Enhanced luminescence properties of Li2MgTiO4: Mn4+, Ge4+ phosphor via single cation substitution for indoor plant cultivation

Red and far-red emitting phosphors have been widely used in phosphor-converted light emitting diode (pc-LED) devices to provide lighting for indoor plant growth, thus achieving desired product qualities. Among the many ways to optimize phosphors’ optical performance, cationic substitution is one of the most effective methods. In this study, red phosphors (Li₂MgTi_1-x-yO₄: xMn⁴⁺, yGe⁴⁺) were synthesized by high temperature solid state method and the optical performance of phosphors were improved with increasing Ge⁴⁺ constituents. In particular, luminescence intensity of Li₂MgTiO₄: 0.002Mn⁴⁺, 0.1Ge⁴⁺ increased by 152% under 468 nm excitation, and the thermostability of emission intensity increases from 22% (y = 0) to 43% (y = 0.1), which is about twice as much. Finally, pc-LED device was fabricated via the red phosphor Li₂MgTiO₄: 0.002Mn⁴⁺,0.1Ge⁴⁺ coated on a 470 nm ultraviolet chip. By changing the proportion of the phosphor, the electroluminescence spectra of pc-LED device could match well with the absorption regions of plant pigments. Therefore, Li₂MgTiO₄: 0.002Mn⁴⁺, 0.1Ge⁴⁺ phosphor has potential application in plant lighting. Furthermore, this work can offer some helpful references for improving luminescent efficiency by simply modulating the chemical composition.     

Tuning the luminescence properties of blue and far-red dual emitting Gd2MgTiO6: Bi3+, Cr3+ phosphor for LED plant lamp

Blue and far-red light play a key role in plant growth, so it is necessary to develop blue and far-red dual emitting phosphors. However, the match between phosphors and plant pigments is not satisfactory. In this work, we synthesized a series of blue and far-red dual emission Gd₂MgTiO₆: Bi³⁺, Cr³⁺ (GMTO: Bi³⁺, Cr³⁺) phosphors and discussed the luminescence performance. The blue emission at 430 nm is ascribed to ³P₁ → ¹S₀ transition of Bi³⁺ and the far-red emission is ascribed to ⁴T₂ → ⁴A₂ and ²E → ⁴A₂ transitions of Cr³⁺. Notably, because of the energy competition between Cr³⁺ ions and host materials, the luminescence tuning realized with the content of Cr³⁺ doping. In addition, an energy-transfer performance occurred from Bi³⁺ ions to Cr³⁺ ions and the photoluminescence intensity of Cr³⁺ can be enhanced by Bi³⁺. The pc-LEDs devices were synthesized by GMTO: Bi³⁺, Cr³⁺ phosphor, and ultraviolet (UV) chips. Finally, the emission of GMTO: Bi³⁺, Cr³⁺ phosphor matched well with the absorption spectra of plant pigments which indicated the potential applications in LED plant lamp.     

Blue-red dual color emitting phosphor Cs2NaLuCl6: Sb3+, Ho3+ for plant growth LEDs

The phosphor-converted light emitting diode (pc-LED) is an efficient light source to adjust growth rhythm and raise yield of plant. Blue and red light play the dominant role in the process of plant growth, thus it is meaningful to search the blue-red dual emission phosphors with high quantum field and better thermal stability for developing plant growth LED. Herein, the blue-red dual emission phosphors were synthesized by co-doping Sb³⁺ and Ho³⁺ into the Cs₂NaLuCl₆, which emitted blue (454 nm) to red (657 nm) light with increasing the content of Ho³⁺ to 25% and their relative intensity could be tuned through adjusting the concentration of Ho³⁺ due to the efficient energy transfer from Sb³⁺ to Ho³⁺. The intensity of blue emission from Sb³⁺ and red emission from Ho³⁺ could maintain 78.4 and 75.8% of the room temperature at 150 °C, respectively. Furthermore, the spectra of fabricated blue and red LEDs match well with the absorption of carotenoid, Phytochrome and Chlorophyll b, implying the samples possess great application potential in plant growth LED.     

Efficient and tunable Mn2+ sensitized luminescence via energy transfer of a novel red phosphor Ca19Mn2(PO4)14: Eu2+ for white LED

The exploration of efficient and high-purity red phosphors is an urgent need in LED development. Due to the compact and compositional-tunable structure of whitlockite compound, manganese-based Ca₁₉Mn₂(PO₄)₁₄ is chosen as phosphor host for Eu²⁺ sensitization. Rietveld refinement, steady-state spectra, decay lifetime analysis and temperature-dependent emission spectra were investigated and clearly discussed. Under 360 nm excitation, Ca₁₉Mn₂(PO₄)₁₄: Eu²⁺ shows a strong Mn²⁺ sensitized emission at 655 nm with FWHM of 82 nm, benefiting from the short-distance-induced high-efficient Eu² -Mn²⁺ energy transfer. Emission engineering of Ca₁₉Mn₂(PO₄)₁₄: Eu²⁺ is achieved by Sr²⁺ co-doping, leading to both tunable peak wavelength (ranging from 650 to 610 nm) and improved intensity (130% of original value). Moreover, Ca₁₉Mn₂(PO₄)₁₄: Eu²⁺ exhibits a promising thermal stability where only 40% of emission intensity is lost at 200 °C. Finally, we explored the working performance of the fabricated RGB phosphor-converted white LED. The present work indicates that Ca₁₉Mn₂(PO₄)₁₄: Eu²⁺ phosphor is of great potential as a promising and efficient red phosphor in phosphor-converted white LED.     

Deep-red-emitting Ca2ScSbO6:Mn4+ phosphors with a double perovskite structure: Synthesis,characterization and potential in plant growth lighting

Mn⁴⁺-activated double-perovskite type Ca₂ScSbO₆ (CSS) phosphors were synthesized via a high-temperature solid-state reaction. The phase purity and crystal structure of obtained samples were investigated by powder X-ray diffraction (XRD). The successful incorporation of Mn⁴⁺ ions into CSS lattice was confirmed by the combination of energy-dispersive X-ray spectra (EDX) and X-ray photoelectron spectra (XPS) results. The luminescent properties of the CSS phosphors, including the photoluminescence (PL) and PL excitation (PLE) spectra, commission international de l'clairage (CIE) chromaticity coordinates, fluorescence decay curves, quantum yields and temperature-dependent PL spectra, were investigated in detail. Under 310-nm excitation, the optimized CSS:0.3%Mn⁴⁺ phosphor exhibited bright deep-red emission covering a narrow band from 640 nm to 720 nm, which overlaps with the absorbance of phytochromes. The Racah parameters B, C, and local crystal strength Dq were calculated to be 870, 2703, and 1984 cm^–1, respectively. Particularly, the emission intensity of CSS:0.3%Mn⁴⁺ still remained 61.4% at 423 K compared with that at room temperature. Therefore, all these outstanding luminescent properties provided the as-synthesized phosphors a great potential in plant growth lighting.     

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.     

Bi3+/Mn4+ co-doped dual-emission phosphors for potential plant lighting

Developing environment-friendly dual-emission phosphors of both blue–cyan and deep-red lights is desirable for the utilized indoor plant lighting research. Notably, the naked 6s and 6p Bi³⁺ ions are sensitive to the lattice sites, which emit from Ultraviolet (UV) to red lights in various crystal compounds. Meanwhile, the ²E → ⁴A_2g transition of Mn⁴⁺ ions promises its deep-red light emissions, which satisfies the demand for specific wavelength lights for plants growth. Hence, a Bi³⁺/Mn⁴⁺ co-doped Sr₂LaGaO₅: Bi³⁺, Mn⁴⁺ (SLGO:Bi³⁺:Mn⁴⁺) phosphor was finally synthesized. The phase, micromorphology and luminescent properties were systematically evaluated. Upon excitation at 350 nm light, dual emissions of both blue–cyan (470 nm) and deep-red (718 nm) lights were observed. Besides, due to the pronounced photoluminescence (PL) spectral overlap between Bi³⁺ and Mn⁴⁺ ions, a potential energy transfer process from Bi³⁺ to Mn⁴⁺ ions was confirmed. The relative PL intensities between Bi³⁺ and Mn⁴⁺ ions can be tuned just by adjusting the Mn⁴⁺ ion concentration. Besides, Li⁺ co-doping has been evidenced to improve the deep-red emissions (718 nm) of SLGO:0.005Mn⁴⁺ due to charge compensation and rationally designed lattice distortion, together with the improved thermal stability. Finally, the emissions of SLGO:Bi³⁺, Mn⁴⁺, Li⁺ phosphor suit properly with the absorption of the four fundamental pigments for plant growth, indicating that the prepared phosphorescent materials may have a prospect in plant light-emitting diodes lighting.     

Mn4+-related photoemission enhancement via energy transfer in La2MgGeO6:Dy3+, Mn4+ phosphor for plant growth light-emitting diodes

A double perovskite-type substrate of La₂MgGeO₆ (LMGO) was successfully synthesized via a high-temperature solid-state reaction method and was codoped with Mn⁴⁺ and Dy³⁺ to form a new deep-red phosphor (LMGO:Mn⁴⁺,Dy³⁺) for artificial plant growth light-emitting diodes (LEDs). This extraordinary phosphor can exhibit strong far-red emission with a maximum peak at 708 nm between 650 and 750 nm, which can be ascribed to the ²E_g → ²A_2 g spin-forbidden transition of Mn⁴⁺. The X-ray diffraction (XRD) patterns and high-resolution transmission electron microscopy (HRTEM) clarified that the La³⁺ sites in the host were partly replaced by Dy³⁺ ions. Moreover, we discovered energy transfers from Dy³⁺ to Mn⁴⁺ by directly observing the significant overlap of the excitation spectrum of Mn⁴⁺ and the emission spectrum of Dy³⁺ as well as the systematic relative decline and growth of the emission bands of Dy³⁺ and Mn⁴⁺, respectively. With the increase in the activator (Mn⁴⁺) concentration, the relationship between the luminescence decay time and the energy transfer efficiency of the sensitizer (Dy³⁺) was studied in detail. Finally, an LED device was fabricated using a 460 nm blue chip, and the as-obtained far-red emitting LMGO:Mn⁴⁺,Dy³⁺ phosphors for Wedelia chinensis cultivation. As expected, the as-fabricated plant growth LED-treated Wedelia chinensis cultured in the artificial climate box with overhead LEDs demonstrated that after 28 days of irradiation, the average plant growth rate and the total chlorophyll content were better than those of specimens cultured using the commercial R-B LED lamps, indicating that the as-prepared phosphor could have a potential application in the agricultural industry.     

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.     

LED-pumped intense red luminescence based on Ba2LaTaO6: Mn4+ double perovskite phosphor

Non-rare earth Mn⁴⁺ ion-doped red oxide phosphors have great potential for applications in warm white light-emitting diodes (wLEDs) due to their low cost and stable physicochemical properties. Herein, a series of Ba₂LaTaO₆ (BLTO): Mn⁴⁺ phosphors were successfully synthesized by the high-temperature solid-state method. The theoretical values of the band gap calculated by the density functional theory are close to the experimental values obtained by the absorption spectroscopy. In addition, the phosphors have a broad excitation band in the wavelength range of 280–550 nm and emit red light at the peak wavelength of 681 nm under excitation. The concentration quenching of the BLTO: Mn⁴⁺ phosphor was caused by dipole-dipole interactions. The activation energy and the average decay lifetimes of the samples were calculated. Meanwhile, the effects of synthesis temperature and Li⁺ ion doping on the luminescence performance of the samples were also investigated. Satisfactorily, the color purity and internal quantum efficiency of the phosphor reached 98.3% and 26.8%, respectively. Further, the samples were prepared as red-light components for warm wLEDs. The correlated color temperature, color rendering index, and luminous efficiency of the representative devices driven by 60 mA current were 5190 K, 83.3, and 81.59 lm/W, respectively. This work shows that the BLTO: Mn⁴⁺ red phosphor with excellent luminescence performance can be well applied to warm wLEDs.     

Tunable luminescence and energy transfer properties of MgY4Si3O13: Ce3+, Tb3+, Eu3+ phosphors

The tricolor-emitting MgY₄Si₃O₁₃: Ce³⁺, Tb³⁺, Eu³⁺ phosphors for ultraviolet-LED have been prepared via a high-temperature solid-state method. X-ray diffraction, photoluminescence emission, excitation spectra and fluorescence lifetime were utilized to characterize the structure and the properties of synthesized samples. Two different lattice sites for Ce³⁺ are occupied from the host structure and the normalized PL and PLE spectra. The emissions of single-doped Ce³⁺/Tb³⁺/Eu³⁺ are located in blue, green and red region, respectively. The energy transfer from Ce³⁺ to Tb³⁺ and from Tb³⁺ to Eu³⁺ has been validated by spectra and decay curves and the energy transfer mode from Tb³⁺ to Eu³⁺ was calculated to be electric dipole-dipole interactions. By adjusting the content of Tb³⁺ and Eu³⁺ in MgY₄Si₃O₁₃: Ce³⁺, Tb³⁺, Eu³⁺, the CIE coordinates can be changed from blue to green and eventually generate white light under UV excitation. All the results indicate that the MgY₄Si₃O₁₃: Ce³⁺, Tb³⁺, Eu³⁺ phosphors are potential candidates in the application of UV-WLEDs.     

Photoluminescence properties of Ce3+/Mn2+ doped calcium zirconium silicate phosphors with energy transfer for white LEDs

A series of Ce³⁺ doped and Ce³⁺/Mn²⁺ co-doped calcium zirconium silicate CaZrSi₂O₇ (CZS) phosphors have been synthesized via conventional high temperature solid state reactions. The luminescence properties, energy transfer between Ce³⁺ and Mn²⁺ have been investigated systematically. Under 320 nm excitation, the phosphor CZS: 0.05Ce³⁺ exhibit strong blue emission ranging from 330 nm to 500 nm, attributed to the spin-allowed 5d-4f transitions of Ce³⁺ ions. There are two different emission centers of Ce³⁺ ions, Ce³⁺(I) and Ce³⁺(II). The emission spectra of Ce³⁺, Mn²⁺ co-doped phosphors shows a broad emission around 550 nm corresponding to the ⁴T₁(⁴G)-⁶A₁(⁶S) spin-forbidden transition of Mn²⁺. The energy transfer between Ce³⁺ and Mn²⁺ is detected and the transfer efficiency of Ce³⁺(II) to Mn²⁺ is faster than that of Ce³⁺(I) to Mn²⁺. The resonant type is identified via dipole-dipole mechanism. Additionally, a blue-shift emission of Ce³⁺ and a red-shift emission of Mn²⁺ have been observed following the increase of Mn²⁺ content in relation to the energy transfer. Thermal quenching has been investigated and the emission spectra show a blue-shift with the temperature increases, which have been discussed in details. CZS: 0.05Ce³⁺, yMn²⁺ phosphors can be tuned from blue to white and even to yellow by adjusting the Mn²⁺ content. All the results indicate that CZS: Ce³⁺, Mn²⁺ phosphor have a potential application for near-UV LEDs.     

Mn4+-activated KLaMgWO6: A new high-efficiency far-red phosphor for indoor plant growth LEDs

Novel Mn⁴⁺-activated KLaMgWO₆ red phosphors with different Mn⁴⁺ concentrations were successfully synthesized via a high-temperature solid-state reaction method. The phase formation, microstructure, photoluminescence properties, decay lifetimes and internal quantum efficiency were discussed to analyze the properties of the as-prepared phosphors. The samples belonged to monoclinic crystal system with enough WO₆ octahedrons that provided suitable sites for Mn⁴⁺ ions. Upon the excitation of 348?nm, KLaMgWO₆:Mn⁴⁺ phosphors gave bright far-red emission around 696?nm due to the ²E_g→⁴A_2g transition of Mn⁴⁺ ions. The critical concentration of Mn⁴⁺ was 0.6?mol% and the concentration quenching mechanism belonged to electric multipolar interaction. Besides, the CIE chromaticity coordinates of the KLaMgWO₆:0.6%Mn⁴⁺ phosphor were (0.7205, 0.2794) which located in deep red range, and its color purity reached up to 96.6%. The KLaMgWO₆:0.6%Mn⁴⁺ sample also exhibited high internal quantum efficiency of 43%. All of the admirable optical properties indicate that the KLaMgWO₆:Mn⁴⁺ phosphors can be applied to indoor plant growth illumination.     

A far-red-emitting (Gd,Y)3(Ga,Al)5O12:Mn2+ ceramic phosphor with enhanced thermal stability for plant cultivation

As for plants, far-red (FR) light with wavelength from 700 nm to 740 nm is critical for processes of photosynthesis and photomorphogenesis. Light-controlled development depends on light to control cell differentiation, structural and functional changes, and finally converge into the formation of tissues and organs. Phosphor converted FR emission under LED excitation is a cost-effective and high-efficient way to provide artificial FR light source. With the aim to develop an efficient FR phosphor that can promote the plant growth, a series of gadolinium yttrium gallium garnet (GYGAG) transparent ceramic phosphors co-doped with Mn²⁺ and Si⁴⁺ have been fabricated via chemical co-precipitation method, followed sintered in O₂ and hot isostatic pressing in this work. Under UV excitation, the phosphor exhibited two bright and broadband red emission spectra due to Mn²⁺: ⁴T₁ → ⁶A₁ spin-forbidden transition, and one of which located in the right FR region. And then, Ce³⁺ ions were co-doped as the activator to enhance the absorption at blue light region and the emission of Mn²⁺. It turns out that the emission band of GYGAG transparent ceramic phosphors matches well with the absorption band of phytochrome P_FR, which means they are promising to be applied in plant cultivation light-emitting diodes (LEDs) for modulating plant growth. Besides, the thermal stability of this material was investigated systematically, and an energy transferring model involves defects was also proposed to explain the phenomenon of abnormal temperature quenching.     

Engineering cation vacancies to improve the luminescence properties of Ca14Al10Zn6O35: Mn4+ phosphors for LED plant lamp

In the recent years, Mn⁴⁺-doped phosphors for indoor plant cultivation have received extensive concern owing to the far-red emission that can match well with the absorption spectra of plant pigments. Whereas, many Mn⁴⁺-doped phosphors still face some challenges such as poor light efficiency and low thermal stability. It is an effective way to resolve these problems via cation vacancies engineering. Herein, the Ca_14−xAl₁₀Zn_6−yO₃₅: Mn⁴⁺ phosphors are successfully synthesized by combustion method. The luminescence intensity of Ca_14−xAl₁₀Zn_6−yO₃₅: Mn⁴⁺ phosphor is enhanced through engineering Ca²⁺ and Zn²⁺ vacancies according to the charge compensation mechanism. The optimal content of each Ca²⁺ and Zn²⁺ vacancy is equal to be 0.3. Furthermore, the defect formation is accompanied with lattice distortion, which plays a vital role in driving the excited phonon traps to reduce the energy loss by non-radiation transitions. Therefore, the thermal stability of Ca_14−xAl₁₀Zn_6−yO₃₅: Mn⁴⁺ phosphor is also improved via engineering cation vacancies. In addition, the Ca_14−xAl₁₀Zn_6−yO₃₅: Mn⁴⁺ phosphors can be effectively excited by blue light and it exhibits far-red emission due to the Mn⁴⁺ spin-forbidden ²E → ⁴A₂ transition. The results suggest that the Ca_14−xAl₁₀Zn_6−yO₃₅: Mn⁴⁺ phosphors can have a tremendous potential in indoor plant cultivation.     

Structure analysis,tuning photoluminescence and enhancing thermal stability on Mn4+-doped La2-xYxMgTiO6 red phosphor for agricultural lighting

Currently, phosphor-converted LEDs (pc-LEDs) are revolutionizing the industry of plant growth lighting. To meet the requirements of this technology, phosphors with tunable photoluminescence, high thermal stability and luminous intensity are required. Herein, we found that the simple substitution of yttrium for lanthanum in La₂MgTiO₆:Mn⁴⁺ (LMT:Mn⁴⁺) system could satisfy above three criteria simultaneously. The photoluminescence properties can be regulated by continuously controlling the chemical composition of La_2-xY_xMgTiO₆:Mn⁴⁺ solid solution. The La sites are occupied by Y ions, causing a significant blue shift in the emission spectra which owing to the change of local crystal field strengthen. Meanwhile, the thermal stability and decay lifetimes are also varied due to the variation of local structure and band gap energy. The thermal stability of the material reaches 83.5% at 150 °C, which is better than the reported La₂MgTiO₆:Mn⁴⁺ and Y₂MgTiO₆:Mn⁴⁺ phosphors. The electronic luminescence (EL) of pc-LED devices using La_2-xY_xMgTiO₆:Mn⁴⁺ red phosphor is evaluated, which matching the absorption regions of plant pigments well, reflecting the superiority of the studied phosphors in plant growth lighting areas.     

Enhance the luminescence properties of Ca14Al10Zn6O35:Ti4+ phosphor via cation vacancies engineering of Ca2+ and Zn2+

Ti⁴⁺-activated zinc calcium aluminate phosphors, owing to their excellent luminescence properties, nontoxicity, environment friendliness and low price, have a certain prospect in the field of plant cultivation. In this study, we have successfully synthesized a series of Ca_14-yAl_10-xZn_6-zO₃₅:xTi⁴⁺ (CAZO:Ti⁴⁺) phosphors through a high-temperature solid-state method. Furthermore, the emission spectrum of CAZO:Ti⁴⁺ located in bluish violet-emitting band, and has an emission peak at 378?nm upon the excitation of 268?nm due to the charge transfer of Ti⁴⁺-O^2-. Moreover, the luminescence intensity of as-synthetized phosphors can be improved by cation vacancies engineering to compensate for charge unbalance. Especially, the luminescence intensity could be further improved when the Ca²⁺ vacancy is 0.35?mol or the Zn²⁺ vacancy is 0.275?mol. Furthermore, the X-ray powder diffraction (XRD) analysis and crystal structure are checked and confirmed that the synthesized material is pure phase. The concentration quenching mechanism, FT-IR spectra, UV–vis absorption properties, lifetimes and electron transition process of Ca_14-yAl_10-xZn_6-zO₃₅: xTi⁴⁺ were discussed in detail. From the above, the phosphor has a potential application for plant growth field due to its broad bluish violet emission.     

Tunable emission of single-phased NaY(WO4)2:Sm3+ phosphor based on energy transfer

A series of NaY(WO₄)₂:Sm³⁺ phosphors were prepared by high temperature solid state reaction. When excited by ultraviolet and blue light, their emission spectra cover entirely visible light region, due to intrinsic luminescence of WO₄^2- group as well as Sm³⁺ 4f-4f transitions. White light emission was obtained from NaY_0.99Sm_0.01(WO₄)₂ phosphor under radiation of 265 nm UV light, and intense yellow and red emission from ⁶H_{J(J=5/2, 7/2, 9/2)} transitions were observed when pumped Sm^{3+ 4}G_5/2 by 405 nm blue light. With incorporation of Sm³⁺ into NaY(WO₄)₂ host, higher-level emission from Sm³⁺ at 650 nm was generated by energy transfer from WO₄^2- to Sm³⁺ under excitation of 265 nm. The corresponding energy transfer mechanism was demonstrated to be a dipole-dipole interaction. In addition, tunable emission from blue to white and, finally, to red was realized by increasing Sm³⁺ doping concentration. The band gap of NaY(WO₄)₂ calculated from diffuse reflection spectra indicates a semiconducting character. All these results show that NaY_1−xSm_x(WO₄)₂ phosphor provides promising application for conversion of frequencies emitted by UV or blue LEDs.     

Synthesis and photoluminescence performance of single-component Ca3YAl3B4O15:Dy3+, Eu3+ white-emitting phosphor for white light-emitting diodes

A single-component Ca₃YAl₃B₄O₁₅ (CYAB):Dy³⁺, Eu³⁺ phosphor was synthesized by the traditional high temperature solid-phase method, Dy³⁺ and Eu³⁺ were codoped in the structure to obtain a warm white emission. The results of XRD and EDS revealed that all samples had the standard Ca₃YAl₃B₄O₁₅ structure, and no impurity phase appeared with codoping. The emission of Dy³⁺ in CYAB consisted of both main peaks at 476 nm and 570 nm, with which a white emission could be observed. Furthermore, a characteristic emission peak of Eu³⁺ appeared at 617 nm in Dy³⁺/Eu³⁺-codoped samples to supplement red component for the white emission of Dy³⁺, due to the energy transfer effect between Dy³⁺ and Eu³⁺. With the amount of Eu³⁺ raised, the correlated colour temperature of CYAB:Dy³⁺, Eu³⁺ phosphor obviously decreased, and a warm white light was successfully realized from the manufactured w-LEDs. Therefore, all results indicated that the single-component Dy³⁺/Eu³⁺ codoped CYAB white-emitting phosphor had a potential application in ultraviolet excited w-LEDs.     

Versatile Ca2LnSbO6:Eu3+/Mn4+ (Ln = La,Y, Gd,and Lu) phosphors for temperature sensing and plant growth LED

A multifunctional double-perovskite-type Ca₂LnSbO₆ (Ln = La, Y, Gd, and Lu) phosphors with Eu³⁺ and Mn⁴⁺ co-doped were successfully synthesized and designed to simultaneously apply to temperature sensing and plant growth LED. With temperature varying from 303 to 523 K, the integrated intensity of Mn⁴⁺ ions (²E_g → ⁴A_2g) markedly decline swifter comparing to Eu³⁺ ions (⁵D₀ → ⁷F₂) due to the thermal quenching effect. It implies that Mn⁴⁺ is susceptive to the temperature in this work. Eu³⁺ exhibits high heat resistance, which can be selected as a calibration parameter for the fluorescence intensity ratio temperature sensor. The maximum relative sensitivity (S_r) values of Ca₂LnSbO₆:1%Eu³⁺, 0.5%Mn⁴⁺ (Ln = La, Y, and Gd) phosphor are estimated as 2.19% K⁻¹ at 443 K, 1.68% K⁻¹ at 503 K, and 1.80% K⁻¹ at 483 K, respectively. They are superior to many recent emerging phosphors. Moreover, upon 365 nm excitation, Ca₂LnSbO₆:1%Eu, 0.5%Mn (Ln = La, Y, Gd, and Lu) phosphors display a wide red emission peaking at 696, 680, 677, and 684 nm, respectively. They come from the overlapped of ²E_g–⁴A_2g of Mn⁴⁺ and ⁵D₀–⁷F₄ transition of Eu³⁺. Their full widths at half maximum are 34, 35, 35, and 29 nm, respectively. They are all perfectly overlapping the absorption curves of chlorophyll a and chlorophyll b, and their fabricated red phosphor-converted light-emitting diode device ulteriorly corroborated the promising applications for plant growth. Markedly, the systematic analysis of their crystal chemistry and site preferentially occupancy is first reported and discussed by the bond valence theory.