CN113223791B - Narrow-linewidth metal type low-voltage pressure-sensitive device and preparation method for electrofluid printing - Google Patents
Narrow-linewidth metal type low-voltage pressure-sensitive device and preparation method for electrofluid printing Download PDFInfo
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- CN113223791B CN113223791B CN202110467238.5A CN202110467238A CN113223791B CN 113223791 B CN113223791 B CN 113223791B CN 202110467238 A CN202110467238 A CN 202110467238A CN 113223791 B CN113223791 B CN 113223791B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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- H01C7/00—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
- H01C7/10—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 voltage responsive, i.e. varistors
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Abstract
The invention discloses a narrow linewidth metal type low-voltage pressure-sensitive device and a preparation method of electrofluid printing; the pressure-sensitive device comprises nano silver particles, ethyl cellulose and polyvinylpyrrolidone, and comprises a main body part and two external contacts, wherein the external contacts are positioned at two ends of the main body part. Cleaning and drying the substrate, printing the pressure-sensitive device on the substrate by adopting the nano silver sol through electrofluid printing, and annealing and curing the printed pressure-sensitive device to obtain the narrow-linewidth metal type low-pressure-sensitive device. The piezoresistor of the pressure-sensitive device is stable, the nonlinear coefficient is large, the leakage current is small, and the microscopic uniformity is good; simple process and low sintering temperature.
Description
Technical Field
The invention belongs to the technical field of electronic materials, and relates to a narrow-linewidth metal type low-voltage pressure-sensitive device and a preparation method of electrofluid printing.
Background
The voltage dependent resistor is a resistor device with nonlinear current-voltage characteristics, and is mainly used for voltage clamping when a circuit bears overvoltage, and absorbing redundant current to protect a sensitive device. The resistor body material of the piezoresistor is a semiconductor at present, so the piezoresistor is a variety of semiconductor resistors. The zinc oxide (ZnO) piezoresistor which is widely used at present has the main material composed of divalent element zinc (Zn) and hexavalent element oxygen (O). At present, the main approach for improving the performance of the zinc oxide piezoresistor is to obtain the high-performance ZnO piezoresistor by improving the formula and the preparation process of the piezoresistor material powder. The grain size and microscopic uniformity determine the electrical performance of the piezoresistor, and the traditional preparation method of the ZnO piezoresistor is to put micron-sized ZnO, Bi, Mn, Sb and other oxides into a ball-milling tank according to a certain proportion, mix and crush the oxides, and then put the mixed and crushed oxides into high temperature of 1100-1500 ℃ to sinter the mixed and crushed oxides into porcelain. Nevertheless, due to the low surface activity of the micron-sized raw material, the higher temperature required for growing the crystal grains, the larger crystal grains resulting in low potential gradient and poor micro-uniformity, the electrical properties of the varistor may not be greatly improved even by more advanced ball milling and doping of the particles. Therefore, there is a need to find new pressure sensitive materials steadily developing towards more miniature, more efficient, cleaner fields in the context of new times.
The existing method for regulating and controlling the nonlinearity of zinc oxide resistance is to use ZnO and MnO 2 、Co 2 O 3 、NiO 2 、Bi 2 O 3 、Sb 2 O 3 The mixture is ball-milled for 6h by a ball mill and then spray-granulated (Liu Yayun, Qi Hai wave, Yang Jun, Liu Ming Xin.) the influence of doped antimony oxide on the performance of the zinc oxide resistor disc [ J ]]The electric porcelain lightning arrester, 2020(05), 124-. Firstly, a sample is subjected to pre-sintering treatment under a temperature curve with the highest temperature of 780 ℃, a special high-resistance layer formula is coated on the side surface, and then sintering is carried out under the temperature curve with the highest temperature of 1020 ℃. And finally, coating, grinding and spraying aluminum on the resistance card. The content of antimony oxide can be changed to influence the performances of the zinc oxide resistance card such as potential gradient, leakage current and the like. Antimony oxide and zinc oxide can form a spinel phase in the sintering process, the size of zinc oxide grains can be inhibited, and the potential gradient of the resistor disc can be adjusted. However, the antimony oxide needs to be dissociated at 800 ℃ so as to be mutually soluble with other powder materialsTherefore, the preparation process has high energy consumption. Meanwhile, powder materials are used as raw materials for grinding in the production process, and the harm of dust to human bodies and the environment needs to be paid attention.
CN 109734435A discloses a nano zinc oxide piezoresistor material and a preparation method thereof. The nano ZnO varistor is obtained by adopting a ball milling technology and adopting nano ZnO powder as a raw material and rare earth element Ce oxide as an additive. The traditional method of taking micron ZnO as a raw material is abandoned, a nano ZnO raw material is adopted, and the surface activity of nano particles is high, so that the sintering temperature of ZnO can be reduced, and energy is saved. However, the ball milling mixing of the powders is not enough to completely destroy the agglomeration of the nano-powder, and the two (or more) powders are still not uniform on the microscopic scale, so that the electrical properties of the powders are difficult to guarantee.
Therefore, the development of a varistor with simple preparation process, low cost and low sintering temperature is urgently needed in the field. Has the performances of stable voltage-dependent voltage, good nonlinearity and small leakage current.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a narrow-linewidth metal type low-voltage pressure-sensitive device and a preparation method for electrofluid printing, wherein the method is simple to operate, easy to obtain raw materials, low in equipment requirement and suitable for industrial mass production; the nano-silver piezoresistor material prepared by the method has stable piezovoltage, good nonlinearity and low leakage current.
In order to achieve the purpose, the technical scheme is realized by the following technical scheme:
a narrow-linewidth metal type low-voltage pressure-sensitive device comprises nano silver particles, ethyl cellulose and polyvinylpyrrolidone, and comprises a main body part and two external contacts, wherein the external contacts are positioned at two ends of the main body part.
Preferably, the length of the line of the main body part is 100-1000um, the width is 1-10um, and the height is 30-300 nm; the diameter of the external contact is 20-100um, and the height is 30-300 nm.
Preferably, the particle size of the nano silver particles is 1-50 nm.
The preparation method of the narrow-linewidth metal type low-voltage pressure-sensitive device for electrofluid printing comprises the following steps:
cleaning and drying the substrate, printing the pressure-sensitive device on the substrate by adopting the nano silver sol through electrofluid printing, and annealing and curing the printed pressure-sensitive device to obtain the narrow-linewidth metal type low-pressure-sensitive device.
Preferably, the substrate is made of one of n-type silicon, p-type silicon and a glass substrate.
Preferably, the nano silver sol is prepared from nano silver particle ink and polyvinylpyrrolidone solution according to a mass ratio of 1: and 3-6, ultrasonically mixing for 2-3 hours to obtain the product.
Preferably, the nano silver particle ink is prepared by the following method: mixing silver acetate with a mixed solvent, adding ethanolamine, and stirring for 2-3 hours to obtain nano silver particle ink; wherein the ratio of the silver acetate to the mixed solvent to the ethanolamine is 1-2 g: 1-5 ml: 0.01-0.05 mol, wherein the volume ratio of the mixed solvent is 5-10: 5-10: 1 of ethylene glycol, ethanol and oleic acid.
Preferably, the polyvinylpyrrolidone solution is prepared by dissolving polyvinylpyrrolidone with a weight-average molecular weight of 200000-500000 and ethyl cellulose in ethylene glycol monomethyl ether; wherein the mass concentration of the polyvinylpyrrolidone in the polyvinylpyrrolidone solution is 10-35%, and the mass concentration of the ethyl cellulose is 0.5-3%.
Preferably, the cleaning refers to ultrasonic oscillation of the substrate for 5-10 min by using isopropanol, tetrahydrofuran, an alkaline cleaning solution, deionized water and isopropanol in sequence;
the drying temperature is 65-75 ℃, and the drying is carried out until the weight is constant;
the temperature of the annealing and curing is 200-500 ℃, and the time of the annealing and curing is 10-30 min.
Preferably, the model of the electrofluid printer used for electrofluid printing is SIJ-S150;
the parameters of electrofluid printing were: the voltage is 200-1200V, the voltage frequency is 100-1500 Hz, the voltage waveform is any one of square waves, triangular waves and sine waves, and the moving speed is 5-50 mm/s.
Compared with the prior art, the invention has the following advantages and beneficial effects:
the electrofluid printing nano-silver piezoresistor provided by the invention has the advantages of simple process and low sintering temperature. When the nano silver voltage dependent resistor is normally used, the nano silver voltage dependent resistor is positioned in a leakage current area, and the extremely high resistance value can inhibit abnormal over-high voltage in a circuit and protect the circuit from being damaged by over-voltage. And releasing surge current when the surge impact occurs. Under the condition of sharp increase of the flux, the device can be fused to protect the circuit due to the characteristics of narrow line width and nanometer effect. The nano-silver piezoresistor material prepared by the method has the advantages of stable piezoresistor, large nonlinear coefficient, small leakage current and good microscopic uniformity.
Drawings
FIG. 1 is a schematic diagram of a narrow linewidth nano silver varistor structure according to the present invention;
FIG. 2 is a plot of the voltammetry characteristics of the narrow linewidth nanosilver piezoresistor of example 1;
fig. 3 is a high voltage fuse diagram (20um, 500x) of the narrow line width nano silver varistor of example 1.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the embodiments and the scope of the present invention are not limited thereto.
The examples of the present invention, in which specific conditions are not specified, were carried out according to conventional conditions or conditions recommended by the manufacturer. The raw materials, reagents and the like which are not indicated for manufacturers are all conventional products which can be obtained by commercial purchase.
The materials used in the following examples are as follows:
nano silver particles (AgNPs) ink: silver acetate (1.66g) is used as a precursor, and a mixed solvent composed of glycol, ethanol and oleic acid in a volume ratio of 10: 10: 1, adding silver acetate into a mixed solvent for uniformly mixing, wherein the dosage is 1ml, 1ml and 0.1ml respectively; 0.02mol of ethanolamine is added dropwise into the mixed solution as a reducing agent under slow stirring. And (3) sealing and stirring the solution at a low speed for 2-3 hours, and filtering to obtain the silver nano ink after the solid in the solution is almost completely dissolved.
PVP solution: the PVP is prepared by dissolving PVP with weight average molecular weight of 400000 and ethyl cellulose in ethylene glycol monomethyl ether, wherein the mass concentration of the PVP and the ethyl cellulose is 20% and 1.5%, respectively.
Nano silver sol: the AgNPs ink and the PVP solution are mixed according to the mass ratio of 1: 4, obtaining the nano silver sol with the grain diameter of 1-50nm after ultrasonic mixing for 2-3 hours.
The substrate was an n-type silicon plate with dimensions 1 x 1 cm.
FIG. 1 is a schematic diagram of the structure of a narrow-linewidth nano-silver varistor of the present invention; the varistor comprises a substrate and a varistor, wherein the varistor comprises a main body part and two wiring parts, and the wiring parts are connected to two ends of the main body part; the length of the main body part is 100-1000um, the width is 1-10um, and the height is 30-300 nm; the diameter of the wiring part is 20-100um, and the height is 30-300 nm.
Example 1
In this embodiment, a nano-silver varistor based on electrofluid printing is provided, and the preparation method is as follows:
(1) substrate cleaning: putting the substrate into an ultrasonic cleaner, and sequentially performing ultrasonic oscillation on the recovered isopropanol, the recovered tetrahydrofuran, the alkaline cleaning solution, the deionized water and the isopropanol for 10min respectively.
(2) Drying the substrate: and (3) putting the cleaned n-type silicon plate into an oven, and drying at 70 ℃.
(3) Printing a narrow-line-width nano-silver piezoresistor: performing electrofluid printing on the nano-silver pressure-sensitive resistor by adopting an electrofluid printer SIJ-S150 through the nano-silver sol; parameters of electrofluid printing: the voltage is 700V, the voltage waveform is triangular wave, the voltage frequency is 1000Hz, and the moving speed is 5 mm/s. As shown in FIG. 1, the main body portion is 100um long, 2um wide and 100nm high. The minor part is 20um in diameter and 100nm high.
(4) And (3) curing: and (3) curing the printed piezoresistor device for 20min at 200 ℃ in an air atmosphere.
Example 2
The difference from example 1 is that the curing temperature is 300 ℃.
Example 3
The difference from example 1 is that the curing temperature is 450 ℃.
Example 4
The difference from example 1 is that the curing temperature is 500 ℃.
Data analysis
The narrow line width nano-silver piezoresistor properties prepared in examples 1-4 are shown in table 1;
TABLE 1
The preparation method of the narrow-linewidth nano silver piezoresistor is simple, and the curing temperature (sintering temperature) is far lower than the sintering temperature (600-1000 ℃) of common zinc oxide piezoresistors on the market.
As can be seen from Table 1: the narrow-linewidth nano silver piezoresistor prepared by the method has larger nonlinear coefficient, the larger the nonlinear coefficient is, the more sensitive the resistance value is to voltage, and the embodiment 1-3 can stably work under low voltage. The narrow-linewidth nano silver piezoresistor prepared by the invention has small leakage current during normal work, hardly generates heat and accumulates heat based on the characteristic of narrow linewidth, thereby not causing the change of the piezovoltage, and having better safety and service life.
FIG. 2 is a plot of voltammetric characteristics of the narrow-linewidth nanosilver piezoresistors of example 1;
as can be seen from fig. 2: the narrow-linewidth nano silver piezoresistor prepared by the invention has excellent low-voltage piezoresistance, and after the piezoresistance is loaded with more than piezoresistance voltage, the resistance of the device can be sharply reduced, the operation of voltage clamping is realized, and redundant electric energy in a circuit is absorbed, so that the circuit of a microelectronic device is protected.
FIG. 3 is a high voltage fuse diagram of the narrow linewidth nanosilver piezoresistor of example 1;
as can be seen from fig. 3: when the common zinc oxide piezoresistor fails, short circuit (low-impedance short circuit) is broken down instantly, and because the resistor is high in melting point, the resistor is difficult to fuse and can accumulate heat, potential safety hazards exist. The difference is that the narrow-linewidth nano silver piezoresistor prepared by the invention is fused to form an open circuit when the nano size effect of the metal particles is low in melting point, so that the function of protecting a circuit can be achieved.
The foregoing shows and describes the general principles, principal features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are given by way of illustration of the principles of the present invention, and that various changes and modifications may be made without departing from the spirit and scope of the invention as defined by the appended claims. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (10)
1. The narrow-linewidth metal type low-voltage pressure-sensitive device is characterized in that components of the pressure-sensitive device consist of nano silver particles, ethyl cellulose and polyvinylpyrrolidone, the pressure-sensitive device comprises a main body part and two external contacts, and the external contacts are positioned at two ends of the main body part.
2. The narrow linewidth metal type low-voltage sensitive device of claim 1, wherein the line length of the main body portion is 100-1000um, the width is 1-10um, and the height is 30-300 nm; the diameter of the external contact is 20-100um, and the height is 30-300 nm.
3. The narrow linewidth metal type low-voltage pressure-sensitive device according to claim 1, wherein the nano silver particles have a particle size of 1 to 50 nm.
4. A method for preparing a narrow linewidth metal type low pressure sensitive device according to any one of claims 1 to 3 by electrofluidic printing, comprising the steps of:
and cleaning and drying the substrate, printing the pressure-sensitive device on the substrate by adopting the nano silver sol through electrofluid printing, and annealing and curing the printed pressure-sensitive device to obtain the narrow-linewidth metal type low-pressure-sensitive device.
5. The method according to claim 4, wherein the substrate is made of one of n-type silicon, p-type silicon and glass substrate.
6. The preparation method according to claim 4, wherein the nano silver sol is a nano silver particle ink and a polyvinylpyrrolidone solution in a mass ratio of 1: and 3-6, ultrasonically mixing for 2-3 hours to obtain the product.
7. The preparation method according to claim 6, wherein the nano silver particle ink is prepared by the following method: mixing silver acetate with a mixed solvent, adding ethanolamine, and stirring for 2-3 hours to obtain nano silver particle ink; wherein the ratio of the silver acetate to the mixed solvent to the ethanolamine is 1-2 g: 1-5 ml: 0.01-0.05 mol, and the volume ratio of the mixed solvent is 5-10: 5-10: 1 of ethylene glycol, ethanol and oleic acid.
8. The method according to claim 6, wherein the polyvinylpyrrolidone solution is prepared by dissolving polyvinylpyrrolidone having a weight-average molecular weight of 200000 to 500000 and ethyl cellulose in ethylene glycol monomethyl ether; wherein the mass concentration of the polyvinylpyrrolidone in the polyvinylpyrrolidone solution is 10-35%, and the mass concentration of the ethyl cellulose is 0.5-3%.
9. The preparation method according to claim 4, wherein the cleaning means ultrasonic oscillating the substrate with isopropanol, tetrahydrofuran, alkaline cleaning solution, deionized water and isopropanol for 5-10 min in sequence; the drying temperature is 65-75 ℃, and the drying is carried out until the weight is constant; the temperature of the annealing and curing is 200-500 ℃, and the time of the annealing and curing is 10-30 min.
10. The method of claim 4, wherein the electrofluid printer used for electrofluid printing is model SIJ-S150; the parameters of electrofluid printing are as follows: the voltage is 200-1200V, the voltage frequency is 100-1500 Hz, the voltage waveform is any one of square waves, triangular waves and sine waves, and the moving speed is 5-50 mm/s.
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| JPH02239602A (en) * | 1989-03-14 | 1990-09-21 | Ngk Insulators Ltd | Manufacture of voltage dependent nonlinear resistor |
| CN102881389B (en) * | 2012-09-28 | 2015-07-08 | 广东风华高新科技股份有限公司 | Piezoresistor and preparation method thereof |
| CN104934103B (en) * | 2015-06-07 | 2017-06-09 | 贵研铂业股份有限公司 | It is a kind of to be adapted to two kinds of environment-friendly type zinc oxide varistor electrode silver plasms of welding procedure and preparation method thereof |
| CN106969860B (en) * | 2017-05-01 | 2019-10-11 | 苏州科技大学 | A kind of preparation method of intelligence Magnetic driving selfreparing flexible pressure-sensitive sensor |
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