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A Tm3+/Yb3+/Bi3+ co-doped GdVO4 phosphor sample has been synthesized using a high-temperature solid-state reaction technique. The X-ray diffraction patterns reveal pure phase formation and crystalline behavior of the synthesized samples. Intense blue and NIR upconversion emissions have been observed upon excitation with a 980 nm diode laser. It is found that the addition of the Bi3+ ion to the phosphor reduces the intensity of blue emission and enhances the NIR emission intensity to the extent that NIR emission is nearly monochromatic [(INIR/IBlue) â¼ 14]. This ratio is further improved up to 70 times (almost monochromatic) by varying the pump power of the diode laser. Thus, this material can be used as a cheap source of monochromatic NIR emission at 800 nm for bioimaging.
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Host-sensitized near-infrared quantum cutting (QC) emission has been demonstrated in Nd(3+) doped Gd(1-x)Nd(x)NbO4 phosphors for various x values. Further, the effect of Bi(3+) ion addition as a sensitizer on near-infrared QC is studied in detail. X-ray diffraction confirms a monoclinic structure for pure and Nd(3+) doped phosphors. Pulsed laser excitation at 266 nm of Gd(1-x)Nd(x)NbO4 and Gd(0.99-x)Nd(x)Bi(0.01)NbO4 causes efficient room-temperature energy transfer from the NbO4(3-) to the Nd(3+) ions and the NbO4(3-) and Bi(3+) ions to the Nd(3+) ions, respectively, which emits more than one near-infrared photon for single impinging ultraviolet photon. The emission band of Nd(3+) shows unusual character where the intensity of the (4)F(3/2)-(4)I(9/2) transition at 888 nm is higher than the intensity of the transition (4)F(3/2)-(4)I(11/2) at 1064 nm, due to energy transfer from GdNbO4 host to Nd(3+) ion. Using photoluminescence lifetime studies, the quantum cutting efficiencies are found to be the maximum 166% and 172% for Gd(0.95)Nd(0.05)NbO4 and Gd(0.94)Nd(0.05)Bi(0.01)NbO4, respectively. The present study could establish Nd(3+) ion as an alternative of Yb(3+) ion for near-infrared quantum cutting. This work facilitates the probing of Nd(3+) ions doped phosphor materials for next generation Si-solar cells.
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The Bi3+/Yb3+-codoped gadolinium tungstate phosphor has been synthesized through a solid-state reaction method. The structural characterization reveals the crystalline nature of the phosphor. The Bi3+-doped phosphor emits visible radiation from the blue to red regions upon excitation with 330 and 355 nm. The addition of Yb3+ to the Bi3+-doped phosphor reduces the emission intensity in the visible region and emits an intense near-infrared (NIR) photon centered at 976 nm through a quantum-cutting (QC) phenomenon. This is due to cooperative energy transfer (CET) from the 3P1 level of Bi3+ to the 2F5/2 level of Yb3+. The presence of Li+ ions in the Bi3+/Yb3+-codoped phosphor enhances the emission intensity in the NIR region up to by 3 times, whereas the emission intensity in the visible region is significantly reduced. The energy transfer (ET) from the Bi3+ ions to the Yb3+ ions is confirmed by lifetime measurements, and the lifetime for the 3P1 level of Bi3+ decreases continuously with increasing Yb3+ concentration. The ET efficiency (ηETE) and corresponding QC efficiency (ηQE) are calculated and found to be 29% and 129%, respectively. The presence of Li+ enhances the QC efficiency of the phosphor up to 43%. Thus, the Bi3+/Yb3+/Li+-codoped phosphor is a promising candidate to enhance the efficiency of a crystalline-silicon-based solar cell through spectral conversion.
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Herein, we report a new concept for garnet materials in terms of the synthesis of nanocrystalline structure at low temperatures and its multimodal luminescence processes. Terbium- and ytterbium-ion-codoped yttrium gallium garnet nanophosphors have been synthesized via solution combustion technique; nearly pure phase nanophosphor samples were obtained. The synthesized nanophosphor shows efficient multimodal upconversion (UC), downshifting (DS), and quantum cutting (QC)/downconversion (DC) luminescence, which is a new paradigm in garnet material. The garnet nanophosphor shows strong green emission through DS and UC processes both. Furthermore, cooperative energy transfer (CET) has been described in detail, and a possible mechanism for the QC process is also proposed. A UV/blue photon absorbed by Tb(3+) ion splits into two near-infrared photons (wavelength range 900-1040 nm), emitted by a Yb(3+) ion pair, with an efficiency of more than 100%. The Yb(3+) concentration dependent ET from Tb(3+) to Yb(3+) has been verified using time domain analysis. An ET efficiency as high as 28% and a corresponding QC efficiency of about 128% (for 15 mol % of Yb(3+) concentration) have been attained. Such a multimode emitting nanophosphor could be very useful in display devices and for enhancing the conversion efficiency of next generation solar cells via spectral modification etc.
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The exploration of multicolor emitting phosphors with single phase is extremely important for n-UV chip excited LED/WLED's and multicolor display devices. In this paper, Dy3+, Ho3+ singly doped and Dy3+/Ho3+ co-doped CaTiO3 phosphor materials have been synthesized by solid state reaction method at 1473 K. The synthesized materials were characterized by XRD, FE-SEM, EDX, FTIR, PL and lifetime measurements. The PL emission spectra of Dy3+ doped CaTiO3 phosphors give intense blue and yellow emissions under UV excitation, while the PL emission spectra of Ho3+ doped CaTiO3 phosphor show intense green emission under UV/blue excitations. Further, to get the multicolor emission including white light, Dy3+ and Ho3+ were co-doped simultaneously in CaTiO3 host. It is found that alongwith colored and white light emissions, it also shows energy transfer from Dy3+ to Ho3+ with 367 nm and from Ho3+ to Dy3+ under 362 nm excitations. The energy transfer efficiency is found to be 67.76% and 69.39% for CaTiO3:4Dy3+/3Ho3+ and CaTiO3:3Ho3+/5Dy3+ phosphors, respectively. The CIE color coordinates, CCT and color purity of the phosphors have been calculated, which show color tunability from whitish to deep green via greenish yellow color. The lifetime of 4F9/2 level of Dy3+ ion and 5S2 level of Ho3+ ion is decreased in presence of Ho3+ and Dy3+ ions, respectively. This is due to energy transfer from Dy3+ to Ho3+ ions and vice versa. A temperature dependent photoluminescence studied of CaTiO3:4Dy3+/2Ho3+ phosphor show a high thermal stability (82% at 423 K of initial temperature 303 K) in the temperature range 303-483 K with activation energy 0.17 eV. The PLQY are 30%, 33% and 35% for CaTiO3:4Dy3+, CaTiO3:4Dy3+/2Ho3+ and CaTiO3:3Ho3+ phosphors, respectively. Hence, Dy3+, Ho3+ singly doped and Dy3+/Ho3+ co-doped CaTiO3 phosphor materials can be used in the field of single matrix perovskite color tunable phosphors which may be used in multicolor display devices, n-UV chip excited LED/WLED's and photodynamic therapy for the cancer treatment.
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In this work, Sm3+-doped and Sm3+/Li+/K+/Mg2+/Ba2+/Gd3+/Bi3+ co-doped CaTiO3 phosphors were synthesized by a solid-state reaction method at 1473 K. The phase of phosphors was identified to be orthorhombic with space group Pnma (62) by XRD measurements. The morphological properties of the prepared samples were studied by SEM measurements. The average crystallite and particle sizes were found to increase in the presence of modifiers and they follow the trend Li+ > Mg2+ > Gd3+ > K+ > Bi3+ > Ba2+. EDX measurements were used to verify the presence of Ca, Ti, O, Sm, K, Mg, Ba, Gd and Bi atoms in the prepared phosphor samples. The Sm3+ ion shows emission peaks at 564, 599 and 646 nm due to 4G5/2 â 6H5/2, 6H7/2 and 6H9/2 transitions upon 407 nm excitation, among which the peak situated at 599 nm has maximum emission intensity. Concentration quenching was observed above 2 mol% of Sm3+ ions in this host. However, the emission intensity of Sm3+ peaks can be enhanced using different modifier (Li+/K+/Mg2+/Ba2+/Gd3+/Bi3+) ions. It was found that the size (ionic radii) and charge compensation of the ion together play a dominant role. The enhancement is more after co-doping with smaller radius ions (Li+, Mg2+ and Gd3+), among which Li+ shows the largest enhancement. This is because ions of smaller size will be able to go closer to the activator ion and the charge imbalance causes a larger field. The CIE color coordinates, correlated color temperature (CCT) and color purity of the phosphors were calculated and show orange-red color emissions with a maximum color purity of â¼93% in the case of CaTiO3:2Sm3+/1.0Li+ phosphor. The lifetime value is increased in the presence of these ions. It is again maximum for the Li+ co-doped CaTiO3:2Sm3+ phosphor sample. Thus, the prepared phosphor samples are suitable sources for orange-red light.
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The Eu3+ doped and Mg2+/Ca2+ co-doped ZnGa2O4 phosphor samples were synthesized by solid-state reaction method and their structural and optical properties studied. The phase, crystallinity and particles size of the phosphor samples were studied by XRD and SEM measurements. EDS analyses were used to identify the elements present in the phosphor materials. The vibrational groups present in the phosphor samples were examined by Fourier transform infrared (FTIR) measurements. Pure ZnGa2O4 emits intense blue light under 260 nm excitation. However, Eu3+ doped and Mg2+/Ca2+ co-doped ZnGa2O4 phosphor samples exhibit intense red emission under 393 nm excitation. A bluish white color is observed in these samples under 290 nm excitation. The maximum PL emission intensity is found at 0.1 mol% Eu3+ doping concentration. For higher concentrations, concentration quenching was observed due to dipole-dipole interaction. The emission intensity is enhanced upto 1.20 and 2.91 times on co-doping of Mg2+ and Ca2+via induced crystal field due to charge imbalance. The emission intensity of the phosphor is found to enhance further on annealing the samples at 873 K. Under various excitation wavelengths, color tunability was seen from blue to bluish-white to red regions. The lifetime of the 5D0 level of the Eu3+ ion improves via doping of Mg2+/Ca2+ ions and it increases appreciably on annealing. The temperature dependent photoluminescence study (TDPL) reveals a thermal quenching behavior of the sample with thermal stability â¼65% and activation energy â¼0.223 eV in the Eu3+/Ca2+ co-doped ZnGa2O4 phosphor sample.
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In this work, the Eu3+, Cr3+ doped and co-doped LaVO4 phosphors have been prepared through a high temperature solid-state reaction method. The powder XRD patterns of phosphors are very sharp and intense, which reflects a highly crystalline nature of phosphors. The XRD data were also refined by a Rietveld refinement method. The particle size of the phosphor samples lies in the sub-micron to micron range. The existence of La, Eu, Cr, V and O elements was verified by EDS spectra. The FTIR spectra show various absorption bands due to different vibrating groups. The optical band gap of the phosphor decreases on increasing concentration of Cr3+ ion. The photoluminescence excitation spectra of Eu3+, Cr3+ co-doped LaVO4 phosphor exhibit bands due to Eu3+ and Cr3+ ions. The Eu3+ doped LaVO4 phosphor exciting at 393 and 316 nm wavelengths gives intense red color at 614 nm due to the 5D0 â 7F2 transition of the Eu3+ ion. When the Cr3+ ion is co-doped in the Eu3+ doped LaVO4 phosphor the emission spectra contain emission bands due to Eu3+ and Cr3+ ions. The emission intensity of Eu3+ doped phosphor reduces due to energy transfer from Eu3+ to Cr3+ ions in presence of Cr3+ ions upon 393 and 386 nm excitations. The lifetime of the 5D0 level of Eu3+ ions decreases in the Eu3+, Cr3+ co-doped LaVO4 phosphor, which also reflects the energy transfer. The Eu3+, Cr3+ co-doped LaVO4 phosphor also produces a large amount of heat upon 980 nm excitation. Thus, the Eu3+, Cr3+ co-doped LaVO4 phosphors may be used for LEDs, solid state lighting and heat generating devices.
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The conversion of NIR light into visible light has been studied in Ho3+/Yb3+/Bi3+ co-doped ZnGa2O4 phosphor for the first time. The crystallinity and particles size of the phosphor increase through Bi3+ doping. The absorption characteristics of Ho3+, Yb3+ and Bi3+ ions are identified by the UV-vis-NIR measurements. The Ho3+ doped phosphor produces intense green upconversion (UC) emission under 980 nm excitations. The emission intensity ~ excitation power density plots show contribution of two photons for the UC emissions. The UC intensity of green emission is weak in the Ho3+ doped phosphor, which enhances upto 128 and 228 times through co-doping of Yb3+ and Yb3+/Bi3+ ions, respectively. The relative and absolute temperature sensing sensitivities of Ho3+/Yb3+/5Bi3+ co-doped ZnGa2O4 phosphor are calculated to be 13.6 × 10-4 and 14.3 × 10-4 K-1, respectively. The variation in concentration of Bi3+ ion and power density produces excellent color tunability from green to red via yellow regions. The CCT also varies with concentration of Bi3+ ion and power density from cool to warm light. The color purity of phosphor is achieved to 98.6% through Bi3+ doping. Therefore, the Ho3+/Yb3+/Bi3+:ZnGa2O4 phosphors can be suitable for UC-based color tunable devices, green light emitting diodes and temperature sensing.
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[This retracts the article DOI: 10.1021/acsomega.8b03473.].
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In this paper, we have studied the structural, optical, dielectric and magnetic properties of Eu3+, Bi3+ co-doped LaVO4 phosphors prepared by solid state reaction method. Rietveld structural analysis of the samples confirms the monoclinic crystal structure with P21/n space group. The particles size of Eu3+ doped LaVO4 phosphor increased in presence of Bi3+ ion. The excitation spectrum of Eu3+, Bi3+ co-doped LaVO4 phosphor reveals bands due to charge transfer state (CTS) and electronic transitions of Eu3+ and Bi3+ ions. The Eu3+ doped LaVO4 phosphor gives intense red emission centred at 613 nm due to 5D0 â 7F2 transition of Eu3+ ion excited at 266, 355 and 394 nm wavelengths. When Bi3+ and Eu3+ ions are co-doped in the LaVO4 phosphor the photoluminescence intensity is enhanced upto two times. The photoluminescence intensity is largest for the 266 nm excitation. This is due to energy transfer from CTS and (1P1, 3P1) levels of the Bi3+ ion to 5D4 level of the Eu3+ ion and increase in the particles size of phosphor. The Eu3+, Bi3+ co-doped LaVO4 phosphors also show excellent dielectric and magnetic properties with a variation in frequency and magnetic field, respectively. Thus, the Eu3+, Bi3+ co-doped LaVO4 phosphor may be useful in fabricating displays devices, red emitting phosphors, dielectric capacitors and magnetic devices.
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Intense red upconversion luminescence was observed in the Er3+/Yb3+/Li+ co-doped ZnGa2O4 phosphor synthesized through the solid state reaction method for the first time. The structural characterization showed a large crystalline nature and an increase in the particle size via Li+ doping. The absorption spectra showed a large number of peaks in the UV-vis-NIR regions due to the Er3+ and Yb3+ ions. The Er3+/Yb3+ co-doped ZnGa2O4 phosphor exhibited green, red and NIR upconversion emissions on excitation with 980 nm radiation. The intensity of the red emission was relatively larger than that of the other emissions. The luminescence intensity versus pump power measurements revealed the number of required photons for these emissions. The phosphor showed very interesting color tunability as a function of Er3+ ion concentration and incident pump power. The luminescence intensity of the Er3+/Yb3+ co-doped phosphor was enhanced more than two times via Li+ doping. The enhancement in the luminescence intensity was proposed to be due to the increase in the crystallinity and particle size of the phosphor. The lifetimes of the 4S3/2 and 4F9/2 levels also increased in the presence of Li+ ions. The variation in the fluorescence intensity ratio (FIR) of the thermally coupled levels (TCLs) of the red emission with incident pump power offered effective optical heating in the phosphor. The temperature-induced FIR using TCLs of red emission exhibited a larger value of temperature sensing sensitivity in the presence of Li+ ions, which was up to 14 × 10-4 K-1. Thus, the Er3+/Yb3+/Li+ co-doped ZnGa2O4 phosphor may be used in photonic, optical heating, and temperature sensing devices.
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In the present investigation, crab shells as seafood wastes were successfully recycled into an extremely useful biomaterial by the thermal treatment method. Thermogravimetric-differential thermal analysis studies concluded that the calcination temperature must be beyond â¼570 °C to get a fine and crystalline apatite powder from the crab shells. Thus, the calcination temperature is taken to be 700 °C. Powder X-ray diffraction analysis of the calcined crab shells revealed hydroxyapatite (HAp)/carbonated HAp (CHAp) with an average crystallite size of 24.4 nm. Scanning electron microscopy revealed the surface morphology of the crab shells-derived apatite powder as needle-like nanorods of HAp of diameter ≈ 100-300 nm and nanospheres of CHAp of diameter ≈ 100-500. Energy-dispersive X-ray spectroscopy showed the presence of calcium, phosphorous, magnesium, and oxygen as major elements in the apatite constituents. Fourier transform infrared as well as Raman spectroscopies confirmed the formation of apatite powder. X-ray photoelectron spectroscopy results indicated the electronic environment and oxidation states of the constituent elements, Ca, C, and P. On the basis of the results obtained from various characterization techniques, the overall study emphasized an environment-friendly and cost-effective approach for recycling of the bio-pollutant and synthesis of ultra-fine, ultra-crystalline apatite-based excellent biomaterial derived from crab shells as seafood wastes with its application as a futuristic biomaterial in bone/teeth implants.
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Three-dimensional nanocomposites exhibit unexpected mechanical and biological properties that are produced from two-dimensional graphene nanoplatelets and oxide materials. In the present study, various composites of microwave-synthesized nanohydroxyapatite (nHAp) and graphene nanoparticles (GNPs), (100 - x)HAp-xGNPs (x = 0, 0.1, 0.2, 0.3, and 0.5 wt %), were successfully synthesized using a scalable bottom-up approach, that is, a solid-state reaction method. The structural, morphological and mechanical properties were studied using various characterization techniques such as X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and universal testing machine (UTM). XRD studies revealed that the prepared composites have high-order crystallinity. Addition of GNPs into nHAp significantly improved the mechanical properties. Three-dimensional nanocomposite 99.5HAp-0.5GNPs exhibited exceptionally high mechanical properties, for example, a fracture toughness of â¼116 MJ/m3, Young's modulus of â¼98 GPa, and compressive strength of 96.04 MPa, which were noticed to be much greater than in the pure nHAp. The MTT assay and cell imaging behaviors were carried out on the gut tissues of Drosophila third instars larvae and on primary rat osteoblast cells for the sample 99.5HAp-0.5GNPs that have achieved the highest mechanical properties. The treatment with lower concentrations of 10 µg/mL on the gut tissues of Drosophila and 1 and 5 µg/mL of this composite sample showed favorable cell viability. Therefore, owing to the excellent porous nature, interconnected surface morphology, and mechanical and biological properties, the prepared composite sample 99.5HAp-0.5GNPs stood as a promising biomaterial for bone implant applications.
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We herein demonstrate novel inorganic-organic hybrid nanoparticles (HNPs) composed of inorganic NPs, NaY0.78Er0.02Yb0.2F4, and an organic ß-diketonate complex, Eu(TTA)3Phen, for energy harvesting applications. Both the systems maintain their core integrity and remain entangled through weak interacting forces. HNPs incorporate the characteristic optical behaviour of both the systems i.e. they give an intense red emission under UV excitation, due to Eu3+ in organic complexes, and efficient green upconversion emission of Er3+ in inorganic NPs for NIR (980 nm) excitation. However, (i) an energy transfer from Er3+ (inorganic NPs) to Eu3+ (organic complex) under NIR excitation, and (ii) an increase in the decay time of 5D0 â 7F2 transition of Eu3+ for HNPs as compared to the Eu(TTA)3Phen complex, under different excitation wavelengths, are added optical characteristics which point to an important role of the interface between both the systems. Herein, the ultra-small size (6-9 nm) and spherical shape of the inorganic NPs offer a large surface area, which improves the weak interaction force between both the systems. Furthermore, the HNPs dispersed in the PMMA polymer have been successfully utilized for luminescent solar collector (LSC) applications.
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We synthesized the Eu(TTA)3Phen complex and present herein a detailed study of its photophysics. The investigations encompass samples dispersed in poly(vinyl alcohol) and in ethanol in order to explore the versatile applicability of these lanthanide-based materials. Details upon the interaction between Eu, TTA, and the Phen ligands are revealed by Fourier transform infrared and UV-visible absorption, complemented by steady state and temporally resolved emission studies, which provide evidence of an efficient energy transfer from the organic ligands to the central Eu(3+) ion. The material produces efficient emission even under sunlight exposure, a feature pointing toward suitability for luminescent solar concentrators and UV light sensing, which is demonstrated for intensities as low as 200 nW/cm(2). The paper further promotes the complex's capability to be used as luminescence-based temperature sensor demonstrated by the considerable emission intensity changes of â¼4.0% per K in the temperature range of 50-305 K and â¼7% per K in the temeperature range 305-340 K. Finally, increasing the optical excitation causes both spontaneous emission amplification and emission peak narrowing in the Eu(TTA)3Phen complex dispersed in poly(vinyl alcohol) - features indicative of stimulated emission. These findings in conjunction with the fairly large stimulated emission cross-section of 4.29 × 10(-20) cm(2) demonstrate that the Eu(TTA)3Phen complex dispersed in poly(vinyl alcohol) could be a very promising material choice for lanthanide-polymer based laser architectures.
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The present study reports significant enhancement in the red upconversion emission of Er(3+) in NaSc0.8Er0.02Yb0.18F4 upconversion nanoparticles (UCNPs), via a two step process, (i) codoping of Gd(3+) ion at Sc(3+) site and (ii) attaching gold nanoparticles (AuNPs) at the surface of these codoped nanostructures, and further probes the use of these Gd:UCNPs@AuNPs for bioimaging application. The Gd(3+) codoping tailors the particle size (reduces) of UCNPs and bring out Er(3+)-Yb(3+) ion pair in close proximity, which promotes the cross relaxation mechanism and boosts the population in red emitting level (4)F9/2. Further, attachment of AuNPs on the surface of UCNPs gives 2-fold advantages, that is, reduction in green band (through resonance energy transfer with efficiency 31.54%) and enhancement in red band (through plasmonic effect). It gives red to green (R/G) ratio nearly 20:1 (almost single band red UC), which is quite promising for imaging application. In addition to this, codoping of Gd(3+) enhances the magnetic moment appreciably and the obtained magnetic moment for NaSc0.75Er0.02Yb0.18Gd0.05F4 UCNPs (â¼1.7 emu/g) is close to the reported values for bioseparation in case of NPs. This shows the potential of the material for multimodal (optical and magnetic both) imaging application. These magnetoluminescence particles were found safe up to 1 mg/mL dose as assessed by cytotoxicity measurement in human cervical cancer (HeLa) and lung cancer (A549) cells. Ultrafine nanoparticles, transparent, and stable colloidal solution and the unique red UC emission endow these NPs as optical probe for imaging applications.
Assuntos
Gadolínio/química , Ouro/química , Imagem Molecular/instrumentação , Nanopartículas/química , Neoplasias/química , Itérbio/química , Ítrio/química , Linhagem Celular Tumoral , Células HeLa , Humanos , Luminescência , Tamanho da PartículaRESUMO
When Eu(3+) ions occupy Ca(2+) sites of CaMoO(4), which has a body centered tetragonal structure with inversion symmetry, only the magnetic dipole transition ((5)D(0)â(7)F(1)) should be allowed according to Judd-Ofelt theory. Even if there are a few distortions in the Eu(3+) environment, its intensity should be more than that of the electric dipole transition ((5)D(0)â(7)F(2)). We report here the opposite effect experimentally and ascribe this to the polarizability effect of the MoO(4) tetrahedron, which is neighboring to EuO(8) (symmetric environment). The contribution of the energy transfer process from the Mo-O charge transfer band to Eu(3+) and the role of Eu(3+) over the surface of the particle could be distinguished when luminescence decay processes were measured at two different excitations (250 and 398 nm). Further, the luminescence intensities and lifetimes increase significantly with increasing heat-treatment temperature of the doped samples. This is attributed to the reduction of H(2)O from the surface of the particles and a non-radiative process after heat treatment.