Beruflich Dokumente
Kultur Dokumente
Le Quoc Minh
Institute of Materials Science,
Vietnam Academy of Science and Technology,
18 Hoang Quoc Viet, Cau Giay distr., Hanoi, Vietnam
and
College of Technology,
Vietnam National University of Hanoi,
144 Xuan Thuy, Hanoi, Vietnam
E-mail: lequocminhvn@gmail.com
Reference to this paper should be made as follows: Anh, T.K., Loc, D.X.,
Huong, T.T., Vu, N. and Minh, L.Q. (2011) Luminescent nanomaterials
containing rare earth ions for security printing, Int. J. Nanotechnol., Vol. 8,
Nos. 3/4/5, pp.335346.
Biographical notes: Tran Kim Anh graduated from Hanoi University in 1970,
received her PhD in Physics from the Institute of Physics, Polish Academy of
Science, Warsaw, Poland, in 1988. She has been an Associate Professor since
1996. She has been the Director of Physics and Chemistry of Advanced Optical
Materials Laboratory since 1998. She received the National Award (group) on
Sciences and Technology in 2005. She has been a Director of Research since
2009. Her research interests include physics and technology of luminescent
nanomaterials containing rare earth ions and nano-structured semiconductors
including ZnO and ZnS as well as planar waveguide.
Dinh Xuan Loc graduated from Hanoi University in 1990, received Masters
Degree in Chemistry in 1999 and has been a Senior Researcher since 2008.
He is currently doing his PhD thesis at the Institute of Materials Science,
Vietnam Academy of Science and Technology. His research interests include
nanomaterials containing rare earth and transition metal ions.
Tran Thu Huong received her Bachelors Degree in Chemistry. She did her
Masters Degree at the International Training Institute of Materials Science in
1999. She received her Doctorate of Philosophy in Materials Science from the
Institute of Materials Science, Vietnam Academy of Science and Technology,
in 2007. Her research interests include luminescent nanomaterials containing
rare earth ions and planar waveguide. She received the Vallet Scholarship
20062007.
1 Introduction
time-resolved and spectrally resolved studies. Many report, for example, about the
applications of nanoparticles in biophotonics [2], luminescent nanomaterials for
biological labelling [3], functionalised europium nanorods for in vitro imaging [4],
development of new ink materials based on luminescent nanomaterials for the security
labels of printing products such as passport and visa documents has encouraged research
in this direction [5]. We studied luminescence, energy transfer and up-conversion
mechanism of Y2O3 doped with Eu3+, Tb3+, Tm3+, Er3+ and Yb3+ ions [6], and security
labels is attractive application. Figure 1 shows an image under UV exposure of a
European visa for corresponding author, in which security part was made with
luminescent materials.
This paper reports on the preparation of luminescent nanomaterials from YVO4:Eu3+,
ZnS:Mn2+, and CePO4:Tb3+ for two important spectral fields at red and green regions.
Their structures, nanoform and optical properties, especially luminescence behaviour,
were shown to depend on preparation conditions and allowed us to obtain a high
luminescence efficiency, nanosize and fine distribution in the liquid phase. We present
also the fabrication capacity of a new ink based on the obtained luminescent
nanomaterials for screen or inkjet printing technology.
Figure 1 Security printing for a European visa (see online version for colours)
2 Experiment
The suspension was centrifuged at 3000 rpm for 10 min. The supernatant was discarded.
The precipitate was suspended in 30 ml deionised water and centrifuged again for several
times. The powder of the nanoparticles was obtained by removing ethanol, which was
treated at 60C for several hours.
Silica coating of the YVO4:Eu3+ nanoparticles
YVO4:Eu3+ nanomaterials were prepared by co-precipitate method. The synthesis
procedure of YVO4:Eu3+ nanoparticles is as follows: The Na3VO4 powder was
completely dissolved in 50 ml of deionised water. Y(NO3)3.6H2O, 99.8%, and
Eu(NO3)3.5H2O, 99.9%, were added to the solution in a 100 ml round-bottomed flask and
this was followed by a magnetic stirring for 120 min. The pH of the solution after the
reaction was in the range of 1212.5 by using 1M NaOH solution. The content ratio of
Y3+ and Eu3+ were 0.9/0.1 moles, respectively. After that, the solution was poured into a
Teflon-lined stainless steel autoclave and heated at 200C from 20 h to 40 h, and then
cooled down slowly to room temperature. The resulting products were collected, and
centrifuged at 5900 rpm, washed several times using water, and then air-dried at 60C for
several hours.
5 ml of an aqueous solution of tetraethylorthosilicate (TEOS) and isopropanol
were mixed in a 100 ml round-bottomed flask. Then, YVO4:Eu3+ nanoparticles were
added to the same flask. The resulting solution was stirred at ambient temperature for 2 h.
The obtained mixture was then refluxed for 24 h. The grafted colloids were finally
purified by ultrafiltration.
Preparation of ZnS:Mn2+ nanoparticles
ZnS:Mn2+ nanomaterials were prepared by co-precipitate method from Zn(CH3COO)2,
Mn(CH3COO)2 and (NH4)2Sx with different concentration of Mn of 0.01, 0.025 and 0.05
at%. Polyvinyl alcohol (PVA) was used as the polymer matrix. Metal solution was mixed
with PVA solution with the weight ratio of metal acetate to PVA of 1/3 for about one
hour while being stirred at 80C. Then, (NH4)2Sx solution was added drop-wise into the
solution above while stirring. The emulsion was vigorously agitated using a magnetic
stirrer for one hour more. The ZnS:Mn2+ nanoparticles were separated from the solution
by centrifugation and washed several times in hot water and ethanol. The powder
of the nanoparticles was obtained by removing the ethanol after being dried at 7080C
for 23 h.
Preparation of CePO4:Tb3+/LaPO4 core/shell nanoparticles
Recently, CePO4:Tb3+ nanorods and nanowires were studied [8,9]. In our laboratory,
CePO4:Tb3+ core nanoparticles were synthesised as follows: two aqueous solutions of
Ce(NO3)3 and Tb(NO3)3 were mixed in an appropriate molar ratio. The solution was
concentrated by heating at 80C until the excess free water had evaporated. The mixture
was dissolved in methanol. Then, tris(2-ethylhexyl)phosphate (TEHP) was added to the
solution under a vacuum at 80C, the water and the methanol ingredients contained
in the solution were distilled away. A freshly prepared solution of crystalline phosphoric
acid dissolved in a mixture of trioctylamine and TEHP was added into the metal solution.
The resulting microemulsion solution was transferred into a stainless Teflon-lined
autoclave and heated at 200C for 4 h. The resulting suspension was naturally cooled
down to room temperature to get to the CePO4:Tb3+ core nanoparticles.
Luminescent nanomaterials containing rare earth ions for security printing 339
2.2 Characterisation
The YVO4:Eu3+, CePO4:Tb3+, and ZnS:Mn2+ nanoparticles were analysed by the D-5000
X-ray diffractometer (Siemens) with Cu K radiation. The morphology of the samples
was observed by using a transmission electron microscope (TEM, JEM-1010)
and a field emission scanning electron microscope (FE-SEM, Hitachi, S-4800).
The photoluminescent (PL) measurements were performed at room temperature by using
a cw He-Cd laser (325 nm) as the excitation source, a Spectrapro 2300i monochromator
(Acton) as the dispersive unit, and a Pixis 256 CCD (Acton) as the detector. PL spectra
of the nanoparticles were also measured by using a spectrometer system Horiba Jobin
Yvon IHR 550 after being excited at 370 nm by a diode. Different wavelengths of
254 nm, 277 nm and 365 nm were used for our studies and applications.
A TEM image of ZnS:Mn2+ is presented in Figure 3. Figure 4 shows a TEM image of the
YVO4:Eu3+ nanoparticles prepared by hydrothermal synthesis. It can be seen from the
figures that the YVO4:Eu3+ sample occurs through the aggregation of the nanocrystals
exhibiting sizes of about 20 nm.
intense peak at 543 nm corresponding to the 5D47F5 transition. Three other peaks are
observed at 489 nm (5D47F6), 583 nm (5D4 7F4), 618 nm (5D47F3), respectively.
Comparing PL intensity of CePO4:Tb3+ nanoparticles and CePO4:Tb3+/LaPO4 core/shell
nanoparticles, it is noted that the PL intensity of CePO4:Tb3+/LaPO4 core/shell sample is
about 20 times higher than that of CePO4:Tb3+ sample.
Figure 6 PL spectra of YVO4:Eu3+ nanoparticles for 5, 3, 7, 1 at.% from top to bottom under
370 nm excitation (see online version for colours)
342 T.K. Anh et al.
The PL spectra of the YVO4:Eu3+ nanoparticles and the YVO4:Eu3+ with core-shell
structure nanoparticles displayed red emission with narrow peaks corresponding to the
intra-4f (5D07Fj, j = 1, 2, 3, 4) transitions of Eu3+ ions.
The peaks were found at 594 nm (5D07F1), 619 nm (5D07F2), 652 nm (5D07F3), and
702 nm (5D47F4), with the strongest emission at 619 nm. One can observe from the peak
at 619 nm that the PL intensity of the SiO2 coated sample is higher than that of the
uncoated one.
3.3 Application
Nano Y2O3 doped with Er3+, Yb3+ was used to prepare infrared cards [11]. Labelled
microplaces were printed using screen technique or inkjet technology [12]. The
CorelDraw, Photoshop and Colour system of RGB (Red, Green, Blue) and CMYK
printing system controlled the inkjet machine and produced the labelled images. Some
different printing samples demonstrate the application (Figure 9).
Luminescent nanomaterials containing rare earth ions for security printing 343
Figure 9 Lotus image of Vietnam Airline logo and VIETNAM letter using ZnS:Mn2+ /PVA
under UV lamp (see online version for colours)
Figure 10 Solution of nanomaterials from CePO4:Tb3+ under a UV lamp (see online version
for colours)
Figure 11 Photo images of the luminescent security on Vietnamese passport and a European visa
under UV lamp (see online version for colours)
344 T.K. Anh et al.
4 Conclusion
Acknowledgements
We are very grateful to Prof. Acad Nguyen Van Hieu, National independent research
project 2/2/742 DTDL NN 2009-2012, the Vietnam Academy of Science and
Technology, Key Laboratory for Electronic Materials and Device, Institute of Materials
Science, Vietnam Television (VTV2), Prof. Pham Thi Minh Chau, Prof. Pham Hong
Duong, Cooperman laboratory and IMAG Corp.
Luminescent nanomaterials containing rare earth ions for security printing 345
19 Anh, T.K., Vu, N., Huong, T.T. and Minh, L.Q. (2004) Nanomaterials containing rare earth
ions for infrared card and planar waveguide application, The 2nd International Workshop on
Nanophysics and Nanotechnology (IWONN04), Hanoi, 2223 October, pp.161164.
20 Beaurepaire, E., Buissette, V., Sauviat, M.P., Giaume, D., Lahlil, K., Mercuri, A.,
Casanova, D., Huignard, A., Martin, J.L., Gacoin, T., Boilot, J.P. and Alexandrou, A. (2004)
Functionalized fluorescent oxide nanoparticles: artificial toxins for sodium channel targeting
and imaging at the single-molecule level, Nano Lett., Vol. 4, No. 11, pp.20792083.
21 Patra, C.R., Bhattacharya, R., Patra, S., Basu, S., Mukherjee, P. and Mukhopadhyay, D.
(2006) Inorganic phosphate nanorods are a novel fluorescent label in cell biology,
J. Nanobiotech., Vol. 4, No. 11, pp.115.
22 Hyppnen, I., Hls, J., Kankare, J., Lastusaari, M. and Pihlgren, L. (2007) Up conversion
properties of nanocrystalline ZrO2:Yb3+, Er3+ phosphors, J. Nanomater., Article ID 16391,
pp.18.
23 Misra, S.N., Gagnani, M.A., Indira, D.M. and Shukla, R.S. (2004) Biological and clinical
aspects of lanthanide coordination compounds, Bioinorg. Chem. Appl., Vol. 2, Nos. 34,
pp.155192.
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Int. J. Nanotechnol., Vol. 8, Nos. 3/4/5, 2011
Contents
159 Editorial
Le Van Hong
161 TiO2/Co nanomaterials: synthesis and properties
Le Van Hong, Ngo Thi Hong Le, Nguyen Chi Thuan, Nguyen Xuan Nghia
and Nguyen Xuan Phuc
174 A comparative study on the NH3 gas-sensing properties of ZnO, SnO2,
and WO3 nanowires
Nguyen Van Hieu, Dang Thi Thanh Le, Nguyen Duc Khoang, Nguyen Van Quy,
Nguyen Duc Hoa, Phuong Dinh Tam, Anh-Tuan Le and Tran Trung
188 Synthesis of vertically aligned carbon nanotubes and diamond films on
Cu substrates for use in high-power electronic devices
Nguyen Van Chuc, Ngo Thi Thanh Tam, Nguyen Van Tu, Phan Ngoc Hong,
Than Xuan Tinh, Tran Tien Dat and Phan Ngoc Minh
201 Enhancing the performance of organic light emitting diodes by using
nanostructured composite films
Nguyen Nang Dinh, Le Ha Chi and Tran Quang Trung
214 Effect of reaction temperature and ligand concentration on the shape
of CdSe nanocrystals
Nguyen Thi Luyen, Le Ba Hai, Nguyen Xuan Nghia, Pham Thu Nga
and Nguyen Thi Thuy Lieu
227 Metallic nanoparticles: synthesis, characterisation and application
Nguyen Hoang Luong, Nguyen Ngoc Long, Le Van Vu, Nguyen Hoang Hai,
Phan Tuan Nghia and Nguyen Thi Van Anh
241 Perovskite nanoparticles synthesised by reactive milling combined with
thermal processing: preparation, morphology and structure
characterisation
Do Hung Manh, Tran Dang Thanh, Nguyen Xuan Phuc, Le Van Hong,
Pham Thanh Phong and Luu Tien Hung
255 Novel nano-structured materials: synthesis and application
Vu Anh Tuan, Tran Manh Cuong, Dang Tuyet Phuong, Tran Thi Kim Hoa,
Bui Thi Hai Linh, Nguyen Dinh Tuyen and Nguyen Quoc Tuan
268 Microstructure of La0.7Sr0.3Mn1xZnxO3 nano-perovskites investigated
by electron microscopy technique
Tran Thi Minh Nguyet, Tran Que Chi, Luu Tien Hung and Michael Hietschold
278 Novel silver nanoparticles: synthesis, properties and applications
Anh-Tuan Le, Pham Thanh Huy, Le Thi Tam, Phuong Dinh Tam,
Nguyen Van Hieu and Tran Quang Huy
291 Application of ultrasound for nanomaterials synthesis
T.V. Chuong, L.Q.T. Dung, N.D.T. Luan and T.T. Huy
300 Electrochemical biosensor for glucose detection using zinc oxide
nanotetrapods
Nguyen Thu Loan, Luu Manh Quynh, Ngo Xuan Dai and Nguyen Ngoc Long
312 SrTi1xNixO3 nanoparticles: synthesis and characterisation
Doan Thi Thuy Phuong, Le Van Hong and Nguyen Van Minh
324 Study on fabrication and photoluminescence of SiC nanorods synthesised
by carbothermal reduction
Huynh Thi Ha, Dao Tran Cao, Le Quang Huy and Nguyen The Quynh
335 Luminescent nanomaterials containing rare earth ions for security printing
Tran Kim Anh, Dinh Xuan Loc, Tran Thu Huong, Nguyen Vu and Le Quoc Minh
347 Optical properties of normal and giant multishell CdSe quantum dots for
potential application in material science
P.T. Nga, V.D. Chinh, V.T.H. Hanh, N.X. Nghia, P.T. Dzung, C. Barthou,
P. Benalloul, J. Laverdant and A. Matre
360 Porous silicon as a promising material for photonics
Bui Huy, Pham Van Hoi, Phan Hong Khoi, Nguyen Thuy Van and Do Thuy Chi
371 Behaviour investigation of hematite nanorods synthesised by hydrothermal
method use in hydrogen fuel storage
Van Dinh Son Tho, Luu Thi Lan Anh, Nguyen Ngoc Trung, Pham Van Thang,
Nguyen Duc Hieu, Pham Phi Hung, Vo Thach Son and Tran Thanh Thai
383 Immobilising of anti-HPV18 and E. coli O157:H7 antibodies on magnetic
silica-coated Fe3O4 for early diagnosis of cervical cancer and diarrhoea
Tran Hoang Hai, Le Hong Phuc, Le Khanh Vinh, Bui Duc Long,
Truong Thuy Kieu, Nguyen Ngoc Bich, Tran Nguyen Lan, Nguyen Quan Hien,
Le Hoang Anh Khoa and Nguyen Ngoc Van Tam
399 Magnetic nanoparticles: study of magnetic heating and
adsorption/desorption for biomedical and environmental applications
Pham Hoai Linh, Do Hung Manh, Tran Dai Lam, Le Van Hong,
Nguyen Xuan Phuc, Nguyen Anh Tuan, Nguyen Thanh Ngoc and Vu Anh Tuan