CN109668942A - Two-dimensional metallic/oxide heterojunction, preparation method and sensor - Google Patents
Two-dimensional metallic/oxide heterojunction, preparation method and sensor Download PDFInfo
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- CN109668942A CN109668942A CN201910082456.XA CN201910082456A CN109668942A CN 109668942 A CN109668942 A CN 109668942A CN 201910082456 A CN201910082456 A CN 201910082456A CN 109668942 A CN109668942 A CN 109668942A
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
- G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
- G01N27/12—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a solid body in dependence upon absorption of a fluid; of a solid body in dependence upon reaction with a fluid, for detecting components in the fluid
- G01N27/125—Composition of the body, e.g. the composition of its sensitive layer
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
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- G01K7/18—Measuring temperature based on the use of electric or magnetic elements directly sensitive to heat ; Power supply therefor, e.g. using thermoelectric elements using resistive elements the element being a linear resistance, e.g. platinum resistance thermometer
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- G—PHYSICS
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
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- G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
- G01N27/12—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a solid body in dependence upon absorption of a fluid; of a solid body in dependence upon reaction with a fluid, for detecting components in the fluid
- G01N27/121—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a solid body in dependence upon absorption of a fluid; of a solid body in dependence upon reaction with a fluid, for detecting components in the fluid for determining moisture content, e.g. humidity, of the fluid
Abstract
The present invention relates to a kind of two-dimensional metallic/oxide heterojunctions, it includes two-dimentional transition metal oxide layer and metallicity two dimension transient metal chalcogenide compound layer, wherein, the two-dimentional transition metal oxide layer and metallicity two dimension transient metal chalcogenide compound layer form hetero-junctions in same two-dimensional material face.Two-dimensional metallic/oxide heterojunction preparation method is to heat the metallicity two dimension transient metal chalcogenide compound layer using local laser, so that a part of the metallicity two dimension transient metal chalcogenide compound layer is converted into two-dimentional transition metal oxide layer.The invention further relates to a kind of using two-dimensional metallic/oxide heterojunction sensor.
Description
Technical field
The present invention relates to field of nanometer technology more particularly to a kind of two-dimensional metallic/oxide heterojunction, preparation method with
And the sensor using the hetero-junctions.
Background technique
Metallicity two dimension transient metal chalcogenide compound nano material has good electric conductivity, in Two-dimensional electron device
Have a wide range of applications potentiality.Metallicity two dimension transient metal chalcogenide compound nano material usually has curing niobium (NbS2)、
Tantalum disulfide (TaS2), vanadium disulfide (VS2), two selenizing niobium (NbSe2), two selenizing tantalum (TaSe2), two selenizing vanadium (VSe2) etc..
The prior art prepares hetero-junctions poor controllability in metallicity two dimension transient metal chalcogenide compound surface growth, difficult
To realize specific position and shape.The hetero-junctions being stacked, contact interface can only be prepared by building hetero-junctions using transfer method
It is poor.Moreover, existing oxide sensor and two-dimensional material sensor cover face the restriction that operating temperature is high or sensitivity is low.
Summary of the invention
In view of this, the present invention provides a kind of metal/oxide hetero-junctions in same two-dimensional material face, preparation side
Method and the sensor for using the hetero-junctions.
A kind of two-dimensional metallic/oxide heterojunction comprising two-dimentional transition metal oxide layer and metallicity two dimension transition
Metal-chalcogenide layer, wherein the two dimension transition metal oxide layer and metallicity two dimension transient metal chalcogenide compound
Layer forms hetero-junctions in same two-dimensional material face.
A kind of sensor comprising two-dimensional metallic/oxide heterojunction and spaced first metal electrode and
Two metal electrodes, wherein the two-dimensional metallic/oxide heterojunction includes: two-dimentional transition metal oxide layer and difference position
The first metallicity two dimension Transition Metal Sulfur in same two-dimensional material face in the two-dimentional transition metal oxide layer both sides
Belong to compound layer and the second metallicity two dimension transient metal chalcogenide compound layer；First metal electrode and first metal
Property the electrical connection of two dimension transient metal chalcogenide compound layer, and second metal electrode and the second metallicity two dimension transition gold
Belong to chalcogenide layer electrical connection.
A kind of preparation method of two-dimensional metallic/oxide heterojunction, method includes the following steps: providing metallicity two dimension
Transient metal chalcogenide compound layer；And in oxygen-containing atmosphere, which is heated using local laser
Belong to compound layer, so that a part of the metallicity two dimension transient metal chalcogenide compound layer is converted into two-dimentional transiting metal oxidation
Nitride layer.
Compared to the prior art, the system of the metal/oxide hetero-junctions provided by the invention in same two-dimensional material face
Preparation Method is simple, and the hetero-junctions be used as sensor when, the sensing material, the good contact interface, novelty that are completely exposed with it
Sensor mechanism, sensitivity with higher.
Detailed description of the invention
Fig. 1 is the preparation method flow chart of two-dimensional metallic/oxide heterojunction provided in an embodiment of the present invention.
Fig. 2 is the overlooking structure diagram of two-dimensional metallic/oxide heterojunction provided in an embodiment of the present invention.
Fig. 3 is the overlooking structure diagram of another two-dimensional metallic/oxide heterojunction provided in an embodiment of the present invention.
Fig. 4 is the overlooking structure diagram of another two-dimensional metallic/oxide heterojunction provided in an embodiment of the present invention.
Fig. 5 is the structural schematic diagram provided in an embodiment of the present invention using two-dimensional metallic/oxide heterojunction sensor.
Fig. 6 is the optical photograph of the linear channel of sensor provided in an embodiment of the present invention.
Fig. 7 is the optical photograph of the serpentine channels of sensor provided in an embodiment of the present invention.
Fig. 8 is the atomic force micrograph (AFM) for the sensor that channel provided in an embodiment of the present invention is linear.
Fig. 9 is the NbS for the sensor that channel provided in an embodiment of the present invention is linear2Electronic diffraction photo
(SAED)。
Figure 10 is the Nb for the sensor that channel provided in an embodiment of the present invention is linear2O5High-resolution transmitted electron it is aobvious
Micro mirror photo (HRTEM).
Figure 11 is the Fast Fourier Transform (FFT) (FFT) in the region 1 of Figure 10.
Figure 12 is the Fast Fourier Transform (FFT) in the region 2 of Figure 10.
Figure 13 is the operation principle schematic diagram of sensor provided in an embodiment of the present invention.
Figure 14 is the current -voltage curve of sensor provided in an embodiment of the present invention electrical testing under high vacuum environment
Figure.
Figure 15 is the current -voltage curve figure that sensor provided in an embodiment of the present invention is tested under different humidity environment.
Figure 16 is the Nb of sensor provided in an embodiment of the present invention2O5Infrared spectrogram.
Figure 17 is electric current-moisture curve figure of sensor provided in an embodiment of the present invention.
Figure 18 is the current versus time curve figure of the response speed of sensor provided in an embodiment of the present invention.
Figure 19 is the current versus time curve figure of the stability of sensor provided in an embodiment of the present invention.
Figure 20 is the current-temperature curve graph of sensor provided in an embodiment of the present invention.
Figure 21 is the resistance-temperature curve and resistivity-time curve graph of sensor provided in an embodiment of the present invention.
Figure 22 is positive temperature coefficient-temperature relation comparison diagram of different temperature sensing materials.
Figure 23 is the invertibity current -voltage curve figure of sensor provided in an embodiment of the present invention.
Figure 24 is sensitivity test result of the sensor provided in an embodiment of the present invention to ammonia concentration.
Figure 25 is response time and the recovery time test result of sensor provided in an embodiment of the present invention.
Figure 26 is the sensitive of ammonia gas sensor provided in an embodiment of the present invention and the ammonia gas sensor of existing other materials
Degree and response time comparison.
Figure 27 is sensor provided in an embodiment of the present invention to gas-selectively test result.
Figure 28 is the Au-Nb of traditional gold electrode contact2O5The structural schematic diagram of-Au sensor.
Figure 29 is the Au-Nb of traditional gold electrode contact2O5The Current Voltage of-Au sensor and sensor provided by the invention
Curve comparison figure.
Figure 30 is the optical photograph of flexible sensor provided in an embodiment of the present invention.
Figure 31 is the humidity and temperature sensing test curve figure of flexible sensor provided in an embodiment of the present invention.
Figure 32 is the ammonia sensing testing curve graph of flexible sensor provided in an embodiment of the present invention.
Figure 33 is electric current-radius of curvature test result of flexible sensor provided in an embodiment of the present invention.
Figure 34 is electric current-number of bends radius test result of flexible sensor provided in an embodiment of the present invention.
Main element symbol description
Specific embodiment
The present invention is described in further detail below in conjunction with the accompanying drawings and the specific embodiments.
In order to make it easy to understand, the present invention first introduces the system of two-dimensional metallic/oxide heterojunction provided in an embodiment of the present invention
Preparation Method.The embodiment of the present invention is only with NbS2/Nb2O5It is illustrated for hetero-junctions.
Referring to Fig. 1, the preparation method of two-dimensional metallic/oxide heterojunction 101 provided in an embodiment of the present invention includes following
Step:
Step S10 provides a metallicity two dimension transient metal chalcogenide compound layer 102；And
Step S20, in oxygen-containing atmosphere, using 20 local heating of the laser metallicity two dimension transient metal chalcogenide compound
Layer 102, so that a part of the metallicity two dimension transient metal chalcogenide compound layer 102 is converted into two-dimentional transition metal oxide
Layer 103.
In the step S10, thickness, shape and the preparation of the metallicity two dimension transient metal chalcogenide compound layer 102
Method is unlimited, can according to need selection.The thickness of the metallicity two dimension transient metal chalcogenide compound layer 102 can be 5
- 100 nanometers of nanometer.The metallicity two dimension transient metal chalcogenide compound layer 102 can be single layer two dimension transient metal chalcogenide
Compound also may include multiple two-dimentional transient metal chalcogenide compounds being stacked.In the present embodiment, the metallicity two
Tieing up transient metal chalcogenide compound layer 102 is the NbS that 100 surface of silicon base is grown in by chemical vapour deposition technique (CVD)2
Layer.The NbS2Layer with a thickness of 30 nanometers, lateral dimension is 15 microns -30 microns, and shape is triangle.The NbS2Layer includes 40-
50 single layer NbS being stacked2。
In the step S20,20 partial sweep of the laser metallicity two dimension transient metal chalcogenide compound layer can be used
102 any a part, and it is unlimited using the partial shape and size of the scanning of laser 20, only if it were not for the metallicity of scanning whole
Two-dimentional transient metal chalcogenide compound layer 102.The oxygen-containing atmosphere is air.The power of the laser 20 can be
10mW-50mW.The scanning speed of the laser 20 can be the 0.1 micro- meter per second of micro- meter per second -1.In the present embodiment, power is utilized
30mW, the laser that 532 nanometers of wavelength, in air with scanning speed for 0.5 micro- meter per second partial sweep NbS2The middle part of layer
Point, make the NbS2The middle section thermal oxide of layer is Nb2O5Layer, and both sides remain as NbS2Layer.The NbS2Layer is metallicity, institute
State Nb2O5Layer is insulator.
Referring to fig. 2, the two-dimensional metallic/oxide heterojunction 101 is the metal-insulator-in same two-dimensional material face
Metal hetero-junction NbS2-Nb2O5-NbS2.Two-dimensional metallic/the oxide heterojunction 101 includes a two-dimentional transition metal oxide
Layer 103 and the metallicity two dimension transient metal chalcogenide chemical combination for being located at 103 both sides of the two-dimentional transition metal oxide layer
Nitride layer 102.It is appreciated that two-dimensional metallic/the oxide heterojunction 101 can also only include a metallicity two dimension transition gold
Belong to chalcogenide layer 102 and a two-dimentional transition metal oxide layer 103, as shown in Figure 3；Or including multiple metallicity two dimensions
Transient metal chalcogenide compound layer 102 and multiple two-dimentional transition metal oxide layers 103 are arranged alternately, as shown in Figure 4.The gold
Attribute two dimension transient metal chalcogenide compound layer 102 and two-dimentional transition metal oxide layer 103 can be set side by side as shown in Figure 2
It sets, it can also be as shown in Figure 3 around setting.
It is appreciated that since the method that the present invention uses local laser thermal oxide prepares two-dimensional metallic/oxide heterojunction
101, the hetero-junctions in same two-dimensional material face can be arrived, and this method can accurately control the two dimension transition metal oxide layer
103 shapes and sizes.Using the sensor of the two-dimensional metallic/oxide heterojunction 101, due to the two-dimensional metallic/oxide
The Nb of hetero-junctions 1012O5Two apparent surfaces are completely exposed, and have biggish gas interface.It is appreciated that of the invention
NbS2-Nb2O5-NbS2Hetero-junctions can be used for preparing other electronic devices.
Referring to Fig. 5, sensor 10 provided in an embodiment of the present invention includes: two-dimensional metallic/oxide heterojunction 101, and
First electrode 104 and second electrode 105.Specifically, the two-dimensional metallic/oxide heterojunction 101 is NbS2-Nb2O5-NbS2
Hetero-junctions.
The first electrode 104 be set to the surface of a metallicity two dimension transient metal chalcogenide compound layer 102 and with
The metallicity two dimension transient metal chalcogenide compound layer 102 electrical connection, the second electrode 105 are set to another metallicity two
It ties up the surface of transient metal chalcogenide compound layer 102 and is electrically connected with the metallicity two dimension transient metal chalcogenide compound layer 102.
The sensor 10 can also include substrate 100, and the two-dimensional metallic/oxide heterojunction 101 is set to 100 table of substrate
Face.The substrate 100 can be the growth substrate of the growth metallicity two dimension transient metal chalcogenide compound layer 102, such as
Silicon wafer；It may be other substrates, for example, the two-dimensional metallic/oxide heterojunction 101 is first transferred to a flexible polymer
Object substrate surface, then prepare the first electrode 104 and second electrode 105.The first electrode 104 and second electrode 105 are
Metal electrode.In the present embodiment, the first electrode 104 and second electrode 105 are golden film, the NbS2-Nb2O5-NbS2It is heterogeneous
Knot is set to silicon substrate surface.
The two dimension transition metal oxide layer 103 forms the channel of the sensor 10.The embodiment of the present invention is made respectively
It is the sensor 10 of snakelike (serpentine) for the sensor 10 and channel that channel is linear (linear).Referring to
Fig. 6-7 is as it can be seen that NbS2-Nb2O5Interfacial contact is good.
Fig. 8 is the atomic force micrograph (AFM) for the sensor that channel provided in an embodiment of the present invention is linear.Referring to
Fig. 8 is as it can be seen that Nb2O5Channel width is about 1 micron, and the Nb formed after thermal oxide2O5The thickness ratio NbS of layer2The thickness of layer
It is thinned about 2 nanometers -3 nanometers.
Fig. 9 is the NbS for the sensor that channel provided in an embodiment of the present invention is linear2Electronic diffraction photo
(SAED).Figure 10 is the Nb for the sensor that channel provided in an embodiment of the present invention is linear2O5High-resolution transmission electron microscopy
Mirror photo (HRTEM).Figure 11 is the Fast Fourier Transform (FFT) (FFT) in the region Figure 10 1.Figure 12 is in quick Fu in the region Figure 10 2
Leaf transformation.By Fig. 9-12 as it can be seen that NbS2For 3R crystal phase, and Nb2O5For the T-Nb of rhombic system2O5。
It is described to use NbS2-Nb2O5-NbS2The sensor 10 of hetero-junctions may be used as humidity sensor, temperature sensor with
And gas sensor.Next, the present invention is first illustrated the working principle of the sensor 10.The work of the sensor 10
Make principle and be based on extraneous factor, such as vapor or ammonia, to Nb2O5The regulation of Surface Hydrogen ionic conductance.
Referring to Figure 13, specifically, Nb2O5For insulator, hydrone in adsorption air and form conductive path,
Carrier is H+.The total conductance of channel is G=N q μ, and wherein N is H+Quantity, q H+Unit charge amount, μ are H+ mobility.Outside
When powering up, NbS2/Nb2O5Interface can occur electrochemical reaction and provide and consume H+, anode reacts 2H2O→O2+4H++
4e-, cathode reacts 2H++2e→H2.Further, reducibility gas NH3It may participate in the anode of 10 electrode of sensor
Electrochemical reaction, specially 2NH3·H2O-6e-→N2+2H2O+6H+。
Figure 14 is the current -voltage curve figure of the sensor 10 electrical testing under high vacuum environment.As seen from Figure 14,
The sensor 10 is not turned on, and is shown as with insulator Nb2O5For the capacitor charging/discharging curve of dielectric layer.Figure 15 is the biography
The current -voltage curve figure that sensor 10 is tested under different humidity environment.As seen from Figure 15, the sensor 10 is connected, described
The electric current of sensor 10 increases with ambient humidity and is increased.Figure 16 is the Nb of the sensor 102O5Infrared spectrogram.By scheming
16 as it can be seen that there are hydrone vibration peaks in the sensor 10, it was demonstrated that Nb2O5There is Water Molecular Adsorption on surface.
Next, the present invention is further tested and is analyzed to the working performance of the sensor 10.
(1) it is used as humidity sensor
Working principle: under isothermal condition, under different air humiditys, Nb2O5Layer surface adsorpting water quantity is different, carries
Flow sub- H+Number is different, and device conductance is caused to change.
Test condition 1: it is 25 DEG C that it is constant, which to test environment temperature, and the constant test voltage of the sensor 10 is 0.8V, is surveyed
It tries envionmental humidity and tapers to 90% from 30%.Figure 17 is electric current-moisture curve figure of the sensor 10.From Figure 17
As it can be seen that the electric current of the sensor 10 can change with humidity and change 3 orders of magnitude, that is, spirit of the sensor 10 to humidity
Sensitivity is very high.
Test condition 2: it is 25 DEG C that it is constant, which to test environment temperature, and the constant test voltage of the sensor 10 is 0.8V, is surveyed
It tries envionmental humidity and is quickly switched into 100% from 50%, then being switched fast is 50%.Figure 18 is the response of the sensor 10
The current versus time curve figure of speed.From Figure 18 as it can be seen that test envionmental humidity from 50% be quickly switched into 100% when, it is described
The response time of sensor 10 be 10 seconds, and test envionmental humidity from 100% be quickly switched into 50% when, the sensor
10 response time is 58 seconds.That is, response speed of the sensor 10 when humidity rises is faster than the sound in humidity decline
Answer speed.This is because Nb2O5The speed of layer surface absorption vapor is faster than the speed of desorption vapor.If testing environment temperature
Degree increases, then Nb2O5The speed of layer desorption vapor can become faster, and the response speed in humidity decline can also become faster.
Test condition 3: it is 25 DEG C that it is constant, which to test environment temperature, and the constant test voltage of the sensor 10 is 0.8V, institute
State sensor 10 respectively relative humidity be 50%, 70%, 90%, 100% test environment in continuous work 1 hour.Figure 19
For the current versus time curve figure of the stability of the sensor 10.From Figure 19 as it can be seen that the sensor 10 is respectively in different humidity
Property retention is stablized in test in continuous 1 hour under environment.
(2) it is used as temperature sensor
Working principle: under the conditions of constant absolute humidity, when temperature difference, Nb2O5Layer surface adsorpting water quantity is different, carries
Flow sub- H+Number is different, and device conductance is caused to change.Specifically, when the temperature increases, Nb2O5The hydrone of layer surface absorption is de-
It is attached, carrier H+Number reduces, Nb2O5Layer resistance increases；When the temperature decreases, Nb2O5The hydrone of layer surface absorption increases, and carries
Flow sub- H+Number increases, Nb2O5Layer resistance reduces.That is, Nb2O5Layer shows as resistance positive temperature coefficient PTCR, and (temperature increases, resistance
It increases).The temperature measurement mechanism is different from the temperature measurement mechanism of existing temperature sensor.
Test condition 1: fixed test environment absolute humidity is constant, steam partial pressure 1.5kPa, the sensor 10
Constant test voltage is 0.8V, and the test environment temperature is increased to 55 DEG C from 25 DEG C.Figure 20 is the electric current-of the sensor 10
Temperature profile.From Figure 20 as it can be seen that the electric current of the sensor 10 can vary with temperature and change the 2-3 order of magnitude, that is, described
Sensor 10 is very high to the sensitivity of temperature.
Test condition 2: fixed test environment absolute humidity is constant, steam partial pressure 1.5kPa, the sensor 10
Constant test voltage is 0.8V, and the sensor 10 works 550 seconds in 25 DEG C of temperature of test environment, tests the sensor
10 resistance.
Test condition 3: fixed test environment absolute humidity is constant, steam partial pressure 1.5kPa, the sensor 10
Constant test voltage is 0.8V, and the test environment temperature is continuously increased to 75 DEG C from 25 DEG C, tests the electricity of the sensor 10
Resistance.
Figure 21 is the resistance-temperature curve and resistivity-time curve graph of the sensor 10.From Figure 21 as it can be seen that the biography
In continuous warming test, device resistance increases with temperature and increases sensor 10, resistance positive temperature coefficient up to 20%/DEG C,
And the sensor 10 current stability at 25 DEG C is good.
Figure 22 is positive temperature coefficient-temperature relation comparison diagram of different temperature sensing materials.From this figure 22, it can be seen that the temperature
Spend the positive temperature coefficient and commercialized BaTiO at present of sensor 103The positive temperature coefficient of ceramic thermal resistance is suitable, and works
Temperature is lower than BaTiO3Ceramics.BaTiO3The operating temperature of ceramics need to usually be higher than 100 DEG C, and the temperature sensor 10 can be
It works between 25 DEG C -75 DEG C.
Test condition 4: fixed test environment absolute humidity is constant, steam partial pressure 1.5kPa, the sensor 10
Constant test voltage is 0.8V, and test temperature is increased to 55 DEG C from 25 DEG C, then is reduced to 25 DEG C.Figure 23 can for the sensor 10
Inverse property current -voltage curve figure.From Figure 23 as it can be seen that the sensor 10 in temperature from when being increased to 55 DEG C for 25 DEG C, electric current is with temperature
Degree increases and declines, and when temperature is from when being reduced to 25 DEG C for 55 DEG C, electric current restores to original numerical value, shows good invertibity.
(3) it is used as ammonia (NH3) sensor
Working principle: in constant-temperature constant-humidity environment, reducibility gas NH3It may participate in the anode of 10 electrode of sensor
Electrochemical reaction, 2NH3·H2O-6e-→N2+2H2O+6H+, ultimately increase carrier H+Number, to influence channel conduction.
The ammonia gas sensor can be in working and room temperature, and working principle is different from the working principle of existing ammonia gas sensor.
Test condition 1: the temperature for testing environment is fixed as 25 DEG C, and relative humidity is fixed as 50%, the sensor 10
Test voltage is constant constant for 0.8V.Figure 24 is sensitivity test result of the sensor 10 to ammonia concentration, wherein sensitive
Degree uses curent change I/I respectively0It is indicated with resistance change Δ R/R.From Figure 24 as it can be seen that the sensor 10 is to concentration
Sensitivity I/I of the ammonia of 1000ppm0Up to 80, to the sensitivity Δ R/R of the ammonia of concentration 50ppm up to 80%, that is, institute
It is very high to the sensitivity of ammonia concentration to state sensor 10.Figure 25 is response time and the recovery time test knot of the sensor 10
Fruit.From Figure 25 as it can be seen that the response time of the sensor 10 is 40 seconds, recovery time is 110 seconds.Figure 26 is ammonia of the invention
The sensitivity of sensor 10 and the existing room temperature ammonia gas sensor based on two-dimensional material and response time compare.It can from Figure 26
See, is substantially better than for the sensitivity of ammonia gas sensor 10 of the invention and response time most of existing based on two-dimensional material
Room temperature ammonia gas sensor.
The excellent properties of ammonia gas sensor 10 of the invention are attributed to its novel sensor mechanism: ammonia participates in electrode reaction
To realize the regulation to Surface Hydrogen ionic conductance.Ammonia gas sensor of the invention can be in working and room temperature, and size can be
Nanoscale.However, ammonia gas sensor of the commercialization based on oxide is charge-doping mechanism at present, not only sensitivity is lower,
200 DEG C of operating temperature need to be higher than.Existing two-dimensional material sensor is similarly charge-doping mechanism, and sensitivity is lower.Commercially
The electrochemical sensor of change uses three electrode labyrinths, generally grade device, cannot achieve micron order device.
Test condition 2: the temperature for testing environment is fixed as 25 DEG C, and relative humidity is fixed as 50%, the sensor 10
Test voltage is constant constant for 0.8V.The sensor 10 is tested respectively to ammonia, hydrogen chloride gas, alcohol gas, acetone gas
The susceptibility of body, ether gas and hexamethylene gas.Figure 27 is the sensor 10 to gas-selectively test result.From Figure 27
As it can be seen that the sensor 10 only apparent response occurs to ammonia, excellent selectivity is shown.
Figure 28 is the Au-Nb of traditional gold electrode contact2O5The structural schematic diagram of-Au sensor.Traditional gold electrode contact
Au-Nb2O5- Au sensor is based on NbS with provided by the invention2-Nb2O5-NbS2The basic phase of structure of the sensor 10 of hetero-junctions
Together, it is distinguished as gold electrode being directly arranged at Nb2O5Both sides, but same channel length and width are all the same.Figure 29 is tradition
The Au-Nb of gold electrode contact2O5- Au sensor is based on NbS with provided by the invention2-Nb2O5-NbS2The sensor 10 of hetero-junctions
I-v curve comparison diagram.As seen from Figure 29, provided by the invention to be based on NbS2-Nb2O5-NbS2The sensor of hetero-junctions
10 than the Au-Nb that traditional gold electrode contacts2O5- Au working sensor electric current is higher, and operating voltage is lower.This is because a step swashs
Light processes the interface contact resistance very little of the metal/oxide hetero-junctions of brought high quality.Work as NbS2-Nb2O5-NbS2Device
When the channel length of part is down to 1 micron, operating voltage can be further reduced to 0.5V-0.8V, be increased using snakelike electrode design
When adding channel width, operating current can reach 100nA.
In another embodiment, the present invention prepares flexible sensor as substrate 100 using PET film.Figure 30 is flexibility
The optical photograph of sensor.Figure 31 is the humidity and temperature sensing test curve figure of flexible sensor.Figure 32 is flexible sensor
Ammonia sensing testing curve graph.By Figure 31-32 as it can be seen that the performance of the flexible sensor and the sensor on rigid silicone matrix bottom
Performance is suitable.Figure 33 is electric current-radius of curvature test result of flexible sensor.Figure 34 is electric current-bending of flexible sensor
Number radius test result.By Figure 33-34 as it can be seen that the minimum test radius of curvature of the flexible sensor is 3 millimeters, with curvature half
10 millimeters of number of bends of diameter are 200 times, and minor change only occurs in electric current, show that the flexible sensor has good mechanicalness
Energy.
In addition, those skilled in the art can also do other variations in spirit of that invention, these are spiritual according to the present invention
The variation done should be all included in scope of the present invention.
Claims (10)
1. a kind of two-dimensional metallic/oxide heterojunction comprising two-dimentional transition metal oxide layer and metallicity two dimension transition gold
Belong to chalcogenide layer, which is characterized in that the two dimension transition metal oxide layer and metallicity two dimension transient metal chalcogenide
It closes nitride layer and forms hetero-junctions in same two-dimensional material face.
2. two-dimensional metallic/oxide heterojunction as described in claim 1, which is characterized in that the two dimension transiting metal oxidation
Nitride layer is Nb2O5Layer, the metallicity two dimension transient metal chalcogenide compound layer are NbS2Layer.
3. two-dimensional metallic/oxide heterojunction as claimed in claim 2, which is characterized in that the two-dimensional metallic/oxide is different
Matter becomes NbS2-Nb2O5-NbS2Hetero-junctions.
4. two-dimensional metallic/oxide heterojunction as claimed in claim 2, which is characterized in that the Nb2O5The thickness of layer is less than
The NbS2The thickness of layer.
5. a kind of sensor comprising two-dimensional metallic/oxide heterojunction and spaced first metal electrode and second
Metal electrode, which is characterized in that the two-dimensional metallic/oxide heterojunction includes: two-dimentional transition metal oxide layer and divides
Not Wei Yu the two-dimentional transition metal oxide layer both sides the first metallicity two dimension transition gold in same two-dimensional material face
Belong to chalcogenide layer and the second metallicity two dimension transient metal chalcogenide compound layer；First metal electrode and described first
The electrical connection of metallicity two dimension transient metal chalcogenide compound layer, and second metal electrode and the second metallicity two dimension mistake
Cross metal-chalcogenide layer electrical connection.
6. sensor as claimed in claim 5, which is characterized in that the two dimension transition metal oxide layer is Nb2O5Layer, institute
It states the first metallicity two dimension transient metal chalcogenide compound layer and the second metallicity two dimension transient metal chalcogenide compound layer is
NbS2Layer.
7. a kind of preparation method of two-dimensional metallic/oxide heterojunction, method includes the following steps:
Metallicity two dimension transient metal chalcogenide compound layer is provided；And
In oxygen-containing atmosphere, which is heated using local laser, so that the metal
A part of property two dimension transient metal chalcogenide compound layer is converted into two-dimentional transition metal oxide layer.
8. the preparation method of two-dimensional metallic/oxide heterojunction as claimed in claim 7, which is characterized in that the metallicity
Two-dimentional transient metal chalcogenide compound layer is the NbS that substrate surface is grown in by chemical vapour deposition technique2Layer, local laser add
After heat, the NbS2Layer is partially converted into Nb2O5Layer.
9. the preparation method of two-dimensional metallic/oxide heterojunction as claimed in claim 7, which is characterized in that the laser
Power is 10mW-50mW, and the scanning speed of the laser is the 0.1 micro- meter per second of micro- meter per second -1.
10. the preparation method of two-dimensional metallic/oxide heterojunction as claimed in claim 7, which is characterized in that described oxygenous
Atmosphere is air.
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