CN115184453A - LiNbO 3 /LiTaO 3 Piezoelectric coating sensor and preparation method thereof - Google Patents

LiNbO 3 /LiTaO 3 Piezoelectric coating sensor and preparation method thereof Download PDF

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CN115184453A
CN115184453A CN202210624331.7A CN202210624331A CN115184453A CN 115184453 A CN115184453 A CN 115184453A CN 202210624331 A CN202210624331 A CN 202210624331A CN 115184453 A CN115184453 A CN 115184453A
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litao
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瓦西里·帕里诺维奇
曾晓梅
杨兵
张翔宇
姜杨慧
张俊
陈燕鸣
黄家辉
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Wuhan University WHU
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Abstract

The invention discloses LiNbO 3 /LiTaO 3 Piezoelectric coating sensor and preparation method thereof, and LiNbO 3 /LiTaO 3 The nano composite piezoelectric coating adopts a gradient multilayer structure and sequentially comprises a bonding layer, a high-temperature diffusion barrier layer, a piezoelectric functional layer, a protective layer, a transition layer and an electrode layer from inside to outside, wherein the bonding layer is pure metal Cr, the high-temperature diffusion barrier layer is AlN, and the piezoelectric functional layer is LiNbO 3 /LiTaO 3 Nano-meterThe multilayer film comprises a protective layer made of Cr, a transition layer made of Ag/Cr and an electrode layer made of Ag. The coating has better piezoelectric property, high temperature resistance, corrosion resistance and irradiation resistance than the conventional piezoelectric coating; gradient structure and nano multilayer structure are fully utilized to form gradual change components, stress of the coating and the matrix is reduced, and the adhesive force is excellent; the structure can meet the requirements of high-temperature stability and low stress of the film and meet the requirements of long service life and high reliability in operation.

Description

LiNbO 3 /LiTaO 3 Piezoelectric coating sensor and preparation method thereof
Technical Field
The invention relates to the field of piezoelectric coating preparation, in particular to LiNbO 3 /LiTaO 3 A piezoelectric coating sensor and a preparation method thereof.
Background
Nondestructive testing (NDT) is widely used in the industrial field for detecting early small defects before fatal failures. Various NDT methods have been developed, and ultrasonic technology of piezoelectric Ultrasonic Sensors (UTs) is one of the commonly used methods for measuring the thinning of a structure and detecting defects and cracks inside the structure due to underground detection capability, simplicity and cost effectiveness, and has been widely used for non-destructive inspection (NDT) of metal structures such as fuselages, engines, pipes, structural parts of nuclear power plants, and the like. Many of these applications, such as corrosion, erosion, defect detection, etc., occur at high temperatures (600℃.). Some industrial applications require higher temperatures, for example 1000-1200 ℃ in the reactor, with nuclear radiation up to 10 deg.C 20 n/cm 2 . Therefore, there is a strong demand for radiation-resistant and high-temperature-resistant ultrasonic sensors.
The film with the piezoelectric effect is very suitable for being applied to the detection direction of defects and pretightening force. The permanent following type sensor of the detected piece can be obtained by directly depositing the coating with excellent ultrasonic excitation performance on the surface of the detected piece.
The most mature at present is titanium zirconiumThe acid lead PZT piezoelectric ceramic is a piezoelectric material with the best piezoelectric sensing performance in the low-temperature field, but the Curie temperature limits the application of the acid lead PZT piezoelectric ceramic in high temperature, and later lead titanate (PbTiO) 3 ) Bismuth titanate (Bi) 4 Ti 3 O 12 ) And aluminum oxide (ZnO) and the like are published in succession, but the temperature resistance is still not ideal, and the aluminum oxide (ZnO) and the like can only be applied to a working environment below 400 ℃ and cannot meet the requirement of industrial places with higher temperature. Researchers have subsequently developed LiNbO using sol-gel spray technology 3 /PZT、LiNbO 3 (LN) /Bi 4 Ti 3 O 12 The composite thick ceramic (larger than 40 mu m) film piezoelectric materials such as (BiT) and the like further improve the ultrasonic sensing performance and the thermal stability, prove the feasibility and the superiority of the composite material, but the sol-gel spraying technology consumes a long time, needs to be combined with post-treatment processes such as drying and the like, and is not suitable for industrial production.
Therefore, there is a need to improve the prior art and develop new piezoelectric coatings that are resistant to high temperatures, corrosion, and radiation.
LiNbO 3 Has the advantages of high use temperature (1110 ℃) and large d33 value (39 pC/N), excellent radiation resistance and LiTaO 3 Is LiNbO 3 Has a large number of chemical groups similar to LiNbO 3 The material has the same characteristics, such as trigonal system, piezoelectricity, high melting point up to 1650 ℃, difficult depolarization, low dielectric loss, good electromechanical coupling, good temperature coefficient and other excellent performances. The invention innovatively provides LiNbO 3 With LiTaO 3 Compounding to prepare LiNbO 3 /LiTaO 3 The multilayer composite coating realizes more effective mechanical energy-electric energy conversion, thereby improving the piezoelectric constant of the material and obtaining better acoustic characteristics.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides high-temperature LiNbO for a corrosion-resistant and radiation-resistant fastener 3 /LiTaO 3 A piezoelectric coating sensor and a preparation method thereof.
The technical scheme of the invention is as follows:
an object of the present invention is to provide LiNbO 3 /LiTaO 3 Piezoelectric coating sensor and preparation method thereof, namely high-temperature LiNbO for corrosion-resistant and radiation-resistant fastener 3 /LiTaO 3 The main body of the piezoelectric coating sensor is LiNbO 3 /LiTaO 3 Nano composite piezoelectric coating, inhibiting LiTaO 3 And LiNbO 3 The density of the piezoelectric coating, the wear resistance and the corrosion resistance of the coating are improved by the growth of columnar crystals.
The other purpose of the invention is to provide high-temperature LiNbO for a corrosion-resistant and radiation-resistant fastener 3 /LiTaO 3 The preparation method of the piezoelectric coating sensor has the advantages of simple and convenient preparation process, easy adjustment, easy realization of industrial production batch, higher processing efficiency and capability of greatly reducing the production cost of manufacturers.
In order to realize the purpose, the technical scheme of the invention is as follows:
in a first aspect, the present invention provides a LiNbO 3 /LiTaO 3 A piezoelectric coated sensor, characterized by: comprising LiNbO 3 /LiTaO 3 A nanocomposite piezoelectric coating; the LiNbO 3 /LiTaO 3 The nano composite piezoelectric coating adopts a gradient multilayer structure and sequentially comprises a bonding layer, a high-temperature diffusion barrier layer, a piezoelectric functional layer, a protective layer, a transition layer and an electrode layer from inside to outside; wherein the bonding layer is a pure metal Cr layer, the high-temperature diffusion barrier layer is an AlN layer, and the piezoelectric function layer is LiNbO 3 /LiTaO 3 The nanometer multi-layer film comprises a Cr layer as a protective layer, an Ag/Cr layer as a transition layer and an Ag layer as an electrode layer.
Preferably, the high-temperature-resistant LiNbO for the fastener 3 /LiTaO 3 The total thickness of the nano composite piezoelectric coating sensor is 25-70 microns, and the sensor comprises an Ag electrode layer.
Further, the thickness of the Cr bonding layer is 0.5-1 micron;
the thickness of the AlN layer high-temperature diffusion impervious layer is 3-5 microns;
the thickness of the piezoelectric functional layer is 10-20 microns, and the piezoelectric functional layer is LiNbO with c-axis orientation 3 /LiTaO 3 Nano multilayer film of LiNbO 3 Single layer thickness of 0.5-2 microns, liTaO 3 A single layer thickness of0.5-2 microns, modulation period of 1-4 microns, liNbO 3 /LiTaO 3 The number of layers is between 5 and 20;
the thickness of the Cr electrode bonding layer/protective layer is 0.5-20 micrometers;
the thickness of the Ag/Cr transition layer is 1-2 microns;
the thickness of the Ag electrode layer is 10-20 microns.
In a second aspect, the invention provides a high-temperature LiNbO for the corrosion-resistant and radiation-resistant fastener 3 /LiTaO 3 The preparation method of the piezoelectric coating sensor is characterized by comprising the following steps: the method comprises the following steps:
s1: plasma cleaning of the substrate: adopting a 99.99% pure Cr target, adjusting the distance between target fasteners to be 100-200mm, and carrying out plasma etching on the surfaces of the fasteners under the conditions of 100-200V of substrate bias voltage, 40-90% of duty ratio and 80-150A of cathode current at 25-300 ℃ and 0.5-2Pa argon atmosphere for 5-20 minutes;
s2: depositing a Cr bonding layer: after etching is finished, a 99.99% pure Cr target is adopted, the distance between target fasteners is adjusted to be 40-100mm, the power supply power is set to be 500-1000W, and a Cr bonding layer is deposited on the surfaces of the fasteners in an argon environment with the temperature of 25-300 ℃ and the pressure of 0.5-3Pa for 5-20 minutes;
s3: depositing an AlN high-temperature diffusion barrier layer: after the deposition of the Cr bonding layer is finished, a 99.99% pure Al target is adopted, the distance between target fasteners is adjusted to be 40-100mm, the power supply power is set to be 500-1000W, the temperature of a sample preparation chamber is set to be 100-300 ℃, 1.5-4Pa Ar and N are introduced 2 Mixed gas, ar/N 2 The ratio is between 0.1 and 9, and an AlN high-temperature diffusion barrier layer is deposited on the surface of the Cr bonding layer for 200 to 300 minutes;
s4: deposition of LiNbO 3 /LiTaO 3 Piezoelectric functional layer: after the AlN layer deposition is finished, 99.99 percent pure LiTaO is adopted 3 Target and LiNbO 3 Adjusting the distance between fasteners of the target material to be 40-100mm, setting the power of a power supply to be 500-1000W and the temperature of a sample preparation chamber to be 150-300 ℃, and depositing LiNbO on the surface of the AlN layer 3 /LiTaO 3 A piezoelectric functional layer;
s5: deposition of Cr electrode bonding/protective layer: sink with a holeAccumulated LiNbO 3 /LiTaO 3 After the piezoelectric functional layer is finished, a 99.99% pure Cr target is adopted, the distance between target fasteners is adjusted to be 40-100mm, the power supply power is set to be 500-1000W, and LiNbO is arranged in an argon environment with the temperature of 25-300 ℃ and the pressure of 0.5-3Pa 3 /LiTaO 3 Depositing a Cr electrode bonding layer/protective layer on the surface for 5-240 minutes;
s6: depositing an Ag/Cr transition layer: after the deposition of the Cr electrode bonding layer/protective layer is finished, an AgCr mixed target is adopted, and the ratio of Ag to Cr is 1:5 to 5:1, adjusting the distance between target fasteners to be 40-100mm, setting the power supply power to be 500-1000W, and depositing an Ag/Cr transition layer on the surface of a Cr layer in an argon environment with the temperature of 25-300 ℃ and the pressure of 0.5-3Pa for 5-20 minutes;
s7: depositing an Ag electrode layer: after the deposition of the Ag/Cr transition layer is finished, adopting a 99.99% pure Ag target, adjusting the distance between target fasteners to be 30-60mm, setting the power of a power supply to be 500-1000W, and depositing an Ag electrode layer on the surface of the Ag/Cr transition layer in an argon environment at 25-300 ℃ and 0.5-3Pa for 30-90 minutes;
s8: naturally cooling after the preparation is finished to obtain the high-temperature LiNbO for the corrosion-resistant and radiation-resistant fastener 3 /LiTaO 3 A piezoelectric coated sensor.
As a preferred scheme, in the step S1, the substrate includes an experimental substrate and an industrial substrate, and the experimental substrate is a monocrystalline silicon wafer or a stainless steel sheet and is used for representing the thickness of the coating, the crystal structure, the elemental composition and the bonding force of the coating; the industrial substrate is Ti6Al4V titanium alloy bolt, inconel 718 bolt, stainless steel bolt, nut, stud, screw, washer, pin, rivet and welding nail, and is used for measuring ultrasonic signals and detecting piezoelectric property, high temperature stability, corrosivity and irradiation resistance in the practical application of the coating.
Further, in the step S4, after the deposition of the AlN high-temperature diffusion barrier layer is finished, the LiTaO is simultaneously turned on 3 Target and LiNbO 3 Target, introducing Ar and O of 1.5-4Pa 2 Mixed gas, ar/O 2 The ratio is between 0.1 and 9; when the fastener is turned to LiTaO 3 The retention time is 30-90 minutes before the target, and LiTaO is formed 3 Coating; when the fastener is rotated to LiNbO 3 The retention time is 30-90 minutes before the target, and LiNbO is formed 3 Coating, the fastener rotates continuously, and 5-20 pairs of LiNbO are formed on the surface of the fastener 3 /LiTaO 3 Coating, preparing the nano multilayer composite piezoelectric functional coating.
Furthermore, after the deposition of the AlN high-temperature diffusion barrier layer is finished, the LiTaO is deposited firstly 3 Coating and post-deposition of LiNbO 3 Coating of LiNbO 3 /LiTaO 3 The outermost layer of the nano-composite piezoelectric coating is also LiNbO 3 ；LiNbO 3 The coating is positioned on the surface, and the characteristic that the coating is an oxide is utilized to protect the piezoelectric coating from being oxidized, improve the high-temperature stability and the irradiation resistance of the piezoelectric coating, and improve the irradiation resistance of the coating to protons and gamma.
The working principle of the invention is as follows:
the piezoelectric nano composite coating adopts a gradient multilayer structure and is provided with a pure metal Cr bonding layer, an AlN high-temperature diffusion barrier layer and LiNbO 3 /LiTaO 3 The nano multilayer piezoelectric functional layer, the Cr protective layer, the Ag/Cr transition layer and the Ag electrode layer are respectively used for the function of the nano multilayer piezoelectric functional layer, so that the nano multilayer piezoelectric functional layer has the characteristics of piezoelectric property, high temperature resistance, irradiation resistance and radiation resistance. The gradient multilayer structure reduces the difference of components between the piezoelectric nano composite coating material and the steel matrix of the fastener, reduces the internal stress of the coating, and avoids the peeling caused by the difference of expansion coefficients during high-temperature and low-temperature impact. Using LiTaO 3 And LiNbO 3 The piezoelectric coating is compounded mainly by utilizing that the piezoelectric coating and the piezoelectric coating are both of a cubic system and have the same structure, thereby being beneficial to growing a multilayer coating with an uninterrupted columnar structure, and the piezoelectric coating have excellent and complementary performances, namely LiNbO 3 Has high use temperature (1110 ℃ (and large d33 value (-39 pC/N) (advantages of LiTaO, excellent radiation resistance and LiTaO) 3 The material also has piezoelectric property, high melting point of 1650 ℃, difficult depolarization, low dielectric loss, good electromechanical coupling, good temperature coefficient and other excellent properties. The multilayer structure is used for releasing the internal stress of the coating, improving the cracking resistance of the coating under the conditions of high-temperature creep and deformation, and simultaneously ensuring the LiNbO of the surface layer 3 /LiTaO 3 The multilayer film is locally cracked or broken, and LiNbO below the multilayer film 3 /LiTaO 3 The layer can quickly form a compact oxide protective film at the crack cracking position, thereby avoiding the further development of corrosion and achieving the effect of self-healing.
The invention firstly aims to overcome the defects that the existing piezoelectric coating is easy to fall off in high-low temperature alternation and the mutual diffusion of elements in a high-temperature environment causes the structural deterioration, adopts a gradient structure and a nano multilayer structure to reduce the stress of the coating and improve the fatigue resistance, particularly provides good adhesion performance for a piezoelectric functional layer by a metal Cr bonding layer and an AlN high-temperature diffusion barrier layer, and effectively reduces the risk of the peeling of the coating in cold and hot circulation and the diffusion of the elements at high temperature. In order to improve the adhesive force, before the coating is deposited, the invention removes oxides, oil stains, dust and other pollutants on the surface of the substrate by setting a substrate bias voltage and utilizing an energy-carrying plasma etching technology, the substrate can be cleaned in the process, the adhesive force of the piezoelectric coating is improved, the oxides and the oil stains on the surface of the fastener are prevented from damaging the combination between the coating and the substrate, the coating is prevented from being peeled off in the high-temperature heating and rapid cooling processes, the dust can cause the uneven coating to form bulges, the layers are disordered, and holes can be left on the coating after the bulges are fallen, so that the ultrasonic stress transmission is damaged.
Another aspect of the invention is to overcome the stress corrosion problem of piezoelectric coatings for fasteners in LiNbO 3 /LiTaO 3 The piezoelectric composite coating has one Cr protecting layer deposited on its surface, and Cr may be used as the transition layer between the piezoelectric coating and Ag electrode to raise the adhesion, and may form compact passive film to lower the sensitivity of the coating to Cl and other corrosive ions and raise the pitting corrosion resistance of the coating.
The third purpose of the invention is to overcome the problem of radiation damage of piezoelectric coating for fasteners, in LiNbO 3 /LiTaO 3 A layer of AlN is deposited between the piezoelectric composite coating and the substrate, the AlN is used as a diffusion barrier layer to improve the stability of high-temperature elements of the coating, and meanwhile, the anti-irradiation performance is excellent, so that the anti-irradiation capability of the coating on protons and gamma can be improved; in addition, the piezoelectric coating main body adopts LiNbO 3 Coating of LiNbO 3 The impulse response and the transmission coefficient have excellent irradiation stabilityThe problem of irradiation damage of the piezoelectric coating for the fastener is solved.
In the technical scheme of the invention, the following principles are combined and mainly explained:
the above LiNbO 3 /LiTaO 3 The nano composite piezoelectric coating adopts a gradient layer structure and sequentially comprises a bonding layer, a high-temperature diffusion barrier layer, a piezoelectric functional layer, a protective layer, a transition layer and an electrode layer from inside to outside, wherein the bonding layer is a pure metal Cr layer, the high-temperature diffusion barrier layer is an AlN layer, and the piezoelectric functional layer is LiNbO 3 /LiTaO 3 The nano multilayer film has a protective layer of Cr layer, a transition layer of Ag/Cr layer and an electrode layer of Ag. The high-temperature resistant and radiation resistant fastener LiNbO 3 /LiTaO 3 The total thickness of the nano composite piezoelectric coating is 25-70 microns.
The thickness of the Cr bonding layer is 0.5-1 μm. Cr is used as a bonding transition layer between the bolt and the piezoelectric coating and between the piezoelectric coating and the Ag electrode so as to improve the adhesive force between the coating and the substrate.
The thickness of the AlN layer high-temperature diffusion impervious layer is 3-5 microns. The stability of high-temperature elements of the coating is improved, the irradiation resistance is excellent, and the irradiation resistance of the coating to protons and gamma rays can be improved.
The thickness of the piezoelectric functional layer is 10-20 microns, and the piezoelectric functional layer is LiNbO with c-axis orientation 3 /LiTaO 3 Nano-multilayer film of LiTaO 3 Single layer thickness of 0.5-2 microns and LiNbO 3 The single layer thickness is 0.5-2 microns, and the modulation period is 1-4 microns. LiNbO 3 The irradiation resistance of the coating to protons and gamma is improved, and the high-temperature stability of the coating is improved; liNbO 3 /LiTaO 3 The composite material has good piezoelectric performance, and realizes stress detection.
The thickness of the Cr protective layer is 0.5-20 microns. Cr is a corrosion-resistant element, can form a compact passive film, reduces the sensitivity of Cl and other corrosive ions, and improves the pitting corrosion resistance of the coating.
The thickness of the Ag/Cr transition layer is 1-2 microns. The Cr/Ag transition layer is used for improving the adhesion between the Cr bonding layer and the Ag electrode layer.
The thickness of the Ag electrode layer is 10-20 microns. Silver has high temperature oxidation resistance, while silver is suitable for use as an acoustic matching layer as a high density metal to improve the sensitivity and bandwidth of the sensor.
In the step S1, the substrate includes an experimental substrate and an industrial substrate, the experimental substrate is a monocrystalline silicon wafer, a stainless steel sheet, or the like, and is used for characterizing a thickness of the coating, a crystal structure, an element component, a coating bonding force, or the like, and providing reference for industrial application, and the industrial substrate is mainly a fastener (Ti) such as a bolt (Ti) or the like 6 Al 4 A V titanium alloy bolt, a inconel 718 bolt, etc.) for measuring ultrasonic signals and inspecting the piezoelectric property, high-temperature stability, corrosiveness and irradiation resistance of the coating;
in the step S4, after the deposition of the AlN high-temperature diffusion barrier layer is finished, the LiTaO is opened simultaneously 3 Target and LiNbO 3 Target, introducing Ar and O of 1.5-4Pa 2 Mixed gas, ar/O 2 Ratio between 0.1 and 9 when the fastener is turned to LiTaO 3 The retention time is 30-90 minutes before the target, and LiTaO is formed 3 Coating of fasteners as they are rotated to LiNbO 3 The retention time is 30-90 minutes before the target, and LiNbO is formed 3 Coating, the fastener rotates continuously, and 5-20 pairs of LiNbO are formed on the surface of the fastener 3 /LiTaO 3 Coating, and preparing the nano multi-layer laminated electrically functional coating.
After the deposition of the AlN high-temperature diffusion barrier layer is finished, firstly depositing LiTaO 3 Coating and post-deposition of LiNbO 3 Coating of LiNbO 3 /LiTaO 3 The outermost layer of the nano-composite piezoelectric coating is also LiNbO 3 。LiNbO 3 The coating is positioned on the surface, and the characteristic that the coating is an oxide per se is utilized to protect the piezoelectric coating from being oxidized, improve the high-temperature stability and the irradiation resistance of the piezoelectric coating, and improve the irradiation resistance of the coating to protons and gamma.
The invention has the following advantages and beneficial effects:
1. the invention firstly converts LiTaO into LiTaO 3 Piezoelectric coating and LiNbO 3 The piezoelectric coating is compounded to construct a nano-multilayer piezoelectric coating, so that the coating has better hardness than the conventional piezoelectric coating,Wear and toughness, liNbO 3 The radiation resistance of the coating to protons and gamma is improved, and simultaneously LiNbO 3 With LiTaO 3 The piezoelectric coating is an oxide, and can be well protected from being oxidized at high temperature without additionally depositing an oxide protective layer, so that the high-temperature stability of the piezoelectric coating is improved, and the LiTaO 3 And LiNbO 3 The structure is consistent, the piezoelectric effect can be further promoted by combining the two, and the stress detection of the fastener can be realized.
2. In the invention, the AlN and the Cr coating are deposited between the piezoelectric composite coating and the substrate, and the AlN inhibits the Cr element from being converted into LiNbO 3 /LiTaO 3 The piezoelectric composite coating diffuses, so that the high-temperature element stability and the irradiation resistance of the coating are improved, and the adhesion between the coating and the substrate is improved by Cr.
3. According to the invention, the Ag electrode layer is deposited on the outermost surface of the whole coating, the Ag has high-temperature oxidation resistance, and meanwhile, the silver is suitable to be used as an acoustic matching layer as high-density metal so as to improve the sensitivity and bandwidth of the sensor and form the intelligent bolt of which the whole life cycle can be measured in situ on line.
3. According to the invention, the Cr coating is deposited on the surface of the piezoelectric composite coating to be used as a protective layer and a bonding layer, and the Cr can form a compact passivation film, so that the sensitivity of corrosive ions is reduced, the pitting corrosion resistance of the coating is improved, and meanwhile, the bonding force between an electrode layer and a piezoelectric layer is improved.
4. According to the invention, the Ag/Cr transition layer is deposited between the Ag electrode layer and the Cr binding layer, so that the adhesion between the Cr binding layer and the Ag electrode layer is improved.
5. The invention fully utilizes the gradient structure and the nano multilayer structure to form gradually changed components, reduces the stress between the coating and the matrix and improves the adhesive force. Compared with the conventional piezoelectric coating material, the invention adopts the multilayer structure technology to inhibit LiTaO 3 And LiNbO 3 The coarsening of the columnar crystal promotes the densification of the piezoelectric coating, which can improve the mechanical energy-electric energy conversion sensitivity of the coating, thereby improving the piezoelectric constant of the material and obtaining better acoustic characteristics.
6. The invention adopts radio frequency magnetron sputtering coating technology to prepare LiNbO 3 /LiTaO 3 Compared with the sol-gel spraying technology, the piezoelectric composite coating has the advantages of high deposition rate, low cost, no need of post-treatment processes such as drying and the like, suitability for industrial mass production, better crystallization and bonding performance, wide adaptability and capability of being applied to other functional coatings and material fields except the piezoelectric coating.
7. The invention regulates and controls the distance of a target material substrate, the power supply, the sample preparation temperature, the type of environmental gas, the air pressure, the sample preparation time, the modulation period and LiNbO 3 /LiTaO 3 The LiNbO with different high-temperature stability, corrosion resistance and radiation resistance can be obtained by the number of the layers of the nano-composite piezoelectric coating and the like 3 /LiTaO 3 A sensor with nano-composite piezoelectric coating. If the working requirement of corrosive environment is required to be met, the Cr protective layer can be thickened properly, and if the working place of high temperature or radiation is required to be met, the top-most LiNbO layer can be thickened properly 3 And (3) piezoelectric coating.
8. The LiNbO for the intelligent fastener prepared by the invention 3 /LiTaO 3 The composite piezoelectric coating has the characteristics of high temperature resistance, irradiation resistance and high bonding force, can work in high-temperature, high-radiation and corrosive industrial places for a long time with high reliability, customizes a permanent following type ultrasonic detection film sensor for the bolt, and forms an intelligent bolt of which the whole life cycle can be measured in situ on line.
Drawings
FIG. 1 is a schematic view of the structure of the coating designed by the present invention.
FIG. 2 is an ultrasonic signal before and after corrosion of the piezoelectric coating of example 2.
FIG. 3 is an ultrasonic signal before and after high temperature annealing of the piezoelectric coating of example 3.
In fig. 1: 1. a substrate; 2. a Cr bonding layer; 3. an AlN high-temperature diffusion barrier layer; 4. LiNbO 3 /LiTaO 3 Compounding a piezoelectric coating; 5. a Cr electrode bonding/protective layer; 6. an Ag/Cr transition layer; 7. and an Ag electrode layer.
In FIG. 2: 8. LiNbO 3 /LiTaO 3 Ultrasonic signals before the nano composite piezoelectric coating is corroded; 9. LiNbO 3 /LiTaO 3 Nanocomposite piezoelectric coatingsUltrasonic signals after corrosion.
Detailed Description
For better understanding of the present invention, the technical solutions of the present invention will be further described in detail with reference to the accompanying drawings and specific embodiments, but the present invention is not limited to the following embodiments.
Example 1
The high-temperature LiNbO for the corrosion-resistant and radiation-resistant fastener in the embodiment 3 /LiTaO 3 The preparation method of the piezoelectric coating sensor comprises the following steps:
s1: plasma beam cleaning of the substrate: adopting a 99.99% pure Cr target, adjusting the distance between a target material and a substrate to be 100-200mm, and performing plasma etching on the surface of the substrate under the conditions of 100-200V of substrate bias voltage, 40-90% of duty ratio and 80-150A of cathode current in an argon environment with the temperature of 25-300 ℃ and the pressure of 0.5-2Pa for 5-20 minutes;
s2: depositing a Cr bonding layer: after etching is finished, adopting a 99.99% pure Cr target, adjusting the distance between the target and the substrate to be 40-100mm, setting the power supply power to be 500-1000W, and depositing a Cr bonding layer with the thickness of 0.5-1 micron on the surface of the substrate in an argon environment with the temperature of 25-300 ℃ and the pressure of 0.5-3Pa for 5-20 minutes;
s3: depositing an AlN high-temperature diffusion barrier layer: after the deposition of the Cr binding layer is finished, a 99.99% pure Al target is adopted, the distance between the target and the substrate is adjusted to be 40-100mm, the power supply power is set to be 500-1000W, the temperature of the sample preparation chamber is set to be 100-300 ℃, and 1.5-4Pa Ar and N are introduced 2 Mixed gas, ar/N 2 Depositing an AlN high-temperature diffusion barrier layer with the thickness of 3-5 microns on the surface of the Cr binding layer for 200-300 minutes at the ratio of 0.1-9;
s4: deposition of LiNbO 3 /LiTaO 3 Piezoelectric functional layer: after the AlN high-temperature diffusion impervious layer is deposited, 99.99 percent pure LiTaO is adopted 3 Target and LiNbO 3 Adjusting the distance between the target and the substrate to 40-100mm, setting the power of the power supply to 500-1000W, the temperature of the sample preparation chamber to 150-300 ℃, and introducing 1.5-4Pa Ar and O 2 Mixed gas, ar/O 2 Preferably, the substrate is rotated to LiTaO in a ratio of between 0.1 and 9 3 The residence time is 30-90 minutes before the target, and LiTaO is formed 3 Coating, and rotating the substrate to LiNbO 3 The retention time is 30-90 minutes before the target, and LiNbO is formed 3 Coating, continuously rotating fastener, and depositing 5-20 pairs of LiNbO on the surface of AlN layer 3 /LiTaO 3 Coating, namely preparing a nano multi-layer piezoelectric functional coating, wherein the total thickness is 10-20 micrometers;
s5: deposition of Cr electrode bonding/protective layer: deposition of LiNbO 3 /LiTaO 3 After the piezoelectric function layer is finished, adopting a 99.99% pure Cr target, adjusting the distance between the target and the substrate to be 40-100mm, setting the power supply to be 500-1000W, and under the argon environment of 0.5-3Pa at the temperature of 25-300 ℃, liNbO 3 /LiTaO 3 Depositing a Cr electrode bonding layer/protective layer with the thickness of 0.5-20 microns on the surface for 5-240 minutes;
s6: depositing an Ag/Cr transition layer: after the deposition of the Cr electrode bonding layer/protective layer is finished, an AgCr mixed target is adopted, and the ratio of Ag to Cr is 1:5 to 5:1, adjusting the distance between target substrates to be 40-100mm, setting the power supply power to be 500-1000W, and depositing an Ag/Cr transition layer with the thickness of 1-2 microns on the surface of the Cr layer in an argon environment with the temperature of 25-300 ℃ and the pressure of 0.5-3Pa for 5-20 minutes;
s7: depositing an Ag electrode layer: after the deposition of the Ag/Cr transition layer is finished, a 99.99% pure Ag target is adopted, the target material substrate spacing is adjusted to be 30-60mm, the power supply power is set to be 500-1000W, and an Ag electrode layer with the thickness of 10-20 micrometers is deposited on the surface of the Ag/Cr transition layer in an argon environment with the temperature of 25-300 ℃ and the pressure of 0.5-3Pa for 30-90 minutes.
S8: naturally cooling after the preparation is finished to obtain the LiNbO for the high-temperature-resistant corrosion-resistant radiation-resistant fastener 3 /LiTaO 3 A nanocomposite piezoelectric coated sensor.
Table 1 shows the corresponding parameter settings of example 1
Figure BDA0003676175200000091
Example 2
In the embodiment, the corrosion-resistant and radiation-resistant high-temperature LiNbO for the fastener 3 /LiTaO 3 The piezoelectric coating sensor is prepared by regulating and controlling target material substrateDistance, power supply power, sample preparation temperature, environmental gas type, gas pressure, sample preparation time, modulation period, liNbO 3 /LiTaO 3 The LiNbO with different high-temperature stability, corrosion resistance and radiation resistance can be obtained by the number of the nano-composite piezoelectric coating layers and the like 3 /LiTaO 3 A sensor with nano-composite piezoelectric coating.
With reference to FIG. 2, at Ti 6 Al 4 And depositing a piezoelectric coating on the V titanium alloy bolt, and verifying the corrosion resistance of the coating.
S1: plasma beam cleaning of the substrate: adopting a 99.99 percent pure Cr target to adjust a target material Ti 6 Al 4 The distance between the V titanium alloy bolts is 140mm, and Ti is subjected to substrate bias voltage of 150V, duty ratio of 80% and cathode current of 100A in an argon atmosphere of 0.8Pa at 200 ℃ under the conditions of 6 Al 4 And carrying out plasma etching on the surface of the V titanium alloy bolt, wherein the etching time is 10 minutes.
S2: depositing a Cr bonding layer: after the etching is finished, adopting a 99.99% pure Cr target, adjusting the bolt spacing of the target material to be 70mm, setting the power of a power supply to be 700W, and performing Ti etching in an Ar environment with the temperature of 150 ℃ and the pressure of 1.5Pa 6 Al 4 The surface of the V titanium alloy bolt was deposited with a Cr bonding layer about 0.7 microns thick for 10 minutes.
S3: depositing an AlN high-temperature diffusion barrier layer: after the deposition of the Cr binding layer is finished, adopting a 99.99% pure Al target, adjusting the bolt spacing of the target material to 60mm, setting the power of a power supply to 900W, setting the temperature of a sample preparation chamber to 250 ℃, and introducing 2.5Pa Ar and N 2 Mixed gas, ar/N 2 The ratio of 1:1, depositing an AlN high-temperature diffusion barrier layer with the thickness of about 2 microns on the surface of the Cr bonding layer for 120 minutes.
S4: deposition of LiNbO 3 /LiTaO 3 Piezoelectric functional layer: after the AlN high-temperature diffusion impervious layer is deposited, 99.99 percent pure LiTaO is adopted 3 Target and LiNbO 3 Adjusting the bolt pitch of the target material to 60mm, setting the power of a power supply to 900W, setting the temperature of a sample preparation chamber to 250 ℃, and introducing 2.5Pa Ar and O 2 Mixed gas, ar/O 2 The ratio of 1:1, depositing LiTaO first 3 Coating and post-deposition of LiNbO 3 Coating when the fastener is turned to LiTaO 3 The residence time is 30 minutes in front of the target, and a 1 micron thick single-layer LiTaO is formed 3 Coating of the fastener when it is turned to LiNbO 3 The stay time is 30 minutes when the target is in front of the target, and a single-layer LiNbO with the thickness of 1 micron is formed 3 Coating, the fastener does not stop rotating, and 10 pairs of LiNbO are deposited on the surface of the AlN layer 3 /LiTaO 3 And the piezoelectric functional layer has a total thickness of about 20 microns and a time duration of 600 minutes.
S5: deposition of Cr electrode bonding/protective layer: deposition of LiNbO 3 /LiTaO 3 After the piezoelectric functional layer is finished, a 99.99% pure Cr target is adopted, the bolt spacing of the target material is adjusted to 70mm, the power supply power is set to 700W, and the target material is subjected to LiNbO in an argon atmosphere at 150 ℃ and 1.5Pa 3 /LiTaO 3 The surface was deposited with a Cr electrode bonding/protective layer about 20 microns thick for 100 minutes.
S6: naturally cooling after the preparation is finished to obtain the LiNbO for the high-temperature-resistant corrosion-resistant radiation-resistant fastener 3 /LiTaO 3 A nanocomposite piezoelectric coated sensor.
S7: and (3) carrying out a corrosion resistance test of the whole of the piezoelectric coating and the bolt, carrying out the corrosion test by spraying 5% sodium chloride solution, setting the corrosion time to be 500h, and measuring ultrasonic signals of the coating before and after corrosion.
Ultrasonic signals of the coating before and after corrosion are shown in FIG. 2, and 8 in FIG. 2 is LiNbO 3 /LiTaO 3 Ultrasonic signal before corrosion of the nano composite piezoelectric coating, 9 is LiNbO 3 /LiTaO 3 And (3) ultrasonic signals after the nano composite piezoelectric coating is corroded. LiNbO 3 /LiTaO 3 The signal of the nano composite piezoelectric coating before annealing is 1.5V, and the signal of the nano composite piezoelectric coating after being corroded by 5% sodium chloride solution for 200h is 1.7V, which indicates that the piezoelectric property of the coating is not damaged by the 5% sodium chloride solution, and LiNbO 3 /LiTaO 3 The nano composite piezoelectric coating sensor has good corrosion resistance.
Table 2 shows the parameter settings in example 2
Figure BDA0003676175200000101
Example 3:
with reference to fig. 3, a coating was deposited on the inconel M9 bolt to verify high temperature stability.
S1: plasma beam cleaning of the substrate: adopting a 99.99% pure Cr target, adjusting the distance between the target material and the bolt of the chromium-nickel-iron superalloy M9 to be 140mm, and carrying out Ti treatment under the conditions of 200 ℃ of substrate bias voltage, 90% of duty ratio and 100A of cathode current in an argon environment with 0.8Pa and 0V of 200 ℃ of temperature 6 Al 4 And carrying out plasma etching on the surface of the V titanium alloy bolt, wherein the etching time is 15 minutes.
S2: depositing a Cr bonding layer: as in example 2.
S3: depositing an AlN high-temperature diffusion barrier layer: parameters settings as in example 2, an AlN high temperature diffusion barrier layer of approximately 5 microns in thickness was deposited on the surface of the Cr bond coat for 300 minutes.
S4: deposition of LiNbO 3 /LiTaO 3 Piezoelectric functional layer: parameter setting and first nine pairs of LiNbO 3 /LiTaO 3 In the piezoelectric coating as in example 2, in order to better improve the high-temperature oxidation resistance and the structural stability of the coating, the last layer of LiNbO is thickened 3 Coating to 2 μm, 10 pairs of LiNbO 3 /LiTaO 3 And the total thickness of the piezoelectric functional layer is about 21 micrometers, and the time is 630 minutes.
S5: deposition of Cr electrode bonding/protective layer: the parameters were set as in example 2, at LiNbO 3 /LiTaO 3 The surface was deposited with a Cr electrode bonding/protective layer about 2 microns thick for 100 minutes.
S6: depositing an Ag/Cr transition layer: after the deposition of the Cr electrode bonding layer/protective layer is finished, ag is adopted 0.3 Cr 0.7 Mixing the target, adjusting the bolt distance of the target material to be 70mm, setting the power supply to be 700W, and depositing an Ag/Cr transition layer with the thickness of about 1.5 microns on the surface of the Cr layer in an argon environment with the temperature of 150 ℃ and the pressure of 1.5Pa for 10 minutes.
S7: depositing an Ag electrode layer: after the deposition of the Ag/Cr transition layer is finished, a 99.99% pure Ag target is adopted, the target bolt spacing is adjusted to be 40mm, the power supply power is set to be 700W, and an Ag electrode layer with the thickness of about 20 microns is deposited on the surface of the Ag/Cr transition layer in an argon environment with the temperature of 150 ℃ and the pressure of 1.5Pa for 90 minutes.
S8: naturally cooling after the preparation is finished to obtain the LiNbO for the high-temperature-resistant corrosion-resistant radiation-resistant fastener 3 /LiTaO 3 A nanocomposite piezoelectric coated sensor.
The ultrasonic film and bolt integral high-temperature annealing experiment is carried out, annealing is carried out under different temperature conditions (100 ℃, 200 ℃, 300 ℃, 400 ℃, 500 ℃, 600 ℃,700 ℃ and 800 ℃), the annealing time of 100 ℃ to 600 ℃ is set to be 500 hours, the annealing time of 700 ℃ is set to be 100 hours, the annealing time of 800 ℃ is set to be 10 hours, and the ultrasonic signals of the coating before and after annealing are measured.
The ultrasonic signals of the coating before and after annealing are shown in figure 3, and the coating is seen to have low fluctuation, the highest signal is 1.5V, the lowest signal is 1.23V, and the difference is only 0.27V, and the coating still has strong ultrasonic signals after 800 ℃, which shows that the piezoelectric property of the coating is not damaged by annealing, liNbO 3 /LiTaO 3 The nano composite piezoelectric coating sensor has good high-temperature stability.
Table 3 shows the corresponding parameter settings of example 3.
Figure BDA0003676175200000121

Claims (7)

1. LiNbO 3 /LiTaO 3 A piezoelectric coated sensor, characterized by: comprising LiNbO 3 /LiTaO 3 A nanocomposite piezoelectric coating; the LiNbO 3 /LiTaO 3 The nano composite piezoelectric coating adopts a gradient multilayer structure and sequentially comprises a bonding layer, a high-temperature diffusion barrier layer, a piezoelectric functional layer, a protective layer, a transition layer and an electrode layer from inside to outside; wherein the bonding layer is a pure metal Cr layer, the high-temperature diffusion barrier layer is an AlN layer, and the piezoelectric function layer is LiNbO 3 /LiTaO 3 The nano multilayer film has a protective layer of Cr layer, a transition layer of Ag/Cr layer and an electrode layer of Ag.
2. The LiNbO according to claim 1 3 /LiTaO 3 A piezoelectric coating sensor, characterized by: the high-temperature resistant LiNbO for the fastener 3 /LiTaO 3 The total thickness of the nano composite piezoelectric coating sensor is 25-70 microns, and the sensor comprises an Ag electrode layer.
3. The LiNbO according to claim 2 3 /LiTaO 3 A piezoelectric coated sensor, characterized by: the high temperature LiNbO 3 /LiTaO 3 In the nano-composite piezoelectric coating:
the thickness of the Cr bonding layer is 0.5-1 micron;
the thickness of the AlN layer high-temperature diffusion impervious layer is 3-5 microns;
the thickness of the piezoelectric functional layer is 10-20 microns, and the piezoelectric functional layer is LiNbO with c-axis orientation 3 /LiTaO 3 Multilayer nanolayered film of LiNbO 3 Single layer thickness of 0.5-2 microns, liTaO 3 Single layer thickness of 0.5-2 microns, modulation period of 1-4 microns, liNbO 3 /LiTaO 3 The number of layers is between 5 and 20;
the thickness of the Cr electrode bonding layer/protective layer is 0.5-20 micrometers;
the thickness of the Ag/Cr transition layer is 1-2 microns;
the thickness of the Ag electrode layer is 10-20 microns.
4. A process for producing the LiNbO according to any one of claims 1 to 3 3 /LiTaO 3 A method of piezoelectric coating a sensor, characterized by: the method comprises the following steps:
s1: plasma cleaning of the substrate: adopting a 99.99% pure Cr target, adjusting the distance between target fasteners to be 100-200mm, and carrying out plasma etching on the surfaces of the fasteners under the conditions of 100-200V of substrate bias voltage, 40-90% of duty ratio and 80-150A of cathode current at 25-300 ℃ and 0.5-2Pa argon atmosphere for 5-20 minutes;
s2: depositing a Cr bonding layer: after etching is finished, a 99.99% pure Cr target is adopted, the distance between target fasteners is adjusted to be 40-100mm, the power supply power is set to be 500-1000W, and a Cr bonding layer is deposited on the surfaces of the fasteners in an argon environment with the temperature of 25-300 ℃ and the pressure of 0.5-3Pa for 5-20 minutes;
s3: depositing an AlN high-temperature diffusion barrier layer: after the deposition of the Cr bonding layer is finished, a 99.99% pure Al target is adopted, the distance between fasteners of the target is adjusted to be 40-100mm, and the arrangement is carried outThe power of the power supply is 500-1000W, the temperature of the sample preparation chamber is 100-300 ℃, and 1.5-4Pa Ar and N are introduced 2 Mixed gas, ar/N 2 The ratio is between 0.1 and 9, and an AlN high-temperature diffusion barrier layer is deposited on the surface of the Cr bonding layer for 200 to 300 minutes;
s4: deposition of LiNbO 3 /LiTaO 3 Piezoelectric functional layer: after the AlN layer deposition is finished, 99.99 percent pure LiTaO is adopted 3 Target and LiNbO 3 Adjusting the distance between fasteners of the target material to be 40-100mm, setting the power of a power supply to be 500-1000W and the temperature of a sample preparation chamber to be 150-300 ℃, and depositing LiNbO on the surface of the AlN layer 3 /LiTaO 3 A piezoelectric functional layer;
s5: deposition of Cr electrode bonding/protective layer: deposition of LiNbO 3 /LiTaO 3 After the piezoelectric functional layer is finished, a 99.99% pure Cr target is adopted, the distance between target fasteners is adjusted to be 40-100mm, the power supply is set to be 500-1000W, and LiNbO is arranged in an argon environment with the temperature of 25-300 ℃ and the pressure of 0.5-3Pa 3 /LiTaO 3 Depositing a Cr electrode bonding layer/protective layer on the surface for 5-240 minutes;
s6: depositing an Ag/Cr transition layer: after the deposition of the Cr electrode bonding layer/protective layer is finished, an AgCr mixed target is adopted, and the ratio of Ag to Cr is 1:5 to 5:1, adjusting the distance between target fasteners to be 40-100mm, setting the power supply power to be 500-1000W, and depositing an Ag/Cr transition layer on the surface of a Cr layer in an argon environment with the temperature of 25-300 ℃ and the pressure of 0.5-3Pa for 5-20 minutes;
s7: depositing an Ag electrode layer: after the deposition of the Ag/Cr transition layer is finished, a 99.99% pure Ag target is adopted, the distance between target fasteners is adjusted to be 30-60mm, the power supply power is set to be 500-1000W, and an Ag electrode layer is deposited on the surface of the Ag/Cr transition layer in an argon environment at 25-300 ℃ and 0.5-3Pa for 30-90 minutes;
s8: naturally cooling after the preparation is finished to obtain the high-temperature LiNbO for the corrosion-resistant and radiation-resistant fastener 3 /LiTaO 3 A piezoelectric coated sensor.
5. The LiNbO according to claim 4 3 /LiTaO 3 The preparation method of the piezoelectric coating sensor is characterized by comprising the following steps: in the step S1, the substrate comprises an experimental substrate and a toolThe industrial substrate is a monocrystalline silicon wafer or a stainless steel sheet and is used for representing the thickness of a coating, a crystal structure, element components and the binding force of the coating; the industrial substrate is Ti6Al4V titanium alloy bolt, inconel 718 bolt, stainless steel bolt, nut, stud, screw, washer, pin, rivet and welding nail, and is used for measuring ultrasonic signals and detecting piezoelectric property, high temperature stability, corrosivity and irradiation resistance in the practical application of the coating.
6. The LiNbO according to claim 5 3 /LiTaO 3 The preparation method of the piezoelectric coating sensor is characterized by comprising the following steps: in the step S4, after the deposition of the AlN high-temperature diffusion barrier layer is finished, the LiTaO is opened at the same time 3 Target and LiNbO 3 Target, introducing Ar and O at 1.5-4Pa 2 Mixed gas, ar/O 2 The ratio is between 0.1 and 9; when the fastener is turned to LiTaO 3 The retention time is 30-90 minutes before the target, and LiTaO is formed 3 Coating; when the fastener is turned to LiNbO 3 The retention time is 30-90 minutes before the target, and LiNbO is formed 3 Coating, the fastener rotates continuously, and 5-20 pairs of LiNbO are formed on the surface of the fastener 3 /LiTaO 3 Coating, preparing the nano multilayer composite piezoelectric functional coating.
7. The LiNbO according to claim 6 3 /LiTaO 3 The preparation method of the piezoelectric coating sensor is characterized by comprising the following steps: after the deposition of the AlN high-temperature diffusion barrier layer is finished, firstly depositing LiTaO 3 Coating and post-deposition of LiNbO 3 Coating of LiNbO 3 /LiTaO 3 The outermost layer of the nano-composite piezoelectric coating is also LiNbO 3 ；LiNbO 3 The coating is positioned on the surface, and the characteristic that the coating is an oxide is utilized to protect the piezoelectric coating from being oxidized, improve the high-temperature stability and the irradiation resistance of the piezoelectric coating, and improve the irradiation resistance of the coating to protons and gamma.
CN202210624331.7A 2022-06-02 2022-06-02 LiNbO 3 /LiTaO 3 Piezoelectric coating sensor and preparation method thereof Pending CN115184453A (en)

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