Hot Carrier Trapping Research Articles

(Invited) From Inside Out: How Synthesis-Structure Correlations Conspire to Determine Photoluminescence Traits and Operational Robustness in Non-Blinking Giant Quantum Dots

“Giant” or thick-shell core/shell quantum dots (gQDs) are an important class of solid-state quantum emitter. Without any encapsulation gQDs are characterized by strongly suppressed blinking, or even non-blinking behavior, and resistance to photobleaching at room temperature. In addition, non-radiative Auger processes are significantly reduced in this class of luminescent nanomaterial. Together, these qualities lead to novel functionality as photon sources for a range of ensemble and single-emitter applications, including down-conversion phosphors, direct excitation light-emitting diodes, single-biomolecule tracking, and single-photon generation. For many applications, operation at elevated temperature and under intense photon flux is also desired, and we have shown that gQDs outperform other emitters in this key metric of operational robustness. Interestingly, performance under these conditions is strongly dependent on the synthetic method employed for shell growth. Previously we revealed the mechanistic pathways responsible for thermally-assisted photodegradation, distinguishing effects of hot-carrier trapping and QD charging (ACS Nano 2018, 12, 5, 4206), and subsequently used solid-state spectroscopy to obtain kinetic and thermodynamic parameters of the photothermal degradation process (ACS Appl. Mater. Interfaces 2020, 12, 27, 30695). Here, I will discuss a comprehensive analysis of gQD structural properties from the inside of the nanocrystal to its surface and demonstrate correlations between specific structural features and both causal synthetic parameters and resulting performance metrics. Two synthetic methods—successive-ionic-layer-adsorption-and-reaction and high-temperature continuous-injection—will be compared. Investigated structural features will include interfacial alloying, stacking-fault density and surface-ligand identity, while correlated functionalities will address quantum yield, single-gQD photoluminescence under thermal/photo-stress, charging behavior and quantum-optical properties. I will show several unexpected conclusions, including the surprising finding that while interfacial alloying is the strongest indicator of gQD stability under stress, the parameter is not the determining factor for Auger suppression. Furthermore, quantum yield is strongly influenced by surface chemistry and can approach unity even in the case of a gQD comprising a thick shell with a high defect density with proper choice of excitation wavelength. Interestingly, we find a strong correlation between the existence of zinc-blende stacking faults and whether the gQD exhibits charged-state or purely excitonic emission, and the interplay between charged emission and excitonic emission can be precisely tuned by “mixing” shell-growth methods (Small Sci. 2023,3, 2300092).

Competition among recombination pathways in single FAPbBr3 nanocrystals.

Single particle level microscopy of immobilized FAPbBr3 nanocrystals (NCs) has elucidated the involvement of different processes in their photoluminescence (PL) intermittency. Four different blinking patterns are observed in the data from more than 100 NCs. The dependence of PL decays on PL intensities brought out in fluorescence lifetime intensity distribution (FLID) plots is rationalized by the interplay of exciton- and trion-mediated recombinations along with hot carrier (HC) trapping. The high intensity-long lifetime component is attributed to neutral exciton recombination, the low intensity-short lifetime component is attributed to trion assisted recombination, and the low intensity-long lifetime component is attributed to hot carrier recombination. Change-point analysis (CPA) of the PL blinking data reveals the involvement of multiple intermediate states. Truncated power law distribution is found to be more appropriate than power law and lognormal distribution for on and off events. Probability distributions of PL trajectories of single NCs are obtained for two different excitation fluences and wavelengths (λex = 400, 440nm). Trapping rate (kT) prevails at higher power densities for both excitation wavelengths. From a careful analysis of the FLID and probability distributions, it is concluded that there is competition between the HC and trion assisted blinking pathways and that the contribution of these mechanisms varies with excitation wavelength as well as fluence.

Hot Carrier Trapping and It's Influence to the Carrier Diffusion in CsPbBr3 Perovskite Film Revealed by Transient Absorption Microscopy.

The defects in perovskite film can cause charge carrier trapping which shortens carrier lifetime and diffusion length. So defects passivation has become promising for the perovskite studies. However, how defects disturb the carrier transport and how the passivating affects the carrier transport in CsPbBr3 are still unclear. Here the carrier dynamics and diffusion processes of CsPbBr3 and LiBr passivated CsPbBr3 films are investigated by using transient absorption spectroscopy and transient absorption microscopy. It's found that there is a fast hot carrier trapping process with the above bandgap excitation, and the hot carrier trapping would decrease the population of cold carriers which are diffusible, then lower the carrier diffusion constant. It's proved that LiBr can passivate the defect and lower the trapping probability of hot carriers, thus improve the carrier diffusion rate. The finding demonstrates the influence of hot carrier trapping to the carrier diffusion in CsPbBr3 film.

Photoluminescence Blinking of Quantum Confined CsPbBr3 Perovskite Nanocrystals: Influence of Size

Quantum confined CsPbBr3 nanocrystals (NCs) with adjustable photoluminescence (PL) in the range of 470–500 nm are particularly desirable for applications in light-emitting diodes and many quantum technologies. Exploration of the full potential of these perovskite NCs requires an understanding of the random fluctuation of their PL at the single-particle level, commonly termed as blinking. In this work, we study the PL blinking of quantum confined single NCs of CsPbBr3 of three different sizes between 3.80 and 5.90 nm in immobilized and fluid conditions to understand the recombination pathways and dynamics of the photogenerated charge carriers. In the immobilized state, the PL intensity trajectories and PL lifetime-intensity distributions of these single NCs reveal the contributions of both Auger recombination and trapping of hot carriers to the PL fluctuation. The results suggest a higher carrier trapping rate constant for smaller NCs. The fluorescence correlation spectroscopy and fluorescence lifetime correlation spectroscopy measurements on freely diffusing NCs show a higher off-state fraction and lower per-particle brightness of the smaller NCs. It is concluded that a larger trap depth and higher probability density of the carriers at the surface in smaller NCs make the trapping process more feasible and detrapping more difficult. The results provide first information on the effect of size on PL blinking of the quantum confined CsPbBr3 NCs, and this knowledge is expected to be useful in better designing photoluminescent samples of this class for optoelectronic applications.

Broadband Tunable Optical Gain from Ecofriendly Semiconductor Quantum Dots with Near-Half-Exciton Threshold.

Optical gain in solution-processable quantum dots (QDs) has attracted intense interest toward next-generation optoelectronics; however, the development of optical gain in heavy-metal-free QDs remains challenging. Herein, we reveal that the ZnSe1-xTex-based QDs show excellent optical gain covering the violet to near-red regime. A new gain mechanism is established in the alloy QDs, which promotes a theoretically threshold-less optical gain thanks to the ultrafast carrier localization and suppression of ground-state absorption by the Te-derived isoelectronic state. Further, we disclose that the hot-carrier trapping represents the main culprit to exacerbate the gain performance. With the increase of Te-to-Se ratio, a sub-band-gap photoinduced absorption (PA) appears and extinguishes the optical gain. To overcome this issue, we modulate the inner ZnSe shell thickness, and the gain is recovered by reducing the overlap between the gain and PA regions in the Te-rich QDs. Our finding represents a significant step toward sustainable QD-based optoelectronics.

Hot Carrier Cooling and Trapping in Atomically Thin WS2 Probed by Three-Pulse Femtosecond Spectroscopy

Transition metal dichalcogenides (TMDs) have shown outstanding semiconducting properties which make them promising materials for next-generation optoelectronic and electronic devices. These properties are imparted by fundamental carrier-carrier and carrier-phonon interactions that are foundational to hot carrier cooling. Recent transient absorption studies have reported ultrafast time scales for carrier cooling in TMDs that can be slowed at high excitation densities via a hot-phonon bottleneck (HPB) and discussed these findings in the light of optoelectronic applications. However, quantitative descriptions of the HPB in TMDs, including details of the electron-lattice coupling and how cooling is affected by the redistribution of energy between carriers, are still lacking. Here, we use femtosecond pump-push-probe spectroscopy as a single approach to systematically characterize the scattering of hot carriers with optical phonons, cold carriers, and defects in a benchmark TMD monolayer of polycrystalline WS2. By controlling the interband pump and intraband push excitations, we observe, in real-time (i) an extremely rapid "intrinsic" cooling rate of ∼18 ± 2.7 eV/ps, which can be slowed with increasing hot carrier density, (ii) the deprecation of this HPB at elevated cold carrier densities, exposing a previously undisclosed role of the carrier-carrier interactions in mediating cooling, and (iii) the interception of high energy hot carriers on the subpicosecond time scale by lattice defects, which may account for the lower photoluminescence yield of TMDs when excited above band gap.

Hot-carrier reliability and performance study of transistors with variable gate-to-drain/source overlap

Flexibility on the gate-to-drain/source overlap length is useful for selecting the best compromise between device performance (including short channel effects and gate scaling, ON-state current, parasitic overlap capacitance), and the device reliability to hot-carrier degradation. In this paper, the performance and reliability of transistors with variable overlap is studied in a 40 nm CMOS technology. A double-hump is observed in the substrate current characteristic in function of the gate voltage for low-overlap transistors. An analysis of the origin of the second substrate current hump is conducted, and it is attributed to impact ionization at the drain-side, source-side or both depending on the overlap. TCAD simulations are performed to explain the two possible origins of the double-hump characteristic, which are degradation of the gate control over the channel due to low overlap or hot-carrier trapping. Finally, electrical characterizations are conducted to measure the degradation rate for various overlap lengths. It is observed that a longer overlap gives the transistor a longer lifetime under hot-carrier stress conditions.

Multiple exciton generation in tin–lead halide perovskite nanocrystals for photocurrent quantum efficiency enhancement

Multiple exciton generation (MEG), the generation of multiple electron–hole pairs from a single high-energy photon, can enhance the photoconversion efficiency in several technologies including photovoltaics, photon detection and solar-fuel production1,2,3,4,5,6. However, low efficiency, high photon-energy threshold and fast Auger recombination impede its practical application1,7. Here we achieve enhanced MEG with an efficiency of up to 87% and photon-energy threshold of two times the bandgap in highly stable, weakly confined formamidinium tin–lead iodide perovskite nanocrystals (FAPb1–xSnxI3 NCs; x ≤ 0.11). Importantly, an MEG-driven increment in the internal photocurrent quantum efficiency exceeding 100% with a low threshold is observed in such NC-sensitized photoconductors under ultraviolet-light illumination. The MEG enhancement mechanism is found to be mediated by the slower cooling and reduced trapping of hot carriers above the MEG threshold after the partial substitution of Pb by Sn. Our findings corroborate the potential importance of narrow-bandgap perovskite NCs for the development of optoelectronics that could benefit from MEG.

Excited-state regulation in eco-friendly ZnSeTe-based quantum dots by cooling engineering

The production of high-quality eco-friendly quantum dots (QDs) is challenging because of the efficient yet elusive nonradiative recombination within. This study examined the effects of cooling engineering on regulating the excited states to realize high-quality ZnSeTe core-shell QDs. The presence of ultrafast hot-carrier trapping and band-edge carrier trapping is responsible for the poor emission efficiency in ZnSeTe QDs. The above processes can be suppressed simultaneously by engineering the cooling process, and the underlying mechanisms are interrogated by combined electronic and spectroscopic characterization. The engineered ZnSeTe QDs exhibited record-high efficiency (>90%) and stability that were comparable to those of the canonical CdSe QDs. Leveraging on the achievement, the ZnSeTe QD-based white light-emitting diodes (WLEDs) showed excellent optical performance, including a high color-rendering index of 80 and an appropriate correlated color temperature of 7391 K. Furthermore, the WLEDs could serve as light sources in eco-friendly visible light communication. These results highlight the feasibility of eco-friendly QDs for practical applications without environmental hazards.

Deep Well Trapping of Hot Carriers in a Hexagonal Boron Nitride Coating of Polymer Dielectrics.

Polymer dielectrics can be cost-effective alternatives to conventional inorganic dielectric materials, but their practical application is critically hindered by their breakdown under high electric fields driven by excited hot charge carriers. Using a joint experiment-simulation approach, we show that a 2D nanocoating of hexagonal boron nitride (hBN) mitigates the damage done by hot carriers, thereby increasing the breakdown strength. Surface potential decay and dielectric breakdown measurements of hBN-coated Kapton show the carrier-trapping effect in the hBN nanocoating, which leads to an increased breakdown strength. Nonadiabatic quantum molecular dynamics simulations demonstrate that hBN layers at the polymer-electrode interfaces can trap hot carriers, elucidating the observed increase in the breakdown field. The trapping of hot carriers is due to a deep potential well formed in the hBN layers at the polymer-electrode interface. Searching for materials with similar deep well potential profiles could lead to a computationally efficient way to design good polymer coatings that can mitigate breakdown.

Deciphering Ultrafast Carrier Dynamics of Eco-Friendly ZnSeTe-Based Quantum Dots: Toward High-Quality Blue-Green Emitters.

Developing non-toxic and high-performance colloidal semiconductor quantum dots (CQDs) represents the inevitable route toward CQD-enabled technologies. Herein, the spectral and dynamic properties of heavy-metal-free ZnSeTe-based CQDs are investigated by transient absorption spectroscopy and theoretical modeling. We for the first time decode the ultrafast hot carrier trapping (<2 ps) and band-edge carrier trapping processes (∼6 ps) in the CQD system, which plagues the emission performance. The ZnSe/ZnSeS/ZnS shell engineering greatly suppresses the non-radiative trapping process and results in a high photoluminescence quantum yield of 88%. We demonstrate that the core/shell nano-heterostructure forms the quasi-type II configuration, in contrast to the presumed type I counterpart. Moreover, the Auger recombination and hot carrier cooling processes are revealed to be ∼454-405 ps and 160-370 fs, respectively, and their relationship with the composition in the spectral range of 470-525 nm is clarified. The above merits render these ZnSeTe CQDs as outstanding blue-green emitters for optoelectronic applications, exemplified by the white light-emitting diodes.

Theory of Plasmonic Hot-Carrier Generation and Relaxation.

Hot-carrier (HC) generation from (localized) surface plasmon decay has recently attracted much attention due to its promising applications in physical, chemical, materials, and energy science. However, the detailed mechanisms of plasmonic HC generation, relaxation, and trapping are less studied. In this work, we developed and applied a quantum-mechanical model and coupled master equation method to study the generation of HCs from plasmon decay and their following relaxation processes with different mechanisms treated on equal footing. First, a quantum-mechanical model for HC generation is developed. Its connection to existing semiclassical models and time-dependent density functional theory (TDDFT) is discussed. Second, the relaxation and lifetimes of HCs are investigated in the presence of electron-electron and electron-phonon interactions. A GW-like approximation is introduced to account for the electron-electron scattering. The numerical simulations on the Jellium nanoparticles with a size up to 1.6 nm demonstrate the electron-electron scattering and electron-phonon scattering dominate different time scale in the relaxation dynamics. We also generalize the model to study the extraction of HCs to attached molecules. The quantum yield of extracting HCs for other applications is found to be size-dependent. In general, the smaller size of NP improves the quantum yield, which is in agreement with recent experimental measurements. Even though we demonstrate this newly developed theoretical formalism with Jellium model, the theory applies to any other atomistic models.

(Invited) Understanding Dynamic RDS(on) in GaN Devices

In this article, we expand on the wide body of experimental and theoretical knowledge of charge trapping phenomena in eGaN devices that cause dynamic on-resistance shifting. We describe in detail a flexible test circuit used to measure RDS(on) in real time as devices are switched in different modes. Using an ultra-fast synchronized clipper FET, we obtain accurate measurements as soon as ~25 ns after the turn-on transition, showing that eGaN FETs switch to a low resistance state immediately without any lingering de-trapping effects that are observed in other GaN technologies. Comparing hard-switching of resistive versus inductive loads, we find very low dynamic RDS(on) shifting in either case when parts are operated at or below datasheet VDSmax. For parts operated well above datasheet limits, we measure long-term RDS(on) growth for 100V and 200V devices, and find the data is in good agreement with our hot carrier trapping model.

Hot carriers perspective on the nature of traps in perovskites

Amongst the many spectacular properties of hybrid lead halide perovskites, their defect tolerance is regarded as the key enabler for a spectrum of high-performance optoelectronic devices that propel perovskites to prominence. However, the plateauing efficiency enhancement of perovskite devices calls into question the extent of this defect tolerance in perovskite systems; an opportunity for perovskite nanocrystals to fill. Through optical spectroscopy and phenomenological modeling based on the Marcus theory of charge transfer, we uncover the detrimental effect of hot carriers trapping in methylammonium lead iodide and bromide nanocrystals. Higher excess energies induce faster carrier trapping rates, ascribed to interactions with shallow traps and ligands, turning these into potent defects. Passivating these traps with the introduction of phosphine oxide ligands can help mitigate hot carrier trapping. Importantly, our findings extend beyond photovoltaics and are relevant for low threshold lasers, light-emitting devices and multi-exciton generation devices.

Get them while they’re hot

Hot carrier solar cells require mechanisms to dramatically reduce the rate at which carriers thermalize in semiconductors. Now, side-valley trapping of hot carriers with long decay lifetimes is shown to increase the chance of extraction of carriers while they are still hot.

Enabling and Controlling Negative Photoconductance of FePS3 Nanosheets by Hot Carrier Trapping

Abstract2D materials have aroused tremendous attention in the last decade, and magnetic materials of the 2D scale are rising to prominence in recent years, which may revolutionize current optical and electronic applications. Photoconductivity is a well‐known optical and electrical property, which should be positive as the conductivity of material increases typically upon the absorption of electromagnetic radiation. Here, a controllable switch fromnegative to positive photoconductivity effect of FePS3 nanosheets is enabledby the modulation of the excitation wavelengths. These effects originate from an ultrafast process of hot carrier trapping, as visualized and investigated by the transient absorption microscopy at a quantitative level. This hot carrier trapping process is about 1.25 ps resulting in a lower diffusion constant state (≈3.5 cm2 s−1), which provides deep insight into the intrinsic properties of 2D FePS3 for further study. The results demonstrate experimentally the possibility to tune the electronic properties of 2D magnetic materials by an optical way, which not only induces the change in the magnitude but also in the sign, leading to more understandings and possibilities in 2D optoelectronic devices with many unexpected and multifunctional properties.

Stress and Recovery Dynamics of Drain Current in GaN HD-GITs Submitted to DC Semi-ON stress

Stress and recovery dynamics of the drain current are analysed in normally-off GaN Hybrid-Drain - embedded Gate Injection Transistors (HD-GITs) submitted to a semi-ON state stress. Under this condition moderate drain current and high drain voltage (350-650 V) are applied simultaneously. During the stress phase the drain current shows a remarkable decrease due to hot carrier trapping and is dependent on the applied drain voltage, stress current and temperature (30–190 °C). This degradation is fully recoverable, either thermally in the temperature range 150–190 °C or by hole injection from the gate. We provide a model for the detrapping time constant taking into account both the thermally-driven process dominating for gate biases VGS < 3 V and hole capture dominant for VGS > 3 V.

Ultrafast Electron Dynamics in Single Aluminum Nanostructures.

Aluminum nanostructures are a promising alternative material to noble metal nanostructures for several photonic and catalytic applications, but their ultrafast electron dynamics remain elusive. Here, we combine single-particle transient extinction spectroscopy and parameter-free first-principles calculations to investigate the non-equilibrium carrier dynamics in aluminum nanostructures. Unlike gold nanostructures, we find the sub-picosecond optical response of lithographically fabricated aluminum nanodisks to be more sensitive to the lattice temperature than the electron temperature. We assign the rise in the transient transmission to electron-phonon coupling with a pump-power-independent lifetime of 500 ± 100 fs and theoretically confirm this strong electron-phonon coupling behavior. We also measure electron-phonon lifetimes in chemically synthesized aluminum nanocrystals and find them to be even longer (1.0 ± 0.1 ps) than for the nanodisks. We also observe a rise and decay in the transient transmissions with amplitudes that scale with the surface-to-volume ratio of the aluminum nanodisks, implying a possible hot carrier trapping and detrapping at the native oxide shell-metal core interface.

Transient Response of h-BN-Encapsulated Graphene Transistors: Signatures of Self-Heating and Hot-Carrier Trapping.

We use transient electrical measurements to investigate the details of self-heating and charge trapping in graphene transistors encapsulated in hexagonal boron nitride (h-BN) and operated under strongly nonequilibrium conditions. Relative to more standard devices fabricated on SiO2 substrates, encapsulation is shown to lead to an enhanced immunity to charge trapping, the influence of which is only apparent under the combined influence of strong gate and drain electric fields. Although the precise source of the trapping remains to be determined, one possibility is that the strong gate field may lower the barriers associated with native defects in the h-BN, allowing them to mediate the capture of energetic carriers from the graphene channel. Self-heating in these devices is identified through the observation of time-dependent variations of the current in graphene and is found to be described by a time constant consistent with expectations for nonequilibrium phonon conduction into the dielectric layers of the device. Overall, our results suggest that h-BN-encapsulated graphene devices provide an excellent system for implementations in which operation under strongly nonequilibrium conditions is desired.

Photophysical Action Spectra of Emission from Semiconductor Nanocrystals Reveal Violations to the Vavilov Rule Behavior from Hot Carrier Effects

Semiconductor nanocrystals are known to have properties of bulk semiconductors as well as molecules. Two rules that govern molecules are that there is no dual emission (Kasha) and there is no spectrum to the emission quantum yield (Vavilov). We show that the latter rule of molecular spectroscopy is generally violated in semiconductor nanocrystals. Through experiments and theory on CdSe and perovskite nanocrystals, these violations are shown to arise via hot carrier effects. Experiments and simple phenomenology reveal that quantum yield spectra arise because of enhanced hot carrier trapping rates. A semiclassical electron-transfer theory rationalizes a microscopic picture of the carrier kinetics. These effects are especially significant when quantifying syntheses of bright emitters such as perovskite nanocrystals. These effects are also a general approach to simple steady-state measurements of the action of hot carrier kinetics.