CN110106485B - Negative temperature coefficient thermosensitive film and preparation method thereof - Google Patents
Negative temperature coefficient thermosensitive film and preparation method thereof Download PDFInfo
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- H01C17/00—Apparatus or processes specially adapted for manufacturing resistors
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- H01C7/04—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material having negative temperature coefficient
Abstract
The invention relates to a negative temperature coefficient thermosensitive film and a preparation method thereof, the film is prepared from an Au/Ti double-layer electrode, a Mn-Co-Ni-Mg-Al based film, insulating silicon dioxide and a silicon substrate, a first annealing treatment is carried out under a protective atmosphere, so that a large number of oxygen vacancies are generated while Mn-Co-Ni-Mg-Al based film crystal grains grow, the oxygen vacancies can provide two additional electrons and also cause the deviation of the stoichiometric ratio of a material, the change of the valence state of a metal cation and the distortion of an oxygen octahedron, and then a second annealing treatment is carried out under an oxygen-containing atmosphere to supplement the oxygen element which is lacked in the film, so that the structure of the film is stable under the conditions of the deviation of the stoichiometric ratio, the change of the valence state of the metal cation and the distortion of the oxygen octahedron, and the thermosensitive performance of the film is further. Experiments show that the thermosensitive constant of the negative temperature coefficient thermosensitive film can reach 7127-8518k, the negative temperature coefficient and the high thermosensitive performance are high, the use effect of the thermistor is ensured, and the application of the negative temperature coefficient thermosensitive film is facilitated.
Description
Technical Field
The invention belongs to the technical field of thermosensitive materials, and particularly relates to a negative temperature coefficient thermosensitive film and a preparation method thereof.
Background
The Negative Temperature Coefficient (NTC) thermistor is a common temperature measurement and control element, has the advantages of high temperature measurement precision, high sensitivity, good reliability, low cost, long service life and the like, and is widely applied to the fields of aviation, oceans, civil use and the like. With the continuous progress of the electronic industry and the information technology level, modern electronic information systems are developing toward the chip-based, and the thermistor is required to have a smaller size.
At present, although a large number of sheet resistor products exist in the market, the volume of the sheet resistor products is too large, and the sheet resistor products cannot meet the requirements of the fields of micro-nano devices and integrated circuit manufacturing on small resistance. Compared with a bulk or thin ceramic thermistor, the negative temperature coefficient thermosensitive film is easier to realize the development goal of chip formation, and has wide application prospect in the fields of semiconductors, integrated circuits, micro-nano devices and the like. Although researchers have successfully prepared NTC thermosensitive films by different methods, such as magnetron sputtering, molecular beam epitaxy, pump laser deposition or chemical solution deposition, the conventional methods have the defects that the NTC thermosensitive film has a lower thermosensitive constant than bulk materials and flake materials, and the development and application of the NTC thermosensitive film are not facilitated.
Disclosure of Invention
The invention aims to provide a negative temperature coefficient thermosensitive film and a preparation method thereof, the film is made of an Au/Ti electrode, a Mn-Co-Ni-Mg-Al based film, insulating silicon dioxide and a silicon substrate, through the first annealing treatment under the protective atmosphere, the Mn-Co-Ni-Mg-Al based film crystal grains grow and simultaneously generate a large number of oxygen vacancies, the oxygen vacancies can provide two additional electrons and also cause the deviation of the stoichiometric ratio of the material, the change of the valence state of metal cations and the distortion of oxygen octahedra, and then, by secondary annealing treatment in an oxygen-containing atmosphere, oxygen elements which are lacked in the film are supplemented, so that the structure of the film is stable under the conditions of deviation of stoichiometric ratio, change of metal cation valence and oxygen octahedron distortion, and the heat-sensitive performance of the film is further improved. Experiments show that the thermosensitive constant of the negative temperature coefficient thermosensitive film can reach 7127-8518k, the negative temperature coefficient and the high thermosensitive performance are high, the use effect of the thermistor is ensured, and the application of the negative temperature coefficient thermosensitive film is facilitated.
The invention relates to a negative temperature coefficient thermosensitive film which is prepared from an Au/Ti double-layer electrode, a Mn-Co-Ni-Mg-Al base film, insulating silicon dioxide and a silicon substrate, wherein the insulating silicon dioxide (3) is arranged on the silicon substrate (4), the Mn-Co-Ni-Mg-Al base film (2) is arranged on the insulating silicon dioxide (3), and the Au/Ti double-layer electrode (1) is arranged at two ends of the surface of the Mn-Co-Ni-Mg-Al base film (2) on the Mn-Co-Ni-Mg-Al base film (2).
The preparation method of the negative temperature coefficient thermosensitive film is carried out according to the following steps:
a. substrate pretreatment: firstly, sequentially immersing a purchased silicon substrate (4) in acetone, absolute ethyl alcohol, deionized water and absolute ethyl alcohol for ultrasonic washing for 4 times, wherein the washing time is 5-10 minutes each time, taking out the silicon substrate (4), and drying the surface of the silicon substrate (4) by using high-purity nitrogen to obtain a pretreated silicon substrate (4);
b. pretreating the Mn-Co-Ni-Mg-Al alloy target: selecting a Mn-Co-Ni-Mg-Al alloy target according to the molar content ratio of Mn, Co, Ni, Mg and Al elements of 2.1:2.4:1.0:4:1, polishing the surface of the Mn-Co-Ni-Mg-Al alloy target, and removing a surface oxidation layer to obtain a pretreated Mn-Co-Ni-Mg-Al alloy target;
preparing a Mn-Co-Ni-Mg-Al-based primary film: placing the Mn-Co-Ni-Mg-Al alloy target pretreated in the step b on a target position in a magnetron sputtering cavity by adopting a magnetron sputtering direct current sputtering method, and then preparing a Mn-Co-Ni-Mg-Al base film on the surface of insulating silicon dioxide (3) arranged on the silicon substrate (4) pretreated in the step a to obtain a semi-finished product Mn-Co-Ni-Mg-Al film;
d. annealing the film for the first time: c, introducing a flow of 20sccm for 1min under the condition that the protective atmosphere is a nitrogen atmosphere, heating the semi-finished product Mn-Co-Ni-Mg-Al film obtained in the step c to 500-900 ℃ at a heating rate of 1-20 ℃/min, preserving the heat for 1-100min, and then performing first annealing treatment for cooling to 18-25 ℃ at a cooling rate of 1-20 ℃/min to obtain a primary annealing film;
e. and (3) annealing the film for the second time: heating the primary annealing film in the step d to 500-900 ℃ at the heating rate of 1-20 ℃/min under the atmosphere of oxygen atmosphere, preserving the heat for 1-100min, and then performing second annealing treatment at the cooling rate of 1-20 ℃/min to 18-25 ℃ to obtain a Mn-Co-Ni-Mg-Al based film (2);
f. and e, performing mask hollow-out growth on the surface of the Mn-Co-Ni-Mg-Al-based film (2) obtained in the step e by adopting an electron beam evaporation, ion sputtering or magnetron sputtering mode to form an Au/Ti double-layer electrode (1), wherein the thickness of the Mn-Co-Ni-Mg-Al-based film (2) and the Au/Ti double-layer electrode (1) is 1.5-2:1nm, and thus obtaining the negative temperature coefficient thermal sensitive film.
Preparing a primary Mn-Co-Ni-Mg-Al-based film (2) in the step c by adopting a magnetron sputtering direct current sputtering method, wherein the atmosphere of magnetron sputtering direct current sputtering is argon atmosphere; the pressure in the cavity of the magnetron sputtering direct current sputtering is 1-15Pa, the working voltage is 100-300V, and the sputtering time is 5-30 min.
The invention provides a negative temperature coefficient thermosensitive film, which comprises an Au/Ti double-layer electrode (1), a Mn-Co-Ni-Mg-Al-based film (2), insulating silicon dioxide (3) and a silicon substrate (4), wherein the Mn-Co-Ni-Mg-Al-based film (2) has a spinel structure, the spinel structure can be regarded as cubic close packing formed by oxygen ions, and the unit cell structure is AB2O4Wherein the A ions occupy the tetrahedral oxygen voids made up of four oxygen atoms and the B ions occupy the octahedral oxygen voids made up of six oxygen atoms; the heat-sensitive properties of spinel-structured heat-sensitive materials depend to a large extent on the hopping conduction between the variable-valence cations located in oxygen octahedra in the crystal structure. Mn-Partial oxygen ions in the oxygen octahedron structure of the Co-Ni-Mg-Al based film (2) can be separated to obtain oxygen vacancies with certain concentration, the oxygen vacancies can provide additional electrons, and the oxygen vacancies also cause the deviation of the stoichiometric ratio of the material, the change of the valence state of metal cations, the distortion of the oxygen octahedron and the like, so that the physical properties of the material are effectively improved and regulated, and the heat-sensitive performance of the film is improved.
According to the preparation method of the negative temperature coefficient thermosensitive film, a large number of oxygen vacancies are generated while the crystal grains of the Mn-Co-Ni-Mg-Al based film (2) grow through first annealing treatment in a protective atmosphere, the oxygen vacancies can provide two additional electrons and also cause deviation of the stoichiometric ratio of materials, change of the valence state of metal cations and distortion of oxygen octahedrons, and then the oxygen elements which are lacked in the Mn-Co-Ni-Mg-Al based film (2) are supplemented through second annealing treatment in an oxygen-containing atmosphere, so that the deviation of the stoichiometric ratio, the change of the valence state of the metal cations and the distortion of the oxygen octahedrons are ensured, the structure of the film is stable, and the thermosensitive performance of the film is further improved.
The invention provides a negative temperature coefficient thermosensitive film, wherein a silicon substrate comprises a silicon substrate and silicon dioxide deposited on the silicon substrate, and the deposition thickness of the silicon dioxide is 200-500 nm; according to the invention, the lattice matching degree of the silicon substrate (4) and the Mn-Co-Ni-Mg-Al-based film (2) needs to be considered, and the insulation property of silicon dioxide is utilized to ensure that the working current of the thermosensitive film only acts on the film. In the present invention, the silicon substrate (4) mainly functions to support and improve the film characteristics;
the formula of the Mn-Co-Ni-Mg-Al based film (2) is Mn2.1Co2.4Ni1.0Mg4Al1. The electrode is an Au/Ti double-layer electrode (1);
pretreating the silicon substrate (4) to remove organic pollution, micro-dust and metal ions on the surface of the substrate; from the chemical composition, the molar content ratio of Mn, Co, Ni, Mg and Al elements of the Mn-Co-Ni-Mg-Al-based primary film is 2.1:2.4:1.0:4: 1; co in the Mn-Co-Ni-Mg-Al based primary film2.4Mn2.1Ni1.0Mg4Al1O4(ii) a The Mn-Co-Ni-Mg-Al based primary thin film consists of MPreparing an n-Co-Ni-Mg-Al alloy target; the chemical composition of the Mn-Co-Ni-Mg-Al alloy target material is consistent with that of the pre-prepared Mn-Co-Ni-Mg-Al base primary film;
the equipment cavity of the magnetron sputtering direct current sputtering method is vacuumized and then is filled with the gas in the atmosphere, and the vacuum degree is 1.4 multiplied by 10-3-2×10-3Pa; the working voltage of the magnetron sputtering direct current sputtering is preferably 100-300V, preferably 120-280V, more preferably 150-250V, and still more preferably 200-250V; the time of magnetron sputtering direct current sputtering is 5-30min, more preferably 7-28min, and still more preferably 10-25 min.
The first annealing treatment comprises the following steps: sequentially heating, preserving heat and cooling, wherein the heating rate is preferably 3-18 ℃/min, more preferably 5-15 ℃/min, and most preferably 10 ℃/min; the temperature is raised to preferably 550-850 ℃, more preferably 600-800 ℃, and finally preferably 650-800 ℃; the heat preservation time is preferably 10-90min, and more preferably 20-80 min; the cooling rate is preferably 3-18 ℃/min, more preferably 5-15 ℃/min, and most preferably 10 ℃/min; cooling to preferably 19-24 deg.C, more preferably 20-23 deg.C;
and the second annealing treatment comprises: sequentially heating, preserving heat and cooling, wherein the heating rate is preferably 3-18 ℃/min, more preferably 5-15 ℃/min, and most preferably 10 ℃/min; the heat preservation time is preferably 10-90min, and more preferably 20-80 min; the cooling rate is preferably 3-18 ℃/min, more preferably 5-15 ℃/min, and most preferably 10 ℃/min; cooling to preferably 19-24 deg.C, more preferably 20-23 deg.C;
the invention carries out the second annealing treatment in the oxygen-containing atmosphere, supplements the oxygen element which is lost in the film, ensures the deviation of the stoichiometric ratio, the change of the valence state of the metal cation and the stability of the film structure under the distortion condition of the oxygen octahedron, and further improves the heat-sensitive performance of the film. The method ensures that the Mn-Co-Ni-Mg-Al based film (2) is of a manganese-based spinel structure by carrying out multi-step annealing treatment on the film obtained by magnetron sputtering direct current sputtering.
In the method, the primary Mn-Co-Ni-Mg-Al-based film can also be prepared by other physical deposition methods such as laser molecular beam epitaxy, electron beam evaporation and the like.
Experimental results show that the thermosensitive constant of the negative temperature coefficient thermosensitive film can reach 7127-8518k, the negative temperature coefficient and the high thermosensitive performance are high, the use effect of the thermistor is ensured, and the application of the negative temperature coefficient thermosensitive film is facilitated. The invention also provides application of the negative temperature coefficient thermosensitive film in the technical field of semiconductors, integrated circuits and micro-nano devices.
Drawings
FIG. 1 is a schematic structural view of a negative temperature coefficient thermosensitive film prepared in example 1 of the present invention;
FIG. 2 is an XRD pattern of a negative temperature coefficient thermosensitive film prepared in example 1 of the present invention;
FIG. 3 is an SEM photograph of a negative temperature coefficient thermosensitive film obtained in example 1 of the present invention;
FIG. 4 is a graph showing a relationship between resistance and temperature of the negative temperature coefficient thermosensitive film prepared in example 1 of the present invention.
Detailed Description
In order to further illustrate the present invention, the following examples are provided to describe the negative temperature coefficient thermosensitive film and the preparation method thereof in detail, but they should not be construed as limiting the scope of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
a. Substrate pretreatment: firstly, sequentially immersing a purchased silicon substrate 4 in acetone, absolute ethyl alcohol, deionized water and absolute ethyl alcohol for ultrasonic washing for 4 times, wherein the washing time is 5 minutes each time, taking out the silicon substrate 4, and drying the surface of the silicon substrate 4 by using high-purity nitrogen to obtain the pretreated silicon substrate 4;
b. pretreating the Mn-Co-Ni-Mg-Al alloy target: selecting a Mn-Co-Ni-Mg-Al alloy target according to the molar content ratio of Mn, Co, Ni, Mg and Al elements of 2.1:2.4:1.0:4:1, polishing the surface of the Mn-Co-Ni-Mg-Al alloy target, and removing a surface oxidation layer to obtain a pretreated Mn-Co-Ni-Mg-Al alloy target;
preparing a Mn-Co-Ni-Mg-Al-based primary film: adopting a magnetron sputtering direct current sputtering method, wherein the atmosphere of magnetron sputtering direct current sputtering is argon atmosphere; b, placing the Mn-Co-Ni-Mg-Al alloy target pretreated in the step b on a target position in the magnetron sputtering cavity, and then preparing a Mn-Co-Ni-Mg-Al base film on the surface of insulating silicon dioxide 3 arranged on the silicon substrate 4 pretreated in the step a to obtain a semi-finished Mn-Co-Ni-Mg-Al film, wherein the air pressure in the cavity for magnetron sputtering direct current sputtering is 1Pa, the working voltage is 100V, and the sputtering time is 5 min;
d. annealing the film for the first time: placing the semi-finished product Mn-Co-Ni-Mg-Al film in a tubular furnace, introducing 20sccm at a flow rate of 1min under the condition that the protective atmosphere is nitrogen, exhausting air in the furnace tube, heating the tubular furnace to 500 ℃ at a heating rate of 1 ℃/min, preserving heat for 1min for heat treatment, and carrying out first annealing treatment for cooling to 18 ℃ at a cooling rate of 1 ℃/min to obtain a primary annealing film;
e. and (3) annealing the film for the second time: after the temperature is reduced to 18 ℃, continuously placing the primary annealing film in a tube furnace, heating to 500 ℃ at the heating rate of 1 ℃/min under the aerobic atmosphere, keeping the temperature for 1min, then carrying out second annealing treatment at the cooling rate of 1 ℃/min to 18 ℃, taking out a sample, and obtaining a Mn-Co-Ni-Mg-Al based film 2;
f. and e, performing mask hollow-out growth on the surface of the Mn-Co-Ni-Mg-Al-based film 2 obtained in the step e by adopting electron beam evaporation to obtain an Au/Ti double-layer electrode 1, wherein the thickness of the Mn-Co-Ni-Mg-Al-based film 2 and the thickness of the Au/Ti double-layer electrode 1 are 1.5:1nm, and thus obtaining the negative temperature coefficient thermal sensitive film.
Example 2
a. Substrate pretreatment: firstly, sequentially immersing a purchased silicon substrate 4 in acetone, absolute ethyl alcohol, deionized water and absolute ethyl alcohol for ultrasonic washing for 4 times, wherein the washing time is 10 minutes each time, taking out the silicon substrate 4, and drying the surface of the silicon substrate (4) by utilizing high-purity nitrogen to obtain the pretreated silicon substrate 4;
b. pretreating the Mn-Co-Ni-Mg-Al alloy target: selecting a Mn-Co-Ni-Mg-Al alloy target according to the molar content ratio of Mn, Co, Ni, Mg and Al elements of 2.1:2.4:1.0:4:1, polishing the surface of the Mn-Co-Ni-Mg-Al alloy target, and removing a surface oxidation layer to obtain a pretreated Mn-Co-Ni-Mg-Al alloy target;
preparing a Mn-Co-Ni-Mg-Al-based primary film: adopting a magnetron sputtering direct current sputtering method, wherein the atmosphere of magnetron sputtering direct current sputtering is argon atmosphere; b, placing the Mn-Co-Ni-Mg-Al alloy target pretreated in the step b on a target position in the magnetron sputtering cavity, and then preparing a Mn-Co-Ni-Mg-Al base film on the surface of insulating silicon dioxide 3 arranged on the silicon substrate 4 pretreated in the step a to obtain a semi-finished Mn-Co-Ni-Mg-Al film, wherein the air pressure in the cavity for magnetron sputtering direct current sputtering is 15Pa, the working voltage is 300V, and the sputtering time is 30 min;
d. annealing the film for the first time: placing the semi-finished product Mn-Co-Ni-Mg-Al film in a tubular furnace, introducing 20sccm at a flow rate of 1min under a nitrogen atmosphere serving as a protective atmosphere, exhausting air in the furnace tube, heating the tubular furnace to 900 ℃ at a heating rate of 20 ℃/min, preserving heat for 100min, and performing first annealing treatment for cooling to 25 ℃ at a cooling rate of 20 ℃/min to obtain a primary annealing film;
e. and (3) annealing the film for the second time: after the temperature is reduced to 25 ℃, continuously placing the primary annealing film in a tube furnace, heating to 900 ℃ at the heating rate of 20 ℃/min under the aerobic atmosphere as the atmospheric atmosphere, preserving the heat for 100min, then carrying out second annealing treatment at the cooling rate of 20 ℃/min to 25 ℃, taking out a sample, and obtaining the Mn-Co-Ni-Mg-Al based film 2;
f. and e, performing mask hollow-out growth on the surface of the Mn-Co-Ni-Mg-Al-based film 2 obtained in the step e by adopting ion sputtering to obtain an Au/Ti double-layer electrode 1, wherein the thickness of the Mn-Co-Ni-Mg-Al-based film 2 and the Au/Ti double-layer electrode 1 is 1.5-2:1nm, and thus obtaining the negative temperature coefficient thermal sensitive film.
Example 3
a. Substrate pretreatment: firstly, sequentially immersing a purchased silicon substrate 4 in acetone, absolute ethyl alcohol, deionized water and absolute ethyl alcohol for ultrasonic washing for 4 times, wherein the washing time is 8 minutes each time, taking out the silicon substrate 4, and drying the surface of the silicon substrate 4 by using high-purity nitrogen to obtain the pretreated silicon substrate 4;
b. pretreating the Mn-Co-Ni-Mg-Al alloy target: selecting a Mn-Co-Ni-Mg-Al alloy target according to the molar content ratio of Mn, Co, Ni, Mg and Al elements of 2.1:2.4:1.0:4:1, polishing the surface of the Mn-Co-Ni-Mg-Al alloy target, and removing a surface oxidation layer to obtain a pretreated Mn-Co-Ni-Mg-Al alloy target;
preparing a Mn-Co-Ni-Mg-Al-based primary film: adopting a magnetron sputtering direct current sputtering method, wherein the atmosphere of magnetron sputtering direct current sputtering is argon atmosphere; b, placing the Mn-Co-Ni-Mg-Al alloy target pretreated in the step b on a target position in the magnetron sputtering cavity, and then preparing a Mn-Co-Ni-Mg-Al base film on the surface of insulating silicon dioxide 3 arranged on the silicon substrate 4 pretreated in the step a to obtain a semi-finished Mn-Co-Ni-Mg-Al film, wherein the air pressure in the cavity for magnetron sputtering direct current sputtering is 10Pa, the working voltage is 200V, and the sputtering time is 10 min;
d. annealing the film for the first time: placing the semi-finished product Mn-Co-Ni-Mg-Al film in a tubular furnace, introducing 20sccm at a flow rate of 20sccm for 1min under the condition that the protective atmosphere is nitrogen, exhausting air in the furnace tube, heating the tubular furnace to 650 ℃ at a heating rate of 10 ℃/min, preserving heat for 20min, and performing first annealing treatment for cooling to 20 ℃ at a cooling rate of 10 ℃/min to obtain a primary annealing film;
e. and (3) annealing the film for the second time: after the temperature is reduced to 20 ℃, continuously placing the primary annealing film in a tube furnace, heating to 650 ℃ at the heating rate of 10 ℃/min under the aerobic atmosphere as the atmospheric atmosphere, preserving the heat for 20min, then carrying out second annealing treatment at the cooling rate of 10 ℃/min to 20 ℃, taking out a sample, and obtaining the Mn-Co-Ni-Mg-Al based film 2;
f. and e, performing mask hollow-out growth on the surface of the Mn-Co-Ni-Mg-Al-based film 2 obtained in the step e by adopting a magnetron sputtering direct current sputtering method to form an Au/Ti double-layer electrode 1, wherein the thickness of the Mn-Co-Ni-Mg-Al-based film 2 and the Au/Ti double-layer electrode 1 is 1.8:1nm, and thus obtaining the negative temperature coefficient thermal sensitive film.
Example 4
a. Substrate pretreatment: firstly, sequentially immersing a purchased silicon substrate 4 in acetone, absolute ethyl alcohol, deionized water and absolute ethyl alcohol for ultrasonic washing for 4 times, wherein the washing time is 9 minutes each time, taking out the silicon substrate 4, and drying the surface of the silicon substrate 4 by using high-purity nitrogen to obtain the pretreated silicon substrate 4;
b. pretreating the Mn-Co-Ni-Mg-Al alloy target: selecting a Mn-Co-Ni-Mg-Al alloy target according to the molar content ratio of Mn, Co, Ni, Mg and Al elements of 2.1:2.4:1.0:4:1, polishing the surface of the Mn-Co-Ni-Mg-Al alloy target, and removing a surface oxidation layer to obtain a pretreated Mn-Co-Ni-Mg-Al alloy target;
preparing a Mn-Co-Ni-Mg-Al-based primary film: placing the Mn-Co-Ni-Mg-Al alloy target material pretreated in the step b on a target position in a magnetron sputtering cavity by adopting a magnetron sputtering direct current sputtering method, wherein the atmosphere of magnetron sputtering is argon atmosphere, the air pressure in the cavity of the magnetron sputtering direct current sputtering is 5Pa, the working voltage is 150V, the sputtering time is 20min, and then preparing a Mn-Co-Ni-Mg-Al base film on the surface of insulating silicon dioxide 3 arranged on the silicon substrate 4 pretreated in the step a to obtain a semi-finished product Mn-Co-Ni-Mg-Al film;
d. annealing the film for the first time: placing the semi-finished product Mn-Co-Ni-Mg-Al film in a tubular furnace, introducing 20sccm at a flow rate of 1min under the condition that the protective atmosphere is nitrogen, exhausting air in the furnace tube, heating the tubular furnace to 800 ℃ at a heating rate of 15 ℃/min, preserving heat for 80min, and carrying out first annealing treatment for cooling to 23 ℃ at a cooling rate of 15 ℃/min to obtain a primary annealing film;
e. and (3) annealing the film for the second time: after the temperature is reduced to 23 ℃, continuously placing the primary annealing film in a tube furnace, heating to 800 ℃ at the heating rate of 15 ℃/min under the aerobic atmosphere, keeping the temperature for 80min, then carrying out second annealing treatment at the cooling rate of 15 ℃/min to 23 ℃, taking out a sample, and obtaining the Mn-Co-Ni-Mg-Al based film 2;
f. and e, performing mask hollow-out growth on the surface of the Mn-Co-Ni-Mg-Al-based film 2 obtained in the step e by adopting electron beam evaporation to form an Au/Ti double-layer electrode 1, wherein the thickness of the Mn-Co-Ni-Mg-Al-based film 2 and the thickness of the Au/Ti double-layer electrode 1 are 2:1nm, and thus obtaining the negative temperature coefficient heat-sensitive film.
Example 5
XRD (X-ray diffraction) tests are carried out on the negative temperature coefficient heat-sensitive film prepared in the example 1, the test result is shown in figure 2, as can be seen from figure 2, the diffraction peak of the spinel structure of the negative temperature coefficient heat-sensitive film prepared in the example is clear and visible, the negative temperature coefficient heat-sensitive film prepared in the example is proved to be crystallized, and XRD (X-ray diffraction) of the negative temperature coefficient heat-sensitive films prepared in other examples is similar to that shown in figure 2, and the diffraction peaks of the spinel structure are shown;
SEM test of the negative temperature coefficient thermosensitive film prepared in example 1 is carried out, the test result is shown in figure 3, as can be seen from figure 3, the prepared negative temperature coefficient thermosensitive film has uniform grain growth size and compact and defect-free surface, the SEM test result of the negative temperature coefficient thermosensitive films obtained in examples 2-4 shows that the film has uniform grain growth size and compact and defect-free surface,
the negative temperature coefficient thermosensitive films prepared in examples 1 to 4 were subjected to resistance-temperature relationship test by the following specific test methods:
placing the prepared negative temperature coefficient thermosensitive film on a temperature-changing probe station, and recording the resistance values of the thermosensitive film at different temperatures by using a digital multimeter, wherein the obtained resistance-temperature relation test data are shown in a table 1;
TABLE 1 EXAMPLES 1-4 TEST DATA OF RESISTANCE-TEMPERATURE RELATIONS OF NTC TEMPERATURE COEFFICIENT THERMAL FILM
A resistance-temperature relationship test chart was prepared according to table 1, as shown in fig. 4, and as can be seen from table 1 and fig. 4, the resistance temperature curve of the negative temperature coefficient thermosensitive film prepared as described above showed an exponential decreasing tendency, which conformed to the negative temperature coefficient resistance temperature relationship, and the thermosensitive constant was calculated from the resistance temperature relationship according to the following formula:
in the formula (I), R1Denotes the temperature T1Resistance of the film, R2Denotes the temperature T2Resistance of the film;
from the resistance-temperature relationship test data of the thermosensitive films described in table 1, the coefficient of thermal sensitivity of example 1 was 7127K, the coefficient of thermal sensitivity of example 2 was 8098K, the coefficient of thermal sensitivity of example 3 was 8518K, and the coefficient of thermal sensitivity of example 4 was 7543K, calculated according to the above-described technical method. The thermosensitive constant value of the negative temperature coefficient thermosensitive film reaches 7127-8518 k.
The negative temperature coefficient thermosensitive film provided by the invention has higher negative temperature coefficient and high thermosensitive performance, ensures the use effect of the thermistor, is beneficial to the application of the negative temperature coefficient thermosensitive film, and has extremely high scientific research and commercial values.
Claims (3)
1. A negative temperature coefficient heat-sensitive film is characterized in that the film is made of an Au/Ti double-layer electrode, a Mn-Co-Ni-Mg-Al base film, insulating silicon dioxide and a silicon substrate, wherein the silicon substrate (4) is provided with the insulating silicon dioxide (3), the insulating silicon dioxide (3) is provided with the Mn-Co-Ni-Mg-Al base film (2), and the Au/Ti double-layer electrode (1) is arranged at two ends of the surface of the Mn-Co-Ni-Mg-Al base film (2);
the preparation method of the negative temperature coefficient thermosensitive film is carried out according to the following steps:
a. substrate pretreatment: firstly, sequentially immersing a purchased silicon substrate (4) in acetone, absolute ethyl alcohol, deionized water and absolute ethyl alcohol for ultrasonic washing for 4 times, wherein the washing time is 5-10 minutes each time, taking out the silicon substrate (4), and drying the surface of the silicon substrate (4) by using high-purity nitrogen to obtain a pretreated silicon substrate (4);
b. pretreating the Mn-Co-Ni-Mg-Al alloy target: selecting a Mn-Co-Ni-Mg-Al alloy target according to the molar content ratio of Mn, Co, Ni, Mg and Al elements of 2.1:2.4:1.0:4:1, polishing the surface of the Mn-Co-Ni-Mg-Al alloy target, and removing a surface oxidation layer to obtain a pretreated Mn-Co-Ni-Mg-Al alloy target;
preparing a Mn-Co-Ni-Mg-Al-based primary film: placing the Mn-Co-Ni-Mg-Al alloy target pretreated in the step b on a target position in a magnetron sputtering cavity by adopting a magnetron sputtering direct current sputtering method, and then preparing a Mn-Co-Ni-Mg-Al base film on the surface of insulating silicon dioxide (3) arranged on the silicon substrate (4) pretreated in the step a to obtain a semi-finished product Mn-Co-Ni-Mg-Al film;
d. annealing the film for the first time: introducing nitrogen atmosphere with the flow of 20sccm for 1min, heating the semi-finished product Mn-Co-Ni-Mg-Al film obtained in the step c to 500-900 ℃ at the heating rate of 1-20 ℃/min, preserving the heat for 1-100min, and then carrying out first annealing treatment at the cooling rate of 1-20 ℃/min to 18-25 ℃ to obtain a primary annealing film;
e. and (3) annealing the film for the second time: heating the primary annealing film in the step d to 500-900 ℃ at the heating rate of 1-20 ℃/min under the atmosphere of oxygen atmosphere, preserving the heat for 1-100min, and then performing second annealing treatment at the cooling rate of 1-20 ℃/min to 18-25 ℃ to obtain a Mn-Co-Ni-Mg-Al based film (2);
f. and e, performing mask hollow-out growth on the surface of the Mn-Co-Ni-Mg-Al-based film (2) obtained in the step e by adopting an electron beam evaporation, ion sputtering or magnetron sputtering mode to form an Au/Ti double-layer electrode (1), wherein the thickness of the Mn-Co-Ni-Mg-Al-based film (2) and the Au/Ti double-layer electrode (1) is 1.5-2:1nm, and thus obtaining the negative temperature coefficient thermal sensitive film.
2. A method for preparing the ntc thermosensitive film according to claim 1, comprising the steps of:
a. substrate pretreatment: firstly, sequentially immersing a purchased silicon substrate (4) in acetone, absolute ethyl alcohol, deionized water and absolute ethyl alcohol for ultrasonic washing for 4 times, wherein the washing time is 5-10 minutes each time, taking out the silicon substrate (4), and drying the surface of the silicon substrate (4) by using high-purity nitrogen to obtain a pretreated silicon substrate (4);
b. pretreating the Mn-Co-Ni-Mg-Al alloy target: selecting a Mn-Co-Ni-Mg-Al alloy target according to the molar content ratio of Mn, Co, Ni, Mg and Al elements of 2.1:2.4:1.0:4:1, polishing the surface of the Mn-Co-Ni-Mg-Al alloy target, and removing a surface oxidation layer to obtain a pretreated Mn-Co-Ni-Mg-Al alloy target;
preparing a Mn-Co-Ni-Mg-Al-based primary film: placing the Mn-Co-Ni-Mg-Al alloy target pretreated in the step b on a target position in a magnetron sputtering cavity by adopting a magnetron sputtering direct current sputtering method, and then preparing a Mn-Co-Ni-Mg-Al base film on the surface of insulating silicon dioxide (3) arranged on the silicon substrate (4) pretreated in the step a to obtain a semi-finished product Mn-Co-Ni-Mg-Al film;
d. annealing the film for the first time: introducing nitrogen atmosphere with the flow of 20sccm for 1min, heating the semi-finished product Mn-Co-Ni-Mg-Al film obtained in the step c to 500-900 ℃ at the heating rate of 1-20 ℃/min, preserving the heat for 1-100min, and then carrying out first annealing treatment at the cooling rate of 1-20 ℃/min to 18-25 ℃ to obtain a primary annealing film;
e. and (3) annealing the film for the second time: heating the primary annealing film in the step d to 500-900 ℃ at the heating rate of 1-20 ℃/min under the atmosphere of oxygen atmosphere, preserving the heat for 1-100min, and then performing second annealing treatment at the cooling rate of 1-20 ℃/min to 18-25 ℃ to obtain a Mn-Co-Ni-Mg-Al based film (2);
f. and e, performing mask hollow-out growth on the surface of the Mn-Co-Ni-Mg-Al-based film (2) obtained in the step e by adopting an electron beam evaporation, ion sputtering or magnetron sputtering mode to form an Au/Ti double-layer electrode (1), wherein the thickness of the Mn-Co-Ni-Mg-Al-based film (2) and the Au/Ti double-layer electrode (1) is 1.5-2:1nm, and thus obtaining the negative temperature coefficient thermal sensitive film.
3. The method for preparing the negative temperature coefficient thermal sensitive film according to claim 2, wherein the primary Mn-Co-Ni-Mg-Al based film (2) prepared in the step c adopts a magnetron sputtering direct current sputtering method, and the atmosphere of the magnetron sputtering direct current sputtering is argon atmosphere; the pressure in the cavity of the magnetron sputtering direct current sputtering is 1-15Pa, the working voltage is 100-300V, and the sputtering time is 5-30 min.
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