CN105036740B - Preparation method of BZT (barium titanate zirconate) target material for magnetron sputtering - Google Patents
Preparation method of BZT (barium titanate zirconate) target material for magnetron sputtering Download PDFInfo
- Publication number
- CN105036740B CN105036740B CN201510362728.3A CN201510362728A CN105036740B CN 105036740 B CN105036740 B CN 105036740B CN 201510362728 A CN201510362728 A CN 201510362728A CN 105036740 B CN105036740 B CN 105036740B
- Authority
- CN
- China
- Prior art keywords
- bzt
- magnetron sputtering
- raw material
- preparation
- targets
- 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.)
- Expired - Fee Related
Links
Landscapes
- Physical Vapour Deposition (AREA)
- Compositions Of Oxide Ceramics (AREA)
Abstract
The invention discloses a preparation method of a BZT (barium titanate zirconate) target material for magnetron sputtering. The method comprises the steps of firstly mixing the raw materials of BaCO3, ZrO2 and TiO2 according to the molecular formula, namely Ba(ZrxTi1-x)O3, of the BTZ and according to the molar mass of components in the Ba(ZrxTi1-x)O3, wherein x is larger than 0 and less than 1, after ball milling, performing presintering at the temperature of 1,000 to 1,200 DEG C, additionally adding 0.5 to 5wt percent of PVA, performing secondary ball milling, and performing compression moulding to form a green body after drying and screening; dumping the green body at the temperature of 600 to 800 DEG C, and sintering at the temperature of 1,300 to 1,400 DEG C, so as to prepare the BZT target material. According to the preparation method provided by the invention, a solid phase method is adopted for the first time, the diameter of the provided BZT target material is 32 to 80mm, can meet the demands of magnetron sputtering with different size requirements, and is suitable for different performance requirement, the surface of the target material is flat, and the warping degree of the target material is less than 5 percent.
Description
Technical field
The invention belongs to electronic information material and components and parts field, more particularly to a kind of to be used to prepare BZT (barium zirconium phthalate)
The preparation method of the BZT targets of thin film.
Background technology
Ferroelectric material is a big class functional material, with piezoelectric effect, electrostriction effect, pyroelectric effect, dielectric tuning
Etc. the physical characteristics for being available for technology application, in information Store, piezoelectric energy-conversion, thermoelectricity camera technique, piezo-electric ignition, thermoelectricity detection etc.
Some row high-technology fields possess and are widely applied.The operation level of electronics can be significantly improved so as to realize lightweight
Change, functionalization and high performance, miniaturization, information-based and high-intelligentization to electronics of future generation etc. all play very important
Effect.
Barium metatitanate. (BaTiO3) it is typical perocskite type ferroelectric material, it has very high dielectric constant, is used to make
For capacitor material, it has also become indispensable material in high frequency circuit element, and it is also widely being applied to dielectric
The aspects such as tuning, frequency modulation and storage.In addition ecological and environmental protection is more paid attention in modern production, due to BaTiO3In based solid solution
Without poisonous lead element, its application is paid close attention to by more and more researcheres.
BZT (barium zirconium phthalate) is with BaTi03For the ceramic material that base carries out the complex perovskite structure after modification by ion-doping
Material, is also a kind of ferroelectric material, has good application prospect in ferroelectric random access memo-ry (DRAM) field.DRAM
It is the core technology of present quasiconductor development, the increase of the density of DRAM depends on the diminution of its capacitor sizes, or selects
Material with very high-k.Thin-film material with good dielectric properties has above-mentioned two advantage concurrently simultaneously so that
The memory density of DRAM is greatly improved.The block materials such as thin-film device difference ceramics, its advantage is small volume, lightweight, work
Frequency can be improved, easily manufactured, the smooth densification in surface, and can be by changing film thickness, type of substrate and electric shape etc.
Carry out the performance of adjusting device.
BZT method for manufacturing thin film is divided into chemical method and physical method.Mainly there is a pulse laser deposition, magnetron sputtering method,
Metal organic chemical vapor deposition method, sol-gal process etc..Magnetron sputtering method belongs to physical method, and it can be with relatively low cost system
Standby practical large area film, film-forming process can adopt ceramic target, it is also possible to the metal used in oxygen atmosphere or conjunction
Gold target material.BZT thin film is prepared using magnetically controlled sputter method, prepare the BZT ceramic targets matched with magnetron sputtering apparatus be to
Close important, BZT ceramic target surface smoothnesss prepared by traditional method are relatively low, the shortcomings of angularity is high, set with magnetron sputtering
It is standby to match the shortcomings of bad and target is easily broken off in sputter procedure, it is impossible to prepare high-quality BZT thin film.
The content of the invention
The purpose of the present invention, be overcome traditional method to prepare BZT ceramic target surface smoothnesss are relatively low, angularity is high etc. lacks
Point, there is provided a kind of to match with magnetron sputtering apparatus, a kind of magnetic control that industrialization prepares in a large number BZT thin film requirements can be met
The sputtering preparation method of BZT targets,
The present invention is achieved by following technical solution.
A kind of magnetron sputtering preparation method of BZT targets, step is as follows：
(1) preparation raw material
It is the compound molecule formula Ba (Zr of barium zirconium phthalate according to BZTxTi1-x)O3, wherein 0<x<1 element molal weight
Than by BaCO3、ZrO2、TiO2Three kinds of raw materials are mixed；
(2) ball millings
It is 1 according to the mass ratio of raw material and deionized water and zirconium ball by the mixed raw material of step (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, pre-burning is carried out then at 1000～1200 DEG C, be incubated 2～4 hours；
(4) secondary ball milling
By the raw material after step (3) pre-burning, the PVA of additional 0.5～5wt%, 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
Raw material after step (4) secondary ball milling is dried, 40～200 mesh sieves are crossed after drying；
(6) molding
Powder after step (5) is sieved is put into compressing for base substrate in tablet machine；
(7) dumping
Base substrate after step (6) molding is put in low temperature oven carries out dumping, and dump temperature is 600～800 DEG C；
(8) sinter
By the base substrate after step (7) dumping in 1300～1400 DEG C of high temperature sinterings, 1-5 DEG C of heating rate/min, during insulation
Between be 3～6 hours, magnetron sputtering BZT targets are obtained.
The raw material of the step (1) is analytical reagent.
The compressing blank diameter of the step (6) is 40～100mm, and operating pressure is 50-150Mpa, the dwell time
For 1-5min.
The dump temperature of the step (7) is 700 DEG C.
The sintering temperature of the step (8) is 1350 DEG C, and temperature retention time is 4 hours.
Base substrate is placed in the step (8) sintering processing being sintered in high temperature furnace, adopts pressure firing method to prevent target
Material flexural deformation.
Beneficial effects of the present invention：
The present invention first using solid phase method be obtained magnetron sputtering BZT targets, there is provided sintering after target it is a diameter of
32mm～80mm, can meet the BZT targets of the magnetron sputtering of different size requirement, to prepare the BZT of different performance requirement
Thin film, and surfacing, target angularity<5%.
Specific embodiment
With reference to specific embodiment, the invention will be further described.
Embodiment 1
(1). dispensing
Prepare BZT targets raw materials used using analytically pure BaCO3、ZrO2、TiO2, according to compound molecule formula Ba of BZT
(ZrxTi1-x)O3, (x=0.15), three kinds of raw materials are according to Ba (Zr0.15Ti0.85)O3The molal weight ratio of middle element is mixed.
(2). ball milling of raw material
It is 1 according to the mass ratio of raw material and deionized water and zirconium ball after above-mentioned three kinds of raw materials mixing：1：1, ball milling 6 is little
When.
(3). pre-burning
By raw material stoving after the completion of ball milling of raw material, it is put in moderate oven and carry out pre-burning in 1200 DEG C, heating rate is 5
DEG C/min, it is incubated as 2 hours.
(4). raw material secondary ball milling
After pre-burning is completed, the PVA of 2wt% is added, be 1 according to the mass ratio of raw material and deionized water and zirconium ball：1：1,
Secondary ball milling 12 hours.
(5). sieve
By the raw material stoving after secondary ball milling, the raw material after drying is after 80 mesh sieves.
(6). compression molding
Powder after sieving is put into into tablet machine carries out tabletting, and blank diameter is 40mm, and thickness is 3mm, to make target
Base substrate uniform force in pressing process, the present invention adopts first isostatic pressing technology, and operating pressure is 50Mpa, and the dwell time is
3min。
(7). dumping
Green compact after the completion of tabletting are put into into low temperature oven carries out dumping, 700 DEG C of dump temperature.
(8). sintering
Base substrate after the completion of dumping is carried out into high temperature sintering in 1375 DEG C, in sintering process, target is prevented using pressure firing method
Material flexural deformation, 5 DEG C/min of heating rate, temperature retention time is 2 hours, and magnetron sputtering BZT targets are obtained.
BZT target diameters after sintering is completed are reduced into 30mm.
Embodiment 2
(1). dispensing
Prepare BZT targets raw materials used using analytically pure BaCO3、ZrO2、TiO2, according to compound molecule formula Ba of BZT
(ZrxTi1-x)O3(x=0.1), three kinds of raw materials are according to Ba (Zr0.1Ti0.9)O3The molal weight ratio of middle element is mixed.
(2). ball milling of raw material
It is 1 according to the mass ratio of raw material and deionized water and zirconium ball after above-mentioned three kinds of raw materials mixing：1：1, ball milling 6 is little
When.
(3). pre-burning
By raw material stoving after the completion of ball milling, being put into moderate oven carries out pre-burning in 1100 DEG C, and heating rate is 5 DEG C/
Min, temperature retention time is 4 hours.
(4). raw material secondary ball milling
The PVA of 1wt% is added in raw material after the completion of pre-burning, is with the mass ratio of deionized water and zirconium ball according to raw material
1：1：1, secondary ball milling 12 hours.
(5). sieve
By the raw material stoving after secondary ball milling, after 80 mesh sieves.
(6). compression molding
Powder after sieving is put into into tablet machine carries out tabletting, and blank diameter is 50mm, and thickness is 3mm, to make target
Base substrate uniform force in pressing process, the present invention adopts first isostatic pressing technology, and operating pressure is 100Mpa, and the dwell time is
4min。
(7). dumping
Green compact after the completion of tabletting are put into into low temperature oven carries out dumping, 700 DEG C of dump temperature.
(8). sintering
Base substrate after the completion of dumping is carried out into high temperature sintering in 1350 DEG C, in sintering process, target is prevented using pressure firing method
Material flexural deformation, heating rate is 4 DEG C/min, and temperature retention time is 4 hours, and magnetron sputtering BZT targets are obtained.
BZT target diameters after sintering is completed are reduced into 40mm.
Embodiment 3
(1). dispensing
According to the compound molecule formula Ba (Zr of BZTxTi1-x)O3(x=0.2), three kinds of raw materials are according to Ba (Zr0.2Ti0.8)O3
The molal weight ratio of middle element is mixed.
(2). ball milling of raw material
It is 1 according to the mass ratio of raw material and deionized water and zirconium ball after above-mentioned three kinds of raw materials mixing：1：1, ball milling 6 is little
When.
(3). pre-burning
By raw material stoving after the completion of ball milling, being put into moderate oven carries out pre-burning in 1100 DEG C, and heating rate is 5 DEG C/
Min, temperature retention time is 4 hours.
(4). raw material secondary ball milling
After pre-burning is completed, the PVA of 0.5wt% is added, be 1 according to the mass ratio of raw material and deionized water and zirconium ball：1：
1, secondary ball milling 12 hours.
(5). sieve
By the raw material stoving after secondary ball milling, after 80 mesh sieves.
(6). compression molding
Powder after sieving is put into into tablet machine carries out tabletting, and blank diameter is 100mm, and thickness is 4mm, to make target
Base substrate uniform force in pressing process, the present invention adopts first isostatic pressing technology, and operating pressure is 150Mpa, and the dwell time is
2min。
(7). dumping
Green compact after the completion of tabletting are put into into low temperature oven carries out dumping, 700 DEG C of dump temperature.
(8). sintering
Base substrate after the completion of dumping is carried out into high temperature sintering in 1325 DEG C, in sintering process, target is prevented using pressure firing method
Material flexural deformation, heating rate is 1.5 DEG C/min, and temperature retention time is 4 hours, and magnetron sputtering BZT targets are obtained.
BZT target diameters after sintering is completed are reduced into 75mm.
The magnetron sputtering of above-described embodiment BZT ceramic targets, can meet the magnetron sputtering apparatus of different size requirement
Needs, and surfacing, target angularity<5%.
Claims (6)
1. a kind of magnetron sputtering preparation method of BZT targets, step is as follows：
(1) preparation raw material
It is the compound molecule formula Ba (Zr of barium zirconium phthalate according to BZTxTi1-x)O3, wherein 0<x<1 element molal weight ratio, will
BaCO3、ZrO2、TiO2Three kinds of raw materials are mixed；
(2) ball millings
It is 1 according to the mass ratio of raw material and deionized water and zirconium ball by the mixed raw material of step (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, pre-burning is carried out then at 1000～1200 DEG C, be incubated 2～4 hours；
(4) secondary ball milling
By the raw material after step (3) pre-burning, the PVA of additional 0.5～5wt%, according to raw material and the quality of deionized water and zirconium ball
Than for 1：1：1 carries out ball milling, and Ball-milling Time is 10～14 hours；
(5) sieve
Raw material after step (4) secondary ball milling is dried, 40～200 mesh sieves are crossed after drying；
(6) molding
Powder after step (5) is sieved is put into compressing for base substrate in tablet machine；
(7) dumping
Base substrate after step (6) molding is put in low temperature oven carries out dumping, and dump temperature is 600～800 DEG C；
(8) sinter
By the base substrate after step (7) dumping in 1300～1400 DEG C of high temperature sinterings, 1-5 DEG C of heating rate/min, temperature retention time is 3
～6 hours, magnetron sputtering BZT targets are obtained.
2. a kind of magnetron sputtering according to claim 1 preparation method of BZT targets, it is characterised in that the step
(1) raw material is analytical reagent.
3. a kind of magnetron sputtering according to claim 1 preparation method of BZT targets, it is characterised in that the step
(6) compressing blank diameter is 40～100mm, and operating pressure is 50-150Mpa, and the dwell time is 1-5min.
4. a kind of magnetron sputtering according to claim 1 preparation method of BZT targets, it is characterised in that the step
(7) dump temperature is 700 DEG C.
5. a kind of magnetron sputtering according to claim 1 preparation method of BZT targets, it is characterised in that the step
(8) sintering temperature is 1350 DEG C, and temperature retention time is 4 hours.
6. a kind of magnetron sputtering according to claim 1 preparation method of BZT targets, it is characterised in that the step
(8) base substrate is placed in the sintering processing being sintered in high temperature furnace, pressure firing method is adopted to prevent target flexural deformation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510362728.3A CN105036740B (en) | 2015-06-26 | 2015-06-26 | Preparation method of BZT (barium titanate zirconate) target material for magnetron sputtering |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510362728.3A CN105036740B (en) | 2015-06-26 | 2015-06-26 | Preparation method of BZT (barium titanate zirconate) target material for magnetron sputtering |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105036740A CN105036740A (en) | 2015-11-11 |
| CN105036740B true CN105036740B (en) | 2017-04-26 |
Family
ID=54443788
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510362728.3A Expired - Fee Related CN105036740B (en) | 2015-06-26 | 2015-06-26 | Preparation method of BZT (barium titanate zirconate) target material for magnetron sputtering |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105036740B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106783173B (en) * | 2016-11-23 | 2018-12-11 | 东莞理工学院 | A kind of all-transparent BZT film varactor and preparation method thereof |
| CN116768621A (en) * | 2023-06-19 | 2023-09-19 | 长安大学 | Preparation process of lead-free piezoelectric ceramic |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101104562B (en) * | 2007-06-04 | 2011-12-21 | 仙桃市中星电子材料有限公司 | Constant pressure hydro-thermal preparation method for barium zirconate titanate powder |
| CN101318817A (en) * | 2008-06-25 | 2008-12-10 | 重庆科技学院 | Process for manufacturing barium zirconium titanate ceramic |
| JP2011162396A (en) * | 2010-02-09 | 2011-08-25 | Tdk Corp | Dielectric ceramic composition and electronic component |
-
2015
- 2015-06-26 CN CN201510362728.3A patent/CN105036740B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN105036740A (en) | 2015-11-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108751982B (en) | Lead-free high-energy-storage-density ceramic material and preparation method thereof | |
| CN109180181B (en) | Lead-free relaxation antiferroelectric ceramic energy storage material and preparation method thereof | |
| CN107162583B (en) | Method for improving dielectric temperature stability of barium titanate-based ceramic based on component gradient | |
| US20080152530A1 (en) | Method of preparing ferroelectric powders and ceramics | |
| CN104591729B (en) | Preparation method of PBZ target for preparing PBZ thin film by virtue of magnetron sputtering method | |
| CN103833354B (en) | A kind of solid solution modification metatitanic acid bismuth sodium system leadless piezo-electric ceramic and preparation method thereof | |
| CN110312692A (en) | Ceramic material, preparation method and use comprising counterfeit cubic phase | |
| CN110330332B (en) | Low-temperature sintering piezoelectric ceramic material without sintering aid and preparation method thereof | |
| CN104291817A (en) | High-Curie-temperature PZT piezoceramic material and preparation method thereof | |
| Buscaglia et al. | Nanostructured barium titanate ceramics | |
| CN110312693A (en) | Show the recognition methods for being originated from the ceramic material of electric field induction strain of reversible transition, preparation method and by its available ceramic material | |
| CN105036740B (en) | Preparation method of BZT (barium titanate zirconate) target material for magnetron sputtering | |
| CN113582667A (en) | Low-temperature co-fired high-energy-storage antiferroelectric ceramic material and preparation method and application thereof | |
| CN101774803A (en) | A (Ba, sr) TiO3-based ceramic medium and its prepn | |
| CN1298672C (en) | Bismuth-sodium titanate-bismuth potassium titanate barium zirconate titanate lead free piezoelectric ceramics | |
| CN102584217B (en) | BaTiO3-Ni0.5Zn0.5Fe2O4 ferroelectric-ferromagnetic composite ceramic thin film prepared by utilizing magnetron sputtering method and preparation method | |
| CN103265288A (en) | Large-dielectric-constant piezoelectric ceramic and preparation method thereof | |
| CN106601903A (en) | C axis height-oriented barium titanate film and in-situ preparation method of the same at medium and low temperature | |
| CN106915964B (en) | Lead-free high-energy-storage-density ceramic material and preparation method thereof | |
| CN108863349A (en) | A kind of barium titanate-based lead-free height Jie temperature-stable ceramic material and preparation method thereof | |
| CN107188555A (en) | A kind of preparation method of ceramic target | |
| CN110282970B (en) | Tin dioxide doped barium titanate based high energy storage density ceramic material and preparation method thereof | |
| KR20040038747A (en) | Method for producing dielectric ceramic material powder, dielectric ceramic and monolithic ceramic capacitor | |
| CN108585837A (en) | A kind of preparation method of bismuth-sodium titanate base high temperature capacitors media ceramic | |
| CN105198410B (en) | A kind of preparation method of core shell structure high energy storage density dielectric ceramics |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20170426 Termination date: 20200626 |