approach, the real anisotropic ＂exciton ＋ film＂ semiconductor system is mapped into an effective fractional-dimensional isotropic space. For different aluminum concentrations and substrate thicknesses, the exci- ton binding energies are obtained as a function of the film thickness. The numerical results show that, for different aluminum concentrations and substrate thicknesses, the exciton binding energies in GaAs films on AlxGal_xAs substrates all exhibit their maxima with increasing film thickness. It is also shown that the binding energies of heavy-hole and light-hole excitons both have their maxima with increasing film thickness.

Study of Squeezed Excitons in Polar Semiconductors

Some properties of excitons in polar semiconductors are studied theoretically by means of squeezed state variational approach. This method makes it possible to consider bilinear terms of the phonon operators as well as linear terms arising from the Lee-Low-Pines （LLP）-like transformation. The exciton ground state energy and binding energy are calculated numerically. It is shown that the squeezing effect is significant in the case of strong exciton-phonon coupling region.

Ionized Acceptor Bound Exciton States in Wurtzite GaN/Al_xGa(1-x)N Cylindrical Quantum Dot

Based on the framework of the effective-mass approximation, the ionized acceptor bound exciton （A- X） binding energy and the emission wavelength are investigated for a cylindrical wurtzite （WZ） GaN/A1x Ga1-xN quantum dot （QD） with finite potential barriers by means of a variational method. Numerical results show that the binding energy and the emission wavelength highly depend on the QD size, the position of the ionized acceptor and the Al composition x of the barrier material AIxGal-xN. The binding energy and the emission wavelength are larger when the acceptor is located in the vicinity of the left interface of the QD. In particular, the binding energy of （ A-, X） complex is insensitive to the dot height when the acceptor is located at the left boundary of the QD. The ionized acceptor bound exciton binding energy and the emission wavelength are both increased if Al composition x is increased.

Efficient transfer of metallophosphor excitons via confined polaritons in organic nanocrystals

We investigate the transfer of phosphorescent energy between co-assembled metallophosphors in crystalline nanostructures [Angew. Chem. Int. Ed. 57 7820(2018) and J. Am. Chem. Soc. 140 4269(2018)]. Neither Dexter's nor Forster's mechanism of resonance energy transfer(RET) could account fully for the observed rates, which exceed 85% with significant temperature dependence. But there exists an alternative pathway on RET mediated by intermediate states of resonantly confined exciton–polaritons. Such a mechanism was used to analyze artificial photosynthesis in organic fluorescents [Phys.Rev. Lett. 122 257402(2019)]. For metallophosphors, the confined modes act as extended states lying between the molecular S_(1) and T_(1) states, offering a bridge for the long-lived T_(1) excitons to migrate from donors to acceptors. Population dynamics with parameters taken entirely based on experiments fits the observed lifetimes of phosphorescence across a broad range of doping and temperature.

Properties of Excitons Bound to Neutral Donors in GaAs-AlxGa1-xAs Quantum-Well Wires

In the effective-mass approximation, using a simple two-parameter wave function and a one-dimensional （ID） equivalent potential model, we calculate variationally the binding energy of an exciton bound to a neutral donor （D^0, X） in finite GaAs-AIxGa1-xAs quantum well wires （QWWs）. At the wire width of 25 A, the binding energy has a peak value, which is also at the position of the peak of the exciton binding energy, and the center-of-mass wave functions of excitons reaches the most centralized distribution. In addition, the changing tendency of the average interparticle distance as the wire width is reverse to that of the binding energy.

Numerical Verification of Transition’s Energies of Excitons in Quantum Well of ZnO with the Finite Difference Method

This paper shows that the experimental results of quantum well energy transitions can be found numerically. The cases of several ZnO-ZnMgO wells are considered and their excitonic transition energies were calculated using the finite difference method. In that way, the one-dimensional Schrödinger equation has been solved by using the BLAS and LAPACK libraries. The numerical results are in good agreement with the experimental ones.

Investigation of Dynamical Parameters of Exciton Confined in CdS Spherical Quantum Dots with a B—Spline Technique

Exciton energies as a function of radii of quantum dots in the range of 5–35 ? are calculated based on effective mass approximation model with the B-spline technique and compared with experimental and other theoretical data for the CdS dots. This method leads to accurate and fast convergent exciton energy, which are in good agreement with experimental data in the whole confinement regime. The effect of penetration of wave function from the inside to the outside of the dots and the effect of dielectric constants are taken into account. The magnitudes of dynamical parameters are discussed. It is found that the different materials surrounding the CdS quantum dot affect not only the potential energy and Coulomb interaction energy of the system, but also the effective masses. The comparison shows that the effective mass approximation model can describe very well the quantum size effects observed experimentally on the exciton ground state energy.