Tunable multicolor and white‐light upconversion luminescence in Yb3+/Tm3+/Ho3+ tri‐doped NaYF4 micro‐crystals

NaYF₄ micro‐crystals with various concentrations of Yb³⁺/Tm³⁺/Ho³⁺ were prepared successfully via a simple and reproducible hydrothermal route using EDTA as the chelating agent. Their phase structure and surface morphology were studied using powder X‐ray diffraction (XRD) and scanning electron microscopy (SEM). The XRD patterns revealed that all the samples were pure hexagonal phase NaYF₄. SEM images showed that Yb³⁺/Tm³⁺/Ho³⁺ tri‐doped NaYF₄ were hexagonal micro‐prisms. Upconversion photoluminescence spectra of Yb³⁺/Tm³⁺/Ho³⁺ tri‐doped NaYF₄ micro‐crystals with various dopant concentrations under 980 nm excitation with a 665 mW pump power were studied. Tunable multicolor (purple, purplish blue, yellowish green, green) and white light were achieved by simply adjusting the Ho³⁺ concentration in 20%Yb³⁺/1%Tm³⁺/xHo³⁺ tri‐doped NaYF₄ micro‐crystals. Furthermore, white‐light emissions could be obtained using different pump powers in 20%Yb³⁺/1%Tm³⁺/1%Ho³⁺ tri‐doped NaYF₄ micro‐crystals at 980 nm excitation. The pump power‐dependent intensity relationship was studied and relevant energy transfer processes were discussed in detail. The results suggest that Yb³⁺/Tm³⁺/Ho³⁺ tri‐doped NaYF₄ micro‐crystals have potential applications in optoelectronic devices such as photovoltaic, plasma display panel and white‐light‐emitting diodes. Copyright © 2014 John Wiley & Sons, Ltd.     

Enhanced green emissions of Er3+/Yb3+ co‐doped Gd2(MoO4)3 by co‐excited up‐conversion processes

Improving the emission from rare earth ions doped materials is of great importance to broaden their application in bio‐imaging, photovoltaics and temperature sensing. The green emissions of Gd₂(MoO₄)₃:Er³⁺/Yb³⁺ powder upon co‐excitation with 980 and 808 nm lasers were investigated in this paper. Distinct enhancement of green emissions was observed compared with single laser excitation. Based on the energy level structure of Er³⁺, the enhancement mechanism was discussed. Moreover, the result of temperature‐dependent enhancement revealed that the enhancement factor reached its maximum (2.5) as the sample heated to 120°C, which is due to the competition of two major thermal effects acting in the co‐excited up‐conversion processes. In addition, the same enhancement of green emissions was also observed in Gd₂(MoO₄)₃:Er³⁺ powder and NaYF₄:Er³⁺/Yb³⁺ powder.     

Effect of Bi3+ addition on the upconversion luminescence properties of NaYbF4:Er

In this study, Bi³⁺ incorporation in NaYbF₄:Er lattice and its influence on upconversion luminescence properties have been investigated in detail using techniques such as temperature‐dependent luminescence, Fourier transform infrared spectroscopy and X‐ray diffraction (XRD). The study was carried out to develop phosphors with improved upconversion luminescence. From photoluminescence and lifetime measurements it is inferred that luminescence intensity from NaYbF₄:Er increases with Bi³⁺ addition. The sample containing 50 at.% Bi³⁺ ions exhibited optimum upconversion luminescence. Increased distance between Yb³⁺–Yb³⁺ and Er³⁺–Er³⁺ due to Bi³⁺ incorporation into the lattice and associated decrease in the extent of dipolar interaction/self‐quenching are responsible for increase in lifetime values and luminescence intensities from Er³⁺ ions. Incorporation of Bi³⁺ into NaYbF₄:Er lattice reduced self‐quenching among Yb³⁺–Yb³⁺ions and this facilitated energy transfer from Yb³⁺ to Er³⁺. This situation also explains decrease in the extent of temperature‐assisted quenching of emission from thermally coupled ²H_11/2 and ⁴S_3/2 levels of Er³⁺. Based on Rietveld refinement of XRD patterns it was confirmed that a maximum of 10 at.% of Bi³⁺added was incorporated into the NaYbF₄:Er lattice and the remaining complex co‐exists as a BiOF phase. These results are of significant interest in the area of development of phosphors based on Yb³⁺–Er³⁺ upconversion luminescence.     

Luminescence properties of Tm3+ ions single‐doped YF3 materials in an unconventional excitation region

According to the spectral distribution of solar radiation at the earth's surface, under the excitation region of 1150 to 1350 nm, the up‐conversion luminescence of Tm³⁺ ions was investigated. The emission bands were matched well with the spectral response region of silicon solar cells, achieved by Tm³⁺ ions single‐doped yttrium fluoride (YF₃) phosphor, which was different from the conventional Tm³⁺/Yb³⁺ ion couple co‐doped materials. Additionally, the similar emission bands of Tm³⁺ ions were achieved under excitation in the ultraviolet region. It is expected that via up‐conversion and down‐conversion routes, Tm³⁺‐sensitized materials could convert photons to the desired wavelengths in order to reduce the energy loss of silicon solar cells, thereby enhancing the photovoltaic efficiency.     

Preparation and up‐conversion luminescence properties of LaOBr:Yb3+/Er3+ nanofibers via electrospinning

LaOBr:Yb³⁺/Er³⁺ nanofibers were synthesized for the first time by calcinating electrospun PVP/[La(NO₃)₃ + Er(NO₃)₃ + Yb(NO₃)₃ + NH₄Br] composites. The morphology and properties of the final products were investigated in detail using scanning electron microscopy (SEM), energy dispersion spectroscopy (EDS), X‐ray diffractometry (XRD) and fluorescence spectroscopy. The results indicate that LaOBr:Yb³⁺/Er³⁺ nanofibers are tetragonal in structure with a space group of P4/nmm. The diameter of LaOBr:Yb³⁺/Er³⁺ nanofibers is ~ 147 nm. Under the excitation of a 980‐nm diode laser, LaOBr:Yb³⁺/Er³⁺ nanofibers emit strong green and red up‐conversion emission centering at 519, 541 and 667 nm, ascribed to the ²H_11/2, ⁴S_3/2 → ⁴I_15/2 and ⁴ F_9/2 → ⁴I_15/2 energy‐level transitions of Er³⁺ ions, respectively. The up‐conversion luminescent mechanism of LaOBr:Yb³⁺/Er³⁺ nanofibers is advanced. Moreover, near‐infrared emission of LaOBr:Yb³⁺/Er³⁺ nanofibers is obtained under the excitation of a 532‐nm laser. The formation mechanism of LaOBr:Yb³⁺/Er³⁺ nanofibers is proposed. LaOBr:Yb³⁺/Er³⁺ nanofibers could be important up‐conversion luminescent materials. Copyright © 2014 John Wiley & Sons, Ltd.     

Over 104-fold amplified upconversion luminescence of lanthanide nanocrystals through optical oscillator-like system

Recently, lanthanide (Ln) luminescent nanocrystals have attracted increasing attention in various fields such as biomedical imaging, lasers, and anticounterfeiting. However, due to the forbidden 4f–4f transition of lanthanide ions, the absorption cross-section and luminescence brightness of lanthanide nanocrystals are limited. To address the challenge, we constructed an optical oscillator-like system to repeatedly simulate lanthanide nanocrystals to enhance the absorption efficiency of lanthanide ions on excitation photons. In this optical system, the upconversion luminescence (UCL) of Tm³⁺ emission of ~450 nm excited by a 980 nm laser can be amplified by a factor beyond 10⁴. The corresponding downshifting luminescence of Tm³⁺ at 1460 nm was enhanced by three orders of magnitude. We also demonstrated that the significant luminescence enhancement in the designed optical oscillator-like system was general for various lanthanide nanocrystals including NaYF₄:Yb³⁺/Ln³⁺, NaErF₄@NaYF₄ and NaYF₄:Yb³⁺/Ln³⁺@NaYF₄:Yb³⁺@NaYF₄ (Ln = Er, Tm, Ho) regardless of the wavelengths of excitation sources (808 and 980 nm). The mechanism study revealed that both elevated laser power in the optical system and multiple excitations on lanthanide nanocrystals were the main reason for the luminescence amplification. Our findings may benefit the future development of low-threshold upconversion and downshifting luminescence of lanthanide nanocrystals and expand their applications.     

Spectral‐converting study of Ba9–3(m+n)/2ErmYbnY2Si6O24 (m = 0.005 – 0.2, n = 0 – 0.3) orthosilicate phosphors

Optical materials composed of Ba_9–3(m+n)/2Er_mYb_nY₂Si₆O₂₄ (m = 0.005–0.2, n = 0–0.3) were prepared using a solid‐state reaction. The X‐ray diffraction patterns of the obtained phosphors were examined to index the peak positions. The photoluminescence (PL) excitation and emission spectra of the Er³⁺‐activated phosphors and the critical emission quenching as a function of Er³⁺ content in the Ba_9–3m/2Er_mY₂Si₆O₂₄ structure were monitored. The spectral conversion properties of Er³⁺ and Er³⁺–Yb³⁺ ions doped in Ba₉Y₂Si₆O₂₄ phosphors were elucidated under diode‐laser irradiation at 980 nm. Up‐conversion emission spectra and the dependence of the emission intensity on pump power for the Ba_8.55Er_0.1Yb_0.2Y₂Si₆O₂₄ phosphor were investigated. The desired up‐conversion of the emitted light, which passed through the green, yellow, orange and red regions of the spectrum, was achieved through the use of appropriate Er³⁺ and/or Yb³⁺ concentrations in the host structure and 980 nm excitation light. The up‐conversion mechanism in the phosphors is described by an energy‐level schematic. Copyright © 2015 John Wiley & Sons, Ltd.     

Structural characterization of Er3+,Yb3+‐doped Gd2O3 phosphor,synthesized using the solid‐state reaction method,and its luminescence behavior

We report the synthesis and structural characterization of Er³⁺,Yb³⁺‐doped Gd₂O₃ phosphor. The sample was prepared using the conventional solid‐state reaction method, which is the most suitable method for large‐scale production. The prepared phosphor sample was characterized using X‐ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FTIR), thermoluminescence (TL), photoluminescence (PL) and CIE techniques. For PL studies, the excitation and emission spectra of Gd₂O₃ phosphor doped with Er³⁺ and Yb³⁺ were recorded. The excitation spectrum was recorded at a wavelength of 551 nm and showed an intense peak at 276 nm. The emission spectrum was recorded at 276 nm excitation and showed peaks in all blue, green and red regions, which indicate that the prepared phosphor may act as a single host for white light‐emitting diode (WLED) applications, as verified by International de I'Eclairage (CIE) techniques. From the XRD data, the calculated average crystallite size of Er³⁺ and Yb³⁺‐doped Gd₂O₃ phosphor is ~ 38 nm. A TL study was carried out for the phosphor using UV irradiation. The TL glow curve was recorded for UV, beta and gamma irradiations, and the kinetic parameters were also calculated. In addition, the trap parameters of the prepared phosphor were also studied using computerized glow curve deconvolution (CGCD). Copyright © 2015 John Wiley & Sons, Ltd.     

Influence of Er3+ concentration on the photoluminescence characteristics and excitation mechanism of Gd2O3:Er3+ phosphor synthesized via a solid‐state reaction method

An Er³⁺‐doped phosphor of Gd₂O₃ (Gd₂O₃:Er³⁺) was prepared using a conventional solid‐state reaction method. The structure and particle size were determined from X‐ray powder diffraction measurements. The average particle size of the phosphor was in between 20 and 50 nm. The particle size and structure of the phosphor were further confirmed by transmission electron microscopy (TEM) analysis. Luminescence spectra were recorded under excitation wavelengths of 275, 380, 515 and 980 nm. The visible upconversion and downconversion luminescence spectra of the Gd₂O₃:Er³⁺ phosphor were investigated as a function of Er³⁺ ion concentration. The upconverted emission at 980 nm excitation shows enhanced red emission with respect to green emission as the dopant concentration increased. Similar results were observed for downconversion emission under 275 and 380 nm excitation wavelengths. The mechanisms responsible for populating the ⁴S_3/2 and ⁴ F_9/2 levels, for green and red emissions, respectively, are different for different excitations and for different concentrations of Er³⁺. Copyright © 2014 John Wiley & Sons, Ltd.     

Photoluminescence properties of rare‐earth‐doped (Er3+,Yb3+) Y2O3 nanophosphors by a combustion synthesis method

In this work, we report the synthesis of Y₂O₃:Er³⁺, Y₂O₃:Yb³⁺ and Y₂O₃:Er³⁺,Yb³⁺ nanophosphors by the combustion synthesis method using urea as fuel. The doping agents were incorporated in the form of erbium nitrate and ytterbium nitrate. X‐Ray diffraction (XRD) patterns revealed that the synthesized particles have a body‐centered cubic structure with space group Ia‐3. The photoluminescence (PL) properties were investigated after UV and infrared irradiation at room temperature. A strong characteristic emission of Er³⁺ and Yb³⁺ ions was identified, and the influence of doping concentration on the PL properties was systematically studied. Energy transfer from Yb³⁺ to Er³⁺ ions was observed in Y₂O₃ nanophosphors. The obtained result may be useful in potential applications such as bioimaging. Copyright © 2015 John Wiley & Sons, Ltd.     

Pure red upconverted and near-infrared luminescence properties of Er3+-doped SnO2 nanocrystals for lighting applications

Tin oxide (SnO₂) nanocrystalline powders doped with erbium ion (Er³⁺) in different molar ratios (0, 3, 5, and 7 mol%) were prepared using a solid-state reaction technique. These samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), ultraviolet-visible absorption, visible upconversion, and near-infrared luminescence techniques. XRD analysis revealed the tetragonal rutile structure of SnO₂ and the average crystallite size was about 32 nm. From Tauc's plots, it was confirmed that the substitution of Er³⁺ ions into the SnO₂ host lattice resulted in the narrowing its band gap. Optical absorption bands at 520 and 654 nm correspond to the 4f electron transitions of Er³⁺ further confirming visible light absorption. Infrared luminescence spectra showed a broad band centred at 1536 nm which is assigned to the ⁴I_13/2 → ⁴I_15/2 transition of Er³⁺. Visible upconverted emission spectra under 980 nm excitation exhibit a strong red luminescence with a main peak at 672 nm which is attributed to the ⁴F_9/2 → ⁴I_15/2 transition of Er³⁺. Power-dependent upconversion spectra confirmed that two photons participated in the upconversion mechanism. Enhancement in the intensities of both visible and infrared luminescence was observed when raising the concentration. The results pave the way for the potential applications of these nanocrystalline powders in energy harvesting applications such as infrared light upconverting layer in solar cells, light emitting diodes, infrared broadband sources and amplifiers, and biological labelling.     

Sensitive detection of sulfide ions in red region based on luminescence resonance energy transfer between upconversion nanoparticles and dye‐670

Many sulfides are toxic substances that easily harm the respiratory tract, therefore affecting respiratory function or damaging other organs of the body, leading to its failure. Therefore, there is a pressing need to develop methods for sensitive detection of sulfur ions (S^2?). Based on luminescence resonance energy transfer (LRET) theory, we report the construction of a near‐infrared (NIR) excitation luminescence probe using NaGdF₄:Yb³⁺,Er³⁺@NaYF₄ upconversion nanoparticles (UCNPs) as the donor and dye‐670 as the receptor for detection of S^2?. When UCNPs and dye‐670 molecules were combined using ligand exchange and electrostatic attraction, LRET occurred and UCNP luminescence was quenched. When S^2? was added to the system, sulfide ions were able to destroy the double bond of the dye, inhibiting LRET and restoring UCNP luminescence. Under optimum condition, the linear range of S^2? detection was 0.65–18.2 μM, and the detection limit was 34.2 nM. This method was applied for determination of S^2? in water with satisfactory results.     

Thermoluminescence dosimetric attributes of Yb3+-doped BaO–ZnO–LiF–B2O3 glass material after Er3+ co-doping

Motivated by our previous study on Sm³⁺ ions as thermoluminescence (TL) sensitizers to the BaO–ZnO–LiF–B₂O₃–Yb₂O₃ glass system, in the current study we examined the effect of Er³⁺ ion co-doping on the TL characteristics of this glass system. The 4f–4f electronic transitions of the Er³⁺ and Yb³⁺ ions were confirmed via the optical absorption spectrum. Notably, the use of Yb³⁺–Er³⁺ ions failed to improve the TL intensity, sensitivity, and trap density. However, they enabled the glass system to function as an activator–quencher system. The linearity range and effective atomic number remained unaffected after co-doping. In addition, the problem of anomalous fading caused a remnant signal of just 58% after a week of storage of the Yb³⁺ monodoped glass. This was resolved by the optimum co-doping of Er³⁺ ions to achieve an 89% signal. The co-doping of Er³⁺ ions to the BaO–ZnO–LiF–B₂O₃–Yb₂O₃ glass system regulated its thermal stability and therefore supplemented its potential for radiation monitoring in food processing and retrospective dosimetry.     

Iridium Oxide‐Assisted Plasmon‐Induced Hot Carriers: Improvement on Kinetics and Thermodynamics of Hot Carriers

Plasmonic nanostructures are capable of driving photocatalysis through absorbing photons in the visible region of the solar spectrum. Unfortunately, the short lifetime of plasmon‐induced hot carriers and sluggish surface chemical reactions significantly limit their photocatalytic efficiencies. Moreover, the thermodynamically favored excitation mechanism of plasmonic photocatalytic reactions is unclear. The mechanism of how the plasmonic catalyst could enhance the performance of chemical reaction and the limitation of localized surface plasmon resonance devices is proposed. In addition, a design is demonstrated through co‐catalyst decorated plasmonic nanoparticles Au/IrO_X upon a semiconductor nanowire‐array TiO₂ electrode that are able to considerably improve the lifetime of plasmon‐induced charge‐carriers and further facilitate the kinetics of chemical reaction. A thermodynamically favored excitation with improved kinetics of hot carriers is revealed through electrochemical studies and characterization of X‐ray absorption spectrum. This discovery provides an opportunity to efficiently manage hot carriers that are generated from metal nanostructures through surface plasmon effects for photocatalysis applications.     

Selective cellular imaging with lanthanide‐based upconversion nanoparticles

Upconversion nanoparticles (UCNPs) with sodium yttrium fluoride, NaYF₄ (host lattice) doped with Yb³⁺ (sensitizer) and Er³⁺ (activator) were synthesized via hydrothermal route incorporating polyethyleneimine (PEI) for their long‐term stability in water. The cationic PEI‐modified UCNPs with diameter 20 ± 4 nm showed a zeta potential value of +36.5 mV and showed an intense, visible red luminescence and low‐intensity green emission with 976 nm laser excitation. The particles proven to be nontoxic to endothelial cells, with a 3‐(4,5‐dimethylthiazol‐2yl)‐2,5‐diphenyltetrazolium bromide (MTT) assay, showing 90% to 100% cell viability, across a wide range of UCNP concentrations (0.3 ng/mL‐0.3 mg/mL) were used in multiphoton imaging. Multiphoton cellular imaging and emission spectroscopy data reported here prove that the UCNPs dispersed in cell culture media are predominantly concentrated in the cytoplasm than the cell nucleus. The energy transfer from PEI‐coated UCNPs to surrounding media for red luminescence in the biological system is also highlighted with spectroscopic measurements. Results of this study propose that UCNPs can, therefore, be used for cytoplasm selective imaging together with multiphoton dyes (eg, 4′,6‐diamidino‐2‐phenylindole (DAPI)) that are selective to cell nucleus.      

Significant Efficiency Enhancement in Ultrathin CZTS Solar Cells by Combining Al Plasmonic Nanostructures Array and Antireflective Coatings

In the few past years, the economic and eco-friendly Cu₂ZnSnS₄ (CZTS) solar cells have caught lots of attentions. However, due to rather poor efficiency, identifying deficiencies and making improvements is necessary. In the present study, the performance improvement of ultrathin CZTS solar cells was achieved through (1) incorporation of anti-reflective coating (ARC) on the surface of cell and (2) embedding Al plasmonic nanostructures with different radius, periods, and vertical positions in the absorber layer. Various thicknesses of CZTS absorber layer were simulated optically and electrically using FDTD and DEVICE solver of Lumerical software. The reference solar cell consists of a 1.5-nm-thick CZTS absorber and exhibit an efficiency of up to 5.67%, short-circuit current density (Jsc) of 18.48 mA cm⁻² and open circuit voltage of 0.58 V. Result showed a remarkable performance enhancement of the solar cell in spite of a very thin absorber layer. For a 500-μm-thick CZTS solar cell with the assistance of ARC and embedding Al plasmonic nanostructures, the efficiency is increased to 7.45% due to an increase in Jsc to 22.62 mA cm⁻² with an open circuit voltage of 0.62 V.

     

Nd3+‐Yb3+/Nd3+‐Yb3+‐Li+ co‐doped Gd2O3 phosphors for up and down conversion luminescence

Frequency up‐conversion (UC) emission from the Nd³⁺‐Yb³⁺/Nd³⁺‐Yb³⁺‐Li⁺ co‐doped gadolinium oxide (Gd₂O₃) phosphors prepared by the solution combustion technique in the visible range have been studied by using 980 nm near infrared (NIR) laser diode excitation. The crystalline structure and formation of the cubic phase has been confirmed with the help of X‐ray diffraction (XRD) studies. XRD peak shifts have been found towards the lower diffraction angle side in the case of the Nd³⁺‐Yb³⁺‐Li⁺ co‐doped phosphors. Surface morphology and particle size information have been observed by using field emission scanning electron microscopy (FESEM) and transmission electron microscopy (TEM) analysis. Down‐conversion emission study under 351 nm excitation in the visible region for the Nd³⁺‐Yb³⁺/Nd³⁺‐Yb³⁺‐Li⁺ co‐doped phosphors has been performed. The UC emission bands lying in the green and red region arising from the Nd³⁺ ions have been enhanced by ~260 times, ~113 times due to incorporation of Li⁺ ions in the Nd³⁺‐Yb³⁺ co‐doped phosphors. Photometric characterization has been done for the Nd³⁺‐Yb³⁺/Nd³⁺‐Yb³⁺‐Li⁺ co‐doped phosphors. The present study suggests the capability of the synthesized phosphors in near‐infrared (NIR) to visible upconverter and luminescent device applications.     

Near‐Infrared Light‐Induced Photocurrent from a (NaYF4:Yb‐Tm)/(Cu2O) Composite Thin Film

Utilization of photons of sub‐bandgap energy, mostly near‐infrared (NIR) photo­ns, is highly desirable for photovoltaic devices. We show that (NaYF₄:Yb‐Tm)/(Cu₂O) composite films formed by electrodeposition exhibit robust photoactive current generation under NIR light excitation. The composite films consist of homogeneous crystalline particles of the fluoride and Cu₂O in sub‐micrometer size. From spectroscopic characterization, it is found that the NaYF₄:Yb‐Tm layer in the composite film converts NIR radiation by up‐conversion into visible emission, which is efficiently absorbed by the covering semiconducting Cu₂O film, producing photoelectrons. Accordingly, the composite films exhibit highly photoactive current generation by means of a photoelectrochemical process driven by NIR irradiation. The methodology demonstrated here may have certain implications for the utilization of NIR radiation in solar cells, photocatalysts, and infrared photodetectors.     

Visible‐near‐infrared luminescent lanthanide ternary complexes based on beta‐diketonate using visible‐light excitation

We used the synthesized dinaphthylmethane (Hdnm) ligand whose absorption extends to the visible‐light wavelength, to prepare a family of ternary lanthanide complexes, named as [Ln(dnm)₃phen] (Ln = Sm, Nd, Yb, Er, Tm, Pr). The properties of these complexes were investigated by Fourier transform infrared (FT‐IR) spectroscopy, diffuse reflectance (DR) spectroscopy, thermogravimetric analyses, and excitation and emission spectroscopy. Generally, excitation with visible light is much more advantageous than UV excitation. Importantly, upon excitation with visible light (401–460 nm), the complexes show characteristic visible (Sm³⁺) as well as near‐infrared (Sm³⁺, Nd³⁺, Yb³⁺, Er³⁺, Tm³⁺, Pr³⁺) luminescence of the corresponding lanthanide ions, attributed to the energy transfer from the ligands to the lanthanide ions, an antenna effect. Now, using these near‐infrared luminescent lanthanide complexes, the luminescent spectral region from 800 to 1650 nm, can be covered completely, which is of particular interest for biomedical imaging applications, laser systems, and optical amplification applications. Copyright © 2015 John Wiley & Sons, Ltd.