Manual Tierras Raras

Volume 44 Number 6 21 March 2015 Pages 12911716
Chem Soc Rev

Chemical Society Reviews
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Themed issue: Photon upconversion nanomaterials

ISSN 0306-0012
REVIEW ARTICLE
Fan Zhang et al.
Lab on upconversion nanoparticles: optical properties and applications
engineering via designed nanostructure
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44, 1346
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Lab on upconversion nanoparticles: optical

properties and applications engineering via
designed nanostructure
Xiaomin Li, Fan Zhang* and Dongyuan Zhao
Over the past decade, high-quality lanthanide doped upconverting nanoparticles (UCNPs) have been
successfully synthesized with the rapid development of nanotechnology. Due to the unique electron
configuration of lanthanide ions, there are rich energy level structures in the near-infrared, visible and
ultraviolet spectral range. However, for UCNPs, only a limited number of ecient upconversion excitation and
emission have been generated due to the limited number of sensitizer (Yb3+) and activator (Tm3+, Er3+, and
Ho3+) ions, and the application is mainly focused on the bio-imaging by using the upconversion luminescence
of UCNPs. Recently, more and more researchers have started to focus on tuning of upconversion optical
properties and developing of multi-functional UCNPs by using the combination of sub-lattice mediated energy
migration, core@shell structural engineering and UCNPs based nanocomposites which greatly expands the
range of applications for lanthanide-doped UCNPs. Therefore, a nanolab can be created on UCNPs, where
the property modulation can be realized via the designed host-dopants combinations, core@shell
nanostructure, energy exchange with alien species (organic dyes, quantum dots, etc.), and so on. In this
paper, we provide a comprehensive survey of the latest advances made in developing lanthanide-doped
Received 11th May 2014
UCNPs, which include excitation and emission energy levels guided designing of the UCNP nanostructure, the
DOI: 10.1039/c4cs00163j
synthesis techniques to fabricate the nanostructure with optimum energy level structure and optical
properties, the fabrication of UCNPs-based nanocomposites to extend the applications by introducing the
www.rsc.org/csr
additional functional components, or integrating the functional moiety into one nanocomposite.
1. Introduction
Department of Chemistry and Laboratory of Advanced Materials, Fudan University,
Shanghai 200433, P. R. China. E-mail: zhang_ fan@fudan.edu.cn
Xiaomin Li
Xiaomin Li was born in Henan,

China, in 1986. He received his BS
degree (2008) and MS degree
(2011) from Henan University
(China). Since then he has been
studying as a PhD student under
the direction of Professor Dongyuan
Zhao in Fudan University, China.
His current research interests
focus on synthesis of inorganic
nanomaterials, optical spectroscopy and bio-applications of
luminescent nanomaterials.
1346 | Chem. Soc. Rev., 2015, 44, 1346--1378
It is known that rare-earth (RE) materials exhibit not only down

conversion (Stokes type) but also ecient upconversion
Fan Zhang
Prof. Fan Zhang received his PhD

in 2008 from Fudan University followed by more than 2 years
postdoctoral experience in University
of California at Santa Barbara
before joining as an associate
professor
in
the
Chemistry
Department of Fudan University in
2010. He became a full professor in
Fudan University in 2013. His
current research interests include
the development of multifunctional
nanostructured materials and
nanotechnology for applications in
biomedical analysis, drug delivery
and cancer therapy.
This journal is The Royal Society of Chemistry 2015
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Review Article
luminescence (UCL) (anti-Stokes).15 Upconversion refers to

nonlinear optical processes characterized by the absorption of
two or more photons, and leads to the emission of a single
photon at the shorter wavelength. The phenomenon has been
known since the 1960s,6 but the use of the upconversion effect
has been limited to bulk glass or crystalline materials712 and
exploited for the development of some remarkably effective
optical devices such as infrared quantum counter detectors,1315
temperature sensors,1618 and compact solid state lasers.1922
Until the late 1990s, nanoscience and nanotechnology experienced fast momentum.2330 Due to the appropriate small size
(which is small enough to go in and out many biological hosts,
such as cytoplasm, karyon and so on) and the unique optical
properties, the bio-applications of UCNPs for bioimaging have
been reasonably recognized.3134
Recent advances in the integration of UCNPs with biological
and other applications have created tremendous excitements.3542 Starting from late 1990s, the field of UCNPs has
undergone a significant expansion and become one of the most
active research areas within the nanoscience community. Exciting developments have been made at very fast pace from many
research groups. The vast number of papers published about
UCNPs over the past two decades clearly witnesses it, which has
increased exponentially, with most of the activity and development happening in the last ten years. Now, UCNPs are emerging
as an important class of nanomaterials owing to their wide
applications in solid-state lasers, three-dimensional flat panel
displays, and especially bio-labels and bio-imaging.3134,43 Compared with the conventional biological labels, such as organic
dyes and quantum dots, UCNPs have many advantages, including the virtually zero auto-fluorescence back ground for the
improved signal-to-noise ratio, large anti-Stokes shifts allowing
us to easily separate the PL from the excitation wavelength,
narrow emission bandwidths allowing the ease of multiplexed
imaging, and high resistance to photo-bleaching making them
suitable for long-term repetitive imaging. In addition, UCNPs are
Dongyuan Zhao received his BS

(1984) and PhD (1990) from Jilin
University. He carried out
postdoctoral research at the
Weizmann Institute of Science
(19931994), University of Houston (19951996), and University
of California at Santa Barbara
(19961998). He has been a Professor (Cheung Kong and Hao
Qing Professorship) in Fudan
University since 1998. He was
elected as an academician of the
Dongyuan Zhao
Chinese Academy of Science in
2007, and a member of The World Academy of Science (TWAS) in
2010. His research interests mainly include synthesis and application of ordered mesoporous materials.
Chem Soc Rev
non-blinking, less light scattering, and allow a deep tissue

penetration because of excitation being in the near-infrared
(NIR) region that is within the optical transparency window.
Moreover, a new direction for theranostic UCNPs utilizes hierarchically built nanostructures to combine UCL imaging with
other imaging modalities such as magnetic resonance imaging
(MRI),44 computed tomography (CT),45 single-photon emission
tomography (SPECT),46 positron emission tomography (PET),47
as well as with therapeutics of photo-thermal therapy (PTT),33
photo-dynamic therapy (PDT),48 gene and drug delivery,49 for
in vitro and in vivo theranostics. Indeed, significant advances in
theranostic UCNPs have recently been made by using the nanochemistry that allow for nano-control of their optical properties
to enhance upconversion at a selected wavelength,50 surface
modification for phase transfer,51 and surface coupling chemistry
for bio-conjugations.52 By way of metaphor, the fabrication of
UCNPs based nanomaterials is just as creating a lab and
making an experiment in the lab. All the unique properties of
UCNPs based combinations can be attributed to the reaction or
combination among different parts.
This review aims to summarize recent progress in the UCNPs
based nanolab, including excitation and emission energy
levels guided designing of UCNP nanostructures, the synthesis
techniques to fabricate the nanostructure with optimum energy
level structure, the fabrication of UCNPs based nanocomposites
to extend the working range of UCNPs by introducing the
additional functional component, or integrating the additional
functional moiety into one nanocomposite. The organization and
the scope of this review are represented in Fig. 1. In Section 2,
we describe recent advances in dopant and host guided fabrication of the UCNP nanolab to realize the high upconversion
eciency and tunable output colors, respectively. Section 3
is dedicated to core@shell structures based luminescence
engineering of the UCNP nanolab. Section 4 aims to describe
LaMer nucleation-growth model directed controlled synthesis
Fig. 1
Schematic illustration of the structure of this review.
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of lanthanide doped UCNPs. Section 5 summarizes recent

advances in the fabrication of UCNPs based nanocomposites
and the corresponding extended applications including
controllable drug loading & releasing, PDT, bio-sensors, solar
cells and so on. Finally, Section 6 concludes the overall current
status, challenges, and future perspectives for the synthesis and
applications of UCNPs.
2. The components of the UCNPs:

dopants and hosts
An inorganic upconversion phosphor consists of a crystalline
host and a dopant (usually lanthanide ions) added in a low
concentration. The dopant provides luminescent centers, and
the host lattice with its crystal structure provides a matrix to
bring these centers into optimal positions. The ion-to-ion
distance and spatial arrangement are especially important in
UCL. Many lanthanide-doped UCNPs are able to emit visible
light under NIR excitation, but highly ecient upconversion
requires a good tunability between the host lattice, dopant ions,
and doping concentration.
2.1
Lanthanide dopants
Lanthanide ions have a 4fn5s25p6 electron configuration with

n = 014. The partly filled 4f shell is responsible for the unique
optical and magnetic properties. For n electrons in 14 available
orbitals there are 14 over n possible configurations and all
configurations can have different energies. This gives rise to a
rich energy level structure in the NIR, visible (Vis) and ultraviolet
(UV) spectral range. Because the outer 5s and 5p shells shield the
4f inner shell, the electronic transitions are independent of the
surrounding host materials. The trivalent ions may be doped in
different host materials, varying from fluorides to oxides,
depending on the application. The large variety of absorption
and emission wavelengths, the independence of host materials
and low vibration energy losses make lanthanide ions ideal for
spectral conversion. Each lanthanide ion has a unique set of
energy levels and generally exhibits a set of sharp emission peaks
with distinguishable spectroscopic fingerprints (Table 1). It has
been demonstrated that most of the lanthanides ions from La to
Table 1
The major emissions and corresponding energy transitions for making multicolored UCNPs by using dierent dopant ions
Activators
3+
Pr
Nd3+
3+
Sm
Eu3+
Gd3+
Tb3+
Dy3+
Ho3+
Er3+
Tm3+
Lu can exhibit upconversion, including Pr,5357 Nd,58,59 Sm,60,61

Eu,60,61 Gd,6264 Tb,60,61 Dy,60,61 Ho,6567 Er,65,6870 Tm.71,72 In
addition, the luminescence from a given lanthanide ion is
almost independent of different host materials due to the weak
coupling of the ff transition with the local crystal field provided
by the host lattice. Thus, these features enable production of a
range of selective color output by selecting different lanthanide
dopants or using their combinations.
In general, upconversion is a slightly more complex nonlinear
optical process characterized by the successive absorption of two
or more pump photons via intermediate long lived energy states
followed by the emission of the output radiation at a shorter
wavelength than the pump one. The most ecient mechanisms
behind the lanthanide ions based upconversion process are twostep excitation (excitation to the ground state followed by excited
state absorption, GSA/ESA) and subsequent energy transfer
upconversion (ETU, also known as addition de photon par
transfers denergies, the APTE eect).6,73,74 GSA/ESA is a single
ion based process, whereas ETU always involves at least two ions.
Owing to the long lifetime of the excited states, single excited
lanthanide ions may sequentially absorb a second photon of
suitable energy at comparatively low excitation densities and
reach an higher excited state. If energy gaps between three or
more subsequent energy levels are very similar within one ion,
sequential excitation to a highly excited state is possible with a
single monochromatic light source, since each absorption step
requires the same photon energy. This single doping upconversion process can be explained with ESA: excitation takes the form
of successive absorption of pump photons by a single ion. The
general energy diagram of the ESA process is shown in Fig. 2 for
a simple three-level system. If excitation energy is resonant with
the transition from ground level G to excited metastable level E1,
photon absorption occurs and populates E1 from G in a process
known as ground state absorption (GSA). A second pump photon
that promotes the ion from E1 to higher-lying state E2 results in
UCL, corresponding to the E2G optical transition.6,73,74
Lanthanide ions with a ladder-like energy level structure are
suitable for the single doping system including Er3+, Tm3+, and
Ho3+ (Fig. 2), which are currently the most common activators
of UCNPs. The eciency of the upconversion process is particularly high for single doping with Er3+, where a similar energy
Major emissions (nm)
Energy transitions
489, 526, 548, 618, 652, 670, 732, 860
430, 482, 525, 535, 580, 600, 664, 766

555,
590,
204,
490,
570
542,
411,
294,
590
615, 690
254, 278, 306, 312
540, 580, 615
645, 658
523, 542, 656
345, 368, 450, 475, 650, 700, 800
1348 | Chem. Soc. Rev., 2015, 44, 1346--1378
Ref.
P0 - H4, I6 - H5, P0 - H5, P0 - H6, P0 - F2, P1 - F3,

P0 - 3F4, 1I6 - 1G4
2
P1/2 - 4I9/2, 2P1/2 - 4I11/2, 2P1/2 - 4I13/2, 4G7/2 - 4I9/2, 2P1/2 - 4I15/2,
4
G7/2 - 4I11/2, 2G7/2 - 4I9/2, 4G7/2 - 4I13/2, 4G7/2 - 4I15/2
4
G5/2 - 6H5/2, 4G5/2 - 6H7/2
5
D0 - 7F1, 5D0 - 7F2, 5D0 - 7F4
6
G7/2 - 8S7/2, 6D9/2 - 8S7/2, 6IJ - 8S7/2, 6P5/2 - 8S7/2, 6P7/2 - 8S7/2
5
D4 - 7F6, 5D4 - 7F5, 5D4 - 7F4, 5D4 - 7F3
4
F9/2 - 6H13/2
5
S2 - 5I8, 5F5 - 5I8
2
H9/2 - 4I15/2, 2H11/2 - 4I15/2, 4S3/2 - 4I15/2, 4F9/2 - 4I15/2
1
I6 - 3H6, 1I6 - 3F4, 1D2 - 3H6, 1D2 - 3F4, 1G4 - 3H6, 1G4 - 3F4,
3
F3 - 3H6, 3H4 - 3H6
3
5357
58 and 59
60 and
60 and
6264
60 and
60 and
6567
65 and
71 and
61
61
61
61
6870
72
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Fig. 2 Excited state absorption (ESA) upconversion processes of single-doped UCNPs and schematic energy level diagrams showing typical
upconversion processes of Er3+, Tm3+, or Ho3+ single doping UCNPs.
gap of about 1.27 eV (B980 nm) exists between two subsequent

pairs of energy levels, namely between 4I11/2 and 4I15/2 states
and between 4I11/2 and the 4F7/2 states (Fig. 2). Thus, the energy
levels of 4I15/2, 4I11/2, and 4F7/2 can be used to generate UCL
using B980 nm excitation. Instead of being directly excited to
the 4F7/2 state, Er3+ ions in the 4I11/2 state can relax to the 4I13/2
state, followed by excitation to the 4F9/2 state with phononassisted energy transfer. Hence, at least three dierent transitions in Er3+ ions are induced by B980 nm photons of the same
energy, thus leading to emission of green at around 525/545 nm
originated from the transitions 2H11/2/4S3/24I15/2, and red at
B660 nm originated from the transition 4F9/24I15/2 after the
sequential absorption of two photons.73,75 Ho3+ ions have two
main upconversion bands of green and red emission at 541 and
647 nm, corresponding to the transitions 5S2/5F45I8 and
5
F55I8, respectively.76,77 The main upconversion band of
Tm3+ ions is in the NIR range at B800 nm originated from
the 3H4 - 3H6 transition. This NIR upconversion band is
located within the optical transparency window for biological
tissues, in which both light absorption and scattering are
significantly reduced.75 This feature makes Tm3+-doped UCNPs
particularly interesting for imaging deep tissue in rodents.
Tm3+ ions have another three UCL bands at around 479, 450,
and 350 nm, generated by the transitions of 1G43H6, 1D23F4,
and 1D23H6, respectively.78 Several reports focused on the
synthesis and investigation of single rare-earth-ion-doped
nanomaterials.7986 However, in single doping nanocrystals,
the two major parameters that affect upconversion processes
are the distance between two neighboring activator ions and
the absorption cross-section of the ions. High doping levels can
lead to deleterious cross-relaxation, resulting in quenching of
excitation energy. The concentration of activator ions should be
kept low and precisely adjusted to avoid the quenching effect.
The upper limit of concentration depends on the exact distance
of the lattice sites occupied by lanthanide ions, but in most
upconversion materials the concentration of Er3+ does not exceed
3% and the concentration of Tm3+ does not above 1%. In
addition, most lanthanide activator ions exhibit low absorption
cross-sections, leading to low pump efficiency. Therefore, the

overall upconversion efficiency for singly doped UCNPs is
relatively low. To increase the absorption of lanthanide-doped
UCNPs, materials are often additionally doped with strongly
absorbing ions called sensitizers, which should also ensure
efficient energy transfer to the activator.
To enhance UCL eciency, a sensitizer with a suciently large
absorption cross-section in the NIR region is usually co-doped
along with the activator to take advantage of the ecient ETU
process between the sensitizer and the activator. Specifically,
excitation takes the form of successive absorption of pump
photons by two neighboring ions. Both the ions can absorb a
pump photon of the same energy, thereby populating the intermediate reservoir level E1 (Fig. 3a). Then one of the ions is
promoted to upper emitting state E2 according to a non-radiative
Fig. 3 (a) Energy transfer upconversion (ETU) processes of activators and

sensitizers co-doping UCNPs. (b) Upconversion excitation and visible
emission scheme of the Yb3+ sensitized Er3+ and Tm3+ systems.68 (c and
d) Photographs of the UCL in 1 wt% colloidal solutions of nanocrystals
excited with 973 nm light.68 (c) Total UCL of the NaYF4:Yb3+,Er3+. (d, e) The
same luminescence through red and green color filters. (f) Total UCL of
the Yb3+, Tm3+doped sample. (Reprinted with permission from ref. 68.
Copyright 2004, Wiley-VCH Verlag GmbH & Co. KGaA.)
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energy transfer process from the neighbor ion, while the ion
relaxes back to ground state G. A short wavelength photon is
released when the promoted photon is back to the ground state
G.6,73,74 Yb3+ possesses an extremely simple energy level scheme
with only one excited 4f level of 2F5/2 (Fig. 3b). The absorption
band of Yb3+ that is located at around 980 nm due to 2F7/22F5/2
transition has a larger absorption cross-section than that of other
lanthanide ions. Additionally, 2F7/22F5/2 transition of Yb3+ is
well resonant with many ff transitions of typical upconverting
lanthanide ions (Er3+, Tm3+, and Ho3+), thus facilitating efficient
energy transfer from Yb3+ to other ions. The ability of the
sensitizer Yb3+ ion to efficiently transfer its absorption energy
to Er3+, Tm3+, and Ho3+ ions enables a single wavelength excitation (B980 nm) of UCNPs doped with these lanthanide ions or
their various combinations for multicolor emissions (Fig. 3c-f).
The selection of different emitters or combinations of lanthanide
dopants is a straightforward approach to tune the upconversion
multicolor emission. The first demonstration of efficient multicolor UCL in colloidal lanthanide-doped nanoparticles was
reported by Haase and co-workers. They utilized Yb3+/Er3+ and
Yb3+/Tm3+ co-doped NaYF4 nanoparticles to yield strong yellow
and blue emissions, respectively.68 Similar observations have also
Review Article
been reported by Capobianco et al. in NaYF4 nanoparticles.87

Later, Nann et al. showed four color emissions from NaYbF4:Tm,
NaYbF4:Ho, NaYbF4:Er, and NaYF4:Yb nanocrystals, respectively.67
Besides the single activator-sensitizer co-doping UCNPs, Liu et al.
further reported on a general and versatile approach to fine-tune
the UCL in a broad range of color output by a single wavelength
excitation at B980 nm by using a dual-activator doping system
(Fig. 4a and b).88 By selecting Er3+ and Tm3+ as activators, Yb3+ as
a sensitizer, the UCL can be deliberately tuned from Vis to
NIR under 980 nm excitation. Our group also demonstrated that
multicolor fine-tuning can be alternatively achieved via the threecomponent dopant UCNP system (NaYF4:Yb,Ho,Tm) (Fig. 4c) in
a multi-photon emission process.89 The co-doped NaYF4:Yb,Tm
system exhibits a blue color emission, resulting from 1D23F4
and 1G43H6. By adding a second emitter (Ho3+) with different
concentrations to the system, the relative intensity ratio of the
dual emissions can be precisely controlled. Consequently, the
adjustable balance of emission intensities enables the tri-doped
particle system to display a tunable color output from blue
to green. Similarly, the Han group has shown a simple and
reproducible thermolysis approach to fabricate multicolor YF3
UCNPs with different lanthanide dopants and combinations.90
Fig. 4 Room temperature upconversion emission spectra of (a) NaYF4:Yb,Er (2560/2 mol%) and (b) NaYF4:Yb,Tm,Er (20/0.2/0.21.5 mol%)
nanoparticles in ethanol solutions (10 mM).88 (c) Ten distinguishable emission colors of UCNPs excited with 980 nm NIR laser, (1) NaYF4:Yb,Tm
(20/0.2 mol%), (26) NaYF4:Yb,Ho,Tm (20/0.2/0.2, 0.5, 1.0, 1.5, 2.0 mol%), (710) NaYF4:Yb,Ho (20, 30, 40, 60/2.0 mol%).89 (d) Luminescent spectra of the
Er based a-phase core@shell nanoparticles with different doping positions.91 (e) Energy level schemes and energy transitions between Yb3+ and Er3+ and
between Er3+ and Er3+ in the doping position induce multi-color emission.91 (f, g) Combinatorial screening of doubly doped NaYF4 nanocrystals: (f) color
map depicting the integrated UCL intensity and green/red spectral purity of 78 binary combinations of 12 lanthanide dopants (2/2 mol%) excited with
lex = 980 nm at 10 W cm 2; (g) normalized upconverted luminescence spectra of NaYF4 UCNPs with 2% Er3+ and 1% co-dopant.92 (Reprinted with
permission from ref. 8892. Copyright 2008, 2011, 2012, 2013, American Chemical Society and Wiley-VCH Verlag GmbH & Co. KGaA.)
1350 | Chem. Soc. Rev., 2015, 44, 1346--1378
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More recently, we have reported that the multicolor UCL can be

deliberately tuned through the doping position control, suggesting
a facile route for development of novel upconversion multiplexed
probes.91 When the same amounts of dopants (Fig. 4d and e) are
doped in the different positions of one consistent sized nanoparticle, the local relative concentration of dopants can be
increased as the doping position is gradually transferred from
the outer shell to the inner core. Due to efficient cross relaxation
processes among Er3+ ions at high doping levels, the red/green
emission ratio can be increased upon increasing the local relative
concentration of Er3+ and Yb3+. Chan et al. used combinatorial
screening of multiply doped NaYF4 nanoparticles to identify a
series of doubly and triply doped UCNPs that exhibit narrow and
spectrally pure emission spectra at various visible wavelengths
(Fig. 4f and g).92 They also elucidated the energy transfer mechanism giving rise to spectrally pure emission by using the comprehensive kinetic model developed by their group. To sum up, given
the broad range of emission wavelengths from lanthanide
dopants, an appropriate selection of different lanthanide dopants
or their combinations can generate a large library of emission
spectra in the NIR-UV spectral region that are particularly useful
for multiplexed labeling and encoding.
2.2
Host matrix
The choice of the host lattice determines the distance between

dopant ions, their relative spatial position, their coordination
numbers, and the type of anions surrounding the dopant. The
properties of the host lattice and its interaction with the dopant
ions therefore have a strong influence on the upconversion
process. Furthermore, the host materials generally require close
lattice matches with dopant ions and low phonon energies. As all
trivalent rare earth ions exhibit similar ionic size and chemical
properties, their inorganic compounds are ideal host materials for
upconverting lanthanide dopant ions. In addition, alkaline earth
ions (Ca2+, Sr2+, and Ba2+) and some transition metal ions
(Zr4+ and Ti4+) also exhibit close ionic size to lanthanide ions.73
Therefore, inorganic compounds containing these ions are also
frequently used as host materials for upconversion processes.9396
However, lanthanide-doping in these nanocrystals is always
accompanied by the formation of crystal defects such as cation
vacancies, the interstitial anions which are used to maintain
charge neutrality, and so on. To maintain a single-crystal phase
of the host for efficient UCL, the dopant concentration should be
stringently controlled. Semiconductor nanocrystals such as ZnS
have also been proposed as upconversion host materials.97
However, it is still debatable whether lanthanide ions in these
nanocrystals are mainly located on the outermost layer of the
nanocrystals due to largely mismatched ionic size between the
host and dopant ions or incorporated homogeneously in the host
lattice. To date, a series of host materials such as LiYF4,71,98100
NaYF4,44,50,70,87,101 NaGdF4,102,103 NaLuF4,104 BaYF5,105,106
KY3F10,107 BaGdF5,108 YOF,109 LuOF,110 LaOF,111 GdOF,110,111
CaF2,112,113 SrF2,112,113 and BaF2112 have been developed and
reviewed in many papers. In this section, we aimed at providing
a review of the latest advances made in the development of the
new host materials and the corresponding new optical properties.
Chem Soc Rev
Generally speaking, the main intra 4f electronic-dipole

transitions of rare-earth ions are forbidden by the quantum
mechanical selection rules, which, however, can be broken by
the local crystal field (host) of the rare-earth ions due to the
capability to intermix their f states with higher electronic
configurations.6,114,115 Consequently, tailoring the host crystal
field of rare-earth ions and thereby the radiation parameters
might become an alternative general strategy to increase the
UCL for various host materials doped with diverse rare-earth
ions. Li+ ions have the smallest cationic radius in the periodic
table of elements, which is favorable for the movement and site
occupation in the host lattice. These advantages make them
attractive for the use in tailoring of the host lattice local crystal
field. It has been demonstrated that Li+ ions can be doped
easily into the host lattice sub-situationally or interstitially, and
this can break the symmetry of the crystal field around the rareearth ions, leading to the enhancement of PL intensity.115118
For example, the Zhang group reported a 25 times enhancement of the visible UCL in Y2O3:Yb,Er nanoparticles by
co-doping with Li+ ions in the host.115 Cai et al. reported that
green and red UCL intensities of NPs were enhanced by about
47 and 23 times in NaxLi1 xGdF4:Yb,Er.116 Nann et al. have
gained more than a 30-fold increase in luminescence intensity
for NaxLi1 xYF4:Yb,Er UCNPs (Fig. 5a).118 Most recently, the
Chen group has developed a unique strategy for the synthesis of
novel LiLuF4:Ln3+ based core@shell UCNPs with typically high
absolute upconversion quantum yield (QY) of 5.0 and 7.6% for
Er3+ and Tm3+, respectively (Fig. 5b and c).119
As we all know, a common strategy for tuning UCL is to
control the doping concentration or species of lanthanide
ions.60,88,89 However, the phenomenon of concentration
quenching of the excited state at high doping levels poses
a significant constraint. Thus, lanthanide ions have to be
stringently kept at a relatively low concentration to minimize
luminescence quenching. Liu et al. described a new class of
KYb2F7 host nanocrystals adopting an orthorhombic crystallographic structure in which the lanthanide ions are distributed
in arrays of tetrad clusters (Fig. 5d and e).120 Importantly, this
unique arrangement enables the preservation of excitation
energy within the sub-lattice domain of the host and eectively
minimizes the migration of excitation energy to defects, even in
stoichiometric compounds with a high Yb3+ content (calculated
as 98 mol%). It means that the KYb2F7 can not only serve as a
host matrix, but also serve as a sensitizer to absorb and
preserve the energy. This allows us to generate an unusual
four-photon-promoted violet upconversion emission from Er3+
with an intensity that is more than eight times higher than
previously reported. The results highlighted that the approach
to enhancing upconversion through energy clustering at the
sub-lattice level of the host may provide new opportunities for
light-triggered biological reactions and PDT.
Furthermore, the host materials can also influence the emission
color of the obtained UCNPs.109,121123 Recently, Liu and co-workers
have employed KMnF3 as a host and obtained high pure singleband red (650, 660 nm) and NIR (800 nm) emissions from Er3+,
Ho3+ and Tm3+ dopants, respectively (Fig. 5f).123 The emission can
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Fig. 5 Host matrix guided fabrication of UCNPs. (a) UCL spectra of NaYF4:Yb,Er (red), LiYF4:Yb,Er (black) and NaxLi1 xYF4:Yb,Er (green) nanocrystals in
chloroform excited by a 980 nm laser diode.118 (b, c) UCL spectra of LiLuF4:Yb,Er and LiLuF4:Yb,Tm core-only and core@shell UCNPs with dierent shell
layers upon NIR excitation at 980 nm.119 (d, e) The orthorhombic phase crystal structure of the KYb2F7 host and UCL of the KYb2F7-based UCNPs.120
(f) UCL spectra of the KMnF3 host based UCNPs: KMnF3:Yb,Er, KMnF3:Yb,Ho and KMnF3:Yb,Tm.123 (Reprinted with permission from ref. 118120 and 123.
Copyright 2009, 2011, 2014, American Chemical Society, Wiley-VCH Verlag GmbH & Co. KGaA and Nature Publishing Group.)
be ascribed to non-radiative energy transfer from 2H9/2 and 4S3/2

levels of the Er3+ dopant to the 4T1 level of Mn2+ of host materials,
followed by back transfer to the 4F9/2 level of Er3+, which is
consistent with the energy transfer mechanism proposed by Zhao
et al.122 Except KMnF3 host materials, the Gao group also reported
the strong single-band red upconversion emission (B669 nm)
under 980 nm excitation by using YOF nanoparticles as a host
matrix.109
In general, the final crystal structure and grain size are quite
related to the parameters of host nanoparticles. As summarized
in Table 2, the size of current synthesized host nanoparticles
doped with lanthanide ions is typically in the range of 20 to
50 nm. However, the optimal size for bioimaging probes is
reported to be less than 10 nm, so that the nanoparticles can be
1352 | Chem. Soc. Rev., 2015, 44, 1346--1378
eciently cleared from the body.50,124,125 Thus, one of the

important goals still need to be achieved is to obtain small
(o10 nm) lanthanide-doped nanoparticles with intense UCL.
With regard to this, much eort has been input to synthesize
ultra-small nanoparticles with intense UCL and many great
achievements have been obtained.50,94,104,125128 For example,
the Prasad group has reported the synthesis of monodispersed
a-NaYF4 host matrix based UCNPs with ultra-small size
(7B10 nm) and high upconversion efficiency (Fig. 6a and b).50
The intensity of NIR emission can increase up to 43 times along
with an increase in the relative content of Yb3+ ions from 20
to 100%. The resultant ultra-small NaYbF4:Tm3+ nanocrystals
manifest NIR UCL, which is 3.6 times more intense than that
from NaYF4:Yb,Tm nanocrystals with a size of 25B30 nm
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Table 2
Chem Soc Rev
Typical lanthanide-doped host matrixes with dierent sizes, crystal structures and morphologies
Host:dopant
Size (nm)
Crystal structure
Morphology
Ref.
YLiF4:Yb,Tm
NaYF4:Yb,Er
NaYF4:Yb,Er
NaYF4:Yb,Er
NaYF4:Yb,Er
NaYF4:Yb,Er
NaYF4:Yb,Tm
NaGdF4:Yb,Er
NaGdF4:Yb,Tm
NaGdF4
NaLuF4:Yb,Er
NaLuF4:Gd,Yb,Tm
BaLuF5
KGdF4:Yb,Tm
KYb2F7:Er
LiLuF4:Yb,Er
KMnF3:Yb,Er
YOF:Yb,Er
CaF2:Yb,Er
YF3:Yb,Er
B80
13.6
187 71
21 0.5
10.5 0.7
4.515
B7
20, 31, 41
10, 15, 25
2.58
18.9
7.8117
o5
B3.7
109 26 12
28 1.5
B30
15 0.4
3.8 0.5
B3.7
Tetragonal
Cubic
Hexagonal
Hexagonal
Hexagonal
Hexagonal
Cubic
Cubic
Hexagonal
Hexagonal
Cubic
Hexagonal
Cubic
Cubic
Orthorhombic
Tetragonal
Cubic
Cubic
Cubic
Orthorhombic
Diamond
Polyhedron
Hexagonal plates
Spheres
Spheres
Spheres
Spheres
Cube
Spheres
Hexagonal
Spheres
Spheres
Dot
Irregular
Ice lolly stick
Rhomboid
Cube
Spheres
Cube
Irregular
71
83
83
218
70
128
50
136
137
127
104
104
126
125
120
119
123
109
94
90
Fig. 6 TEM images of the ultra-small (o10 nm) lanthanide-doped UCNPs. (a, b) Cubic phase NaYF4:Yb,Tm;50 (c, d) hexagonal phase NaYF4:Yb,Er;128
(e, f) hexagonal phase NaGdF4;127 (g, h) cubic phase CaF2:Yb,Er@CaF2;94 (i, j) NaLuxGd1 xF4:Yb,Er;104 (k, l) orthorhombic YF3:Yb,Er.41 (Reprinted with
permission from ref. 41, 50, 94, 104, 127 and 128. Copyright 2010, 2011, 2012, 2013, American Chemical Society, Wiley-VCH Verlag GmbH & Co. KGaA
and Royal Society of Chemistry.)
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reported previously. Chen et al. presented a simple and

reproducible thermolysis approach to synthesize 3.7 nm-sized
lanthanide-doped UCNPs by using YF3 as a host matrix (Fig. 6k
and l).90 The UCL intensity of these ultra-small nanoparticles
was found to be about ten times brighter than that of the CaF2
host with a size of B4.5 nm, which were reported to be some of
the smallest efficient UCNPs. The Cohen group also described
the controlled synthesis of b-phase NaYF4:Yb,Er nanocrystals
with a protein size from 4.5 to 15 nm (Fig. 6c and d).
The core@shell b-phase NaYF4:Yb,Er@NaYF4 nanoparticles
less than 10 nm exhibit higher luminescence efficiency
(0.18 0.01%) than the core nanoparticles with 37 nm in size
(0.14 0.01%).128 Most recently, Liu et al. have synthesized the
sub-10 nm hexagonal NaLuF4 host nanoparticles, which displayed bright UCL with a QY of 0.47 0.06% (Fig. 6i and j).104
Mahalingam et al. showed the upconversion process via interparticle energy transfer in lanthanide-doped BaLuF5 matrix
nanocrystals with a sub-5 nm size for the first time.126
van Veggel and co-workers reported the synthesis of monodisperse 2.5B8.0 nm NaGdF4 host nanoparticles by optimizing
the reaction parameters associated with both the nucleation
and growth phases in a high boiling point binary solvent
mixture (Fig. 6e and f).127 Most recently, the Chen group has
developed a strategy based on sodium co-doping for the synthesis of monodisperse and ultra-small CaF2:Ln3+ (Ln = Ce, Tb;
Yb, Er; Yb, Tm) UCNPs through a co-precipitation route. The
resulting sub-10 nm CaF2:Ln3+ core-only and core@shell nanoparticles with tunable shell thickness yielded an enhanced UCL
(Fig. 6g and h).94
3. Core@shell structure based

luminescence engineering of the
UCNPs nanolab
In addition to lanthanide-doped core-only UCNPs, much progress has also been made in the synthesis of UCNPs with
core@shell structures in the past decade. It should be noted
that the small lattice mismatch between the core and shell
materials is the important preconditions for the fabrication of
high quality core@shell structures. In the UCNPs nanolab,
the core@shell structure plays a very important role in the
luminescence engineering of UCNPs, because core@shell
nanoparticles not only provide an excellent platform to combine
dierent properties or functional units into one single nanoparticle, but also oer an eective solution to problems associated
with the core-only nanoparticles.
3.1
Enhancing UCL with core@shell structure
Nano-sized lanthanide-doped UCNPs normally have a high

proportion of dopant ions distributed on the surface of particles.
Luminescence is readily quenched by high energy oscillators
arising from surface defects and weakly bound impurities,
ligands, and solvents due to the lack of eective protection by
the host lattice. Excitation energy of the interior ions can also
be transferred to the surface through adjacent dopant ions and
1354 | Chem. Soc. Rev., 2015, 44, 1346--1378
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eventually dissipated non-radiatively. To compensate for the

deficiencies, growing a shell with small lattice mismatch
around the core to reduce non-radiative decay losses of the
surface luminescence can provide an eective way to improve
the optical properties of UCNPs. In such core@shell structures,
the dopant ions are confined in the interior core of the
nanocrystals. The shell can eectively suppress energy loss on
the crystal surface, leading to an enhanced luminescence
eciency. The first demonstration of the core@shell structured
UCNPs was reported by Lezhnina and co-workers, which
was focused on EuF3@GdF3, GdF3@EuF3, LaF3:Yb,Ho@LaF3,
LaF3:Nd@LaF3 core@shell nanoparticles.129 In 2007, Chow
et al. realized B7 and 29 times luminescence enhancement
for NaYF4:Yb,Er and NaYF4:Yb,Tm nanocrystals after coating
with NaYF4 shells, respectively.130 Since then, many core@shell
nanocomposites have been prepared to improve the eciency,
such as NaYF4:Yb,Er(Tm)@NaGdF4,131133 NaYF4:Yb,Er(Tm)@
NaYF4,130,134,135 NaGdF4:Yb,Tm(Er,Nd)@NaGdF4,136138 NaGdF4:
Yb,Er(Tm, Ce, Tb)@NaYF4,91,139 CeF3:Tb@LaF3,140142 KYF4:
Yb,Er@KYF4,143 YOF:Yb,Er@YOF,109 and so on.
Interestingly, the Liu group has recently showed that the
epitaxial growth of an optically inert NaYF4 layer around a
lanthanide-doped NaGdF4@NaGdF4 core@shell nanoparticle
could eectively prevent surface quenching of excitation energy
(Fig. 7a and b).61 To verify the eect of the activator emission
enhancement by NaYF4 layer protection, they further investigated
a series of NaGdF4:Yb,Tm@NaGdF4:A@NaGdF4 core@shell@shell
nanoparticles (A = Eu, Tb, Dy, Sm). The results show that
Gd excitation energy can migrate through the Gd shell and
dissipate through the trapping by the surface defects or solvent
molecules. The photoluminescence studies show that the Tb3+
emission in the core@shell@shell nanoparticles is essentially
not improved. When Gd3+ ions in the outermost shell were
gradually replaced by optically inert Y3+, a steady enhancement
of the activator emission was observed. Taken together, the
results conclusively suggest that the suppression of surface
quenching to Gd3+ ions is primarily responsible for the enhanced
activator emissions.
The shell composites of the core@shell UCNPs mentioned
above are all host shells without dopants. Because of the simple
and single property of the host shell, the enhancement of the
luminescence eciency is very limited. So the design and fabrication of the UCNPs with more ecient core@shell structure is
desirable.36,102,144 For example, Capobianco and co-workers
showed a strong enhancement of the green and red emission
bands of NaGdF4:Yb,Er particles by growing the Yb3+ doped
NaGdF4 shells around cores (Fig. 7c and d).102 In addition to the
ETU process in the NaGdF4:Yb,Er cores, additional energy transfer
from excited Yb3+ ions in the shell to Er3+ ions in the core increases
the overall eciency of nanoparticles. The upconversion emission of the active coreactive shell particles is more intense by a
factor of about 3 (green) and 10 (red) compared to the standard
core@shell particles with a doped core and an inert shell.
The fabrication of core@shell structures is a very eective
strategy to improve the optical property of UCNPs. However,
only a few papers reported a precise link between the shell
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Fig. 7 (a, b) Schematic illustration of the energy transfer mechanism in the core@shell structured and NaYF4-coated core@shell@shell structured
nanoparticles and proposed energy transfer mechanisms in the core@shell@shell nanoparticles.61 (c, d) General depiction and the upconversion
mechanism of the NaGdF4:Er3+,Yb3+@NaGdF4:Yb3+ active-core@active-shell nanoparticles under 980 nm excitation.102 (Reprinted with permission from
ref. 61 and 102. Copyright 2009, 2012, American Chemical Society and Wiley-VCH Verlag GmbH & Co. KGaA.)
thickness of core@shell nanoparticles and their optical properties, mainly because the core@shell structures have only
been inferred from indirect measurements. Recently, with the
high-angle annular dark-field (HAADF) technology, our group
and van Veggel et al. have shown that the core@shell nanoparticles synthesized by the most widely used seed mediated
heating-up method did not have a uniform shell, meaning that
the core was partially covered by the shell (Fig. 8a and b).131,133,145
Therefore, the core nanoparticles cannot be passivated eciently
to decrease the core surface defects and insulated from the
environmental eect. Furthermore, we also realized the direct
imaging of NaYF4:Yb,Er@NaGdF4 core@shell structure at the
sub-nanometer level for the first time using a cryo-transmission
electron microscope (Cryo-TEM) and a rigorous electron
energy loss spectroscope (EELS) at a low operation temperature
(96 K).131 A strong linear link between the NaGdF4 shell
thickness and optical response of the hexagonal NaYF4:
Yb,Er@NaGdF4 core@shell nanocrystals has been established.
In order to avoid the growth of the heterogeneous shell, a
reproducible multi-cycle batch method to grow host shells on
NaYF4:Yb,Er nanocrystals with monolayer (ML) thickness has
been demonstrated for the first time.131 During the epitaxial
growth of the host shell layer-by-layer, surface defects of
the UCNP cores can be gradually passivated by the homogeneous shell deposition process, which results in the obvious
enhancement in overall upconversion emission intensity and
lifetime and more resistance to quenching by water molecules.
Furthermore, we also developed a facile one-pot successive

layer-by-layer (SLBL) method to realize the successive shell
coating by using high boiling-point ReOA (rare-earth chlorides
dissolved in oleic acid) and NaTFAOA (sodium trifluoroacetate
dissolved in oleic acid) as shell precursors (Fig. 8c and d).91
This protocol is flexible to deposit the uniform multi-shell by
successive introduction of the shell precursor solutions instead
of the lengthy multi-cycle batch operation.131 As a result of the
high quality uniform shell and advanced core@shell structures,
the UCL efficiency can be improved up to 0.51 0.08%.
Therefore, we believe that high quality UCNPs with more reasonable and advanced structures would be fabricated by simply
changing amounts or species of the shell precursors with this
SLBL method.
Actually, the most eective way to enhance upconversion
intensity is by increasing the number of emitters.6 However, high
doping levels of emitters lead to deleterious resonant energy
transfer, resulting in quenching of excitation energy.73 It has
been extensively demonstrated that the optimal dopant concentration is B2 mol% for emitter Er3+, as far as upconversion
nanomaterial NaYF4:Yb,Er is concerned,146 and no eort has yet
been made to surpass this limitation. Recently, Kong and Zhang
et al. have demonstrated that the well accepted upper limitation
of the concentration quenching threshold could increase from
2 to 5 mol% for Er3+ by a designed spatial separation strategy of
the emitter doping area.147 The separated layer eectively minimizes the energy transfer between the emitters in the inside and
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Fig. 8 (a) The scheme and TEM images of the heterogeneous and
homogeneous properties of the shells.131 (b) Low-magnification
HR-HAADF image of the NaYF4@NaGdF4 core@shell nanocrystals. The
white arrows show the non-uniformity of the shell, meaning that the core
is only partially covered by the shell.145 (c, d) Typical TEM and HAADFSTEM images of the obtained b-NaGdF4:Yb,Er@NaYF4 core@shell UCNPs
by using the SLBL method.91 (Reprinted with permission from ref. 91, 131
and 145. Copyright 2011, 2012, 2013, American Chemical Society.)
outside layers and largely lowers the possibility of trapping of

excitation energy by defects, resulting in enhancement of the UCL.
Actually, the quenching eect with high doping levels of emitters
has been demonstrated in 2008 by Qian and Zhang.144 They
reported the synthesis of hexagonal NaYF4:Yb,Tm@NaYF4:Yb,Er
nanocrystals with Tm and Er doped in the core and the shell,
respectively (Fig. 9a and b). Dierent from the Tm/Er co-doped
NaYF4 nanocrystals in which Tm fluorescence was quenched,
both Tm and Er fluorescence was observed from the core@shell
nanocrystals. NaYF4:Yb,Tm@NaYF4:Yb,Er@NaYF4:Yb,Tm nanocrystals with a sandwich structure were also synthesized and the
luminescence from Er and Tm were greatly enhanced. Furthermore, the Liu group showed that the spatial confinement of
dissimilar dopant ions within specific regions of the core@shell
nanoparticles was critical for generating ecient energy
migration-mediated upconversion (EMU) (Fig. 9c and d).60 The
core@shell structure was designed to eliminate cross relaxation
induced energy loss due to direct interaction between the YbTm
pair and the activator in their work. To verify the requirements of
a core@shell structure separating the YbTm pair and the activator (Eu, Tb, Dy, Sm), they prepared a series of NaGdF4@NaGdF4
core@shell nanoparticles with the core homogeneously doped
with Yb3+, Tm3+, and Tb3+ at different doping levels. By comparing
the emission spectra of these core@shell nanoparticles with the
YbTm pair and activators at separated layers, it was found that
the homogenously doped nanoparticles with Tb3+, Eu3+, Dy3+,
Sm3+ all exhibited weak emission intensities, in stark contrast to
strong emissions from the heterogeneously doped counterpart.
1356 | Chem. Soc. Rev., 2015, 44, 1346--1378
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The decreased emission intensity can be attributed to cross

relaxation between Tm3+ and Tb3+ (or Eu3+, Dy3+, Sm3+). The
suppressed emission peaks of Tm3+ centered at 360 and 450 nm
also proved the interaction between Tm3+ and Tb3+ (or Eu3+, Dy3+,
Sm3+). Note that the cross relaxation between Tm3+ and Tb3+ can
be slightly eliminated at a low Tb3+ dopant content. However, a
low concentration of Tb3+ is also unfavorable for trapping the
excitation energy of Gd3+. As a result, a suppressed EMU process
occurs with significant luminescence quenching.
Besides rare earth based shells, the heterogeneous core@
shell structures have also been investigated for the enhancement of the upconversion eciency of the core nanoparticles.
Wang et al. reported B300-fold enhancement of UCL in NaYF4:
Ln3+@CaF2 heterogeneous core@shell nanoparticles with a size
of 10B13 nm in comparison to the parent NaYF4:Ln3+ nanoparticles.148 The hetero shell of CaF2 was chosen as well to coat
NaYbF4:Tm, leading to a 35-fold enhancement of NIR-to-NIR
up-conversion intensity and reaching a QY as high as 0.6%
under an excitation power density of 0.3 W cm 2.149 Han et al.
reported on 2 orders of magnitude enhancement of NIR-to-UV
UCL in NaYF4:Yb,Tm@CaF2 core@shell nanoparticles compared to the core nanoparticles.150 As compared to the typically
used NaYF4 shell, CaF2 coating is found to be more eective
in resisting quenching in aqueous medium to preserve the
upconverting emissions, and more ecient in suppression of
lanthanide leakage.
3.2 Tuning upconversion emission using core@shell
structures
The use of core@shell architectures with two or more lanthanide
activators incorporated into the core and dierent shells is a
typical strategy to tune the luminescence of UCNPs, while
maintaining a high luminescence eciency.151 This strategy
also explores dierent combinations of lanthanide activators to
produce multicolor emissions, but exercises a spatial isolation
of these lanthanide activators using an appropriate core@shell
structure. It eliminates deleterious cross relaxations between
the lanthanide activators and suppresses the surface-related
quenching mechanism in the core nanoparticles, thus yielding
a range of tunable emission with high eciency. Recently,
Liu et al. have reported the tuning of upconversion properties
for a rather wide range of activators by using the combination of gadolinium sublattice mediated energy migration and
core@shell structural engineering, which would expand the
range of applications for lanthanide-doped nanoparticles.60 The
results show that many lanthanide ions, including Tb3+, Eu3+,
Dy3+ and Sm3+, without long lived intermediary energy states can
also serve as the activators to generate tunable upconversion
emissions spanning the visible spectral region. Similarly, the
Chen group designed a novel strategy to fabricate uniform
NaGdF4 NPs that were composed of a NaGdF4:Yb,Tm core and a
NaGdF4:Eu shell in order to achieve dual-mode up/downconversion
luminescence from identical Eu3+ ions (Fig. 10c and d). The use
of such core@shell structures allows the elimination of the
deleterious cross-relaxations between doped Eu3+, Yb3+and
Tm3+ ions, which therefore yields a 10 times enhancement in
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Fig. 9 (a, b) Schematic illustration and UCL spectra of the formation of the core@shell NaYF4:Yb,Tm@NaYF4:Yb,Er (AB) and NaYF4:Yb,Tm@NaYF4:
Yb,Er@NaYF4:Yb,Tm (ABA) core@shell@shell nanocrystals.144 (c, d) Schematic design of a lanthanide-doped NaGdF4:Yb,Tm@NaGdF4:X core@shell
nanoparticle for EMU (X: activator ion), and proposed energy transfer mechanisms in the core@shell nanoparticle.60 (Reprinted with permission from
ref. 60 and 144. Copyright 2008, 2011, American Chemical Society and Nature Publishing Group.)
the UCL of Eu3+ as compared with the triply-doped core-only

counterparts.152 Zhang et al. reported on hexagonal phase
core@shell structured NaYF4:Yb,Tm@NaYF4:Yb,Er144 and
sandwich structured core@shell@shell NaYF4: Yb,Tm@NaYF4:
Yb,Er@NaYF4:Yb,Tm, NaYF4:Yb,Er@NaYbF4:Tm@NaYF4:Yb,
Tm, NaYF4:Yb,Tm@NaYbF4:Er@NaYF4:Yb,Er, and NaYF4:
Yb,Tm@NaYbF4:Er@NaYF4:Yb,Tm nanoparticles to produce
multiple emission peaks and for multi-color cellular imaging
(Fig. 10a and b).36
3.3
Tuning of the excitation wavelength
One major limitation of conventional UCNPs is the low conversion eciency especially under a low-intensity laser excitation, mainly due to the extremely weak absorption of sensitizer
Yb3+ ions in the NIR wavelength range.153155 Moreover, owing
to the very narrow NIR absorption spectral window of UCNPs,
980 nm laser is the most commonly used NIR excitation source
to generate UCL. However, the use of 980 nm NIR laser as an
excitation source for biological applications has an intrinsic
disadvantage: water, as the most significant component of the
animal and human body, exhibits a high photon absorbance at
around 980 nm.156 The intensity of the laser beam would be
overwhelmingly attenuated while diffusing in biological tissues,
resulting in a limited penetration ability. Furthermore, the
absorbed light energy would transform into thermal energy,

often causing serious sample overheating in conjunction with
substantial cell and tissue damage under continuous irradiation.
Therefore, to make UCNPs more suitable for biological applications, it is necessary to enhance the absorption of NIR light and
optimize the excitation light wavelength into an appropriate
range. In contrast to 980 nm NIR laser, the use of 800 nm NIR
laser as the excitation source may both overcome the overheating
issues and significantly improve the penetration depth for deep
tissue imaging since the NIR region at around 700900 nm
reaches a minimum absorbance for all bio-molecules.156
Unfortunately, the UCL of conventional UCNPs could be hardly
detected under excitation of 800 nm, due to the extremely
low absorption cross section of commonly used activators
(Er3+, Tm3+ and Ho3+) and a sensitizer (Yb3+) at around
800 nm. To overcome this problem, it is essential to combine
UCNPs with other components which have large absorption at
around 800 nm. Nd3+ ions could become a quite potential
candidate as the sensitizer to realize the UCL of UCNPs, due
to the intense absorption cross-section of Nd3+ around 800 nm
and efficient energy transfer from excited Nd3+ to Yb3+ ions.
Therefore, assisted by the delicate designing of the core@shell
nanostructure, the excitation wavelength of UCNPs can be blueshifted to B800 nm.
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Fig. 10 (a, b) Upconversion spectra and optical images of core@shell structure based multicolor UCNPs. Layer components of UCNPs in (b) (from top to
bottom) and (c) (from left to right) are as follows, respectively: A:Yb,Er; A:Yb,Tm; B:Er; A:Yb,Er@B:Tm@A:Yb,Tm; A:Yb,Tm@B:Er@A:Yb,Er; A:Yb,Tm@B:
Er@A:Yb,Tm; NaYF4 is defined as A, and NaYbF4 is defined as B.36 (c) Schematic illustration of the general strategy to achieve the dual-mode
luminescence of Eu3+ in NaGdF4:Yb,Tm nanoparticles.152 (d) Excitation (lem = 615 nm), down conversion (lexc = 273 nm) and upconversion (lexc =
976 nm) emission spectra for dual-mode NaGdF4:Yb,Tm@NaGdF4:Eu core@shell nanoparticles.152 (Reprinted with permission from ref. 36 and 152.
Copyright 2010, 2013, Elsevier Ltd. and Wiley-VCH Verlag GmbH & Co. KGaA.)
The intrinsic excitation wavelength of colloidal dispersible

UCNPs was first engineered by the Han group according to the
fabrication of cascade sensitization of Nd/Yb/Er (Tm) tri-doped
core@shell b-NaYF4 colloidal UCNPs.157 Nevertheless, the
doping concentration of Nd in the tri-doped system must be
constrained to a very low level (less than 1%) to minimize the
quenching of the excitation energy through ecient energy
back transfer from activators to 4IJ manifolds of Nd3+. Thus,
directly doping Nd3+ into UCNPs always results in much lower
UCL under 800 nm irradiation than that under 980 nm irradiation.
Afterwards, Xie et al. developed a new type of NaYF4:Yb,Nd,A@
NaYF4:Nd (A = Tm, Er, Ho) core@shell UCNPs which can be
eectively excited at 795 nm. The core@shell UCNPs were
synthesized through spatially confined doping of neodymium
(Nd3+) ions (Fig. 11a and b).158 The use of Nd3+ ions as
sensitizers facilitates the energy transfer and photon upconversion of a series of lanthanide activators (Er3+, Tm3+, and Ho3+)
at a biocompatible excitation wavelength (795 nm) and also
significantly minimizes the overheating problem associated
with 980 nm excitation. Importantly, the core@shell design
enabled high-concentration doping of Nd3+ (B20%) in the shell
layer and thus markedly enhanced the UCL from the activators,
providing highly attractive luminescent biomarkers for bioimaging without auto-fluorescence and concern of overheating.
1358 | Chem. Soc. Rev., 2015, 44, 1346--1378
Similarly, to address the spatial separation of the activator and

Nd3+, the Yan group also synthesized b-NaGdF4:Yb,Er@
NaGdF4:Nd core@shell nanoparticles. The new excitation band
located at 808 nm could achieve high upconversion excitation
eciency similar to that at 980 nm, but with a greatly minimized tissue overheating eect.159 Wen et al. described a novel
design, based on nanostructural engineering to separate
unwanted electronic transitions for constructing a new class
of materials displaying tunable upconversion emissions
spanning from UV to the visible spectral region by single
wavelength excitation at 808 nm.160 These results demonstrate
that core@shell nanostructures can be harnessed to integrate
and coordinate several distinct optical processes for realizing
unusual upconversion of NIR light in the medical spectral
window (about 800 nm) into tunable emissions spanning
from UV to the visible spectral region. Most recently, Zhong
et al. have fabricated a quenching-shield sandwich structure
(NaYF4:Yb,Er@NaYF4:Yb@NaNdF4:Yb) to eliminate the photon
quenching for 800 nm excited UCL of Nd3+ sensitized nanoparticles (Fig. 11c).161 This unique nanostructure is essential to
eliminate the deleterious cross-relaxation pathways between the
activator and the sensitizer by means of a precisely controlled
transition layer (NaYF4:Yb). The optimized emission intensity of
the quenching-shield sandwich structure upon 800 nm excitation
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Fig. 11 (a, b) Schematic design and luminescence photographs of the NaYF4:Yb,Nd,X@NaYF4:Nd (X = Tm, Er, Ho) core@shell nanoparticles for photon
upconversion under 800 nm excitation.158 (c) Schematic illustration of the proposed energy transfer mechanisms in the quenching shield NaYF4:Yb,X@
NaYF4:Yb@NaNdF4:Yd (X = Tm, Er, Ho) sandwich-structured UCNPs upon 800 nm excitation.161 (d, e) General strategy to achieve the upconversion and
downconversion dual-mode luminescence with multi-layer NGdF4:Nd@NaYF4@NaGdF4:Nd,Yb,Er@NaYF4 Core@Shell1@Shell2@Shell3 nanoparticle and
the corresponding HAADF-STEM image of the obtained multi-layer nanoparticles.162 (Reprinted with permission from ref. 158, 161 and 162. Copyright
2013, American Chemical Society, Wiley-VCH Verlag GmbH & Co. KGaA and Nature Publishing Group.)
is even brighter than that at 980 nm with a low excitation power

density, as a result of the higher absorption cross-section of
the sensitizer Nd3+ ion. Core@shell1@shell2@shell3 structured
NaGdF4:Nd@NaYF4@NaGdF4:Nd,Yb,Er @NaYF4 nanocrystals
were also well designed and synthesized in our group
(Fig. 11d),162 each of the parts assumes the respective role and
work together to achieve dual-mode up/downconversion
(UC/DC) luminescence upon the low heat eect 800 nm excitation. Nd3+, Yb3+, Er3+ tri-doped NaGdF4:Nd,Yb,Er UC layers [NIR
(800 nm)-to-Visible (540 nm)] with a constitutional ecient
800 nm excitable property were achieved for the in vitro bioimaging with low auto-fluorescence and photo-damage eects.
Moreover, typical NIR (800 nm)-to-NIR (860895 nm) DC luminescence of Nd3+ has also been realized with this designed nanostructure. Due to the low heat effect, high penetration depth of the
excitation and the high efficiency of the DC luminescence, the
in vivo high contrast DC imaging of a whole body nude mouse
were achieved at the same time.
4. LaMer nucleation-growth model

directed controllable synthesis of
lanthanide doped UCNPs
Development of facile synthesis strategies for high quality
lanthanide-doped UCNPs with controlled composition, crystalline phase, shape, and size is crucial to tune their chemical and
optical properties and explore their potential applications in

diverse fields. With the development of nanotechnology, a
variety of methods have been established to synthesize dierent
kinds of UCNPs with controlled crystalline phases and sizes,
including co-precipitation,68,69,88,163168 thermal decomposition,83,87,101,169,170 hydro(solvo)-thermal synthesis,2,76,93,171177
solgel process,95,96,178,179 and combustion synthesis,66 which
have been reviewed in many papers.6,7375,77,155,180,181 In this
review, we mainly focus on the thermolysis strategy, including
one-pot heating-up, layer-by-layer growth, and Ostwald-ripening
methods, which are most widely used, as they can offer precise
control over the phase, shape, size, and stoichiometric composition of the core only and the core@shell UCNPs.
The research on the preparation of uniform colloidal
particles dates back to the 1940s. LaMer and his colleagues
pioneered the concept of burst nucleation during the preparation of various oil aerosols and sulfur hydrosols.182184
In this process, many nuclei are generated at the same time,
and then these nuclei start to grow without additional nucleation
simultaneously. This is the essence of the burst-nucleation
process which makes it possible to control size distribution of
particles during growth. Otherwise, if the nucleation process
occurred throughout the whole particle formation process,
the growth histories of the particles would differ largely
from one another, and consequently the control of the size
distribution would be very difficult. Burst nucleation has
been adopted as an important concept in the synthesis of
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Fig. 12 Schematic depicting the four stages of the preparation of monodisperse nanocrystals in the framework of the LaMer model.184 (Reprinted
with permission from ref. 184. Copyright 2000, Annual Reviews.)
monodispersed nanocrystals. It is well known that to prepare

highly uniform nanocrystals, it is necessary to induce a single
nucleation event and to prevent additional nucleation during
the subsequent growth process. As a synthetic strategy, this
method is often referred to as the separation of nucleation
and growth.182184 LaMer and his colleagues firstly utilized the
homogeneous nucleation process to separate nucleation and
growth. In this process, nuclei appear in a homogeneous
solution without any seed for heterogeneous nucleation.
In this homogeneous nucleation process, there exists a high
energy barrier to nucleation, because the system spontaneously
changes from the homogeneous to heterogeneous phase. The
LaMer plot, as shown in Fig. 12, is very useful for visualizing how
the energy barrier works to induce the burst nucleation.184
The concentration of the monomer, which is the minimum
subunit of bulk crystals, constantly increases with time. Note
that precipitation does not occur in stage I even under supersaturated conditions (S 4 1), because the energy barrier for
spontaneous homogeneous nucleation is extremely high.
In stage II, when the nucleation occurs, the degree of supersaturation is high enough to overcome the energy barrier for
nucleation, thus resulting in the formation and accumulation
of stable nuclei. Since the rate of monomer consumption
resulted from the nucleation and growth processes exceeds
the rate of monomer supply, the monomer concentration
decreases until it reaches the level at which the net nucleation
rate (the number of nuclei formed per unit time) is zero. Below
this level, the system enters the growth stage (stage III), in
which nucleation is effectively stopped and the particles keep
growing as long as the solution is supersaturated. Once monomer concentration is sufficiently depleted, growth can proceed
by Ostwald ripening (stage IV). Here, sacrificial dissolution of
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smaller (higher-surface-energy) particles results in growth of

larger particles and, thereby, fewer particles in the system.
The thermolysis strategy generally employs organometallic
compounds as precursors, which decompose in a high boiling
point organic solvent with the assistance of surfactants at an
elevated temperature. The commonly used precursors are metallic
trifluoroacetate salts or oleatum; the solvent can be 1-octadecene
(ODE), paran oil, etc.; the surfactants can be oleic acid (OA),
oleylamine (OM) or trioctylphosphine oxide (TOPO), which typically contain a functional capping group to coordinate the
metallic elements and the long hydrocarbon chain to prevent
nanoparticle aggregation. By carefully tailoring the experimental
variables, such as the nature of solvents, concentration of metal
precursors, reaction temperature, and time, high-quality UCNPs
with a narrow size distribution, good crystallinity, and exceptional
optical properties can be readily obtained from the thermolysis
process. The thermolysis strategy can be divided into three routes:
a one-pot heating-up method for the synthesis of both core only
and core@shell UCNPs;60,131,137,145 one-pot successive layer-bylayer (SLBL)91,119,162 and Ostwald-ripening methods for the fabrication of core@shell UCNPs.185 It should be noted that all the
three routes are developed under the direction of the LaMer
nucleation-growth model. So, in this section we focus on the
LaMer nucleation-growth model directed controllable synthesis of
lanthanide-doped UCNPs.
4.1
One-pot heating-up method
For a one-pot heating-up method, the nucleation and growth

match with the LaMer model for the synthesis of monodisperse
UCNPs. For the synthesis of the core UCNPs, the precursors are
mixed at a low temperature and then brought to the temperature
at which precursor reaction or decomposition occurs suciently
quickly to result in supersaturation (stage I). Supersaturation is
again relieved by a burst nucleation (stage II), after which
temperature is controlled to avoid additional nucleation events,
allowing monomer addition to existing nuclei to occur more
rapidly than new monomer formation (stage III).
The seed-mediated growth method for the synthesis of
core@shell nanocrystals is the most apparent case for the
separation of nucleation and growth, wherein nucleation is
physically separated from growth by using preformed nanocrystals as seed nuclei. This method utilizes heterogeneous
nucleation to suppress the formation of additional nuclei by
homogeneous nucleation. In this method, the reaction can
enter into stage III directly. Preformed nuclei are introduced
into the reaction solution and then the monomers are supplied
to precipitate on the surface of the existing nuclei. The lower
monomer concentration should be kept during growth to
suppress homogeneous nucleation. So, the one-pot heating-up
method can be not only used in the synthesis of core only
nanoparticles but also make a great success in the fabrication
of core@shell UCNPs (Fig. 13a). The whole experiment procedure is nearly the same as the synthesis of the core nanoparticles except the presence of the seed nanoparticles.
The first step is to synthesize the core nanoparticles which
are then used as seeds in the second step to induce further
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Fig. 13 (a, b) Schematic depiction of conventional heating-up multi-cycle method (a), and the SLBL method (b) for the synthesis of core@shell UCNPs.
(c, d) Schematic illustration of the LaMer plot and the SLBL method for the controlled synthesis of core@shell UCNPs by using the SLBL method.91
(Reprinted with permission from ref. 91. Copyright 2013, American Chemical Society.)
epitaxial growth. To ensure an epitaxial growth and to create a

homogeneous interface between the core and the outer shell, the
host material of the shell should exhibit a low lattice mismatch
with the core material. Then, the epitaxial growth can be implemented in the growth solution. The monomer of shells in the
growth solution, produced by thermal decomposition of corresponding chemical precursors in the solvents of OA and ODE,
is able to gradually and stably deposit on the seeding core nanoparticles and finally form the shell layer (stage III in LaMer plot).
4.2 One-pot successive layer-by-layer method for the
fabrication of core@shell UCNPs
Although a one-pot heating-up method has been considered to be
the most commonly used method for the fabrication of core@
shell UCNPs, a few shortcomings should still be improved. For
example, recent work reported by van Veggel et al. showed that the
core@shell nanoparticles synthesized by the one-pot heating-up
method do not have a uniform shell (the core is only partially
covered by shell), indicating that the core nanoparticles cannot be
passivated eciently to decrease the core surface defects and
insulated from the environmental eect.133,145 On the other hand,

it was found that the size distribution of the obtained core@shell
nanoparticles was larger than that of the original core. Furthermore, the bimodal size distribution was always observed when a
high volume of shell precursors was introduced.60 We assume
that the non-uniform shell and broader or bimodal size distribution of the obtained core@shell UCNPs result from the fast
deposition speed or independent nucleation of the shell precursors induced by excessive introducing of the shell precursors.
Although a homogeneous shell could be obtained by using the
multi-cycle path (reducing the amount of shell precursors of each
cycle) (Fig. 13a),131 owing to the selection of the low boiling point
NaOHNH4Fmethanol precursor, the multi-cycle path must
undergo a lengthy cooling and volatile solvent removing process
during the growth of every layer of the shell. For the reason of
batch operation, this process is considered to be time-consuming,
laborious, and user unfriendly, especially for the synthesis of
complicated multi-shell UCNPs. Based on the LaMer nucleationgrowth model,182,183 our group developed a facile one-pot successive layer-by-layer method to realize the successive shell coating by
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using high boiling-point ReOA and NaTFAOA as shell precursors (Fig. 13b).91 This protocol is flexible to deposit the uniform multi-shell by successive introduction of the shell precursor
solutions instead of the lengthy multi-cycle batch operation. This
protocol is flexible to deposit the uniform multi-shell on both
hexagonal and cubic phase cores by successive introduction of the
shell precursor solutions. The shell thickness of nanoparticles can
be well controlled from 1 ML (B0.36 nm) to more than 20 ML
(B8 nm) by simply tuning the amounts of the shell precursors.
Furthermore, the tunable doping positions (core and shell doping)
can also be achieved by adjusting the species and addition
sequence of the shell precursors. With the SLBL method, the
preformed nuclei were dissolved into the reaction solution and
then the shell precursors were alternately introduced, and the
formed monomers were supplied to precipitate on the surface of
the nuclei. The monomer concentration was kept low during the
growth to suppress homogeneous nucleation because its production and consumption maintained the balance. The released
monomers could be continuously consumed to deposit as a shell
without homogeneous nucleation (Fig. 13c). As discussed in
Section 3, the most distinguished feature of core@shell UCNPs
synthesized from the SLBL method is that the shell is very
uniform. It means that the cores are completely covered by the
shell, which is quite different from the non-uniform shell NPs
synthesized by the commonly used one-pot heating-up method
(the core is only partially covered by shell, Fig. 8a and b). As a
result of the high quality uniform shells, the optical properties of
the obtained core@shell nanoparticles could be improved in UCL
efficiency and stability. Most recently, our group reported for the
first time that the homogeneous doping approach based on the
SLBL method can greatly improve the efficiency of the UCNPs.186
The quantum yield as high as 0.89 0.05% is realized for the
homogeneous doping NaGdF4:Yb,Er/NaYF4 UCNPs, which is
nearly 2 times higher than that of the heterogeneous doping
NaGdF4:Yb,Er/NaYF4 UCNPs (0.47 0.05%). The influences of
spatial distributions and local relative concentrations of the
dopants on the optical properties of UCNPs were investigated at
the single particle level. It was found that heterogeneous
doping indeed existed during the spontaneous growth process
of the nanoparticles. The heterogeneous doping property can
further induce many negative effects on the optical properties
of UCNPs, especially the luminescence efficiency. The spatial
distributions and local relative concentrations of the dopants
can be well controlled by the SLBL homogeneous doping
method at the monolayer level and homogeneously distributed
at the single particle level. With the similar SLBL method, the
highly efficient LiLuF4:Ln3+@LiLuF4 core@shell UCNPs and
dual-mode up/down converting NaGdF4:Nd@NaYF4@NaGdF4:
Nd,Yb,Er@NaYF4 core@shell1@shell2@shell3 (Fig. 11d and e)
have been well established.119,162
4.3 Ostwald-ripening strategy for the fabrication of
core@shell UCNPs
The Ostwald ripening process is referred as the last stage in the
LaMer plot, in the process larger particles with smaller surfaceto-volume ratios are favored over energetically less stable
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smaller particles, resulting in the growth of larger particles at

the expense of smaller ones. The fabrication of core@shell
UCNPs by using the common physical phenomenon of Ostwald
ripening (i.e. self-focusing by Ostwald ripening) was developed
by van Veggel and co-workers.185 In their study, small a-NaYF4
sacrificial nanoparticles (SNPs) were synthesized first and then
used as shell precursors. The subsequent injection of SNPs into
a hot solution of NaYF4 core nanoparticles (defocusing) can
induce the rapid dissolution of SNPs and their deposition onto
the larger core nanoparticles (self-focusing), thereby resulting
in the formation of genuine core@shell structured UCNPs with
a well defined shape, narrow size distribution, and tunable
shell growth. More importantly, the shell thickness and multiple layers of such core@shell UCNPs can be precisely controlled
by manipulating the number of SNPs injected and/or repeating
the above defocusing and self-focusing cycle. Furthermore, this
method is flexible and can be easily extended to prepare other
high-quality core@shell NPs with dierent compositions.
5. Fabrication of UCNP-based
nanocomposites and applications
Multifunctional nanocomposites have recently attracted increasing
attention, with the hope to extend the applications of the unique
UCL property further. The introduction of another component to
UCNPs can use UCL as a wavelength transformation to extend the
working range, or integrating the additional functional moiety into
one nanocomposite. This extends the scope of their potential
applications.
5.1
UCNPSiO2 nanocomposites
Silanization is a popular technique for surface modification of

nanoparticles since silica is highly biocompatible, the ease of
surface modification (e.g., COOH, NH2, SH, etc.), which
allows for bio-labeling, drug targeting and delivery. Furthermore,
the silica-coated functional nanoparticles can be protected by
the SiO2 shell against the influence of physiological conditions
and outside environments. Two routes can be adopted to coat
silica, depending on the polar nature of the capping ligands on
ber method, which can
the nanoparticle surface. One is the Sto
be utilized to coat silica on hydrophilic UCNPs. A precise
control of the amounts of involved reagents as well the pH
value can lead to a uniform growth of silica layers onto
UCNPs.3,164,187,188 For example, Zhang et al. coated a very
uniform and thin silica shell (13 nm) onto polyvinylpyrrolidone
(PVP)-stabilized hydrophilic NaYF4 nanoparticles to form a
core@shell structure.164 The b-NaYF4@SiO2 core@shell nanorods were also synthesized in our group.187 Another route is the
reverse micro-emulsion (water-in-oil) method to realize silica
coating onto UCNPs with hydrophobic capping ligands.189193
This method utilizes chemical reactions (the hydrolysis of
TEOS) in nano-confined hydrophilic cavity (nano-reactor
space) generated by a homogeneous mixture of ammonia,
cyclohexane, surfactant (Igepal CO-520, TritonX-100) and TEOS.
This strategy could be used to obtain silica shells with
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varying thicknesses. As mentioned above, one of the most

salient advantages is the ease of surface modification of SiO2.
Taking NH2 functionalization as an example, it just needs
replacing a part of TEOS with (3-aminopropyl)triethoxysilane
(APTES) and the surface of the obtained UCNPs@SiO2 can be
modified with NH2.194 With the help of the surface functional
group, the alien species can easily be combined with UCNPs.
Folic acid (FA), which has been widely used as a targeting agent,
can be easily conjugated with the amine functionalized
UCNPs@SiO2 nanocomposites to realize the targeting imaging
or delivery. With the help of SiO2 shells, the scope of potential
applications of upconversion nanomaterials is extremely
extended. In 2009, Zhang and co-workers first demonstrated
the potential of UCNPs based gene delivery.195 The anti-Her2
antibody and folic acid modified NaYF4@SiO2 nanoparticles
were prepared and used for luminescence imaging and targeted
delivery of siRNA. The results showed that GL3 siRNAs were
delivered to SK-BR-3 cells with the Her2 receptor by using the
nanoparticles, and their delivery could be tracked. And then, a
FRET system based on ultra-fine silica coated NaYF4 UCNPs
was designed by the same group to study the intracellular fate
of siRNA in live cells.196 A FRET phenomenon between the
UCNP donor and the siRNA intercalating dye BOBO-3 acceptor
Chem Soc Rev
was simultaneously used to study their intracellular uptake,

release and bio-stability. Chien and co-workers formulated
UCNPs@SiO2 nanocomposites as the NIR-triggered targeting
and drug delivery vehicles that successfully deliver in vitro
and in vivo for NIR photo-controlled targeting, bioimaging,
and chemotherapy.197 To achieve photo-targeting, the tumorhoming agent (i.e., folic acid) has been constructed as a photoresponsive molecule. For the chemotherapeutic effect, the
anti-tumor drug doxorubicin is thiolated on the surface of SiO2
to form a disulfide bond that can be cleaved by lysosomal
enzymes within the cells. The caged UCNPs can serve as a
platform for the improvement of selective targeting and possible
reduction of adverse side effects from chemotherapy. Zhai et al.
reported a novel design based on a combination of UCNPs@SiO2
nanoparticles and polyoxometalates, for electrically controlled
fluorescence switches and sensitive detection of antioxidants
in aqueous solution.198 Besides the surface conjugation of
organic groups or guest molecules, the small nanoparticles can
also be anchored on the surface of the UCNPs@SiO2 nanocomposites according to the surface functional groups. The
Shi group reported a tri-modal imaging probe of NaY/GdF4:
Yb,Er,Tm@SiO2Au@PEG5000 nanocomposites with a uniform
size (less than 50 nm) (Fig. 14).45 The as-designed nano-probes
Fig. 14 Schematic illustration of the synthesis of Au loaded UCNPs@SiO2 nanocomposite (A); TEM images of UCNPs (B), UCNP@SiO2 (C), Au loaded
UCNPs@SiO2 nanocomposite (D and E); backscattered morphological and compositional SEM images of the Au loaded UCNPs@SiO2 nanocomposite
(F and G, respectively).45 (Reprinted with permission from ref. 45. Copyright 2012, Elsevier Ltd.)
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showed: (i) strong UCL ranging from Vis to NIR for fluorescence
imaging, (ii) T1-weighted MRI by reducing T1 relaxation time
and (iii) an enhanced Hounsfield unit (HU) value as a CT
contrast agent. The structure was optimized based on a comprehensive investigation into the influence of the distance between
the NaY/GdF4:Yb,Er,Tm core and Au nanoparticles at the surface
by adjusting the thickness of SiO2 layers. Combined with the
magnetic and UCL of the Gd3+ ion doped UCNPs, Chen et al.
developed a new kind of UCNPs/MB-based PDT drug, NaYF4:
Er,Yb,Gd@SiO2MB with a diameter less than 50 nm.199 The
bio-compatibility, bio-distribution, bimodal imaging, and PDT
effects of the antibody-conjugated nanoparticles were systematically investigated.
As mentioned above, the alien species are mainly anchored
on the outer surface of UCNPs@SiO2 nanocomposites, indicating
that only a low amount of alien species is introduced due to
the limited area of the outer surface of UCNPs@SiO2 nanocomposites. Taking the advantages of the mesoporous silica
nanoparticles (MSNs) in applications of delivery systems, including
high surface areas, large pore volume, tunable pore sizes, good
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biocompatibility, and the ease of surface functionalization, the

nanocomposites of UCNPs and MSNs were also developed in the
past few years. The formation of mesoporous silica is nearly
the same as the synthesis of dense SiO2 (as mentioned above)
except the presence of the structure-directing agent (i.e. cetyltrimethylammonium bromide, CTAB).187 In general, there are
mainly two routes to get the nanocomposites. The first route is
based on coating mesoporous silica (mSiO2) layers on the surface
of UCNPs@SiO2 to form the UCNPs@SiO2@mSiO2 core@shell@
shell structure (Fig. 15a).187,200202 The second route is based on
over coating with mSiO2 layer on the surface of UCNPs directly in
one step (Fig. 15f).203205 For example, Liu et al. reported the
fabrication of the mSiO2 layer directly on the hydrophobic surface
of UCNPs (OA capping) in the presence of a large amount of
CTAB.203 In this process, CTAB serves not only as the stabilizing
surfactant for transferring hydrophobic NaYF4:Tm,Yb UCNPs
to the aqueous phase but also the organic template for the
formation of mesoporous structures in the solgel reaction.
The mSiO2 layer, with open mesopores, large surface areas, is
immobilized on UCNPs, and can offer many sites for the
Fig. 15 The synthetic routes for mesoporous silica over-coating. (a) Two-step approach for the fabrication of the UCNPs@SiO2@mSiO2 nanocomposite.202
(be) TEM images of UCNPs (b), UCNPs@SiO2 (c), UCNPs@SiO2@mSiO2 nanocomposites (d, e).202 (f) One-step method for the mSiO2 over-coating on the
hydrophobic surface of UCNPs.203 (gi) TEM images of the UCNPs@mSiO2 nanocomposite.203 (Reprinted with permission from ref. 202 and 203. Copyright
2012, National Academy of Sciences, USA and Wiley-VCH Verlag GmbH & Co. KGaA.)
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accommodation of functional biomolecules or drugs onto the

surface of UCNPs.
Over the past decade, much research on light controlled
drug delivery and release systems has been carried out extensively because light as an external stimulus oered controllable
drug release both spatially and temporally and thus exhibited
great potential for further biomedical applications. Many
papers have been reported on photo-responsive controlled
release motifs designed based on UV excitation.206209 However,
biomedical applications prefer longer wavelength NIR light that
has deep penetration into tissue and is less detrimental to
healthy cells. Therefore, with the combined unique advantages
of UCNPs and mSiO2, NIR-triggered guest delivery and release
applications have appeared and expanded greatly in recent
years.201,205,210 In 2012, Zhang et al. reported a new design to
remotely active biomolecules by encapsulating photo-caged
DNA/siRNA molecules into the mesochannels of mSiO2 shells
of the NaYF4:Yb,Tm@mSiO2 UCNPs, which offered a high
biocompatibility and more efficient loading and delivery
of biomolecules in deep tissues (Fig. 25a and b).202 Lin and
co-authors developed a facile methodology to construct a multifunctional anticancer drug nanocarrier by combining the special
advantages of UCNPs and mSiO2. b-NaYF4:Yb,Er@NaGdF4:Yb is
chosen as it can provide the dual modality of UCL and MRI.204
Then mSiO2 is directly coated onto the UCNPs to form discrete,
monodisperse, highly uniform, and core@shell structured nanospheres, which are subsequently functionalized with a hydrophilic polymer, poly(ethylene glycol) (PEG), to improve the
colloidal stability and biocompatibility. The obtained multifunctional nanocomposites can be used as anticancer drug
delivery carriers and applied for imaging. Most recently, Shi
et al. have reported a general strategy for NIR light-triggered
anticancer drug release based on the azobenzene (azo) modified
mSiO2-coated UCNP structure.205 As shown in Fig. 16, under
excitation of NIR light, the UCNPs emit photons in the UV/Vis
Fig. 16 NIR light-triggered DOX release by making use of the upconversion

property of UCNPs and transcis photoisomerization of azo molecules grafted
in the mesopore network of a mSiO2 layer.205 (Reprinted with permission from
ref. 205. Copyright 2013, Wiley-VCH Verlag GmbH & Co. KGaA.)
Chem Soc Rev
region which can be absorbed immediately by the photoresponsive azo molecules in the mesoporous silica layer to create
a continuous rotationinversion movement. The back and forth
wagging motion of the azo molecules can act as a molecular
impeller that propels the release of a drug molecule.
In recent years, PDT based on the photochemical reactions
mediated by the interaction of the photo-sensitizer (PS) with
specific light and molecular oxygen has attracted a great deal of
attention owing to its advantages of highly localized, specific tumor
treatments, outpatient therapy, high cure rates, cost eectiveness,
and so on. However, the PS used in conventional PDT is mostly
activated by visible or even UV light, which is limited to treating
tumors on or just under the skin and less eective when treating
large and deep seated tumors. The use of NIR light in PDT can
aord greater penetration depths than that of Vis light because the
absorbance for most biomolecules reaches a minimum in the
window. Therefore combined with the ability of converting NIR
light to Vis photon properties of the UCNPs and high loading
capacity of the mSiO2, many NIR-triggered PDT were designed
based on the nanocomposites of UCNPs and mSiO2.48,199,200 The
mSiO2-coated NaYF4@SiO2 nanocomposites with a core@shell@
shell structure were synthesized by the Zhang Group and used for
synergistic imaging and PDT of cancer cells.200 A thin layer of silica
is coated onto NaYF4 UCNPs to form NaYF4@SiO2 nanoparticles
and another layer of mSiO2 is further coated onto the nanoparticles
to form a core@shell@shell structure. PSs are incorporated into the
porous mSiO2 shells. After exposed to NIR light, the nanoparticles
can convert NIR light to visible light which activates the PS to
produce reactive oxygen species to kill cancer cells. The PS encapsulated in mSiO2 is protected from degradation in the harsh
biological environment. Then, the same group used the mSiO2
coated UCNPs as nano-transducers to convert deeply penetrating
NIR light to visible wavelengths and carriers of PSs (Fig. 17a-d).48
It is worth noting that they used the multicolor-emission capability
of UCNPs at a single excitation wavelength for simultaneous activation of two PSs for enhanced PDT. The bio-regulatory molecule nitric
oxide (NO) plays important roles in cancer biology and has been
implicated in both tumor growth and suppression. Furthermore, NO
is a g-radiation sensitizer that can enhance selective killing of
neoplastic tissues. For these reasons, our group used UCNPs to
facilitate NO releasing from a precursor by 980 nm irradiation
(Fig. 17e).201 The results showed that NIR-to-Vis upconversion by
Yb3+/Er3+ doped NaYF4 nanocrystals could trigger photoreactions of
the NO precursor, Roussins black salt anion. It was a potential game
changer in multi-photon excitation based therapeutic delivery of NO
and other small molecule bio-regulators.
Thanks to the rapid development of nanotechnology, various
silica based nano-drug carriers have come into being. Besides
mentioned above, rattle-type (or yolkshell) nano-capsules, which
possess movable cores, porous shells and interstitial hollow
spaces in between, provide an attractive nano-platform for drug
delivery due to their unique hollow structure, multifunctional
properties, and biological potential in the fields of nanomedicine. By a surface-protected etching strategy,211213 Fan
et al. fabricated the multifunctional rattle-structured (NaYF4:
Yb,Er@NaGdF4 UCNPs as the core, a porous silica layer as the
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Fig. 17 (ad) NaYF4:Yb,Er@SiO2@mSiO2 nanocomposite as an agent of PDT.48 (a, b) TEM images of the NaYF4:Yb,Er@SiO2@mSiO2 nanocomposite at low
((a) scale bar, 100 nm) and high magnification ((b) scale bar, 50 nm). (c) The UCL spectrum of the nanocomposite under 980 nm NIR laser excitation and the
absorption spectra of ZnPc and MC540 photosensitizers. (d) Schematic of NaYF4:Yb,Er@SiO2@mSiO2 nanocomposite co-loaded with ZnPc and MC540
photosensitizers for PDT. (e) Scheme for the synthesis of the UCNPs@SiO2@mSiO2 nanocomposites and for NIR light triggered photochemical nitric oxide
release.201 (Reprinted with permission from ref. 48 and 201. Copyright 2012, Nature Publishing Group and Wiley-VCH Verlag GmbH & Co. KGaA.)
outer shell, and a controllable internal cavity between them) nanotheranostics.214 The NaYF4:Yb,Er@NaGdF4 core can serve as a
magnetic/luminescent dual-mode imaging agent, the internal
cavity can be used for loading of the guest molecules. Zhao
et al. also demonstrated UCNPs@mSiO2 yolkshell nanoparticles
which displayed intense NIR-to-UV emission and large pore
volume and loaded with hydrophobized phototrigger-conjugated
drug (Fig. 18a-f).215 Most recently, the Shi group has reported the
synthesis of multifunctional NaYF4:Yb,Tm @NaGdF4 corehollow
mSiO2 shell nanoparticles and their application in simultaneous
NIR-triggered drug delivery and in situ quantitative drug release
monitoring by both UCL and longitudinal relaxation time (T1)
MRI imaging in real time (Fig. 18g-n).216
5.2
UCNPs based FRETLRET nanocomposites
Optical sensing and assays play vital roles in theranostics due

to the capability to detect and hint biochemical entities or
molecular targets as well as to precisely monitor specific
1366 | Chem. Soc. Rev., 2015, 44, 1346--1378
fundamental physiological processes. UCNPs are promising

for these endeavors due to the unique frequency converting
capability of biocompatible NIR light that is silent to tissues.
They have the potential to reach a high detection sensitivity
deeply located in the living body systems. However, UCNPs
usually respond little to changes in the surroundings, because
the UCL arises from 4f4f orbital electronic transitions with
concomitant wave functions localized within a single lanthanide
ion. The shielding of 4f electrons by the outer complete
5s and 5p shells results in high resistance to photobleaching,
photochemical degradation and other changes in chemical
surrounding. Therefore, to be useful in a biochemical recognition process, UCNPs have to be used in combination with
suitable recognition elements such as indicator dyes. Fortunately,
energy transfer processes provide a chance to introduce an
analyte-responsive chromophore as the optical detection component, and the wavelength conversion ability of UCNPs can
extend the working wavelength of this chromophore from
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Fig. 18 (a, b) Schematic illustration of the NIR-regulated PDD and the photolysis of the pro-drug under UCL from the yolkshell UCNPs@mSiO2
nanocomposite.215 TEM images of (c) the NaYF4:Yb,Tm, (d) NaYF4:Yb,Tm@NaLuF4, and (e, f) yolkshell UCNPs@mSiO2 nanocomposites.215 (g) The
formation process of the hollow structure UCNPs@mSiO2 nanocomposites.216 TEM images of (h) UCNP@SiO2, (i) UCNP@SiO2@mSiO2, and (j) hollow
structure UCNPs@mSiO2 nanocomposite. (kn) STEM images and corresponding elemental mappings of the hollow structure UCNPs@mSiO2
nanocomposites.216 (Reprinted with permission from ref. 215 and 216. Copyright 2014, Wiley-VCH Verlag GmbH & Co. KGaA.)
the original short wavelength region to the NIR range. The

energy transduction between UCNPs and the chromophore was
rster resonance energy transfer
generally implemented by a Fo
(FRET) or luminescence resonance energy transfer (LRET)
mechanism. In this section, we summarized UCNPs-based
FRETLRET nanocomposites and corresponding applications
in detection of ions (cyanide, mercury, etc.), sensing of small
gas molecules (oxygen, carbon dioxide, ammonia, etc.), as well
as UCNP-based bioassays for biomolecules.
FRET, a mechanism describing the non-radiative and
distance-dependent energy transfer between two chromophores, is a powerful tool used in several fields of science.75,217
LRET is a radiative process where light emitted by the donor is
absorbed by acceptor molecules. The dierence between LRET
and FRET resides in that the energy transfer process in LRET is
radiative, whereas it is non-radiative for FRET. When utilizing
UCNPs as energy donors and the dye or quantum dots (QDs)
as energy acceptors, it oers a large freedom for tuning of
upconversion emission wavelengths. Indeed, Zhang et al.
reported that an expanded range of multicolor emission could
be obtained from the core@shell NaYF4:Yb,Er(Tm)@SiO2

nanostructures whereby organic dyes or QDs were encapsulated
into the silica shells.218 For each type of lanthanide-doped
UCNPs, a wide range of multiple colors can be produced
through the FRET from UCNPs to the organic dyes or QDs that
produce new emission colors. In nanocomposites designed for
detection based on the FRET process, the distance between the
energy donor and the acceptor and the spectral overlap are
factors that can be controlled to influence the energy-transfer
process (Fig. 19). The energy acceptor chosen for upconversion
detection of nanocomposites on the basis of the FRET process
should have absorption corresponding to the UCL of UCNPs.
The distance between the donor and the acceptor in the FRET
process should be small enough to ensure highly ecient
energy transfer. The UCL is usually chosen as the detection
signal, which can be turned on or o when the FRET process is
turned o or on, respectively.217 Some FRETLRET detection
examples based on the UCNP nanocomposites are introduced
below. Zhang et al. developed a kind of energy transfer sensor
to determine Hg2+ in aqueous media in which a NaYF4:Yb,Tm
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Fig. 19 Design principle of the upconversion nanocomposites for upconversion FRET detection based on changing the spectra overlap (a)
and alternation of the distance between donor and acceptor (b).217 (Reprinted with permission from ref. 217. Copyright 2013, Wiley-VCH Verlag
GmbH & Co. KGaA.)
UCNPsSYBR Green (a DNA intercalating dye function) nanocomposite is employed as a donoracceptor pair.219 By monitoring the ratio of the acceptor emission to the donor emission,
they can quantitatively detect the presence of the mercuric
ions with a limit of detection (LOD) of 0.06 nM. Li et al.
reported on a highly selective water soluble probe for UCL
sensing of intracellular Hg2+ ions, where the chromophoric
ruthenium complex (N719) was labeled on the surface of
NaYF4:Yb,Er,Tm nanoparticles.220 The absorption peak of
N719, centered at 541 nm, matched the green UCL of UCNPs
to facilitate efficient LRET from Er3+ to N719 molecules,
causing quenching of the green UCL. The addition of Hg2+
can induce a blue shift of the maximum absorption wavelength of N719 from 541 to 485 nm, which decreases the
spectral overlap between the green UCL and the absorption of
N719, and breaks the LRET process, leading to recovery of the
green UCL. The N719UCNP nanocomposite can be applied
for bioimaging of Hg2+ ions in living cells. The LOD of Hg2+
ions in water is reported to be down to 1.95 ppb (parts per
billion), which is even lower than the maximum level (2 ppb)
of Hg2+ in drinking water set by the United States Environmental Protection Agency. Using a similar principle, the
Li group developed a nanocomposite composed of UCNPs
(NaYF4:Yb,Er,Tm) and a CN sensitive chromophoric iridium(III)
complex Ir1 (Fig. 20a),221 and hydrophobic heptamethine cyanine
dye (hCy7) modified by two long alkyl moieties and amphiphilic
polymer (P-PEG)-modified UCNPs (hCy7-UCNPs) as a highly
sensitive water-soluble probe for UCL monitoring and bioimaging of methyl-mercury (Fig. 20b).222
1368 | Chem. Soc. Rev., 2015, 44, 1346--1378
Besides the detection of hazardous ions in liquid, determination of the concentration of gas molecules such as oxygen,
carbon dioxide, ammonia, etc. has great significance in analytical biochemistry, clinical medical diagnosis, and bioprocess
monitoring. The use of UCNPs based FRETLRET nanocomposites for gas molecule sensing has attracted a great
deal of attention because of their outstanding properties. For
example, the oxygen sensor based on UCNP nanocomposites
was presented by the Wolfbeis group, in which NaYF4:Yb,Tm
UCNPs as nanolamps and iridium(III) complexes as oxygen
indicators were both incorporated in an ethyl cellulose thin
film.223 The fluorescence of the iridium(III) complex, produced
by FRETLRET from UCNPs, is sensitive to molecular oxygen
concentration, which can quantify the content of oxygen
molecules. Using a similar principle, they designed NaYF4:
Yb,Erbromothymol blue (BTB) nanocomposites and NaYF4:
Yb,Erphenol red nanocomposites to determine carbon dioxide,
and ammonia, respectively. The LOD is measured to be about
0.11% for CO2 and 400 mM for ammonia.224,225
As a good case of the combination of diagnosis and therapy
by using the UCNPs based FRET nanocomposites, Xing et al.
designed a personalized NIR light-activated nano-platform by
combining a photo-activatable Pt(IV) prodrug and a caspase
imaging peptide conjugated with silica-coated UCNPs for the
remote control of anti-tumor platinum prodrug activation, and
simultaneously for real-time imaging of apoptosis induced by
activated cytotoxicity by using the FRET eect of the nanocomposites.226 Upon NIR light irradiation, the converted emission from UCNPs@SiO2 could locally activate the Pt(IV) prodrug
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Fig. 20 CN (a) and methyl-mercury (b) detection by using the UCNPs-based FRET nanocomposites.221,222 (Reprinted with permission from ref. 221 and 222.
Copyright 2011, 2013, American Chemical Society.)
and thus eciently induce potent anti-tumor cytotoxcity in

both cisplatin-sensitive and resistant tumor cells. Moreover,
such NIR light-controlled tumor inactivation can trigger the
cellular apoptosis and the highly activated caspase could cleave
the NIR imaging peptide probe from the nanoparticle surface,
thus greatly turning on the quenched NIR fluorescence of Cy5.
These systematic studies indicated that the Pt(IV) probe
UCNPs@SiO2 could not only provide a promising strategy to
remotely control the localized activation of the Pt(IV) prodrug at
the target tumor sites, but more importantly, the developed
Pt(IV) probe UCNPs@SiO2 conjugates may serve as personalized
tumor markers to image in real time and evaluate the antitumor therapy at the cellular level.
5.3 Inorganic nanocrystals functionalized UCNP
nanocomposites
The rapid development in nanotechnology has allowed the
engineering of various functional nanomaterials with multiple
discrete function-related components integrated in one nanoparticle for applications in multimodality bio-applications to
circumvent the limitations of each single mode application. So
in this section, we describe some potentially useful designs and
applications of UCNPnanocrystal multifunctional nanocomposites, such as UCNPsmagnetic nanoparticles (UCNPsMNPs),
UCNPmetal and UCNPsemiconductor nanocomposites etc.,
which have been attracting increased research attention because

of their easily accessible multifunctional properties.
5.3.1 UCNPMNP
multifunctional
nanocomposites.
Conventional chemotherapy is commonly used in the clinical
management of many cancers, often with severe side effects due
to the cytotoxicity of the agents and genetic heterogeneity of
tumors, that is, their phenotypic drug sensitivity or resistivity.227
Nano-engineered drug-delivery systems could improve the
clinical performance of conventional chemotherapeutic agents
and reduce overall toxicity by enhancing the specificity of the
drugs delivery through tumor targeting and making elevated
local dosages possible.228 A major goal in nano-medicine is the
coherent implementation of multifunctional platforms within a
single targeted nano-delivery system that would simultaneously
perform diagnosis, targeted delivery and efficient therapy
(theranostics).229,230 Along these lines, luminescent and MNPs
have been used as bio-labeling, contrast agents, and for MRI and
targeted drug delivery, leading recently to major advances in bioapplications.229,230 As one of the most important members in the
luminescence materials family, the fabrication of UCNPsMNPs
multifunctional nanocomposites attract much attention due to
the unique properties of UCNPs.33,231234 Our group fabricated
nanorattles consisting of hydrophilic lanthanide doped NaYF4
shells each containing a loose magnetic nanoparticle with the
aid of the intermediate layer of SiO2.231 This multi-functional
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Fig. 21 (A) Synthetic procedure for the drug-loaded Fe3O4@SiO2@NaYF4:Yb,Er nanorattles. (B) Schematic illustration for the targeting of DOX-loaded
multifunctional drug carrier to tumor cells assisted by an externally applied magnetic field. (C) Tumor location defined by the nanocomposite intensity
increases with 1 h magnetic field treatment. (D) The luminescence signal measured from the whole tumor in vivo and ex vivo. (E) Tumor volume changes
of saline-treated mice compared to mice treated with multi-functional nanorattles, DOX, and DOX loaded nanorattles over 21 day in the absence and
presence of magnetic field.231 (Reprinted with permission from ref. 231. Copyright 2012, American Chemical Society.)
mesoporous nanostructure with both UCL and magnetic properties has excellent water dispersibility and a high drug-loading
capacity. As shown in Fig. 21, the Fe3O4@SiO2 nanoparticles
were synthesized from monodispersed Fe3O4 nanocrystals with
B20 nm in diameter as a core, using a reverse micro-emulsion
method. Due to the presence of a SiO2 layer, a layer of
Y,Yb,Er(OH)CO3H2O is easily deposited on the Fe3O4@SiO2
nanospheres via a homogeneous precipitation method. After
the thermal treatment at high temperature and the flowing
ion-exchange process, the multifunctional Fe3O4@SiO2@
a-NaYF4,Yb,Er UCNPMNP nanocomposites can be obtained.
The material emits visible UCL upon NIR excitation and can
be directed by an external magnetic field to a specific target,
making it an attractive system for a variety of biological applications. Measurements on cells incubated with the nanorattles
show that they have low cytotoxicity and excellent cell imaging
properties. In vivo experiments yield highly encouraging tumor
shrinkage with the anti-tumor drug and significantly enhance
tumor targeting in the presence of an applied magnetic field.
Cheng et al. described a novel class of multifunctional UCNP
MNPAu nanocomposites.33 The nanocomposites were prepared
by layer-by-layer self-assembly (Fig. 22). Ultra small superparamagnetic dopamine (DA) modified Fe3O4 MNPs are
adsorbed on the surface of poly(acrylic acid) (PAA)-modified
NaYF4 based UCNPs by electrostatic attraction to form a
UCNPsMNPs complex, on top of which a thin gold shell is
formed by seed-induced reduction growth. The layer of MNPs
between UCNPs and the Au shell not only affords magnetic
properties but also significantly reduces the luminescence
quenching effects of the gold nanostructure on UCNPs. The
multifunctional UCNPMNPAu nanocomposites are then coated
by PEG to impart stability to physiological solutions used for
in vitro targeted UCL, MRI and dark-field light scattering imaging.
The surface plasmon resonance absorption contributed by the
gold shell is utilized for dual-targeted photo-thermal ablation of
1370 | Chem. Soc. Rev., 2015, 44, 1346--1378
Fig. 22 Strategy for the UCNPsFe3O4Au multi-functional nanocomposite

synthesis and functionalization.33 (Reprinted with permission from ref. 33.
Copyright 2011, Wiley-VCH Verlag GmbH & Co. KGaA.)
cancer cells. Shen and co-workers reported the Fe3O4NaYF4:

Yb,Er UCNPMNP nanocomposite synthesized by a ligand
anchoring strategy (Fig. 5).234 Fe3O4 nanoparticles are localized
at the surface of UCNPs assisted by cross linkers. Compared with
other chemical linkage methods for hybrid nano-structures, this
cross linker anchoring strategy comprises the ligand exchange
process, crystallization of Fe3O4 nanoparticles and integration
into UCNPMNP nanocomposites in a sequential one-pot reaction. The process is facile and effective for the construction of
multifunctional nanocomposites in a solvothermal system. This
approach is not limited by lattice mismatch for different functional components, and is applicable to QDs and noble metal
nanoparticles, etc. The obtained UCNPMNP nanocomposites
can well preserve the UCL and room-temperature superparamagnetism, which enable both effective optical detection
and magnetic trapping. Most recently, Chen et al. have developed
a new method to synthesize PEGylated UCNPMNP nanocomposites with an iron oxide core and a luminescent shell of uniform
thickness with the assistance of a polyelectrolyte.235
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5.3.2 UCNPmetal nanocomposites. It is well known that

metal nanostructures (i.e. plasmonic substrates) can efficiently
collect light and enhance the intensity due to surface plasmon
resonances (SPR). These effects have been widely used for
enhancing various optical processes, such as Raman scattering
and downconversion luminescence.236240 So in this section we
focus on the fabrication of UCNPmetal nanocomposites, which
is an important way to enhance the UCL according to the SPR
effect of metals.241253 The optical properties of a photoluminescence material positioned in close proximity to colloidal metal
nanoparticles are affected by the near field electrodynamical
environment.254 The modified fields cause an enhancement or
quenching of the photoluminescence relative to the native state,
which depends sensitively on the distance between the luminescent material and the metal surface. A judicious balance of two
factors needs to be worked out for plasmonic modulation
of luminescence. Quenching predominantly would occur if
the luminescent nanoparticle is brought into contact with the
metallic surface directly. Conversely, the enhancement of the
luminescence occurs upon moving the nanoparticle away from
the metal surface and is maximized at some critical distance.
The guiding principle is that the luminescence efficiency of the
nanoparticles can be enhanced by tuning the SPR peak to the
excitation/emission wavelength. Recently, a number of nanostructured systems of metal-cores, spacer molecules and photoluminescence materials have been examined. The distance
dependency of photoluminescence enhancement and quenching
has so far been observed with organic dyes,254 QDs,255 and rareearth complexes with organic molecules,256 polyelectrolytes254 or
silica255 as spacers. In 2010, we reported a facile method to
fabricate metal core enhanced Er3+ doped UCNPs based on a
core@spacer@shell approach. Ag@SiO2@Y2O3:Er nanocomposites
with different SiO2 spacer thickness were synthesized (Fig. 23).257
We found that the UCL enhancements or quenching was
dependent on the dielectric silica spacer thickness. The
average photoluminescence intensity could reach a maximum
value of 4 times that from the pure Y2O3:Er shell at an optimal
Chem Soc Rev
spacer thickness of 30 nm. Almost at the same time, the Duan

group reported a new approach for the modulation of UCL
through plasmonic interactions between UCNPs and gold
nano-structures.242 The attachment of gold nanoparticles
onto UCNPs can more than double the UCL intensity. The
quantitative analysis of the confocal images showed that an
intensity enhancement factor of approximately 2.6 could be
achieved. This enhancement is at least partly attributed to
surface-plasmon-coupled emission, which can increase the
radiative decay rate and emission efficiency. Interestingly, they
also found that the formation of a gold shell could significantly
suppress the emission because of considerable scattering of
excitation irradiation.
The SPR peaks of the above introduced metal nanoparticles
are confined to the visible region at around 500550 nm, which
overlap with the green emission and therefore a selective
enhancement occurs for this emission peak only. Although
gold nanoshells have been coated on the nanocrystals by the
Duan group, it greatly suppressed the emission from the
nanocrystals due to the strong scattering of the excitation
irradiation. It is predicted that simultaneous enhancement
for all the upconversion emission peaks can be achieved if
the SPR peak is tuned to the NIR region and made resonant
with the absorption of UCNPs at 980 nm thereby substantially
increasing the excitation flux via a local field enhancement
effect. Recently, Priyam et al. have reported a poly-(amino acid)
templated gold nanoshell encapsulation of silica coated
NaYF4:Yb,Er UCNPs and tuned the SPR peaks in a wide wavelength range from the visible to NIR region with a highly intense
single plasmon peak. The luminescence was dramatically transformed from quenching into an enhancement effect.252 The
photoluminescence intensities of the three upconversion emission peaks at 660 (red), 545 (green) and 410 nm (blue) can be
enhanced for 2.1, 2.6 and 3.3 times, respectively.
It has been demonstrated that UCL can be enhanced not only
by the metal nanoparticles but also by plasmonic metal microarrays (Fig. 24). Most recently, Zhang et al. have investigated a
Fig. 23 Fabrication of the UCNPsmetal nanocomposites for bioimaging: tuning of the UCL by the SPR effect.257 (a) Synthetic procedure of the
Ag@SiO2@Y2O3:Er nanocomposites. TEM images of (b) Ag@SiO2 nanospheres (c) Ag@SiO2@Y2O3:Er nanospheres, (d) Ag@Y2O3:Er hollow nanospheres.
(Reprinted with permission from ref. 257. Copyright 2010, American Chemical Society.)
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Fig. 24 UCNPmetal nanocomposites for enhancing UCL. (a) Schematic

structure of a spin cast layer of Au or Ag nanoparticles, a thin Al2O3 layer,
and a monolayer of UCNPs for enhancing UCL.241 (b) Enhanced UCL on
the glass and optimized Au D2PA substrate.258 (Reprinted with permission
from ref. 241 and 258. Copyright 2012, American Chemical Society and
Wiley-VCH Verlag GmbH & Co. KGaA.)
plasmon-enhanced UCL of NaYF4:Yb3+,Er3+ nanocrystals on a 3D

plasmonic antenna architecture, the disk-coupled dots-on-pillar
antenna array (D2PA) (Fig. 24b).258 They optimized the D2PA
structure by tuning the pillar height (h), and consequently the
resonance frequency of the substrate, and found that, when
h = 75 nm, the resonance frequency matched the pumping
lasers frequency and the enhancement factor of UCL reached
its maximum, 310 fold. Furthermore, Kagan and co-workers
demonstrated amplification of luminescence for hexagonal
NaYF4 doped with Yb3+, Er3+ or Yb3+, Tm3+ by close proximity
to metal nanoparticles (Fig. 24a).241 They present a configuration
in which close-packed monolayers of UCNPs were separated
from a dense multilayer of metal nanoparticles (Au or Ag) by a
Review Article
nanometer scale oxide. Metal-enhanced UCL was found to be

dependent on the thickness of the oxide spacer layer and the
type of metal nanoparticles with enhancements of up to 5.2 fold
proximal to Au and of up to 45 fold proximal to Ag nanoparticles.
5.3.3 UCNPsemiconductor nanocomposites. Over the
past few years, a lot of efforts have been made for the
fabrication and control of size and shape of semiconductor
nanostructures, because of their importance in catalysis,
electronics, photonics, optoelectronics, sensing, and potential
applications in nano-devices. One of the most important
characteristics of semiconductors is the ability to absorb the
light with a specific range of wavelengths, which is corresponding to their band gap. The absorbed light can be converted
to electricity, luminescence, or heat. Combined with the unique
optical properties of UCNPs, some UCNPsemiconductor nanocomposites have been developed to extend the potential applications of UCNPs.
Xiao et al. constructed a multifunctional coresatellite nanocomposite by decorating ultra-small CuS semiconductor nanoparticles onto the surface of silica-coated UCNPs (Fig. 25a-e).259
The nanocomposite could not only convert NIR light into heat
for effective thermal ablation but also induce a highly localized
radiation dose boost to trigger substantially enhanced radiation damage both in vitro and in vivo. With the synergistic
interaction between photothermal ablation and the enhanced
radiotherapy, the tumor could be eradicated without visible
recurrence in 120 days. Moreover, the novel nanocomposite
facilitates excellent UCL/MRI/CT tri-modal imaging. Yan and
co-authors prepared a new nanocomposite, CdSe/NaYF4:Yb,Er,
Fig. 25 (a) Schematic of UCNPCuS nanocomposites for enhanced RT/PTA synergistic therapy.259 (be) TEM images of (b) UCNPS, (c) UCNP@SiO2NH2,
and (d, e) UCNPCuS nanocomposites at different magnifications.259 (f) TEM image of the UCNPCdSe nanocomposites and (g) NIR photoresponse ability
of the nanocomposite.260 (Reprinted with permission from ref. 259 and 260. Copyright 2010, 2013, American Chemical Society.)
1372 | Chem. Soc. Rev., 2015, 44, 1346--1378
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that up-converts NIR photons and uses the created exciton to

generate charge carriers in CdSe-based films, leading to a
reversible and stable NIR photoconductivity switch (Fig. 25f
and g).260 The Liu group reported a novel design, based on a
combination of lanthanide-doped UCNPs and MnO2 semiconductor nanosheets, for rapid, selective detection of glutathione
in aqueous solutions and living cells.261 In this approach,
MnO2 nanosheets formed on the surface of UCNPs serve as
efficient quenchers for UCL. The UCL can be turned on by
introducing glutathione that reduces MnO2 into Mn2+. The
ability to monitor the glutathione concentration intracellularly
may enable rational design of a convenient platform for targeted
drug and gene delivery.
For conventional solar cells, one of the major energy loss
mechanisms is the transmission of sub-bandgap photons. The
use of upconversion materials provides a solution to the
transmission loss by converting two sub-bandgap photons into
one above-bandgap photon. Indeed, UCNPs have been coupled
to a wide range of solar cells including crystalline Si,262 amorphous Si thin-film,263 organic,264 and dye-sensitized solar cells
(DSSCs).265 Su et al. demonstrated a new method to utilize
UCNPs in a hetero-nanostructured photo anode for enhanced
NIR light harvesting.266 They showed that upconversion is
responsible for the observed photo-response upon NIR exposure.
This is the first demonstration of photo-electrochemical electrodes
with UCNPs embedded in porous photonic crystals. The
interconnected pores of the photonic crystals render the nanoparticles spatially positioned in close proximity to CdSe quantum
dots, leading to an enhanced energy transfer and light harvesting.
This proof-of-concept is highly applicable to other types of solar
cells such as thin-film, liquid-junction and organic solar cells
where infrared photons with sub-bandgap energies can be
harvested for improved photon-to-electricity conversion eciency
by broadening the spectral response. Most recently, Zhao and
co-workers have designed and employed a highly uniform core
double-shell structured b-NaYF4:Er,Yb@SiO2@TiO2 hexagonal
Fig. 26 Schematic of the experimental process of the core@doubleshell-structured b-NaYF4:Er,Yb@SiO2@TiO2 hexagonal sub-microprisms
and the configuration of the DSC device.267 (Reprinted with permission
from ref. 267. Copyright 2013, Wiley-VCH Verlag GmbH & Co. KGaA.)
Chem Soc Rev
sub-microprisms and employed in DSSCs internally for the first

time (Fig. 26).267 These sub-microprisms can act as effective
scattering centers to enhance the light harvesting. By coating
with the amorphous SiO2 insulating layer around the
b-NaYF4:Er,Yb UCNPs, the electron trapping and capture caused
by surface defects and ligands of bare b-NaYF4:Er,Yb crystals can
be thoroughly avoided. At a certain mixing mass ratio of 10%,
an efficiency of 8.65% was obtained, which was 120% higher than
that of a device based on bare NaYF4:Er,Yb crystals and an
enhancement of about 10.9% was achieved when compared to
the reference cell. Then, they also used the same double-shell
b-NaYF4:Yb,Er@SiO2@TiO2 sub-microplates as scattering and
upconverting layers for DSSCs. Due to their effective light
scattering and upconverting effects, the performance of DSSCs
was significantly enhanced, resulting in an efficiency of 7.70%,
which is a noticeable improvement of B29.41% compared to
the cell without the bifunctional layer (5.95%).268
6. Conclusions and perspectives

In this paper, we summarized recent progress in UCNPs,
including excitation and emission energy levels guided designing
of UCNP nanostructure, the synthesis techniques to fabricate the
nanostructure with optimum energy level structure, the fabrication of UCNPs-based nanocomposites to extend the working
range of UCNPs by introducing the additional functional component, or integrating the additional functional moiety into
one nanocomposite.
Despite the UCNPs have attracted a great deal of attention in
a wide range of applications due to their unique optical and
chemical properties, practical applications of UCNPs set
demanding requirements on their optical properties, size, surface chemistry, as well as their ability to incorporate with alien
species. New advancements in diverse aspects are needed to
make rapid progress in this field to fulfill requirements of the
practical applications. So, we would like to highlight some
future directions that can produce pronounced eects in the
field. Firstly, the brightness of UCNPs is still unsatisfactory, in
particular, under a low excitation density of 10 210 1 W cm 2.
Manipulation of the local environment around the lanthanide
dopants by delicate designing and optimizing of the structure
of the UCNPs may be a promising direction to enhance the
quantum yield. Through the development of UCNPs, the structures of the nanoparticles become more and more advanced,
ingenious. Thus the structure, especially the core@shell structure, becomes more and more complicated, indicating that the
traditional synthesis method hardly fulfils the practical needs.
So the second anticipation is the development of the new
synthesis approach which can fulfill the requirements for the
fabrication of complicated multi-shell structured UCNPs. Last
but not the least, most of the equipment used to characterise
the optical properties of UCNPs are based on the home-made
instruments. Standard measurement facilities and protocols
are highly required to allow the quantitative comparison of
optical properties.
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Acknowledgements
The work was supported by NSFC (grants 21322508, 21101029,
21273041, and 21210004), China National Key Basic Research
Program (973 Project) (No. 2013CB934100, 2012CB224805, and
2010CB933901), Program for New Century Excellent Talents
in University (NCET), the Shanghai Rising-Star Program
(12QA1400400), and the State Key Laboratory of Pollution
Control and Resource Reuse Foundation (No. PCRRF12001).
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Volume 44 Number 6 21 March 2015 Pages 12911716

Chem Soc Rev

Themed issue: Photon upconversion nanomaterials

Chem Soc Rev

Cite this: Chem. Soc. Rev., 2015,

View Journal | View Issue

Lab on upconversion nanoparticles: optical

Received 11th May 2014

Xiaomin Li was born in Henan,

1346 | Chem. Soc. Rev., 2015, 44, 1346--1378

It is known that rare-earth (RE) materials exhibit not only down

Prof. Fan Zhang received his PhD

This journal is The Royal Society of Chemistry 2015

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luminescence (UCL) (anti-Stokes).15 Upconversion refers to

Dongyuan Zhao received his BS

This journal is The Royal Society of Chemistry 2015

Chem Soc Rev

non-blinking, less light scattering, and allow a deep tissue

Schematic illustration of the structure of this review.

Chem. Soc. Rev., 2015, 44, 1346--1378 | 1347

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Chem Soc Rev

of lanthanide doped UCNPs. Section 5 summarizes recent

2. The components of the UCNPs:

Lanthanide ions have a 4fn5s25p6 electron configuration with

Lu can exhibit upconversion, including Pr,5357 Nd,58,59 Sm,60,61

Major emissions (nm)

489, 526, 548, 618, 652, 670, 732, 860

430, 482, 525, 535, 580, 600, 664, 766

1348 | Chem. Soc. Rev., 2015, 44, 1346--1378

P0 - H4, I6 - H5, P0 - H5, P0 - H6, P0 - F2, P1 - F3,

This journal is The Royal Society of Chemistry 2015

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Chem Soc Rev

gap of about 1.27 eV (B980 nm) exists between two subsequent

This journal is The Royal Society of Chemistry 2015

cross-sections, leading to low pump efficiency. Therefore, the

Fig. 3 (a) Energy transfer upconversion (ETU) processes of activators and

Chem. Soc. Rev., 2015, 44, 1346--1378 | 1349

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been reported by Capobianco et al. in NaYF4 nanoparticles.87

1350 | Chem. Soc. Rev., 2015, 44, 1346--1378

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More recently, we have reported that the multicolor UCL can be

The choice of the host lattice determines the distance between

This journal is The Royal Society of Chemistry 2015

Chem Soc Rev

Generally speaking, the main intra 4f electronic-dipole

Chem. Soc. Rev., 2015, 44, 1346--1378 | 1351

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Chem Soc Rev

be ascribed to non-radiative energy transfer from 2H9/2 and 4S3/2

1352 | Chem. Soc. Rev., 2015, 44, 1346--1378

eciently cleared from the body.50,124,125 Thus, one of the

This journal is The Royal Society of Chemistry 2015

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Chem Soc Rev

This journal is The Royal Society of Chemistry 2015

Chem. Soc. Rev., 2015, 44, 1346--1378 | 1353

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Chem Soc Rev