Articles

https://doi.org/10.1038/s41566-020-00714-6

NIR II-responsive photon upconversion through

energy migration in an ytterbium sublattice
Bo Zhou 1 ✉, Long Yan1, Jinshu Huang1, Xuelong Liu1, Lili Tao2 and Qinyuan Zhang 1 ✉

Smart control of photon upconversion is a key strategy for lanthanide-based materials used in biological and photonic applica-
tions. However, this has remained a challenge for the upconversion luminescence of lanthanides under excitation in the second
near-infrared (NIR II) biowindow instead of at the conventional 980 and 808 nm wavelengths. Here, we report a conceptual
design for an energy-migratory ytterbium sublattice in an erbium-sensitized multilayer core–shell nanostructure that is able to
achieve photon upconversion from a broad range of lanthanide ions (Yb3+, Tm3+, Ho3+, Gd3+, Eu3+ and Tb3+) under 1,530 nm irra-
diation. The quasi-single-band upconversion in the first near-infrared (NIR I) biowindow is also realized through fine manipula-
tion of the introduced cross-relaxations. By establishing an interfacial energy-transfer-mediated nanostructure, we also gain a
deep insight into the mechanistic features of the energy migration. These results open new opportunities in a variety of frontier
applications, such as information security.

P
hoton upconversion is a nonlinear anti-Stokes process featur-
ing high-energy (short-wavelength) photon emission under
low-energy (long-wavelength) photon irradiation1. This phe-
nomenon has been observed in a broad range of materials, from bulk
to films, phosphors and nanomaterials. Lanthanide ions have been
shown to be ideal candidates for photon upconversion due to their
unique electronic configurations with abundant discrete energy
levels1–4. The emergence of lanthanide-doped nanoparticles has
provided more opportunities related to their many biological appli-
cations5–14, as well as other frontier fields such as three-dimensional
(3D) volumetric displays15, super-resolution nanoscopy16, infor-
mation storage and security17,18 and upconversion lasers19,20. Many
mechanistic efforts have been made to manipulate photon upcon-
version, including a core–shell structure design for upconver-
sion of lanthanides without intermediate states21, Nd3+-sensitized
upconversion6,22,23, colour-switchable upconversion15,24,25 and a
photon-avalanche-like process for amplified stimulated emission16.
Recently, it has been shown that interfacial energy transfer (IET) is
also an efficient way to tune upconversion and examine the interac-
tions between lanthanides on a nanometre length scale26,27.
Despite the great progress made in research on upconver-
sion, previous works have been heavily dependent on excitation
wavelengths in the short near-infrared region (for example, 980
and 808 nm). The longer infrared second near-infrared (NIR II)
spectral region, particularly at around 1,530 nm, has attracted
increasing interest because of its great promise in deep-tissue and
high-resolution imaging28,29. It is also associated with optical com-
munications, where versatile lasers and optical components are
commercially available30,31. Research on NIR II-responsive photon
upconversion would contribute markedly to fundamental research
into luminescent materials as well as their biological and photonic
applications. However, most lanthanide ions are non-responsive to
the 1,530 nm wavelength due to the mismatch of metastable energy
levels and a lack of feasible pump configurations1. Although Er3+
has a good spectral response around 1,490–1,550 nm (refs. 32–34),
it cannot function well as the NIR II sensitizer in the commonly
used sensitizer–activator co-doping scheme because of deleteri-
ous quenching interactions35. It has thus remained a challenge to
achieve smart control of photon upconversion from a series of lan-
thanide ions upon NIR II excitation.
Recently, Yb3+ has demonstrated good energy-migratory per-
formance to accompany its usual role as a sensitizer in conven-
tional upconversion materials (for example, in an Yb–Er coupled
system)6,22. The use of such energy migration can effectively
enhance Nd3+-sensitized upconversion and mediate upconversion
and downshifting luminescence dynamics with tuning of the rise
and decay times7,36,37. Therefore, a combination of sensitizing Er3+
and a migratory Yb sublattice in a well-designed nanostructure
could offer new opportunities for the development of efficient and
versatile upconversion materials.
Here, we describe a novel mechanistic strategy to realize
NIR II-responsive upconversion from a series of lanthanide ions.
As illustrated in Fig. 1a, the upconversion scheme was estab-
lished by constructing an energy-migratory Yb sublattice in an
erbium-sensitized nanostructure in which the sensitizer and emit-
ter are spatially separated. We show that the excitation energy
can be efficiently transported from sensitizer to emitter through
the Yb3+-mediated energy-migration channel. In this design, Er3+
can work well as a sensitizer to harvest the 1,530 nm irradiation
energy via its 4I13/2 ← 4I15/2 absorption transition. Notably, the good
spectral overlap between upconverted Er3+ emission (4I11/2 → 4I15/2
transition) and Yb3+ absorption (2F5/2 ← 2F7/2 transition) at around
977 nm greatly boosts resonant energy transfer from Er3+ to Yb3+
(Fig. 1b,c). Another key feature of the migratory Yb sublattice is
that it can effectively isolate any unwanted deleterious interactions
between sensitizer and emitter that could quench the upconversion
luminescence. As a result, this design makes it possible to achieve
photon upconversion from a broad range of lanthanide ions under
1,530 nm excitation (Fig. 1d). Moreover, it inspires us to revisit and
break stereotypes about the conventional role of each lanthanide ion

State Key Laboratory of Luminescent Materials and Devices, Guangdong Provincial Key Laboratory of Fiber Laser Materials and Applied Techniques,
1

and Guangdong Engineering Technology Research and Development Center of Special Optical Fiber Materials and Devices, South China University of
Technology, Guangzhou, China. 2School of Materials and Energy, Guangdong University of Technology, Guangzhou, China. ✉e-mail: zhoubo@scut.edu.cn;
qyzhang@scut.edu.cn

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a b c
Yb sublattice Spectral overlap Yb3+ emission
Er3+
Er3+
ET Yb3+ Er3+/Yb3+

Normalized intensity

Normalized intensity
4
I9/2 ET EM
4 Em. Yb3+ : Er3+ : Yb3+ :
I11/2
Energy

4
2
F5/2
2
F5/2 ← F7/22 I11/2 → 4I15/2 2
F5/2 → 2F7/2
4
I13/2
Ex.

2
4
I15/2 F7/2
3+ 3+
Er Yb Yb3+ A3+ 900 1,000 1,100 900 1,000 1,100
(Sensitizer) (Migratory region) (Emitter ) Wavelength (nm) Wavelength (nm)

d
Typical upconversion transitions
Er3+ : 4G11/2 → 4I15/2

Er3+ : 2H11/2 → 4I15/2

Ho3+ : 5F4,5S2 → 5I8

Ho3+ : 5F4,5S2 → 5I7

Gd3+ : 6P7/2 → 8S7/2

Yb3+ : 2F5/2 → 2F7/2

Er3+ : 2H9/2 → 4I15/2

Er3+ : 4I11/2 → 4I15/2

Er3+ : 4S3/2 → 4I15/2

Er3+ : 4F9/2 → 4I15/2

Er3+ : 4I9/2 → 4I15/2

Tm3+ : 1G4 → 3H6

Tm3+ : 3H4 → 3H6

Tm3+ : 1D2 → 3H6

Tm3+ : 1G4 → 3F4

Tm3+ : 1D2 → 3F4

Tm3+ : 3F3 → 3H6

Eu3+ : 5D0 → 7F1
Eu3+ : 5D0 → 7F2

Eu3+ : 5D0 → 7F4

Tb3+ : 5D4 → 7F6

Tb3+ : 5D4 → 7F5

Tb3+ : 5D4 → 7F4
Tm3+ : 1I6 → 3H6

Tm3+ : 1I6 → 3F4

Ho3+ : 5F5 → 5I8

Ho3+ : 5I6 → 5I8

Excitation
wavelength

UV NIR

300 400 500 600 700 800 900 1,000 1,100 1,200 1,300 1,530
Wavelength (nm)

Fig. 1 | NIR II-responsive photon upconversion through energy migration in an Yb sublattice. a, Schematic of the conceptual upconversion model,
achieved by constructing a migratory Yb sublattice in an erbium-sensitized nanostructure, and the energy transport process involved. ET, energy transfer;
EM, energy migration; Ex., excitation; Em., emission. b, Spectral overlap between Er3+ emission and Yb3+ absorption allows an efficient energy transfer
from Er3+ at its 4I11/2 level to Yb3+ at its 2F5/2 level. c, A comparison of near-infrared upconversion emission profiles from NaErF4:Yb(10 mol%)@NaYF4 and
NaErF4@NaYF4 core–shell nanoparticles under 1,530 nm excitation. d, A summary of the upconversion transitions of lanthanide ions that are available
under 1,530 nm excitation.

in upconversion systems towards versatile control of luminescence Figs. 3 and 4). The outermost NaYF4 layer in these samples was used
dynamics. Because of the NIR II excitation wavelength, this concep- to eliminate possible surface quenching effects (Supplementary
tual design is also able to reach a much larger anti-Stokes shift com- Fig. 5). Acting as a control, the absence of a migratory NaYbF4
pared to upconversion systems at short near-infrared excitations. interlayer in the sample only resulted in much weaker Tm3+ emis-
As a proof of concept, we designed a set of multilayer core–shell sion, in particular in the short-wavelength range (Supplementary
nanostructures, separately incorporating each lanthanide dopant Fig. 6), and no Tm3+ emission was recorded for the sample with-
(Fig. 2a). The possibility of upconversion from Tm3+ at 1,530 nm out doping of Yb3+ in the interlayer (Supplementary Fig. 7). This
excitation was first examined by preparing NaErF4:Yb/Y@NaYbF4@ implies the existence of strong interactions between Er3+ and Tm3+,
NaYF4:Yb/Tm@NaYF4 multilayer core–shell nanoparticles (Type-I which seriously quench the emission of Tm3+. This observation
design in Fig. 2a) using a modified co-precipitation method is in agreement with structural designs for multicolour switch-
(Supplementary Methods)26. These nanoparticles exhibit a mono- able upconversion, in which an inert interlayer is essential for
disperse characteristic with an average size of 57.3 nm (top panel of Tm3+ emissions24,25,38. Further control experiments indicated that
Fig. 2b, Supplementary Fig. 1 and Supplementary Table 1) and are in a 2.9-nm-thick interlayer can effectively isolate interfacial interac-
the hexagonal phase according to their Fourier-transform diffrac- tions (Supplementary Fig. 8), a thinner migratory layer with high
tion pattern (right bottom panel of Fig. 2b) and X-ray diffraction Yb3+ concentration is much better than a thicker migratory layer
results (Fig. 2c and Supplementary Fig. 2a). The observation of clear with low Yb3+ concentration, and the NaYbF4 layer has an optimal
lattice fringes with a d-spacing of 0.52 nm in Fig. 2b (left bottom thickness (Supplementary Figs. 9 and 10). The presence of an appro-
panel) reveals its good crystalline property. Besides an increment in priate amount of Yb3+ in the sensitizing core and luminescent layer
size (Supplementary Fig. 2b), the multilayer core–shell nanostruc- can further improve the total energy-transport process, whereas
ture is also evidenced by the distributions of each lanthanide ele- it is almost useless for the simple co-doping of all lanthanides in
ment (Fig. 2d). the core region, as shown for NaErF4:Yb/Tm@NaYF4 nanoparticles
Under 1,530 nm excitation, typical upconverted emissions of (Supplementary Fig. 11). It should be noted that direct activa-
Tm3+ ranging from the near-infrared (for example, 802 nm from the tion of Tm3+ by Er3+ is only available for a very low Er3+ concen-
3
H4 → 3H6 transition) to the visible (for example, 476 nm from tration39, such as NaYF4:Er/Tm(2/0.5 mol%)@NaYF4, resulting in
the 1G4 → 3H6 transition) and ultraviolet (for example, 360 nm from very weak upconversion (Supplementary Fig. 12). These results
the 1D2 → 3H6 transition) were observed, separate from the green clearly confirm the critical role of the energy-migratory Yb sublat-
and red emissions of the Er3+ sensitizer (Fig. 2e and Supplementary tice in achieving upconversion emission of Tm3+ upon excitation

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a
Type I Type II Type III Er3+ Yb3+
Tm3+ Gd3+
Eu3+, Tb3+
Energy migration
Energy transfer
NIR II excitation
Tm3+ (Ho3+) Gd3+ Eu3+ (Tb3+) Upconverted emission

b c e
Er3+ emission

Intensity (a.u.)

200 nm Tm3+ emission

(0 PDF#16-0334
0.5 01)
2n ×5
m ×5

20 40 60 80
Gd3+ emission

Intensity (a.u.)
10 nm 2θ (°)

d ×5

Eu3+ emission
×20

100 nm Tm Y+Er Yb+Er

Tb3+ emission

×20

Er Yb Y Y+Yb 300 400 500 600 700 800

Wavelength (nm)

Fig. 2 | Sample designs, characterization and upconversion emissions. a, Schematic of three structural designs of the samples (Types I–III) and the energy
transport processes involved. b, Transmission electron microscopy (TEM) image (top), high-resolution TEM image (bottom left) and Fourier-transform
diffraction pattern (bottom right) of the as-synthesized NaErF4:Yb/Y(10/40 mol%)@NaYbF4@NaYF4:Yb/Tm(50/1 mol%)@NaYF4 multilayer core–shell
nanoparticles. c, X-ray diffraction pattern of the sample from b. Data from hexagonal NaYF4 is also plotted (PDF#16-0334). d, Element mappings of Er,
Yb, Tm, Y and some overlaps of them for the sample in b. e, Upconversion emission spectra obtained from the NaErF4:Yb/Y(10/40 mol%)@NaYbF4@
NaYF4:Yb/Tm(50/2 mol%)@NaYF4, NaErF4:Yb/Y(10/40 mol%)@NaYbF4@NaGdF4:Yb/Tm(50/1 mol%)@NaYF4 and NaErF4:Yb/Y(10/40 mol%)@
NaYbF4@NaGdF4:Yb/Tm(50/1 mol%)@NaYF4:A (A = Eu, Tb; 5 mol%) multilayer core–shell nanoparticles together with a control sample of
NaErF4:Yb/Y(10/40 mol%)@NaYF4 core–shell nanoparticles under 1,530 nm excitation.

at 1,530 nm. Details of the energy-transport process are illustrated
schematically in Supplementary Fig. 13.
Strikingly, the observation of ultraviolet Tm3+ emissions under
1,530 nm irradiation would further enable photon upconversion
of more lanthanide ions towards emissions at specific wavelengths.
Indeed, the presence of Gd3+ in the luminescent layer (Type-II
design in Fig. 2a) led to its 311 nm emission (6P7/2 → 8S7/2 transi-
tion; Fig. 2e and Supplementary Fig. 14). It is worth noting that
the anti-Stokes shift of this emission is as large as 1,219 nm, a value
that is not achievable for conventional 980 or 808 nm upconver-
sion systems. By further introducing the lanthanides of Eu3+ and
Tb3+ into the outermost shell layer (Type-III design in Fig. 2a), their
typical upconversion emissions, such as the red emission of Eu3+
at 615 nm (5D0 → 7F2 transition), were also easily accessible (Fig. 2e
and Supplementary Fig. 15). In the above two sample designs, Tm3+
was involved in the upconversion process, as its ladder-like energy
levels can further upconvert the energy that Yb3+ transfers to the
shell (Supplementary Fig. 16). The Yb-mediated energy migration
also applies to the upconversion of Ho3+ under 1,530 nm excita-
tion (Supplementary Figs. 13b and 17). Notably, energy migration
among Er3+ ions in the core region cannot be taken into consider-
ation (Supplementary Fig. 18), although it is a primary origin of
the energy loss for an erbium-based host such as NaErF4 (ref. 40).
These observations have extensively demonstrated that the migra-
tory Yb sublattice-mediated nanostructure is a general approach to
the 1,530-nm-responsive upconversion of lanthanide ions.
Although highly effective for upconversion, the sample designs in
Fig. 2a cannot be used to examine the mechanism of energy migration
because of the presence of different Yb3+ compositions in the migra-
tory interlayer and other regions (Supplementary Fig. 19). To gain a
deeper insight into this issue, we designed a NaYF4:Nd(40 mol%)@
NaYF4:Yb(0–100 mol%)@NaYF4:Ho(2 mol%) core–shell–shell
nanostructure to confine Yb3+ in the interlayer, enabling the detec-
tion of Yb-mediated energy migration (Fig. 3a,b and Supplementary
Fig. 20a). In detail, Nd3+ was used in the core to sensitize Yb3+ in
the migratory interlayer through an IET process, from Nd3+ (at its
4
F3/2 state) to Yb3+ (at its 2F5/2 state), at 808 nm excitation (Fig. 3c).
Ho3+ was adopted in the outermost shell to detect energy migration
in the interlayer because it can be activated by the Yb-to-Ho IET
process, with the resultant observation of Ho3+ emission (Fig. 3d).

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a c d
Without Yb3+ Without Yb3+
Nd3+
NaYF4:Nd With Yb3+ With Yb3+
Yb3+
NaYF4:Yb(0–100 mol%) Yb3+
Ho3+ emission
NaYF4:Ho Ho3+

Intensity (a.u.)

Intensity (a.u.)
NIR Visible

800 900 1,000 1,100 500 550 600 650

Wavelength (nm) Wavelength (nm)
Sensitizing Migratory Detecting
core interlayer shell
b e f
Emission
5 1.5 Absorption
F4,5S2
Spectral

Normalized intensity
IET 5
F5 overlap

Intensity (a.u.)

Lifetime (ms)
IET EM
4 1.0
Energy

F3/2
542 nm

645 nm

2
F5/2
808 nm

Em.
0.5
2 Ho3+ emission
F7/2 5
I8
4
I9/2 Yb3+ lifetime
Nd3+ Yb3+ Yb3+ Yb3+ Ho3+
0
NaYF4:Nd NaYF4:Yb NaYF4:Ho 0 20 40 60 80 100 900 1,000 1,100
Yb3+ content (mol%) Wavelength (nm)

Fig. 3 | Mechanistic investigation of energy migration in the Yb sublattice. a, Schematic of the proposed NaYF4:Nd@NaYF4:Yb(0–100 mol%)@
NaYF4:Ho core–shell–shell nanostructure for investigating energy migration in the Yb sublattice by recording the change in Ho3+ emission from the
outermost detecting shell layer with irradiation at 808 nm. b, The energy transport process involved in the design of a. c, Near-infrared emission spectra of
NaYF4:Nd(40 mol%)@NaYF4:Yb(10 mol%) and NaYF4:Nd(40 mol%)@NaYF4 core–shell nanoparticles under 808 nm excitation. d, Upconversion emission
spectra of NaYF4:Nd(40 mol%)@NaYF4:Yb(50 mol%)@NaYF4:Ho(2 mol%) and NaYF4:Nd(40 mol%)@NaYF4@NaYF4:Ho(2 mol%) nanoparticles under
808 nm excitation. Inset: Ho3+ emission photograph of the former sample. e, Dependence of Ho3+ emission intensity and lifetime of Yb3+ at its 2F5/2 state
on the concentration of Yb3+ in the NaYF4:Nd(40 mol%)@NaYF4:Yb(0–100 mol%)@NaYF4:Ho(2 mol%) core–shell–shell nanoparticles with excitation at
808 nm. f, Emission and absorption spectral overlap for the 2F5/2 ↔ 2F7/2 transitions of Yb3+.

It should also be noted that both Yb3+ and Ho3+ are non-responsive
to the incident 808 nm excitation. Therefore, this design allows an
in-depth study of energy migration over the Yb sublattice by moni-
toring changes in the Ho3+ emission profile.
As shown in Fig. 3e and Supplementary Fig. 20b, under 808 nm
excitation, the emission intensity of Ho3+ depends closely on the
Yb3+ concentration in the migratory interlayer. The initial increase
in Ho3+ emission with increasing Yb3+ concentration in the inter-
layer can be understood by a reduction of interionic Yb3+ separa-
tion that can, in principle, facilitate more efficient energy migration,
according to Dexter’s theory1,41. The decline in emission observed
at much higher Yb3+ content might result from the concentration
effect, which may cause additional energy loss. This is in accor-
dance with the decrease in the lifetime of Yb3+ in the 2F5/2 state dur-
ing this process (Fig. 3e and Supplementary Fig. 21a). Intriguingly,
the interlayer with low Yb3+ concentration (for example, 10 mol%)
begins to show migratory performance, possibly due to its simple
electronic energy levels with a broad spectral overlap between
the associated emission and absorption transitions (Fig. 3f). An
Yb3+ content of 50 mol% produced an optimum energy-migration
property with an Yb3+–Yb3+ separation of 5.25 Å (Supplementary
Fig. 22)42. These observations suggest that Yb3+ is a good candidate
to enable upconversion of lanthanides via its energy-migration
property. On the other hand, intense Yb3+ intrinsic emission at
around 977 nm was also recorded (Supplementary Fig. 21b), imply-
ing that there is competition between energy migration and spon-
taneous radiation at the migratory 2F5/2 level. However, this might
leave room to further improve the migration performance over the
Yb sublattice by suppressing its spontaneous radiative transition
(Supplementary Fig. 23).
We next investigated how to realize NIR I single-band upconver-
sion of Tm3+ at around 802 nm, a commonly used wavelength region
for bioapplications6,23. To minimize unwanted visible emission
from the Er3+ sensitizer, Ce3+ was introduced into the core matrix
to depopulate its visible-emitting levels through cross-relaxation.
Figure 4a shows four typical cross-relaxation processes (CR1–4)
that can occur at the 4S3/2, 4F9/2, 4I9/2 and 4I11/2 levels of Er3+, respec-
tively. Note that CR1–3 can help populate Er3+ at 4I11/2, while CR4
is a depopulating process for this energy level because it reduces
the energy transfer from Er3+ (4I11/2) to Yb3+ (2F5/2). Consequently,
optimization of the Ce3+ concentration is needed. As shown in
Fig. 4b and Supplementary Fig. 24, the visible upconversion of Er3+
is effectively depressed in the presence of increased Ce3+ in the
core region. When Ce3+ reaches 0.4 mol%, the 802 nm emission
intensity accounts for over 90% of the total upconversion emis-
sion spectrum (Fig. 4c). This percentage is well maintained over
a broad range of pump power densities (up to 1.86 × 102 W cm−2;
Fig. 4c and Supplementary Fig. 25). In these samples, the presence
of a small amount of Ce3+ did not lead to its emission, and had
almost no impact on the size and morphology of the nanoparticles
(Supplementary Figs. 26 and 27). Thus, we can experimentally con-
sider it to be an NIR II-to-NIR I quasi-single-band upconversion
for samples with Ce3+ content higher than 0.4 mol%. This is particu-
larly attractive for biological applications. A detailed investigation

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a b
20 Ce3+ (mol%)
2
H11/2
4 0
CR1 S3/2
0.2
4 ET 0.4
15 CR2 F9/2 3
F2,3

NaYF4 protecting layer

0.6
Energy (×103 cm–1)

4
I9/2 3
H4
CR3 ET EM 0.8

Intensity (a.u.)
10 4 1.0
I11/2
CR4 2
F5/2 3
H5
4
I13/2 3
F4
5
802 nm
1,530 nm
2
F7/2 2
F7/2
4
0 2
F5/2 I15/2 3
H6
Ce3+ Er3+ Yb3+ Yb3+ Yb3+ Yb3+ Tm3+ 400 500 600 700 800
Wavelength (nm)

c 100 d e
90% 4
I11/2 With Ce3+
1.0 4
I9/2 Without Ce3+
80 4
802 nm F9/2
Normalized intensity

4
S3/2

Intensity (a.u.)
60
γ (%)

100 90% Eu3+ emissions

0.5
40
γ (%)

50
×10
20 0
0 50 100 150 200
Power density (W cm–2)
0 0
0 0.2 0.4 0.6 0.8 1.0 0 0.2 0.4 0.6 0.8 1.0 500 600 700
Ce3+ content (mol%) Ce3+ content (mol%) Wavelength (nm)

Fig. 4 | Tuning photon upconversion through Ce3+-mediated cross-relaxation. a, Schematic of Ce3+-mediated cross-relaxations (CR1–4) towards
quasi-single-band upconversion of Tm3+ in the NIR I biowindow. CR1: [Er3+ (4S3/2), Ce3+ (2F5/2)] → [Er3+ (4F9/2), Ce3+ (2F7/2)]; CR2: [Er3+ (4F9/2), Ce3+
(2F5/2)] → [Er3+ (4I9/2), Ce3+ (2F7/2)]; CR3: [Er3+ (4I9/2), Ce3+ (2F5/2)] → [Er3+ (4I11/2), Ce3+ (2F7/2)]; CR4: [Er3+ (4I11/2), Ce3+ (2F5/2)] → [Er3+ (4I13/2), Ce3+ (2F7/2)].
b, Upconversion emission spectra of NaErF4:Yb/Y/Ce(10/40/x; x = 0–1.0 mol%)@NaYbF4@NaYF4:Yb/Tm(49/1 mol%)@NaYF4 multilayer core–shell
nanoparticles under 1,530 nm excitation. c, The integrated intensity percentage (γ) of 802 nm emission as a function of Ce3+ concentration for the samples
in b. Inset: the percentage of the sample doping with 0.4 mol% Ce3+ under different pump power densities. d, Dependence of the upconversion emissions
of Er3+ on Ce3+ concentration for NaErF4:Y/Ce(50/x; x = 0–1.0 mol%)@NaYF4 core–shell nanoparticles. e, Upconversion emission spectra of NaErF4:Yb/Y/
Ce(10/40/x; x = 0, 0.4 mol%)@NaYbF4@NaGdF4:Yb/Tm(50/1 mol%)@NaYF4:Eu(5 mol%) nanoparticles under 1,530 nm excitation.

showed that emission at 802 nm has much deeper penetration depth Er3+ at such an energy level. This is in agreement with estimates of
in pork tissue slides than that at 662 nm under 1,530 nm excitation cross-relaxation rates that are smaller for CR4 than the other three
(Supplementary Fig. 28). As a control, visible upconversion light processes (Supplementary Figs. 32 and 33, Supplementary Scheme 1
from a typical 808 nm excitation scheme (for example, NaYF4:Yb/ and Supplementary Table 2)1,43–45. Introducing Ce3+ into the Type-II
Er@NaYF4:Nd core–shell nanoparticles) was barely observed, even and Type-III samples can also improve the upconversion emis-
with a 0.9-mm-thin pork tissue slide (Supplementary Fig. 29). sions of emitters, although they are still relatively weak (Fig. 4e and
To shed more light on the cross-relaxation, the impact of Ce3+ on Supplementary Fig. 34). On the other hand, there was almost no
the 4I9/2 and 4I11/2 energy levels of Er3+ was investigated further. The quenching effect observed for Er3+ at its 4I13/2 state due to the pres-
emissions from these two levels were almost completely covered by ence of Ce3+ (Supplementary Fig. 35), which helps in maintaining
those of Tm3+ (at 802 nm) or Yb3+ (at 977 nm) for the aforemen- an efficient excitation scheme at a wavelength of 1,530 nm.
tioned sample (Fig. 4a and Supplementary Fig. 30), making it dif- As an added benefit, the use of an energy-migratory Yb sub-
ficult to distinguish them precisely from the measured spectrum. lattice provides an approach to manipulating the upconversion
Here, the control sample of NaErF4:Y/Ce@NaYF4 was prepared by dynamics to achieve switchable control of emission colours. The
substituting inert Y3+ for Yb3+ in the core region as well as removing NaErF4@NaYbF4 core–shell nanostructure design resulted in a
the other layers to get rid of the interfering emission bands. As dis- red-to-green colour change on switching the excitation from 980
played in Fig. 4d and Supplementary Fig. 31, the near-infrared and to 1,530 nm (Fig. 5a, Supplementary Fig. 36a and Supplementary
visible emissions of Er3+ were recorded and show a rapid decline at Table 3). This might be attributable to the NaYbF4 shell, which
a higher Ce3+ dopant concentration, suggesting the occurrence of provides an energy-transport channel to suppress red upconver-
cross-relaxation at these energy levels. Strikingly, an initial increase sion emission by depopulating the intermediate state (4I11/2) upon
in 977 nm emission was observed for the sample doped with a small 1,530 nm excitation (Supplementary Fig. 36b)35,46. Control samples
amount of 0.2 mol% Ce3+. This implies that, at lower Ce3+ concen- without the NaYbF4 shell or with only Yb3+ in the core did not give
tration, cross-relaxation at the 4I11/2 level might be less efficient than rise to the colour-switchable performance (Supplementary Figs. 37
that at higher energy levels, resulting in a positive population of and 38). Such smart control of output emission colours offers an

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Articles
a b
980-nm excitation
Intensity (a.u.)
1,530-nm excitation
400 500 600
Wavelength (nm)
c
Laser
1 cm
QR pattern
980-nm irradiation
Fig. 5 | Colour-switchable output and its application. a, Upconversion emission spectra of NaErF4@NaYbF4 under 980 nm (top) and 1,530 nm (bottom)
excitations. Insets: corresponding emission photographs. b, The use of 1,530 nm irradiation to decode a ‘dragonfly-on-lotus’ pattern (right), which presents
as dazzle light under 980 nm irradiation (left). c, Schematic of decoding the information patterned in a quick-response (QR) code by scanning with a
mobile phone. The patterns in b and c were prepared using the sample in a and control nanoparticles of NaYF4:Yb/Ho/Ce(20/2/10 mol%)@NaYF4,
NaYF4:Yb/Er(20/2 mol%)@NaYF4 and NaYF4:Yb/Tm(30/1 mol%)@NaYF4.
opportunity for information security. A green ‘dragonfly-on-lotus’
pattern made of NaErF4@NaYbF4 nanoparticles was clearly dis-
tinguished from dazzle light (at 980 nm irradiation) by the use
of 1,530 nm excitation (Fig. 5b, Supplementary Fig. 39 and
Supplementary Table 4). Further preparing a quick-response (QR)
code using these nanoparticles demonstrated their potential to be
applied in anti-counterfeiting (Fig. 5c).
In conclusion, we have mechanistically demonstrated that the
energy-migration-mediated nanostructure is an efficient and gen-
eral approach to realizing NIR II-responsive upconversion from
a broad range of lanthanide ions. Our results provide a thorough
understanding of energy migration in an Yb sublattice and its intrin-
sic role during the dynamic control of upconversion. Moreover, they
should help stimulate new concepts for photon upconversion and
the development of a new class of luminescent materials. On a sepa-
rate note, the Yb sublattice still yields radiation from its migratory
energy level, which will result in competition with energy migration
and limit its performance. We anticipate that future investigations
will search for new strategies to minimize the intrinsic spontane-
ous radiation of the migratory sublattice, develop facile synthetic
methods for multilayer core–shell nanostructures and even simplify
the sample structural designs. Given its versatility and general tun-
ability, the striking conceptual model described here shows great
potential for frontier applications such as biophotonics, information
security and anti-counterfeiting.
Online content
Any methods, additional references, Nature Research report-
ing summaries, source data, extended data, supplementary infor-
mation, acknowledgements, peer review information; details of
author contributions and competing interests; and statements of
data and code availability are available at https://doi.org/10.1038/
s41566-020-00714-6.
Nature Photonics
700 0.5 cm 0.5 cm
980-nm irradiation 1,530-nm irradiation
Laser
1 cm
1,530-nm irradiation
Received: 9 September 2019; Accepted: 2 October 2020;
Published: xx xx xxxx
References
1. Auzel, F. Upconversion and anti-Stokes processes with f and d ions in solids.
Chem. Rev. 104, 139–174 (2004).
2. Haase, M. & Schäfer, H. Upconverting nanoparticles. Angew. Chem. Int. Ed.
50, 5808–5829 (2011).
3. Bünzli, J.-C. G. & Piguet, C. Taking advantage of luminescent lanthanide
ions. Chem. Soc. Rev. 34, 1048–1077 (2005).
4. Zhou, B., Shi, B., Jin, D. & Liu, X. Controlling upconversion nanocrystals for
emerging applications. Nat. Nanotechnol. 10, 924–936 (2015).
5. Idris, N. M. et al. In vivo photodynamic therapy using upconversion
nanoparticles as remote-controlled nanotransducers. Nat. Med. 18,
1580–1585 (2012).
6. Liu, B. et al. Poly (acrylic acid) modification of Nd3+-sensitized upconversion
nanophosphors for highly efficient UCL imaging and pH-responsive drug
delivery. Adv. Funct. Mater. 25, 4717–4729 (2015).
7. Fan, Y. et al. Lifetime-engineered NIR-II nanoparticles unlock multiplexed
in vivo imaging. Nat. Nanotechnol. 13, 941–946 (2018).
8. Ibarra-Ruiz, A. M., Burbano, D. C. R. & Capobianco, J. A. Photoluminescent
nanoplatforms in biomedical applications. Adv. Phys. X 1, 194–225 (2016).
9. Gu, Y. et al. High-sensitivity imaging of time-domain near-infrared light
transducer. Nat. Photon. 13, 525–531 (2019).
10. Song, X. et al. Graphene oxide modified lanthanide nanoprobes for
tumor-targeted visible/NIR-II luminescence imaging. Angew. Chem. Int. Ed.
58, 18981–18986 (2019).
11. Liu, Q. et al. Single upconversion nanoparticle imaging at sub-10 W cm−2
irradiance. Nat. Photon. 12, 548–553 (2018).
12. Ma, Y. et al. Mammalian near-infrared image vision through injectable and
self-powered retinal nanoantennae. Cell 177, 243–255 (2019).
13. Chen, S. et al. Near-infrared deep brain stimulation via
upconversion nanoparticle-mediated optogenetics. Science 359,
679–684 (2018).
14. Ai, X. et al. Multispectral optoacoustic imaging of dynamic redox correlation
and pathophysiological progression utilizing upconversion nanoprobes. Nat.
Commun. 10, 1087 (2019).
15. Deng, R. et al. Temporal full-colour tuning through non-steady-state
upconversion. Nat. Nanotechnol. 10, 237–242 (2015).
Nature Photonics | www.nature.com/naturephotonics
Nature Photonics
16. Liu, Y. et al. Amplified stimulated emission in upconversion nanoparticles for
super-resolution nanoscopy. Nature 543, 229–233 (2017).
17. Lu, Y. et al. Tunable lifetime multiplexing using luminescent nanocrystals.
Nat. Photon. 8, 32–36 (2014).
18. Lee, J. et al. Ultra-wideband multi-dye-sensitized upconverting nanoparticles
for information security application. Adv. Mater. 29, 1603169 (2017).
19. Chen, X. et al. Confining energy migration in upconversion nanoparticles
towards deep ultraviolet lasing. Nat. Commun. 7, 10304 (2016).
20. Fernandez-Bravo, A. et al. Continuous-wave upconverting nanoparticle
microlasers. Nat. Nanotechnol. 13, 572–577 (2018).
21. Wang, F. et al. Tuning upconversion through energy migration in core–shell
nanoparticles. Nat. Mater. 10, 968–973 (2011).
22. Song, N., Zhou, B., Yan, L., Huang, J. & Zhang, Q. Understanding the
role of Yb3+ in the Nd/Yb coupled 808-nm-responsive upconversion. Front.
Chem. 6, 673 (2019).
23. Wang, Y. F. et al. Nd3+-sensitized upconversion nanophosphors: efficient
in vivo bioimaging probes with minimized heating effect. ACS Nano 7,
7200–7206 (2013).
24. Li, X. et al. Filtration shell mediated power density independent orthogonal
excitations–emissions upconversion luminescence. Angew. Chem. Int. Ed. 55,
2464–2469 (2016).
25. Dong, H. et al. Versatile spectral and lifetime multiplexing nanoplatform with
excitation orthogonalized upconversion luminescence. ACS Nano 11,
3289–3297 (2017).
26. Zhou, B. et al. Enabling photon upconversion and precise control of
donor–acceptor interaction through interfacial energy transfer. Adv. Sci. 5,
1700667 (2018).
27. Zhou, B. et al. Constructing interfacial energy transfer for photon up- and
down-conversion from lanthanides in a core–shell nanostructure. Angew.
Chem. Int. Ed. 55, 12356–12360 (2016).
28. Smith, A. M., Mancini, M. C. & Nie, S. Bioimaging: second window for
in vivo imaging. Nat. Nanotechnol. 4, 710–711 (2009).
29. Zhong, Y. et al. Boosting the down-shifting luminescence of rare-earth
nanocrystals for biological imaging beyond 1,500 nm. Nat. Commun. 8,
737 (2017).
30. Zhai, X. et al. Sub-10-nm BaYF5:Yb3+,Er3+ core–shell nanoparticles with
intense 1.53-μm fluorescence for polymer-based waveguide amplifiers.
J. Mater. Chem. C 1, 1525–1530 (2013).
31. Sun, T. et al. Integrating temporal and spatial control of electronic transitions
for bright multiphoton upconversion. Nat. Commun. 10, 1811 (2019).
32. Chen, G., Ohulchanskyy, T. Y., Kachynski, A., Ågren, H. & Prasad, P. N.
Intense visible and near-infrared upconversion photoluminescence in
colloidal LiYF4:Er3+ nanocrystals under excitation at 1,490 nm. ACS Nano 5,
4981–4986 (2011).
Nature Photonics | www.nature.com/naturephotonics
Articles
33. Martín-Rodríguez, R. et al. Highly efficient IR to NIR upconversion
in Gd2O2S:Er3+ for photovoltaic applications. Chem. Mater. 25,
1912–1921 (2013).
34. Liu, L. et al. Er3+ sensitized 1,530 nm to 1,180 nm second near-infrared
window upconversion nanocrystals for in vivo biosensing. Angew. Chem. Int.
Ed. 57, 7518–7522 (2018).
35. Yan, L. et al. Self-sensitization induced upconversion of Er3+ in core–shell
nanoparticles. Nanoscale 10, 17949–17957 (2018).
36. Zuo, J. et al. Precisely tailoring upconversion dynamics via energy
migration in core–shell nanostructures. Angew. Chem. Int. Ed. 57,
3054–3058 (2018).
37. Zhou, L. et al. High-capacity upconversion wavelength and lifetime binary
encoding for multiplexed biodetection. Angew. Chem. Int. Ed. 57,
12824–12829 (2018).
38. Wu, M., Yan, L., Wang, T., Zhou, B. & Zhang, Q. Controlling red
colour-based multicolour upconversion through selective photon blocking.
Adv. Funct. Mater. 26, 1804160 (2019).
39. Cheng, X. et al. Er3+ sensitized photon upconversion nanocrystals. Adv. Funct.
Mater. 28, 1800208 (2018).
40. Johnson, N. J. et al. Direct evidence for coupled surface and concentration
quenching dynamics in lanthanide-doped nanocrystals. J. Am. Chem. Soc.
139, 3275–3282 (2017).
41. Dexter, D. L. A theory of sensitized luminescence in solids. J. Chem. Phys. 21,
836–850 (1953).
42. Nadort, A., Zhao, J. & Goldys, E. M. Lanthanide upconversion luminescence
at the nanoscale: fundamentals and optical properties. Nanoscale 8,
13099–13130 (2016).
43. Teitelboim, A. et al. Energy transfer networks within upconverting
nanoparticles are complex systems with collective, robust
and history-dependent dynamics. J. Phys. Chem. C 123,
2678–2689 (2019).
44. Strohhöfer, C. & Polman, A. Enhancement of Er3+ 4I13/2 population in Y2O3 by
energy transfer to Ce3+. Opt. Mater. 17, 445–451 (2001).
45. Meng, Z. et al. Large improvement in quantum fluorescence yield of
Er3+-doped fluorozirconate and fluoroindate glasses by Ce3+ codoping. J. Appl.
Phys. 88, 2187–2190 (2000).
46. Fischer, S., Bronstein, N. D., Swabeck, J. K., Chan, E. M. & Alivisatos, A. P.
Precise tuning of surface quenching for luminescence enhancement in core–
shell lanthanide-doped nanocrystals. Nano Lett. 16, 7241–7247 (2016).
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Articles
Methods
All experimental details including samples synthesis, characterization and optical
measurements are provided in the Supplementary Information.
Data availability
The data that support the plots within this paper and other findings of this study
are available from the corresponding authors upon reasonable request.
Acknowledgements
This work is supported by the National Natural Science Foundation of China (grants
51972119, 51702101 and 51472088), the Local Innovative and Research Teams Project of
Guangdong Pearl River Talents Program (2017BT01X137), the Young Top-notch Talents
of Guangdong Pearl River Talents Program (2017GC010278) and the One-Hundred
Young Talents Program of Guangdong University of Technology (220413145).
Nature Photonics
Author contributions
B.Z. and Q.Z. conceived and supervised the project. B.Z. designed the experiment.
L.Y. synthesized the samples with the help of J.H. and X.L. L.Y., J.H., X.L., L.T. and B.Z.
performed the characterization and optical measurements. B.Z. and Q.Z. wrote the
manuscript, with input from all authors.
Competing interests
The authors declare no competing interests.
Additional information
Supplementary information is available for this paper at https://doi.org/10.1038/
s41566-020-00714-6.
Correspondence and requests for materials should be addressed to B.Z. or Q.Z.
Reprints and permissions information is available at www.nature.com/reprints.
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