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Light upconverting core–shell nanostructures:

nanophotonic control for emerging applications
Cite this: Chem. Soc. Rev., 2015,
44, 1680
Guanying Chen,*ab Hans Ågren,c Tymish Y. Ohulchanskyya and Paras N. Prasad*ad

Light upconverting nanostructures employing lanthanide ions constitute an emerging research field recognized
with wide ramifications and impact in many areas ranging from healthcare, to energy and, to security. The
core–shell design of these nanostructures allows us to deliberately introduce a hierarchy of electronic
energy states, thus providing unprecedented opportunities to manipulate the electronic excitation,
energy transfer and upconverted emissions. The core–shell morphology also causes the suppression
of quenching mechanisms to produce efficient upconversion emission for biophotonic and photonic
applications. Using hierarchical architect, whereby each shell layer can be defined to have a specific feature,
the electronic structure as well as the physiochemical structure of the upconverting nanomaterials can be
tuned to couple other electronic states on the surface such as excitations of organic dye molecules or
localized surface plasmons from metallic nanostructures, or to introduce a broad range of imaging or
Received 16th May 2014 therapeutic modalities into a single conduct. In this review, we summarize the key aspects of nanophotonic
DOI: 10.1039/c4cs00170b control of the light upconverting nanoparticles through governed design and preparation of hierarchical
shells in the core–shell nanostructures, and review their emerging applications in the biomedical field, solar
[Link]/csr energy conversion, as well as security encoding.

1. Introduction incoherent light sources such as bulb lamps and light emitting
diodes. This low power excitation density is in marked contrast
Photon upconversion (UC) refers to an anti-Stokes process in to the high power density excitation (4106 W cm 2) required in
which two or more low energy photons are sequentially or step- nonlinear multiphoton absorption in which an expensive ultra-
wise absorbed via real intermediate long-lived electronic states, short pulsed laser has to be employed.3 The idea of photon UC
resulting in an excitation of a higher electronic state, emitting a originated from Bloembergen in 1959, who proposed that
higher energy photon.1,2 It is distinct from conventional multi- infrared (IR) light could be detected by sequential absorption
photon absorption induced fluorescence, whereby multiple of an ion in a solid material.7 This concept was then realized
photons are simultaneously absorbed using virtual intermedi- and formulated independently by Auzel,8 Ovsyankin and
ate electronic states to produce photons with higher energy,3 Feofilov9,10 in the mid-1960s. For a long time, the investigation
and from conventional nonlinear sum frequency generation of photon UC remained centered on f-ion (lanthanide) or d-ion
(typically, second harmonic generation), where two incident (transition metal) doped bulk crystalline materials or glasses
photons (at different or the same frequencies) are parametrically for use in UC lasers, IR detection, optical storage, etc.1 It is
annihilated in a non-centrosymmetric medium to produce a only recently that photon UC in nanomaterials has captured
photon with summed energy.4–6 The advantage offered by worldwide attention, because of the advantage offered by
sequential excitation is the possibility of generating UC with nanochemistry to fabricate unique nanostructures with nano-
an excitation power density as low as B10 1 W cm 2, which is photonic control of the excitation dynamics.11 Photon UC has
easily provided by low cost continuous-wave laser diodes or been reported for many types of nanomaterials, such as
lanthanide-doped nanostructures,12 transition metal-doped
a
Institute for Lasers, Photonics, and Biophotonics and Department of Chemistry,
nanoparticles,13 defects-doped nanostructures,14 quantum
University at Buffalo, State University of New York, Buffalo, New York 14260, nanostructures,15 as well as nanoparticles containing organic
USA. E-mail: pnprasad@buff[Link] molecules as donor–acceptor pairs in triplet–triplet annihila-
b
School of Chemical Engineering and Technology, Harbin Institute of Technology, tion UC.15,16 Lanthanide-doped UC nanoparticles (UCNPs) are a
Harbin, Heilongjiang 150001, People’s Republic of China.
major thrust area of current research on UC in nanoparticles.
E-mail: chenguanying@[Link]
c
Department of Theoretical Chemistry & Biology, Royal Institute of Technology,
The discussion within this review will be limited to this type
S-10691 Stockholm, Sweden of UC, with a focus on the emerging hierarchical core–shell
d
Department of Chemistry, Korea University, Seoul 136-701, Korea structured UCNPs.

1680 | Chem. Soc. Rev., 2015, 44, 1680--1713 This journal is © The Royal Society of Chemistry 2015
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Review Article Chem Soc Rev

Lanthanide-doped UCNPs can be considered as dilute either a dielectric material17 or a wide band gap semiconductor.18
guest–host systems, where trivalent lanthanide ions are dis- UC is often more efficient in dielectric materials (e.g., sodium
persed as guests in an appropriate inorganic host lattice with yttrium fluoride, NaYF4), as they are more favorable to incorporate
dimensions of less than 100 nm.2 The inorganic host lattice can be trivalent lanthanide ions without the need for generating vacancies
Published on 22 October 2014. Downloaded by Indian Institute of Technology Chennai on 3/5/2024 [Link] AM.

Guanying Chen received his BS Hans Ågren graduated with a

and PhD degrees in optics in PhD in 1979 in experimental
2004, and 2009, respectively, atomic and molecular physics at
from Harbin Institute of Technol- the University of Uppsala,
ogy, P. R. China. He is a professor Sweden, under the supervision of
at the School of Chemical Nobel laureate Kai Siegbahn.
Engineering and Technology, After a couple of Post Doc years
Harbin Institute of Technology, in USA he became in 1981 an
and a senior research scientist at assistant professor in Quantum
the Institute for Lasers, Photonics, Chemistry at Lund University.
and Biophotonics, University at He became the first holder of the
Buffalo, State University of New chairs in Computational Physics
Guanying Chen York. He was a postdoctoral fellow Hans Ågren at Linköping University in 1991
(2010–2011) at University at Buf- and in Theoretical Chemistry at
falo, State University of New York, and Royal Institute of Technology. the Royal Institute of Technology (KTH), Stockholm, in 1998. He
His interests include lanthanide-doped nanomaterials, heads the Department of Theoretical Chemistry and Biology at KTH
nanostructured solar cells, and nanoparticles-based diagnostics and which houses ca. 20 scientists and 40 PhD students, with research
therapeutics. activities in theoretical modeling primarily in the areas of
molecular/nano/biophotonics and electronics, in catalysis and in
X-ray science. The research is a mix of method development and
problem oriented applications in collaboration with experi-
mentalists. Hans Ågren participates in several national and
international networks in his research areas. He has received the
Swedish Bjurzon and Roos’ awards.

Tymish Y. Ohulchanskyy holds Paras N. Prasad is a SUNY

his PhD degree in optics and Distinguished Professor of
laser physics from the Taras Chemistry, Physics, Electrical
Shevchenko National University Engineering and Medicine; the
of Kyiv (Kyiv, Ukraine). After Samuel P. Capen Chair of
finishing his PhD in 2001, he Chemistry; the Executive
joined the Institute for Lasers, Director of Institute for Lasers,
Photonics and Biophotonics Photonics, and Biophotonics,
(ILPB) at the University at University at Buffalo, State
Buffalo, State University of New University of New York; the
York, Buffalo, NY, USA. He is visiting Distinguished Professor
currently a Research Associate at Korea University. He was
Tymish Y. Ohulchanskyy Professor in the Department of Paras N. Prasad named among top 50 science
Chemistry in the University of and technology leaders in the
Buffalo and Deputy Director of Photomedicine at ILPB. His world by Scientific American in 2005. He has published over 700
research interests lie in the area of photophysics and physical scientific and technical papers, four monographs (Introduction to
chemistry of organic materials and organic, inorganic and hybrid Nanomedicine and Nanobioengineering, Nanophotonics,
nanostructures, and their photonic and biomedical applications. Introduction to Biophotonics, Introduction to Nonlinear Optical
Multimodal agents for medical imaging, cancer theranostics and Effects in Molecules and Polymers) and eight edited books. He has
targeted cancer phototherapy are of particular interest. received many scientific awards and honors (Morley Medal;
Schoellkopf Medal; Guggenheim Fellowship; Fellow of the APS,
OSA, and SPIE, etc.). His interests include biophotonics, nano-
photonics, nanomedicine, metamaterials, and solar cells.

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for charge compensation, and generally have lower phonon single conduct. The advantages provided by the core–shell
cutoff energy, which is important to minimize nonradiative structure encompass:
energy losses.2,19 Light absorption and emission in the lanthanide (i) Higher upconversion efficiency due to suppression of the
dopants involves the 4f–4f orbital electronic transitions with surface-related quenching effect produced by an epitaxial
concomitant wave-functions localized within a single lanthanide growth of a shell layer. The shell layer is able to provide an
ion. The electronic energy gap of a lanthanide ion does not effective passivation of lattice defects located on the surface of a
Published on 22 October 2014. Downloaded by Indian Institute of Technology Chennai on 3/5/2024 [Link] AM.

change with a change in the size or shape of UCNPs.11 As a result, core nanoparticle, as well as to create a perfect spatial isolation
lanthanide doped materials generally do not exhibit quantum of the core nanoparticle from the surrounding environment.
confinement effects that are clearly manifested in semiconducting This results in significant enhancement of the upconversion
materials. Each lanthanide element has a unique electronic efficiency which is dependent on the shell type, the defects in
configuration, with a system of well-defined, fine structured the shell, and the thickness of the shell layer.
energy levels. The fine ladder-like structure of long-lived energy (ii) Nanoscopic control of ion–ion interactions through
levels covers a broad range of energy. Owing to the pioneering spatial confinement of different types of lanthanide dopants
work by Dieke,20 Judd,21 Ofelt,22 Wybourne,23 and others in in separated shell layers or the core domain. The interaction
theoretical and experimental studies of the 4f N electronic between lanthanide ions of the same or different types can be
structure, most of the energy levels of trivalent lanthanide ions precisely engineered by an appropriate arrangement of the
(known as Dieke energy levels), which determine the optical electronic energy level hierarchy for lanthanides in different
properties of lanthanides, have already been established. shell layers as well as by manipulating the shell thickness to
Because of shielding of the 4f electrons by the outer complete control the interaction strength. This directed interaction provides
5s and 5p shells, trivalent lanthanide ions can display line-like powerful tools to manipulate the energy transfer processes which
sharp, stable emission under photoexcitation. By a judicious are the essence of photon upconversion. As such, the excitation
selection of one or more lanthanide dopants, UCNPs are able to wavelength, the emission color, the absorption of nanoparticles, as
generate upconverted photoluminescence (UCPL) at selective well as any quenching effect can be manipulated for a favorable
wavelengths, after being excited with light of longer wavelength. photon upconversion effect.
Thus, an energy upconversion takes place, when light is con- (iii) Coupling with new excitation electronic states of dyes or
verted from the infrared (IR) region to the near infrared (NIR) localized surface plasmon resonance (LSPR) for enhanced or
one, NIR to shorter NIR, NIR to visible (VIS), or NIR to ultraviolet broad band upconversion. The nature of 4f–4f electronic transi-
(UV), etc. This light upconversion feature opens up numerous tions in lanthanide ions results in low extinction and a narrow
opportunities for the applications of energy nanoconverters, absorption band, posing limitations for light harvesting as well
such as in high-contrast deep tissue bioimaging,24,25 photo- as for upconversion efficiency of UCNPs. Coupling them with
dynamic therapy in deep tissue,26 remote photoactivation,27 LSPR, using a core–shell structure, may result in plasmonically
security and display,28 biosensing,29 temperature sensing,30,31 induced upconversion emission enhancement.35 Introducing
drug release and gene delivery,32 as well as in solar cells.33,34 an organic dye shell layer to the surface of UCNPs can cause
However, conventional lanthanide-doped UCNPs have a number interaction of the electronic states of dye molecules with that of
of problems which still limit their practical applications. Some 4f electrons for energy transfer to lead to upconversion, taking
examples are low upconversion efficiency associated with advantage of the high extinction coefficient and large spectral
nanosize-induced surface-related quenching effects, undesired width of organic dyes for light harvesting. These types of core–
interactions between lanthanide ions that seriously constrain shell architecture will alleviate the limitations posed by the
the upconversion design, limited excitation light harvesting nature of 4f electrons.
ability and the excitation wavelength tunability, as well as (iv) Generation of new functionalities and multifunction-
limited functionalities for imaging and therapy. Despite their alities for theranostic applications. The limited functionality
promising applications in many areas, these limitations prevent of conventional UCNPs can be significantly extended by an
rapid evolvement of UCNPs from laboratory bench to clinical, epitaxial growth of functional layers that produce new imaging
technological and industrial applications. functionalities (for example, the growth of Gd3+-containing
Hierarchical design of the core–shell UCNPs, whereby each shell layer creates the capability for magnetic resonance imaging).36
shell layer can be defined within a regulated scale to introduce Along with enriched optical properties, the group of lanthanide
a specific feature, provides a range of unique nanophotonic elements also has unique magnetic, X-ray absorption, and
solutions to address the challenges associated with conven- radiation enhancement properties.2 Appropriate doping of
tional UCNPs and offers new imaging and therapeutic proper- lanthanide ions into the multiple shell layers or the core
ties, while completely conserving all the merits of conventional domain can introduce multimodal imaging abilities in a hierar-
UCNPs. With the ability of nanochemistry to produce a shell of chical core–shell structure without interfering with each other,
stoichiometric composition and a shell thickness with mono- thus accelerating the uses of UCNPs as multimodal imaging
layer precision, the electronic structure as well as the physio- probes. In addition, the UCNPs can be further coated with a
chemical structure of the upconverting system can be purposely non-epitaxial silica or polymer shell which is able to entrap,
aligned for nanophotonic control of upconversion or to intro- encapsulate, or complex drugs, providing therapeutic oppor-
duce a broad range of imaging or therapeutic modalities into a tunities for drug/gene delivery and light-activated therapy

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(such as photodynamic therapy (PDT) or photothermal therapy distributions within a single nanoparticle (or the ion–ion dis-
(PTT)).26,37 A combination of imaging modalities, provided by tance within a single nanoparticle). Typically, UCNPs contain
the epitaxial core–shell structure, and the therapeutic modalities, lanthanide emitters with a ladder-like system of energy levels
created by the non-epitaxial shell, promises use of UCNPs-based (e.g., Er3+, Tm3+, and Ho3+ ions), as well as of a sensitizer
nanostructures as new generation theranostic nanoplatforms. (e.g., Yb3+ ions) to harvest the excitation energy and then non-
Indeed, core–shell UCNPs produce numerous unprecedented radiatively transfer to the emitters (energy transfer upconversion
Published on 22 October 2014. Downloaded by Indian Institute of Technology Chennai on 3/5/2024 [Link] AM.

abilities to manipulate the excitation dynamics (the emission mechanism).2

properties, including color, efficiency, and lifetime, energy Nanophotonics is an emerging frontier which deals with the
transfer, and cooperative optical transitions) to create UC emission interaction of light with matter on a nanometer size scale.19
of needs, and to provide new multifunctionalities for effective A core–shell epitaxial structure can produce important mani-
diagnostics and therapeutics as well as for other nanophotonic festation in defining a local coordinating environment for surface
applications such as in solar energy conversion. In this work, we lanthanides, which is distinct from that for the interior lanthanide
review nanophotonic control of upconversion in hierarchically ions (i.e., a bulk crystal field) due to the size-reduction induced
designed core–shell nanostructures based on UCNPs, as well as structural distortion, surface defects, coordinated organic ligands,
their application in biomedical applications, solar cells, and etc. Moreover, core–multishell epitaxial structures provide
security encoding. opportunities to engineer the distribution of lanthanide ions
as well as to appropriately arrange their energy levels within a
nanostructure. As a consequence, a core–shell structure pro-
2. Nanophotonic control of vides nanophotonic means to tailor light excitation harvesting,
upconversion in core–shell upconversion efficiency, upconversion emission wavelengths,
nanoparticles directed energy transfer, cross relaxation, as well as the dopant
concentration quenching threshold.2 A core–shell hierarchical
Photon upconversion employing lanthanides can be produced architecture also offers a structural flexibility for enhancing
via six fundamental mechanisms, i.e., excited state absorption, a specific upconversion or introducing multifunctionalities.
energy transfer upconversion, cooperative sensitization upcon- In the following Sections of 2.1–2.7, we will summarize seven
version, cooperative upconversion, cross relaxation, and photon approaches that have been typically used for nanophotonic
avalanche.1,2 The essence of these mechanisms is sequential control of a core–shell nanostructure (Fig. 1).
excitation through the excited states of a single lanthanide ion The core–shell nanostructures utilized in recent studies can
or ion–ion interactions in the excited states to allow energy be broadly classified into two categories: (1) a core–shell nano-
transfer between two or more lanthanide ions.2,11 These features particle containing epitaxial layers with a matched or nearly
are regulated by the f–f transition nature of lanthanide ions, the matched crystalline lattice; and (2) a core–shell nanoparticle
local environment around them, as well as the lanthanide ion containing non-epitaxial layers. The core nanoparticle here

Fig. 1 Seven directions for nanophotonic control of upconversion in a core–shell nanostructure.

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Fig. 2 Different types of core–shell structures. The upper panel illustrates core–shell UCNPs with epitaxial layers: (a) core–shell UCNPs with an ‘‘inert’’
(i.e., without any absorbing/emitting lanthanide dopant) shell layer; the colored balls in the core area depict lanthanide dopants; the red circles at the interface
represent surface quenching sites; the black arrows indicate random energy transfer pathways. (b) Core–shell UCNPs with an active shell layer (i.e., layers
containing ‘‘active’’ lanthanide dopants); and (c) core–shell UCNPs with multiple shell layers. Core–multishell type (c) is exemplified using five layers, in which
layer 1 and layer 3 (the gray striped ones) can be either inert layers to avoid undesirable interactions between the active layers (the colored ones), or active layers
to enhance the interactions between different active domains. The bottom panel depicts core–shell UCNPs with non-epitaxial layers: (d) UCNPs@silica core–
shell nanoparticles, (e) core–shell–shell UCNPs@silica@metal (or metal@silica@UCNPs) nanoparticles, and (f) UCNPs coated with organic dye molecules.

can be either conventional UCNPs without any epitaxial shell or a range of intermediate excited states involved in producing UC
core–shell UCNPs with epitaxial shell layers. Fig. 2 gives the emission, resulting in more pronounced quenching than in the
examples of six types of core–shell UCNPs from these two categories, case of Stokes-shifted (downconversion) luminescence, which
which constitute most of the current core–shell design to produce involves one exclusive emitting state. Direct quenching is a
selective UC emissions as well as to deliver multifunctionalities to general surface-related quenching mechanism for all types of
reach comprehensive imaging and therapeutic modalities. luminophores with nanoscale dimension.
(ii) Energy migration induced quenching. The electronic
2.1. Core–shell structure to control surface-related quenching excitation energy of dopants located inside can randomly
Suppression of surface-related quenching effects is a typical migrate inside UCNPs and travel to other dopant centres on/
way of enhancing upconversion efficiency of UCNPs through around the surface or directly to the surface quenching sites.
control of the local environment of surface lanthanide ions. This type of surface-related quenching mechanisms requires
Although this approach has been frequently utilized, the involved the existence of long-lived energy states favorable for excitation
specific mechanisms remain experimentally unverified albeit few energy hopping. This is generally the case for conventional
attempts.38–40 Surface-related quenching effects for the core UCNPs, for example, NaYF4:Yb3+/Ln3+ (Ln = Er, Ho, Tm),41–43
UCNPs stem from the high surface-to-volume ratio produced by which contain a high concentration of sensitizer (Yb3+ Z 18%)
the nanometer dimension, which exposes most of the lanthanide that has an exclusive long-lived state. However, the mechanism
dopants to surface induced deactivation (surface defects, ligands, of energy migration induced quenching has not been experi-
and solvents that possess high energy phonons). The partition of mentally substantiated until this point. On the other hand, the
exposed lanthanide dopants strongly depends on the size of the migration of excitation energy is also a necessary prerequisite for
synthesized core nanoparticles, but also is influenced by the adequate activation of lanthanide emitters to produce efficient
nature of the surrounding environment.11,40 In principle, surface upconversion emission. An optimized lanthanide concentration
related quenching mechanisms can be divided into two types: for nanoparticles that are devoid of any shell originates from a
(i) Direct quenching. Dopants located on or close to surface delicate balance between quenching and emission produced by
are directly deactivated by neighboring quenching centres energy migration. A controlled suppression or elimination of an
through nonradiative relaxation involving phonons from the energy-migration-induced quenching mechanism (using core–
surrounding environment. This deactivation pathway applies to shell structure) might result in determination of distinct optimized

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lanthanide concentration that will be a big step in development (for a few monolayer thicknesses less than B2.4 nm)63 or by an
of the efficient UCNPs. exponential function, with the optimized shell thickness
The two types of surface-related quenching mechanisms can (i.e., thickness which effectively enhances the UCPL intensity
be addressed through an epitaxial growth of one or multiple without an excessive increase of the overall size of the UCNPs)
inert (i.e., not containing lanthanide dopants) outer shell layer determined to be around 6 nm.64 More insights are needed to
on the core nanoparticle (Fig. 2a), which passivates the imper- shed light on this dependence of the UCPL intensity on the
Published on 22 October 2014. Downloaded by Indian Institute of Technology Chennai on 3/5/2024 [Link] AM.

fections in the host lattice (often located at the core particle shell thickness and thereby to provide guidance for an optimi-
surface), and shields the core from the surrounding ligands zation of a shell, which should be thin but adequate enough to
(which are necessary for solvent dispersion) and solvents of prevent the quenching by the environment.
high phonon energy. The distance between the UCNP core and Heterogeneous active core–inert shell. Heterogeneous core–
the surrounding environment, created by the inert epitaxial shell nanoparticles with the core and the shell host matrix
shell, prevents quenching of the excited states of the surface of different compositions (Fig. 2a) have also been investigated
lanthanide ions and curbs the migration of excitation energy for improvement of UCPL. For example, Yan et al. reported
into the surrounding environment.2,11 The epitaxial shell layer B300-fold enhancement of UC emission yield in the 10–13 nm
can be the same as the host lattice of the core nanoparticle or of cubic NaYF4:Ln3+@CaF2 heterogeneous core–shell nanoparticles
different composition but having a low lattice mismatch with in comparison to the parent NaYF4:Ln3+ nanoparticles.65 Such
that of the core nanoparticle. The quality as well as the thick- enhancement is extraordinary, as only several ten folds enhance-
ness of the shell is of paramount importance to minimize ments were reported for homogenous core–shell UCNPs (see
surface-related quenching mechanisms. The following describe above). This suggests the importance of the selection of shell
some variations of this type of core–shell structures. types which are evidently different in the ability to passivate the
Homogenous active core–inert shell. A homogenous active (i.e., imperfections on the core nanoparticle surface and to minimize
containing ‘‘active’’ lanthanide dopants) core–inert shell nano- the quenching effects from the environment. We demonstrated
particle refers to the one where the core and the shell materials that a hetero-shell of CaF2 can enhance NIR-to-NIR UCPL
have an identical host lattice (Fig. 2a). This type of core–shell from B20 nm NaYbF4:Tm3+ by about 35-fold, causing UCQY
structure has been investigated for a myriad of host lattice to be as high as 0.6% under a low excitation power density of
materials for a broad range of core sizes and shell thicknesses. 0.3 W cm 2.25 Han et al. reported that NIR-to-UV UC emission
For example, upconversion enhancement up to tens of times in a series of cubic NaYF4:(20–100%)Yb3+/Tm3+@CaF2 epitaxial
has been observed in (NaYF4:Yb3+/Ln3+)/NaYF4 (Ln = Er or core–shell nanoparticles can be enhanced by two orders of
Tm),44–50 (KYF4:Yb3+/Er3+)@KYF4,51 (SrF2:Yb3+/Er3+)@SrF2,52 magnitude, when compared with the core nanoparticles.66
(NaGdF4:Yb3+/Tm3+)@NaGdF4,40,53 (KGdF4:Yb3+/Tm3+)@KGdF4,54 It was suggested that if compared to the typically used NaYF4
(YOF:Yb3+/Er3+)@YOF,55 (YF3:Yb3+/Ln3+)@YF3 (Ln = Er, Tm, or shell, the CaF2 coating is more effective in resisting quenching
Er/Tm),56 (LaF3:Yb3+/Tm3+)/LaF3, (BaLaF5:Yb3+/Tm3+)/BaLaF5,57 in aqueous medium to preserve the upconverted emission and
and (NaLuF4:Gd3+/Yb3+/Er3+)@NaLuF4,58 when excited under also in suppression of any lanthanide chemical leakage.65 The
NIR excitation at B980 nm. Absolute quantum yield measure- core–shell NaYF4:Ln3+@NaGdF4 nanoparticles with fixed or
ments verified that 30 nm (NaYF4:Yb3+/Er3+)@NaYF4 core–shell tunable shell thicknesses have also been successfully prepared
UCNPs were 3 times more efficient than the NaYF4:Yb3+/Er3+ to yield much more efficient upconversion luminescence.67,68
core nanoparticles of the same size.59 This result provides a Note that UCPL from the cubic form NaYF4 is known to be
direct evidence on the effectiveness of an inert shell to suppress about one order of magnitude less efficient than that from
the surface-related quenching effect to increase the upconver- the hexagonal form NaYF4.69 However, the reported UCPL of
sion efficiency. It is important to note that the UC quantum NaYF4:Yb3+/Tm3+@CaF2 is higher or comparable to that of the
yield (UCQY) or efficiency is dependent on the excitation power corresponding hexagonal NaYF4:Yb3+/Tm3+@NaYF4 core–shell
density due to the nonlinearity of the UC processes. As a result, nanoparticles, revealing the great potential of developing
the UCQY should be always considered in the accompaniment new heterogeneous core–shell type structures to significantly
of the excitation power density. We have reported an absolute increase the upconversion efficiency. Indeed, our recent work
upconversion efficiency of B4% in NaYF4:Er3+@NaYF4 core–shell on B24 nm hexagonal (NaYbF4:Tm3+/Gd3+)@NaYF4 core–shell
nanoparticles under 1523 nm excitation with a power density of structure showed a B350 fold UCPL enhancement as compared
20 W cm 2.60 More recently, (LiLuF4:Yb3+/Er3+)@LiLuF4 nano- to UCPL from the B22 nm core nanoparticles.70
particles manifested a quantum yield of 5.0%, while (LiLuF4:Yb3+/
Tm3+)@LiLuF4 nanoparticles reached as high as 7.6% under 2.2. Core–shell structure to enhance light harvesting
laser power density of 127 W cm 2 at B980 nm.61 These newly Generally, UCNPs have severely limited light absorbing ability
determined values of upconversion efficiency of core–shell due to their low extinction coefficient and narrow band absorp-
nanoparticles are close to or higher than the previously tion of lanthanide ions. This problem mainly arises from the
reported ones for bulk materials,62 confirming the effectiveness dipole–dipole forbidden nature of 4f–4f transitions as well
of a shell to suppress surface-related quenching mechanisms. as from well-shielded localized electronic wave-function for
The relation between the intensity of UCPL and the thickness lanthanide ions in UCNPs, which severely limit use of UCNPs
of the shell can be described either by a linear dependence in many applications. An engineering of the core–shell structure

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provides a new dimension to alleviate or resolve the absorption 2.2.2. The shell containing organic dyes. Energy transfer
related issues by introducing absorption from new type of from the electronic manifold of organic dye molecules to
lanthanides or by coupling lanthanide ions with electronic states lanthanide ions in NaYF4:Yb3+/Er3+ UCNPs has been established
from organic dyes. Indeed, instead of utilizing an inert epitaxial to dramatically enhance UC green emission intensity (by a factor
shell material as discussed in the above section, a reasonable of B3300 times) due to a significantly broadened absorption
concentration of light absorbing dopants can also be introduced in spectral range as well as a greatly increased absorption strength.80
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the shell layer or multiple shell layers to enhance light harvesting The structure can be illustrated using Fig. 2f; the core is the
(Fig. 2b and c). The introduced dopants can be the sensitizer NaYF4:Yb3+/Er3+ UCNPs to which dye molecules are covalently
lanthanide ions (e.g., Yb3+) to increase the absorption of the attached. The organic dye shell will produce an ‘‘antenna effect’’
nanoparticles at a certain wavelength (e.g., B980 nm), or multiple to sensitize the small sized UCNPs, exploiting three important
types of lanthanide ions to broaden the light excitation/emission features: (i) there exists a large amount of lanthanide ions located
range. Moreover, the shell can also be organic in nature, contain- at or around the nanoparticle surface due to the unique high
ing a number of dye molecules to provide an intensive and broad ‘‘surface-to-volume’’ ratio offered by the nanoscale dimension;
absorption band for light harvesting, followed by nonradiative (ii) typically, the NIR absorption of a dye molecule is three
transfer of the harvested energy to lanthanide ions in the core. The orders of magnitude more intense than the absorption of a
shell layer now takes three roles: (i) suppression of surface-related lanthanide ion, and several times broader than its absorption
deactivation; this role is the same as in the core–shell structure band; (iii) energy transfer from the singlet state of an organic
with an inert shell. (ii) Enhancement of UCPL produced by dye to the 4f–4f transition of lanthanide is quantum mechani-
interaction of the lanthanide dopants in the shell with the cally allowed via a Föster mechanism involving higher-order
lanthanide dopants located in the core nanoparticles (Fig. 2b). multipolar interactions (e.g., dipole–quadrupole), or a Dexter
(iii) Harvesting of light over a broad spectral wavelength range mechanism involving double electron exchange.81 This fact has long
by different types of lanthanide ions in different shells (Fig. 2c) been established for lanthanide-coordinated metal complexes.81
or using an organic dye shell (Fig. 2f). Dye-sensitized upconversion provides a paradigm to broadly harvest
2.2.1. The shell containing absorbing lanthanide dopants. NIR light and convert it into visible light. However, the net UCQYs
Capobianco et al. first reported on NaGdF4:Yb3+/Er3+@NaGdF4:Yb3+ obtained by Zou et al. remained relatively low (less than 0.1%),80
active core–active shell nanoparticles, displaying a significant as the utilized nanoparticle has a quite poor UC efficiency, and
increase in the intensity of NIR-to-visible upconversion, when the spectral overlapping between the emission of the organic dye
compared to either the NaGdF4:Yb3+/Er3+ active-core@NaGdF4 (IR 806) and the absorption of Yb3+ ion is extremely limited.
inert-shell, and NaGdF4:Yb3+/Er3+ core only nanoparticles.71 The Increase of the UCQYs in dye-sensitized UCNPs is an appealing
active core–active shell strategy has also been utilized in the direction.
NaYF4:Yb3+/Er3+@NaYF4:Yb3+,72–74 (CaF2:Yb3+/Tm3+/Ho3+)/
NaYF4:Yb , LaPO4:Er @LaPO4:Yb nanorods,76 (NaLuF4:Gd3+/
3+ 75 3+ 3+ 2.3. Core–shell structure to suppress cross relaxation
Yb3+/Er3+)@NaLuF4:Yb3+,58 BaGdF5:Yb3+/Er3+@BaGdF5:Yb3+ nano- The cross relaxation process is the main problem for the well-
particles,77 as well as in BaF2:Ln3+@SrF2:Ln3+ nanoparticles.77 known conventional ‘‘concentration quenching effect’’, dimini-
We recently reported a significant enhancement of UCPL shing the luminescence of lanthanides. This loss mechanism
(B240 times) in cubic (NaYF4:Yb3+/Tm3+)/NaYbF4/NaYF4 active is primarily considered for a Stokes-shifted downconversion
core–active shell–inert shell nanoparticles, using directed energy luminescence, but its impact on the UC luminescent efficiency
migration in the second shell layer.78 In addition to the suppres- becomes significant with increase in concentration of the
sion of core surface-related quenching, the active layer provided activators, such as Tm3+, Er3+, and Ho3+ ions. Moreover, with
enhancement of upconversion through energy transfer from the utilization of several types of lanthanide ion dopants in the
Yb3+ ions-contained in the active-shell to the dopant ions in the same domain, cross relaxation between different types of ions
core. However, caution has to be exercised when utilizing this turns into a serious concern. From a fundamental point of view,
strategy, as the introduction of Yb3+ into the shell layer at the same the cross relaxation process originates from Coulomb inter-
time elevates energy-migration induced surface-related quenching actions between two lanthanide dopant ions which is strongly
mechanism (see Section 2.1). An optimized Yb3+ concentration in dependent on the ion–ion distance determined by the dopants
the shell needs to be established. It was shown that the core– concentration in the nanoparticle.1 Through optimization of
shell–shell design of the (NaGdF4:Er3+)@(NaGdF4:Ho3+)@NaGdF4 the dopant concentration, the cross relaxation process can be
nanoparticles resulted in enhanced NIR light harvesting due to minimized; however, the concentration of dopants has to be
combined light harvesting capabilities of both Er3+ and Ho3+.79 low, which limits the luminescence efficiency. One solution to
The drawback however is that high doping concentrations of Er3+ this problem is to separate the appropriate lanthanide ions in
and Ho3+ may cause adverse cross relaxations, inducing quenching the core and the shell to create a spatial confinement that can
beyond the interfaces, even though the dopants are in different result in a highly efficient UC, reducing detrimental effects
layers. The concept of incorporating lanthanide dopants into of the cross relaxation process (Fig. 2c). For example, the
distinct layers in the active core–multiple shell structure can optimized concentration for Er3+ ions was determined to be B2%
provide unprecedented capabilities for nanophotonic control of for NaYF4:Yb3+/Er3+ microsized particles;69 this parameter is then
uncoupled upconversion in each domain (Fig. 2c). typically used in most studies with NaYF4:Yb3+/Er3+ nanoparticles.

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Recently, Kong and Zhang et al. demonstrated that this com- It was demonstrated that cascade sensitized Nd3+/Yb3+/Er3+(Tm3+)
monly accepted upper threshold for concentration quenching tri-doped (b-NaYF4:Ln3+)@b-NaYF4 colloidal UCNPs can shift the
of Er3+ can be raised from 2 to 5% by spatial separation of the typically used excitation at B980 nm to a B800 nm.84 This
emitter doping area inside nanoparticles.82 This concept was system consists of a primary sensitizer (Nd3+), a bridging
later exploited by Zhao et al. to engineer the distribution of sensitizer (Yb3+) and a lanthanide emitter Er3+(Tm3+). The
activators inside one single nanoparticle to enhance upconver- Nd3+ ions absorb photons at B800 nm, while the Yb3+ ions
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sion luminescence efficiency. In a comparison with conventional act as bridge, to receiving the energy from the Nd3+ ions and
heterogeneous doping, which associates with fluctuations of transfer it to the emitters Er3+(Tm3+). The hierarchy of involved
dopant concentrations inside one nanoparticle, a layer-by-layer energy levels, in conjunction with the interactions of these
deposition of multilayer shells with a defined dopant concen- three lanthanide ions, allows energy to be transported in the
tration is able to homogenize the distribution of dopants within way we described above. A serious problem, existing in this
one single nanoparticle, thus yielding a two-fold increase in the system, is that Nd3+ ions exhibit efficient cross relaxation with the
absolute upconversion yield of NaGdF4:Yb3+/Er3+@NaYF4 UCNPs emitter Er3+(Tm3+) ion. Overcoming this obstacle (suppressing
due to a reduction of cross relaxation-induced quenching effect.83 cross relaxation process) requires the concentration of Nd3+ ion
We exemplified here a recent success of using the concept of to be as low as B1%, limiting the light absorption ability and,
suppressing cross relaxation in a core–shell design to shift the correspondingly, the upconversion efficiency of this system. Yan
typically used excitation wavelength at 980 nm to a more et al. and Liu et al. demonstrated later that doping Nd3+ into a
biocompatible wavelength at B800 nm. A motivation behind shell layer can minimize the cross relaxation process between the
this is that a laser at B980 nm can produce heat to damage the Nd3+ ions and the emitters (Er3+, Tm3+, Ho3+), while maintaining
biological tissue when long irradiation is involved, due to a a high Nd3+ ion concentration of B10–15%.85,86 This is of
noticeable water absorption at this wavelength. At the same time, particular importance for the brightness of the system, as a
water is much more transparent for NIR light at 800 nm (Fig. 3a). high concentration of Nd3+ not only can increase the absorption

Fig. 3 (a) Absorption spectrum of water in the range of 680–1000 nm and the core–shell design of NaYF4:Yb3+/A3+@NaYF4:Nd3+/Yb3+ (A = Tm, Er, Ho);
(b) core–shell design for NaYF4:Nd3+/Yb3+/A3+@NaYF4:Nd3+; (c) illustration of the involved lanthanide energy levels of a core–shell design of
NaYF4:Yb3+/Er3+@NaYF4:Yb3+@NaYF4:Nd3+ with a transition layer to create a larger distance between Nd3+ and Er3+ ions. All designs are based on
the cascaded energy flow Nd3+ - Yb3+ - A3+ (A = Er or Tm) (excited at B800 nm). The deleterious cross relaxation between Nd3+ and A3+ (A = Er or Tm)
in (a)–(c) is minimized by spatial isolation of the lanthanide dopants into the core domain as well as into the shell domain. In (b), a very limited
concentration of Nd3+ (1 mol%) is employed to minimize the cross relaxation process, still enhancing energy transfer across the interface. Reproduced
with permission from ref. 85, 86 and 89. Copyright 2013 American Chemical Society. Copyright 2014, John Wiley and Sons.

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of the nanoparticle, but also can increase the cascaded energy layer (the second layer) and the Eu3+-doped layer (the core
transfer efficiency. Indeed, the total UCPL intensity of domain), the degree of energy transfer can be engineered to
(b-NaYF4:Yb3+/Er3+)@b-NaYF4:Nd3+ or (b-NaYF4:Yb3+/Tm3+)@ allow for zero, partial, or full energy transfer from a donor ion
b-NaYF4:Nd3+ UCNPs was several tens of times higher than that (Tb3+) to an acceptor ion (Eu3+). Chen et al. illustrated a general
of (b-NaYF4:Nd3+/Yb3+/Er3+)@b-NaYF4 or (b-NaYF4:Nd3+/Yb3+/ strategy to achieve the dual-mode luminescence of Eu3+
Tm3+)@b-NaYF4 nanoparticles, respectively (Fig. 3a and b).86 in (NaGdF4:Yb3+/Tm3+)/NaGdF4:Eu3+ core–shell nanoparticles
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A core–shell design to minimize the cross relaxation process in that involves a controlled use of energy migration.53 Another
Nd3+-sensitized systems has also been explored by others, by example is provided by Liu et al. who prepared NaGdF4:Yb3+/
introduction of a transition layer between the Nd3+-containing Tm3+@NaGdF4@NaGdF4:Tb3+ core–shell–shell nanoparticles
layer and the Yb3+-containing layer (Fig. 3c) or growth of the with varied NaGdF4 shell thickness to show that the excitation
anisotropic core–shell structure.87–90 These new core–shell designs energy can travel through the Gd3+ sub-lattice for a substantial
resulted in the enhanced upconversion luminescence intensity, distance of over 5 nm, without energy losses.12
more tunable color output, as well as realization of dual modal Wang et al. reported on light management through a directed
upconversion and downconversion bioimaging. However, the energy transfer in NaYbF4@Na(Yb,Gd)F4@NaGdF4 core–shell–
absolute quantum yield of UCPL for the reported Nd3+-sensitized shell nanoparticles, where different types of lanthanide dopants
core–shell nanoparticles remains either unevaluated or rather were doped into different domains (Fig. 4).87 To manage the
low. The UCPL at B540 nm from the quenching-shielded energy level for favorable energy flow, Nd3+ were doped into
sandwich structured UCNPs with Er3+ (Fig. 3c), that seems to the core domain to harvest light excitation at B800 nm, Yb3+/X3+
outperform most of the current Nd3+-sensitized core–shell (X = Er, Ho, Tm) were doped into the inner shell domain to
UCNPs, was characterized by UCQY of 0.11  0.05% under produce colored upconversion emission, while the Z3+ (Z = Eu,
excitation at 800 nm (20 W cm 2),89 which is much lower than Tb, Dy) were doped into the outmost shell domain to addi-
the highest UCQY (5%) reported for Yb3+/Er3+-doped core–shell tionally tune the upconversion luminescence. Through the Yb3+
nanoparticles when excited at 980 nm (but with higher power sub-lattice network, the harvested energy by Nd3+ ions can
density of 127 W cm 2).61 transfer to the emitter X3+ (X = Er, Ho, or Tm) in the inner
shell domain. The Gd3+ ion has long been known as a good
2.4. Core–shell to nanoscopically control energy transfer sensitizer for Eu3+, Tb3+, Dy3+ and Sm3+ when excited in the
Nonradiative energy transfer from the excited states of lanthanide UV range,92,93 which can also be activated through Yb3+/X3+
ions plays vital roles in all pertinent UC luminescence phenomena; (X = Tm, Er, or Ho) pairs through a five- or six-photon UC
the ability to precisely control its direction and rate has numerous process when excited at B980 nm.94–96 However, UC emission
manifestations in academic interests as well as in technological in the UV range from the Yb3+/Tm3+, which is much more
applications. The main source of nonradiative energy transfer intense than UCPL from Yb3+/Er3+ or Yb3+/Ho3+ ion pairs, typically
arises from the fundamental multipolar and/or exchange inter- results in activation of Gd3+ ions with significantly higher efficiency.
actions between two lanthanide ions. In general, the energy Because of the unique large energy gap of Gd3+ (B32 000 cm 1), the
transfer probability for electric multipolar interactions is pro- absorbed energy can be contained and migrate in the Gd3+ sub-
portional to the inverse of the sth power of the ion–ion lattice network, crossing the core/shell interface to reach the
distance: for dipole–dipole (s = 6), dipole–quadrupole (s = 8), Z3+ (Y = Eu, Tb, or Dy) sites. As a result, if the Tm3+ ions are
and quadrupole–quadrupole (s = 10) interactions.1,19 The selectively doped, the energy in the high-lying excited state of
exchange interaction is falling even on a shorter distance, Tm3+ can be transferred to the migrator ions (Gd3+), and then
exponentially with the separation distance of ions, as it requires to the emitters Z3+ (Y = Eu, Tb, or Dy) and be released as
the overlap between wave functions of two ions.81 This strong luminescence. The color tunability is provided by the electronic
dependence of multipolar/exchange interactions on the ion- structure of Eu3+, Tb3+, or Dy3+, which are excited through this
pair distance at the nanoscale provides an opportunity to use energy migration process. The issue of the surface-related
the control of nanostructure to optimize the ion-pair inter- quenching mechanism in this system is addressed by growing
action. In particular, the demonstrated ability to control the an inert shell NaYF4.97 It can be concluded that the nanoscopic
shell layer thickness with the monolayer accuracy provides a control of energy transfer in hierarchical core–multishell nano-
method to manipulate the energy transfer at a nanoscale (see particles opens a new realm for controlling upconversion, by
Section 3.2), in conjunction with a rational alignment of energy tailoring the absorption wavelength, the extinction coefficient,
levels in different shell layers. This manipulation of energy the UCPL wavelength, the lifetime and efficiency.
transfer between different lanthanide dopants has been imple-
mented in B10 nm LaF3 based core–shell nanostructures, 2.5. Core–shell structure to tune the color of upconversion
where the core domain contains the Eu3+ dopant, the first layer emission
is an inert LaF3, the active second layer contains the Tb3+ 2.5.1. A combination of spatially isolated lanthanide ions.
dopants, and the third layer is an inert LaF3.91 The core–shell The use of a core–shell architecture with two or more lanthanide
structure is similar to Fig. 2c, with the difference that the 4th activators incorporated into the core and different shells is a
and the 5th layers do not exist. It is found that by varying the typical strategy to tune the luminescence of UCNPs, while main-
thickness of the undoped first layer between the Tb3+-doped taining a high luminescence efficiency. This strategy also explores

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Fig. 4 (a) Schematic illustration of the principle of energy flow in a NaYbF4@Na(Yb,Gd)F4@NaGdF4 core–shell–shell structure. (b) The corresponding
energy levels of Nd3+ doped in the core domain, Yb3+/X3+ (X = Er, Ho, Tm) in the inner shell, as well as the Z3+ (Y = Eu, Tb, or Dy) ions in the outmost shell.
The involved upconversion mechanisms (absorption, energy migration and flow, as well as the luminescence) are shown. Reproduced with permission
from ref. 87. Copyright 2013, John Wiley and Sons.

different combinations of lanthanide activators to produce to produce multiple emission peaks.98 Emissions from both
multicolor emission and exercises a spatial isolation of these Tm3+ and Er3+ in these UCNPs were shown to be non-quenched,
lanthanide activators using an appropriate core–shell structure. in contrast to the UCPL from Tm3+/Er3+-codoped NaYF4 nano-
It eliminates deleterious cross relaxation between the lanthanide particles. A range of sandwich-structured core–shell–shell
activators and suppresses surface-related quenching mechanism nanoparticles of NaYF4:Yb3+/Er3+@NaYbF4:Tm3+@NaYF4:Yb3+/
in the core nanoparticles, thus yielding a range of tunable Tm3+, NaYF4:Yb3+/Tm3+@NaYbF4:Er3+@NaYF4:Yb3+/Er3+, and
emission with high efficiency. NaYF4:Yb3+/Tm3+@NaYbF4:Er3+@NaYF4:Yb3+/Tm3+ UCNPs have
Lanthanide emitters (activators) of Er3+, Tm3+, Ho3+, and also been developed, exhibiting tunable UC emissions for multi-
3+
Pr ions have long-lived intermediate states, which typically color cellular imaging.99 Ultrasmall UCNPs with hierarchical
can be sensitized by Yb3+ ions to produce efficient UC emission core–shell–shell architecture (NaGdF4:Yb3+/Tm3+@NaGdF4:Yb3+/
when excited at B980 nm. The use or combined use of these Er3+@NaGdF4) have been prepared following a microwave-based
activators with precisely controlled concentration is able to thermolysis procedure, producing upconversion emission with
produce three primary UC colors (blue, green, and red) and a the color output tuned by varying the position of the dopants
range of UC outputs with other colors, even a white light output. inside the nanoparticles (Fig. 5).100
Doping two or more of these activators into one single domain is a Lanthanide emitters like Eu3+, Tb3+, Dy3+ and Sm3+, which
straight forward way to tune the UC output, but does often do not have long-lived intermediate energy states, can only be
introduce the deleterious cross relaxation process resulting in a directly excited at NIR light through a simultaneous multi-
decrease in the UC intensity. Core–shell structured UCNPs can photon absorption process or a cooperative sensitization upcon-
minimize this cross relaxation process (see Section 2.3 and version (CSU) process via simultaneous extraction of the energy
Fig. 2c) while retaining the color tunability through spatial contained in an excited Yb3+ ion pair. These lanthanide ions
confinement of the emitters. Zhang et al. reported on hexagonal- can be utilized for tuning upconversion through nanoscopic
phase NaYF4:Yb3+/Tm3+@NaYF4:Yb3+/Er3+ and NaYF4:Yb3+/ control of energy migration in core–multishell structures (see
Tm3+@NaYF4:Yb3+/Er3+@NaYF4:Yb3+/Tm3+ core–shell nanoparticles Section 2.4).

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Fig. 5 Tuning upconversion luminescence using ultrasmall core–shell–shell NaGdF4:Yb3+/Tm3+@NaGdF4:Yb3+/Er3+@NaGdF4 architectures. Reproduced
with permission from ref. 100. Copyright 2014, American Chemical Society.

2.5.2. Tuning upconversion through energy transfer. Energy 2.6. Core–shell UCNPs for coupling with localized surface
transfer from a donor to an acceptor can involve two pathways: plasmon
(1) nonradiative energy transfer via multipolar or exchange Localized surface plasmon resonance (LSPR) is a collective
interactions; (2) radiative energy transfer, i.e., luminescence oscillation of free charge carriers at the interface of metallic or
resonance energy transfer (LRET), where light emitted by the self-doped semiconductor nanomaterials and dielectric medium;
donor is absorbed by an acceptor molecule. When utilizing the LSPR is generated by incident light when the resonance occurs
UCNPs as an energy donor and dyes or quantum dots (QDs) as an between frequency of light photons and the natural frequency
energy acceptor, it offers a larger freedom for upconversion of surface charge carriers. The plasmon resonant frequency for
emission wavelengths than for the UCPL produced merely by the plasmonic nanostructures is revealed itself as a maximum in the
lanthanide ions. An expanded range of multicolor emission was optical absorption spectrum (typically in visible and close NIR
obtained from the core–shell NaYF4:Yb3+/Er3+(Tm3+)@silica nano- ranges for Au and Ag metallic nanostructures).19,33 In an aniso-
structures by encapsulating organic dyes or QDs into the silica tropic nanostructures such as nanorods, LSPR along the long-
shell to produce additional luminescence via nonradiative energy itudinal direction can be tuned over a wide range by changing the
transfer or LRET processes (Fig. 6A).101 Alternatively, one or aspect ratio.103 The LSPR is able to greatly enhance the electro-
more bands of the UC emission from either NaYF4:Yb3+/Er3+ or magnetic field near the particle’s surface, which falls off rapidly
NaYF4:Yb3+/Tm3+ nanoparticles can be selectively quenched by with distance from the surface. This enhanced field produces an
organic luminescence quenchers or gold nanoparticles contained increase in the emission efficiency of an emitter located near the
in the shell layer to produce a tunable color-coded output (Fig. 6B).102 surface of the plasmonic nanostructure.104 However, coupling to

Fig. 6 Schematic illustration of tuning upconversion luminescence using non epitaxial UCNPs–silica core–shell structure, where (A) luminescent
emitters and (B) luminescent quenchers are loaded in the silica shell.

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structures with LSPR can also affect the emission in a different 2.7. Core–shell UCNPs for introducing new functionalities
way. Close contact of the emitter with the metallic surface This section provides an account of integration of various function-
introduces large non-radiative decay, resulting in a drastic alities on a single UCNP platform using a core–shell architecture,
quenching of emission.105 That is why the distance between which can be of great value for biomedical applications. Appro-
the emitter and the plasmonic nanostructure has to be opti- priate tailoring of this core–shell nanoplatform is able to produce
mized to obtain the plasmonic enhancement of emission. This multifunctionality, either by minimizing interference between
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optimization can be facilitated by using a core–shell type

incorporated functionalities or in contrast by bringing synergy of
architecture (Fig. 2e). LSPR has been used to enhance the
interaction between them. These functionalities can be utilized for
efficiency of the UCPL of UCNPs involving a large variety of
biomedical imaging, sensing, various applications in diagnostics or
configurations.106–112
therapeutics. An important new direction is to entail these core–
Among the reported work, core–shell nanostructures of
shell structures for theranostic applications, whereby both diagno-
metallic@silica@UCNPs or UCNPs@silica@metallic (refer to
stic and therapeutic functions are combined.
Fig. 2e for schematic configuration) are of particular importance,
2.7.1. New imaging modality. Biomedical imaging has become
as they provide a single platform to couple LSPR and UCPL at the
one of the most relied-upon tools in life sciences and healthcare.
nanoscale. The distance between the metallic nanoparticles and
It embraces optical imaging, magnetic resonance imaging (MRI),
the UCNPs can be precisely controlled to achieve the optimum
computed tomography (CT), positron emission tomography (PET),
enhancement of UCPL by varying the thickness of the spacer
single-photon emission computed tomography (SPECT), and
silica shell. A number of previous reports have used a silica layer
photoacoustic (PA) imaging.123 A nanoparticle platform for
as a spacer,35,113–118 but some studies showed plasmonic-induced
imaging contrast agents may allow for complementary use of
UCPL quenching.119–121 Time-resolved measurements did reveal
the existing imaging techniques and for a development of novel
that the emission process is influenced in both cases. The
imaging methods, that can lead to early detection, screening,
reported enhancements vary widely and the exact enhancement
diagnosis, and image-guided treatment of human diseases. The
mechanisms are not clearly understood. The plasmonically
core–shell structure enables incorporation of appropriate imaging
induced enhancement is generally more pronounced for a
modalities into the core as well as in different shell layers (Fig. 2c),
multiphoton-induced UCPL band and at a low excitation power
without interference between them (refer to the advantages of
density, when saturation effects are not in play. Detailed measure-
core–shell architecture discussed in 2.1–2.6).
ments and analysis of the enhancement factors for different UCPL
An epitaxial core–shell structure with the shell containing
bands are necessary to establish the enhancement mechanism,
along with theoretical guidance to produce optimized plasmonic magnetic elements (Gd3+, Dy3+, Mn2+, and Ho3+ ions) is able to
structures of appropriate shape, size and situated at an optimum produce a new MRI imaging modality without or with limited
distance from the UCNPs. Lu et al. in their recent study ‘‘Plasmon influence on UCPL from the core.124–129 For example, ‘‘smart’’
Enhancement Mechanism for the Upconversion Processes in lanthanide-based theranostic NaDyF4:Yb3+/NaGdF4:Yb3+/Er3+
NaYF4:Yb3+/Er3+ Nanoparticles: Maxwell versus Förster’’ compared core–shell nanoprobes are able to circumvent the up-converting
UCPL from NaYF4:Yb3+/Er3+ UCNPs deposited on a silver nano- poisoning effect of Dy3+ ions to produce efficient up-conversion
grating and that from the ones on a flat silver film, and has shown fluorescence, while offering not only excellent dark T2-weighted
that the intensity of the green and red UCPL (Er3+ emission) on MR contrast, but also tunable bright and dark T1 MR contrast
the nanograting was up to 16 and 39 times higher.122 The UCPL properties.129 Core–shell Fe3O4@NaYF4:Yb3+/Er3+ nanocomplexes
intensity was found to depend quadratically on the excitation have been prepared for T2-weighted magnetic resonance and
power in the weak excitation power limit and linearly in the strong upconversion luminescence imaging.130 An epitaxial core–shell
excitation power limit. Importantly, the authors identified and structure with high X-ray attenuation element (e.g., Lu3+ or
separated two main mechanisms contributing to plasmon Yb3+) in either in the core or in the shell offers a new modality
enhancement of luminescence upconversion: absorption of for CT imaging,131,132 while positioning the radionuclide 153Sm
lanthanide ions and energy transfer between them. The absorp- in the outmost shell layer allows for SPECT imaging133 or the
18
tion enhancement is described by the Maxwell’s equations, F radionuclide for PET imaging.134 Recent progress in the use
while the energy transfer obeys the Förster’s theory. It was of core–shell hierarchical design for multimodal imaging appli-
further determined that the absorption enhancement played cations is discussed in Section 5.1.2.
the dominant role, while the energy transfer enhancement was 2.7.2. Therapeutic functionality. In general, the UCNPs
small and effective only in the weak excitation regime. The themselves lack the functionality to produce a therapeutic
expressions for the overall enhancement factors for the upcon- effect. A pertinent effect using lanthanide-doped nanoparticles
verted luminescence intensity in the weak and strong excitation (not UCNPs) is demonstrated by Strek et al. where high concen-
limits were derived. It can be assumed that the work of Lu et al. tration Nd3+ containing NaYF4 is able to provide a local temperature
sheds light on how surface plasmon enhances the upconver- increase when excited at B532 nm, potentially having applications
sion in lanthanide ions materials and may allow comparison in photothermal therapy (PTT).135 A silica coating of UCNPs (Fig. 2d)
among the widely varying reports in the literature, thus offering provides possibilities to incorporate various therapeutic func-
a foundation for more advanced engineering of plasmon tionalites into the UCNPs.136,137 The importance of silica coating
enhanced upconversion materials. resides in that it can be produced with controllable porosity,

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which provides promise for therapeutic loading and controlled by us as well as by others in recent reviews,2,17,146,147 they are
release. The controlled release can take place in a sustained way not discussed in this work.
via slow diffusion through voids or channels in the silica,138,139
or activated by UV upconversion light by the action of a NIR 3.1. General nanochemical approaches to prepare epitaxial
light penetrating deep through a biological medium.140 Silica core–shell UCNPs with a single shell layer
also has a well-developed surface chemistry to introduce a Three techniques have been typically used to produce a single
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variety of plasmonic nanomaterials (e.g., metallic nanoshells, shell layer on the core nanoparticle surface.
metallic nanoparticles, self-doped plasmonic semiconductors) (i) Seed-mediated epitaxial growth. This is the most widely
on to them, thus providing abilities to implement photothermal used chemistry to prepare high quality epitaxial core–shell
therapy (PTT) and/or photoacoustic imaging using silica coated structure nanoparticles with a uniform morphology and size.
UCNPs. Indeed, silica coating imparts a large variety of therapeutic The essence in a preparation of the high quality inorganic
functions to UCNPs, entailing them to be used as theranostic nanoparticles with a narrow size distribution is to well separate
core–shell UCNPs. Use of polymeric coating instead of silica to the nucleation stage and the growth stage in time.148 As a
incorporate various therapeutic functions is also being actively result, ‘‘burst nucleation’’ is typically required in the growth
pursued.141 In addition, NaYF4:Yb3+/Tm3+@TiO2, NaLuF4:Yb3+/ solution to produce abundant nuclei that can then be utilized
Tm3+/Gd3+@TiO2, NaYF4:Yb3+/Er3+@Bi2MoO6 core–shell nano- to direct the deposition of the monomer in the growth stage,
particles have been prepared which show excellent NIR- but without generating new nuclei for new nanocrystals to form
driven photocatalytic activity as a result of using upconversion (in the case of synthesis of lanthanide-doped nanoparticles by
luminescence to activate the TiO2 photocatalyst positioned in the thermolysis method).42,93,149 In the case of UCNPs, the
the shell.142–144 The ability to produce reactive oxygen species monomer can be defined as the minimal subunit of the host
(ROS) or free radicals from a TiO2 shell layer shows promises bulk crystal. For seed-mediated epitaxial growth, the core
for the use of these core–shell structures as attractive pro-drugs nanoparticles are utilized as ‘‘nuclei’’ for seeding the growth
for NIR light-activated therapy. This potential has recently been of the shell layer. As the core UCNPs have been prepared before
verified in a study where the amount of ROS produced from the growth, the nucleation and the growth stages are therefore
NaYF4:Yb3+/Tm3+@TiO2 nanoparticles was shown to be suffi- automatically separated ensuring high quality core–shell nano-
cient for killing cancer cells in vitro.145 The use of varied types particle to be formed. Seed-mediated growth applies to both
of core–shell structure for therapeutic applications is discussed homogenous and heterogeneous core–shell UCNPs discussed
in Sections 5.1.3 and 5.1.4. in Section 2; the only difference is in the variance of shell
precursors used in the growth solution. However, in order to
create a homogenous interface between the core and the outer
3. Preparation of hierarchical shell, the host lattice of the shell material is required to exhibit
core–shell upconversion nanoparticles a low lattice mismatch with the core material. Moreover, the
concentration of shell precursor is typically low in regard to the
Use of nanophotonic approaches to control the excitation concentration of the core nanoparticles to avoid formation of
dynamics of upconversion in a core–shell structure signifi- new nuclei by shell precursors, which might then evolve into
cantly relies on the ability of nanochemistry to produce shells nanoparticles of shell host material alone rather than the core–
in a precisely defined manner. This is of particular importance shell UCNPs. The thickness of the shell can be controlled via
for epitaxial core–multishell upconversion nanoparticles, as adjusting the shell precursor concentration, which can be
each shell may play a specific distinct role. This means that determined according to chemical stoichiometric calculation.
the host lattice, thickness, crystal structure, as well as concen- In addition, the shell precursors can be either directly injected
tration and type of dopants might vary in different shell layers, into the growing solution of the core nanoparticles to induce a
yet the entire multishell coating has to be grown in a well- further growth of the shell, or the core nanoparticles can be
defined manner. This section provides an account of nano- centrifuged out, and the shell layer is grown in a separate step.
chemical approaches to prepare these epitaxial core–shell These two variants of loading shell precursors also provide two
structures with single or multiple shell layers with monolayer alternatives for layer-by-layer growth of core–multishell struc-
deposition precision, as well as to synthesize non-epitaxial ture UCNPs as described in Section 3.2.
mesoporous silica coated UCNPs and plasmonic core–shell (ii) Seed-mediated Ostwald-ripening. Ostwald ripening refers to
nanoparticles. The core only UCNPs have been typically pre- the process which favors larger particles with smaller surface to
pared using solution-based colloidal nanochemistry via three volume ratios over the energetically less stable smaller particles,
main types of synthetic approaches: (i) thermal decomposition, resulting in the growth of larger particles at the expense of smaller
(ii) Ostwald-ripening, and (iii) hydrothermal methods. By care- ones. As a result, the Ostwald ripening process is able to dissolve
fully adjusting experimental parameters, such as concentra- energetically less stable small sacrificial nanoparticles into mole-
tions of precursors, type of solvents, reaction temperature and cules of shell materials, which can then deposit on the larger
time, the core only UCNPs with a high crystallinity, narrow size stable core nanoparticles. Veggel and co-workers recently exploited
distribution and exceptional optical properties can be pre- this process to perform layer-by-layer shell growth onto larger core
pared. As this nanochemistry has been thoroughly presented nanoparticles.47 Small sacrificial alpha-NaYF4 nanoparticles were

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firstly synthesized and used as the shell precursor. Subsequent NaYbF4@Na(Yb,Gd)F4@NaGdF4,87 NaGdF4:Yb3+/Tm3+@NaGdF4@
injection of these sacrificial nanoparticles into a hot solution of NaGdF4:Tb3+,12 NaYF4:Yb3+/Er3+@NaYF4:Yb3+@NaYF4:Nd3+
NaYF4:Ln3+ core nanoparticles induces a rapid dissolution of the (Zhong, Adv. Mater., Nd),89 (NaGdF4:Er3+)@(NaGdF4:Ho3+)@
sacrificial nanoparticles and their deposition onto the larger core NaGdF4,79 (NaYF4:Yb3+/Tm3+)/NaYbF4/NaYF4,78 and NaGdF4:Nd3+/
NPs (a self-focusing Ostwald-ripening process), which resulted in NaYF4/NaGdF4:Nd3+,Yb3+,Er3+/NaYF4.88 It is worth noting that
a formation of the core–shell structured nanoparticles with a well- Zhao et al. was the first to show that the core–shell NaYF4:Yb3+/
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defined shape, narrow size distribution, with control to provide a Er3+@NaGdF4 UCNPs can be prepared by employing monolayer-
tunable shell growth. Thus, the shell thickness can be precisely by-monolayer deposition,63 opening a new era for nanophotonic
controlled by manipulating the amount of the injected sacrificial control of upconversion in the core–shell nanostructure with a
nanoparticles. This method is flexible and holds promise to sub-nanometer precision.
prepare other high-quality homogeneous and heterogeneous Although the multi-step approach is able to prepare a core–
core–shell nanoparticles. multishell structure with precision and flexibility, it utilizes
(iii) Cation exchange reaction. This strategy involves a reversible prolonged heating, volatile solvent removal, centrifugation and
chemical reaction between an insoluble solid and a solution, washing for growth of each shell. Hence, the preparation
during which cationic ions are interchanged. As a result, cationic process is time-consuming and laborious, especially when a
ions from the surface of UCNPs are replaced by other cations few shell layers are needed. To overcome this, a protocol of one
present in solution, thus producing a unique heterogeneous core– pot successive layer-by-layer (SLBL) deposition was introduced.
shell structure. One of the earliest examples of use of this It utilizes seed-mediated epitaxial growth, which is flexible to
technique was the preparation of GdF3@LnF3 core–shell NPs by deposit uniform multishells on both hexagonal and cubic
Veggel and Dong.150 They exposed the GdF3 core NPs to an phase cores via successive introduction of the shell precursor
aqueous solution containing excess Ln3+ ions and observed a solutions (Ln-OA and Na-TFA-OA dissolved in high boiling-
partial replacement of Gd3+ ions in the GdF3 NPs by Ln3+ from the point OA–ODE mixture) (Fig. 7).152 The shell thickness was
solution. The same group used the cation exchange approach to shown to be well controlled in the range from 1 monolayer
prepare multifunctional NaYF4:Yb3+/Tm3+@NaGdF4 core–shell (0.36 nm) to more than 20 monolayers (8 nm) by simply
NPs with tunable shell thickness, enhanced UCPL and out- adjusting the amounts of the shell precursors. The stoichio-
standing paramagnetic performance.127 More recently, Wang metric doping of lanthanides into the shell as well as into the
and Deng reported on in situ cation exchange of hexagonal phase core domain provides a large degree of freedom for engineering
NaYF4:Yb3+/Er3+ nanoparticles with Gd3+ ions during synthesis, light upconversion in a core–shell structure. The principle
which retained the small particle size of B12 nm, but increased of SLBL protocol has implications for the one pot growth of
the UCPL by about 29 times.151 However, extended use of the core–multishell nanostructures through the Ostwald-ripening
cation exchange method to prepare core–multishell UCNPs is strategy, when sacrificial nanoparticles are employed as the
problematic, as it is ineffective to precisely control the exchanging shell precursor.
parts of UCNPs and yield a uniform shell. Notwithstanding, it still
provides a versatile alternative to impart new imaging modality to 3.3. Mesoporous silica coating
UCNPs through the formation of a core–shell structure. Silica coating is a strategy for inorganic surface treatment to
make nanoparticles water-dispersible and biocompatible as
3.2. Layer-by-layer approach to prepare core–multishell well as to introduce new therapeutic functionalities when using
UCNPs with monolayer thickness precision mesoporous silica to entrap a therapeutic agent and deliver it to the
The chemistry to produce core–multishell UCNPs relies on the disease site. Silica is known to be highly stable, biocompatible, and
deposition of shells in a layer-by-layer way. A straightforward optically transparent. When utilized as a coating material, surface
approach is to use a multi-step approach to prepare each silanization can flexibly offer abundant functional groups (e.g.,
shell using seed-mediated epitaxial growth or seed-mediated –COOH, –NH2, –SH, etc.), allowing for conjugation with bio-
Ostwald-ripening methods described above in Section 3.1. That molecules. Generally, there are two types of conventional chemistry
is to say the core–1st shell UCNPs is utilized as the seeds for the to coat nanoparticles with silica: (i) Stöber method, which applies to
core–1st shell–2nd shell UCNPs, which are in turn utilized as the hydrophilic UCNPs using well-established sol–gel chemistry
the seeds for the core–1st shell–2nd shell–3rd shell UCNPs, and that involves the hydrolysis and condensation of alkoxide-based
then so forth. The stoichiometric nature of involved chemical precursors, such as tetraethyl orthosilicate (TEOS); (ii) reverse
reactions producing a shell causes its thickness to be precisely micelle microemulsion, which applies to UCNPs that has hydro-
proportional to the shell precursor dosage, which can be phobic capping ligands. This method utilizes chemical reactions in
calculated according to the increase in molar mass caused by nano-confined hydrophilic cavities generated by a homogeneous
deposition of the shell of a defined thickness. This essentiality mixture of ammonia, cyclohexane, surfactant (e.g., Igepal CO-520),
provides an exciting opportunity to deposit each shell layer with and tetraethyl orthosilicate (TEOS). Since therapeutic upconversion
a single monolayer precision. A multi-step method has been nanoparticles typically exploit mesoporous silica coated core–shell
employed by many researchers to prepare core–multishell UCNP structures, we focus here on chemistries to prepare them.
UCNPs, such as NaYF4:Yb3+/Er3+@NaYbF4:Tm3+@NaYF4:Yb3+/ Readers interested in UCNPs with non-mesoporous silica coating
Tm3+,99 NaGdF4:Yb3+/Tm3+@NaGdF4:Yb3+/Er3+@NaGdF4,100 are recommended to refer to recent reviews on this topic.2,17,147

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Fig. 7 Schematic illustration of one pot successive layer-by-layer (SLBL) deposition to prepare epitaxial core–multishell UCNPs (upper panel), and HAADF
STEM images of particles with varied shell thickness (lower panel). Reproduced with permission from ref. 152. Copyright 2013, American Chemical Society.

A mesoporous silica shell on UCNPs can be obtained by molecules grafted in the mesopore network of a mesoporous silica
three methods, as illustrated in Fig. 8. (i) The calcination layer.155 Lin et al. have utilized CTAB as a template to fabricate a
method (Fig. 8a), which typically takes three steps. The first set of multifunctional mesoporous core–shell structured nano-
step is to produce an amorphous silica shell on top of UCNPs, composites such as Fe3O4@SiO2@mSiO2@NaYF4:Yb3+/Er3+,156
which is then coated with an organically modified silica shell Gd2O3:Er3+@SiO2@mSiO2,157 b-NaYF4:Yb3+/Er3+@b-NaGdF4:Yb3+/
using the Stöber method, where a combination of tetraethyl- Er3+@mSiO2 nanocomposites (Fig. 8f–h)158 and NaYF4:Yb3+/
orthosilicate and octadecyltrimethoxysilane with an appropri- Er3+@SiO2@mSiO2,159 to be used as efficient nanoagents for drug
ate ratio is used as a silica precursor. Finally, calcination at delivery and optical imaging. A critical review by Lin and co-workers
high temperature (B500 1C) yields a mesoporous silica on on this topic has appeared recently.138 (iii) Etching method (Fig. 8i).
top of UCNPs@amorphous silica core–shell nanostructure. This method usually involves the growth of two dense silica shells
Zhang et al. have utilized this method to prepare the core–shell twice, and the second shell growth usually employs a water-phase
NaYF4:Yb3+/Er3+@SiO2@mSiO2 nanoparticles to incorporate a Stöber method. Subsequently, a surface-protected hot water etching
photosensitizer or a genetic material into the mesoporous silica process (using PVP as a surface protector) at B95 1C can etch away
for upconversion photodynamic therapy (UC PDT) or controlled the first silica shell and produce mesoporous pores in the second
drug release in order to explore activation by deep penetrating silica shell, yielding a ‘‘yolk’’ nanostructure with a mesoporous
NIR light excitation (Fig. 8b –d).26,27,153 (ii) The organic template silica shell. Shi et al. have utilized this method to produce a yolk
method (Fig. 8e), which utilizes a surfactant [for example, cetyl nanostructure of NaYF4:Yb3+/Er3+@NaGdF4@mSiO2 to be used for
trimethylammonium bromide (CTAB) or hexadecyl trimethyl synergetic chemo-/radiotherapy as well as to deliver magnetic/
ammonium chloride (CTAC)] as a template. In this method, the luminescent dual-modal imaging modality.160 The same nano-
first step is to produce a hydrophilic complex of CTAB or CTAC with structure has also been utilized for real-time in vivo quantitative
UCNPs, which is then processed with the Stöber method to create a monitoring of drug release determined by the varied signal inten-
template-patterned silica shell. Subsequent extraction of the CTAB sities of both MRI and UCPL.161 The same group prepared
or CTAC using ion exchange (e.g., with sodium chloride) yields a NaYF4:Yb/Tm@NaYF4@hmSiO2 using a similar approach for selec-
patterned mesoporous silica shell. Cichos and Karbowiak devel- tive hypoxia imaging in vivo upon NIR excitation (Fig. 8j–l).162
oped a general and versatile procedure based on CTAB to produce a
controlled thin mesoporous silica layer on the top of lanthanide- 3.4. Coupling of UCNPs with plasmonics using core–shell
doped NaGdF4 nanoparticles and PbS quantum dots.154 Shi et al. architecture
utilized a CTAC template to prepare NaYF4:Yb3+/Tm3+@mSiO2 Coupling of plasmonic properties with UCNPs can be of great
core–shell UCNPs for light-regulated drug release by making use importance for obtaining plasmonically enhanced UCPL (see
of the NIR-to-UV mediated trans–cis photoisomerization of azo Section 2.6). On the other hand, even if the plasmonic effect on

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Fig. 8 Coating of UCNPs with a mesoporous silica shell. (a) Schematic of the calcination method; (b–d) corresponding TEM images of NaYF4:Yb3+/Er3+,
NaYF4:Yb3+/Er3+@silica, and mesoporous-silica-coated NaYF4:Yb3+/Er3+@silica nanoparticles obtained using the calcination method. (e) Schematic
of the template method; (f) TEM image of b-NaYF4:Yb3+/Er3+@b-NaGdF4:Yb3+/Er3+@mSiO2 nanocomposites, prepared using CTAB as a template,
(g, h) TEM and dark-field STEM image of NaYF4:Tm3+/Yb3+@NaYF4@mSiO2 prepared using CTAC as a template. (i) Schematic of the etching method;
(j) TEM image of NaYF4:Yb/Tm@NaYF4, (k) HAADF STEM image of NaYF4:Yb/Tm@NaYF4@dSiO2@mSiO2, (l) HAADF STEM image of NaYF4:Yb/Tm@NaYF4@hmSiO2
(d SiO2, dense layer silica; mSiO2 mesoporous layer silica, hmSiO2 obtained by etching the dense silica layer in hot water). Reproduced with permission from
ref. 153, 158 and 162. Copyright 2009 and 2013, John Wiley and Sons. Copyright 2014, American Chemical Society.

UCPL is not revealed, the core–shell architectured hybrid of upcon- (i) Metallic@silica@UCNPs nanostructure. Fig. 9a illustrates a
version and plasmonic nanosystems might be of significance for typical procedure for creating metallic@silica@UCNPs core–
a number of applications exploiting both plasmonic and UCPL shell–shell nanostructure, where a plasmonic metallic core of
features (e.g., optical and photoacoustic imaging, imaging guided silver (Ag) nanospheres is utilized as an example.113 The first
photothermal therapy, etc.). Two variants for the fabrication of the step is to coat silica onto metallic nanoparticles by using
plasmonic core–shell structures (Fig. 9) are described below. either the Stöber method or the reverse micelle microemulsion

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Fig. 9 (a) Schematic illustration for preparing core–shell–shell structures of metallic@silica@UCNPs, along with (b–d) TEM images of the nanostructures
obtained in each step. (e) Schematic illustration for synthesizing UCNPs@silica@metallic core–shell–shell structure, along with (f) and (g) TEM images of
the corresponding samples. Reproduced with permissions from ref. 113 and 121. Copyright 2010 American Chemical Society and 2013 Ivy Spring
International Publisher.

method (Fig. 9b). By controlling the coating process, the on LSPR enhanced UCPL in Au@SiO2@Y2O3:Yb3+/Er3+ nano-
resulting metallic@SiO2 (e.g., Ag@SiO2) can have a uniform particles which are prepared by utilizing the chemistry
diameter and contain one metallic nanoparticle positioned at the described here.35 An optimization of the silica spacer’s thick-
centre. The thickness of the silica can also be precisely controlled ness resulted in a maximum B10 fold enhancement of the
via adjusting the amount of the utilized TEOS as well as by green UC emission of Er3+ ions, when excited at B980 nm. It is
varying other parameters. In the second step, the metallic@SiO2 to be noted that the chemistry described in this section can be
can then be coated with a layer of Y:Ln(OH)CO3
H2O through extended to prepare other multifunctional core–shell nanoparticle
a homogeneous precipitation method from yttrium nitrate, platforms, e.g., core–shell–shell Fe3O4@SiO2@NaYF4:Yb3+/Er3+
lanthanide nitrate, and urea (e.g., at 90 1C for 2 h) (Fig. 9c). that integrate the magnetic properties and the UCPL properties
Finally, heat treatment at high temperature (e.g., 700 1C for 3 h) for targeted chemotherapy.163 For this, the metallic nanoparticles
can convert the Y:Ln(OH)CO3
H2O layer into a crystallized are replaced by Fe3O4, and the Fe3O4@SiO2@Y2O3:Yb3+/Er3+
lanthanide-doped Y2O3 upconverting layer (Fig. 9d). The thick- is further subject to ion-exchange in the presence of HF and
ness of this layer is determined by the thickness of the layer of NaF solution to form the Fe3O4@SiO2@NaYF4:Yb3+/Er3+ multi-
Y:Ln(OH)CO3
H2O. This procedure was employed by Zhang functional nanoplatform.
et al. to prepare Ag@SiO2@Y2O3:Er3+ nanoparticles.113 An optimized (ii) UCNPs@silica@metallic nanostructure. The chemistry or
LSPR UC enhancement of B40 times was reported, along with the procedure to prepare UCNPs@silica@metallic nanoparticles
the use of this nanoplatform for bioimaging. Ge et al. reported is illustrated in Fig. 9e.120,121 The first step involves coating silica

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onto UCNPs by using either the Stöber method or the reverse spectroscopy (EELS), energy-dispersive X-ray spectroscopy (EDX),
micelle microemulsion method (Fig. 9g). An amino-functionalized PL lifetime, PL intensity, etc. Typically, the formation of a core–
silica can be produced by refluxing the NaGdF4:Yb3+/Er3+@silica shell structure can be indicated by the presence of five character-
nanoparticles dispersed in ethanol with the addition of a hint istic features (Fig. 10): (i) the increase of the average size, due to
amount of 3-aminopropyltriethoxysilane (APTES) at an elevated the introduction of a new layer onto the core only nanoparticles.
temperature for a reasonable time range (e.g., at 80 1C for 1 hour). The average size values can be directly obtained through aver-
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As the amino group has a strong affinity to the metallic element, aging of the size of nanoparticles in TEM images, or calculated
the amino-functionalized silica can directly hold the synthesized through the XRD pattern via Scherrer’s equation. (ii) The variance
metallic nanoparticles with a loosely coordinated ligand of UCPL intensity. The formation of an epitaxial core–shell
(e.g., poly-vinylpyrrolidone) (Fig. 9f).121 We have prepared structure can significantly increase UCPL due to suppression of
NaGdF4:Yb3+/Er3+@silica@Au nanostructures using this nano- surface-related quenching mechanisms. Non-epitaxial core–shell
chemistry for biomodal optical imaging as well as for studies structure, e.g., UCNPs@silica and UCNPs@metallic, also can
of LSPR interaction with UCPL.121 Li et al. reported on affect the UCPL due to the interaction between the core and the
NaYF4:Yb3+/Er3+@silica@Au satellites for tunable green-to-red non-epitaxial shell. (iii) The variance of UCPL lifetime. An
upconversion emissions using the absorption capability of epitaxial core–shell structure generally can result in a pro-
gold.120 This chemistry has also been utilized to prepare longed UCPL lifetime as compared to that of the core only
PEGylated NaY/GdF4:Yb3+,Er3+,Tm3+@SiO2–Au@PEG5000 nano- nanoparticles. This is due to spatial isolation of the lanthanide
particles with a uniform size of less than 50 nm for CT, MR, as ions from the surrounding surface quenchers as well as the
well as for upconversion luminescence bioimaging.164 It is passivation of surface defects of the core nanoparticles. (iv) The
important to note that when replacing the silica shell with TEM contrast between the core domain and the shell domain in
ligands containing functional groups, the chemistry as well as a single nanoparticle. (v) The variance of element content
the procedure outlined can be utilized to grow UCNPs/ligands/ between the core domain and the shell domain in a single
metallic nanostructures to deliver a combined and/or synergistic nanoparticle. The last two features are able to provide direct
plasmonic and UCPL properties.110 evidence of the formation of a core–shell structure, which will
be discussed in the following two sections.

4. Characterization of core–shell 4.1. Imaging of core–shell structures

upconversion nanoparticles The primary limitation for characterization techniques to demon-

strate the formation of a core–shell structure is that it may be
A range of characterization tools can be utilized to indirectly unable to clearly distinguish the structural and compositional
suggest or directly verify the presence of a core–shell structure. variance between the shell layer and the core. TEM only discerns
These characterization tools encompass X-ray diffraction the core–shell structure when the core and the shell have signifi-
(XRD), transmission electron microscopy (TEM), X-ray photo- cant difference in composition and crystallinity (and the corre-
electron spectroscopy (XPS) based on tunable synchrotron sponding difference in electron scattering) to create a good
radiation, high-angle annular dark-field (HAADF) scanning phase contrast between the core and the shell. Usually, non-
transmission electron microscopy (STEM), electron energy loss epitaxial core–shell UCNP nanostructures can be visualized in

Fig. 10 Schematic illustration of five strategies to characterize formation of a core–shell structure. The imaging contrast and the elemental variance
provide direct evidence to verify the formation, while the other three strategies yield indirect evidence to suggest the formation.

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such way; for example, the core–shell structure of the UCNPs@silica Zhao et al.88 However, the utilization of this technique requires
and Ag@silica@UCNPs can be easily discerned in regular TEM an adequate difference between the atomic number of the
phase contrast imaging.113,121 However, TEM phase contrast elements in the core and the shell.
imaging does not generally work for epitaxial core–shell UCNPs,
since the core and the shell are compositionally similar or 4.2. Element mapping in a single nanoparticle
identical, and have similar crystallinity. The element difference between the core and the shell provides
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Although to date there is a lack of tools to discern the another way to discern the heterogeneous core–shell structure.
homogenous core–shell epitaxial structure, HAADF can be still Veggel et al. first reported direct evidence for such core–shell
utilized to discriminate the heterogeneous epitaxial core–shell structure (NaYF4@NaGdF4 UCNPs) formation using XPS pro-
structure, as the contrast of HAADF is approximately proportional duced by tunable synchrotron radiation.67 The intensity ratio of
to the square of the atomic number of the element contained, the Y3+ 3d peak to the Gd3+ 4d peak increases with an elevation
producing a z-contrast image.25 This technique was also used of the kinetic energy of the synchrotron radiation, indicating
by Veggel et al., Zhao et al, and Chen et al. to demonstrate the that the Gd3+ from the shell screens the Y3+ intensity from
formation of NaYF4@NaGdF4 (Fig. 11a) or NaGdF4@NaYF4 the core, and thus providing direct evidence for a core–shell
heterogeneous core–shell structure, in which the Y-rich domain structure. While this characterization technique does deliver a
appears to be darker than the Gd-rich domain.63,68,165 We have confirmation of a core–shell structure, it is an ensemble
utilized HAADF to characterize the alpha-NaYbF4:Tm3+@CaF2 measurement and does not provide elemental details about a
core–shell structure, the image of which shows a clear contrast single core–shell UCNP. With respect to this, the line scan of
between the core which appears bright (ytterbium Z = 70), EDX and EELS can provide the precise element distribution of
and the shell which appears dark (calcium Z = 20) (Fig. 11b).25 single core–shell nanostructures.165 The characterization cap-
Yan et al. and Chen et al. employed this technique to demon- abilities of EDX are due to that each element has a unique
strate the formation of NaYF4:Yb3+/Er3+@CaF2 (Fig. 11c) and atomic structure, yielding a unique, well energy separated, set
CaF2:Yb3+/Er3+@CaF2 core–shell structure, respectively.65,166 of peaks in its X-ray spectrum, as in the case of NaYF4/NaGdF4
HAADF-STEM images of core–shell and core–multishell core–shell structure (Fig. 12d and e).165 In our previous work,
NaGdF4:Nd@NaYF4, NaGdF4:Nd@NaYF4@NaGdF4:Nd,Yb,Er, EDX line scan conducted with STEM imaging on a NaYbF4/CaF2
(Fig. 11d and e) and NaGdF4:Nd@NaYF4@NaGdF4:Nd,Yb,Er@ nanoparticle showed a higher Ca concentration in the peri-
NaYF4 (Fig. 11f) nanoparticles were also presented recently by pheral region and a higher Yb concentration in the central

Fig. 11 HAADF STEM image of (a) NaYF4@NaGdF4, (b) (NaYbF4:0.5%Tm3+)@CaF2, (c) NaYF4:Yb3+/Er3+@CaF2, (d) NaGdF4:Nd3+/NaYF4, (e) NaGdF4:Nd3+/
NaYF4/NaGdF4:Nd3+,Yb3+,Er3+ and (f) NaGdF4:Nd3+/NaYF4/NaGdF4:Nd3+,Yb3+,Er3+/NaYF4 nanoparticles with resolved core–shell structures. Reproduced
with permission from ref. 25, 88 and 165. Copyright 2012 American Chemical Society. Copyright 2013 Nature Publishing Group.

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Fig. 12 (a) HAADF image of a single NaYF4:Yb3+/Er3+@NaGdF4 nanocrystal. EELS spectra of yttrium L2,3 (b) and gadolinium M4,5 (c) edges taken from the
probe location on the inferred NaYF4:Yb3+/Er3+ core and NaGdF4 shell. (d) TEM image of one single NaYF4@NaGdF4 nanoparticle, as well as (e) the
corresponding results of an EDS line scan. Reproduced with permission from ref. 63 and 165. Copyright 2012 American Chemical Society.

region of the crystal, verifying the designed heterogenous core– 5. Applications of core–shell UCNPs
shell structure.25 In EELS, a material is exposed to a beam of
electrons with a known, narrow range of kinetic energies. 5.1. Biomedical applications
Some of the electrons will undergo inelastic scattering, which 5.1.1. Deep 3D bioimaging. Optical imaging is one of the
means that they lose energy and have their paths slightly most important techniques used in biomedical imaging as it is
and randomly deflected. The amount of energy loss can be capable of providing cellular or molecular level information with
measured using an electron spectrometer and interpreted, almost single molecule sensitivity.167,168 Owing to their unique
in terms of what caused the energy loss. Zhao et al. demon- and versatile spectral properties and exceptional stability, UCNPs
strated the use of cryo-TEM operating at 96 K to minimize are found to be excellent optical probes for photoluminescence
the electron beam damage and provided evidence of a core– bioimaging, as they are devoid of many drawbacks attributed to
shell structure (Fig. 12a–c). A linear correlation between the other photoluminescent probes, namely broad emission and
NaGdF4 shell thickness and the optical properties of mono- susceptibility to bleaching for organic luminophores, blinking
disperse hexagonal NaYF4:Yb3+/Er3+@NaGdF4 core–shell nano- and toxicity for semiconductor QDs, etc.2 The UCNPs, possessing
particles was demonstrated, revealing the importance of the spectrally narrow and tunable emission bands excitable by a
shell thickness.63 single wavelength in NIR, can be readily employed as probes for

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multiplexed bioimaging.169 Numerous studies reported the use power density below 0.7 W cm 2 convenient for imaging would
of UCNPs as targeted probes for cellular imaging in vitro,169,170 be appealing, possibly leading to even further improved imaging
but full advantages of UCPL imaging with UCNPs are revealed depth and SBR. We note that the total UC QY, covering the UV,
in the in vivo imaging, since the anti-Stokes character of the visible, and NIR PL spectral range of (LiLuF4:Yb3+/Tm3+)@LiLuF4
emission excludes manifestation of the auto-fluorescence from core–shell UCNPs is reported to be 7.6% at a high excitation
the biological tissues, resulting in a decrease in the imaging power density of 127 W cm 2.61 This suggests the possibility of
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background. In addition, the imaging background produced by achieving a high UC QY for the NIR UCPL of (LiLuF4:Yb3+/
the scattering of excitation light can be reduced by using short- Tm3+)@LiLuF4 core–shell UCNPs. It becomes very attractive to
pass filters with the imaging camera, since the emitted light is characterize their NIR UC QY at the excitation power density
considerably shifted in wavelengths relative to excitation. suitable for in vivo imaging, and apply these UCNPs for optical
Another benefit of UCPL imaging with UCNPs is that the bioimaging. Andersson-Engels et al. recently showed that deep
excitation of the upconversion emission lies in the NIR spectral tissue optical imaging of core–shell (NaYF4:Yb3+/Tm3+)@NaYF4
range, more importantly in the ‘‘optical transparency window’’ upconverting nanoparticles can be enabled by exploiting higher
for the biological tissues (B700–1000 nm). NIR light of this intrinsic QY through the use of millisecond single pulse
spectral range attenuates less and penetrates deeper in the excitation with high peak power.175 This provides new possibi-
tissue as a result of both lower absorption of the tissue lities for better deep tissue optical imaging (and also optical
constitutions and reduced scattering for NIR light.171,172 In a tomography) using reported core–shell UCNPs and a pulsed
marked contrast to the multiphoton imaging employing NIR laser with optimized parameters.
excitation from expensive ultrashort-pulsed lasers, a low-cost cw Another promising direction for UCPL bioimaging is to
laser diode can be utilized as the NIR excitation source for UCPL utilize excitation other than B980 nm, since water absorbance
imaging, with an excitation density of B10 1 W cm 2.2,12,173 We at this wavelength can cause significant heating of a biological
have pioneered a UCPL bioimaging approach in which both tissue under irradiation. S. He with co-authors explored the
excitation (980 nm) and emission (800 nm) wavelengths are in heating effect under 980 nm irradiation and proposed the use
the optical transmission window, utilizing the NIR-to-NIR of the 915 nm laser, which produces less heating, to excite cubic
upconversion in Tm3+/Yb3+-codoped NaYF4 UCNPs.24 In this NaYbF4:Yb3+/Tm3+ UCNPs in the UCPL bioimaging in vitro and
work, a NIR-to-NIR UCPL imaging of a Balb-c mouse intra- in vivo.176 It should be however noted that that UCPL in this
venously injected with UCNPs was reported, with the signal to case still originates from the absorption of Yb3+ ions, which has
background ratio (SBR) evaluated to be on the order of B10. a maximum at B980 nm and is much weaker at 915 nm. Since
It is important to emphasize that as the UC QY is strongly UCPL is proportional to the absorption of the exciting light by
dependent on the excitation power density, UCNPs with a high UCNPs, an efficient UCPL imaging with excitation at B980 nm
UC quantum yield at low power excitation density is of critical could be achieved at a lower excitation power than for 915 nm
importance for deep tissue imaging. This is because, according excitation, without producing significant heating. A compari-
to the American National Standard Z136.1-2007 (American son of UCPL imaging at B980 nm and 915 nm (or another
National Standard for Safe Use of Lasers), the employed excita- wavelength from the spectral range of Yb3+ absorption), along
tion power density for a B980 nm cw laser has to be lower than with evaluation of the thermal effect produced by both wave-
the safety threshold of 0.73 W cm 2 when applied to human lengths, is needed to conclude how beneficial it would be to
skin. Moreover, the strong scattering properties of a tissue will excite at 915 nm for the UCPL imaging employing UCNPs
produce a significantly lower excitation density (than the exci- containing Yb3+ ions.
tation density at the tissue surface) at the location of UCNPs The heating effect caused by long time irradiation at 980 nm
inside the tissue. As illustrated in Section 2.1, the core–shell can be also significantly reduced when using other NIR excitation
design is an important strategy to reach a high UC QY. wavelengths, introduced through doping of other NIR absorbing
Introduction of the core–shell architectured UCNPs with lanthanide ions. In particular, to tune the NIR absorption of the
boosted UC QY allows us to further improve sensitivity of NIR-to- nanoparticles, incorporation of Nd3+ ions can be proposed.84–86
NIR UCPL in vivo imaging. The alpha-(NaYbF4:0.5%Tm3+)@CaF2 Very recently, Zhong et al. reported the NaYF4:Yb3+20%,
core–shell UCNPs manifest a UC QY as high as 0.6% under an Er3+2%@NaYF4:Yb3+10%@NaNdF4:Yb3+10% core–shell–shell
excitation of 0.3 W cm 2.25 As a result, high contrast optical UCNPs (ErCSS), which are excitable at 800 nm owing to
imaging (the SBR is B310) of live animals (mice) was achieved. incorporation of Nd3+ ions into the outer shell.89 The absolute
We have also demonstrated that NIR-to-NIR UCPL imaging is quantum yield for the UCPL peaked at B540 nm is 0.11%
possible through a B3.2 cm thick animal tissue (pork), which under excitation at 800 nm with a power density of 20 W cm 2.
constitutes a leap forward for 3D optical imaging of deeper Fig. 13a illustrates contributions of the Nd3+ and Yb3+ ions into
tissues using UCNPs.25 It is worth noting that the NIR UC QY absorption of ErCSS. As a result of the difference in extinction,
of hexagonal NaLuF4:Gd3+/Yb3+/Tm3+, reported by Li et al., UCPL under 800 nm excitation was found to be B8 times
reaches about 0.47% under an excitation density of 17.5 W cm 2 brighter than under 980 nm excitation (Fig. 13b). It should be
at 980 nm, thus enabling an optical imaging depth of about noted that the intensity of UCPL from ErCSS excited at 980 nm
2 cm.174 An epitaxial growth of a shell layer onto this type of was similar to that from the conventional NaYF4:Yb3+20%,
UCNPs and characterization of the UC QY under excitation Er3+2%@NaYF4 core–shell UCNPs of similar size (Fig. 13b).

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Fig. 13 Comparison of UCPL under excitation at 800 nm and 980 nm for Nd3+-doped core–shell–shell UCNPs (ErCSS) and conventional
Yb3+-sensitized core–shell UCNPs (ErCS). (a) Absorption spectra of ErCSS (20 mg mL 1 in hexane). (b) UCPL photographs of ErCSS and ErCS excited
at 800 (top) and 980 nm (bottom) with 0.5 W cm 2 diode lasers. (c) UCPL from Nd3+-sensitized nanoparticles excited at 800 nm (left) and from
Yb3+-sensitized nanoparticles excited at 980 nm (right). Excitation with a power density of 400 mW cm 2 was used. (d) Temperature-distribution image
recorded after 7 min irradiation (Sp1: 980 nm; Sp2: 800 nm; 20 W cm 2). Inset: temperature increase with time under 800 and 980 nm. Reproduced with
permission from ref. 89. Copyright 2014 John Wiley and Sons.

The possibility of in vivo UCPL imaging with ErCSS and ErCS tissue imaging, when compared with the use of well-established
was evaluated and compared. After penetrating of the exciting NIR-to-NIR Yb3+/Tm3+-doped core–shell UCNPs.25
light through ca. 1 cm of lean pork, a much higher SBR image 5.1.2. Multimodal bioimaging. While UCPL is the key
was acquired from 800 nm-excited UCNPs than from the control feature of UCNPs and provides a basis for their application in
sample with 980 nm excitation (Fig. 13c). Due to the difference in bioimaging, they can also open the door for other possibilities
water absorption at 800 and 980 nm, after penetrating through in the biomedical field. There is a growing interest in the
5 cm of water, the UCPL of the Nd3+-sensitized UCNPs was development of nanoparticle probes that can function as multi-
about 125 times stronger than that of the conventional Yb3+- ple contrast agents for simultaneous use in different medicinal
sensitized UCNPs.89 The lower water absorption of the 800 nm imaging modalities providing complementary diagnostic infor-
laser source not only results in a deeper penetration depth, but mation (e.g., optical, MRI, PET, SPECT, CT). Correlation between
can also help to minimize tissue overheating. As shown in these imaging techniques using a single multimodal nanoprobe
Fig. 13d, a much higher temperature distribution can be will accelerate the diagnostic process, while reducing the stress
observed for the 980 nm irradiated area, compared with the on the patient related to multiple steps necessary for complete
800 nm irradiated one. While the temperature of 800 nm laser diagnostic using the current imaging technology.123 As dis-
heated water was raised from initially 24 1C to 25.7 1C, water cussed in Section 2.7.1, with the use of a hierarchical core–shell
under 980 nm irradiation was heated to a temperature as high approach, a range of imaging modalities can be incorporated
as 45.9 1C (same excitation power density and exposure time into UCNPs, thus supporting their use as multimodal nano-
were used in both cases). probes. For example, epitaxial core–shell UCNPs of NaYF4:Yb3+/
Although UCNPs with Nd3+ sensitized UCPL do show a Er3+@NaGdF4,177 NaYF4:Yb3+/Tm3+@NaGdF4,127 and NaYbF4:
promising potential for deep tissue imaging, it should be how- Tm3+@NaGdF4,60 as well as non-epitaxial epitaxial core–shell
ever noted that, since the green UC emission of Er3+ at B540 nm UCNPs of NaYF4:Tm3+/Yb3+/Gd3+@mSiO2,178 and NaYF4:Ln3+@Si-
is outside the optical transparency window and can be strongly DTTA-Gd3+,179 have been reported to exhibit both T1 MR relaxivity
attenuated by biological tissues, further studies are necessary to (provided by Gd3+ ions) and UCPL. Bioconjugation of the
provide evidence for superior advantage of these UCNPs for deep angiopep-2 peptide, using EDC chemistry, on the surface of

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PEGylated (NaYF4:Tm3+/Yb3+/Gd3+)@NaGdF4 core–shell nano- offers an optically inert layer for remarkable enhancement of
particles enables them to cross the BBB barrier to biotarget the UCPL. More importantly, the NaLuF4:Yb3+/Tm3+@NaGdF4
glioblastoma, and then function as a simultaneous MRI/NIR-to- (153Sm) core–shell UCNPs have been reported for use in SPECT/
NIR UCPL bimodal imaging agent, which showed a much CT/MR/UCPL four-modal bioimaging, providing an excellent
enhanced imaging performance in comparison with the clinically paradigm for multimodal imaging using a core–shell architecture
used single MRI contrast (Gd-DTPA) and fluorescent dye (5-ALA).180 (Fig. 14).186 Furthermore, in this work, in vivo tumor angiogenesis
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Moreover, Liu et al. developed multifunctional nanoparticles, analysis was performed by combining CT and SPECT imaging
NaYF4:Yb3+/Er3+@Fe3O4@Au, which incorporated optical and with confocal UCL imaging, showing the potential of using
T2 magnetic properties useful for dual-modal imaging, while multimodal imaging for early detection of disease onset and
utilizing the gold shell for photothermal therapy.37 Li et al. real-time monitoring of a therapeutic approach.
reported seed-mediated synthesis of NaYF4:Yb3+/Tm3+@FexOy In all the aforementioned multimodal designs, the provision
and Fe3O4@NaLuF4:Yb3+/Er3+/Tm3+ core–shell nanostructure as of imaging modalities is as follows: (i) the Gd3+, Fe3O4, and
imaging agents for T2 MRI and UCPL bimodal imaging.132,181 TaOx are utilized to empower the MRI imaging. The Gd3+ ions
Use of the same Fe3O4 core but a different (b-NaGdF4:Yb3+, at the shell surface are preferred, which can interact more
Tm3+) shell and a polyelectrolyte coating allowed Anker with efficiently with the proton. (ii) High Z elements, e.g., Lu3+ or
co-authors to obtain UCNPs which are stabilized against aggre- Yb3+, are used to produce strong attenuation of X-rays to realize
gation through PEGylation and capable of serving as bimodal CT imaging. (iii) The Yb3+/Er3+(Tm3+) lanthanide ion pairs are
(UCPL/MRI) imaging probes, providing both T1 and T2 MRI doped, preferably in the core, to implement UCPL imaging.
contrast due to availability of both a ferromagnetic core and a Positioning these dopants in the core also exploits the use of
paramagnetic shell.182 shell protection to suppress the surface-related quenching
In addition to MRI and UCPL biomodal imaging, trimodal mechanism and produce efficient UCPL. (iv) The radionuclide
CT/MRI/UCPL imaging as well as four modal SPECT/CT/MR/ (or radioisotope) of 153Sm and the 18F are utilized to entail for
UCPL imaging have also been recently reported, exploiting the SPECT imaging and PET imaging, respectively. These radio-
capability of a core–shell structure to incorporate multiple isotopes are often introduced into the shell layer at a later stage
modalities. For example, core–shell nanostructures of Fe3O4@ during the sample preparation, to avoid adverse interaction
NaLuF4:Yb3+/Er3+/Tm3+ and NaLuF4:Yb3+/Tm3+@SiO2-GdDTPA have with synthetic chemicals. In all, the strategy to construct multi-
been reported as imaging probes for tri-modality CT/MRI/UCPL modal imaging nanoprobes using the core–shell structure is to
imaging.132,183 TaOx-decorated NaYF4:Yb3+/Er3+/Tm3+@NaGdF4 appropriately position each type of imaging contrast element
core–shell UCNPs were reported by Shi et al. for in vivo CT/MR/ without producing interference between different types.
UCPL trimodal imaging.184 The same type of trimodal imaging Novel bioimaging techniques are being developed these
was realized through the design and synthesis of the multi- days which can be combined with the conventional medical
shell structured NaYF4:Yb/Tm@NaLuF4@NaYF4@NaGdF4 nano- imaging modalities using core–shell structured UCNPs as a
particles.185 While Gd3+ ions in the outermost shell provide platform. For example, Niu et al. recently presented a combination
T1-weighted MRI, the thick NaLuF4 shell epitaxially grown on of the UCPL and surface enhanced Raman scattering imaging
the core not only constitutes a CT functional layer, but also (SERS) using core–multishell architecture.187 The silica coated

Fig. 14 Schematic illustration of NaLuF4:Yb3+/Tm3+@NaGdF4(153Sm) core–shell UCNPs for SPECT/CT/MR/UCPL four-modal bioimaging. In this design,
the Yb3+/Tm3+ ion pair provides the UCPL optical property; the Gd3+ ions in the epitaxial shell provide the ability for T1 MR imaging; the Lu3+ ions in the
core host lattice lead to strong absorption of X-ray to enable for CT imaging, and the 153Sm in the shell (half-life, 46.3 hours) is a radioisotope which
produces gamma rays for SPECT imaging. Reproduced with permission from ref. 186. Copyright 2013 American Chemical Society.

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UCNPs (NaYF4:Yb,Er@SiO2) served as a photoluminescent core. the use of a biological model, which is needed to assess the
Ag nanoparticles in situ grown on a silica layer with different potential use of these photon nanoconverters in biomedical field.
kinds of Raman reporters adsorbed on the surface formed an Recently, light-regulated release in vitro and in vivo has been
SERS-functional layer, while the last layer of denatured bovin shown by a number of groups, using nonepitaxial UCNPs@silica
serum albumin (dBSA) was coated on the tag UCPL/SERS tag to nanostructures which have strong NIR-to-UV upconversion, and
improve the colloidal stability and biocompatibility. The com- provide an adequate space (mesopores and the surface) in the
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bined UCPL/SERS imaging modalities with the synthesized silica shell to hold pertinent molecules (genetic materials,
nanoprobes were demonstrated in vitro and in vivo.187 In another chemotherapeutic drugs, etc.). Another important advantage
recent report, the UCPL signal provided by UCNPs in a core–shell of the core–shell structure is the nanoscale distance between
nanostructure was shown to be partly converted to the high the light-sensitive molecules in the silica shell and the core
photoacoustic (PA) signal which can be utilized in the photo- UCNPs that can allow for an efficient photoactivation process.
acoustic tomography (PAT).188 The core UCNPs (NaYF4:Yb3+,Er3+) The involved light-activatable molecules can be either a caged
were coated with a shell of a-cyclodextrin (a-CD). The UCPL molecule, one moiety of which can be cleaved upon UV irradia-
signal for UCNPs-a-CD core–shell nanoparticles dispersed in tion to release (or uncage), or a photoisomerizable molecule,
water was found to be noticeably quenched in comparison with the structure or spatial conformation of which can be changed
that from the core alone UCNPs dispersed in cyclohexane. At the upon UV irradiation. Zhang et al. reported on mesoporous silica
same time, the PA signal from the UCNPs-a-CD nanoparticles coated NIR-to-UV NaYF4:Yb3+/Tm3+@NaYF4 nanostructures to
under 980 nm excitation was greatly enhanced, permitting use of release the photocaged nucleic acids in much deeper tissues
these nanoparticles as efficient probes for PAT in vivo. It is compared to conventional systems (Fig. 15A and B).27 The use of
suggested that UCPL quenching in UC-a-CD in aqueous solution, photo-uncaging processes has also been reported by Xing et al.,
resulted from non-radiative relaxation of the excited states, lead- Li et al., as well as by us for light-controlled release using various
ing to an increase in intrinsic heat generation under 980 nm core–shell nanostructures.66,197,198 Shi et al. reported on in vitro
excitation and subsequent PA signal enhancement. control of Dox drug release using NaYF4:Yb3+/Tm3+@NaYF4
With their multiple imaging capabilities, UCNPs are able to coated with an azo-modified mesoporous silica, which exploits
provide a powerful nanocarrier platform for imaging guided the NIR-to-UV light-controlled trans–cis photoisomerization of
drug delivery. Using the hierarchical core–shell approach, the azo molecules grafted in the mesopore network of a mesoporous
UCNPs-based multifunctional nanoparticles can be not only silica layer (Fig. 15C and D).155 Real time monitoring of NIR-to-
endowed with UCPL, MR and CT imaging abilities, but also UV drug release in vitro and in vivo using simultaneous UCPL
loaded with a therapeutic agent, serving as nanocarriers for and MRI imaging has also been demonstrated by them using
targeted, imaging guided drug delivery.189–191 NaYF4:Yb3+/Tm3+@NaGdF4 UCNPs coated with an azo-modified
5.1.3. NIR-light controlled photoactivation and drug release. mesoporous silica.161 It is worth noting that epitaxial core–shell
This section focuses on the application of core–shell UCNPs as NIR-to-UV UCNPs are preferred for these light-regulated pro-
NIR-to-UV photon nanoconverters to initiate a UV-mediated cesses, as it can deliver more UV light for use than UCNPs that
photochemical process in situ. The UV-triggered photochemistry are devoid of an epitaxial shell, mainly due to the higher UC
can be potentially applied to control chemical reactivity with a efficiency.
spatial and temporal precision for the widest application range. 5.1.4. Photodynamic therapy. Photodynamic therapy (PDT)
However, its practical usage is significantly limited by problems is an important noninvasive treatment modality of cancer and
associated with the delivery of UV light to the reaction site. other diseases, which is conducted using light-sensitive com-
In the case of biological systems, that would be a severe photo- pounds called photosensitizers (PS) or PDT drugs. PS are non-
toxicity and considerably limited penetration depth of UV light in toxic in the ‘‘dark’’, not the light-activated state, but become
biological media.2,66 The utilization of biocompatible, deep pene- cytotoxic, generating reactive species (e.g., excited state of
trating NIR light for in situ generation of UV light by the UCNPs is molecular oxygen, 1O2,), upon exposure to light of appropriate
expected to provide powerful leverage in chemical biology, since wavelengths matching PS optical absorption.123 PDT has been
such photon nanoconverters can spatiotemporally restrict photo- approved by the Food and Drug Administration in the United
chemical reactions in the nanometer regime with minimal photo- States as well as by equivalent agencies in other countries for
damage, enable exceptional light penetration depth, and produce treatment of certain types of cancer as well as for macular
desired photochemical effects with a precise control. degeneration and some skin diseases.167 The photosensitizers
The importance of NIR-to-UV UC for photochemistry was used in conventional PDT are mostly activated by visible light,
first illustrated by Branda et al. who showed photoswitching which has limited penetration through a biological tissue
in dithienylethene using either the NaYF4:Yb3+/Tm3+ and (consult Fig. 16a). Therefore, the application of these visible
the NaYF4:Yb3+/Tm3+@NaYF4:Yb3+/Er3+@NaYF4 core–shell–shell light photosensitizers is limited to treating surface tumors on
UCNPs.192,193 They also demonstrated photo-release of caged or just below the skin or on the lining of internal organs or
compounds,194 photo-release of bio macromolecules from cavities, and is consequently less effective when treating deep
hydrogels,195 as well as dissociation of block copolymer and thick tumors. As NIR light in the range of B700–1100 nm
micelles using epitaxial core–shell NaYF4:Yb3+/Tm3+@NaYF4 has a much greater penetration depth in tissues than the visible
NIR-to-UV UCNPs.196 However, none of these reports involves light, the NIR-excitable UCNPs can efficiently convert the deep

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Fig. 15 NIR light-controlled release of (A, B) genetic materials using photo-uncaging, and (C, D) the chemotherapeutic drug doxorubicin (Dox), using a
photomechanical path. (A) Plasmid DNA and siRNA are caged with DMNPE and then uncaged by NIR-to-UV light conversion by the core–shell UCNPs–
silica nanostructure. The inset shows the penetration depth of UV and NIR light in the skin. (B) Loading of caged plasmid DNA–siRNA into the mesopores
of the core–shell UCNPs–silica nanostructure. (C) Synthetic procedure for an epitaxial core–shell upconverting nanoparticle coated with a mesoporous
silica outer layer. (D) NIR light-triggered Dox release by the NIR-to-UV conversion, which causes trans–cis photoisomerization of azo molecules grafted
in the mesopore network of a mesoporous silica layer. Reproduced with permission from ref. 27 and 155. Copyright 2012 National Academy of Sciences,
and 2013 John Wiley and Sons.

Fig. 16 (a) Schematic illustration of the penetration depth of different wavelength in a tissue model; (b) upconversion nanoparticle as a frequency
conversion nanotransducer to convert the NIR excitation to visible illumination for activation of photosensitizers, producing reactive singlet molecular
oxygen for photochemical treatment of diseased sites.

penetrating NIR light within this window to visible or UV UCNP-photosensitizer systems has been established for in vitro
wavelengths that can excite conventional photosensitizers to PDT201,202 A general non-epitaxial core–shell structure has been
produce a cytotoxic agent promising their application in PDT of utilized, where UCNPs constitute the core and the photosensitizer
thick tumors.123 contained in silica or a polymer as the shell. We illustrate these
Though the potential of UC PDT for deep tissues was pointed core–shell nanostructures in Fig. 16b, based on the typically used
out earlier,167 the inability to achieve efficient upconversion in mesoporous silica coated UCNPs. A close proximity between the
water dispersible nanoparticles has been limiting its use in PDT photosensitizer/s encased in the mesoporous silica shell and
until recently.199 Taking advantage of an efficient energy transfer the UCNP core allows for energy transfer from the core to the
(a mechanism of Luminescence Resonance Energy Transfer, photosensitizers, thereby activating the photosensitizers to
LRET)200 from blue, green, and red emitting UCNPs to photo- generate cytotoxic species (1O2) from oxygen molecules, which
sensitizers with appropriate absorption, a broad spectrum of exist in the environment in its ground electronic state (3O2).

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In vivo UC PDT was first demonstrated by Liu et al. using band gap cell from 28.2% to 33.5–43.6%.206 Potential impacts
PEGylated amphiphilic polymer-coated hexagonal NaYF4:Yb3+/ of UC are now fueling the development of appropriate UC
Er3+ UCNPs in association with the chlorine 6 photosensitizer.203 materials and their use in photovoltaics.
However, the tumor-selectivity of this UCNP-photosensitizer UCNPs are able to work efficiently in the NIR range of
nanosystem is not shown in this work due to the lack of a tumor B800–1600 nm. Some of the examples are: (i) Nd3+/Yb3+/
targeting ligand. Also, the employed NaYF4:Yb3+/Er3+ UCNPs Ln3+(Ln = Er, Tm, Ho) are able to harvest photons at
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without an epitaxial shell have lower UC QY which results in B800 nm and then produce visible upconversion at B480,
reduced treatment efficacy. Mesoporous silica-coated NaYF4:Yb3+/ 550, or 650 nm;84,86 (ii) Yb3+/Ln3+(Ln = Er, Tm, Ho) are capable
Er3+ UCNPs with a tumor-targeting agent have been developed, of up-conversion from 980 nm to B480, 550 or B650 nm;207,208
which not only allow selective accumulation in tumor, but also (iii) Ho3+ can upconvert light at B1180 nm to B550 nm and
permit a high loading of photosensitizers (consult Fig. 16b).26,153 B650 nm; (iv) Er3+ can upconvert light at B1500 nm to
Visible UC emission with two main peaks, green (B540 nm) and B550 nm and B650 nm.33,209 The upconversion in NaYF4:Er3+
red (B660 nm), is well matched with the absorption of two powders was shown to significantly improve the response of a
photosensitizers, merocyanine 540 (MC540) and zinc(II) phthalo- silicon solar cell at 1532 nm,210 while the use of LaF3:Yb3+/Er3+
cyanine (ZnPc), thus yielding greater PDT efficacy compared to and YF3:Yb3+/Er3+ UCNPs resulted in an impressive increase in
approaches using a single photosensitizer.26 In vivo studies have the efficiency of dye-sensitized solar cells (DSSCs) at B980 nm.211,212
shown tumor growth inhibition in tumor-bearing mice using We have also reported an improvement of the DSSC efficiency
intratumoral injection of non-targeted UCNPs or intravenous through infiltration of B20 nm colloidal NaYF4:Yb3+/Er3+
injection of UCNPs conjugated with a tumor-targeting agent, UCNPs into the TiO2 pores in the DSSC device. This increase
followed by UC PDT. was ascribed to a combination of the overall increased light
As it is noted above, the use of UCNPs makes possible UCPL absorption of visible solar light by the dye in the DSSC (due to
imaging at an unprecedented depth of more than 3 cm, the light scattering by UCNPs), and the upconversion of NIR
utilizing an excitation of 980 nm and an upconversion emission light absorbed by UCNPs.213 This bifunctional role (scattering/
at 800 nm (see Section 5.1.1).25 It is important to note that while upconversion) was then explored later in a DSSC using non-
during imaging, NIR light goes in (980 nm) and comes out epitaxial core–shell b-NaYF4:Yb3+/Er3+@SiO2 UCNPs (Fig. 17a–c) and
(800 nm), PDT requires only one way for NIR light (i.e., 980 nm) core–shell–shell b-NaYF4:Yb3+/Er3+@SiO2@TiO2 sub-microprisms,
to propagate and excite photosensitizers. This peculiarity has both producing an impressive efficiency increase of 6–11%.214,215
strong implications for the possibility to treat deep-seated It is worth noting that the performance of an inverted polymer
tumors using UC PDT. However, the efficacy of upconversion bulk heterojunction (BHJ) solar cell has also been improved by
PDT strongly depends on the efficiency (brightness) of the utilizing the bifunctional role of NaYF4:Yb3+/Er3+ UCNPs incor-
UCNPs. New designs of high-quality epitaxial core–shell UCNPs porated into a blend of PCDTBT:PCBM (Fig. 17d).216 The use
that outperform present forms with improved optical proper- of epitaxial core–shell hexagonal NaYF4:Yb3+/Er3+@NaYF4
ties are required for PDT in deeper tissues, in particular, at an UCNPs with highly efficient UC was also reported, which can
excitation density lower than B10 1 W cm 2, to compensate enhance the overall DSSC efficiency by B11.9% under AM
for attenuation of the excitation light and make possible PDT of 1.5 sun irradiation.217 Plasmonic core–shell nanostructures of
deeper tissues. NaYF4:Yb3+/Er3+/Gd3+ (18/2/30 mol%) nanorods coated with Au
nanoparticles or an Au shell were prepared and applied to the
5.2. Applications in solar energy harvesting front of a-Si:H solar cells, which resulted in a 16- to 72-fold
The loss of sub-band-gap photons is one of the major obstacles improvement of the photocurrent under 980 nm light in
on the way of improving efficiency of solar cells, as only absorp- comparison with the cell without an upconverter.218 In addition,
tion of photons with energy higher than the band-gap can a novel core–shell NaYF4:Yb3+/Er3+@TiO2 nanoparticle was utilized
generate electron–hole pairs contributing to electric current.33 to prepare the photoelectrode (PE) of a DSSC which showed a
For example, the c-Si solar cells have a low semiconductor band 23.1% enhancement of the energy conversion efficiency when
gap, and thus a relatively small part of solar irradiation is compared with the one with a pure TiO2 PE and 99.1% higher
unabsorbed and thus lost (transmission loss). However, even than the efficiency of the PE from a mixture of the TiO2 and the
in such case, the energy loss still can be as high as B20%.204 NaYF4:Yb3+/Er3+ UCNPs.219 More recently, a hetero-nanostructured
Without altering the already existing designs and merits of a photoanode with core–shell–shell NaYF4:Yb3+/Er3+@NaYF4@TiO2
solar cell, UC technology provides a solution to circumvent this nanostructures embedded in porous photonic crystals has been
transmission loss by converting two or more sub-band-gap prepared for use in CdSe quantum dots sensitized solar cell
photons into one above-band-gap photon. Indeed, theoretical (Fig. 17e).220
calculations indicate that the Shockley–Queisser efficiency Despite recent progress in the application of a range of novel
limit for a c-silicon solar cell can be increased from B30% to and efficient core–shell UCNPs in different types of solar cells,
40.2%, when combined with ideal upconverters under non- up to now the reported improvement of the overall solar cell
concentrated air mass (AM) 1.5 solar irradiation.205 Moreover, even efficiency remains rather limited. This is mainly because of two
with a very narrow absorption bandwidth between 0.1–0.5 eV, limitations. First of them is that the UC efficiency of current
upconverters can boost the Shockley–Queisser efficiency of a 1.7 eV core–shell UCNPs is still far from perfect, as most of the absorbed

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Fig. 17 (a) Principle of use of photon upconversion provided by core–shell b-NaYF4:Yb3+/Er3+@SiO2 UCNPs in the photoelectrode of a DSSC.
Upconversion luminescence of a photoelectrode with (c) and without (b) core–shell UCNPs confirmed the existence of core–shell UCNPs in the photo
electrode. (d) The structure of an inverted polymer solar cell device which incorporates UCNPs, along with the corresponding energy level structure.
(e) Energy flow in hetero-nanostructures from NaYF4:Yb3+/Er3+@NaYF4 core–shell UCNPs to visible light-absorbing CdSe nanoparticles to TiO2 photonic
structures upon near-infrared photoexcitation. Energy diagram illustrating charge injection from excited CdSe into TiO2 and the transport of
photoinjected electrons to the electrode surface for hydrogen generation. Reproduced with permission from ref. 214, 216 and 220. Copyright 2014
Royal Society of Chemistry. Copyright 2014 Elsevier. Copyright 2013 John Wiley and Sons.

NIR light still cannot be efficiently converted into visible range. collectively upconverted by a set of lanthanide ions. A straight-
Particularly, the efficiency of most current UCNPs is extremely low forward method to broaden the range of spectral sensitivity of
under AM 1.5 solar irradiation due to a low spectral sun irradiance UCNPs is to prepare a core–multiple shell nanostructure in
on the order of B1 W m 2 nm 1 or B0.01 W cm 2 nm 1. For which several types of lanthanide ions are separately doped into
laser irradiance close to sun irradiance, the reported highest the core nanoparticles or in spatially isolated different shell layers
UC QY is B0.6% in alpha-(NaYbF4:0.5%Tm3+)@CaF2 core–shell (Fig. 2c). This design minimizes any possible cross relaxation
UCNPs for an excitation of 0.3 W cm 2.25 Design and fabrica- between different types of lanthanide activators, and thus ensures
tion of UCNPs which will be much more efficient UCNPs under a relatively high efficiency, while spectrally broadening the NIR
low light irradiance is needed; this can be potentially achieved light harvesting (see Section 2.2). In addition, dye-sensitized
through nanophotonic control of utilizing a hierarchical core– upconversion in lanthanides circumvents the drawback of low
shell structure. The second limitation arises from the narrow, and narrow absorption of lanthanide ions, opening up the
discrete, and rather weak absorption of doped lanthanide ion possibility of using an antenna effect to implement broad-
owing to the nature of f–f transition. This severely restricts the band upconversion.80
harvesting capabilities of nanomaterials doped with lanthanide
ions of the same type. The calculations by Briggs et al., however, 5.3. Security encoding applications
revealed that the lanthanide-based upconverters can signifi- The UV-excitable Stokes fluorescence from organic dyes (i.e.,
cantly increase cell efficiencies from 28% to over 34% with UV-to-VIS downconversion) has been used for protection against
improved quantum yield, despite their narrow bandwidths. counterfeiting of bills, checks and other securities (e.g., as well as
Should upconverter quantum yields be boosted beyond their for fingerprint detection). However, the problem with the appli-
current values, cell efficiency enhancement of several absolute cation of organic dye fluorescence in anti-counterfeiting is that
percent is predicted for the efficiency of a solar cell. These it is easy to duplicate and fake. The fingerprint application of
calculations highlight the promise of upconversion for photo- organic fluorophores suffers from background fluorescence and
voltaics and stress the critical roles of upconverter absorption, selectivity at the expense of generality. Since the naked eye is
bandwidth and quantum yield in the push towards technological sensitive in the visible range, while having no response to the
viability.206 Thus, development of efficient UC materials that NIR light, this recognition offers an opportunity to address the
are broadly responsive to infrared light is in need. Fortunately, security and the fingerprint detection applications by utilization
a number of wavelengths in the range of 800–1550 nm can be of NIR-to-visible UCPL. Indeed, an encrypted 3D pattern that is

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Fig. 18 (a) The printed image secured with high Tm3+ containing UCNPs, which becomes visible when high laser power density (B106 W cm 2) is
utilized. (b) Imaging of encoded UCNPs with portable (Apple iPhone 4S) decoder in challenging settings (from left to right, pharmaceutical blister packs,
currency, and credit cards). Top: image acquisition using a portable decoder, middle and bottom: acquired image when exposed to 1 W 980 nm laser
excitation (middle) and in the absence of NIR excitation (bottom). Reproduced with permission from ref. 171 and 173. Copyright 2013 and 2014 Nature
Publishing Group.

invisible to a human eye under regular illumination, but flares increase upconversion luminescence intensity by orders of
up at a specific wavelength (i.e., a laser diode of a specific magnitude (see Section 2). As a result, the use of epitaxial core–
wavelength), provides a unique way to secure the object. shell UCNPs in future studies will facilitate optical detection of
Using traditional photolithography, we fabricated a well-defined secured patterns with considerably improved detection limit.
pattern with single or multiple layers (3-D) from NaYF4:Er3+/Yb3+
and NaYF4:Tm3+/Yb3+ UCNPs with the specifically modified surface.
These security patterns became visible to the naked eye when 6. Concluding remarks
irradiated by a laser diode at B975 nm, illustrating elegance
suitability of UCNPs for security.28 More recently, Meruga et al. In this review, we have summarized nanophotonic approaches
developed a specially tailored ink, which comprised oleic to control the excitation dynamics in core–shell upconversion
acid-capped NaYF4:Er3+/Yb3+ and NaYF4:Tm3+/Yb3+ UCNPs in nanoparticles (UCNPs), and various synthetic nanochemistries to
toluene and methyl benzoate with poly(methyl methacrylate) as prepare epitaxial and non-epitaxial core–shell UCNPs. A range of
the binding agent. The ink was used to print quick response advanced characterization tools to provide indirect or direct
codes, which can be scanned by a smart phone.221 Jin et al. also evidences for the formation of a core–shell structure is also
demonstrated the utilization of high Tm3+ containing UCNPs described to generate guidelines for the UC field. We have also
for security printing use under an extremely high excitation presented some exciting examples of the emerging utilization of
density (on the order of B106 W cm 2) to produce an ultrabright core–shell UCNPs for photonic applications, such as high contrast
visible upconverted emission for detection (Fig. 18a).222 Ressier deep optical bioimaging, multimodal bioimaging, light-regulated
et al. used atomic force microscopy (AFM) nanoxerography to photoactivation and drug release, photodynamic therapy, solar
fabricate micrometer sized quick response codes through 3D energy conversion and security applications. Indeed, a core–shell
close-packed assemblies of core–shell (NaYF4:Gd3+/Yb3+/Er3+)/ structure provides numerous opportunities to manipulate excita-
NaYF4 UCNPs.223 Importantly, Lee et al. reported a facile encod- tion, energy transfer, and the emission, to tune desired UC
ing strategy that combines spatial patterning with UCNPs using properties for improving technology in a pertinent way. The
polymers, single-wavelength NIR excitation and portable charge ability to incorporate a broad range of imaging and therapeutic
coupled device (CCD)-based decoding to distinguish particles modalities into a single conduct, along with the capability of
patterned by means of flow lithography (Fig. 18b).224 Yuan et al. surface engineering for molecular targeting, promise their
showed that UCNPs functionalized with a lysozyme-binding usage in the emerging field of theranostic applications for next
aptamer can be used to detect fingerprints through recognizing generation personalized medicine. However, there still exist
lysozyme in the fingerprint ridges.225 This extends the security use technical challenges for core–shell UCNPs, some of which are
of UCNPs to fingerprinting, which have long been utilized as one listed here:
of the most useful types of physical evidence and also utilized in (i) The reported UC QY for core–shell UCNPs remains rather
areas such as forensic investigations and access control. limited for all in vivo uses (including optical imaging, PDT,
Most of the reported security application studies have as well as for light-regulated photoactivation or drug release)
utilized lanthanide-doped core UCNPs without any epitaxial especially under low irradiance of B0.1 W cm 2. This value is
shell. It is known that an epitaxial core–shell structure is able to close to the safety threshold (B0.73 W cm 2 for the 980 nm

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cw laser diode when applied to the human skin, according to the might result in much more efficient UCPL. Moreover, the absolute
American National Standard for Safe Use of Lasers). Moreover, a efficiency of most of the current systems remains unassessed,
significant attenuation in the tissue will result in a significantly suggesting necessity of a spotlight research to allow comprehen-
lower irradiance value than the threshold, when the excitation sive comparison of Nd3+/Yb3+ containing UCNPs with the typically
light reaches the UCNPs inside the tissue. To date, the reported used Yb3+-containing core or core–shell UCNPs.
highest UCQY for nanostructures is 7.6% for (LiLuF4:Yb3+/ (v) The integration of a broad spectrum of imaging modalities
Published on 22 October 2014. Downloaded by Indian Institute of Technology Chennai on 3/5/2024 [Link] AM.

Tm3+)@LiLuF4 core–shell UCNPs at an excitation density of such as optical imaging, MRI, PET, SPECT and CT into a single
127 W cm 2.61 Due to the strong dependence on the excitation nanoparticle platform, may provide complementary information
density, this UC QY will become significantly lower at to allow accurate comprehensive diagnostics in a reduced time
B0.1 W cm 2. The alpha-(NaYbF4:0.5%Tm3+)@CaF2 core–shell frame. Moreover, the ability to incorporate therapeutic entities in
UCNPs were reported to display a UC QY of 0.6% under an a non-epitaxial shell produces opportunities for imaging-guided
excitation of 0.3 W cm 2, but that is still not satisfactory. therapy as well as for real-time assessment of a therapeutic effect.
Nanophotonic approaches to control the excitation dynamics of With this hierarchical core–shell approach, introduction of bio-
core–shell UCNPs to produce adequate UCQY under irradiation of molecules (which can help nanoparticles to cross various bio-
B0.1 W cm 2 will be appealing for all types of in vivo applications. logical barriers and target an intended site through a molecular
(ii) The core–shell UCNPs have limited light harvesting recognition mechanism) onto the surface of multimodal or multi-
ability, reducing their brightness for various bioapplications, functional core–shell nanostructures will be more beneficial.
as well as their use in solar cells. The absorption band for each
type of lanthanide ion is quite narrow and low because of the
nature of the involved f–f transition, and it is specific for the Abbreviations
lanthanide element, severely limiting the infrared light harvest-
UC Upconversion
ing capability. It will be attractive to utilize a core–multiple
IR Infrared
shell structure (Fig. 2c) to incorporate a set of lanthanide ions
UCNPs Upconversion nanoparticles
into the core as well as the shells to collectively broaden the
NIR Near infrared
absorption of NIR light, without introducing cross relaxation
PL Photoluminescence
processes. Moreover, the combined use of two or more NIR dyes
PDT Photodynamic therapy
to sensitize the f–f transition will also be attractive, harvesting a
PTT Photothermal therapy
broad range of NIR light.
LSPR Localized surface plasmon resonance
(iii) Concentration quenching of the emitters, typically pro-
QY Quantum yield
duced by the cross relaxation processes, sets a serious limita-
MRI Magnetic resonance imaging
tion on the improvement of the brightness of UCNPs by simply
CT Computed tomography
increasing the concentration. Despite recent results having
PET Positron emission tomography
shown that the concentration quenching can be removed or
SPECT Single-photon emission computed tomography
reduced under high irradiance at B106 W cm 2 (mainly because
PA Photoacoustic
high irradiance can activate the lanthanides at a rate higher than
TEOS Tetraethyl orthosilicate
the quenching rate), the concentration quenching effect still
APTES (3-Aminopropyl)triethoxysilane
dominates for the low excitation power density.222,226 The neces-
CTAB Cetyl trimethylammonium bromide
sity of high irradiance might limit the UCNP use in a number of
CTAC Hexadecyl trimethyl ammonium chloride
applications, restricting its appeal. A core–shell nanostructure is
PVP Polyvinylpyrrolidone
effective in eliminating the deleterious cross relaxations, as well
XRD X-ray diffraction
as in suppression of surface-related quenching mechanisms. As
TEM Transmission electron microscopy
a consequence, it will be advantageous to utilize a core–multiple
XPS X-ray photoelectron spectroscopy
shell structure to incorporate a high concentration of activators/
HAADF High-angle annular dark-field
emitters without concentration quenching, and also to produce
STEM Scanning transmission electron microscopy
an ultra-bright core–shell UCNPs under both low and high laser
EELS Electron energy loss spectroscopy
irradiance.
EDX Energy-dispersive X-ray spectroscopy
(iv) To reduce the possible heat-induced effects in an aqueous-
CCD Charge coupled device
based environment, the commonly used excitation wavelength of
B980 nm (for Yb3+-containing UCNPs) is reported to be success-
fully shifted to B800 nm, using a core–shell structure incorporat- Acknowledgements
ing the Nd3+ ions to sensitize Yb3+ ions (consult Section 2.3).
This opens up new possibilities to explore the use of Nd3+/Yb3+ This work was supported by the grants from the Air Force Office
containing UCNPs for a range of applications. Since the UC of Scientific Research (Grant No. 95500910361), the Swedish
efficiency in this system relies on the efficiency of energy Energy Agency (project 32076-1), the Natural Science Founda-
transfer from the Nd3+ ions in the shell to the Yb3+ ions in tion of China (Grant No. 51102066), the Fundamental Research
the core, a careful engineering of the energy transfer process Funds for the Central Universities, and the Program for Basic

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