An Efficient Dual‐Mode Solar Spectral Modification for c‐Si Solar Cells in Tm3+/Yb3+ Codoped Tellurite Glasses

A series of Tm³⁺/Yb³⁺ codoped tellurite glasses, which demonstrate an interesting dual‐mode solar spectral converting for c‐Si solar cells, have been successfully prepared by conventional high‐temperature melt‐quenching technique. The photoluminescence (PL), photoluminescence excitation (PLE) spectra along with the decay curves have been studied systematically. The results indicate that the transparent glasses show two distinguishable near infrared (NIR) spectral converting behaviors, that is, quantum cutting (QC) and downshifting (DS) processes, sensitized by narrow f–f transition absorption of Tm³⁺:³H₆ → ¹G₄ at 465 nm and broad absorption band due to charge‐transfer state (CTS) of Yb³⁺‐O^2? at 320 nm, respectively. The Tm³⁺/Yb³⁺ codoped tellurite glasses convert ultraviolet (240–400 nm) and blue (450–490 nm) photons into NIR (920–1100 nm) ones, which well match the optimal spectral response of silicon (Si) solar cells. The prepared tellurite glass can be potentially utilized as spectral converter to improve the photovoltaic conversion of c‐Si solar cells. The dual‐mode solar spectrum converting material might explore a novel approach to realize UV‐Vis to NIR downconversion for Si solar cells application.     

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.     

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.     

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.     

Effect of topological structure on photoluminescence of PbSe quantum dot‐doped borosilicate glasses

Borosilicate glasses doped with PbSe quantum dots (QDs) were prepared by a conventional melt‐quenching process followed by heat treatment, which exhibit good thermal, chemical, and mechanical stabilities, and are amenable to fiber‐drawing. A broad near infrared (NIR) photoluminescence (PL) emission (1070‐1330 nm) band with large full‐width at half‐maximum (FWHM) values (189‐266 nm) and notable Stokes shift (100‐210 nm) was observed, which depended on the B₂O₃ concentration. The PL lifetime was about 1.42‐2.44 μs, and it showed a clear decrease with increasing the QDs size. The planar [BO₃] triangle units forming the two‐dimensional (2D) glass network structure clearly increased with increasing B₂O₃ concentration, which could accelerate the movement of Pb²⁺ and Se^2? ions and facilitate the growth of PbSe QDs. The tunable broadband NIR PL emission of the PbSe QD‐doped borosilicate glass may find potential application in ultra‐wideband fiber amplifiers.     

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.     

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.     

Effect of TeO2 on Near‐Infrared Emission from Bismuth Centers in Borogermanate Glasses

Bi‐doped xTeO₂–(60?x)GeO₂–15B₂O₃–20MgO–5Al₂O₃ glasses were prepared by the conventional melt‐quenching method and their absorption and fluorescence spectra were characterized. Broadband near‐infrared (NIR) emission from Bi centers centered around 1240 nm with a full width at half maximum (FWHM) of 250 nm was observed, and the position of the emission peak strongly depends on the excitation wavelength. Increasing TeO₂ concentration results in the strong coloration of the glass, leading to the reduction and finally, complete quenching of the NIR emission. Based on Raman, X‐ray photoelectron spectroscopy and transmission microscopy observation, the coloration of the glass at high TeO₂ concentration can be ascribed to the precipitation of elemental Te nanoparticles of around 3–8 nm, which effectively suppresses the NIR emission by reabsorption. The precipitation of Te nanoparticles in an oxide glass may find novel applications in photonics and relevant fields.     

Er3+ ‐Doped Y2O3 Nanophosphors for Near‐Infrared Fluorescence Bioimaging Applications

Rare‐earth‐doped ceramic nanophosphor (RED‐CNP) materials are promising near‐infrared (NIR) fluorescence bioimaging (FBI) agents that can overcome problems of currently used organic dyes including photobleaching, phototoxicity, and light scattering. Here, we report a NIR–NIR bioimaging system by using NIR emission at 1550 nm under 980 nm excitation which can allow a deeper penetration depth into biological tissues than ultraviolet or visible light excitation. In this study, erbium‐doped yttrium oxide nanoparticles (Er³⁺:Y₂O₃) with an average particle size of 100 and 500 nm were synthesized by surfactant‐assisted homogeneous precipitation method. NIR emission properties of Er³⁺:Y₂O₃ were investigated under 980 nm excitation. The surface of Er³⁺:Y₂O₃ was electrostatically PEGylated using poly (ethylene glycol)‐b‐poly(acrylic acid) (PEG‐b‐PAAc) block copolymer to improve the chemical durability and dispersion stability of Er³⁺:Y₂O₃ under physiological conditions. In vitro cytotoxic effects of bare and PEG‐b‐PAAc‐modified Er³⁺:Y₂O₃ were investigated by incubation with mouse macrophage cells (J774). Microscopic and macroscopic FBI were demonstrated in vivo by injection of bare or PEG‐b‐PAAc‐modified Er³⁺:Y₂O₃ into C57BL/6 mice. The NIR fluorescence images showed that PEG‐b‐PAAc modification significantly reduced the agglomeration of Er³⁺:Y₂O₃ in mice and enhanced the distribution of Er³⁺:Y₂O₃.     

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.     

Intense upconversion luminescence and energy‐transfer mechanism of Ho3+/Yb3+ co‐doped SrLu2O4 phosphor

A series of novel SrLu₂O₄: x Ho³⁺, y Yb³⁺ phosphors (x=0.005‐0.05, y=0.1‐0.6) were synthesized by a simple solid‐state reaction method. The phase purity, morphology, and upconversion luminescence were measured by X‐ray diffraction (XRD), scanning electron microscopy (SEM), and photoluminescence (PL) spectroscopy. The doping concentrations and sintering temperature were optimized to be x=0.01, y=0.5 and T=1400°C to obtain the strongest emission intensity. Under 980 nm laser diode excitation, the SrLu₂O₄:Ho³⁺, Yb³⁺ phosphors exhibit intense green upconversion (UC) emission band centered at 541 nm (⁵F₄,⁵S₂→⁵I₈) and weak red emission peaked at 673 nm (⁵F₅→⁵I₈). Under different pump‐power excitation, the UC luminescence can be finely tuned from yellow‐green to green light region to some extent. Based on energy level diagram, the energy‐transfer mechanisms are investigated in detail according to the analysis of pump‐power dependence and luminescence decay curves. The energy‐transfer mechanisms for green and red UC emissions can be determined to be two‐photon absorption processes. Compared with commercial NaYF₄:Er³⁺, Yb³⁺ and common Y₂O₃:Ho³⁺, Yb³⁺ phosphors, the SrLu_1.49Ho_0.01Yb_0.5O₄ sample shows good color monochromaticity and relatively high UC luminescence intensity. The results imply that SrLu₂O₄:Ho³⁺, Yb³⁺ can be a good candidate for green UC material in display fields.     

Predictable tendency of Bi NIR emission in Bi‐doped magnesium aluminosilicate laser glasses

Because of superbroad luminescence in the range of near infrared (NIR), Bi‐doped glasses and fibers have received more attentions recently for the applications in super broadband optical fiber amplifiers or new wavelength lasers. As the luminescence comes from the transitions between naked 6p orbitals of bismuth, it is very susceptible to slight changes of local field around Bi. Therefore, it is always very challenging to predict NIR emission of bismuth in advance. Here, we found bismuth NIR emission shows predictable tendency in ternary glass system of MgO–Al₂O₃–SiO₂. The emission peak shifts red along the content of magnesium upon the excitation of 484 nm, which follows a single exponential growth equation. In the meantime, the full width at half maximum (FWHM) is broadened while the lifetime keeps decreasing. Glass structure analysis on basis of FTIR, ²⁷Al NMR, ²⁹Si NMR spectra reveals that these changes correlate to integrity of glass network, the increased disorder of local field around bismuth and the enhanced interaction between bismuth and host, which are perhaps due to the linear increase of nonbridging oxygen, and the enhanced Si–O asymmetric stretching vibrations along with magnesium, respectively. Electron probe microanalysis shows good homogeneity of Si, Al, Mg, Bi, and O distribution within the samples, and yoyo experiments of heating and cooling between 30°C and 300°C reveal the good resistance of such doped glasses to thermal degradation. This makes the glasses promising in applications of fiber devices even under extreme condition such as at higher temperature. The finding in this work should be helpful for the design of Bi‐doped laser glasses in future.     

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.     

A Novel Blue‐Emitting Phosphor of Eu2+‐Activated Magnesium Haloborate Mg3B7O13Cl

Eu²⁺‐doped magnesium haloborate Mg₃B₇O₁₃Cl was synthesized by the conventional high‐temperature solid‐state reaction. The phase formation was confirmed by X‐ray powder diffraction (XRD) measurements and structure refinement. The photoluminescence excitation and emission spectra, and decay curves were measured. Under the excitation of near‐UV light, Eu²⁺‐doped Mg₃B₇O₁₃Cl presents a narrow blue‐emitting band centered at 423 nm. The maximum absolute quantum efficiency (QE) of Mg₃B₇O₁₃Cl:Eu²⁺ phosphor was measured to be 80% excited at 385 nm light at 300 K. The thermal stability of the blue luminescence was evaluated by the luminescence decays as a function of temperature. The phosphor shows an excellent thermal stability on temperature quenching effects. Moreover, Mg₃B₇O₁₃Cl:Eu²⁺ phosphor shows scintillation characteristics excited by X‐ray irradiation at room temperature and presents a blue luminescence band with a fast lifetime of 600 ns.     

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.     

Color‐Tunable Up‐Conversion Emission and Infrared Photoluminescence and Dielectric Relaxation of Er3+/Yb3+ Co‐Doped Bi2Ti2O7 Pyrochlore Thin Films

The color‐tunable up‐conversion (UC) emission and infrared photoluminescence and dielectric relaxation of Er³⁺/Yb³⁺ co‐doped Bi₂Ti₂O₇ pyrochlore thin films prepared by a chemical solution deposition method have been investigated. The pyrochlore phase structure of Bi₂Ti₂O₇ can be stabilized by Er³⁺/Yb³⁺ co‐doping. Intense color‐tunable UC emission and infrared photoluminescence can be detected on the thin films excited by a 980 nm diode laser. Two UC emission bands centered at 548 and 660 nm in the spectra can be assigned to ²H_11/2, ⁴S_3/2 → ⁴I_15/2 and ⁴F_9/2 → ⁴I_15/2 transitions of Er³⁺ ions, respectively. A Stokes infrared emission centered at 1530 nm is due to ⁴I_13/2 → ⁴I_15/2 transition of Er³⁺ ions. The dependence of UC emission intensity on pumping power indicates that the UC emission of the thin films is a two‐photon process. The thin films also exhibit a relatively high dielectric constant and a low dissipation factor as well as a good bias voltage stability. Temperature‐ and frequency‐dependent dielectric relaxation has been confirmed. This study suggests that Er³⁺/Yb³⁺ co‐doped Bi₂Ti₂O₇ thin films can be applied to new multifunctional photoluminescence dielectric thin‐film devices.     

Preparation and photoluminescence enhancement of Au nanoparticles with ultra-broad plasmonic absorption in glasses

The metal nanoparticles with ultra-broad localized surface plasmonic resonance (LSPR) absorption have been widely used to enhance the up conversion luminescence (UCL) of rare-earth doped nanoparticles. However, there have been no reports on the preparation of metal nanoparticles with the ultra-broad LSPR in the glasses. In this work, the gold nanoparticles with the ultra-broad LSPR were prepared for the first time in the rare-earth doped tellurite glasses by the high-temperature melting method, and the influence of ultra-broad LSPR on the UCL of Er³⁺–Yb³⁺ and Er³⁺–Yb³⁺–Nd³⁺ co-doped tellurite glasses was investigated upon 980 and 808 nm excitation, respectively. With the precipitation of the Au NPs, about seven and 12-fold enhancements were obtained for the green and red UCL of Er³⁺–Yb³⁺ co-doped tellurite glasses excited at 980 nm, respectively, and about 5.9 and sevenfold enhancements were observed for the green and red UCL of Er³⁺–Yb³⁺–Nd³⁺ co-doped tellurite glasses excited at 808 nm, respectively. The UCL mechanism related to UCL enhancement was confirmed. The results demonstrated that the enhanced excitation field and the increasing rate of radiative decay were responsible for the enhancement of UCL.     

Synthesis,Crystal Structure,and Enhanced Luminescence of Garnet‐Type Ca3Ga2Ge3O12:Cr3+ by Codoping Bi3+

Garnet‐type compound Ca₃Ga₂Ge₃O₁₂ and Cr³⁺‐doped or Cr³⁺/Bi³⁺ codped Ca₃Ga₂Ge₃O₁₂ phosphors were prepared by a solid‐state reaction. The crystal structure of Ca₃Ga₂Ge₃O₁₂ host was studied by X‐ray diffraction (XRD) analysis and further determined by the Rietveld refinement. Near‐infrared (NIR) photoluminescence (PL) and long‐lasting phosphorescence (LLP) emission can be observed from the Cr³⁺‐doped Ca₃Ga₂Ge₃O₁₂ sample, and the enhanced NIR PL emission intensity and LLP decay time can be realized in Cr³⁺/Bi³⁺ codped samples. The optimum concentration of Cr³⁺ in Ca₃Ga₂Ge₃O₁₂ phosphor was about 6 mol%, and optimum Bi³⁺ concentration induced the energy‐transfer (ET) process between Bi³⁺ and Cr³⁺ ions was about 30 mol%. Under different excitation wavelength from 280 to 453 nm, all the samples exhibit a broadband emission peaking at 739 nm and the intensity of NIR emission increases owing to the ET behavior from Bi³⁺ to Cr³⁺ ions. The critical ET distance has been calculated by the concentration‐quenching method. The thermally stable luminescence properties were also studied and the introduction of Bi³⁺ can also improve the thermal stability of the NIR emission.