Fact-checked by Grok 2 weeks ago

Photon upconversion

Photon upconversion is a photophysical process that converts two or more lower-energy photons, typically in the near-infrared region, into a single higher-energy photon, such as in the visible or ultraviolet spectrum, through anti-Stokes emission.^[1] This nonlinear optical phenomenon enables the harvesting of otherwise unused sub-bandgap light in applications like solar energy conversion.^[1] The primary mechanisms of photon upconversion include energy transfer upconversion (ETU) in lanthanide-doped inorganic nanoparticles, where sequential energy transfers between rare-earth ions like Yb³⁺ and Er³⁺ populate higher excited states, and triplet-triplet annihilation (TTA) in organic or hybrid systems, involving photosensitizers that generate triplet excitons which annihilate to produce a higher-energy singlet state.^[2] Lanthanide-based systems, dominant since their development in the 1960s, offer sharp emissions and photostability but require high excitation densities, while TTA-based approaches achieve higher quantum yields under low-power, non-coherent light like sunlight.^[1] Recent hybrid organic-inorganic interfaces, such as those using quantum dots or perovskites, enhance efficiency by improving triplet energy transfer and reducing losses from oxygen quenching.^[3] Photon upconversion holds transformative potential in energy technologies, including enhancing photovoltaic device efficiencies beyond the Shockley-Queisser limit by upconverting infrared photons for silicon solar cells and bifacial panels, and enabling visible-light-driven photocatalysis for hydrogen production or pollutant degradation.^[1] In biomedicine, it facilitates deep-tissue imaging and photodynamic therapy using near-infrared excitation to minimize autofluorescence and improve penetration.^[2] Other notable applications span anti-counterfeiting inks, optical data storage, and displays. As of 2025, advances such as gold quantum clusters and indium phosphide quantum dots have enabled quantum yields up to 12% under low-power ambient conditions, though challenges persist for achieving broad practical efficiencies exceeding 10% in diverse environments.^[4]^[5]^[6] Advances in nanostructured materials, such as silica-coated TTA nanoparticles with yields up to 4.5% in aqueous environments, underscore its growing relevance.^[2]

Fundamentals

Definition and Historical Development

Photon upconversion is a nonlinear optical process whereby the sequential absorption of two or more lower-energy (longer-wavelength) photons results in the emission of a single higher-energy (shorter-wavelength) photon.^[7]^[8] This phenomenon defies the conventional Stokes shift, in which emitted light typically has a longer wavelength than the absorbed light due to energy losses during relaxation.^[9] Upconversion enables the conversion of infrared or near-infrared radiation into visible or ultraviolet light, with applications spanning imaging, sensing, and energy harvesting.^[10] The foundational concept of photon upconversion was proposed by physicist Nicolaas Bloembergen in 1959, who envisioned a solid-state infrared quantum counter capable of detecting and amplifying infrared photons through multi-step excitation in doped crystals.^[11] Bloembergen's theoretical framework laid the groundwork for harnessing rare-earth ions to accumulate energy from multiple photons, though practical realization required further experimental validation.^[10] The process was first experimentally demonstrated in 1966 by François Auzel, who observed efficient upconversion in lanthanide-doped materials, such as those involving ytterbium-erbium pairs, marking the shift from theoretical prediction to observable anti-Stokes emission exceeding thermal limits.^[12]^[13] Throughout the 1960s, key advancements emerged from systematic studies of rare-earth ions in solid hosts, elucidating the role of energy transfer mechanisms and enabling controlled multi-photon excitations that produced visible emission from infrared input.^[13] Interest in upconversion waned temporarily after these early developments but resurged in the 2000s, driven by nanotechnology's ability to synthesize high-quality upconverting nanoparticles with enhanced brightness and biocompatibility.^[14] This interest has continued into the 2020s with discoveries such as superfluorescence in lanthanide-doped nanoparticles in 2022 and a resurgence in photon avalanche mechanisms as of 2024-2025.^[15]^[16] At its core, the quantum mechanical basis of upconversion involves intermediate excited states that facilitate the stepwise absorption of photons, allowing energy accumulation without rapid thermal dissipation, thus enabling the nonlinear conversion process.^[8]^[10]

Energy Conservation and Efficiency Considerations

Photon upconversion processes adhere to energy conservation principles, wherein the total energy from multiple absorbed lower-energy photons must exceed the energy of the emitted higher-energy photon. This is achieved through the population of long-lived intermediate excited states, which temporarily store absorbed energy before sequential excitation or energy transfer leads to the final emitting state. These intermediate states, often metastable in lanthanide ions, enable the nonlinear summation of photon energies without violating thermodynamic constraints.^[13] Key efficiency metrics for upconversion include the quantum yield (QY), defined as the ratio of the number of upconverted photons emitted to the total number of photons absorbed, expressed as \text{QY} = \frac{N_\text{em}}{N_\text{abs}}. Another critical parameter is the power dependence of emission intensity, where the upconverted emission I_\text{em} scales with excitation intensity I_\text{exc} as I_\text{em} \propto I_\text{exc}^n, with n representing the number of photons involved; for common two-photon processes, n = 2. These metrics quantify the process efficiency, which is inherently nonlinear and sensitive to excitation conditions.^[17]^[13] Efficiency in upconversion is primarily limited by thermal losses and non-radiative decay rates, which compete with radiative emission by dissipating energy as heat through phonon interactions in the host lattice. Under ideal conditions with negligible non-radiative pathways, the theoretical maximum quantum yield approaches 100%, but practical systems suffer from multiphonon relaxation and cross-relaxation, resulting in typical quantum yields below 5%. For instance, in lanthanide-doped materials, typical quantum yields range from 0.01% to 0.1% at moderate excitation powers, with optimized systems achieving up to 10.3% as of 2023, highlighting the need for low-phonon hosts to minimize these losses.^[13]^[17]^[18] The dynamics of excited state populations are modeled using rate equations, such as the simplified form for the intermediate state population N_2:

\frac{dN_2}{dt} = \sigma I N_1 - (k_r + k_\text{nr}) N_2

where \sigma is the absorption cross-section, I is the excitation intensity, N_1 is the ground state population, k_r is the radiative decay rate, and k_\text{nr} is the non-radiative decay rate. This equation illustrates how absorption populates the excited state while decay processes, particularly non-radiative ones, deplete it, directly impacting overall efficiency. In more complex upconversion schemes, additional terms account for energy transfer and higher-order excitations.^[13]

Physical Mechanisms

Excited State Absorption and Energy Transfer Upconversion

Excited state absorption (ESA) is a core mechanism in photon upconversion, involving the sequential absorption of multiple low-energy photons by a single lanthanide ion to populate higher-energy states. In this process, the ion first undergoes ground-state absorption (GSA) to reach an intermediate excited state, followed by the absorption of a second photon from that excited state to ascend to a higher level, from which visible or near-visible emission can occur.^[13] This stepwise excitation is facilitated by the discrete, ladder-like energy level structure of lanthanide ions, such as Er³⁺ or Tm³⁺, which allows efficient coupling with near-infrared excitation sources like 980 nm light.^[13] ESA is particularly prominent in systems where ion concentrations are low, minimizing inter-ion interactions, and has been observed in materials like Er³⁺-doped Y₂O₃, enabling anti-Stokes emission exceeding the excitation energy by factors of 10–100 kT.^[13] Energy transfer upconversion (ETU) represents another primary sequential process, distinguished by the involvement of multiple ions: a sensitizer ion absorbs low-energy photons and transfers the excitation energy to an activator ion through successive steps, effectively climbing the activator's energy ladder.^[13] This mechanism was first theoretically proposed in 1966 and experimentally demonstrated in lanthanide systems, marking a shift from single-ion processes to cooperative ion interactions.^[13] A representative example is the Yb³⁺-Er³⁺ pair in hosts like NaYF₄, where Yb³⁺ sensitizes by absorbing 980 nm photons to its ²F₅/₂ state and transfers energy to Er³⁺, first populating the ⁴I₁₁/₂ intermediate state and then the ⁴F₇/₂ higher state via a second transfer, resulting in green emission around 540 nm.^[19] ETU's efficiency stems from the broad absorption of the sensitizer and precise energy matching between donor and acceptor levels, making it the dominant pathway in most practical lanthanide upconverters.^[19] The energy transfer in ETU occurs primarily through Förster-Dexter mechanisms, where the Förster process governs long-range dipole-dipole coupling (typically up to 10 nm), and the Dexter mechanism handles short-range electron exchange (below 1 nm).^[20] The Förster transfer rate, which scales inversely with the sixth power of the inter-ion distance, is expressed as

W_{ET} = \frac{1}{\tau_D} \left( \frac{R_0}{r} \right)^6

where \tau_D is the excited-state lifetime of the donor, R_0 is the characteristic Förster radius (dependent on spectral overlap and orientation factors), and r is the donor-acceptor separation.^[20] Cross-relaxation, a deleterious process where energy is shared between two activator ions (e.g., one Er³⁺ in ⁴F₇/₂ relaxing to ⁴I₁₃/₂ while exciting another from the ground state to ⁴I₁₁/₂), can quench upconversion by promoting non-radiative decay and reducing population in emissive states.^[19] Such effects are mitigated in core-shell nanostructures that spatially separate sensitizer and activator layers.^[19] Overall, ETU's reliance on ion proximity and transfer rates directly influences upconversion quantum yields, often achieving efficiencies up to several percent under moderate excitation intensities.^[20]

Avalanche Upconversion

Avalanche upconversion, also known as photon avalanche (PA), is a highly nonlinear mechanism in which an initial low-efficiency excitation triggers a multiplicative buildup of excited states through a positive feedback loop, resulting in dramatically enhanced upconversion emission above a power threshold. In this process, pump photons are absorbed via non-resonant ground-state absorption (GSA) to populate a long-lived intermediate excited state (acting as "carriers") with initially weak cross-section. These excited ions then transfer energy to ground-state ions through cross-relaxation, effectively "ionizing" additional ions into the intermediate state and amplifying its population. The increased density enhances the excited-state absorption (ESA) rate to a higher emitting level, closing the feedback loop and leading to avalanche-like escalation of the excited population. This mechanism is particularly prevalent in wide-bandgap host materials doped with lanthanide ions, such as fluorides, where the large bandgap reduces non-radiative decay and supports the necessary energy level structure.^[16] The process demands high pump intensities, typically exceeding 10 kW/cm² in nanoparticles and lower in bulk crystals (e.g., ~0.5 W/cm² in fibers), to surpass the threshold where the feedback dominates over losses; below threshold, emission is negligible, while above it, the output scales with pump power raised to exponents as high as 26, reflecting the multiplicative nature. The feedback involves energy transfer processes akin to Auger mechanisms, where the de-excitation of one ion excites another, sustaining the loop until steady-state balance with relaxation rates. In hybrid systems, this can follow initial energy transfer upconversion to seed the intermediate population. Optimal conditions include resonant ESA pumping (e.g., at 1064 nm for Tm³⁺) and dopant concentrations around 8% to balance self-quenching.^[16]^[21]^[22] Prominent examples include Tm³⁺-doped crystals like LiYF₄ or NaYF₄, where excitation at ~1064 nm populates the ³H₄ intermediate state, leading to intense blue emission from the ¹G₄ level via PA, with thresholds as low as 1.7 kW/cm² in microcavity configurations. These systems have enabled applications in high-power upconversion lasers, achieving low-threshold continuous-wave operation at 800 nm for uses in optical amplification and sensing. The avalanche gain factor can be approximated as G \approx \exp(\alpha L), where \alpha is the pump-dependent absorption coefficient modulated by the density of intermediate-state ions, and L is the interaction length along the propagation path.^[23]^[16]

Triplet-Triplet Annihilation Upconversion

Triplet-triplet annihilation (TTA) upconversion is a collision-based process occurring primarily in organic and molecular systems, where low-energy photons are converted to higher-energy emission through the interaction of excited triplet states. In this mechanism, a sensitizer molecule absorbs a low-energy photon and undergoes intersystem crossing to its triplet excited state (T1). This triplet energy is then transferred to an acceptor (annihilator) molecule via triplet-triplet energy transfer (TTET), populating the acceptor's T1 state. Subsequently, two acceptor T1 states collide and annihilate, producing one higher-energy singlet excited state (S1) and one ground-state molecule; the S1 state then relaxes radiatively, emitting an upconverted photon with energy approximately twice that of the initial excitation. The TTA step follows spin statistical rules, where the encounter of two triplets yields a singlet with up to 50% probability, enabling a theoretical maximum upconversion quantum yield of 50%.^[24]^[25] Sensitized TTA enhances efficiency by employing heavy-atom-containing sensitizers to promote rapid intersystem crossing. Palladium(II) porphyrins, such as Pd-octaethylporphyrin or Pd-phthalocyanine derivatives, are widely used due to their strong absorption in the visible to near-infrared (NIR) range and efficient ISC facilitated by the heavy-atom effect, achieving ISC quantum yields near unity. These sensitizers transfer triplet energy to annihilators like polyaromatic hydrocarbons with minimal back-transfer losses, provided the sensitizer's T1 energy exceeds that of the annihilator by at least 0.3 eV. This approach allows for tunable excitation wavelengths, particularly in the NIR, where direct S1 absorption is inefficient.^[24] The TTA process was first demonstrated in the 1960s using phenanthrene as the sensitizer and anthracene as the annihilator in solution, marking the initial observation of upconverted emission from singlet annihilation. Modern systems have advanced to visible-to-NIR conversion using dyes such as perylene diimides or BODIPY derivatives as annihilators paired with Pd-porphyrin sensitizers, achieving upconversion quantum yields exceeding 20% under low-intensity excitation. These examples highlight TTA's potential in organic media for applications requiring anti-Stokes emission. The annihilation kinetics are described by the bimolecular rate equation, where the rate of triplet decay due to TTA is given by k_{\text{TT}} [\text{T}_1]^2, with k_{\text{TT}} as the rate constant.

Materials and Synthesis

Lanthanide-Doped Upconverting Nanoparticles

Lanthanide-doped upconverting nanoparticles (UCNPs) are nanoscale materials, typically composed of a host lattice such as NaYF₄ doped with trivalent lanthanide ions like Yb³⁺ and Er³⁺ or Tm³⁺, that enable photon upconversion through energy transfer processes such as excited-state absorption and energy transfer upconversion (ETU).^[26] These nanoparticles exhibit exceptional optical properties, including sharp emission lines and long-lived excited states on the millisecond scale, arising from parity-forbidden ⁴f-⁴f transitions within the lanthanide ions, which are shielded by outer 5s and 5p orbitals.^[26] In typical designs, Yb³⁺ serves as the sensitizer to absorb near-infrared excitation at around 980 nm, while Er³⁺ or Tm³⁺ acts as the activator to emit visible or near-ultraviolet light through sequential energy transfer.^[27] Synthesis of these nanoparticles commonly employs methods like co-precipitation, sol-gel, and hydrothermal approaches, which allow precise control over composition, phase (cubic or hexagonal), and morphology using NaYF₄ as the preferred host due to its low phonon energy and chemical stability.^[28] Co-precipitation involves mixing rare-earth precursors with fluoride sources in coordinating solvents like oleic acid or 1-octadecene at elevated temperatures, yielding uniform particles with high doping levels.^[28] Hydrothermal synthesis, often conducted in autoclaves with surfactants such as ethylenediaminetetraacetic acid (EDTA), enables the production of hexagonal-phase NaYF₄:Yb,Er nanoparticles with sizes tunable from 10 to 100 nm, where the hexagonal phase generally offers higher upconversion efficiency than the cubic phase.^[29] The seminal synthesis of hexagonal NaYF₄:Yb,Er and NaYF₄:Yb,Tm nanocrystals was reported in 2004 by Heer et al., marking a breakthrough in achieving bright multicolor upconversion in colloidal dispersions. Recent advances as of 2025 include microemulsion-based synthesis for improved uniformity and smaller sizes, enabling enhanced photostability and multimodal imaging applications.^[30] Additionally, photon-avalanching nanoparticles, such as NaYF₄ doped with Tm³⁺ and other lanthanides, have emerged with steep nonlinear responses for low-power upconversion.^[16] Key properties of these UCNPs include minimal quantum confinement effects, as the localized 4f electrons of lanthanides are largely unaffected by particle size down to 10 nm, unlike in semiconductor quantum dots; instead, efficiency depends on surface effects and doping concentration.^[27] Typical sizes range from 10 to 100 nm, balancing high surface-to-volume ratios for enhanced energy transfer with reduced quenching at larger dimensions.^[27] To mitigate surface quenching from vibrational energy transfer to ligands or solvents, core-shell structures are widely adopted, such as NaYF₄:Yb,Er cores coated with an undoped NaYF₄ shell (typically 2-5 nm thick), which can enhance emission intensity by up to 30-fold by passivating surface defects and confining lanthanide ions.^[31] For biomedical applications, biocompatibility is improved through silica coating, which encapsulates the hydrophobic UCNPs in a hydrophilic SiO₂ shell (5-20 nm thick), reducing cytotoxicity and enabling aqueous dispersion while preserving upconversion efficiency; studies have shown these silica-coated NaYF₄:Yb,Er nanoparticles exhibit low toxicity in vitro and in vivo at concentrations up to 100 μg/mL.^[32]

Semiconductor-Based Upconverters

Semiconductor-based upconverters primarily utilize quantum-confined nanostructures, such as quantum dots (QDs) and nanorods, to achieve photon upconversion through processes that convert lower-energy photons into higher-energy emissions. These materials leverage the quantum confinement effect in semiconductors like CdSe and PbS, where spatial restriction of charge carriers modifies electronic states to enable nonlinear optical responses. Unlike traditional upconversion systems, semiconductor nanostructures offer broadband absorption and potential for integration into devices due to their solution-processable nature. Key types include spherical QDs, such as CdSe for visible-range emissions and PbS for near-infrared (NIR) absorption, as well as anisotropic nanorods that enhance directional charge transport. Upconversion in these systems occurs via direct band-to-band processes, such as sequential two-photon absorption allowing sub-bandgap excitation to produce above-bandgap emission, or phonon-assisted absorption. Recent studies have demonstrated upconversion photoluminescence (UCPL) quantum yields approaching unity in CdSe/CdS core/shell QDs under visible excitation via phonon assistance.^[33] As of 2025, perovskite-based QDs, such as CsPbX₃ (X = Cl, Br, I), have gained prominence for efficient upconversion due to their defect tolerance and tunable bandgaps, enabling applications in solar energy harvesting.^[34] Synthesis of these nanostructures typically employs colloidal methods, particularly hot-injection techniques, to achieve precise size control and monodispersity. In the hot-injection process, organometallic precursors like cadmium oleate or lead oxide are dissolved in high-boiling solvents such as octadecene, followed by rapid injection of a chalcogenide source (e.g., selenium or sulfur dissolved in trioctylphosphine) at elevated temperatures around 300°C, promoting uniform nucleation and growth. Ligand stabilization with oleic acid is crucial, as it passivates surface defects, prevents aggregation, and enables dispersion in nonpolar solvents, yielding QDs with sizes from 2 to 10 nm. A defining property of these QDs is their tunable bandgap, achieved through size-dependent quantum confinement; for instance, PbS QDs with diameters of 1-10 nm exhibit bandgap energies shifting from ~0.6 eV (near-IR emission around 2000 nm) to ~1.4 eV (visible-NIR around 900 nm), while CdSe QDs in the same size range tune from ~2.0 eV (red emission) to ~1.7 eV (near-IR edge). This tunability arises from the inverse relationship between particle size and effective bandgap, allowing customization of absorption and emission spectra for specific applications. Additionally, semiconductor QDs possess absorption cross-sections orders of magnitude higher than those of lanthanide-doped nanoparticles, often exceeding 10^6 M^{-1} cm^{-1} due to direct bandgap transitions, compared to the narrow f-f transitions in lanthanides with cross-sections below 10^{-19} cm^2 per ion. Despite these advantages, challenges persist, particularly from nonradiative recombination processes like Auger effects, which compete with radiative decay in multiexciton states. Efforts to mitigate this include core-shell architectures, such as PbS/CdS, which spatially separate carriers to reduce losses.^[35]^[36]

Organic and Hybrid Upconversion Systems

Organic upconversion systems primarily rely on triplet-triplet annihilation (TTA) mechanisms involving molecular sensitizers and annihilators, such as dye molecules or polymers, to convert low-energy photons into higher-energy emissions. These systems offer tunable absorption and emission profiles through molecular design, enabling applications in flexible optoelectronics and photochemistry. Representative examples include BODIPY-based sensitizers paired with perylene annihilators, which facilitate red-to-blue upconversion with anti-Stokes shifts up to 0.80 eV and quantum yields reaching 15.1% in solution under 635 nm excitation. Perylene derivatives serve as efficient triplet acceptors in TTA processes, enhancing energy transfer due to their long-lived triplet states and vibronic absorption features around 400–450 nm. A seminal advancement occurred in 2010 when the Castellano group demonstrated solid-state organic upconversion in rubbery polymers like ethylene oxide-epichlorohydrin copolymers, incorporating palladium octaethylporphyrin (PdOEP) sensitizers and 9,10-diphenylanthracene (DPA) annihilators, achieving measurable emission despite lower efficiencies (around 0.02% in rigid hosts like PMMA) compared to solutions. Synthesis of these organic systems often employs self-assembly techniques or encapsulation within micelles to promote chromophore diffusion and solubility, particularly in aqueous environments. For instance, TTA-UC nanomicelles solubilize hydrophobic dyes like PdOEP/DPA using non-ionic surfactants, yielding up to 6.5% quantum efficiency under 0.1 W/cm² in aerated water.^[2] These methods leverage the inherent flexibility of polymeric hosts, such as polyurethanes with low glass transition temperatures, enabling moldable solids that maintain upconversion at power densities below 1 mW/cm², alongside low toxicity profiles suitable for biomedical contexts.^[37] Hybrid upconversion systems integrate organic dyes with inorganic nanoparticles to broaden spectral response and enhance light harvesting via the antenna effect, where dyes absorb sub-bandgap photons and transfer energy to lanthanide ions.^[38] A key example involves near-infrared dyes like IR-808 adsorbed onto β-NaYF₄:Yb,Er nanoparticles, extending absorption from 980 nm to 700–1100 nm and enabling broadband upconversion to green emission.^[38] Synthesis typically occurs through self-assembly by mixing dye solutions with ligand-capped nanoparticles, followed by optional micelle encapsulation for stability, which imparts mechanical flexibility and reduced toxicity relative to purely inorganic counterparts.^[39] These hybrids achieve upconversion quantum yields up to 20% under low excitation powers (e.g., <1 mW/cm² at 514.5 nm), surpassing traditional lanthanide systems in non-coherent conditions due to efficient sensitization.^[37] The combination exploits organic components' solution-processability for device integration while benefiting from nanoparticle stability, with demonstrated anti-Stokes shifts exceeding 0.5 eV in energy-cascaded configurations. Recent progress as of 2025 includes earth-abundant transition metal complexes as sensitizers in sensitized TTA-UC, improving scalability.^[40]

Applications

Biomedical Imaging and Therapy

Photon upconversion materials, particularly lanthanide-doped upconverting nanoparticles (UCNPs), enable near-infrared (NIR) to visible light conversion, facilitating deep-tissue penetration in biomedical imaging while minimizing photodamage and tissue absorption.^[41] This NIR excitation wavelength (typically 980 nm) allows for imaging depths exceeding several centimeters in biological tissues, far surpassing traditional visible light probes limited to superficial applications.^[42] Key advantages include reduced autofluorescence from biological samples, leading to higher signal-to-noise ratios and sharper contrast in vivo.^[43] For targeted tumor imaging, UCNPs have been conjugated with folate to exploit overexpression of folate receptors on cancer cells, enabling selective accumulation and visualization in models such as breast and ovarian tumors.^[44] In photodynamic therapy (PDT), upconversion enables NIR activation of photosensitizers (PS) that generate reactive oxygen species (ROS) for cell destruction, overcoming the limited tissue penetration of direct visible light excitation for PS.^[45] This approach has been demonstrated in cancer treatment, where UCNPs transfer upconverted energy to PS like chlorin e6, achieving efficient ROS production and tumor ablation under NIR irradiation.^[46] Differential cancer bioimaging and therapy benefit from pH-responsive UC nanocapsules, which disassemble in the acidic tumor microenvironment (pH ~6.5) to release payloads and enhance upconversion efficiency for precise in vivo discrimination of malignant tissues, as shown in 2010s studies with doxorubicin-loaded PLGA-UCNP systems.^[47] Challenges in semiconductor-based upconverters, such as quantum dots, include fluorescence blinking that can degrade imaging stability, though lanthanide UCNPs mitigate this through steady emission.^[48] A notable application extends to antimicrobial therapy, where a 2014 study demonstrated UCNP-mediated PDT effectively killing multidrug-resistant bacteria like Staphylococcus aureus by NIR-triggered ROS generation, offering a non-antibiotic alternative for infections.^[49] Upconversion probes continue to advance toward clinical use, with investigations in the 2020s focusing on multimodal imaging and therapy platforms for enhanced safety and efficacy in preclinical studies.^[50]

Photovoltaics and Energy Harvesting

Photon upconversion plays a crucial role in enhancing photovoltaic performance by addressing spectral losses in solar cells, particularly for single-junction silicon devices where infrared photons below the bandgap (~1.1 eV) pass through unabsorbed. In this configuration, an upconversion layer is typically placed at the rear of the solar cell, converting two or more low-energy near-infrared photons into a single higher-energy visible photon that can be reabsorbed by the cell's active material, thereby increasing the short-circuit current density and overall quantum efficiency.^[51] This mechanism is especially effective under non-concentrated sunlight, as it recycles otherwise wasted sub-bandgap light without requiring complex structural changes to the cell itself.^[52] For tandem solar cells, upconversion layers can be integrated between sub-cells to redirect upconverted photons to the appropriate absorber, further optimizing spectral matching in multi-junction architectures. Common materials for these upconversion layers include lanthanide-doped films, such as ytterbium-erbium (Yb/Er) co-doped garnets or glasses applied to the photovoltaic backsheet or as rear reflectors to minimize light escape. For instance, Yb³⁺ acts as a sensitizer absorbing ~980 nm light, transferring energy to Er³⁺ activators that emit in the green (~550 nm), aligning with silicon's absorption band.^[52] Laboratory prototypes incorporating such layers have demonstrated modest but verifiable efficiency gains, typically 1-2% absolute under 1-sun illumination, with external quantum efficiency contributions from upconversion reaching up to 1.07% in broad-spectrum tests.^[53] Theoretical analyses by Trupke et al. indicate that an ideal upconverter could elevate the efficiency limit of a silicon solar cell from ~30% to 40.2% under AM1.5 illumination, representing a potential ~10% absolute boost by fully utilizing sub-bandgap photons. Beyond direct cell integration, upconversion enhances energy harvesting in luminescent solar concentrators (LSCs), where it broadens the absorption spectrum into the near-infrared, guiding upconverted light to edge-mounted photovoltaic cells via total internal reflection. Examples include upconversion-assisted dual-band LSCs using Yb/Er-doped nanoparticles combined with down-shifting dyes, achieving power conversion efficiencies up to 5-7% in small-scale devices coupled to perovskite solar cells.^[54] In dye-sensitized solar cells (DSSCs) tailored for indoor photovoltaics, triplet-triplet annihilation upconversion sensitizers extend low-light response by converting ambient near-infrared to visible wavelengths, improving efficiency under LED or fluorescent illumination relative to standard DSSCs.^[55] Recent advancements, particularly in 2023, have focused on broadband upconversion for perovskite solar cells, incorporating dye-hybridized nanoparticles or TTA mechanisms to harvest a wider near-infrared range (800-1000 nm), resulting in increases in photocurrent density of up to ~3 mA/cm² and pushing device efficiencies to around 21%.^[56] These developments emphasize core-shell nanostructures for reduced non-radiative losses, enabling scalable integration while maintaining stability under operational conditions.^[57]

Anti-Counterfeiting and Optical Devices

Photon upconversion materials are widely utilized in anti-counterfeiting applications through specialized inks and tags that convert ultraviolet or near-infrared excitation into visible emission, providing covert authentication features invisible under normal lighting. These upconverting nanoparticles, often lanthanide-doped, enable high-resolution patterns printed via inkjet technology, suitable for integration into security documents like banknotes and passports since the early 2010s. For instance, multicolor luminescent patterns with controlled emission have been demonstrated for secure printing, offering robust protection against forgery.^[58]^[59] The inherent advantages of upconversion in anti-counterfeiting stem from its nonlinear optical response, where emission intensity scales superlinearly with excitation power, making replication challenging with standard imaging devices that rely on linear processes. This property, combined with the spectral tunability of lanthanide emissions, allows for complex multi-color codes and dynamic authentication schemes, such as quick response codes that reveal under specific wavelengths. Research highlights the feasibility of these inks in screen-printed security features, emphasizing their photostability and low toxicity for practical deployment.^[60]^[61] In optical devices, upconversion facilitates advanced lasers and amplifiers by enabling efficient conversion of low-energy photons into higher-energy outputs. Lanthanide-doped nanomaterials serve as gain media in upconversion lasers, supporting compact designs that lase from near-infrared to ultraviolet regimes with low thresholds, as demonstrated in microcavity configurations. These systems leverage sequential energy transfer for high beam quality and tunability, finding use in photonic integrated circuits.^[62]^[63] Erbium-doped fiber optics incorporate upconversion for signal regeneration in amplifiers, where dual-photon absorption at around 800 nm pumps the system, enhancing gain at 850 nm wavelengths and mitigating noise in long-haul communications. This upconversion-pumped operation improves efficiency over traditional schemes, particularly for extended L-band transmission. Semiconductor-based upconverters can complement these as compact NIR-to-visible sources in hybrid devices.^[64]^[65] Upconversion also enhances organic light-emitting diodes (OLEDs) by promoting blue emission through triplet-triplet annihilation, where low-energy triplets convert to higher-energy singlets, reducing turn-on voltages to as low as 1.47 V while achieving external quantum efficiencies around 3%. Recent prototypes optimize donor-acceptor interfaces to minimize losses, enabling stable deep-blue output at 462 nm suitable for displays and lighting.^[66]^[67]

References

[1]
Photon Upconversion for Photovoltaics and Photocatalysis: A Critical Review
### Summary of Photon Upconversion for Photovoltaics and Photocatalysis: A Critical Review
[2]
Designing Next Generation of Photon Upconversion - NIH
In this review, we focus on the latest breakthroughs in such new version of upconversion nanoparticle, including their design, preparation, and applications.
[3]
https://www.annualreviews.org/doi/full/10.1146/annurev-physchem-090722-011335
[4]
What is Upconversion? - Edinburgh Instruments
Photon upconversion is the sequential absorption of two or more long wavelength photons leading to the emission of a photon with a shorter wavelength.
[5]
Upconversion - RP Photonics
Upconversion is a process where light can be emitted with photon energies higher than those of the light generating the excitation.
[6]
Photon Upconversion in Small Molecules - PMC - NIH
Upconversion (UC) is a process that describes the emission of shorter-wavelength light compared to that of the excitation source.
[7]
Photon-Upconverting Materials: Advances and Prospects for ...
Nov 10, 2016 · The concept of UC was conceived by physicist N. Bloembergen [1] in 1959 to develop an infrared (IR) photon detector for counting infrared ...
[8]
Solid State Infrared Quantum Counters | Phys. Rev. Lett.
Solid State Infrared Quantum Counters. N. Bloembergen, Harvard University, Cambridge, Massachusetts. PDF Share. Phys. Rev. Lett. 2, 84 – Published 1 February, ...
[9]
History of upconversion discovery and its evolution - ScienceDirect
Upconversion, from basic physics evolved into an indispensable optical tool in low energy photon excitation which contrary to previously used UV and blue ...
[10]
Upconversion and Anti-Stokes Processes with f and d Ions in Solids
The role of energy transfers in upconversion processes was not recognized until 1966 ... François Auzel - GOTR, UMR 7574-CNRS, 1, Place A-Briand, 92195 Meudon ...
[11]
Upconversion in Nanostructured Materials: From Optical Tuning to ...
Dec 29, 2017 · It was not until the 2000s, when high-quality upconversion nanoparticles (UCNPs) became routinely accessible by means of several synthetic ...
[12]
The upconversion quantum yield (UCQY): a review to standardize ...
1. 1.1. The upconversion (UC) process consists of the absorption of low energy photons and the subsequent emission of a relatively high energy photon.
[13]
Energy-Transfer Editing in Lanthanide-Activated Upconversion ...
Jan 7, 2019 · This outlook outlines the fundamental mechanism for photon upconversion, reviews the current state of the art of lanthanide-activated upconversion nanocrystals.Missing: seminal | Show results with:seminal
[14]
Energy transfer in lanthanide upconversion studies for extended ...
Sep 22, 2014 · This review presents a fundamental understanding of energy transfer in lanthanide-supported photon upconversion.
[15]
Recent advances in fundamental research on photon avalanches on ...
Feb 14, 2025 · PA in lanthanide-based materials is a nonlinear upconverting (UC) mechanism, in which a fractional increase in pumping power results in a ...
[16]
Enhanced photon avalanche | Nature Physics
Aug 11, 2025 · The absorption of multiple photons triggers a chain reaction and a buildup of many excited states, resulting in a photon avalanche.
[17]
https://www.tandfonline.com/doi/full/10.1080/14686996.2021.1967698
[18]
Photon avalanche upconversion in various Tm3+-doped materials
Numerous photon avalanche observations have been reported up to room temperature in Tm3+-doped compounds leading to the strong blue emission (1G4→3H6) of Tm3+ ...
[19]
https://pubs.acs.org/doi/10.1021/acscentsci.8b00827
[20]
On the Quantum Yield of Photon Upconversion via Triplet–Triplet ...
Jun 22, 2020 · Photon upconversion (UC), the process of combining two or more low-energy photons to generate a higher-energy excited state, is of interest ...Author Information · References
[21]
Lanthanide-doped upconversion nanoparticles | Physics Today
Sep 1, 2015 · François Auzel and Jay Chivian and colleagues developed upconversion processes based on energy transfer from one lanthanide ion to another. In ...
[22]
Upconversion Nanoparticles: Design, Nanochemistry, and ...
Mar 10, 2014 · (168) It is known that the quantum-confinement effect is not available for lanthanide ions that are doped into UCNPs. (92) Thus, unlike QDs ...
[23]
Upconversion Nanoparticles: Synthesis, Surface Modification ... - NIH
This method is the first reported synthesis of NaYF4:Yb,Er/Tm UCNPs. 4. Modification of RE doped NaYF4 UCNPs. In general, RE doped NaYF4 UCNPs synthesized ...
[24]
Controlled synthesis and morphology dependent upconversion ...
Jun 12, 2007 · Size and morphology controlled NaYF4:Yb, Er nanocrystals were synthesized via the hydrothermal method. Polydentate ligands, such as EDTA and ...
[25]
Synthesis of Hexagonal-Phase Core−Shell NaYF 4 Nanocrystals ...
(13) Recently, a method was reported for synthesizing core−shell β-NaYF4:Yb,Er(Tm)/β-NaYF4 nanoparticles with both the core and shell composed of hexagonal- ...
[26]
Biocompatibility of silica coated NaYF 4 upconversion fluorescent ...
The results from this study revealed that the silica coated NaYF 4 upconversion nanocrystals displayed good in vitro and in vivo biocompatibility.
[27]
Phonon-assisted up-conversion photoluminescence of quantum dots
Jul 13, 2021 · Phonon-assisted up-conversion photoluminescence can boost energy of an emission photon to be higher than that of the excitation photon by absorbing vibration ...
[28]
Auger Up-Conversion of Low-Intensity Infrared Light in Engineered ...
Nov 29, 2016 · A more practical approach to stepwise up-conversion involves the use of Auger recombination. In this process, sequential absorption of two ...
[29]
Semiconductor quantum dots: Technological progress and future ...
Aug 6, 2021 · As QDs become smaller, quantum confinement increases the effective bandgap, leading to a blue shift of the absorption and emission spectra. An ...
[30]
https://www.frontiersin.org/journals/photonics/articles/10.3389/fphot.2024.1363223/full
[31]
https://pubs.acs.org/doi/10.1021/la802343f
[32]
Energy-Cascaded Upconversion in an Organic Dye-Sensitized Core ...
Here, we introduce a concept of multistep cascade energy transfer, from broadly infrared-harvesting organic dyes to sensitizer ions in the shell of an ...
[33]
A review on upconversion nanoparticles in biomedical applications ...
NIR excitation is particularly advantageous in biomedical contexts because it offers deeper tissue penetration and minimizes photodamage to living cells and ...
[34]
Upconversion Nanoparticles for Bioimaging and Regenerative ...
This technique allows real-time images, presents high sensitivity, and is low cost. However, its disadvantage is its limited penetration depth in tissues. In ...
[35]
Upconverting Nanoparticles as a New Bio-Imaging Strategy ...
UCNPs are a better alternative to traditional optical imaging due to several advantages, such as resistance to photobleaching, low background autofluorescence ...
[36]
Folic Acid-Conjugated LaF 3 :Yb,Tm@SiO 2 Nanoprobes for ...
The UCNPs@SiO 2 -FA exhibits good stability, water dispersibility and solubility, low cytotoxicity, good biocompatibility, highly selective targeting, ...
[37]
Upconversion Nanoparticles for Photodynamic Therapy and Other ...
Owing to the high tissue penetration ability of NIR light, NIR-excited UCNPs can be used to activate PS molecules in much deeper tissues compared to ...<|separator|>
[38]
Near-Infrared Light-Triggered Photodynamic Therapy and Apoptosis ...
Apr 16, 2020 · In this study, a light source with a wavelength of 808 nm was used as an excitation source for Nd-doped UCNPs to solve the overheating effect.
[39]
Fabrication of pH-responsive PLGA(UCNPs/DOX) nanocapsules ...
Dec 21, 2017 · Moreover, the PLGA(UCNPs/DOX) nanocapsules exhibited pH-responsive drug releasing behavior, causing the loaded DOX easily releasing at cancer ...
[40]
Upconversion Nanoparticles: A Versatile Solution to Multiscale ... - NIH
The aim of this review is to line up some issues associated with conventional fluorescent probes, and to address the recent advances of upconverting ...
[41]
Multifunctional upconverting nanoparticles for near-infrared ...
Jul 22, 2014 · To integrate photodynamic therapy with photothermal therapy for improved multidrug-resistant bacteria therapy, we have constructed a novel ...Missing: upconversion | Show results with:upconversion
[42]
(PDF) Enhancing glioma treatment with 3D scaffolds laden with ...
Oct 21, 2024 · Upconversion nanoparticles (UCNPs) are being actively explored as promising agents for detection and monitoring of tumor growth, and as ...<|separator|>
[43]
Upconversion as a spear carrier for tuning photovoltaic efficiency
Feb 14, 2024 · Upconversion converts sub-bandgap photons into higher energy photons, harvesting unutilized solar energy and increasing light-harvesting ...
[44]
Advances in upconversion enhanced solar cell performance
Sep 15, 2021 · The energy transfer upconversion (ETU) mechanism comprises two Ln3+ ions, one of them being a sensitizer and the other acting as an activator. ...
[45]
Enhancement of silicon solar cell efficiency by upconversion
Aug 24, 2010 · The device of silicon solar cell and applied upconverter showed an external quantum efficiency of 0.34% at an irradiance of 1090 W m − 2 ( 0.03 ...Missing: improvement | Show results with:improvement
[46]
Photon upconversion-assisted dual-band luminescence solar ...
Jun 4, 2020 · We demonstrate an LSC-PV, which is based on the combination of an upconversion (UC)-assisted dual band harvesting LSC and perovskite solar cells (PSCs).
[47]
[PDF] Review of Materials Used in TTA-Photon Upconversion Integrated ...
Dec 15, 2024 · Since the upconversion mechanism is applied on sub-bandgap photons, solar cells with high bandgap values like DSSC increase efficiency once ...
[48]
Triplet–triplet annihilation mediated photon upconversion solar ...
Apr 3, 2023 · Triplet–triplet annihilation mediated photon upconversion (TTA-UC) is emerging as a way to overcome losses due to the transmission of photons below the PV/ ...
[49]
A multiband NIR upconversion core-shell design for enhanced light ...
Nov 25, 2024 · Here, we report the design of an efficient multiband UC system based on Ln 3+ /Yb 3+ -doped core-shell upconversion nanoparticles.Missing: prototypes | Show results with:prototypes
[50]
Inkjet printing of upconversion nanoparticles for anti-counterfeit ...
We report a digital and flexible inkjet printing based approach for producing high-resolution and high-luminescence anti-counterfeit patterns.Missing: commercialization | Show results with:commercialization
[51]
Colour tuneable upconversion photonic materials for anti ...
Ultimate generation of luminescent security inks have been used to detect counterfeiting including applications in banknotes, quick response codes (QR codes) ...Missing: nanoparticles passports<|control11|><|separator|>
[52]
High-security anti-counterfeiting through upconversion luminescence
In this review, we focus on recent advances in anti-counterfeiting technology that exploits the remarkable tunability of upconversion luminescence.Missing: commercialization | Show results with:commercialization
[53]
[PDF] Highly luminescent upconversion material for anti-counterfeiting ...
We used a screen printing process to print security codes and investigated the feasibility of phosphorus-based secu- rity inks for anti-counterfeiting ...
[54]
Advanced lanthanide doped upconversion nanomaterials for lasing ...
Lanthanide doped upconversion materials are potential gain media for microlasers from near infrared (NIR) to visible and UV regimes.
[55]
Lanthanide-doped nanocrystals in high-Q microtoroids for stable on ...
Jun 14, 2022 · The strong light matter interaction in high- Q microtoroids greatly enhances the upconversion emission and dramatically reduces the laser ...
[56]
Erbium-doped fiber amplifiers: theory of upconversion-pumped ...
A model is presented for erbium-doped fiber amplifiers that operate by an upconversion process in which two pump photons at ~800 nm are absorbed and can ...Missing: regeneration | Show results with:regeneration
[57]
Progress in Er-doped fibers for extended L-band operation of ...
Erbium (Er)-doped fiber amplifiers (EDFAs) have revolutionized optical fiber communication, facilitating long-distance, large-capacity, and high-reliability ...Missing: regeneration | Show results with:regeneration
[58]
Blue organic light-emitting diode with a turn-on voltage of 1.47 V
Sep 20, 2023 · An ultralow voltage turn-on at 1.47 V for blue emission with a peak wavelength at 462 nm (2.68 eV) is demonstrated in an OLED device with a typical blue- ...
[59]
Enhancing Electron Transfer for Highly Efficient Upconversion OLEDs
Aug 21, 2024 · This mechanism can significantly lower the turn-on voltage of blue UC-OLEDs compared to conventional blue OLEDs, potentially addressing issues ...