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At least 19 records

Low-Threshold Visible-to-Ultraviolet Solid-State Triplet-Fusion Upconversion

Visible-to-ultraviolet (UV) triplet-triplet annihilation (TTA) upconversion is an energy-relevant photon-management strategy that converts visible photons into UV photons capable of driving high-energy photochemical processes. Practical implementation requires solid-state thin films, which often require high excitation power. Here, we demonstrate the first solid-state visible-to-UV TTA upconversion thin-film device, using 1,4-bis((tricyclopentylsilyl)ethynyl)naphthalene (TCPS-NAP) as the annihilator and tris(2-phenylpyridine)iridium(III) (Ir(ppy) 3 ) as the sensitizer on silver. Under incoherent 455 nm excitation, the device exhibits blue-to-UV upconversion with a threshold of 4.8 mW/cm 2 . Using surface plasmons in the planar silver film, we achieve green-to-UV upconversion with a 1.11 eV anti-Stokes shift and 6.9 mW/cm 2 threshold, a 12.2 × threshold enhancement over far-field 532 nm excitation. In solution, TCPS-NAP shows excimer-dominated anti-Stokes emission rather than UV upconversion. These results establish a platform for harvesting low-intensity visible light to drive UV processes while demonstrating that solution-phase screening does not predict solid-state upconversion performance.

Luminescence↗

Plasmon-enhanced ultralow-threshold solid-state triplet fusion upconversion

Triplet fusion upconversion has potential applications in solar cells, photoredox catalysis, additive manufacturing and bioimaging. However, solid-state upconversion systems have struggled to measure up to their solution-phase counterparts, often requiring enormous optical power densities to operate at the maximum efficiency. Here we substantially improve the performance of upconversion films through excitation with surface plasmons that propagate along a planar silver-film interface, leading to an absorption enhancement that reduces the intensity threshold I th by a factor of 19 and enhances the external quantum efficiency by a factor of 17. From this, we achieve I th values as low as 3.4 mW cm −2 and an external quantum efficiency up to 0.094%. To demonstrate real-world viability, we couple the upconversion film to plasmons generated by the near-field of excitons in an organic light-emitting diode. As a result, this scheme is then used to fabricate a white-emitting organic light-emitting diode where blue emission sources from plasmon-excited upconversion, achieving a high colour rendering index of 86.2 and setting precedent for blue emission in the absence of high-energy polarons or triplets.

36 MATERIALS SCIENCE↗

Infrared upconversion as a means of seeing in the dark

A new approach to seeing in the dark is described which is based on the principles of nonlinear optics employing a crystal such as lithium iodate. A nonlinear optical device capable of producing photons at higher frequencies from lower-frequency incident light is shown to upconvert infrared light directly into visible light. The major advantages of the infrared upconversion process is that it permits the infrared signal to be detected by photon-counting devices presently available for the visible spectral region, and that it can provide sensitivity to infrared radiation without the need for cryogenic cooling of the detector used. Early works on infrared upconversion are reviewed. The development of applications is discussed as to astronomical spectroscopy and infrared image upconversion involving either angular or positional resolution elements. The demonstration of infrared upconversion in rectangular waveguides of single-crystal GaAs by Anderson et al. (1971) indicates future possibilities in upconversion by the use of integrated optics devices.

Gurski, T. R.↗

Development, applications, and future of infrared upconversion

Infrared upconversion is a technique that converts linearly polarized infrared photons to photons of higher frequency. The technique can be applied advantageously to the detection of IR radiation because the upconverted signal can be detected by photon-counting devices available for the visible spectral region. In addition, unlike presently available IR detectors, an upconversion device can provide sensitivity to IR radiation without the need for cryogenic cooling. Infrared upconversion was first demonstrated in 1961. By 1974, approximately 100% quantum conversion efficiency and a bandwidth of 1.81 microns had been attained. Photometric detection of IR radiation from various astronomical objects had also been demonstrated. Research is presently under way on the application of upconversion to astronomical spectroscopy and to imaging. The major drawback to the upconversion technique is the sheer bulk of the apparatus involved. It is anticipated that this problem can be overcome by applying the developing technology of integrated optics.

Gurski, T. R.↗

Application of upconversion detection to pulsed CO2 lidar

In this paper the application of an upconversion detector to pulsed CO2 lidar is investigated. In this device a nonlinear IR crystal would be used to convert 10-micron lidar radiation into the visible region for conventional detection with a photomultiplier tube. A pulsed CO2 lidar can be substantially improved with an upconversion detector configured for rejection of thermal background radiation using a narrowband filter for the upconverted signal or a cold filter front end. The sensitivity of the upconversion detector with the narrowband visible wavelength filter is estimated to be 2 orders of magnitude better than that of the usual direct detection diode. The cold filter can improve upconversion detection to nearly the signal-shot limit. These upconversion detectors are not limited by speckle noise as is a pulsed heterodyne detector.

Itabe, T.↗

Plasmons Enable Ultralow Threshold Solid-State Triplet Fusion Upconversion with a 2D Sensitizer

Solid-state triplet−triplet annihilation (TTA) upconversion has significant potential for application in light harvesting, optoelectronic devices, and bioimaging. However, the high optical powers required to achieve efficient upconversion have inhibited its adoption. In this work, we demonstrate plasmon-enhanced near-infrared (NIR)-to-blue TTA upconversion in a monolayer WSe2/organic heterojunction. Under far-field excitation, the device reaches a threshold of 19 mW/cm 2 and an external quantum efficiency (EQE) of 0.17% with an anti-Stokes shift of 1.1 eV. Plasmon excitation lowers the threshold to 0.9 mW/cm 2 and improves the EQE to 3.6%. We attribute the plasmon enhancement to surface plasmon polariton (SPP) near-field enhancement and dark-exciton absorption. Optimization of the WSe 2 transfer process is identified as a key factor for the device performance. This work demonstrates that plasmon excitation overcomes the low far-field absorption of 2D transition-metal dichalcogenide (TMD) sensitizers. Consequently, monolayer TMDs can achieve solid-state upconversion with a performance among the best reported.

2D materials↗

Photon Upconversion at Organic-Inorganic Interfaces

Photon upconversion is a process that combines low-energy photons to form useful high-energy photons. There are potential applications in photovoltaics, photocatalysis, biological imaging, etc. Semiconductor quantum dots (QDs) are promising for the absorption of these low-energy photons due to the high extinction coefficient of QDs, especially in the near infrared (NIR). This allows the intriguing use of diffuse light sources such as solar irradiation. In this review, we describe the development of this organic-QD upconversion platform based on triplet-triplet annihilation, focusing on the dark exciton in QDs with triplet character. Then we introduce the underlying energy transfer steps, starting from QD triplet photosensitization, triplet exciton transport, triplet-triplet annihilation, and ending with the upconverted emission. Design principles to improve the total upconversion efficiency are presented. We end with limitations in current reports and proposed future directions. This review provides a guide for designing efficient organic-QD upconversion platforms for future applications, including overcoming the Shockley-Queisser limit for more efficient solar energy conversion, NIR-based phototherapy, and diagnostics in vivo.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Upconversion of Infrared Light by Graphitic Microparticles Due to Photoinduced Structural Modification

Recent reports of upconversion and white light emission from graphitic particles warrant an explanation of the physics behind the process. A model is offered, wherein the upconversion is facilitated by photoinduced electronic structure modification allowing for multiphoton processes. As per the prediction of the model, it is experimentally shown that graphite upconverts infrared light centered around 1.31 μm (0.95 eV) to broadband white light centered around 0.85 μm (1.46 eV). The results suggest that upconversion from shortwave infrared (≈3 μm, 0.45 eV) to visible region may be possible. The experiments show that the population dynamics of the electronic states involved in this upconversion process occur in the timescale of milliseconds.

Sharma, Rohin↗

Upconversion on the Micrometer Scale: Impact of Local Heterogeneity

The properties of perovskite/naphtho[2,3-a]pyrene (NaPy) upconversion devices are investigated by a combination of atomic force microscopy and photoluminescence mapping to understand the role of microscopic heterogeneity in the ensemble device properties. The results emphasize strong microscopic inhomogeneity across the perovskite/NaPy upconversion device due to local formation of NaPy microcrystals. NaPy shows emission from three distinct states in the solid state: S 1 ′ emission at 520 nm, excimer emission at 560 nm, and S 1 ″ emission at 620 nm. Clear spatial differences in the emission spectrum under 405 nm excitation are found, highlighting that there is a strong microcrystal-to-microcrystal variation in the optical properties─emphasizing a need for multimodal measurements. Furthermore, our results indicate that microcrystals with strong emission from the strongly coupled low-energy state S 1 ″ (J-dimer) show much higher upconversion intensity than those with dominant emission from the high-energy S 1 ′ state (I-aggregate). Hence, our results suggest that microcrystals with strong emission from the low-energy state S 1 ″ act as isolated hotspots for upconversion.

Crystals↗

Infrared upconversion for astronomy

The field of infrared upconversion for astronomy is reviewed. The basic theory of upconversion is presented, along with a brief historical summary of upconversion techniques. Several investigators have employed upconverters in astronomical studies, but have met with only modest success. Upconversion will become a useful detection method for astronomy only if substantial but perhaps foreseeable improvements can be realized.

Boyd, R. W.↗

Sub-10 nm upconversion nanocrystals for long-term single-particle tracking

Lanthanide-doped upconversion nanoparticles are attractive single-molecule imaging probes due to their high photostability and anti-Stokes luminescence. However, achieving both small particle size and strong brightness has remained a major challenge, as reducing size often leads to dimmer emission. Herein, we fabricate a sub-10 nm cascade actively protected upconversion nanoparticles, which shows a 33-fold enhanced upconversion efficiency at the single-particle level compared to larger ~19 nm conventional nanoparticles. Theoretical modeling and time-resolved measurements show that emission loss mainly comes from energy leakage of Er 3+ ions to surface defects. By introducing a NaYbF 4 layer as photon-harvesting and protective intermediate layer, we minimize this energy loss and significantly boost brightness. A monolayer of inert NaLuF 4 can effectively suppress the surface quenching to Yb 3+ . Using these ultra-small bright probes, we successfully tracked single epidermal growth factor receptor molecules on live cells for up to one hour, revealing dynamic switching between different diffusion modes.

Qiu, Xiaochen [Fudan Univ., Shanghai (China); Shen↗

Infrared upconversion for astronomical applications

The performance of an upconversion system is examined for observation of astronomical sources in the low to middle infrared spectral range. Theoretical values for the performance parameters of an upconversion system for astronomical observations are evaluated in view of the conversion efficiencies, spectral resolution, field of view, minimum detectable source brightness and source flux. Experimental results of blackbody measurements and molecular absorption spectrum measurements using a lithium niobate upconverter with an argon-ion laser as the pump are presented. Estimates of the expected optimum sensitivity of an upconversion device which may be built with the presently available components are given.

Abbas, M. M.↗

Infrared upconversion for astronomical applications

The performance of an upconversion system is examined for observation of astronomical sources in the low to middle IR spectral range. Theoretical values for the performance parameters of an upconversion system for astronomical observations are evaluated in terms of the conversion efficiencies, spectral resolution, field of view minimum detectable source brightness, and source flux. Experimental results of blackbody measurements and molecular absorption-spectrum measurements using a lithium niobate upconverter with an argon-ion laser as the pump are presented. Estimates are given of the expected optimum sensitivity of an upconversion device that may be built with presently available components.

Abbas, M. M.↗

Infrared upconversion for astronomy

The basic theory of upconversion is presented, along with a brief historical summary of upconversion techniques. Upconverters were used in astronomical studies, but have met with only modest success. Upconversion will become a useful detection method for astronomy only if substantial but perhaps forseeable, improvements can be realized.

Boyd, R. W.↗

Internal CW parametric upconversion

A demonstration of CW parametric upconversion of 3.39-micron IR radiation inside a He-Ne laser's optical cavity is reported. The upconversion was achieved with the aid of a 5145-A argon laser pump and a lithium niobate crystal; the circulating power available inside the pump laser's cavity was used to maximize the efficiency of the upconversion process. Losses associated with the pump blocking filters and with the lithium niobate crystal are discussed. It is concluded that despite the high losses (approximately 12%) associated with the lithium niobate, the highest measured power conversion efficiency of 0.0038 compares favorably with the best CW external conversion efficiency reported to date.

Falk, J.↗

Monitoring Delamination of Thermal Barrier Coatings by Near-Infrared and Upconversion Luminescence Imaging

Previous work has demonstrated that TBC delamination can be monitored by incorporating a thin luminescent sublayer that produces greatly increased luminescence intensity from delaminated regions of the TBC. Initial efforts utilized visible-wavelength luminescence from either europium or erbium doped sublayers. This approach exhibited good sensitivity to delamination of electron-beam physical-vapor-deposited (EB-PVD) TBCs, but limited sensitivity to delamination of the more highly scattering plasma-sprayed TBCs due to stronger optical scattering and to interference by luminescence from rare-earth impurities. These difficulties have now been overcome by new strategies employing near-infrared (NIR) and upconversion luminescence imaging. NIR luminescence at 1550 nm was produced in an erbium plus ytterbium co-doped yttria-stabilized zirconia (YSZ) luminescent sublayer using 980-nm excitation. Compared to visible-wavelength luminescence, these NIR emission and excitation wavelengths are much more weakly scattered by the TBC and therefore show much improved depth-probing capabilities. In addition, two-photon upconversion luminescence excitation at 980 nm wavelength produces luminescence emission at 562 nm with near-zero fluorescence background and exceptional contrast for delamination indication. The ability to detect TBC delamination produced by Rockwell indentation and by furnace cycling is demonstrated for both EB-PVD and plasma-sprayed TBCs. The relative strengths of the NIR and upconversion luminescence methods for monitoring TBC delamination are discussed.

Eldridge, J. I.↗

Directive giant upconversion by supercritical bound states in the continuum

Photonic bound states in the continuum (BICs), embedded in the spectrum of free-space waves with diverging radiative quality factor, are topologically non-trivial dark modes in open-cavity resonators that have enabled important advances in photonics. However, it is particularly challenging to achieve maximum near-field enhancement, as this requires matching radiative and non-radiative losses. Here we propose the concept of supercritical coupling, drawing inspiration from electromagnetically induced transparency in near-field coupled resonances close to the Friedrich–Wintgen condition. Supercritical coupling occurs when the near-field coupling between dark and bright modes compensates for the negligible direct far-field coupling with the dark mode. This enables a quasi-BIC field to reach maximum enhancement imposed by non-radiative loss, even when the radiative quality factor is divergent. Our experimental design consists of a photonic-crystal nanoslab covered with upconversion nanoparticles. Near-field coupling is finely tuned at the nanostructure edge, in which a coherent upconversion luminescence enhanced by eight orders of magnitude is observed. The emission shows negligible divergence, narrow width at the microscale and controllable directivity through input focusing and polarization. This approach is relevant to various physical processes, with potential applications for light-source development, energy harvesting and photochemical catalysis.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Enhanced upconversion and photoconductive nanocomposites of lanthanide-doped nanoparticles functionalized with low-vibrational-energy inorganic ligands

Upconverting nanoparticles (UCNPs) convert near-infrared (IR) light into higher-energy visible light, allowing them to be used in applications such as biological imaging, nano-thermometry, and photodetection. It is well known that the upconversion luminescent efficiency of UCNPs can be enhanced by using a host material with low phonon energies, but the use of low-vibrational-energy inorganic ligands and non-epitaxial shells has been relatively underexplored. Here, we investigate the functionalization of lanthanide-doped NaYF4 UCNPs with low-vibrational-energy Sn2S64- ligands. Raman spectroscopy and elemental mapping are employed to confirm the binding of Sn2S64- ligands to UCNPs. This binding enhances upconversion efficiencies up to a factor of 16, consistent with an increase in the luminescent lifetimes of the lanthanide ions. Annealing Sn2S64--capped UCNPs results in the formation of a nanocomposite comprised of UCNPs embedded within an interconnected matrix of SnS2, enabling each UCNP to be electrically accessible through the semiconducting SnS2 matrix. This facilitates the integration of UCNPs into electronic devices, which we demonstrate through the fabrication of a UCNP-SnS2 photodetector that detects UV and near-IR light. Our findings show the promise of using inorganic capping agents to enhance the properties of UCNPs while facilitating their integration into optoelectronic devices.

Pan, Jia-Ahn↗