Mn2+-Coactivated

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Article Cite This: ACS Omega 2018, 3, 16714−16720

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Tricolor- and White Light−Emitting Ce3+/Tb3+/Mn2+-Coactivated Li2Ca4Si4O13 Phosphor via Energy Transfer Xiaojiao Kang,† Song Lu,‡ Hongcheng Wang,† Dongxiong Ling,† and Wei Lü*,† †

School of Electrical Engineering and Intelligentization, Dongguan University of Technology, Dongguan 523808, China School of Materials Science and Engineering, Harbin Institute of Technology (Shenzhen), Shenzhen 518055, China

ACS Omega 2018.3:16714-16720. Downloaded from pubs.acs.org by 37.18.42.52 on 12/06/18. For personal use only.

‡

ABSTRACT: Single-component tunable Li2Ca4Si4O13:Ce3+,Tb3+,Mn2+ phosphors were successfully synthesized at 950 °C. Li2Ca4Si4O13:Ce3+,Tb3+ exhibits two luminescence peaking at 430 and 550 nm, which originated from the allowed 5d → 4f transition of the Ce3+ ion and the 5 D4 → 7FJ (J = 6, 5, 4, 3) transition of the Tb3+ ion, respectively. Moreover, by codoping Ce3+ ions in the Li2Ca4Si4O13:Mn2+ system, yellow-red emission from the forbidden transition of Mn2+ could be enhanced. Under UV excitation, dual energy transfers (ETs), namely, Ce3+ → Mn2+ and Ce3+ → Tb3+, are present in the Li2Ca4Si4O13:Ce3+,Tb3+,Mn2+ system. The ET process was confirmed by the overlap of the excitation spectra, variations in the emission spectra, ET efficiency, and decay times of phosphors. In addition, quantum yields and CIE chromatic coordinates are presented. The emission color of these phosphors can be tuned precisely from blue to green via ET of Ce3+ → Tb3+ and from blue to yellow via ET of Ce3+ → Mn2+. White light can also be achieved upon excitation of UV light by properly tuning the relative composition of Tb3+/Mn2+. This result indicates that the developed phosphor may be regarded as a good tunable emitting phosphor for UV light-emitting diodes. Ce3+ to Tb3+ and Ce3+ to Mn2+ in Ca3Gd7(PO4)(SiO4)5O2 host,11 and Lü et al. reported some results on the spectral pr oper ti es and ET o f a col or-tu nable CaScA lSiO6:Ce3+,Tb3+,Mn2+ phosphor.12 Single-composition trichromatic Sr3.5Y6.5O2(PO4)(1.5)(SiO4)4.5:Ce3+/Tb3+/Mn2+ and NaCaBO3:Ce3+,Tb3+,Mn2+ phosphors via ET are also reported by Liu and Zhang et al.13,14 Recently, other researchers have also suggested the ET mechanism in proper single-host lattices, such as Ca 19Mg 2(PO 4)14 :Ce3+,Tb3+ ,Mn2+ and Ca9ZnK(PO4)7:Ce3+,Tb3+,Mn2+, indicating that the obtained samples may be a promising candidate for UV-convertible devices.15−18 In these systems, for either Mn2+ or Tb3+ ions, because of their prohibited 4T1 → 6A1 transition and 4f−4f weak absorption, respectively, both have weak emissions.15,16 However, in codoping of Ce3+ with the allowed transition as sensitizer, ET will occur from Ce3+ to Mn2+ or Tb3+, which allows for efficient emission of Mn2+ and Tb3+ ions and tunability of the emission colors from blue to orange/red and green, respectively. This feature was used in the development of new tridoped phosphors.19−30 In this paper, we report our recent results on the photoluminescence (PL) properties and the ET mechanism of Li2Ca4Si4O13:Ce3+,Tb3+,Mn2+ phosphor. To the best of our knowledge, no study has been conducted on Ce3+/Tb3+/Mn2+

1. INTRODUCTION White light−emitting diode (w-LED), because of its highly efficient luminance, long service life, improved performance, and environment-friendly properties, has gained considerable attention in order to address global energy shortage.1−5 In the generation of white light with LED chips, basically two methods are used. The first method is by mixing red, green, and blue (RGB) lights emitted by different LED chips, which, because of the required complex electro-optical design to control different colors, is seldom used. The second method is by using UV or blue LED chips and down-converting phosphors.6−8 To circumvent the disadvantages of these approaches, researchers have focused on investigating singlephased phosphors with RGB components, which could emit white light during energy transfer (ET) between activators in an efficient and durable way and with excellent color-rendering indices. Thus, in order to avoid high cost, device complication, and intrinsic color balance in the use of multiple-emitting components, it is crucial to find new single-component and UV chip pumped phosphors for w-LED. Different emission colors can be obtained with single-phased phosphors by codoping ion pairs through ET, which was investigated extensively for the pairs of Ce3+ and Mn2+ or Tb3+ among single-component lattices. Li et al. reported on a colortuning luminescence of Mg2Y8(SiO4)6O2:Ce3+/Mn2+/Tb3+ via ET,9 whereas Huang and Chen described a single-composition Ca 3 Y(GaO) 3 (BO 3 ) 4 :Ce 3+ ,Mn 2+ ,Tb 3+ phosphor for UVLEDs.10 Then, again, Zhang et al. investigated the ET from © 2018 American Chemical Society

Received: August 8, 2018 Accepted: November 23, 2018 Published: December 5, 2018 16714

DOI: 10.1021/acsomega.8b01952 ACS Omega 2018, 3, 16714−16720

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codoped in the Li2Ca4Si4O13 host. We generated green/ yellow/white lights with high color stabilities using Tb3+ and Mn2+ at different relative dopant concentrations. Additionally, we systematically investigated the mechanisms of ET from Ce3+ to Tb3+ or Mn2+ and their decay times.

2. RESULTS AND DISCUSSION 2.1. X-ray Diffraction. We collected and used X-ray diffraction (XRD) patterns to study the samples in order to identify their compositions and phase purities. The representative XRD patterns for LCSO, LCSO:Ce3+,Tb3+, LCSO:Ce3+,Mn2+, and LCSO:xCe3+,yTb3+,zMn2+ samples are showed in Figure 1. The selected samples have pure phases, and their

Figure 1. Powder XRD patterns of LCSO, LCSO:Ce3+,Tb3+, LCSO:Ce3+,zMn2+, and LCSO:xCe3+,yTb3+,zMn2+ samples.

Figure 2. (a) Excitation and emission spectra of LCSO:xCe3+. (b) PL intensity of LCSO:xCe3+ samples with different Ce3+ contents.

XRD patterns exactly originate from the pure tetragonal phase of Li2Ca4Si4O13 according to JCPDS file no. 31-0714. No other phase was detected, which indicates that all of the Mn2+, Tb3+, and Ce3+ ions are dissolved in Li2Ca4Si4O13. 2.2. Luminescence Properties of LCSO:Ce3+ and ET of LCSO:Ce3+,Tb3+. Both PL excitation (PLE) and PL spectra for as-prepared LCSO:xCe3+ samples are shown in Figure 2a. Three distinctive bands peaked at 259, 296, and 353 nm (the strongest) were found spanning a broad absorption from 200 to 400 nm for the PLE spectrum monitored at 420 nm. These peaks are caused by transitions to 2F5/2 and 2F7/2 state from the lowest 5d state because of spin−orbit coupling. The PL spectrum extends from 400 to 550 nm and peaks at 450 nm, caused by the 5d → 4f transitions from Ce3+. Figure 2b shows the concentration dependence of the emitting intensities of LCSO:xCe3+ with various Ce3+ concentrations. After excitation at 330 nm, the emitting intensities increase with Ce3+ ion contents until the highest point x = 0.04, after which the intensities decline because of concentration quench. Between several excitation bands of Tb3+ and the broad Ce3+ emission band, a significant spectral overlap is observed in Figure 3. Because of transitions from 5D4 → 7F5, a main emission line and well-known green fluorescence occur in LCSO:0.1Tb3+ at 543 nm. Moreover, several weak lines appear at 485, 580, and 620 nm, corresponding to 5D4 to 7FJ (J = 3, 4, 5, 6) multiple transitions, respectively. Because of the prohibited Tb3+ f−f absorbing transitions in the UV region, LCSO:0.1Tb3+ demonstrates very weak emissions excited by UV light compared to the PL spectrum of LCSO:0.04Ce3+. An apparent overlap between the Tb3+ PLE and Ce3+ PL spectra indicates a possible Ce3+−Tb3+ ET in LCSO. The PLE and PL spectra in

Figure 3. PL and PLE spectra in LCSO:0.04Ce3+ (a), LCSO:0.1Tb3+ (b), and LCSO:0.04Ce3+,0.1Tb3+ (c).

LCSO:0.04Ce3+,0.1Tb3+ are illustrated in Figure 3c. A profile with similarities to the Ce3+ single-doped samples appears with that of the Ce3+,Tb3+ codoped samples. The Tb3+ emitting intensity is enormously increased relative to Ce3+ emissions, which validates a Ce3+−Tb3+ ET. To understand the effect of ET on the luminescent properties (Figure 4), we studied PL spectra dependence on Tb3+ dopant contents for LCSO:0.04Ce3+,yTb3+ phosphors excited by UV (λex = 330 nm) (y = 0, 0.02, 0.04, 0.06, 0.08, 0.10, 0.12). The PL intensities of Ce3+ decrease monotonically with increasing Tb3+ concentrations because of the effective Ce3+−Tb3+ ET. Meanwhile, those of Tb3+ at 550 nm increase until the y value is above 0.06 when the emission intensities of 16715


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I0 ∝ C n /3 (2) I where I and I0 respectively represent the luminescence intensities of the samples in the present and absent state of Tb3+, and C represents total Ce3+ and Tb3+ concentration. The correlation of (I0/I) with Cn/3 with n = 6, 8, and 10 corresponds to a dipole−dipole, dipole−quadrupole, and quadrupole−quadrupole interaction. The linear fittings of the relationship between Cn/3 and (I0/I) are demonstrated in Figure 6, and a good linear correlation is obtained at n = 8,

Figure 4. PL spectra of LCSO:0.04Ce3+,yTb3+ (y = 0−0.12) under 330 nm UV excitation.

Tb3+ are saturated. Moreover, the Tb3+ emitting intensities start to decrease when the Tb3+ dopant content (y) is over 0.06 because of the internal quench of concentrations of Tb3+− Tb3+. The Ce3+ decay curves were measured for the investigation of the ET processes in LCSO:Ce3+,Tb3+. The Ce3+ decay curves in LCSO:0.04Ce3+,yTb3+ phosphor (y = 0, 0.02, 0.04, 0.06, 0.08, 0.10, 0.12) samples were also collected (Figure 5).

Figure 6. Dependence of I/I0 vs Cn/3 of Ce3+ and Tb3+ on C6/3, C8/3, and C10/3 in LCSO: Ce3+,Tb3+.

indicating a dipole−quadrupole for Ce3+−Tb3+ ET. According to spectral overlap theory, RC can be calculated by the formula R C8 = 3.024 × 1012λS2fq

FS(E)FA(E)dE

(3) E4 where f q represents oscillator strength in quadrupole transitions, ∫ FS(E)FA(E)/E4 dE represents spectral overlapping among the normalized shape of the Ce3+ emission FS(E) and the Tb3+ excited FA(E), E (eV) is the energy in the transfer, and RC (Å) represents the sensitizer−acceptor average distance. Correspondingly, during the sensitizer’s emissions, it is approximately 0.0051 eV−5. λS (Å) of the wavelength position. So far, it has not been obtained for the oscillator strength in Tb3+ quadrupole transitions ( fq). However, Verstegen et al. suggested that 10−3 to 10−2 is approximately the fq/fd ratio, where fd = 10−6 is the Tb3+ electric dipole transition strength.36 According to the parameters mentioned above, Rdq C of dipole−quadrupole interactions is 11.53−15.38 Å. 2.3. Luminescence Properties and ET of LCSO:Ce3+,Mn2+. As a transition metal ion with 3d5 configuration, its position of the broad emitting bands is largely determined by its host. In LCSO host, the intensity luminescence of Mn2+ emission is too weak to be detected owing to prohibited Mn2+ d−d transitions. Thus, the PLE and PL spectra of a series of Mn2+ and Ce3+ codoped LCSO phosphors are illustrated in Figure 7. The PLE spectrum of Mn2+ emissions is similar to that of Ce3+. Thus, Mn2+ ions can be excited by UV or nearUV light, which strongly verify an effective Ce3+−Mn2+ ET. The effective resonance-type Ce3+−Mn2+ ET is relatively common and was observed in several Ce3+ and Mn2+ codoped phosphors, including Ca3Sc2Si3O12:Ce3+,Mn2+ and Ca9Y-

Figure 5. Fluorescence decay curves of Ce3+ as a function of the Tb3+ contents. Inset: The calculated ET efficiency with different doping Tb3+ contents.

The lifetimes can be defined in equation τD = ∫ ∞ 0 ID(t)dt, where ID(t) is the decay function of donors in the absence of acceptors, which have normalized to its initial intensity. The Ce3+−Tb3+ ET features are reflected by the fluorescence intensities, which decrease with increasing Tb3+ concentrations.31−33 The efficiency of Ce3+−Tb3+ ET is calculated with the formula ηCe−Tb = 1 − τ /τ0

∫

(1)

where τ0 and τ are the decay lifetimes of the sensitizer Ce in the absence and presence of activator Tb3+, respectively. The calculated value is illustrated in Figure 5, which will increase monotonously with the y values until the highest 45% corresponding to a y value of 0.12. Ce 3+ to Tb 3+ ET occurs during electric−multipole interaction and could be determined through spectral overlap method, as follows, in line with Dexter’s ET expression for multipolar interactions34−36 3+

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Figure 7. PL and PLE spectra of LCSO:0.04Ce3+,0.2Mn2+.

(PO4)7:Ce3+,Mn2+.37,38 The PL spectrum demonstrates multicolor emissions consisting of an orange band excited at 365 nm caused by Mn2+ 4T1−6A1 transitions and a blue band caused by Ce3+ f−d transitions, respectively. Therefore, the red emission in LCSO:Ce3+,Mn2+ phosphors originates from ET from Ce3+ to Mn 2+ . The detailed PL spectra of the series of LCSO:0.04Ce3+,zMn2+ phosphors are shown in Figure 8,

Figure 9. (a) Decay curves of Ce3+ in LCSO:0.02Ce3+,zMn2+ (z = 0, 0.12, and 0.24) under 330 nm excitation and monitored at 430 nm. (b) Lifetimes of the sensitizer Ce3+ and the ET efficiency (ηCe−Tb) with different doping Mn2+ contents.

Figure 8. Variation of PL spectra of LCSO:0.04Ce3+,zMn2+ (z = 0− 0.24) phosphors excited with 330 nm UV light.

which are excited by a wavelength of 330 nm, with the z value from 0 to 0.24. With increasing Mn2+ concentration, two broad bands with emission peaks at 450 and 580 nm are detected. Because of Ce3+−Mn2+ ET, the emission intensities of Mn2+ ions increase systematically. Additionally, concentration quench may induce the decrease in Mn2+ emission intensity. In LCSO:0.04Ce3+,zMn2+ (z = 0, 0.04, 0.08, 0.12, 0.16, 0.2, 0.24), the decay curves of Ce3+ fluorescence were measured (Figure 9a), which reveals that the Ce3+ lifetime decreases with increased Mn2+ concentrations and verifies its Ce3+−Mn2+ ET efficiency (calculated with eq 1; refer to Figure 9b). The efficiency of ET significantly increases, and the maximum value is approximately 30.4% of Mn2+ concentration at z = 0.24, which clarifies that Ce3+ contributes to the yellow emission energy of Mn2+. The relationship of (I0/I) to Cn/3 is shown in Figure 10. Similar to the investigated and observed results of other research groups, the ET of Ce3+−Mn2+ arises from the dipole−quadrupole mechanism.39,40 2.4. Quantum Yields and Chromaticity of LCSO:Ce3+,Tb3+,Mn2+. The absolute internal quantum yield (QY) of the obtained phosphors was measured to explore the potential

Figure 10. Experimental data plots of I/I0 vs Cn/3.

of the as-synthesized LCSO:Ce3+,Tb3+,Mn2+ phosphors. Upon excitation at 365 nm UV radiation, the absolute internal QY of LCSO:0.04Ce3+,yTb3+ (y = 0−12%) phosphors are 60.3, 62.1, 64.5, 67.3, 61.7, 55.9, and 47.2%. For LCSO:0.04Ce3+,zMn2+ (z = 0−24%) samples, the absolute internal QY is 65.3, 48.8, 31.6, 27.2, 23.4, 20.9, and 13.1%. The internal QY values decrease obviously with the increase in Mn2+ concentration, which may be in relation to two factors: First, the energy should be lost in the Ce3+ → Mn2+ ET process. Second, the internal quantum efficiency can be expressed as ηin = WR/(WR 16717


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+ WNR), where WR and WNR represent the radiative transition rate and the nonradiative decay rate, respectively. This suggests that the nonradiative decay rate is much higher than the radiative decay rate, leading to low internal quantum efficiency of the Mn2+ ions. The maximum internal QY in the asprepared samples can reach 67.3%. The high QYs of our samples indicate that LCSO functions well to dope rare-earth ions as a matrix. For LCSO:Ce3+,yTb3+,zMn2+ at varied contents (y and z), their CIE chromaticity diagrams is shown in Figure 11. The color point evolves from blue

ions will emit a green and red emission band, respectively. In particular, the inset in Figure 11 shows a series of digital photos of the selected LCSO:0.04Ce3+,yTb3+,zMn2+ phosphors upon UV lamp excitation at 365 nm. The material exhibits tunable color emission. LCSO:0.04Ce3+,0.24Mn2+ can emit white light and thus can be used as a single-component multicolor-emitting phosphor for UV LEDs.

3. CONCLUSIONS In summary, we have synthesized a series of emission-tunable Li2Ca4Si4O13:Ce3+,Tb3+,Mn2+ phosphors by solid-state reaction. The ETs from Ce3+ to Tb3+ and from Ce3+ to Mn2+ in Li2Ca4Si4O13 were observed. The ET from Ce3+ to Tb3+ in Li2Ca4Si4O13:Ce3+,Tb3+ phosphors is a resonant type via the dipole−quadrupole mechanism, and the calculated critical distance (RC) is 11.53−15.38 Å. The ET from Ce3+ to Mn2+ was investigated based on PL and PLE spectra, decay curves, and effect of Ce3+/Mn2+ concentration. Color emission and luminescence internal QY (13−67%) can be tuned by controlling the contents of Ce3+, Tb3+, and Mn2+. Hence, Li2Ca4Si4O13:Ce3+,Tb3+,Mn2+ could be a white light-emitting phosphor for UV-excited w-LEDs. 4. EXPERIMENTAL SECTION 4.1. Sample Preparation. Li2Ca4−x−y−zSi4O13:xCe3+,yTb3+,zMn2+ (LCSO:xCe3+,yTb3+,zMn2+) were synthesized by a high-temperature solid-state reaction. Stoichiometric amounts of starting materials, including CaCO3 (A. R.), Li2CO3 (A. R.), SiO2 (A. R.), CeO2 (99.99%), Tb4O7 (99.99%), and MnCO3 (A. R.), were thoroughly mixed in an agate mortar for 0.5 h. The mixed powders were calcined at 950 °C under a reducing atmosphere of H2 (5%) and N2 (95%) for 4 h. The samples were cooled to room temperature to obtain the final products. 4.2. Measurements and Characterization. The structure and crystallinity of the sample was identified by powder XRD analysis (Bruker AXS D8, Cu Kα radiation, λ = 1.5405 Å, 40 kV, 40 mA). PL and PLE spectra were collected on a Hitachi F7000 spectrometer (700 V, 150 W xenon lamp, EX/ EM slit of 2.5 nm, scanning rate of 1200 nm/min). Luminescence decay profiles were obtained from a Lecroy Wave Runner 6100 digital oscilloscope (1 GHz) by using a tunable laser (pulse width = 4 ns, gate = 50 ns) as the excitation source (Continuum Sunlite OPO). PL internal QYs were measured by using the absolute PL QY measurement system (C9920-02, Hamamatsu Photonics K. K., Japan). All of the measurements were performed at room temperature.

Figure 11. CIE chromaticity diagram of the as-prepared samples under 365 nm UV lamp excitation and the selected digital photos.

(0.155, 0.112) to white (0.249, 0.267) by changing the Mn2+ concentrations and from blue (0.155, 0.112) to green (0.298, 0.524) by changing the content of Tb3+. The tunable color point results from the ET processes of Ce3+ → Tb3+ and Ce3+ → Mn2+, which is deduced from the energy-level model in Figure 12. Upon excitation at 365 nm, Ce3+ ions can be effectively excited. Then some Ce3+ ions go back to the ground state of 2F7/2 or 2F5/2 spontaneously by a radiative process, and other excited Ce3+ ions transfer its energy to the 5D2/5D3 state of Tb3+ and 4A1 (4G) state of Mn2+. Finally, Tb3+ and Mn2+

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AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected]. Phone: +86-769-22862125. Fax: +86-769-22862125. ORCID

Wei Lü: 0000-0002-1342-0958 Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS This work was financially supported by the National Natural Science Foundation of China (grant nos. 51772287 and 61771138), Guangdong Science and Technology Planning Program (grant no. 2017A010102019), and Dongguan

Figure 12. Energy-level diagram of ET from Ce3+ ions to Tb3+/Mn2+. 16718


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Industry University Research Cooperation Project (no. 2015509102211). It was also supported by high-level talent grants from Dongguan University of Technology (GC20090504, GB200902-26, GB200902-27).

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ACS Omega

Article

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