Broadband Near‐Infrared Down‐Shifting by Yb–O Charge‐Transfer Band in Yb3+ Singly Doped Tellurite Glasses

Yb³⁺ singly doped tellurite as‐prepared glasses and glass ceramics were synthesized by high‐temperature melt‐quenching method. The excitation and emission spectra have shown that there is an efficient near‐infrared (NIR) down‐shifting due to the sensitization of a novel Yb³⁺–O^2? charge‐transfer (CT) band. The CT band in the present host is located at around 320 nm at room temperature, which is much lower than that in other oxide hosts reported before. The possible energy‐transfer mechanism from the Yb³⁺–O^2? CT band to the ²F_5/2 multiplet of Yb³⁺ ions is discussed in detail. The concentration quenching is not observed even when the Yb³⁺‐doped concentration is increased up to 40 mol%. The excitation of this strong broad CT band causes intense NIR emission of Yb³⁺:²F_5/2→²F_7/2 from 920 to 1120 nm, making the tellurite glasses suitable for efficient photovoltaic (PV) application as a spectral conversion material for the crystalline Si (c‐Si) solar cells.     

Near‐Infrared Quantum Cutting via Downconversion Energy Transfers in Ho3+/Yb3+ Codoped Tellurite Glass Ceramics

The different concentration of Ho³⁺/Yb³⁺ codoped tellurite glasses were prepared by high‐temperature melting‐quenching method. On excitation of Ho³⁺ ions with blue photon at 449 nm as well as ultraviolet (UV) photon at 360 nm, the near infrared emission at 977 nm from Yb³⁺ and 981, 1020 nm from Ho³⁺, which could be absorbed by silicon and enhance the efficiency of the silicon‐based solar cell, were observed. The energy‐transfer process of Ho³⁺ and Yb³⁺ ions and involved mechanism have been investigated and discussed. The first‐order energy transfer (ET) through cross relaxation and a back ET from Yb³⁺ to Ho³⁺ occurred in the near‐infrared quantum cutting (NIR QC) system are proposed and verified. The NIR quantum efficiency achieved 166% when Yb³⁺ doping concentration is 20 mol%.     

High Nd3+→Yb3+ energy transfer efficiency in tungsten‐tellurite glass: A promising converter for solar cells

This work reports on the energy transfer efficiency for Nd³⁺/Yb³⁺ co‐doped tellurite glasses (80TO₂‐20WO₃, in mol%,). The correlation between Yb³⁺ ion concentration and the downconversion mechanism was investigated using optical and thermal lens spectroscopies, which enabled investigation of the radiative and nonradiative processes, respectively, involved in energy transfer from neodymium to ytterbium. The Nd³⁺ near‐infrared fluorescence disappeared almost entirely when the maximum concentration of Yb³⁺ ions (4 mol%) was doped into the host. In contrast, there was a corresponding increase in the ytterbium emission at around 980 nm. When ytterbium was added, there was also a simultaneous reduction in the amount of heat generated by the sample due to a reduction in the nonradiative decay rate, corroborating the suspected high energy transfer efficiency of Nd³⁺→Yb³⁺. The results indicate that tungsten‐tellurite glasses may be of potential use in solar cells for matching the solar emission spectrum to the semiconductor cell.     

Enhanced Sunlight Excited 1‐μm Emission in Cr3+–Yb3+ Codoped Transparent Glass‐Ceramics Containing Y3Al5O12 Nanocrystals

Cr³⁺–Yb³⁺ codoped transparent glass‐ceramics containing Y₃Al₅O₁₂ nanocrystals were prepared by heat treatment of as‐prepared glass sample and characterized by X‐ray diffraction and transmission electron microscopy. The efficient energy transfer from Cr³⁺ to Yb³⁺ ions through multi‐phonon‐assisted process was confirmed by the luminescence spectrum and fluorescent lifetime measurements. When excited by the lights from a solar simulator in the wavelength region of 400–800 nm, greatly enhanced near‐infrared emission around 1 μm was achieved from Cr³⁺–Yb³⁺ codoped glass ceramic compared with that from as‐prepared glass and Ce³⁺–Yb³⁺ codoped glass ceramic. These results demonstrate that the Cr³⁺–Yb³⁺ codoped glass ceramic is a promising material for enhancement of the efficiency of solar energy utilization.     

Transmission electron microscopic and optical spectroscopic studies of Ni2+/Yb3+/Er3+/Tm3+ doped dual‐phase glass‐ceramics

Ni²⁺/Yb³⁺/Er³⁺/Tm³⁺ codoped transparent glass‐ceramics (GCs) containing both hexagonal β‐YF₃ and spinel‐like γ‐Ga₂O₃ dual‐phase nanoparticles (NCs) are synthesized by melt‐quenching and subsequent heating procedures. Two techniques of transmission electron microscopy (TEM) nanoanalytics and optical spectroscopy are conjugated to understand the distribution of the rare‐earth ions (REs) and transition metals (TMs) in the nanostructured GCs. It is found that the REs are located predominantly in β‐YF₃, whereas the TMs in γ‐Ga₂O₃ NCs. As a result, energy transfer (ET) between the REs and TMs is considerably suppressed due to the large spatial separation (> 3 nm), but it is enhanced between the REs partitioned in the β‐YF₃ NCs. This has important implications for intended and demanding photoluminescence functions. For example, an ultrabroadband near‐infrared (NIR) emission in the wavelength region of 1000‐2000 nm covering the entire telecommunications window is observed for the first time. Meanwhile, intense upconversion (UC) emissions covering the 3 primary colors and locating in the first biological window can be also recorded under excitation by a single pump source at 980 nm.     

Improved broadband near-infrared luminescence in Nd3+/Tm3+ co-doping tellurite glass with Ag NPs

The near-infrared (NIR) luminescence in S+E+O bands of tellurite glasses doped with Nd³⁺/Tm³⁺ and Ag nanoparticles (NPs) was investigated. The tellurite glasses were prepared by melt-quenching and heat-treated techniques. Under the excitation of 808 nm laser, Nd³⁺/Tm³⁺ doped tellurite glasses produced three NIR luminescence bands of 1.33, 1.47 and 1.85 μm, originating from Nd³⁺:⁴F_3/2→⁴I_13/2, Tm³⁺:³H₄→³F₄ and Tm³⁺:³F₄→³H₆ transitions respectively. Interestingly, a broadband luminescence spectrum ranging from 1280 to 1550 nm with the FWHM (full width at half maximum) about 201 nm was obtained due to the overlapping of the first two NIR bands. Further, the peak intensity of this broadband luminescence was increased by 75% after the introduction of Ag NPs with diameter in 10–20 nm. The analysis of fluorescence decay shows that compared with the enhanced local electric field, the energy transfer from Ag species to Nd³⁺ and Tm³⁺ ions plays a major role in luminescence enhancement. The findings in this work indicate that tellurite glass co-doped with Nd³⁺/Tm³⁺ and Ag NPs is a potential gain material applied in the S+E+O-band photonic devices.     

Improving the NIR light‐harvesting of perovskite solar cell with upconversion fluorotellurite glass

Upconversion glasses are capable of converting the sub‐bandgap NIR light into photons of a particular wavelength which can be efficiently utilized by solar cells. Herein, the Yb³⁺/Er³⁺ co‐doped fluorotellurite upconversion glasses were prepared. The most intense upconversion luminescence (UCL) under 980‐nm LD excitation was obtained in the glass with Yb³⁺‐to‐Er³⁺ molar ratio of 10:1. The dependences of UCL on the pump power and temperature were investigated. The UCL can be mainly attributed to the two‐photon involved energy transfer processes and is very stable to the change in temperature even when heated up to 200°C. The subsequent implementation of the glass as upconverter for a MAPbI_3‐xCl_x‐based perovskite solar cell (PSC) resulted in an open circuit voltage of 0.83 V and a short circuit current density of 0.32 mA/cm². This application of upconversion glass for enhancing the NIR light harvesting offers a promising way to improve the photo‐electric conversion efficiencies of PSCs.     

Spectral Conversion From Ultraviolet to Near Infrared in Yb3+‐Doped Pyrovanadate Zn2V2O7 Particles

Yb³⁺‐doped Zn₂V₂O₇ particles were synthesized via the Pechini method. The crystal structure and morphology of the polycrystalline samples were investigated by X‐ray powder diffraction and scanning electron microscopy measurements, respectively. The reflectance spectrum, photoluminescence excitation, emission spectra, and the absolute quantum efficiency of the IR emission (900–1100) were measured. The intense near‐IR emission around 1000 nm attributed to the ²F_5/2 → ²F_7/2 transition of Yb³⁺ was observed under the excitation of ultraviolet light in the Yb³⁺‐doped pyrovanadate. The efficient energy transfer from VO₄ groups into Yb³⁺ ions was confirmed by the optical spectra and fluorescent lifetime measurements. These results demonstrate that the Yb³⁺‐doped pyrovanadate particles are promising materials for spectral conversion from visible sunlight to near‐infrared emission and it may have potential application for spectral convertor to enhance the photoelectric conversion efficiency of c‐Si solar cells.     

Thermal Stability and Spectral Properties of Tm<Superscript>3+</Superscript>-Yb<Superscript>3+</Superscript> CO-Doped Tellurite Glasses

Glasses of the system 75TeO₂–20ZnO–5La₂O₃–0.8Tm₂O₃–xYb₂O₃ were prepared by high temperature melt cooling method. Results of differential scanning calorimetry indicate that, all glass samples have excellent thermal stability. Judd–Ofelt strength parameters, spontaneous emission probabilities, fluorescence branching rations, fluorescence radiative lifetime of Tm³⁺ ions in tellurite glass were calculated. The impact of Yb³⁺ concentration on the fluorescence properties of Tm³⁺ ions in the S band under the pumping wavelength of 465 nm was investigated in a suggestion that, ³H₄ radiative lifetimes will be prolonged and the performance of optical amplifier gain of Tm³⁺ in tellurite glass co-doped with 0.5 mol % Yb³⁺ ions will be improved.     

Near‐infrared quantum cutting of Eu2+/Yb3+ codoped chalcohalide glasses

Near‐infrared (NIR) quantum cutting involving the emission of two NIR photons for each visible photon absorbed is realized from Eu²⁺/Yb³⁺ codoped chalcohalide glasses. Excitation, emission and decay spectra are measured to prove the occurrence of cooperative energy transfer (ET) from Eu²⁺ to Yb³⁺. The maximum ET efficiency obtained is as high as 85%. The ET from Eu²⁺ to Yb³⁺ is followed by dipole‐dipole interaction. The possible mechanism of ET is discussed.     

Intense 2.85 μm mid-infrared emissions in Yb3+/Ho3+ codoped and Yb3+/Er3+/Ho3+ tridoped TBLL fluorotellurite glasses and their energy transfer mechanism

Yb³⁺/Ho³⁺ codoped and Yb³⁺/Er³⁺/Ho³⁺ tridoped TeO₂–BaF₂–LaF₃–La₂O₃ (TBLL) fluorotellurite glasses with low OH^? absorption (0.026 cm^-1), high glass transition temperature (434 °C) and low phonon energy (784 cm^-1) were prepared. Their mid-infrared fluorescence properties and related energy transfer (ET) mechanism were studied under 980 nm excitation. A strong emission at 2.85 μm was realized in Yb³⁺/Ho³⁺ codoped tellurite glass, which was attributed to the high-efficiency ET from Yb³⁺ ions to Ho³⁺, and the ET efficiency was 91.1%. Further introduction of Er³⁺ ions induced stronger 2.85 μm emission, and the ET efficiency was improved to 96.2%, ascribed to the establishment of more ET channels and Er³⁺ ions playing the role of ET bridge between Yb³⁺ and Ho³⁺ ions. These results indicate that the Yb³⁺/Er³⁺/Ho³⁺ tridoped tellurite glass could be a hopeful gain medium material for the ～3 μm fiber laser.     

Tailorable Multicolor Up‐conversion Emissions in Tm3+/Ho3+/Yb3+ Co‐Doped LiLa(MoO4)2

Using a modified sol–gel method, LiLa(MoO₄)₂: Tm³⁺/Ho³⁺/Yb³⁺ phosphors with tailorable up‐conversion (UC) emission colors were prepared. Under the excitation of a 980 nm laser diode, up‐conversion red and green emissions in Ho³⁺/Yb³⁺ co‐doped and blue emission in Tm³⁺/Yb³⁺ co‐doped LiLa(MoO₄)₂ were observed, respectively. The intensities of the RGB (red, green, and blue) emissions could be controlled by varying concentrations of Tm³⁺ or Ho³⁺, and the optimal composition was also determined. In Tm³⁺/Ho³⁺/Yb³⁺ co‐doped LiLa(MoO₄)₂, the UC emission colors could be tuned from blue through white to yellow by adjusting the concentrations of Tm³⁺ or Ho³⁺. The UC excitation mechanisms were also investigated based on the power dependence of UC luminescence intensity.     

Enhanced near-infrared emission in Yb3+-Cr3+ codoped KZnF3 glass ceramics excited by a solar simulator

Cr³⁺-Yb³⁺ codoped bulk glass-ceramics containing KZnF₃ nanocrystals are fabricated by thermal treatment of cast glass samples and characterized by X-ray diffraction and transmission electron microscopy. The luminescent properties of the glass and glass ceramic are investigated from the measured photoluminescence spectra and fluorescent lifetime. The measurement results demonstrate that Cr³⁺ and Yb³⁺ ions are both predominantly hosted in the KZnF₃ nanocrystals, and the energy absorbed by Cr³⁺ ions is efficiently transferred to Yb³⁺ ions when excited at 450?nm. Compared to the glass, the near-infrared emission in the Cr³⁺-Yb³⁺ codoped glass ceramics is significantly enhanced when the excitation wavelength lies in the range λ~400–800?nm of a solar simulator. Results indicate that the Cr³⁺-Yb³⁺ codoped KZnF₃ glass ceramic provides a promising material for spectral conversion from visible sunlight to near-infrared emission and a novel gain material for solar pumped fiber laser.     

Infrared to Visible Up‐Conversion Emission in Er3+/Yb3+ Codoped Fluoro–Phosphate Glass–Ceramics

Erbium Er³⁺ and ytterbium Yb³⁺ codoped fluoro‐phosphate glasses belonging to the system NaPO₃–YF₃–BaF₂–CaF₂ have been prepared by the classical melt‐quenching technique. Glasses containing up to 10 wt% of erbium and ytterbium fluorides have been obtained and characterized using differential scanning calorimetry (DSC) and UV–visible and near‐infrared spectroscopy. Transparent and homogeneous glass–ceramics have been then reproducibly synthetized by appropriate heat treatment above glass transition temperature of a selected parent glass. Structural investigations of the crystallization performed through X‐ray diffractometry (XRD) and scanning electron microscopy (SEM) have evidenced the formation of fluorite‐type cubic crystals based during the devitrification process. Finally, infrared to visible up‐conversion emission upon excitation at 975 nm has been studied on the Er³⁺ and Yb³⁺ codoped glass–ceramics as a function of thermal treatment time. A large enhancement of intensity of the up‐conversion emissions–about 150 times‐ has been observed in the glass–ceramics if compared to the parent glass one, suggesting an incorporation of the rare‐earth ions (REI) into the crystalline phase.     

Emission from Mo‐O charge‐transfer state and Yb3+ emission in Eu3+‐doped and nondoped molybdates under UV excitation

Molybdates of Li⁺ and Yb³⁺ are studied to investigate the luminescence under UV excitation. LiYb(MoO₄)₂ and Eu³⁺‐doped LiYb₁‐_xEux(MoO₄)₂ (x=001–1.0) phosphors were synthesized by solid state reaction under mixing of Eu₂O₃, Yb₂O₃, Li₂CO₃ and MoO₂ in air atmosphere. Two broad absorption bands centered at 333 and 236 nm are observed in LiYb(MoO₄)₂ compound. They are attributed to the ¹A₁→¹T₁ and ¹T₂ transitions due to the O^2?→Mo⁶⁺ electron transfers in MoO₄ tetrahedron. An emission band with a peak at about 440 nm is found, which is attributed to the ³T₁→¹A₁ transition of MoO₄. Appearance of near‐infrared (NIR) Yb³⁺ emission observed under UV excitation is understood by the MoO₄→Yb³⁺ Foerster‐Type energy transfer due to spectral overlap between the low‐energy tail of the broad 440 nm emission band and the high‐energy tail of the broad Yb³⁺ absorption band and due to short Yb³⁺‐MoO₄ distance. Yb³⁺ emission observed in LiYb_1?xEu_x(MoO₄)₂ by Eu³⁺ excitation is understood by the Eu³⁺→Yb³⁺ energy transfer by cross‐relaxation (CR) process between the ⁵D₀→⁷F₆ Eu³⁺ transition and the ²F_7/2→²F_5/2 Yb³⁺ transition. The CR efficiency shows maximum efficiency of 0.24 at x=0.15 of higher acceptor Yb³⁺ concentration than donor Eu³⁺ concentration. Three Yb³⁺ emission bands with peaks at 994, 1002, and 1023 nm are observed, depending on the excitation wavelength. This is explained by less‐shielded 4f electrons of Yb³⁺ by the 5s²5p⁶ outermost electron shells, which are also responsible for unusual broadband Yb³⁺ absorption and emission. From appearance of NIR Yb³⁺ emission under excitation by not only UV light but also red light, these compounds are expected to be suitable for efficient photovoltaic application to Si‐based solar cells.     

Ce3+‐ and Dy3+‐Doped Oxyfluoride Borosilicate Glasses with Near White Luminescence

A series of Ce³⁺/Dy³⁺‐doped oxyfluoride borosilicate glasses prepared by melt‐quenching method are investigated for light‐emitting diodes applications. These glasses are studied via X‐ray diffraction (XRD), optical absorption, photoluminescence (PL), color coordinate, and Fourier transform infrared (FT‐IR) spectra. We find that the absorption and emission bands of Ce³⁺ ions move to the longer wavelengths with increasing Ce³⁺ concentrations and decreasing B₂O₃ and Al₂O₃ contents in the glass compositions. We also discover the emission behavior of Ce³⁺ ions is dependent on the excitation wavelengths. The glass structure variations with changing glass compositions are examined using the FT‐IR spectra. The influence of glass network structure on the luminescence of Ce³⁺/Dy³⁺ codoped glasses is studied. Furthermore, the near‐ideal white light emission (color coordinate x = 0.32, y = 0.32) from the Ce³⁺/Dy³⁺ codoped glasses excited at 350 nm UV light is realized.     

Host sensitized near-infrared emission in Nd3+-Yb3+ Co-doped Na2GdMg2V3O12 phosphor

Yb³⁺/Nd³⁺ singly and co-doped Na₂GdMg₂V₃O₁₂ phosphors with near-infrared (NIR) emission were synthesized via sol-gel method. The phase purity and structure of samples were characterized by X-ray diffraction (XRD), the photoluminescence emission (PL) and excitation (PLE) spectra along with decay curves were also measured. Near infrared (NIR) emissions (850–1150 nm) from acceptors Yb³⁺ or Nd³⁺ matching well with the response curve of the silicon solar cell were obtained, in which VO₄³⁻ groups acted as sensitizers by capturing near ultraviolet photons which are not absorbed efficiently by silicon solar cell and transferred them to Yb³⁺/Nd³⁺ by energy transfer processes. The NIR emission intensities of the Nd³⁺-Yb³⁺co-doped samples Na₂GdMg₂V₃O₁₂ were enhanced greatly in comparison with that of Nd³⁺/Yb³⁺ singly doped samples, and the possible energy transfer processes were also discussed in detail. Results indicate that the obtained samples are potential solar spectral down-conversion (DC) convertors to enhance the conversion efficiency of the silicon solar cells.     

Molecular‐Like Ag Clusters and Eu3+ Co‐Sensitized Efficient Broadband Spectral Modification with Enhanced Yb3+ Emission

AgNO₃/EuF₃/YbF₃ tri‐doped oxyfluoride glass was prepared by a melt‐quenching method, in which a high‐efficient broadband spectral modification can be realized due to the simultaneous energy‐transfer processes of Eu³⁺→Yb³⁺, molecular‐like Ag (ML‐Ag) clusters→Yb³⁺, and ML‐Ag clusters→Eu³⁺→Yb³⁺. The spectral measurements indicated that besides the F‐center brought by the fluorides, the formation of the ML‐Ag clusters and the evolution of silver species within the glass matrix were also closely related to the introduction of Eu³⁺ and Yb³⁺ ions and which in return greatly affected the luminescence properties of these rare‐earth ions. As the UV‐visible irradiation in the wavelength region of 250–600 nm can be efficiently converted into near‐infrared emission around 1000 nm in the AgNO₃/EuF₃/YbF₃ tri‐doped glass, which thus has promising application in enhancing the photovoltaic conversion efficiency of the silicon solar cell.     

Near/mid‐infrared emission and energy transfer of Er/Tm‐Yb co‐doped β‐NaYF4 microcrystals

The well‐formed high quality β‐NaYF₄:Er³⁺/Tm³⁺, Yb³⁺ microcrystals with near/mid‐infrared (NIR/MIR) emission are synthesized by the solvothermal method. Obvious 1.4 μm, 1.8 μm emissions, and 1.5 μm emission are observed in as‐prepared β‐NaYF₄:Tm³⁺, Yb³⁺ and β‐NaYF₄:Er³⁺, Yb³⁺ microcrystals, respectively. To obtain MIR emission, the as‐prepared β‐NaYF₄:Er³⁺, Yb³⁺ microcrystals are heat‐treated at different temperature schedule and atmosphere, it demonstrates there is great effect on the morphology and crystal structure when heat‐treated at different temperature, while little effect under different heat‐treated atmosphere. Subsequently, after heat‐treatment at 575°C in air, owing to the efficient elimination of internal defects and partly surface hydroxyl/citrate groups, an obvious 2.7 μm MIR emission is successfully detected in heat‐treated β‐NaYF₄:Er³⁺, Yb³⁺ microcrystals for the first time.     

Efficient Near‐Infrared Emission of Ce3+–Nd3+ CoDoped (Sr0.6Ca0.4)3(Al0.6Si0.4)O4.4F0.6 Phosphors for c‐Si Solar Cell

Ce³⁺, Nd³⁺ codoped (Sr_0.6Ca_0.4)₃(Al_0.6Si_0.4)O_4.4F_0.6 phosphors were synthesized through the high‐temperature solid‐state reaction method. Luminescence spectra, absorption spectra, and decay lifetimes of these samples have been measured to prove the energy‐transfer process from Ce³⁺ to Nd³⁺. Under UV and blue light excitation, (Sr_0.6Ca_0.4)₃(Al_0.6Si_0.4)O_4.4F_0.6:Ce³⁺,Nd³⁺ phosphors exhibit near‐infrared (NIR) emission, mainly peaking at 1093 nm and secondarily at 916 nm. The NIR emission matches well with the band gap of c‐Si. Results of this work suggest that the (Sr_0.6Ca_0.4)₃(Al_0.6Si_0.4)O_4.4F_0.6:Ce³⁺, Nd³⁺ phosphors have potential application as down‐shifting luminescent convertor for enhancing the photoelectric conversion efficiency of c‐Si solar cell.