YBO3: Ce3+, Yb3+ based near-infrared quantum cutting phosphors: Synthesis and application to solar cells

Ce³⁺ and Yb³⁺ co-doped YBO₃ phosphors were facilely fabricated by a hydrothermal method. The investigations reveal that hexagonal YBO₃: Ce³⁺, Yb³⁺ nanoparticles aggregate to form cyclic structure after annealing at 900 °C. An efficient near-infrared (NIR) quantum cutting phenomenon involving the emission of two NIR photons (971 nm) for each ultraviolet (UV) photon (360 nm) absorbed is observed based on the cooperative energy transfer (CET) from Ce³⁺ to Yb³⁺ in YBO₃ with a CET efficiency of 41.9%. Moreover, YBO₃: Ce³⁺, Yb³⁺/SiO₂ films with anti-reflection and NIR quantum cutting abilities were prepared by dip-coating method. The as prepared composite films can convert UV photons into NIR photons between 950 nm and 1050 nm, which well matched with the spectral response of the silicon-based solar cell. The experimental results indicate that the photoelectric conversion efficiency of silicon solar cell can be effectively improved by assembling the YBO₃: Ce³⁺, Yb³⁺/SiO₂ bi-functional film, and the corresponding conversion efficiency is about 0.521% higher than the pure glass and 0.252% higher than the pure SiO₂ anti-reflection (AR) film. In a word, this work provides a simple strategy to develop optical films with AR and NIR quantum cutting abilities for solar energy conversion.     

White light emission from novel host-sensitized single-phase Y2WO6: Ln3+ (Ln3+=Eu3+, Dy3+) phosphors

A series of Eu³⁺- or Dy³⁺-doped and Eu³⁺/Dy³⁺ co-doped Y₂WO₆ in pure phase was synthesized via high-temperature solid-state reaction. X-ray diffraction, diffuse reflection spectra, photoluminescence excitation and emission spectra, the CIE chromaticity coordinates and temperature-dependent emission spectra were exploited to investigate the phosphors. Upon UV excitation at 310 nm, efficient energy transfer from the host Y₂WO₆ to dopant ions in Eu³⁺ or Dy³⁺ single-doped samples was demonstrated and those phosphors were suitable for the UV LED excitation. The intense red emission was observed in Y₂WO₆: Eu³⁺, and blue and yellow ones were observed in Y₂WO₆: Dy³⁺. Concentration quenching in Y₂WO₆: Dy³⁺ phosphors could be attributed to the electric dipole-dipole interaction. In Eu³⁺/Dy³⁺ co-doped Y₂WO₆ phosphors energy transfer process only took place from the host to Eu³⁺/Dy³⁺ ions and warm white-light emission can be obtained by adjusting the dopant concentrations. The temperature-dependent luminescence indicated Eu³⁺/Dy³⁺ co-doped Y₂WO₆ was thermally stable. Our overall results suggested that Y₂WO₆: Ln³⁺ (Ln³⁺=Eu³⁺, Dy³⁺) as warm white-light emitting host-sensitized phosphor might be potentially applied in WLEDs.     

Photoluminescence and energy transfer of efficient and thermally stable white-emitting Ca9La(PO4)7:Ce3+, Tb3+, Mn2+ phosphors

The development of novel single-component white-emitting phosphors with high thermal stability is essential for improving the illumination quality of white light-emitting diodes. In this work, we synthesized a series of Ce³⁺, Tb³⁺, Mn²⁺ single- and multiple-doped Ca₉La(PO₄)₇ (CLPO) phosphors with β-Ca₃(PO₄)₂-type structure by the simple high-temperature solid-state reaction. The crystallization behavior, crystal structure, surface morphology, photoluminescence performance, decay lifetime and thermal stability were systematically investigated. The PL spectra and decay curves have evidenced the efficient energy transfer from Ce³⁺ to Tb³⁺ and from Ce³⁺ to Mn²⁺ in the CLPO host, and corresponding energy transfer efficiency reaches 41.8% and 54.1%, respectively. The energy transfer process of Ce³⁺→Tb³⁺ and Ce³⁺→Mn²⁺ can be deduced to the resonant type via dipole-dipole and dipole-quadrupole interaction mechanism, and corresponding critical distance were determined to be 12.23 and 14.4 Å, respectively. Based on the efficient energy transfer, the white light emission can be successfully achieved in the single-component CLPO:0.15Ce³⁺, 0.10Tb³⁺, 0.04Mn²⁺ phosphor, which owns CIE chromaticity coordinates of (0.3245, 0.3347), CCT of 5878 K, internal and external quantum efficiency of 84.51% and 69.32%. Especially, compared with the emission intensity at 25 °C, it still remains 98.5% at 150 °C and 92.0% at 300 °C. Based on these results, the single-component white light emission phosphor CLPO:0.15Ce³⁺, 0.10Tb³⁺, 0.04Mn²⁺ is a potential candidate for UV-converted white LEDs.     

Luminescence properties and energy transfer of GdAl3(BO3)4:Ce3+, Tb3+ phosphor

Ce³⁺ and Tb³⁺ singly doped and co-doped GdAl₃(BO₃)₄ phosphors were synthesized by solid state reaction. The crystal structure, the luminescent properties, the lifetimes and the temperature-dependent luminescence characteristic of the phosphors were investigated. Through an effective energy transfer, the emission spectra of GdAl₃(BO₃)₄:Ce³⁺, Tb³⁺ phosphor contains both a broad band in the range of 330–400 nm originated from Ce³⁺ ions and a series of sharp peaks at 484, 541, 583, and 623 nm due to Tb³⁺ ions. The energy transfer from Ce³⁺ to Tb³⁺ in GdAl₃(BO₃)₄ host is demonstrated to be phonon assisted nonradiative energy transfer via a dipole–dipole interaction.     

Near-infrared quantum cutting in Ho3+, Yb3+-codoped BaGdF5 nanoparticles via first- and second-order energy transfers

Infrared quantum cutting involving Yb³⁺ 950–1,000 nm (² F_5/2 → ² F_7/2) and Ho³⁺ 1,007 nm (⁵S₂,⁵F₄ → ⁵I₆) as well as 1,180 nm (⁵I₆ → ⁵I₈) emissions is achieved in BaGdF₅: Ho³⁺, Yb³⁺ nanoparticles which are synthesized by a facile hydrothermal route. The mechanisms through first- and second-order energy transfers were analyzed by the dependence of Yb³⁺ doping concentration on the visible and infrared emissions, decay lifetime curves of the ⁵ F₅ → ⁵I₈, ⁵S₂/⁵F₄ → ⁵I₈, and ⁵ F₃ → ⁵I₈ of Ho³⁺, in which a back energy transfer from Yb³⁺ to Ho³⁺ is first proposed to interpret the spectral characteristics. A modified calculation equation for quantum efficiency of Yb³⁺-Ho³⁺ couple by exciting at 450 nm was presented according to the quantum cutting mechanism. Overall, the excellent luminescence properties of BaGdF₅: Ho³⁺, Yb³⁺ near-infrared quantum cutting nanoparticles could explore an interesting approach to maximize the performance of solar cells.     

Improvement the near-infrared luminescence properties of double perovskite phosphor La(Mg0.5Sn0.5In0.5Sc0.5)0.5O3:Cr3+ via co-doping Yb3+

In recent years, the broadband near-infrared (NIR) spectroscopy technology has been widely used in the field of nondestructive testing. However, these existing NIR phosphors showed relatively short emission wavelengths, narrower half-maximum full-width (FWHM), and narrower half-peak widths, importantly, few phosphors presented the emission from 950 nm to 1100 nm. In order to solve these problems, the Yb³⁺/Cr³⁺ ions codoped La(Mg_0.5Sn_0.5In_0.5Sc_0.5)_0.5O₃ (LMSIS) was synthesized by the solid-state method, and the emission spectrum of LMSIS:Cr³⁺ can be extended to the NIR long-wave region due to the energy transfer of Yb³⁺ and Cr³⁺, and the thermal stability of the phosphor can be improved due to the inherent temperature stability of the Yb³⁺ f-f transition. The NIR phosphor converted light emitting diodes (pc-LEDs) were fabricated by combining the LMSIS:0.003Cr³⁺, 0.0015Yb³⁺ with blue LED chip, which can be expected to be used in the field of broadband near-infrared non-destructive detection.     

Thermally enhanced near-infrared luminescence in CaSc2O4: Yb3+/Nd3+ nanorods for temperature sensing and photothermal conversion

Non-invasive photothermal therapy (PTT) is proposed as a powerful method for cancer treatment, in which a precise temperature monitoring is strongly recommended during the photothermal conversion process to prevent the damage of normal cells. Herein, ultra-sensitive optical thermometry with excellent resolution and outstanding light-to-heat conversion are simultaneously realized in CaSc₂O₄: Yb³⁺/Nd³⁺ nanorods. The temperature sensing of the nanorods is accomplished through fluorescence intensity ratio (FIR) technology based on the thermally coupled levels (TCLs) Nd³⁺: ⁴F_j (j = 7/2, 5/2, 3/2), of which the obtained absolute sensitivity is about 6.5 times larger than the optimal value of TCLs-based thermometers reported previously. Meanwhile, an intense thermal enhancement of Nd³⁺: ⁴F_j (j = 7/2, 5/2, 3/2) → ⁴I_9/2 transition is found due to the efficiency improvement of phonon-assisted energy transfer process between Yb³⁺ ions and Nd³⁺ ions. The penetrability of the near-infrared light emitting by Nd³⁺ ions is determined by a simple ex vivo experiment, indicating a penetration depth of 8 mm in the biological tissues with negligible effect on FIR values. Beyond that, the nanorods show remarkable photothermal conversion capacity under the excitation of 980 nm wavelength. The properties mentioned above show enormous potentiality of the present nanorods for PTT along with a real-time temperature sensing.     

Warm white-light generation in Ca9MgNa(PO4)7:Sr2+, Mn2+, Ln (Ln=Eu2+, Yb3+, Er3+, Ho3+, and Tm3+) under near-ultraviolet and near-infrared excitation

To obtain warm white-light emission, a series of Ca₉MgNa(PO₄)₇:Sr²⁺, Mn²⁺, Ln (Ln=Eu²⁺, Yb³⁺, Er³⁺, Ho³⁺, and Tm³⁺) phosphors were designed and their photoluminescence properties under near-ultraviolet and near-infrared excitation were studied. For near-ultraviolet excitation, blue-white emission is produced initially in the Eu²⁺ single-doped Ca₉MgNa(PO₄)₇, whose excitation band can well match with the near ultraviolet LED chip. By introducing Sr²⁺ ions into Ca₉MgNa(PO₄)₇:Eu²⁺, the Eu²⁺ emission band beyond 500 nm is enhanced obviously. Correspondingly, the emitting light color is tuned to nearly white. To generate warm white light further, Mn²⁺ is doped into the Ca_8.055MgNa(PO₄)₇:0.045Eu²⁺, 0.9Sr²⁺ and the correlated color temperature is decreased largely. For near-infrared excitation, the green, red, and blue emissions have been obtained in the Yb³⁺-Er³⁺, Yb³⁺-Er³⁺, and Yb³⁺-Er³⁺ co-doped Ca₉MgNa(PO₄)₇ phosphors, respectively. And warm white light is also produced in the Ca₉MgNa(PO₄)₇:Yb³⁺, Er³⁺, Ho³⁺, Tm³⁺ under 980 nm excitation.     

Luminescent properties and energy transfer mechanism of NaGd(MoO4)2:Sm3+, Eu3+ phosphors

Sm³⁺ singly doped NaGd(MoO₄)₂ and Sm³⁺, Eu³⁺ co-doped NaGd(MoO₄)₂ phosphors by using sodium citrate as chelating agent were synthesized via hydrothermal method. The structure and morphology were characterized by means of X-ray diffraction (XRD) and field emission scanning electron microscopy (FE-SEM). During the synthesis process, the Na₃Cit concentration plays a crucial role in determining the morphology and particle size of the products. The optimal doping concentration in Sm³⁺ singly doped NaGd(MoO₄)₂ phosphor was confirmed. The relevant parameters of energy transfer in the NaGd(MoO₄)₂: Sm³⁺, Eu³⁺ phosphors have been calculated based on the fluorescent dynamic analysis. Finally, on the analysis of luminescent spectra and fluorescent dynamics, the main energy transfer mechanism between Sm³⁺ and Eu³⁺ in NaGd(MoO₄)₂ phosphor is confirmed to be electric dipole-dipole interaction, and energy transfer pathway is from ⁴G_5/2 state of Sm³⁺ to ⁵D₀ state of Eu³⁺ rather than ⁵D₁ of Eu³⁺ ions.     

Color-tunable up-conversion emission from Yb3+/Er3+/Tm3+/Ho3+ codoped KY(MoO4)2 microcrystals based on energy transfer

Tunable up-conversion luminescent material KY(MoO₄)₂: Yb³⁺, Ln³⁺ (Ln=Er, Tm, Ho) has been synthesized by a typical hydrothermal process. Under 980 nm laser diode (LD) excitation, the emission intensity and the corresponding luminescence colors of KY(MoO₄)₂: Yb³⁺, Ln³⁺ (Ln=Er, Tm, Ho) have been investigated in detail. The energy transfer from the Yb³⁺ sensitizer to Ho³⁺, Er³⁺ and Tm³⁺ activators plays an important role in the development of color-tunable single- phased phosphors. The emission intensity keep balance through control of the Ho³⁺ co-doping concentrations, white light was experimentally shown at KY(MoO₄)₂: 20 mol% Yb³⁺, 0.8 mol% Er³⁺, 0.5 mol% Tm³⁺, 1.0 mol% Ho³⁺ phosphor with further calcination at 800 °C for 4 h under 980 nm laser excitation. The color tunability, high quality of white light and high intensity of the emitted signal make these up-conversion (UC) phosphors excellent candidates for applications in solid-state lighting.     

High sensitive Ln3+/Tm3+/Yb3+ (Ln3+ = Ho3+, Er3+) tri-doped Ba3Y4O9 upconverting optical thermometric materials based on diverse thermal response from non-thermally coupled energy levels

Upconversion (UC) optical thermometers using the fluorescence intensity ratio (FIR) technique arising from the thermally coupled energy levels (TCLs) are still suffering from low sensitivity owing to the restriction of small energy gap. In the present study, a strategy to strive for superior temperature sensitivity and signal discriminability is employed with the help of non-thermally coupled energy levels (NTCLs). A novel tri-doped Ba₃Y₄O₉: Ho³⁺/Tm³⁺/Yb³⁺ phosphor with rhombohedral symmetry was successfully prepared via a solid-state reaction method, and the temperature sensing performance was evaluated by analyzing temperature-dependent upconversion emission spectra. The emission intensities of both Ho³⁺ and Tm³⁺ activators can be almost completely restored to their original values when the temperature of the sample is cooled to room temperature. The temperature-dependent FIR between NTCLs can be fitted well by a derived three-term equation with the correlation coefficient above 99.6%, and the FIR of NTCLs exhibits high temperature sensitivity over a wide temperature range owing to the different temperature responses of the NTCLs. The maximum absolute sensitivity S_A and relative sensitivity S_R values reaches as high as 0.0552?K^?1 and 1.49% K^?1, respectively, which are much higher than those of the previously reported bulk UC optical temperature sensing materials. Moreover, the emission bands of NTCLs are well separated, which endows the material a good signal discriminability for temperature detection. Excellent temperature sensing performance is also demonstrated in Er³⁺/Tm³⁺/Yb³⁺ tri-doped Ba₃Y₄O₉, evidencing the validity of this strategy. These results indicate that the present UC materials can be potential candidates for optical temperature sensors, and the present strategy will provide a thought for developing other innovative UC temperature sensing materials.     

LiBAlF6:Cr3+ (B = Ca,Sr) fluoride phosphors with ultra-broad near-infrared emission for NIR pc-LEDs

Compared with oxide-based NIR phosphors, fluoride phosphors have received great attention recently due to their good thermal resistance and high photoelectric efficiency. In this work, novel LiBAlF₆:Cr³⁺ (B = Ca, Sr) with low phonon energy and relatively weak electron-phonon coupling were synthesized through a facile hydrothermal approach. Benefiting from low Dq/B, an ultra-broad NIR emission extending from 650 nm to 1100 nm can be achieved in these phosphors under excitation of blue light. Among them, LiSrAlF₆:Cr³⁺ presents a FWHM of 155 nm. At 423 K, LiCaAl_0.4F₆: 0.6Cr³⁺ and LiSrAl_0.4F₆: 0.6Cr³⁺ maintain 66.63% and 55.47% of their initial intensities, respectively. Better thermal stability of LiCaAlF₆: Cr³⁺ could be attributed to the broad band gap and weak electron-phonon coupling effect. Photoelectric conversion efficiencies of 5.002% and 5.468% at 300 mA could be obtained for NIR pc-LEDs packaged with LiCaAl_0.4F₆: 0.6Cr³⁺ and LiSrAl_0.4F₆: 0.6Cr³⁺, respectively. A slightly internal bruise inside apple and water level behind trademark in bottle could be clearly detected, revealing that LiBAlF₆:Cr³⁺ (B = Ca, Sr) phosphors have great application potential in infrared inspection.     

Sr3GdLi(PO4)3F:Eu2+, Mn2+: A tunable blue-white color emitting phosphor via energy transfer for near-UV white LEDs

A series of Eu²⁺ and Mn²⁺ co-doping Sr₃GdLi(PO₄)₃F phosphors have been synthesized through high temperature solid state reaction. Eu²⁺ single doped Sr₃GdLi(PO₄)₃F phosphors have an efficient excitation in the range of 230–430 nm, which is in good agreement with the commercial near-ultraviolet (n-UV) LED chips, and gives intense blue emission centering at 445 nm. The critical distance of the Eu²⁺ ions in Sr₃GdLi(PO₄)₃F is computed and demonstrated that the concentration quenching mechanism of Eu²⁺ is mostly caused by the dipole-dipole interaction. By co-doping Eu²⁺ and Mn²⁺ ions in the Sr₃GdLi(PO₄)₃F host, the energy transfer from Eu²⁺ to Mn²⁺ that can be discovered. With the increase of Mn²⁺ content, emission color can be adjusted from blue to white under excitation of 380 nm, corresponding to chromatic coordinates change from (0.189, 0.108) to (0.319, 0.277). The energy transfer from Eu²⁺ to Mn²⁺ ions is proven to be a dipole-dipole mechanism on the basis of the experimental results and analysis of photoluminescence spectra and decay curves. This study infers that the obtained Sr₃GdLi(PO₄)₃F:Eu²⁺, Mn²⁺ phosphors may be a potential candidate for n-UV LEDs.     

REVO4‐Based Nanomaterials (RE = Y,La, Gd,and Lu) as Hosts for Yb3+/Ho3+, Yb3+/Er3+, and Yb3+/Tm3+ Ions: Structural and Up‐Conversion Luminescence Studies

Rare‐earth vanadates of the form REVO₄ (RE = Y, La, Gd, and Lu) doped by Yb³⁺/Ho³⁺, Yb³⁺/Er³⁺_, or Yb³⁺/Tm³⁺ lanthanide ions were successfully synthesized using the sol–gel method and annealing at 600°C in an air atmosphere. The structure and morphology of the prepared nanocrystals were investigated by X‐ray diffraction, thermogravimetric analysis, transmission electron microscopy, and energy‐dispersive X‐ray spectroscopy. All prepared materials were homogenous and had nanosized dimensions. Their elemental compositions were confirmed by optical emission spectrometry. Spectroscopic analysis of the materials was carried out by measuring excitation and emission spectra, luminescence decays, and dependence between the intensity of the luminescence and the laser energy. Following effective excitation by NIR radiation, Ln³⁺ co‐doped vanadate matrices exhibited a strong up‐conversion (UC) luminescence. Differences in spectroscopic properties between monoclinic LaVO₄ and tetragonal YVO₄, GdVO₄, or LuVO₄ doped by Ln³⁺ ions were observed, indicating the influence of the crystal structure on the UC emission. Drawing conclusions from these spectroscopic investigations, the UC mechanisms were proposed, including energy‐transfer processes between Yb³⁺ ions and emitting ions.     

A novel tunable green-to-red emitting phosphor Ca4LaO(BO3)3:Tb,Eu via energy transfer with high quantum yield

A novel green phosphor composed of Ca₄LaO(BO₃)₃:Tb³⁺ (CLBO:Tb) has been synthesized by a combustion method with urea. Its crystal structure, temperature-dependent luminescence, and quantum yield (QY) have been characterized by X-ray diffraction (XRD) and photoluminescence (PL) spectra with heating device and integrate sphere. No concentration quenching has been observed when all of La³⁺ ions are substituted with Tb³⁺ ions. Green phosphor Ca₄TbO(BO₃)₃ (CTBO) has 200% luminescence intensity of commercially available phosphor LaPO₄:Ce, Tb (LPO:Ce, Tb) under 378 nm excitation. The QY of CTBO is as high as 98%. Through a Dexter energy transfer mechanism, Eu³⁺ ions are efficiently sensitized by Tb³⁺, resulting in an emission with color tunable from green to red under ultraviolet excitation. A possible mechanism of energy transfer from Tb³⁺ to Eu³⁺ has been investigated by PL spectra and decay measurements. The energy transfer efficiency from Tb³⁺ to Eu³⁺ increases linearly with concentration of Eu³⁺ increasing.     

Influence of Bi3+ as a sensitizer and SiO2 shell coating as a protecting layer towards the enhancement of red emission in LnVO4: Bi3+, Eu3+ @ SiO2 (Ln=Gd,Y and Gd/Y) powder phosphors for optical display devices

Enhanced red luminescence in LnVO₄: Bi³⁺, Eu³⁺ @ SiO₂ phosphors has been improved mainly in three stages by investigating the effects of: (i) host composition (Gd, Y and Gd/Y), (ii) co-doping Bi³⁺ as a sensitizer and finally (iii) SiO₂ shell coating. XRD data revealed that the produced phosphors possess crystalline, pure phase with tetragonal structure. Silica coating on phosphor particles have been characterized by SEM/EDAX, TEM, PL and with the presence Si–O–Si, Si–O vibrational modes from the FT-IR spectra. Absorption band edges due to VO₄^3?, shifted to higher wavelength with Bi-concentration, owing to the presence of Bi–O bond in addition to V–O. The emission intensities of ⁵D₀→⁷F₂ transition are stronger than ⁵D₀→⁷F₁; indicating the lower inversion symmetry near Eu³⁺, ions. Red emission intensity due to the efficient energy transfer from VO₄^3? to Eu³⁺ via Bi³⁺ ions in Y_0.949VO₄: Bi³⁺_0.001, Eu³⁺_0.05 phosphor was improved significantly, i.e. 1.6 times compared to Y_0.95VO₄: Eu³⁺_0.05. This was further enhanced 2.25 times by SiO₂ shell coating. Thus, Y_0.949VO₄: Bi³⁺_0.001, Eu³⁺_0.05 @ SiO₂ are suggested to be a promising red phosphor for application in display devices or lighting.