Single High-energy Photon Research Articles

Singlet fission photovoltaic cells as dual-wavelength laser power converters compatible with highly efficient solar cells

I applied photovoltaic cells equipped with singlet fission (SF) of molecular systems to dual-wavelength laser power converters (DW-LPCs) that efficiently convert two laser lights of different wavelengths to electricity. When the SF-DW-LPC is illuminated by eye-safe laser light of 1470 nm wavelength emitted from a laser diode, a single photon is converted to a single carrier. On the other hand, a single high-energy photon emitted from a high-power and low-cost laser diode of 808 nm is converted to two carriers by SF owing to its endothermic feature, even though the photon energy is slightly lower than twice the fundamental energy gap. Furthermore, the SF-DW-LPC operates as a highly efficient solar cell. These functions are required for optical wireless power transmission to moving objects including electric vehicles and flying drones. I modeled the photovoltaic process with SF and evaluated the limiting conversion efficiencies by detailed-balance calculations. Conversion efficiencies of the SF-DW-LPC for these two laser lights are competitive with those of the conventional single-junction LPCs dedicated to these wavelengths, respectively. The efficiency under solar light is close to that of the optimally designed SF solar cell. Furthermore, the SF-DW-LPC outperforms other types of DW-LPCs designed on the basis of intermediate band, triplet–triplet annihilation, and multiple exciton generation solar cells. Endothermic SF and carrier/energy extraction into the neighboring acceptors have already been demonstrated. However, molecular systems that apply to 1470 nm have not yet been realized, which is the top-priority issue to be solved to realize highly efficient SF-DW-LPCs.

Efficient Carrier Multiplication in Self-Powered Near-Ultraviolet γ-InSe/Graphene Heterostructure Photodetector with External Quantum Efficiency Exceeding 161.

Carrier multiplication (CM) in semiconductors, the process of absorbing a single high-energy photon to form two or more electron-hole pairs, offers great potential for the high-response detection of high-energy photons in the ultraviolet spectrum. However, compared to two-dimensional semiconductors, conventional bulk semiconductors not only face integration and flexibility bottlenecks but also exhibit inferior CM performance. To attain efficient CM for ultraviolet detection, we designed a two-terminal photodetector featuring a unilateral Schottky junction based on a two-dimensional γ-InSe/graphene heterostructure. Benefiting from a strong built-in electric field, the photogenerated high-energy electrons in γ-InSe, an ideal ultraviolet light-absorbing layer, can efficiently transfer to graphene without cooling. It results in efficient CM within the graphene, yielding an ultrahigh responsivity of 468 mA/W and a record-high external quantum efficiency of 161.2% when it is exposed to 360 nm light at zero bias. This work provides valuable insights into developing next-generation ultraviolet photodetectors with high performance and low-power consumption.

Photon Upconversion Cooperates with Downshifting in Chiral Systems: Modulation, Amplification, and Applications of Circularly Polarized Luminescence

AbstractCircularly polarized luminescence (CPL)‐active materials are increasingly recognized for their potential applications such as 3D imaging, data storage, and optoelectronic devices. Typically, CPL materials have required high‐energy (HE) photons for excitation to emit low‐energy (LE) circularly polarized light, a process known as downshifting CPL (DSCPL). However, the emergence of upconverted CPL (UCCPL), where the absorption of multi LE photons results in the emission of a single HE photon with circular polarization, has recently attracted considerable attention. This minireview highlights the intricate relationship between upconversion and CPL phenomena. During upconversion, the dissymmetry factor (glum) value can be improved in certain systems. Additionally, the integration of both LE and HE photons in upconversion‐downshifting‐synergistic systems offers avenues for dual‐excitation or dual‐emission CPL functionalities. More in detail, the emerging UCCPL based on various photon upconversion mechanisms and their synergy with DSCPL are introduced. Additionally, several examples that demonstrate the applications of UCCPL are presented to highlight the future opportunities.

Photon Upconversion Cooperates with Downshifting in Chiral Systems: Modulation, Amplification, and Applications of Circularly Polarized Luminescence.

Circularly polarized luminescence (CPL)-active materials are increasingly recognized for their potential applications such as 3D imaging, data storage, and optoelectronic devices. Typically, CPL materials have required high-energy (HE) photons for excitation to emit low-energy (LE) circularly polarized light, a process known as downshifting CPL (DSCPL). However, the emergence of upconverted CPL (UCCPL), where the absorption of multi LE photons results in the emission of a single HE photon with circular polarization, has recently attracted considerable attention. This minireview highlights the intricate relationship between upconversion and CPL phenomena. During upconversion, the dissymmetry factor (glum) value can be improved in certain systems. Additionally, the integration of both LE and HE photons in upconversion-downshifting-synergistic systems offers avenues for dual-excitation or dual-emission CPL functionalities. More in detail, the emerging UCCPL based on various photon upconversion mechanisms and their synergy with DSCPL are introduced. Additionally, several examples that demonstrate the applications of UCCPL are presented to highlight the future opportunities.

Boosting UV responsivity of silicon photodetectors through efficient quantum-cutting with La3+, Yb3+ co-doped perovskite quantum dots

Quantum cutting involves the absorption of a single high-energy photon, followed by the release of its energy through the emission of two or more lower-energy photons. This approach holds promise as a method to improve the ultraviolet (UV) performance of silicon photodetectors (Si PDs). In this study, we successfully fabricated La3+, Yb3+ co-doped CsPbClBr2 perovskite quantum dots (PQDs) using a modified hot-injection method, achieving a remarkable photoluminescent quantum yields (PLQYs) of 181 %. Subsequently, we spin-coated a film of La3+, Yb3+ co-doped CsPbClBr2 PeQDs, serving as a light conversion material, onto the front surface of Si PDs. The resulting configuration exhibited enhanced responsivity (0.131 A/W) and external quantum efficiency (55.6 %), long-term stability at 360 nm, and expanded responsiveness into the deep UV region (200 nm). Simultaneously, the responsivity and external quantum efficiency in the visible and near-infrared regions exhibited minimal reduction. This significant performance can be attributed to two key factors: (1) The higher efficient quantum cutting PLQYs (181 %) of La3+, Yb3+ co-doped CsPbClBr2 PeQDs and (2) the presence of fewer traps and a larger tolerance factor resulting from La3+ and Yb3+ co-doping.

An ensemble of excited molecules collectively emits multiple-frequency real and virtual photons.

The interplay of molecules gives rise to collective phenomena absent in a single molecule. Many examples of collective phenomena have been reported as their knowledge is essential for understanding the behavior of matter. Here, we consider molecules sufficiently separated from each other to not form chemical bonds. If these molecules are excited, e.g., by a weak laser, can they concertedly relax by emitting a single high-energy photon possessing the total energy of all the relaxing molecules? We show that this concerted emission process is indeed possible. We estimate its probability and analyze its dependence on molecular properties, intermolecular distances, and relative orientations of the molecules. A numerical example on two pyridine molecules is given. The concerted emission found is a fundamental process expected to be operative in gas phase and clusters. Its true relevance lies in its intimate relationship to concerted emission of virtual photons and thus to collective energy transfer ionizing neighboring systems. The estimated rates and examples discussed of this collective intermolecular Coulombic decay shed much light on recent puzzling experiments.

Testing neutrino dipole portal by long-lived particle detectors at the LHC

We discuss the potential of using detectors aimed for searching long-lived particles (LLP) at the high-luminosity LHC run, to probe the neutrino dipole models. This is achieved by taking the heavy neutral leptons (HNL) of the models as candidates of the LLPs. Taking into account the dipole couplings to the weak bosons, d_{W,Z}, which control the production of the HNLs at the LHC, we discuss the reach on the electromagnetic dipole couplings, d_gamma , by searching for a single high-energy photon at LLP detectors. Four typical scenarios are considered in this paper, scenario A, B with d_{W}=0 or d_{Z}=0, and scenario C, D with d_{W,Z}gg d_gamma . We show the sensitivity on d_gamma , can be fairly different depending on the relations between the d_{W,Z} and d_gamma . And the LLP detectors can potentially extend the sensitivity on dipole couplings during the high-luminosity runs of the LHC in certain scenarios.

Efficient Multiple Exciton Generation in Monolayer MoS2.

Utilization of the excess energy of photoexcitation that is otherwise lost as thermal effects can improve the efficiency of next-generation light-harvesting devices. Multiple exciton generation (MEG) in semiconducting materials yields two or more excitons by absorbing a single high-energy photon, which can break the Shockley-Queisser limit for the conversion efficiency of photovoltaic devices. Recently, monolayer transition metal dichalcogenides (TMDs) have emerged as promising light-harvesting materials because of their high absorption coefficient. Here, we report efficient MEGs with low threshold energy and high (86%) efficiency in a van der Waals (vdW) layered material, MoS2. Through different experimental approaches, we demonstrate the signature of exciton multiplication and discuss the possible origin of decisive MEG in monolayer MoS2. Our results reveal that vdW-layered materials could be a potential candidate for developing mechanically flexible and highly efficient next-generation solar cells and photodetectors.

Nonlinear X-ray Compton scattering: A new mathematical model for X-ray wave mixing mechanism

The present report deals with a modification of the nonlinear X-ray Compton scattering expression by introducing an index of refraction R. XFEL-based two hard X-ray photons with the energy ω around 9 keV were effectively mixed up to form a single high-energy photon (18 keV) in a prior publication (Fuchs et al., 2015). Using the Volkov correction, an alternative estimation of scattered X-ray photon energy ω′ via a nonlinear process was expressed. Applying this theoretical model, it was determined that an 18 keV single high-energy scattered photon can be produced by mixing two 9 keV photons with a field strength parameter χ ranging from 0.1 to 0.2.

Dye-Sensitized Multiple Exciton Generation in Lead Sulfide Quantum Dots.

Multiple exciton generation (MEG), the generation of multiple excitons from the absorption of a single high-energy photon, is a strategy to go beyond the limiting efficiencies that define current-day solar cells by harvesting some of the thermalization energy losses that occur when photons with an energy greater than the semiconductor bandgap are absorbed. In this work, we show that organic dyes can sensitize MEG in semiconductor quantum dots (QDs). In particular, we found that surface-anchored pyrene ligands enhanced the photon-to-charge carrier quantum yield of PbS QDs from 113 ± 3% to 183 ± 7% when the photon energy was 3.9 times the band gap. A wavelength dependence study shows that the enhancement is positively correlated with the pyrene absorptivity. Transient absorption and steady-state photoluminescence measurements suggest that the MEG sensitization is based on an initial fast electron transfer from the pyrene ligands to the PbS QDs producing hot-electrons in the QDs that subsequently undergo MEG. This work demonstrates that hybrid and synergistic organic/inorganic interactions can be a successful strategy to enhance MEG.

Belle II sensitivity to long–lived dark photons

In this letter we point out that the BelleII experiment has a unique sensitivity to visibly decaying long-lived dark photons. Concentrating on the signatures with a single high-energy photon in association with a displaced pair of charged particles, we find that BelleII will be able to probe large regions of parameter space that cannot be covered by any other running or proposed experimental facility. While the signature with charged muons or pions in the final state is expected to be background-free after all selections are applied, the case of final state electrons is more involved and requires an in-depth study. We discuss possible ways to further suppress backgrounds and the corresponding experimental prospects.

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.

Multiexciton dynamics in CsPbBr3 nanocrystals: the dependence on pump fluence and temperature

Multiexcitons generation is a process of generating electron–hole pairs in nanostructured semiconductors by absorbing a single high-energy photon. The multiexciton process is essential for the performance of optoelectronic devices based on perovskite nanomaterials. In this paper, ultrafast time-resolved transient absorption spectroscopy is used to study the ultrafast dynamics of CsPbBr3 nanocrystals. It is found that the multiexcitons Auger recombination lifetime increases with the decrease of pump fluence, while it is on the contrary for the hot carrier cooling time. The increase in the number of photons absorbed by each nanocrystal under high pump fluence slows down the relaxation of hot carriers to the band edge. The hot carrier cooling lifetime increases from 0.25 to 0.85 ps when the pump fluence increases from 6 to 127 μJ cm−2. Temperature-dependent transient absorption spectroscopy exhibits that the relaxation process of hot carriers slows down sharply when the lattice temperature decreases from 280 to 80 K. Moreover, the exciton binding energy 46 meV of CsPbBr3 nanocrystals is obtained by temperature-dependent steady-state photoluminescence spectroscopy. These findings provide insights for applications such as solar cells and light-emitting devices based on CsPbBr3 nanocrystals.

Signal detection using biphotons and potential application in axion-like particle search

This paper presents a new optical system for detecting light signals associated with the change in incoming photon number. The system employs quantum correlation of photon pairs created via spontaneous parametric down-conversion (SPDC). The signal, if present, will perturb the flux of the incident photon stream. The perturbed photon stream is first projected through a birefringent crystal where SPDC occurs, converting a single high-energy photon into a pair of low-energy photons. The photons in each pair eventually arrive at separate detectors. By examining the biphoton correlation using the probability distribution of the photons at the detectors, which varies depending on the displacement of the main “pump” photon stream and the change in the number of photons, the small optical displacement of the photon stream and its variance can be determined. The change in incident photon number, in other words, the presence of light signal does not influence the average of the measured optical displacement values. Nevertheless, the change in optical displacement measurement variance when the number of incident photons has changed detects the light signal. This optical setup enables the detection of light signals with low noise and remarkably high precision and sensitivity using quantum correlation. The proposed technique has potential application for axion-like particle search in experimental high energy physics.

Blueshifts of high-order harmonic generation in crystalline silicon subjected to intense femtosecond near-infrared laser pulse

We present the generation of high order harmonics in crystalline silicon subjected to intense near-infrared 30fs laser pulses. The harmonic spectrum extends from the near infrared to the extreme ultraviolet spectral region. Depending on the pulsed laser intensity, we distinguish two regimes of harmonic generation: (i) perturbative regime: electron-hole pairs born during each half-cycle of the laser pulse via multiphoton and tunnel transitions are accelerated in the laser electric field and gain kinetic energy; the electron-hole pairs then recombine in the ground state by emitting a single high-energy photon. The resultant high harmonic spectrum consists of sharp peaks at odd harmonic orders. (ii) non-perturbative regime: the intensity of the harmonics increases, their spectral width broadens and the position of harmonics shifts to shorter wavelengths. The blueshifts of high harmonics in silicon are independent on the harmonic order which may be helpful in the design of continuously tunable XUV sources.

Warm white broadband emission and tunable long lifetimes in Yb3+ doped Gd2O3 nanoparticles

Upconversion luminescence materials have stimulated growing attention in photovoltaic cell owning to the ability of converting a few low-energy photons into a single high-energy photon. However, there still remains a daunting challenge to achieve upconversion emission covering the entire visible spectrum in a single material. Here, an incandescent broadband white upconversion emission covering the entire visible region is realized in a single Gd2O3:Yb3+ nanoparticles by utilization of adverse multiphonon relaxation. Importantly, tunable long fluorescence lifetime can be synchronously implemented in the single material, where the lifetime range spans one order of magnitude. Furthermore, benefiting from the broadband emission, the luminescence intensity achieves 482-fold improvement as the power increase from 0.53 W to 1.51 W. These broadband emissions are enabled by engineering the pathways of nonradiative de-excitation via multiphonon relaxation. Based on the kinetic analysis and mechanism research, the photon avalanche is demonstrated to play an important role for broadband emission. The warm white emission together with its tunable long lifetime provides a new avenue for developing single emitter-based white-light-emission materials for next-generation display and lighting technologies.

Singlet Fission in Tetraaza-TIPS-Pentacene Oligomers: From fs Excitation to μs Triplet Decay via the Biexcitonic State

Generating two long-living low-energy excitations after absorption of a single high-energy photon has stoked interest in singlet fission (SF) to enhance solar energy conversion in photovoltaics. To this end, survival of the triplet states is critical. This process is investigated in diethynylbenzene-linked tetraaza-triisopropylsilylethynyl-pentacene dimers, for which SF is energetically feasible and facilitated by the close distances between the azapentacenes. The ortho and meta connectivities are explored and compared with the tetraazapentacene molecule and the (1,3,5) trimer. Efficient SF (potential ΦT ≥ 160%) is demonstrated in all oligomers by quantitative kinetic analysis of broadband transient absorption and fluorescence signals. Together with dynamics of the starting singlet, the triplet pair, and the final free triplet state, our results show an intermediate component with spectral properties compatible with a biexcitonic state. Long-living triplets represent only a fraction of the high number of transient triplet pair intermediates, which undergo triplet-triplet annihilation as well as fusion between neighboring pentacenes. Therefore, our work provides new insight into the SF in covalent dimers and paves the way for the application of these materials for carrier multiplication.

Multi-mode photocatalytic performances of CdS QDs modified CdIn2S4/CdWO4 nanocomposites with high electron transfer ability

In general, quantum dots have the property of generating a plurality of charge carriers using hot electrons or using a single high-energy photon to improve the photocatalytic properties of the material. In this paper, CdS QDs@CdIn2S4/CdWO4 modified by CdS QDs was synthesized by the microwave-assisted hydrothermal method, and its composition, crystal structure, morphology, and surface physicochemical properties were well characterized. Electron microscopy results showed that CdS QDs@CdIn2S4/CdWO4 composite material exhibited a sheet structure with a length of ca. 350 nm and a width of ca. 50 nm, and CdS QDs uniformly distributes with a diameter of about 5 nm on the sheet structure. UV-visible diffuse reflectance tests showed that the combination of CdS QDs and CdIn2S4 can extend the light absorption range of CdWO4 to the visible region. Photoluminescence spectroscopy confirmed that CdS QDs had efficient electron transport capabilities. The multi-mode photocatalytic activity of CdS QDs@CdIn2S4/CdWO4 showed an excellent ability to degrade organic pollutants. Under the conditions of no co-catalyst and Na2S-Na2SO3 as the sacrificial agent, the hydrogen production of CdS QDs@CdIn2S4/CdWO4 can reach 221.3 μmol g−1 when exposed to visible light (λ > 420 nm) for 8 h.

Enhanced Multiple Exciton Generation in PbS|CdS Janus-like Heterostructured Nanocrystals.

Generating multiple excitons by a single high-energy photon is a promising third-generation solar energy conversion strategy. We demonstrate that multiple exciton generation (MEG) in PbS|CdS Janus-like heteronanostructures is enhanced over that of single-component and core/shell nanocrystal architectures, with an onset close to two times the PbS band gap. We attribute the enhanced MEG to the asymmetric nature of the heteronanostructure that results in an increase in the effective Coulomb interaction that drives MEG and a reduction of the competing hot exciton cooling rate. Slowed cooling occurs through effective trapping of hot-holes by a manifold of valence band interfacial states having both PbS and CdS character, as evidenced by photoluminescence studies and ab initio calculations. Using transient photocurrent spectroscopy, we find that the MEG characteristics of the individual nanostructures are maintained in conductive arrays and demonstrate that these quasi-spherical PbS|CdS nanocrystals can be incorporated as the main absorber layer in functional solid-state solar cell architectures. Finally, based upon our analysis, we provide design rules for the next generation of engineered nanocrystals to further improve the MEG characteristics.

Recent advance in multiple exciton generation in semiconductor nanocrystals

The multiple exciton generation (MEG), a process in which two or even more electron-hole pairs are created in nanostructured semiconductors by absorbing a single high-energy photon, is fundamentally important in many fields of physics, e.g., nanotechnology and optoelectronic devices. Many high-performance optoelectronic devices can be achieved with MEG where quite an amount of the energy of an absorbed photon in excess of the band gap is used to generate morei additional electron-hole pairs instead of rapidly lost heat. In this review, we present a survey on both the research context and the recent progress in the understanding of MEG. This phenomenon has been experimentally observed in the 0D nanocrystals, such as PbX (X=Se, S, and Te), InX (X=As and P), CdX (X=Se and Te), Si, Ge, and semi-metal quantum dots, which produce the differential quantum efficiency as high as 90%10%. Even more remarkably, experiment advances have made it possible to realize MEG in the one-dimensional (1D) semiconductor nanorods and the two-dimensional (2D) nano-thin films. Theoretically, three different approaches, i.e., the virtual exciton generation approach, the coherent multiexciton mode, and the impact ionization mechanism, have been proposed to explain the MEG effect in semiconductor nanostructures. Experimentally, the MEG has been measured by the ultrafast transient spectroscopy, such as the ultrafast transient absorption, the terahertz ultrafast transient absorption, the transient photoluminescence, and the transient grating technique. It is shown that the properties of nanostructured semiconductors, e.g., the composition, structure and surface of the material, have dramatic effects on the occurrence of MEG. As a matter of fact, it is somewhat hard to experimentally confirm the signature of MEG in nanostructured semiconductors due to two aspects:i) the time scale of the MEG process is very short; ii) the excitation fluence should be extremely low to prevent the multi-excitons from being generated by multiphoton absorption. There are still some controversies with respect to the MEG effect due to the challenge in both the experimental measurement and the explanation of signal data. The successful applications of MEG in practical devices, of which each is composed of the material with lower MEG threshold and higher efficiency, require the extraction of multiple charge carriers before their ultrafast annihilation. Such an extraction can be realized by the ultrafast electron transfer from nanostructured semiconductors to molecular and semiconductor electron acceptors. More recently, an experiment with PbSe quantum dot photoconductor has demonstrated that the multiple charge extraction is even as high as 210%. It is proved that MEG is of applicable significance in optoelectronic devices and in ultra-efficient photovoltaic devices. Although there are still some challenges, the dramatic enhancement of the efficiency of novel optoelectronic devices by the application of MEG can be hopefully realized with the rapid improvement of nanotechnology.