CN113777137A - Gas sensor based on chromium phthalocyanine monomolecular layer film and preparation method and application thereof - Google Patents
Gas sensor based on chromium phthalocyanine monomolecular layer film and preparation method and application thereof Download PDFInfo
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- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 title claims abstract description 163
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 title claims abstract description 156
- 229910052804 chromium Inorganic materials 0.000 title claims abstract description 155
- 239000011651 chromium Substances 0.000 title claims abstract description 152
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000007789 gas Substances 0.000 claims abstract description 113
- 239000010410 layer Substances 0.000 claims abstract description 42
- 238000001514 detection method Methods 0.000 claims abstract description 25
- 238000001179 sorption measurement Methods 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 15
- 230000035945 sensitivity Effects 0.000 claims abstract description 13
- 239000002356 single layer Substances 0.000 claims abstract description 12
- 238000001704 evaporation Methods 0.000 claims description 47
- 230000008020 evaporation Effects 0.000 claims description 47
- 238000010438 heat treatment Methods 0.000 claims description 42
- 239000012159 carrier gas Substances 0.000 claims description 35
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 34
- 239000010453 quartz Substances 0.000 claims description 30
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 30
- 239000000463 material Substances 0.000 claims description 27
- 229910052751 metal Inorganic materials 0.000 claims description 19
- 239000002184 metal Substances 0.000 claims description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 17
- 230000008021 deposition Effects 0.000 claims description 11
- 238000011084 recovery Methods 0.000 claims description 11
- 238000011049 filling Methods 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 238000007789 sealing Methods 0.000 claims description 10
- 239000007888 film coating Substances 0.000 claims description 9
- 238000009501 film coating Methods 0.000 claims description 9
- 239000012774 insulation material Substances 0.000 claims description 9
- 238000000859 sublimation Methods 0.000 claims description 9
- 230000008022 sublimation Effects 0.000 claims description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 239000010703 silicon Substances 0.000 claims description 5
- 229910001220 stainless steel Inorganic materials 0.000 claims description 5
- 239000010935 stainless steel Substances 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 4
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052918 calcium silicate Inorganic materials 0.000 claims description 3
- 239000000378 calcium silicate Substances 0.000 claims description 3
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 239000000919 ceramic Substances 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims description 2
- 239000011810 insulating material Substances 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 abstract description 11
- 230000004044 response Effects 0.000 abstract description 9
- 238000003795 desorption Methods 0.000 abstract description 3
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 abstract 1
- 238000000151 deposition Methods 0.000 description 9
- 239000012535 impurity Substances 0.000 description 8
- 239000013078 crystal Substances 0.000 description 5
- 230000007547 defect Effects 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 239000000428 dust Substances 0.000 description 4
- 239000002052 molecular layer Substances 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 125000004430 oxygen atom Chemical group O* 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- CTSLXHKWHWQRSH-UHFFFAOYSA-N oxalyl chloride Chemical compound ClC(=O)C(Cl)=O CTSLXHKWHWQRSH-UHFFFAOYSA-N 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 229910001430 chromium ion Inorganic materials 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- -1 phthalocyanine compound Chemical class 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- 239000011540 sensing material Substances 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
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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
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Abstract
The invention discloses a monolayer film gas sensor based on chromium phthalocyanine and a preparation method and application thereof. The invention uses the chromium phthalocyanine monomolecular layer film as the sensor, has short response time and improves the detection efficiency of harmful gases. The method can be used for detecting harmful gases in air such as sensing formaldehyde, phosgene and the like, and has the characteristics of high adsorption and desorption speed, low cost, high precision, easy large-area preparation, strong adsorption strength, good sensitivity and selectivity and the like.
Description
Technical Field
The invention relates to a gas sensor based on a chromium phthalocyanine monomolecular layer film, a preparation method and application thereof, belonging to the technical field of gas sensors.
Background
Formaldehyde (H)2CO) and phosgene (COCl)2) The air is extremely toxic, colorless and volatile gas at room temperature, and is a pollutant which exists in the air and has great influence on the environment. Long term exposure to low concentrations of H2CO or COCl2Can cause a number of serious diseases. Thus, for low concentrations of H present in air2CO or COCl2The detection of (2) is of great significance. Currently, Sc (scandium) -doped BN nanotubes, TiO2Materials such as surfaces and metal organic frameworks have been shown to be effective in detecting and capturing these two toxic gases. But the industrial application is limited due to the defects of long recovery time, weak adsorption strength, poor sensitivity and selectivity and the like. The optical, electrical and electrochemical properties of organic molecules are very quick to respond to external environment changes, have better molecular recognition and specificity selection, and are very suitable for sensing materials with high sensitivity and high selectivity, so that organic crystal materials or films with the thickness of tens of nanometers are mostly adopted at home and abroad as active layer parts for gas detection.
The metal phthalocyanine has a unique macrocyclic conjugated structure, is an organic semiconductor material with excellent performance, and can be used as a sensitive material to prepare an organic gas sensor. Compared with the traditional metal oxide semiconductor sensor, the metal phthalocyanine gas sensor has the advantages of rich raw material sources, low cost, simple preparation process, easy compatibility of other technologies and the like. More importantly, compared with an organic sensor, the MPC molecule has structure tailorability, the structure of the material is regulated and controlled by changing the central metal and the surrounding substituent groups, so that the MPC molecule has higher detection sensitivity and good selectivity on specific gas molecules at room temperature, and in the existing research, the feasibility of partial metal phthalocyanine on partial gas sensing is proved, so that the phthalocyanine compound is a small molecular material which is more researched in the aspect of sensors.
When the traditional active layer with the thickness of dozens of nanometers is used as gas for detection, the influence of the gas on the electric conductivity of the device needs to be diffused to a channel from the surface of the active layer, so that the response efficiency of the sensor is reduced, and the response time is prolonged. The monomolecular film is thin, so that the distance from the surface of the active layer to a channel is greatly reduced (the monomolecular organic active layer with the large distance is spanned), high response efficiency can be achieved, the response time of the sensor is shortened, and gas can directly influence a carrier transport layer.
Disclosure of Invention
One of the objects of the present invention is to provide a gas sensor based on a chromium phthalocyanine monomolecular layer film, which uses a metal chromium-doped phthalocyanine monomolecular film to detect, sense and adsorb harmful gases in the air, and which uses the high sensitivity and good recovery time after adsorption of the metal chromium-doped phthalocyanine to regenerate and reuse the chromium phthalocyanine. The gas sensor uses the phthalocyanine monomolecular film nested by metal chromium to absorb and sense formaldehyde and phosgene molecules in the air, and the good recovery performance of the chromium phthalocyanine is utilized to ensure that the chromium phthalocyanine can be repeatedly used in the detection of the formaldehyde and the phosgene; the gas sensor utilizes the characteristic that the monomolecular layer film shortens the response time, so that the response efficiency of the sensor in the detection of formaldehyde and phosgene is improved; the intermediate metal ion of the chromium phthalocyanine is a chromium ion.
The preparation method of the gas sensor based on the chromium phthalocyanine monomolecular layer film comprises the following steps:
step (1): cleaning and drying instruments and equipment before film coating, wherein pretreatment such as oil removal, dust removal and the like is carried out on a plated part before film coating so as to ensure the cleanness and dryness of the plated part and avoid the defects of pockmark, poor adhesion and the like of a bottom coating;
step (2): introducing carrier gas to heat the high-purity chromium phthalocyanine of the evaporation source to a target temperature of 400-500 ℃, and keeping the temperature until the deposition rate is stable; wherein the high-purity chromium phthalocyanine is placed in a quartz tube, the chamber of the quartz tube is evacuated to remove impurities such as air in the quartz tube, and a carrier gas such as nitrogen (N) is introduced2) Heating the high-purity chromium phthalocyanine to a predetermined target temperature in the presence of the carrier gas, after the predetermined target temperature is reachedKeeping the temperature for a period of time until the deposition rate is stable;
and (3): after the deposition rate is stable, rapidly conveying the chromium phthalocyanine gas obtained by heating and sublimating in the step (2) to an evaporation area through a carrier gas, starting a beam baffle to start evaporation, and obtaining a chromium phthalocyanine monomolecular layer film as an active layer of the gas sensor in the evaporation area; the chromium phthalocyanine gas is rapidly conveyed to the evaporation area through the carrier gas in order to avoid chromium phthalocyanine from forming a chromium phthalocyanine monomolecular film outside the evaporation area, wherein the evaporation rate is 1.0-2.0, preferably 1.5 nm/min, so that the evaporation molecular layer can grow in a two-dimensional growth mode, the evaporation time is controlled to be 1-2 min, preferably 1 min, and the chromium phthalocyanine film layer is obtained to serve as an active layer.
The high-purity chromium phthalocyanine of the evaporation source in the step (2) is prepared by the following method:
a: putting a chromium phthalocyanine raw material, namely chromium phthalocyanine with the purity of 95 percent, into a heating area in a horizontal tube furnace; wherein before preparation, instrument equipment, such as a quartz tube and a substrate, needs to be cleaned and dried; the horizontal tube furnace is a single-temperature-section tube furnace or a multi-temperature-section tube furnace, as long as one temperature section can heat the chromium phthalocyanine source material, the chromium phthalocyanine source material is put into a sealing tube of the horizontal tube furnace, and the sealing tube can be a quartz tube or a tube made of any other material which does not affect the crystallinity of the chromium phthalocyanine source material, including but not limited to tubes made of stainless steel, silicon, alumina, ceramics, glass and the like. These materials may also be placed in the form of a substrate in the sealed tube;
b: vacuumizing, heating the chromium phthalocyanine source material in a step heating manner in a carrier gas atmosphere, and preserving heat; vacuumizing a quartz tube cavity to remove impurities such as air in the quartz tube, wherein a carrier gas can be nitrogen, heating a chromium phthalocyanine source material to a preset target temperature in the presence of the carrier gas, and finally, preserving heat for a period of time after the preset target temperature is reached;
c: the sublimed chromium phthalocyanine gas after heating is rapidly transported to a chromium phthalocyanine growth area through a carrier gas, and high-purity chromium phthalocyanine is obtained in the growth area; during the transportation process, the rapid operation of the chromium phthalocyanine sublimation gas is to avoid the chromium phthalocyanine from growing chromium phthalocyanine crystals outside a growth area, wherein the growth area is adjacent to the heating area, and when the growth area is far away from the heating area, a temperature insulation material is filled in a gap between the heating area and the growth area, and the temperature insulation material comprises, but is not limited to, calcium silicate and aluminum silicate; a small quartz tube may be placed in the thermal insulation material to guide the carrier gas of the sublimation gas of chromium phthalocyanine through; the number and the diameter of the small quartz tubes can be set according to requirements, and the flow rate of the carrier gas passing through the thermal insulation material is greatly improved compared with the flow rate (L/min) at the inlet by arranging the small quartz tubes. Thereby, the sublimation gas carrying chromium phthalocyanine is enabled to rapidly reach the growth area; there may also be other regions between the growth region and the heating region, for example one or more intermediate temperature regions, and between the intermediate temperature regions or between the intermediate temperature regions and the other regions, there may be gaps as required, in which a temperature insulating material is filled, in which a small quartz tube is placed so as to guide the carrier gas of the chromium phthalocyanine gas to pass through.
Compared with the traditional metal phthalocyanine chemical synthesis method, the preparation method of the chromium phthalocyanine does not need vacuum or pressurization, is simple and convenient to operate, has high synthesis speed and high purity, is convenient to regulate and control the performance of the metal phthalocyanine material, and has unchanged physical and chemical properties after long-time storage.
The invention also provides a using method of the gas sensor based on the chromium phthalocyanine monomolecular layer film, which comprises the following specific steps:
step (1): placing the gas sensor based on the chromium phthalocyanine monomolecular layer film in a closed cavity, and filling air;
step (2): filling detection gas with preset concentration into the closed cavity and maintaining the atmosphere of the detection gas with the preset concentration, wherein the detection gas is H2CO、COCl2Or a mixture of the two.
The invention is characterized in that: the invention uses the chemical adsorption and effective desorption of the chromium phthalocyanine to the gas molecules, the molecules of harmful gases such as formaldehyde and phosgene in the air are firstly adsorbed to the surface of the chromium phthalocyanine for detection and sensing, and then the good recovery performance of the chromium phthalocyanine is utilized to ensure that the gas molecules adsorbed on the surface can be effectively desorbed in a short time, so that the chromium phthalocyanine can be recovered and the gas molecules are detected and sensed again. The gas sensor of the invention has the characteristics of short recovery time, strong adsorption strength, and good sensitivity and selectivity.
Compared with the prior art, the invention has the beneficial effects that:
(1) compared with the traditional metal phthalocyanine chemical synthesis method, the method adopts the principle of physical vapor deposition to prepare and purify the chromium phthalocyanine, and the purity can reach 99.99 percent. The method does not need vacuum or pressurization, has simple and convenient operation, high synthesis speed and high purity, is convenient for regulating and controlling the performance of the metal phthalocyanine material, and has unchanged physicochemical properties after long-term storage.
(2) The monomolecular film prepared by adopting the vacuum evaporation technical principle has thin thickness, greatly reduces the distance from the surface of the active layer to a channel (the organic active layer with the distance of spanning a single molecule to be thick), thereby achieving high response efficiency, shortening the response time of the sensor and directly influencing a carrier transport layer by gas.
(3) The chromium phthalocyanine of the invention is used as an organic film material and is mixed with the detected gas formaldehyde (H)2CO) and phosgene (COCl)2) The interaction between the two is stronger, and the detection of gas molecules is more sensitive. Meanwhile, by using the chromium phthalocyanine monomolecular layer as the gas sensor of the active layer, all the chromium phthalocyanine molecules in the active layer can be contacted with gas without being blocked when the sensor works, and the interaction can be sensitively reflected in the change of an output curve.
Drawings
FIG. 1 is the structure of chromium phthalocyanine CrPc;
FIG. 2 shows formaldehyde H from example 12The structure of the adsorption of CO on chromium phthalocyanine CrPc;
FIG. 3 shows the phosgene COCl of example 22Structure diagram of adsorption on chromium phthalocyanine CrPc;
the reference numbers in the figures: 1-carbon atom, 2-hydrogen atom, 3-nitrogen atom, 4-chromium atom, 5-oxygen atom, 6-chlorine atom.
Detailed Description
The invention is further described with reference to the following drawings and detailed description.
Example 1: the gas sensor of the embodiment uses the metal chromium doped phthalocyanine monomolecular film to detect, sense and adsorb harmful gases in the air, and utilizes the high sensitivity and good recovery time after adsorption of the metal chromium doped phthalocyanine to regenerate and repeatedly use the chromium phthalocyanine. The preparation method of the gas sensor comprises the following steps:
step (1): cleaning and drying instruments and equipment before film coating, wherein pretreatment such as oil removal, dust removal and the like is carried out on a plated part before film coating so as to ensure the cleanness and dryness of the plated part and avoid the defects of pockmark, poor adhesion and the like of a bottom coating;
step (2): placing high-purity chromium phthalocyanine (purity is 99.99%) in quartz tube, vacuumizing the quartz tube to remove impurities such as air in the quartz tube, and introducing carrier gas nitrogen (N)2) Heating the high-purity chromium phthalocyanine of the evaporation source to a target temperature of 400 ℃, and preserving heat until the deposition rate is stable;
and (3): after the deposition rate is stable, rapidly conveying the chromium phthalocyanine gas obtained by heating and sublimating in the step (2) to an evaporation area through a carrier gas, starting a beam baffle to start evaporation, and obtaining a chromium phthalocyanine monomolecular layer film as an active layer of the gas sensor in the evaporation area; the chromium phthalocyanine gas is rapidly conveyed to the evaporation area through the carrier gas in order to avoid chromium phthalocyanine from forming a chromium phthalocyanine monomolecular film outside the evaporation area, wherein the evaporation rate is selected to be 1.5 nm/min, so that the evaporation molecular layer is ensured to grow in a two-dimensional growth mode, and the evaporation time is controlled to be 1 min, so that the chromium phthalocyanine film layer is obtained and used as an active layer.
The high-purity chromium phthalocyanine of the evaporation source in the step (2) is prepared by the following steps:
a: putting a chromium phthalocyanine raw material with the purity of 95% into a heating area in a horizontal tube furnace; wherein before preparation, instrument equipment such as a quartz tube and a substrate needs to be cleaned and dried; wherein the horizontal tube furnace is a single-temperature-section tube furnace, the chromium phthalocyanine source material is put into a sealing tube of the single-temperature-section tube furnace, and the sealing tube is a quartz tube;
b: vacuumizing the cavity of the quartz tube to remove impurities such as air in the quartz tube, heating the chromium phthalocyanine source material in a stepped heating mode in the atmosphere of carrier gas nitrogen, and preserving heat;
c: the sublimed chromium phthalocyanine gas after heating is rapidly transported to a chromium phthalocyanine growth area through a carrier gas, and high-purity chromium phthalocyanine is obtained in the growth area, and the structure of the high-purity chromium phthalocyanine is shown in figure 1; wherein the rapid running of the chromium phthalocyanine sublimation gas during transport is to avoid chromium phthalocyanine crystal growth outside a growth region, wherein the growth region is adjacent to the heating region.
The application method of the gas sensor based on the chromium phthalocyanine monolayer film prepared in the embodiment comprises the following specific steps:
step (1): placing the gas sensor based on the chromium phthalocyanine monomolecular layer film in a closed cavity, and filling air;
step (2): filling detection gas with preset concentration into the closed cavity and maintaining the atmosphere of the detection gas with the preset concentration, wherein the detection gas is H2And (3) CO gas.
FIG. 2 shows formaldehyde H2Structure diagram of CO adsorption on chromium phthalocyanine CrPc, 5 in the figure being an oxygen atom, wherein the oxygen atom is at a distance 1.884 a from the chromium atom, formaldehyde H2The charge transfer number between CO and CrPc is 0.079 e, the adsorption energy is-0.63 eV, and the sensitivity is good.
Example 2: the gas sensor of the embodiment uses the metal chromium doped phthalocyanine monomolecular film to detect, sense and adsorb harmful gases in the air, and utilizes the high sensitivity and good recovery time after adsorption of the metal chromium doped phthalocyanine to regenerate and repeatedly use the chromium phthalocyanine. The preparation method of the gas sensor comprises the following steps:
step (1): cleaning and drying instruments and equipment before film coating, wherein pretreatment such as oil removal, dust removal and the like is carried out on a plated part before film coating so as to ensure the cleanness and dryness of the plated part and avoid the defects of pockmark, poor adhesion and the like of a bottom coating;
step (2): high purity chromium phthalocyanine (purity 99.9)9 percent of the mixture is put in a quartz tube, the cavity of the quartz tube is vacuumized to remove impurities such as air in the quartz tube, and carrier gas nitrogen (N) is introduced2) Heating the high-purity chromium phthalocyanine of the evaporation source to a target temperature of 450 ℃, and preserving heat until the deposition rate is stable;
and (3): after the deposition rate is stable, rapidly conveying the chromium phthalocyanine gas obtained by heating and sublimating in the step (2) to an evaporation area through a carrier gas, starting a beam baffle to start evaporation, and obtaining a chromium phthalocyanine monomolecular layer film as an active layer of the gas sensor in the evaporation area; the chromium phthalocyanine gas is rapidly conveyed to the evaporation area through the carrier gas in order to avoid chromium phthalocyanine from forming a chromium phthalocyanine monomolecular film outside the evaporation area, wherein the evaporation rate is selected to be 2.0 nm/min, so that the evaporation molecular layer is ensured to grow in a two-dimensional growth mode, and the evaporation time is controlled to be 1.5 min, so that the chromium phthalocyanine film layer is obtained and used as an active layer.
The high-purity chromium phthalocyanine of the evaporation source in the step (2) is prepared by the following steps:
a: a chromium phthalocyanine source material (purity: 95.0%) was placed in a heating zone in a horizontal tube furnace; wherein before preparation, instrument equipment such as a quartz tube and a substrate needs to be cleaned and dried; wherein the horizontal tube furnace is a multi-temperature section tube furnace, the chrome phthalocyanine source material is put into a sealing tube of the single-temperature section tube furnace, and the sealing tube is a stainless steel tube;
b: vacuumizing the stainless steel pipe cavity to remove impurities such as air in the stainless steel pipe, heating the chromium phthalocyanine source material in a stepped heating mode in the atmosphere of carrier gas nitrogen, and preserving heat;
c: the sublimed chromium phthalocyanine gas after heating is rapidly transported to a chromium phthalocyanine growth area through a carrier gas, and high-purity chromium phthalocyanine is obtained in the growth area; during the transportation process, the chromium phthalocyanine sublimation gas is rapidly operated to avoid the chromium phthalocyanine from growing a chromium phthalocyanine crystal outside a growth area, wherein the growth area is not adjacent to a heating area, a heat insulation material calcium silicate is filled in a gap between the growth area and the heating area, and a small quartz tube is placed in the heat insulation material so as to guide the carrier gas of the chromium phthalocyanine sublimation gas to pass through.
The application method of the gas sensor based on the chromium phthalocyanine monolayer film prepared in the embodiment comprises the following specific steps:
step (1): placing the gas sensor based on the chromium phthalocyanine monomolecular layer film in a closed cavity, and filling air;
step (2): filling detection gas with preset concentration into the closed cavity and maintaining the atmosphere of the detection gas with the preset concentration, wherein the detection gas is COCl2A gas.
FIG. 3 is phosgene COCl2Structural drawing of the adsorption on chromium phthalocyanine CrPc, 6 being a chlorine atom, where the oxygen atom is at a distance of 4.035A from the chromium atom, phosgene COCl2The charge transfer number between the conductive material and CrPc is 0.055 e, the adsorption energy is-0.31 eV, and the conductive material has good sensitivity.
Example 3: the gas sensor of the embodiment uses the metal chromium doped phthalocyanine monomolecular film to detect, sense and adsorb harmful gases in the air, and utilizes the high sensitivity and good recovery time after adsorption of the metal chromium doped phthalocyanine to regenerate and repeatedly use the chromium phthalocyanine. The preparation method of the gas sensor comprises the following steps:
step (1): cleaning and drying instruments and equipment before film coating, wherein pretreatment such as oil removal, dust removal and the like is carried out on a plated part before film coating so as to ensure the cleanness and dryness of the plated part and avoid the defects of pockmark, poor adhesion and the like of a bottom coating;
step (2): placing high-purity chromium phthalocyanine (purity is 99.99%) in quartz tube, vacuumizing the quartz tube to remove impurities such as air in the quartz tube, and introducing carrier gas nitrogen (N)2) Heating the high-purity chromium phthalocyanine of the evaporation source to a target temperature of 500 ℃, and preserving heat until the deposition rate is stable;
and (3): after the deposition rate is stable, rapidly conveying the chromium phthalocyanine gas obtained by heating and sublimating in the step (2) to an evaporation area through a carrier gas, starting a beam baffle to start evaporation, and obtaining a chromium phthalocyanine monomolecular layer film as an active layer of the gas sensor in the evaporation area; the chromium phthalocyanine gas is rapidly conveyed to the evaporation area through the carrier gas in order to avoid chromium phthalocyanine from forming a chromium phthalocyanine monomolecular film outside the evaporation area, wherein the evaporation rate is selected to be 1.0nm/min, so that the evaporation molecular layer is ensured to grow in a two-dimensional growth mode, and the evaporation time is controlled to be 2min, so that the chromium phthalocyanine film layer is obtained and used as an active layer.
The high-purity chromium phthalocyanine (purity of 99.99%) of the evaporation source in the step (2) is prepared by the following steps:
a: a chromium phthalocyanine source material (purity: 95.0%) was placed in a heating zone in a horizontal tube furnace; wherein before preparation, instrument equipment such as a quartz tube and a substrate needs to be cleaned and dried; wherein the horizontal tube furnace is a multi-temperature section tube furnace, the chrome phthalocyanine source material is put into a sealing tube of the single-temperature section tube furnace, and the sealing tube is a silicon tube;
b: vacuumizing the cavity of the silicon tube to remove impurities such as air in the silicon tube, heating the chromium phthalocyanine source material in a stepped heating mode in the atmosphere of carrier gas nitrogen, and preserving heat;
c: the sublimed chromium phthalocyanine gas after heating is rapidly transported to a chromium phthalocyanine growth area through a carrier gas, and high-purity chromium phthalocyanine is obtained in the growth area; during the transportation process, the chromium phthalocyanine sublimation gas is rapidly operated to avoid the chromium phthalocyanine from growing chromium phthalocyanine crystals outside a growth area, wherein the growth area is not adjacent to a heating area, a heat insulation material aluminum silicate is filled in a gap between the growth area and the heating area, and a small quartz tube is placed in the heat insulation material so as to guide the carrier gas of the chromium phthalocyanine sublimation gas to pass through.
The application method of the gas sensor based on the chromium phthalocyanine monolayer film prepared in the embodiment comprises the following specific steps:
step (1): placing the gas sensor based on the chromium phthalocyanine monomolecular layer film in a closed cavity, and filling air;
step (2): filling detection gas with preset concentration into the closed cavity and maintaining the atmosphere of the detection gas with the preset concentration, wherein the detection gas is H2CO and COCl2The mixed gas of (1).
In the embodiment, the chemical adsorption and effective desorption of the chromium phthalocyanine on gas molecules are applied, molecules of harmful gases such as formaldehyde and phosgene in the air are adsorbed on the surface of the chromium phthalocyanine for detection and sensing, and then the gas molecules adsorbed on the surface can be effectively desorbed in a short time by utilizing the good recovery performance of the chromium phthalocyanine, so that the chromium phthalocyanine can be recovered, and the gas molecules are detected and sensed again. The gas sensor of the embodiment has the characteristics of short recovery time, strong adsorption strength, and good sensitivity and selectivity.
Although the embodiments of the present invention have been described in conjunction with the accompanying drawings, those skilled in the art may make various modifications and variations without departing from the spirit and scope of the invention, and such modifications and variations fall within the scope defined by the appended claims.
Claims (9)
1. The gas sensor is characterized in that the gas sensor uses a phthalocyanine monomolecular film doped with metal chromium to detect, sense and adsorb harmful gases in the air, and the gas sensor utilizes the high sensitivity of the phthalocyanine doped with metal chromium and good recovery time after adsorption to regenerate and repeatedly use the chromium phthalocyanine.
2. The chromium phthalocyanine monolayer film-based gas sensor according to claim 1, wherein: the preparation method of the gas sensor comprises the following steps:
step (1): cleaning and drying instrument equipment before film coating;
step (2): introducing carrier gas to heat the high-purity chromium phthalocyanine of the evaporation source to a target temperature, and preserving heat until the deposition rate is stable;
and (3): and (3) after the deposition rate is stable, rapidly conveying the chromium phthalocyanine gas obtained by heating and sublimating in the step (2) to an evaporation area through a carrier gas, starting a beam baffle to start evaporation, and obtaining a chromium phthalocyanine monomolecular layer film as an active layer of the gas sensor in the evaporation area.
3. A chromium phthalocyanine monolayer film-based gas sensor according to claim 2, wherein: the target temperature in the step (2) is 400-500 ℃, the evaporation rate in the step (3) is 1.0-2.0 nm/min, and the evaporation time is 1-2 min.
4. A chromium phthalocyanine monolayer film-based gas sensor according to claim 2, wherein: the high-purity chromium phthalocyanine of the evaporation source in the step (2) is prepared by the following method:
a: putting a chromium phthalocyanine raw material into a heating area in a horizontal tube furnace;
b: vacuumizing, heating the chromium phthalocyanine source material in a step heating manner in a carrier gas atmosphere, and preserving heat;
c: the heated and sublimated chromium phthalocyanine gas is rapidly transported to a chromium phthalocyanine growth area through a carrier gas, and high-purity chromium phthalocyanine is obtained in the growth area.
5. The chromium phthalocyanine monolayer film-based gas sensor according to claim 4, wherein: the horizontal tube furnace in the step A is a single-temperature-section tube furnace or a multi-temperature-section tube furnace, the chromium phthalocyanine source material is put into a sealing tube of the horizontal tube furnace, the sealing tube is a quartz tube, a stainless steel tube, a silicon tube, an alumina tube, a ceramic tube or a glass tube, and the chromium phthalocyanine material in the step A is chromium phthalocyanine with the purity of 95%.
6. The chromium phthalocyanine monolayer film-based gas sensor according to claim 4, wherein: the carrier gas in step B is nitrogen, and the growth area in step C is adjacent to the heating area in the horizontal tube furnace.
7. The chromium phthalocyanine monolayer film-based gas sensor according to claim 4, wherein: the growing region is not adjacent to the heating region, and the gap between the growing region and the heating region is filled with a thermal insulation material which is calcium silicate or aluminum silicate.
8. A chromium phthalocyanine monolayer film-based gas sensor according to claim 7, wherein: a small quartz tube is placed in the heat-insulating material in the gap between the growth area and the heating area so as to guide the carrier gas of the chromium phthalocyanine sublimation gas to pass through.
9. The use method of the chromium phthalocyanine monolayer film-based gas sensor as claimed in any one of claims 1 to 8, which comprises the following steps:
step (1): placing the gas sensor based on the chromium phthalocyanine monomolecular layer film in a closed cavity, and filling air;
step (2): filling detection gas with preset concentration into the closed cavity and maintaining the atmosphere of the detection gas with the preset concentration, wherein the detection gas is H2CO、COCl2Or a mixture of the two.
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Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB8825692D0 (en) * | 1987-11-06 | 1988-12-07 | Nat Res Dev | Gas sensor using phthalocyanine |
| JPH01140052A (en) * | 1987-11-26 | 1989-06-01 | Matsushita Electric Ind Co Ltd | Gas sensor and manufacture thereof |
| US4900817A (en) * | 1988-05-31 | 1990-02-13 | Edison Polymer Innovation Corporation | Multiring phthalocyanine compounds |
| JP2005233682A (en) * | 2004-02-17 | 2005-09-02 | Itagaki Masayoshi | Gas sensor and its manufacturing method |
| CN104086555A (en) * | 2014-06-20 | 2014-10-08 | 昆明学院 | New-crystal-structural cobalt phthalocyanine (J-CoPc) nanowires and preparation method thereof |
| CN104297320A (en) * | 2013-07-17 | 2015-01-21 | 国家纳米科学中心 | Organic monolayer thin film field effect gas sensor and preparation method thereof |
| CN104610269A (en) * | 2015-01-23 | 2015-05-13 | 昆明学院 | Novel crystal structure NiPc (omega-NiPc) nanowire and preparation method thereof |
| CN106706718A (en) * | 2016-12-08 | 2017-05-24 | 东北大学 | Three-layer-structure sensitive layer phthalocyanine gas sensitive sensor and preparation method thereof |
| CN108362741A (en) * | 2018-02-27 | 2018-08-03 | 上海交通大学 | A kind of preparation method and its application method of the gas sensor based on metal phthalocyanine |
| CN110289349A (en) * | 2019-06-27 | 2019-09-27 | 东北大学 | A kind of regulatable composition metal phthalocyanine thin film of magnetism and preparation method thereof |
| JP2020204486A (en) * | 2019-06-14 | 2020-12-24 | 富士通株式会社 | Gas sensor and manufacturing method of gas sensor |
| CN113135926A (en) * | 2021-04-23 | 2021-07-20 | 昆明学院 | Novel crystal structure indium phthalocyanine nanowire and preparation method thereof |
-
2021
- 2021-09-24 CN CN202111118819.4A patent/CN113777137A/en active Pending
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB8825692D0 (en) * | 1987-11-06 | 1988-12-07 | Nat Res Dev | Gas sensor using phthalocyanine |
| JPH01140052A (en) * | 1987-11-26 | 1989-06-01 | Matsushita Electric Ind Co Ltd | Gas sensor and manufacture thereof |
| US4900817A (en) * | 1988-05-31 | 1990-02-13 | Edison Polymer Innovation Corporation | Multiring phthalocyanine compounds |
| JP2005233682A (en) * | 2004-02-17 | 2005-09-02 | Itagaki Masayoshi | Gas sensor and its manufacturing method |
| CN104297320A (en) * | 2013-07-17 | 2015-01-21 | 国家纳米科学中心 | Organic monolayer thin film field effect gas sensor and preparation method thereof |
| CN104086555A (en) * | 2014-06-20 | 2014-10-08 | 昆明学院 | New-crystal-structural cobalt phthalocyanine (J-CoPc) nanowires and preparation method thereof |
| CN104610269A (en) * | 2015-01-23 | 2015-05-13 | 昆明学院 | Novel crystal structure NiPc (omega-NiPc) nanowire and preparation method thereof |
| CN106706718A (en) * | 2016-12-08 | 2017-05-24 | 东北大学 | Three-layer-structure sensitive layer phthalocyanine gas sensitive sensor and preparation method thereof |
| CN108362741A (en) * | 2018-02-27 | 2018-08-03 | 上海交通大学 | A kind of preparation method and its application method of the gas sensor based on metal phthalocyanine |
| JP2020204486A (en) * | 2019-06-14 | 2020-12-24 | 富士通株式会社 | Gas sensor and manufacturing method of gas sensor |
| CN110289349A (en) * | 2019-06-27 | 2019-09-27 | 东北大学 | A kind of regulatable composition metal phthalocyanine thin film of magnetism and preparation method thereof |
| CN113135926A (en) * | 2021-04-23 | 2021-07-20 | 昆明学院 | Novel crystal structure indium phthalocyanine nanowire and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| DENIS M,ET AL: "Highly transparent low-symmetry zinc phthalocyanine-based monolayers for NO2 gas detection", 《THE SOLID FILMS》 * |
| 罗金龙,等: "基于酞菁铜材料的有机太阳能电池研究与展望", 《云南大学学报(自然科学版)》 * |
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