Enhanced UVB emission and analysis of chemical states of Ca5(PO4)3OH:Gd3+,Pr3+ phosphor prepared by co-precipitation

Hydroxyapatite (Ca₅(PO₄)₃OH) is a well-known bioceramic material used in medical applications because of its ability to form direct chemical bonds with living tissues. This mineral is currently used as a host for rare-earth ions (e.g. Gd³⁺, Pr³⁺, Tb³⁺, etc.) to prepare phosphors that can be used in light emitting devices of different types. In this study Ca₅(PO₄)₃OH:Gd³⁺,Pr³⁺ phosphors were prepared by the co-precipitation method and were characterised by x-ray diffraction, x-ray photoelectron spectroscopy, scanning electron microscopy, high resolution transmission electron microscopy, energy dispersive x-ray spectroscopy and photoluminescence spectroscopy. The x-ray diffraction pattern was consistent with the hexagonal phase of Ca₅(PO₄)₃OH referenced in JCPDS card number 73-0293. The x-ray photoelectron spectroscopy data indicated that Ca²⁺ occupied two different lattice sites, referred to as Ca1 and Ca2. The photoluminescence data exhibited a narrowband emission located at 313 nm, which is associated with the ⁶P_7/2→⁸S_7/2 transition of the Gd³⁺ ion. This emission is classified as ultraviolet B and it is suitable for use in phototherapy lamps to treat various skin diseases. The photoluminescence intensity of the 313 nm emission was enhanced considerably by Pr³⁺ co-doping.     

Ca8Mg(SiO4)4Cl2:Ce3+, Tb3+: A potential single-phased phosphor for white-light-emitting diodes

A single-phased white-light-emitting phosphor Ca₈Mg(SiO₄)₄Cl₂:Ce³⁺, Tb³⁺ (CMSC:Ce³⁺, Tb³⁺) is synthesized by a high temperature solid-state reaction method, and its photoluminescence properties are investigated. The obtained phosphor exhibits a strong excitation band between 250 and 410 nm, matching well with the dominant emission band of a UV light-emitting-diode (LED) chip. Energy transfer from Ce³⁺ to Tb³⁺ ions has been investigated and demonstrated to be a resonant type via a dipole–dipole mechanism. The energy transfer efficiency as well as the critical distance is also estimated. Furthermore, the phosphors can generate light from yellow-green through white and eventually to blue by properly tuning the relative ratio of Ce³⁺ to Tb³⁺ ions grounded on the principle of energy transfer. The results show that this phosphor has potential applications as a single-phased phosphor for UV white-light LEDs.     

White LED based on nano-YAG:Ce3+/YAG:Ce3+,Gd3+ hybrid phosphors

Nano-YAG:Ce³⁺ and YAG:Ce³⁺,Gd³⁺ phosphors were synthesized by glycothermal method. The X-ray diffraction (XRD) measurements showed that the samples can be well-crystallized at 600 °C. The transition electron microscope (TEM) showed that the particles have sizes mostly in the range between 35 and 100 nm. The YAG:Ce nano-phosphor had a wide emission band ranging from blue to yellow peaking at 532 nm, due to the transition from the lowest 5d band to ²F_7/2, ²F_5/2 states of the Ce³⁺ ion. Red-shift of emission peak wavelength from 532 nm to 568 nm has been achieved as doping Gd³⁺ ions into the YAG:Ce³⁺ to substitute some Y³⁺ ions. White LEDs were fabricated by combining GaN (460 nm) chip with the YAG:Ce³⁺ and YAG:Ce³⁺,Gd³⁺. Color rendering index of the white LED as a function of the ratios of theses two kinds of phosphors was studied. As the ratio of YAG:Ce³⁺,Gd³⁺ phosphor increased, the color rendering index of the LED improved significantly under the forward bias of 20 mA. As the ratio of YAG:Ce³⁺ and YAG:Ce³⁺,Gd³⁺ was 11:9, the white LED had a color rendering index, CIE chromaticity coordinates and color temperature T_c of 85, (0.3116, 0.3202) and 6564 K, respectively.     

Potential tunable white-emitting phosphor LiSr4(BO3)3:Ce3+, Eu2+ for ultraviolet light-emitting diodes

A novel Ce³⁺/Eu²⁺ co-activated LiSr₄(BO₃)₃ phosphor has been synthesized by traditional solid-state reaction. The samples could display varied color emission from blue towards white and ultimately to yellow under the excitation of ultraviolet (UV) light with the appropriate adjustment of the relative proportion of Ce³⁺/Eu²⁺. The resonance-type energy transfer mechanism from Ce³⁺ to Eu²⁺ in LiSr₄(BO₃)₃:Ce³⁺, Eu²⁺ phosphors is dominant by electric dipole–dipole interaction, and the critical distance is calculated to be about 29.14 Å by the spectra overlap method. White light was observed from LiSr₄(BO₃)₃:mCe³⁺, nEu²⁺ phosphors with chromaticity coordinates (0.34, 0.30) upon 350 nm excitation. The LiSr₄(BO₃)₃:Ce³⁺, Eu²⁺ phosphor has potential applications as an UV radiation-converting phosphor for white light-emitting diodes.     

Luminescent properties of Mg3Ca3(PO4)4: Eu2+ blue-emitting phosphor for white light emitting diodes

A blue-emitting phosphor, Eu²⁺-activated Mg₃Ca₃(PO₄)₄ phosphor was synthesized by conventional solid-state reaction. X-ray powder diffraction (XRD) analysis confirmed the phase formation. Photoluminescence (PL) results showed that Mg₃Ca₃(PO₄)₄: Eu²⁺ could be efficiently excited by UV–visible light from 250 to 430 nm, which matched well with the emission wavelengths of near-UV and UV LED chips. The effects of the doped-Eu²⁺ concentration in Mg₃Ca₃(PO₄)₄: Eu²⁺ on the PL were also investigated. The result reveals that Mg₃Ca₃(PO₄)₄: Eu²⁺ is a potential blue-emitting phosphor for white LEDs.     

Dy3+ emission in M5(PO4)3F (M = Ca, Ba) phosphor

Ultrafine M₅(PO₄)₃F:Dy³⁺ (M = Ca, Ba) phosphors were prepared via combustion process using metal nitrates as precursors. The formation of crystalline phosphate was confirmed by X-ray diffraction pattern. The PL excitation spectra show the excitation peaks observed at 250 to 400 nm due to f → f transition of Dy³⁺ ion, which are useful for solid-state lighting purpose (mercury free excitation). The PL emission of Dy³⁺ ion by 348 nm excitation gave an emission at 489 nm (blue), 582 nm (yellow) and 675 nm (red). All the characteristics of BYR emissions like BGR indicate that Dy doped Ca₅(PO₄)₃F and Ba₅(PO₄)₃F phosphors are good candidates that can be applied in solid-state lighting phosphor (mercury free excited lamp phosphor) and white light LED.      

A novel red-emitting phosphor Ca9Bi(PO4)7:Eu3+ for near ultraviolet white light-emitting diodes

Red phosphors Ca₉Bi_1-x(PO₄)₇:xEu³⁺ (x = 0.06, 0.10, 0.20, 0.30, 0.40, 0.50, 0.60, 0.70, 0.80 and 1.00) were synthesized by a conventional solid-state reaction (SSR) route. The X-ray diffraction patterns, photoluminescence spectra, ultraviolet–visible reflection spectroscopy, decay time and the International Commission on Illumination (CIE) chromaticity coordinates of these compounds were characterized and analyzed. The Eu-doped Ca₉Bi(PO₄)₇ phosphors exhibited strong red luminescence which peaks located at 615 nm due to the ⁵D₀→⁷F₂ electric dipole transition of Eu³⁺ ions after excitation at 393 nm. Ultraviolet–visible spectra indicated that the band-gap of Ca₉Bi_0.30(PO₄)₇:0.70Eu³⁺ is larger than that of Ca₉Bi(PO₄)₇. The results indicate that the phosphor Ca₉Bi_0.30(PO₄)₇:0.70Eu³⁺ can be a suitable red-emitting phosphor candidate for LEDs.     

Photon cascade emission of Gd3+ in Tm3+-doped and un-doped LiGd(PO3)4 under low-voltage electron beam and vacuum ultraviolet excitation

Low-voltage cathodoluminescence and vacuum ultraviolet-excited photoluminescence were investigated for Tm³⁺-doped phosphor LiGd(PO₃)₄:0.05Tm³⁺ and un-doped phosphor LiGd(PO₃)₄, showing that the photon cascade emission of Gd³⁺ can be fulfilled upon low-voltage electron beam and 195 nm light excitation, but this process can not be realized at 160 nm excitation. The different spectroscopic feature was discussed in terms of the excitation type and the energy transfer.     

Photoluminescence and structural characteristics of a new orange phosphor: Ca2.6Sr2.4(PO4)3Cl:Eu3+

A novel orange-emitting phosphor, Ca_2.6Sr_2.4(PO₄)₃Cl:Eu³⁺, was prepared by a modified solid-state reaction and X-ray powder diffraction (XRD) analysis confirmed the formation of Ca_2.6Sr_2.4(PO₄)₃Cl:Eu³⁺. Photoluminescence (PL) results showed that the phosphor can be efficiently excited by UV-visible light from 380 to 500 nm, and exhibited bright orange emission. The effects of the doped-Eu³⁺ concentration in Ca_2.6Sr_2.4(PO₄)₃Cl:Eu³⁺ on the PL were investigated in detail. The results showed that the relative PL intensity decreases with Eu³⁺ concentration increasing due to concentration quenching. TEM images show that the grain size of Ca_2.6Sr_2.4(PO₄)₃Cl:Eu³⁺ is about 45 nm, which is in full agreement with the theoretical calculation data from the XRD patterns.     

Luminescence and energy transfer of white-light emitting CaAl2SiO6:Ce3+, Tb3+ phosphors

A novel white-light emitting CaAl₂SiO₆: Ce³⁺, Tb³⁺ phosphor has been prepared by a sol–gel method. X-ray diffractometry and spectrofluorometry were used to characterize structural and optical properties of the samples. The results indicate that the crystal structure of the phosphor is a single phase of CaAl₂SiO₆. The excitation band of the phosphor covers a wide region from 240 nm to 380 nm. CaAl₂SiO₆: Ce³⁺, Tb³⁺ phosphors show four emission bands: one at 400 nm for Ce³⁺ and three at 487 nm, 543 nm and 585 nm for Tb³⁺. With appropriate tuning of Tb³⁺ content, white light with different hues can be achieved under UV radiation. The energy transfer mechanism from Ce³⁺ to Tb³⁺ in CaAl₂SiO₆ host was demonstrated to be dipole–dipole interaction.     

Photoluminescence properties of Ca9Lu(PO4)7:Ce3+, Mn2+ prepared by conventional solid-state reaction

A new red-emitting phosphor Ca₉Lu(PO₄)₇:Ce³⁺, Mn²⁺ has been synthesized by solid-state reaction, and its luminescence properties have been investigated. The broad red emission peaked at 645 nm of Mn²⁺ is greatly enhanced by the sensitizer Ce³⁺ due to efficient energy transfer from Ce³⁺ to Mn²⁺. The energy transfer was demonstrated to belong to a resonant type via a dipole–quadrupole mechanism. The critical distance for Ce³⁺→Mn²⁺ energy transfer was calculated to be 15.04 Å by concentration quenching method. Preliminary results indicate that the phosphor might be a promising red phosphor for UV-based white LEDs.     

Photoluminescence and thermoluminescence characterization of Eu- and Dy -activated Ca3(PO4)2 phosphor

Rare-earth-doped polycrystalline Ca₃(PO₄)₂:Eu, Ca₃(PO₄)₂:Dy and Ca₃(PO₄)₂:Eu,Dy phosphors prepared by a modified solid-state synthesis has been studied for its X-ray diffraction, thermoluminescence (TL) and photoluminescence (PL) characteristics. The PL emission spectra of the phosphor suggest the presence of Eu³⁺ ion in Ca₃(PO₄)₂:Eu and Dy³⁺ ion in Ca₃(PO₄)₂:Dy lattice sites. The TL glow curve of the Ca₃(PO₄)₂:Eu compounds has a simple structure with a prominent peak at 228 °C, while Ca₃(PO₄)₂:Dy peaking at 146 and 230 °C. TL sensitivity of phosphors are compared with CaSO₄: Dy and found 1.52 and 1.20 times less in Ca₃(PO₄)₂:Eu and Ca₃(PO₄)₂:Dy phosphors, respectively. The Ca₃(PO₄)₂:Eu,Dy phosphors shows switching behavior under two different excitation wavelengths and enhancement in PL intensity of Dy³⁺ ions were reported. The paper discusses the photoluminescence and thermoluminescence behavior of Eu³⁺ and Dy³⁺ ion in Ca₃(PO₄)₂ hosts, it may be applicable to solid-state lighting as well as thermoluminescence dosimetry applications.     

Thermally stimulated luminescence of Ca3(PO4)2 and Ca9Ln(PO4)7 (Ln = Pr,Eu, Tb,Dy, Ho,Er, Lu)

The series of whitlockite compounds Ca₃(PO₄)₂ and Ca₉Ln(PO₄)₇ (Ln = Pr, Eu, Tb, Dy, Ho, Er, Lu) was studied in radioluminescence (RL) and thermally stimulated luminescence (TSL) excited by X-rays. f-f emission lines of Ln³⁺ were observed in RL for Ca₉Ln(PO₄)₇ (Ln = Pr, Eu, Tb, Dy, Ho, Er) whereas d-d emission band of the impurity Mn²⁺ was observed in Mn:Ca₃(PO₄)₂ and Mn:Ca₉Lu(PO₄)₇ at 655 nm. In TSL, the Eu, Ho and Er compounds did not show any signal. As Eu³⁺, Ho³⁺ and Er³⁺ present the highest Ln³⁺/Ln⁴⁺ ionization potential (IP) of the series, this was interpreted as the inability of these lanthanides to trap a hole. On the contrary Pr³⁺ in Ca₉Pr(PO₄)₇, Tb³⁺ in Ca₉Tb(PO₄)₇, Dy³⁺ in Ca₉Dy(PO₄)₇, Mn²⁺ in Mn:Ca₃(PO₄)₂ and Mn:Ca₉Lu(PO₄)₇ were identified as hole traps and radiative recombination centers in the TSL mechanism. Ca₉Tb(PO₄)₇ was found to be a high intensity green persistent phosphor whereas Mn:Ca₉Lu(PO₄)₇ is a red persistent phosphor suitable for in vivo imaging application.     

VUV sensitisation of Eu emission by Tb in Ba3Tb(PO4)3-Eu

The luminescence properties of Ba₃Tb_0.9Eu_0.1(PO₄)₃ and Ba₃Gd_0.9Eu_0.1(PO₄)₃ phosphors were studied for excitation over the 120-300 nm wavelength range. It is found that Tb³⁺, which exhibits a strong vacuum-ultraviolet (VUV) absorption band, provides sensitisation of Eu³⁺ emission in this host. This effect can be used to develop phosphors with enhanced conversion efficiency of the VUV radiation into visible light.     

Luminescence in Dy<Superscript>3+</Superscript> and Eu<Superscript>3+</Superscript> Activated K<Subscript>3</Subscript>Al<Subscript>2</Subscript>(PO<Subscript>4</Subscript>)<Subscript>3</Subscript>

The Dy³⁺ and Eu³⁺ activated K₃Al₂ (PO₄)₃ phosphors were prepared by a combustion synthesis. From a powder X-ray diffraction (XRD) analysis the formation of K₃Al₂ (PO₄)₃ was confirmed. In the photoluminescence emission spectra, the K₃Al₂(PO₄)₃:Dy³⁺ phosphor emits two distinctive colors: blue and yellow whereas K₃Al₂(PO₄)₃:Eu³⁺ emits red color. Thus the combination of colors gives BYR (blue–yellow–red) emissions can produce white light. These phosphors exhibit a strong absorption between 340 and 400 nm which suggest that present phosphor is a promising candidate for producing white light-emitting diodes (LED).     

On the Luminescence of Ce<Superscript>3+</Superscript>, Eu<Superscript>3+</Superscript>, and Tb<Superscript>3+</Superscript> in Novel Borate LiSr<Subscript>4</Subscript>(BO<Subscript>3</Subscript>)<Subscript>3</Subscript>

This paper reports on the photoluminescence (PL) and time-resolved properties of Ce³⁺, Eu³⁺, and Tb³⁺ in novel LiSr₄(BO₃)₃ powder phosphors. Ce³⁺ shows an emission band peaking at 420 nm under 350-nm UV excitation. Energy transfer from Ce³⁺ to Mn²⁺ takes place in the co-doped samples. Eu³⁺ shows red emission under near UV excitation. LiSr₄(BO₃)₃:Eu³⁺ phosphor could be a suitable candidate for phosphor-converted solid state lighting. The luminescence lifetime is 2.13 ms for Eu³⁺ in LiSr₄(BO₃)₃:0.001Eu³⁺. As Eu³⁺ concentration increasing, the decay curves deviate from exponential behavior. Tb³⁺ shows the strongest ⁵D₄→⁷ F₅ emission line at 540 nm. Decay curves of ⁵D₄→⁷ F₅ and ⁵D₃→⁷ F₅ emission with different Tb³⁺ concentrations were also measured. Cross-relaxation process is discussed based on the decay curves.     

Synthesis and photoluminescence properties of MZr2(PO4)3:Eu3+; Bi3+ (M=Na; K) phosphors

A series of new red phosphors, MZr₂(PO₄)₃:Eu³⁺; Bi³⁺ (M=Na; K), were synthesized using the solidstate reaction method, and their photoluminescence spectra were measured. The MZr₂(PO₄)₃:Eu³⁺; Bi³⁺ (M=Na; K) phosphors were efficiently excited by an ultraviolet (UV; 395 nm) source, and showed intense orange-red emission at 595 nm. Further investigation of the concentration-dependent emission spectra indicated that the MZr₂(PO₄)₃:Eu³⁺; Bi³⁺ (M=Na; K) phosphors exhibit the strongest luminescence intensity when y = 0.01 in NaZr_2(0:95−y)(PO₄)₃:Eu_0.10³⁺, Bi_2y ³⁺ and y = 0.09 in NaZr_2(0.95−y)(PO₄)₃:Eu_0.10³⁺, Bi_2y ³⁺, whereas the relative PL intensity decreases with increasing Bi³⁺ concentration due to concentration quenching. The addition of Bi³⁺ widens the excitation band of NaZr_2(0.95−y)(PO₄)₃:Eu_0.10³⁺, Bi_2y ³⁺ around 320 nm, which provides the useful idea of broadening the excitation band around 300–350 nm to fit the ultraviolet chip.     

Synthesis and luminescence properties of green phosphors Ca6Sr4(Si2O7)3Cl2:Eu2+ for white light emitting diodes

Divalent europium-activated chlorosilicate Ca₆Sr₄(Si₂O₇)₃Cl₂:Eu²⁺ phosphors were synthesized by a conventional solid-state reaction under reductive atmosphere. These phosphors can be efficiently excited by UV–visible light from 320 to 420 nm, which matches that of a near UV-emitting InGaN chip. Under the 360 nm excitation, Ca₆Sr_3.97(Si₂O₇)₃Cl₂:0.03Eu²⁺ phosphor shows a strong and broad emission centering at 515 nm, which is attributed to the 5d→4f transition of Eu²⁺ ion. The mechanism of concentration quenching was determined to be the dipole–dipole interaction and the critical energy-transfer distance of Eu²⁺ was calculated as 3.31 nm. The CIE chromaticity coordinates of Ca₆Sr_3.96(Si₂O₇)₃Cl₂:0.03Eu²⁺ phosphor are (0.127, 0.770) according to the emission spectrum. It can be expected that Ca₆Sr₄(Si₂O₇)₃Cl₂:Eu²⁺ phosphor is a promising candidate as the green component for near-ultraviolet InGaN-based white LED.     

A novel red phosphor BaZn2(PO4)2:Sm3+, R+ (R=Li,Na, K)

BaZn₂(PO₄)₂:Sm³⁺ phosphor was synthesized by a high temperature solid-state reaction in atmosphere. BaZn₂(PO₄)₂:Sm³⁺ phosphor can be efficiently excited by ultraviolet and blue light, and the emission spectrum consists of three emission peaks at 568, 606 and 660 nm. By increasing the Sm³⁺ doped content, the emission intensity of the phosphor can reach the maximum at 0.02 mol Sm³⁺, then the concentration quenching occurs. By introducing the compensator charge R⁺ (R=Li, Na, K) into the BaZn₂(PO₄)₂:Sm³⁺ phosphor, its emission intensity can be enhanced. The Commission International de l'Eclairage (CIE) chromaticity coordinates of Ba_0.96Zn₂(PO₄)₂:0.02Sm³⁺, 0.02K⁺ phosphor were (x=0.623, y=0.361). The results indicate that BaZn₂(PO₄)₂:Sm³⁺, R⁺ (R=Li, Na, K) may be a promising red phosphor for white light-emitting diodes.     

Luminescence of calcium orthoborate doped by Ce3+ ions

The luminescence properties of calcium orthoborate Ca₃(BO₃)₂ doped with cerium are studied upon x-ray (～30 keV) and VUV (3.5–15 eV) synchrotron excitation. The emission bands peaked at 392 and 420 nm are attributed to interconfigurational transitions of Ce³⁺ ions. The short-wavelength emission band at 340 nm is caused by radiative decay of exciton-like states. The fundamental absorption edge of Ca₃(BO₃)₂ is found to be near 7.1 eV. Based on thermoluminescence data and other information, the behavior of defects in Ca₃(BO₃)₂:Ce³⁺ is studied.