技术领域Technical field
本发明涉AlN超声波传感器技术领域，特别涉及一种AlN超声波传感器、制备方法及其应用。The present invention relates to the technical field of AlN ultrasonic sensors, and in particular to an AlN ultrasonic sensor, a preparation method and its application.
背景技术Background technique
AlN因其具备较高的使用温度(居里温度～2800℃)，因而成为高温探头的主要选择，而且与常用的锆钛酸铅(PZT)相比，AlN具有生物相容性和金属氧化物半导体(CMOS)兼容性。已有文献利用射频溅射的方式，在铝合金和低碳钢基体上沉积制备出可以在600℃～900℃条件下长时间使用的高温超声传感器；也有报道表明通过射频溅射沉积直接在常用工程材料上制备的c轴取向AlN薄膜，证实其是高温无损检测应用的一种有前途、有效的超声换能器。AlN has become the main choice for high-temperature probes due to its high operating temperature (Curie temperature ~ 2800°C). Moreover, compared with the commonly used lead zirconate titanate (PZT), AlN has biocompatibility and metal oxide Semiconductor (CMOS) compatibility. There are existing literatures that use radio frequency sputtering to deposit on aluminum alloy and low carbon steel substrates to prepare high-temperature ultrasonic sensors that can be used for a long time at 600°C to 900°C. There are also reports that use radio frequency sputtering to deposit directly on commonly used sensors. The c-axis oriented AlN film prepared on engineering materials confirms that it is a promising and effective ultrasonic transducer for high-temperature non-destructive testing applications.
然而当前罕有在硬质合金上制备AlN传感器的先例，也缺乏对纵横波能量占比的调控研究，以及耐高温、抗氧化、防扩散的电极材料的研究。However, there are currently few precedents for preparing AlN sensors on cemented carbide, and there is also a lack of research on the control of the proportion of longitudinal and transverse wave energy, as well as research on high-temperature-resistant, oxidation-resistant, and anti-diffusion electrode materials.
发明内容Contents of the invention
为了解决现有技术存在的问题，本发明提供了一种AlN超声波传感器的制备方法，包括，In order to solve the problems existing in the prior art, the present invention provides a method for preparing an AlN ultrasonic sensor, including:
步骤一：衬底前期准备：先采用砂纸打磨衬底，获得粗质表面，利于增强涂层与衬底的结合，防止高温环境中涂层与衬底分离，再采用离子束刻蚀方式进行清洁得到预处理的衬底，离子束刻蚀可以除去可见颗粒物，降低涂层脱落风险；Step 1: Preliminary preparation of the substrate: first use sandpaper to polish the substrate to obtain a rough surface, which will help enhance the bonding between the coating and the substrate and prevent separation of the coating and the substrate in high temperature environments, and then use ion beam etching to clean it. Obtain a pre-treated substrate, and ion beam etching can remove visible particles and reduce the risk of coating peeling;
步骤二：沉积AlON非晶涂层和AlN压电涂层：使用磁控溅射法，开始沉积时腔内氧含量为1.26×10-3Pa～1.89×10-3Pa，调整沉积参数在预处理的衬底表面依次形成AlON非晶涂层和AlN压电涂层，所述参数包括轴向距离(即衬底距离溅射中心的距离)、靶基距离、射频功率、环境温度、腔内气压、Ar/N2的流量比和沉积时间中的至少一种；Step 2: Deposit AlON amorphous coating and AlN piezoelectric coating: Use magnetron sputtering method. When starting deposition, the oxygen content in the cavity is 1.26×10-3 Pa ~ 1.89×10-3 Pa. Adjust the deposition parameters in advance. The treated substrate surface is sequentially formed with an AlON amorphous coating and an AlN piezoelectric coating. The parameters include the axial distance (i.e., the distance between the substrate and the sputtering center), target base distance, radio frequency power, ambient temperature, and chamber temperature. At least one of gas pressure, flow ratio of Ar/N2 and deposition time;
步骤三：在AlN压电涂层表面制备电极层，得到AlN超声波传感器。Step 3: Prepare an electrode layer on the surface of the AlN piezoelectric coating to obtain an AlN ultrasonic sensor.
进一步地，步骤一中，所述衬底包括硬质合金、不锈钢、螺栓、硅片中的一种；Further, in step one, the substrate includes one of cemented carbide, stainless steel, bolts, and silicon wafers;
进一步地，步骤一中，打磨具体为，在研磨机上，先用400～600目的粗砂纸砂纸在300～500r/min的转速下打磨1～3min，除去衬底表面的杂质，再用1200～2000目的细砂纸在200～350r/min的转速下打磨2～5min，获得粗糙度适当的粗质表面，增强涂层与衬底的结合；Further, in step one, the grinding is specifically as follows: first use 400-600 mesh coarse sandpaper on a grinder to grind for 1-3 minutes at a rotation speed of 300-500 r/min to remove impurities on the surface of the substrate, and then use 1200-2000 grit sandpaper to grind the surface of the substrate. Purpose: Polish with fine sandpaper for 2 to 5 minutes at a speed of 200 to 350 r/min to obtain a rough surface with appropriate roughness and enhance the bonding between the coating and the substrate;
进一步地，步骤二中，所述沉积参数具体包括，轴向距离为0～6cm、靶基距离为3～10cm、射频功率700～900W、温度30～250℃、总气流0.8～3.0Pa、Ar和N2的流量比1/2～2/1、时间4～20h。Further, in step 2, the deposition parameters specifically include: axial distance is 0~6cm, target-base distance is 3~10cm, radio frequency power is 700~900W, temperature is 30~250°C, total air flow is 0.8~3.0Pa, Ar The flow ratio to N2 is 1/2 to 2/1, and the time is 4 to 20 hours.
进一步地，步骤二中，所述腔内氧含量可以通过真空度控制，而真空度通过机械泵、分子泵的抽气时长决定，抽气时长为1h时，真空度达到9×10-3Pa，腔内氧含量为1.89×10-3Pa；抽气时长为1.5h时，真空度达到6×10-3Pa，腔内氧含量为1.26×10-3Pa。Further, in step two, the oxygen content in the cavity can be controlled by the vacuum degree, and the vacuum degree is determined by the pumping time of the mechanical pump and the molecular pump. When the pumping time is 1 hour, the vacuum degree reaches 9×10-3 Pa. , the oxygen content in the cavity is 1.89×10-3 Pa; when the pumping time is 1.5h, the vacuum degree reaches 6×10-3 Pa, and the oxygen content in the cavity is 1.26×10-3 Pa.
进一步地，步骤二中，由于沉积初期腔室内存在一定残余氧气，氧含量为1.26×10-3Pa～1.89×10-3Pa，会优先生成0.5～5μm厚AlON非晶层(AlON具备耐高温性能和抗化学腐蚀性能，可在一定程度上提升传感器恶劣工况下的稳定性)，随着沉积时间增多，腔内氧气逐渐消耗，开始生成AlN压电涂层，AlN压电涂层厚2～20μm。Furthermore, in step two, since there is a certain amount of residual oxygen in the chamber at the initial stage of deposition, and the oxygen content is 1.26×10-3 Pa ~ 1.89 × 10-3 Pa, a 0.5 ~ 5 μm thick AlON amorphous layer will be generated preferentially (AlON has high temperature resistance performance and chemical corrosion resistance, which can improve the stability of the sensor under harsh working conditions to a certain extent). As the deposition time increases, the oxygen in the cavity gradually consumes, and the AlN piezoelectric coating begins to form. The thickness of the AlN piezoelectric coating is 2 ~20μm.
进一步地，电极层使用银浆点涂法、AB胶与碳粉混合法、第一沉积法中的一种方法制备得到；Further, the electrode layer is prepared by one of the methods of silver paste dispensing method, AB glue and carbon powder mixing method, and first deposition method;
银浆点涂法包括，将银浆涂覆于AlN压电涂层表面，固化得到厚50μm～500μm的电极层；The silver paste spot coating method includes coating the silver paste on the surface of the AlN piezoelectric coating and curing to obtain an electrode layer with a thickness of 50 μm to 500 μm;
AB胶与碳粉混合法包括，将耐高温A、耐高温B胶和碳粉以质量比1～2：1：1～5混合后涂覆于AlN压电涂层表面，固化得到厚50μm～500μm的电极层；The mixing method of AB glue and carbon powder includes mixing high-temperature resistant A glue, high-temperature resistant B glue and carbon powder in a mass ratio of 1 to 2:1:1 to 5, then applying it to the surface of the AlN piezoelectric coating, and curing to obtain a thickness of 50 μm~ 500μm electrode layer;
第一沉积法包括，The first deposition method includes,
S1、使用电弧离子镀，固定衬底与Cr靶材的相对位置，调整靶基距离为10～15cm、电流90～100A、Ar气流0.8～1.5Pa，时间0.5～1min，在AlN压电涂层表面沉积10～200nm厚的第一Cr层；S1. Use arc ion plating to fix the relative position of the substrate and Cr target, adjust the distance between the target and the target to 10~15cm, the current 90~100A, the Ar gas flow 0.8~1.5Pa, the time 0.5~1min, and the AlN piezoelectric coating is The first Cr layer with a thickness of 10~200nm is deposited on the surface;
S2、采用电弧离子镀与磁控溅射相结合的方式，旋转样品架，在第一Cr层表面沉积1～2μm的第一Cr和Ag复合层；S2. Use a combination of arc ion plating and magnetron sputtering to rotate the sample holder and deposit a 1 to 2 μm first Cr and Ag composite layer on the surface of the first Cr layer;
S3、采用磁控溅射法，固定衬底与Ag靶材的相对位置，调整靶基距离为5～10cm、射频功率500～900W、温度30～50℃、Ar气流0.8～1.5Pa、时间5～30min，在第一Cr和Ag复合层表面沉积5～30μm的第一Ag层。S3. Use the magnetron sputtering method to fix the relative position of the substrate and the Ag target. Adjust the target distance to 5 to 10 cm, RF power to 500 to 900 W, temperature to 30 to 50°C, Ar gas flow to 0.8 to 1.5 Pa, and time to 5 ~30 minutes, deposit a first Ag layer of 5~30 μm on the surface of the first Cr and Ag composite layer.
进一步地，还在带有AlN压电涂层的衬底的背面使用第二沉积法制备保护层，保护层可以隔绝氧气，抑制高温环境中氧气对衬底的破坏，提高高温环境下传感器的抗氧化性能，使得所制备的传感器经900℃高温处理，超声信号依然处于可用范围。Furthermore, a second deposition method is used to prepare a protective layer on the back of the substrate with an AlN piezoelectric coating. The protective layer can isolate oxygen, inhibit the damage of oxygen to the substrate in high-temperature environments, and improve the resistance of the sensor in high-temperature environments. Due to its oxidation properties, the ultrasonic signal of the prepared sensor is still within the usable range after being processed at a high temperature of 900°C.
进一步地，所述第二沉积法包括，Further, the second deposition method includes,
T1、使用电弧离子镀，固定衬底与Cr靶材的相对位置，调整靶基距离为10～15cm、电流90～100A、Ar气流0.8～1.5Pa，时间0.5～1min，在带有AlN压电涂层的衬底的背面沉积10～200nm厚的第二Cr层；T1. Use arc ion plating, fix the relative position of the substrate and Cr target, adjust the target distance to 10~15cm, current 90~100A, Ar gas flow 0.8~1.5Pa, time 0.5~1min, with AlN piezoelectric A second Cr layer with a thickness of 10 to 200 nm is deposited on the back side of the coated substrate;
T2、采用电弧离子镀与磁控溅射相结合的方式，旋转样品架，在第二Cr层表面沉积1～2μm的第二Cr和Ag复合层；T2. Use a combination of arc ion plating and magnetron sputtering to rotate the sample holder and deposit a 1-2 μm second Cr and Ag composite layer on the surface of the second Cr layer;
T3、采用磁控溅射法，固定衬底与Ag靶材的相对位置，调整靶基距离为5～10cm、射频功率500～900W、温度30～50℃、Ar气流0.8～1.5Pa、时间1～10min，在第二Cr和Ag复合层表面沉积1～10μm的第二Ag层。T3. Use the magnetron sputtering method to fix the relative position of the substrate and the Ag target. Adjust the target distance to 5 to 10 cm, RF power to 500 to 900 W, temperature to 30 to 50°C, Ar gas flow to 0.8 to 1.5 Pa, and time to 1 ~10 min, deposit a second Ag layer of 1 ~ 10 μm on the surface of the second Cr and Ag composite layer.
步骤S1或步骤T2具体包括，Step S1 or step T2 specifically includes:
将Cr靶材与Ag靶材相邻放置，将带有AlN压电涂层衬底的表面或带有AlN压电涂层的衬底的背面介于Cr靶材与Ag靶材中垂线的交点，样品架保持旋转，使得Cr与Ag束流可以均匀地到达带有AlN压电涂层衬底的表面或带有AlN压电涂层的衬底的背面，沉积Cr的具体参数为靶基距离为10～15cm、电流90～100A、Ar气流0.8～1.5Pa、时间10～20min；沉积Ag的具体参数为靶基距离为5～10cm、射频功率500～900W、温度30～50℃、Ar气流0.8～1.5Pa、时间10～20min。Place the Cr target and Ag target adjacent to each other, and place the surface of the substrate with AlN piezoelectric coating or the back side of the substrate with AlN piezoelectric coating between the perpendicular line between the Cr target and the Ag target. At the intersection point, the sample holder keeps rotating so that the Cr and Ag beams can evenly reach the surface of the substrate with AlN piezoelectric coating or the back side of the substrate with AlN piezoelectric coating. The specific parameters for depositing Cr are the target base The distance is 10~15cm, the current is 90~100A, the Ar gas flow is 0.8~1.5Pa, the time is 10~20min; the specific parameters for depositing Ag are the target-base distance is 5~10cm, the radio frequency power is 500~900W, the temperature is 30~50℃, Ar Air flow 0.8~1.5Pa, time 10~20min.
本发明也提供了一种AlN超声波传感器，使用上述的AlN超声波传感器的制备方法制备而成，包括非晶层AlON、压电层AlN、表面电极层、背面复合保护层，电极层涉及到银浆、AB胶与导电金属材料以及第一沉积法制备的复合电极涂层。The invention also provides an AlN ultrasonic sensor, which is prepared using the above-mentioned preparation method of the AlN ultrasonic sensor, and includes an amorphous layer AlON, a piezoelectric layer AlN, a surface electrode layer, and a back composite protective layer. The electrode layer involves silver paste. , AB glue and conductive metal materials and the composite electrode coating prepared by the first deposition method.
本发明还提供了上述的AlN超声波传感器在温度测量的应用。The present invention also provides the application of the above-mentioned AlN ultrasonic sensor in temperature measurement.
相对于现有技术，本发明具有以下的有益效果：Compared with the prior art, the present invention has the following beneficial effects:
1、本发明对于衬底的预处理，首先采用砂纸打磨衬底，获得粗质表面，一方面除去衬底表面的杂质，同时粗质表面利于增强AlN与衬底的结合，防止高温环境中涂层与衬底分离；1. In the present invention, for the pretreatment of the substrate, the substrate is first polished with sandpaper to obtain a rough surface. On the one hand, the impurities on the surface of the substrate are removed. At the same time, the rough surface is conducive to enhancing the combination of AlN and the substrate and preventing coating in high temperature environments. Separation of layers from substrate;
2、本发明可以通过调控衬底与靶材的相对位置(即靶基距离和轴向距离共同作用)，以获得沿不同方向生长的压电涂层，进而调控纵横波的能量占比，还能通过调控射频功率、环境温度、腔内气压、Ar/N2的流量比、沉积时间等工艺参数，调控纵波、横波的信号幅值；2. The present invention can obtain piezoelectric coatings that grow in different directions by regulating the relative position of the substrate and the target (that is, the target-base distance and the axial distance work together), thereby regulating the energy proportion of longitudinal and transverse waves, and also It can control the signal amplitude of longitudinal and transverse waves by adjusting process parameters such as RF power, ambient temperature, chamber pressure, Ar/N2 flow ratio, and deposition time;
3、本发明在衬底与AlN压电涂层间包含了一层AlON非晶层，AlON具备耐高温性能和抗化学腐蚀性能，可在一定程度上提升传感器恶劣工况下的稳定性；3. The present invention includes a layer of AlON amorphous layer between the substrate and the AlN piezoelectric coating. AlON has high temperature resistance and chemical corrosion resistance, which can improve the stability of the sensor under harsh working conditions to a certain extent;
4、本发明采用第一沉积法制备的复合电极涂层包含Cr涂层、Cr和Ag的多层复合结构、Ag涂层，而Cr和Ag的多层复合结构相当于在纯Ag涂层与纯Cr涂层间加了一层两者的多层复合过渡层，使得涂层间结合良好，同时Ag粒子难以穿透进入AlN压电层内，削弱了对压电材料结构与压电性能的破坏，同时抑制高温下电极元素扩散现象；4. The composite electrode coating prepared by the first deposition method of the present invention includes a Cr coating, a multi-layer composite structure of Cr and Ag, and an Ag coating. The multi-layer composite structure of Cr and Ag is equivalent to the combination of pure Ag coating and A multi-layer composite transition layer of the two is added between the pure Cr coatings, which makes the coatings well bonded. At the same time, it is difficult for Ag particles to penetrate into the AlN piezoelectric layer, weakening the effect on the piezoelectric material structure and piezoelectric properties. Destruction, while inhibiting the diffusion of electrode elements at high temperatures;
5、本发明的AlN超声波传感器，在衬底背面也沉积了复合保护层，复合保护层包含Cr涂层、Cr和Ag的多层复合结构、Ag涂层，隔绝氧气，抑制高温环境中氧气对衬底的破坏，提高高温环境下传感器的抗氧化性能；5. The AlN ultrasonic sensor of the present invention also deposits a composite protective layer on the back of the substrate. The composite protective layer includes a Cr coating, a multi-layer composite structure of Cr and Ag, and an Ag coating, which isolates oxygen and inhibits the impact of oxygen in high-temperature environments. Destruction of the substrate improves the oxidation resistance of the sensor in high temperature environments;
6、本发明制备的传感器经900℃高温处理，超声信号依然处于可用范围，AlN传感器同时具备优异的高低温热疲劳性能，可以经历多次高温与低温的往复循环，且从800℃～900℃高温降回室温后，超声信号能快速恢复。6. The sensor prepared by the present invention has been processed at a high temperature of 900°C, and the ultrasonic signal is still within the usable range. The AlN sensor has excellent high and low temperature thermal fatigue performance at the same time, and can experience multiple reciprocating cycles of high and low temperatures, and can range from 800°C to 900°C. After the high temperature drops back to room temperature, the ultrasonic signal can be quickly restored.
附图说明Description of drawings
为了更清楚地说明本发明实施例或现有技术中的技术方案，下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图是本发明的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图。In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed to be used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings in the following description are: For some embodiments of the present invention, those of ordinary skill in the art can also obtain other drawings based on these drawings without exerting creative efforts.
图1示出了通过靶基距离和轴向距离共同作用调控AlN压电涂层沉积的示意图；Figure 1 shows a schematic diagram of controlling the deposition of AlN piezoelectric coating through the combined action of target base distance and axial distance;
图2示出了本发明的一些优选的实施方式中AlN超声波传感器的结构示意图；Figure 2 shows a schematic structural diagram of an AlN ultrasonic sensor in some preferred embodiments of the present invention;
图3示出了本发明的一些优选的实施方式中在第一Cr层表面沉积第一Cr和Ag复合层的示意图；Figure 3 shows a schematic diagram of depositing the first Cr and Ag composite layer on the surface of the first Cr layer in some preferred embodiments of the present invention;
图4示出了本发明实施例1制备的AlN超声波传感器的超声信号图；Figure 4 shows the ultrasonic signal diagram of the AlN ultrasonic sensor prepared in Example 1 of the present invention;
图5示出了本发明实施例2制备的AlN超声波传感器的超声信号图；Figure 5 shows the ultrasonic signal diagram of the AlN ultrasonic sensor prepared in Embodiment 2 of the present invention;
图6示出了本发明实施例3制备的AlN超声波传感器的超声信号图；Figure 6 shows the ultrasonic signal diagram of the AlN ultrasonic sensor prepared in Embodiment 3 of the present invention;
图7(a)示出了本发明实施例4中在溅射中心制备的AlN压电涂层表面的SEM图像，图7(b)示出了本发明实施例4中在溅射中心制备的AlN压电涂层截面的SEM图像，图7(c)为本发明实施例4中在距离溅射中心5cm处的截面SEM图像和氧原子占比，图7(d)为本发明实施例4中在距离溅射中心0cm、3cm、5cm处的XRD图谱，图7(e)为本发明实施例4中在距离溅射中心0cm、3cm、5cm处的制备的传感器激发的超声波信号，图7(f)为本发明实施例4中在距离溅射中心0cm处的介电常数和介电损耗数值；Figure 7(a) shows the SEM image of the surface of the AlN piezoelectric coating prepared at the sputtering center in Example 4 of the present invention, and Figure 7(b) shows the SEM image of the surface of the AlN piezoelectric coating prepared at the sputtering center in Example 4 of the present invention. SEM image of the cross-section of the AlN piezoelectric coating. Figure 7(c) is the cross-sectional SEM image at 5 cm from the sputtering center and the proportion of oxygen atoms in Example 4 of the present invention. Figure 7(d) is Example 4 of the present invention. The XRD patterns at 0cm, 3cm, and 5cm from the sputtering center, Figure 7(e) are the ultrasonic signals excited by the sensor prepared at 0cm, 3cm, and 5cm from the sputtering center in Example 4 of the present invention, Figure 7 (f) is the dielectric constant and dielectric loss value at a distance of 0 cm from the sputtering center in Example 4 of the present invention;
图8(a)示出了本发明实施例5的AlN超声波传感器在温度30、200、400、600、800℃时的超声信号，图8(b)示出了本发明实施例5的AlN超声波传感器在温度30、200、400、600、800℃时横波与纵波的飞行时间；Figure 8(a) shows the ultrasonic signals of the AlN ultrasonic sensor in Embodiment 5 of the present invention at temperatures of 30, 200, 400, 600, and 800°C. Figure 8(b) shows the AlN ultrasonic sensor in Embodiment 5 of the present invention. The flight time of transverse waves and longitudinal waves when the sensor is at temperatures of 30, 200, 400, 600, and 800 degrees Celsius;
图9(a)示出了本发明实施例5的AlN超声波传感器在进行二次退火时在温度30、200、400、600、700℃时的超声信号，图9(b)示出了本发明实施例5的AlN超声波传感器在进行二次退火时温度30、200、400、600、700℃时横波与纵波的飞行时间；Figure 9(a) shows the ultrasonic signals of the AlN ultrasonic sensor in Embodiment 5 of the present invention at temperatures of 30, 200, 400, 600 and 700°C during secondary annealing. Figure 9(b) shows the present invention. Flight times of transverse waves and longitudinal waves at temperatures of 30, 200, 400, 600, and 700°C for the AlN ultrasonic sensor of Example 5 during secondary annealing;
图10(a)示出了实施例6的AlN超声波传感器在温度30、400、800℃时的超声信号，图10(b)示出了实施例6的AlN超声波传感器在不同温度时横波与纵波的TOF，图10(c)为实施例6的AlN超声波传感器的纵横波幅值随退火温度的变化，图10(d)为实施例6的AlN超声波传感器的电阻率随退火温度的变化；Figure 10(a) shows the ultrasonic signals of the AlN ultrasonic sensor in Example 6 at temperatures of 30, 400, and 800°C. Figure 10(b) shows the transverse and longitudinal waves of the AlN ultrasonic sensor in Example 6 at different temperatures. TOF, Figure 10(c) shows the change of the longitudinal and transverse wave amplitudes of the AlN ultrasonic sensor of Example 6 with the annealing temperature, and Figure 10(d) shows the change of the resistivity of the AlN ultrasonic sensor of Example 6 with the annealing temperature;
图11示出了本发明对比例1中涂层截面的SEM图像；Figure 11 shows an SEM image of the cross-section of the coating in Comparative Example 1 of the present invention;
图12示出了本发明对比例2中涂层截面的SEM图像；Figure 12 shows an SEM image of the cross-section of the coating in Comparative Example 2 of the present invention;
附图标记说明：Explanation of reference symbols:
1、衬底；2、AlON非晶涂层；3、AlN压电涂层；4、第一Cr层；4’、第二Cr层；5、第一Cr和Ag复合层；5’、第二Cr和Ag复合层；6、第一Ag层；6’、第二Ag层；7、Al靶材；8、带有第一Cr层的衬底；9、样品架、10、支撑架；11、纯Cr靶材；12、纯Ag靶材。1. Substrate; 2. AlON amorphous coating; 3. AlN piezoelectric coating; 4. First Cr layer; 4', second Cr layer; 5. First Cr and Ag composite layer; 5', third Two Cr and Ag composite layers; 6. First Ag layer; 6', second Ag layer; 7. Al target; 8. Substrate with first Cr layer; 9. Sample holder, 10. Support frame; 11. Pure Cr target material; 12. Pure Ag target material.
具体实施方式Detailed ways
在本发明中所披露的范围的端点和任何值都不限于该精确的范围或值，这些范围或值应当理解为包含接近这些范围或值的值。对于数值范围来说，各个范围的端点值之间、各个范围的端点值和单独的点值之间，以及单独的点值之间可以彼此组合而得到一个或多个新的数值范围，这些数值范围应被视为在本发明中具体公开。本发明中所使用的原料，如无特殊说明，均为常规的市售产品；本发明中所使用的方法，如无特殊说明，均为本领域的常规方法。The endpoints of ranges and any values disclosed in this disclosure are not limited to the precise range or value, but these ranges or values are to be understood to include values approximating those ranges or values. For numerical ranges, the endpoint values of each range, the endpoint values of each range and individual point values, and the individual point values can be combined with each other to obtain one or more new numerical ranges. These values Ranges should be considered to be specifically disclosed in this disclosure. The raw materials used in the present invention, unless otherwise specified, are all conventional commercially available products; the methods used in the present invention, unless otherwise specified, are conventional methods in the field.
本发明首先基于磁控溅射制备AlN的各种参数调整，研究各种参数对于超声信号的影响，参数包括轴向距离、靶基距离、射频功率、环境温度、腔内气压、Ar/N2的流量比和沉积时间中的至少一种。图1示出了通过靶基距离和轴向距离共同作用调控AlN压电涂层沉积的示意图，在样品架9上放置1A、1B、1C、1D、1E轴向距离不同的五个衬底，1A处于溅射中心，1A与Al靶材7的夹角α1大于衬底1B、1C的夹角α2，衬底1D、1E的夹角α3最低，通过调控夹角α(即靶基距离和轴向距离共同作用)的大小，获得纵横波能量占比不同的AlN压电涂层。The present invention first adjusts various parameters of AlN prepared by magnetron sputtering, and studies the influence of various parameters on ultrasonic signals. The parameters include axial distance, target-base distance, radio frequency power, ambient temperature, intracavity air pressure, Ar/N2 At least one of flow ratio and deposition time. Figure 1 shows a schematic diagram of controlling the deposition of AlN piezoelectric coating through the combined action of target distance and axial distance. Five substrates 1A, 1B, 1C, 1D, and 1E with different axial distances are placed on the sample holder 9. 1A is at the sputtering center. The angle α1 between 1A and the Al target 7 is greater than the angle α2 between the substrates 1B and 1C. The angle α3 between the substrates 1D and 1E is the lowest. By adjusting the angle α (i.e., the distance between the target base and the axis The size of the AlN piezoelectric coating with different proportions of longitudinal and transverse wave energy is obtained.
选出合适的参数，提高AlN超声波传感器的检测性能，此外不同于常规的磁控溅射方法。本发明中沉积初期腔室内存在一定残余氧气，会优先生成0.5～3μm厚的AlON非晶涂层(AlON具备耐高温性能和抗化学腐蚀性能，可在一定程度上提升传感器恶劣工况下的稳定性)，随着沉积时间增多，腔内氧气逐渐消耗，开始生成AlN压电涂层，基于沉积参数得到厚度8～20μm的AlN压电涂层。因此本发明的AlN压电涂层形成在AlON非晶涂层上。Select appropriate parameters to improve the detection performance of the AlN ultrasonic sensor, which is different from the conventional magnetron sputtering method. In the present invention, there is a certain residual oxygen in the chamber at the initial stage of deposition, which will preferentially generate a 0.5-3 μm thick AlON amorphous coating (AlON has high temperature resistance and chemical corrosion resistance, which can improve the stability of the sensor under harsh working conditions to a certain extent. property), as the deposition time increases, the oxygen in the cavity is gradually consumed, and the AlN piezoelectric coating begins to be generated. Based on the deposition parameters, an AlN piezoelectric coating with a thickness of 8 to 20 μm is obtained. Therefore, the AlN piezoelectric coating of the present invention is formed on the AlON amorphous coating.
然而，使用银浆点涂法制备电极层在高温下容易脱落，导致无法引出超声信号，不能在高温下使用。However, the electrode layer prepared using the silver paste spot coating method is easy to fall off at high temperatures, resulting in the inability to elicit ultrasonic signals and cannot be used at high temperatures.
在本发明的一些优选的实施方式中，使用第一沉积法在AlN压电涂层表面制备电极层制备AlN超声波传感器，这样电极层不容易脱落，但在高温下衬底背面仍然存在被高温氧化的问题，在长时间的高温下，传感器的超声信号消失。In some preferred embodiments of the present invention, the first deposition method is used to prepare an electrode layer on the surface of the AlN piezoelectric coating to prepare an AlN ultrasonic sensor. In this way, the electrode layer is not easy to fall off, but the back side of the substrate is still oxidized at high temperatures. The problem is that under high temperature for a long time, the ultrasonic signal of the sensor disappears.
在本发明的一些优选的实施方式中，还使用第二沉积法在带有AlN压电涂层的衬底的背面沉积保护层制备如图2所示的AlN超声波传感器，包括衬底1，衬底1表面还包括由下至上的AlON非晶涂层2、AlN压电涂层3、第一Cr层4、第一Cr和Ag复合层5、第一Ag层6；衬底1背面还包括由上至下的第二Cr层4’、第二Cr和Ag复合层5’、第二Ag层6’；AlN压电涂层2表面上方的第一Cr层4、第一Cr和Ag复合层5、第一Ag层6构成电极层，衬底背面下方的第二Cr层4’、第二Cr和Ag复合层5’、第二Ag层6’构成保护层。In some preferred embodiments of the present invention, a second deposition method is also used to deposit a protective layer on the back of the substrate with an AlN piezoelectric coating to prepare an AlN ultrasonic sensor as shown in Figure 2, including a substrate 1, a substrate The surface of the substrate 1 also includes an AlON amorphous coating 2, an AlN piezoelectric coating 3, a first Cr layer 4, a first Cr and Ag composite layer 5, and a first Ag layer 6 from bottom to top; the back side of the substrate 1 also includes The second Cr layer 4', the second Cr and Ag composite layer 5', and the second Ag layer 6' from top to bottom; the first Cr layer 4, the first Cr and Ag composite layer above the surface of the AlN piezoelectric coating 2 Layer 5 and the first Ag layer 6 constitute the electrode layer, and the second Cr layer 4', the second Cr and Ag composite layer 5' and the second Ag layer 6' under the back surface of the substrate constitute the protective layer.
其中，第一沉积法和第二沉积法相似，第一Cr层4和第二Cr层4’的制备方法相同，第一Cr和Ag复合层5和第二Cr和Ag复合层5’制备的方法相同，区别在于：第一Ag层的6厚度大于第二Ag层6’，通过控制沉积时间来调控。Among them, the first deposition method and the second deposition method are similar, the preparation methods of the first Cr layer 4 and the second Cr layer 4' are the same, and the first Cr and Ag composite layer 5 and the second Cr and Ag composite layer 5' are prepared by The method is the same, except that the thickness of the first Ag layer 6 is greater than that of the second Ag layer 6', and is controlled by controlling the deposition time.
采用电弧离子镀与磁控溅射相结合的方式，在第一Cr层4表面沉积第一Cr层和Ag复合层5的示意图如图3所示。首先将带有第一Cr层的衬底8置于样品架9上，样品架9置于支撑架10上，纯Cr靶材11与纯Ag靶材12相邻放置，将支撑架10设置为旋转模式，其会带动样品架9一同围绕支撑架10的轴匀速旋转，使得腔室内的Cr束流和Ag束流可以均匀地到达带有第一Cr层的衬底8的表面，从而得到第一Cr和Ag复合层5。相当于在第一Ag层6与第一Cr层4间加了一层两者的多层复合过渡层，使得涂层间结合良好，同时Ag粒子难以穿透进入AlN压电涂层3，削弱了对压电材料结构与压电性能的破坏，同时抑制高温下电极元素扩散现象。The schematic diagram of depositing the first Cr layer and the Ag composite layer 5 on the surface of the first Cr layer 4 by combining arc ion plating and magnetron sputtering is shown in Figure 3. First, the substrate 8 with the first Cr layer is placed on the sample holder 9, the sample holder 9 is placed on the support frame 10, the pure Cr target 11 and the pure Ag target 12 are placed adjacent to each other, and the support frame 10 is set as Rotation mode, which will drive the sample holder 9 to rotate at a constant speed around the axis of the support frame 10, so that the Cr beam and Ag beam in the chamber can evenly reach the surface of the substrate 8 with the first Cr layer, thereby obtaining the third A Cr and Ag composite layer 5. It is equivalent to adding a multi-layer composite transition layer between the first Ag layer 6 and the first Cr layer 4, so that the bonding between the coatings is good, and at the same time, it is difficult for Ag particles to penetrate into the AlN piezoelectric coating 3, weakening the It avoids damaging the structure and piezoelectric properties of piezoelectric materials, while inhibiting the diffusion of electrode elements at high temperatures.
下面将结合本发明具体实施例和说明书附图，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the specific embodiments of the present invention and the accompanying drawings. Obviously, the described embodiments are only some of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts fall within the scope of protection of the present invention.
实施例1Example 1
一种AlN超声波传感器的制备方法，步骤如下，A method for preparing an AlN ultrasonic sensor. The steps are as follows:
(1)衬底前期准备：采用砂纸打磨硬质合金衬底，获得粗质表面，具体操作为：在研磨机上，先用600目的粗砂纸砂纸打磨2min、转速350r/min，快速除去衬底表面的杂质，再用2000目的细砂纸打磨2min、转速350r/min，获得粗糙度适当的粗质表面，利于增强涂层与衬底的结合；随后采用离子束刻蚀除去打磨后硬质合金表面的可见颗粒物，降低涂层脱落风险，离子束刻蚀结束后得到预处理的硬质合金；(1) Preliminary preparation of the substrate: Use sandpaper to grind the carbide substrate to obtain a rough surface. The specific operation is: on the grinder, first use 600-grit coarse sandpaper to grind for 2 minutes at a rotation speed of 350r/min to quickly remove the substrate surface. The impurities are then polished with 2000-grit fine sandpaper for 2 minutes at a speed of 350r/min to obtain a rough surface with appropriate roughness, which is conducive to enhancing the bonding between the coating and the substrate; then ion beam etching is used to remove the impurities on the polished cemented carbide surface. Visible particles reduce the risk of coating peeling, and the pre-treated cemented carbide is obtained after ion beam etching;
(2)沉积AlON非晶涂层和AlN压电涂层：将预处理的硬质合金置于溅射中心处(轴向距离为零)，射频功率900W、温度150℃、总气流1.0Pa、Ar/N2的流量比1/1、时间8h，调节靶基距离依次调为5.5cm、6cm、8cm，由于机械泵、分子泵抽气时长为1.5h，腔内真空度为6×10-3Pa，即沉积初期腔室内的氧含量为1.26×10-3Pa，会优先生成AlON非晶层，随着沉积时间增多，腔内氧气逐渐耗尽，开始生成AlN压电涂层，如此在预处理的硬质合金的表面依次形成AlON非晶涂层和AlN压电涂层；(2) Deposit AlON amorphous coating and AlN piezoelectric coating: Place the pretreated cemented carbide at the sputtering center (axial distance is zero), RF power 900W, temperature 150°C, total air flow 1.0Pa, The flow ratio of Ar/N2 is 1/1, the time is 8 hours, and the distance between the target and the base is adjusted to 5.5cm, 6cm, and 8cm. Since the pumping time of the mechanical pump and molecular pump is 1.5h, the vacuum degree in the cavity is 6×10- 3 Pa, that is, the oxygen content in the chamber at the initial stage of deposition is 1.26×10-3 Pa, and the AlON amorphous layer will be generated preferentially. As the deposition time increases, the oxygen in the chamber is gradually depleted, and the AlN piezoelectric coating begins to be generated. In this way, The surface of the pretreated cemented carbide is sequentially formed with an AlON amorphous coating and an AlN piezoelectric coating;
(3)电极层制备：将银浆涂覆于AlN压电涂层表面，固化得到300μm厚的电极层，得到AlN超声波传感器。(3) Electrode layer preparation: Coat the silver paste on the surface of the AlN piezoelectric coating, and solidify to obtain a 300 μm thick electrode layer to obtain an AlN ultrasonic sensor.
测试了本实施例中，靶基距离5.5cm、6cm、8cm下制备的AlN超声波传感器的超声信号数据，结果如图4所示。在图4中可以看出，靶基距离为60mm时，所制备的传感器具备最佳的超声信号，不仅纵波信号优于55mm和80mm的，甚至还出现了横波。因而，可以通过调控靶基距离，获取想要的纵波或纵横双波。In this example, the ultrasonic signal data of the AlN ultrasonic sensors prepared at target-base distances of 5.5cm, 6cm, and 8cm were tested, and the results are shown in Figure 4. As can be seen in Figure 4, when the target-base distance is 60mm, the prepared sensor has the best ultrasonic signal. Not only the longitudinal wave signal is better than that of 55mm and 80mm, but also transverse waves appear. Therefore, the desired longitudinal wave or dual longitudinal and transverse waves can be obtained by adjusting the distance between the target and the base.
实施例2Example 2
一种AlN超声波传感器的制备方法，步骤如下，A method for preparing an AlN ultrasonic sensor. The steps are as follows:
(1)衬底前期准备：同实施例1，得到预处理的硬质合金；(1) Substrate preliminary preparation: Same as Example 1, to obtain pretreated cemented carbide;
(2)沉积AlON非晶涂层和AlN压电涂层：将预处理的硬质合金置于溅射中心处，调控靶基距离8cm、射频功率900W、总气流1.0Pa、Ar/N2的流量比1/1、时间8h，调节温度依次为100℃、150℃、200℃，在预处理的硬质合金表面进行AlN压电涂层沉积，由于机械泵、分子泵抽气时长为1.5h，腔内真空度为6×10-3Pa，即沉积初期腔室内的氧含量为1.26×10-3Pa，在预处理的硬质合金的表面依次形成AlON非晶涂层和AlN压电涂层；(2) Deposit AlON amorphous coating and AlN piezoelectric coating: Place the pretreated cemented carbide at the sputtering center, control the target distance to 8cm, the radio frequency power to 900W, the total air flow to 1.0Pa, and the Ar/N2 The flow ratio is 1/1, the time is 8 hours, and the adjusted temperatures are 100°C, 150°C, and 200°C. AlN piezoelectric coating is deposited on the pretreated cemented carbide surface. Since the mechanical pump and molecular pump pumping time is 1.5 hours , the vacuum degree in the chamber is 6×10-3 Pa, that is, the oxygen content in the chamber at the initial stage of deposition is 1.26×10-3 Pa, and the AlON amorphous coating and the AlN piezoelectric coating are sequentially formed on the surface of the pretreated cemented carbide. layer;
(3)电极层制备：将银浆涂覆于AlN压电涂层表面，固化得到300μm厚的电极层，得到AlN超声波传感器。(3) Electrode layer preparation: Coat the silver paste on the surface of the AlN piezoelectric coating, and solidify to obtain a 300 μm thick electrode layer to obtain an AlN ultrasonic sensor.
测试了本实施例中温度为100℃、150℃、200℃下制备的AlN超声波传感器的超声信号数据，结果如图5所示。在图5中可以看出，温度越高，获得的超声信号越强。因为随着腔内温度升高，吸附于衬底表面的原子和原子团可以获得更高的能量，利于AlN压电涂层的形成，而且制样温度越高，衬底温度也越高，会降低结构缺陷、促进柱状结构的致密化，利于激发超声信号。The ultrasonic signal data of the AlN ultrasonic sensor prepared at temperatures of 100°C, 150°C, and 200°C in this example was tested, and the results are shown in Figure 5. As can be seen in Figure 5, the higher the temperature, the stronger the ultrasonic signal obtained. Because as the temperature in the cavity increases, the atoms and atomic groups adsorbed on the surface of the substrate can obtain higher energy, which is conducive to the formation of the AlN piezoelectric coating. Moreover, the higher the sample preparation temperature, the higher the substrate temperature, which will reduce Structural defects promote the densification of the columnar structure, which is conducive to the stimulation of ultrasonic signals.
实施例3Example 3
一种AlN超声波传感器的制备方法，步骤如下，A method for preparing an AlN ultrasonic sensor. The steps are as follows:
(1)衬底前期准备：同实施例1，得到预处理的硬质合金；(1) Substrate preliminary preparation: Same as Example 1, to obtain pretreated cemented carbide;
(2)沉积AlON非晶涂层和AlN压电涂层：调控靶基距离8cm、射频功率900W、温度200℃、总气流1.0Pa、Ar/N2的流量比1/1、时间8h，调节离溅射中心距离分别为0cm(位于溅射中心)、3cm、4cm、5cm，在预处理的硬质合金表面进行AlN压电涂层沉积，由于机械泵、分子泵抽气时长为1.5h，腔内真空度为6×10-3Pa，即沉积初期腔室内的氧含量为1.26×10-3Pa，在预处理的硬质合金的表面依次形成AlON非晶涂层和AlN压电涂层；(2) Deposit AlON amorphous coating and AlN piezoelectric coating: adjust the target distance to 8cm, RF power to 900W, temperature to 200°C, total airflow to 1.0Pa, flow ratio of Ar/N2 to 1/1, and time to 8h. The distances from the sputtering center are 0cm (located at the sputtering center), 3cm, 4cm, and 5cm respectively. AlN piezoelectric coating is deposited on the pretreated cemented carbide surface. Since the pumping time of the mechanical pump and molecular pump is 1.5h, The vacuum degree in the chamber is 6×10-3 Pa, that is, the oxygen content in the chamber at the initial stage of deposition is 1.26×10-3 Pa. AlON amorphous coating and AlN piezoelectric coating are sequentially formed on the surface of the pretreated cemented carbide. ;
(3)电极层制备：将银浆涂覆于AlN压电涂层表面，固化得到300μm厚的电极层，得到AlN超声波传感器。(3) Electrode layer preparation: Coat the silver paste on the surface of the AlN piezoelectric coating, and solidify to obtain a 300 μm thick electrode layer to obtain an AlN ultrasonic sensor.
测试了本实施例中其它参数固定下，离溅射中心距离分别为0cm、3cm、4cm、5cm制备的AlN超声波传感器的超声信号数据，结果如图6所示。在图6中可以看出，靶基距为80mm时，不论距离溅射中心距离多大，均只获得了纯纵波，因为距离靶材较远，各个衬底与靶材的夹角α接近90°，可近似看成垂直入射，因而可以获得优异的纯纵波。且距离溅射中心越近，获得的超声信号越强。远离溅射中心，到达衬底表面的靶材物质密度降低，缺乏原材料，沉积的涂层厚度降低，信号减弱。In this example, the ultrasonic signal data of the AlN ultrasonic sensor prepared at a distance of 0 cm, 3 cm, 4 cm, and 5 cm from the sputtering center were tested with other parameters fixed. The results are shown in Figure 6. As can be seen in Figure 6, when the target-base distance is 80mm, no matter how far away from the sputtering center is, only pure longitudinal waves are obtained. Because the distance from the target is far, the angle α between each substrate and the target is close to 90°. , can be approximately regarded as vertical incidence, so excellent pure longitudinal waves can be obtained. And the closer to the sputtering center, the stronger the ultrasonic signal obtained. Away from the sputtering center, the density of the target material reaching the substrate surface decreases, there is a lack of raw materials, the thickness of the deposited coating decreases, and the signal weakens.
实施例4Example 4
一种AlN超声波传感器的制备方法，步骤如下A preparation method of AlN ultrasonic sensor, the steps are as follows
(1)衬底前期准备：衬底选择硬质合金和Si片，其他同实施例1，得到预处理的硬质合金和Si片；(1) Preliminary preparation of substrate: Select cemented carbide and Si flakes as the substrate. Others are the same as in Example 1 to obtain pretreated cemented carbide and Si flakes;
(2)沉积AlON非晶涂层和AlN压电涂层：调控靶基距离6cm、射频功率900W、温度150℃、总气流1.0Pa、Ar/N2的流量比1/1、时间8h，调节离溅射中心距离分别为0cm、3cm、5cm，在预处理的硬质合金表面和预处理的Si片进行AlN压电涂层沉积，由于机械泵、分子泵抽气时长为1.5h，腔内真空度为6×10-3Pa，即沉积初期腔室内的氧含量为1.26×10-3Pa，在预处理的硬质合金的表面依次形成AlON非晶涂层和AlN压电涂层；(2) Deposit AlON amorphous coating and AlN piezoelectric coating: adjust the target distance to 6cm, RF power to 900W, temperature to 150℃, total airflow to 1.0Pa, flow ratio of Ar/N2 to 1/1, and time to 8h. The distances from the sputtering center are 0cm, 3cm, and 5cm respectively. The AlN piezoelectric coating is deposited on the pretreated cemented carbide surface and the pretreated Si wafer. Since the pumping time of the mechanical pump and molecular pump is 1.5h, the exhaust time in the cavity is The vacuum degree is 6×10-3 Pa, that is, the oxygen content in the chamber at the initial stage of deposition is 1.26×10-3 Pa. AlON amorphous coating and AlN piezoelectric coating are sequentially formed on the surface of the pretreated cemented carbide;
(3)电极层制备：将银浆涂覆于AlN压电涂层表面，固化得到300μm厚的电极层，得到硬质合金为衬底的AlN超声波传感器和Si片为衬底的AlN超声波传感器。(3) Electrode layer preparation: Coat the silver paste on the surface of the AlN piezoelectric coating, and solidify to obtain a 300 μm thick electrode layer, thereby obtaining an AlN ultrasonic sensor with a cemented carbide substrate and an AlN ultrasonic sensor with a Si substrate.
测量了Si片上涂层的表面形貌、断面形貌和断面氧原子占比；测量硬质合金上涂层的超声信号、XRD、介电常数和介电损耗数值。The surface morphology, cross-sectional morphology and proportion of oxygen atoms in the cross-section of the coating on the Si wafer were measured; the ultrasonic signal, XRD, dielectric constant and dielectric loss values of the coating on the cemented carbide were measured.
图7(a)为距离溅射中心0cm处制备的AlN压电涂层表面SEM的图像，图7(b)为距离溅射中心0cm处制备的AlN压电涂层的截面SEM图像，图7(c)为距离溅射中心5cm处的截面SEM图像和氧原子占比，图7(d)为距离溅射中心0cm、3cm、5cm处的XRD图谱，图7(e)为距离溅射中心0cm、3cm、5cm处的制备的传感器激发的超声波信号，图7(f)为距离溅射中心0cm处的介电常数和介电损耗数值。可见，在距离衬底表面最近的1.5μm内，截面形貌表明该涂层为非晶结构，同时该处涂层的氧原子占比高于其他区域，表明该处生成了富氧涂层，即AlON非晶层；而在1.5μm外的涂层为柱状晶结构，氧原子占比远低于1.5μm内的，即AlN压电涂层。位于溅射中心处，AlN压电涂层具有垂直衬底生长的柱状晶和(002)择优生长取向。偏离溅射中心，AlN压电涂层具有倾斜柱状晶，距离溅射中心5cm处具有(103)择优生长取向，距离溅射中心3cm处生长取向介于0cm和5cm之间。同时AlN压电涂层晶格生长取向与激发出的声波类型具有一一对应关系，即衬底在溅射区的位置可以有效地影响横波和纵波的能量占比：在距离溅射中心0cm处，获得的AlN压电涂层为(002)c轴方向择优生长，激发的纵波能量占比高于横波；在距离溅射中心5cm处，获得的AlN压电涂层为(103)方向择优生长，激发的横波能量占比高于纵波；而在距离溅射中心3cm处，获得的AlN压电涂层为(002)、(103)两个方向生长，激发的纵波、横波能量占比相当。因而可以通过调控衬底与靶材的相对位置，以获得沿不同方向生长的AlN压电涂层，进而调控纵横波的能量占比。Figure 7(a) is an SEM image of the surface of the AlN piezoelectric coating prepared at a distance of 0 cm from the sputtering center. Figure 7(b) is a cross-sectional SEM image of the AlN piezoelectric coating prepared at a distance of 0 cm from the sputtering center. Figure 7 (c) is the cross-sectional SEM image and the proportion of oxygen atoms at 5cm from the sputtering center. Figure 7(d) is the XRD pattern at 0cm, 3cm, and 5cm from the sputtering center. Figure 7(e) is the distance from the sputtering center. The ultrasonic signals excited by the prepared sensors at 0cm, 3cm, and 5cm. Figure 7(f) shows the dielectric constant and dielectric loss values at 0cm from the sputtering center. It can be seen that within 1.5 μm closest to the substrate surface, the cross-sectional morphology shows that the coating has an amorphous structure. At the same time, the proportion of oxygen atoms in the coating here is higher than in other areas, indicating that an oxygen-rich coating is generated there. That is, the AlON amorphous layer; while the coating outside 1.5 μm has a columnar crystal structure, and the proportion of oxygen atoms is much lower than that within 1.5 μm, that is, the AlN piezoelectric coating. Located at the sputtering center, the AlN piezoelectric coating has columnar crystals grown perpendicular to the substrate and a (002) preferred growth orientation. Offset from the sputtering center, the AlN piezoelectric coating has tilted columnar crystals, with a (103) preferred growth orientation 5cm away from the sputtering center, and a growth orientation between 0cm and 5cm at 3cm away from the sputtering center. At the same time, the lattice growth orientation of the AlN piezoelectric coating has a one-to-one correspondence with the type of excited acoustic waves. That is, the position of the substrate in the sputtering zone can effectively affect the energy proportion of transverse waves and longitudinal waves: at a distance of 0cm from the sputtering center , the AlN piezoelectric coating obtained preferentially grows in the (002) c-axis direction, and the proportion of excited longitudinal wave energy is higher than the transverse wave; at a distance of 5cm from the sputtering center, the AlN piezoelectric coating obtained preferentially grows in the (103) direction , the proportion of excited shear wave energy is higher than that of longitudinal wave; and at a distance of 3cm from the sputtering center, the obtained AlN piezoelectric coating grows in two directions (002) and (103), and the proportion of excited longitudinal wave and transverse wave energy is equal. Therefore, the relative position of the substrate and the target can be adjusted to obtain AlN piezoelectric coatings that grow in different directions, thereby controlling the energy proportion of longitudinal and transverse waves.
对比实施3、实施例4，两个实施例均是调控衬底离溅射中心距离，获得对超声信号的调控，区别在于实施例3所用靶基距离为8cm，而实施例4所用靶基距离为6cm，结果实施例3中不论衬底离溅射中心距离为多少，获得的均为纯纵波，而实施例4却依据衬底离溅射中心距离从近到远，依次获得了纵波显著、纵横双波相当、横波显著的三种波形，即距离溅射中心越远，纵波能量占比降低，横波能量占比升高。原因在于，纵横波能量占比的调控，不能单一的调控衬底离溅射中心距离，而应结合靶基距离，即衬底与靶材的夹角α，若靶基距离过远，不论衬底离溅射中心距离为多少，夹角α均接近90°，在整个溅射区间均可看作垂直入射，激发的超声信号为纯纵波。总结为，纵横波能量占比取决于夹角α，即靶基距离和轴向距离共同作用，缺一不可。Comparing Example 3 and Example 4, both examples regulate the distance between the substrate and the sputtering center to obtain control of the ultrasonic signal. The difference is that the target distance used in Example 3 is 8 cm, while the target distance used in Example 4 is 6cm. As a result, in Example 3, pure longitudinal waves were obtained regardless of the distance between the substrate and the sputtering center. However, Example 4 obtained significant longitudinal waves, There are three waveforms with equal longitudinal and transverse waves and significant transverse waves. That is, the farther away from the sputtering center, the proportion of longitudinal wave energy decreases and the proportion of transverse wave energy increases. The reason is that the control of the proportion of longitudinal and transverse wave energy cannot solely control the distance between the substrate and the sputtering center, but should be combined with the target distance, that is, the angle α between the substrate and the target. If the distance between the target and the target is too far, the distance between the substrate and the sputtering center will be affected. What is the distance between the bottom and the sputtering center? The angle α is close to 90°. The entire sputtering interval can be regarded as vertical incidence, and the excited ultrasonic signal is a pure longitudinal wave. In summary, the proportion of longitudinal and transverse wave energy depends on the angle α, that is, the target-base distance and the axial distance work together, and both are indispensable.
实施例5Example 5
一种AlN超声波传感器的制备方法，步骤如下A preparation method of AlN ultrasonic sensor, the steps are as follows
(1)衬底前期准备：同实施例1，得到预处理的硬质合金；(1) Substrate preliminary preparation: Same as Example 1, to obtain pretreated cemented carbide;
(2)沉积AlON非晶涂层和AlN压电涂层：将预处理的硬质合金置于溅射中心处，调控靶基距离6cm、射频功率900W、温度150℃、总气流1.0Pa、Ar/N2的流量比1/1、时间8h，由于机械泵、分子泵抽气时长为1.5h，腔内真空度为6×10-3Pa，即沉积初期腔室内的氧含量为1.26×10-3Pa，在预处理的硬质合金的表面依次形成AlON非晶涂层和AlN压电涂层；(2) Deposit AlON amorphous coating and AlN piezoelectric coating: Place the pretreated cemented carbide at the sputtering center, control the target distance to 6cm, RF power to 900W, temperature to 150°C, total airflow to 1.0Pa, Ar The flow ratio of /N2 is 1/1 and the time is 8 hours. Since the pumping time of the mechanical pump and molecular pump is 1.5 hours, the vacuum degree in the chamber is 6×10-3 Pa, that is, the oxygen content in the chamber in the early stage of deposition is 1.26×10-3 Pa, AlON amorphous coating and AlN piezoelectric coating are formed on the surface of the pretreated cemented carbide in sequence;
(3)在AlN压电涂层表面沉积电极层：(3) Deposit an electrode layer on the surface of the AlN piezoelectric coating:
a、采用电弧离子镀：调控靶基距离为12cm、电流90A、Ar气流1.0Pa，时间1min，在AlN压电涂层表面沉积100nm厚的第一Cr涂层，增强电极层与AlN压电涂层的结合，；a. Use arc ion plating: adjust the target-base distance to 12cm, current 90A, Ar gas flow 1.0Pa, time 1min, deposit a 100nm-thick first Cr coating on the surface of the AlN piezoelectric coating, and enhance the connection between the electrode layer and the AlN piezoelectric coating. The combination of layers;
b、采电弧离子镀与磁控溅射相结合的方式，同时产生Cr与Ag束流，沉积第一Cr和Ag复合层，此步骤中，Cr靶材与Ag靶材相邻放置，带有AlN压电涂层的硬质合金的表面介于两者中垂线的交点，而承载AlN压电涂层的硬质合金的样品架将一直旋转，使得Cr与Ag束流可以均匀地同时到达AlN压电涂层，沉积2μm的第一Cr和Ag复合层。获取Cr的具体参数为靶基距离为12cm、电流90A、Ar气流1.0Pa、时间15min；获取Ag的具体参数为靶基距离为8cm、射频功率700W、温度40℃、Ar气流1.0Pa、时间15min；b. Use a combination of arc ion plating and magnetron sputtering to generate Cr and Ag beams at the same time to deposit the first Cr and Ag composite layer. In this step, the Cr target and the Ag target are placed adjacent to each other, with The surface of the AlN piezoelectric-coated cemented carbide is located at the intersection of the two vertical lines, and the sample holder carrying the AlN piezoelectric-coated cemented carbide will always rotate so that the Cr and Ag beams can arrive evenly at the same time. AlN piezoelectric coating, depositing a first Cr and Ag composite layer of 2 μm. The specific parameters for obtaining Cr are target-base distance of 12cm, current 90A, Ar gas flow 1.0Pa, and time 15min; specific parameters for obtaining Ag are target-base distance 8cm, RF power 700W, temperature 40°C, Ar gas flow 1.0Pa, and time 15min. ;
c、采用磁控溅射技术，调控靶基距离8cm、射频功率700W、温度40℃、Ar气流1.0Pa、时间10min，在第一Cr和Ag复合层表面沉积5μm的第一Ag层；c. Using magnetron sputtering technology, control the target distance to 8cm, RF power to 700W, temperature to 40°C, Ar gas flow to 1.0Pa, and time to 10min to deposit a 5 μm first Ag layer on the surface of the first Cr and Ag composite layer;
(4)带有AlN压电涂层的硬质合金的背面制备防护层：使用步骤3中a和b相同的方法，在带有AlN压电涂层的硬质合金的背面依次沉积100nm厚的第二Cr涂层、2μm的第二Cr和Ag复合层，随后依然采用磁控溅射技术，调控靶基距离8cm、射频功率700W、温度40℃、Ar气流1.0Pa、时间5min，在第二Cr和Ag复合层表面沉积2.5μm的第二Ag层，得到AlN超声波传感器。(4) Preparation of protective layer on the back of the cemented carbide with AlN piezoelectric coating: Use the same method as a and b in step 3 to deposit 100nm thick layer on the back of the cemented carbide with AlN piezoelectric coating. The second Cr coating, the second Cr and Ag composite layer of 2 μm, and then the magnetron sputtering technology was still used to control the target distance to 8cm, the radio frequency power to 700W, the temperature to 40℃, the Ar gas flow to 1.0Pa, and the time to 5min. A second Ag layer of 2.5 μm was deposited on the surface of the Cr and Ag composite layer to obtain an AlN ultrasonic sensor.
在退火炉中设置温度上升曲线，在升温过程中直接实时测量30～800℃温度下的超声信号。图8(a)示出了实施例5的AlN超声波传感器在温度30、200、400、600、800℃时的超声信号，图8(b)示出了温度30、200、400、600、800℃时横波与纵波的飞行时间(TOF)，可以看出本实施例的AlN超声波传感器可以同时激发出横波与纵波，基于本实施例中在溅射中心处沉积AlN压电涂层，这表明本实施例中在溅射中心处沉积AlN压电涂层制备的AlN超声波传感器获得的纵波幅值优于横波；此外，即使在800℃的高温下依然可以获取很强的声波信号，意味着本实施例制备的AlN超声波传感器具备800℃耐高温性能；同时随着环境温度的增加，超声信号出现时延现象，横波与纵波的TOF线性增加，因而可以通过TOF的变化，获取传感器所处的环境温度。Set a temperature rise curve in the annealing furnace, and directly measure the ultrasonic signal at a temperature of 30 to 800°C in real time during the temperature rise process. Figure 8(a) shows the ultrasonic signals of the AlN ultrasonic sensor of Example 5 at temperatures of 30, 200, 400, 600, and 800°C, and Figure 8(b) shows the temperatures of 30, 200, 400, 600, and 800°C. The time-of-flight (TOF) of transverse waves and longitudinal waves at ℃ can be seen that the AlN ultrasonic sensor in this embodiment can excite transverse waves and longitudinal waves at the same time. Based on the AlN piezoelectric coating deposited at the sputtering center in this embodiment, this shows that this In the embodiment, the AlN ultrasonic sensor prepared by depositing the AlN piezoelectric coating at the sputtering center obtains a longitudinal wave amplitude that is better than the transverse wave; in addition, a strong acoustic wave signal can still be obtained even at a high temperature of 800°C, which means that this implementation The AlN ultrasonic sensor prepared in this example has high temperature resistance of 800°C. At the same time, as the ambient temperature increases, the ultrasonic signal exhibits a time delay phenomenon, and the TOF of transverse and longitudinal waves increases linearly. Therefore, the ambient temperature of the sensor can be obtained through changes in TOF. .
将实施例5的AlN超声波传感器在完成30～800℃退火后，待传感器与退火炉降至室温后，再次重复一次同样的退火，并实时测量30～800℃温度下的超声信号。图9(a)示出了在温度30、200、400、600、700℃时的超声信号，图9(b)示出了温度30、200、400、600、700℃时横波与纵波的TOF。可见，当AlN超声波传感器经过800℃退火后冷却至室温后，其信号幅值与TOF值也会恢复至原点，而第二次退火处理，依然可以获得如第一次退火中完全一致的变化规律。意味着本实施例获得的AlN传感器具备优异的高低温热疲劳性能，可以经历多次高温与低温的往复循环，且从800℃高温降回室温后，超声信号能快速恢复。After the AlN ultrasonic sensor of Example 5 is annealed at 30 to 800°C, the sensor and the annealing furnace are lowered to room temperature, and then the same annealing is repeated again, and the ultrasonic signal at 30 to 800°C is measured in real time. Figure 9(a) shows the ultrasonic signals at temperatures of 30, 200, 400, 600, and 700°C. Figure 9(b) shows the TOF of transverse and longitudinal waves at temperatures of 30, 200, 400, 600, and 700°C. . It can be seen that when the AlN ultrasonic sensor is cooled to room temperature after annealing at 800°C, its signal amplitude and TOF value will also return to the original point, and the second annealing treatment can still obtain the same change pattern as in the first annealing. . This means that the AlN sensor obtained in this embodiment has excellent high and low temperature thermal fatigue performance, can experience multiple high and low temperature reciprocating cycles, and can quickly recover the ultrasonic signal after cooling from a high temperature of 800°C back to room temperature.
实施例6Example 6
与实施例5基本相同，区别之处在于：在步骤(2)中将预处理的硬质合金置于离溅射中心3cm处。It is basically the same as Example 5, except that in step (2), the pretreated cemented carbide is placed 3 cm away from the sputtering center.
在退火炉中设置温度上升曲线，在升温过程中直接实时测量30～900℃温度下的超声信号。图10(a)示出了实施例6的AlN超声波传感器在温度30、400、800℃时的超声信号，图10(b)示出了不同温度时横波与纵波的TOF。图10(c)为纵横波幅值随退火温度的变化，图10(d)为电阻率随退火温度的变化。可见，偏离溅射中心3cm处获得的纵横波能量相当，实施例6的AlN超声波传感器可以同时激发出横波与纵波；环境温度高达900℃时，依然可以获取很强的声波信号，具备900℃耐高温性能；同时随着环境温度的增加，超声信号出现时延现象，即横波与纵波的TOF增加，且TOF值与退火温度存在函数关系，纵波TOF＝1.307+4.681×10-5T+2.024×10-8T2，横波TOF＝2.186+9.67×10-5T+5.088×10-8T2，因而可以通过TOF的变化，获取传感器所处的环境温度；此外，电阻率也与退火温度存在强相关性，退火温度升高，电阻率降低。Set a temperature rise curve in the annealing furnace, and directly measure the ultrasonic signal at a temperature of 30 to 900°C in real time during the temperature rise process. Figure 10(a) shows the ultrasonic signals of the AlN ultrasonic sensor of Embodiment 6 at temperatures of 30, 400, and 800°C, and Figure 10(b) shows the TOF of transverse waves and longitudinal waves at different temperatures. Figure 10(c) shows the change of longitudinal and transverse wave amplitude with annealing temperature, and Figure 10(d) shows the change of resistivity with annealing temperature. It can be seen that the energy of longitudinal and transverse waves obtained 3cm away from the sputtering center is equivalent. The AlN ultrasonic sensor of Example 6 can simultaneously excite transverse waves and longitudinal waves. When the ambient temperature is as high as 900°C, a strong acoustic wave signal can still be obtained, and it has a 900°C resistance. High temperature performance; at the same time, as the ambient temperature increases, the ultrasonic signal appears a time delay phenomenon, that is, the TOF of the transverse wave and the longitudinal wave increases, and there is a functional relationship between the TOF value and the annealing temperature, the longitudinal wave TOF=1.307+4.681×10-5 T+2.024× 10-8 T2 , transverse wave TOF=2.186+9.67×10-5 T+5.088×10-8 T2 , so the ambient temperature of the sensor can be obtained through the change of TOF; in addition, the resistivity also has a relationship with the annealing temperature There is a strong correlation, as the annealing temperature increases, the resistivity decreases.
对比例1Comparative example 1
与实施例4相比，区别之处在于：步骤(1)中选择Si片作为衬底；步骤(2)中，机械泵、分子泵抽气时长为2.5h，腔内真空度为3×10-3Pa，即沉积初期腔室内的氧含量为6.3×10-4Pa。Compared with Embodiment 4, the difference is that: in step (1), a Si wafer is selected as the substrate; in step (2), the pumping time of the mechanical pump and molecular pump is 2.5 hours, and the vacuum degree in the cavity is 3×10-3 Pa, that is, the oxygen content in the chamber at the initial stage of deposition is 6.3×10-4 Pa.
SEM截面形貌如图11，表明在整个断面，涂层均为AlN纯柱状晶结构，即未形成AlON非晶层。The SEM cross-sectional morphology is shown in Figure 11, which shows that throughout the cross-section, the coating has a pure columnar crystal structure of AlN, that is, no AlON amorphous layer is formed.
对比例2Comparative example 2
与实施例4相比，区别之处在于：步骤(1)中选择Si片作为衬底；步骤(2)中，机械泵、分子泵抽气时长为0.75h，腔内真空度为2×10-2Pa，即沉积初期腔室内的氧含量为4.2×10-3Pa。Compared with Example 4, the difference is that: in step (1), Si wafer is selected as the substrate; in step (2), the pumping time of the mechanical pump and molecular pump is 0.75h, and the vacuum degree in the cavity is 2×10-2 Pa, that is, the oxygen content in the chamber at the initial stage of deposition is 4.2×10-3 Pa.
SEM截面形貌如图12，表明在整个断面，涂层均为AlON非晶层，未形成AlN柱状晶压电层，超声信号为零。The SEM cross-sectional morphology is shown in Figure 12, which shows that throughout the cross-section, the coating is an AlON amorphous layer, no AlN columnar crystal piezoelectric layer is formed, and the ultrasonic signal is zero.
因此，结合实施例4和对比例1～2，可知，若沉积初期腔室内的氧含量过低，则无法形成AlON非晶层；若沉积初期腔室内的氧含量过高，则无法形成AlN柱状晶压电层。即应适当调控沉积初期的氧含量，获得AlON非晶层、AlN柱状晶压电层占比适当的涂层结构。Therefore, combining Example 4 and Comparative Examples 1 to 2, it can be seen that if the oxygen content in the chamber at the initial stage of deposition is too low, the AlON amorphous layer cannot be formed; if the oxygen content in the chamber at the early stage of deposition is too high, the AlON columnar layer cannot be formed. crystal piezoelectric layer. That is to say, the oxygen content in the early stage of deposition should be appropriately controlled to obtain a coating structure with appropriate proportions of AlON amorphous layer and AlN columnar crystal piezoelectric layer.
对比例3Comparative example 3
与实施例4相比不包括步骤(4)，即制备的AlN超声波传感器与实施例4相比不存在保护层。结果退火过程中，仅700℃、10min，衬底背面就被氧化，出现较厚的氧化层，氧化层为绝缘层，阻碍了信号传输，引出的超声信号骤降。Compared with Example 4, step (4) is not included, that is, compared with Example 4, the prepared AlN ultrasonic sensor does not have a protective layer. As a result, during the annealing process, at only 700°C and 10 minutes, the back side of the substrate was oxidized, and a thick oxide layer appeared. The oxide layer was an insulating layer, hindering signal transmission, and the induced ultrasonic signal dropped sharply.
对比例4Comparative example 4
与实施例4相比，区别之处在于：步骤(1)中未采用砂纸打磨硬质合金衬底。Compared with Example 4, the difference is that sandpaper is not used to polish the cemented carbide substrate in step (1).
结果制备的传感器未激发出良好的超声信号，尤其在高温处理过程中，甚至出现涂层与衬底脱离现象，因为涂层与衬底结合差，高温促进了间隙的生成，破坏了传感性能。As a result, the prepared sensor did not excite good ultrasonic signals. Especially during high-temperature processing, the coating and the substrate even detached. Because the coating and the substrate were poorly bonded, the high temperature promoted the generation of gaps and destroyed the sensing performance. .
对比例5Comparative example 5
与实施例4相比，区别之处在于：步骤(1)中未采用离子束刻蚀硬质合金衬底。Compared with Example 4, the difference is that in step (1), ion beam is not used to etch the cemented carbide substrate.
结果制备的AlN压电层和传感器在高温热处理之前，就存在大面积脱落行为，同样未激发出良好的超声信号。As a result, the prepared AlN piezoelectric layer and sensor had large-area peeling behavior before high-temperature heat treatment, and also failed to excite good ultrasonic signals.
因此，结合实施例4和对比例3～5，可知，良好的传感器需要高质量的AlN压电涂层、电极层，同样也需要其他保护方案，如砂纸打磨衬底、离子束刻蚀衬底，获得具有一定粗糙度和洁净的衬底表面，以增强涂层与衬底的紧密结合，获得强超声信号；若要求传感器具有800℃～900℃高温下检测的能力，不仅需要砂纸打磨衬底、离子束刻蚀衬底，还需要进一步采用本发明所述的第二沉积法在衬底背面沉积保护层，以隔绝氧气，抑制高温环境中氧气对衬底的破坏，提高高温环境下传感器的抗氧化性能。Therefore, combined with Example 4 and Comparative Examples 3 to 5, it can be seen that a good sensor requires high-quality AlN piezoelectric coating and electrode layer, and also requires other protection solutions, such as sandpaper polishing of the substrate and ion beam etching of the substrate. , to obtain a substrate surface with a certain roughness and cleanness to enhance the tight combination of the coating and the substrate and obtain a strong ultrasonic signal; if the sensor is required to have the ability to detect at high temperatures of 800°C to 900°C, not only the substrate needs to be polished with sandpaper , ion beam etching the substrate, it is also necessary to further use the second deposition method of the present invention to deposit a protective layer on the back of the substrate to isolate oxygen, inhibit the damage of oxygen to the substrate in high-temperature environments, and improve the performance of the sensor in high-temperature environments. Antioxidant properties.
最后应说明的是：以上所述仅为本发明的优选实施例而已，并不用于限制本发明，尽管参照前述实施例对本发明进行了详细的说明，对于本领域的技术人员来说，其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分技术特征进行等同替换，凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。Finally, it should be noted that the above are only preferred embodiments of the present invention and are not intended to limit the present invention. Although the present invention has been described in detail with reference to the foregoing embodiments, for those skilled in the art, it is still The technical solutions described in the foregoing embodiments may be modified, or equivalent substitutions may be made to some of the technical features. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention shall be included in within the protection scope of the present invention.
| Application Number | Priority Date | Filing Date | Title |
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| CN202310837395.XACN116988008A (en) | 2023-07-07 | 2023-07-07 | AlN ultrasonic sensor, preparation method and application thereof |
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| CN202310837395.XACN116988008A (en) | 2023-07-07 | 2023-07-07 | AlN ultrasonic sensor, preparation method and application thereof |
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| CN102548309A (en)* | 2010-12-21 | 2012-07-04 | 鸿富锦精密工业（深圳）有限公司 | Shell and manufacturing method thereof |
| CN111341874A (en)* | 2020-03-09 | 2020-06-26 | 合肥工业大学 | Self-driven broadband photodetector based on Si microhole/CuO vertical structure heterojunction and preparation method thereof |
| CN112687526A (en)* | 2020-12-25 | 2021-04-20 | 广东省科学院半导体研究所 | Preparation method of nitride semiconductor material and annealing treatment method thereof |
| CN114171720A (en)* | 2020-08-21 | 2022-03-11 | 北京石墨烯研究院 | Battery pole piece and preparation method thereof, and lithium ion battery |
| CN115184453A (en)* | 2022-06-02 | 2022-10-14 | 武汉大学 | LiNbO3/LiTaO3 piezoelectric coating sensor and preparation method |
| CN116026489A (en)* | 2023-02-21 | 2023-04-28 | 武汉大学 | Metal nitride film ultrasonic temperature sensor and temperature measurement method |
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102548309A (en)* | 2010-12-21 | 2012-07-04 | 鸿富锦精密工业（深圳）有限公司 | Shell and manufacturing method thereof |
| CN111341874A (en)* | 2020-03-09 | 2020-06-26 | 合肥工业大学 | Self-driven broadband photodetector based on Si microhole/CuO vertical structure heterojunction and preparation method thereof |
| CN114171720A (en)* | 2020-08-21 | 2022-03-11 | 北京石墨烯研究院 | Battery pole piece and preparation method thereof, and lithium ion battery |
| CN112687526A (en)* | 2020-12-25 | 2021-04-20 | 广东省科学院半导体研究所 | Preparation method of nitride semiconductor material and annealing treatment method thereof |
| CN115184453A (en)* | 2022-06-02 | 2022-10-14 | 武汉大学 | LiNbO3/LiTaO3 piezoelectric coating sensor and preparation method |
| CN116026489A (en)* | 2023-02-21 | 2023-04-28 | 武汉大学 | Metal nitride film ultrasonic temperature sensor and temperature measurement method |
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