CN117328026A - AlScN piezoelectric coating material with high mechanical property and high temperature resistance, and preparation method and application thereof - Google Patents

AlScN piezoelectric coating material with high mechanical property and high temperature resistance, and preparation method and application thereof Download PDF

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Publication number
CN117328026A
CN117328026A CN202311213045.2A CN202311213045A CN117328026A CN 117328026 A CN117328026 A CN 117328026A CN 202311213045 A CN202311213045 A CN 202311213045A CN 117328026 A CN117328026 A CN 117328026A
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alscn
alscn piezoelectric
functional layer
coating material
piezoelectric
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姜杨慧
杨兵
张俊
瓦西里
曾晓梅
张翔宇
王豪斌
王晨阳
曾橹维
黄家辉
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Wuhan University WHU
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    • 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
    • C23C14/0021—Reactive sputtering or evaporation
    • C23C14/0036—Reactive sputtering
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C21/00—Alloys based on aluminium
    • 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
    • C23C14/02—Pretreatment of the material to be coated
    • C23C14/021—Cleaning or etching treatments
    • C23C14/022—Cleaning or etching treatments by means of bombardment with energetic particles or radiation
    • 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
    • C23C14/02—Pretreatment of the material to be coated
    • C23C14/024—Deposition of sublayers, e.g. to promote adhesion of the coating
    • C23C14/025—Metallic sublayers
    • 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
    • C23C14/0641—Nitrides
    • 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
    • C23C14/54—Controlling or regulating the coating process
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01L—MEASURING FORCE, STRESS, TORQUE, WORK, MECHANICAL POWER, MECHANICAL EFFICIENCY, OR FLUID PRESSURE
    • G01L1/00—Measuring force or stress, in general
    • G01L1/16—Measuring force or stress, in general using properties of piezoelectric devices
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01L—MEASURING FORCE, STRESS, TORQUE, WORK, MECHANICAL POWER, MECHANICAL EFFICIENCY, OR FLUID PRESSURE
    • G01L1/00—Measuring force or stress, in general
    • G01L1/25—Measuring force or stress, in general using wave or particle radiation, e.g. X-rays, microwaves, neutrons
    • G01L1/255—Measuring force or stress, in general using wave or particle radiation, e.g. X-rays, microwaves, neutrons using acoustic waves, or acoustic emission

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  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Acoustics & Sound (AREA)
  • Health & Medical Sciences (AREA)
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Abstract

The invention provides a preparation method of an AlScN piezoelectric coating material with high mechanical property and high temperature resistance, which comprises the following steps: an AlScN piezoelectric functional layer is formed on the surface of a matrix by adopting an alloy target material composed of Al and Sc through magnetron sputtering; the AlScN piezoelectric functional layer grows in various orientations in the deposition process by controlling the volume ratio of argon to nitrogen, the temperature, the sputtering power, the deposition pressure and the target base distance in the magnetron sputtering. The AlScN piezoelectric coating material prepared by the method has good mechanical property, temperature resistance and corrosion resistance, can be deposited on a substrate, can simultaneously excite longitudinal waves, longitudinal transverse waves and transverse waves to realize defect detection and stress measurement of steel plates, welding seams and steel pipes in various media, has long-term stable service capability under high temperature and severe working conditions without a protective layer, meets long-term use requirements, is easy for mass production, and has popularization and application prospects.

Description

AlScN piezoelectric coating material with high mechanical property and high temperature resistance, and preparation method and application thereof
Technical Field
The invention belongs to the technical field of coating materials, and particularly relates to an AlScN piezoelectric coating material with high mechanical properties and high temperature resistance and a preparation method thereof, and an application of the AlScN piezoelectric coating material with the high mechanical properties and the high temperature resistance in ultrasonic detection.
Background
Ultrasonic detection is one of the most important means for detecting special equipment by virtue of the advantages of convenience, rapidness, no harm to human bodies and the like. The ultrasonic sensor is widely applied to the fields of defect detection, stress measurement, thickness measurement, bolt shaft force measurement and the like. Taking bolt stress measurement as an example, according to the principle of acoustic elasticity, the propagation speed of ultrasonic waves in a bolt is related to the bolt stress, the propagation speed of ultrasonic waves can be known by observing the propagation time of ultrasonic waves in the bolt, a functional relation between the propagation time of ultrasonic waves and the axial stress of the bolt is established, and a correlation coefficient in a functional relation is obtained through a calibration test, so that the bolt stress value can be quantitatively measured by measuring the propagation time of ultrasonic waves in the bolt, and the health condition of bolt connection is judged. The ultrasonic detection pretightening force technology has the advantages of high precision, good instantaneity, strong penetrating power and the like. The film with the piezoelectric effect has the advantages of simple preparation method, high stability and wide applicability, and is very suitable for being applied to the pretightening force detection direction. At present, the patch type ultrasonic stress detection method has been applied for many years, but the piezoelectric wafer is generally adhered to the bolt by epoxy resin or adhesive, so that the piezoelectric wafer is easy to fall off. And the thickness of the adhesive layer cannot be measured, so that the detection accuracy is greatly affected.
However, the existing ultrasonic sensor is mainly suitable for a normal temperature environment (< 100 ℃). Along with the development of high-temperature high-pressure special equipment in high parametrization, ultrasonic detection under high-temperature conditions is focused gradually, and development of a high-temperature-resistant ultrasonic sensor is urgently needed. Difficulties in developing ultrasonic sensors at high temperatures mainly include: the curie temperature of the piezoelectric wafer is limited. The traditional PZT material has low Curie temperature, is not suitable for a piezoelectric wafer serving as a high-temperature probe, and the high-temperature piezoelectric film is extremely easy to crack and fall off with a matrix under the conditions of repeated high and low temperatures and in the long-term use process, so that the improvement of the binding force between the piezoelectric film and the matrix material is the key of the stable operation of the sensor; meanwhile, matching, backing and the like prepared by using the polymer are not high-temperature resistant; the preparation of high temperature and corrosion resistant ultrasonic sensor on special equipment and the development of assembly process, the working temperature of special equipment is up to 400 ℃, so that environmental-friendly sensing device and the assembly process of the sensing device and a matrix are required to be developed through selection.
Currently, piezoelectric materials that can be used to excite ultrasound mainly include ZnO and AlN, both of which are hexagonal wurtzite structures, whose properties for producing the piezoelectric effect depend entirely on their crystallographic orientation without polarization. Compared with ZnO piezoelectric material and AlN piezoelectric material, sc doped AlN has better piezoelectric performance and larger piezoelectric coupling coefficient, however Sc doping can cause obvious increase of stress of AlN coating, and cracking, falling and other conditions of the coating are easily caused, so that the piezoelectric coating is invalid.
Based on the method, the piezoelectric coating material which has high mechanical property, high temperature resistance, high corrosion resistance and strong binding force with the matrix and can excite different ultrasonic waves according to application requirements is provided, and has important significance for realizing high-precision and high-efficiency measurement of the pretightening force of the bolt, defect detection and stress measurement of base materials such as a steel plate, a welding line, a steel pipe and the like, and can prevent the piezoelectric coating from falling off, avoid the corrosion caused by using a coupling agent on the steel matrix and the bolt material and prolong the service life of equipment.
Disclosure of Invention
The invention aims at providing a preparation method of an AlScN piezoelectric coating material which has high mechanical property, high temperature resistance, high corrosion resistance, stronger binding force with a matrix and can excite different ultrasonic waves.
The AlScN piezoelectric coating material has the advantages of high mechanical property, high temperature resistance, high corrosion resistance, stronger binding force with a matrix and capability of exciting different ultrasonic waves.
The invention further provides an application of the AlScN piezoelectric coating material with high mechanical property in measuring the pretightening force of the matrix.
The technical scheme adopted by the invention for realizing one of the purposes is as follows: the preparation method of the AlScN piezoelectric coating material with high mechanical property comprises the following steps: an AlScN piezoelectric functional layer is formed on the surface of a matrix by adopting an alloy target material composed of Al and Sc through magnetron sputtering;
in the magnetron sputtering, the temperature is 100-250 ℃, mixed gas of argon and nitrogen in a volume ratio of 3:1-1:3 is introduced, the sputtering power is 700-900W, the deposition air pressure P=0.4-3.0 Pa, the target base distance d=40-80 mm, and the deposition time is 3-10 h.
In the preparation method, the AlScN piezoelectric functional layer is prepared by utilizing radio frequency magnetron sputtering, the sputtering temperature is controlled to be 100-250 ℃, the temperature rise can enable particles to have higher energy, and the particles can be ensured to have enough energy to migrate to the surface of a substrate within the temperature range so as to deposit an AlScN coating; the volume ratio of argon to nitrogen is controlled, so that the atomic percentages of Al, sc and N particles in the vacuum cavity can be controlled, the collision probability among the particles can be regulated, and the growth orientation of the coating can be regulated; the sputtering power of 700-900W is adopted, and under the sputtering power, the energy of particles can be adjusted, and the thickness of a prepared coating is controlled; the deposition air pressure (the pressure after the reaction gas is introduced into the vacuum chamber) is controlled to be P=0.4-3.0 Pa, the target base distance (the vertical distance between the target and the matrix) is d=40-80 mm, and the average free path of Al, sc and N particles can be regulated and controlled, so that AlScN coatings with various oriented growth can be prepared in the deposition range. Under the preparation conditions, the AlScN piezoelectric functional layer with high hardness, high wear resistance and high corrosion resistance and strong bonding capability with the matrix can be prepared.
Preferably, the temperature of the magnetron sputtering is 150-250 ℃.
Further, before the magnetron sputtering, vacuumizing treatment is carried out to ensure that the vacuum degree is not more than 7 multiplied by 10 -3 Pa。
Further, the alloy target consists of 60wt.% to 90wt.% Al and 10 wt.% to 40wt.% Sc. Preferably, the alloy target consists of 70wt.% Al and 30wt.% Sc.
Further, the diameter of the alloy target is 140-160 mm, and the thickness of the alloy target is 4-8 mm. In the invention, the diameter and thickness of the target material have a certain corresponding relation with the power of magnetron sputtering and the like. The application adopts the target material with larger diameter to be matched with higher sputtering power, so that more samples can be prepared simultaneously in the coating deposition process, the deposition efficiency is higher, the mass production is easy, and the popularization and the use are easier.
Further, the growth orientation of the AlScN piezoelectric functional layer on the surface of the substrate comprises (002) diffraction crystal faces and/or (103) diffraction crystal faces.
According to the invention, through adjusting deposition parameters in the magnetron sputtering process, including deposition air pressure and target base distance, the AlScN piezoelectric functional layer can be enabled to present various growth orientations on the surface of the substrate, various ultrasonic waveforms can be excited, and then AlScN piezoelectric coating materials capable of exciting different ultrasonic waves can be prepared according to detection requirements:
preferably, the coating exhibits a diffraction crystal plane of (103) when the deposition gas pressure p=0.4 Pa and the target base distance is 55 mm.
Preferably, when the deposition gas pressure P=0.6 Pa and the target base distance is 55 mm.ltoreq.d.ltoreq.60 mm, the coating exhibits a (002) diffraction crystal plane of preferential growth. The cross section morphology of the AlScN piezoelectric functional layer prepared at the moment is in a columnar crystal structure which is vertical to the growth of the matrix, and the AlScN piezoelectric functional layer has higher hardness and wear resistance.
Accordingly, in addition to the above specific conditions, for example: in the magnetron sputtering, when the target base distance is 55mm less than or equal to d less than or equal to 60mm, the deposition air pressure P is controlled to be not more than 0.6Pa and P is controlled to be not more than 0.4Pa; or when P=0.6 Pa, controlling the target base distance to be 40mm less than or equal to d less than 55mm or 60mm less than or equal to d less than or equal to 80mm, and enabling the AlScN piezoelectric functional layer to display multi-orientation growth on the surface of the substrate.
Preferably, in the magnetron sputtering, the temperature is 100-250 ℃, mixed gas of argon and nitrogen with the volume ratio of 1:1 is introduced, the sputtering power is 700-900W, the deposition air pressure P=1.0-2.0 Pa, the target base distance d=50-70 mm, and the deposition time is 3-10 h. At this time, the AlScN piezoelectric functional layer exhibits typical multi-oriented growth including (002) crystal plane and (103) diffraction crystal plane on the substrate surface.
Under the condition, the AlScN piezoelectric coating material prepared by the method can emit the combined wave of the longitudinal wave and the transverse wave simultaneously under the condition of being excited. A great number of researches show that when the stress is detected by using a transverse wave and longitudinal wave combined method, besides constants related to the performance and the geometric shape of the material, only the time of flight and the initial temperature of the longitudinal wave transverse wave in the idle state of the bolt are needed to be measured, and then the real-time load of the bolt can be obtained under the condition of not calibrating the original stress by simultaneously solving an eight-order polynomial.
Further, the AlScN piezoelectric functional layer has a thickness of 5 to 20 μm. The AlScN piezoelectric functional layer prepared by the conventional method has the advantages that the stress of the AlN coating is obviously increased due to the doping of Sc, when the coating is too thick, the conditions of cracking, falling and the like of the coating are easily caused, and the piezoelectric coating is invalid, so that the thickness of the AlScN piezoelectric functional layer is required to be strictly controlled (the thickness is usually less than 5 microns). On the contrary, according to the preparation method, by optimizing various parameters in the preparation method, the hardness and the wear resistance of the AlScN piezoelectric functional layer are improved, meanwhile, the binding force between the coating and the matrix is remarkably improved, the preparation requirement of the AlScN piezoelectric functional layer with larger thickness is met, the performance of the excited ultrasonic wave is more excellent, and the excited ultrasonic wave has larger amplitude.
Further, the preparation method comprises the following steps: and depositing a bonding layer on the surface of the matrix, preparing an AlScN piezoelectric function layer on the surface of the bonding layer, and finally preparing an electrode layer on the surface of the AlScN piezoelectric function layer. The bonding layer can increase the bonding force between the substrate and the coating, avoid the problems of cracking and falling of the coating in the long-term use process, and the electrode layer can provide an external electrode for the bolt, so that stable voltage can be applied to the two poles of the bolt, and ultrasonic waves can be excited. The material of the bonding layer includes Cr, and one of Cr, ti, ag, ag-Cr can be used as the electrode layer.
Preferably, the preparation method of the invention can comprise the following steps:
s1, carrying out plasma etching on the surface of a substrate in an argon atmosphere at the temperature of 100-250 ℃;
s2, depositing a Cr binding layer on the surface of the substrate subjected to plasma etching at 0.5-1 Pa and 50-250V;
s3, forming an AlScN piezoelectric functional layer on the surface of the Cr bonding layer by adopting an alloy target material composed of Al and Sc through magnetron sputtering;
s4, depositing an electrode layer on the surface of the AlScN piezoelectric functional layer under the conditions of 0.25-1 Pa of vacuum degree, 0-100V of bias voltage and 0-80A of current, wherein the electrode layer is made of one of Cr, ti, ag, ag-Cr, and thus the preparation of the AlScN piezoelectric coating material is completed.
The second technical scheme adopted by the invention for realizing the second purpose is as follows: there is provided an AlScN piezoelectric coating material manufactured by the manufacturing method according to one of the objects of the present invention.
The AlScN piezoelectric coating material consists of a bonding layer, an AlScN piezoelectric functional layer and an electrode layer. The AlScN piezoelectric coating material prepared by the method has good mechanical property, temperature resistance and corrosion resistance, and can meet the requirements of long-term use under severe working conditions and high-temperature environments under the condition that a protective layer is not needed.
Further, the AlScN piezoelectric functional layer has a hardness of more than 15GPa, a bonding strength with a matrix of more than 10MPa, and a working temperature range of-196-700 ℃.
The third technical scheme adopted by the invention for achieving the purpose is as follows: the application of the AlScN piezoelectric coating material with high mechanical property is provided, and the AlScN piezoelectric coating material excites various ultrasonic waveforms for the pretightening force detection of bolts or the defect detection and stress measurement of steel plates, welding seams and steel pipes.
In some preferred embodiments, the matrix of the AlScN piezoelectric coating material is an intelligent bolt, and according to the preparation method provided by the invention, a bonding layer, an AlScN piezoelectric functional layer and an electrode layer are sequentially deposited on the surface of the intelligent bolt. According to the specific requirement of bolt pretightening force measurement, relevant parameters in the preparation method of the AlScN piezoelectric coating material are adjusted in a targeted manner, so that the intelligent bolt with the piezoelectric coating material on the surface can excite different waveforms (longitudinal waves, transverse waves or longitudinal and transverse waves). The characteristics can simplify the calculation step of the bolt pretightening force, improve the measurement accuracy, and the piezoelectric coating of the intelligent bolt has the advantages of high mechanical property, good temperature resistance and stronger binding force with the bolt matrix, and can widen the working temperature range and prolong the service life of the intelligent bolt.
Compared with the prior art, the invention has the beneficial effects that:
(1) According to the preparation method of the AlScN piezoelectric coating with high mechanical property and high temperature resistance, the AlScN piezoelectric coating is prepared by utilizing radio frequency magnetron sputtering, and piezoelectric coating materials capable of simultaneously exciting different waveforms are prepared by adjusting different air pressures and distances between a target and a matrix, so that accurate measurement of the pretightening force of a bolt is realized. In addition, the AlScN piezoelectric coating prepared by the method has high hardness, high wear resistance and high corrosion resistance, does not need to additionally deposit a protective layer, and is simple and efficient in preparation process. In addition, the equipment required by the preparation method of the piezoelectric coating is relatively close to the existing industrial equipment, the industrial production batch is easy to realize, the processing efficiency is high, and the production cost of factories can be greatly reduced.
(2) The AlScN piezoelectric coating material prepared by the invention adopts an AlScN coating with high piezoelectric coefficient, high electromechanical coupling coefficient and low epitaxial growth temperature, so that the AlScN piezoelectric coating material can be applied to various matrix materials with larger acoustic attenuation coefficients. The AlScN piezoelectric coating material has the hardness of more than 15GPa, the bonding strength with a matrix of more than 10MPa, the working temperature range of-196-700 ℃, high wear resistance and corrosion resistance, and can ensure that the piezoelectric coating can stably work on the surfaces of various alloy bolts for a long time, reduce the possibility of failure and meet the application and test requirements under severe working conditions.
(3) According to the invention, the AlScN coating material with high mechanical strength, high temperature resistance and high wear resistance is deposited on the surface of the substrate, and the AlScN coating material is used as an acoustic-electric conversion layer for exciting ultrasound, so that a nondestructive detection technology can be realized; in addition, the AlScN coating material can emit longitudinal waves and transverse waves simultaneously under ultrasonic excitation, so that the pretightening force of the intelligent bolt can be measured with high precision (error is less than 5%) and high efficiency.
Drawings
FIG. 1 is a schematic diagram of the overall structure of an apparatus for preparing AlScN piezoelectric coating material according to an embodiment of the present invention;
FIG. 2 shows XRD patterns of AlScN piezoelectric functional layers deposited under different air pressures according to examples 1 to 5 of the present invention;
FIG. 3 is a graph showing the surface and cross-sectional morphology of AlScN piezoelectric coatings obtained under different deposition distances according to examples 2, 14, and 15 of the present invention;
FIG. 4 shows the nano-scale of AlScN piezoelectric functional layers obtained under different air pressures in examples 1, 2 and 5 of the present inventionHardness data of hardness test; wherein, (a) is hardness and elastic modulus; (b) Is H/E and H 3 /E 2 ；
FIG. 5 is an SEM image of an AlScN piezoelectric functional layer prepared at a deposition pressure of 0.6Pa according to example 2 of the present invention, obtained by a frictional wear test;
FIG. 6 is a waveform chart of the AlScN piezoelectric functional layer excited with different ultrasonic waves obtained under different air pressures in examples 1-5 of the present invention;
FIG. 7 is a graph showing the ultrasonic wave patterns excited by AlScN piezoelectric coatings obtained under different deposition time conditions in examples 2, 11, and 13 of the present invention;
FIG. 8 is an XRD pattern and an ultrasonic waveform of a sample obtained in example 2 of the present invention under the condition that the deposition pressure is 0.6Pa, and the AlScN piezoelectric functional layer is annealed at 600℃for different periods of time; wherein, (a) is an XRD pattern; (b) ultrasonic waveform patterns;
FIG. 9 is a graph showing the morphology of an AlScN piezoelectric functional layer obtained in example 2 of the present invention under the condition of deposition pressure of 0.6Pa after annealing for different times at 600 ℃;
FIG. 10 is an ultrasonic waveform diagram of intelligent bolt excitation prepared under the conditions that the deposition air pressure is 0.6Pa, the deposition distance is 60mm and the deposition time is 7 h;
wherein 1-radio frequency magnetron sputtering (RF); 2-Al-Sc alloy target material; 3-bolt samples; 4-an etching source; 5-sample holder; 6-a workpiece frame; 7-a heater; 8, an extraction opening; 9-furnace door.
Detailed Description
The technical solutions of the present invention will be clearly and completely described in connection with the embodiments, and it is obvious that the described embodiments are only some embodiments of the present invention, 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.
It should be noted that, without conflict, the embodiments of the present invention and features of the embodiments may be combined with each other.
The invention will be further illustrated, but is not limited, by the following examples.
The main parameters involved in the preparation of AlScN piezoelectric functional layers in each example of the present invention are shown in Table 1 below.
TABLE 1
FIG. 1 shows the apparatus used in the present invention, wherein the vacuum chamber of the apparatus is defined by furnace walls and has a size of 400x400x400mm. The vacuum chamber is provided with an extraction opening 8, and the vacuum pumping unit is used for vacuumizing the vacuum chamber through the extraction opening 8. The upper two corners of the vacuum chamber are provided with heaters 7, the heating power is 25 kilowatts, and the heating efficiency is improved; the lower two corners of the vacuum chamber are etching sources 4, so that impurities on the surface of the substrate can be removed, and the surface of the substrate is ensured to be clean. The Al-Sc alloy target 2 is arranged on a furnace wall and is connected with a radio frequency magnetron sputtering (RF) 1, the sputtering power can be adjusted, the back of the Al-Sc alloy target 2 faces a furnace door 9, the front of the Al-Sc alloy target is a sample 3, the sample is placed on a sample frame 5, and the sample frame is arranged on a workpiece frame 6. This arrangement greatly increases the plasma density in the vacuum chamber and the workpiece is completely immersed in the plasma. The deposition rate, hardness and adhesive force of the coating are greatly improved. The target structure is optimized, so that the magnetic field distribution is more uniform, the magnetron sputtering target surface is uniformly etched, and the uniformity of the coating is improved.
Example 1
The AlScN piezoelectric functional layer is prepared on a stainless steel and Si substrate, and the specific preparation method is as follows:
pretreating the surface of the matrix, removing impurities attached to the surface of the matrix, regulating the temperature of a vacuum chamber to 150 ℃, and vacuumizing to 3 multiplied by 10 -3 Pa, adopting an Al-Sc alloy target (composed of 70wt.% Al and 30wt.% Sc), controlling the surface of the matrix to be opposite to the center of the target, adjusting the base distance of the target to be 55mm, and depositing an AlScN piezoelectric functional layer on the surface of the matrix by a magnetron sputtering preparation technology;
in the magnetron sputtering process, mixed gas with the flow ratio of argon (purity 99.99%) to nitrogen (purity 99.99%) of 1:1 is introduced until the air pressure (deposition air pressure) in the cavity is 0.4Pa, a radio frequency power supply is turned on, the sputtering power is 900W, the sputtering time is 5 hours, and an AlScN piezoelectric functional layer is deposited on the surface of the substrate.
Examples 2 to 5
Examples 2 to 5 differ from example 1 in that the air pressure in the cavity was adjusted to 0.6Pa, 1.0Pa, 1.5Pa and 2.0Pa, respectively, and the remaining conditions were unchanged, and an AlScN piezoelectric functional layer was deposited on the substrate surface.
Example 6
Example 6 differs from example 1 in that the vacuum chamber temperature was adjusted to 250 ℃, the air pressure in the chamber was 3.0Pa, and the remaining conditions were unchanged, and an AlScN piezoelectric functional layer was deposited on the substrate surface.
Examples 7 and 8
Examples 7 and 8 differ from example 1 in that the temperature of the vacuum chamber was adjusted to 100 ℃, the gas pressure in the chamber was adjusted to 2.0Pa, the flow rates of argon (purity 99.99%) and nitrogen (purity 99.99%) were adjusted to 3:1 and 1:3, respectively, and the conditions were unchanged, to deposit an AlScN piezoelectric functional layer on the substrate surface.
Example 9
Example 9 differs from example 2 in that: and adjusting the target base distance to 50mm, and depositing an AlScN piezoelectric functional layer on the surface of the substrate under the same conditions.
Example 10
Example 10 differs from example 1 in that: the temperature of the vacuum chamber is regulated to 250 ℃, the air pressure in the cavity is regulated to 2.2Pa, the target base distance is regulated to 55mm, the sputtering power is regulated to 750W, the sputtering time is 10h, the other conditions are unchanged, and an AlScN piezoelectric functional layer is formed on the surface of the substrate by deposition.
Example 11
Example 11 differs from example 2 in that: vacuum is adjusted to 5 multiplied by 10 -3 Pa, adjusting the sputtering time to 9h, and depositing an AlScN piezoelectric functional layer on the surface of the substrate under the same other conditions.
Example 12
Example 12 differs from example 2 in that: adjustment ofThe temperature of the vacuum chamber is 100 ℃, and the vacuum pumping is adjusted to 4 multiplied by 10 - 3 Pa, adjusting sputtering time to 7h, and depositing an AlScN piezoelectric functional layer on the surface of the substrate under the same other conditions.
Example 13
Example 13 differs from example 2 in that: vacuum-pumping is adjusted to 7 multiplied by 10 -3 Pa, the sputtering time is adjusted to be 3h respectively, the rest conditions are unchanged, and an AlScN piezoelectric functional layer is deposited on the surface of the substrate.
Examples 14 and 15
Examples 14 and 15 differ from example 2 in that: vacuum is adjusted to 4 multiplied by 10 -3 Pa, adjusting the target base distance to be 60mm and 70mm respectively, adjusting the sputtering time to be 5h and 9h respectively, and depositing an AlScN piezoelectric functional layer on the surface of the substrate under the same conditions.
Performance testing
XRD pattern of (one) coating
FIG. 2 shows XRD patterns of AlScN piezoelectric functional layers deposited under different air pressures according to examples 1 to 5 of the present invention. As can be seen from the figure, when the deposition air pressure is 0.4Pa, the diffraction peak of (002) is not generated in the film, only the diffraction peak of (103) is generated, and the preferential orientation growth of the c axis is not shown, because the deposition air pressure is low, the average free path of particles is large, the particles have higher energy, the surface of the film can be bombarded by high-energy Al, sc and N particles, the structure of the surface is damaged, and the growth orientation of the film is changed, so that the growth orientation of the film is shown as the growth orientation of (103). As the deposition gas pressure increases to 0.6Pa, the diffraction peak of (002) appears in the XRD pattern of the film, which is shown as a high c-axis preferential growth orientation, because at this deposition gas pressure, the energy of the particles optimally migrates and rearranges, so that the film has the most remarkable c-axis preferential growth. With further increase of the sputtering air pressure from 1.0Pa to 2.0Pa, the grain size of the film surface gradually decreases, and diffraction peaks of (002) and (103) appear in the film, because the lower mean free path causes the particles to have lower energy, so that the grain size of the particles gradually decreases, the intensity of the (002) diffraction peak of the film gradually increases, and the intensity of the (103) diffraction peak gradually decreases.
Surface topography of (II) coating
Fig. 3 is a graph showing examples 2, 14 and 15 of surface and topography of the AlScN coating prepared at different target pitches, which can be seen to have a significant effect on the surface topography of the AlScN film, when the deposition gas pressure was 55mm, the film exhibited a clearer grain size and a distinct grain boundary, and as the target pitch increased to 60mm, the grain size of the surface of the film increased, which is the grain size that incorporated between the deposited grains to a larger size as the target pitch increased. As the target matrix distance continues to increase, the kinetic energy of the particles is insufficient to deposit over a greater distance such that they grow in a manner that appears as a stack of clusters, and as the deposition process continues, the number of atoms deposited on the substrate surface increases, and the gaps between clusters are filled, such that the surface of the film exhibits a "corrugated" growth morphology. The section morphology of the film shows that no cracking and cracking occur between the film and the substrate, and the bonding force is good; the thin film exhibited significant columnar grain growth when the target pitch of deposition was 55mm, and the columnar grain structure thereof began to become insignificant when the target pitch was 70mm, due to the cluster stack growth thereof.
(III) hardness and wear resistance test
Fig. 4 shows the hardness data of the nano hardness test of the AlScN piezoelectric functional layers obtained in examples 1, 2 and 5 of the present invention under different air pressures, and it can be seen from the graph that the AlScN coatings prepared in examples 1, 2 and 5 all have high hardness, and the hardness is greater than 15GPa. Furthermore, the AlScN piezoelectric functional layer prepared in example 2 under the condition of the air pressure of 0.6Pa had significantly higher hardness than those of examples 1 and 5, and the hardness thereof was as high as 20GPa.
Further, FIG. 5 is an SEM image and element composition change of AlScN piezoelectric functional layers prepared under deposition pressure of 0.4Pa-2.0Pa according to examples 1-5 of the present invention by performing wire sweep after a frictional wear test (loading 50g of Cu-Zn alloy balls for 30 min). It can be seen from the graph that after the above-mentioned friction and abrasion experiments, no significant abrasion was caused to the AlScN piezoelectric functional layers prepared in examples 1 to 5, and the AlScN coating prepared in example 2 had the narrowest abrasion mark, which indicates that the coatings prepared in examples 1 to 5 all had good abrasion resistance, and the AlScN coating prepared in example 2 had stronger abrasion resistance. In addition, the bonding strength between the AlScN piezoelectric functional layer and the matrix is tested, and test results show that the bonding strength between the AlScN piezoelectric functional layer and the matrix prepared by the embodiments of the invention exceeds 10MPa.
(IV) excitation Performance test
Electrodes were prepared by depositing electrode layers (including Cr, ag, ti, ag-Cr, etc.) or spot-coating silver paste on the surfaces of AlScN piezoelectric functional layers prepared in examples 1 to 5, and excitation performance tests were performed.
FIG. 6 is a waveform chart showing different ultrasonic waves excited by AlScN piezoelectric functional layers obtained under different air pressures in examples 1 to 5 of the present invention. It can be seen from the figure that the waveform is mainly transverse wave (SW) when the deposition air pressure is 0.4Pa, the waveform is mainly Longitudinal Wave (LW) when the deposition air pressure is 0.6Pa, and the waveform is a transverse-longitudinal mixed waveform when the deposition air pressure is 1.0-2.0 Pa, and the various waveforms can satisfy defect detection and stress measurement of steel plates, welding seams, steel pipes and the like in solid, liquid and medium in gas.
FIG. 7 is a graph showing the ultrasonic wave patterns excited by AlScN piezoelectric coatings obtained under different deposition time conditions in examples 2, 11, and 13 of the present invention; as can be seen from the figure, the increase of the deposition time does not change the ultrasonic signal excited by the film, the film excites ultrasonic longitudinal wave signals, and the amplitude of the ultrasonic signal is gradually increased along with the increase of the deposition time, which is related to the structure of the film with (002) diffraction crystal face, the film with (002) diffraction crystal face can excite ultrasonic longitudinal wave, and the intensity of (002) diffraction peak is gradually increased along with the increase of the deposition time, so that the ultrasonic signal excited by the prepared AlScN film is also gradually increased.
(V) high temperature resistance test
FIG. 8 is an XRD pattern and an ultrasonic waveform of a sample obtained in example 2 of the present invention after annealing an AlScN piezoelectric functional layer at 600℃for various times under a deposition pressure of 0.6 Pa. As is evident from the figure, 600 ℃ does not affect the orientation of the sample and the ultrasound signal.
Fig. 9 is a graph showing the morphology of a sample after annealing at 600 ℃ for different times of the AlScN piezoelectric functional layer obtained in example 2 of the present invention under the condition that the deposition air pressure is 0.6Pa, and it can be clearly seen from the graph that the surface morphology of the sample is not damaged at 600 ℃.
The experimental junction shows that the AlScN piezoelectric functional layer prepared by the method can be used for a long time at high temperature, and can meet the use requirement of a working temperature range of-196-700 ℃.
Application example
The application example adopts a high-temperature alloy bolt with the length of 50mm as a matrix, and an AlScN piezoelectric coating material is deposited on the surface of the matrix, so that the intelligent bolt with high mechanical and high temperature resistance performance and different ultrasonic waves can be excited is prepared. The preparation method of the intelligent bolt comprises the following steps:
step 1: controlling the distance between the target and the matrix to be 40-80 mm, and vacuumizing to 3X 10 at 100-150 DEG C -3 ～7×10 -3 Pa, introducing 50sccm argon (purity 99.99%), starting bias voltage and arc power supply, and performing plasma etching on the substrate under the conditions of-150V, duty ratio 80%, air pressure 0.5Pa and current 70A to remove impurities attached to the surface of the substrate and improve the bonding force of the film layer and the substrate;
step 2: after etching, preparing a bonding layer Cr on the bolt substrate under the condition of 0.5-1 Pa and 50-250V bias voltage, so that the internal stress can be eliminated, the bonding force between the coating and the substrate can be increased, and the thickness of the bonding layer is about 500nm;
step 3: after the preparation of the bonding layer, vacuumizing to 3X 10 at 100-150 DEG C -3 ～7×10 -3 Pa, the position of the control bolt is opposite to the center of the target, mixed gas of argon (purity 99.99%) and nitrogen (purity 99.99%) is introduced, the flow ratio of the argon to the nitrogen is from 3:1-1:3, the air pressure in the cavity is 0.4 Pa-3 Pa, a radio frequency power supply is started, the sputtering power is 700W-900W, the sputtering time is 3 h-10 h, and an AlScN piezoelectric functional layer is formed;
step 4: after the AlScN piezoelectric functional layer is prepared, depositing an electrode layer under the conditions of 0.25-1 Pa, 0-100V bias and 0-80A current, wherein the electrode layer is selected from one of Ag, ag-Cr and Ti; after the preparation is finished, naturally cooling to room temperature, and obtaining the intelligent bolt which has high mechanical and high temperature resistance and can excite different ultrasonic waves on the surface of the matrix.
FIG. 10 shows ultrasonic waveforms excited by an intelligent bolt prepared under the conditions of 0.6Pa of deposition air pressure, 60mm of target base distance and 7 hours of deposition time, wherein the excited waveforms mainly comprise ultrasonic Longitudinal Waves (LW).
The above application example only uses a superalloy bolt substrate as an example, and the preparation method of the AlScN piezoelectric coating material is also applicable to substrates such as stainless steel, aluminum, hard alloy, titanium and the like, and is not limited herein.
The foregoing is merely illustrative of the preferred embodiments of the present invention and is not intended to limit the embodiments and scope of the present invention, and it should be appreciated by those skilled in the art that equivalent substitutions and obvious variations may be made using the teachings of the present invention, which are intended to be included within the scope of the present invention.

Claims (10)

1. The preparation method of the AlScN piezoelectric coating material with high mechanical property and high temperature resistance is characterized by comprising the following steps: an AlScN piezoelectric functional layer is formed on the surface of a matrix by adopting an alloy target material composed of Al and Sc through magnetron sputtering;
in the magnetron sputtering, the temperature is 100-250 ℃, mixed gas of argon and nitrogen in a volume ratio of 3:1-1:3 is introduced, the sputtering power is 700-900W, the deposition air pressure P=0.4-3.0 Pa, the target base distance d=40-80 mm, and the deposition time is 3-10 h.
2. The method of claim 1, wherein the alloy target consists of 60wt.% to 90wt.% Al and 10 wt.% to 40wt.% Sc.
3. The method according to claim 1, wherein the diameter of the alloy target is 140-160 mm and the thickness of the alloy target is 4-8 mm.
4. The method according to claim 1, wherein the growth orientation of the AlScN piezoelectric functional layer on the substrate surface comprises (002) diffraction crystal plane and/or (103) diffraction crystal plane.
5. The method according to claim 1, wherein the AlScN piezoelectric functional layer has a thickness of 5 to 20. Mu.m.
6. The method of claim 1, wherein a bonding layer is deposited on the surface of the substrate, an AlScN piezoelectric functional layer is deposited on the surface of the bonding layer, and an electrode layer is deposited on the surface of the AlScN piezoelectric functional layer.
7. The method of manufacturing according to claim 6, comprising the steps of:
s1, carrying out plasma etching on the surface of a substrate in an argon atmosphere at the temperature of 100-250 ℃;
s2, depositing a Cr binding layer on the surface of the substrate subjected to plasma etching at 0.5-1 Pa and 50-250V;
s3, forming an AlScN piezoelectric functional layer on the surface of the Cr bonding layer by adopting an alloy target material composed of Al and Sc through magnetron sputtering;
and S4, depositing an electrode layer on the surface of the AlScN piezoelectric functional layer under the conditions of 0.25-1 Pa of vacuum degree, 0-100V of bias voltage and 0-80A of current, thus completing the preparation of the AlScN piezoelectric coating material.
8. An AlScN piezoelectric coating material having high mechanical properties and high temperature resistance, characterized in that it is produced by the production method according to any one of claims 1 to 7; the AlScN piezoelectric coating material consists of a bonding layer, an AlScN piezoelectric functional layer and an electrode layer.
9. The AlScN piezoelectric coating material of claim 8, wherein the hardness of the AlScN piezoelectric functional layer is 15-20 GPa, the bonding strength with the substrate is more than 10MPa, and the working temperature range is-196-700 ℃.
10. Use of an AlScN piezoelectric coating material of high mechanical properties and high temperature resistance as claimed in claim 8 or 9, characterized in that the AlScN piezoelectric coating material excites various ultrasonic waveforms for the pretension detection of bolts or for the defect detection and stress measurement of steel plates, welds, steel pipes.
CN202311213045.2A 2023-09-19 2023-09-19 AlScN piezoelectric coating material with high mechanical property and high temperature resistance, and preparation method and application thereof Pending CN117328026A (en)

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