CN114034404B - Electrical nano thermometer for measuring local temperature of surface plasmon nano structure and temperature measuring method - Google Patents
Electrical nano thermometer for measuring local temperature of surface plasmon nano structure and temperature measuring method Download PDFInfo
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- 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
- G01K7/18—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 linear resistance, e.g. platinum resistance thermometer
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Abstract
The invention discloses an electric nanometer thermometer and a temperature measuring method for measuring the local temperature of a surface plasmon nanometer structure, wherein the electric nanometer thermometer comprises a metal triangular antenna and a metal sensing strip on a heat insulation substrate, the vertex of the metal triangle is over against the center of the metal sensing strip, a nanometer gap is formed between the metal triangular antenna and the metal sensing strip, two ends of the metal sensing strip are respectively connected with two electrode terminals, and a voltmeter and an ammeter containing source are respectively connected with the metal sensing strip through the electrode terminals at the two ends of the metal sensing strip. The invention measures the temperature by measuring the resistance of the sensor strip through the voltammetry, overcomes the diffraction limit of the traditional optical method, has the spatial resolution of the nanometer scale, and has high precision (0.1K), large range (78-750K) and fast response time (< 1.5 s).
Description
Technical Field
The invention belongs to the technical field of surface plasmon photothermal effect, and particularly relates to an electric nanometer thermometer and a temperature measuring method for measuring the local temperature of a surface plasmon nanometer structure.
Background
The surface plasmon micro-nano structure can bind a light field in a sub-wavelength scale to form a hot spot, and can convert light energy into heat energy through a photothermal effect and generate local high temperature. In recent years, the mechanism and application of photothermal effect have become hot spots of plasmonics, and have shown promise in the fields of solar devices, medical treatment, chemical catalysis, surface treatment, and the like. Among them, accurate measurement of local temperature rise in the nanometer scale is very important for commercial applications. However, the commonly used far-field optical means, such as temperature calibration using raman shift, fluorescence intensity or lifetime, are limited by the diffraction limit, and the measured average temperature is about one order of magnitude lower than the temperature of the local hot spot area, and thus the temperature at the nanometer scale cannot be resolved; however, the existing nanoscale temperature detection methods, such as the plasma energy expansion temperature measurement method, are often complex in equipment, low in resolution ratio or limited in working temperature.
The principle of the resistance nanometer thermometer is that the metal resistance changes linearly with the temperature, and the temperature can be obtained by measuring the resistance through a voltammetry method. The method has the advantages of high sensitivity, wide working temperature and the like, but the thermal sensing resistor is difficult to be matched with a thermoelectric region in space, so that the accurate temperature of a hot spot region with a nanometer scale cannot be obtained by a conventional electrical method. Therefore, it is necessary to develop a nano thermometer with high spatial and temperature resolution and wide working temperature range, which will broaden the application of the surface plasmon micro-nano structure in the fields of energy, chemistry, biology and the like.
In view of the above, the gist of the present invention is to provide an electrical nano thermometer for measuring a localized temperature of a surface plasmon nanostructure and a temperature measuring method thereof.
Disclosure of Invention
The invention aims to provide an electric nanometer thermometer for measuring the local temperature of a surface plasmon nanometer structure, which has the spatial resolution of nanometer scale, high precision (0.1K), large range (78-750K) and quick response time (< 1.5 s), and can be widely used for temperature monitoring and analysis in various applications based on the surface plasmon photothermal effect.
In order to realize the purpose, the invention adopts the following technical scheme:
the utility model provides a measure electricity nanometer thermometer of surface plasmon nanometer structure local temperature, electricity nanometer thermometer includes adiabatic substrate and the metal triangular antenna and the metal sensing strip of constructing on adiabatic substrate, and the summit of metal triangular antenna is just to the center of metal sensing strip, and both keep a distance of a nanometer clearance, and two electrode terminals are respectively connected to metal sensing strip both ends, and voltmeter and contain the source ampere meter and connect metal sensing strip through the electrode terminal at metal sensing strip both ends respectively.
Preferably, the heat insulating substrate is one of a silicon wafer, glass, and sapphire.
Preferably, methods for constructing the metal triangular antenna and the metal sensor strip on the heat insulating substrate are EBL (electron beam lithography), evaporation, and the like.
Preferably, the metal triangular antenna, the metal sensor strip and the electrode are made of one of platinum, gold and nickel, and further preferably platinum.
Preferably, the side length of the metal triangular antenna is 1-2 μm, the length of the metal sensor strip is 500-800nm, the width of the metal sensor strip is 100-300nm, and the thicknesses of the metal sensor strip and the metal sensor strip are equal and are 10-100nm. The metal triangular antenna is preferably an equilateral or isosceles triangle.
Preferably, the width of the nanogap is 10 to 120nm, and more preferably 80nm.
A temperature measurement method of an electrical nanometer thermometer based on the measurement of the surface plasmon photothermal effect comprises the following steps:
(1) Controlling the temperature of the metal sensing strip to be 78-750K through an external temperature control device, measuring the resistance of the metal sensing strip by a voltammetry method at intervals of certain temperature values (preferably, the interval value is 10K), and fitting to obtain a resistance-temperature linear relation;
(2) Focusing a laser beam on the positive center of the metal triangular antenna, measuring the resistance of the metal sensing strip through a voltammetry method after the laser beam is stabilized, and obtaining the local temperature caused by the surface plasmon photothermal effect according to the resistance-temperature linear relation.
Preferably, the laser is a continuous or pulse laser, the wavelength is 500-800nm, the spot diameter is 0.8-2 μm, and the continuous laser is preferred.
Compared with the prior art, the invention has the following beneficial effects:
(1) According to the invention, by means of the gap surface plasmon based on the metal triangular antenna and the metal sensing strip, the error caused by too far distance between a hot spot area and a sensing area is solved;
(2) The invention measures the temperature by measuring the resistance of the sensor strip through the voltammetry, overcomes the diffraction limit of the traditional optical method, and has the spatial resolution of nanometer scale; the electric nanometer thermometer has high precision (0.1K), wide range (78-750K) and quick response time (< 1.5 s);
(3) The measuring method provided by the invention is simple and has high repeatability.
Drawings
FIG. 1 is a schematic structural view of an electrical nano-thermometer according to the present invention;
FIG. 2 is an SEM image of electrical nanotemperature of example 1;
FIG. 3 is a temperature-resistance calibration line of example 1;
FIG. 4 is a graph showing the temperature change with time in the case of applying laser light intermittently and increasing the laser power gradually in example 1;
fig. 5 is a graph of the temperature rise with the change of the laser power under the situation that the laser power is gradually increased in the embodiment 1;
fig. 6 is a graph of temperature rise as a function of laser power for different nanogap widths.
Reference numerals: 1 is a thermally insulating substrate; 2 is a metal triangular antenna; 3 is a metal sensor strip; 4 is four electrode terminals; 5 is a voltmeter; 6 is a source-containing ammeter; and 7 is a laser.
Detailed Description
The invention is described in further detail below with reference to the figures and the detailed description.
Example 1
As shown in fig. 1-2, an electrical nano thermometer for measuring local temperature of a surface plasmon nanostructure comprises a heat insulation substrate 1, and a metal triangular antenna 2 and a metal sensing strip 3 which are constructed on the heat insulation substrate 1, wherein the vertex of the metal triangular antenna 2 is right opposite to the center of the metal sensing strip 3, the two metal sensing strips are separated by a nano gap, two ends of the metal sensing strip 3 are respectively connected with two electrode terminals (four electrode terminals 4), and a voltmeter 5 and a source-containing ammeter 6 are respectively connected with the metal sensing strip 3 through the electrode terminals at the two ends of the metal sensing strip 3.
The embodiment provides a preparation method of an electric nanometer thermometer for measuring the local temperature of a surface plasmon nanometer structure, which comprises the following steps:
(1) And (2) spinning PMMA photoresist with the thickness of 200nm on a silicon dioxide (with the thickness of 300 nm)/silicon chip, annealing for 10 minutes at the temperature of 418K, and etching a metal triangular antenna, a metal sensing strip and a template with four electrode terminals by EBL, wherein the side length of the metal triangular antenna is 1.6 mu m, the length of the metal sensing strip is 800nm, the width of the metal sensing strip is 280nm, the vertex of the metal triangular antenna is aligned to the center of the metal sensing strip, and the interval is 80nm.
(2) And (3) evaporating metal platinum on the silicon chip to obtain a film with the thickness of 20nm, and washing away the residual PMMA to obtain the electric nanometer thermometer.
The temperature measuring method comprises the following steps:
the calibration method comprises the following steps: the electric nano thermometer is placed in a thermostat, a Keithley source meter is used for respectively connecting electrode terminals at two ends of the metal sensing strip, the temperature is gradually increased from 78K to 430K, the resistance of the metal sensing strip at different temperatures is obtained by measuring current and voltage, and a resistance-temperature calibration straight line is obtained, as shown in figure 3.
The measuring method comprises the following steps: a532 nm solid-state continuous light laser 7 is used for exciting the right center of the metal triangular antenna, the laser power is 12.8mW, the diameter is 2 micrometers, a Keithley source meter is respectively connected with electrode terminals at two ends of a metal sensing strip, the resistance of the metal sensing strip is obtained by measuring current and voltage, and the temperature rise caused by the plasmon photothermal effect on the surface of the gap is obtained by combining the resistance and a temperature calibration straight line. As shown in FIG. 4, when the laser is applied, the resistance of the metal sensor bars climbs in 1.5 s; when the laser is turned off, the resistance of the metal sensor bars returns to the initial value within 1.5 s. Further, when the laser light is continuously irradiated at a fixed power, the fluctuation of the resistance is within ± 0.006 Ω, corresponding to a temperature measurement accuracy of 0.1K. As shown in fig. 5, when the laser power is 12.8mW, the temperature rise of the metal sensor strip is 450K, i.e. 750K. The thermometer can work normally at 78K in the combination calibration process, so that the temperature measurement range of the thermometer can reach 78-750K.
As shown in fig. 6, when the width of the nanogap is 25, 70 and 116nm, the temperature rise of the metal sensor strip can reach 401.0, 334.2 and 433.3K, and the corresponding laser power is 15.0, 14.0 and 15.0mW respectively. However, at a nanogap width of 200nm, the temperature rise was only 6.8K at a power of 15.0mW. This is due to the concentration of photothermal effects in the hot spot region on the nanometer scale.
Example 2
As shown in fig. 1, an electrical nano thermometer for measuring local temperature of a surface plasmon nanostructure comprises a heat insulation substrate 1, and a metal triangular antenna 2 and a metal sensing strip 3 which are constructed on the heat insulation substrate 1, wherein the vertex of the metal triangular antenna 2 is right opposite to the center of the metal sensing strip 3, the two metal triangular antennas and the metal sensing strip are separated by a nano gap, two ends of the metal sensing strip 3 are respectively connected with two electrode terminals (four electrode terminals 4), and a voltmeter 5 and a source-containing ammeter 6 are respectively connected with the metal sensing strip 3 through the electrode terminals at the two ends of the metal sensing strip 3.
The embodiment provides a preparation method of an electric nanometer thermometer for measuring the local temperature of a surface plasmon nanometer structure, which comprises the following steps:
(1) And (2) spinning PMMA photoresist with the thickness of 200nm on a silicon dioxide (with the thickness of 300 nm)/silicon chip, annealing for 10 minutes at the temperature of 418K, and etching a metal triangular antenna, a metal sensing strip and a template of a four-electrode terminal through EBL, wherein the side length of the metal triangular antenna is 1 mu m, the length of the metal sensing strip is 500nm, the width of the metal sensing strip is 100nm, the vertex of the metal triangular antenna is aligned to the center of the metal sensing strip, and the interval is 10nm.
(2) And (3) evaporating metal platinum on the silicon chip to obtain a film with the thickness of 20nm, and washing away the residual PMMA to obtain the electric nanometer thermometer.
The temperature measuring method comprises the following steps:
the calibration method comprises the following steps: and placing the electric nanometer thermometer in a thermostat, respectively connecting electrode terminals at two ends of the metal sensing strip by using a Keithley source meter, gradually increasing the temperature from 78K to 430K, and measuring current and voltage to obtain the resistance of the metal sensing strip at different temperatures so as to obtain a resistance-temperature calibration straight line.
The measuring method comprises the following steps: the method comprises the steps of exciting the center of a metal triangular antenna by a 780nm solid-state continuous light laser, enabling the laser power to be 12.8mW and the diameter to be 2 microns, respectively connecting electrode terminals at two ends of a metal sensing strip by a Keithley source meter, obtaining the resistance of the metal sensing strip by measuring current and voltage, and obtaining the temperature rise caused by the gap surface plasmon photothermal effect by combining the resistance and a temperature calibration straight line.
Example 3
As shown in fig. 1, an electrical nano thermometer for measuring local temperature of a surface plasmon nanometer structure includes a heat insulation substrate 1, a metal triangular antenna 2 and a metal sensing strip 3 constructed on the heat insulation substrate 1, wherein the vertex of the metal triangular antenna 2 is right opposite to the center of the metal sensing strip 3, the two are separated by a nano gap, two ends of the metal sensing strip 3 are respectively connected with two electrode terminals (four electrode terminals 4), and a voltmeter 5 and an ammeter 6 containing source are respectively connected with the metal sensing strip 3 through the electrode terminals at the two ends of the metal sensing strip 3.
The embodiment provides a method for preparing and measuring the temperature of an electric nanometer thermometer for measuring the local temperature of a surface plasmon nanometer structure, which comprises the following steps:
(1) And (2) spinning and coating PMMA photoresist with the thickness of 200nm on a silicon dioxide (thickness of 300 nm)/silicon chip, annealing for 10 minutes at the temperature of 418K, and etching a metal triangular antenna, a metal sensing strip and a template of a four-electrode terminal through EBL, wherein the side length of the metal triangular antenna is 2 mu m, the length of the metal sensing strip is 800nm, the width of the metal sensing strip is 200nm, the vertex of the metal triangular antenna is aligned to the center of the metal sensing strip, and the interval is 116nm.
(2) And evaporating metal platinum on the silicon wafer to be 20nm thick, and washing away residual PMMA to obtain the electric nanometer thermometer.
The calibration method comprises the following steps: and placing the electric nanometer thermometer in a thermostat, respectively connecting electrode terminals at two ends of the metal sensing strip by using a Keithley source meter, gradually increasing the temperature from 78K to 430K, and measuring current and voltage to obtain the resistance of the metal sensing strip at different temperatures so as to obtain a resistance-temperature calibration straight line.
The measuring method comprises the following steps: a500 nm pulse laser is used for exciting the center of the metal triangular antenna, the laser power is 12.8mW, the diameter is 0.8 mu m, a Keithley source meter is respectively connected with electrode terminals at two ends of the metal sensing strip, the resistance of the metal sensing strip is obtained by measuring current and voltage, and the temperature rise caused by the gap surface plasmon photothermal effect is obtained by combining the resistance-temperature calibration straight line.
Example 4
As shown in fig. 1, an electrical nano thermometer for measuring local temperature of a surface plasmon nanometer structure includes a heat insulation substrate 1, a metal triangular antenna 2 and a metal sensing strip 3 constructed on the heat insulation substrate 1, wherein the vertex of the metal triangular antenna 2 is right opposite to the center of the metal sensing strip 3, the two are separated by a nano gap, two ends of the metal sensing strip 3 are respectively connected with two electrode terminals (four electrode terminals 4), and a voltmeter 5 and an ammeter 6 containing source are respectively connected with the metal sensing strip 3 through the electrode terminals at the two ends of the metal sensing strip 3.
The embodiment provides a method for preparing and measuring the temperature of an electric nanometer thermometer for measuring the local temperature of a surface plasmon nanometer structure, which comprises the following steps:
(1) And spin-coating PMMA photoresist with the thickness of 200nm on glass, annealing for 10 minutes at the temperature of 418K, and etching a metal triangular antenna, a metal sensing strip and a template of a four-electrode terminal by EBL, wherein the side length of the metal triangular antenna is 1.6 mu m, the length of the metal sensing strip is 800nm, the width of the metal sensing strip is 280nm, the vertex of the metal triangular antenna is aligned to the center of the metal sensing strip, and the interval is 60nm.
(2) And evaporating metal gold on the silicon wafer to be 20nm thick, and washing away residual PMMA to obtain the electric nanometer thermometer.
The calibration method comprises the following steps: and placing the electric nanometer thermometer in a thermostat, respectively connecting electrode terminals at two ends of the metal sensing strip by using a Keithley source meter, gradually increasing the temperature from 78K to 430K, and measuring current and voltage to obtain the resistance of the metal sensing strip at different temperatures so as to obtain a resistance-temperature calibration straight line.
The measuring method comprises the following steps: a532 nm solid-state continuous light laser is used for exciting the center of a metal triangular antenna, the laser power is 12.8mW, the diameter is 1 micron, a Keithley source meter is respectively connected with electrode terminals at two ends of a metal sensing strip, the resistance of the metal sensing strip is obtained by measuring current and voltage, and the temperature rise caused by the gap surface plasmon photothermal effect is obtained by combining the resistance and a temperature calibration straight line.
Example 5
As shown in fig. 1, an electrical nano thermometer for measuring local temperature of a surface plasmon nanostructure comprises a heat insulation substrate 1, and a metal triangular antenna 2 and a metal sensing strip 3 which are constructed on the heat insulation substrate 1, wherein the vertex of the metal triangular antenna 2 is right opposite to the center of the metal sensing strip 3, the two metal triangular antennas and the metal sensing strip are separated by a nano gap, two ends of the metal sensing strip 3 are respectively connected with two electrode terminals (four electrode terminals 4), and a voltmeter 5 and a source-containing ammeter 6 are respectively connected with the metal sensing strip 3 through the electrode terminals at the two ends of the metal sensing strip 3.
The embodiment provides a method for preparing and measuring the temperature of an electric nanometer thermometer for measuring the local temperature of a surface plasmon nanometer structure, which comprises the following steps:
(1) And (3) spin-coating PMMA photoresist with the thickness of 200nm on sapphire, annealing for 10 minutes at the temperature of 418K, and etching a metal triangular antenna, a metal sensing strip and a template of a four-electrode terminal by EBL, wherein the side length of the metal triangular antenna is 1.6 mu m, the length of the metal sensing strip is 800nm, the width of the metal sensing strip is 280nm, the vertex of the metal triangular antenna is aligned to the center of the metal sensing strip, and the interval is 80nm.
(2) And (3) evaporating metal nickel on the silicon chip to be 20nm thick, and washing away residual PMMA to obtain the electric nanometer thermometer.
The calibration method comprises the following steps: the electric nanometer thermometer is placed in a thermostat, keithley source meters are respectively connected with electrode terminals at two ends of the metal sensing strip, the temperature is gradually increased from 78K to 430K, the resistance of the metal sensing strip at different temperatures is obtained through measuring current and voltage, and a resistance-temperature calibration straight line is obtained.
The measuring method comprises the following steps: a532 nm solid-state continuous light laser is used for exciting the right center of a metal triangular antenna, the laser power is 12.8mW, the diameter is 2 microns, a Keithley source meter is respectively connected with electrode terminals at two ends of a metal sensing strip, the resistance of the metal sensing strip is obtained by measuring current and voltage, and the temperature rise caused by the gap surface plasmon photothermal effect is obtained by combining a resistance-temperature calibration straight line.
The method can be realized by upper and lower limit values and interval values of intervals of process parameters (such as temperature, time and the like), and embodiments are not listed.
Conventional technical knowledge in the art can be used for the details which are not described in the present invention.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and are not limited. Although the present invention has been described in detail with reference to the embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (6)
1. An electric nanometer thermometer for measuring the local temperature of a surface plasmon nanometer structure is characterized by comprising a heat insulation substrate, a metal triangular antenna and a metal sensing strip, wherein the metal triangular antenna and the metal sensing strip are constructed on the heat insulation substrate, the vertex of the metal triangular antenna is over against the center of the metal sensing strip, a nanometer gap is formed between the metal triangular antenna and the metal sensing strip, two ends of the metal sensing strip are respectively connected with two electrode terminals, and a voltmeter and an ammeter containing a source are respectively connected with the metal sensing strip through the electrode terminals at the two ends of the metal sensing strip;
the side length of the metal triangular antenna is 1-2 mu m, the length of the metal sensing strip is 500-800nm, the width of the metal sensing strip is 100-300nm, and the thicknesses of the metal sensing strip and the metal sensing strip are equal and are 10-100nm; the width of the nanogap is 10-120nm.
2. The electrical nanothermometer for measuring localized temperatures of surface plasmonic nanostructures according to claim 1, wherein the thermally insulating substrate is one of a silicon wafer, glass, and sapphire.
3. The electrical nanothermometer for measuring localized temperatures of surface plasmonic nanostructures according to claim 1, wherein the methods of constructing the metal triangular antenna and the metal sensor bars on the thermally insulating substrate are EBL and evaporation.
4. The electrical nanothermometer for measuring localized temperatures of surface plasmonic nanostructures of claim 1, wherein the metal triangular antenna, metal sensor strip and electrodes are fabricated from one of platinum, gold and nickel.
5. A method of thermometry using an electrical nanothermometer according to any of claims 1-4 for measuring localized temperature of a surface plasmon nanostructure, said thermometry comprising the steps of:
calibration: controlling the temperature of the metal sensing strip to be between 78 and 750K through an external temperature control device, measuring the resistance of the metal sensing strip at intervals of certain numerical temperature through a voltammetry method, and fitting to obtain a resistance-temperature linear relation;
measuring the temperature: and focusing a laser beam on the right center of the metal triangular antenna, measuring the resistance of the metal sensing strip by a voltammetry method after the laser beam is stabilized, and obtaining the local temperature caused by the surface plasmon photothermal effect according to the calibrated resistance-temperature linear relation.
6. The method according to claim 5, wherein the laser is a continuous or pulsed laser having a wavelength of 500 to 800nm and a spot diameter of 0.8 to 2 μm.
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