The fabrication and characterization of a supramolecular Cu-based metallogel thin-film based Schottky diode

Article abstract of DOI:10.1039/d1nj00394a

In the present study, a stable supramolecular Cu(ii)-metallogel has been synthesized based on copper(ii) acetate monohydrate and succinic acid, engineered as a low-molecular-weight organic gelator. The mechanical assets of the Cu-H₄L metallogel have been explored through a rheological investigation. Further, the aggregation of the synthesized metallogel has been well establishedviaseveral experiments using Job plots and ESI-MS. Apart from this, the morphology of the synthesized supramolecular metallogel was scrutinizedviaFESEM, TEM, and AFM studies, revealing the self-assembled thread-like morphology of the Cu-H₄L metallogel. The functional group, elemental composition, crystalline behaviour, and thermal stability of the Cu-H₄L metallogel were probedviaFT-IR, XPS, P-XRD, and TGA studies, respectively. The optical properties of the Cu-H₄L metallogel reflected its semiconducting nature. Thus, based on the semiconducting properties of the Cu-H₄L metallogel, we have successfully fabricated an active electronic device: a ‘Schottky diode’.

Full text of DOI:10.1039/d1nj00394a

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The fabrication and characterization of a
supramolecular Cu-based metallogel thin-film
Cite this: New J. Chem., 2021,
4
5, 6273
based Schottky diode†
a
b
a
a
Vivek Kumar, Rishibrind Kumar Upadhyay,
Daraksha Bano, Subhash Chandra,
a
b
a
Deepak Kumar, Satyabrata Jit
and Syed Hadi Hasan
*
In the present study, a stable supramolecular Cu(II)-metallogel has been synthesized based on copper(II)
acetate monohydrate and succinic acid, engineered as a low-molecular-weight organic gelator. The
4
mechanical assets of the Cu–H L metallogel have been explored through a rheological investigation.
Further, the aggregation of the synthesized metallogel has been well established via several experiments
using Job plots and ESI-MS. Apart from this, the morphology of the synthesized supramolecular
metallogel was scrutinized via FESEM, TEM, and AFM studies, revealing the self-assembled thread-like
Received 25th January 2021,
Accepted 8th March 2021
morphology of the Cu–H
behaviour, and thermal stability of the Cu–H
studies, respectively. The optical properties of the Cu–H
4
L metallogel. The functional group, elemental composition, crystalline
L metallogel were probed via FT-IR, XPS, P-XRD, and TGA
L metallogel reflected its semiconducting
L metallogel, we have successfully
4
DOI: 10.1039/d1nj00394a
4
nature. Thus, based on the semiconducting properties of the Cu–H
fabricated an active electronic device: a ‘Schottky diode’.
4
rsc.li/njc
Metal–semiconductor (MS) junctions are the crucial part of
1
. Introduction
1
6
effectively all semiconducting optoelectronic devices. The
Investigation of gel-like soft resources has been of emerging formation of such an MS junction interface greatly affects the
1
7
interest because of their many applications extending from quality and performance of devices. During the last few years,
1
,2
research to manufacturing areas. Supramolecular gels have there has been considerable attention paid to experimental
1
potential applicability in several fields including catalysis,
lithography,
studies of MS-based Schottky barrier diodes (SBDs). The
electrochemical present disclosure generally relates to SBDs that have a metal
devices, chemo-sensors, cell culturing, biomedicine, medical for the Schottky layer and the semiconductor material for the
2
,3
3
optoelectronic devices,
4
5
5
6,7
7
8,9
10
diagnostics, drug delivery,
wastewater treatment, tissue drift layer is selected to provide a low barrier height Schottky
9
11
12
engineering, sensor science, and semiconductors. During junction between the drift layer and the Schottky layer. Schottky
the last two decades, the discovery of a new low molecular barrier height is a key property of the MS interface of SBDs,
1
8
weight conducting metallogelator has been accompanied by a which governs the electronic transfer across the interface,
decisive development in the field of coordination polymers and and the electrical characteristics such as voltage drop and
metal–organic frameworks that may allow the fabrication of switching speed of such devices are dependent on the current
1
3
novel metallogels with challenging features.
In recent transport behaviour through the structure of the MS interface.
research, conductive metallogels have turned out to be SBDs provide great advantages over a traditional analogous p–n
1
4
captivating functionalized materials because of their advance- diode as they have lower barrier height; thus, a lower voltage is
1
5
19
ment in optical, electronic, and electrical devices.
However, the synthesis of conductive metallogels, having
self-healing property to fabricate electronic devices, is the semiconducting properties of a synthesized metallogel
required to turn on the device.
Taking all these considerations into account, we have examined
1
1
still a challenging task in the scientific community.
4
(Cu–H L) and successfully fabricated a MS junction based
thin-film device (Ag/Cu–H L) at room temperature (RT). The
4
calculated direct energy band gap of the metallogel was
a
Department of Chemistry, Nano-materials Laboratory, IIT BHU, Varanasi-221005,
India. E-mail: shhasan.apc@itbhu.ac.in; Tel: +91 9839089919
B3.06 eV, which showed the improved optical properties
1
2,20
b
over those of previously reported literature.
characteristics of the Ag/Cu–H L based thin-film device display
a nonlinear rectifying behaviour, suggesting the formation of a
The I–V
Department of Electronics Engineering, IIT BHU, Varanasi-221005, India
Electronic supplementary information (ESI) available. See DOI: 10.1039/
†
4
d1nj00394a
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SBD. The important SBD parameters of the fabricated device 2.4. Synthesis of the metallogel
such as rectification ratio, ideality factor, and barrier height
were extracted from current–voltage characteristics by
Cheung’s method. It is, therefore, of critical importance to
In a typical synthesis process, the gelator H
.04 mmol) was dissolved in DMF (0.6 mL) in a vial. Then a
freshly prepared Cu(OAc) (8.0 mg, 0.04 mmol) solution in DMF
0.4 mL) was added in one shot. A green-coloured stiff gel was
formed instantly at RT without any external mechanical
influence. The thus formed gelatinous material was examined
by conventional inverted vial method, which confirmed the
sustainability of the gel.
4
L (14 mg,
0
2
reduce the barrier height of the Ag/Cu–H L interface to improve
4
(
4
the on-state voltage drop in Ag/Cu–H L devices. Moreover, from
extensive studies it has been found that our designed semi-
conducting thin-film based SBD has the advantages of
enhanced electrical conductivity, high chemical stability and
low-cost production process.
2.5. Device fabrication
For MS junction device fabrication, indium doped tin oxide
2
2
. Experimental
(ITO)-coated glass substrates (15 ꢀ 15 mm ) were ultrasonically
cleaned using standard wet cleaning successively in soap
solution for 20 minutes, deionized water for 15 minutes,
acetone for 10 minutes, and isopropanol for 10 minutes, before
2.1. Materials
Succinic acid, hydrazine hydrate, salicylaldehyde, copper
acetate monohydrate and solvents were acquired from S.D.
Fine Private Ltd. Throughout all the experiments, the chemicals
were used without additional purification.
finally being treated via plasma cleaning in the presence of
19,20
argon for 20 minutes.
Initially, supramolecular Cu-based
metallogel was deposited on the ITO-coated glass substrate and
annealed at 100 1C for 30 min. In the second step, B80 nm
thickness of metal (Ag) was deposited for a contact electrode by
using a thermal evaporator unit. The evaporated metal (Ag)
formed circular dots of 1 mm in radius on the top of
the semiconductor device using a shadow mask technique.
The thicknesses of the Cu–H L gel layer (B200 nm) were
measured using an F20 Filmmetrics (USA) instrument.
2.2. Characterization
The UV-visible spectra were obtained with a Thermo Scientific
EVOLUTION 201 spectrophotometer. A PerkinElmer Spectrum
spectrophotometer was used for FT-IR characterization.
2
0
1
4
H NMR study was conducted with a Bruker AVANCE III HD
2
0
5
00 spectrometer. A Micromass MS Technologies SCIEX X500R
QTOF was used for recording the ESI-MS spectra. A Tecnai G2
0 TWIN was used for capturing TEM micrographs. Rheology of
2
3
. Results and discussion
the metallogel was investigated with an Anton Paar MCR 702
twin drive rheometer. The SEM images were collected with an
EVO scanning electron microscope (MA15/18). Powder XRD
data were accumulated in the range of angle 2y = 10–901 using
a Rigaku MiniFlex 600 Detector D-tex Ultra.
To synthesize the metallogel, first, we designed the gelator
(H L), derived from succinic acid, as shown in Scheme 1.
4
The direct gelation test was performed by adding different
2
+
2+
2+
2+
2+
2+
2+
metal cations such as Cd , Co , Zn , Cu , Ni , Pb , Mn ,
Fe , and Sn into the as-synthesized gelator (H L) in DMF, as
4
2
+
2+
2
.3. Synthesis of the gelator (H
4
L)
shown in Fig. S1 (ESI). It can be noticed that among these metal
cations, specifically Cu(OAc)2 was capable of forming a gel
with gelator H L. The morphological characteristics of the
4
synthesized metallogel were investigated by SEM, TEM, and
AFM analyses.
1
8
The reported ligand was synthesized by the reaction mixture
of methanolic solution of succinic acid (1.00 g, 8.46 mmol) and
a catalytic amount of concentrated sulphuric acid which was
refluxed overnight. Afterwards, a clear solution of dimethyl
succinate was obtained with a pleasant smell. Further, this
methanolic mixture was refluxed with hydrazine hydrate
(863 mg, 16.9 mmol) under an in-situ condition for 6 hours,
leading to white crystals of succinoyldihydrazine, which were
isolated by filtration. Then, dihydrazone was prepared by
reacting a solution of succinoyldihydrazine (1.0 g, 6.8 mmol)
with salicylaldehyde in methanol (1.67 g, 13.6 mmol).
Subsequently, a white precipitate was obtained at RT, which
was dried and collected after washing with methanol, resulting
in a yield of 82% of gelator.
1
H NMR of the synthesized gelator was conducted in [D ]
6
1
DMSO. H NMR (500 MHz, [D ] DMSO, 25 1C): d = 11.72 (s, 1 H,
6
–
8
OH); 11.29 (s, 1 H, –OH); 11.17 (s, 1 H, NH); 10.15 (s, 1 H, NH);
.35 (s, 1 H, CHQN); 8.28 (s, 1 H, CHQN); 6.85–7.65 (m, 8H,
Ar-H); 2.93 (m, 2 H); 2.50 (m, 2 H).
4
Scheme 1 The synthetic scheme of the Cu–H L based metallogel.
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ꢁ
1
ꢁ1
3
.1. UV-visible study
bands shifted to 1610 cm
(
(Dn = 55) and 1505 cm
ꢁ
1
Dn = 62 cm ) compared to those of the gelator, advocating
the involvement of {CQN and {CQO in complexation.
Thus, it could be expected that coordination of Cu with the
synthesized gelator (H L) occurs through the O, N, O linkage.
A UV-visible absorption spectroscopy investigation showed the
complexation behaviour of the gelator with Cu(II) in DMF.
As shown in Fig. 1, a UV-visible titration experiment was
performed between gelator and Cu(II) metal ion by varying the
metal-to-gelator ratio. The UV-visible spectrum of the gelator
exhibited two sharp bands at 281 nm and 290 nm, which may
be due to the p–p* transition. A less intense band at 322 nm
corresponds to the n–p* transition. The alternate band
appeared at 281 nm, and that at 290 nm was due to the unlike
planarity of the ligand. On further multiple inclusions of
Cu(OAc)
2
4
2
+
4
3.3. Morphological study
The morphological characteristics of the synthesized metallogel
were investigated by FESEM, TEM, and AFM analyses.
The microstructural pattern of supramolecular Cu–H L based
4
2
1
2
2
metallogel was explored by FESEM. The interconnected
collection of thread-like nanofiber morphology of the gel has
an average size B1 mm, as shown in Fig. 3a. Morphological
properties of the metallogel dictate the compactness of thin
intertwined nanofibers. The network formation of nanofibers
was confirmed by the TEM and AFM analyses of the metallogel,
as revealed in Fig. 3b and c, respectively. This result revealed the
formation of an intermingled network of nanofibers along with
an average diameter of B6 nm and lengths of several
micrometers. Supramolecular noncovalent interaction between
ꢁ3
2
(1 ꢀ 10
M, DMF, 25 1C) to this solution, a
substantial change was observed: the vanishing of the band
at 322 nm and a new peak appeared at 380 nm, indicating that
2
+
22
Cu formed a complex with the gelator. And the shift of
wavelength (Dl = 62 nm), with the origin of an isosbestic point
at 342 nm, specifies the existence of an equilibrium state
throughout the complexation of gelator and Cu(II) ion. In the
range of 1–1.2 equivalent of gelator/Cu(II), the appearance of a
saturation point indicates the possibility of 1 : 1 coordination,
which was further confirmed by Job’s plot for [Cu(II)]/[Cu(II)] +
the Cu(II) source and the gelator H L in DMF could be effective
for the self-assembly growth which leads to the Cu(II) ion based
stable metallogel.
4
[gelator] vs. absorbance monitored at 380 nm.
The powder X-ray diffraction pattern of the xerogel, formed
3.2. FT-IR analysis
using Cu–H L metallogel, in the 2y range of 101 to 901 showed
4
a common broad diffraction peak at 21.61 indicating the
The gelator H L showed (Fig. 2a) a strong broad band in the
4
2
5–27
ꢁ1
ꢁ1
amorphous behaviour of the gel,
as shown in Fig. S2 (ESI†).
region of 3200 cm and a hump at 3430 cm , which arise due
to the vibration of secondary –NH groups and naphtholic/
Thermogravimetric analysis (TGA) is a substantial method
to determine the thermal stability of a material, including
2
3
phenolic –OH groups, respectively. The FT-IR spectrum of
2
8
ꢁ
1
ꢁ1
polymers. In this technique, a change in the weight of a
sample is measured with respect to an increase in temperature.
the gelator also showed bands at 1665 cm and 1567 cm due
1
8
to the ({CQN) and ({CQO) vibrations respectively. As
4
TGA measurement was carried out on 15.8 mg of the Cu(II)-H L
shown in Fig. 2b, the spectrum of the xerogel has a strong
ꢁ
1
ꢁ
1
xerogel at a heating rate of 10 1C min
in a nitrogen
broad band in the region of 3436 cm , which suggests the –OH
1
8
atmosphere using a thermogravimetric analyzer (instrument
model: TGA-50, Shimadzu (Asia Pacific) Pte Ltd). The continuous
weight loss and temperature were analyzed thoroughly after
recording (Fig. 4). The result showed that up to 200 1C not as
much weight loss was observed; this indicates the thermal
stability of the gel material when it is exposed to heat at 200 1C.
The oxidation state of Cu was determined by XPS. In the
high-resolution XPS spectrum of Cu 2p of the synthesized
xerogel, two peaks were observed at 936.1 and 956.0 eV, along
with two satellite peaks at 942.7 and 946.2 eV, which correspond
to the 2p and 2p1/2 of copper, confirming the presence of Cu(II)
band of lattice/coordinated water molecules. The synthesized
ꢁ
1
xerogel did not show any band in the region of 3200 cm
(
1
8
–NH); that is attributed to the enol form in the complex.
In the FT-IR spectrum of the xerogel, {CQN and {CQO
3
/2
2
9
30,31
state (Fig. 5). The high-resolution XPS spectra
O 1s, and Cu 2p of Cu–H L metallogel were obtained, as shown
in Fig. S3 (ESI†).
of C 1s, N 1s,
4
3.4. Mass spectral analysis
The Job’s plot method (Fig. 6a) indicates that the stoichiometric
2
+
ratio of the complex formed during gelation between Cu and
gelator H L in DMF solvent is 1 : 1, under experimental
4
conditions. This was further confirmed by ESI-MS spectral analysis
of the diluted metallogel. As shown in Fig. 6b, the molecular ion (m/z)
peak spectrum was recorded by ESI positive mode. A base peak
ꢁ
5
Fig. 1 The UV-visible titration evaluation of H
4
L alone (1 ꢀ 10 M, DMF,
(1 ꢀ 10ꢁ M, DMF, black dotted lines).
3
red line) and with Cu(OAc)
2
18 4 4
was found for an isotopic abundance of gelator [C18H N O ]:
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2+
Fig. 2 FT-IR analysis of the gelator (a) and the xerogel (b), showing the coordination of Cu through O, N, O linkages.
ꢁ3
4 2
Fig. 3 (a) An SEM image of the vacuum-dried metallogel. (b) TEM and (c) AFM images of the metallogel (H L/Cu(OAc) ; B10 M).
Fig. 5 The high-resolution Cu 2p XPS spectrum of the synthesized
xerogel.
4
Fig. 4 The TGA curve of the xerogel from the Cu(II)–H L metallogel.
3.5. Rheological analysis
3
54.2, and its calculated base peak was observed at m/z 354.1. A semi-solid nature with viscoelasticity of the Cu based
2ꢁ
However, the base peak for diluted metallogel [C H CuN O ]
metallogel was confirmed by a rheological study such as
1
8
16
4 4
was found at m/z 415.2 and its estimated peak was at 415.1. angular frequency and strain sweep studies. The storage
0
00
Therefore, the molecular ion abundance pattern of ESI-MS modulus (G ) and loss modulus (G ) measurements of the gel
spectra is smoothly matched with the calculated peak. The are directly associated with the function of shear strain and
ꢁ
1
molecular abundance pattern of the metallogel well matched shear stress, respectively, at 25 1C and a frequency of 10 rad s
.
2ꢁ
0
with a 1 : 1 proposed coordination mechanism between H
2
L
In the viscoelastic region, G of the metallogel showed the
stored energy in the system during the application of shear.
2
+
and Cu based on Job’s plot and UV-visible study.
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4 4
Fig. 6 (a) A Job plot showing [Cu(II)]/[Cu(II)] + [gelator] vs. absorbance monitored at 380 nm. (b) The ESI-MS spectrum of [C18H16CuN O ], presenting the
2+
4
experimental isotopic abundance pattern for 1 : 1 H L vs. Cu .
0
0
For a liquid-like sample, G indicates energy change during respectively. Parameter A, which is unity in an ideal case,
3
2
dissolution under oscillatory stress.
The rheological is a constant. With the extrapolation of the linear region of a
0
2
experiment showed that G of the Cu-based metallogel was plot of (ahn) vs. hn (Fig. 8) to a = 0 absorption, the direct optical
higher than G by an order of B1 of shear stress at a fixed band gap (E ) was evaluated as 3.06 eV for the Cu–H L
00
g
4
concentration of the gel (Fig. 7). We have also observed that the metallogel.
0
00
value of shear stress of G and G intersect at the point B1.9 Pa.
This point is the gel destruction point, which is known as a
gel–sol transition point. A frequency sweep measurement was
3
.7. Strategy for device fabrication
ꢁ
1
By using the above optical properties of the synthesized metal-
logel, a Schottky diode was designed, as shown in Scheme 2.
It is evident from the Taucs plot analysis (Fig. 8) that our
synthesized organo-metallogel (Cu–H L) is a semiconducting-
range material. Hence, we have fabricated a metal (Ag)–semi-
conductor (Cu–H L) junction based thin-film device and
investigated the current–voltage (I–V) characteristics of the
device. The I–V measurements of the organo-metallogel
conducted between 0.1 and 100 rad s . The viscoelastic value
ꢁ
1
2
ꢁ1
of the gel was in the range of 10 to 10 rad s , indicating that
G
0
00
and G values increase linearly with increasing applied
4
frequency. This result exhibited the elastic nature of gel.
0
00
As shown in Fig. 7, it was observed that the value of G 4 G ,
4
which indicates the retention of the structural property of the
4
Cu–H L metallogel.
(
Cu–H
of the semiconductor parameter analyzer at a bias voltage from
2 V to +2 V at RT. I–V characteristics of fabricated devices have
4
L) based thin-film device were conducted with the help
3
.6. Optical characterization
The optical characteristics were probed by UV-visible spectro-
scopy. The UV-visible spectrum (solid state) of a thin film of the
Cu–H
calculation of the direct optical band gap of thin-film Cu–H
metallogel was performed using Tauc’s equation:
ꢁ
been examined, as shown in Fig. 9. By using the I–V characteristics
4
L metallogel was recorded in the range 250–600 nm. The
of the Ag/Cu–H L based thin-film device, the interface between Ag
and Cu–H L exhibits a nonlinear rectifying behaviour, which
indicates the formation of a Schottky diode. The obtained I–V
characteristics of the semiconductor gel at RT were further
analyzed by assuming the standard thermionic theory and
4
4
L
4
2
0,33
2
(
ahn) = A(hn ꢁ E )
(1)
g
34–36
where E
g
, h, a and n stand for optical bandgap, Planck’s Cheung’s equation
and we calculated key parameters of the
constant, absorption coefficient, and frequency of light, fabricated device. To analyze the I–V graph, we first employed the
0
0
0
00
0
00
0
Fig. 7 (a) Dynamic shear stress against G and G . (b) Dynamic oscillation strain vs. G and G . (c) Frequency sweep measurements of G and G .
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following standard equation:
Table 1 A comparison table including the charge transport parameters of
4
the Ag/Cu–H L device
ON/OFF Series
Barrier
Ideality
ꢀ
qV
ꢁꢀ
ꢀ
ꢁꢁ
Device name
Fe@MEA
ratio
resistance (O) height (eV) factor Ref.
ꢁqV
I ¼ I0 exp
1 ꢁ exp ꢁ
(2)
0
0
Z KT
375
12.44
18 8.46
—
13.9
5306
81.7
410
—
0.72
0.52
0.47
0.79
0.67
0.61
1.33
3.45
2.78
1.58
1.99
3.0
38
39
40
41
42
Present
work
Z KT
[
C
Cd
4
L
34Cu
2
(NCO)
6
]
O
n
40
H
2
N
6
Au/CuO/P-Si/Al
Cu/ZnO
—
Ag/Cu–H
4
L
70
65
ꢀꢁ
ꢁ
qfB
ꢂ
2
I0 ¼ AA T exp
(3)
KT
0
where I , q, K, T, V, A, Z and A* represent reverse saturation
current, electronic charge, Boltzmann constant, temperature (K),
voltage, effective diode area, ideality factor and Richardson
constant, respectively. The effective diode area was calculated as
2
0
3
.0314 cm and the Richardson constant was considered as
ꢁ
2
ꢁ2
4
2 A K cm for the Cu–H L gel based devices.
We have also calculated the series resistance (R
s
), ideality
0
factor (Z ) and barrier height (f
B
) by using following equations:
Fig. 8 The UV-visible absorption spectrum (inset) and Tauc plot for Cu–
L.
ꢀ
ꢁ
0
H
4
dV
Z KT
q
¼
þ IRs
(4)
(5)
dðln IÞ
ꢀ
ꢁ
ꢂ
A T2
KT
f ¼
ln
B
q
J0
The estimated value of reverse saturation current was 3.80 ꢀ
ꢁ6
10
A and values of the calculated barrier height (f ), ideality
B
factor (Z), opening voltage (V) and series resistance (R ) for the
s
synthesized complex-based SBD respectively are B0.61 eV,
B3.0, B0.5 volts and B65 O (Table 1). For a better under-
standing of the charge transport phenomena in the fabricated
device, we analyzed the logarithmic-scale I–V characteristics
which are shown in Fig. 10, which can be divided into two
slopes defined as region-I and region-II. In region-I, current
follows a linear behavior with voltage which corresponds to the
Scheme 2 A schematic representation of the fabrication of a Schottky
diode based on the synthesized Cu–H L metallogel.
4
Fig. 9 I–V characteristic graph for the ITO/Cu–H
4
L/Ag-based thin-film
4
Fig. 10 log I vs. log V curve for the ITO/Cu–H L/Ag-based thin-film
device.
device.
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ohmic regime. In region-II, current follows a nonlinear
behavior with voltage and current is proportional to V . This
7 J. Jagur-Grodzinski, Polym. Adv. Technol., 2010, 21,
27–47.
2
corresponds to the trap free space charge limited current
8 A. Biswas, S. Mukhopadhyay, R. S. Singh, A. Kumar,
N. K. Rana, B. Koch and D. S. Pandey, ACS Omega, 2018,
3
7
(SCLC) region.
3, 5417–5425.
9
N. Malviya, C. Sonkar, R. Ganguly, D. Bhattacherjee,
K. P. Bhabak and S. Mukhopadhyay, ACS Appl. Mater.
Interfaces, 2019, 11, 47606–47618.
4
. Conclusions
Herein, we have developed the practical synthesis of a new
modular and functional metallogel, based on a succinic acid
derivative and Cu(OAc) in DMF. The gel-phase material was
1
1
1
1
1
1
1
1
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confirmed based on rheological experiments and also
established was the mechanical stability of the metallogel.
Well-defined cross-linked nanofibers of the supramolecular
Cu -based metallogel were confirmed via SEM, TEM, and
AFM analyses. FT-IR, UV-visible, ESI-MS and Job plot results
established the mechanism of the metallogel. The optical
band-gap measurements of the metallogel based on the succinic
acid-derived compound (H L) and Cu(OAc) suggest the semi-
conducting nature of the metallogel. Additionally, we fabricated
an MS junction thin-film electronic device from Ag metal and the
4
semiconducting Cu–H L gel. The nonlinear charge transportation
of the device obtained from the I–V characteristic graph confirmed
the fabrication of a Schottky diode. Thus, the present study of
2
+
4 S. Ganta and D. K. Chand, Inorg. Chem., 2018, 57,
3634–3645.
4
2
5 S. Dhibar, A. Dey, A. Dey, S. Majumdar, D. Ghosh, P. P. Ray
and B. Dey, ACS Appl. Electron. Mater., 2019, 1, 1899–1908.
6 R. Jana, A. Dey, M. Das, J. Datta, P. Das and P. P. Ray, Appl.
Surf. Sci., 2018, 452, 155–164.
7 H. Sheng, S. Muthukumar, N. W. Emanetoglu and Y. Lu,
Appl. Phys. Lett., 2002, 80, 2132–2134.
4
ITO/Cu–H L/Ag suggests the future possibility of achieving
supramolecular Cu metallogel based electronic devices for
advanced technology.
2
+
18 R. Borthakur, A. Kumar, A. Lemtur and R. A. Lal, RSC Adv.,
013, 3, 15139–15147.
2
1
9 R. K. Upadhyay, A. P. Singh, D. Upadhyay, S. Ratan,
C. Kumar and S. Jit, IEEE Photonics Technol. Lett., 2019, 31,
1151–1154.
Conflicts of interest
20 R. K. Upadhyay, A. P. Singh, D. Upadhyay, A. Kumar,
C. Kumar and S. Jit, IEEE Electron Device Lett., 2019, 40,
There are no conflicts to declare.
1961–1964.
Acknowledgements
21 M. Sutradhar, T. Roy Barman, J. Kxlanke, M. G. B. Drew and
E. Rentschler, Polyhedron, 2013, 53, 48–55.
The present work is financially supported by the IIT (BHU),
Varanasi and MHRD, New Delhi, India. The authors are grateful
to the CIFC, IIT (BHU) and Department of Chemistry, IIT (BHU)
for providing the instrumentation facilities. The authors are
also grateful to Mayank Varshney, Manoj Sharma, and Anton
Paar for providing the rheological facilities.
2
2
2
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