Heteroepitaxial Growth of Multiblock Ln-MOF Microrods for Photonic Barcodes

Article abstract of DOI:10.1002/anie.201907433

Micro/nanoscale multicolor barcodes with unique identifiability and a small footprint play significant roles in applications such as multiplexed labeling and tracking systems. Now, a strategy is reported to design multicolor photonic barcodes based on 1D Ln-MOF multiblock heterostructures, where the domain-controlled emissive colors and different block lengths constitute the fingerprint of a corresponding heterostructure. The excellent heteroepitaxial growth characteristics of MOFs enable the effective modulation of the coding structures, thereby remarkably increasing the encoding capacity. The as-prepared multicolor barcodes enable an efficient authentication and exhibit great potential in fulfilling the functions of anti-counterfeiting, information security, and so on. The results will pave an avenue to novel hybrid MOFs for optical data recording and security labels.

Full text of DOI:10.1002/anie.201907433

A Journal of the Gesellschaft Deutscher Chemiker
Angewandte
International Edition Chemie
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Accepted Article
Title: Heteroepitaxial Growth of Multiblock Ln-MOF Microrods for
Photonic Barcodes
Authors: Yong Sheng Zhao, Yinan Yao, Zhenhua Gao, Yuanchao Lv,
Xianqing Lin, Yingying Liu, Yuxiang Du, and Fengqin Hu
This manuscript has been accepted after peer review and appears as an
Accepted Article online prior to editing, proofing, and formal publication
of the final Version of Record (VoR). This work is currently citable by
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content of this Accepted Article.
To be cited as: Angew. Chem. Int. Ed. 10.1002/anie.201907433
Angew. Chem. 10.1002/ange.201907433
Link to VoR: http://dx.doi.org/10.1002/anie.201907433
http://dx.doi.org/10.1002/ange.201907433

Angewandte Chemie International Edition
10.1002/anie.201907433
COMMUNICATION
Heteroepitaxial Growth of Multiblock Ln-MOF Microrods for
Photonic Barcodes
+
+
Yinan Yao , Zhenhua Gao , Yuanchao Lv, Xianqing Lin, Yingying Liu, Yuxiang Du, Fengqin Hu,* and
Yong Sheng Zhao*
Abstract: Micro/nanoscale multicolor barcodes with unique
identifiability and small footprint play significant roles in
applications such as multiplexed labeling and tracking systems. In
this work, we report strategy to design multicolor photonic
materials constructed from metal ions and organic linkers,[6] not
only possess the high stability of inorganic materials but also
ensure the excellent processability of organic materials,
representing an effective solution to the above problems. For
example, the outstanding ability to flexibly self-assemble into
various 1D micro/nanostructures,[7] such as wires, tubes, and rod,
makes MOFs a fundamental model for designing novel optical
barcodes. The versatile spectra from luminescent MOFs, which
origins from the organic ligand or metal ion, enable the
generation of a large library of optical encoding.[8] In addition, the
excellent compatibility of MOFs allows for fabricating hybrid
nanostructures, making it possible to integrate different
identifiable patterns in a single nanostructure. Especially,
incorporating diverse lanthanide (Ln) ions with a series of well-
resolved emission peaks, would offer a good platform for digital
encoding.[10] Therefore, the 1D Ln-MOF heterostructures would
provide an innovative encoding scheme for the development of
multicolor barcodes with high coding capacity.
a
a
barcodes based on 1D Ln-MOF multiblock heterostructures, where
the domain-controlled emissive colors and different block lengths
constitute the fingerprint of a corresponding heterostructure. The
excellent heteroepitaxial growth characteristics of MOFs enable the
effective modulation of the coding structures, thereby remarkably
increasing the encoding capacity. The as-prepared multicolor
barcodes enable an efficient authentication and exhibit great
potential in fulfilling the functions of anti-counterfeiting, information
security, and so on. The results will pave an avenue to novel hybrid
MOFs for optical data recording and security labels.
[
9]
Micro/nanoscale barcodes have attracted great attention due to
their promising applications in multiplexed bioassays, materials
tracking, and information security.[
1]
The ever-increasing
Herein, we propose a strategy to design microscale barcodes
with high coding capacity based on the 1D Ln-MOF multiblock
heterostructures, which were prepared through a stepwise
epitaxial growth. The as-prepared Ln-MOF heterostructures
exhibit the domain-controlled emissive colors and identifiable
block lengths, which constitutes the intrinsic fingerprint of a
heterostructure and allows for the definition of a practical
barcode. Furthermore, the well controllable growth of Ln-MOFs
enabled us to obtain distinct barcodes through tuning the block
lengths and the number of blocks in the heterostructures, which
remarkably enlarges the encoding capacity. The as-designed
microscale barcodes facilitate an efficient authentication and
exhibit great potential in fulfilling data recording and information
tracking. These results offer a comprehensive understanding of
the function-oriented construction of hybrid MOF materials and
open up a new way to achieve miniaturized security labels.
The strategy for multicolor barcodes based on Ln-MOF
heterostructures is schematically illustrated in Figure 1a. Under
UV radiation, spatially separated colors are emitted along the 1D
Ln-MOF heterostructures. When each segment of the
heterostructure is excited locally with a focused laser beam, the
photoluminescence (PL) spectra of each block exhibits the
specific sharp peaks corresponding to characteristic emission
bands of the Ln ion, which constitutes a fingerprint of the
structure and might be utilized to create a multicolor barcode.
Moreover, the doping flexibility during the growth of MOFs
allows to modulate the geometry of the heterostructures by
alternately introducing different Ln ions, which may endow the
multicolor barcodes with high coding capacity. Therefore,
controlled preparation of 1D Ln-MOF heterostructures with
axially tunable composition is a necessary prerequisite for
producing multicolor barcodes.
demand for high security level in anti-counterfeiting applications
calls for micro/nanoscale multicolor barcodes with accurate
recognition and high encoding capacity.[2] One-dimensional (1D)
segmented structures with domain-controlled colors, can be
readily distinguished by the identifiable patterns, which have
shown great potential for achieving multicolor barcodes.[
Recently, the 1D segmented structures have been demonstrated
in inorganic semiconductors through integrating emitting
components with distinct optical bandgaps. Unfortunately,
these materials with strong covalent or ionic bonds always
require fabrication conditions of (ultra-)high temperature and
vacuum. Compared with their inorganic counterparts, organic
materials, with excellent flexibility and processability, have also
been utilized to construct numerous 1D segmented structures
with various optoelectronic functionalities.[5] However, the
fabricated structures often suffer from low thermal instability due
to the weak intermolecular interactions, which would hinder their
practical applications.
3]
[4]
Metal-organic frameworks (MOFs),
a kind of crystalline
[
[
a]
Y. Yao[+], Prof. F.Hu
College of Chemistry,
Beijing Normal University,
Beijing 100875, China
E-mail: fqhu@bnu.edu.cn.
Dr Z. Gao[+], Dr. Y. Lv, Dr. X. Lin, Y. Liu, Y, Du, Prof. Y. S. Zhao
Key Laboratory of Photochemistry,
b]
Institute of Chemistry, Chinese Academy of Sciences,
Beijing 100190, China
University of Chinese Academy of Sciences, Beijing 100049, China
E-mail: yszhao@iccas.ac.cn
These authors contributed equally to this work.
Supporting information for this article is given via a link at the end of
the document.
[+
]
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Angewandte Chemie International Edition
10.1002/anie.201907433
COMMUNICATION
Here, 1,3,5-benzenetricarboxylic acid (BTC) was selected as
organic linker to construct 1D Ln-MOF heterostructures due to
the following reasons: (1) the self-assembly of BTC and Ln ions
would benefit the construction of 1D microrod owing to their 1D
preferential packing interactions (Figure S1-2),[7b] providing the
fundamental building blocks for the fabrication of 1D Ln-MOF
heterostructures; (2) the Ln-BTC MOFs exhibit characteristic
lanthanide-centre luminescence due to the effective ligand-to-
metal energy transfer process (Figure S3); (3) different Ln-BTC
MOFs with distinct emission characteristics show the
isomorphous structures (Figure 1b, Table S1). making it possible
to realize the 1D multicolor Ln-MOF heterostructures without
lattice mismatch;[11] (4) The Ln-MOFs demonstrate excellent
thermostability and high stibility under various environments,
which enable their applications as security labels (Figure S4-6).
finally obtained. As shown in Figure 1d, the as-assembled Ln-
MOF
microstructures
exhibit
red-green-red
triblock
heterostructures under UV radiation, which confirmed the
successful epitaxial growth of the preformed MOFs. The
scanning electron microscopy (SEM) image (Figure S8) reveals
that the Ln-MOF heterostructures exhibit 1D microrod-like
morphology with smooth and continuous surface, confirming the
strong coordination interaction at interfaces without lattice
mismatch.
According to the step-by-step assembly process, the emissive
color of each segment strongly depends on the composition of
the corresponding block. Therefore, by adjusting the emissive
centers in each segment, we could modulate the diversity of the
multicolor heterostructures. For instance, the green-red-green
triblock heterostructures can be further acquired by changing the
addition sequence of the Ln ions precursors into the reaction
(
Figure 1e). In addition, PL of the mixed Ln-MOFs has been
a
b
Tb-BTC
Pump light
proved to be tuned through controlling the proportional variation
of Eu3+ and Tb3+ in the host frameworks.[12] Here, the mixed Ln-
MOFs with highly efficient orange luminescence were fabricated
by co-doping Eu3+ ions into the Tb-BTC host microrods (Figure
S9). The elemental mapping results indicate that the Eu
distribution is nearly overlapped with Tb mapping, suggesting
Eu-BTC
Simulated Tb-BTC
＋
＋
10
20
30
40
50
3+
that Eu ions are well dispersed within the Tb-BTC microrods
Two theta / degree
Eu3+ ion
Tb3+ ion
(Figure S10). The obtained mixed Ln-MOFs can subsequently
act as seeds for the epitaxial growth of the Eu-MOFs, resulting
in the formation of the red-orange-red triblock heterostructures
(Figure 1f). These as-prepared multicolor microstructures exhibit
excellent emissive colors, which should be attributed to the
efficient ligand-to-metal energy transfer in each segment.
c
d
Organic ligand
MOF
2
precursor
MOF
1
seed
Epitaxial growth
Eu@Tb-MOF
MOF
2
on MOF
1
Tb@Eu-MOF
e
f
Eu/Tb@Eu-MOF
a
3.5
2
S
1
ISC
ET
T
1
5D
4
5D
0
S
0
7
FJ
7
FJ
0
Figure 1. (a) Schematic illustration of a multicolor barcode based on a single
Ln-MOF heterostructure. (b) X-ray powder diffraction (XRD) patterns of the
simulated Tb-BTC, the Ln-BTC. The XRD patterns of Ln-BTC powder well
match those of the simulated results from the single crystal diffraction of Tb-
BTC, clearly indicating that pure Ln-BTC phase was obtained and the two
kinds of MOFs have the isomorphous structures. (c) Schematic representation
of the epitaxial growth process in a solvothermal reactor containing seeding
crystals, BTC and different Ln ions. (d-f) PL images of the triblock
heterostructures showing visually emissive colors. UV band (330-380 nm) of a
mercury lamp was used to excite the samples. Scale bars are 10 μm.
Ligand
Tb3+
Eu3+
b
d
c
Scan
Spot
1
2
1’
Spot 1
5
e
Spot 2
f
SS pp oo tt 11 ’’
5
D0
7F
5D
7F
D0
7F
5D
7F
5D
4
2
5D
5D
7F
5D
7F
2
5D
7F
7F
5D
7F
0
4
5
4
4
0
5D
7F
5D
7F
0
0
0
0
7F
4
6
4
3
4
1
3
1
3
The 1D multicolor Ln-MOF heterostructures were fabricated
via a facile stepwise solvothermal synthesis (Figure 1c). In a
typical preparation, Tb-MOFs with green emitting colors were
initially synthesized, which can be used as seeds for the growth
of the second MOF. Then the solution of Eu ions was
subsequently added into the as-prepared Tb-MOF microcrystals.
The isostructural Ln-MOFs with high crystallinity can be
beneficial for the epitaxial growth of the Eu-MOFs (Figure S7).
After aging for 2 hours, the hybrid Ln-MOF microstructures were
5
00
600
700
800 400
500
600
700 500
600
700
80
Wavelength (nm)
Wavelength (nm)
Wavelength (nm)
3+
Figure 2. (a) Jablonsky energy level diagram for schematic illustration of the
ligand-to-metal energy transfer process. (b) Bright-field and PL images of a
Ln-MOF heterostructure. Scale bar is 10 μm. (c) Schematic illustration of a
heterostructure excited with a focused laser beam. (d-f) The corresponding PL
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COMMUNICATION
spectra collected from three different areas (marked as 1, 2, 1’ shown in
Figure 2c).
information of a specific barcode strongly depends on both the
PL spectra and block length of each segment. Therefore,
effective modulation of the coding structures is essential to the
generation of distinct barcodes.
Figure 2a depicted the energy transfer process between BTC
and Ln ions according to their intrinsic energy levels. The
organic ligand BTC with high molar absorption coefficient can
efficiently absorb the energy of the excitation light, resulting in
According to the above-mentioned growth mechanism, the Ln-
MOF heterostructures with specific block length is resulted from
the flexible co-assembly process of the Ln ions and the organic
ligand. The length of each segment is primarily associated with
the concentration of the precursor solutions. It was found that
the increase of the precursor concentration would induce the
formation of longer 1D MOFs (Figure S13), making it possible to
produce multiblock heterojunctions with tunable length of each
block. In a typical synthesis, the seeds with approximately
uniform length were first synthesized, and subsequently, by
tuning the concentration of the epitaxy precursor solution (the
epitaxy precursor-to-seed molar ratio: 0.3, 0.6, 1.0, respectively),
the red-green-red triblock heterostructures with different block
lengths were successfully obtained (Figure 3b-d). Therefore, the
optimized assembly method provides opportunity for controllably
fabricating diverse Ln-MOF heterostructures, which enables the
production of countless unique and irreproducible barcodes
-
1 [7b]
the transition to its singlet state (30488 cm ). The gap (6098
-
1
-1
cm ) between the singlet and triplet excited states (24390 cm )
of BTC is favorable for an efficient intersystem crossing process,
according to Reinhoudt’s empirical rules.[ Furthermore, the
energy level of the triplet excited state matches well with the D
13]
5
0
3+
5
3+
of Eu and
4
D of Tb , which would facilitate energy transfer
from BTC to these Ln ions, and thus lead to the strong
luminescence with a high quantum yield (Figure S11).
The segregated Ln-MOF heterostructures with recognizable
features provide an opportunity to encode each microstructure.
Taking the Tb@Eu-MOF microcrystal as an example (Figure 2b),
the PL of a single heterostructure at different micro-area was
characterized
photoluminescence system (Figure S12). Each part (marked as
, 2, 1’ in Figure 2c) of the heterostructure was selectively
focused and excited with a continuous-wave (CW) laser beam
375 nm), and the corresponding PL spectra were exhibited in
with
a
home-built
far-field
micro-
(Figure 3e–g).
1
(
Coding Rule
a
Figure 2d-f. The two red-emitting tips (1 and 1’) show a series of
sharp peaks located at about 590, 615, 652 and 700 nm,
+
+
1
2
1’
Encoding
5
7
corresponding to the transitions from D
0
→ F
J
(J = 1, 2, 3 and 4,
d×18%
d×64%
Barcode 2
Barcode 1’
d×18%
respectively) of Eu3+ centers. By contrast, the middle green-
18%
64%
18%
Barcode 1
emitting block (marked as 2) exhibits four sharp peaks located at
about 487, 543, 580 and 620 nm, which are ascribed to the
transitions from D → F (J = 6, 5, 4 and 3, respectively) of the
4 J
Length ratio
ratio=0.3:1
ratio=0.6:1
ratio=1:1
5
7
b
c
d
Tb3+ ions. These sharp peaks constitute the fingerprint of a
specific microstructure; therefore, we can distinguish each
microstructure based on their intrinsic PL spectrum, just like the
recognition of the commodity by a specific barcode. A typical
barcode contains a series of black bars with different widths
representing consecutive digits. The obtained Ln-MOF
heterostructures are ideally suited for spectroscopic encoding
based on these well-resolved PL spectra. Here, the barcodes
are defined as follows: each solid bar is located in the
wavelength position, and the bar width is defined by the relative
PL intensity of the same wavelength. Therefore, the PL
spectrum from each segment can be expediently converted into
a specific barcode, which would enable the digital identification
of each segment in the heterostructure.
e
f
i
g
h Tb3+ ion
j
Organic ligand
k
In addition to the spectroscopic encoding based on the
recognizable PL spectra, each segment with different color-
length endows the heterostructure with length-encoded
character, which provides a platform to develop graphical
encoding. As shown in Figure 3a, according to different block
lengths in the heterostructure, the as-designed barcodes were
compressed with the corresponding length ratio, which can be
defined as the sub-barcodes. The built-up barcode was
subsequently generated by combining the three parts of the sub-
barcodes. There is a one-to-one match between each multicolor
barcode and the Ln-MOF heterostructure, thus we can deduce a
specific barcode from a Ln-MOF heterostructure by integrating
the spectroscopic and graphical encoding. The encoding
Figure 3. (a) Schematic illustration of the encoding strategy based on the Ln-
MOF heterostructure. (b-d) PL images of segmented structure with varied
block lengths. The block length can be precisely controlled by adjusting the
epitaxy precursor-to-seed ratio in the reaction system. Scale bars are 10 μm.
(
e-g) Different barcodes corresponding to the heterostructures in Figure b-d.
(h) Schematic illustration for the epitaxial growth of the penta-block structures.
i) PL image of the 1D penta-block heterojunctions. Scale bar is 5 μm. (j, k)
(
The magnified PL image and corresponding barcode of the structure. Scale
bar is 5 μm.
Benefiting from the flexible stepwise co-assembly process,
the heterojunctions with more blocks might be fabricated via a
multi-step assembly process (Figure 3h), which would further
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Angewandte Chemie International Edition
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COMMUNICATION
with a Ln-MOF heterostructure. (b) PL spectra of the heterostructure collected
from different blocks. (c) Obtained Barcode-1 generated from the spectra
shown in (b) according to the coding rule. An authenticated artwork can
circulate in the supply chain (green arrow). The unknown artwork may be
introduced directly to the purchaser (red arrow). (d) Digital photograph of an
unknown artwork with a heterostructure. (e) PL spectra of the heterostructure
from the unknown artwork. (f) The Barcode-2 generated from the spectra in (e).
increase the coding capacity. For instance, by feeding the
triblock Tb@Eu-MOFs heterostructures again with the precursor
of Tb3+ ions in the reaction system, we were able to synthesize
1D penta-block heterostructures exhibiting alternate green/red
emissions (Figure 3i, j). Based on the proposed coding rule, the
barcode with more encoding information can be generated as
shown in Figure 3k. Considering the diversity and flexibility of
the multicolor-banded microstructures, these tiny barcodes are
expected to be expediently identifiable and difficult to replicate,
showing great potential to function as the “security tag” with
practical anti-counterfeiting applications.[14]
(
g) The comparison between Barcode-1 and Barcode-2 for artwork
authentication.
In summary, we have constructed
a type of Ln-MOF
heterostructure for multicolor barcode. The Ln-MOF
heterostructures were controllably fabricated by using
a
The application of as-prepared Ln-MOF heterostructures as
barcodes in commodity circulation is demonstrated in Figure 4.
As a proof-of-concept illustration, a Ln-MOF heterostructure was
embedded into an artwork as the “security tag” by the
manufacturer (Figure 4a). The corresponding PL spectrum and
length information of each segment were recorded from the Ln-
MOF heterostructure (Figure 4b). According to the coding rule,
the Barcode-1 can be acquired. The Barcode-1 was further input
into a cloud for future reference (Figure 4c), and then the
artwork, together with the tag, went into circulation (green arrow).
The Barcode-2 can be obtained by means of encoder from the
heterostructure and input into the cloud for an online inquiry
stepwise heteroepitaxial growth. The as-prepared Ln-MOF
demonstrated distinct multiblock emissive colors that constitute
a unique signature of the heterostructure and allow for the
definition of a barcode. Different barcodes were designed
through modulating the types of the heterostructure, which can
further increase the coding capacity. Moreover, the as-designed
microscale barcodes can enhance the security as the labels and
exhibit great potential in anti-counterfeiting applications. We
hope these results would provide enlightenment for the rational
design and controllable synthesis of hybrid MOFs with precise
heterostructures for applications of data recording and
information security.
(
Figure 4d-g). If Barcode-2 is consistent with the Barcode-1, the
matching result is TRUE, confirming that the artwork is
authentic; otherwise, the artwork is counterfeit. Furthermore, the
multicolor Ln-MOF barcodes generated from the specific
synthetic methods and encoding rules can enhance the security
protection, which can further be extended to other secret media,
such as identity documents and banknotes.
Acknowledgements
This work was supported financially by the Ministry of Science
and Technology of China (No. 2017YFA0204502), and National
Natural Science Foundation of China (Nos. 21790364 and
21533013).
a
d
Manufacturer
?
Keywords: heteroepitaxial growth • Ln-MOF • metal-organic
framework • photonic barcodes • anti-counterfeiting
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This article is protected by copyright. All rights reserved.

Angewandte Chemie International Edition
10.1002/anie.201907433
COMMUNICATION
COMMUNICATION
+
+
Multicolor photonic barcodes have
been designed based on 1D Ln-MOF
multiblock heterostructures. The
Yinan Yao , Zhenhua Gao , Yuanchao
Lv, Xianqing Lin, Yingying Liu, Yuxiang
Du, Fengqin Hu,* and Yong Sheng
Zhao*
excellent
heteroepitaxial
growth
Heteroepitaxial growth
characteristics of MOFs enable the
effective modulation of the coding
Page No. – Page No.
＋
＋
structures,
thereby
remarkably
Heteroepitaxial Growth of Multiblock
Ln-MOF Microrods for Photonic
Barcodes
increasing the encoding capacity.
The as-prepared multicolor barcodes
enable an efficient authentication
and pave an avenue to novel hybrid
MOFs for optical data recording and
security labels.
Photonic barcodes
Pump light
Encoding
This article is protected by copyright. All rights reserved.