CN114088777A - Ammonia gas sensor based on organic heterojunction structure and preparation method thereof - Google Patents
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- SLIUAWYAILUBJU-UHFFFAOYSA-N pentacene Chemical compound C1=CC=CC2=CC3=CC4=CC5=CC=CC=C5C=C4C=C3C=C21 SLIUAWYAILUBJU-UHFFFAOYSA-N 0.000 claims description 14
- 238000009825 accumulation Methods 0.000 claims description 10
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- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
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- 239000002184 metal Substances 0.000 claims description 8
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- 238000001514 detection method Methods 0.000 description 6
- 230000008020 evaporation Effects 0.000 description 6
- 230000009471 action Effects 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
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- KJOLVZJFMDVPGB-UHFFFAOYSA-N perylenediimide Chemical compound C=12C3=CC=C(C(NC4=O)=O)C2=C4C=CC=1C1=CC=C2C(=O)NC(=O)C4=CC=C3C1=C42 KJOLVZJFMDVPGB-UHFFFAOYSA-N 0.000 description 3
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241001089723 Metaphycus omega Species 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
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- 238000001228 spectrum Methods 0.000 description 1
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- 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
- G01N27/126—Composition of the body, e.g. the composition of its sensitive layer comprising organic polymers
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- B81C1/00373—Selective deposition, e.g. printing or microcontact printing
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- B81C1/00841—Cleaning during or after manufacture
- B81C1/00849—Cleaning during or after manufacture during manufacture
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- G01—MEASURING; TESTING
- 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
- G01N27/127—Composition of the body, e.g. the composition of its sensitive layer comprising nanoparticles
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Abstract
The invention discloses an ammonia gas sensor based on an organic heterojunction structure and a preparation method thereof, and belongs to the technical field of semiconductor gas sensors. The sensor structure comprises: an ITO glass substrate (1), an electrode (2), a P-type organic semiconductor film (3) and an N-type organic semiconductor film (4); the P-type organic semiconductor thin film (3) and the N-type organic semiconductor thin film (4) form an accumulation-type heterojunction. The preparation method comprises the steps of cleaning a substrate, depositing a P-type organic semiconductor film, depositing an N-type organic semiconductor film, preparing an electrode and the like. The ammonia sensor prepared by the invention has the advantages of small volume, light weight, simple structure, normal work at room temperature, low cost and easy mass production.
Description
Technical Field
The invention belongs to the technical field of semiconductor gas sensors, and relates to a resistance type ammonia gas sensor with an organic accumulation type heterojunction structure and a preparation method thereof.
Background
Ammonia is an important raw material in industries such as chemical industry, pharmaceutical industry and the like, is widely used as a refrigerant, and is one of the most productive inorganic compounds in the world. Ammonia is an alkaline substance and is irritating and corrosive to the contacting skin tissue. Meanwhile, the concentration of ammonia gas is also an important index of the spoilage degree of meat products and the environment of the breeding industry. Due to the wide application and harmfulness of ammonia gas and the mapping effect of ammonia gas concentration on food quality and breeding environment, the detection of ammonia gas concentration, particularly the real-time accurate detection of low-concentration ammonia gas, is very important.
The metal oxygen-based ammonia gas sensor has the characteristics of simple preparation method and low cost, the electrical property of the metal oxygen-based ammonia gas sensor can be changed due to the reversible interaction between ammonia molecules and adsorbed environmental oxygen, but the metal oxygen-based ammonia gas sensor is difficult to work at high sensitivity and normal temperature, has longer response and recovery time, and limits the application of the metal oxygen-based ammonia gas sensor in the field of rapid detection of ammonia gas with extremely low concentration; the graphene ammonia sensor has great potential, but needs further maturity and breakthrough in the aspects of sensitive sensing mechanism and technology; the ammonia sensor with the organic field effect tube structure senses ammonia gas through source-drain current or threshold voltage, but the ammonia sensor is low in sensitivity, the influence factors of the performance of the field effect tube are numerous, and the accuracy of the ammonia sensor is seriously influenced by poor stability and consistency; although the spectrum and mass spectrometry can realize accurate detection of gas with extremely low concentration, the device is expensive, the operation is complex, the time consumption is long, and the method is not suitable for the requirements of portable rapid real-time detection.
Disclosure of Invention
The invention aims to solve the technical problems of low sensitivity, high working temperature, long response recovery time and the like in low-concentration test of the traditional ammonia sensor, and provides the ammonia sensor based on the organic heterojunction structure, which has the advantages of high sensitivity, high response speed, simple structure, small volume, light weight and normal-temperature work.
The technical problem is solved by the following technical scheme:
an ammonia gas sensor based on an organic heterojunction structure, the structure is as follows: an ITO glass substrate 1, an electrode 2, a P-type organic semiconductor film 3 and an N-type organic semiconductor film 4; wherein the electrode 2 is an indium tin oxide electrode obtained by etching a layer of indium tin oxide deposited on an ITO glass substrate 1 or is deposited on a P-type organic semiconductor film 3 by utilizing a mask plateThe gold electrode, P-type organic semiconductor film 3, was pentacene (C) deposited on an ITO glass substrate 122H14) Film, N-type organic semiconductor film 4 is a bisbromoperylene diimide (C) deposited on the P-type organic semiconductor film 336H8N2F10) The thin films, the P-type organic semiconductor thin film 3 and the N-type organic semiconductor thin film 4 constitute an accumulation-type heterojunction.
The working principle of the ammonia gas sensor based on the organic heterojunction structure is that an accumulation type heterojunction is formed by utilizing a P type organic semiconductor layer and an N type organic semiconductor layer, and under the action of an accumulation effect, the carrier concentration at two sides of the heterojunction is increased, so that the defect state in an organic film is effectively filled, and a high-conductivity region is formed; the discontinuous N-type bisbromoperylene diimide generates anion free radicals under the action of ammonia gas, so that the electron concentration in a thin film layer is changed; the mobility of electrons in a high-conductivity region is enhanced, the mobility is high, holes are excited in the P-type organic semiconductor layer under the action of an interface potential barrier, the resistance of a channel in the P-type layer is changed by the increase of the concentration of the holes, and the sensitivity of ammonia sensing is improved by the large change of the resistance when the channel is formed.
A preparation method of an ammonia gas sensor based on an organic heterojunction structure comprises the steps of cleaning a substrate, depositing a P-type organic semiconductor film, depositing an N-type organic semiconductor film and preparing an electrode;
the substrate is cleaned by ultrasonic cleaning of ITO glass in 99.7% ethanol and acetone solution for 15 min; washing residual solvent with deionized water after cleaning, drying the ITO glass sheet by high-purity nitrogen, and placing the ITO glass sheet at a vacuum cavity substrate;
the deposition of the P-type organic semiconductor film refers to that the P-type organic semiconductor film is deposited under the vacuum condition (<4×10-4Pa), thermally depositing a P-type organic semiconductor pentacene on the processed ITO glass substrate 1 to obtain a P-type organic semiconductor film (2), wherein the deposition thickness is 30-100nm, the deposition rate is 0.02nm/s, the deposition rate is controlled by adjusting the temperature of an organic evaporation source, and the film formation thickness is observed by a quartz crystal oscillator;
the N-type organic semiconductor film deposition is that N-type bis-bromoperylene diimide sensitive to ammonia gas is subjected to vacuum thermal deposition on a P-type organic semiconductor film (2) to obtain an N-type organic semiconductor film 4, the deposition thickness is 2-4 nm, the deposition rate is 0.02nm/s, the deposition rate is controlled by adjusting the temperature of an organic evaporation source, and the film formation thickness is observed through a quartz crystal oscillator;
the preparation of the electrodes refers to depositing 100nm indium tin oxide on an ITO glass substrate 1 by using magnetron sputtering equipment after the step of cleaning the substrate, etching electrodes with the length of 10mm and the width of 2mm on two opposite sides of the ITO glass substrate 1 by using a photoetching technology, wherein the distance between the electrodes is 30 mu m; or after the step of depositing the P-type organic semiconductor film, depositing a metal electrode Au with the thickness of 0.1 μm on the P-type organic semiconductor film (2) by using an electrode mask with the length of 30 μm and the width of 1.5mm, wherein the deposition rate is 0.08 nm/s.
Preferably, the pentacene and the bisbromoperylene diimide have a purity of 99% or more.
Has the advantages that:
1. according to the invention, through the organic accumulation type heterojunction structure, the response speed is effectively improved, and a step-shaped response recovery curve is formed; the accurate, rapid and stable detection of the ammonia gas with extremely low concentration can be realized;
2. the invention integrates the whole structure of the ammonia sensor on the same ITO glass, thus being easy to form the accumulation effect of an organic heterojunction; the filling effect of the accumulation effect on the trap state, the mutual excitation effect of carriers on two sides of the heterojunction and the great change of resistance during the formation of the channel in the P-type layer can be combined to realize quick response and high-sensitivity sensing;
3. the ammonia sensor prepared by the invention has the advantages of small volume, light weight, simple structure, normal work at room temperature, low cost and easy mass production.
Description of the drawings:
FIG. 1 is a schematic structural view of example 1;
FIG. 2 is a schematic structural view of example 2;
FIG. 3 is a graph showing the operation of the ammonia gas sensor prepared according to the present invention.
Detailed Description
Example 1
The specific structure of each part of the invention is described with reference to the attached figure 1:
a layer of indium tin oxide is deposited on an ITO glass substrate 1 by utilizing a magnetron sputtering device, and an electrode 2 is etched on the ITO glass by utilizing a photoetching technology.
A P-type organic semiconductor film 3 obtained by depositing pentacene and an N-type organic semiconductor film 4 (the molecular structure of which is shown in the following figure) obtained by depositing bisbromoperylene diimide sensitive to ammonia form an organic heterojunction, and a fast-response and high-sensitivity ammonia sensor is constructed under the action of an accumulation effect.
The dibromine perylene diimide thin film is of an extremely thin discontinuous structure, the P-type organic semiconductor thin film is pentacene with the purity of more than 99%, and the pentacene are deposited on the ITO glass successively at the deposition rate of 0.02 nm/s.
Preparing an ammonia gas sensor based on an organic heterojunction structure:
(1) depositing 100nm indium tin oxide on a silicon-boron-based substrate glass by using magnetron sputtering equipment, and etching electrodes with the length of 10mm and the width of 2mm on the left side and the right side of the ITO glass by using a photoetching technology, wherein the distance between the electrodes is 30 mu m;
(2) carrying out ultrasonic cleaning on the etched ITO glass sheet in 99.7% ethanol and acetone in sequence, wherein the cleaning time is 15 minutes each time; washing residual solvent with deionized water, drying with high-purity nitrogen, and placing on a vacuum cavity substrate;
(3) under vacuum (<4×10-4Pa), thermally evaporating a high-purity pentacene material onto ITO glass, wherein the deposition thickness is 45nm, the deposition rate is 0.02nm/s, the deposition rate is controlled by adjusting the temperature of an organic evaporation source, and the film-forming thickness is observed by a quartz crystal oscillator;
(4) and (3) carrying out vacuum thermal deposition on the dibromine perylene diimide film on the pentacene film, wherein the deposition thickness is 4nm, the deposition rate is 0.02nm/s, the deposition rate is controlled by adjusting the temperature of an organic evaporation source, and the film formation thickness is observed by a quartz crystal oscillator.
Example 2
The specific structure of each part of the invention is described with reference to the attached figure 2:
an organic heterojunction is formed by a P-type organic semiconductor film 3 and an N-type organic semiconductor film (4) sensitive to ammonia gas, and under the action of an accumulation effect, the carrier concentration at two sides of the heterojunction is increased, so that the defect state in the organic film is effectively filled, and a high-conductivity region is formed. The N-type organic semiconductor film (4) is an extremely thin dibromo perylene diimide film with a discontinuous structure, and the P-type organic semiconductor film 3 is pentacene with the purity of more than 99%. After pentacene is deposited on the silicon-boron-based substrate glass, a metal electrode Au is deposited by using a mask plate, and finally the bisbromoperylene diimide film is deposited on the P-type organic semiconductor film 3 through thermal evaporation coating.
Preparing an ammonia gas sensor based on an organic heterojunction structure:
(1) respectively carrying out ultrasonic cleaning on the silicon-boron-based substrate glass in 99.7% ethanol and acetone (at the temperature of 50 ℃), and cleaning each solvent for 15 minutes;
(2) washing residual solvent with deionized water, drying with high-purity nitrogen, and placing on a vacuum cavity substrate;
(3) under vacuum (<4×10-4Pa), performing thermal evaporation on pentacene to obtain a silicon-boron-based substrate glass, wherein the deposition thickness is 45nm, the deposition rate is 0.02nm/s, and the deposition rate and the film thickness are controlled by a quartz crystal oscillator;
(4) depositing a metal electrode Au with the thickness of 0.1 mu m by using an electrode mask plate with the length of 30 mu m and the width of 1.5mm, wherein the deposition rate is 0.08nm/s, the deposition rate is controlled by adjusting the temperature of an organic evaporation source, and the film-forming thickness is observed by a quartz crystal oscillator;
(5) and (3) carrying out vacuum thermal deposition on the dibromine perylene diimide on the pentacene film, wherein the deposition thickness is 2nm, the deposition rate is 0.02nm/s, the deposition rate is controlled by adjusting the temperature of an organic evaporation source, and the film forming thickness is observed by a quartz crystal oscillator.
Example 3
The sensor gas prepared in example 2 was tested as follows:
(1) introducing ammonia gas and dry air into a flow meter (S48300/HMT, Beijing BORIBA METRON Instrument Co., Ltd.) at the same time, and controlling the flow rate thereof by a computer, wherein the proportioning concentrations of the ammonia gas are respectively 20ppm, 10ppm, 5ppm and 1 ppm;
(2) the sensor constructed in the example 2 is placed in a closed testing chamber of 20mL of polytetrafluoroethylene;
(3) connecting the anode and the cathode with a keithley2400 digital source meter through a contact copper wire;
(4) opening a valve, sequentially introducing ammonia gas with the concentrations of 20ppm, 10ppm, 5ppm and 1ppm into a closed test cavity, opening a keithley2400 digital source meter, and reading data;
the test results are shown in the attached figure 3 and can be obtained by analysis: the responsivity was also significantly improved with the increase in ammonia concentration, with a response time of 10s to 15s, and the average sensitivities at ammonia concentrations of 20ppm, 10ppm, 5ppm, and 1ppm, calculated as 6.25%/ppm, and the resistance change was 20 M.OMEGA./ppm, respectively.
According to the embodiment and the test effect, the response speed is effectively improved through the organic accumulation type heterojunction structure, the step-shaped response recovery curve is formed under different ammonia gas concentrations, the sensitivity reaches 20 MOmega/ppm, and the accurate, rapid and stable detection of the ammonia gas with extremely low concentration can be realized.
The sensor prepared by the invention has the advantages of small volume, light weight, simple structure and preparation, normal work at room temperature, low cost and easy mass production.
Claims (4)
1. An ammonia gas sensor based on an organic heterojunction structure, the structure is as follows: an ITO glass substrate (1), an electrode (2), a P-type organic semiconductor film (3) and an N-type organic semiconductor film (4); the organic thin film transistor is characterized in that the electrode (2) is an indium tin oxide electrode obtained by etching a layer of indium tin oxide deposited on an ITO glass substrate (1) or a gold electrode obtained by depositing a mask plate on a P-type organic semiconductor thin film (3), the P-type organic semiconductor thin film (3) is a pentacene thin film deposited on the ITO glass substrate (1), the N-type organic semiconductor thin film (4) is a bisbromoperylene diimide thin film deposited on the P-type organic semiconductor thin film (3), and the P-type organic semiconductor thin film (3) and the N-type organic semiconductor thin film (4) form an accumulation type heterojunction.
2. A preparation method of the ammonia gas sensor based on the organic heterojunction structure, which is disclosed by claim 1, comprises the steps of cleaning a substrate, depositing a P-type organic semiconductor film, depositing an N-type organic semiconductor film and preparing an electrode;
the substrate is cleaned by ultrasonic cleaning of ITO glass in 99.7% ethanol and acetone solution for 15 min; washing residual solvent with deionized water after cleaning, drying the ITO glass sheet by high-purity nitrogen, and placing the ITO glass sheet at a vacuum cavity substrate;
the P-type organic semiconductor film is deposited by thermally depositing a P-type organic semiconductor pentacene on a treated ITO glass substrate (1) under a vacuum condition to obtain a P-type organic semiconductor film (2), wherein the deposition thickness is 30-100nm, and the deposition rate is 0.02 nm/s;
the N-type organic semiconductor film is deposited by performing vacuum thermal deposition on N-type bisbromoperylene diimide sensitive to ammonia gas on a P-type organic semiconductor film (2) to obtain an N-type organic semiconductor film (4), wherein the deposition thickness is 2-4 nm, and the deposition rate is 0.02 nm/s;
the preparation of the electrodes refers to depositing 100nm indium tin oxide on an ITO glass substrate (1) by using magnetron sputtering equipment after the step of cleaning the substrate, etching electrodes with the length of 10mm and the width of 2mm on two opposite sides of the ITO glass substrate (1) by using a photoetching technology, and enabling the space between the electrodes to be 30 mu m; or after the step of depositing the P-type organic semiconductor film, depositing a metal electrode Au with the thickness of 0.1 μm on the P-type organic semiconductor film (2) by using an electrode mask with the length of 30 μm and the width of 1.5mm, wherein the deposition rate is 0.08 nm/s.
3. The method for preparing the ammonia gas sensor based on the organic heterojunction structure as claimed in claim 2, wherein the vacuum condition is pressure when depositing the P-type organic semiconductor film<4×10-4Pa。
4. The method for preparing the ammonia gas sensor based on the organic heterojunction structure as claimed in claim 2, wherein the purity of the pentacene and the bisbromoperylene diimide is more than 99%.
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| US20100218593A1 (en) * | 2007-10-15 | 2010-09-02 | Marcel Bouvet | Semiconductor tranducer and its use in a sensor for detecting electron-donor or electron-acceptor species |
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