CN117630142A - Heterojunction material based on two-dimensional inorganic material/one-dimensional organic material, and preparation method and application thereof - Google Patents
Heterojunction material based on two-dimensional inorganic material/one-dimensional organic material, and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a heterojunction material based on two-dimensional inorganic materials/one-dimensional organic materials, and a preparation method and application thereof. The composite material comprises two-dimensional inorganic materials and one-dimensional organic materials; the inorganic material comprises a two-dimensional material and/or a nano-sheet of molybdenum sulfide and/or graphene; the organic material includes a phthalocyanine-based semiconductor material. The preparation method comprises the following steps: (1) The inorganic material (MoS 2 ) The nano-sheets of (2) are dispersed in an anhydrous organic solvent to obtain a dispersion liquid; (2) Adding the micro-nano wires of the organic material into the dispersion liquid, mixing, and heating and refluxing to obtain the heterojunction material based on the two-dimensional inorganic material/the one-dimensional organic material. The heterojunction material based on the two-dimensional inorganic material/one-dimensional organic material is applied to the preparation of gas sensingIn the device. MoS of the invention 2 The gas sensor prepared from the CuPc composite material has the advantages of good stability, quick response recovery time, high sensitivity and good selectivity.
Description
Technical Field
The invention belongs to the field of preparation of gas-sensitive materials and high-performance gas sensors, and relates to a heterojunction material based on a two-dimensional inorganic material/a one-dimensional organic material, and a preparation method and application thereof.
Background
In recent years, two-dimensional materials have been widely used in gas sensors. Such as: in 2012, hai Li et al, obtained single and multilayer MoS by mechanical tape-based stripping 2 A film. A Field Effect Transistor (FET) was then fabricated by photolithographic techniques, for the first time for NO detection. Based on single-layer MoS 2 The FET of (2-4) is based on 2-4 MoS, although having a fast response characteristic which is unstable in air 2 Exhibits stable and sensitive characteristics, and LOD is 0.8ppm.2021, li Liangshu et al prepared MoS by hydrothermal method 2 And a resistive device was obtained by instillation method, which was resistant to carbon monoxide (CO) and hydrogen sulfide (H) at 100 DEG C 2 S) has good selectivity and the device exhibits good repeatability and linear relationship.
However, when a single two-dimensional material is used as a sensitive layer, stacking phenomenon is easy to occur, so that the material and target gas cannot be fully contacted, and the sensitivity of the sensor is reduced, and therefore, the performance of the gas sensor based on the single two-dimensional material needs to be improved.
Disclosure of Invention
The invention aims to provide a heterojunction material based on two-dimensional inorganic materials/one-dimensional organic materials, and a preparation method and application thereof.
The invention provides a heterojunction material based on two-dimensional inorganic materials/one-dimensional organic materials, which comprises two-dimensional inorganic materials and one-dimensional organic materials;
the inorganic material comprises a two-dimensional material and/or a nano-sheet of molybdenum sulfide and/or graphene;
the organic material includes a phthalocyanine-based semiconductor material.
In the materials, the mass ratio of the inorganic material to the organic material is 20:3-20;
the phthalocyanine-based semiconductor material includes at least one of copper phthalocyanine (CuPc), cobalt phthalocyanine (CoPc), zinc phthalocyanine (ZnPc), and lead phthalocyanine (PbPc).
In the above materials, the mass ratio of the inorganic material to the organic material is 4:1-2.
In the above material, the particle size of the inorganic material is 300nm to 2000nm;
the length of the organic material is 10-200 mu m.
The invention also provides a preparation method of the heterojunction material based on the two-dimensional inorganic material/the one-dimensional organic material, which comprises the following steps:
(1) The inorganic material (MoS 2 ) The nano-sheets of (2) are dispersed in an anhydrous organic solvent to obtain a dispersion liquid;
(2) Adding the micro-nano wires of the organic material (such as copper phthalocyanine in particular) into the dispersion liquid, mixing, heating and refluxing to obtain the heterojunction material based on the two-dimensional inorganic material/the one-dimensional organic material.
In the preparation method, in the step (1), the method for preparing the nano-sheets of the inorganic material comprises the following steps: and preparing the inorganic material into nano sheets by adopting a grinding auxiliary liquid phase stripping method.
In the preparation method, in the step (2), the method for preparing the micro-nanowires of the organic material comprises the following steps: 1) Mixing the organic material with the organic solvent, and performing ultrasonic treatment to obtain an organic material suspension;
2) Standing the organic material suspension, filtering, and taking supernatant;
3) Immersing the substrate into the supernatant, taking out and drying to obtain the substrate with micro-nano particles on the surface;
4) And placing the substrate with the micro-nano particles on the surface in a two-section temperature-controlled tube furnace, and growing on the surface of the substrate by adopting a physical gas phase transportation method to obtain the micro-nano wire of the organic material.
In the preparation method, the growth conditions of the physical vapor transport method are as follows:
the carrier gas comprises nitrogen or argon;
the velocity of the carrier gas flow may be 10-50 sccm, specifically 20sccm, 10-20 sccm, 20-50 sccm, 10-30 sccm or 10-40 sccm;
the growth time can be 3.5-4.5 h, and can be specifically 4h, 3.5-4 h or 4-4.5 h;
the growth temperature can be 380-420 ℃, specifically 400 ℃, 380-400 ℃ and 400-420 ℃.
In the preparation method, the volume ratio of the mass of the organic material to the organic solvent is 1mg:1 to 6.7ml;
the anhydrous organic solvent comprises ethanol;
the heating reflux time is 1-3 h, and can be specifically 2h or 1-3 h;
the step (2) of heating reflux is followed by centrifugation and filtering to remove sediment;
the centrifugal speed is 6000-9000 r/min, and can be 8000r/min, 6000-8000 r/min, 8000-9000 r/min or 6500-8500 r/min.
The heterojunction material based on the two-dimensional inorganic material/the one-dimensional organic material is applied to the preparation of a gas sensor.
The invention has the following advantages:
the invention is successfully carried out on MoS 2 Forming heterojunction by surface composite CuPc to obtain MoS 2 a/CuPc composite material having a thickness of the order of microns; the preparation method is simple, the gas sensitivity in the gas sensor prepared by the method is determined through experiments, and MoS is selected from the raw materials 2 Ratio to CuPc. MoS of the invention 2 The gas sensor prepared from the CuPc composite material has the advantages of good stability, quick response recovery time, high sensitivity and good selectivity.
Drawings
FIG. 1 shows an embodiment of the present invention based on a single MoS 2 Sensor pairs of 3-CM, 5-CM, 7-CM, 10-CM and 20-CM 1000ppm CH 2 O、C 3 H 6 O、C 2 H 6 O and 98% rh (a) average sensitivity (b) response time and (c) recovery time.
FIG. 2 is a graph of the slave based on a single MoS 2 Three-dimensional PCA plots derived from the average responses of six sensors of 3-CM, 5-CM, 7-CM, 10-CM and 20-CM.
FIG. 3 is MoS 2 SEM pictures of CuPc composite material, FIGS. 3 (a) - (f) are MoS respectively 2 The mass ratio of the copper to CuPc is 20: 3. 4: 1. 20: 7. 2:1 and 1:1。
FIG. 4 is an optical microscope image of CoPc micro-nanowires at various carrier gas flow rates; wherein, a in FIG. 4 is 400 ℃/3h/100sccm; b is 400 ℃/3h/50sccm; c is 400 ℃/3h/25sccm.
FIG. 5 is an optical microscope image of a CoPc micro-nanowire at different growth times; wherein, a in FIG. 5 is 400 ℃/3h/25sccm; b is 400 ℃/4h/25sccm; c is 400 ℃/5h/25sccm.
FIG. 6 is an optical microscope image of CoPc micro-nanowires at different growth temperatures; wherein, a in FIG. 6 is 390 ℃/3h/25sccm; b is 400 ℃/3h/25sccm; c is 410 ℃/3h/25sccm.
FIG. 7 is a MoS-based at room temperature 2 Sensor pairs of 3-CM, 5-CM, 7-CM, 10-CM and 20-CM 1000ppm CH 2 O、C 3 H 6 O、C 2 H 6 Response curves for O and 98% rh.
Detailed Description
The experimental methods used in the following examples are conventional methods unless otherwise specified.
Materials, reagents and the like used in the examples described below are commercially available unless otherwise specified.
Example 1
1. Preparation of CuPc micro-nanowires
The preparation is carried out by a physical gas phase transportation method through a two-stage temperature-controlled tubular furnace. In order to improve the yield of the micro-nanowires, the substrate of the growth area is pretreated, and the steps are as follows:
(1) Putting 1mg of purified CuPc into a beaker, adding 20ml of ethanol, sealing and performing ultrasonic treatment for 1h; because the organic micro-nano material has small mechanical strength, the organic micro-nano material is easily broken into tiny particles under the action of ultrasound, and CuPc suspension is formed in ethanol;
(2) After the ultrasonic treatment is finished, standing the suspension for 24 hours at room temperature; the larger particles settled at the bottom of the beaker, leaving smaller micro-nano particles in the supernatant;
(3) Clamping the cleaned silicon wafer substrate by using tweezers, immersing the silicon wafer substrate into the supernatant, taking out the silicon wafer substrate, and naturally drying the silicon wafer substrate on filter paper; the micro-nano particles in the suspension are transferred to the substrate;
(4) In the preparation process of a physical gas phase transportation method, micro-nano particles on the surface of a substrate serve as crystal nuclei to induce the growth of CuPc micro-nano wires. At the growth temperature of 400 ℃ and N after 4 hours 2 When the flow rate of the carrier gas is 20ml/min, the micro-nano wire with the length of more than 100 mu m is obtained.
2、MoS 2 Preparation of nanosheets
Preparation of MoS by grinding-assisted liquid phase stripping method 2 A nano-sheet. Firstly, 100mg MoS was weighed 2 Grinding the raw materials in an agate mortar for 2 hours, adding an appropriate amount of NMP during grinding, drying the sample in a vacuum oven for 12 hours after grinding, dispersing the sample in 45vol% absolute ethyl alcohol, carrying out ultrasonic treatment for 1 hour, centrifuging the dispersion for 20 minutes (1500 r/min), obtaining MoS2 nano-sheets, and drying the MoS2 nano-sheets in air for later use.
3、MoS 2 Preparation of CuPc composite material
First, 20mg MoS was prepared 2 Dispersing the nanosheets in 20ml absolute ethanol solvent, adding CuPc micro-nanowires with different proportions, magnetically stirring, heating and refluxing for 2h, centrifuging at 8000r/min, and collecting precipitate to obtain MoS with different proportions 2 CuPc composites, named 3-CM, 5-CM, 7-CM, 10-CM and 20-CM, respectively, correspond to MoS 2 The mass ratio of the copper to CuPc is 20: 3. 4: 1. 20: 7. 2:1 and 1:1.
4. Construction of sensor
Mixing the MoS with the above mixture at different ratio 2 Dispersing CuPc composite material in absolute ethyl alcohol at a concentration of 10mg/ml to obtain 5 parts of MoS 2 CuPc composite dispersion. The above 5 parts of the dispersion were then uniformly coated (2. Mu.l MoS) 2 CuPc composite dispersion) for preparing MoS-based on ceramic substrates 2 The sensing chip of the CuPc composite material is dried in a forced air drying oven for about 24 hours (60 ℃), then a voltage of 2V is applied and aged in air for about 48 hours to ensure good sensing stability.
For the MoS of the invention 2 The CuPc composite material is subjected to gas-sensitive sensing test, a constant voltage of 2V is applied to the sensor, and the sensor is subjected to room temperatureThe relative current change when switching from air to target gas was recorded by a homemade semiconductor tester, and the test results are shown in fig. 1.
As can be seen in FIG. 1, the results of the gas-sensitive sensing test show that the MoS of the present invention 2 Response of CuPc composite material to target gas and MoS 2 Related to the ratio of CuPc, with MoS 2 The ratio to CuPc is reduced, moS 2 The response of the CuPc composite material to four target gases increases and decreases, when MoS 2 MoS at a ratio of 20:7 to CuPc 2 The gas sensitive properties of the/CuPc composite are best. And based on a single MoS 2 Compared with the sensor of (2), 7-CM for 1000ppm CH 2 O、C 3 H 6 O、C 2 H 6 O and 98% RH (relative humidity, i.e. for H 2 O response) increases by 122.7, 734.6, 1639.8 and 440.5, respectively. Because electrons are released to MoS during the reaction of the reduced gas molecules 2 In the CuPc composite material, the 7-CM current increases rapidly, indicating that there is good synergy between the materials at this ratio.
As shown in fig. 2, the identification performance of the sensor array was further evaluated by 3D PCA based on PCA and radar chart analysis. The coordinates of the four samples to be tested can be distinguished, and the sensors of the four samples can basically complete identification. To further investigate the gas sensitivity of the sensor array, its thermodynamic and kinetic parameters are combined, converted into a pattern signal and combined with image recognition techniques. The reaction amplitude and reaction time correspond to thermodynamic and kinetic parameters, respectively. The six sensors have six reaction amplitudes and six reaction times for each analyte. Six new parameters, including thermal and kinetic, can be obtained from the ratio of the six reaction values to the six reaction times. Six new parameters were used to construct a visual hexagon with significant differences. The identification performance of the sensor array of the invention is high.
Builds up MoS-based 2 The CuPc composite material sensor array basically realizes the identification and detection of four target gases, and the data is imported and drawn through Origin softwareAfter the data processing of the graph, the sensor array shows higher recognition capability. Through radar map analysis and database construction, the conversion of digital signals like image signals is realized, so that the visualization, identification and detection of target analytes are realized, and the method has larger development potential and application prospect in the future Internet of things era.
As can be seen in FIG. 2, the MoS of the present invention 2 the/CuPc composite material shows good sensitivity to the four atmospheres mentioned above, while showing good selectivity.
As shown in FIG. 3, the MoS of the present invention 2 SEM image of CuPc composite. As can be seen from FIG. 3, the MoS of the present invention 2 The CuPc composite material is MoS 2 The surface recombination of (a) to form heterojunction CuPc characterizes MoS by SEM 2 The morphology of the/CuPc heterojunction is shown in fig. 3. 3-CM, 5-CM, 7-CM, 10-CM and 20-CM are all composed of MoS 2 SEM image of nanoplatelets and CuPc micro-nanowire composites. As is evident from the figure, with MoS 2 Variation of ratio to CuPc content MoS 2 The morphology of the CuPc heterojunction changes with the change, and the graph (a) is the morphology of 3-CM, moS 2 The nanoplatelets wrap CuPc micro-nanowires. FIG. b shows a morphology of 5-CM, moS increased compared to 3-CM CuPc micro-nanowire content 2 The nanoplates are stacked on CuPc micro-nanowires. FIG. (c) is a morphology of 7-CM, moS 2 The nano-sheets are permeated in the network structure of the CuPc micro-nano wires, so that gas molecules can fully contact materials, and the gas sensitivity performance is improved. The graph (d) is that a MoS2 nano-sheet is tightly adhered on the CuPc micro-nano wire to form MoS 2 CuPc heterojunction. And the graph (e) is 10-CM morphology, and the CuPc micro-nano wires can be piled up to form a conductive path independently, and the conductivity is mainly based on the CuPc micro-nano wires. The pattern (f) is 20-CM morphology, identical to 10-CM.
Example 2
Under the same conditions as in example 1, the difference is that: changing the carrier gas flow rate, as shown in FIG. 4, a is 400 ℃/3h/100sccm; b is 400 ℃/3h/50sccm; c is 400 ℃/3h/25sccm. From the results in FIG. 4, it can be seen that longer micro-nanowires can be obtained when the flow rate is 25 sscm. The CoPc is mostly micro-nano wires and grows uniformly. And it was found through experiments that longer lengths of the CoPc micro-nanowires can also be obtained as the carrier gas flow rate decreases, so that the carrier gas flow rate of 20sccm in example 1 of the present invention is preferable.
Under the same conditions as in example 1, the difference is that: changing the growth time, as shown in FIG. 5, a is 400 ℃/3h/25sccm; b is 400 ℃/4h/25sccm; c is 400 ℃/5h/25sccm. From the results in fig. 5, it can be seen that the longer the time, the thicker the CuPc micro-nanowire diameter, but the less the length change. After 4h there was little change in length. It is explained that after 4h, the longitudinal growth of CuPc has reached saturation, and with increasing duration CuPc only grows laterally, so 4h is the optimal growth time.
Under the same conditions as in example 1, the difference is that: changing the growth temperature, as shown in FIG. 6, a is 390 ℃/3h/25sccm; b is 400 ℃/3h/25sccm; c is 410 ℃/3h/25sccm. As can be seen from the results in fig. 6, the change in temperature also affects the growth of CoPc; when the temperature reaches 410 ℃, the diameter of the CoPc micro-nanowire becomes gradually larger. The CoPc micro-nano wires growing at 400 ℃ are large in quantity and uniform, and are more suitable for preparing organic micro-nano materials.
In summary, the optimal conditions for the growth of the CuPc micro-nanowires are obtained by changing the gas flow rate, the growth time and the growth temperature, namely, the growth temperature is 400 ℃ and the growth time is 4 hours, N 2 When the flow rate of the carrier gas is 20sccm, the micro-nano wires with the length of more than 100 μm are obtained.
Comparative example
Under the same conditions as in example 1, a single two-dimensional material MoS was prepared 2 And 3-CM, 5-CM, 7-CM, 10-CM and 20-CM materials, and gas sensitive testing was performed. The results are shown in FIG. 7, FIG. 7 is based on MoS at room temperature 2 Sensor pairs of 3-CM, 5-CM, 7-CM, 10-CM and 20-CM 1000ppm CH 2 O、C 3 H 6 O、C 2 H 6 Response curves for O and 98% rh.
From the analysis of the results in fig. 1, 3 and 7, it can be seen that: single two-dimensional material MoS 2 When a sensitive layer is formed, a stacking phenomenon is easy to occur, so that a material cannot be fully contacted with a target gas, and the sensitivity of the sensor is low.
Claims (10)
1. A heterojunction material based on two-dimensional inorganic materials/one-dimensional organic materials, which is characterized in that: the composite material comprises two-dimensional inorganic materials and one-dimensional organic materials;
the inorganic material comprises a two-dimensional material and/or a nano-sheet of molybdenum sulfide and/or graphene;
the organic material comprises a metal phthalocyanine semiconductor material.
2. A material according to claim 1, characterized in that: the mass ratio of the inorganic material to the organic material is 20:3-20;
the metal phthalocyanine semiconductor material comprises at least one of copper phthalocyanine, cobalt phthalocyanine, zinc phthalocyanine and lead phthalocyanine.
3. A material according to claim 1 or 2, characterized in that: the mass ratio of the inorganic material to the organic material is 4:1-2.
4. A material according to any one of claims 1-3, characterized in that: the particle size of the inorganic material is 300 nm-2000 nm;
the length of the organic material is 10-200 mu m.
5. A method for preparing a heterojunction material based on two-dimensional inorganic materials/one-dimensional organic materials as claimed in any one of claims 1 to 4, comprising the steps of:
(1) Dispersing the nano-sheets of the inorganic material in an anhydrous organic solvent to obtain a dispersion liquid;
(2) Adding the micro-nano wires of the organic material into the dispersion liquid, mixing, and heating and refluxing to obtain the heterojunction material based on the two-dimensional inorganic material/the one-dimensional organic material.
6. The method of manufacturing according to claim 5, wherein: in step (1), a method for preparing the nano-sheets of inorganic material comprises the following steps: and preparing the inorganic material into nano sheets by adopting a grinding auxiliary liquid phase stripping method.
7. The method according to claim 5 or 6, wherein: in step (2), a method for preparing the micro-nanowires of organic material comprises the steps of: 1) Mixing the organic material with the organic solvent, and performing ultrasonic treatment to obtain an organic material suspension;
2) Standing the organic material suspension, filtering, and taking supernatant;
3) Immersing the substrate into the supernatant, taking out and drying to obtain the substrate with micro-nano particles on the surface;
4) And placing the substrate with the micro-nano particles on the surface in a two-section temperature-controlled tube furnace, and growing on the surface of the substrate by adopting a physical gas phase transportation method to obtain the micro-nano wire of the organic material.
8. The method of manufacturing according to claim 7, wherein: the growth conditions using the physical vapor transport method are as follows:
the carrier gas comprises nitrogen or argon;
the velocity of the carrier gas flow is 10-50 sccm;
the growth time is 3.5-4.5 h;
the growth temperature is 380-420 ℃.
9. The method of manufacturing according to claim 5, wherein: the volume ratio of the mass of the organic material to the organic solvent is 1mg:1 to 6.7ml;
the anhydrous organic solvent comprises ethanol;
the heating reflux time is 1-3 h;
the step (2) of heating reflux is followed by centrifugation and filtering to remove sediment;
the centrifugal speed is 6000-9000 r/min.
10. Use of a two-dimensional inorganic material/one-dimensional organic material based heterojunction material as claimed in any of claims 1 to 4 for the preparation of a gas sensor.
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