Coordination Polymer Framework Based On-Chip Micro-Supercapacitors with AC Line-Filtering Performance

Article abstract of DOI:10.1002/anie.201700679

On-chip micro-supercapacitors (MSCs) are important Si-compatible power-source backups for miniaturized electronics. Despite their tremendous advantages, current on-chip MSCs require harsh processing conditions and typically perform like resistors when filtering ripples from alternating current (AC). Herein, we demonstrated a facile layer-by-layer method towards on-chip MSCs based on an azulene-bridged coordination polymer framework (PiCBA). Owing to the good carrier mobility (5×10^?3 cm² V^?1 s^?1) of PiCBA, the permanent dipole moment of azulene skeleton, and ultralow band gap of PiCBA, the fabricated MSCs delivered high specific capacitances of up to 34.1 F cm^?3 at 50 mV s^?1 and a high volumetric power density of 1323 W cm^?3. Most importantly, such MCSs exhibited AC line-filtering performance (?73° at 120 Hz) with a short resistance–capacitance constant of circa 0.83 ms.

Full text of DOI:10.1002/anie.201700679

Angewandte
Communications
Chemie
International Edition: DOI: 10.1002/anie.201700679
German Edition: DOI: 10.1002/ange.201700679
Nanotechnology Very Important Paper
Coordination Polymer Framework-Based On-Chip Micro-
Supercapacitors with AC Line-Filtering Performance
Chongqing Yang+, Karl Sebastian Schellhammer+, Frank Ortmann+, Sai Sun+, Renhao Dong,
Melike Karakus, Zoltꢀn Mics, Markus Lçffler, Fan Zhang, Xiaodong Zhuang,*
Enrique Cꢀnovas,* Gianaurelio Cuniberti, Mischa Bonn, and Xinliang Feng*
Abstract: On-chip micro-supercapacitors (MSCs) are impor-
tant Si-compatible power-source backups for miniaturized
electronics. Despite their tremendous advantages, current on-
chip MSCs require harsh processing conditions and typically
perform like resistors when filtering ripples from alternating
current (AC). Herein, we demonstrated a facile layer-by-layer
method towards on-chip MSCs based on an azulene-bridged
coordination polymer framework (PiCBA). Owing to the good
carrier mobility (5 ꢁ 10À3 cm2 VÀ1 sÀ1) of PiCBA, the permanent
dipole moment of azulene skeleton, and ultralow band gap of
PiCBA, the fabricated MSCs delivered high specific capaci-
tances of up to 34.1 FcmÀ3 at 50 mVsÀ1 and a high volumetric
power density of 1323 WcmÀ3. Most importantly, such MCSs
exhibited AC line-filtering performance (À738 at 120 Hz) with
a short resistance–capacitance constant of circa 0.83 ms.
in particular, compatibility with the Si industry.[1b,2] Recent
studies have focused on the thin-film fabrication of MSCs by
using nanostructured functional materials such as gra-
phene,[1d,3] graphene-based nanocomposites,[4] monolithic car-
bide-derived carbon,[1a] mesoporous conducting polymers,[5]
and several other pseudocapacitive materials.[6] However,
most devices based on these materials require harsh process-
ing operation steps such as the high-temperature fabrication
of electrode films, metal electrode deposition, electrode gap
generation by oxygen plasma, and the wet chemistry etching
method. Such procedures lead to the easy cracking and
delamination of active films from substrates, such as with Si
wafers and Kapton films.[1b] Therefore, the development of Si-
compatible MSCs with easy and cheap fabrication procedures
is essential to enable their practical applications.
Alternating current (AC) line-filtering, which can filter
the AC ripple on the line-powered devices, is one of the most
important tasks in the field of renewable electronic power
systems such as power generation by using wind and tidal
power.[7] However, traditional aluminum electrolytic capaci-
tors (AECs), which are widely used for this purpose, have
a low energy density and large volume size. Therefore,
supercapacitors, particularly MSCs, that possess an AC line-
filtering ability, high energy density, and minimal size, are
ideal alternatives to AECs. Traditionally, porous carbon-
based supercapacitors exhibit poor AC line-filtering perfor-
mance (resistance–capacitance [RC] time constant ꢀ 1 s)
compared with AECs (RC time constants = 8.3 ms)[7c]
because of the slow and internal response of the polar-
ization[7c] and limited signal propagation[7a] from the electro-
des. Recently, directly growing graphene and graphene-
carbon-nanotube (CNT)-on-nickel current collectors have
been reported by using chemical vapor deposition,[7a,c] yield-
ing short RC time constants of less than 200 ms, which can be
attributed to the strong connection between the electrode and
active materials. Nevertheless, the reported electrode fabri-
cation on metal current collectors necessitates complicated
processing procedures.
Herein, we demonstrate a simple, potentially up-scalable
method for the room-temperature fabrication of on-chip
MSCs by using a layer-by-layer (LBL) growth of an azulene-
bridged coordination polymer framework (PiCBA) on a Si
wafer-supported Au surface. The PiCBA exhibits good carrier
mobility of 5 ꢀ 10À3 cm2 VÀ1 sÀ1. The manufactured on-chip
MSCs deliver a high specific volumetric capacitance of up to
34.1 FcmÀ3 at 50 mVsÀ1, and a power density of up to
1323 WcmÀ3 (energy density of 4.7 mWhcmÀ3), for which the
high intrinsic capacitance of PiCBA is supported by theoret-
O
n-chip electrochemical energy storage devices,[1] such as
micro-supercapacitors (MSCs) and microbatteries, have
attracted tremendous attention in the past few years because
of the rapid development of mobile electronics, wireless
sensors, and medical implants. Compared with micro-batter-
ies, on-chip MSCs have many advantages owing to their rapid
energy-harvesting features, burst-mode power delivery, and,
[*] C. Yang,[+] S. Sun,[+] Prof. F. Zhang, Dr. X. Zhuang
School of Chemistry and Chemical Engineering, Shanghai Jiao Tong
University
Dongchuan Road 800, 200240 Shanghai (China)
E-mail: zhuang@sjtu.edu.cn
C. Yang,[+] Dr. R. Dong, Dr. X. Zhuang, Prof. X. Feng
Center for Advancing Electronics Dresden (cfaed) & Department of
Chemistry and Food Chemistry, Technische Universitꢀt Dresden
01062 Dresden (Germany)
E-mail: xinliang.feng@tu-dresden.de
K. S. Schellhammer,[+] Dr. F. Ortmann,[+] Prof. G. Cuniberti
Institute for Materials Science, Max Bergmann Center of Biomate-
rials, Dresden Center for Computational Materials Science & Center
for Advancing Electronics Dresden, Technische Universitꢀt Dresden
01062 Dresden (Germany)
M. Karakus, Dr. Z. Mics, Dr. E. Cꢁnovas, Prof. M. Bonn
Max Planck Institute for Polymer Research
55128 Mainz (Germany)
E-mail: canovas@mpip-mainz.mpg.de
Dr. M. Lçffler
Dresden Center for Nanoanalysis (DCN), Center for Advancing
Electronics Dresden (cfaed), Technische Universitꢀt Dresden
01062 Dresden (Germany)
[+] These authors contributed equally to this work.
Supporting information for this article can be found under:
http://dx.doi.org/10.1002/anie.201700679.
Angew. Chem. Int. Ed. 2017, 56, 1 – 6
ꢀ 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
1
These are not the final page numbers!

Angewandte
Communications
Chemie
ical calculations. Notably, the as-fabricated MSCs exhibit an
AC line-filtering performance (À738 at 120 Hz) with a short
RC time constant of approximately 0.83 ms, superior to that
of the AECs.
0.1 mm2) of the obtained coordination polymer film. We
identified regions at the PiCBA edge by SEM, in which the
film is partially folded when transferred onto the Cu grid,
demonstrating the flexible nature of the obtained PiCBA film
(Figure 1b and Supporting Information, Figure S4). The
AFM image and cross-sectional analysis (Supporting Infor-
mation, Figure S5) reveal that the average thickness of the
PiCBA film is approximately 1.1 nm, which is consistent with
the calculated thickness of a single-layer PiCBA film (1.2 nm,
Figure 4a). These results strongly suggest that the coordina-
tion between the isocyanide groups and Co ions renders the
formation of free-standing coordination polymer frameworks.
To further analyze the chemical structure of the PiCBA
film, Fourier-transform infrared (FT-IR) spectroscopy and X-
ray photoelectron spectroscopy (XPS) were employed. The
broad peak centered at 2078 cmÀ1 for PiCBA (Supporting
The fabrication of PiCBA film is shown in Figure 1a. The
azulene-based building block, 2,2’-diisocyano-1,1’,3,3’-tetrae-
thoxycarbonyl-6,6’-biazulene (denoted as iCBA, Supporting
Information) was synthesized according to a reported proce-
dure with minor modifications.[8] The terminal isocyanide
groups of iCBA can coordinate with various metal atoms and
metal ions such as Au, Pt, Pd, Co, Ni and Fe.[9] Taking
advantage of this feature, a PiCBA monolayer film was
prepared through a coordination reaction between iCBA and
Co ions (CoCl2·6H2O) at the water–air interface in a Lang-
muir–Blodgett trough (Supporting Information, Figure S1
and S2). After transferring the PiCBA film onto a Si wafer or
copper grid, the morphology of the obtained film was studied
by optical microscopy (OM), scanning electron microscopy
(SEM), transmission electron microscopy (TEM), and atomic
force microscopy (AFM). The OM and TEM images (Fig-
ure 1b and the Supporting Information, Figure S3 and 1b)
Information, Figure S6) exhibits an obvious shift to lower
À1
ꢁ
energy compared with the N C stretching at 2132 cm for
iCBA.[9b,e] This can be attributed to the N C···Co stretches
caused by the electronic perturbation of the s bond donated
by the N C groups to the Co atoms. This shift is direct
[10]
ꢁ
[9g]
ꢁ
indicate
a
uniform macroscopic lateral dimension (ca.
evidence of the strong coordination between Co and isocy-
anide in the PiCBA film. The Co:N atomic ratio is calculated
to be 1:3.6 (Supporting Information, Figures S7,S8, and
Table S1), which is close to the theoretical stoichiometric
ratio (Co:N = 1:4). This result strongly suggests a high degree
of coordination in PiCBA films through one Co cation and
four isocyanide groups.[9f] The N 1s core level spectrum for
PiCBA (Figure 1c) is deconvoluted into two peaks at 398.1
and 400.4 eV, which are assigned to the isocyanide coordi-
nated with CoII and edge isocyanide species, respectively.[11]
To study layer-dependent UV/Vis absorption spectra, multi-
layer PiCBA films were prepared. The linear increase in the
absorbance (at 349 nm; Figure 1d, inset) demonstrated the
uniformity of each PiCBA layer (Supporting Information,
Figure S9).[12]
Time-resolved terahertz spectroscopy was used to eval-
uate the photoconductivity within the PiCBA framework.[13]
Figure 1e shows the time-resolved real conductivity as
a function of pump–probe delay (400-nm excitation and the
ca. 0.6 THz probe). The signal is defined by an ultra-fast rise
of approximately 100 fs followed by a decay of approximately
1 ps, consistent with the generation of quasi-free electron–
hole (e–h) pairs, which subsequently condense into localized
states.[14] Figure 1 f shows the frequency-resolved complex
photoconductivity over the circa 2 THz probe bandwidth (at
a pump–probe delay of 0.45 ps); the response can be well-
described by the Drude–Smith model.[14] From the data, the
carrier mobility in the sample was estimated as m(PiCBA) =
5 ꢀ 10À3 cm2 VÀ1 sÀ1. This relatively large mobility (for exam-
ple, similar to THz mobility estimates on conjugated polymer
nanosheets[13]) represents a lower-bound estimate as we
assumed that all absorbed photons generate quasi-free
charges immediately after pump excitation. In parallel, the
conductivity of bilayer PiCBA films (thickness ꢀ 2.0 nm) was
as high as 2.4 ꢀ 10À4 ScmÀ1 (Supporting Information, Fig-
ure S10), which is the highest value to date for such synthetic
and ultrathin polymer films or coordination polymer films
Figure 1. a) Synthesis of PiCBA through the coordination reaction
À
between isocyanide and cobalt ions (R= COOC2H5). b) TEM image
shows a large area of a PiCBA film on a copper grid. c) N 1s core level
spectra of PiCBA film and iCBA. d) Layer-dependent UV/Vis spectra of
PiCBA film on a quartz wafer. Inset: Linear relationships between the
absorbance at 349 nm and the layer number. e) The photoconductivity
of PiCBA as a function of the pump-probe delay (excitation wavelength,
400 nm, 90 mJ·cmÀ2). f) Frequency-resolved complex-valued photocon-
ductivity in the PiCBA film (0.45 ps after photoexcitation). Black solid
and red open symbols represent the measured real and imaginary
components, respectively, and lines through the data points represent
best fit obtained using the Drude–Smith model.
2
www.angewandte.org
ꢀ 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed. 2017, 56, 1 – 6
These are not the final page numbers!

Angewandte
Communications
Chemie
and even comparable to some polymers in thick films (150–
300 nm) or in bulk states.[15]
Given its rich aromatic skeleton, ultra-low band gap
(Supporting Information, Figure S11 and Table S2), good
carrier mobility, and the permanent dipole moment of the
azulene unit, PiCBA is a promising candidate for energy
storage. Hence, the PiCBA layers were directly integrated to
fabricate MSCs. First, the iCBA molecules were adsorbed
onto the Au surface of the interdigitated Au-SiO2 substrate
(Supporting Information, Figure S12) through the upright h1
coordination of the terminal isocyanide carbon atoms[9f]
(Figure 2a). Then, the substrate was rinsed in a CoCl2
Figure 2. a–c) Schematic of LBL fabrication of a PiCBA film on Au
interdigital electrodes. (i) The Au interdigital electrode was immersed
in iCBA solution for 24 h, followed by rinsing in fresh CHCl3 and then
(ii) immersed in CoCl2 solution for another 60 s, followed by rinsing in
DI water, iCBA solution for 60 s, and fresh CHCl3, respectively, to form
the 1-layer PiCBA film. This process was repeated nine times to obtain
a 10-layer PiCBA-Au electrode.
Figure 3. a) CV curves of PiCBA-based MSCs in the H2SO4-PVA gel
electrolyte at different scan rates, showing a typical double-layer
capacitive behavior even at different scan rates. b) Cv evolution of the
MSCs at different scan rates. c) Complex plane plot of the impedance
of the PiCBA-based microdevices. Inset displays a magnification of the
high-frequency region. d) Impedance phase angle on the frequency for
the PiCBA-based microdevices. e) Plot of capacitance (Cv’=volumetric
real capacitance and Cv’’=volumetric imaginary capacitance) versus
the frequency of PiCBA-based MSCs. f) Ragone plots for PiCBA. This
demonstrates that the PiCBA exhibits outstanding electrochemical
energy storage with high power density compared with commercially
applied Li-thin-film batteries,[17a] electrolytic capacitors,[1c] polyaniline
(PANI) nanowires,[17b] CNT-graphene carpets,[17c] Ti3C2Tx,[1a] and carbon
onions.[17a]
aqueous solution, deionized water, iCBA monomer solution,
and fresh CHCl3 sequentially 10 times to allow the in situ
formation of 10-layer PiCBA films on the Au electrode
(Figure 2b and Supporting Information, S13). The cross-
section SEM images (Supporting Information, Figure S14;
prepared by focused ion beam) indicated that the 10-layer
PiCBA films had an estimated total thickness of approx-
imately 30 nm, which is slightly larger than the theoretical
value (2.1 nm ꢀ 11 = 23.1 nm, see calculation section) due to
the possible dislocation effect (see Raman spectra in the
Supporting Information, Figure S15).[16] Finally, the H2SO4-
polyvinyl alcohol (H2SO4-PVA) gel electrolyte was cast on
the PiCBA-Au:SiO2 substrate and allowed to solidify over-
night to form a solid–state PiCBA-Au MSC with an in-plane
geometry (Figure 2c).
The electrochemical performance of the 10-layer PiCBA-
based MSC was evaluated using cyclic voltammetry (CV),
with scan rates ranging from 50 mVsÀ1 to 1000 VsÀ1 (Fig-
ure 3a and the Supporting Information, Figure S16). The
PiCBA films showed an enhanced current range with a nearly
rectangular CV curve, even at 100 VsÀ1, suggesting typical
double-layer capacitive behavior. The areal capacitance (CA)
and stack capacitance (Cv) for the whole in-plane PiCBA-
based device were subsequently calculated based on the CV
results (Figure 3b and the Supporting Information, Fig-
Information, Table S3). Notably, the Cv of the PiCBA films
decreased gradually with increasing scan rates; for example,
the capacitance remained at 7.7 FcmÀ3 at a scan rate of
100 VsÀ1. Even at the ultra-high scan rate of 1000 VsÀ1, the
PiCBA films delivered a Cv of 2.7 FcmÀ3, demonstrating
a high capacitance and rate performance of PiCBA-based
MSCs.
Electrochemical impedance spectroscopy further con-
firmed the excellent ion transport within the in-plane
device. Figure 3c shows a pronounced pure capacitance
behavior of the PiCBA-based device, even for frequencies
as high as 14.7 kHz, benefitting from the completely acces-
sible surface of the PiCBA films. Figure 3c (inset) indicates
displaced behavior at low impedance. Moreover, the equiv-
alent series resistance of the whole device, calculated from the
intercept of the real axis, is 70.1 W, which can be attributed to
the internal ion-transport resistance of the PiCBA materials
with the polymer-gel electrolyte.[18] The dependence of the
phase angle on the frequency indicates capacitive and
inductive behavior at low and high frequencies, respectively
(Figure 3d).[7c] The phase angle of the device reached À788 at
ure S17). The whole device exhibited
a Cv of circa
34.1 FcmÀ3, at a scan rate of 50 mVsÀ1, which is among the
highest values reported for polymer-based MSCs (Supporting
Angew. Chem. Int. Ed. 2017, 56, 1 – 6
ꢀ 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
3
These are not the final page numbers!

Angewandte
Communications
Chemie
frequencies of circa 14 Hz, suggesting that the performance of
the MSCs is 87% of that of an ideal capacitor (defined by
a phase angle of À908). Additionally, the characteristic
frequency (f0) of the system, corresponding to the maximum
of the dispersed energy curve (obtained from the phase angle
of 458) was 3620 Hz, with a relaxation time constant t0 (t0 = 1/
f0, the minimum time needed to discharge the energy from the
whole device with an efficiency of > 50%) of approximately
0.27 ms. This value is orders of magnitude higher than that
obtained for activated carbon-based MSCs (< 5 Hz,
< 200 ms)[19] and onion-like carbon MSCs (< 100 Hz,
< 10 ms)[17a] and much higher than that for graphene-CNT
MSCs (ca. 1343 Hz and 0.74 ms).[7a] Importantly, the whole
device showed an impedance phase angle as large as À738 at
a frequency of 120 Hz, indicating a high AC line-filtering
efficacy.[7a] The series-RC circuit model was then employed to
further assess the RC time constant (tRC) in the PiCBA-based
device. Figure 3e shows that the tRC from the imaginary
capacitance calculated from the Nyquist plot was as short as
0.83 ms, which is comparable to the state-of-the-art MSCs
based on vertically oriented graphene (< 0.2 ms),[7c] thermally
reduced graphene oxide (2.3 ms),[20] and graphene-conductive
polymer hybrids (0.47 ms).[7b]
To further evaluate the overall performance of the MSCs,
the volumetric power and energy densities were calculated.
The plot in Figure 3 f demonstrates that the PiCBA-based
MSCs exhibited a high energy density of up to 4.7 mWhcmÀ3
at 50 mVsÀ1, an order of magnitude higher than that obtained
for electrolytic capacitors[1c] and MSCs based on graphene-
CNT carpets.[7a] In addition, the device exhibited a power
density of 1323 WcmÀ3, which is at least five orders of
magnitude higher than that of commercial thin-film lithium
batteries.[1c] To our best knowledge, this is the first report of
coordination polymer-based MSCs with such high power and
energy densities (Table S3). Furthermore, the PiCBA-based
MSCs showed good cycling stability, with 86% capacitance
maintained after 350 cycles (Supporting Information, Fig-
ure S18).
To understand the excellent capacitive performance of
PiCBA, density functional theory (DFT) simulations were
performed (Supporting Information). The optimization of the
unit cell yields an approximately square Bravais lattice, with
the symmetry of the structure slightly broken by the torsion of
the azulene units (Figure 4a). Figure 4b shows the band
structure and density of states (DOS). Two spin-up bands
cross the Fermi level, indicating metallic behavior of the
PiCBA framework in this configuration, while the narrow
bandwidth is consistent with the observed mobility. Note that
the splitting of the four bands close to zero energy in
Figure 4a is on the order of the thermal energy and may not
be observed in ambient temperature experiments. The
quantum areal capacitance (Cq) extracted from the DFT
calculations reaches 150 mFcmÀ2 and is clearly larger than that
obtained from experiments at standard scan rates (Figure 4c);
this can be explained by the limiting scenario of a disorder-
free system. To include the effects of disorder on Cq, the DOS
of the four bands closest to the Fermi level was broadened
(Figure S18). With DOS broadening, the quantum capaci-
tance decreased below 50 mFcmÀ2, which is closer to exper-
imental observations. The calculations indicate that the
charge densities of these bands are spread over the azulene
units (Figure 4d) and the dispersion of these bands is rather
small, which appears to be mainly because of the metal
centers as well as partly because of the torsion between the
azulene units. This result, based on unprecedented theoretical
work on the energy storage abilities of azulene-containing
polymer films, suggests that the PiCBA films deliver high
capacitance owing to the extreme charge affinity of azulene
groups.
In conclusion, we have developed an LBL approach for
the room-temperature preparation of coordination polymer
frameworks based on-chip MSCs. Remarkably, the fabricated
on-chip MSCs delivered high specific capacitances, excellent
specific volumetric power, and energy densities as well as
promising AC line-filtering performance with an extremely
short RC time. The coordination-polymer-framework elec-
trode possesses a permanent dipole moment of the azulene-
Figure 4. a) Relaxed unit cell (blue square) of the PiCBA framework. The calculations reveal an almost square Bravais lattice with a=20.948 ꢂ,
b=20.944 ꢂ, and fꢀ90.08. b) Simulated band structure and density of states (DOS). The Fermi level crosses two spin-up bands, indicating
metallic behavior of the material. c) Calculated quantum capacitance based on the two bands crossing the Fermi level for zero disorder. d) Charge
density of the lower band crossing the Fermi level at the G point as well as close to the Brillouin zone boundary at X, namely k=(0.4, 0.0, 0.0).
The charge density of the second band is almost identical at the G point and complementarily delocalized horizontally at (0.4, 0.0, 0.0).
4
www.angewandte.org
ꢀ 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed. 2017, 56, 1 – 6
These are not the final page numbers!

Angewandte
Communications
Chemie
Lee, D. Kim, D. Kim, S. Oh, J. Yun, J. Kim, S. Lee, J. Ha, Energy
Environ. Sci. 2015, 8, 1764 – 1774.
based skeleton, ultra-low band gap, and good carrier mobility,
rendering it as a promising material for both energy storage
and optoelectronic applications.
[7] a) J. Lin, C. Zhang, Z. Yan, Y. Zhu, Z. Peng, R. Hauge, D.
Natelson, J. Tour, Nano Lett. 2013, 13, 72 – 78; b) Z. Wu, Z. Liu,
K. Parvez, X. Feng, K. Mullen, Adv. Mater. 2015, 27, 3669 – 3675;
c) J. Miller, R. Outlaw, B. Holloway, Science 2010, 329, 1637 –
1639.
Acknowledgements
[8] T. Maher, A. Spaeth, B. Neal, C. Berrie, W. Thompson, V. Day,
M. Barybin, J. Am. Chem. Soc. 2010, 132, 15924 – 15926.
[9] a) J. Applegate, M. Okeowo, N. Erickson, B. Neal, C. Berrie, N.
Gerasimchukand, M. Barybin, Chem. Sci. 2016, 7, 1422 – 1429;
b) S. Lin, R. McCarley, Langmuir 1999, 15, 151 – 159; c) S.
Otsuka, T. Yoshida, Y. Tatsuno, J. Am. Chem. Soc. 1971, 93,
6462 – 6469; d) J. Bꢃrubꢃ, K. Gagnon, D. Fortin, A. Decken, P.
Harvey, Inorg. Chem. 2006, 45, 2812 – 2823; e) M. Ansell, E.
Cogan, C. Page, Langmuir 2000, 16, 1172 – 1179; f) N. Kataoka,
H. Kon, J. Phys. Chem. 1969, 73, 803 – 809; g) B. Fox, M. Millard,
A. DiPasquale, A. Rheingold, J. Figueroa, Angew. Chem. Int.
Ed. 2009, 48, 3473 – 3477; Angew. Chem. 2009, 121, 3525 – 3529;
h) W. Brennessel, J. Ellis, Angew. Chem. Int. Ed. 2007, 46, 598 –
600; Angew. Chem. 2007, 119, 604 – 606.
The authors thank financial support from 973 Programs of
China (2013CBA01602), Natural Science Foundation of
China (51403126), ERC Grant on 2DMATER, UP-GREEN
and EU Graphene Flagship, COORNET (SPP 1928) as well
as the German Science Council, Center of Advancing
Electronics Dresden, EXC1056, (cfaed) and OR 349/1. We
acknowledge the Center for Information Services and High
Performance Computing (ZIH) at TU Dresden Partnership
for Advanced Computing in Europe (PRACE) for computa-
tional resources.
[10] C. Becker, Inorg. Chim. Acta 1979, 36, L441 – L443.
[11] D. Beach, R. Bertoncello, G. Granozzi, W. Jolly, Organometallics
1985, 4, 311 – 316.
Conflict of interest
[12] a) E. Amir, R. Amir, L. Campos, C. Hawker, J. Am. Chem. Soc.
2011, 133, 10046 – 10049; b) E. Puodziukynaite, H. Wang, J.
Lawrence, A. Wise, T. Russell, M. Barnes, T. Emrick, J. Am.
Chem. Soc. 2014, 136, 11043 – 11049.
[13] a) R. Ulbricht, E. Hendry, J. Shan, T. Heinz, M. Bonn, Rev. Mod.
Phys. 2011, 83, 543 – 586; b) Y. Su, Z. Yao, F. Zhang, H. Wang, Z.
Mics, E. Cꢄnovas, M. Bonn, X. Zhuang, X. Feng, Adv. Funct.
Mater. 2016, 26, 5893.
The authors declare no conflict of interest.
Keywords: AC line-filtering · azulene · coordination polymers ·
layer-by-layer methods · micro-supercapacitors
[14] a) D. G. Cooke, F. C. Krebs, P. U. Jepsen, Phys. Rev. Lett. 2012,
108, 056603; b) S. A. Jensen, R. Ulbricht, A. Narita, X. Feng, K.
Mꢂllen, T. Hertel, D. Turchinovich, M. Bonn, Nano Lett. 2013,
13, 5925; c) E. Hendry, J. M. Schins, L. P. Candeias, L. D. A.
Siebbeles, M. Bonn, Phys. Rev. Lett. 2004, 92, 196601; d) E.
Hendry, M. Koeberg, J. M. Schins, L. D. A. Siebbeles, M. Bonn,
Phys. Rev. B 2004, 70, 033202.
[15] a) S. Takaishi, M. Hosoda, T. Kajiwara, H. Miyasaka, M.
Yamashita, Y. Nakanishi, Y. Kitagawa, K. Yamaguchi, A.
Kobayashi, H. Kitagawa, Inorg. Chem. 2009, 48, 9048 – 9050;
b) D. Rodrꢅguez-San-Miguel, P. Amo-Ochoa, F. Zamora, Chem.
Commun. 2016, 52, 4113 – 4127; c) S. Cai, Y. Zhang, A. Pun, B.
He, J. Yang, F. Toma, I. Sharp, O. Yaghi, J. Fan, S. Zheng, W.
Zhang, Y. Liu, Chem. Sci. 2014, 5, 4693 – 4700.
[1] a) J. Chmiola, C. Largeot, P. Taberna, P. Simon, Y. Gogotsi,
Science 2010, 328, 480 – 483; b) P. Huang, C. Lethien, S. Pinaud,
K. Brousse, R. Laloo, V. Turq, M. Respaud, A. Demortiꢁre, B.
Daffos, P. Taberna, B. Chaudret, Y. Gogotsi, P. Simon, Science
2016, 351, 691 – 695; c) M. El-Kady, V. Strong, S. Dubin, R.
Kaner, Science 2012, 335, 1326 – 1330; d) W. Gao, N. Singh, L.
Song, Z. Liu, A. Reddy, L. Ci, R. Vajtai, Q. Zhang, B. Wei, P.
Ajayan, Nat. Nanotechnol. 2011, 6, 496 – 500; e) H. Ning, J. Pikul,
R. Zhang, X. Li, S. Xu, J. Wang, J. Rogers, W. King, P. Braun,
Proc. Natl. Acad. Sci. USA 2015, 112, 6573 – 6578; f) X. Zhuang,
Y. Mai, D. Wu, F. Zhang, X. Feng, Adv. Mater. 2015, 27, 403 – 427;
g) F. Bonaccorso, L. Colombo, G. Yu, M. Stoller, V. Tozzini, A.
Ferrari, R. Ruoff, V. Pellegrini, Science 2015, 347, 1246501.
[2] Perspective articles: a) Z. Wu, X. Feng, H. Cheng, Nat. Sci. Rev.
2014, 1, 277 – 292; b) X. Wang, Y. Chen, O. Schmidt, C. Yan,
Chem. Soc. Rev. 2016, 45, 1308 – 1330; c) Y. Shao, M. F. El-Kady,
L. J. Wang, Q. Zhang, Y. Li, H. Wang, M. F. Mousavi, R. B.
Kaner, Chem. Soc. Rev. 2015, 44, 3639 – 3665.
[16] S. Sakaida, K. Otsubo, O. Sakata, C. Song, A. Fujiwara, M.
Takata, H. Kitagawa, Nat. Chem. 2016, 8, 377 – 383.
[17] a) D. Pech, M. Brunet, H. Durou, P. Huang, V. Mochalin, Y.
Gogotsi, P. Taberna, P. Simon, Nat. Nanotechnol. 2010, 5, 651 –
654; b) C. Meng, J. Maeng, S. John, P. Irazoqui, Adv. Energy
Mater. 2014, 4, 1301269; c) M. Beidaghi, C. Wang, Adv. Funct.
Mater. 2012, 22, 4501 – 4510.
[18] M. El-Kady, R. Kaner, Nat. Commun. 2013, 4, 1475.
[19] D. Pech, M. Brunet, P. Taberna, P. Simon, N. Fabre, F.
Mesnilgrente, V. Conꢃdꢃra, H. Durou, J. Power Sources 2010,
195, 1266 – 1269.
[3] a) Z. Wu, K. Parvez, X. Feng, K. Mꢂllen, Nat. Commun. 2013, 4,
2487; b) J. Lin, Z. Peng, Y. Liu, F. Ruiz-Zepeda, R. Ye, E.
Samuel, M. Yacaman, B. Yakobson, J. Tour, Nat. Commun. 2014,
5, 5714.
[4] Z. Wu, K. Parvez, S. Li, S. Yang, Z. Liu, S. Liu, X. Feng, K.
Mꢂllen, Adv. Mater. 2015, 27, 4054 – 4061.
[5] S. Liu, P. Gordiichuk, Z. Wu, Z. Liu, W. Wei, M. Wagner, N.
Mohamed-Noriega, D. Wu, Y. Mai, A. Herrmann, K. Mꢂllen, X.
Feng, Nat. Commun. 2015, 6, 8817.
[20] T. Nathan-Walleser, I. Lazar, M. Fabritius, F. Tçlle, Q. Xia, B.
Bruchmann, S. Venkataraman, M. Schwab, R. Mꢂlhaupt, Adv.
Funct. Mater. 2014, 24, 4706 – 4716.
[6] a) R. Li, R. Peng, K. Kihm, S. Bai, D. Bridges, U. Tumuluri, Z.
Wu, T. Zhang, G. Compagnini, Z. Feng, A. Hu, Energy Environ.
Sci. 2016, 9, 1458 – 1467; b) B. Lim, J. Yoon, J. Yun, D. Kim, S.
Hong, S. Lee, G. Zi, J. Ha, ACS Nano 2014, 8, 8844 – 8855; c) G.
Manuscript received: January 19, 2017
Final Article published: && &&, &&&&
Angew. Chem. Int. Ed. 2017, 56, 1 – 6
ꢀ 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
5
These are not the final page numbers!

Angewandte
Communications
Chemie
Communications
Nanotechnology
C. Yang, K. S. Schellhammer, F. Ortmann,
S. Sun, R. Dong, M. Karakus, Z. Mics,
M. Lçffler, F. Zhang, X. Zhuang,*
E. Cꢁnovas,* G. Cuniberti, M. Bonn,
X. Feng*
&&&& — &&&&
Coordination Polymer Framework-Based
On-Chip Micro-Supercapacitors with AC
Line-Filtering Performance
On-chip micro-supercapacitors based on
an azulene-bridged coordination polymer
framework are prepared by a facile layer-
by-layer approach. The as-fabricated on-
chip micro-supercapacitors deliver high
specific capacitances, specific volumetric
power, and energy densities as well as
promising AC-line filtering performance
with an extremely short RC time.
6
www.angewandte.org
ꢀ 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed. 2017, 56, 1 – 6
These are not the final page numbers!