CN113091939B - Preparation method of high-sensitivity temperature sensor based on graphene/barium strontium titanate heterojunction - Google Patents
Preparation method of high-sensitivity temperature sensor based on graphene/barium strontium titanate heterojunction Download PDFInfo
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- CN113091939B CN113091939B CN202110333309.2A CN202110333309A CN113091939B CN 113091939 B CN113091939 B CN 113091939B CN 202110333309 A CN202110333309 A CN 202110333309A CN 113091939 B CN113091939 B CN 113091939B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 137
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 137
- 229910052454 barium strontium titanate Inorganic materials 0.000 title claims abstract description 95
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000000919 ceramic Substances 0.000 claims abstract description 40
- 238000000034 method Methods 0.000 claims abstract description 35
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910052802 copper Inorganic materials 0.000 claims abstract description 27
- 239000010949 copper Substances 0.000 claims abstract description 27
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000005530 etching Methods 0.000 claims abstract description 20
- 238000001035 drying Methods 0.000 claims abstract description 19
- 239000007788 liquid Substances 0.000 claims abstract description 19
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims abstract description 17
- 239000004926 polymethyl methacrylate Substances 0.000 claims abstract description 17
- 238000005245 sintering Methods 0.000 claims abstract description 17
- 239000007790 solid phase Substances 0.000 claims abstract description 13
- 238000004528 spin coating Methods 0.000 claims abstract description 8
- 230000035945 sensitivity Effects 0.000 claims abstract description 7
- 238000005520 cutting process Methods 0.000 claims abstract description 6
- 229910010252 TiO3 Inorganic materials 0.000 claims description 21
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 238000004140 cleaning Methods 0.000 claims description 10
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052737 gold Inorganic materials 0.000 claims description 4
- 239000010931 gold Substances 0.000 claims description 4
- 238000005498 polishing Methods 0.000 claims description 4
- 238000001771 vacuum deposition Methods 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 3
- 238000004090 dissolution Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 4
- 239000012071 phase Substances 0.000 abstract description 23
- 230000007704 transition Effects 0.000 abstract description 19
- 230000008859 change Effects 0.000 abstract description 16
- 230000004044 response Effects 0.000 abstract description 5
- 238000001514 detection method Methods 0.000 abstract description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 8
- 238000001179 sorption measurement Methods 0.000 description 6
- 239000010410 layer Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- WOIHABYNKOEWFG-UHFFFAOYSA-N [Sr].[Ba] Chemical compound [Sr].[Ba] WOIHABYNKOEWFG-UHFFFAOYSA-N 0.000 description 3
- 229910002113 barium titanate Inorganic materials 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000001069 Raman spectroscopy Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- WPYVAWXEWQSOGY-UHFFFAOYSA-N indium antimonide Chemical compound [Sb]#[In] WPYVAWXEWQSOGY-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01K—MEASURING TEMPERATURE; MEASURING QUANTITY OF HEAT; THERMALLY-SENSITIVE ELEMENTS NOT OTHERWISE PROVIDED FOR
- G01K7/00—Measuring temperature based on the use of electric or magnetic elements directly sensitive to heat ; Power supply therefor, e.g. using thermoelectric elements
- G01K7/16—Measuring temperature based on the use of electric or magnetic elements directly sensitive to heat ; Power supply therefor, e.g. using thermoelectric elements using resistive elements
- G01K7/22—Measuring temperature based on the use of electric or magnetic elements directly sensitive to heat ; Power supply therefor, e.g. using thermoelectric elements using resistive elements the element being a non-linear resistance, e.g. thermistor
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- Physics & Mathematics (AREA)
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- General Physics & Mathematics (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a preparation method of a high-sensitivity temperature sensor based on a graphene/barium strontium titanate heterojunction, belongs to the field of temperature sensors, and aims to solve the problem that the sensitivity and response speed of the existing temperature sensor are low. The preparation method comprises the following steps: 1. preparing barium strontium titanate ceramic by adopting a solid phase sintering method; 2. cutting graphene loaded on a copper sheet, and spin-coating polymethyl methacrylate on the graphene; 3. putting the spin-coated graphene into copper etching liquid, and fishing the graphene from the copper etching liquid; 4. transferring graphene onto a polished surface of barium strontium titanate ceramic, and drying; 5. putting the dried barium strontium titanate ceramic into acetone to dissolve polymethyl methacrylate; 6. and (5) placing the graphene-barium strontium titanate heterojunction into an oven for drying. When the temperature is increased to the vicinity of the phase transition temperature of the barium strontium titanate, the current respectively increases at a higher rate than the room temperature, and has a higher current change rate in a narrower phase transition temperature region, thereby having higher detection sensitivity.
Description
Technical Field
The invention belongs to the field of temperature sensors, and particularly relates to a preparation method of a high-sensitivity graphene/barium strontium titanate heterostructure temperature sensor.
Background
A temperature sensor is a device capable of converting a temperature signal into an electrical signal and outputting the electrical signal, wherein the conversion into a resistance signal is the most common and easily designed method, and a device commonly used for measuring temperature is a thermocouple and a thermistor, wherein the thermistor related to a semiconductor is a principle of converting an increase signal of temperature into a resistance decrease signal. Although thermistors are widely studied in the field of temperature sensors, there are still a lot of key problems in the aspects of key materials and device structures of temperature sensors facing the requirements of high sensitivity and high response speed, for example, the problem that high current causes self-heating of the thermistors is needed to be solved, so that the exploration of novel high-sensitivity high-response speed temperature sensor materials and device structures is still a new challenge.
The appearance of the graphene opens a new research thought for the research of high-speed response devices. Ideal single-layer graphene has a perfectly symmetrical tapered band structure. The bonds in the molecular structure are conjugated to form large pi bonds, which also enables carriers to move at high speed, and the theoretical carrier mobility is about 200000cm 2/Vs, far exceeding indium antimonide (about 77000cm 2/Vs) which has been previously considered to be the largest carrier mobility. But the type of substrate can affect the carrier mobility of graphene. Specifically, the self-polarized electric field of the ferroelectric dipole in the ferroelectric material has a significant effect on the graphene carrier characteristics and resistivity in the graphene/ferroelectric thin film heterostructure. These ferroelectric dipoles will disappear during the phase transition, while the curie temperature can be adjusted by ion doping with dopants such as BaTiO 3、PbZrTiO3 and (K, na) NbO 3.
Disclosure of Invention
The invention aims to solve the problem of low sensitivity and response speed of the existing temperature sensor, and provides a preparation method of a high-sensitivity temperature sensor based on a graphene/barium strontium titanate heterojunction.
The preparation method of the high-sensitivity temperature sensor based on the graphene/barium strontium titanate heterojunction is realized according to the following steps:
1. Preparing barium strontium titanate ceramic according to the stoichiometric ratio of Ba xSr1-xTiO3 by adopting a solid-phase sintering method and polishing;
2. cutting graphene loaded on a copper sheet, and spin-coating a layer of polymethyl methacrylate on the graphene to obtain spin-coated graphene;
3. putting the spin-coated graphene into copper etching liquid, fishing the graphene from the copper etching liquid, and putting the graphene into deionized water for cleaning to obtain cleaned graphene;
4. Transferring the cleaned graphene onto a polished surface of the barium strontium titanate ceramic by adopting a wet transfer method, and then putting the barium strontium titanate ceramic into a drying oven for drying to obtain the dried barium strontium titanate ceramic;
5. putting the dried barium strontium titanate ceramic into acetone to dissolve polymethyl methacrylate on the surface of graphene, and then putting the ceramic into deionized water to clean the ceramic, so as to obtain a graphene-barium strontium titanate heterojunction;
6. And (3) putting the graphene-barium strontium titanate heterojunction into an oven for drying to obtain the high-sensitivity temperature sensor based on the graphene/barium strontium titanate heterojunction.
The chemical general formula of the Graphene/barium strontium titanate heterojunction is Graphene/Ba xSr1- xTiO3 (x is more than or equal to 0.1 and less than or equal to 0.4).
The preparation method of the high-sensitivity temperature sensor based on the graphene/barium strontium titanate heterojunction has the following beneficial effects:
The number of positive and negative charges adsorbed by the ferroelectric dipoles in different directions in the barium strontium titanate has adsorption and rejection effects on large pi bonds in the graphene. This behavior affects the carrier mobility and resistivity of graphene. Specifically, the physical state change of the large pi bond has a significant influence on the charge transfer characteristic, an electric dipole near the curie temperature of the barium strontium titanate heterostructure disappears along with the temperature increase, and meanwhile, positive and negative charges adsorbed on the surface of the barium strontium titanate also disappear, so that the physical state of the large pi bond in the graphene is changed, and the carrier mobility of the graphene is also changed along with the change. Thus, when small temperature adjustments are made around the curie temperature of the barium strontium titanate, the current of the graphene/barium strontium titanate heterostructure varies significantly at a constant applied voltage.
According to the graphene/barium strontium titanate heterostructure provided by the invention, the phase transition temperature of the barium strontium titanate is 0-90 ℃, the current of the heterojunction can be greatly changed under a certain constant voltage condition near the phase transition temperature of the barium strontium titanate, when the temperature is increased to near the phase transition temperature, the current respectively increases at a higher rate compared with the room temperature, and the current has a higher current change rate in a narrower phase transition temperature region, so that the graphene/barium strontium titanate heterostructure has higher detection sensitivity.
The ceramic material prepared by adopting the solid-phase sintering method has the advantages of simple process and equipment, easily available raw materials, low cost and easy device integration, is suitable for industrial production, and provides guarantee for the application of the graphene/ferroelectric material heterojunction in the field of temperature sensors.
Drawings
FIG. 1 is a flow chart of the preparation of a high sensitivity temperature sensor of the graphene/barium strontium titanate heterojunction of the present invention;
FIG. 2 is a graph showing the variation of dielectric constant with temperature of Ba 0.7Sr0.3TiO3 obtained in example 3, the frequencies being 1kHz, 10kHz, 100kHz and 1MHz in order along the arrow direction;
FIG. 3 is a graph of G peak of graphene as a function of temperature;
FIG. 4 is a graph of 2D peak versus temperature for graphene;
FIG. 5 is a graph showing the variation of the graphene/Ba 0.7Sr0.3TiO3 heterojunction current obtained in example 3 with temperature under constant voltage conditions;
Fig. 6 is a graph showing the temperature change of the heterojunction resistance of graphene/Ba 0.7Sr0.3TiO3 obtained in example 3 under constant voltage conditions.
Detailed Description
The first embodiment is as follows: the preparation method of the high-sensitivity temperature sensor based on the graphene/barium strontium titanate heterojunction is implemented according to the following steps:
1. Preparing barium strontium titanate ceramic according to the stoichiometric ratio of Ba xSr1-xTiO3 by adopting a solid-phase sintering method and polishing;
2. cutting graphene loaded on a copper sheet, and spin-coating a layer of polymethyl methacrylate on the graphene to obtain spin-coated graphene;
3. putting the spin-coated graphene into copper etching liquid, fishing the graphene from the copper etching liquid, and putting the graphene into deionized water for cleaning to obtain cleaned graphene;
4. Transferring the cleaned graphene onto a polished surface of the barium strontium titanate ceramic by adopting a wet transfer method, and then putting the barium strontium titanate ceramic into a drying oven for drying to obtain the dried barium strontium titanate ceramic;
5. putting the dried barium strontium titanate ceramic into acetone to dissolve polymethyl methacrylate on the surface of graphene, and then putting the ceramic into deionized water to clean the ceramic, so as to obtain a graphene-barium strontium titanate heterojunction;
6. And (3) putting the graphene-barium strontium titanate heterojunction into an oven for drying to obtain the high-sensitivity temperature sensor based on the graphene/barium strontium titanate heterojunction.
The embodiment constructs a temperature sensor through graphene and ferroelectric materials, and the sensor can work under different temperature conditions based on a graphene/ferroelectric heterostructure.
The second embodiment is as follows: the difference between the embodiment and the specific embodiment is that the value of x in the chemical formula Ba xSr1- xTiO3 in the step one is 0.1-0.4.
And a third specific embodiment: this embodiment differs from the one or two embodiments in that the solid phase sintering method in step one is sintering at 1200 to 1450 ℃ for 6 to 12 hours.
The specific embodiment IV is as follows: this embodiment differs from the third embodiment in that the solid phase sintering method in step one is sintering at 1300 ℃ for 8 hours.
Fifth embodiment: the difference between the embodiment and the first to fourth embodiments is that the size of the copper sheet cut in the second step is (4-8) × (2-5) mm.
Specific embodiment six: the difference between the embodiment and the specific embodiment is that the graphene subjected to the spin coating in the step three is placed into copper etching liquid for treatment for 10-50 minutes.
The purpose of the etching of this embodiment is to detach the graphene from the copper load in order to transfer it to the barium strontium titanate polished surface.
Seventh embodiment: the difference between the embodiment and one to six embodiments is that the graphene is washed in deionized water for 5-30 minutes in the step three, and the washing is repeated for 3-5 times.
According to the method, the residual etching liquid on the graphene is removed through deionized water cleaning treatment, and the influence of the etching liquid on the heterostructure is avoided.
Eighth embodiment: the difference between the embodiment and one of the embodiments one to seven is that the drying temperature in the fourth step is 50-80 ℃ and the drying time is 30-90 minutes.
Detailed description nine: the difference between the embodiment and one to eight embodiments is that in the fifth step, the dried barium strontium titanate ceramic is put into acetone for dissolution treatment for 5 to 30 minutes.
The dried barium strontium titanate ceramic in the embodiment can be put into acetone for repeated treatment for 3 to 5 times. The purpose of using acetone is to completely dissolve polymethyl methacrylate, remove its effect on heterostructures, and at the same time facilitate the simultaneous evaporation of electrodes on graphene and barium strontium titanate.
Detailed description ten: the difference between the present embodiment and one of the first to ninth embodiments is that the drying temperature in the sixth step is 50 to 80 ℃ and the drying time is 30 to 90 minutes.
Eleventh embodiment: the present embodiment differs from the one to one of the specific embodiments in that the step six is to deposit a gold electrode on the graphene surface of the high-sensitivity temperature sensor based on the graphene/barium strontium titanate heterojunction by using a vacuum evaporation method.
Example 1: the preparation method of the high-sensitivity temperature sensor based on Graphene/barium strontium titanate heterojunction (Graphene/Ba 0.9Sr0.1TiO3) is implemented according to the following steps:
1. Weighing raw materials BaCO 3,TiO2 and SrCO 3 according to the stoichiometric ratio of Ba 0.9Sr0.1TiO3, adopting a solid phase sintering method to sinter for 8 hours at 1250 ℃, preparing Ba 0.9Sr0.1TiO3 ceramic and polishing;
2. Cutting graphene loaded on a copper sheet, and spin-coating a layer of polymethyl methacrylate on the graphene to obtain spin-coated graphene so as to play a bearing role in transferring the graphene;
3. Placing the spin-coated graphene into copper etching liquid for 30 minutes, fishing the graphene from the copper etching liquid by utilizing a copper net, placing the graphene into deionized water for cleaning for 20 minutes, and removing the etching liquid remained on the graphene to obtain cleaned graphene;
4. Transferring the cleaned graphene onto a polished surface of the barium strontium titanate ceramic by adopting a wet transfer method, and then putting the barium strontium titanate ceramic into a baking oven to be baked for 60 minutes at 60 ℃ to obtain the baked barium strontium titanate ceramic;
5. putting the dried barium strontium titanate ceramic into acetone for 20 minutes, dissolving polymethyl methacrylate on the surface of graphene, repeatedly putting into acetone for 3 times, completely removing the polymethyl methacrylate, and then putting into deionized water for cleaning to obtain a graphene-barium strontium titanate heterojunction;
6. and (3) placing the graphene-barium strontium titanate heterojunction into an oven to be dried at 60 ℃ for 60 minutes, and obtaining the high-sensitivity temperature sensor based on the graphene/barium strontium titanate heterojunction.
In the embodiment, two gold electrodes are evaporated on the surface of the graphene/barium strontium titanate heterojunction by using a vacuum evaporation method before testing.
Example 2: the preparation method of the high-sensitivity temperature sensor based on Graphene/barium strontium titanate heterojunction (Graphene/Ba 0.8Sr0.2TiO3) is implemented according to the following steps:
1. weighing raw materials BaCO 3,TiO2 and SrCO 3 according to the stoichiometric ratio of Ba 0.8Sr0.2TiO3, and adopting a solid phase sintering method to sinter for 8 hours at 1300 ℃ to prepare Ba 0.8Sr0.2TiO3 ceramic;
2. Cutting graphene loaded on a copper sheet, and spin-coating a layer of polymethyl methacrylate on the graphene to obtain spin-coated graphene so as to play a bearing role in transferring the graphene;
3. Placing the spin-coated graphene into copper etching liquid for 35 minutes, fishing the graphene from the copper etching liquid by utilizing a copper net, placing the graphene into deionized water for cleaning for 20 minutes, and removing the etching liquid remained on the graphene to obtain cleaned graphene;
4. transferring the cleaned graphene onto a polished surface of the barium strontium titanate ceramic by adopting a wet transfer method, and then putting the barium strontium titanate ceramic into a baking oven to be baked for 50 minutes at 60 ℃ to obtain the baked barium strontium titanate ceramic;
5. putting the dried barium strontium titanate ceramic into acetone for 20 minutes, dissolving polymethyl methacrylate on the surface of graphene, repeatedly putting into acetone for 3 times, completely removing the polymethyl methacrylate, and then putting into deionized water for cleaning to obtain a graphene-barium strontium titanate heterojunction;
6. And (3) placing the graphene-barium strontium titanate heterojunction into an oven to be dried for 50 minutes at 60 ℃ to obtain the high-sensitivity temperature sensor based on the graphene/barium strontium titanate heterojunction.
Example 3: this example differs from example 1 in that step one, raw materials BaCO 3,TiO2 and SrCO 3 were weighed in accordance with the stoichiometric ratio of Ba 0.7Sr0.3TiO3, and sintered at 1350 ℃ for 10 hours by a solid phase sintering method to prepare Ba 0.7Sr0.3TiO3 ceramic.
Example 4: this example differs from example 1 in that step one, raw materials BaCO 3,TiO2 and SrCO 3 were weighed in accordance with the stoichiometric ratio of Ba 0.6Sr0.4TiO3, and sintered at 1350 ℃ for 10 hours by a solid phase sintering method to prepare Ba 0.6Sr0.4TiO3 ceramic.
Fig. 1 is a preparation flow chart of a graphene/barium strontium titanate heterostructure, which corresponds to examples 1-4, wherein the preparation process of the graphene/barium strontium titanate heterostructure can be seen from the figure, the graphene with the specification of (4-8) x (2-5) mm loaded on a copper sheet is cut, a layer of polymethyl methacrylate is spin-coated on the graphene, the spin-coated graphene is placed in copper etching liquid for 10-50 minutes, after the graphene is cleaned, the cleaned graphene is transferred to a polished surface of barium strontium titanate by adopting a wet transfer method, the graphene/barium strontium titanate heterostructure is formed initially, the cleaned graphene/barium strontium titanate heterostructure is dried and then placed in acetone, polymethyl methacrylate is completely dissolved, and after the cleaned and dried again, a gold electrode with a certain area is deposited by adopting a vacuum evaporation method, so that preparation is provided for electrical property test.
Fig. 2 is a graph showing the dielectric constant of Ba 0.7Sr0.3TiO3 as a function of temperature, which corresponds to example 3, showing that the dielectric constant at different temperatures initially increases with increasing test frequency and then decreases. The single dielectric peak appears at about 30 ℃, and due to the transition from ferroelectric phase to paraelectric phase, the phase transition temperature of Ba 0.7Sr0.3TiO3 is about 30 ℃ (wherein the phase transition temperature of the barium strontium titanate ceramics obtained in examples 1,2 and 4 is about 90 ℃, -60 ℃ and-0 ℃), respectively, and the phase transition temperature is about 30 ℃ and is the region where the electric dipole exists and disappears, at the same time, the adsorption charge also disappears, so that the physical state of the graphene with large pi bond is changed, the mobility of the carrier in the graphene is further influenced, and the macroscopic appearance is the change of heterojunction current and resistance.
Fig. 3 and fig. 4 are graphs of the G peak and the 2D peak of graphene along with the temperature change, which correspond to examples 1 to 4, and it is known from the graph that the G peak and the 2D peak have a relatively obvious rule along with the temperature change, because the graphene and the strontium barium titanate are in a state of mutual adsorption before the strontium barium titanate is subjected to phase change, the transverse vibration of the graphene is affected in the current-voltage test process, the adsorption state of the graphene and the strontium barium titanate disappears after the phase change, and the transverse shrinkage of the graphene is not limited in the current-voltage test process, so that the G peak area of the temperature change raman shows an increasing trend near the phase change temperature, and the temperature continues to be increased and tends to be stable. On the other hand, before the phase transition, the adsorption effect of positive charges on the surface of barium strontium titanate on large pi bonds of graphene leads to larger longitudinal vibration of the graphene, and after the phase transition, the adsorption state disappears and the longitudinal vibration is reduced, so that the 2D peak area of the temperature-changing Raman shows a tendency of reducing near the phase transition temperature, and the temperature is continuously increased and tends to be stable.
FIG. 5 is a graph showing the variation of the graphene/Ba 0.7Sr0.3TiO3 heterojunction current with temperature under constant voltage conditions; this figure corresponds to example 3, with a current of 16.33. Mu.A at room temperature, initially increasing slightly with increasing temperature. When the ambient temperature crosses the phase transition temperature of barium strontium titanate, the current starts to increase significantly, from 16.38 μa to 16.99 μa, by 0.3% and 4% respectively, which results indicate that the relative change in heterostructure current is higher near the barium strontium titanate phase transition temperature.
Fig. 6 is a graph showing the variation of the heterojunction resistance of graphene/Ba 0.7Sr0.3TiO3 with temperature under constant voltage conditions. The graph corresponds to example 3, with relative percentages of change in resistance between 27 and 31℃being 0.3% and 3.9%, respectively, with an average change ratio of 0.9%/. Degree.C. But at temperatures below the phase transition temperature, the average change ratio is only 0.06%/°c, which is above 0.38%/°c of the phase transition temperature. Therefore, the resistance of the heterostructure decreases most around the barium strontium titanate phase transition temperature.
Claims (11)
1. The preparation method of the high-sensitivity temperature sensor based on the graphene/barium strontium titanate heterojunction is characterized by comprising the following steps of:
1. Preparing barium strontium titanate ceramic according to the stoichiometric ratio of Ba xSr1-xTiO3 by adopting a solid-phase sintering method and polishing;
2. cutting graphene loaded on a copper sheet, and spin-coating a layer of polymethyl methacrylate on the graphene to obtain spin-coated graphene;
3. putting the spin-coated graphene into copper etching liquid, fishing the graphene from the copper etching liquid, and putting the graphene into deionized water for cleaning to obtain cleaned graphene;
4. Transferring the cleaned graphene onto a polished surface of the barium strontium titanate ceramic by adopting a wet transfer method, and then putting the barium strontium titanate ceramic into a drying oven for drying to obtain the dried barium strontium titanate ceramic;
5. putting the dried barium strontium titanate ceramic into acetone to dissolve polymethyl methacrylate on the surface of graphene, and then putting the ceramic into deionized water to clean the ceramic, so as to obtain a graphene-barium strontium titanate heterojunction;
6. Placing the graphene-barium strontium titanate heterojunction into an oven for drying to obtain a high-sensitivity temperature sensor based on the graphene/barium strontium titanate heterojunction; when the temperature adjustment is made around the curie temperature of the barium strontium titanate, the current of the graphene/barium strontium titanate heterostructure varies significantly at a constant applied voltage.
2. The method for manufacturing a high-sensitivity temperature sensor based on a graphene/barium strontium titanate heterojunction according to claim 1, wherein x in the chemical formula Ba xSr1-xTiO3 is 0.1-0.4.
3. The method for manufacturing a high-sensitivity temperature sensor based on a graphene/barium strontium titanate heterojunction according to claim 1, wherein the solid-phase sintering method is a sintering method at 1200-1450 ℃ for 6-12 hours.
4. The method for manufacturing a high sensitivity temperature sensor based on a graphene/barium strontium titanate heterojunction according to claim 3, wherein the solid phase sintering method is a sintering method at 1300 ℃ for 8 hours.
5. The method for manufacturing the high-sensitivity temperature sensor based on the graphene/barium strontium titanate heterojunction, which is disclosed in claim 1, is characterized in that the size of the copper sheet cut in the second step is (4-8) x (2-5) mm.
6. The preparation method of the high-sensitivity temperature sensor based on the graphene/barium strontium titanate heterojunction, which is disclosed in claim 1, is characterized in that graphene subjected to spin coating in the step three is placed into copper etching liquid for treatment for 10-50 minutes.
7. The method for preparing the high-sensitivity temperature sensor based on the graphene/barium strontium titanate heterojunction according to claim 1, wherein the graphene is put into deionized water for cleaning for 5-30 minutes in the step three, and the cleaning is repeated for 3-5 times.
8. The method for preparing a high-sensitivity temperature sensor based on a graphene/barium strontium titanate heterojunction according to claim 1, wherein the temperature of the drying in the fourth step is 50-80 ℃ and the drying time is 30-90 minutes.
9. The method for preparing the high-sensitivity temperature sensor based on the graphene/barium strontium titanate heterojunction, which is disclosed in claim 1, is characterized in that the dried barium strontium titanate ceramic is put into acetone for dissolution treatment for 5-30 minutes in the fifth step.
10. The method for preparing the high-sensitivity temperature sensor based on the graphene/barium strontium titanate heterojunction, which is disclosed in claim 1, is characterized in that the temperature of drying in the step six is 50-80 ℃ and the drying time is 30-90 minutes.
11. The method for preparing the high-sensitivity temperature sensor based on the graphene/barium strontium titanate heterojunction according to claim 1, which is characterized in that a gold electrode is deposited on the graphene surface of the high-sensitivity temperature sensor based on the graphene/barium strontium titanate heterojunction by adopting a vacuum evaporation method.
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| DE102013019839A1 (en) * | 2013-11-27 | 2015-05-28 | Karlsruher Institut für Technologie | Passive temperature sensor, operation and manufacture of the sensor |
| KR101575012B1 (en) * | 2014-11-20 | 2015-12-08 | 신라대학교 산학협력단 | A temperature sensor using a reduced graphene oxide film |
| CN105136325A (en) * | 2015-08-19 | 2015-12-09 | 东南大学 | Flexible temperature sensor with self-packaging and preparation method thereof |
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| US11378467B2 (en) * | 2018-07-24 | 2022-07-05 | Indian Institute Of Science | Highly sensitive reduced graphene oxide-nickel composite based cryogenic temperature sensor |
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| DE102013019839A1 (en) * | 2013-11-27 | 2015-05-28 | Karlsruher Institut für Technologie | Passive temperature sensor, operation and manufacture of the sensor |
| KR101575012B1 (en) * | 2014-11-20 | 2015-12-08 | 신라대학교 산학협력단 | A temperature sensor using a reduced graphene oxide film |
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