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Optics Express

Optics Express

  • Editor: C. Martijn de Sterke
  • Vol. 18, Iss. 7 — Mar. 29, 2010
  • pp: 7543–7553

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Synthesis and luminescent properties of CaTiO3: Pr3+ microfibers prepared by electrospinning method

Chong Peng, Zhiyao Hou, Cuimiao Zhang, Guogang Li, Hongzhou Lian, Ziyong Cheng, and Jun Lin  »View Author Affiliations


Optics Express, Vol. 18, Issue 7, pp. 7543-7553 (2010)
http://dx.doi.org/10.1364/OE.18.007543


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Abstract

One-dimensional Pr3+-doped CaTiO3 microfibers were fabricated by a simple and cost-effective electronspinning process. X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), thermogravimetric and differential analysis (TG-DTA), scanning electron microscopy (SEM), energy-dispersive X-ray spectrum (EDS), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), photoluminescence (PL), quantum efficiency (QE), and cathodoluminescence (CL) spectra as well as kinetic decays were used to characterize the samples. Under ultraviolet excitation and low-voltage electron beams (1-3 kV) excitation, the CaTiO3:x Pr3+ samples show the red emission at 612 nm, corresponding to 1D2-3H4 transition of Pr3+. The luminescence intensity, quantum efficiency, and the lifetime have been studied as a function of the doping concentration of Pr3+ in the CaTiO3 samples.

© 2010 OSA

1. Introduction

Field emission displays (FEDs) have gained a great interest and been thought as a next-generation flat-panel display for their good performances, such as great brightness, wide horizontal and vertical view angle, high contract ratio, light weight, short response time, wide work temperature range and high efficiency with low power consumption [1

A. Vecht, D. Smith, S. Chadha, C. Gibbons, J. Koh, and D. Morton, “New electron excited light emitting materials,” J. Vac. Sci. Technol. B 12(2), 781–784 (1994). [CrossRef]

–8

S. Cho, J. Yoo, and J. Lee, “Synthesis and low-voltage characteristics of CaTiO3: Pr3+ luminescent powders,” J. Electrochem. Soc. 143(10), L231 (1996). [CrossRef]

]. Compared with cathode ray tubes (CRTs), FEDs operate at significantly lower excitation voltages and higher current densities, phosphors used in FEDs must be efficient at low voltages and be resistant to Coulombic aging and saturation at high current densities. Sulfide-based phosphors mostly in CRTs lose efficiency due to the degradation at high current density [3

P. Holloway, T. Trottier, J. Sebastian, S. Jones, X. Zhang, J. Bang, B. Abrams, W. Thomes, and T. Kim, “Degradation of field emission display phosphors,” J. Appl. Phys. 88(1), 483 (2000). [CrossRef]

–5

G. Li, C. Li, Z. Hou, C. Peng, Z. Cheng, and J. Lin, “Nanocrystalline LaOCl:Tb(3+)/Sm(3+) as promising phosphors for full-color field-emission displays,” Opt. Lett. 34(24), 3833–3835 (2009). [CrossRef] [PubMed]

]. Thus, oxide phosphors have gained more interests for their better thermal and chemical stability and environmental friendliness compared with sulfides [6

L. Wang, X. Liu, Z. Hou, C. Li, P. Yang, Z. Cheng, H. Lian, and J. Lin, “Electrospinning synthesis and luminescence properties of one-dimensional Zn2SiO4: Mn2+ microfibers and microbelts,” J. Phys. Chem. C 112, 18882–18888 (2008).

,7

H. Li, Z. Wang, S. Xu, and J. Hao, “Improved performance of spherical BaWO4: Tb3+ phosphors for field-emission displays,” J. Electrochem. Soc. 156(5), J112 (2009). [CrossRef]

].

Perovskite CaTiO3 presents a good conductivity (band gap energy of 3.7 eV) [8

S. Cho, J. Yoo, and J. Lee, “Synthesis and low-voltage characteristics of CaTiO3: Pr3+ luminescent powders,” J. Electrochem. Soc. 143(10), L231 (1996). [CrossRef]

], and recently get attention for its biocompatibility [9

N. Ohtsu, K. Sato, A. Yanagawa, K. Saito, Y. Imai, T. Kohgo, A. Yokoyama, K. Asami, and T. Hanawa, “CaTiO3 coating on titanium for biomaterial application-optimum thickness and tissue response,” J. Biomed. Mater. Res. A 82A(2), 304–315 (2007). [CrossRef]

]. The luminescence properties of CaTiO3 doped with trivalent praseodymium (Pr) have been increasingly investigated as the CIE coordinates of a red cathodoluminescence signal were measured at x = 0.680 and y = 0.311 [10

P. Diallo, P. Boutinaud, R. Mahiou, and J. Cousseins, “Red luminescence in Pr3+-doped calcium titanates,” Phys. Status Solidi 160(1), 255–263 (1997) (a). [CrossRef]

,11

H. Takashima, K. Shimada, N. Miura, T. Katsumata, Y. Inaguma, K. Ueda, and M. Itoh, “Low-driving-voltage electroluminescence in perovskite films,” Adv. Mater. 21(36), 3699–3702 (2009). [CrossRef]

]. Resent years, much work has focused on optimizing suitable phosphors in terms of morphology, particle size, stoichiometry, composition, and surface chemistry [1

A. Vecht, D. Smith, S. Chadha, C. Gibbons, J. Koh, and D. Morton, “New electron excited light emitting materials,” J. Vac. Sci. Technol. B 12(2), 781–784 (1994). [CrossRef]

,2

X. Liu, P. Jia, J. Lin, and G. Li, “Monodisperse spherical core-shell structured SiO2–CaTiO3: Pr3+ phosphors for field emission displays,” J. Appl. Phys. 99(12), 124902 (2006). [CrossRef]

,12

T. Li, M. Shen, L. Fang, F. Zheng, and X. Wu, “Effect of Ca deficiencies on the photoluminescence of CaTiO3: Pr3+ ,” J. Alloy. Comp. 474(1-2), 330–333 (2009). [CrossRef]

–18

S. Yin, D. Chen, W. Tang, and Y. Yuan, “Synthesis of CaTiO3: Pr, Al phosphors by sol-gel method and their luminescence properties,” J. Mater. Sci. 42(8), 2886–2890 (2007). [CrossRef]

]. CaTiO3 has been synthesized by hydrothermal [19

M. Lencka and R. Riman, “Thermodynamics of the hydrothermal synthesis of calcium titanate with reference to other alkaline-earth titanates,” Chem. Mater. 7(1), 18–25 (1995). [CrossRef]

] / solvothermal method [20

X. F. Yang, I. D. Williams, J. Chen, J. Wang, H. F. Xu, H. M. Konishi, Y. X. Pan, C. L. Liang, and M. M. Wu, “Perovskite hollow cubes: morphological control, three-dimensional twinning and intensely enhanced photoluminescence,” J. Mater. Chem. 18(30), 3543–3546 (2008). [CrossRef]

], coprecipitation technique [21

X. Zhang, J. Zhang, X. Ren, and X. Wang, “The dependence of persistent phosphorescence on annealing temperatures in CaTiO3: Pr3+ nanoparticles prepared by a coprecipitation technique,” J. Solid State Chem. 181(3), 393–398 (2008). [CrossRef]

], polymeric precursor method [22

A. de Figueiredo, V. Longo, S. de Lazaro, V. Mastelaro, F. De Vicente, A. Hernandes, M. Siu Li, J. Varela, and E. Longo, “Blue-green and red photoluminescence in CaTiO3: Sm,” J. Lumin. 126(2), 403–407 (2007). [CrossRef]

], and sol-gel method [2

X. Liu, P. Jia, J. Lin, and G. Li, “Monodisperse spherical core-shell structured SiO2–CaTiO3: Pr3+ phosphors for field emission displays,” J. Appl. Phys. 99(12), 124902 (2006). [CrossRef]

,18

S. Yin, D. Chen, W. Tang, and Y. Yuan, “Synthesis of CaTiO3: Pr, Al phosphors by sol-gel method and their luminescence properties,” J. Mater. Sci. 42(8), 2886–2890 (2007). [CrossRef]

] instead of solid state method in order to get higher efficiency. One-dimensional (1D) and Quasi-one-dimensional (Q-1D) nanomaterials have attracted great research interest [23

R. Caruso, J. Schattka, and A. Greiner, “Titanium dioxide tubes from sol-gel coating of electrospun polymer fibers,” Adv. Mater. 13(20), 1577–1579 (2001). [CrossRef]

,27

D. Li and Y. Xia, “Electrospinning of nanofibers: reinventing the wheel?” Adv. Mater. 16(14), 1151–1170 (2004). [CrossRef]

] because of their specific and fascinating properties, such as high luminescence efficiency, superior mechanical toughness, metal insulator transition, and lowered threshold [24

E. Wong, P. Sheehan, and C. Lieber, “Nanobeam mechanics: elasticity, strength, and toughness of nanorods and nanotubes,” Science 277(5334), 1971–1975 (1997). [CrossRef]

,25

Y. Arakawa and H. Sakaki, “Multidimensional quantum well laser and temperature dependence of its threshold current,” Appl. Phys. Lett. 40(11), 939 (1982). [CrossRef]

,28

Z. Hou, R. Chai, M. Zhang, C. Zhang, P. Chong, Z. Xu, G. Li, and J. Lin, “Fabrication and luminescence properties of one-dimensional CaMoO(4): Ln(3+) (Ln = Eu, Tb, Dy) nanofibers via electrospinning process,” Langmuir 25(20), 12340–12348 (2009). [CrossRef] [PubMed]

]. The electrospinning technique has been used to synthesis 1D structure materials since 1934 [26

A. Formhals, “Process and apparatus for preparing artificial threads,” (US Patents, 1934).

]. And now it has been demonstrated that a variety of materials can be electrospun to form uniform fibers, such as organic, inorganic, and hybrid polymers (organic-inorganic composites) [6

L. Wang, X. Liu, Z. Hou, C. Li, P. Yang, Z. Cheng, H. Lian, and J. Lin, “Electrospinning synthesis and luminescence properties of one-dimensional Zn2SiO4: Mn2+ microfibers and microbelts,” J. Phys. Chem. C 112, 18882–18888 (2008).

,27

D. Li and Y. Xia, “Electrospinning of nanofibers: reinventing the wheel?” Adv. Mater. 16(14), 1151–1170 (2004). [CrossRef]

–29

G. Dong, Y. Chi, X. Xiao, X. Liu, B. Qian, Z. Ma, E. Wu, H. Zeng, D. Chen, and J. Qiu, “Fabrication and optical properties of Y2O3: Eu3+ nanofibers prepared by electrospinning,” Opt. Express 17(25), 22514–22519 (2009). [CrossRef]

]. The diameter of fibers prepared by the method can range from nanometers to several micrometers.

Accordingly, in the present work, we developed a facile method that combines electrospinning technique with heat treatment to prepare microscale Pr3+ doped CaTiO3 red emission material. Furthermore, we investigated the structure, morphology, and photoluminescence (PL) and cathodoluminescence (CL) properties of the resulting samples in detail.

2. Experimental

CaCl2 2H2O (98.0%, analytical reagent, A. R.) was purchased from Shantou Xilong Chemical Factory. Tetrabutyl titanate [Ti(OC4H9)4, A. R.] was purchased from Tianjin Guangfu Fine Chemical Factory. Poly(vinylpyrrolidone) (PVP, Mw = 1 300 000) was purchased from Aldrich. All of the materials were used without further purification. Ethanol C2H5OH (A.R.) was used as solvent.

Ca1-xTiO3: xPr3+ (x = 0.0005, 0.001, 0.002, 0.003, 0.004, 0.005) were synthesized by electrospinning method succeed with high temperature treatment. First, Pr6O11 was dissolved in dilute hydrochloric acid HCl (AR) solution under stirring and heating to obtain PrCl3 solution. Stoichiometric PrCl3 solution was transferred to a 25 mL beaker which was then heated in an oven to remove the water. After cooling, stoichiometric CaCl2 · 2H2O, Ti(OC4H9)4, 7 mL alcohol and 0.6011g PVP were added. The mixture was stirred 3 hours to get viscous solution for further electrospinning. A typical electrospinning setup consists of a syringe through which the solution to be electrospun is forced, a high-voltage power supply, a flat tip needle, and a grounded collector. The above viscous solution was placed in a 10 mL hypodermic syringe. The anode if the high-voltage power supply was clamped to the syringe needle tip and the cathode was connected to the grounded collector plate. The applied voltage was 10 kV, the distance between the needle tip and the collector was 15 cm, and the flow rate of the spinning solution was controlled at 1 mL/h by a syringe pump (TJ-3A/W0109-1B, Boading Longer Precision Pump Co., Ltd., China). The electrospun products were then calcined at 500, 600, 700, 800 °C for 2h with a heating rate of 1 °C /min. In this way, Ca1-xTiO3:x Pr3+ microfibers were fabricated.

The X-ray powder diffraction (XRD) measurements were carried out on a Rigaku-Dmax 2500 diffractometer using Cu Kα radiation (λ = 0.15405 nm). Fourier transform infrared spectroscopy (FTIR) spectra were measured with a Perkin-Elmer 580B infrared spectrophotometer using the KBr pellet technique. Thermogravimetric and differential thermal analysis (TG-DTA) data were recorded with a Thermal Analysis instrument (SDT 2960, TA Instruments, New Castle, DE) with heating rate of 10 °C·min−1. The morphology and composition of the samples were inspected using a field emission scanning electron microscope (FESEM, XL30, Philips) equipped with an energy-dispersive X-ray spectroscope (EDS, JEOL JXA-840). Transmission electron microscopy (TEM) and high-resolution transmission electron microscopy (HRTEM) micrographs were obtained from a FEI Tecnai G2 S-Twin transmission electron microscope with a field emission gun operating at 200 kV. The photoluminescence (PL) measurements were performed on a Hitachi F-4500 spectrophotometer equipped with a 150 W xenon lamp as the excitation source. The cathodoluminescent (CL) measurements were carried out in an ultrahigh-vacuum chamber (<10−8 Torr), where the samples were excited by an electron beam at a voltage range of 1-3 kV with different filament currents, and the emission spectra were recorded using an F-4500 spectrophotometer. The luminescence decay curves were obtained from a Lecroy Wave Runner 6100 digital oscilloscope (1 GHz) using a tunable laser (pulse width = 4 ns, gate = 50 ns) as excitation source (Continuum Suncite OPO). The quantum efficiency of the phosphor samples was performed by the quantum yield measurement system (C9920-02, Hamamatsu Photonics K. K., Japan). All the measurements were performed at room temperature (RT).

3. Results and discussion

3.1 Formation and morphology

The XRD patterns of the CaTiO3:0.001 Pr3+ microfibers annealed from 500 to 800 °C are shown in Fig. 1 . When the precursor sample is calcined at 500 °C (Fig. 1a), there is no obverse diffraction peak, indicating the sample still remains amorphous below this temperature. After annealing at 600 °C (Fig. 1b), well-defined diffraction peaks appear, all of them can be assigned exactly to the orthorhombic phase of CaTiO3 (JCPDS No. 22-0153). After annealing at 700 (Fig. 1c) and 800 (Fig. 1d) °C, all the diffraction peaks increase in intensity due to the increase of crystallinity. No additional peaks are detected in this dropping level, indicating that the Pr3+ can be effectively built into the CaTiO3 host lattice. The ionic radius of Pr3+ is closed to that of Ca2+ and far away from that of Ti4+ [12

T. Li, M. Shen, L. Fang, F. Zheng, and X. Wu, “Effect of Ca deficiencies on the photoluminescence of CaTiO3: Pr3+ ,” J. Alloy. Comp. 474(1-2), 330–333 (2009). [CrossRef]

]. Thus, Pr3+ is usually thought to occupy Ca2+ site.

Fig. 1 X-ray diffraction patterns for CaTiO3:0.001 Pr3+ microfibers annealed at (a) 500, (b) 600, (c) 700, (d) 800 °C, respectively, as well as the JCPDS card 22-0153 of CaTiO3 for comparison.

The charge compensation may occur by the formation of intrinsic defects such as negatively charged Ca vacancies, positively charged oxygen vacancies and/or by reduction of Ti4+ to Ti3+. Many works have indicated that the optical performances of Pr3+-doped CaTiO3 depend critically on charge compensation. The defects are undesirable because their presence in the phosphors, even at low concentration, can contribute to quench the Pr3+ luminescence [14

J. Tang, X. Yu, L. Yang, C. Zhou, and X. Peng, “Preparation and Al3+ enhanced photoluminescence properties of CaTiO3: Pr3+ ,” Mater. Lett. 60(3), 326–329 (2006). [CrossRef]

].

The FT-IR spectra of the as-spun PVP fibers, the as-prepared precursor for CaTiO3:0.001 Pr3+ fibers, and CaTiO3:0.001 Pr3+ fibers annealed at 800 °C are shown in part a, b and c of Fig. 2 , respectively. Although there is a little difference, the broad band at 3421 cm−1 in Fig. 2a and the broad band at 3420 cm−1 in Fig. 2b are both assigned to the symmetric stretching vibration of –OH groups. The FT-IR spectrum (Fig. 2a) of PVP fibers shows a characteristic stretching band corresponding to the amide carbonyl group at 1657 cm−1 (C = O group), whereas there is a red shift of the amide carbonyl group to 1653 cm−1 in Fig. 2b. The bands at 2956, 2955, 1465, 1464, 1424 (Fig. 2a, b) can be attributed to the –CH2 absorption of PVP. The bands at 1292 cm−1 (Fig. 2a) and 1293 cm−1 (Fig. 2b) can be attributed to the absorption of tertiary amine group of PVP [6

L. Wang, X. Liu, Z. Hou, C. Li, P. Yang, Z. Cheng, H. Lian, and J. Lin, “Electrospinning synthesis and luminescence properties of one-dimensional Zn2SiO4: Mn2+ microfibers and microbelts,” J. Phys. Chem. C 112, 18882–18888 (2008).

]. In Fig. 2c, for the CaTiO3:0.001 Pr3+ microfibers annealed at 800 °C, strong absorption peaks at 556 cm−1 and 443 cm−1 are present, which are attributed to the stretching vibration of the Ti–O bond (from TiO3 2- groups) [30

J. Last, “Infrared-absorption studies on barium titanate and related materials,” Phys. Rev. 105(6), 1740–1750 (1957). [CrossRef]

]. The weak –OH vibration can also be observed at 3422 cm−1 in CaTiO3:0.001 Pr3+ fibers due to the absorption of trace of water in the course of measurement.

Fig. 2 FT-IR spectra of CaTiO3:0.001 Pr3+ and PVP fibers: (a) as-spun PVP fibers. (b) as-prepared precursor for CaTiO3:0.001 Pr3+ fibers, and (c) CaTiO3:0.001 Pr3+ fibers calcined at 800 °C.

The TG-DTA curves of the as-spun composite fibers heat-treated in air with a rate of 10 °C /min is shown in Fig. 3 . TG curve shows three distinct stages of weight loss. The first weight loss (23%) step is observed between 40 and 250 °C due to the evaporation of alcohol. The second weight loss (53%) from 250 to 480 °C can be attributed to the decomposition of PVP. As observed in the DTA curve, the peak at 334 °C of the DTA curve corresponds to the decomposition of nitrates and the degradation of PVP, which has two degradation mechanisms involving both intra- and inter-molecular transfer reactions [31

S. Azhari and M. Diab, “Thermal degradation and stability of poly (4-vinylpyridine) homopolymer and copolymers of 4-vinylpyridine with methyl acrylate,” Polym. Degrad. Stabil. 60(2-3), 253–256 (1998). [CrossRef]

]. The exothermic peak at 448 °C is the result of the oxidation of carbon and carbon monoxide released by the Tetrabutyl titanate and PVP decomposition [6

L. Wang, X. Liu, Z. Hou, C. Li, P. Yang, Z. Cheng, H. Lian, and J. Lin, “Electrospinning synthesis and luminescence properties of one-dimensional Zn2SiO4: Mn2+ microfibers and microbelts,” J. Phys. Chem. C 112, 18882–18888 (2008).

]. The third weight loss (18%) step between 480 and 700 °C accompanied with an exothermic peak at 520 °C in the DTA curve because of the crystallization of the CaTiO3 phase, basically agreeing with the results of XRD and FT-IR.

Fig. 3 TG-DTA curves of the as-spun precursor for CaTiO3:0.001 Pr3+ fibers.

The morphology and the structure of the samples are investigated by SEM and TEM. Figure 4 shows the SEM micrographs of as-prepared CaTiO3:0.001 Pr3+ samples. From the low-magnification SEM micrograph of the as-formed precursor (Fig. 4a) and those annealed at 800 °C (Fig. 4c), it can be seen that the samples consist of uniform fibers with length of several tens of micrometers. It also can be observed that the as-formed fibers have smooth surface and the diameter range from 630 to 960 nm (Fig. 4b). Due to the decomposition of the organic species and the formation of inorganic phase, the surface become rude and the diameter decrease, ranging from to 230 to 360 nm (Fig. 4d) after being annealed at 800 °C for 2 hours. The EDS was used to characterize the composition of the fibers annealed at 800 °C, as in Fig. 4e. The presence of O, Ti and Ca in Fig. 4e further indicates the formation of calcium titanate in the fibers. The doping concentration of Pr3+ is too small to be shown obviously.

Fig. 4 SEM images for the as-formed precursor for CaTiO3:0.001 Pr3+ microfibers: image with low magnification (a) and high magnification (b). Those annealed at 800 °C: image with low magnification (c) and large magnification (d). And EDS of the microfibers annealed at 800 °C (e).

TEM and high-resolution TEM (HRTEM) images of the CaTiO3:0.001 Pr3+ microfibers annealed at 800 °C are shown in Fig. 5 , respectively. In Fig. 5a, it is observed that the fibers are further composed of fine and closely linked nanoparticles which orderly arranged along the axial direction of single fiber. The SEAD pattern in inset of Fig. 5a shows that the microfibers are polycrystalline. From the HRTEM image of CaTiO3:0.001 Pr3+ microfibers (Fig. 5b), we can see crystalline phase (CaTiO3) with well-resolved lattice fringes. The distance (0.39 nm) between the adjacent lattice fringes just corresponding to the interplanar distance of CaTiO3 (101) planes, agreeing well with the d (101) spacing of the literature value (JCPDS No. 22-0153). These results further confirm the presence of highly crystalline CaTiO3 in the fibers after annealing at high temperature, agreeing well with the XRD results.

Fig. 5 TEM (a) and HRTEM (b) images of CaTiO3:0.001 Pr3+ microfibers annealed at 800 °C.

3.2 Luminescence properties

Under short wavelength ultraviolet (UV) irradiation, CaTiO3:0.001 Pr3+ microfibers exhibit strong emission band (about 40 nm range) in the range of 590–630 nm with a maximum peak at 612 nm (Fig. 6b ). The characteristic luminescence of the phosphors is determined by the electronic structure of the doped Pr3+, while the width and the relative intensity of the spectra frequently depend on the crystal symmetry of the host matrix. The broadening of the spectral line of Pr3+ may also arise from the large slits (EX = 5.0 nm. EM = 5.0 nm) during the measurement. The room temperature PL emission spectrum (Fig. 6b) originates from intra 4f 1D2-3H4 transition [10

P. Diallo, P. Boutinaud, R. Mahiou, and J. Cousseins, “Red luminescence in Pr3+-doped calcium titanates,” Phys. Status Solidi 160(1), 255–263 (1997) (a). [CrossRef]

] of Pr3+ at the alkaline–earth site by comparison of ionic sizes. The excitation spectrum (Fig. 6a) obtained by monitoring the emission of Pr3+ 1D2-3H4 transition at 612nm mainly consists of three broad bands which are located at 325nm (A), 372nm (B), and 277nm (C), respectively. Band C is due to the 4f 2→4f5d excitation of Pr3+ [32

W. Jia, D. Jia, T. Rodriguez, D. Evans, R. Meltzer, and W. Yen, “UV excitation and trapping centers in CaTiO3: Pr3+ ,” J. Lumin. 119–120, 13–18 (2006). [CrossRef]

], and band B is attributed to low-lying Pr-to-metal (Pr3+-Ti4+) intervalence charge transfer state (CTS) [33

P. Boutinaud, E. Pinel, M. Dubois, A. Vink, and R. Mahiou, “UV-to-red relaxation pathways in CaTiO3: Pr3+ ,” J. Lumin. 111(1-2), 69–80 (2005). [CrossRef]

], and band A arise from the band edge absorption of CaTiO3 host due to O(2p)-Ti(3d) transition [10

P. Diallo, P. Boutinaud, R. Mahiou, and J. Cousseins, “Red luminescence in Pr3+-doped calcium titanates,” Phys. Status Solidi 160(1), 255–263 (1997) (a). [CrossRef]

]. The weak peaks at 460, 481, 490, and 499 nm in the enlarged curve (in Fig. 6a) are due to the f-f transition of Pr3+ from 3H4 to 3P2, 3P1, 1I6 and 3P0 [32

W. Jia, D. Jia, T. Rodriguez, D. Evans, R. Meltzer, and W. Yen, “UV excitation and trapping centers in CaTiO3: Pr3+ ,” J. Lumin. 119–120, 13–18 (2006). [CrossRef]

], respectively. Jia et al. [32

W. Jia, D. Jia, T. Rodriguez, D. Evans, R. Meltzer, and W. Yen, “UV excitation and trapping centers in CaTiO3: Pr3+ ,” J. Lumin. 119–120, 13–18 (2006). [CrossRef]

] found that the relative intensity of the three excitation bands and the peaks of the 4f states depended on the sample synthesis conditions.

Fig. 6 PL excitation (a) and emission (b) spectra of the CaTiO3:0.001 Pr3+ microfibers annealed at 800 °C.

Under the 277 nm excitation, there is no 4f5d→4f 2 luminescence of Pr3+ in CaTiO3: Pr3+, indicating that a nonradiative relaxation from the lowest 4f5d level to the 1D2 state occurs. When phosphors are excited at 325 nm, the spectroscopic behavior can be compared to the behavior of large gap semiconductors (e.g., rare-earth-doped ZnS phosphors), since the excitation of the red luminescence id achieved through the conduction band states of host matrix and then transferred to the 4f shell of Pr3+ ions [10

P. Diallo, P. Boutinaud, R. Mahiou, and J. Cousseins, “Red luminescence in Pr3+-doped calcium titanates,” Phys. Status Solidi 160(1), 255–263 (1997) (a). [CrossRef]

]. The excitation band at 372 nm is ascribed to a low-lying Pr-to-metal (Pr3+-Ti4+) intervalence charge transfer state, as the final nonradiative relaxation pathway is to the emitting 1D2 level in Pr3+ doped CaTiO3 [33

P. Boutinaud, E. Pinel, M. Dubois, A. Vink, and R. Mahiou, “UV-to-red relaxation pathways in CaTiO3: Pr3+ ,” J. Lumin. 111(1-2), 69–80 (2005). [CrossRef]

].

Figure 7 shows the dependence of the photoluminescence (PL) emission intensity and the quantum efficiency on Pr3+ doping concentration (x) in CaTiO3:x Pr3+. It can be found that the PL emission intensity of Pr3+ increases with the increase of its concentration (x) first, reaching a maximum value with Pr3+ concentration of 0.1 mol %, and then decreases with increasing the Pr3+ concentration (x) due to the concentration quenching effect. Thus, the optimum concentration for Pr3+ red emission is 0.1 mol % of Ca2+ in CaTiO3 phosphor. Additionally, the quantum efficiency also increases with Pr3+ concentration (x) rise firstly, have the largest value with Pr3+ concentration of 0.1 mol %, and then decreases with the increase of the Pr3+ concentration (x). The concentration quenching effect gives an example how the deficiencies affect the photoluminescence of CaTiO3:x Pr3+ in the present work. In principle, if two Pr3+ ions occupy two Ca2+ sites, there must generate one Ca vacancies according to charge compensation. More Pr3+ doped into the lattice, more Ca vacancies created. The intensity of photoluminescence decreases significantly by the energy transfer process by cross-relaxation between the Pr3+ neighbors ions and as well energy transfer with Pr3+ and Ca vacancies [34

T. Mazzo, M. Moreira, I. Pinaatti, F. Picon, E. Leite, I. Rosa, J. Varela, L. Perazolli, and E. Longo, “CaTiO3:Eu3+ obtained by microwave assisted hydrothermal method: A photoluminescent approach,” Opt. Mater. (to be published).

].

Fig. 7 PL emission intensity and quantum efficiencies of Pr3+ as a function of its concentration (x) in Ca1-xTiO3:xPr3+ microfibers.

PL emission spectra of CaTiO3:x Pr3+ microfibers with different Pr3+ ion concentrations and the corresponding CIE chromaticity diagram are shown in Fig. 8 . In Fig. 8a, the PL emission intensities have maximum value when the Pr3+ doping concentration is 0.1 mol %, which has been shown in Fig. 7. Figure 8b presents the corresponding CIE chromaticity coordinates positions. The CIE chromaticity coordinates change from x = 0.4119, y = 0.2566 (purplish pink) to x = 0.5934, y = 0.3052 (red) when the doping concentration of Pr3+ ions varying from x = 0.05 mol % to x = 0.1 mol % in CaTiO3:x Pr3+ samples. The corresponding luminescence color can change from purplish pink to red. However, the corresponding luminescence color turns back to pink when increase the Pr3+ doping concentration.

Fig. 8 PL spectra of Ca1-xTiO3:xPr3+ microfibers with different Pr3+ ion concentrations (a) and the corresponding CIE chromaticity diagram (b).

The photoluminescence decay curve of CaTiO3:0.001 Pr3+ fibers is shown in Fig. 9a . The decay curve for the 1D2-3H4 of Pr3+ fit into a double exponential function as I = A1 exp(-t/τ1) + A2 exp(-t/τ2), and the fitting results are shown inside of Fig. 9a. Two lifetimes, a slow one, τ1 = 155.10 μs, and a fast one, τ2 = 37.17 μs, have been obtained for the 612 nm emission of Pr3+. The average lifetime determined to be by the formula τ = (A1τ1 2 + A2τ2 2)/ (A1τ1 + A2τ2) [35

T. Fujii, K. Kodaira, O. Kawauchi, N. Tanaka, H. Yamashita, and M. Anpo, “Photochromic behavior in the fluorescence spectra of 9-anthrol encapsulated in Si- Al glasses prepared by the sol- gel method,” J. Phys. Chem. B 101(50), 10631–10637 (1997). [CrossRef]

]. In Fig. 9b, the lifetime of Pr3+ in CaTiO3:x Pr3+ microfibers increases with the increase of its doping concentration (x) first and then decreases with the increase of its concentration (x), although there is a little increase when x = 0.3 mol % compared with x = 0.2 mol %.

Fig. 9 Decay curve (a) for the luminescence of CaTiO3:0.001 Pr3+ microfibers and lifetime of Ca1-xTiO3:xPr3+ samples as a function of the concentration (x) of Pr3+.

The CaTiO3:x Pr3+ microfibers also exhibit a strong red emission under low voltage excitation. The CL spectrum and photograph for CaTiO3:0.003 Pr3+ under the excitation of electric beam (accelerating voltage = 3 kV, filament current = 100 mA) are shown in Fig. 10a . Different from the PL intensity, the CL intensity of CaTiO3:x Pr3+ have largest value at x = 0.003, it may be because the different excitation mechanisms under UV excitation and low-voltage electron beam. The CL intensity for the CaTiO3:0.003 Pr3+ microfibers phosphor have been investigated as a function of the accelerating voltage and the filament current, as shown in part b and c of Fig. 10, respectively. When the filament current is fix at 100mA, the CL intensity increases with the increase of the accelerating voltage from 1.0 to 3.0 kV (Fig. 10b). Similarly, under a 3.0 kV electron beam excitation, the CL intensity also increases with increasing the filament current from 88 to 100 mA (Fig. 10c). The increase of CL intensity with increasing electron energy and filament current are attributed to the deeper penetration of the electron into the phosphor's body and the larger electron beam current intensity. The electron penetration depth can be estimated by the empirical formula L[Å] = 250(A/ρ)(E/Z 1/2)n, where n = 1.2/(1 – 0.29 log10 Z), A is the atomic or molecule weight of the material, ρ is the bulk density, Z is the atomic number or the number of the electrons per molecule in the case compounds, and E is the accelerating voltage (kV) [36

C. Feldman, “Range of 1-10 kev electrons in solids,” Phys. Rev. 117(2), 455–459 (1960). [CrossRef]

]. For cathodoluminescence, the Pr3+ ions are exited by the plasmons produced by the incident electrons. The deeper the electron penetration depth, the more plasmons will be produced, which results in more Pr3+ ions being excited and thus the CL intensity increase. The corresponding CIE chromaticity diagram (accelerating voltage = 3 kV, filament current = 100 mA) is shown in Fig. 10d. Although the CIE chromaticity coordinates (x = 0.4885, y = 0.3362) locates at yellowish pink, the digital photograph for CaTiO3:0.003 Pr3+ (inset of Fig. 10a) indicate the luminescence is red, same as eye can see.

Fig. 10 The typical cathodoluminescence spectrum of CaTiO3:0.003 Pr3+ microfibers under an electron beam excitation (3 kV) (a), the cathodoluminescence intensity of CaTiO3:0.003 Pr3+ as a function of accelerating voltage (b) and filament current (c) and the corresponding CIE chromaticity diagram (3 kV, 100 mA) (d).

4. Conclusions

A simple and versatile electronspinning method was explored to prepare single-distributed one-dimensional CaTiO3:x Pr3+ microfibers. The diameter of the obtained microfibers ranges from 230 to 360 nm. Under ultraviolet excitation and low-voltage electron beam exaltation, the CaTiO3:x Pr3+ phosphor shows a red (612 nm) emission corresponding to 1D2-3H4 transition of Pr3+, and the CL intensity increases with increasing accelerating voltage and filament current. The optimum doping concentration of Pr3+ is different under ultraviolet excitation and low-voltage electron beam excitation, which is 0.1 mol % and 0.3 mol % of Ca2+ in CaTiO3 microfibers, respectively. The phosphors we synthesized show potential in FED applications.

Acknowledgements

This project is financially supported by the National Basic Research Program of China (2007CB935502, 2010CB327704), and the National Natural Science Foundation of China (NNSFC) (50702057, 50872131, 20921002, 60977013).

References and links

1.

A. Vecht, D. Smith, S. Chadha, C. Gibbons, J. Koh, and D. Morton, “New electron excited light emitting materials,” J. Vac. Sci. Technol. B 12(2), 781–784 (1994). [CrossRef]

2.

X. Liu, P. Jia, J. Lin, and G. Li, “Monodisperse spherical core-shell structured SiO2–CaTiO3: Pr3+ phosphors for field emission displays,” J. Appl. Phys. 99(12), 124902 (2006). [CrossRef]

3.

P. Holloway, T. Trottier, J. Sebastian, S. Jones, X. Zhang, J. Bang, B. Abrams, W. Thomes, and T. Kim, “Degradation of field emission display phosphors,” J. Appl. Phys. 88(1), 483 (2000). [CrossRef]

4.

N. Hirosaki, R. Xie, K. Inoue, T. Sekiguchi, B. Dierre, and K. Tamura, “Blue-emitting AlN: Eu2+ nitride phosphor for field emission displays,” Appl. Phys. Lett. 91(6), 061101 (2007). [CrossRef]

5.

G. Li, C. Li, Z. Hou, C. Peng, Z. Cheng, and J. Lin, “Nanocrystalline LaOCl:Tb(3+)/Sm(3+) as promising phosphors for full-color field-emission displays,” Opt. Lett. 34(24), 3833–3835 (2009). [CrossRef] [PubMed]

6.

L. Wang, X. Liu, Z. Hou, C. Li, P. Yang, Z. Cheng, H. Lian, and J. Lin, “Electrospinning synthesis and luminescence properties of one-dimensional Zn2SiO4: Mn2+ microfibers and microbelts,” J. Phys. Chem. C 112, 18882–18888 (2008).

7.

H. Li, Z. Wang, S. Xu, and J. Hao, “Improved performance of spherical BaWO4: Tb3+ phosphors for field-emission displays,” J. Electrochem. Soc. 156(5), J112 (2009). [CrossRef]

8.

S. Cho, J. Yoo, and J. Lee, “Synthesis and low-voltage characteristics of CaTiO3: Pr3+ luminescent powders,” J. Electrochem. Soc. 143(10), L231 (1996). [CrossRef]

9.

N. Ohtsu, K. Sato, A. Yanagawa, K. Saito, Y. Imai, T. Kohgo, A. Yokoyama, K. Asami, and T. Hanawa, “CaTiO3 coating on titanium for biomaterial application-optimum thickness and tissue response,” J. Biomed. Mater. Res. A 82A(2), 304–315 (2007). [CrossRef]

10.

P. Diallo, P. Boutinaud, R. Mahiou, and J. Cousseins, “Red luminescence in Pr3+-doped calcium titanates,” Phys. Status Solidi 160(1), 255–263 (1997) (a). [CrossRef]

11.

H. Takashima, K. Shimada, N. Miura, T. Katsumata, Y. Inaguma, K. Ueda, and M. Itoh, “Low-driving-voltage electroluminescence in perovskite films,” Adv. Mater. 21(36), 3699–3702 (2009). [CrossRef]

12.

T. Li, M. Shen, L. Fang, F. Zheng, and X. Wu, “Effect of Ca deficiencies on the photoluminescence of CaTiO3: Pr3+ ,” J. Alloy. Comp. 474(1-2), 330–333 (2009). [CrossRef]

13.

B. Yan and K. Zhou, “In situ sol-gel composition of inorganic/organic polymeric hybrid precursors to synthesize red-luminescent CaTiO3: Pr3+ and CaTi0. 5Zr0. 5O3: Pr3+ phosphors,” J. Alloy. Comp. 398(1-2), 165–169 (2005). [CrossRef]

14.

J. Tang, X. Yu, L. Yang, C. Zhou, and X. Peng, “Preparation and Al3+ enhanced photoluminescence properties of CaTiO3: Pr3+ ,” Mater. Lett. 60(3), 326–329 (2006). [CrossRef]

15.

R. Yadav, A. F. Khan, A. Yadav, H. Chander, D. Haranath, B. K. Gupta, V. Shanker, and S. Chawla, “Intense red-emitting Y4Al2O9:Eu3+ phosphor with short decay time and high color purity for advanced plasma display panel,” Opt. Express 17(24), 22023–22030 (2009). [CrossRef] [PubMed]

16.

M. Peng, N. Da, S. Krolikowski, A. Stiegelschmitt, and L. Wondraczek, “Luminescence from Bi2+-activated alkali earth borophosphates for white LEDs,” Opt. Express 17(23), 21169–21178 (2009). [CrossRef] [PubMed]

17.

W. B. Im, Y. Fourré, S. Brinkley, J. Sonoda, S. Nakamura, S. P. DenBaars, and R. Seshadri, “Substitution of oxygen by fluorine in the GdSr2AlO5:Ce3+ phosphors: Gd1-xSr2+xAlO5-xFx solid solutions for solid state white lighting,” Opt. Express 17(25), 22673–22679 (2009). [CrossRef]

18.

S. Yin, D. Chen, W. Tang, and Y. Yuan, “Synthesis of CaTiO3: Pr, Al phosphors by sol-gel method and their luminescence properties,” J. Mater. Sci. 42(8), 2886–2890 (2007). [CrossRef]

19.

M. Lencka and R. Riman, “Thermodynamics of the hydrothermal synthesis of calcium titanate with reference to other alkaline-earth titanates,” Chem. Mater. 7(1), 18–25 (1995). [CrossRef]

20.

X. F. Yang, I. D. Williams, J. Chen, J. Wang, H. F. Xu, H. M. Konishi, Y. X. Pan, C. L. Liang, and M. M. Wu, “Perovskite hollow cubes: morphological control, three-dimensional twinning and intensely enhanced photoluminescence,” J. Mater. Chem. 18(30), 3543–3546 (2008). [CrossRef]

21.

X. Zhang, J. Zhang, X. Ren, and X. Wang, “The dependence of persistent phosphorescence on annealing temperatures in CaTiO3: Pr3+ nanoparticles prepared by a coprecipitation technique,” J. Solid State Chem. 181(3), 393–398 (2008). [CrossRef]

22.

A. de Figueiredo, V. Longo, S. de Lazaro, V. Mastelaro, F. De Vicente, A. Hernandes, M. Siu Li, J. Varela, and E. Longo, “Blue-green and red photoluminescence in CaTiO3: Sm,” J. Lumin. 126(2), 403–407 (2007). [CrossRef]

23.

R. Caruso, J. Schattka, and A. Greiner, “Titanium dioxide tubes from sol-gel coating of electrospun polymer fibers,” Adv. Mater. 13(20), 1577–1579 (2001). [CrossRef]

24.

E. Wong, P. Sheehan, and C. Lieber, “Nanobeam mechanics: elasticity, strength, and toughness of nanorods and nanotubes,” Science 277(5334), 1971–1975 (1997). [CrossRef]

25.

Y. Arakawa and H. Sakaki, “Multidimensional quantum well laser and temperature dependence of its threshold current,” Appl. Phys. Lett. 40(11), 939 (1982). [CrossRef]

26.

A. Formhals, “Process and apparatus for preparing artificial threads,” (US Patents, 1934).

27.

D. Li and Y. Xia, “Electrospinning of nanofibers: reinventing the wheel?” Adv. Mater. 16(14), 1151–1170 (2004). [CrossRef]

28.

Z. Hou, R. Chai, M. Zhang, C. Zhang, P. Chong, Z. Xu, G. Li, and J. Lin, “Fabrication and luminescence properties of one-dimensional CaMoO(4): Ln(3+) (Ln = Eu, Tb, Dy) nanofibers via electrospinning process,” Langmuir 25(20), 12340–12348 (2009). [CrossRef] [PubMed]

29.

G. Dong, Y. Chi, X. Xiao, X. Liu, B. Qian, Z. Ma, E. Wu, H. Zeng, D. Chen, and J. Qiu, “Fabrication and optical properties of Y2O3: Eu3+ nanofibers prepared by electrospinning,” Opt. Express 17(25), 22514–22519 (2009). [CrossRef]

30.

J. Last, “Infrared-absorption studies on barium titanate and related materials,” Phys. Rev. 105(6), 1740–1750 (1957). [CrossRef]

31.

S. Azhari and M. Diab, “Thermal degradation and stability of poly (4-vinylpyridine) homopolymer and copolymers of 4-vinylpyridine with methyl acrylate,” Polym. Degrad. Stabil. 60(2-3), 253–256 (1998). [CrossRef]

32.

W. Jia, D. Jia, T. Rodriguez, D. Evans, R. Meltzer, and W. Yen, “UV excitation and trapping centers in CaTiO3: Pr3+ ,” J. Lumin. 119–120, 13–18 (2006). [CrossRef]

33.

P. Boutinaud, E. Pinel, M. Dubois, A. Vink, and R. Mahiou, “UV-to-red relaxation pathways in CaTiO3: Pr3+ ,” J. Lumin. 111(1-2), 69–80 (2005). [CrossRef]

34.

T. Mazzo, M. Moreira, I. Pinaatti, F. Picon, E. Leite, I. Rosa, J. Varela, L. Perazolli, and E. Longo, “CaTiO3:Eu3+ obtained by microwave assisted hydrothermal method: A photoluminescent approach,” Opt. Mater. (to be published).

35.

T. Fujii, K. Kodaira, O. Kawauchi, N. Tanaka, H. Yamashita, and M. Anpo, “Photochromic behavior in the fluorescence spectra of 9-anthrol encapsulated in Si- Al glasses prepared by the sol- gel method,” J. Phys. Chem. B 101(50), 10631–10637 (1997). [CrossRef]

36.

C. Feldman, “Range of 1-10 kev electrons in solids,” Phys. Rev. 117(2), 455–459 (1960). [CrossRef]

OCIS Codes
(160.2540) Materials : Fluorescent and luminescent materials
(160.4760) Materials : Optical properties
(160.5690) Materials : Rare-earth-doped materials
(300.6280) Spectroscopy : Spectroscopy, fluorescence and luminescence

ToC Category:
Materials

History
Original Manuscript: January 20, 2010
Revised Manuscript: March 12, 2010
Manuscript Accepted: March 14, 2010
Published: March 26, 2010

Citation
Chong Peng, Zhiyao Hou, Cuimiao Zhang, Guogang Li, Hongzhou Lian, Ziyong Cheng, and Jun Lin, "Synthesis and luminescent properties of CaTiO3: Pr3+ microfibers prepared by electrospinning method," Opt. Express 18, 7543-7553 (2010)
http://www.opticsinfobase.org/oe/abstract.cfm?URI=oe-18-7-7543


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References

  1. A. Vecht, D. Smith, S. Chadha, C. Gibbons, J. Koh, and D. Morton, “New electron excited light emitting materials,” J. Vac. Sci. Technol. B 12(2), 781–784 (1994). [CrossRef]
  2. X. Liu, P. Jia, J. Lin, and G. Li, “Monodisperse spherical core-shell structured SiO2–CaTiO3: Pr3+ phosphors for field emission displays,” J. Appl. Phys. 99(12), 124902 (2006). [CrossRef]
  3. P. Holloway, T. Trottier, J. Sebastian, S. Jones, X. Zhang, J. Bang, B. Abrams, W. Thomes, and T. Kim, “Degradation of field emission display phosphors,” J. Appl. Phys. 88(1), 483 (2000). [CrossRef]
  4. N. Hirosaki, R. Xie, K. Inoue, T. Sekiguchi, B. Dierre, and K. Tamura, “Blue-emitting AlN: Eu2+ nitride phosphor for field emission displays,” Appl. Phys. Lett. 91(6), 061101 (2007). [CrossRef]
  5. G. Li, C. Li, Z. Hou, C. Peng, Z. Cheng, and J. Lin, “Nanocrystalline LaOCl:Tb(3+)/Sm(3+) as promising phosphors for full-color field-emission displays,” Opt. Lett. 34(24), 3833–3835 (2009). [CrossRef] [PubMed]
  6. L. Wang, X. Liu, Z. Hou, C. Li, P. Yang, Z. Cheng, H. Lian, and J. Lin, “Electrospinning synthesis and luminescence properties of one-dimensional Zn2SiO4: Mn2+ microfibers and microbelts,” J. Phys. Chem. C 112, 18882–18888 (2008).
  7. H. Li, Z. Wang, S. Xu, and J. Hao, “Improved performance of spherical BaWO4: Tb3+ phosphors for field-emission displays,” J. Electrochem. Soc. 156(5), J112 (2009). [CrossRef]
  8. S. Cho, J. Yoo, and J. Lee, “Synthesis and low-voltage characteristics of CaTiO3: Pr3+ luminescent powders,” J. Electrochem. Soc. 143(10), L231 (1996). [CrossRef]
  9. N. Ohtsu, K. Sato, A. Yanagawa, K. Saito, Y. Imai, T. Kohgo, A. Yokoyama, K. Asami, and T. Hanawa, “CaTiO3 coating on titanium for biomaterial application-optimum thickness and tissue response,” J. Biomed. Mater. Res. A 82A(2), 304–315 (2007). [CrossRef]
  10. P. Diallo, P. Boutinaud, R. Mahiou, and J. Cousseins, “Red luminescence in Pr3+-doped calcium titanates,” Phys. Status Solidi 160(1), 255–263 (1997) (a). [CrossRef]
  11. H. Takashima, K. Shimada, N. Miura, T. Katsumata, Y. Inaguma, K. Ueda, and M. Itoh, “Low-driving-voltage electroluminescence in perovskite films,” Adv. Mater. 21(36), 3699–3702 (2009). [CrossRef]
  12. T. Li, M. Shen, L. Fang, F. Zheng, and X. Wu, “Effect of Ca deficiencies on the photoluminescence of CaTiO3: Pr3+,” J. Alloy. Comp. 474(1-2), 330–333 (2009). [CrossRef]
  13. B. Yan and K. Zhou, “In situ sol-gel composition of inorganic/organic polymeric hybrid precursors to synthesize red-luminescent CaTiO3: Pr3+ and CaTi0. 5Zr0. 5O3: Pr3+ phosphors,” J. Alloy. Comp. 398(1-2), 165–169 (2005). [CrossRef]
  14. J. Tang, X. Yu, L. Yang, C. Zhou, and X. Peng, “Preparation and Al3+ enhanced photoluminescence properties of CaTiO3: Pr3+,” Mater. Lett. 60(3), 326–329 (2006). [CrossRef]
  15. R. Yadav, A. F. Khan, A. Yadav, H. Chander, D. Haranath, B. K. Gupta, V. Shanker, and S. Chawla, “Intense red-emitting Y4Al2O9:Eu3+ phosphor with short decay time and high color purity for advanced plasma display panel,” Opt. Express 17(24), 22023–22030 (2009). [CrossRef] [PubMed]
  16. M. Peng, N. Da, S. Krolikowski, A. Stiegelschmitt, and L. Wondraczek, “Luminescence from Bi2+-activated alkali earth borophosphates for white LEDs,” Opt. Express 17(23), 21169–21178 (2009). [CrossRef] [PubMed]
  17. W. B. Im, Y. Fourré, S. Brinkley, J. Sonoda, S. Nakamura, S. P. DenBaars, and R. Seshadri, “Substitution of oxygen by fluorine in the GdSr2AlO5:Ce3+ phosphors: Gd1-xSr2+xAlO5-xFx solid solutions for solid state white lighting,” Opt. Express 17(25), 22673–22679 (2009). [CrossRef]
  18. S. Yin, D. Chen, W. Tang, and Y. Yuan, “Synthesis of CaTiO3: Pr, Al phosphors by sol-gel method and their luminescence properties,” J. Mater. Sci. 42(8), 2886–2890 (2007). [CrossRef]
  19. M. Lencka and R. Riman, “Thermodynamics of the hydrothermal synthesis of calcium titanate with reference to other alkaline-earth titanates,” Chem. Mater. 7(1), 18–25 (1995). [CrossRef]
  20. X. F. Yang, I. D. Williams, J. Chen, J. Wang, H. F. Xu, H. M. Konishi, Y. X. Pan, C. L. Liang, and M. M. Wu, “Perovskite hollow cubes: morphological control, three-dimensional twinning and intensely enhanced photoluminescence,” J. Mater. Chem. 18(30), 3543–3546 (2008). [CrossRef]
  21. X. Zhang, J. Zhang, X. Ren, and X. Wang, “The dependence of persistent phosphorescence on annealing temperatures in CaTiO3: Pr3+ nanoparticles prepared by a coprecipitation technique,” J. Solid State Chem. 181(3), 393–398 (2008). [CrossRef]
  22. A. de Figueiredo, V. Longo, S. de Lazaro, V. Mastelaro, F. De Vicente, A. Hernandes, M. Siu Li, J. Varela, and E. Longo, “Blue-green and red photoluminescence in CaTiO3: Sm,” J. Lumin. 126(2), 403–407 (2007). [CrossRef]
  23. R. Caruso, J. Schattka, and A. Greiner, “Titanium dioxide tubes from sol-gel coating of electrospun polymer fibers,” Adv. Mater. 13(20), 1577–1579 (2001). [CrossRef]
  24. E. Wong, P. Sheehan, and C. Lieber, “Nanobeam mechanics: elasticity, strength, and toughness of nanorods and nanotubes,” Science 277(5334), 1971–1975 (1997). [CrossRef]
  25. Y. Arakawa and H. Sakaki, “Multidimensional quantum well laser and temperature dependence of its threshold current,” Appl. Phys. Lett. 40(11), 939 (1982). [CrossRef]
  26. A. Formhals, “Process and apparatus for preparing artificial threads,” (US Patents, 1934).
  27. D. Li and Y. Xia, “Electrospinning of nanofibers: reinventing the wheel?” Adv. Mater. 16(14), 1151–1170 (2004). [CrossRef]
  28. Z. Hou, R. Chai, M. Zhang, C. Zhang, P. Chong, Z. Xu, G. Li, and J. Lin, “Fabrication and luminescence properties of one-dimensional CaMoO(4): Ln(3+) (Ln = Eu, Tb, Dy) nanofibers via electrospinning process,” Langmuir 25(20), 12340–12348 (2009). [CrossRef] [PubMed]
  29. G. Dong, Y. Chi, X. Xiao, X. Liu, B. Qian, Z. Ma, E. Wu, H. Zeng, D. Chen, and J. Qiu, “Fabrication and optical properties of Y2O3: Eu3+ nanofibers prepared by electrospinning,” Opt. Express 17(25), 22514–22519 (2009). [CrossRef]
  30. J. Last, “Infrared-absorption studies on barium titanate and related materials,” Phys. Rev. 105(6), 1740–1750 (1957). [CrossRef]
  31. S. Azhari and M. Diab, “Thermal degradation and stability of poly (4-vinylpyridine) homopolymer and copolymers of 4-vinylpyridine with methyl acrylate,” Polym. Degrad. Stabil. 60(2-3), 253–256 (1998). [CrossRef]
  32. W. Jia, D. Jia, T. Rodriguez, D. Evans, R. Meltzer, and W. Yen, “UV excitation and trapping centers in CaTiO3: Pr3+,” J. Lumin. 119–120, 13–18 (2006). [CrossRef]
  33. P. Boutinaud, E. Pinel, M. Dubois, A. Vink, and R. Mahiou, “UV-to-red relaxation pathways in CaTiO3: Pr3+,” J. Lumin. 111(1-2), 69–80 (2005). [CrossRef]
  34. T. Mazzo, M. Moreira, I. Pinaatti, F. Picon, E. Leite, I. Rosa, J. Varela, L. Perazolli, and E. Longo, “CaTiO3:Eu3+ obtained by microwave assisted hydrothermal method: A photoluminescent approach,” Opt. Mater. (to be published).
  35. T. Fujii, K. Kodaira, O. Kawauchi, N. Tanaka, H. Yamashita, and M. Anpo, “Photochromic behavior in the fluorescence spectra of 9-anthrol encapsulated in Si- Al glasses prepared by the sol- gel method,” J. Phys. Chem. B 101(50), 10631–10637 (1997). [CrossRef]
  36. C. Feldman, “Range of 1-10 kev electrons in solids,” Phys. Rev. 117(2), 455–459 (1960). [CrossRef]

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