CN112941488A - Temperature sensor based on doped transition metal nitride and preparation method thereof - Google Patents

Temperature sensor based on doped transition metal nitride and preparation method thereof Download PDF

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CN112941488A
CN112941488A CN202110104485.9A CN202110104485A CN112941488A CN 112941488 A CN112941488 A CN 112941488A CN 202110104485 A CN202110104485 A CN 202110104485A CN 112941488 A CN112941488 A CN 112941488A
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transition metal
metal nitride
nitride film
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CN112941488B (en
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刘景全
李秀妍
尤敏敏
林祖德
李艳杰
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Shanghai Jiaotong University
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Abstract

The invention provides a temperature sensor based on doped transition metal nitride and a preparation method thereof, which comprises the steps of introducing cation vacancy into a transition metal nitride film to form the doped transition metal nitride film in the process of preparing the transition metal nitride film or after the preparation of the transition metal nitride film is finished; and the crystal structure of the doped transition metal nitride film is subjected to phase change by regulating and controlling the concentration of the cation vacancy, so that an ideal doped transition metal nitride film is obtained; and preparing the target temperature sensor by adopting the doped transition metal nitride film through an MEMS (micro electro mechanical system) processing technology. The invention provides a preparation method based on a doped transition metal nitride temperature sensor, which regulates and controls a temperature sensitive film structure and resistance by regulating and controlling vacancy concentration, and finally enables a temperature area and sensitivity of the temperature sensor to be adjustable, thereby having guiding significance for developing resistance type doped transition metal nitride film temperature sensors suitable for different target temperature areas.

Description

Temperature sensor based on doped transition metal nitride and preparation method thereof
Technical Field
The invention relates to the technical field of transition metal nitride film temperature sensors, in particular to a doped transition metal nitride based temperature sensor and a preparation method thereof, and the performance of the transition metal nitride film temperature sensor is mainly regulated and controlled based on a novel theoretical mechanism, namely a vacancy regulation and control mechanism.
Background
Temperature monitoring is extremely important in aerospace, national defense science and technology, medical treatment, biomedicine and daily life. Therefore, researchers have been working on the improvement of temperature sensing technology, mainly including the improvement of temperature region, sensitivity and test accuracy of temperature sensing. At present, temperature sensors are mainly classified into resistance type temperature sensors, PN junction type temperature sensors, thermocouple type temperature sensors, and optical temperature sensors.
The resistance-type temperature sensor converts resistance change caused by temperature into corresponding electric signals, and then detects the temperature by detecting the electric signals. The preparation and measurement mode is simple, the precision is high, and the temperature sensor is the most widely applied temperature sensor at present. In recent years, thin film resistive temperature sensors based on transition metal nitrides have been widely used because of their high sensitivity in the low temperature region. In 2014, the Lake Shore company in the U.S. developed a ZrO-based materialxNyCommercial low temperature sensors of thin films. However, the temperature sensitive regions of the currently developed thin film resistance temperature sensors of transition metal nitrides are all in a low temperature region (less than 50K), the temperature region and the sensitivity are difficult to control, and it is difficult to develop a temperature sensor with an ideal temperature region and sensitivity.
Disclosure of Invention
In view of the problems in the prior art, the present invention aims to provide a method for preparing a doped transition metal nitride-based temperature sensor.
In order to solve the above problems, a first aspect of the present invention provides a method for manufacturing a temperature sensor based on doped transition metal nitride, comprising:
introducing cation vacancies into the transition metal nitride film to form doping based on a vacancy regulation mechanism in the process of preparing the transition metal nitride film or after the preparation of the transition metal nitride film is finished;
the crystal structure of the doped transition metal nitride film is subjected to phase change by regulating and controlling the concentration of the cation vacancy, so that the temperature region and the sensitivity of the doped transition metal nitride film structure, the resistor and the temperature sensor are regulated and controlled, and an ideal doped transition metal nitride film is obtained;
the doped transition metal nitride film prepared by the process is used for preparing a target temperature sensor by an MEMS (micro-electromechanical systems) processing process.
Preferably, the doped transition metal nitride thin film includes, but is not limited to, a transition metal element selected from any one of titanium (Ti), zirconium (Zr), hafnium (Hf), vanadium (V), niobium (Nb), tantalum (Ta), chromium (Cr), and the like.
Preferably, in the process of preparing the transition metal nitride film, cation vacancies are introduced into the transition metal nitride film to form doping based on a vacancy regulation mechanism; the phase change of the crystal structure of the doped transition metal nitride film is realized by regulating and controlling the concentration of the cation vacancy, and the method specifically comprises the following steps:
controlling the reaction gas N2The flow rate of (a);
introducing low-valence anion doping elements in the process of preparing the transition metal nitride film to enable the low-valence anions to replace N in the transition metal nitride3-Creating cation vacancies; and the doping concentration is controlled, so that the cation vacancy concentration is regulated and controlled;
doping high-valence cation elements in the process of preparing the transition metal nitride film, so that the high-valence cations replace cations in the transition metal nitride and introduce cation vacancies; the doping concentration is controlled by controlling the voltage and power applied to the doping element target material, so that the cation vacancy concentration is regulated and controlled;
the thickness of the film is reduced; namely, by introducing stress into the transition metal nitride film, cation vacancy is generated in the crystal structure of the doped transition metal nitride film.
Preferably, the introduction of the low valence anion doping element is carried out in the process of preparing the transition metal nitride film, wherein the low valence anion doping element includes but is not limited to any one of O, S, Cl, Br, F or I.
Preferably, the high-valence cation element is doped in the process of preparing the transition metal nitride thin film, wherein the high-valence cation element includes but is not limited to any one of elements such as Si, Sn, Pb, Ge or Mn.
Preferably, a low-valence anion doping element is introduced in the process of preparing the transition metal nitride film, so that the low-valence anions replace N in the transition metal nitride3-Generating cation vacancies, and controlling the doping concentration to regulate the cation vacancy concentration, which specifically comprises the following steps:
doping O element in the process of preparing the transition metal nitride film: introducing oxygen in the magnetron sputtering process, namely adding an oxygen gas path or using N2/O2Mixing the gases, and increasing the oxygen flow or increasing the N2/O2O in the mixed gas2The ratio of the cation vacancy can be increased;
doping S, Cl, Br, F and I in the process of preparing the transition metal nitride film, wherein the elements are as follows: introducing corresponding H in the process of film deposition2S, HCl, HBr, HF or HI gas, and the cation vacancy can be increased by increasing the gas flow;
the doping of the element Cl in the process of preparing the transition metal nitride film can be realized in the following wayThe realization is as follows: introducing Cl in the process of film deposition2Gas, make Cl-Substituted N3-Creating cation vacancies.
Other methods of introducing the low-valent anionic element are also within the scope of this patent.
Preferably, the high-valence cationic elements are doped in the process of preparing the transition metal nitride film, and the doping of the high-valence cationic elements is realized by adopting the following method:
when the transition metal nitride film is deposited, the target position of Si, Sn, Pb, Ge or Mn is increased in the deposition chamber, and the doping element is introduced by adopting a codeposition method to ensure that high-valence cation Si4+、Sn4+、Pb4+、Ge4+Or Mn5+The cations in the isosubstitutional transition metal nitride introduce cation vacancies. However, the doped high-valence cation element includes, but is not limited to, Si, Sn, Pb, Ge or Mn.
Preferably, adjusting the voltage and power applied to the dopant element target site adjusts the cation vacancy concentration.
Preferably, after the preparation of the transition metal nitride film is finished, cation vacancies are introduced into the transition metal nitride film based on a vacancy regulation mechanism to form a doped transition metal nitride film; wherein the content of the first and second substances,
introducing low-valence anions by adopting an oxidation method and introducing the low-valence anions by adopting the oxidation method to replace MNxHigh valence cation N in thin film crystal structure3-Introducing high-valence cations Si by atom or ion implantation4+、Sn4+、Pb4+、Ge4+Or Mn5 +Any one of (1) substituted for MNxHigh valence cations M in thin film crystal structures3+Atoms, thereby introducing cation vacancies.
Preferably, the transition metal nitride thin film is prepared using a physical vapor deposition method, a pulsed laser deposition method, a chemical vapor deposition method, or an electron beam evaporation method.
Preferably, the preparation of the transition metal nitride thin film by using a physical vapor deposition method comprises the following steps:
s1: fixing a target prepared by adopting transition metal elements on a target platform, and placing a cleaned insulating substrate on a sample platform;
s2: and when the deposition chamber is vacuumized to be below the background vacuum, introducing a certain flow of high-purity Ar gas to bombard the target material in an ionization mode, and introducing a certain flow of high-purity nitrogen gas as reaction gas to form a layer of transition metal nitride on the insulating substrate.
Preferably, the insulating substrate is made of any one or a composite of more than two of sapphire, alumina ceramic, beryllium oxide ceramic, aluminum nitride ceramic, silicon carbide ceramic and silicon oxide substrate;
preferably, the thickness of the insulating substrate is 0.5 μm to 5 mm.
In a second aspect, the invention provides a doped transition metal nitride-based temperature sensor, which is prepared by the preparation method of the doped transition metal nitride-based temperature sensor.
Compared with the prior art, the invention has at least one of the following beneficial effects:
the method of the invention provides a preparation method of a temperature sensor based on doped transition metal nitride, which is based on a vacancy mechanism regulation principle: the transition metal nitride film is MNxCrystal structure of composition, when in MNxBased on the principle that the film resistance can be enlarged along with the increase of the concentration of the cation vacancies, and the corresponding temperature sensitive region can move like a high-temperature region, the temperature sensitive film structure, the resistance, the temperature region and the sensitivity of the temperature sensor based on the doped transition metal nitride film can be improved by controlling the concentration of the introduced vacancies, the temperature sensitive temperature region can be regulated and controlled, the high-sensitivity temperature region can be regulated and controlled from low temperature to normal temperature, and the defect that the traditional temperature sensor based on the transition metal nitride film is only suitable for the sensitive sensing of the low-temperature region and the high-sensitivity temperature region is broken through the fact that the traditional temperature sensor based on the doped transition metal nitride film is only suitable for the sensitive sensing of the low-temperature region and the high-sensitivity temperature regionThe limit of (2).
The method of the invention has wide application range, and is suitable for various transition metal elements such as titanium (Ti), zirconium (Zr), hafnium (Hf), vanadium (V), niobium (Nb), tantalum (Ta), chromium (Cr) and the like; there are also many ways to introduce cation vacancies, including controlling the reactant gas N2The flow rate of (a); doping low-valent anions; doping high-valence cations; controlling the thickness of the film; the method is flexible, can be reasonably selected according to experimental conditions, and has strong universality.
Drawings
Other features, objects and advantages of the invention will become more apparent upon reading of the detailed description of non-limiting embodiments with reference to the following drawings:
FIG. 1 is a general technical scheme of a fabrication method for a doped transition metal nitride based temperature sensor according to a preferred embodiment of the present invention;
FIG. 2 is a schematic diagram illustrating the change in lattice structure (containing cation vacancies) of a doped transition metal nitride thin film in a fabrication method for a doped transition metal nitride temperature sensor according to a preferred embodiment of the present invention;
FIG. 3 is a process flow diagram of a method for fabricating a doped transition metal nitride based temperature sensor in accordance with a preferred embodiment of the present invention;
fig. 4 is a schematic diagram of the performance of a temperature sensor for zirconium oxynitride according to a preferred embodiment of the present invention.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
Referring to fig. 1, a general technical scheme of a fabrication method of a doped transition metal nitride-based temperature sensor according to a preferred embodiment of the present invention is shown; the method comprises the following steps:
introducing cation vacancies into the transition metal nitride film to form a doped transition metal nitride film based on a vacancy regulation mechanism in the process of preparing the transition metal nitride film or after the preparation of the transition metal nitride film is finished;
the crystal structure of the transition metal nitride doped film is subjected to phase change by regulating and controlling the concentration of the cation vacancies, namely the film structure is subjected to phase change along with the accumulation of the cation vacancies, the band gap of the film is opened, the resistance is increased, the temperature sensitivity of the transition metal nitride doped film based temperature sensor is increased, and the temperature sensitive region moves to a high-temperature region; the ideal temperature sensor based on the doped transition metal nitride film is obtained by regulating the vacancy concentration, regulating the temperature sensitive film structure and the resistance, regulating the temperature zone and the sensitivity of the temperature sensor based on the doped transition metal nitride film.
And preparing the target temperature sensor by adopting the obtained transition metal nitride doped film through an MEMS (micro electro mechanical system) processing technology. The method specifically comprises the following steps: the temperature sensor based on the doped transition metal nitride film is developed through a series of processes of cleaning, photoetching, film etching, metal electrode sputtering, photoetching, metal electrode etching, cutting and the like of a doped transition metal nitride film sample.
In order to enable the performance of the thin film type resistance temperature sensor based on the doped transition metal nitride to be adjustable and controllable, the preparation of different types of transition metal nitrides MN based on a vacancy regulation mechanism is providedxA method of thin film temperature sensor. Vacancy mechanism regulation principle: increasing the N atom ratio, and substituting higher-valence cation for MNxCation M in (1)3+By atoms or by using the anions N of lower valency3-Or the MN can be achieved by reducing the thickness of the film and increasing the internal stressxThe film generates cation vacancy, and the regulation and control on the cation vacancy can ensure that MN isxThe crystal structure of the film is subjected to phase change, and the purpose of regulating and controlling the normal temperature resistance and the resistance-temperature relation is finally realized. Based on the method, the temperature sensitive area and the sensitivity of the temperature sensor based on the doped transition metal nitride film are adjustable and controllable.
In other preferred embodiments, the step of preparing the target temperature sensor by the MEMS process using the obtained doped transition metal nitride thin film may be performed according to the following steps:
s01: the method comprises the following steps of patterning a transition metal nitride doped film, specifically: throwing photoresist on the transition metal nitride doped film, preparing patterned photoresist by exposing and developing the photoresist, and transferring the photoresist pattern to the temperature sensitive film by ion beam etching to obtain the required temperature sensitive film pattern;
s02: sputtering an electrode material on the patterned temperature sensitive film and patterning the electrode, specifically: directly sputtering an electrode material on the patterned temperature sensitive film, spin-coating photoresist on the electrode material, preparing the patterned photoresist by exposing and developing the photoresist, and transferring the photoresist pattern to the electrode material by ion beam etching to form a required electrode structure. As a preferable mode, an electrode transition layer is arranged between the temperature sensitive film and the electrode and is used as a bonding layer of the electrode and the temperature sensitive film, and the electrode transition layer is any one of molybdenum, chromium and titanium metal films. The electrode material is copper or gold. The thickness of the electrode transition layer can be 5nm-500nm, and the thickness of the electrode is 50nm-1 μm.
S03: and cutting the patterned device to obtain the independent device.
In other partially preferred embodiments, during the process of preparing the transition metal nitride film, as shown with reference to fig. 1, cation vacancies may be introduced into the transition metal nitride film by any one of the following methods:
controlling the reaction gas N2The flow rate of (a); the introduction of cation vacancy by controlling the nitrogen atom ratio in the process of preparing the transition metal nitride film can be realized by controlling the introduction of N in the process of film deposition2Gas flow rate realization of (1), N2The higher the flow rate, the higher the N atom fraction, and the more and more cation vacancies will be present in order to maintain electroneutrality.
Introducing low-valence anion doping elements to generate cation vacancies in the process of preparing the transition metal nitride film; when a lower anion such as O2-，S2-Or Cl-Substituted for MNxHigh valence anion N in thin film crystal structure3-Atomic timeEquivalent to an acceptor, the additional acceptor charge at equilibrium needs to be compensated by ionized negatively charged cation vacancies, the number of which is directly proportional to the doping concentration. And the doping concentration is controlled, so that the cation vacancy concentration is regulated and controlled. In a preferred embodiment, the low-valent anion doping element includes any of O, S, Cl, Br, F, I, and the like.
High-valence cation elements are doped in the process of preparing the transition metal nitride film to introduce cation vacancies; when a high valence cation such as Si4+、Sn4+、Pb4+、Ge4+Or Mn5+Substituted for MNxHigh valence cations M in thin film crystal structures3+When in atom, the number of electrons is reduced, the number is equivalent to an acceptor, extra acceptor charges need to be compensated by ionized cation vacancies with negative charges under the equilibrium condition, and the number of the cation vacancies is in direct proportion to the doping concentration. The doping concentration can be controlled by controlling the voltage and power applied to the doping element target material, so that the cation vacancy concentration is regulated and controlled, and the cation vacancy concentration and the power are in a direct proportion relationship. In a preferred embodiment, the high-valence cationic element is not limited to elements such as Si, Sn, Pb, Ge, and Mn.
The thickness of the film is reduced; namely, by introducing stress into the transition metal nitride film, cation vacancy is generated in the crystal structure of the doped transition metal nitride film. As a preferable mode, the performance of the doped transition metal nitride film can be regulated and controlled by reducing the sputtering time, reducing the thickness of the film, introducing stress into the film so as to introduce cation vacancies and controlling the performance of the doped transition metal nitride film in the film deposition process.
In some other preferred embodiments, the introduction of the low-valence anion doping element is performed during the preparation of the transition metal nitride film, that is, the cation vacancy concentration is controlled by introducing the low-valence anion doping element, and the introduction of the low-valence anion doping element is performed by any one of the following methods:
doping O element in the process of preparing the transition metal nitride film: introducing oxygen during the film deposition process, i.e. by adding oxygen gas path or using N2/O2Mixing the gases N2/O2The volume ratio is controlled to be within the range of 9999:1 to 9:1, the flow rate is within the range of 6sccm to 50sccm, and the oxygen flow rate is increased or the N is increased2/O2O in the mixed gas2The ratio of the cation vacancy can be increased;
doping S, Cl, Br, F or I elements in the process of preparing the transition metal nitride film: introducing corresponding H in the process of film deposition2S, HCl, HBr, HF or HI gas, and the cation vacancy can be increased by increasing the gas flow;
the doping of the Cl element in the process of preparing the transition metal nitride film can be realized by the following steps: introducing Cl in the process of film deposition2Gas, make Cl-Substituted N3-Creating cation vacancies.
Of course, in addition to the introduction of the low-valent anion element by the above method, the low-valent anion element may be introduced by other methods, and is not limited to the introduction method proposed in the present embodiment.
In other preferred embodiments, high-valence cation elements are doped in the process of preparing the transition metal nitride film, namely, the cation vacancy concentration is regulated and controlled by doping the high-valence cation elements; specifically, during the film deposition process, target sites of Si, Sn, Pb, Ge or Mn are added in a deposition chamber, a doping element is introduced by adopting a codeposition method, and high-valence cations such as Si4+，Sn4+,Pb4+,Ge4+，Mn5+Substituted transition metal nitride MNxThereby introducing cation vacancies. The doping concentration can be controlled by controlling the voltage and power applied to the doping element target material, so that the vacancy concentration and the film performance can be regulated and controlled.
In other preferred embodiments, referring to fig. 1, after the transition metal nitride film is prepared, cation vacancies are introduced into the transition metal nitride film to form a doped transition metal nitride film, and specifically, the cation vacancies may be introduced by any one of the following methods:
after the transition metal nitride film is deposited, cation vacancies are introduced by an oxidation method:
adopts oxidation method to introduce low-valence anion to replace MNxHigh valence cation N in thin film crystal structure3-Atoms, thereby introducing cation vacancies. Specifically, the transition metal nitride film is placed in a high vacuum chamber, a small amount of oxygen is introduced to replace N with oxygen to form cation vacancies, and the cation concentration can be controlled by controlling the oxygen introduction time, wherein the cation vacancies are in direct proportion to the oxygen introduction time.
Introducing cation vacancies by ion implantation after the transition metal nitride film is deposited:
in particular to a method for implanting high-valence cations such as Si by adopting an ion implantation method4+，Sn4+,Pb4+,Ge4+，Mn5+Substituted for MNxHigh valence cations M in thin film crystal structures3+Atoms, thereby introducing cation vacancies. The cation concentration can be controlled by controlling the ion implantation concentration, and the cation concentration and the ion implantation concentration are in a direct proportion relation.
In some other preferred embodiments, the preparing the transition metal nitride thin film includes: the transition metal nitride thin film is prepared by a physical vapor deposition method, a pulsed laser deposition method (PLD), a chemical vapor deposition method (CVD), or an electron beam evaporation method (EBE).
As a preferred mode, the transition metal nitride film is prepared by adopting a physical vapor deposition method, and the preparation method comprises the following steps:
s1: fixing a target prepared by adopting transition metal elements on a target platform, and placing a cleaned insulating substrate on a sample platform; the transition metal elements include: any of titanium, zirconium, hafnium, vanadium, niobium, tantalum, or chromium; because the substrate needs to have insulation, high thermal conductivity and low temperature resistance, the insulating substrate is made of any one or more composite materials of sapphire, alumina ceramic, beryllia ceramic, aluminum nitride ceramic, silicon carbide ceramic and silicon oxide substrate; the thickness of the insulating substrate is 100 mu m-5 mm.
S2: when the deposition chamber is vacuumized to be below the background vacuum, introducing a certain flow of high-purity Ar gas to bombard the target material in an ionization mode, and simultaneously introducing a certain flow of high-purity nitrogen gas as reaction gas to form transitionA metal nitride. High purity Ar gas and N2The flow rate can be in a wider range of 6sccm to 50 sccm. Transition metal nitride MNxThe thickness of the film is 5nm-10 μm.
In one embodiment, a method for manufacturing a doped transition metal nitride-based temperature sensor is provided, which comprises the following steps:
preparing a zirconium nitride film by adopting a PVD method; and the performance of the film is regulated and controlled by regulating and controlling the cation concentration based on a vacancy regulation and control mechanism in the deposition process of the zirconium nitride film; and preparing the temperature sensor by an MEMS (micro-electromechanical systems) processing technology after the film is prepared.
Specifically, a high-purity target (99.99%) prepared from a transition metal element Zr is used as a sputtering target, sapphire is used as an insulating substrate and placed on a sample holder, when the vacuum is pumped to be below the background vacuum, the temperature of the insulating substrate is controlled to be between room temperature and 1000 ℃, and a certain flow of high-purity argon gas is introduced.
By doping with low-valent anions O in the magnetron sputtering process2-Introducing zirconium vacancy to form a doped transition metal nitride film, so introducing N2/O2The flow rate of the mixed gas is changed from 6sccm to 50 sccm. Referring to FIG. 2, a schematic diagram of the creation of zirconium vacancies for a zirconium nitride film structure is shown. When a small amount of oxygen is introduced in the magnetron sputtering process, the cluster zirconia is not formed enough due to the low O content, compared with pure ZrNxIn the film, O atoms can be uniformly doped in a NaCl-ZrN crystal structure in a substitutional N atom mode, and because the number of electrons on the outermost O layer is 6, Zr-O bonding consumes less Zr compared with Zr-N bonding, so that Zr around O in the NaCl-ZrN crystal structure generates dangling bonds, and the dangling bonds are unstable in the structure and can introduce Zr vacancies. The appearance and the number of the zirconium vacancies have the regulation and control function on the structure and the electrical property of the zirconium oxynitride film, and the N can be controlled2/O2The mixed gas flow controls the concentration of zirconium vacancies.
After the zirconium oxynitride film is deposited, a micro sensor is prepared based on an MEMS (micro electro mechanical systems) processing technology, and the specific process flow is shown in figure 3 and comprises the following steps:
ultrasonically cleaning the prepared zirconium oxynitride film for 5-15 min by using acetone, alcohol and water respectively, and referring to the figure shown in (a) in figure 3;
spin-coating a photoresist on the zirconium oxynitride temperature-sensitive film, as shown in fig. 3 (b);
patterning the photoresist by exposure and development, as shown in fig. 3 (c);
etching the zirconium oxynitride temperature sensitive film by adopting an ion beam, and transferring a photoresist pattern onto the zirconium oxynitride temperature sensitive film to obtain a patterned zirconium oxynitride temperature sensitive film, which is shown in (d) in FIG. 3;
sputtering a chromium film and a gold film on the patterned zirconium oxynitride temperature-sensitive film in sequence, as shown in (e) of fig. 3;
spin-coating a photoresist on the gold thin film, as shown in fig. 3 (f);
patterning the photoresist by exposure and development, as shown in fig. 3 (g);
etching Cr/Au by adopting an ion beam to transfer the photoresist pattern to a Cr/Au electrode to prepare a patterned Cr/Au electrode, and referring to (h) in FIG. 3;
and cutting the prepared patterned device into independent devices, wherein cutting can be performed by knife cutting or laser cutting, and the line width is 10-500 μm.
The electrode structure can be a parallel interdigital electrode structure, the interdigital number of the parallel interdigital electrode structure is 5-30, the interdigital electrode width is 10-100 μm, the finger spacing is 10-500 μm, and the electrode structure can also be an annular interdigital electrode, a parallel electrode, an annular electrode and the like. The transition metal oxynitride has semiconductor characteristics at low temperature, and the material of the temperature sensitive film layer can be expanded to any one of transition metal oxynitrides of titanium, zirconium, niobium, tantalum and the like.
Referring to fig. 4, a schematic diagram of temperature region control of the prepared zirconium oxynitride temperature sensor is shown, which shows that the performance of the zirconium oxynitride film can be controlled by controlling the O-doping concentration, and the temperature sensitive region of the sensor is controlled from a low temperature region to a normal temperature region.
The foregoing description of specific embodiments of the present invention has been presented. It should be noted that the present invention is not limited to the above specific embodiments, and those skilled in the art can make various changes or modifications within the scope of the claims without affecting the spirit of the present invention.

Claims (11)

1. A preparation method based on a doped transition metal nitride temperature sensor is characterized by comprising the following steps:
introducing cation vacancies into the transition metal nitride film to form a doped transition metal nitride film based on a vacancy regulation mechanism in the process of preparing the transition metal nitride film or after the preparation of the transition metal nitride film is finished;
the crystal structure of the doped transition metal nitride film is subjected to phase change by regulating and controlling the concentration of the cation vacancy, so that the temperature area and the sensitivity of the doped transition metal nitride film structure, the resistor and the temperature sensor are regulated and controlled, and an ideal doped transition metal nitride film is obtained;
the target temperature sensor is prepared by adopting the transition metal nitride doped thin film prepared by the process and adopting an MEMS processing process.
2. The method as claimed in claim 1, wherein the method comprises using any one of transition metal elements including titanium, zirconium, hafnium, vanadium, niobium, tantalum or chromium to prepare the transition metal nitride thin film.
3. The preparation method of the doped transition metal nitride-based temperature sensor according to claim 1, wherein in the process of preparing the transition metal nitride film, cation vacancies are introduced into the transition metal nitride film based on a vacancy control mechanism to form the doped transition metal nitride film; the phase change of the crystal structure of the doped transition metal nitride film is realized by regulating and controlling the concentration of the cation vacancy, and the method specifically comprises the following steps:
controlling the reaction gas N2The flow rate of (a);
introducing low-valence anion doping elements in the process of preparing the transition metal nitride film to ensure that the low-valence anionsBy substitution of N in transition metal nitrides3-Generating cation vacancies, and controlling the concentration of the cation vacancies by controlling the doping concentration;
doping high-valence cation elements in the process of preparing the transition metal nitride film, so that the high-valence cations replace cations in the transition metal nitride and introduce cation vacancies; the doping concentration is controlled by controlling the voltage and power applied to the doping element target material, so that the cation vacancy concentration is regulated and controlled;
the thickness of the film is reduced; namely, by introducing stress into the transition metal nitride film, cation vacancy is generated in the crystal structure of the doped transition metal nitride film.
4. The method for preparing the doped transition metal nitride temperature sensor according to claim 3, wherein a low valence anion doping element is introduced during the process of preparing the transition metal nitride film, wherein the low valence anion doping element comprises any one of O, S, Cl, Br, F or I elements.
5. The method as claimed in claim 4, wherein a low valence anion doping element is introduced during the process of preparing the transition metal nitride film, so that the low valence anion can substitute for N in the transition metal nitride3-Generating cation vacancies, and controlling the doping concentration to regulate the cation vacancy concentration, which specifically comprises the following steps:
doping O element in the process of preparing the transition metal nitride film: introducing oxygen in the process of depositing the transition metal nitride film, namely adding an oxygen gas path or using N2/O2Mixing the gases, and increasing the oxygen flow or increasing the N2/O2O in the mixed gas2The ratio of the cation vacancy can be increased;
doping any element of S, Cl, Br, F, I and S in the process of preparing transition metal nitride filmElement: introducing corresponding H in the process of depositing the transition metal nitride film2Any one of S, HCl, HBr, HF, or HI, and the cation vacancies can be increased by increasing the gas flow rate;
the doping of the Cl element in the process of preparing the transition metal nitride film can be realized by the following steps: introducing Cl in the process of film deposition2Gas, make Cl-Substituted N3-Creating cation vacancies.
6. The method for preparing the doped transition metal nitride-based temperature sensor according to claim 3, wherein the high-valence cation element is doped in the process of preparing the transition metal nitride thin film, wherein the high-valence cation element comprises any one of Si, Sn, Pb, Ge or Mn elements.
7. The method for preparing the doped transition metal nitride temperature sensor according to claim 6, wherein the doping of the high-valence cationic elements is realized by the following method in the process of preparing the transition metal nitride thin film:
in the process of depositing the transition metal nitride film, any target position of Si, Sn, Pb, Ge or Mn is added in a deposition chamber, and a doping element is introduced by adopting a codeposition method to ensure that high-valence cation Si4+、Sn4+、Pb4+、Ge4+Or Mn5+Any of the high-valence cations in (1) substitutes for cations in the transition metal nitride to introduce cation vacancies.
8. The method for preparing the doped transition metal nitride-based temperature sensor according to claim 1, wherein after the preparation of the transition metal nitride thin film is completed, cation vacancies are introduced into the transition metal nitride thin film based on a vacancy-regulating mechanism to form the doped transition metal nitride thin film; wherein, a low-valence anion is introduced to replace MN by adopting an oxidation methodxHigh valence cation N in thin film crystal structure3-Atom or adoptIntroducing high-valence cation Si by ion implantation method4+、Sn4 +、Pb4+、Ge4+Or Mn5+Any one of (1) substituted for MNxHigh valence cations M in thin film crystal structures3+Atoms, thereby introducing cation vacancies.
9. The method of any one of claims 1-8, further comprising:
the transition metal nitride film is prepared by adopting a physical vapor deposition method, a pulse laser deposition method, a chemical vapor deposition method or an electron beam evaporation method.
10. The method of claim 9, wherein the temperature sensor is formed by doping transition metal nitride,
the preparation method of the transition metal nitride film by adopting a physical vapor deposition method comprises the following steps:
s1: fixing a target prepared by adopting transition metal elements on a target platform, and placing a cleaned insulating substrate on a sample platform;
s2: and when the deposition chamber is vacuumized to be below the background vacuum, introducing a certain flow of high-purity Ar gas to bombard the target material in an ionization mode, and introducing a certain flow of high-purity nitrogen gas as reaction gas to form a layer of transition metal nitride on the insulating substrate.
11. A doped transition metal nitride based temperature sensor, obtained by the method for manufacturing a doped transition metal nitride based temperature sensor according to any one of claims 1 to 10.
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