Author’s Accepted Manuscript

Effects of Fe doping on photoluminescent and

magnetic properties of CaTiO3:Eu3+

Jianchao Xia, Huamei Li, Huilin You, Zheng Wu,

Jie Chen, Zhigang Lu, Lin Chen, Mengshuang
Wang, Yanmin Jia
www.elsevier.com/locate/ceri

PII: S0272-8842(18)32290-9
DOI: https://doi.org/10.1016/j.ceramint.2018.08.215
Reference: CERI19250
To appear in: Ceramics International
Received date: 31 July 2018
Revised date: 15 August 2018
Accepted date: 19 August 2018
Cite this article as: Jianchao Xia, Huamei Li, Huilin You, Zheng Wu, Jie Chen,
Zhigang Lu, Lin Chen, Mengshuang Wang and Yanmin Jia, Effects of Fe doping
on photoluminescent and magnetic properties of CaTiO3:Eu3+, Ceramics
International, https://doi.org/10.1016/j.ceramint.2018.08.215
This is a PDF file of an unedited manuscript that has been accepted for
publication. As a service to our customers we are providing this early version of
the manuscript. The manuscript will undergo copyediting, typesetting, and
review of the resulting galley proof before it is published in its final citable form.
Please note that during the production process errors may be discovered which
could affect the content, and all legal disclaimers that apply to the journal pertain.
 Effects of Fe doping on photoluminescent and magnetic properties of

CaTiO3:Eu3+

Jianchao Xia1, Huamei Li1, Huilin You1, Zheng Wu2,*, Jie Chen1 , Zhigang Lu1 , Lin Chen1,

Mengshuang Wang1 , Yanmin Jia1,*

1
Department of Physics, Zhejiang Normal University, Jinhua 321004, China;

2
College of Geography and Environmental Sciences, Zhejiang Normal University, Jinhua,

321004, China

wuzheng@zjnu.edu.cn (Z. Wu)

ymjia@zjnu.edu.cn (Y. Jia).

*Corresponding authors.

Abstract

In this work, photoluminescent and ferromagnetic bifunctional properties were found in

Fe-doped CaTiO3:Eu3+ ceramic materials synthesized via ceramic sintering method. With

appropriate amount of Fe doping in CaTiO3:Eu3+ ceramic, both photoluminescent intensities

and magnetization strength of samples increase. When doping content of Fe is 0.05 mol%,

the ceramic has optimal photoluminescent intensity. After 0.05 mol% Fe-doped CaTiO3:Eu3+

ceramic material experiences 0.15 T external magnetic treatment for 12 h, main red emission

at 615 nm ([5D0→7F2]) increases ~80%, and 593 nm emission ([5D0→7F1]) increases ~109%.

This study is helpful for understanding effects of Fe doping on photoluminescent and

magnetic properties of CaTiO3:Eu3+ ceramic and provides valuable reference for effects of Fe

impurities on photoluminescent and magnetic properties of other materials.

1
Keywords

Powders: solid state reaction; Magnetic properties; Functional applications.

1. Introduction

Perovskite-structured calcium titanate (CaTiO3), which is one of the most important

oxides, has been extensively studied because of its good mechanical resistance and corrosion

resistance [1-3]. In recent years, rare earth ions have been doped into CaTiO3 to enhance

luminescence properties and capacitance response for applications in field emission display

devices [4-6]. Among all of forms of CaTiO3 doped with rare earth ions, trivalent europium

(Eu3+) ion-doped CaTiO3 has attracted considerable attention because of its potential

application as red phosphors under near ultraviolet excitation [7-9].

Iron (Fe), which is one of the most abundant metal elements in the earth, is always

present in synthesized ceramic materials because of the purity of raw chemical materials [10].

Fe impurities may have an impact on photoluminescent and magnetic properties. Therefore,

it is imperative to determine what the effects of Fe doping are on photoluminescent and

magnetic properties of CaTiO3:Eu3+.

In this work, Fe-doped CaTiO3:Eu3+ ceramic materials were synthesized via a ceramic

sintering method. The ceramic displays photoluminescent and ferromagnetic bifunctional

properties. An appropriate amount of Fe doping in CaTiO3:Eu3+ ceramic may lead to

enhanced photoluminescent intensities and magnetization strength. When the doping content

of Fe is 0.05 mol%, the ceramic has optimal photoluminescent intensity.

2
2. Materials and testing methods

Ca0.95Eu0.05TiO3:xFe ceramics with different values of x were prepared using a ceramic

sintering method. All raw materials used were spectral grade in purity. Powder mixtures of

CaCO3, TiO2, and Eu2O3 in a stoichiometric composition were mixed with various amounts

of Fe3O4 and alcohol; the mixture was then dried and calcined at 900 °C for 4 h in air. The

powder was then mixed with polyvinyl alcohol solution and formed under pressure into

disk-shaped samples with diameter of 10 mm. Finally, the sample was sintered at 1400 °C for

4 h in a Nabertherm YFX5/16Q-YC type furnace (China).

X-ray diffraction (XRD) patterns of ceramic powders were recorded using an X’Pert

PRO SUPER X-ray powder diffractometer (the Netherlands) with Cu Kα radiation (λ=0.1541

nm). Photoluminescence and photoluminescence excitation spectra were recorded using an

FLS920 spectrofluorometer (UK). Magnetization-magnetic field (M-H) loops were measured

using a PPMS-9 physical properties measurement system (USA).

3. Results and discussion

XRD patterns of CaTiO3:5 mol% Eu3+ (CTE) with different Fe-doping concentrations (0

mol%, 0.05 mol%, 0.1 mol%, 0.2 mol%, 0.3 mol%, 0.5 mol%, and 0.7 mol%) are shown in

Fig. 1(a). Because of substitution of Ca2+ by the Eu3+ in the A site of CaTiO3 samples, a small

shift in peak position is observed, according to JCPDS card No. 22-0153 [11]. Expanded

XRD patterns of the (200) diffraction peak in the range of 32.5º-33.5º are shown in Fig. 1(b).

When the Fe-doping concentration is 0.3 mol%, there is an obvious shift toward low angle

sides, and this may be due to variation in the lattice parameter of CTE [12].

3
 Fig. 2 displays excitation and emission spectra of 0.05 mol% Fe-doped CTE. Under

excitation around 465 nm, the samples show strong red emission, which has a broad band

feature associated with the 5D0→7FJ (J=1, 2, 3, 4) transition of Eu3+ in CaTiO3 [13]. Sharp

peaks around 593 nm, 615 nm, 654 nm, and 692 nm are obviously observed, and the main

emission peak is 615 nm. Therefore, the excitation spectrum is characterized at an emission

wavelength of ~615 nm. Sharp peaks around 362 nm, 377 nm, 382 nm, 394 nm, 415 nm, and

465 nm are clearly observed in Fig. 2, and these may be attributed to 7F0→5D4, 7F0→5L7,

7
F0→5G2, 7F0→5L6, 7F0→5D3, and 7F0→5D2 transitions, respectively [14,15]. The excitation

band of Fe-doped CTE covers the emission wavelength of all commercial blue light-emitting

diodes (450 nm-470 nm), which implies that Fe-doped CTE is a potential candidate for

red-emission fluorescent materials.

Fe concentration dependence on the intensity of the 5D0→7F2 transition of Fe-doped

CTE is shown in Fig. 3, and the luminescent intensity of pure CTE is defined as the reference.

With an increase in Fe concentration, the emission intensity first shows an increase. When the

Fe-doped concentration is 0.05 mol%, the emission intensity reaches a maximum. When the

Fe-doped concentration exceeds 0.05 mol%, the emission intensity is strongly quenched

because of photo-excited electrons that are preferentially captured by trap centers generated

by Fe3+ ions [16-18].

Emission spectra of 0.05 mol% Fe-doped CTE under a 0.15 T magnetic field for 0 and

12 h are shown in Fig. 4. In practical applications, a low magnetic direct-current (DC) field

can be directly provided using common magnets such as commercial NdFeB magnets [19].

After 12 h of external magnetic field treatment, the luminescence intensities under an

4
excitation of 465 nm (emission peaks of 615 nm [5D0→7F2] and 593 nm [5D0→7F1]) of 0.05

mol% Fe-doped CTE increase compared to those with 0 h of external magnetic field

treatment. The main red emission of 615 nm ([5D0→7F2]) increases ~80%, and the 593 nm

emission ([5D0→7F1]) increases ~109%. [5D0→7F1] is a magnetic dipole transition, and

[5D0→7F2] is an electric dipole transition that is sensitive to the environment around Eu3+ [11].

The increased fluorescence intensity after experiencing treatment with an external magnetic

field may be because of the weakened effect of electronic cross-relaxation under the magnetic

field. On the other hand, under a magnetic field, the absorption peak moves close to the

exciting resonance line, and this increases the absorbance at the excitation wavelength and

further induces an increase in photoluminescent intensity [20].

M~H loops of pure CTE and 0.05 mol % Fe-doped CTE samples at 5 K and 300 K are

shown in Fig. 5. M-H loops of 0 and 0.05 mol% Fe-doped CTE samples are nonlinear at 5 K.

With 0.05 mol% Fe doping, the linearization of the M-H loop at 300 K increases, and this

indicates that iron-iron super-exchange at high temperature is dominant [14]. Also, the

magnetization strength of the 0.05 mol% Fe-doped CTE sample is higher than that of pure

CTE, although the magnetization strength is not very high [21]. The results show that an

appropriate amount of Fe doping may enhance magnetization strength.

4. Conclusions

In this work, it is found that with an appropriate amount of Fe doping, the CaTiO3:Eu3+

ceramic material displays enhanced photoluminescent and magnetic properties. When the

doping content of Fe is 0.05 mol%, the ceramic has optimal photoluminescent intensity. After

5
0.05 mol% Fe-doped CaTiO3:Eu3+ ceramic material experiences 0.15 T external magnetic

treatment for 12 h, main red emission at 615 nm ([5D0→7F2]) increases ~80%, and 593 nm

emission ([5D0→7F1]) increases ~109%. This study is helpful for determining the effects of

Fe doping on photoluminescent and magnetic properties of CaTiO3:Eu3+ ceramic.

Acknowledgements

This work was supported by the National Natural Science Foundation of China

(51502266), the Public Welfare Technology Application Research Project of Zhejiang

Province, China (LGG18E020005), and Zhejiang Xinmiao Talent Project

(2018R404021).

References

[1] K.S. Srikanth, S. Patel, S. Steiner, R. Vaish, Pyroelectric signals in

(Ba,Ca)TiO3-xBa(Sn,Ti)O3 ceramics: A viable alternative for lead-based ceramics, Scr. Mater.

146 (2018) 146-149.

[2] X.M. Zhang, J.H. Zhang, Z.G. Nie, M.Y. Wang, X.G. Ren, X.J. Wang, Enhanced red

phosphorescence in nanosized CaTiO3:Pr3+ phosphors, Appl. Phys. Lett. 90 (2007) 151911.

[3] X.F. Yuan, X.B. Shi, M.R. Shen, W. Wang, L. Fang, F.G. Zheng, X.L. Wu, Luminescent

properties of Pr3+ doped (Ca, Zn) TiO3: powders and films, J. Alloys Comp. 485 (2009)

831-836.

[4] X. Liu, P. Jia, J. Lin, G. Li, Monodisperse spherical core-shell structured

SiO2-CaTiO3:Pr3+ phosphors for field emission displays, J. Appl. Phys. 99 (2006)

6
124902-124909.

[5] G. Phaomei, W.R. Singh, R.S. Ningthoujam, Solvent effect in monoclinic to hexagonal

phase transformation in LaPO4:RE (RE=Dy3+, Sm3+) nanoparticles: Photoluminescence study,

J. Lumin. 131 (2011) 1164-1171.

[6] C.S. Lewis, H. Liu, J. Han, L. Wang, S. Yue, N.A. Brennan, S.S. Wong, Probing charge

transfer in a novel class of luminescent perovskite-based heterostructures composed of

quantum dots bound to RE-activated CaTiO3 phosphors, Nanoscale 8 (2016) 2129-2142.

[7] Y. Wu, Z. Sun, K. Ruan, Y. Xu, H. Zhang, Enhancing photoluminescence with Li-doped

CaTiO3:Eu3+ red phosphors prepared by solid state synthesis, J. Lumin. 155 (2014) 269-274.

[8] S. Som, A.K. Kunti, V. Kumar, V. Kumar, S. Dutta, M. Chowdhury, S.K. Sharma, J.J.

Terblans, H.C. Swart, Defect correlated fluorescent quenching and electron phonon coupling

in the spectral transition of Eu3+ in CaTiO3 for red emission in display application, J. Appl.

Phys. 115 (2014) 193101.

[9] S. Som, S. Dutta, V. Kumar, A. Pandey, V. Kumar, A.K. Kunti, J. Priya, S.K. Sharma, J.J.

Terblans, H.C. Swart, CaTiO3:Eu3+, a potential red long lasting phosphor: energy migration

and characterization of trap level distribution, J. Alloys Comp. 622 (2015) 1068-1073.

[10] N. Dauphas, M. Roskosz, E.E. Alp, D.R. Neuville, M.Y. Hu, C.K. Sio, F.L.H. Tissot, J.

Zhao, L. Tissandier, E. Médard, C. Cordier, Magma redox and structural controls on iron

isotope variations in Earth's mantle and crust, Earth Planet. Sc. Lett. 398 (2014) 127-140.

[11] M. Shivram, S.C. Prashantha, H. Nagabhushana, S.C. Sharma, K. Thyagarajan, R.

Harikrishna, B.M. Nagabhushana, CaTiO3:Eu3+ red nanophosphor: low temperature synthesis

and photoluminescence properties, Spectrochim. Acta A: Mol. Biomol. Spectrosc. 120 (2014)

7
395-400.

[12] S-J. Han, J.W. Song, C.-H. Yang, S.H. Park, J.-H. Park, Y.H. Jeong. A key to room

temperature ferromagnetism in Fe-doped ZnO:Cu, Appl. Phys. Lett. 81 (2002) 4212-4214.

[13] T. M. Mazzo, M. L. Moreira, I. M. Pinatti, F. C. Picon, E. R. Leite, I. L. V. Rosa, J. A.

Varela, L. A. Perazolli, E. Longo, CaTiO3:Eu3+ obtained by microwave assisted hydrothermal

method: a photoluminescent approach, Opt. Mater. 32 (2010) 990-997.

[14] C.-H. Liang, Y.-C. Chang, Y.-S. Chang, Synthesis and photoluminescence characteristics

of color-tunable BaY2ZnO5:Eu3+ phosphors, Appl. Phys. Lett. 93 (21), 211902 (2008).

[15] J. Fu, Q. Zhang, Y. Li, H. Wang, Preparation and photoluminescence characteristics of a

new promising red NUV phosphor CaTiO3:Eu3+, J. Alloys Comp. 485 (2009) 418-421.

[16] C. Jiang, L. Fang, M. Shen, F. Zheng, X. Wu, Effects of Eu substituting positions and

concentrations on luminescent, dielectric, and magnetic properties of SrTiO3 ceramics, Appl.

Phys. Lett. 94 (2009) 071110.

[17] M.V. Limaye, S.B. Singh, R. Das, P. Poddar, S.K. Kulkarni, Room temperature

ferromagnetism in undoped and Fe doped ZnO nanorods: Microwave-assisted synthesis, J.

Solid State Chem. 184 (2011) 391-400.

[18] Y.S. Wang, P. J. Thomas, P. O’ Brien, Optical properties of ZnO nanocrystals doped with

Cd, Mg, Mn, and Fe Ions, J. Phys. Chem. B 110 (2006) 21412-21415.

[19] R. K. Zheng, Y. Wang, H. L. W. Chan, C. L. Choy, and H. S. Luo, Control of the strain

and magnetoresistance of LaMnO3+δ thin films using the magnetostriction of Terfenol-D alloy,

J. Appl. Phys. 108 (2010) 124103.

[20] J. Zhang, Z. Ma, J. Han, G. Du, Y. Zhou, L. Li, Z. Cheng, Absorption induced

8
photoluminescence intensity modulation of Er3+:YVO4 single crystal under pulsed high

magnetic field, J. Lumin. 144 (2013) 53-56.

[21] X.X. Wei, C. Song, K.W. Geng, F. Zeng, B. He, F. Pan, Local Fe structure and

ferromagnetism in Fe-doped ZnO films, J. Phys.-Condens. Mat. 18 (2006) 7471-7479.

Fig. 1 The XRD patterns of CTE samples with different Fe-doping concentrations. (a) XRD

pattern in a wide angle range. (b) The expanded XRD patterns of (200) diffraction peak in the

range of 32.5º-33.5º.

Fig. 2 The excitation (λem=615 nm) and emission (λex=465 nm) spectra of 0.05 mol %

Fe-doped CTE sample.

Fig. 3 The intensity of the 5D0→7F2 transition of Fe-doped CTE versus Fe concentration. The

luminescent intensity of the pure CTE is defined as 1.

Fig. 4 The emission spectrum of 0.05 mol % Fe-doped CaTiO3:Eu3+ after experiencing 0.15 T

external magnetic field treatments for 12 h.

Fig. 5 The M~H loops for the pure CTE and 0.05 mol % Fe-doped CTE samples at 5 K and

300 K temperatures.

9
10
11
12