Research Article

www.acsami.org

Dual-Mode Luminescence Modulation upon Visible-Light-Driven

Photochromism with High Contrast for Inorganic Luminescence
Ferroelectrics
Qiwei Zhang, Xuewen Zheng, Haiqin Sun, Wenqing Li, Xusheng Wang, Xihong Hao,*,
and Shengli An

School of Materials and Metallurgy, Inner Mongolia University of Science and Technology, 7 Arerding Street, Kun District,
Baotou 014010, Peoples Republic of China

Functional Materials Research Laboratory, School of Materials Science and Engineering, Tongji University, 4800 Caoyang Road,
Shanghai 201804, Peoples Republic of China
S Supporting Information
*

ABSTRACT: A luminescence ferroelectric oxide, Na0.5Bi2.5Nb2O9 (NBN), system

with bismuth layer structure introduced by lanthanide ion (Er3+) has been
demonstrated to exhibit reversible, high-contrast luminescence modulation (95%)
and excellent fatigue resistance based on visible-light-driven photochromism (407 nm
or sunlight). The coloration and decoloration process can be eectively read out by
dual modes, upconversion and downshifting, and reversibly converted between green
and dark gray by alternating visible light or sunlight irradiation and thermal stimulus.
The luminescence modulation degree upon photochromic reactions is strongly
dependent upon irradiation light wavelength and irradiation time. After undergoing
several cycles, there are no signicant degradations, showing high reversibility.
Considering its high-contrast photoswitchable luminescence feature and intrinsic
ferroelectricity of NBN host, NBN-based multifunctional materials can be suggested
as a promising candidate for new potentials in photonic storage and optoelectronic
multifunctional devices.
KEYWORDS: ferroelectric oxide, luminescence modulation, fatigue resistance, photochromism, reversibility, photonic storage

materials exhibit sensitivity to ultraviolet (UV) light,1113 with

only a few sensitive to visible light, and they usually exhibit poor
reversibility (e.g., dicultly being photocolored once for thermal
bleached WO3 or MoO3) and low fatigability; it is dicult to
eciently use most commercially available laser sources and
solar energy. Therefore, developing new PC materials with
visible light sensitivity still remains a critical challenge to their
practical applications.
We recently reported the PC behavior of bismuth layer
structure ferroelectrics [Na0.5Bi2.5Nb2O9 (NBN)] and introduced Eu or Pr ions into the NBN host to realize reversible
luminescence modulation upon PC reactions.14,15 We believe
that the combination of luminescence, PC, and ferroelectrics may
lead to future multifunctional optoelectronic applications.1618
This may open up new avenues for the discovery of a new series
of functionalized materials capable of modulating the luminescence emission through incorporation of dierent dopants
(activators and sensitizers) and a suitable host with the bismuth
layer structure of general formula (Bi2O2)2+(An 1BnO3n + 1)2,
where A is a mono-, di-, or trivalent element, B is some highly

INTRODUCTION
In recent years, inorganic photochromic compounds changing
their color upon light irradiation have attracted considerable
attention, have shown great promise in optical data storage,
switches, and optoelectronic devices, and have been extensively
investigated.13 They have been demonstrated to display some
advantages over organic counterparts: better thermal stability,
strength, chemical resistance, and macroscopic shape molding
(thin lms, coatings, etc.).4,5 Although the research on them is
well-known, such as transition metal oxides (WO3, MoO3, TiO2,
and V2O5), polyoxometalates, alkali metal azides, sodalite, and
the related hybrid materials, most studies are mainly focused on
the phenomenon of photochromism (PC),6,7 while studies on
their luminescence modulation upon PC reactions are extremely
rare,8 in particular on reversible photoswitching behavior. The
photoswitching of luminescence is particularly valuable for
optical storage and is considered to be one of the most attractive
concepts for the realization of a nondestructive optical readout
among several methods or ideas, such as refractive index, electric
conductance, magnetic interactions, etc.9,10 Thus far, limited
success has been made in switching the luminescence with high
luminescence contrast and excellent reproducibility of inorganic
materials because of insucient conversion or irreversible
reactions. In addition, most of the reported inorganic PC
2016 American Chemical Society

Received: December 15, 2015

Accepted: January 28, 2016
Published: January 28, 2016
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RESULTS AND DISCUSSION

XRD patterns of various amounts of Er2O3-doped NBN samples
(NBN:xEr, where x = 0, 0.01, 0.02, 0.04, 0.06, and 0.08) are
shown in Figure 2a. The main phase of NBN [Joint Committee

charged cation, and n is the number of octahedral layers in

perovskite layers.19 Despite the reversible luminescence photoswitching upon photochromic reactions in the NBN system,
there is still a roadblock toward practical applications: low
luminescent emission contrast (<70%).
Herein, we report a new luminescent PC material of Er-doped
NBN ferroelectrics with excellent reproducibility and high contrast
luminescence switching through resonance energy transfer,
fabricated by conventional solid-state reactions, as shown in
Figure 1. The reversible luminescence switching can be modulated

Figure 2. (a) XRD patterns of NBN:xEr samples and (b) rened peaks
near (008) and (115).

Figure 1. Schematic illustrations for PL and PC of the NBN:Er

material.

on Powder Diraction Standards (JCPDS) 42-0397] is obviously

observed, and no additional peaks are found, except for a little
amount of secondary phase of BiNbO4.20 The diraction peaks
of samples are shifted to the higher angle side with the increase
of Er concentrations (Figure 2b). These shifts demonstrate
shrinkage of the NBN cell volume as a result of a relatively
smaller ionic radius of Er3+ (CN = 6; 0.890 ) than that of Bi3+
(CN = 6; 1.02 ) or Na+ (CN = 6; 1.03 ) in the A sites of the
perovskite layer.21 Figure S1 of the Supporting Information
displays the typical plate-like grain morphology of Aurivillius
layer materials as a result of the anisotropic nature of the crystal
structure. All samples exhibit the well-sintered and dense
microstructure. The samples with high Er2O3 levels (x 0.06)
have a new phase consisting of vermiculate-shaped grains with
a very small size of 0.5 m, which is consistent with the XRD
results.
Figure 3 shows the room-temperature PL (sometimes also
called DS) and UC spectra of NBN:xEr samples with dierent

by dual modes: upconversion (UC) and downshifting (DS).

The correlation between the luminescence modulation degree
and irradiation wavelength and the modulated mechanism are also
reported.

Research Article

EXPERIMENTAL SECTION

Material Synthesis Procedure. Samples of Er-doped NBN

ceramics with compositions of (Na0.5Bi0.5)1 xErxBi2Nb2O9 (x = 0,
0.01, 0.02, 0.04, 0.06, and 0.08), abbreviated as NBN:xEr, were
fabricated by a solid-state reaction method. High-purity Na2CO3 (Alfa
Aesar, 99.5%), Bi2O3 (Alfa Aesar, 99.975%), Nb2O5 (Alfa Aesar, 99.5%),
and Er2O3 (Tianjin Chemical Reagent, 99.99%) as raw materials were
weighted and mixed with alcohol. After the mixed powders were
calcined at 900 C in an alumina crucible for 4 h in air, all samples were
pressed into disk-shaped pellets of 15 mm diameter and 1 mm thickness
and sintered at 1100 C for 2 h in air.
Material and Property Characterization. X-ray diraction
(XRD) patterns were collected using Cu K1 radiation ( = 1.540 56 ,
D8 Advanced, Bruker, Germany). Surface morphologies were detected
by scanning electron microscopy (SEM, Quanta 400, Genesis). The
sunlight coloration was carried out under a AM 1.5G spectrum from a
solar simulator (PLX-SXE300UV, Beijing Perfect Light Technology
Co., Ltd., China). An ultraviolet/visible (UV/vis) spectrophotometer
(U-3900, Hitachi, Japan) was used to characterize the diuse reectance
spectra. Electron paramagnetic resonance (EPR) spectroscopy was
obtained using a spectrometer (ER200-SRC, Bruker, Germany).
Luminescence modulation at various wavelengths (360, 407, 450, 470,
490, 524, and 600 nm) and reproducibility upon PC reactions were
performed using a spectrouorometer (F-4600, Hitachi, Japan), and a
xenon lamp equipped with F4600 was taken into account as not only
photoirradiation sources but also exciting light sources. The excitation
slit in F4600 was set up to 2.5 nm for the photoirradiation. During
photoluminescence (PL) measurements, the excitation and emission
slits were set up to 1 and 2.5 nm. The laser diode (LD) of 407 nm with
200 mW was chosen to obtain the saturated coloration. The UC spectra
were measured by a 980 nm LD (100, Zolix, China) linked to F4600.
The decay curves of the samples before and after irradiation were
measured by a combined steady-state and time-resolved uorescence
spectrometer (FLS920, Edinburgh Instruments, U.K.). Frequency
dependence of the dielectric constant and loss was measured using a
E4980A LCR meter (Agilent, Palo Alto, CA). The polarization (P)
versus electric eld (E) curves were carried out by a ferroelectric
test system (Precision Premier II, Radiant Technologies, Inc.,
Albuquerque, NM).

Figure 3. (a) DS and (b) UC emission spectra of NBN:xEr. The right

inset is the photographic image of the UC emission of NBN:0.04Er.

compositions.22 In Figure 3a, the PL spectra at excitation of

490 nm exhibit a strong green emission located at 550 nm and a
weak emission at 530 nm, which can be easily observed by the
naked eye. Generally, these emissions are mainly attributed to the
characteristic ff transition emissions of Er3+ ions from 4S3/2
4
I15/2 (550 nm) and 2H11/2 4I15/2 transitions, respectively.
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Here, electrons are excited to higher levels of 4F5/2 and 4F7/2 and
then relax to lower levels (Figure S2 of the Supporting
Information). The PL emission intensity at 550 nm gradually
increases and reaches their maximum as the doped level is to be
0.04 mol. Higher doping levels would lead to the decrease of
emission intensity as a result of the concentration-quenching
eect.23 Figure 3b displays the room-temperature UC emission
spectra under a 980 nm LD excitation. Clearly, the emission
spectra include two parts: a strong green band centered at
550 nm assigned to the 4S3/2 4I15/2 transition and a relatively
weak red emission at 675 nm assigned to 4F9/2 4I15/2 transitions.24 The photograph of the NNB:0.04Er sample under
980 nm excitation is shown in the inset of Figure 3b. The
dependence of UC emission intensity upon compositions is
similar to that of PL emission. These results are in accordance
with those of the literature in other Er-doped hosts.25 Besides,
through the relation of the laser powder (P) and UC emission
intensity (I): I Pn (n is the number of photons) (Figure S3 of
the Supporting Information), the obtained n values are 1.38 and
1.34 for green and red emissions, respectively, indicating that the
two-photon absorption is responsible for UC emission.
Figure 4a shows photographs presenting the reversible color
change of samples with sunlight irradiation coloration (5 s of

These locations of absorption peaks are almost coinciding with

the PL peaks, as observed in Figure 3a. Upon sunlight irradiation
in a very short time of 1 s, a broad absorption band appears in
the visible light range from 400 to 700 nm. Further increasing
irradiation time only slightly changes the absorption degree.
Upon 5 s sunlight irradiation, the absorption is almost saturated,
whose strongest absorption peak (the dierence between
reectance intensity before and after irradiation, abs) occurs
at 450 nm (inset of Figure 4a). To evaluate the color switching
reversibility, the sample of x = 0.04 is processed repeatedly with
sequential sunlight irradiation of 5 s and thermal bleaching of
the temperature of 200 C for 10 min. The recorded reectance
intensity at a xed wavelength (450 nm) maintains almost
10 cycles without any obvious loss, showing a complete reversibility of the color switching (Figure 4c). In comparison to other
compositions, the sample with x = 0.04 shows the strongest
absorption to visible light (Figure 4d).
Figure 5 shows the luminescence spectral changes excited by
490 and 980 nm upon visible light irradiation ( = 407 nm) from

Figure 4. (a) Photographs of NBN:xEr before and after sunlight

irradiation. (b) Reection spectra for the NBN:0.04Er by visible light
irradiation (0, 1, 3, 5, and 10 s) and the dierence absorption (abs). (c)
Reectance intensity changes of the NBN:0.04Er by alternating sunlight
irradiation (AM 1.5G) and heat treatment. (d) Dierence absorption
(abs) at 450 nm versus Er concentrations.

irradiation time) and thermal stimulus bleaching (200 C for

10 min). Upon sunlight irradiation using a solar simulator of
AM 1.5G, the initial green or pale green samples switched to dark
gray in a short time (5 s). When the colored sample is placed at
the heating stage with a temperature of 200 C, the dark gray
quickly reverts to its initial color. The process of the coloration
and decoloration can be completely repeated by alternating
sunlight irradiation and thermal stimulus. The color change can
be well-reected by measuring the reection spectra, as shown
in Figure 4b. Before irradiation, there exist some absorption bands centered at about 320, 488, 520, and 656 nm in the
diuse reectance spectra, wherein the broad band at 320 nm
corresponds to the absorption edge of the NBN host (3.26 eV) .
There is no change of the absorption edge by Er3+ substitution
for (Bi0.5Na0.5)2+ (Figure S4 of the Supporting Information).

Figure 5. (a) PL and (b) UC spectral changes of the NBN:xEr samples

under dierent irradiation times at room temperature.

a xenon lamp of F4600. Upon visible light ( = 407 nm)

irradiation, the PL or UC emission intensities are signicantly
decreased along with the PC and the irradiation areas gradually
change to dark gray (Figure S5 of the Supporting Information).
The decreased degree (Rt) after irradiation is dened as
Rt = (R0 Rt)/R0 100 (%), where R0 and Rt are the initial
emission intensity and the intensity under dierent irradiation times of 10, 20, and 30 s and 1, 2, 3, and 4 min, from the
4
S3/2 4I15/2 transition at 550 nm. From Figure 5a, the
luminescence switching contrast (Rt) is estimated to be 89.27%
after irradiation time of 4 min for the sample with x = 0.01, and
the Rt value can reach its maximum of about 95.62% under
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irradiation of 5 s with 407 nm light of LD with 200 mW.
Correspondingly, the Rt values of the samples with x = 0.02,
0.04, 0.06, and 0.08 are 87.97% (maximum of 95.45%), 86.01%
(maximum of 94.17%), 85.14% (maximum of 92.80%), and
76.76% (maximum of 87.11%), respectively. It can be observed
the Rt value exhibits a decreased trend with Er concentrations,
which may be related to dopant-induced defects.26 The curves of the
emission intensity versus irradiation time show nonlinear behavior,
well satisfying the exponential relaxation model.27 In comparison
to the degree of luminescence modulation based on PL emission
excited by 490 nm, the Rt value from UC emission is slightly lower
(Figure 5b) but the saturated Rt values (average value) are still up
to 88.93% for x = 0.01, 89.17% for x = 0.02, 87.44% for x = 0.04,
89.24% for x = 0.06, and 73.14% for x = 0.08. The high
luminescence contrast above is desired for signal readout, which is
essential for nondestructive photochromic readout applications.9
Besides, the degree of the luminescence modulation is also
strongly dependent upon the wavelength of irradiation light,
apart from irradiation intensity and time above. We take the
sample of x = 0.04 as an example; the PL emission spectral
changes with dierent wavelength irradiations of 360, 450,
470, 490, 524, and 600 nm are shown in Figure 6, wherein a

Figure 7. PL luminescence modulation (Rt) upon alternating 407 nm

visible light irradiation and thermal stimulus under ve periods: (a)
x = 0.01, (b) x = 0.02, (c) x = 0.04, (d) x = 0.06, and (e) x = 0.08.

Figure 6. PL spectral changes of the NBN:0.04Er sample under dierent

irradiation times by irradiation of 360, 450, 470, 490, 524, and 600 nm.

xenon lamp in F4600 is regarded as an irradiation light source.

Interestingly, 407 nm light irradiation results in a higher
luminescence contrast than that of other wavelengths, indicating
that the NBN:xEr system is very sensitive to the visible light
region (407 nm) near the absorption edge during the PC process.
Moreover, reversible luminescence intensity changes upon
photochromic reactions are also observed by alternating visible
light irradiation (407 nm) and thermal stimulus (200 C for
10 min). Figures 7 and 8 give the PL and UC emission intensity
changes (Rt versus number of cycles) of all samples. It is found
that the luminescence switching is highly eective, with almost
no obvious decay of emission intensity, which indicates the
reversible luminescence switching capability.
The mechanism of visible light coloration and luminescence
modulation can be interpreted in terms of the free or trapped

Figure 8. UC luminescence modulation (Rt) upon alternating 407 nm

visible light irradiation and thermal stimulus under 10 cycles: (a)
x = 0.01, (b) x = 0.02, (c) x = 0.04, (d) x = 0.06, and (e) x = 0.08.

charge carrier and intervanlence-charge transfer (IVCT).28,29

Upon irradiation with visible light, electrons from the low-energy
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PC eects was realized and a larger luminescence contrast of

about 95% was achieved under visible light irradiation of 5 s.
The colorationdecoloration process can be eectively read out
by two ways: UC and DS, which can well satisfy the requirements
of nondestructive luminescent readout for optical storage
devices. The luminescence is reversibly quenched by alternating
visible light irradiation and thermal stimulus, and after undergoing several cycles, the luminescence emission intensity has no
signicant degradation, showing very excellent reproducibility.
This high luminescence contrast combined with excellent
reversibility makes the material a promising application in
detecting, imaging, data storage, energy conversion, and other
smart uses.

states in Er-doped NBN are promoted to higher energy levels

(defect levels or metal f orbitals) and trapped at the donor level
(oxygen vacancies, VO ) within the forbidden gap of NBN.14
These f electrons facilitate the absorption of visible light via
IVCT among the formed F centers and ff transitions of Er3+
ions, which gives rise to a strong absorption in the region of 400
700 nm (Figure 4b), thus leading to the observed PC (Figure 4a).
The light-induced charge transfer is conrmed by the electron
spin resonance (ESR) spectra at room temperature, as shown
in Figure S6 of the Supporting Information.30 This is observed
indirectly through the appearance of the weak axial spectra of Bi3+
in the NBN host after sunlight irradiation of 5 s. Because the UC
or PL emission characteristic is located in the same absorption
region of Er-doped NBN, the resonance energy transfer from
Er ions to NBN host occurs, thus leading to a signicant
luminescence quenching (Figure 9).2,8 When heated to 200 C

ASSOCIATED CONTENT

S Supporting Information
*

The Supporting Information is available free of charge on the

ACS Publications website at DOI: 10.1021/acsami.5b12262.
SEM images of NBN:xEr samples (Figure S1), PL and
photoluminescence excitation (PLE) spectra of
NBN:0.04Er (Figure S2), UC emission intensity at
dierent pumping powers (Figure S3), reectance spectra
changes of NBN:xEr samples before and after sunlight
irradiation of 5 s (Figure S4), photographs of the NBN:xEr
samples before and after 407 nm irradiation of 4 min
(Figure S5), ESR signals of NBN:0.04Er sample before
and after sunlight irradiation of 5 s (Figure S6), PL
luminescence modulation (Rt) upon alternating 407 nm
visible light irradiation under dierent thermal treatment
temperatures for NBN:0.04Er sample (Figure S7), decay
curves of NBN:0.04Er before and after sunlight irradiation
of 5 s (Figure S8), patterned imaging of NBN ceramic
pellet written by sunlight irradiation through a copper grid
with circular pores of 1 mm diameter (Figure S9),
frequency dependence of dielectric constant and loss for
NBN:xEr (Figure S10), and polarization versus electric
eld hysteresis loops for NBN:xEr (Figure S11) (PDF)

Figure 9. Mechanism of luminescence modulation for NBN:Er samples.

for 10 min, the colored samples would completely return to

their initial color state; subsequently, the resonance energy
transfer would disappear, with the luminescence emission
recovered (Figure 4c). The degree of the resonance energy
transfer (luminescence quenching degree) strongly depends
upon the thermal treatment temperature. With an increasing
heating temperature for samples with sucient coloration, the
luminescence quenching degree increases, as shown in Figure S7
of the Supporting Information. Furthermore, the luminescence
decay dynamics for the NBN:0.04Er sample before and after
sunlight irradiation of 5 s further reveal the charge-transfer
process (Figure S8 of the Supporting Information). The average
decay lifetime is found to be 67.3651 s (b) before irradiation
while slightly decreasing to 66.8104 s (a) after irradiation.
The energy transfer rate can be estimated to be 0.123 ns1,
according to the formula: KET = (1/a) (1/b). By employing
the patterned illumination (a simple mask), the dierent images
could be successfully recorded and erased on the NBN materials,
as shown in Figure S9 of the Supporting Information. Such a
high-contrast luminescence switching coupled with multifunctionality, PC, PL (UC and DS), and its ferro-/piezoelectricity (Figures S10 and S11 of the Supporting Information),
may have new application potentials in photonic storage and
optoelectronic multifunctional devices.

AUTHOR INFORMATION

Corresponding Author

*E-mail: zqw8000@imust.edu.cn and/or xhhao@imust.edu.cn.

Notes

The authors declare no competing nancial interest.

ACKNOWLEDGMENTS
This work was supported by the Natural Science Foundation of
China (51562030 and 51462028), the Natural Science Foundation
of Inner Mongolia (2015BS0503 and 2014MS0522), the Research
Fund for Higher Education of Inner Mongolia (NJZZ14158), and
the Young Academic Core Program of Inner Mongolia University
of Science and Technology (2015QNGG04).

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In summary, we developed a new photochromic system with
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DOI: 10.1021/acsami.5b12262
ACS Appl. Mater. Interfaces 2016, 8, 47894794