Comparative characterization of microstructure and luminescence of europium doped hydroxyapatite nanoparticles via coprecipitation and hydrothermal method

Accepted Manuscript Title: Comparative characterization of microstructure and luminescence of europium doped hydroxyapatite nanoparticles via coprecipitation and hydrothermal method Author: Thang-Cao Xuan Nguyen Ngoc Trung Vuong-Hung Pham PII: DOI: Reference: S0030-4026(15)01205-X http://dx.doi.org/doi:10.1016/j.ijleo.2015.09.136 IJLEO 56341 To appear in: Received date: Accepted date: 10-11-2014 11-9-2015 Please cite this article as: T.-C Xuan TrungV.-H Pham Comparative characterization of microstructure and luminescence of europium doped hydroxyapatite nanoparticles via coprecipitation and hydrothermal method, Optik - International Journal for Light and Electron Optics (2015), http://dx.doi.org/10.1016/j.ijleo.2015.09.136 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 proof before it is published in its final 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 Comparative characterization of microstructure and luminescence of europium doped hydroxyapatite nanoparticles via coprecipitation and hydrothermal method ip t Thang-Cao Xuana, Nguyen Ngoc Trung b, Vuong-Hung Phama, * a Advanced Institute for Science and Technology (AIST), Hanoi University of Science and Technology (HUST), No 01, Dai Co Viet road, Hanoi, Vietnam b us cr School of Engineering Physics, Hanoi University of Science and Technology (HUST), No 01, Dai Co Viet road, Hanoi, Vietnam *Corresponding author: Vuong-Hung Pham Ac ce p te d M an [Tel: +84-4-36230435, Fax: 84 43 6230 293, E-mail: vuong.phamhung@hust.edu.vn] Keywords: nanoparticles; luminescence; hydroxyapatite, europium, hydrothermal, Nanobiophosphors Page of 10 Abstract This paper reports the first attempt to compare the microstructure and luminescence of europium doped hydroxyapatite (HA) nanostructure to achieve strong and stable luminescence of hydroxyapatite nanophosphor, ip t particularly, by co-precipitation and hydrothermal synthesis method The Raman spectra analysis indicates that all modes are related to the HA phase The morphology of Eu doped HA nano particles was depended on the cr synthesized method that was observed to have a nanowire structure to nanorod morphology The creation of highly Ac ce p te d M an nanophosphor, which was potential application in nanomedicine us nanocrystalline Eu-doped HA with nanorod morphology resulted in a significantly enhancing luminescence of the Page of 10 Introduction Hydroxyapatite (HA) has received considerable attention in nanomedicine in designing the functional materials because of its highly biocompatibility and easily to acceptation a wide variety of dopants based on ip t flexibility of the apatitic structure [1,2] In order to obtain a nanoparticle for potential application in bioimaging and nanomedicine, a combination of various properties is needed: excellent biocompatiblity, photostability, sphere shape cr nanoparticles [3,4 ] Therefore, considerable effort has been made to functionalize hydroxyapatite nanoparticle by incorporation of its materials with organics dye [5,6], semiconductor quantum dots [7,8], and rare earth elements us [9,10] Organics dyes conjugated into nanoparticles are considered as the effective materials for bioimaging but there is still a risk of photobleaching and in vivo instability because organic dye placed in aqueous biological an environments reduces luminescent intensity over the time [11] Another promising approach to enhance the performance of bioimaging materials is to conjugate their materials with a semiconductor such as CdS [12], ZnSe M [13], and (CdSe) [14], which would not face with late photobleaching but there is still a concern of its late toxicity [15,16] d As one of the rare earth elements, europium has received considerable attention as an activator for doping te into calcium based materials due to their exhibiting importance advantages compared with available phosphor such as lower toxicities, photostabilities, high thermal and chemical stabilities, and high luminescence quantum yield Ac ce p [17,18] Nevertheless, there are only a few reports on the synthesis of luminescence hydroxyapatite for potential applications as bioimaging and nanomedicine [19, 20, 21,22] In particular, in our knowledge, there are no reports on the comparative characterization of the microstructure and luminescence of europium doped HA nanoparticle via coprecipitation and hydrothermal method Therefore, this study reports a way of controlling the microstructure, crystallinities and light emission of the Eu doped HA, as well as the mechanism in a variation of luminescence of two different methods The microstructure and chemical composition of the Eu doped HA were characterized by transmission electron microscope (TEM) The crystal structure of the specimen was characterized by Raman spectroscopy The luminescence was also determined by photoluminescence Page of 10 Experimental procedure Europium doped hydroxyapatite was synthesized through a coprecipitation and hydrothermal method, as follows: an aqueous solution with stoichiometric amount of (NH4)2 HPO4 (0.2M, 99% purity, Aldrich) were added ip t over an aqueous solution containing Ca (NO3)2 4H2O (0.2M, 99% purity, Aldrich), and 0.3 mol % Eu(NO3)3 Eu(NO3)3 were obtained by dissolving stoichiometric Eu2O3 (99% purity, Aldrich) in HNO3 with vigorous stirring cr The reaction mixture was stirred for 0.5 h followed by precipitation method at 80 oC and the pH was adjusted to 11 by using aqueous ammonia For hydrothermal synthesis, the mixture was transferred into 200 ml Teflon-lined us autoclave, and then the autoclave was sealed and maintained at 150 oC for 12 h The resulting precipitates were washed three times, and then dried at 100 oC for 6h The crystalline structures of the Eu doped HA were an characterized by a micro Raman spectroscopy (Renishaw, United Kingdom) The microstructure of the Eu doped HA was determined by field emission scanning electron microscopy (JEOL, JSM-6700F, JEOL Techniques, Tokyo, M Japan) Photoluminescence (PL) tests were performed to evaluate the optical properties of the Eu doped HA NANO LOG spectrofluorometer (Horiba, USA) equipped with 450 W Xe arc lamp and double excitation te Results and discussion The PL spectra were recorded automatically during the measurements d monochromators was used Ac ce p Figures (A) and (B) show the typical Raman patterns of the Eu doped HA processed with the variation of synthesis method The coprecipitation specimen of Eu doped Si-HA showed a Raman shift = ~ 962 cm-1 corresponding to the symmetric stretching ν mode of PO4 3- of the crystalline hydroxyapatite, as well as peaks at Raman shift = ~ 433 cm-1 was attributed to bending ν of the PO4 3- ion (Fig (A)) On the other hand, when a hydrothermal synthesis was applied, strong Raman peak situated at about ~ 962 cm-1 and ~ 433 cm-1 was assigned to the to the symmetric stretching ν mode of PO4 3- and bending ν of the PO4 3-, respectively with additional peak at 1054 cm -1 corresponding to the antisymmetric stretching ν of the PO4 3- ion (Fig (B) These results indicate that all Raman modes are related to the HA phase Page of 10 Fig Raman spectra of Eu doped HA (A) co- us cr ip t precipitation, (B) hydrothermal method an The representative microstructure of the Eu doped HA nanophosphor was characterized by TEM, as shown in Figs (A) – (D) The co-precipitation specimen showed a long nanowire microstructure (Fig 2(A)) with length M up to 500 nm and diameter less than 50 nm On the other hand, the hydrothermal specimen showed nanorod-like morphology with aspect ratio of (Fig 2(C)), which is expected to enhance luminescence due to the high packing d density and reduction of light scattering Electron diffraction (ED) revealed that all the Eu doped HA displayed te nanocrystal materials However, it should be noted that the crystalline of the sample increases with the hydrothermal method Ac ce p synthesis method (Fig 2(D), which is due to the application of higher synthesis temperature via hydrothermal Fig TEM and Electron diffraction (ED) analysis of the Eu doped HA ((A), (B)): coprecipitation, ((C), (D)): hydrothermal Page of 10 The photoluminescence of the Eu doped HA were evaluated by photoluminescence spectroscopy (PL), a nondestructive method which is very useful for analyzing the efficiency of trapping, migration and transfer of charge carriers and understanding the crystallization behavior of the luminescent materials [23,24] The typical photoluminescence spectra of the Eu doped HA are shown in Figs All the Eu doped HA showed strong visible Do F3 , 5Do Do F1, 5Do 7 F2, ip t emission peaks appeared at about 590, 616, 650 and 700 nm and they can attributed to the F4 transitions within Eu3+ ion, respectively However, it should be noted that PL intensity of Eu cr doped HA increased with the sample prepared by hydrothermal method It is well known that the coprecipitation us method that generally creates amorphous or less crystalline materials, the hydrothermal technique allows for the creation of well-crystalline structure via higher temperature [25,26,27] The enhancing PL intensities of Eu doped an HA should be mainly due to their well-crystalline of the sample prepared by hydrothermal method Fig Photoluminescence spectra of Eu hydrothermal method Ac ce p te d M doped HA with coprecipitation and Conclusions We herein demonstrated that the photoluminescence of hydroxyapatite could be obtained effectively by doping with rare earth europium The Raman spectra analysis indicates the formation of HA single phase Photoluminescence intensity of the Eu doped HA increases on the sample prepared by hydrothermal method with the characteristic emission of Eu 3+ This enhancement of the PL was mainly attributed to the particle morphology Page of 10 and well-crystalline material via hydrothermal method These phosphors show potential application in nanomedicine where require a combination of biocompatibility and light emission Acknowledgment ip t This research is funded by Vietnam National Foundation for Science and Technology Development (NAFOSTED) under grant number “103.99-2013.05” Author acknowledges technical support for TEM imaging cr from Bui Van Dong, Geology, Geotechnique, Geo-environment Climate Change lab, Vietnam National University us References [1] A.A Chaudhry, S Haque, S Kellici, P Boldrin, I Rehman, F.A Khalid, J.A Darr, Instant nano-hydroxyapatite: an a continuous and rapid hydrothermal synthesis, Chem Commun (2006) 2286-2288 M [2] C Yang, P Yang, W Wang, S Gai, J Wang, M Zhang, J Lin, Synthesis and characterization of Eu-doped hydroxyapatite through a microwave assisted microemulsion process, Solid State Sci 11 (2009) 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diffraction (ED) analysis of the Eu doped HA ((A), (B)): coprecipitation, ((C), (D)): ip t hydrothermal Ac ce p te d M an us cr Fig Photoluminescence spectra of Eu doped HA with coprecipitation and hydrothermal method Page 10 of 10 .. .Comparative characterization of microstructure and luminescence of europium doped hydroxyapatite nanoparticles via coprecipitation and hydrothermal method ip t Thang-Cao... nanoparticles; luminescence; hydroxyapatite, europium, hydrothermal, Nanobiophosphors Page of 10 Abstract This paper reports the first attempt to compare the microstructure and luminescence of. .. of europium doped hydroxyapatite (HA) nanostructure to achieve strong and stable luminescence of hydroxyapatite nanophosphor, ip t particularly, by co-precipitation and hydrothermal synthesis method