In this part, the author presents in detail the results of investigating the
influence of several factors on the operation of the sensor such as
immobilize enzyme temperature and enzyme immobilize time. The
results show that the enzyme immobilize temperature from 30oC to 40oC
and the enzyme immobilize time from 40 to 60 minutes are appropriate
and the performance of the sensor is the best. From the study results, the
authors selected a enzyme immobilize temperature of 30°C and a enzyme
immobilize time of 60 minutes to immobilize the urease enzyme on the
interdigitated electrodes using glutaraldehyde (GA) vapor as cross-linking
agent in fabrication the enzyme-GrISFET sensor for the detection of
atrazine herbicide residues will be discussed in detail in the next part of
this thesis.
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oncentrations.
6
Figure 2.8: TEM images of two VA-CNTs growth
in the same CVD condition in two cases: a) without
water vapor; b) with water vapor
The SEM
results (fig. 2.7)
show that the
addition of water
vapor during
CVD has
significantly
altered the
length, diameter and growth rate of CNTs. The length of the CNTs
increased from 6.5 μm to 40.5 μm corresponding without and with water
vapor, respectively (corresponding to the growth rate of CNTs increased
from 200 nm/min to 1330 nm/min). In addition, the density of CNTs also
increased and CNTs became more uniform when water vapor was
introduced during the CVD process. Figure 2.8 is a TEM image of two
samples of VA-CNTs synthesized without water vapor (Fig. 2.8a) and
with water vapor at 60 sccm during CVD process (Fig. 2.8b). The TEM
images can clearly distinguish amorphous carbon and structural defects of
carbon nanotubes. During CNTs growth, under certain conditions, CNTs
are formed in a bamboo structure (as bamboo crops) which are considered
undesirable structural defects. Unlike the CNTs grown with H2O vapor,
the CNTs have a hollow structure, straight, thin tube, small diameter and
uniform. The analysis of Raman spectra evidences increased
graphitization of CNTs samples with addition of water vapor during CVD
process.
In addition, the effect of water vapor flow rate on the growth rate
and properties of the VA-CNTs was also investigated. We have grown
VA-CNTs using 0.033 g.mL-1 CoFe1.5O4 (M3) catalyst, in the same CVD
condition: at 750°C, Ar/H2/C2H2 = 300/100/30 sccm, and CVD time 30
min, with different water vapor flow rates: 20 sccm, 40 sccm, 60 sccm
7
and 80 sccm. The
SEM results (Fig.
2.10) show that at
60 sccm of water
vapor flow rate
the length, the
density of CNTs is
highest and the
orentiation of
CNTs is also best
among four water
vapor flow rate
investigated.
2.2.3.3. Influence of the ratio of catalyst components
In this study, we have grown VA-CNTs using four cobalt ferrit
samples M1, M2, M3, M4 at different ratios of Co2+:Fe3+ = x:y precursors,
in the same 0.033 g.mL-1
concenstration and in the
same CVD condition.
The results of SEM (fig.
2.12) show that adding
the Co2+ component to
the catalyst mixture plays
a very important role in
improving the growth
rate, length, density or
yield of the VA–CNTs.
The highest length of the
VA-CNTs was 128.3 ±
a) b
)
c
)
d
)
Figure 2.10: SEM images of VA-CNTs samples
VA-CNTs growth from CoFe1,5O4 (M1) 0.033
g.mL-1catalyst in the same CVD condition with
with different water vapor flow rate
Figure 2.12: SEM images of VA-CNTs
growth from 04 catalysts with component
ratios Co2+:Fe3+ = x : y: a) x:y =0:3, b)
x:y =1:2, c) x:y =1:1.5, d) x:y =1:1,
respectively, in the same CVD condition.
8
5.5 μm on the (M3) catalyst with a Co2+:Fe3+ ratio of 1:1.5
(corresponding to a 40% added Co2+) which is significantly higher than
that of the non-Co2+ (M1) catalyst sample. The density of VA-CNTs that
are grown on the (M3) catalyst are also much higher than those of others
VA-CNTs. This is explained by the differences in physical properties
such as transition temperature, melting temperature, and this causes the
metal particles to separate, reducing the diffusion and agglomeration of
small catalyst particles into large particles of catalyst particles at a high
temperature in CVD conditions. This makes the catalyst particles disperse
more evenly than the surface of the substrate and keeping the initial small
size of the catalyst particle, facilitating the formation and development of
the VA-CNT material. However, if too much Co2+ content was added,
which meant that the proportion of Fe3+ was reduced, the height and
density of CNTs decreased (fig. 2.12d), which reduced the yield of VA-
CNTs.
2.3. Fabrication of horizontally aligned CNTs (HA-CNTs)
2.3.1. Preparation of substrate and catalyst material
We used a silicon wafer with a 90 nm thick-SiO2 as substrate for the
catalysts to fabricate HA-CNTs. We used FeCl3.6H2O salts as catalyst
precursors. The salt was
dispersed with deionized
water at different
concentrations of 0.1M,
0.01M, and 0.001M.
The solution was then
deposited on the clean
silicon substrate by
spin-coating at a spin
rate of 6000 rpm.
Figure 2.18: Fabrication process HA-
CNTs material by thermal CVD method.
9
2.3.2. Fabrication process of HA-CNTs
The procedure and steps for fabrication of HA-CNTs by thermal CVD
method are divided into 4 stages as described in fig. 2.18.
2.3.3. Fabrication results of HA-CNTs
2.3.3.1. Influence of catalyst solution concentration
We have growth HA-CNTs using a solution of FeCl3 with different
solution concentrations: 0.001M, 0.01M, and 0.1M under the same CVD
conditions: the growth temperature of 1000°C, Ar/C2H5OH:H2 of 20:30
sccm, and CVD time of 60 min. Figure 2.20 shows the SEM of HA-CNTs
grown using FeCl3 with different concentrations of solution: 0.001M,
0.01M, 0.1M. The SEM results show that the density of CNTs increases
with increasing the concentration of FeCl3 catalyst solution from 0.001 M
to 0.01 M. However, when the solution concentration was too high (fig.
2.20c), the CNTs
were not straight,
overlapping, coils
and quickly end
the long growing
process. By
counting the
number of CNTs
at different distances (1 mm, 5 mm, 10 mm, and 15 mm) from the
catalytic, we can plot the density distribution of CNTs by the length of
the substrate corresponding to different catalyst solutions. The difference
in density and length of the HA-CNTs is due to the difference in size of
the catalyst particles when we change the concentration of the catalyst
solution. In this study, the FeCl3 catalyst solution concentration of 0.01 M
was appropriate. HA-CNTs were formed at this concentration with high
density and good orientation.
Figure 2.20: SEM images of HA-CNTs grown
using FeCl3 with different solution concentrations:
a) 0.001M, b) 0.01M, c) 0.1M.
10
2.3.3.2. Influence of CVD temperature
The HA-CNTs were
grown at four different
temperatures from
850°C to 1000°C with
growth conditions:
synthesis time of 60
min, Ar/C2H5OH:H2 =
20:30 sccm. The SEM
images (fig. 2.23)
indicates that the density
of CNTs increases with
increasing temperature
from 850°C to 950°C. The explanation is that a higher growth
temperatures promote a higher density of nanotube nucleations resulting
in a higher density of ulralong nanotubes. However, when the
temperature was too high, other carbon products, such as amorphous
carbon begin to deposit and cover the catalyst particles, and affecting on
the germination and growth processes of CNTs. Under our experiment
condition, the optimum temperature for the growth process of HA-CNTs
was 950oC.
2.3.3.3. Influence of carbon source flow rate
We study the influence of ethanol flow rate on the CNTs density and
alignment. The results of SEM images (fig. 2.24) show that the CNTs
density increases with increasing ethanol flow rate. The highest CNTs
density achieves when the ethanol/Ar flow rate was 40 sccm
(~150 tubes/mm). However, at this flow rate of ethanol, the density of
CNTs decreases rapidly and the ratio of CNTs extending all the length of
substrate was low (~25/150 tubes). For others cases, the ethanol flow rate
Figure 2.23: SEM images of HA-CNTs
grown at four different temperatures: a)
850oC, b) 900oC, c) 950oC, d) 1000oC
11
was 30 sccm for the
highest density of
CNTs (~80 tubes/mm),
CNTs have good
orientation, high purity
and the ratio of CNTs
extending all the length
of substrate is about
30/80. As a result, the
optimum flow rate of
ethanol/Ar to grow the
HA-CNTs was 30
sccm.
2.3.4. Growth mechanism and structure of HA-CNTs materials
To demonstrate the
growth mechanism
and aligned along the
gas streamlines of
HA-CNTs in fast-
heating CVD
method, we
proceeded to grow
HA-CNTs on a
SiO2/Si substrate with a slit of 60 μm width and directly growth HA-
CNTs on field effect transistor (FET) electrodes consisting of 19 pairs of
S-D electrodes (source-drain) with an electrode spacing of 30 μm and the
total thickness of the metal layers of the electrode is 188 μm (Cr/Pt =
8/180 μm). The catalyst used to grow HA-CNTs in this case is 0.01M
FeCl3 solution with the CVD conditions were optimized: temperature
Figure 2.25: a,b) Optical microscopy and SEM
image of a SiO2/Si substrate with a slit c) SEM
image of HA-CNTs SiO2/Si substrate with a gap
of 60 μm
Figure 2.24: SEM images of HA-CNTs
grown using 0,01 M FeCl3 with different
flow rate of ethanol/Ar: a) 10 sccm, b) 20
sccm, c) 30 sccm, d) 40 sccm.
12
950oC, 60 minutes
CVD time and gas
Ar/ethanol: H2O flow
rate = 30/30 sccm.
The results of SEM
images (fig. 2.25
and fig. 2.26) shows
that the HA-CNTs
grown accross the
slit and accross the
rough surface of
FET electrode. The
structure of the HA-
CNTs materials was
determined by image
analysis of HRTEM,
Raman spectrum.
The results of the
HRTEM analysis
(fig. 2.28c) and the
Raman spectrum
(fig. 2.29) show that
CNTs have a
diameter of 1.5 nm
and 70% of HA-
CNTs are double
wall CNTs
(DWCNTs), 30% the remaining are single wall (SWCNTs) and about
50% of them are semiconductor.
Figure 2.26: SEM image describes structure of
FET electrode and HA-CNTs grown on the FET
Figure 2.28: a)Illustration of the experimental
setup of HA-CNTs growing on the TEM grid,
b) SEM images and c)HRTEM image of a HA-
CNT on the TEM grid.
Figure 2.29: Raman spectrum of HA-CNTs.
13
CHAPTER 3:
FABRICATION OF GRAPHENE MATERIAL BY
THERMAL CHEMICAL VAPOR DEPOSITION METHOD
3.1. Thermal CVD system used for fabrication of graphene
The thermal CVD system used to fabricate graphene films is also the
thermal CVD system used to fabricate oriented CNTs materials but has
improved the vacuum system.
3.2. Prepare catalyst material
Catalyst material for synthesis of graphene films is poly-crystalline Cu
foils (25 m-thick) of 99.8% purity (Alfa-Aesar). Cu foils were cut into
small pieces of 2-5 cm2 and cleaned before growing graphene.
3.3. Fabrication
process of graphene
material on Cu
substrate
The procedure and
steps for fabrication of
graphene by thermal
CVD method are
divided into four stages
as described in fig. 3.2.
3.4. Fabrication results of graphene films on the Cu substrate
3.4.1. Influence of surface morphology of Cu substrate
To study the influence of surface morphology of Cu substrate to the
quality of graphene films, we compared the quality of graphene films
grown on the Cu substrate treated by two different methods: 5% HNO3
acid for 10 minutes and treatment by the electrochemical polishing
method using 85% H3PO4 acid at 1.9 V for 15 minutes. Results of the
measurement and calculation are obtained from Raman spectra (fig. 3.8)
Figure 3.2: Fabrication process graphene
material by thermal CVD method
atmospheric pressure condition
14
of graphene show that
the graphene films were
fabricated on Cu
substrate which was
treated the surface by
the electrochemical
polishing method
having the highest
quality and the lowest
number of layers (about
2 layers) in the three
graphene materials
investigated. The quality
of graphene is shown via values: I2D/IG = 1.28 is the highest, ID/IG = 0.18
is the lowest, the full width at half maximum (FWHM) = 38.05 cm-1 is
the lowest, and the position of 2D = 2731.68 is the lowest. Therefore,
electrochemical polishing method was chosen to treat the surface of Cu
before synthesizing graphene films in all subsequent analyzes.
3.4.2. Influence of the CVD temperature
To study the influence of the growth temperature on the graphene
quality, we used five electropolished Cu samples and grown at different
temperatures from 850oC to 1030oC with the same CVD condition: CH4
as a carbon source, a synthesis time of 30 minutes, Ar/H2/CH4 flow rates
of 1000/300/20 sccm. Raman spectra in Fig. 3.10 show that no graphene
growth occurs at 8000C. With a higher temperature 8000C, the appears the
graphene character peaks inclusion D peak, G peak, 2D peak at the
positions 1370 cm-1, 1590 cm-1 and 2734 cm-1 respectively. Thus,
fabricate graphene on the Cu substrate surface with the CH4 catalyst
source gas which requests the temperature CVD satisfy the condition
Figure 3.8: Raman spectra of graphene
films on Cu substrate in three cases: a)
before treatment, b) after treatment by
HNO3 5% and c) after treatment by the
electrochemical polishing method.
15
Hình 3.10: Raman spectrum of graphene films
on Cu substrate grown at different
temperatures from 850oC to 1030oC with the
same CVD condition
higher 8500C. The
quality factor
(number of layers,
uniformity, defect,
impurity) of the
graphene film was
identified via 2D peak
position, FWHM,
I2D/ID and ID/IG. The
results show that the
CVD temperature
10000C is the suitable
for fabricating the
graphene fims on the Cu substrate with the CH4 source gas.
3.4.3. Influence of hydrocarbon source flow rate
To study the influence of the hydrocarbon source flow rate on the
graphene quality, we grown graphene at different flow rates of CH4: 0.5
sccm; 2 sccm; 5 sccm; 10 sccm; 20 sccm and 30 sccm, with the same
CVD condition: the growth temperature of 1000°C, a synthesis time of 30
minutes, Ar/H2 flow rates of 1000/300 sccm. Fig. 3.13, and fig. 3.15
present Raman spectra and HRTEM images of graphene films on the Cu
Figure 3.13: a) Raman spectra and b-e) Lorentzian lineshape of 2D band
of graphene films on the Cu substrate with at different flow rate of CH4
16
substrate with at
different flow rate
of CH4,
respectively. The
analyst results
shown that the
number of layers
and quality of
graphene films were grately affected by CH4 flow rates. High quality
single layer graphene films can be manufactured under atmospheric
pressure conditions if the CH4 flow rate is low enough. The number of
graphene layers incresed and quality of graphene decresed when the CH4
flow rate was too high. According to our experimental results, the CH4
flow rate of 5 to 10 sccm was the optimum to obtain 1-2 layers of
graphene films with high uniform and good quality.
3.4.4. Influence of pressure
Pressure has been revealed as key factor during graphene growth. To
study the influence of the pressure on the graphene quality, we compared
the quality of graphene films grown on the Cu substrate grown by two
different conditions: The first grown in atmospheric pressure (APCVD) at
1000°C, a CVD time of 30 minutes, Ar/H2/CH4 flow rates of
1000/300/10 sccm and the second grown in low pressure (LPCVD) at
1000oC, pressure of the reactor of 60 torr, a synthesis time of 30 minutes,
H2/CH4 flow rates of 20/0.3 sccm. We also study influence of the reactor
vacuum levels on the graphene quality by changing pressure of the
reactor from 80 torr to 20 torr. Results of the measurement and
calculation are obtained from Raman mapping spectra (fig. 3.16 and fig.
3.17) show that the graphene films synthesized by LPCVD method were
higher quality and more uniform than those synthesized by APCVD. The
Figure 3.15: HRTEM images of graphene films
on the Cu substrate with flow rate of CH4: a) 10
sccm, b) and c) 30 sccm
17
quality and uniformity of the
graphene films increases with
decreasing the pressure in the
reaction chamber. This
because of the sublimation of
Cu at lower pressure, decrease
the number of the sharp
structures, thereby making the
Cu surface smoother. That is
the cause lead to increase the
quality and uniformity of
graphene films. The lower
pressure of the reactor, the lower the density of impurities and residual
oxygen. That is also a reason why the graphene films quality increases.
Using LPCVD method with pressure of 60 torr, CVD temperature of
1000oC, synthesis time of 30 minutes, H2/CH4 flow rates of 20/0.3 sccm,
graphene films is formed with a maximum area about 10 cm2 with a high
uniformity and less structural defects. About 70% of the graphene film
area is monolayer, 30% of the remaining area is bilayers.
Figure 3.16: Raman spectra of graphene films on the Cu substrate
were synthesized by APCVD and LPCVD methods
Figure 3.17: Raman spectra of
graphene films on the Cu substrate
were synthesized with differrent
pressure of the reaction chamber.
18
CHAPTER 4
ENZYME-GrISFET SENSOR FOR TRACE-DETECTION
OF HERBICIDE ATRAZINE
4.1. Basis of the graphene material selection for fabricating the
enzyme-GrISFET sensor
In this section, we present the basis of the graphene material
selection for fabricating the enzyme-GrISFET sensor, including: the
synthesis technology, the material properties, the mobility of the carrier
charges of the graphene conductive channel and the effective surface area
of the material.
4.2. Fabrication of the enzyme-GrISFET sensor
The procedure for fabrication of the enzyme-GrISFET sensor as
described in fig. 4.3. Fig. 4.9 is an optical microscopy of the enzyme-
GrISFET sensor.
4.3. Application of enzyme-GrISFET sensor for detection of pesticide
residue atrazine
The atrazine detection
in solution was
performed via the
competitive inhibition
mechanism of itself with
respect to the catalytic
activity of the enzyme
urease. Under the
inhibition of atrazine, the
Figure 4.9: Optical microscopy of
the enzyme-GrISFET sensor
Hình 4.3: Fabrication process of the
enzyme-GrISFET sensor
Figure 4.10: Atrazine detection mechanism
of the enzyme-GrISFET sensor.
19
catalytic ability for the urea substance hydrolysis reaction of the urease
enzyme was decreased which lead to the NH4+ ion concentration and the
OH- ion concentration generated by the hydrolysis reaction decreases,
those are the causes which decrease the p (n) doping effect into the
conductivity channel. This leads to the change in the transmission
characteristic of the sensor, namely the potential position changes at
Dirac point (V0) in the horizontal direction as well as changing the
current-out signal intensity ΔIds (fig. 4.10).
4.4. Results and discussion
4.4.1. The structural morphology of the enzyme-GrISFET sensor
The surface
morphology of the
enzyme-GrISFET
sensor was
considered by the
(FESEM) after
synthesis (fig.
4.14).
4.4.2. Determining the saturated concentration of urea substance for
the enzyme-GrISFET sensor
Saturated
concentration of
urea substrate is the
concentration which
the urease enzyme
membrane reacted
100% of its activity,
and then the output
current intensity Ids
of the sensor does not change despite the concentration of urea substrate
increase. Fig. 4.16 describes the Ids-Vg characteristics of enzyme-
Figure 4.16: The characteristic Ids-Vg of
enzyme-GrISFET sensor for Vds = 1 V, Vg in the
0 V - 3 V range, step 0.05 V with the urea
substance concentration range of 5 - 35 mM
Figure 4.14: The optical and SEM images of the
electrode after graphene were transferred
20
GrISFET sensor for Vds = 1 V, Vg in the 0 V - 3 V ranger with the step
0.05 V and the urea concentration range of 5 mM to 35 mM. Observing
Fig. 4.16a image, we can recognize that when increases the urea
substance concentration from 5 mM to 30 mM, the current-out signal
intensity ΔIds doubly increases from 0.15 mA to 0.30 mA and the position
of Dirac point (Vo) was shifted towards higher negative values. However,
continuously increasing the substance concentration to 35 mM, the value
ΔIds hardly increases as well as there is no the movement of the V0 point.
4.4.3. The response characteristic of the enzyme-GrISFET sensor
In this part, the author discusses in detail the installation steps, setting
parameters to determine the transmission characteristic Ids - Vds, Ids - Vg
of the enzyme-GrISFET sensor and how to determine, calculate the
sensor's parameters such as leakage current, transconductance,
capacitance, electron and hole mobility in the graphene channel.
4.4.4. The effect of the fabrication process on the output signal
In this part, the author presents in detail the results of investigating the
influence of several factors on the operation of the sensor such as
immobilize enzyme temperature and enzyme immobilize time. The
results show that the enzyme immobilize temperature from 30oC to 40oC
and the enzyme immobilize time from 40 to 60 minutes are appropriate
and the performance of the sensor is the best. From the study results, the
authors selected a enzyme immobilize temperature of 30°C and a enzyme
immobilize time of 60 minutes to immobilize the urease enzyme on the
interdigitated electrodes using glutaraldehyde (GA) vapor as cross-linking
agent in fabrication the enzyme-GrISFET sensor for the detection of
atrazine herbicide residues will be discussed in detail in the next part of
this thesis.
4.4.5. Enzyme-GrISFET sensor application for detection of pesticide
residue atrazine
4.4.5.1. Sensor characteristics which are inhibited by atrazine
To investigate the sensor characteristics by inhibition of atrazine, we
21
processed to measure their
electrical characterization
processed in the solution
containing atrazine with
concentration of 2 10-2
ppb. Observing the
fig.4.22 we found that the
variations of the drain-
source current ΔIds of the
sensor significantly
decreases from 304 μA to
136 μA and the Dirac
point of graphene Vo
shifts to higher positive values from 0.75 V to 1.25 V when it is inhibited
by atrazine with the concentration 2 10-2 ppb. This result was also
observed in other report. The working principle of our atrazine sensors is
based on the inhibition of atrazine toward urease in the hydrolysis
reaction of urea substance. The hydrolysis of urea substance provided
ions (NH4+, OH−) that would be adsorped onto electrode surfaces, then
led to the increase in charge
density and mobility on
graphene layer. When
atrazine is introduced, it acts
as an inhibitor to reduce
activity of enzyme, lowers the
concentrations of ions at the
electrodes and subsequently
decreases current signal as
also as shift of Vo.
4.4.5.2 The repeatability of
the enzyme-GrISFET sensor.
Fig. 4.23: The six times of
measurement results of the
characteristics Ids-Vg, with Vg from 0 V
to 3 V, Vds = 1V at the atrazine
concentration Catz = 2 10-4 ppb.
Fig. 4.22. The characteristic
transmission Ids-Vg of the GrISFET
sensor with Vg from 0 V to 3 V step 0,5 V,
Vds = 1V, in two cases (before, after) that
is inhibited by the atrazine 2 10-2 ppb.
0.0 0.5 1.0 1.5 2.0 2.5 3.0
6.4
6.5
6.6
6.7
6.8
I d
si
=
1
36
(
A
)
I d
so
=
3
04
(
A
)
ATZ = 0
ATZ = 2 x 10
-2
ppb
I d
s (
m
A
)
Vg (V)
Vo = 1.25 V
ATZ = 2 x 10
-2
ppb
Vo = 0.75 V
ATZ = 0
22
To consider the repeatability of the sensor, we continuously
repeated the six times measurement and comparing the results after the
measurements. From these measurements we can calculate the standard
deviation of sensor Sy = 9.2 at the atrazine concentration of 2 10-4 ppb.
This is an important value in calculating the limit of detector (LOD) of
the sensor.
4.4.5.3 Detection litmit of the GrISFET biosensor
To determine the
LOD of the enzyme-
GrISFET sensor for the
detection of the
herbicide atrazine in
solution, we use
saturated urea solution
(30 mM) and various
carbaryl solutions with
concentrations ranging
from 2 10-4 ppb to 20
ppb were prepared in
deionized water. For
each measurement, the
sensors were incubated for 30 mins at room temperature in the herbicide
solution and then their electrical characterization Ids - Vg was immediately
processed in urea solution. The electrical characteristics Ids - Vg of the
sensor is measured with the voltage of the Vg is sweeped from 0 V to 3 V,
step of 0,05 V, the voltage applied to the drain – the source Vds is 1V. The
current responses of atrazine enzyme-GrISFET sensor at different sample
concentrations are shown in Fig. 4.25. We found that the atrazine level
can be monitored by either position or intensity of Dirac point. When the
concentration of atrazine increased from 2 10-4 ppb to 20 ppb, the
position of Dirac point was shifted towards higher positive values from
0.1 1
6.4
6.5
6.6
6.7
ATZ = 0
ATZ = 2 x 10
-4
ppb
ATZ = 2 x 10
-3
ppb
ATZ = 2 x 10
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