WO2023279669A1 - Piezoelectric material for directionally regulating growth orientation of pmn-pt film by using cofe2o4, and preparation method therefor - Google Patents

Piezoelectric material for directionally regulating growth orientation of pmn-pt film by using cofe2o4, and preparation method therefor Download PDF

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WO2023279669A1
WO2023279669A1 PCT/CN2021/139351 CN2021139351W WO2023279669A1 WO 2023279669 A1 WO2023279669 A1 WO 2023279669A1 CN 2021139351 W CN2021139351 W CN 2021139351W WO 2023279669 A1 WO2023279669 A1 WO 2023279669A1
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pmn
layer
substrate
sto
cfo
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钟高阔
李江宇
陈骞鑫
程明强
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中国科学院深圳先进技术研究院
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N30/00—Piezoelectric or electrostrictive devices
    • H10N30/704—Piezoelectric or electrostrictive devices based on piezoelectric or electrostrictive films or coatings
    • H10N30/706—Piezoelectric or electrostrictive devices based on piezoelectric or electrostrictive films or coatings characterised by the underlying bases, e.g. substrates
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N30/00—Piezoelectric or electrostrictive devices
    • H10N30/01—Manufacture or treatment
    • H10N30/09—Forming piezoelectric or electrostrictive materials
    • H10N30/092—Forming composite materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N30/00—Piezoelectric or electrostrictive devices
    • H10N30/01—Manufacture or treatment
    • H10N30/09—Forming piezoelectric or electrostrictive materials
    • H10N30/093—Forming inorganic materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N30/00—Piezoelectric or electrostrictive devices
    • H10N30/80—Constructional details
    • H10N30/85—Piezoelectric or electrostrictive active materials
    • H10N30/852—Composite materials, e.g. having 1-3 or 2-2 type connectivity
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N30/00—Piezoelectric or electrostrictive devices
    • H10N30/80—Constructional details
    • H10N30/85—Piezoelectric or electrostrictive active materials
    • H10N30/853—Ceramic compositions
    • H10N30/8536—Alkaline earth metal based oxides, e.g. barium titanates
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N30/00—Piezoelectric or electrostrictive devices
    • H10N30/80—Constructional details
    • H10N30/85—Piezoelectric or electrostrictive active materials
    • H10N30/853—Ceramic compositions
    • H10N30/8542—Alkali metal based oxides, e.g. lithium, sodium or potassium niobates
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N30/00—Piezoelectric or electrostrictive devices
    • H10N30/80—Constructional details
    • H10N30/85—Piezoelectric or electrostrictive active materials
    • H10N30/853—Ceramic compositions
    • H10N30/8548—Lead-based oxides
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • This application relates to the field of PMN-PT thin film materials, more specifically, it relates to a piezoelectric material that uses CoFe 2 O 4 to regulate the growth orientation of PMN-PT thin films.
  • piezoelectric materials including ZnO nanowires, BaTiO 3 (BTO) films, and lead zirconate titanate piezoelectric ceramic (PZT) films.
  • BTO BaTiO 3
  • PZT lead zirconate titanate piezoelectric ceramic
  • the piezoelectric charge coefficient d33 is as high as 2500pC/N, nearly 4 times higher than PZT materials, 20 times higher than BTO materials, and 90 times higher than ZnO materials.
  • PMN-PT materials In order to make PMN-PT materials more widely used in energy harvesters, it is often necessary to grow PMN-PT materials on different substrates or substrates with different orientations, but PMNs grown on different substrates or substrates with different orientations -The growth orientation of PT materials is also different. PMN-PT materials with different growth orientations have anisotropy and different properties, which is not conducive to studying the piezoelectric charge coefficient and other material properties of PMN-PT materials with the same orientation under different substrate materials. .
  • the application provides a piezoelectric material and its Preparation.
  • the present application provides a piezoelectric material that utilizes CoFe 2 O 4 to regulate the growth orientation of PMN-PT film, and adopts the following technical scheme:
  • a piezoelectric material that uses CoFe 2 O 4 to regulate the growth orientation of PMN-PT film including:
  • control layer formed on the bottom electrode layer, the control layer is a CoFe 2 O 4 (CFO) layer grown based on the bottom electrode layer;
  • CFO CoFe 2 O 4
  • the substrate, the bottom electrode layer, the control layer and the epitaxial layer form a substrate/bottom electrode layer/CFO/PMN-PT epitaxial structure, and the epitaxial orientation of the PMN-PT layer is [111].
  • PMN-PT epitaxial thin film materials with specific orientations can be prepared on different substrates or substrates with different orientations, which solves the problem that it is difficult to obtain PMNs with the same orientation under different substrates.
  • the problem of PT epitaxial film material in order to study the material properties of PMN-PT epitaxial film under different substrate materials.
  • the constituent elements of the substrate include Sr and Ti.
  • the substrate is a SrTiO 3 (STO) substrate.
  • STO SrTiO 3
  • the crystal plane orientation of the STO substrate is [100] or [110] or [111].
  • the constituent elements of the bottom electrode layer include Sr and Ru.
  • the bottom electrode layer is a SrRuO 3 (SRO) layer.
  • the thickness of the bottom electrode layer is 10-30 nm
  • the thickness of the control layer is 20-40 nm
  • the thickness of the epitaxial layer is 180-200 nm
  • the total thickness of the epitaxial structure is 210-270 nm.
  • the thickness of the bottom electrode layer is 20-25 nm
  • the thickness of the control layer is 25-35 nm
  • the thickness of the epitaxial layer is 185-195 nm
  • the total thickness of the epitaxial structure is 230-255 nm.
  • the present application provides a method for preparing a piezoelectric material that uses CoFe 2 O 4 to regulate the growth orientation of PMN-PT film, and adopts the following technical scheme:
  • a method for preparing a piezoelectric material utilizing CoFe 2 O directional regulation of PMN - PT film growth orientation comprising the following steps:
  • PMN-PT epitaxial films with specific epitaxial orientations can be stably obtained on different substrates or substrates with different orientations, and the process difficulty is low, simple and convenient, and the quality of the obtained epitaxial films is good, greatly reducing the production costs and post-processing costs.
  • the generation of the bottom electrode layer in step (2), the generation of the control layer in step (3) and the generation of the epitaxial layer in step (4) all use pulsed laser deposition methods.
  • step (1) includes the following steps:
  • the deposition parameters of the SRO bottom electrode layer in step (2) are: the vacuum degree of the deposition chamber is ⁇ 5 ⁇ 10 -6 Pa, the deposition temperature is 690 ⁇ 710°C, the oxygen partial pressure is 110 ⁇ 130mTorr, the laser energy is 320 ⁇ 340mJ, and the pulse
  • the laser frequency is 5 ⁇ 10Hz
  • the deposition temperature rate is 20 ⁇ 40°C/min
  • the deposition rate is 3 ⁇ 5nm/min
  • the distance between the substrate and the target during deposition is 55 ⁇ 80mm.
  • the deposition parameters of the CFO control layer in step (3) are: the vacuum degree of the deposition chamber is ⁇ 5 ⁇ 10 -7 Pa, the deposition temperature is 700 ⁇ 720°C, the oxygen partial pressure is 100 ⁇ 120mTorr, the laser energy is 330 ⁇ 350mJ, and the pulsed laser
  • the frequency is 5 ⁇ 10Hz
  • the deposition temperature rate is 20 ⁇ 40°C/min
  • the deposition rate is 3 ⁇ 5nm/min
  • the distance between the substrate and the target during deposition is 55 ⁇ 80mm.
  • the deposition parameters of the PMN-PT epitaxial layer in step (4) are: the vacuum degree of the deposition chamber is ⁇ 1 ⁇ 10 -7 Pa, the deposition temperature is 600 ⁇ 620°C, the oxygen partial pressure is 180 ⁇ 220mTorr, and the laser energy is 280 ⁇ 320mJ.
  • the pulse laser frequency is 1 ⁇ 5Hz, the deposition temperature rate is 20 ⁇ 30°C/min, the deposition rate is 3 ⁇ 5nm/min, and the distance between the substrate and the target during deposition is 60 ⁇ 80mm.
  • cooling the prepared STO/SRO/CFO/PMN-PT epitaxial structure film material includes the following steps:
  • the epitaxial relationship of the prepared STO/SRO/CFO/PMN-PT epitaxial structure film material is STO[100]//SRO[100]//CFO[111]//PMN-PT[111] or STO[ 110]//SRO[110]//CFO[111]//PMN-PT[111] or STO[111]//SRO[111]//CFO[111]//PMN-PT[111].
  • the present application includes at least one of the following beneficial technical effects:
  • This application utilizes the control function of the CFO control layer to prepare PMN-PT epitaxial thin film materials with specific orientations on different substrates or substrates with different orientations, which solves the difficulty of obtaining PMN-PT with the same orientation under different substrates.
  • the problem of epitaxial thin film materials in order to study the material properties of PMN-PT epitaxial thin films under different substrate materials.
  • This application innovatively proposes a method for directional control of the growth orientation of PMN-PT epitaxial film materials, which can stably obtain PMN-PT epitaxial films with specific epitaxial orientations on different substrates or substrates with different orientations, and the process Low difficulty, simple and convenient, the quality of the obtained epitaxial film is good, which greatly reduces the production cost and post-processing cost, and the PMN-PT epitaxial film produced on different substrates or substrates with different orientations has excellent performance, which is beneficial to The rapid development of PMN-PT film in a single field.
  • Fig. 1 is the schematic diagram of PMN-PT epitaxial structure film material in the embodiment of the present application and comparative example
  • Fig. 2 is the XRD figure of the PMN-PT epitaxial structure film material prepared by the embodiment 1-3 of the present application;
  • Fig. 3 is the XRD figure of the PMN-PT epitaxial structure thin film material prepared by comparative example 1-3 of the present application;
  • Fig. 4 is the RSM diagram of the PMN-PT epitaxial structure film material prepared in Example 1 of the present application;
  • Fig. 5 is the P-V figure of the PMN-PT epitaxial structure film material that the embodiment of the present application and comparative example prepare;
  • Fig. 6 is the SHG diagram of the PMN-PT epitaxial structure thin film material prepared in the examples and comparative examples of the present application.
  • the piezoelectric energy harvester inside the human body By harvesting inexhaustible biomechanical energy and converting it into electrical energy, such as heart movement, muscle contraction/relaxation and blood circulation, the electrical energy converted by biomechanical energy can be directly implanted recharge the battery of a portable device or stimulate the heart.
  • Various types of piezoelectric materials have been tried, including ZnO nanowires, BaTiO 3 (BTO) films, and lead zirconate titanate piezoelectric ceramic (PZT) films. But its relatively low output current severely limits its applications in consumer electronics and biomedical devices, for example, cardiac pacemakers need to operate at 100 ⁇ A and 3V.
  • PMN-PT materials In order to make PMN-PT materials more widely used in energy harvesters, it is often necessary to grow PMN-PT materials on different substrates or substrates with different orientations. However, the growth orientations of PMN-PT materials grown on different substrates or substrates with different orientations are also different. PMN-PT materials with different growth orientations have anisotropy, which is not conducive to the study of PMNs with the same orientation under different substrate materials. -Material properties such as piezoelectric charge coefficient of PT materials. This application has innovatively researched a PMN-PT epitaxial film material with a specific orientation that can be prepared on different substrates or substrates with different orientations, which solves the difficulty of obtaining the same orientation PMN-PT epitaxial film under different substrates material problem.
  • a piezoelectric material that utilizes CoFe 2 O 4 to control the growth orientation of PMN-PT films including a substrate with a specific crystal plane orientation, a bottom electrode layer formed on the substrate, and a bottom electrode layer formed on the bottom electrode layer The control layer, and the epitaxial layer formed on the control layer.
  • the substrate is a SrTiO 3 (STO) substrate with a crystal plane orientation of [100]
  • the bottom electrode layer is a SrRuO 3 (SRO) layer grown on the STO substrate
  • the control layer is CoFe 2 O 4 grown on the SRO bottom electrode layer (CFO) layer
  • the epitaxial layer is a 0.62Pb(Mg 1/3 Nb 2/3) O 3 -0.38PbTiO 3 (PMN-PT) layer grown based on the CFO control layer.
  • the STO substrate, the SRO bottom electrode layer, the CFO control layer and the PMN-PT epitaxial layer form a film material with the epitaxial structure of STO/SRO/CFO/PMN-PT, and the epitaxial relationship of the STO/SRO/CFO/PMN-PT epitaxial structure is as follows: STO[100]//SRO[100]//CFO[111]//PMN-PT[111].
  • the preparation method of the above-mentioned STO/SRO/CFO/PMN-PT epitaxial structure film material is the following steps:
  • the pulsed laser deposition system uses the pulsed laser deposition system to switch the SRO target to the main target position, bombard the SRO target to deposit the SRO layer on the STO substrate as the bottom electrode layer, and control the distance between the SRO target and the STO substrate during bombardment as 75mm, the thickness of the bottom electrode layer formed by deposition is 23nm; during the deposition process, the vacuum degree of the deposition chamber is controlled to be ⁇ 5 ⁇ 10 -6 Pa, the deposition temperature is 700°C, the oxygen partial pressure is 120mTorr, the laser energy is 330mJ, the pulse laser frequency is 9.9Hz, and the deposition temperature The rate is 30°C/min, and the deposition rate is 5nm/min.
  • the vacuum degree of the deposition chamber is controlled to be ⁇ 5 ⁇ 10 -7 Pa
  • the deposition temperature is 710°C
  • the oxygen partial pressure is 110mTorr
  • the laser energy is 340mJ
  • the pulse laser frequency is 9.9Hz
  • the deposition temperature rate is 30°C/min
  • the deposition rate is 5nm /min.
  • the PMN-PT target to the main target position, bombard the PMN-PT target to deposit an epitaxial layer on the CFO layer, control the distance between the PMN-PT target and the substrate to 75mm during bombardment, and deposit the formed
  • the thickness of the epitaxial layer is 190nm; during the deposition process, the vacuum degree of the deposition chamber is controlled to be ⁇ 1 ⁇ 10 -7 Pa, the deposition temperature is 610°C, the oxygen partial pressure is 200mTorr, the laser energy is 300mJ, the pulse laser frequency is 5Hz, the deposition temperature rate is 25°C/min, and the deposition The speed is 5nm/min, and the STO/SRO/CFO/PMN-PT epitaxial structure film material with a total thickness of 243nm is obtained.
  • Example 1 The difference from Example 1 is that the crystal plane orientation of the STO substrate is [110], and the epitaxial relationship of the obtained STO/SRO/CFO/PMN-PT epitaxial structure film material is STO[110]//SRO[110]/ /CFO[111]//PMN-PT[111].
  • Example 1 The difference from Example 1 is that the crystal plane orientation of the STO substrate is [111], and the epitaxial relationship of the obtained STO/SRO/CFO/PMN-PT epitaxial structure film material is STO[111]//SRO[111]/ /CFO[111]//PMN-PT[111].
  • Example 1 The difference from Example 1 is that the deposition of the CFO control layer is not carried out, and the epitaxial relationship of the obtained STO/SRO/PMN-PT epitaxial structure film material is STO[100]//SRO[100]//PMN-PT[100 ].
  • Example 2 The difference from Example 2 is that the deposition of the CFO control layer is not carried out, and the epitaxial relationship of the obtained STO/SRO/PMN-PT epitaxial structure film material is STO[110]//SRO[110]//PMN-PT[110 ].
  • Example 3 The difference from Example 3 is that the deposition of the CFO control layer is not carried out, and the epitaxial relationship of the obtained STO/SRO/PMN-PT epitaxial structure film material is STO[111]//SRO[111]//PMN-PT[111 ].
  • the PMN-PT films grown on STO substrates with different orientations are all PMN-PT films with specific orientations, as in Example 1 using STO [100] orientation growth PMN-PT[111] film, Example 2 uses STO[110] orientation to grow PMN-PT[111] film, and Example 3 uses STO[111] orientation to grow PMN-PT[111] film.
  • the RSM diagram represents the extension relationship of STO[100]//SRO[100]//CFO[111]//PMN-PT[111].
  • the circles from front to back represent STO, SRO, CFO and
  • the orientation of the PMN-PT film proves the accuracy of Figure 2 and Figure 3.

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  • Chemical & Material Sciences (AREA)
  • Ceramic Engineering (AREA)
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Abstract

The present application discloses a piezoelectric material for directionally regulating the growth orientation of a PMN-PT film by using CoFe2O4. A PMN-PT film material comprises a substrate having a specific crystal plane orientation, a bottom electrode layer formed on the substrate, a regulation layer formed on the bottom electrode layer, and an epitaxial layer formed on the regulation layer; the regulation layer is a CFO layer grown based on the bottom electrode layer, the epitaxial layer is a PMN-PT layer grown based on the regulation layer, and an epitaxial orientation of the PMN-PT layer is [111]. A preparation method for said piezoelectric material comprises: selecting an STO substrate having a crystal plane orientation of [100] or [110] or [111] as a substrate, growing an SRO layer on the STO substrate, growing a CFO layer on the SRO bottom electrode layer, and growing a PMN-PT layer on the CFO regulation layer. According to the present application, PMN-PT epitaxial film materials having specific orientations can be prepared on different substrates or substrates having different orientations.

Description

利用CoFe2O4定向调控PMN-PT薄膜生长取向的压电材料及其制备方法Piezoelectric material and its preparation method using CoFe2O4 to control the growth orientation of PMN-PT thin film 技术领域technical field
本申请涉及PMN-PT薄膜材料的领域，更具体地说，它涉及一种利用CoFe 2O 4定向调控PMN-PT薄膜生长取向的压电材料。 This application relates to the field of PMN-PT thin film materials, more specifically, it relates to a piezoelectric material that uses CoFe 2 O 4 to regulate the growth orientation of PMN-PT thin films.
背景技术Background technique
随着科学技术的发展和社会的进步，近年来，基于不规则振动运动和机械变形的能量收集系统是自供电医学电子领域的一个很有前途的研究方向。操纵人体内部的压电能量收集器具有特别的医学意义，通过收集取之不尽的生物力学能量并将其转化为电能，如心脏运动、肌肉收缩/松弛和血液循环，不仅为植入式心率检测与传输系统的运行提供了可能，也为自供电人工起搏器的研制提供了可能，通过生物力学能量转化的电能可直接给植入式装置的电池充电或刺激心脏。With the development of science and technology and the progress of society, energy harvesting systems based on irregular vibratory motion and mechanical deformation are a promising research direction in the field of self-powered medical electronics in recent years. Manipulating piezoelectric energy harvesters inside the human body is of particular medical interest, not only for implanted heart rate by harvesting inexhaustible biomechanical energy and converting it into electricity The operation of the detection and transmission system opens up the possibility of developing a self-powered artificial pacemaker, which can directly charge the battery of an implanted device or stimulate the heart through the conversion of biomechanical energy.
目前研究上已经尝试各种类型的压电材料，包括ZnO纳米线，BaTiO 3（BTO）薄膜和锆钛酸铅压电陶瓷（PZT）薄膜。尽管上述的能量收集器可以为操作小型电子设备提供电力，其相对较低的输出电流严格限制了其在消费类电子产品以及生物医学设备的应用范围，例如，心脏起搏器需要在100μA和3V下工作。 Various types of piezoelectric materials have been tried, including ZnO nanowires, BaTiO 3 (BTO) films, and lead zirconate titanate piezoelectric ceramic (PZT) films. Although the aforementioned energy harvesters can provide power to operate small electronic devices, their relatively low output currents severely limit their applications in consumer electronics as well as biomedical devices. down to work.
技术问题technical problem
因此，研究上开始利用具有更高的压电电荷系数的材料来提高能量收集器的输出电流效率，其中单晶铌镁酸铅－钛酸铅（PMN-PT）是一种高压电电荷系数压电材料，其压电电荷系数d33高达2500pC/N，比PZT材料高近4倍，比BTO材料高20倍，比ZnO材料高90倍。Therefore, research has begun to use materials with higher piezoelectric charge coefficients to improve the output current efficiency of energy harvesters, among which single crystal lead magnesium niobate-lead titanate (PMN-PT) is a high-voltage electric charge coefficient Piezoelectric materials, the piezoelectric charge coefficient d33 is as high as 2500pC/N, nearly 4 times higher than PZT materials, 20 times higher than BTO materials, and 90 times higher than ZnO materials.
为了使PMN-PT材料应用于能量收集器的领域更广泛，往往需要在不同衬底或不同取向的衬底上生长PMN-PT材料，但是在不同衬底或不同取向的衬底上生长的PMN-PT材料的生长取向也不同，不同生长取向的PMN-PT材料存在各向异性，性能也不同，不利于在不同衬底材料下研究相同取向的PMN-PT材料的压电电荷系数等材料性能。In order to make PMN-PT materials more widely used in energy harvesters, it is often necessary to grow PMN-PT materials on different substrates or substrates with different orientations, but PMNs grown on different substrates or substrates with different orientations -The growth orientation of PT materials is also different. PMN-PT materials with different growth orientations have anisotropy and different properties, which is not conducive to studying the piezoelectric charge coefficient and other material properties of PMN-PT materials with the same orientation under different substrate materials. .
技术解决方案technical solution
为了改善在不同衬底或不同取向的衬底上生长的PMN-PT材料的生长取向不同的问题，本申请提供一种利用CoFe 2O 4定向调控PMN-PT薄膜生长取向的压电材料及其制备方法。 In order to improve the problem of different growth orientations of PMN - PT materials grown on different substrates or substrates with different orientations, the application provides a piezoelectric material and its Preparation.
第一方面，本申请提供一种利用CoFe 2O 4定向调控PMN-PT薄膜生长取向的压电材料，采用如下的技术方案： In the first aspect, the present application provides a piezoelectric material that utilizes CoFe 2 O 4 to regulate the growth orientation of PMN-PT film, and adopts the following technical scheme:
一种利用CoFe 2O 4定向调控PMN-PT薄膜生长取向的压电材料，包括： A piezoelectric material that uses CoFe 2 O 4 to regulate the growth orientation of PMN-PT film, including:
衬底，所述衬底具有特定晶面取向；a substrate having a specific crystal plane orientation;
底电极层，形成于所述衬底上；a bottom electrode layer formed on the substrate;
调控层，形成于所述底电极层上，所述调控层为基于所述底电极层生长的CoFe 2O 4（CFO）层； a control layer formed on the bottom electrode layer, the control layer is a CoFe 2 O 4 (CFO) layer grown based on the bottom electrode layer;
外延层，形成于所述调控层上，所述外延层为基于所述调控层生长的[(X)Pb(Mg YNb 1-Y)O 3-(1-X)PbTiO 3(X=0.6~0.7；Y=0.2~0.4)]（PMN-PT）层； An epitaxial layer, formed on the control layer, the epitaxial layer is [(X)Pb(MgY Nb 1-Y ) O 3 -(1-X)PbTiO 3 (X=0.6 ~0.7; Y=0.2~0.4)] (PMN-PT) layer;
所述衬底、所述底电极层、所述调控层以及所述外延层形成衬底/底电极层/CFO/PMN-PT外延结构，所述PMN-PT层的外延取向为[111]。The substrate, the bottom electrode layer, the control layer and the epitaxial layer form a substrate/bottom electrode layer/CFO/PMN-PT epitaxial structure, and the epitaxial orientation of the PMN-PT layer is [111].
通过采用上述技术方案，利用CFO调控层的调控作用，在不同衬底或不同取向的衬底上都能制备得到特定取向的PMN-PT外延薄膜材料，解决了在不同衬底下难以得到相同取向PMN-PT外延薄膜材料的问题，以便于研究不同衬底材料下的PMN-PT外延薄膜的材料性能。By adopting the above technical scheme and utilizing the control function of the CFO control layer, PMN-PT epitaxial thin film materials with specific orientations can be prepared on different substrates or substrates with different orientations, which solves the problem that it is difficult to obtain PMNs with the same orientation under different substrates. - The problem of PT epitaxial film material, in order to study the material properties of PMN-PT epitaxial film under different substrate materials.
优选的，所述衬底的组成元素包括Sr和Ti。Preferably, the constituent elements of the substrate include Sr and Ti.
优选的，所述衬底为SrTiO 3（STO）基片。 Preferably, the substrate is a SrTiO 3 (STO) substrate.
优选的，所述STO基片的晶面取向为[100]或[110]或[111]。Preferably, the crystal plane orientation of the STO substrate is [100] or [110] or [111].
优选的，所述底电极层的组成元素包括Sr和Ru。Preferably, the constituent elements of the bottom electrode layer include Sr and Ru.
优选的，所述底电极层为SrRuO 3（SRO）层。 Preferably, the bottom electrode layer is a SrRuO 3 (SRO) layer.
优选的，所述底电极层的厚度为10~30nm，所述调控层的厚度为20~40nm，所述外延层的厚度为180~200nm，所述外延结构的总厚度为210~270nm。Preferably, the thickness of the bottom electrode layer is 10-30 nm, the thickness of the control layer is 20-40 nm, the thickness of the epitaxial layer is 180-200 nm, and the total thickness of the epitaxial structure is 210-270 nm.
优选的，所述底电极层的厚度为20~25nm，所述调控层的厚度为25~35nm，所述外延层的厚度为185~195nm，所述外延结构的总厚度为230~255nm。Preferably, the thickness of the bottom electrode layer is 20-25 nm, the thickness of the control layer is 25-35 nm, the thickness of the epitaxial layer is 185-195 nm, and the total thickness of the epitaxial structure is 230-255 nm.
第二方面，本申请提供一种利用CoFe 2O 4定向调控PMN-PT薄膜生长取向的压电材料的制备方法，采用如下的技术方案： In the second aspect, the present application provides a method for preparing a piezoelectric material that uses CoFe 2 O 4 to regulate the growth orientation of PMN-PT film, and adopts the following technical scheme:
一种利用CoFe 2O 4定向调控PMN-PT薄膜生长取向的压电材料的制备方法，包括以下步骤： A method for preparing a piezoelectric material utilizing CoFe 2 O directional regulation of PMN - PT film growth orientation, comprising the following steps:
（1）选取特定晶面取向的衬底；(1) Select a substrate with a specific crystal plane orientation;
（2）在选取的特定晶面取向的衬底上生成底电极层；(2) Generate the bottom electrode layer on the selected substrate with a specific crystal plane orientation;
（3）在底电极层上生成CFO层作为调控层；(3) Generate a CFO layer on the bottom electrode layer as a control layer;
（4）在CFO调控层上生成PMN-PT层作为外延层，形成外延结构为衬底/底电极层/CFO/PMN-PT的薄膜材料。(4) Generate a PMN-PT layer on the CFO control layer as an epitaxial layer to form a thin film material with an epitaxial structure of substrate/bottom electrode layer/CFO/PMN-PT.
通过采用上述技术方案，能够稳定地在不同衬底或不同取向衬底上得到具有特定外延取向的PMN-PT外延薄膜，并且工艺难度低，简单方便，制得的外延薄膜质量好，极大地降低了生产成本和后期处理成本。By adopting the above technical scheme, PMN-PT epitaxial films with specific epitaxial orientations can be stably obtained on different substrates or substrates with different orientations, and the process difficulty is low, simple and convenient, and the quality of the obtained epitaxial films is good, greatly reducing the production costs and post-processing costs.
优选的，包括以下步骤：Preferably, the following steps are included:
（1）选取STO基片作为衬底，STO基片的晶面取向为[100]或[110]或[111]；(1) Select the STO substrate as the substrate, and the crystal plane orientation of the STO substrate is [100] or [110] or [111];
（2）在STO基片上生成SRO层作为底电极层；(2) Generate an SRO layer on the STO substrate as the bottom electrode layer;
（3）在SRO底电极层上生成CFO层作为调控层；(3) Generate a CFO layer on the SRO bottom electrode layer as a control layer;
（4）在CFO调控层上生成PMN-PT层作为外延层，形成外延结构为STO/SRO/CFO/PMN-PT的薄膜材料。(4) Generate a PMN-PT layer on the CFO control layer as an epitaxial layer to form a thin film material with an epitaxial structure of STO/SRO/CFO/PMN-PT.
优选的，步骤（2）中生成底电极层、步骤（3）中生成调控层以及步骤（4）中生成外延层均采用脉冲激光沉积方法。Preferably, the generation of the bottom electrode layer in step (2), the generation of the control layer in step (3) and the generation of the epitaxial layer in step (4) all use pulsed laser deposition methods.
优选的，步骤（1）包括以下步骤：Preferably, step (1) includes the following steps:
a.选取晶面取向为[100]或[110]或[111]的STO基片进行清洁，用无尘棉签蘸取少量酒精溶液擦拭STO基片表面至基片表面无其他杂质；a. Select an STO substrate with a crystal plane orientation of [100] or [110] or [111] for cleaning, and use a dust-free cotton swab to dip a small amount of alcohol solution to wipe the surface of the STO substrate until there are no other impurities on the surface of the substrate;
b.用导电银浆溶液在加热背板表面进行涂覆，将清洁处理后STO基片粘接于加热背板上；b. Coat the surface of the heating backplane with a conductive silver paste solution, and bond the cleaned STO substrate to the heating backplane;
c.将STO基片与加热背板一起放置于脉冲激光沉积系统的生长腔内。c. Place the STO substrate together with the heating backplate in the growth chamber of the pulsed laser deposition system.
优选的，步骤（2）中SRO底电极层的沉积参数为：沉积腔真空度≤5×10 -6Pa，沉积温度690~710℃，氧分压110~130mTorr，激光能量320~340mJ，脉冲激光频率5~10Hz，沉积温度速率20~40℃/min，沉积速率3~5nm/min，沉积时基底与靶材之间的距离为55~80mm。 Preferably, the deposition parameters of the SRO bottom electrode layer in step (2) are: the vacuum degree of the deposition chamber is ≤5×10 -6 Pa, the deposition temperature is 690~710°C, the oxygen partial pressure is 110~130mTorr, the laser energy is 320~340mJ, and the pulse The laser frequency is 5~10Hz, the deposition temperature rate is 20~40°C/min, the deposition rate is 3~5nm/min, and the distance between the substrate and the target during deposition is 55~80mm.
优选的，步骤（3）中CFO调控层的沉积参数为：沉积腔真空度≤5×10 -7Pa，沉积温度700~720℃，氧分压100~120mTorr，激光能量330~350mJ，脉冲激光频率5~10Hz，沉积温度速率20~40℃/min，沉积速率3~5nm/min，沉积时基底与靶材之间的距离为55~80mm。 Preferably, the deposition parameters of the CFO control layer in step (3) are: the vacuum degree of the deposition chamber is ≤5×10 -7 Pa, the deposition temperature is 700~720°C, the oxygen partial pressure is 100~120mTorr, the laser energy is 330~350mJ, and the pulsed laser The frequency is 5~10Hz, the deposition temperature rate is 20~40°C/min, the deposition rate is 3~5nm/min, and the distance between the substrate and the target during deposition is 55~80mm.
优选的，步骤（4）中PMN-PT外延层的沉积参数为：沉积腔真空度≤1×10 -7Pa，沉积温度600~620℃，氧分压180~220mTorr，激光能量280~320mJ，脉冲激光频率1~5Hz，沉积温度速率20~30℃/min，沉积速率3~5nm/min，沉积时基底与靶材之间的距离为60~80mm。 Preferably, the deposition parameters of the PMN-PT epitaxial layer in step (4) are: the vacuum degree of the deposition chamber is ≤1×10 -7 Pa, the deposition temperature is 600~620°C, the oxygen partial pressure is 180~220mTorr, and the laser energy is 280~320mJ. The pulse laser frequency is 1~5Hz, the deposition temperature rate is 20~30°C/min, the deposition rate is 3~5nm/min, and the distance between the substrate and the target during deposition is 60~80mm.
优选的，对制得的STO/SRO/CFO/PMN-PT外延结构薄膜材料进行冷却处理，包括以下步骤：Preferably, cooling the prepared STO/SRO/CFO/PMN-PT epitaxial structure film material includes the following steps:
i.将制得的STO/SRO/CFO/PMN-PT外延结构薄膜材料在600~620℃、180~220mTorr的条件下放置1~1.5h；i. Place the prepared STO/SRO/CFO/PMN-PT epitaxial structure film material under the conditions of 600~620°C and 180~220mTorr for 1~1.5h;
ii.保持氧分压不变，以5~7℃/min的降温速度将STO/SRO/CFO/PMN-PT外延结构薄膜材料缓慢冷却至室温。ii. Keep the oxygen partial pressure constant, and slowly cool the STO/SRO/CFO/PMN-PT epitaxial structure film material to room temperature at a cooling rate of 5-7°C/min.
优选的，制得的STO/SRO/CFO/PMN-PT外延结构薄膜材料的外延关系为STO[100]//SRO[100]//CFO[111]//PMN-PT[111]或STO[110]//SRO[110]//CFO[111]//PMN-PT[111]或STO[111]//SRO[111]//CFO[111]//PMN-PT[111]。Preferably, the epitaxial relationship of the prepared STO/SRO/CFO/PMN-PT epitaxial structure film material is STO[100]//SRO[100]//CFO[111]//PMN-PT[111] or STO[ 110]//SRO[110]//CFO[111]//PMN-PT[111] or STO[111]//SRO[111]//CFO[111]//PMN-PT[111].
有益效果Beneficial effect
综上所述，本申请包括以下至少一种有益技术效果：In summary, the present application includes at least one of the following beneficial technical effects:
1、本申请利用CFO调控层的调控作用，在不同衬底或不同取向的衬底上都能制备得到特定取向的PMN-PT外延薄膜材料，解决了在不同衬底下难以得到相同取向PMN-PT外延薄膜材料的问题，以便于研究不同衬底材料下的PMN-PT外延薄膜的材料性能。1. This application utilizes the control function of the CFO control layer to prepare PMN-PT epitaxial thin film materials with specific orientations on different substrates or substrates with different orientations, which solves the difficulty of obtaining PMN-PT with the same orientation under different substrates. The problem of epitaxial thin film materials, in order to study the material properties of PMN-PT epitaxial thin films under different substrate materials.
2、本申请创新性地提出了PMN-PT外延薄膜材料的定向调控生长取向的方法，能够稳定地在不同衬底或不同取向衬底上得到具有特定外延取向的PMN-PT外延薄膜，并且工艺难度低，简单方便，制得的外延薄膜质量好，极大地降低了生产成本和后期处理成本，且在不同衬底或不同取向衬底上生成的PMN-PT外延薄膜具有优异的性能，有利于PMN-PT薄膜在单一领域的飞速发展。2. This application innovatively proposes a method for directional control of the growth orientation of PMN-PT epitaxial film materials, which can stably obtain PMN-PT epitaxial films with specific epitaxial orientations on different substrates or substrates with different orientations, and the process Low difficulty, simple and convenient, the quality of the obtained epitaxial film is good, which greatly reduces the production cost and post-processing cost, and the PMN-PT epitaxial film produced on different substrates or substrates with different orientations has excellent performance, which is beneficial to The rapid development of PMN-PT film in a single field.
附图说明Description of drawings
图1是本申请实施例和对比例中PMN-PT外延结构薄膜材料的示意图；Fig. 1 is the schematic diagram of PMN-PT epitaxial structure film material in the embodiment of the present application and comparative example;
图2是本申请实施例1-3制备得到的PMN-PT外延结构薄膜材料的XRD图；Fig. 2 is the XRD figure of the PMN-PT epitaxial structure film material prepared by the embodiment 1-3 of the present application;
图3是本申请对比例1-3制备得到的PMN-PT外延结构薄膜材料的XRD图；Fig. 3 is the XRD figure of the PMN-PT epitaxial structure thin film material prepared by comparative example 1-3 of the present application;
图4是本申请实施例1制备得到的PMN-PT外延结构薄膜材料的RSM图；Fig. 4 is the RSM diagram of the PMN-PT epitaxial structure film material prepared in Example 1 of the present application;
图5是本申请实施例和对比例制备得到的PMN-PT外延结构薄膜材料的P-V图；Fig. 5 is the P-V figure of the PMN-PT epitaxial structure film material that the embodiment of the present application and comparative example prepare;
图6是本申请实施例和对比例制备得到的PMN-PT外延结构薄膜材料的SHG图。Fig. 6 is the SHG diagram of the PMN-PT epitaxial structure thin film material prepared in the examples and comparative examples of the present application.
本发明的实施方式Embodiments of the present invention
操纵人体内部的压电能量收集器通过收集取之不尽的生物力学能量并将其转化为电能，如心脏运动、肌肉收缩/松弛和血液循环，通过生物力学能量转化的电能可直接给植入式装置的电池充电或刺激心脏。目前研究上已经尝试各种类型的压电材料，包括ZnO纳米线，BaTiO 3（BTO）薄膜和锆钛酸铅压电陶瓷（PZT）薄膜。但其相对较低的输出电流严格限制了其在消费类电子产品以及生物医学设备的应用范围，例如，心脏起搏器需要在100μA和3V下工作。因此，研究上开始利用具有更高的压电电荷系数的单晶铌镁酸铅－钛酸铅（PMN-PT）来提高能量收集器的输出电流效率，其压电电荷系数d33高达2500pC/N，比PZT材料高近4倍，比BTO材料高20倍，比ZnO材料高90倍。 Manipulate the piezoelectric energy harvester inside the human body By harvesting inexhaustible biomechanical energy and converting it into electrical energy, such as heart movement, muscle contraction/relaxation and blood circulation, the electrical energy converted by biomechanical energy can be directly implanted recharge the battery of a portable device or stimulate the heart. Various types of piezoelectric materials have been tried, including ZnO nanowires, BaTiO 3 (BTO) films, and lead zirconate titanate piezoelectric ceramic (PZT) films. But its relatively low output current severely limits its applications in consumer electronics and biomedical devices, for example, cardiac pacemakers need to operate at 100μA and 3V. Therefore, research has begun to use single crystal lead magnesium niobate-lead titanate (PMN-PT) with a higher piezoelectric charge coefficient to improve the output current efficiency of the energy harvester, and its piezoelectric charge coefficient d33 is as high as 2500pC/N , nearly 4 times higher than PZT materials, 20 times higher than BTO materials, and 90 times higher than ZnO materials.
为了使PMN-PT材料应用于能量收集器的领域更广泛，往往需要在不同衬底或不同取向的衬底上生长PMN-PT材料。但是在不同衬底或不同取向的衬底上生长的PMN-PT材料的生长取向也不同，不同生长取向的PMN-PT材料存在各向异性，不利于在不同衬底材料下研究相同取向的PMN-PT材料的压电电荷系数等材料性能。本申请创新性地研究出了一种在不同衬底或不同取向的衬底上都能制备得到特定取向的PMN-PT外延薄膜材料，解决了在不同衬底下难以得到相同取向PMN-PT外延薄膜材料的问题。In order to make PMN-PT materials more widely used in energy harvesters, it is often necessary to grow PMN-PT materials on different substrates or substrates with different orientations. However, the growth orientations of PMN-PT materials grown on different substrates or substrates with different orientations are also different. PMN-PT materials with different growth orientations have anisotropy, which is not conducive to the study of PMNs with the same orientation under different substrate materials. -Material properties such as piezoelectric charge coefficient of PT materials. This application has innovatively researched a PMN-PT epitaxial film material with a specific orientation that can be prepared on different substrates or substrates with different orientations, which solves the difficulty of obtaining the same orientation PMN-PT epitaxial film under different substrates material problem.
为了更方便理解本申请的技术方案，以下结合附图和实施例对本申请作进一步详细说明，但不作为本申请限定的保护范围。In order to facilitate understanding of the technical solution of the present application, the present application will be described in further detail below in conjunction with the accompanying drawings and embodiments, but it is not regarded as the protection scope limited by the present application.
实施例Example
实施例1Example 1
参照图1，一种利用CoFe 2O 4定向调控PMN-PT薄膜生长取向的压电材料，包括具有特定晶面取向的衬底、形成于衬底上的底电极层、形成于底电极层上的调控层、以及形成于调控层上的外延层。 Referring to Figure 1, a piezoelectric material that utilizes CoFe 2 O 4 to control the growth orientation of PMN-PT films, including a substrate with a specific crystal plane orientation, a bottom electrode layer formed on the substrate, and a bottom electrode layer formed on the bottom electrode layer The control layer, and the epitaxial layer formed on the control layer.
衬底为晶面取向是[100]的SrTiO 3（STO）基片，底电极层为基于STO衬底生长的SrRuO 3（SRO）层，调控层为基于SRO底电极层生长的CoFe 2O 4（CFO）层，外延层为基于CFO调控层生长的0.62Pb(Mg 1/3Nb 2/3)O 3-0.38PbTiO 3（PMN-PT）层。 The substrate is a SrTiO 3 (STO) substrate with a crystal plane orientation of [100], the bottom electrode layer is a SrRuO 3 (SRO) layer grown on the STO substrate, and the control layer is CoFe 2 O 4 grown on the SRO bottom electrode layer (CFO) layer, and the epitaxial layer is a 0.62Pb(Mg 1/3 Nb 2/3) O 3 -0.38PbTiO 3 (PMN-PT) layer grown based on the CFO control layer.
STO衬底、SRO底电极层、CFO调控层以及PMN-PT外延层形成外延结构为STO/SRO/CFO/PMN-PT的薄膜材料，STO/SRO/CFO/PMN-PT外延结构的外延关系为STO[100]//SRO[100]//CFO[111]//PMN-PT[111]。The STO substrate, the SRO bottom electrode layer, the CFO control layer and the PMN-PT epitaxial layer form a film material with the epitaxial structure of STO/SRO/CFO/PMN-PT, and the epitaxial relationship of the STO/SRO/CFO/PMN-PT epitaxial structure is as follows: STO[100]//SRO[100]//CFO[111]//PMN-PT[111].
上述STO/SRO/CFO/PMN-PT外延结构薄膜材料的制备方法为以下步骤：The preparation method of the above-mentioned STO/SRO/CFO/PMN-PT epitaxial structure film material is the following steps:
（1）选取晶面取向为[100]的STO进行清洁及粘接处理，具体步骤如下：(1) Select the STO with a crystal plane orientation of [100] for cleaning and bonding. The specific steps are as follows:
a.用无尘棉签蘸取少量酒精溶液擦拭STO基片表面至基片表面无其他杂质；a. Use a dust-free cotton swab to dip a small amount of alcohol solution to wipe the surface of the STO substrate until there are no other impurities on the surface of the substrate;
b.用导电银浆溶液在加热背板表面进行涂覆，将清洁处理后STO基片粘接于加热背板上；b. Coat the surface of the heating backplane with a conductive silver paste solution, and bond the cleaned STO substrate to the heating backplane;
c.将STO基片与加热背板一起放置于脉冲激光沉积系统的生长腔内。c. Place the STO substrate together with the heating backplate in the growth chamber of the pulsed laser deposition system.
（2）利用脉冲激光沉积系统，将SRO靶材切换至主靶位，轰击SRO靶材在STO基片上沉积形成SRO层作为底电极层，轰击时控制SRO靶材与STO基底之间的距离为75mm，沉积形成的底电极层厚度为23nm；沉积过程中控制沉积腔真空度≤5×10 -6Pa，沉积温度700℃，氧分压120mTorr，激光能量330mJ，脉冲激光频率9.9Hz，沉积温度速率30℃/min，沉积速率5nm/min。 (2) Use the pulsed laser deposition system to switch the SRO target to the main target position, bombard the SRO target to deposit the SRO layer on the STO substrate as the bottom electrode layer, and control the distance between the SRO target and the STO substrate during bombardment as 75mm, the thickness of the bottom electrode layer formed by deposition is 23nm; during the deposition process, the vacuum degree of the deposition chamber is controlled to be ≤5×10 -6 Pa, the deposition temperature is 700°C, the oxygen partial pressure is 120mTorr, the laser energy is 330mJ, the pulse laser frequency is 9.9Hz, and the deposition temperature The rate is 30°C/min, and the deposition rate is 5nm/min.
（3）将CFO靶材切换至主靶位，轰击CFO靶材在SRO层上沉积形成CFO层作为调控层，轰击时控制SRO靶材与基底之间的距离为75mm，沉积形成的调控层厚度为30nm；沉积过程中控制沉积腔真空度≤5×10 -7Pa，沉积温度710℃，氧分压110mTorr，激光能量340mJ，脉冲激光频率9.9Hz，沉积温度速率30℃/min，沉积速率5nm/min。 (3) Switch the CFO target to the main target position, bombard the CFO target to deposit a CFO layer on the SRO layer as a control layer, control the distance between the SRO target and the substrate to be 75mm during bombardment, and control the thickness of the control layer formed by deposition During the deposition process, the vacuum degree of the deposition chamber is controlled to be ≤5×10 -7 Pa, the deposition temperature is 710°C, the oxygen partial pressure is 110mTorr, the laser energy is 340mJ, the pulse laser frequency is 9.9Hz, the deposition temperature rate is 30°C/min, and the deposition rate is 5nm /min.
（4）将PMN-PT靶材切换至主靶位，轰击PMN-PT靶材在CFO层上沉积形成外延层，轰击时控制PMN-PT靶材与基底之间的距离为75mm，沉积形成的外延层厚度为190nm；沉积过程中控制沉积腔真空度≤1×10 -7Pa，沉积温度610℃，氧分压200mTorr，激光能量300mJ，脉冲激光频率5Hz，沉积温度速率25℃/min，沉积速率5nm/min，得到总厚度为243nm的STO/SRO/CFO/PMN-PT外延结构薄膜材料。 (4) Switch the PMN-PT target to the main target position, bombard the PMN-PT target to deposit an epitaxial layer on the CFO layer, control the distance between the PMN-PT target and the substrate to 75mm during bombardment, and deposit the formed The thickness of the epitaxial layer is 190nm; during the deposition process, the vacuum degree of the deposition chamber is controlled to be ≤1×10 -7 Pa, the deposition temperature is 610°C, the oxygen partial pressure is 200mTorr, the laser energy is 300mJ, the pulse laser frequency is 5Hz, the deposition temperature rate is 25°C/min, and the deposition The speed is 5nm/min, and the STO/SRO/CFO/PMN-PT epitaxial structure film material with a total thickness of 243nm is obtained.
（5）对制得的STO/SRO/CFO/PMN-PT外延结构薄膜材料进行冷却处理，步骤如下：(5) Cooling the prepared STO/SRO/CFO/PMN-PT epitaxial structure film material, the steps are as follows:
i.将制得的STO/SRO/CFO/PMN-PT外延结构薄膜材料在温度为610℃、氧分压为200mTorr的条件下放置1h；i. Place the prepared STO/SRO/CFO/PMN-PT epitaxial structure thin film material at a temperature of 610°C and an oxygen partial pressure of 200mTorr for 1h;
ii.保持氧分压不变，以5℃/min的降温速度将STO/SRO/CFO/PMN-PT外延结构薄膜材料缓慢冷却至室温，得到STO/SRO/CFO/PMN-PT外延结构薄膜材料成品。ii. Keeping the oxygen partial pressure constant, slowly cool the STO/SRO/CFO/PMN-PT epitaxial structure film material to room temperature at a cooling rate of 5°C/min to obtain the STO/SRO/CFO/PMN-PT epitaxial structure film material finished product.
实施例2Example 2
与实施例1的区别在于，STO基片的晶面取向为[110]，得到的STO/SRO/CFO/PMN-PT外延结构薄膜材料的外延关系为STO[110]//SRO[110]//CFO[111]//PMN-PT[111]。The difference from Example 1 is that the crystal plane orientation of the STO substrate is [110], and the epitaxial relationship of the obtained STO/SRO/CFO/PMN-PT epitaxial structure film material is STO[110]//SRO[110]/ /CFO[111]//PMN-PT[111].
实施例3Example 3
与实施例1的区别在于，STO基片的晶面取向为[111]，得到的STO/SRO/CFO/PMN-PT外延结构薄膜材料的外延关系为STO[111]//SRO[111]//CFO[111]//PMN-PT[111]。The difference from Example 1 is that the crystal plane orientation of the STO substrate is [111], and the epitaxial relationship of the obtained STO/SRO/CFO/PMN-PT epitaxial structure film material is STO[111]//SRO[111]/ /CFO[111]//PMN-PT[111].
对比例comparative example
对比例1Comparative example 1
与实施例1的区别在于，不进行CFO调控层的沉积，得到的STO/SRO/PMN-PT外延结构薄膜材料的外延关系为STO[100]//SRO[100]//PMN-PT[100]。The difference from Example 1 is that the deposition of the CFO control layer is not carried out, and the epitaxial relationship of the obtained STO/SRO/PMN-PT epitaxial structure film material is STO[100]//SRO[100]//PMN-PT[100 ].
对比例2Comparative example 2
与实施例2的区别在于，不进行CFO调控层的沉积，得到的STO/SRO/PMN-PT外延结构薄膜材料的外延关系为STO[110]//SRO[110]//PMN-PT[110]。The difference from Example 2 is that the deposition of the CFO control layer is not carried out, and the epitaxial relationship of the obtained STO/SRO/PMN-PT epitaxial structure film material is STO[110]//SRO[110]//PMN-PT[110 ].
对比例3Comparative example 3
与实施例3的区别在于，不进行CFO调控层的沉积，得到的STO/SRO/PMN-PT外延结构薄膜材料的外延关系为STO[111]//SRO[111]//PMN-PT[111]。The difference from Example 3 is that the deposition of the CFO control layer is not carried out, and the epitaxial relationship of the obtained STO/SRO/PMN-PT epitaxial structure film material is STO[111]//SRO[111]//PMN-PT[111 ].
如图2所示，通过XRD能够明显看出，当加入调控层CFO时，不同取向STO基底上生长制备得到的均为特定取向的PMN-PT薄膜，如实施例1使用STO[100]取向生长PMN-PT[111]薄膜，实施例2使用STO[110]取向生长PMN-PT[111]薄膜，实施例3使用STO[111]取向生长PMN-PT[111]薄膜。As shown in Figure 2, it can be clearly seen from XRD that when the control layer CFO is added, the PMN-PT films grown on STO substrates with different orientations are all PMN-PT films with specific orientations, as in Example 1 using STO [100] orientation growth PMN-PT[111] film, Example 2 uses STO[110] orientation to grow PMN-PT[111] film, and Example 3 uses STO[111] orientation to grow PMN-PT[111] film.
如图3所示，通过XRD能够明显看出，当没有调控层CFO时，不同取向STO基底上生长制备得到是相对应生长取向的PMN-PT薄膜，如对比例1使用STO[100]取向生长PMN-PT[100]薄膜，对比例2使用STO[110]取向生长PMN-PT[110]薄膜，对比例3使用STO[111]取向生长PMN-PT[111]薄膜。As shown in Figure 3, it can be clearly seen from XRD that when there is no control layer CFO, PMN-PT films with corresponding growth orientations are grown on STO substrates with different orientations, such as Comparative Example 1 using STO [100] orientation growth PMN-PT[100] film, comparative example 2 uses STO[110] orientation to grow PMN-PT[110] film, and comparative example 3 uses STO[111] orientation to grow PMN-PT[111] film.
如图4所示，RSM图表示STO[100]//SRO[100]//CFO[111]//PMN-PT[111]的外延关系，从前往后的圈依次代表STO、SRO、CFO以及PMN-PT薄膜的取向，证明图2和图3的准确性。As shown in Figure 4, the RSM diagram represents the extension relationship of STO[100]//SRO[100]//CFO[111]//PMN-PT[111]. The circles from front to back represent STO, SRO, CFO and The orientation of the PMN-PT film proves the accuracy of Figure 2 and Figure 3.
如图5所示，实施例1、2、3得到的特定取向的PMN-PT薄膜，其SHG图像一致，表明三种PMN-PT薄膜取向一致，而对比例1、2、3分别得到的不同取向的PMN-PT薄膜，其SHG图像不同代表其取向不同。As shown in Figure 5, the specific orientation PMN-PT films obtained in Examples 1, 2, and 3 have the same SHG images, indicating that the three PMN-PT films have the same orientation, while Comparative Examples 1, 2, and 3 obtained different Different SHG images of oriented PMN-PT films represent different orientations.
如图6所示，有无调控层对于PMN-PT外延薄膜材料的P-V图没有明显影响，证明加入调控层并不会影响PMN-PT外延薄膜材料的性能。As shown in Figure 6, the presence or absence of the control layer has no significant effect on the P-V diagram of the PMN-PT epitaxial thin film material, which proves that the addition of the control layer will not affect the performance of the PMN-PT epitaxial thin film material.
本具体实施例仅仅是对本申请的解释，其并不是对本申请的限制，本领域技术人员在阅读完本说明书后可以根据需要对本实施例做出没有创造性贡献的修改，但只要在本申请的权利要求范围内都受到专利法的保护。This specific embodiment is only an explanation of this application, and it is not a limitation of this application. Those skilled in the art can make modifications to this embodiment without creative contribution according to needs after reading this specification, but as long as the rights of this application All claims are protected by patent law.

Claims (16)

  1. 一种利用CoFe 2O 4定向调控PMN-PT薄膜生长取向的压电材料，其特征在于，包括： A kind of piezoelectric material utilizing CoFe 2 O directional control PMN - PT thin film growth orientation, is characterized in that, comprises:
    衬底，所述衬底具有特定晶面取向；a substrate having a specific crystal plane orientation;
    底电极层，形成于所述衬底上；a bottom electrode layer formed on the substrate;
    调控层，形成于所述底电极层上，所述调控层为基于所述底电极层生长的CoFe 2O 4（CFO）层； a control layer formed on the bottom electrode layer, the control layer is a CoFe 2 O 4 (CFO) layer grown based on the bottom electrode layer;
    外延层，形成于所述调控层上，所述外延层为基于所述调控层生长的[(X)Pb(Mg YNb 1-Y)O 3-(1-X)PbTiO 3(X=0.6~0.7；Y=0.2~0.4)]（PMN-PT）层； An epitaxial layer, formed on the control layer, the epitaxial layer is [(X)Pb(MgY Nb 1-Y ) O 3 -(1-X)PbTiO 3 (X=0.6 ~0.7; Y=0.2~0.4)] (PMN-PT) layer;
    所述衬底、所述底电极层、所述调控层以及所述外延层形成衬底/底电极层/CFO/PMN-PT外延结构，所述PMN-PT层的外延取向为[111]。The substrate, the bottom electrode layer, the control layer and the epitaxial layer form a substrate/bottom electrode layer/CFO/PMN-PT epitaxial structure, and the epitaxial orientation of the PMN-PT layer is [111].
  2. 根据权利要求1所述的利用CoFe 2O 4定向调控PMN-PT薄膜生长取向的压电材料，其特征在于：所述衬底的组成元素包括Sr和Ti。 The piezoelectric material for controlling the growth orientation of PMN-PT thin films by using CoFe 2 O 4 according to claim 1, characterized in that: the constituent elements of the substrate include Sr and Ti.
  3. 根据权利要求2所述的利用CoFe 2O 4定向调控PMN-PT薄膜生长取向的压电材料，其特征在于：所述衬底为SrTiO 3（STO）基片。 The piezoelectric material for controlling the growth orientation of PMN-PT thin films by using CoFe 2 O 4 according to claim 2, characterized in that: the substrate is a SrTiO 3 (STO) substrate.
  4. 根据权利要求3所述的利用CoFe 2O 4定向调控PMN-PT薄膜生长取向的压电材料，其特征在于：所述STO基片的晶面取向为[100]或[110]或[111]。 The piezoelectric material utilizing CoFe 2 O 4 to regulate the growth orientation of PMN-PT film according to claim 3, characterized in that: the crystal plane orientation of the STO substrate is [100] or [110] or [111] .
  5. 根据权利要求1所述的利用CoFe 2O 4定向调控PMN-PT薄膜生长取向的压电材料，其特征在于：所述底电极层的组成元素包括Sr和Ru。 The piezoelectric material for controlling the growth orientation of PMN-PT film by using CoFe 2 O 4 according to claim 1, characterized in that: the constituent elements of the bottom electrode layer include Sr and Ru.
  6. 根据权利要求5所述的利用CoFe 2O 4定向调控PMN-PT薄膜生长取向的压电材料，其特征在于：所述底电极层为SrRuO 3（SRO）层。 The piezoelectric material for controlling the growth orientation of PMN-PT film by using CoFe 2 O 4 according to claim 5, characterized in that: the bottom electrode layer is a SrRuO 3 (SRO) layer.
  7. 根据权利要求1-6中任一项所述的利用CoFe 2O 4定向调控PMN-PT薄膜生长取向的压电材料，其特征在于：所述底电极层的厚度为10~30nm，所述调控层的厚度为20~40nm，所述外延层的厚度为180~200nm，所述外延结构的总厚度为210~270nm。 According to any one of claims 1-6, the piezoelectric material utilizing CoFe 2 O directional control PMN - PT film growth orientation is characterized in that: the thickness of the bottom electrode layer is 10-30nm, and the control The thickness of the layer is 20-40nm, the thickness of the epitaxial layer is 180-200nm, and the total thickness of the epitaxial structure is 210-270nm.
  8. 根据权利要求7所述的利用CoFe 2O 4定向调控PMN-PT薄膜生长取向的压电材料，其特征在于：所述底电极层的厚度为20~25nm，所述调控层的厚度为25~35nm，所述外延层的厚度为185~195nm，所述外延结构的总厚度为230~255nm。 The piezoelectric material utilizing CoFe 2 O directional control PMN - PT film growth orientation according to claim 7, characterized in that: the thickness of the bottom electrode layer is 20-25 nm, and the thickness of the control layer is 25-20 nm. 35nm, the thickness of the epitaxial layer is 185-195nm, and the total thickness of the epitaxial structure is 230-255nm.
  9. 权利要求1-8中任一项所述的利用CoFe 2O 4定向调控PMN-PT薄膜生长取向的压电材料的制备方法，其特征在于，包括以下步骤： Utilize CoFe described in any one in claim 1-8 O The preparation method of the piezoelectric material of directional control PMN-PT thin film growth orientation, is characterized in that, comprises the following steps:
    （1）选取特定晶面取向的衬底；(1) Select a substrate with a specific crystal plane orientation;
    （2）在选取的特定晶面取向的衬底上生成底电极层；(2) Generate the bottom electrode layer on the selected substrate with a specific crystal plane orientation;
    （3）在底电极层上生成CFO层作为调控层；(3) Generate a CFO layer on the bottom electrode layer as a control layer;
    （4）在CFO调控层上生成PMN-PT层作为外延层，形成外延结构为衬底/底电极层/CFO/PMN-PT的薄膜材料。(4) Generate a PMN-PT layer on the CFO control layer as an epitaxial layer to form a thin film material with an epitaxial structure of substrate/bottom electrode layer/CFO/PMN-PT.
  10. 根据权利要求9所述的利用CoFe 2O 4定向调控PMN-PT薄膜生长取向的压电材料的制备方法，其特征在于，包括以下步骤： Utilize CoFe according to claim 9 O The preparation method of the piezoelectric material of directional regulation and control PMN-PT thin film growth orientation, is characterized in that, comprises the following steps:
    （1）选取STO基片作为衬底，STO基片的晶面取向为[100]或[110]或[111]；(1) Select the STO substrate as the substrate, and the crystal plane orientation of the STO substrate is [100] or [110] or [111];
    （2）在STO基片上生成SRO层作为底电极层；(2) Generate an SRO layer on the STO substrate as the bottom electrode layer;
    （3）在SRO底电极层上生成CFO层作为调控层；(3) Generate a CFO layer on the SRO bottom electrode layer as a control layer;
    （4）在CFO调控层上生成PMN-PT层作为外延层，形成外延结构为STO/SRO/CFO/PMN-PT的薄膜材料。(4) Generate a PMN-PT layer on the CFO control layer as an epitaxial layer to form a thin film material with an epitaxial structure of STO/SRO/CFO/PMN-PT.
  11. 根据权利要求10所述的利用CoFe 2O 4定向调控PMN-PT薄膜生长取向的压电材料的制备方法，其特征在于，步骤（2）中生成底电极层、步骤（3）中生成调控层以及步骤（4）中生成外延层均采用脉冲激光沉积方法。 The method for preparing a piezoelectric material utilizing CoFe 2 O 4 to regulate the growth orientation of PMN-PT film according to claim 10, characterized in that the bottom electrode layer is formed in step (2), and the control layer is formed in step (3) And the generation of the epitaxial layer in step (4) adopts the pulsed laser deposition method.
  12. 根据权利要求11所述的利用CoFe 2O 4定向调控PMN-PT薄膜生长取向的压电材料的制备方法，其特征在于，步骤（1）包括以下步骤： The method for preparing a piezoelectric material using CoFe 2 O 4 to regulate the growth orientation of a PMN-PT film according to claim 11, wherein the step (1) comprises the following steps:
    a.选取晶面取向为[100]或[110]或[111]的STO基片进行清洁，用无尘棉签蘸取少量酒精溶液擦拭STO基片表面至基片表面无其他杂质；a. Select the STO substrate with crystal plane orientation of [100] or [110] or [111] for cleaning, and use a dust-free cotton swab to dip a small amount of alcohol solution to wipe the surface of the STO substrate until there are no other impurities on the surface of the substrate;
    b.用导电银浆溶液在加热背板表面进行涂覆，将清洁处理后STO基片粘接于加热背板上；b. Coat the surface of the heating backplane with a conductive silver paste solution, and bond the cleaned STO substrate to the heating backplane;
    c.将STO基片与加热背板一起放置于脉冲激光沉积系统的生长腔内。c. Place the STO substrate together with the heating backplate in the growth chamber of the pulsed laser deposition system.
  13. 根据权利要求11所述的利用CoFe 2O 4定向调控PMN-PT薄膜生长取向的压电材料的制备方法，其特征在于，步骤（2）中SRO底电极层的沉积参数为：沉积腔真空度≤5×10 -6Pa，沉积温度690~710℃，氧分压110~130mTorr，激光能量320~340mJ，脉冲激光频率5~10Hz，沉积温度速率20~40℃/min，沉积速率3~5nm/min，沉积时基底与靶材之间的距离为55~80mm。 The method for preparing a piezoelectric material using CoFe 2 O 4 to regulate the growth orientation of a PMN-PT film according to claim 11, wherein the deposition parameters of the SRO bottom electrode layer in step (2) are: the vacuum degree of the deposition chamber ≤5×10 -6 Pa, deposition temperature 690~710℃, oxygen partial pressure 110~130mTorr, laser energy 320~340mJ, pulsed laser frequency 5~10Hz, deposition temperature rate 20~40℃/min, deposition rate 3~5nm /min, the distance between the substrate and the target during deposition is 55~80mm.
  14. 根据权利要求11所述的利用CoFe 2O 4定向调控PMN-PT薄膜生长取向的压电材料的制备方法，其特征在于，步骤（3）中CFO调控层的沉积参数为：沉积腔真空度≤5×10 -7Pa，沉积温度700~720℃，氧分压100~120mTorr，激光能量330~350mJ，脉冲激光频率5~10Hz，沉积温度速率20~40℃/min，沉积速率3~5nm/min，沉积时基底与靶材之间的距离为55~80mm。 The method for preparing a piezoelectric material using CoFe 2 O 4 to regulate the growth orientation of PMN-PT films according to claim 11, wherein the deposition parameters of the CFO control layer in step (3) are: the vacuum degree of the deposition chamber ≤ 5×10 -7 Pa, deposition temperature 700~720℃, oxygen partial pressure 100~120mTorr, laser energy 330~350mJ, pulsed laser frequency 5~10Hz, deposition temperature rate 20~40℃/min, deposition rate 3~5nm/ min, the distance between the substrate and the target during deposition is 55~80mm.
  15. 根据权利要求11所述的利用CoFe 2O 4定向调控PMN-PT薄膜生长取向的压电材料的制备方法，其特征在于，步骤（4）中PMN-PT外延层的沉积参数为：沉积腔真空度≤1×10 -7Pa，沉积温度600~620℃，氧分压180~220mTorr，激光能量280~320mJ，脉冲激光频率1~5Hz，沉积温度速率20~30℃/min，沉积速率3~5nm/min，沉积时基底与靶材之间的距离为60~80mm。 The method for preparing a piezoelectric material utilizing CoFe 2 O 4 to regulate the growth orientation of a PMN-PT film according to claim 11, wherein the deposition parameters of the PMN-PT epitaxial layer in step (4) are: deposition chamber vacuum Degree≤1×10 -7 Pa, deposition temperature 600~620℃, oxygen partial pressure 180~220mTorr, laser energy 280~320mJ, pulsed laser frequency 1~5Hz, deposition temperature rate 20~30℃/min, deposition rate 3~ 5nm/min, the distance between the substrate and the target during deposition is 60~80mm.
  16. 根据权利要求11所述的利用CoFe 2O 4定向调控PMN-PT薄膜生长取向的压电材料的制备方法，其特征在于，对制得的STO/SRO/CFO/PMN-PT外延结构薄膜材料进行冷却处理，包括以下步骤： Utilize CoFe according to claim 11 O The preparation method of the piezoelectric material of directional control PMN-PT thin film growth orientation, it is characterized in that, the STO/SRO/CFO/PMN-PT epitaxial structure thin film material that makes Cooling treatment, including the following steps:
    i.将制得的STO/SRO/CFO/PMN-PT外延结构薄膜材料在600~620℃、180~220mTorr的条件下放置1~1.5h；i. Place the prepared STO/SRO/CFO/PMN-PT epitaxial structure film material under the conditions of 600~620°C and 180~220mTorr for 1~1.5h;
    ii.保持氧分压不变，以5~7℃/min的降温速度将STO/SRO/CFO/PMN-PT外延结构薄膜材料缓慢冷却至室温。ii. Keep the oxygen partial pressure constant, and slowly cool the STO/SRO/CFO/PMN-PT epitaxial structure film material to room temperature at a cooling rate of 5-7°C/min.
    根据权利要求10-16中任一项所述的利用CoFe 2O 4定向调控PMN-PT薄膜生长取向的压电材料的制备方法，其特征在于，制得的STO/SRO/CFO/PMN-PT外延结构薄膜材料的外延关系为STO[100]//SRO[100]//CFO[111]//PMN-PT[111]或STO[110]//SRO[110]//CFO[111]//PMN-PT[111]或STO[111]//SRO[111]//CFO[111]//PMN-PT[111]。 Utilize CoFe2O according to any one of claim 10-16 The preparation method of the piezoelectric material of directional control PMN-PT film growth orientation, it is characterized in that, the prepared STO/SRO/CFO/PMN-PT The epitaxial relationship of epitaxial structure thin film material is STO[100]//SRO[100]//CFO[111]//PMN-PT[111] or STO[110]//SRO[110]//CFO[111]/ /PMN-PT[111] or STO[111]//SRO[111]//CFO[111]//PMN-PT[111].
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