A LiCaPO4:Eu2+ phosphor with high photoluminescence was synthesized using a polymerizable complex (PC) method employing a water-soluble polyethylene glycol-conjugated phosphate ester (PEG-P). PEG-P could be obtained from a reaction among polyethylene glycol 300, phosphorus pentoxide, and pyrophosphoric acid. The PEG-P prepared was stable in an aqueous condition. A transparent solution and gel were obtained when the PEG-P was used as a source of P during the PC method, whereas the use of H3PO4 caused an undesirable precipitate. The LiCaPO4:Eu2+ obtained via the PC method employing the PEG-P showed higher emission intensity than those synthesized by a solid state reaction method and the PC method employing H3PO4. The high luminescence properties of the sample synthesized using the PEG-P may be attributed to high homogeneity of constituents in the sample.
Phosphate phosphors have been well-known as one of the most important luminescence materials because of their excellent thermal stability and high emission intensity as well as lower temperature synthesis [1,2]. Among them, Eu2+-activated ABPO4 phosphors (A and B are monoand divalent cations, respectively) have been reported as blue-emitting phosphors excited by near UVLEDs. For instance, KSrPO4:Eu2+, KBaPO4:Eu2+, and LiCaPO4:Eu2+ have excellent luminescence properties including quantum efficiency and thermal quenching behavior. Therefore, they are considered to be potential application as phosphors for the white light emitting diodes [3-5].
Several kinds of methods were applied to synthesis of inorganic powders, such as solid state reaction (SSR), solution-based method, and combustion process. In the synthesis of phosphors, the SSR method is the most extensively used. However, the SSR method includes some drawbacks such as low homogeneity, and non-uniform particles morphology and size. Generally, solution-based synthesis is considered to be a desirable approach because it can produce highly homogeneous compounds in the atomic level [6,7]. Homogeneity of constituents and control of morphology and size of particles are requisites for highly efficient phosphors. One of limitations in a synthesis of phosphate phosphors using solution methods is requirement of appropriate P source, which is soluble and stable in an aqueous condition. The use of conventional phosphate reagents such as phosphoric acid or ammonium phosphate produce precipitates with metal ions in an aqueous condition [
Solution-based synthesis highly requires the use of appropriate raw materials, which do not produce precipitate with any metals present in a given aqueous solution. Therefore, development of a new water-soluble P source that does not form precipitates with other metal ions is indispensable to realization of synthesis of extremely homogeneous phosphate compounds with high performance by aqueous solution-based methods. It is known that precipitates between phosphorus and metals could be prevented by introduction of condensed chain-structured phosphates [9,10]. Recently, we have succeeded in a synthesis of a phosphate phosphor with high luminescence by a solution method using such a phosphate oligomer [
Pyrophosphoric acid (10 mmol phosphorus, Kanto Chemical) and polyethylene glycol 300 (PEG300, 10 mmol Kanto Chemical) were mixed at 323 K and kept for 2 h. Phosphorus pentoxide P4O10 (10 mmol phosphorus, Wako Chemical) was weighed in an inert atmosphere to prevent its hydrolysis, and then slowly added into the mixture. After P4O10 was dispersed homogeneously, temperature of the mixture increased to 358 K and kept for 5 h. Finally, 10 mmol of PEG300 was added, and the reaction was continued for 12 h at 358 K. The entire reaction was conducted in N2 atmosphere. Gel with high viscosity was formed and it was dissolved in distilled water. The gel was dissolved in D2O, and pH was adjusted to 13 using 10 M NaOH to prepare a solution for NMR analysis. 1H and 31P{1H} NMR spectra of the prepared PEG-P were recorded on a Bruker AVANCE 400 spectrometer (400 MHz for 1H resonance) to analyze the chemical structure of PEG-P. The phosphorus concentration of diluted PEG-P was determined using an inductively-coupled plasma (ICP) method (Perkin Elmer; Optima 3300XL) prior to its use for the synthesis of Eu2+-doped LiCaPO4 by the PC method described in the following section.
A Eu2+-doped LiCaPO4 phosphor was synthesized via the PC method employing the PEG-P as a P source. LiNO3 (99%, Kanto Chemical), Ca(NO3)2∙4H2O (99.5%, Kanto Chemical), and Eu(NO3)3, which was prepared by dissolution of Eu2O3 in HNO3, were dissolved in a citric acid (CA) solution at a ratio of Li:Ca:Eu:CA = 1:0.97:0.03:8. The mixture was firstly heated at 353 K to allow chelation for 2 h, and then, the PEG-P and propylene glycol (PG) were added into the solution at a molar ratio of 1:8. The temperature was subsequently increased to 423 K to promote gel formation. The formed gel was heated at 1123 K in air to remove the organic content, and then it was reduced at 1373 K under a flow of Ar containing 4% H2 for 3 h. To enhance the phase purity, post-heat treatment was conducted at 1073 K for 18 h in an Ar/4%H2 atmosphere. A Eu2+-doped LiCaPO4 phosphor was also synthesized by the PC method using H3PO4 as the P source. In addition, synthesis using the SSR method was carried out for comparison by stoichiometric mixing raw materials including Eu2O3 (Furuuchi Chemical), and Li2CO3 (Wako Chemical), CaCO3, and (NH4)H2PO4 (both from Kanto Chemical). X-ray diffraction analysis (XRD, Bruker AXS; D2 Phaser) was conducted. Excitation and emission spectra of phosphors were recorded using a fluorescence spectrometer (Hitachi; F-4500) at room temperature. Quantum efficiencies of the samples were evaluated using fluorescence spectrometer (Jasco; FP-6500).
Scheme 1 shows estimated chemical structures of the synthesized PEG-P; (a) monoand (b) di-esters, and
area corresponding to the peak “2” was greatly decreased after the reaction, and finally, it could be estimated that more than 90% of PEG 300 was bonded with phosphate. From the 31P{1H} NMR spectrum, it could be confirmed that the PEG-P contained H3PO4, monoester, and diester with ratio of 17.4:72.5:10.1 (
To demonstrate the advantages of the use of PEG-P in a solution-based method, a LiCaPO4 doped with Eu2+ phosphor was synthesized by the PC method employing the PEG-P.
This is due to decomposition of LiCaPO4 at such a high temperature. Reaction between Li3PO4 and Ca3(PO4)2 appears to be possible when the corresponding phase diagram for these two compounds is taken into account [15,16]. The post-heat treatment of the above-mentioned sample at 1073 K for 18 h (
the mixture solution while PEG-P didn’t make any precipitate. It can be expected that low homogeneity led to formation of a large amount of Li3PO4 and Ca3(PO4)2 and these phases remained even after post-heat treatment. As mentioned above, phase purity is closely related to photoluminescence properties. The use of a novel PEG-P as a P source in the PC method could improve phase purity of LiCaPO4, and it is one of advantages of the PEG-P in the PC method.
cipitate between H3PO4 and metals during the mixing step in the PC method implies poor homogeneity despite of a solution-based method. The SSR method could produce better condition of sample compared to that of the PC method employing H3PO4, because it exhibited higher emission intensity. Formation of undesirable precipitate in the PC method is thought to be a critical factor for homogeneity. The strongest emission intensity was observed from the sample synthesized via the PC method using the PEG-P as a P source. The internal quantum efficiencies of LiCaPO4: prepared using the SSR method and the PC method employing PEG-P under excitation at 375 nm were 53.7% and 67.6%, respectively, although the corresponding absorption rate (81.3%) of the sample prepared by the PC method using PEG-P was slightly smaller than that of the one prepared by the SSR method (82.7%). The PEG-P was stable in the aqueous condition and the use of PEG-P didn’t produce any precipitates with coexisting metal ions, and it allowed us to obtaining a highly homogeneous phosphor sample. As a result, despite of a lower absorption rate, the sample obtained from the PC method using PEG-P showed the high emission intensity and enhanced quantum efficiency.
A stable and water soluble phosphate ester was prepared by the reaction using pyrophosphoric acid, phosphorus pentoxide, and PEG300. The method could produce P source with less H3PO4. It was confirmed that the synthesized PEG-P didn’t make any precipitate in a mixture of metal salts while the use of H3PO4 resulted in formation of a precipitate. An almost single phase of LiCaPO4 was obtained using the PEG-P, while SSR and PC method using H3PO4 led to formation of impurity phases, which were Li3PO4 and Ca3(PO4)2. As a result, the phosphor prepared by the PC method using the synthesized
PEG-P exhibited enhanced photoluminescence properties, such as the highest emission intensity and quantum efficiency compared to other methods. Enhanced photoluminescence properties seemed to be attributed to homogeneous distribution of constituents in the atomic level. Therefore, the PEG-P is expected to be applicable in the solution-based synthesis of various kinds of phosphate-based ceramic compositions with enhanced material properties.
This work was partially supported by a Grant-in-Aid for Scientific Research on Innovative Areas of “Fusion Materials: Creative Development of Materials and Exploration of Their Function through Molecular Control” (no. 2206) from the Ministry of Education, Culture, Sports, Science and Technology (MEXT), Japan and a Grantin-Aid for JSPS Fellows (24∙9285) from Japan Society for the Promotion of Science (JSPS).