ARTICLE IN PRESS

Journal of Luminescence 116 (2006) 117126

www.elsevier.com/locate/jlumin

Luminescence temperature and pressure studies of Zn2SiO4

phosphors doped with Mn2+ and Eu3+ ions
Fuhai Sua,, Baoshan Maa, Kun Dinga, Guohua Lia, Shaopeng Wangb,
Wei Chenb,, Alan G. Jolyc, David E. McCreadyc
a
State Key Laboratory for Superlattices and Microstructures, Institute of Semiconductors, Chinese Academy of Sciences,
P.O. Box 912, Beijing 100083, Peoples Republic of China
b
Nomadics, Inc., 1024 South Innovation Way, Stillwater, OK 74074, USA
c
Pacific Northwest National Laboratory, P.O. Box 999, Richland, WA 99354, USA
Received 1 September 2004
Available online 29 April 2005

Abstract

Zn2SiO4:Mn2+, Zn2SiO4:Eu3+ and Zn2SiO4:Mn2+,Eu3+ phosphors were prepared by a sol-gel process and their
luminescence spectra were investigated. The emission bands from intra-ion transitions of Mn2+ and Eu3+ samples were
studied as a function of pressure. The pressure coefcient of Mn2+ emission was found to be 25.370.5 and
28.570.9 meV/GPa for Zn2SiO4:Mn2+ and Zn2SiO4:Mn2+,Eu3+, respectively. The Eu3+ emission shows only weak
pressure dependence. The pressure dependences of the Mn2+ and Eu3+ emissions in Zn2SiO4:Mn2+,Eu3+ are slightly
different from that in Zn2SiO4:Mn2+ and Zn2SiO4:Eu3+ samples, which can be attributed to the co-doping of Mn2+
and Eu3+ ions. The Mn2+ emission in the two samples, however, exhibits analogous temperature dependence and
similar luminescence lifetimes, indicating no energy transfer from Mn2+ to Eu3+ occurs.
r 2005 Elsevier B.V. All rights reserved.

PACS: 78.55.m; 74.25.Gz; 71.70.Ch

Keywords: Zn2SiO4; Mn2+; Eu3+; Hydrostatic pressures; Luminescence; Crystal eld

1. Introduction stability and transparency in the ultraviolet

Zinc silicate is an ideal host material for
transition metal ions because of its chemical
Corresponding authors.
E-mail addresses: sufuhai@hotmail.com (F. Su),
ghli@red.semi.ac.cn (G. Li), wchen@nomadics.com (W. Chen).
(UV)-visible range. Transition and rare-earth ions
are excellent luminescent centers as a result of their
inner shell electronic transitions. Consequently,
transition and rare-earth ion doped zinc silicates
have been studied extensively as efcient lumines-
cent materials [16]. Mn2+ doped Zn2SiO4 phos-
phors emit green light when excited by UV light or

0022-2313/$ - see front matter r 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.jlumin.2005.03.010
 ARTICLE IN PRESS
118 F. Su et al. / Journal of Luminescence 116 (2006) 117126
cathode rays. These materials have been widely
investigated as novel luminescent materials in
lamps, cathode ray tubes (CRTs) and plasma
display panels due to their high luminescence
efciency [7]. Similarly, Zn2SiO4:Eu3+ has at-
tracted attention because of its strong emission in
the red which is in accordance with the standard
made by the CIE (commission International de
1 Eclairage, France). Therefore, the phosphor
has some desirable features that make it applicable
to TV and CRT screen applications [5]. Co-
doping of Mn2+ and Eu3+ into Zn2SiO4 may
provide a phosphor with both green and red
emissions, making it potentially useful for full-
color displays.
For co-doped phosphors, it is important to
reveal the interactions between the dopants in
order to get high efciency and adequate color
index. Pressure and temperature dependences of
the luminescence can provide useful information
about the interactions between doped ions and the
coupling between the dopants and the host crystal
lattices. The variation in hydrostatic pressure or
temperature can change the inter-atomic distance.
This can change the overlap among adjacent
electronic orbitals as well as the crystal eld
surrounding the dopant. Therefore, the study of
luminescence spectral properties as a function of
pressure or temperature may provide insight about
the interactions between the luminescent centers or
between the centers and the host lattice. In this
paper, we report the pressure and temperature
behaviors of Zn2SiO4 phosphors doped with
Mn2+ and Eu3+ ions.
2. Experimental
The samples were prepared as follows. First,
calculated amounts of Zn(CH3COO)2, Mn(NO3)2
Eu(NO3)3 and 0.5 g of polyvinyl alcohol (PVA)
were dissolved in 50 ml water by thoroughly
stirring under argon protection. Afterwards,
4.5 mM Na2SiO3 (2 g of 27% saturated solution)
was added slowly and NaOH solution (about
10 ml of 0.1 M NaOH) was used to adjust the pH
value to 10. The solution was reuxed overnight in
an Argon atmosphere after which centrifugation at
5000 rpm for 15 min allowed separation of the
solid samples from the solution. The resulting
powders were dried at 400 1C under nitrogen
overnight revealing white solids. Finally, the solids
were annealed at 1000 1C under nitrogen. The
glass-like solid obtained has strong green and red
luminescence. Three different samples were pre-
pared: Zn2SiO4 doped with 8% Mn2+; Zn2SiO4
doped with 6% Eu3+; and Zn2SiO4 co-doped with
8% Mn2+ and 3% Eu3+.
The phase identity of the phosphors was
examined by X-ray powder diffraction (XRPD)
using a Philips XPert MPD system (PW3040/00
type) equipped with a 1.8 kW Cu source
(
(l 1:54056 A). The PL measurements under
hydrostatic pressure were done in a diamond-anvil
cell (DAC) at room temperature. The samples,
together with a small piece of ruby, were placed in
a stainless-steel gasket with a hole of 300 mm in
diameter. A 4:1 methanolethanol mixture was
used as the pressure-transmitting medium. The
pressure was determined by using the standard
ruby-uorescence technique and varied from 0 to
6 GPa. The photoluminescence (PL) measure-
ments at different temperatures were performed
by xing samples on the cold nger of a closed-
cycle refrigeration system. The temperature varied
from 10 to 300 K. The 325 nm line of a HeCd
laser and the 454.5 nm line of an Ar+ ion
laser were used as the excitation source. The
emitted light was dispersed by a JY-HRD1 double
grating monochromator and detected by a cooled
GaAs photomultiplier tube operating in photon-
counting mode. The excitation spectra under
atmospheric pressure were measured with a
uorometer (FluoroMax-2 from Jobin Yvon-
Spex). The sample was placed on a custom-built
solid sample holder.
The lifetimes and time-resolved spectra were
collected using the output of nanosecond pulsed
optical parametric oscillator/amplier (Spectra
Physics MOPO-730). The output was directed
onto the samples and the emission collected
at right angle and focused into a mono-
chromator equipped with either a cooled CCD
detector for spectral measurements, or a
standard photomultiplier tube for lifetime mea-
surements.
 ARTICLE IN PRESS

F. Su et al. / Journal of Luminescence 116 (2006) 117126 119

3. Results and discussion (a)

2
ex =325nm (b) Zn2SiO4:Mn2+,Eu3+
Zn2SiO4:Mn2+
3.1. Atmospheric pressure photoluminescence and

Intensity (arb.units)
photoluminescence excitation spectra 5
D0-7FJ

A1-4A(4G)
Fig. 1 shows the XRPD patterns of the 4
Zn2SiO4:Mn2+ and Zn2SiO4:Mn2+,Eu3+, sam-

A1-4T2(4D)
A1-4E(4D)

A1-4T2
1
J=0

A1-4T1
ples. The two samples exhibit almost identical 3

6
i

6
XRPD patterns corresponding to the Willemite

6
i

6
structure of the usual rhombohedral phase of i
Zn2SiO4 [8]. The Mn2+ and Eu3+ ions substitute
for the Zn2+ in the Zn2SiO4 host, which has 400 500 600 700 200 300 400 500
tetrahedral sites [911]. No XRPD peaks from Wavelength (nm) Wavelength (nm)
impurities are observed in the samples, thus, it is
Fig. 2. (a) The PL spectra from Zn2SiO4:Mn2+, Zn2SiO4:Eu3+,
reasonable to assume that Mn2+ and Eu3+ ions
and Zn2SiO4:Mn2+,Eu3+ samples and (b) the excitation
substitute for Zn2+ sites in the Zn2SiO4 host spectra of Zn2SiO4:Mn2+, and Zn2SiO4:Mn2+,Eu3+ obtained
lattice. However, it must be pointed out that by monitoring the green emission at 530 nm and measured at
defects such as F-centers appear along with the room temperature and atmospheric pressure. The sharp peak in
substitution of Eu3+ to preserve charge neutrality. the excitation spectra at 265 nm arises from the second-order
diffraction of the excitation wavelength.
The PL spectra of Zn2SiO4:Mn2+, Zn2SiO4:
Mn2+,Eu3+ and Zn2SiO4:Eu3+ at atmospheric
pressure are displayed in Fig. 2(a). The
Zn2SiO4:Mn2+ displays a broad green emission (J 024) of Eu3+, respectively [5]. Fig. 2(b)
peaking at 525 nm due to the 4T16A1 transition of shows the PL excitation (PLE) spectra of
Mn2+ ions. The PL spectra of Zn2SiO4:Eu3+ Zn2SiO4:Mn2+ and Zn2SiO4:Mn2+,Eu3+ ob-
shows more complex behavior (Fig. 2(a)). The tained by monitoring the green emission at
emission peaks at 578, 590, 610, 654, and 703 nm 520 nm. There is a broad peak at about 270 nm,
are attributed to the transitions of 5D0 to 7FJ which is more intense compared with other
excitation peaks. An analogous broad peak about
276 nm was also observed in TMA2MnBr4 com-
plexes [12]. The broad peak is likely associated
(140)

with the crystal eld transitions of higher energy in

(113)

Zn2SiO4:Mn2+,Eu3+
(220)

Mn2+ ions. The larger intensity of the band with

(223)

(333)

(713)

respect to the other dd bands of lower energy can

(710)
Intensity (counts)

be a consequence of increased mixing with ligand-

(300)

(006)
(630)
(520)
(110)

(600)

(523)
(603)

metal charge transfer states. The excitation peaks

at 356, 380, 420, 435, and 490 nm are assigned
to the transitions of 6A1 (S)4E (4D), 6A1 (S)
4
Zn2SiO4:Mn2+ T2 (4D), 6A1 (S)4A1, 4E (4G), 6A1 (S)4T2 (4G)
and 6A1 (S)4T1 (4G) of Mn2+, respectively [2,13].
It should be pointed out that the shape of the
excitation spectra is similar to that in
TMA2MnBr4 complexes [12]. Upon comparison
10 20 30 40 50 60 with the assignment of transition energies of Mn2+
2Theta (deg.) in the reference, the 6A1 (S)4T1 (4G) transition in
Fig. 1. The XRPD patterns of Zn2SiO4:Mn2+,Eu3+ (upper) Zn2SiO4:Mn should be at about 445 nm and
and Zn2SiO4:Mn2+ (lower) samples prepared by sol-gel corresponding to the shoulder of the broad band
process. from the 6A1 (S)4T2 (4G) transition. However,
 ARTICLE IN PRESS
120 F. Su et al. / Journal of Luminescence 116 (2006) 117126
our calculated result for 6A1 (S)4T1 (4G) transi-
tion according to the crystal eld theory is close to
the 490 nm, which agrees with that reported in
other references [2,13]. The energies of these
excited states are almost identical in
Zn2SiO4:Mn2+ and Zn2SiO4:Mn2+,Eu3+ as listed
in Table 1. An estimate of the Racah parameters
(B and C) and crystal eld strength (Dq) is
obtained from the excitation peaks based on the
crystal eld theory [14]. The measured energies of
the PLE peaks and the obtained values of B, C,
and Dq are listed in Table 1. The errors of B, C,
and Dq are about 20, 50 and 90 cm1, assuming
the measurement error of the peak position is
within 1 nm. Within the error of the data, the
calculated values of B, C and Dq in
Zn2SiO4:Mn2+ are almost identical to that in
Zn2SiO4:Mn2+,Eu3+. This indicates that the co-
doping of Eu3+ does not change the crystal eld
strength around Mn2+ sites to any appreciable
amount.
3.2. PL spectra pressure dependence
The emission spectra for the samples at different
pressures are presented in Fig. 3. The Eu3+
emission peaks do not change dramatically with
pressure, either in peak position or in bandwidth.
However, their intensities decrease with the
increase of pressure. The Mn2+ emission in
Zn2SiO4:Mn2+ and Zn2SiO4:Mn2+,Eu3+ shifts
to longer wavelengths with increasing pressure
and the emission intensity decreases rapidly.
Table 1
Excitation peak energies and crystal eld parameters for Zn2SiO4:Mn2+ and Zn2SiO4:Mn2+,Eu3+ samples
6
Excitation peak energy A1 (S)4E (4D)
6
A1 (S)4T2 (4D)
6
A1 (S)4A1,4E (4G)
6
A1 (S)4T2 (4G)
6
A1 (S)4T1 (4G)
Crystal eld parameters B 622720
C 3504750
Dq
According to previous results, the Mn2+ emission
slowly diminishes when the concentration of
Mn2+ increases above 5 mol%, due to energy
transfer between Mn2+ ions [1]. Sohn et al. [2]
have also observed this interaction between Mn2+
ions. It was found that the radiationless energy
transfer rate is proportional to R6, where R is the
distance between Mn2+ ions taking part in the
energy transfer [2]. Therefore, one possible cause
of the rapid decrease of the Mn2+ emission
intensity at higher pressures is the slight pressure-
induced decrease of the distance between Mn2+
ions. Another factor responsible for the decrease in
intensity is likely associated with the pressure-
induced low-symmetry crystal-eld effects. In
general, the linear compressibility shows the
directional properties to a certain extent, thus
the symmetry of the crystal-eld surrounding the
Mn2+ ions may lower with increasing pressure.
The change in symmetry can inuence the 4T16A1
transition efciency of Mn2+.
Zn2SiO4 undergoes a phase transformation at
about 2.5 GPa, where hexagonal Zn2SiO4-I
changes to tetragonal Zn2SiO4-II [15]. Neverthe-
less, no discontinuity in the PL spectra with
increasing pressures is observed for either Mn2+
or Eu3+ ions doped Zn2SiO4. This might be
associated with the fact that the Zn2+ ions are
still in tetrahedral coordinated sites in the
Zn2SiO4-II phase and the interatomic distance of
ZnO in Zn2SiO4-II is quite similar to that of
Willemite [16]. To compare the pressure behaviors
of Mn2+ emission in Zn2SiO4:Mn2+ and
Zn2SiO4:Mn2+ (cm1) Zn2SiO4:Mn2+,Eu3+ (cm1)
Observed Calculated Observed Calculated
28050 280907590 28097 279947590
26316 26343
23736 237407450 23753 237457450
23095 226487600 23116 225717600
20367 204567500 20387 204707500
607720
3535750
562790 563790
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F. Su et al. / Journal of Luminescence 116 (2006) 117126 121

3+
(a) Zn2SiO4:Mn2+,Eu3+ (b) Zn2SiO4:Mn2+ (c) 2 Zn2SiO4:Eu
ex =454.5nm ex =454.5nm ex =325nm
5D -7F
0 J
J=0 P=0.35GPa
P=0.21GPa
Intensity (arb.units)

5D -7F
x2
0 J 4
2 1
J=0 3
585 600
1 P=0.16GPa 1.25
1 1.89
3
2.32
1.2 x2.4 2.76

x5 3.13
2.1 3.77

3.2 4.65
4.25
4.4

500 550 600 650 700 500 550 600 500 550 600 650 700 750
Wavelength (nm)
Fig. 3. The PL spectra at selected pressures from (a) Zn2SiO4:Mn2+,Eu3+, (b) Zn2SiO4:Mn2+, and (c) Zn2SiO4:Eu3+ samples. The
inset in Fig. 5(a) represents the magnied spectrum of the 5D07F0 and 5D07F1 emissions of Eu3+ ions (P 0:16 GPa).

2.40 where a is the pressure coefcient and E0

2.38 Zn2SiO4:Mn2+ represents the emission energy at P 0 GPa. The
2.36 Zn2SiO4:Mn2+,Eu3+
obtained pressure coefcients for Zn2SiO4:Mn2+
2.34 and Zn2SiO4:Mn2+,Eu3+ are 25.370.5 and
Energy (eV)

2.32 28.570.9 meV/GPa, respectively. The absolute

2.30 value of the pressure coefcient for Zn2SiO4:
2.28 Mn2+,Eu3+ is somewhat larger than that for
2.26
Zn2SiO4:Mn2+.
The pressure behavior of the Mn2+ emission
2.24
maximum may be analyzed using crystal eld
2.22
theory, which has been successfully used to
2.20
-1 0 1 2 3 4 5 describe the pressure dependence of Mn2+ emis-
Pressure (GPa) sion from ZnS:Mn2+ [1719]. The pressure shift of
the peak energy of the Mn2+ emission, dE/dP, can
Fig. 4. Pressure dependence of the peak energy of the Mn2+ be expressed as a function of dDq/dP and dB/dP,
emission from Zn2SiO4:Mn2+ and Zn2SiO4:Mn2+,Eu3+. The
providing that the Racah parameter ratio C/B is
solid lines are the least-squares t to the data using a linear
relationship. independent of the pressure [17]:
dE dDq 1 dB
d E 0  Dqd , (2)
dP dP B dP
Zn2SiO4:Mn2+,Eu3+, plots of the peak energies of where E0 is the PL peak energy of Mn2+ emission
Mn2+ emission as a function of pressure are at P 0 GPa and d d(E/B)/d(Dq/B) is the
displayed in Fig. 4. The two straight lines in the slope of the curve E/B vs. Dq/B at the value of
plot represent the result of the least-squares t to Dq/B derived from the corresponding transition
4
the experimental data using a linear relation: T1 to 6A1 in the SuganoTanabe diagram.
The value of d is 10 for Mn2+ ions [14].
EP E 0 aP, (1) Eq. (2) predicts the pressure dependence of
 ARTICLE IN PRESS

122 F. Su et al. / Journal of Luminescence 116 (2006) 117126

Mn2+ emission, which is determined by the
pressure-induced variation of Dq and B. The Dq
term is proportional to Rn, where R represents
the distance between the Mn2+ ion and surround-
ing O ions. In a point charge model, the value of n
is 5 [17]. Therefore, the rst term of the equation
can be written as

1
dE dDq 50
10  kDq; (3)
dP dP 3
where k 1=V dV =dP is the volume com-
pressibility. Although there is no reported value of
k for Zn2SiO4, the bulk modulus of most silicates
is between 110 and 170 GPa [2022]. Assuming
that the bulk modulus of Zn2SiO4 is also in the
above range, the calculated rst term of Eq. (3) is
between 7 and 10 meV/GPa for the two samples.
In addition, there is no available data of dB/dP for
Zn2SiO4:Mn2+, so it is difcult to calculate the
pressure coefcient precisely. If the value obtained
for ZnS:Mn2+ (3.48 cm1/GPa [23]) is used to
estimate the pressure coefcients, the obtained
results are in the range of 2428 meV/GPa for the
two samples. These results are in accordance
with the experimental data, suggesting that the
pressure coefcient for the Mn2+ emission in
Zn2SiO4:Mn2+ can be described by the above
crystal eld theory. It should be mentioned that
the derivative of the Racah parameter B depends
tion metal complexes, and the crystal eld strength
as a function of metalligand distance generally
does not agree with the point charge model. The
values of the exponent n derived from molecular
orbital wave function calculations on different
transition metal complexes are between 3.5 and 6
[26]. In the present case, it is possible that the co-
doping of Eu3+ changes the local compressibility
of the Mn-ligand system. In addition, the co-
doping with a few percent of Eu3+ ions may lower
the point symmetry of the Mn2+ site which may
cause a difference in the pressure shifts of Mn2+
emission in Zn2SiO4:Mn2+ and Zn2SiO4:
Mn2+,Eu3+.
The pressure dependence of the Eu3+ emission
energies are plotted in Fig. 5. For comparison, the
different Eu3+ transitions are shifted vertically.
From Fig. 5(a) it can be observed that the Eu3+
emission from Eu3+-doped Zn2SiO4 exhibits a
weak red shift with increasing pressure. The
pressure coefcient obtained by least-squares
25 (a)
5
D0-7F0
20
5
D0-7F1
15 5
D0-7F2
10
5
D0-7F3
5
E(P)-E0 (meV)

5
on the ligands covalency and crystal compressi- D0-7F4
0
bility, therefore the value of dB/dP from different 30
Mn2+ doped complexes may show large discre- (b) 5
25 D0-7F0
pancies. For a more precise quantitative calcula-
tion for the pressure dependence of Mn2+ 20
emission from Zn2SiO4:Mn2+, dB/dP needs to be 5
D0-7F1
obtained directly from experiment. 15
According to the above discussion, the crystal 10 5
D0-7F2
eld strength Dq and Racah parameter B is almost
5
identical in Mn2+ singly-doped and Mn2+, Eu3+
5
co-doped Zn2SiO4 phosphors. Therefore, factors 0 D0-7F4

other than crystal eld parameters should be 0 1 2 3 4

considered in order to explain the variation in
pressure coefcients between the two samples. The
quantity d(Dq)/dP in Eq. (2) has been found to be
dependent on the local compressibility [24,25]. The
exponent n in the relation of Dq on R is sensitive
to the surroundings around doped ions in transi-
Pressure (GPa)
Fig. 5. The variation of the peak energies of Eu3+ transition,
E(p)E0, from (a) Zn2SiO4:Eu3+ and (b) Zn2SiO4:Mn2+,Eu3+
as a function of pressure, where E0 is the emission energy at
P 0 GPa. The data are offset on the vertical axis for
comparison. The solid lines are the least-squares ts to the data.
 ARTICLE IN PRESS

F. Su et al. / Journal of Luminescence 116 (2006) 117126 123

Table 2
The pressure coefcients for Mn2+ and Eu3+ emissions in three samples obtained from the least-squares t to the experimental data
using a linear relation

Zn2SiO4:Mn2+ Zn2SiO4:Eu3+ (meV/ Zn2SiO4:Mn2+,Eu3+

(meV/GPa) GPa) (meV/GPa)

Mn2+ 4
T16A1 25.370.5 28.570.9
5
D07F0 0.4570.1 0.6270.2
5
D07F1 0.6470.05 1.570.3
Eu3+ 5
D07F2 0.4570.05 0.2670.1
5
D07F3 0.7170.1
5
D07F4 0.6970.08 1.1170.15
average pressure shift (Eu3+) 0.59 0.56

linear t for the emission energy from the 6D04FJ 3000

(a) Zn2SiO4:Eu3+
(J 0, 1, 2, 3, 4) transition is shown in Table 2.
2700
The pressure dependences for the transitions of
5
D04FJ (J 04) are nearly the same. 2400
Nv (cm-1)

The crystal eld parameters of Eu3+ can be

estimated from the Stark splitting of 5D04F1 2100

Intensity (a.u.)
E2 E1 E3
emission peaks. According to crystal eld theory, 1800
the crystal eld strength parameter Nv can be 5
D0- F17

determined by the following relation [27,28]: 1500

584 592 600
r Wavelength (nm)
4p 1200
Nn B20 2 2B22 2 , (4) (b) Zn2SiO4:Eu3+
5 -2
Formal Negative Charge

Zn2SiO4:Mn2+,Eu3+
where B20 and B22 are crystal eld parameters and -3
related to the Stark splitting of the 7F1 energy level
[24]: -4

E 1 E b 15B20 , -5
p
1 6 -6
E2 Eb  B20 B22 ,
10 10
p -7
1 6
E3 Eb  B20  B22 , 5 0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0
10 10
Pressure (GPa)
where the Ei (i 1, 2, 3) are the three Stark split
levels as shown in Fig. 6 and Eb is the average Fig. 6. (a) The crystal-eld strength (Nv) derived from the Stark
splitting of the 5D07F1 transition in Zn2SiO4:Eu3+, and (b) the
energy of the three experimental 7F1 levels. Based formal negative charge for Zn2SiO4:Eu3+ and Zn2SiO4:Mn2+,
on the measured Stark splitting of the 5D07F1 Eu3+ as the function of the pressure. The inset displays the
emission at different pressures for Zn2SiO4:Eu3+, three Stark split peaks of the 5D07F1 transition.
the variation of the crystal eld strength described
by Nv with pressure is plotted in Fig. 6(a). It is
clear that the crystal eld strength increases
gradually with the increase of the pressure. the emission peaks of the 5D07F1 and 5D07F4
The pressure behavior of the Eu3+ emissions in transitions shift to lower energies at a faster rate
Zn2SiO4:Mn2+,Eu3+ (Fig. 5b) are different from with increasing pressure than in Zn2SiO4:Eu3+.
that in Zn2SiO4:Eu3+. In Zn2SiO4:Mn2+,Eu3+, However, the 5D07F0 transition shifts to higher
 ARTICLE IN PRESS

124 F. Su et al. / Journal of Luminescence 116 (2006) 117126

energy and the 5D07F2 transition is almost
unchanged as the pressure increases. Therefore,
the splitting between 7FJ states with respect to
different J show distinct changes with increasing
pressure in Zn2SiO4:Mn2+,Eu3+, whereas these
splittings are almost independent on the pressure
in Zn2SiO4:Eu3+. The presence of Mn2+ ions
likely lowers the symmetry of the crystal eld
surrounding Eu3+ or changes the local compres-
sibility of the Eu-ligand system, and thus inu-
ences the pressure dependence of the crystal eld.
This can account for the different behavior of
Eu3+ transition in the two samples. In addition, it
is interesting that the average pressure-induced
shift of the 5D07FJ emission from Zn2SiO4:
Mn2+,Eu3+ is about 0.56 meV/GPa, which is
almost identical to the value (0.59 meV/GPa)
from Zn2SiO4:Eu3+ as shown in Table 2. Previous
results from Eu3+ doped into glasses also show a
pressure regime where the energy shift induced by
the increased pressure displays a very weak
redshift [28]. These observations have been ex-
plained by the formation of pressure-induced high-
eld Eu3+ sites related to the higher formal
negative charges on the ligand [27,28]. The sum
of the formal negative charge (q) on the oxygen
ligands is associated with the electronegativity of
the Eu3+ ion and can be derived from the energy
(v) of the 5D07F0 transition [28,29]
vcm1 17273 2:29q  0:76q2 . (6)
The variation of formal negative charge induced
by pressure for the two samples is shown in
Fig. 6(b). The value of the formal negative charge
in Zn2SiO4:Eu3+ shows a weak decreasing trend
with elevated pressure but the formal charge in
Zn2SiO4:Mn2+,Eu3+ increases.
3.3. The PL spectra temperature dependence
The luminescence temperature dependence may
provide insight into explaining the pressure
dependences. The energy position and bandwidths
of the emission peaks from Mn2+ and Eu3+ ions
are almost independent of temperature for the
three samples (Fig. 7). For Zn2SiO4:Mn2+ and
Zn2SiO4:Mn2+,Eu3+, the Mn2+ emission be-
comes weaker in intensity with decreasing tem-
perature. This phenomenon is consistent with the
pressure induced decrease of the intensity. The
lower temperature tends to shorten the distance
between Mn2+ ions. Therefore, the radiationless
energy transfer between Mn2+ ions should be
enhanced. Another possible reason for the increase

(a) Zn2SiO4:Mn,Eu (b) Zn2SiO4:Mn (c) Zn2SiO4:Eu

10K T= 10K

30K 30K
Intensity (arb.units)

50K 60K
10K 90K 90K
40K 150K 13 0K
90K
220K 18 0K
150K
240K
220K
T=300K 300K
T=300K

500 600 700 400 500 600 700 500 600 700
Wavelength (nm)

Fig. 7. The PL spectra at different temperatures for (a) Zn2SiO4:Mn2+,Eu3+, (b) Zn2SiO4:Mn2+ and (c) Zn2SiO4:Eu3+ samples.

of intensity with temperature may be thermally
activated energy transfer from other defects to
Mn2+ ions. As the temperature increases, thermal
activation can release carriers trapped at defect
sites to the conduction band of the host. These
carriers can be trapped at the Mn2+ sites,
enhancing the luminescence with increasing tem-
perature.
The intensity of Eu3+ emission also shows an
increase at elevated temperature in Zn2SiO4:Eu3+.
However, the Eu3+ emission from Zn2SiO4:
Mn2+,Eu3+ diminishes slightly as the temperature
increases. Interactions between Mn2+ and Eu3+
ions such as energy transfer are possible reasons
for the difference in pressure and temperature
behaviors between Zn2SiO4:Mn2+ and Zn2SiO4:
Mn2+,Eu3+. Time-resolved luminescence spectra
and lifetimes can reveal whether there is energy
transfer between Mn2+ and Eu3+ ions. The time-
resolved spectra of Zn2SiO4:Mn2+,Eu3+ following
excitation at 395 nm are shown in Fig. 8. In the
inset of Fig. 8, the luminescence decay curves of
the Mn2+ and Eu3+ emission from Zn2SiO4:
Mn2+,Eu3+ are plotted. The decay curve of the
Mn2+ emission from Zn2SiO4:Mn2+ is also shown
for comparison. The decay curves of Mn2+ and
Eu3+ emission from Zn2SiO4:Mn2+,Eu3+ can be
Logarithmic Intensity (a.u.)
Zn2SiO4:Mn2+,Eu3+
Intensity (arb.units)
Zn2SiO4:Mn2+
em:525 nm
0.00 0.01
time (second)
460 480 500 520 540 560 580 600 620 640
Fig. 8. Time-resolved spectra obtained at 5 and 50 ms delay
after excitation of 395 nm laser line for Zn2SiO4:Mn2+,Eu3+.
The inset displays the luminescence lifetime decay curves of the
Mn2+ and Eu3+ emission from Zn2SiO4:Mn2+ (solid line) and
Zn2SiO4:Mn2+,Eu3+ (dashed line).
ARTICLE IN PRESS
F. Su et al. / Journal of Luminescence 116 (2006) 117126 125
t well with a single exponential function and the
obtained lifetimes are 1070.1 and 3.470.1 ms,
respectively. In Zn2SiO4:Mn2+, the decay curve
can be well t by a bi-exponential function, with
lifetimes of 10.270.1 and 1.2470.1 ms, respec-
tively. The slow component corresponds to the
decay of the Mn2+ emission, which is consistent
with that in Zn2SiO4:Mn2+,Eu3+. If there is
energy transfer from Mn2+ to Eu3+, the decay
lifetime of Mn2+ should be shortened in the co-
doped phosphor. However, the decay lifetimes of
Mn2+ in the two samples are almost identical,
indicating no energy transfer occurs. This conclu-
sion is consistent with the results from the pressure
and temperature measurements.
4. Conclusions
We have investigated the luminescence spectra
of Zn2SiO4:Mn2+, Zn2SiO4:Eu3+, and Zn2SiO4:
Mn2+,Eu3+ phosphors under different pressures
and temperatures. The emission bands consist of
intra-ion transitions of Mn2+ and Eu3+ in these
samples. The excitation spectra of the Mn2+ ion
in Zn2SiO4:Mn2+ is consistent with that in
Zn2SiO4:Mn2+,Eu3+, which implies that the co-
doping of Eu3+ ions does not change the crystal
eld surrounding Mn2+. The Mn2+ emission
em:610 nm Zn2SiO4:Mn2+,Eu3+
shifts to longer wavelengths with increasing
ex=395 nm
pressure and the pressure dependence of Mn2+
emission can be well described by crystal eld
theory. The Eu3+ emission has very weak pressure
dependence. The pressure dependence of the
crystal eld strength and the electronegativity for
0.02 0.03 0.04
delay: 5s Eu3+ ions have been obtained. The pressure
dependences of the Mn2+ and Eu3+ emissions in
Zn2SiO4:Mn2+,Eu3+ are slightly different from
that in Zn2SiO4:Mn2+ and Zn2SiO4:Eu3+ sam-
delay: 50s ples, which may be associated with the co-doping
of Mn2+ and Eu3+ ions. The Mn2+ emission
intensity exhibits a diminishing trend with decreas-
Wavelength (nm) ing temperature and increasing pressure for the
two samples doped with Mn2+ ions. This effect is
likely related to carrier migration among Mn2+
ions. The temperature dependence of the Eu3+
intensity displays opposite trends in the
Zn2SiO4:Eu3+ and Zn2SiO4:Mn2+,Eu3+ samples,
 ARTICLE IN PRESS
126 F. Su et al. / Journal of Luminescence 116 (2006) 117126
however time-resolved measurements display no
sign of energy transfer between the Mn2+ and
Eu3+ ions.
Acknowledgments
This work was supported by the National
Natural Science Foundation of China (Contract
No. 60476045, 10334040) and the special funds for
Major State Basic Research Project of China (No.
G2001CB3095) at IOS. W.C. and S.P.W. would
like to thank Nomadics, Inc., USA, the National
Science Foundation (NSF, Grant No. DMI-
0132030), the National Institutes of Health
(NIH, 1R43CA110091-01) and the Department
of Energy (DOE, DE-FG02-04ER84023) for
grants. Part of the research described in this paper
was performed at the W.R. Wiley Environmental
Molecular Sciences Laboratory, a national scien-
tic user facility sponsored by the Department of
Energys Ofce of Biological and Environmental
Research and located at the Pacic Northwest
National Laboratory (PNNL). PNNL is operated
by Battelle for the US Department of Energy
under contract DE-AC06-76RLO1830.
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