CN108365096B - Preparation method and application of block copolymer semiconductor nanowire with spiral structure - Google Patents
Preparation method and application of block copolymer semiconductor nanowire with spiral structure Download PDFInfo
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Abstract
The invention discloses a preparation method and application of a block copolymer semiconductor nanowire with a helical structure. The block copolymer semiconductor nanowire can be used as a semiconductor layer of an organic field effect transistor ammonia sensor, can improve the sensitivity of ammonia sensing and reduce the detection limit, and can change the density and the diameter of the nanowire only by changing the preparation process conditions. The invention prepares the segmented copolymer semiconductor nanowire with the helical structure by a blending method for the first time, and the segmented copolymer semiconductor nanowire is applied to ammonia sensing and obtains higher sensing performance.
Description
Technical Field
The invention relates to the field of organic semiconductor nano structures and devices, in particular to a preparation method and application of a block copolymer semiconductor nano wire with a spiral structure.
Background
Ammonia (NH3) is an important chemical raw material and is widely used in the fields of industrial production, food storage, safety requirements and the like. The ammonia gas has strong toxicity, so that poisoning symptoms such as edema of respiratory tract and gastric mucosa can be generated when a human body is exposed to a low-concentration ammonia gas environment, and neurotoxicity can be generated when the human body is serious, tissue dissolution and necrosis are caused, and asphyxiation death is caused.
The conjugated polymer organic field effect transistor has the potential advantages of large-area solution processing, flexible device preparation, low cost and the like, and has received extensive attention and research in recent years. The organic field effect transistor device has the characteristic of signal amplification, has good detection and recording functions on tiny current values and changes, can sensitively detect the current change between a source electrode and a drain electrode of the device caused by the action of ammonia gas, and can quickly and sensitively carry out recovery and repeated test after detection; the conjugated polymer organic semiconductor has strong molecular structure plasticity, and can reasonably regulate and control the sensing characteristic through the design of the molecular structure so as to pointedly improve the specific recognition of the functional material to the substance to be detected.
Nanowires generally refer to lines having diameters between 1-100 nanometers. When the special microstructure of the nano wire is used for preparing an active layer of an organic field effect transistor, the material consumption of the device is small, the specific surface area is large, and the molecular arrangement is regular and the electrical performance is high. The gas sensor with the nanowire structure has the advantages of high responsiveness, good sensitivity, quick response and recovery and the like when the active layer of the gas sensor is provided with the nanowire structure. The helical structure of the polymer is mainly a special supermolecular structure formed by self-assembly of polymer chains induced by pi-pi interaction generated by electrons in molecules, and the structure has wide application in optical and biological detection, but has no application in gas sensing at present.
Currently, no known organic field effect transistor based on a block copolymer semiconductor nanowire is used for gas sensing, in addition, the regulation of the morphology of a block copolymer generally needs to adjust a molecular chain from a polymerization level by changing the molecular weight or the block ratio of the copolymer, the preparation difficulty is high, and the regulation of the morphology (density and diameter) of the nanowire only through the preparation condition of the nanowire is not reported at present.
Disclosure of Invention
The invention aims to provide a preparation method and application of a block copolymer semiconductor nanowire with a helical structure, and aims to solve the technical problems of how to form the helical structure by utilizing the interaction inside a molecular structure, regulate and control the appearance of the block copolymer nanowire and apply the block copolymer nanowire to an organic field effect transistor gas sensor.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the preparation method of the block copolymer semiconductor nanowire with the helical structure is characterized by comprising the following steps: the method comprises the following steps:
(1) respectively dissolving the block copolymer semiconductor material and the polymer insulating material in respective organic solvents, and mixing to form a blending solution, wherein the mass ratio of the block copolymer semiconductor material to the polymer insulating material in the blending solution is 1:80-1: 40;
(2) spin-coating the blended solution obtained in the step (1) on a substrate, and then vacuumizing to remove the residual solvent, thereby forming a double-layer film with a polymer insulating material as a bottom layer and a block copolymer semiconductor material as a top layer on the substrate;
(3) soaking the double-layer film formed on the substrate in the solution to separate the double-layer film from the substrate and float on the surface of the transition solution, then putting the substrate in the transition solution to be in contact with the surface of the double-layer film, turning over the double-layer film and fishing out the double-layer film, thereby forming the turning double-layer film with the segmented copolymer semiconductor material as the bottom layer and the polymer insulating material as the top layer on the substrate;
(4) and (3) soaking the inverted double-layer film obtained in the step (3) by adopting an orthogonal solvent to dissolve the insulating material in the orthogonal solvent so as to remove the polymer insulating material, namely obtaining the block copolymer semiconductor nanowire, wherein the block copolymer semiconductor nanowire forms a spiral structure due to the self-assembly characteristic of the self-insulating section.
The preparation method of the segmented copolymer semiconductor nanowire with the spiral structure is characterized by comprising the following steps: the density and diameter of the block copolymer semiconductor nanowire obtained in the step (4) are determined by the mass ratio of the block copolymer semiconductor material to the polymer insulating material in the blending solution in the step (1), the mass ratio of the block copolymer semiconductor material to the polymer insulating material in the blending solution is 1:80-1:40, and the larger the mass ratio is, the larger the density and the larger the diameter of the finally obtained block copolymer semiconductor nanowire are.
The preparation method of the segmented copolymer semiconductor nanowire with the spiral structure is characterized by comprising the following steps: and (4) forming the block copolymer semiconductor nanowire with the microsphere structure in the step (4) when the mass ratio of the block copolymer semiconductor material to the polymer insulating material in the mixed solution in the step (1) is 1: 40.
The preparation method of the segmented copolymer semiconductor nanowire with the spiral structure is characterized by comprising the following steps: the block copolymer semiconductor material in the step (1) is poly (4-isocyano-benzoic acid 5- (2-dimethylamino-ethoxy) -2-nitro-benzyl ester) -b-poly (3-hexylthiophene), namely PPI (-DMAENBA) -b-P3HT, or polyphenylisocyano-b-poly (3-hexylthiophene), namely PPI-b-P3 HT;
the polymer insulating material in the step (1) is polymethyl methacrylate (PMMA);
the organic solvent in the step (1) is selected from chlorobenzene or o-dichlorobenzene.
The preparation method of the segmented copolymer semiconductor nanowire with the spiral structure is characterized by comprising the following steps: in the step (1), a block copolymer semiconductor material is dissolved in an organic solvent to form a solution A, and a polymer insulating material is dissolved in the same organic solvent to form a solution B; uniformly mixing the solution A and the solution B to obtain a mixed solution;
the concentration of the block copolymer semiconductor material in the solution A is 0.5-1mg/mL, and the concentration of the polymer insulating material in the solution B is 130 mg/mL; by controlling the mass ratio of the solution a and the solution B, the polymer insulating material and the block copolymer semiconductor material can be delaminated at the time of the spin coating of step (2).
The preparation method of the segmented copolymer semiconductor nanowire with the spiral structure is characterized by comprising the following steps: the spin coating speed in step (2) was 2000 rmp.
The preparation method of the segmented copolymer semiconductor nanowire with the spiral structure is characterized by comprising the following steps: and (4) in the step (3), the transition solution is a potassium hydroxide aqueous solution.
The preparation method of the segmented copolymer semiconductor nanowire with the spiral structure is characterized by comprising the following steps: and (4) the orthogonal solvent in the step (4) is acetone or ethyl acetate.
The preparation method of the segmented copolymer semiconductor nanowire with the spiral structure is characterized by comprising the following steps: the helical structure in the step (4) is formed by the self-assembly characteristic of the insulating section of the block copolymer semiconductor nanowire, namely the insulating section of the block copolymer semiconductor nanowire forms the helical structure through strong pi electron interaction, and the nanowire with the helical structure can be obtained as long as the insulating section can generate strong intramolecular pi electron interaction.
Use of a block copolymer semiconductor nanowire of helical structure, characterized in that: as a semiconductor layer of the organic field effect transistor ammonia sensor, the sensing sensitivity of the organic field effect transistor ammonia sensor is improved and the detection limit is reduced based on the specific adsorption capacity of the spiral structure of the block copolymer semiconductor nanowire and the functional group on the side group of the spiral structure to ammonia.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention applies the block copolymer semiconductor to the organic field effect transistor sensor for the first time.
2. The invention realizes the regulation and control of the density, diameter and length of the segmented copolymer nanowire by using the process conditions for the first time.
3. The invention utilizes the polymer blending system solution method to prepare the segmented copolymer nanowire and the organic field effect transistor sensor based on the segmented copolymer nanowire, and has the advantages of simple operation, good repeatability, low requirements on equipment and process conditions, no need of using large-scale precise instruments and equipment and the like.
4. The field effect transistor sensor prepared by the method has the advantages of high sensitivity, good selectivity, low detection limit, stable performance and the like due to the large specific surface area and the thin thickness of the active layer, and has important application prospect in the aspect of improving the sensing characteristic of the gas sensor.
Drawings
FIG. 1a) is the molecular structural formula of PPI (-DMAENBA) -b-P3HT, b) is the molecular structural formula of PPI-b-P3 HT.
FIG. 2 is an atomic force microscope picture (left) and a transmission electron microscope picture (right) of the nanowire PPI (-DMAENBA) -b-P3HT obtained in the example.
FIGS. 3a, 3b and 3c show the shapes of block copolymer nanowires obtained by the mass ratio of the block copolymer semiconductor material to the polymer insulating material of 1:80, 1:60 and 1:40, respectively.
FIG. 4 is a schematic structural diagram of an organic field effect transistor sensor with a PPI (-DMAENBA) -b-P3HT nanowire obtained by an embodiment.
FIG. 5 is a transfer curve and an output curve of an organic field effect transistor sensor of a nanowire of PPI (-DMAENBA) -b-P3HT obtained in example, wherein a solid line and a dotted line in the output curve are output curves of the organic field effect transistor based on nanowires obtained by mass ratio of 1:40 and 1:80 of a block copolymer semiconductor material and a polymer insulating material, respectively.
Detailed Description
The following examples are given for the detailed implementation and specific operation of the present invention, but the scope of the present invention is not limited to the following examples.
Example 1
This example prepares PPI (-DMAENBA) -b-P3HT nanowires and organic field effect transistor sensors based thereon as follows:
(1) dissolving PPI (-DMAENBA) -B-P3HT in o-dichlorobenzene to form a solution A with the concentration of 2mg/mL, and dissolving PMMA in chlorobenzene to form a solution B with the concentration of 130 mg/mL; and uniformly mixing the solution A and the solution B to form a blending solution, wherein the mass ratio of PPI (-DMAENBA) -B-P3HT to PMMA in the blending solution is 1:80, or 1:60, or 1: 40. The molecular structural formula of PPI (-DMAENBA) -b-P3HT and PPI-b-P3HT is shown in figure 1.
(2) Heating an n-type silicon wafer in a concentrated sulfuric acid-hydrogen peroxide mixed solution, and then cleaning the n-type silicon wafer to be used as a substrate; spin-coating the blend solution on a substrate at 2000rpm by spin coating and vacuum-drying at room temperature for 12 hours to form a double-layer film with a PMMA film as a bottom layer and PPI (-DMAENBA) -b-P3HT nanowire as a top layer on the substrate;
(3) taking a silicon wafer with silicon dioxide on the surface (the silicon dioxide on the surface is modified by poly (2, 3-bis (difluoromethyl) -2,3,4,4,5, 5-cyclo-hexafluoro-tetrahydrofuran) Cytop) as a substrate, floating the double-layer film in a potassium hydroxide solution with the mass concentration of 5%, turning over the substrate and fishing out the double-layer film to form a turning over double-layer film with a PPI (-DMAENBA) -b-P3HT nanowire as a bottom layer and a PMMA film as a top layer on the substrate; and (4) washing by using ethyl acetate to remove the PMMA film, thus obtaining PPI (-DMAENBA) -b-P3HT nano wires.
FIG. 2 is an atomic force microscope picture of the nanowire of PPI (-DMAENBA) -b-P3HT obtained in this example, it can be seen that the thickness of the nanowire with uniform distribution is about 10 nm, and the density of the nanowire is increased significantly when the mass ratio is changed from 1:80 to 1:60, and the diameter of the nanowire is increased from 35-55 nm to 40-65 nm; when the mass ratio is changed from 1:60 to 1:40, the nanowires become spherical structures linked to each other by the nanowires, and the diameters of the nanowires are also reduced to 20-40 nm.
(4) And evaporating gold electrodes on the ultrathin film to be used as a source electrode and a drain electrode, wherein the length and the width of a channel are respectively 80 mu m and 1000 mu m, and the substrate silicon is used as a grid electrode, so that the PPI (-DMAENBA) -b-P3HT nanowire organic field effect transistor sensor is obtained, and the structure of the sensor is shown in figure 3.
The response curve of the PPI (-DMAENBA) -b-P3HT nanowire organic field effect transistor sensor obtained in the example to ammonia gas was tested as follows:
the electrical properties of the devices were tested using a Keithley 4200 semiconductor device analyzer to obtain transfer curves (V) of the devicesD(-80V) and output curve, the results are shown in fig. 4.
Controlling the flow of ammonia gas by adopting a flowmeter, and sequentially introducing ammonia gas and compressed air into a device channelAnd (3) testing the gas sensing characteristics of the device on ammonia gas. The results are shown in fig. 5 (the ordinate of fig. 5 indicates the ratio of Δ I/I (0) current change amount, that is:
) Therefore, the sensitivity of the sensor is calculated to be 68 percent; and the response recovery speed of the sensor is high, and the response time and the recovery time are respectively 4.87s and 55.14 s.
The present invention is not limited to the above preferred embodiments, and any modifications, equivalent substitutions and improvements made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Example 2
This example prepares a helical-structured nanowire and an organic field effect transistor sensor based thereon in the same manner as in example 1, except that PPI (-DMAENBA) -b-P3HT is replaced with PPI-b-P3 HT. The performance of the resulting helical structured nanowires and sensors was similar to example 1.
Claims (9)
1. The preparation method of the block copolymer semiconductor nanowire with the helical structure is characterized by comprising the following steps: the method comprises the following steps:
(1) respectively dissolving the block copolymer semiconductor material and the polymer insulating material in respective organic solvents, and mixing to form a blending solution, wherein the mass ratio of the block copolymer semiconductor material to the polymer insulating material in the blending solution is 1:80-1: 40;
(2) spin-coating the blended solution obtained in the step (1) on a substrate, and then vacuumizing to remove the residual solvent, thereby forming a double-layer film with a polymer insulating material as a bottom layer and a block copolymer semiconductor material as a top layer on the substrate;
(3) soaking the double-layer film formed on the substrate in the solution to separate the double-layer film from the substrate and float on the surface of the transition solution, then putting the substrate in the transition solution to be in contact with the surface of the double-layer film, turning over the double-layer film and fishing out the double-layer film, thereby forming the turning double-layer film with the segmented copolymer semiconductor material as the bottom layer and the polymer insulating material as the top layer on the substrate;
(4) soaking the inverted double-layer film obtained in the step (3) in an orthogonal solvent to dissolve the insulating material in the orthogonal solvent to remove the polymer insulating material, so that the block copolymer semiconductor nanowire is obtained, and the block copolymer semiconductor nanowire forms a spiral structure due to the self-assembly characteristic of the self-insulating section; the helical structure is formed by the self-assembly characteristic of the insulating segment of the block copolymer semiconductor nanowire, namely the insulating segment of the block copolymer semiconductor nanowire forms the helical structure through strong pi electronic interaction, and the nanowire with the helical structure can be obtained as long as the insulating segment can generate strong intramolecular pi electronic interaction.
2. The method for producing a block copolymer semiconductor nanowire having a helical structure according to claim 1, wherein: the density and diameter of the block copolymer semiconductor nanowire obtained in the step (4) are determined by the mass ratio of the block copolymer semiconductor material to the polymer insulating material in the blending solution in the step (1), the mass ratio of the block copolymer semiconductor material to the polymer insulating material in the blending solution is 1:80-1:40, and the larger the mass ratio is, the larger the density and the larger the diameter of the finally obtained block copolymer semiconductor nanowire are.
3. The method for producing a block copolymer semiconductor nanowire having a helical structure according to claim 1 or 2, characterized in that: and (4) forming the block copolymer semiconductor nanowire with the microsphere structure in the step (4) when the mass ratio of the block copolymer semiconductor material to the polymer insulating material in the mixed solution in the step (1) is 1: 40.
4. The method for producing a block copolymer semiconductor nanowire having a helical structure according to claim 1, wherein: the block copolymer semiconductor material in the step (1) is poly (4-isocyano-benzoic acid 5- (2-dimethylamino-ethoxy) -2-nitro-benzyl ester) -b-poly (3-hexylthiophene), namely PPI (-DMAENBA) -b-P3HT, or polyphenylisocyano-b-poly (3-hexylthiophene), namely PPI-b-P3 HT; the polymer insulating material in the step (1) is polymethyl methacrylate (PMMA); the organic solvent in the step (1) is selected from chlorobenzene or o-dichlorobenzene.
5. The method for producing a block copolymer semiconductor nanowire having a helical structure according to claim 1, wherein: in the step (1), a block copolymer semiconductor material is dissolved in an organic solvent to form a solution A, and a polymer insulating material is dissolved in the same organic solvent to form a solution B; uniformly mixing the solution A and the solution B to obtain a mixed solution; the concentration of the block copolymer semiconductor material in the solution A is 0.5-1mg/mL, and the concentration of the polymer insulating material in the solution B is 130 mg/mL; by controlling the mass ratio of the solution a and the solution B, the polymer insulating material and the block copolymer semiconductor material can be delaminated at the time of the spin coating of step (2).
6. The method for producing a block copolymer semiconductor nanowire having a helical structure according to claim 1, wherein: the spin coating speed in step (2) was 2000 rmp.
7. The method for producing a block copolymer semiconductor nanowire having a helical structure according to claim 1, wherein: and (4) in the step (3), the transition solution is a potassium hydroxide aqueous solution.
8. The method for producing a block copolymer semiconductor nanowire having a helical structure according to claim 1, wherein: and (4) the orthogonal solvent in the step (4) is acetone or ethyl acetate.
9. Use of a block copolymer semiconductor nanowire of helical structure, characterized in that: as a semiconductor layer of the organic field effect transistor ammonia sensor, the sensing sensitivity of the organic field effect transistor ammonia sensor is improved and the detection limit is reduced based on the specific adsorption capacity of the spiral structure of the block copolymer semiconductor nanowire and the functional group on the side group of the spiral structure to ammonia.
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