CN104591729A - 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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- CN104591729A CN104591729A CN201410827242.8A CN201410827242A CN104591729A CN 104591729 A CN104591729 A CN 104591729A CN 201410827242 A CN201410827242 A CN 201410827242A CN 104591729 A CN104591729 A CN 104591729A
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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 elemental molar mass 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, particularly one is for the preparation of the preparation method of the PBZ target of PBZ (lead zirconates barium) film.
Background technology
Antiferroelectric materials has good piezoelectricity, pyroelectricity and dielectric properties, and the easily feature such as integrated and become and study the functional materials of novelty and the focus of device in the world with semiconductor technology, especially along with the development of electronic technology, information technology and control techniques, the miniaturization of device and integrated, proposes new requirement to material.
Lead base pottery is a kind of material all in the fields such as electric flux storage, energy transformation, Large travel range actuator with widespread use.But, plumbous compound and steam thereof are all poisonous, and excessive suction can bring very large infringement to the health of human body.For this reason, the research institution of various countries does not all stint and drops into the research and development that a large amount of manpower and materials carry out about leadless electronic pottery, and object just replaces lead base pottery to find lead-free to go.But up to the present, the properties of lead-free ceramics not only cannot be compared with the latter far away, and stability is also not as good as lead base pottery.Such as, PbZrO3 is that the energy storage density of the anti-ferroelectric ceramic material of base can reach 1J/cm
3above, the energy storage density being made into electrical condenser is 0.2 ~ 0.3J/cm
3, than the energy storage density 0.017J/cm of the oiled paper capacitor of high-quality
3large 10-20 doubly.
PBZ (lead zirconates barium) is a kind of stupalith of leaded complex perovskite structure, is also a kind of antiferroelectric materials, has good performance, and at MEMS, the aspects such as data storage have good application prospect.Because traditional body phase material and large volume multilayered structure electric capacity (MLCCs) are owing to being subject to the impact of self body phase material microstructure and properties, high strength of electric field can not be born, thus result in relatively low energy storage density, be not suitable for the energy storage technology under high strength of electric field.After PBZ material film, the strength of electric field higher than strong tens times of body phase material disruptive strength can be obtained under lower operating voltage, thus can obtain high energy storage density and the change of large electric heating temperature, improve the energy transformation performance of material.
Summary of the invention
Object of the present invention, is the preparation method of the PBZ target providing a kind of magnetron sputtering, prepares the requirement of PBZ film in a large number to meet industrialization.
The present invention is achieved by following technical solution.
Adopt magnetron sputtering method to prepare a preparation method for the PBZ target of PBZ film, step is as follows:
(1) preparation raw material
According to the compound molecule formula (Pb of PBZ and lead zirconates barium
1-xba
x) ZrO
3the wherein element molar mass ratio of 0<x<1, by Pb
3o
4, BaCO
3, ZrO
2three kinds of raw materials mix;
(2) ball millings
By step (1) mixed raw material, be that 1:1:1 carries out ball milling according to the mass ratio of raw material and deionized water and zirconium ball, Ball-milling Time is 4 ~ 8 hours;
(3) pre-burning
By the raw material stoving after step (2) ball millings, then carry out pre-burning in 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%, be that 1:1:1 carries out ball milling according to the mass ratio of raw material and deionized water and zirconium ball, 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) shaping
It is base substrate that powder after step (5) being sieved puts into tabletting machine compression moulding, for allowing target uniform force in pressing process, adopt isostatic pressing technology first, operating pressure is 100-200Mpa, dwell time is 1-5min, and compacting diameter is the magnetron sputtering target of 40 ~ 100mm;
(7) binder removal
Base substrate after shaping for step (6) is put into low temperature oven and carries out binder removal, dump temperature is 600 ~ 800 DEG C;
(8) sinter
By base substrate after step (7) binder removal in 1100-1300 DEG C of high temperature sintering, soaking time is 3 ~ 7 hours, obtained magnetron sputtering PBZ target; In sintering process, for avoiding target in sintering process, adopting to bury and burning and press firing method to prevent Pb from volatilizing 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 soaking time is 6 hours.
Described step (8) base substrate is placed in retort furnace sinter.
Beneficial effect of the present invention:
The present invention adopts solid phase method to obtain the PBZ target of magnetron sputtering first, and after the sintering provided, target diameter is 32mm ~ 80mm, can meet the PBZ target of the magnetron sputtering of different size requirement, to prepare the PBZ film of different performance requirement.
Embodiment
PBZ method for manufacturing thin film generally comprises physical method and chemical process; Physical method comprises pulsed laser deposition (PLD), sputtering, vacuum-evaporation, molecular beam epitaxy (MBE) etc., chemical process mainly comprises sol-gel (Sol_Gel), chemical vapour deposition (CVD, MOCVD) etc.Magnetron sputtering method belongs to physical method, and it can with the large area film of lower cost preparation practicality, and masking can use ceramic target, and metal or alloy target also can be used in oxygen atmosphere to obtain required film by reactive sputtering.
Embodiment 1
(1). batching
The analytically pure Pb of the preparation raw materials used employing of PBZ target
3o
4, BaCO
3, ZrO
2, the compound molecule formula of PBZ is (Pb
1-xba
x) ZrO
3(x=0.15), three kinds of raw materials are according to (Pb
0.85ba
0.15) ZrO
3the molar mass ratio of middle element mixes.
(2). raw material ball milling
Above-mentioned three kinds of starting material mix according to required ratio, are 1:1:1 according to the mass ratio of raw material and deionized water and zirconium ball, ball milling 6 hours.
(3). pre-burning
By raw material stoving after one time ball milling completes, put into warm retort furnace and carry out pre-burning after oven dry, heat up 5 DEG C/min, and soaking time is 2 hours, and temperature is 950 DEG C.
(4). raw material secondary ball milling
After pre-burning completes, adding the PVA of 1wt%, is 1:1:1 according to the mass ratio of raw material and deionized water and zirconium ball, secondary ball milling 12 hours.
(5). sieve
Secondary ball milling completes post-drying, and 80 mesh sieves crossed by the raw material after oven dry.
(6). compression molding
Powder after sieving is put into tabletting machine and is carried out compressing tablet, and diameter is 40mm, and for allowing target uniform force in pressing process, adopt isostatic pressing technology, operating pressure is 100Mpa, and the dwell time is 3min.
(7). binder removal
Green compact after compressing tablet completes are put into low temperature oven and are carried out binder removal, dump temperature 700 DEG C.
(8). sintering
Carry out high temperature sintering after binder removal completes, sintering temperature is 1200 DEG C, and heat up 5 DEG C/min, and soaking time is 6 hours, obtained magnetron sputtering PBZ target.
PBZ target reduced after having sintered is 32mm.
Embodiment 2
(1). batching
The analytically pure Pb of the preparation raw materials used employing of PBZ target
3o
4, BaCO
3, ZrO
2, the compound molecule formula of PBZ is (Pb
1-xba
x) ZrO
3(x=0.2), three kinds of raw materials are according to (Pb
0.8ba
0.2) ZrO
3the molar mass ratio of middle element mixes.
(2). raw material ball milling
Above-mentioned three kinds of starting material mix according to required ratio, are 1:1:1 according to the mass ratio of raw material and deionized water and zirconium ball, ball milling 6 hours.
(3). pre-burning
By raw material stoving after one time ball milling completes, put into warm retort furnace and carry out pre-burning after oven dry, heat up 5 DEG C/min, and soaking time is 1 hour, and temperature is 1000 DEG C.
(4). raw material secondary ball milling
After pre-burning completes, adding the PVA of 1wt%, is 1:1:1 according to the mass ratio of raw material and deionized water and zirconium ball, secondary ball milling 12 hours.
(5). sieve
Secondary ball milling completes post-drying, and 80 mesh sieves crossed by the raw material after oven dry.
(6). compression molding
Powder after sieving is put into tabletting machine and is carried out compressing tablet, and diameter is 50mm, and for allowing target uniform force in pressing process, adopt isostatic pressing technology, operating pressure is 100Mpa, and the dwell time is 4min.
(7). binder removal
Green compact after compressing tablet completes are put into low temperature oven and are carried out binder removal, dump temperature 700 DEG C.
(8). sintering
Carry out high temperature sintering after binder removal completes, sintering temperature is 1250 DEG C, 5 DEG C/min, and soaking time is 4 hours, obtained magnetron sputtering PBZ target.
PBZ target reduced after having sintered is 40mm.
Embodiment 3
(1). batching
The analytically pure Pb of the preparation raw materials used employing of PBZ target
3o
4, BaCO
3, ZrO
2, the compound molecule formula of PBZ is (Pb
1-xba
x) ZrO
3(x=0.4), three kinds of raw materials are according to (Pb
0.6ba
0.4) ZrO
3the molar mass ratio of middle element mixes.
(2). raw material ball milling
Above-mentioned three kinds of starting material mix according to required ratio, are 1:1:1 according to the mass ratio of raw material and deionized water and zirconium ball, ball milling 6 hours.
(3). pre-burning
By raw material stoving after one time ball milling completes, put into warm retort furnace and carry out pre-burning after oven dry, heat up 5 DEG C/min, and soaking time is 1 hour, and temperature is 1000 DEG C.
(4). raw material secondary ball milling
After pre-burning completes, adding the PVA of 1wt%, is 1:1:1 according to the mass ratio of raw material and deionized water and zirconium ball, secondary ball milling 12 hours.
(5). sieve
Secondary ball milling completes post-drying, and 80 mesh sieves crossed by the raw material after oven dry.
(6). compression molding
Powder after sieving is put into tabletting machine and is carried out compressing tablet, and diameter is 100mm, and for allowing target uniform force in pressing process, adopt isostatic pressing technology, operating pressure is 150Mpa, and the dwell time is 5min.
(7). binder removal
Green compact after compressing tablet completes are put into low temperature oven and are carried out binder removal, dump temperature 700 DEG C.
(8). sintering
Carry out high temperature sintering after binder removal completes, sintering temperature is 1300 DEG C, and heat up 5 DEG C/min, and soaking time is 4 hours, obtained magnetron sputtering PBZ target.
PBZ target reduced after having sintered is 80mm.
Claims (5)
1. adopt magnetron sputtering method to prepare a preparation method for the PBZ target of PBZ film, step is as follows:
(1) preparation raw material
According to the compound molecule formula (Pb of PBZ and lead zirconates barium
1-xba
x) ZrO
3the wherein element molar mass ratio of 0<x<1, by Pb
3o
4, BaCO
3, ZrO
2three kinds of raw materials mix;
(2) ball millings
By step (1) mixed raw material, be that 1:1:1 carries out ball milling according to the mass ratio of raw material and deionized water and zirconium ball, Ball-milling Time is 4 ~ 8 hours;
(3) pre-burning
By the raw material stoving after step (2) ball millings, then carry out pre-burning in 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%, be that 1:1:1 carries out ball milling according to the mass ratio of raw material and deionized water and zirconium ball, 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) shaping
It is base substrate that powder after step (5) being sieved puts into tabletting machine compression moulding, for allowing target uniform force in pressing process, adopt isostatic pressing technology first, operating pressure is 100-200Mpa, dwell time is 1-5min, and compacting diameter is the magnetron sputtering target of 40 ~ 100mm;
(7) binder removal
Base substrate after shaping for step (6) is put into low temperature oven and carries out binder removal, dump temperature is 600 ~ 800 DEG C;
(8) sinter
By base substrate after step (7) binder removal in 1100-1300 DEG C of high temperature sintering, soaking time is 3 ~ 7 hours, obtained magnetron sputtering PBZ target; In sintering process, for avoiding target in sintering process, adopting to bury and burning and press firing method to prevent Pb from volatilizing and target flexural deformation.
2. a kind of preparation method adopting magnetron sputtering method to prepare the PBZ target of PBZ film according to claim 1, it is characterized in that, the raw material of described step (1) is analytical reagent.
3. a kind of preparation method adopting magnetron sputtering method to prepare the PBZ target of PBZ film according to claim 1, it is characterized in that, the dump temperature of described step (7) is 700 DEG C.
4. a kind of preparation method adopting magnetron sputtering method to prepare the PBZ target of PBZ film according to claim 1, it is characterized in that, the sintering temperature of described step (8) is 1200 DEG C, and soaking time is 6 hours.
5. a kind of preparation method adopting magnetron sputtering method to prepare the PBZ target of PBZ film according to claim 1, it is characterized in that, described step (8) base substrate is placed in retort furnace sinter.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN112537954A (en) * | 2020-12-17 | 2021-03-23 | 中山智隆新材料科技有限公司 | Preparation method of IGZO target material |
| CN114873639A (en) * | 2022-03-30 | 2022-08-09 | 郑州大学 | Ba 3 Zr 2 S 7 Film, preparation method and application thereof |
| CN115304359A (en) * | 2022-05-27 | 2022-11-08 | 先导薄膜材料（广东）有限公司 | Additive-free high-mobility oxide target material and preparation method thereof |
Citations (1)
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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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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Non-Patent Citations (1)
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| 中国科学院上海硅酸盐化学与工学研究所: "《铁电材料及其应用《译文集》第2辑》", 31 December 1974 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN112537954A (en) * | 2020-12-17 | 2021-03-23 | 中山智隆新材料科技有限公司 | Preparation method of IGZO target material |
| 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 |
| CN114873639A (en) * | 2022-03-30 | 2022-08-09 | 郑州大学 | Ba 3 Zr 2 S 7 Film, preparation method and application thereof |
| CN115304359A (en) * | 2022-05-27 | 2022-11-08 | 先导薄膜材料（广东）有限公司 | Additive-free high-mobility oxide target material and preparation method 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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