CN118913470A - Negative temperature coefficient thermistor temperature sensor and manufacturing method and application thereof - Google Patents
Negative temperature coefficient thermistor temperature sensor and manufacturing method and application thereof Download PDFInfo
- Publication number
- CN118913470A CN118913470A CN202410969622.9A CN202410969622A CN118913470A CN 118913470 A CN118913470 A CN 118913470A CN 202410969622 A CN202410969622 A CN 202410969622A CN 118913470 A CN118913470 A CN 118913470A
- Authority
- CN
- China
- Prior art keywords
- temperature coefficient
- optionally
- negative temperature
- coefficient thermistor
- silicon substrate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01K—MEASURING TEMPERATURE; MEASURING QUANTITY OF HEAT; THERMALLY-SENSITIVE ELEMENTS NOT OTHERWISE PROVIDED FOR
- G01K7/00—Measuring temperature based on the use of electric or magnetic elements directly sensitive to heat ; Power supply therefor, e.g. using thermoelectric elements
- G01K7/16—Measuring temperature based on the use of electric or magnetic elements directly sensitive to heat ; Power supply therefor, e.g. using thermoelectric elements using resistive elements
- G01K7/22—Measuring temperature based on the use of electric or magnetic elements directly sensitive to heat ; Power supply therefor, e.g. using thermoelectric elements using resistive elements the element being a non-linear resistance, e.g. thermistor
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/08—Oxides
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/10—Glass or silica
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Nonlinear Science (AREA)
- General Physics & Mathematics (AREA)
- Thermistors And Varistors (AREA)
Abstract
The invention discloses a negative temperature coefficient thermistor temperature sensor and a manufacturing method and application thereof, belonging to the detection field, the thermistor temperature sensor comprises a monocrystalline silicon substrate block and a negative temperature coefficient thermosensitive film which is grown on a silicon dioxide layer of the monocrystalline silicon substrate block, wherein the negative temperature coefficient thermosensitive film is a Mn-Co-Ni-Cu-O thermosensitive film and has a spinel structure. According to the invention, cu is introduced, 1/3 thickness precutting is performed on a monocrystalline silicon substrate, and a twice magnetron sputtering process is adopted, so that the brittleness and plasticity of the thermosensitive film are optimized, the in-plane residual stress of the thermosensitive film is reduced, the Mn-Co-Ni-Cu-O thermosensitive film with the thickness of more than 7 mu m is prepared, and the surface of the thermosensitive film is perfect and well combined with a silicon dioxide layer, and cracking and falling do not occur; the resistance is less than 500 omega, and annealing heat treatment is not needed; the invention has simple and efficient technical route and very high production efficiency and yield.
Description
Technical Field
The invention relates to the field of detection, in particular to a negative temperature coefficient thermistor temperature sensor and a manufacturing method and application thereof.
Background
The Negative Temperature Coefficient (NTC) thermistor temperature sensor has the advantages of high temperature measurement precision, high sensitivity, good stability, low price, long service life and the like, and has wide and important application in the fields of aerospace, marine environment, household appliances and the like. However, as integrated circuit process is smaller and smaller, wafer multiparameter, multi-module integration is higher and higher, requiring NTC thermistors with smaller dimensions, higher measurement accuracy, and less uncertainty.
At present, a plurality of block, flake and sphere thermistor temperature sensors exist in the market, but the problems of large volume, complex manufacturing process, large product batch performance difference, further improvement of measurement precision and accuracy and the like exist, and the requirements of the fields of integrated circuits, advanced manufacturing, micro-nano processing and the like on smaller size, higher measurement precision and smaller measurement uncertainty of the temperature sensors cannot be met.
Compared with block, slice and sphere thermosensitive temperature sensors, the negative temperature coefficient thermosensitive film has the most possible application requirements of integrated circuits, advanced manufacturing and micro-nano devices. At present, some research groups successfully prepare the negative temperature coefficient thermosensitive film through a magnetron sputtering method, a molecular beam epitaxy method, a pump laser deposition method or a chemical solution deposition method and the like. The method for preparing the thermosensitive film by magnetron sputtering is a main existing method, and the technical route is as follows: firstly, preparing a thermosensitive film on a monocrystalline silicon wafer with a silicon dioxide layer by magnetron sputtering, wherein the thickness of the prepared thermosensitive film is usually tens to hundreds of nanometers, and the thickness of the prepared thermosensitive film cannot exceed 1 mu m because a brittle thermosensitive film is prepared on a (4-8) inch monocrystalline silicon wafer by magnetron sputtering. If the thickness of the brittle thermosensitive film exceeds 1. Mu.m, the in-plane residual stress thereof is large, which may cause cracking or peeling of the film from the substrate.
However, if the thickness of the thermosensitive film is too small (several tens to several hundreds nanometers), the resistance is very large, usually (100 to 1000) kΩ, and the resistance is too large, so that the temperature measurement accuracy and resolution of the thermosensitive film may be poor. Therefore, in order to reduce the thermistor, the prepared thermosensitive film must be subjected to multiple annealing heat treatments, which can reduce the thermistor and release the residual stress in the surface of the thermosensitive film. After annealing heat treatment, an electrode is prepared on the surface of the thermosensitive film by using an evaporation coating or other technologies. After the electrode is prepared, a laser cutting machine is used for cutting the wafer in full thickness, and a separated single thermosensitive device is obtained. Because a large number of heat sensitive devices are arranged on a large wafer, the large wafer can be practically used after being cut and separated.
The existing technical route for preparing the thermosensitive film by magnetron sputtering has the following problems: 1) The prepared thermosensitive film needs to be subjected to annealing heat treatment for multiple times to reduce the resistance and the residual stress in the surface, so that the technical route is long and the operation is complex; 2) The heat sensitive film is easy to oxidize in the process of annealing heat treatment for a plurality of times, so that the chemical composition of the heat sensitive film is changed; 3) The electrode is prepared by using evaporation coating or other technologies, so that the complexity and operability of a technical route are increased, and the electrode prepared by the technologies is easy to break and fail; 4) Finally, the thermosensitive devices on the wafer are cut and separated, so that the thermosensitive devices are easy to pollute and damage, and the yield is reduced. These problems have prevented the development and application of negative temperature coefficient thermosensitive film temperature sensors in the fields of integrated circuits and the like.
Disclosure of Invention
Object of the Invention
In order to overcome the defects, the invention aims to provide a simple and efficient negative temperature coefficient thermistor temperature sensor with high production efficiency and yield, and a manufacturing method and application thereof.
Solution scheme
In order to achieve the purpose of the invention, the technical scheme adopted by the invention is as follows:
In a first aspect, the present invention provides a negative temperature coefficient thermistor temperature sensor, comprising a monocrystalline silicon substrate block and a negative temperature coefficient thermosensitive film grown on a silicon dioxide layer of the monocrystalline silicon substrate block, wherein the negative temperature coefficient thermosensitive film is a Mn-Co-Ni-Cu-O thermosensitive film, and has a spinel structure; the mass ratio of Mn, co, ni, cu, O in the negative temperature coefficient thermosensitive film is (28-32) to (14-16) to (0.1-2.5) to (20-28).
Further, platinum wires are adhered to two sides of the negative temperature coefficient thermosensitive film, and optionally silver colloid is adopted for adhesion.
Further, the negative temperature coefficient thermosensitive film has a thickness of 7 μm or more, alternatively 7.5 μm or more, alternatively 7.7 μm or more.
Further, the negative temperature coefficient of thermal film has a resistance of less than 700 Ω, alternatively less than 500 Ω.
Further, the size of the negative temperature coefficient thermosensitive film is (2 to 10) mm× (2 to 10) mm, alternatively 5mm×5mm.
Further, the negative temperature coefficient thermosensitive film is formed by adopting Mn-Co-Ni-Cu-O alloy targets through multiple deposition by a physical deposition coating method; optionally, the physical deposition coating method comprises a magnetron sputtering method, a laser molecular beam epitaxy method or an electron beam evaporation method; optionally, the number of depositions is at least two.
Further, in the negative temperature coefficient thermosensitive film, the mass ratio of Mn, co, ni, cu, O is (28-30) to (15-15.5) to (0.5-2) to (23-28), optionally 30:30 to (15-15.5) to (0.5-2) to (23-24).
Further, the spinel structure unit cell has a structure of AB 2O4 in which a ions occupy oxygen tetrahedral voids composed of four oxygen atoms and B ions occupy oxygen octahedral voids composed of six oxygen atoms.
In a second aspect, there is provided a monocrystalline silicon substrate for preparing the negative temperature coefficient thermistor temperature sensor according to the first aspect, wherein grooves which are longitudinally and transversely interwoven are cut on the monocrystalline silicon substrate, and a plurality of small units are formed and used for being divided into a plurality of monocrystalline silicon substrate blocks along the grooves.
Further, the depth of the groove on the monocrystalline silicon substrate is 160-320 mu m; optionally, the depth of the groove is 1/4-1/2 of the thickness of the monocrystalline silicon substrate, and optionally 1/3;
further, the small units are square units, optionally the square units have a size of (2-10) mm× (2-10) mm, optionally 5mm×5mm.
In a third aspect, a method for manufacturing a thermosensitive film with negative temperature coefficient is provided, which includes the following steps:
1) Pretreating an Mn-Co-Ni-Cu-O alloy target material to remove a surface oxide layer and pollutants;
2) Pretreating the monocrystalline silicon substrate according to the second aspect to remove surface impurities and pollutants;
3) And (2) carrying out physical deposition coating on the single crystal silicon substrate pretreated in the step (2) by adopting the Mn-Co-Ni-Cu-O alloy target pretreated in the step (1), and at least coating twice to obtain the negative temperature coefficient thermosensitive film.
Further, in the step 3), the method for physically depositing the plating film includes: when coating, performing first sputtering coating under inert atmosphere, cooling, performing second sputtering coating, and cooling; and by analogy, obtaining the negative temperature coefficient thermosensitive film through at least two sputtering coating films.
Further, the time of the first sputtering coating is (150-250) min, optionally 200min.
Further, the second sputtering coating time is (250-350 min), optionally 300min.
Further, the power of the sputter coating is (200-260) W, optionally 240W.
Further, the inert atmosphere is argon or helium.
Further, the flow rate of the inert atmosphere is (48-52) sccm, alternatively 50sccm.
Further, the vacuum degree of sputtering is (10 -7～10-8) Torr, alternatively 10 -7 Torr.
Further, in the step 3), before starting coating, the Mn-Co-Ni-Cu-O alloy target is pre-sputtered to remove pollutants and impurities on the surface of the target.
Further, the method further comprises a segmentation step: and (3) dividing the negative temperature coefficient thermosensitive film obtained in the step (3), and optionally dividing along the corresponding position of the groove of the monocrystalline silicon substrate.
In a fourth aspect, a method for manufacturing a negative temperature coefficient thermistor temperature sensor according to the first aspect is provided, liquid silver colloid is added to two sides of the negative temperature coefficient thermosensitive film manufactured by the manufacturing method according to the third aspect with proper size, a platinum wire electrode extends into the liquid silver colloid, and the negative temperature coefficient thermistor temperature sensor is obtained through stabilization, solidification and drying.
In a fifth aspect, there is provided a negative temperature coefficient thermistor temperature sensor according to the first aspect, a monocrystalline silicon substrate according to the second aspect, a negative temperature coefficient thermosensitive film prepared by a manufacturing method according to the third aspect, and an application of a negative temperature coefficient thermistor temperature sensor prepared by a manufacturing method according to the fourth aspect in integrated circuits, advanced manufacturing and micro-nano processing.
Advantageous effects
According to the application, cu is introduced, 1/3 thickness precutting is performed on a monocrystalline silicon substrate, and a twice magnetron sputtering process is adopted, so that the brittleness and plasticity of the thermosensitive film are optimized, the in-plane residual stress of the thermosensitive film is reduced, the Mn-Co-Ni-Cu-O thermosensitive film with the thickness of more than 7.7 mu m is prepared, and the surface of the thermosensitive film is intact and well combined with a silicon dioxide layer, and cracking and falling do not occur; the prepared thermosensitive film resistor is less than 500 omega, and annealing heat treatment is not needed; compared with the prior art, the technical route provided by the application is simple and efficient, and has very high production efficiency and yield.
Drawings
One or more embodiments are illustrated by way of example and not limitation in the figures of the accompanying drawings. The word "exemplary" is used herein to mean "serving as an example, embodiment, or illustration. Any embodiment described herein as "exemplary" is not necessarily to be construed as preferred or advantageous over other embodiments.
FIG. 1 is a diagram of one embodiment of a prepared negative temperature coefficient thermistor temperature sensor of the present invention.
FIG. 2 is a photograph and a block diagram of a single crystal silicon substrate of the present invention pre-cut to 1/3 thickness; wherein A is a physical photo; b is a top view structure diagram of the monocrystalline silicon substrate, and C is a partial structure of the cross-sectional view.
Fig. 3 is a photograph of a real estate of a prepared negative temperature coefficient thermistor temperature sensor of the present invention.
FIG. 4 is an SEM image of a Mn-Co-Ni-Cu-O thermosensitive film prepared in example 1 of the present invention.
FIG. 5 is an AFM image of a Mn-Co-Ni-Cu-O thermosensitive film prepared in example 1 of the present invention.
FIG. 6 is a TEM image of a Mn-Co-Ni-Cu-O thermosensitive film prepared in example 1 of the present invention.
FIG. 7 is a macroscopic morphology of the Mn-Co-Ni-Cu-O thermosensitive film prepared in comparative example 1 of the present invention.
FIG. 8 is a graph showing the temperature-resistance relationship of a NTC thermistor temperature sensor according to example 1 of the present invention; wherein the devices 1 and 2 are two randomly extracted from the prepared devices, and the solid lines corresponding to the devices 1 and 2 are the actual temperature-resistance measurement data of the devices; the device 1, 2 fits a fit line representing the temperature-resistance actual measurement data of the device 1, 2, respectively.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In addition, numerous specific details are set forth in the following description in order to provide a better illustration of the invention. It will be understood by those skilled in the art that the present invention may be practiced without some of these specific details. In some embodiments, materials, elements, methods, means, etc. well known to those skilled in the art are not described in detail in order to highlight the gist of the present invention.
Throughout the specification and claims, unless explicitly stated otherwise, the term "comprise" or variations thereof such as "comprises" or "comprising", etc. will be understood to include the stated element or component without excluding other elements or components.
The negative temperature coefficient thermosensitive film comprises a platinum wire electrode, a Mn-Co-Ni-Cu-O thermosensitive film, insulating silicon dioxide and a monocrystalline silicon substrate, wherein the Mn-Co-Ni-Cu-O thermosensitive film has a spinel structure which can be regarded as cubic close packing formed by oxygen ions, and the unit cell structure is AB 2O4, wherein A ions occupy oxygen tetrahedral gaps formed by four oxygen atoms, and B ions occupy oxygen octahedral gaps formed by six oxygen atoms; the thermosensitive properties of spinel structured thermosensitive materials are largely dependent on the jumping conduction between variable valence cations in the oxygen octahedra in the crystal structure. Partial oxygen ions in the oxygen octahedral structure of the Mn-Co-Ni-Cu-O thermosensitive film can be separated to obtain oxygen vacancies with certain concentration, and the oxygen vacancies can provide extra electrons, also cause deviation of stoichiometric ratio of the material, change of valence state of metal cations, oxygen octahedral distortion and the like, so that the physical properties of the material are effectively improved and regulated, and the thermosensitive performance of the film is improved. Experiments show that the negative temperature coefficient thermosensitive film resistor is smaller than 500 omega, has excellent thermosensitive performance and temperature measurement precision, ensures the use effect of the thermosensitive sensor, and is beneficial to the application of the negative temperature coefficient thermosensitive film in the field of integrated circuits.
In a first aspect, the present invention provides an embodiment of a negative temperature coefficient thermistor temperature sensor, as shown in fig. 1, comprising a single crystal silicon substrate block 1 'and a negative temperature coefficient thermosensitive film 3 grown on a silicon dioxide layer 10 of the single crystal silicon substrate block 1', the negative temperature coefficient thermosensitive film 3 being a Mn-Co-Ni-Cu-O thermosensitive film having a spinel structure.
The single crystal silicon substrate block 1' refers to a small block formed by dividing the single crystal silicon substrate block. When in use, 80 mu m diameter platinum wire is adhered on two sides of the negative temperature coefficient thermosensitive film by using silver colloid to form an electrode.
Further, the thickness of the negative temperature coefficient thermosensitive film 3 is not less than 7 μm, optionally not less than 7.5 μm, optionally not less than 7.7 μm. And has a resistance of less than 700 Ω, optionally less than 500 Ω.
Further, the size of the negative temperature coefficient thermosensitive film 3 is (2 to 10) mm× (2 to 10) mm, optionally 5mm×5mm.
Further, the negative temperature coefficient thermosensitive film 3 is formed by adopting Mn-Co-Ni-Cu-O alloy targets through a physical deposition coating method for multiple times; optionally, the physical deposition coating method comprises a magnetron sputtering method, a laser molecular beam epitaxy method or an electron beam evaporation method; optionally, the number of depositions is at least two.
Further, the mass ratio of Mn, co, ni, cu, O to (28-32), 14-16, 0.1-2.5, 20-28, 28-30, 15-15.5, 0.5-2, 23-28, 30:30, 15-15.5, 0.5-2 and 23-24 in the negative temperature coefficient thermosensitive film 3.
Further, the spinel structure unit cell has a structure of AB 2O4 in which a ions occupy oxygen tetrahedral voids composed of four oxygen atoms and B ions occupy oxygen octahedral voids composed of six oxygen atoms.
In a second aspect, the present invention provides an embodiment of a monocrystalline silicon substrate 1 for preparing the negative temperature coefficient thermistor temperature sensor according to the first aspect, as shown in fig. 2, grooves 2 are cut on the monocrystalline silicon substrate 1, and a plurality of small units (one small unit corresponds to one monocrystalline silicon substrate block 1 ') are formed and used for dividing the grooves 2 into a plurality of monocrystalline silicon substrate blocks 1'.
Further, the depth of the groove 2 on the monocrystalline silicon substrate 1 is 160-320 μm; optionally, the depth of the groove 2 is 1/4-1/2 of the thickness of the monocrystalline silicon substrate, and is optionally 1/3;
Further, the small cells are square cells, optionally square cells having a size of (2-10) mm× (2-10) mm, optionally 5mm×5mm.
Further, the invention provides a preferred preparation method, which comprises the following steps:
Example 1
The manufacturing method of the negative temperature coefficient thermistor temperature sensor of the embodiment comprises the following steps:
1) Pretreatment of Mn-Co-Ni-Cu-O alloy targets: preparing a Mn-Co-Ni-Cu-O alloy target by Mn, co, ni, cu and O elements according to the mass fraction ratio of 30:30:15.5:0.5:24, sequentially polishing the surface of the Mn-Co-Ni-Cu-O alloy target by using 300-mesh, 600-mesh, 1200-mesh and 1800-mesh silicon carbide sand paper, cleaning and drying after polishing, and removing a surface oxide layer to obtain the pretreated Mn-Co-Ni-Cu-O alloy target;
2) 1/3 thickness cutting of monocrystalline silicon substrate: cutting the monocrystalline silicon substrate with the silicon dioxide layer to 1/3 thickness by using a silicon wafer laser cutting machine, longitudinally and transversely cutting the surface of the silicon dioxide layer, and interweaving transverse grooves and longitudinal grooves on the monocrystalline silicon substrate to form a plurality of square small blocks with the thickness of 5mm multiplied by 5mm, wherein the whole monocrystalline silicon substrate is still a complete monocrystalline silicon wafer, and the whole monocrystalline silicon wafer is shown in fig. 2; the monocrystalline silicon substrate 1/3 thickness of the step is pre-cut, so that the technical route for preparing the thermosensitive film by magnetron sputtering can be optimized, and the production efficiency and the yield are improved.
3) Pretreatment of a monocrystalline silicon substrate: immersing the cut monocrystalline silicon substrate in acetone, absolute ethyl alcohol, deionized water and absolute ethyl alcohol in sequence for ultrasonic washing for 2 times, wherein each washing time is 5 minutes, taking out the monocrystalline silicon substrate, and drying the surface of the monocrystalline silicon substrate by utilizing high-purity nitrogen to obtain a pretreated monocrystalline silicon substrate;
4) Pre-sputtering Mn-Co-Ni-Cu-O alloy targets: installing the Mn-Co-Ni-Cu-O alloy target subjected to pretreatment in the step 1) on a target position at the bottom of a cavity of a direct current magnetron sputtering instrument, installing the monocrystalline silicon substrate subjected to pretreatment in the step 3) on a substrate table at the top of the cavity of the direct current magnetron sputtering instrument, closing a cavity of the magnetron sputtering instrument, starting a vacuum system to vacuumize, starting a molecular pump and closing the mechanical pump after the vacuum degree of the cavity is pumped to be less than 10 -2 Torr by a mechanical pump, setting Ar gas flow to be 50sccm after the vacuum degree of the cavity is pumped to be less than 10 -7 Torr, setting sputtering power of the alloy target to be 240W, and blocking the Mn-Co-Ni-Cu-O alloy target by a baffle plate extending above the target position to enable the Mn-Co-Ni-Cu-O alloy target to perform pre-sputtering for 30min, so as to remove pollutants and impurities on the surface of the alloy target;
5) Mn-Co-Ni-Cu-O thermosensitive film preparation: after the alloy target is pre-sputtered for 30min, the baffle above the alloy target is withdrawn, and film plating on the monocrystalline silicon substrate is started; ar gas flow is kept at 50sccm, power is kept at 240W, after sputtering coating is carried out for 200min, voltage and current are turned off, the whole magnetron sputtering system is cooled for 60min, then voltage and current are recovered, sputtering coating is continued for 300min, after sputtering coating is finished, voltage and current are turned off, after cooling for 40min, a cavity is opened, and the prepared Mn-Co-Ni-Cu-O thermosensitive film is taken out.
After the step is completed by adopting two times of magnetron sputtering (200min+300min), the measurement by using a universal meter shows that the film resistance is (0-3) kΩ. The inventor early experiments found that the resistance was (20-60) kΩ after one magnetron sputtering (200 min). The larger the resistance is, the lower the temperature measurement precision and resolution of the thermosensitive film are, and even the thermosensitive film does not have negative temperature characteristics. The invention increases the thickness of the thermosensitive film and reduces the resistance of the thermosensitive film through multiple times of sputtering. The invention adopts the monocrystalline silicon substrate with the groove, can reduce the in-plane residual stress of the thermosensitive film to avoid the cracking and falling of the film, thereby improving the temperature measurement precision and accuracy of the thermosensitive film device and solving the difficult problem that the continuous accumulated stress cannot be released after the film thickness is increased in the prior art to cause the cracking and falling.
6) The Mn-Co-Ni-Cu-O thermosensitive film and the monocrystalline silicon substrate are broken along the grooves and divided into small blocks with the length of 5mm multiplied by 5mm (because of the longitudinal grooves and the transverse grooves on the monocrystalline silicon substrate, most sputtering materials enter the groove bottom during sputtering, and a small part of the sputtering materials are adhered between the small blocks with the length of 5mm multiplied by 5mm, because the grooves exist, the monocrystalline silicon substrate is easily broken along the groove bottom, namely, the small blocks with the length of 5mm multiplied by 5mm are easily broken due to the weak connection between the small blocks.
7) Then liquid silver glue is dripped on two ends of each small thermosensitive film block, one end of a platinum wire with the length of 1.5cm and the diameter of 80 mu m is rapidly stretched into the silver glue solution drop by forceps, the silver glue is kept stable (20-30) s, after solidification, forceps are loosened, 1-2 drops of silver glue are continuously dripped on the bonding end of the platinum wire, and the whole thermosensitive resistor device is placed at a ventilated drying position for drying (4-5) hours, and a physical photo is shown in fig. 3.
Example 2
The difference from example 1 is that the alloy target material has different proportions, specifically, mn, co, ni, cu and O elements are prepared into Mn-Co-Ni-Cu-O alloy target material according to the mass fraction ratio of 30:30:15:2:23, and the rest steps are the same as example 1.
Example 3
The difference from example 1 is that the alloy target material has different proportions, specifically Mn, co, ni, cu and O elements are prepared according to the mass fraction ratio of 28:28:15.5:0.5:28, mn-Co-Ni-Cu-O alloy target material is prepared, and the rest steps are the same as those of example 1.
Example 4
Number of sputtering times
The difference from example 1 is that the number of sputtering times is different, specifically, only one sputtering deposition is performed, and the remaining steps are the same as those of example 1.
In the above embodiment, other physical deposition coating methods such as laser molecular beam epitaxy and electron beam evaporation may be used to prepare the Mn-Co-Ni-Cu-O thermosensitive film.
Comparative example 1
The difference from example 1 is that step 2) precutting was not performed on the single crystal silicon substrate, the Mn-Co-Ni-Cu-O thin film was cut in step 6), and steps 1), 3), 4), and 5) were the same as example 1.
Comparative example 2
The difference from comparative example 1 is that in step 5), annealing treatment is performed, the film sample is put into an annealing furnace, the annealing oxidation treatment temperature is 700 ℃ and the annealing time is 120 minutes, and the annealed thermosensitive film is obtained.
Comparative example 3
The difference from comparative example 1 is that step 5) is sputtered only once: after the alloy target is pre-sputtered for 30min, the baffle above the alloy target is withdrawn, and film plating on the monocrystalline silicon is started; ar gas flow is kept at 50sccm, power is kept at 240W, after sputtering film plating is carried out for 200min, voltage and current are turned off, after cooling is carried out for 40min, a cavity is opened, and the prepared Mn-Co-Ni-Cu-O thermosensitive film is taken out.
Test example 1
The thickness of each of the examples and comparative examples was measured, and the morphology of the thermosensitive film was observed.
According to detection, the Mn-Co-Ni-Cu-O thermosensitive films of examples 1, 2, 3 and 4 have thicknesses of 7.7 mu m, 7.6 mu m, 7.7 mu m and 2.9 mu m respectively, and the surfaces of the films are all good and well combined with a silicon dioxide layer on a monocrystalline silicon substrate, so that cracking and falling do not occur. The Mn-Co-Ni-Cu-O heat-sensitive films of comparative examples 1 and 2 had thicknesses of 7.7 μm and 7.8 μm, respectively, and the film surfaces were cracked and peeled off although the thicknesses were also more than 7.7. Mu.m, as shown in FIG. 7. Comparative example 3 the thickness of the thermosensitive film was 2.9 μm after the number of sputtering was reduced, but contamination and damage were liable to occur when the single crystal silicon substrate was divided.
Test example 2
The resistances of the examples and comparative examples were measured using an unbalanced bridge method: the method relates to the working principle and method of the bridge, and comprises the steps of pre-adjusting bridge balance and measuring the relation between the resistance value and the temperature of the alloy material at different temperatures. The unbalanced bridge has higher sensitivity and is suitable for measuring the resistance temperature coefficient of the alloy material. When the preset temperature is stable, the output voltage of the unbalanced bridge and the resistance value of the thermistor measured by the digital multimeter are recorded at the same time, and then the process is repeated at different temperatures so as to reach enough measurement points. The Mn-Co-Ni-Cu-O thermosensitive films of examples 1,2, 3, 4 were measured to have resistances of 420. OMEGA., 390. OMEGA., 670. OMEGA., 1825. OMEGA, respectively. The resistances of comparative examples 1,2, and 3 were 430 Ω, 370 Ω, and 1925 Ω.
The results of test examples 1 and 2 show that the Mn-Co-Ni-Cu-O thermistors prepared in examples 1,2 and 3 are small and are not easy to crack and fall off. The thermosensitive films prepared in example 4 and comparative example 3 are large in resistance, the thermosensitive film in example 4 is not easy to crack and fall off, and the thermosensitive film in comparative example 3 is easy to crack and fall off, so that the production efficiency is low. The Mn-Co-Ni-Cu-O thermosensitive films prepared in comparative examples 1 and 2 were also small in resistance, but they were liable to crack and fall off, and were low in production efficiency.
Test example 3
The Mn-Co-Ni-Cu-O thermosensitive films of examples 1 to 4 were respectively subjected to scanning electron microscope (Scanning Electron Microscope, SEM), atomic force microscope (Atomic Force Microscope, AFM), transmission electron microscope (Transmission Electron Microscope, TEM) and were photographed, and the SEM, AFM and TEM images of example 1 were respectively shown in FIGS. 4, 5 and 6, which revealed that the surfaces of the thermosensitive films were very flat, the roughness was (15 to 20) nm, the film thickness was 7.7. Mu.m, the thermosensitive films were composed of columnar crystals, densely grown, and the crystal structure was mainly a spinel structure.
Test example 4
The relationship between the resistance and the temperature is measured by adopting an unbalanced bridge method, a resistance-temperature relationship line is drawn, and the result is shown as figure 8, and the result shows that the thermosensitive device has a very remarkable resistance-temperature linear relationship and has a negative temperature coefficient characteristic.
According to the application, cu is introduced, 1/3 thickness precutting is performed on a monocrystalline silicon substrate, and a twice magnetron sputtering process is adopted, so that the brittleness and plasticity of the thermosensitive film are optimized, the in-plane residual stress of the thermosensitive film is reduced, the Mn-Co-Ni-Cu-O thermosensitive film with the thickness of more than 7.7 mu m is prepared, and the surface of the thermosensitive film is intact and well combined with a silicon dioxide layer, and cracking and falling do not occur; the prepared thermosensitive film resistor is less than 500 omega, and annealing heat treatment is not needed; compared with the prior art, the technical route provided by the application is simple and efficient, and has very high production efficiency and yield.
The invention uses silver colloid to adhere the platinum wire with the diameter of 80 μm on the two sides of the thermosensitive film to form the electrode, only tens of seconds are needed to adhere one electrode, the time and cost are low, the electrode adhesion scheme is very simple, the adhesion efficiency and success rate are extremely high, and the invention is very beneficial to the practical manufacture and application of the thermistor temperature sensor.
According to the invention, through pre-cutting the monocrystalline silicon substrate with 1/3 thickness, mn-Co-Ni-Cu-O thermosensitive films grown by magnetron sputtering can be formed into square small blocks with the area of 5mm multiplied by 5mm which are mutually independent; the scheme can reduce the residual stress generated in the growth process of the thermosensitive film, avoid cracking and falling of the thermosensitive film, and can directly split and divide the prepared thermosensitive film by breaking, so that the method is simple and efficient.
The negative temperature coefficient thermosensitive film sensor comprises a platinum wire electrode, a Mn-Co-Ni-Cu-O thermosensitive film, insulating silicon dioxide and a monocrystalline substrate, wherein the Mn-Co-Ni-Cu-O thermosensitive film has a spinel structure which can be regarded as cubic close packing formed by oxygen ions, and the unit cell structure is AB 2O4, wherein A ions occupy oxygen tetrahedral gaps formed by four oxygen atoms, and B ions occupy oxygen octahedral gaps formed by six oxygen atoms; the thermosensitive properties of spinel structured thermosensitive materials are largely dependent on the jumping conduction between variable valence cations in the oxygen octahedra in the crystal structure. The oxygen octahedral structure of the Mn-Co-Ni-Cu-O thermosensitive film can be separated to obtain oxygen vacancies with a certain concentration, and the oxygen vacancies can provide extra electrons, also cause deviation of stoichiometric ratio of materials, change of valence state of metal cations, oxygen octahedral distortion and the like, so that the physical properties of the materials are effectively improved and regulated, and the thermosensitive performance of the film is improved.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims (10)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410969622.9A CN118913470B (en) | 2024-07-18 | A negative temperature coefficient thermistor temperature sensor, its manufacturing method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410969622.9A CN118913470B (en) | 2024-07-18 | A negative temperature coefficient thermistor temperature sensor, its manufacturing method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN118913470A true CN118913470A (en) | 2024-11-08 |
| CN118913470B CN118913470B (en) | 2026-02-10 |
Family
ID=
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN118913470B (en) * | 2024-07-18 | 2026-02-10 | 中国计量科学研究院 | A negative temperature coefficient thermistor temperature sensor, its manufacturing method and application |
Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4777090A (en) * | 1986-11-03 | 1988-10-11 | Ovonic Synthetic Materials Company | Coated article and method of manufacturing the article |
| RU2042220C1 (en) * | 1992-08-05 | 1995-08-20 | Научно-исследовательский институт "ГИРИКОНД" | Material for thermoresistor with negative temperature resistance coefficient |
| JPH07235405A (en) * | 1993-12-27 | 1995-09-05 | Komatsu Ltd | Thermistor sintered body |
| CN102800449A (en) * | 2012-07-26 | 2012-11-28 | 东莞市东思电子技术有限公司 | Chip thermistor and manufacturing method thereof |
| CN105006316A (en) * | 2015-06-03 | 2015-10-28 | 常熟市林芝电子有限责任公司 | Vacuum sputtering electrode of ceramic thermistor and manufacturing method thereof |
| CN105241569A (en) * | 2015-09-21 | 2016-01-13 | 中国科学院宁波材料技术与工程研究所 | Metal-doped amorphous carbon film temperature-sensing element and preparation method therefor |
| CN107686973A (en) * | 2017-09-08 | 2018-02-13 | 电子科技大学 | A kind of titanium ruthenium is co-doped with vanadium dioxide thermosensitive material film and preparation method thereof |
| CN108070835A (en) * | 2016-11-14 | 2018-05-25 | 中国科学院上海硅酸盐研究所 | A kind of vanadium dioxide thin film with high temperature coefficient of resistance and its low temperature deposition method |
| CN109338290A (en) * | 2018-11-02 | 2019-02-15 | 中国航空工业集团公司上海航空测控技术研究所 | A kind of film temperature sensor for aero engine turbine blades |
| CN109516781A (en) * | 2018-11-29 | 2019-03-26 | 江苏大学 | A kind of quaternary system negative temperature coefficient thermistor material and preparation method thereof |
| CN109735807A (en) * | 2019-02-27 | 2019-05-10 | 华中科技大学 | A kind of preparation method of negative temperature coefficient heat-sensitive film |
| CN110230029A (en) * | 2019-06-27 | 2019-09-13 | 西安邮电大学 | A kind of preparation method of spinel structure nickel manganese oxide film |
| CN112663002A (en) * | 2020-09-04 | 2021-04-16 | 中科传感(佛山)科技有限公司 | Thermistor film preparation method based on direct-current reactive co-sputtering |
| CN114134457A (en) * | 2021-12-07 | 2022-03-04 | 中国科学院新疆理化技术研究所 | Preparation method of composite NTC thermosensitive film with grating-like structure |
Patent Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4777090A (en) * | 1986-11-03 | 1988-10-11 | Ovonic Synthetic Materials Company | Coated article and method of manufacturing the article |
| RU2042220C1 (en) * | 1992-08-05 | 1995-08-20 | Научно-исследовательский институт "ГИРИКОНД" | Material for thermoresistor with negative temperature resistance coefficient |
| JPH07235405A (en) * | 1993-12-27 | 1995-09-05 | Komatsu Ltd | Thermistor sintered body |
| CN102800449A (en) * | 2012-07-26 | 2012-11-28 | 东莞市东思电子技术有限公司 | Chip thermistor and manufacturing method thereof |
| CN105006316A (en) * | 2015-06-03 | 2015-10-28 | 常熟市林芝电子有限责任公司 | Vacuum sputtering electrode of ceramic thermistor and manufacturing method thereof |
| CN105241569A (en) * | 2015-09-21 | 2016-01-13 | 中国科学院宁波材料技术与工程研究所 | Metal-doped amorphous carbon film temperature-sensing element and preparation method therefor |
| CN108070835A (en) * | 2016-11-14 | 2018-05-25 | 中国科学院上海硅酸盐研究所 | A kind of vanadium dioxide thin film with high temperature coefficient of resistance and its low temperature deposition method |
| CN107686973A (en) * | 2017-09-08 | 2018-02-13 | 电子科技大学 | A kind of titanium ruthenium is co-doped with vanadium dioxide thermosensitive material film and preparation method thereof |
| CN109338290A (en) * | 2018-11-02 | 2019-02-15 | 中国航空工业集团公司上海航空测控技术研究所 | A kind of film temperature sensor for aero engine turbine blades |
| CN109516781A (en) * | 2018-11-29 | 2019-03-26 | 江苏大学 | A kind of quaternary system negative temperature coefficient thermistor material and preparation method thereof |
| CN109735807A (en) * | 2019-02-27 | 2019-05-10 | 华中科技大学 | A kind of preparation method of negative temperature coefficient heat-sensitive film |
| CN110230029A (en) * | 2019-06-27 | 2019-09-13 | 西安邮电大学 | A kind of preparation method of spinel structure nickel manganese oxide film |
| CN112663002A (en) * | 2020-09-04 | 2021-04-16 | 中科传感(佛山)科技有限公司 | Thermistor film preparation method based on direct-current reactive co-sputtering |
| CN114134457A (en) * | 2021-12-07 | 2022-03-04 | 中国科学院新疆理化技术研究所 | Preparation method of composite NTC thermosensitive film with grating-like structure |
Non-Patent Citations (2)
| Title |
|---|
| 周鸿仁, 刘秀蓉, 徐蓓娜: "直流磁控溅射铂电阻薄膜", 电子科技大学学报, no. 06, 28 December 1997 (1997-12-28) * |
| 王光耀 等: "集成电路高精度晶圆测温技术研究", 计量科学与技术, vol. 67, no. 4, 30 April 2023 (2023-04-30) * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN118913470B (en) * | 2024-07-18 | 2026-02-10 | 中国计量科学研究院 | A negative temperature coefficient thermistor temperature sensor, its manufacturing method and application |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101322258B (en) | Piezoelectric element and method for manufacturing the same | |
| JPH05507115A (en) | Method and structure for forming alpha Ta in thin film form | |
| JP6308435B2 (en) | Metal nitride material for thermistor, manufacturing method thereof, and film type thermistor sensor | |
| CN104838453B (en) | Thermistor metal nitride materials and its manufacture method and film-type thermistor (temperature) sensor | |
| CN104170031A (en) | Metal nitride film for thermistor, process for producing same, and thermistor sensor of film type | |
| CN105144309B (en) | Thermistor metal nitride materials and its manufacture method and film-type thermistor (temperature) sensor | |
| JP6308436B2 (en) | Metal nitride material for thermistor, manufacturing method thereof, and film type thermistor sensor | |
| Herth et al. | Thermal annealing of AlN films for piezoelectric applications | |
| WO2025001332A1 (en) | Nanotwinned silver material and preparation method therefor | |
| CN118913470B (en) | A negative temperature coefficient thermistor temperature sensor, its manufacturing method and application | |
| CN110911352B (en) | A kind of diffusion barrier layer for Cu interconnect and its preparation method and application | |
| CN118913470A (en) | Negative temperature coefficient thermistor temperature sensor and manufacturing method and application thereof | |
| US3884788A (en) | Substrate preparation for liquid phase epitaxy of mercury cadmium telluride | |
| CN223346291U (en) | Negative temperature coefficient thermistor temperature sensor and monocrystalline silicon substrate for preparing same | |
| JP5796720B2 (en) | Temperature sensor and manufacturing method thereof | |
| JP2013205317A (en) | Temperature sensor and method of manufacturing the same | |
| CN117821902A (en) | High-performance water-soluble sacrificial material and preparation method and application thereof | |
| JP2017174974A (en) | Metal nitride material for thermistor, manufacturing method thereof, and film type thermistor sensor | |
| CN104797734B (en) | Metal nitride material for thermistor, manufacturing method thereof, and thin film type thermistor sensor | |
| JP2004342705A (en) | Tantalum nitride thin-film resistor and its manufacturing method | |
| CN1949459A (en) | Method for directly preparing Cr-Si silicide resistance film on surface of monocrystalline silicon substrate | |
| JP2016136609A (en) | Metal nitride material for thermistor, manufacturing method thereof, and film type thermistor sensor | |
| CN119779525B (en) | A fourth-subgroup transition metal nitride solid solution strain sensitive film with ultra-low temperature coefficient of resistance and preparation method thereof | |
| JP2004311624A (en) | Laminate and manufacturing method thereof | |
| JP2000185968A (en) | Conductive metal oxide sintered body and use thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant |