CN104591729B - Preparation method of PBZ target for preparing PBZ thin film by virtue of magnetron sputtering method - Google Patents
Preparation method of PBZ target for preparing PBZ thin film by virtue of magnetron sputtering method Download PDFInfo
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Abstract
The invention discloses a preparation method of a PBZ target for preparing a PBZ thin film by virtue of a magnetron sputtering method. The preparation method comprises the following steps: firstly mixing Pb3O4, BaCO3 and ZrO2 according to molar ratio of a compound formula (Pb1-xBax)ZrO3 of PBZ, namely barium lead zirconate, wherein x is more than 0 and less than 1; carrying out primary ball milling, presintering and secondary ball milling, tabletting to form a blank body with the diameter of 40mm-100mm by virtue of an isostatic pressing technique, and after discharging rubber, sintering the blank body at 1100-1300 DEG C, so as to prepare the PBZ target for magnetron sputtering. According to the preparation method, the PBZ is prepared by virtue of a solid phase method for the first time, is applied to magnetron sputtering, can meet different size requirements and is used for preparing the PBZ thin films with different performance requirements.
Description
Technical field
The invention belongs to electronic information material and components and parts field, it is used for preparing PBZ (lead zirconates barium) particularly to one kind
The preparation method of the PBZ target of thin film.
Background technology
Antiferroelectric materials has good piezoelectricity, pyroelectricity and dielectric properties, and the spy such as easily integrated with semiconductor technology
Put and become the focus studying novel functional material and device in the world, especially as electronic technology, information technology and control
The development of technology, the miniaturization of device and integrated, material is proposed with new requirement.
Lead base pottery is that one kind all has extensive answering in the fields such as electric flux storage, energy conversion, big displacement actuator
Material.But, the compound of lead and its steam are all poisonous, and excessive suction can bring very big damage to the health of human body
Evil.For this reason, the research institution of various countries all do not stint put into a large amount of manpower and materials carry out with regard to leadless electronic pottery research and development,
Purpose is intended merely to find lead-free and goes to replace lead base pottery.But, up to the present, the properties of lead-free ceramicses are not only
Much cannot compare with the latter, and stability is also not as good as lead base pottery.For example, PbZrO3Anti-ferroelectric ceramic material for base
Energy storage density can reach 1J/cm3More than, the energy storage density being made into capacitor is 0.2～0.3J/cm3, than the oil immersion of high-quality
The energy storage density 0.017J/cm of paper dielectric capacitor3Big 10-20 times.
PBZ (lead zirconates barium) is a kind of ceramic material of leaded complex perovskite structure, is also a kind of antiferroelectric materials,
There is good performance, in MEMS, the aspect such as data storage has good application prospect.Due to traditional body phase material and greatly
Volume multiple structure electric capacity (MLCCs) is due to being affected by itself body phase material microstructure and properties it is impossible to bear high electricity
Field intensity, thus result in relatively low energy storage density, is not suitable for the energy storage technology under high electric-field intensity.PBZ material film
Afterwards, strong higher than body phase material breakdown strength tens times of electric field intensity can be obtained under relatively low operating voltage, thus energy
Enough obtain high energy storage density and big electric heating temperature becomes, improve the energy conversion performance of material.
Content of the invention
The purpose of the present invention, is to provide a kind of preparation method of the PBZ target of magnetron sputtering, big to meet industrialization
Amount preparation PBZ thin film requires.
The present invention is achieved by following technical solution.
A kind of preparation method of the PBZ target preparing PBZ thin film using magnetron sputtering method, step is as follows：
(1) preparation raw material
It is the compound molecule formula (Pb of lead zirconates barium according to PBZ1-xBax)ZrO3Wherein 0<x<1 mol ratio, by Pb3O4、
BaCO3、ZrO2Three kinds of raw materials are mixed；
(2) ball millings
By mixed for step (1) raw material, the mass ratio according to raw material and deionized water and zirconium ball is 1：1：1 carries out ball
Mill, Ball-milling Time is 4～8 hours；
(3) pre-burning
By the raw material stoving after (2) ball millings of step, carry out pre-burning then at 800～1000 DEG C, be incubated 1～4 hour；
(4) secondary ball milling
By the raw material after step (3) pre-burning, the PVA of additional 0.5～1wt%, according to raw material and deionized water and zirconium ball
Mass ratio is 1：1：1 carries out ball milling, and Ball-milling Time is 10～14 hours；
(5) sieve
After secondary ball milling, raw material is dried, and after drying, 40～200 mesh sieves crossed by raw material；
(6) molding
Powder after step (5) is sieved put in tablet machine compressing for base substrate, be to allow target in pressing process
Uniform force, using isostatic pressing technology, operating pressure is 100-200Mpa, and the dwell time is 1-5min, compacting a diameter of 40～
The magnetron sputtering target of 100mm；
(7) dumping
Base substrate after step (6) molding is put into and in low temperature oven, carries out dumping, dump temperature is 600～800 DEG C；
(8) sinter
By base substrate after step (7) dumping in 1100-1300 DEG C of high temperature sintering, temperature retention time is 3～7 hours, prepared magnetic control
PBZ target is used in sputtering；Adopt and bury burning or pressure firing method to prevent Pb volatilization and target flexural deformation.
The raw material of described step (1) is analytical reagent.
The dump temperature of described step (7) is 700 DEG C.
The sintering temperature of described step (8) is 1200 DEG C, and temperature retention time is 6 hours.
Described step (8) is base substrate to be placed in Muffle furnace be sintered.
Beneficial effects of the present invention：
The present invention is obtained the PBZ target of magnetron sputtering first using solid phase method, and after the sintering providing, target is a diameter of
32mm～80mm, can meet the PBZ target of the magnetron sputtering of different size requirement, to prepare the PBZ of different performance requirement
Thin film.
Specific embodiment
PBZ method for manufacturing thin film generally comprises physical method and chemical method；Physical method includes pulsed laser deposition
(PLD), sputtering, vacuum evaporation, molecular beam epitaxy (MBE) etc., chemical method mainly includes sol-gel (Sol_Gel), chemistry
Vapour deposition (CVD, MOCVD) etc..Magnetron sputtering method belongs to physical method, and it can be with the practical big face of relatively low cost preparation
Long-pending thin film, masking can be with ceramic target it is also possible to be obtained by reactive sputtering using metal or alloy target in oxygen atmosphere
Obtain required thin film.
Embodiment 1
(1). dispensing
Preparation PBZ target raw materials used using analytically pure Pb3O4、BaCO3、ZrO2, the compound molecule formula of PBZ is
(Pb1-xBax)ZrO3(x=0.15), three kinds of raw materials are according to (Pb0.85Ba0.15)ZrO3The molal weight ratio of middle element is mixed.
(2). ball milling of raw material
Above-mentioned three kinds of raw materials mix according to required ratio, and the mass ratio according to raw material and deionized water and zirconium ball is 1：1：
1, ball milling 6 hours.
(3). pre-burning
By raw material stoving after the completion of ball milling, put into middle temperature Muffle furnace after drying and carry out pre-burning, heat up 5 DEG C/min,
Temperature retention time is 2 hours, and temperature is 950 DEG C.
(4). raw material secondary ball milling
After pre-burning completes, add the PVA of 1wt%, the mass ratio according to raw material and deionized water and zirconium ball is 1：1：1,
Secondary ball milling 12 hours.
(5). sieve
Secondary ball milling completes post-drying, and 80 mesh sieves crossed by the raw material after drying.
(6). compression molding
Powder after sieving is put into tablet machine and is carried out tabletting, a diameter of 40mm, is to allow target stress in pressing process
Uniformly, using isostatic pressing technology, operating pressure is 100Mpa, and the dwell time is 3min.
(7). dumping
Green compact after the completion of tabletting are put into low temperature oven and are carried out dumping, 700 DEG C of dump temperature.
(8). sintering
Carry out high temperature sintering, sintering temperature is 1200 DEG C, heat up 5 DEG C/min, temperature retention time is 6 hours after the completion of dumping,
Prepared magnetron sputtering PBZ target.
PBZ target diameter after sintering completes is reduced into 32mm.
Embodiment 2
(1). dispensing
Preparation PBZ target raw materials used using analytically pure Pb3O4、BaCO3、ZrO2, the compound molecule formula of PBZ is
(Pb1-xBax)ZrO3(x=0.2), three kinds of raw materials are according to (Pb0.8Ba0.2)ZrO3The molal weight ratio of middle element is mixed.
(2). ball milling of raw material
Above-mentioned three kinds of raw materials mix according to required ratio, and the mass ratio according to raw material and deionized water and zirconium ball is 1：1：
1, ball milling 6 hours.
(3). pre-burning
By raw material stoving after the completion of ball milling, put into middle temperature Muffle furnace after drying and carry out pre-burning, heat up 5 DEG C/min,
Temperature retention time is 1 hour, and temperature is 1000 DEG C.
(4). raw material secondary ball milling
After pre-burning completes, add the PVA of 1wt%, the mass ratio according to raw material and deionized water and zirconium ball is 1：1：1,
Secondary ball milling 12 hours.
(5). sieve
Secondary ball milling completes post-drying, and 80 mesh sieves crossed by the raw material after drying.
(6). compression molding
Powder after sieving is put into tablet machine and is carried out tabletting, a diameter of 50mm, is to allow target stress in pressing process
Uniformly, using isostatic pressing technology, operating pressure is 100Mpa, and the dwell time is 4min.
(7). dumping
Green compact after the completion of tabletting are put into low temperature oven and are carried out dumping, 700 DEG C of dump temperature.
(8). sintering
Carry out high temperature sintering, sintering temperature is 1250 DEG C, 5 DEG C/min, temperature retention time is 4 hours, is obtained after the completion of dumping
Magnetron sputtering PBZ target.
PBZ target diameter after sintering completes is reduced into 40mm.
Embodiment 3
(1). dispensing
Preparation PBZ target raw materials used using analytically pure Pb3O4、BaCO3、ZrO2, the compound molecule formula of PBZ is
(Pb1-xBax)ZrO3(x=0.4), three kinds of raw materials are according to (Pb0.6Ba0.4)ZrO3The molal weight ratio of middle element is mixed.
(2). ball milling of raw material
Above-mentioned three kinds of raw materials mix according to required ratio, and the mass ratio according to raw material and deionized water and zirconium ball is 1：1：
1, ball milling 6 hours.
(3). pre-burning
By raw material stoving after the completion of ball milling, put into middle temperature Muffle furnace after drying and carry out pre-burning, heat up 5 DEG C/min,
Temperature retention time is 1 hour, and temperature is 1000 DEG C.
(4). raw material secondary ball milling
After pre-burning completes, add the PVA of 1wt%, the mass ratio according to raw material and deionized water and zirconium ball is 1：1：1,
Secondary ball milling 12 hours.
(5). sieve
Secondary ball milling completes post-drying, and 80 mesh sieves crossed by the raw material after drying.
(6). compression molding
Powder after sieving is put into tablet machine and is carried out tabletting, a diameter of 100mm, is to allow target stress in pressing process
Uniformly, using isostatic pressing technology, operating pressure is 150Mpa, and the dwell time is 5min.
(7). dumping
Green compact after the completion of tabletting are put into low temperature oven and are carried out dumping, 700 DEG C of dump temperature.
(8). sintering
Carry out high temperature sintering, sintering temperature is 1300 DEG C, heat up 5 DEG C/min, temperature retention time is 4 hours after the completion of dumping,
Prepared magnetron sputtering PBZ target.
PBZ target diameter after sintering completes is reduced into 80mm.
Claims (5)
1. a kind of preparation method of the PBZ target preparing PBZ thin film using magnetron sputtering method, step is as follows：
(1) preparation raw material
It is the compound molecule formula (Pb of lead zirconates barium according to PBZ1-xBax)ZrO3Wherein 0<x<1 mol ratio, by Pb3O4、
BaCO3、ZrO2Three kinds of raw materials are mixed；
(2) ball millings
By mixed for step (1) raw material, the mass ratio according to raw material and deionized water and zirconium ball is 1：1：1 carries out ball milling, ball
Consume time as 4～8 hours；
(3) pre-burning
By the raw material stoving after (2) ball millings of step, carry out pre-burning then at 800～1000 DEG C, be incubated 1～4 hour；
(4) secondary ball milling
By the raw material after step (3) pre-burning, the PVA of additional 0.5～1wt%, according to the quality of raw material and deionized water and zirconium ball
Than for 1：1：1 carries out ball milling, and Ball-milling Time is 10～14 hours；
(5) sieve
After secondary ball milling, raw material is dried, and after drying, 40～200 mesh sieves crossed by raw material；
(6) molding
Powder after step (5) is sieved put in tablet machine compressing for base substrate, be to allow target stress in pressing process
Uniformly, using isostatic pressing technology, operating pressure is 100-200Mpa, and the dwell time is 1-5min, suppresses a diameter of 40～100mm
Magnetron sputtering target；
(7) dumping
Base substrate after step (6) molding is put into and in low temperature oven, carries out dumping, dump temperature is 600～800 DEG C；
(8) sinter
By base substrate after step (7) dumping in 1100-1300 DEG C of high temperature sintering, temperature retention time is 3～7 hours, prepared magnetron sputtering
Use PBZ target；Adopt and bury burning or pressure firing method to prevent Pb volatilization and target flexural deformation.
2. the preparation method of a kind of PBZ target preparing PBZ thin film using magnetron sputtering method according to claim 1,
It is characterized in that, the raw material of described step (1) is analytical reagent.
3. the preparation method of a kind of PBZ target preparing PBZ thin film using magnetron sputtering method according to claim 1,
It is characterized in that, the dump temperature of described step (7) is 700 DEG C.
4. the preparation method of a kind of PBZ target preparing PBZ thin film using magnetron sputtering method according to claim 1,
It is characterized in that, the sintering temperature of described step (8) is 1200 DEG C, and temperature retention time is 6 hours.
5. the preparation method of a kind of PBZ target preparing PBZ thin film using magnetron sputtering method according to claim 1,
It is characterized in that, described step (8) is base substrate to be placed in Muffle furnace be sintered.
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| CN105272227A (en) * | 2015-10-30 | 2016-01-27 | 天津大学 | Preparation method of mid-temperature sintered barium lead zirconate ceramic |
| CN111333417A (en) * | 2020-03-09 | 2020-06-26 | 西北工业大学 | Eutectic fluorescent composite ceramic and preparation method and application thereof |
| CN112537954B (en) * | 2020-12-17 | 2022-04-15 | 中山智隆新材料科技有限公司 | Preparation method of IGZO target material |
| CN114873639B (en) * | 2022-03-30 | 2023-06-23 | 郑州大学 | Ba (Bay) 3 Zr 2 S 7 Film, preparation method and application thereof |
| CN115304359B (en) * | 2022-05-27 | 2023-04-07 | 先导薄膜材料（广东）有限公司 | Additive-free high-mobility oxide target material and preparation method thereof |
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| CN103993286A (en) * | 2014-05-30 | 2014-08-20 | 天津大学 | Method for preparing Ba1-xSrxTiO3/Bi1.5MgNb1.5O7 (BST/BMN) composite film voltage-controlled varactor tube |
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| CN103993286A (en) * | 2014-05-30 | 2014-08-20 | 天津大学 | Method for preparing Ba1-xSrxTiO3/Bi1.5MgNb1.5O7 (BST/BMN) composite film voltage-controlled varactor tube |
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