CN112062568A - 一种利用热应变诱导宽温区电卡效应plzst基薄膜的制备方法 - Google Patents

一种利用热应变诱导宽温区电卡效应plzst基薄膜的制备方法 Download PDF

Info

Publication number
CN112062568A
CN112062568A CN202010979496.7A CN202010979496A CN112062568A CN 112062568 A CN112062568 A CN 112062568A CN 202010979496 A CN202010979496 A CN 202010979496A CN 112062568 A CN112062568 A CN 112062568A
Authority
CN
China
Prior art keywords
plzst
film
lanio
substrate
thermal strain
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202010979496.7A
Other languages
English (en)
Inventor
彭彪林
陆秋萍
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Guangxi University
Original Assignee
Guangxi University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Guangxi University filed Critical Guangxi University
Priority to CN202010979496.7A priority Critical patent/CN112062568A/zh
Publication of CN112062568A publication Critical patent/CN112062568A/zh
Pending legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/50—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on rare-earth compounds
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/46—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates
    • C04B35/462—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/46—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates
    • C04B35/462—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates
    • C04B35/472—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on lead titanates
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/62218—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products obtaining ceramic films, e.g. by using temporary supports
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
    • C04B2235/3227—Lanthanum oxide or oxide-forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3232—Titanium oxides or titanates, e.g. rutile or anatase
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3244—Zirconium oxides, zirconates, hafnium oxides, hafnates, or oxide-forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3293—Tin oxides, stannates or oxide forming salts thereof, e.g. indium tin oxide [ITO]
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3296—Lead oxides, plumbates or oxide forming salts thereof, e.g. silver plumbate
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/60—Aspects relating to the preparation, properties or mechanical treatment of green bodies or pre-forms
    • C04B2235/602—Making the green bodies or pre-forms by moulding
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/60—Aspects relating to the preparation, properties or mechanical treatment of green bodies or pre-forms
    • C04B2235/606—Drying
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
    • C04B2235/6567—Treatment time
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/66—Specific sintering techniques, e.g. centrifugal sintering
    • C04B2235/661—Multi-step sintering
    • C04B2235/662—Annealing after sintering
    • C04B2235/663—Oxidative annealing

Abstract

本发明涉及一种利用热应变诱导宽温区电卡效应PLZST基薄膜的制备方法，属于化学工程技术领域。一种利用热应变诱导宽温区电卡效应PLZST基薄膜的制备方法，包括以下步骤：将LaNiO3前驱体溶液旋涂于衬底上制得第一湿膜，将所得的第一湿膜干燥、热解，退火制得单层LaNiO3薄膜；重复以上步骤制得多层LaNiO3/Si(100)或LaNiO3/Pt(111)复合基底；将PLZST前驱体溶液旋涂于衬底上，制得第二湿膜；对所得的第二湿膜干燥、热解，制得单层PLZST薄膜；重复制得多层PLZST薄膜，其中在制备多层PLZST薄膜之前或之后还包括退火的步骤。本发明制备方法相对简单，可以通过改变衬底的种类和热处理方式来调控薄膜的结构和电卡性能。

Description

一种利用热应变诱导宽温区电卡效应PLZST基薄膜的制备 方法
技术领域
本发明涉及一种利用热应变诱导宽温区电卡效应PLZST基薄膜的制备方法，属于化学工程技术领域。
背景技术
近年来，随着电子科技、信息和控制技术朝着微型化、高集成化方向的发展，以及高科技领域对于快速制冷的需求，基于铁电/反铁电薄膜/厚膜中电卡制冷的研究越来越多。与基于磁卡效应的磁制冷的快速发展相比，电卡制冷在过去很长一段时间里几乎没有进展，因为只能观察到较小的△T和△S，直至2006年才在反铁电PZT薄膜中发现了大的电卡效应(△T＝12k，△S＝8JK-1kg-1)。然而，实际商业应用中除了需要较大的△T值和高冷却效率外，还需要一个宽广的的操作温度范围。
发明内容
本发明的目的在于提供一种利用热应变诱导宽温区电卡效应PLZST基薄膜的制备方法。本发明通过利用具有宽温区、大的电卡效应铁电体材料PbxLa(1-x)(ZrySnzTi(1-y-z))O3(PLZST)，是一种具有宽温区、大的电卡效应铁电体材料，通过溶胶凝胶合成法在不同基底上面、采用不同的热处理制备出的PLZST薄膜材料，可以通过改变衬底的种类和热处理方式来调控薄膜的电卡性能。
本发明的目的通过如下技术方案实现：
一种利用热应变诱导宽温区电卡效应PLZST基薄膜的制备方法，包括以下步骤：
1)将LaNiO3前驱体溶液旋涂于衬底上制得第一湿膜，所述衬底为Si(100)或Pt(111)；
2)将步骤1)所得的第一湿膜干燥、热解，退火制得单层LaNiO3薄膜；
3)重复步骤1)和步骤2)，制得多层LaNiO3/Si(100)或LaNiO3/Pt(111)复合基底；
4)将PLZST前驱体溶液旋涂于衬底上，制得第二湿膜，所述衬底为Pt(111)、步骤3)制得的多层LaNiO3/Si(100)复合基底、步骤3制得的LaNiO3/Pt(111)复合基底中的任一一种；
5)当衬底为Pt(111)或LaNiO3/Si(100)复合基底时，按照如下步骤进行处理制得一层PLZST薄膜，
5-1)、将第二湿膜干燥、热解、退火制得一层PLZST薄膜，
当衬底为LaNiO3/Pt(111)复合基底时，可按照以下任一步骤进行处理制得一层PLZST，
5-2)、将第二湿膜干燥、热解、退火制得一层PLZST薄膜，
5-3)、将第二湿膜干燥、热解制得一层PLZST薄膜；
6)按照如下任一步骤进行处理制备多层PLZST薄膜：
6-1)、重复步骤4)和步骤5-1)制得多层PLZST薄膜，
6-2)、重复步骤4)和步骤5-2)制得多层PLZST薄膜；
6-3)、重复步骤4)和步骤5-3)制得未退火的PLZST薄膜，退火制得完全退火的多层PLZST薄膜。
优选的是，步骤1)所述的LaNiO3前驱体溶液浓度为0.2-0.3M。
优选的是，步骤1)所述旋涂转速为4000-6000rpm，旋涂时间为30-60s。
优选的是，步骤2)所述干燥温度为120-250℃，干燥时间为3-5min，所述热解温度为400-550℃，热解时间为3-5min，所述退火温度为700-800℃，退火时间为3-5min，退火环境为空气氛围。
优选的是，步骤3)制得6层LaNiO3薄膜。
优选的是，步骤4)所述的PLZST通式为PbxLa(1-x)(ZrySnzTi(1-y-z))O3，其中0<x<1,0<y<1,0<z<1，所述的PLZST前驱体溶液浓度为0.2-0.3M。
优选的是，步骤4)所述旋涂转速为4000-6000rpm，旋涂时间为30-60s。
优选的是，步骤5-1)、步骤5-2)和步骤5-3)所述干燥温度均为120-250℃，干燥时间均为3-5min，所述热解温度均为400-550℃，热解时间均为3-5min，步骤5-1)和步骤5-2)所述退火温度均为700-800℃，退火时间均为3-5min，退火环境均为空气氛围。
优选的是，步骤6-1)、步骤6-2)、步骤6-3)重复次数均为8次。
优选的是，步骤6-3)所述退火温度为700-800℃，退火时间为30-60min，退火环境为空气氛围。
本发明的有益效果是：获得具有纯度高、致密性好、平均晶粒尺寸小、电场击穿强度大、电卡效应大、操作温度范围广等优点的薄膜；本发明制备方法相对简单，可以通过改变衬底的种类和热处理方式来调控薄膜的结构和电卡性能，是一种方便快捷的制备技术。
附图说明
图1为本发明实施例1得到的PLZST薄膜的电卡性能；
图2为本发明实施例2得到的PLZST薄膜的电卡性能；
图3为本发明实施例3得到的PLZST薄膜的电卡性能；
图4为本发明实施例4得到的PLZST薄膜的电卡性能。
具体实施方式
下面结合具体实施例，对本发明作进一步详细的阐述，但本发明的实施方式并不局限于实施例表示的范围。这些实施例仅用于说明本发明，而非用于限制本发明的范围。此外，在阅读本发明的内容后，本领域的技术人员可以对本发明作各种修改，这些等价变化同样落于本发明所附权利要求书所限定的范围。
实施例1
(1)按照摩尔比(1.05×0.5):0.2:0.5:0.1:0.7分别称取5％过量Pb的Pb(CH3COO)3、Sn(CH3COO)4、La(OC2H5)3、Zr(OC3H7)4和Ti(OCH(CH3)2)4制备Pb0.5La0.5(Zr0.1Sn0.2Ti0.7)O3前驱体溶液。
将过量Pb的Pb(CH3COO)3、Sn(CH3COO)4和La(OC2H5)3于100℃溶解在冰醋酸中得到Pb/Sn/La溶液，同时将Zr(OC3H7)4和Ti(OCH(CH3)2)4于室温溶解在冰醋酸和CH3COCH2COCH3的混合溶液中得到Zr/Ti溶液，然后将Pb/Sn/La溶液和Zr/Ti溶液混合并于50℃下搅拌30min，接着在混合Pb/Sn/La/Zr/Ti溶液中加入适当的添加剂(乳酸、1-丙醇和水)并放置20h，最后得到浓度为0.2M的Pb0.5La0.5(Zr0.1Sn0.2Ti0.7)O3前驱体溶液；
(2)将步骤(1)得到的PLZST前驱体溶液使用匀胶机以4000rpm的转速分别旋涂30s在Pt(111)衬底上面，得到湿膜；
(3)将步骤(2)制得的湿膜首先在120℃干燥3min，然后在400℃热解3min，最后在700℃于空气氛围中退火3min，得到一层PLZST薄膜；
(4)重复步骤(2)和步骤(3)8次，得到8层PLZST薄膜。
实施例2
(1)按照摩尔比1:1分别称取原料Ni(CH3COO)2、La(NO3)3于室温溶解在冰醋酸、水和甲酰胺的混合溶液中。然后将溶液放置20h，最后得到浓度为0.2M的LaNiO3前驱体溶液；
(2)将步骤(1)得到的LaNiO3前驱体溶液使用匀胶机以4000rpm的转速旋涂30s在Si(100)衬底上面，得到第一湿膜；
(3)将步骤(2)制得的湿膜首先在120℃干燥3min，然后在400℃热解3min，最后在700℃于空气氛围中退火3min，得到一层LaNiO3薄膜；
(4)重复步骤(2)和步骤(3)6次，得到具有6层LaNiO3的LaNiO3/Si(100)复合基底；
(5)按照摩尔比(1.05×0.5):0.2:0.5:0.1:0.7分别称取5％过量Pb的Pb(CH3COO)3、Sn(CH3COO)4、La(OC2H5)3、Zr(OC3H7)4和Ti(OCH(CH3)2)4制备Pb0.5La0.5(Zr0.1Sn0.2Ti0.7)O3前驱体溶液。
将过量Pb的Pb(CH3COO)3、Sn(CH3COO)4和La(OC2H5)3于120℃溶解在冰醋酸中得到Pb/Sn/La溶液，同时将Zr(OC3H7)4和Ti(OCH(CH3)2)4于室温溶解在冰醋酸和CH3COCH2COCH3的混合溶液中得到Zr/Ti溶液，然后将Pb/Sn/La溶液和Zr/Ti溶液混合并于50℃下搅拌30min，接着在混合Pb/Sn/La/Zr/Ti溶液中加入适当的添加剂(乳酸、1-丙醇和水)并放置20h，最后得到浓度为0.2M的Pb0.5La0.5(Zr0.1Sn0.2Ti0.7)O3前驱体溶液前驱体溶液；
(6)将步骤(5)得到的PLZST前驱体溶液使用匀胶机以4000rpm的转速旋涂30s在步骤(4)得到的LaNiO3/Si(100)复合基底上面，得到第二湿膜；
(7)将步骤(6)制得的湿膜首先在120℃干燥3min，然后在400℃热解3min，最后在700℃于空气氛围中退火3min，得到一层PLZST薄膜；
(8)重复步骤(6)和步骤(7)8次，得到8层PLZST薄膜。
实施例3
(1)按照摩尔比1:1分别称取原料Ni(CH3COO)2、La(NO3)3于室温溶解在冰醋酸、水和甲酰胺的混合溶液中。然后将溶液放置25h，最后得到浓度为0.25M的LaNiO3前驱体溶液；
(2)将步骤(1)得到的LaNiO3前驱体溶液使用匀胶机以5000rpm的转速旋涂40s在Pt(111)衬底上面，得到第一湿膜；
(3)将步骤(2)制得的湿膜首先在200℃干燥4min，然后在450℃热解4min，最后在750℃于空气氛围中退火4min，得到一层LaNiO3薄膜；
(4)重复步骤(2)和步骤(3)6次，得到具有6层LaNiO3的LaNiO3/Pt(111)复合基底；
(5)按照摩尔比(1.05×0.1):0.3:0.9:0.2:0.5分别称取5％过量Pb的Pb(CH3COO)3、Sn(CH3COO)4、La(OC2H5)3、Zr(OC3H7)4和Ti(OCH(CH3)2)4制备Pb0.1La0.9(Zr0.2Sn0.3Ti0.5)O3前驱体溶液。
将过量Pb的Pb(CH3COO)3、Sn(CH3COO)4和La(OC2H5)3于110℃溶解在冰醋酸中得到Pb/Sn/La溶液，同时将Zr(OC3H7)4和Ti(OCH(CH3)2)4于室温溶解在冰醋酸和CH3COCH2COCH3的混合溶液中得到Zr/Ti溶液，然后将Pb/Sn/La溶液和Zr/Ti溶液混合并于80℃下搅拌35min，接着在混合Pb/Sn/La/Zr/Ti溶液中加入适当的添加剂(乳酸、1-丙醇和水)并放置25h，最后得到浓度为0.25M的Pb0.1La0.9(Zr0.2Sn0.3Ti0.5)O3前驱体溶液；
(6)将步骤(5)得到的PLZST前驱体溶液使用匀胶机以5000rpm的转速旋涂35s在步骤(4)得到的LaNiO3/Pt(111)复合基底上面，得到第二湿膜；
(7)将步骤(6)制得的湿膜首先在200℃干燥4min，然后在450℃热解4min，最后在750℃于空气氛围中退火4min，得到一层PLZST薄膜；
(8)重复步骤(6)和步骤(7)8次，得到8层PLZST薄膜。
实施例4
(1)按照摩尔比1:1分别称取原料Ni(CH3COO)2、La(NO3)3于室温溶解在冰醋酸、水和甲酰胺的混合溶液中。然后将溶液放置30h，最后得到浓度为0.3M的LaNiO3前驱体溶液；
(2)将步骤(1)得到的LaNiO3前驱体溶液使用匀胶机以6000rpm的转速旋涂60s在Pt(111)衬底上面，得到第一湿膜；
(3)将步骤(2)制得的湿膜首先在250℃干燥5min，然后在550℃热解5min，最后在800℃于空气氛围中退火5min，得到一层LaNiO3薄膜；
(4)重复步骤(2)和步骤(3)6次，得到具有6层LaNiO3的LaNiO3/Pt(111)复合基底；
(5)按照摩尔比(1.05×0.1):0.3:0.9:0.2:0.5分别称取5％过量Pb的Pb(CH3COO)3、Sn(CH3COO)4、La(OC2H5)3、Zr(OC3H7)4和Ti(OCH(CH3)2)4制备Pb0.1La0.9(Zr0.2Sn0.3Ti0.5)O3前驱体溶液。
将过量Pb的Pb(CH3COO)3、Sn(CH3COO)4和La(OC2H5)3于120℃溶解在冰醋酸中得到Pb/Sn/La溶液，同时将Zr(OC3H7)4和Ti(OCH(CH3)2)4于室温溶解在冰醋酸和CH3COCH2COCH3的混合溶液中得到Zr/Ti溶液，然后将Pb/Sn/La溶液和Zr/Ti溶液混合并于100℃下搅拌45min，接着在混合Pb/Sn/La/Zr/Ti溶液中加入适当的添加剂(乳酸、1-丙醇和水)并放置30h，最后得到浓度为0.3M的Pb0.1La0.9(Zr0.2Sn0.3Ti0.5)O3前驱体溶液；
(6)将步骤(5)得到的PLZST前驱体溶液使用匀胶机以6000rpm的转速旋涂60s在步骤(4)得到的LaNiO3/Pt(111)复合基底上面，得到第二湿膜；
(7)将步骤(6)得到的湿膜首先在250℃干燥5min，然后在550℃热解5min，得到一层未退火的PLZST薄膜；
(8)重复步骤(6)和步骤(7)8次，得到8层未退火的PLZST薄膜；
(9)将步骤(8)得到的未退火的PLZST薄膜在800℃于空气氛围中退火60min，得到完全退火的PLZST薄膜。
实施例5
采用与实施例3相同的方法制备PLZST薄膜，不同的是，步骤(7)的退火温度为800℃，退火时间为5min。
实施例6
采用与实施例4相同的方法制备PLZST薄膜，不同的是，步骤(9)的退火温度为700℃，退火时间为30min。
本发明制备方法相对简单，适合推广使用，制备所得的薄膜性能良好，满足使用要求。

Claims (10)

1.一种利用热应变诱导宽温区电卡效应PLZST基薄膜的制备方法，其特征在于，所述方法包括以下步骤：
1)将LaNiO3前驱体溶液旋涂于衬底上制得第一湿膜，所述衬底为Si(100)或Pt(111)；
2)将步骤1)所得的第一湿膜干燥、热解，退火制得单层LaNiO3薄膜；
3)重复步骤1)和步骤2)，制得多层LaNiO3/Si(100)或LaNiO3/Pt(111)复合基底；
4)将PLZST前驱体溶液旋涂于衬底上，制得第二湿膜，所述衬底为Pt(111)、步骤3)制得的多层LaNiO3/Si(100)复合基底、步骤3制得的LaNiO3/Pt(111)复合基底中的任一一种；
5)当衬底为Pt(111)或LaNiO3/Si(100)复合基底时，按照如下步骤进行处理制得一层PLZST薄膜，
步骤5-1)、将第二湿膜干燥、热解、退火制得一层PLZST薄膜，
当衬底为LaNiO3/Pt(111)复合基底时，可按照以下任一步骤进行处理制得一层PLZST，
5-2)、将第二湿膜干燥、热解、退火制得一层PLZST薄膜，
5-3)、将第二湿膜干燥、热解制得一层PLZST薄膜；
6)按照如下任一步骤进行处理制备多层PLZST薄膜：
6-1)、重复步骤4)和步骤5-1)制得多层PLZST薄膜，
6-2)、重复步骤4)和步骤5-2)制得多层PLZST薄膜，
6-3)、重复步骤4)和步骤5-3)制得未退火的PLZST薄膜，退火制得完全退火的多层PLZST薄膜。
2.根据权利要求1所述的利用热应变诱导宽温区电卡效应PLZST基薄膜的制备方法，其特征在于，步骤1)所述的LaNiO3前驱体溶液浓度为0.2-0.3M。
3.根据权利要求1所述的利用热应变诱导宽温区电卡效应PLZST基薄膜的制备方法，其特征在于，步骤1)所述旋涂转速为4000-6000rpm，旋涂时间为30-60s。
4.根据权利要求1所述的利用热应变诱导宽温区电卡效应PLZST基薄膜的制备方法，其特征在于，步骤2)所述干燥温度为120-250℃，干燥时间为3-5min，所述热解温度为400-550℃，热解时间为3-5min，所述退火温度为700-800℃，退火时间为3-5min，退火环境为空气氛围。
5.根据权利要求1所述的利用热应变诱导宽温区电卡效应PLZST基薄膜的制备方法，其特征在于，步骤3)制得6层LaNiO3薄膜。
6.根据权利要求1所述的利用热应变诱导宽温区电卡效应PLZST基薄膜的制备方法，其特征在于，步骤4)所述的PLZST通式为PbxLa(1-x)(ZrySnzTi(1-y-z))O3，其中0<x<1,0<y<1,0<z<1,所述的PLZST前驱体溶液浓度为0.2-0.3M。
7.根据权利要求1所述的利用热应变诱导宽温区电卡效应PLZST基薄膜的制备方法，其特征在于，步骤4)所述旋涂转速为4000-6000rpm，旋涂时间为30-60s。
8.根据权利要求1所述的利用热应变诱导宽温区电卡效应PLZST基薄膜的制备方法，其特征在于，步骤5-1)、步骤5-2)和步骤5-3)所述干燥温度均为120-250℃，干燥时间均为3-5min，所述热解温度均为400-550℃，热解时间均为3-5min，步骤5-1)和步骤5-2)所述退火温度均为700-800℃，退火时间均为3-5min，退火环境均为空气氛围。
9.根据权利要求1所述的利用热应变诱导宽温区电卡效应PLZST基薄膜的制备方法，其特征在于，步骤6-1)、步骤6-2)、步骤6-3)重复次数均为8次。
10.根据权利要求1所述的利用热应变诱导宽温区电卡效应PLZST基薄膜的制备方法，其特征在于，步骤6-3)所述退火温度为700-800℃，退火时间为30-60min，退火环境为空气氛围。
CN202010979496.7A 2020-09-17 2020-09-17 一种利用热应变诱导宽温区电卡效应plzst基薄膜的制备方法 Pending CN112062568A (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010979496.7A CN112062568A (zh) 2020-09-17 2020-09-17 一种利用热应变诱导宽温区电卡效应plzst基薄膜的制备方法

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010979496.7A CN112062568A (zh) 2020-09-17 2020-09-17 一种利用热应变诱导宽温区电卡效应plzst基薄膜的制备方法

Publications (1)

Publication Number Publication Date
CN112062568A true CN112062568A (zh) 2020-12-11

Family

ID=73682362

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010979496.7A Pending CN112062568A (zh) 2020-09-17 2020-09-17 一种利用热应变诱导宽温区电卡效应plzst基薄膜的制备方法

Country Status (1)

Country Link
CN (1) CN112062568A (zh)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1990418A (zh) * 2005-12-29 2007-07-04 同济大学 作为热释电材料的反铁电薄膜及其制备方法和应用
CN101100396A (zh) * 2007-07-26 2008-01-09 同济大学 一种高锆含量铅系复合反铁电薄膜的低温制备方法
CN102154636A (zh) * 2010-12-17 2011-08-17 济南大学 一种p型高透射率（100）-取向的LaNiO3纳米薄膜的制备方法
CN102683577A (zh) * 2011-10-28 2012-09-19 闫静 BiFe1-yMnyO3外延复合薄膜及其制备方法
CN111128682A (zh) * 2019-12-27 2020-05-08 广西大学 一种通过衬底调控电卡性能薄膜的制备方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1990418A (zh) * 2005-12-29 2007-07-04 同济大学 作为热释电材料的反铁电薄膜及其制备方法和应用
CN101100396A (zh) * 2007-07-26 2008-01-09 同济大学 一种高锆含量铅系复合反铁电薄膜的低温制备方法
CN102154636A (zh) * 2010-12-17 2011-08-17 济南大学 一种p型高透射率（100）-取向的LaNiO3纳米薄膜的制备方法
CN102683577A (zh) * 2011-10-28 2012-09-19 闫静 BiFe1-yMnyO3外延复合薄膜及其制备方法
CN111128682A (zh) * 2019-12-27 2020-05-08 广西大学 一种通过衬底调控电卡性能薄膜的制备方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PENG, BIAOLIN等: "Thermal strain induced large electrocaloric effect of relaxor thin film on LaNiO3/Pt composite electrode with the coexistence of nanoscale antiferroelectric and ferroelectric phases in a broad temperature range", 《NANO ENERGY》 *

Similar Documents

Publication Publication Date Title
CN111128682A (zh) 一种通过衬底调控电卡性能薄膜的制备方法
CN108892503B (zh) 一种高电卡效应薄膜材料及其制备方法
CN112062562B (zh) 一种knn基超高击穿电场单晶薄膜材料的制备方法
CN101271956A (zh) 一种高分子辅助沉积高温超导涂层导体超导层的方法
CN103708828A (zh) 一种钛酸铋钠-钛酸钡无铅复合压电厚膜的制备方法
CN112062563B (zh) 一种psint基高熵铁电薄膜材料的制备方法
CN108735349B (zh) 一种含离子液体的银纳米线透明导电薄膜及其制备方法
CN113698205B (zh) 一种基于稀土镍基氧化物的复合型热敏电阻材料及其制备方法和应用
CN109354057B (zh) 一种氧化锡纳米晶及其制备方法及太阳能电池制备方法
CN106935398A (zh) 一种铋掺杂钛酸锶薄膜电容器及其制备方法
CN112062568A (zh) 一种利用热应变诱导宽温区电卡效应plzst基薄膜的制备方法
CN111525021A (zh) 一种兼具正负电卡效应的钛酸铋钠基薄膜及其制备方法
CN106952828A (zh) 一种p型金属氧化物薄膜晶体管的制备方法
CN112062564B (zh) 一种pmn-psn超高击穿电场薄膜材料的制备方法
CN112142464A (zh) 一种通过频率调控Nb掺杂的PZST基驰豫反铁电薄膜制备方法
CN105914243B (zh) 一种具有铁电性能的薄膜光电器件及其制备方法
CN106887331B (zh) 高储能密度电容器用氧化铝基电介质薄膜及其制备方法
CN111081879B (zh) 一种钙钛矿光吸收层及其制备方法
CN112062578A (zh) 一种提高介电材料电场击穿强度的方法
KR101554943B1 (ko) 이트륨 산화물로 표면 처리된 폴리이미드 유기절연체 및 이를 이용한 박막 트랜지스터
CN112062552A (zh) 一种利用相变诱导无铅薄膜材料制备方法
CN114716157B (zh) 一种用于高温加速度传感器的铁电薄膜及其制备方法
CN112062553B (zh) 一种超宽温区负电卡效应Pb(ZrxTi1-x)O3基薄膜的制备方法
CN103497000A (zh) La2Zr2O7缓冲层薄膜的制备方法
CN115465890B (zh) 一种镧掺杂铪酸铅电介质薄膜的制备方法和应用

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication

Application publication date: 20201211

RJ01 Rejection of invention patent application after publication