Wannier-Mott excitons in semiconductors with a superlattice

The effect of the motion of a Wannier-Mott exciton in semiconductors with a superlattice formed by heterojunctions on the exciton binding energy and wave function is analyzed. This effect arises as a result of the fact that the dispersion laws of the electron and hole that form an exciton in a superlattice differ from the quadratic law. The investigated one-dimensional superlattice consists of alternating semiconductor layers with different energy positions of the conduction and valence bands, i.e., with one-dimensional wells and barriers. The exciton state in a superlattice consisting of quantum dots is analyzed. It is demonstrated that the closer the electron and hole effective masses, the greater the dependence of the binding energy on the exciton quasi-momentum. The possibility of replacing the tunneling excitation transfer between superlattice cells with the dipole-dipole one at certain exciton quasi-wave vector values is investigated.

     

Exciton binding energy in semiconductor quantum dots

In the adiabatic approximation in the context of the modified effective mass approach, in which the reduced exciton effective mass μ = μ(a) is a function of the radius a of the semiconductor quantum dot, an expression for the exciton binding energy E _ex(a) in the quantum dot is derived. It is found that, in the CdSe and CdS quantum dots with the radii a comparable to the Bohr exciton radii a _ex, the exciton binding energy E _ex(a) is substantially (respectively, 7.4 and 4.5 times) higher than the exciton binding energy in the CdSe and CdS single crystals.     

Exciton‐Charge Annihilation in Organic Semiconductor Films

Time‐resolved optical spectroscopy is used to investigate exciton‐charge annihilation reactions in blended films of organic semiconductors. In donor–acceptor blends where charges are photogenerated via excitons, pulsed optical excitation can deliver a sufficient density of temporally overlapping excitons and charges for them to interact. Transient absorption spectroscopy measurements demonstrate clear signatures of exciton‐charge annihilation reactions at excitation densities of ≈10¹⁸ cm^?3. The strength of exciton‐charge annihilation is consistent with a resonant energy transfer mechanism between fluorescent excitons and resonantly absorbing charges, which is shown to generally be strong in organic semiconductors. The extent of exciton‐charge annihilation is very sensitive not only to fluence but also to blend morphology, becoming notably strong in donor–acceptor blends with nanomorphologies optimized for photovoltaic operation. The results highlight both the value of transient optical spectroscopy to interrogate exciton‐charge annihilation reactions and the need to recognize and account for annihilation reactions in other transient optical investigations of organic semiconductors.     

High triplet energy electron transport type exciton blocking materials for stable blue phosphorescent organic light-emitting diodes

High triplet energy electron transport materials with dibenzothiophene and dibenzofuran cores modified with a diphenyltriazine unit were investigated as electron transport type exciton blocking materials for stable blue phosphorescent organic light-emitting diodes. The two exciton blocking materials showed high triplet energy above 2.80 eV and enhanced quantum efficiency of the blue phosphorescent devices by more than 40% while maintaining stability of the pristine blue devices without the high triplet energy exciton blocking layer.     

Over 17.4% Efficiency of Layer-by-Layer All-Polymer Solar Cells by Improving Exciton Utilization in Acceptor Layer

Layer-by-layer all-polymer solar cells (LbL all-PSCs) are prepared with PM6 and PY-IT by using sequential spin coating method. The exciton dissociation efficiency in acceptor layer near electrode is rather low due to the limited exciton diffuse distance and impossible energy transfer from narrow bandgap acceptor to wide bandgap donor. In this study, less PM6 is incorporated into PY-IT layer to enhance exciton dissociation in PY-IT layer near electrode. A power conversion efficiency (PCE) of 17.45% is achieved in the LbL all-PSCs incorporating 10 wt% PM6 into PY-IT layer, which is much larger than 16.04% PCE of PM6/PY-IT-based LbL all-PSCs. Over 8% PCE enhancement can be realized by incorporating 10 wt% PM6 into PY-IT layer, which is attributed to the enhanced exciton utilization efficiency in PY-IT layers near electrode. The enhanced exciton utilization efficiency in PY-IT layer can be confirmed from the quenched photoluminescence (PL) emission in PY-IT:PM6 films. Meanwhile, charge transport in acceptor layers can be optimized by incorporating less PM6, as confirmed from the optimized molecular arrangement. This study indicates that the strategy of incorporating less donor into acceptor layer has great potential in fabricating efficient LbL all-PSCs by improving exciton utilization efficiency in acceptor layer near electrode.     

Exciton–Exciton Annihilation in Mixed‐Phase Polyfluorene Films

Singlet–singlet annihilation is studied in polyfluorene (PFO) films containing different fractions of β‐phase chains using time‐resolved fluorescence. On a timescale of >15 ps after excitation, the results are fitted well by a time‐independent annihilation rate, which indicates that annihilation is controlled by 3D exciton diffusion. A time‐dependent annihilation rate is observed during the first 15 ps in the glassy phase and in the β‐phase rich films, which can be explained by the slowdown of exciton diffusion after excitons reach low‐energy sites. The annihilation rate in the mixed‐phase films increases with increasing fraction of β‐phase present, indicating enhanced exciton diffusion. The observed trend agrees well with a model of fully dispersedβ‐phase chromophores in the surrounding glassy phase with the exciton diffusion described using the line‐dipole approximation for an exciton wavefunction extending over 2.5 nm. The results indicate that glassy andβ‐phase chromophores are intimately mixed rather than clustered or phase‐separated.     

Near‐Field Energy Transfer Using Nanoemitters For Optoelectronics

Effective utilization of excitation energy in nanoemitters requires control of exciton flow at the nanoscale. This can be readily achieved by exploiting near‐field nonradiative energy transfer mechanisms such as dipole‐dipole coupling (i.e., Förster resonance energy transfer) and simultaneous two‐way electron transfer via exchange interaction (i.e., Dexter energy transfer). In this feature article, we review nonradiative energy transfer processes between emerging nanoemitters and exciton scavengers. To this end, we highlight the potential of colloidal semiconductor nanocrystals, organic semiconductors, and two‐dimensional materials as efficient exciton scavengers for light harvesting and generation in optoelectronic applications. We present and discuss unprecedented exciton transfer in nanoemitter–nanostructured semiconductor composites enabled by strong light–matter interactions. We elucidate remarkably strong nonradiative energy transfer in self‐assembling atomically flat colloidal nanoplatelets. In addition, we underscore the promise of organic semiconductor–nanocrystal hybrids for spin‐triplet exciton harvesting via Dexter energy transfer. These efficient exciton transferring hybrids will empower desired optoelectronic properties such as long‐range exciton diffusion, ultrafast multiexciton harvesting, and efficient photon upconversion, leading to the development of excitonic optoelectronic devices such as exciton‐driven light‐emitting diodes, lasers, and photodetectors.     

Band‐Edge Exciton Fine Structure and Exciton Recombination Dynamics in Single Crystals of Layered Hybrid Perovskites

2D perovskite materials have recently reattracted intense research interest for applications in photovoltaics and optoelectronics. As a consequence of the dielectric and quantum confinement effect, they show strongly bound and stable excitons at room temperature. Here, the band‐edge exciton fine structure and in particular its exciton and biexciton dynamics in high quality crystals of (PEA)₂PbI₄ are investigated. A comparison of bulk and surface exciton lifetimes yields a room temperature surface recombination velocity of 2 × 10³ cm s^?1 and an intrinsic lifetime of 185 ns. Biexciton emission is evidenced at room temperature, with a binding energy of ≈45 meV and a lifetime of 80 ps. At low temperature, exciton state splitting is observed, which is caused by the electron–hole exchange interaction. Transient photoluminescence resolves the low‐lying dark exciton state, with a bright/dark splitting energy estimated to be 10 meV. This work contributes to the understanding of the complex scenario of the elementary photoexcitations in 2D perovskites.     

Excitons in single and double GaAs/AlGaAs/ZnSe/Zn(Cd)MnSe heterovalent quantum wells

Exciton photoluminescence spectra, photoluminescence excitation spectra, and magnetophotoluminescence spectra of single (GaAs/AlGaAs/ZnMnSe) and double (GaAs/AlGaAs/ZnSe/ZnCdMnSe) heterovalent quantum wells formed by molecular beam epitaxy are studied. It is shown that the exciton absorption spectrum of such quantum wells mainly reproduces the resonant exciton spectrum expected for usual quantum wells with similar parameters, while the radiative exciton recombination have substantial distinctions, in particular the additional localization mechanism determined by defects generated by heterovalent interface exists. The nature of these localization centers is not currently clarified; their presence leads to broadening of photoluminescence lines and to an increase in the Stokes shift between the peaks of luminescence and absorption, as well as determining the variation in the magnetic g factor of bound exciton complexes.     

Structural and Optical Properties of ZnO Nanotips Grown on GaN Using Metalorganic Chemical Vapor Deposition

ZnO nanotips are grown on epitaxial GaN/c-sapphire templates by metalorganic chemical vapor deposition. X-ray diffraction (XRD) studies indicate that the epitaxial relationship between ZnO nanotips and the GaN layer is (0002)ZnO||(0002)GaN and (101̄0)ZnO||(101̄0)GaN. Temperature-dependent photoluminescence (PL) spectra have been measured. Sharp free exciton and donor-bound exciton peaks are observed at 4.4 K with photon energies of 3.380 eV, 3.369 eV, and 3.364 eV, confirming high optical quality of ZnO nanotips. Free exciton emission dominates at temperatures above 50 K. The thermal dissociation of these bound excitons forms free excitons and neutral donors. The thermal activation energies of the bound excitons at 3.369 eV and 3.364 eV are 11 meV and 16 meV, respectively. Temperature-dependent free A exciton peak emission is fitted to the Varshni’s equation to study the variation of energy bandgap versus temperature.     

“Exciton Recovery” Strategy in Hot Exciton Emitter toward High-Performance Non-Doped Deep-Blue and Host-Sensitized Organic Light-Emitting Diodes

The “hot exciton” mechanism based on high-lying reverse intersystem crossing process has great advantages in achieving high-performance deep-blue organic light-emitting diodes (OLEDs). Nevertheless, how to solve the loss of high-lying excitons to improve device performance further is a pressing and challenging issue. To break through this shackle, a novel deep-blue emitter based on “exciton recovery” strategy is successfully design, namely CAT. By combining the transient absorption spectrum, theoretical calculation, magneto-electroluminescence, and transient-electroluminescence measurements, the multi-channeled pathways of excitons utilization via hot exciton and triplet-triplet annihilation processes is comprehensively demonstrated, and the proportion of singlet excitons by each channel. Finally, a high exciton utilization efficiency is successfully achieved, and the non-doped OLED based on CAT exhibit an excellent external quantum efficiency of 10.39% with the CIE coordinates of (0.15, 0.087). Furthermore, the sensitized blue fluorescent OLED by CAT as host also achieves excellent performance. More importantly, the operational lifetime of the “multi-channel” sensitized device is evaluated for the first time, performing the remarkable LT₅₀ (lifetime to 50% of the initial luminance) of 320 h at 540 cd m⁻². These results fully reveal the significance of the “exciton recovery” strategy and give new inspiration for exploring high-performance blue OLEDs.     

Photoluminescence excitation spectroscopy of the dense exciton gasinvolved in the lasing transition in ZnSe epitaxial layers

The lasing transition in ZnSe epitaxial layers has been investigated at 77 K. The lowest lasing threshold (I_th) was achieved when the layers were resonantly excited at the photon energy of the exciton level. It was found that the exciton level at the excitation intensity just above the I_th was red-shifted by about 16 meV compared with the free exciton line (2.792 eV) under weak excitation condition. The energy difference between the exciton line and the lasing peak was about 19 meV at I=I_th and increased with increasing excitation intensity up to I=8×I_th. This suggests that the stimulated emission occurs due to the inelastic exciton-exciton scattering process at this temperature     

Determination of the minimum island size for full exciton localization due to thickness fluctuations in Zn1−xCdxSe quantum wells

Fluctuations of the thickness of quantum wells (QWs) of few monolayers are one of the causes of exciton localization. Here, we present the results of the determination of the minimum lateral dimensions of islands produced by thickness fluctuations in Zn_1−xCd_xSe QWs, which cause full exciton localization. We have calculated the localization energy of excitons in the frame of the factorized-envelope approximation. We found that the excitons are well localized in the islands of the QW when their lateral dimensions are larger than ∼15 times the exciton Bohr radius.     

Parameters of excitons in monoclinic zinc diarsenide

Optical functions of ZnAs₂ single crystal were calculated using the Kramers-Kronig relations on the basis of measured reflectance spectra. Absorption spectra were analyzed near the band gap taking into account the contributions of both the exciton ground state and continuum. The free exciton parameters were determined.     

Influence of polaron effects on the ground state of weak-coupling exciton in semiconductor quantum dots

The influence of polaron effects on the effective potential of weak-coupling exciton in semiconductor quantum dots (QDs) is studied based on the Lee-Low-Pines-Huybrechts variational method. The results show that the effective potential of the exciton consists of three parts: coulomb potential, induced potential and confining potential. Numerical calculations for the GaAs quantum dot, as an example, are performed. The result indicates that the effective potential of the exciton increases with the electron-hole distance. It is found that the polaron effects have remarkable influence on the states of the exciton: helpful to the stability of the light-hole exciton, but unfavorable to the stability of the heavy-hole exciton.     

GaN基量子阱激子结合能和激子光跃迁强度

采用变分法,计算了GaN基量子阱中激子结合能和激子光跃选强度。计算结果表明,GaN基量子阱中激子结合能为10－55meV,大于体材料中激子结合能,并随着阱宽减小而增加,在临界阱宽处达到最大。结间带阶同样对激子结合能有着较大的影响,更大带阶对应更大的结合能。同时量子限制效应增加了电子空穴波函数空间重叠,因此加强了激子光跃迁振子强度,导致GaN/AlN量子阱中激子光吸收明显强于体材料中激子光吸收。     

Management of Host–Guest Triplet Exciton Distribution for Stable,High-Efficiency,Low Roll-Off Solution-Processed Blue Organic Light-Emitting Diodes by Employing Triplet-Energy-Mediated Hosts

High-quality hosts are indispensable for simultaneously realizing stable, high efficiency, and low roll-off blue solution-processed organic light-emitting diodes (OLEDs). Herein, three solution processable bipolar hosts with successively reduced triplet energies approaching the T₁ state of thermally activated delayed fluorescence (TADF) emitter are developed and evaluated for high-performance blue OLED devices. The smaller T₁ energy gap between host and guest allows the quenching of long-lived triplet excitons to reduce exciton concentration inside the device, and thus suppresses singlet-triplet and triplet-triplet annihilations. Triplet-energy-mediated hosts with high enough T₁ and better charge balance in device facilitate high exciton utilization efficiency and uniform triplet exciton distribution among host and TADF guest. Benefited from these synergetic factors, a high maximum external quantum efficiency (EQE_max) of 20.8%, long operational lifetime (T₅₀ of 398.3 h @ 500 cd m⁻²), and negligible efficiency roll-off (EQE of 20.1% @ 1000 cd m⁻²) are achieved for bluish-green TADF OLEDs. Additionally introducing a narrowband emission multiple-resonance TADF material as terminal emitter to accelerate exciton dynamic and improve exciton utilization, a higher EQE_max of 23.1%, suppressed roll-off and extended lifetime of 456.3 h are achieved for the sky-blue sensitized OLEDs at the same brightness.     

Surface relaxation frequency of ground-state exciton in quantum wells

We derive and analyze the relaxation frequency ν of exciton in a quantum well using the self-consistent Green's function method. The exciton relaxation is caused by the individual electron and hole scattering from the randomly-rough well interface. We reveal two types of ground-state exciton resonance and obtain the criteria for the transition from the asymmetric (sharp) resonance to the symmetric (broad) one. The dependence of the excitron–surface relaxation on the microscopic parameters of the interface defects, the average well width d and on the exciton characteristics is analyzed analytically. Specifically, in the case of sharp resonance the frequency ν∝d⁻⁶, whereas for broad resonance ν∝d⁻³. Moreover, ν is proportional to the ratio of the total exciton mass M over the squared reduced mass μ² (ν∝M/μ²).     

Impurity induced disordering of GaInAs quantum wells with barriers of AlGaInAs or of GaInAsP

Impurity induced disordering of GaInAs quantum well structures with barriers of AlGaInAs and of GaInAsP has been investigated using boron and fluorine. The impurities were introduced by ion implantation followed by thermal annealing. Annealing unimplanted P-based quaternary material at temperatures greater than 500° C caused a blue shift of the exciton peak. At annealing temperatures greater than 650° C red shifts in the exciton peak of unimplanted Al-based quaternary material were observed. Boron implantation caused small blue shifts of the exciton peak in both material systems at low annealing temperatures. Much larger blue shifts were observed in the fluorine implanted samples.     

Enhanced power conversion efficiency of organic solar cells by embedding Ag nanoparticles in exciton blocking layer

We demonstrate the power conversion efficiency of bulk heterojunction organic solar cells can be enhanced by introducing Ag nanoparticles into organic exciton blocking layer. The Ag nanoparticles were incorporated into the exciton blocking layer by thermal evaporation. Compared with the conventional cathode contact materials such as Al, LiF/Al, devices with Ag nanoparticles incorporated in the exciton blocking layer showed lower series resistances and higher fill factors, leading to a 3.2% power conversion efficiency with a 60 nm active layer; whereas, the conventional devices have only 2.0–2.3% power conversion efficiency. Localized surface plasmon resonances by the Ag nanoparticles and their contribution to photocurrent were also discussed by simulating optical absorptions using a FDTD (finite-difference-time-domain) method.