CN103820760A - Barium strontium titanate thin film and preparation method and application thereof - Google Patents
Barium strontium titanate thin film and preparation method and application thereof Download PDFInfo
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- CN103820760A CN103820760A CN201310740835.6A CN201310740835A CN103820760A CN 103820760 A CN103820760 A CN 103820760A CN 201310740835 A CN201310740835 A CN 201310740835A CN 103820760 A CN103820760 A CN 103820760A
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- strontium titanate
- barium strontium
- lanthanum
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Abstract
The invention discloses a barium strontium titanate thin film and a preparation method and an application of the barium strontium titanate thin film. The thin film is prepared by codoping lanthanum to position A of barium strontium titanate and manganese to position B of barium strontium titanate. The thin film is prepared as follows: a BST ceramic sputtering target material codoped with La and Mn is firstly prepared, then the obtained BST ceramic sputtering target material codoped with La and Mn is used to prepare a lanthanum nickelate bottom electrode on a silicon substrate, then the obtained lanthanum nickelate bottom electrode is used to deposit the barium strontium titanate thin film according to a radio frequency magnetron sputtering method. The magnetron sputtering method is used to prepare the barium strontium titanate thin film codoped with La and Mn, and the prepared BST thin film is in a perovskite structure, has a simple pattern, does not have other patterns, and has a preferred orientation (100); particularly, the barium strontium titanate thin film has the advantages of high dielectric adjustability, low dielectric loss and moderate dielectric constant, and is expected to be used to prepare a dielectric tuning device.
Description
Technical field
The present invention relates to a kind of barium strontium titanate and its preparation method and application, belong to ferroelectric material technical field.
Background technology
In recent years, strontium-barium titanate (BST) film is owing to having high specific inductivity, lower dielectric loss, and high dielectric tuning, and its Curie temperature T
ccan compare continuously the excellent specific properties such as adjustable according to barium strontium, can be used for ferroelectric thin-membrane phase shifter.Ferroelectric thin-membrane phase shifter fast response time, cost are low, lightweight, power consumption and volume little, in phased array radar application, there is very large advantage.
But, the problem that bst thin film exists dielectric tuning rate and dielectric loss to be difficult to take into account.Bst thin film is at ferroelectric phase (T
cbelow) time, dielectric tuning rate is larger, and dielectric loss is larger; At paraelectric phase (T
cabove) time, dielectric tuning rate is less, and dielectric loss is also less, thereby has restricted the application of bst thin film aspect dielectric tuning device.Therefore, in recent years, countries in the world scientist has carried out doping vario-property research to bst thin film, to improving the electric property of bst thin film.By the doping of A position or B position, can optimize the electrical property of bst thin film, but dielectric loss is generally higher, figure of merit is on the low side, and less to the research of binary codoped bst thin film both at home and abroad, especially (La, Mn) codoped so far there are no report.The preparation method of the bst thin film of the doping vario-property of report has sol-gel method (sol-gel method), pulsed laser deposition (PLD method) at present, and adopt magnetron sputtering method rarely found, because thin film composition and target have certain deviation, be difficult to accurately control thin film composition.But the film compactness that adopts sol-gel method to make is poor, has pore, is prone to crack performance, and membrane structure and growth velocity have selectivity to substrate and electrode, and uniformity of film is poor, are difficult to make high quality large area film.Also there is lack of homogeneity, be difficult to make the defect problem of high quality large area film in the film that in addition, adopts PLD method to make.
Summary of the invention
For the existing the problems referred to above of prior art, the present invention aim to provide a kind of comprehensive dielectric properties excellence barium strontium titanate and a kind of simple to operate, can obtain the application of the preparation method of big area, uniform thin film and the one of this film.
For achieving the above object, the technical solution used in the present invention is as follows:
A kind of barium strontium titanate is film strontium-barium titanate (BST) A position and manganese (Mn) being obtained strontium-barium titanate (BST) B position codoped by lanthanum (La).
As preferred version, the doping of lanthanum (La) is 0.2～0.6mol% of the mole number of titanium (Ti) wherein, and the doping of manganese (Mn) is 0.5～1.0mol% of the mole number of titanium (Ti) wherein.
As further preferred version, described film has following compositing formula:
Ba
0.6sr
0.4tiO
3+ 0.6mol%La+0.5mol%Mn or Ba
0.6sr
0.4tiO
3+ 0.6mol%La+1.0mol%Mn, the mete-wand of molar percentage is wherein the mole number of titanium (Ti).
A method of preparing barium strontium titanate of the present invention, comprises the steps:
A) prepare the BST ceramic sputtering target material of La, Mn codoped;
B) utilize the La that step a) obtains, the BST ceramic sputtering target material of Mn codoped on silicon substrate substrate, to prepare nickel acid lanthanum bottom electrode;
C) the nickel acid lanthanum bottom electrode, the described barium strontium titanate of employing radio-frequency magnetron sputter method deposition that utilize step b) to obtain.
As preferred version, step a) comprises following operation: prepare burden by the BST pottery composition of La, Mn codoped, carry out ball milling and make fully to mix; Add binding agent, carry out moulding, then at 800～900 ℃ and 1250～1400 ℃, carry out successively plastic removal and sintering, then carry out mechanical workout, cleaning, obtain the BST ceramic sputtering target material of La, Mn codoped.
As further preferred version, proportion material is BaCO
3, SrCO
3, TiO
2, La
2o
3and MnCO
3powder.
As preferred version further, when batching, make the excessive 20mol% of BaO, make SrO excessive 10mol% simultaneously.
As further preferred version, the polyvinyl alcohol water solution that described binding agent is 5～7wt%, its consumption is 5～7% of powder total mass.
As preferred version, step b) comprises following operation: the silicon substrate substrate after cleaning is put into magnetic control sputtering device, 10
-4～10
-5under the vacuum tightness of Pa, be heated to 400～500 ℃, passing into volume ratio is the oxygen of 1:9～3:7 and the mixed gas of argon gas, when air pressure reaches after 2.0～3.0Pa, adopt DC sputtering nickel deposited acid lanthanum (LNO) film, sputtering power is 80～90W, sputtering time is 10～30 minutes, obtains nickel acid lanthanum/silica/silicon (LNO/SiO
2/ Si) laminated film, finally to LNO/SiO
2the laminated film of/Si carries out (temperature rate is 5～15 ℃/sec) annealing fast at 600～800 ℃, obtains nickel acid lanthanum bottom electrode.
As preferred version, step c) comprises following operation: under the air pressure of 2.0～3.0Pa that the nickel acid lanthanum bottom electrode that step b) is obtained is 0～30% in oxygen partial pressure, be warming up to 600～700 ℃, adopt radio-frequency magnetron sputter method, sputter 1～3 hour under the power of 60～90W, deposition obtains lanthanum and manganese codoped barium strontium titanate, after sputter, be warming up to 650～800 ℃ with the speed of 1～2 ℃/min, anneal 1～2 hour, finally be cooled to room temperature with the speed of 1～2 ℃/min, obtain take silicon chip as substrate base, lanthanum nitrate is the lanthanum of bottom electrode and manganese codoped barium strontium titanate.
Barium strontium titanate of the present invention can be applicable to make dielectric tuning device.
The invention has the advantages that: by design lanthanum and manganese codoped barium-strontium titanate ceramic target, realized and adopted magnetron sputtering method to prepare lanthanum and manganese codoped barium strontium titanate; And the bst thin film making is perovskite structure, single-phase, without dephasign, and has (100) preferred orientation; Especially, there is high dielectric adjustable, low-dielectric loss and moderate specific inductivity, be expected to be applied to making dielectric tuning device.In addition, the substrate that bst thin film prepared by the present invention is selected is silicon substrate, is more suitable in compatible mutually with semiconductor integrated circuit technology, and suitability is strong.
Accompanying drawing explanation
Fig. 1 is the comparison diagram of the XRD figure spectrum of the lanthanum prepared of embodiment 1, manganese codoped barium strontium titanate and pure bst thin film;
Fig. 2 is surface and the section SEM figure of the lanthanum prepared of embodiment 1, manganese codoped barium strontium titanate;
Fig. 3 is that the specific inductivity of the lanthanum prepared of embodiment 1, manganese codoped barium strontium titanate and pure bst thin film and dielectric loss are with electric field change curve comparison figure;
Fig. 4 is that the dielectric adjustable of the lanthanum prepared of embodiment 1, manganese codoped barium strontium titanate and pure bst thin film and figure of merit (FOM) are with electric field change curve comparison figure;
Fig. 5 is that the specific inductivity of the lanthanum prepared of embodiment 2, manganese codoped barium strontium titanate and pure bst thin film and dielectric loss are with electric field change curve comparison figure.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment are only not used in and limit the scope of the invention for the present invention is described.
Raw material BaCO used in the present invention
3powder, SrCO
3powder and TiO
2the purity of powder is all not less than 99.0%, La
2o
3the purity of powder is not less than 99.99%, MnCO
3the purity of powder is not less than 87.92%.
Embodiment 1
A) prepare the BST ceramic sputtering target material of La, Mn codoped;
Be Ba by compositing formula
0.6sr
0.4tiO
3+ 0.6mol%La+0.5mol%Mn prepares burden, and first presses Ba that is:
0.6sr
0.4tiO
3stoichiometric ratio and make BaO and SrO in original stoichiometric ratio, excessive 20mol% and 10mol% take BaCO respectively
3, SrCO
3and TiO
2powder, then take respectively as TiO
2the La of the 0.3mol% of the mole number of powder
2o
3the MnCO of powder, 0.5mol%
3powder, carries out wet ball grinding 24h, then dry, cross 40 mesh sieves, be pressed into the disk that diameter is 60mm in advance, then at 1100 ℃ pre-burning 2h, then use wet ball grinding 24h, dry, grind, cross 20 mesh sieves; Be incorporated as the 6wt% polyvinyl alcohol water solution of 6wt% of mixed powder total mass as binding agent, be pressed into the disk that diameter is 90mm, at 800 ℃, sintering 2h at plastic removal 1h, 1350 ℃, finally carries out mechanical workout, cleaning, obtains the BST ceramic sputtering target material of La, Mn codoped.
B) utilize the La that step a) obtains, the BST ceramic sputtering target material of Mn codoped on silicon substrate substrate, to prepare nickel acid lanthanum bottom electrode;
Target prepared by previous step is placed on the target position of magnetic control sputtering device, the silicon substrate substrate after cleaning is put into magnetic control sputtering device, 10
-4～10
-5under the vacuum tightness of Pa, be heated to 400～500 ℃, passing into volume ratio is the oxygen of 1:9～3:7 and the mixed gas of argon gas, when air pressure reaches after 2.0～3.0Pa, adopt DC sputtering deposition lanthanum nickelate thin film, sputtering power is 80～90W, sputtering time is 10～30 minutes, then at 600～800 ℃, carries out (temperature rate is 5～15 ℃/sec) annealing fast, obtains nickel acid lanthanum bottom electrode.
C) utilize nickel acid lanthanum bottom electrode, the employing radio-frequency magnetron sputter method that step b) obtains to deposit barium strontium titanate of the present invention;
Under the 2.0～3.0Pa air pressure that is 0～20% in oxygen partial pressure by nickel acid lanthanum bottom electrode obtained in the previous step, be warming up to 600～700 ℃, adopt radio-frequency magnetron sputter method, sputter 1～3 hour under the power of 60～90W, deposition lanthanum, manganese codoped barium strontium titanate, after sputter, be warming up to 650～800 ℃ with the speed of 1～2 ℃/min, anneal 1～2 hour, finally be cooled to room temperature with the speed of 1～2 ℃/min, obtain take silicon chip as substrate base, nickel acid lanthanum as the lanthanum of bottom electrode, manganese codoped barium strontium titanate (brief note as: BST-LM1).
Fig. 1 is the comparison diagram of the XRD figure spectrum of the BST-LM1 film prepared of the present embodiment and pure bst thin film, as seen from Figure 1: BST-LM1 film has typical cubic perovskite structure, mainly contain (100), (110) two diffraction peaks, and there is (100) preferred orientation.
Fig. 2 is surface and the section SEM figure of the BST-LM1 film prepared of the present embodiment, as seen from Figure 2: the densification of prepared BST-LM1 film surface, flawless, LNO film, BST-LM1 film wherein are all columnar growth, LNO film thickness is about 175nm, and the thickness of BST-LM1 film is about 291nm.
Fig. 3 is that the specific inductivity of the BST-LM1 film prepared of the present embodiment and pure bst thin film and dielectric loss are with electric field change curve comparison figure, as seen from Figure 3: the specific inductivity of BST-LM1 film under null field significantly improves, dielectric loss is lower simultaneously, under null field, be only 0.0170, approach with the dielectric loss 0.0112 of pure bst thin film.
Fig. 4 is that the dielectric adjustable of the BST-LM1 film prepared of the present embodiment and pure bst thin film and figure of merit (FOM) are with electric field change curve comparison figure, as seen from Figure 4: BST-LM1 is under 700kV/cm electric field, adjustability is up to 60%, figure of merit reaches 35, greatly be better than the dielectric properties of pure bst thin film, and there is comparability with the bst thin film of growing in single crystalline substrate.
In addition, because the doping of lanthanum manganese is very little, cannot in EDS and XPS measuring precision, measure its doping, but analyze through EDS, Ba/ (Ba+Sr)=0.63, (Ba+Sr)/Ti=1.049, the component of BST-LM1 film approaches design component Ba
0.6sr
0.4tiO
3, meet the accuracy requirement of thin film composition.
Embodiment 2
The difference of the present embodiment and embodiment 1 is only: while preparing the BST ceramic sputtering target material of La, Mn codoped, be Ba by compositing formula
0.6sr
0.4tiO
3+ 0.6mol%La+1.0mol%Mn prepares burden.
The lanthanum making by preparation method described in embodiment 1, manganese codoped barium strontium titanate (brief note is: BST-LM2).Fig. 5 is that the specific inductivity of the BST-LM2 film prepared of the present embodiment and pure bst thin film and dielectric loss are with electric field change curve comparison figure, as seen from Figure 5: the K dielectric constant of BST-LM2 film under null field decreases, but adjustability improves, dielectric loss is lower simultaneously, same approaching with the dielectric loss of pure bst thin film.
Finally be necessary described herein: above embodiment is only for being described in more detail technical scheme of the present invention; can not be interpreted as limiting the scope of the invention, some nonessential improvement that those skilled in the art's foregoing according to the present invention is made and adjustment all belong to protection scope of the present invention.
Claims (10)
1. a barium strontium titanate, is characterized in that: be film strontium-barium titanate A position and manganese being obtained strontium-barium titanate B position codoped by lanthanum.
2. barium strontium titanate as claimed in claim 1, is characterized in that: the doping of lanthanum is 0.2～0.6mol% of the mole number of titanium wherein, and the doping of manganese is 0.5～1.0mol% of the mole number of titanium wherein.
3. barium strontium titanate as claimed in claim 1 or 2, is characterized in that, described film has following compositing formula:
Ba
0.6sr
0.4tiO
3+ 0.6mol%La+0.5mol%Mn or Ba
0.6sr
0.4tiO
3+ 0.6mol%La+1.0mol%Mn, the mole number that the mete-wand of molar percentage is wherein titanium.
4. a method of preparing the barium strontium titanate described in claim 1 or 2, is characterized in that, comprises the steps:
A) prepare the BST ceramic sputtering target material of La, Mn codoped;
B) utilize the La that step a) obtains, the BST ceramic sputtering target material of Mn codoped on silicon substrate substrate, to prepare nickel acid lanthanum bottom electrode;
C) the nickel acid lanthanum bottom electrode, the described barium strontium titanate of employing radio-frequency magnetron sputter method deposition that utilize step b) to obtain.
5. method as claimed in claim 4, is characterized in that, step a) comprises following operation: prepare burden by the BST pottery composition of La, Mn codoped, carry out ball milling and make fully to mix; Add binding agent, carry out moulding, then at 800～900 ℃ and 1250～1400 ℃, carry out successively plastic removal and sintering, then carry out mechanical workout, cleaning, obtain the BST ceramic sputtering target material of La, Mn codoped.
6. method as claimed in claim 5, is characterized in that: proportion material is BaCO
3, SrCO
3, TiO
2, La
2o
3and MnCO
3powder; When batching, make the excessive 20mol% of BaO, make SrO excessive 10mol% simultaneously.
7. method as claimed in claim 5, is characterized in that: the polyvinyl alcohol water solution that described binding agent is 5～7wt%, its consumption is 5～7% of powder total mass.
8. method as claimed in claim 4, is characterized in that, step b) comprises following operation: the silicon substrate substrate after cleaning is put into magnetic control sputtering device, 10
-4～10
-5under the vacuum tightness of Pa, be heated to 400～500 ℃, passing into volume ratio is the oxygen of 1:9～3:7 and the mixed gas of argon gas, when air pressure reaches after 2.0～3.0Pa, adopt DC sputtering deposition lanthanum nickelate thin film, sputtering power is 80～90W, and sputtering time is 10～30 minutes, then at 600～800 ℃, anneals, the temperature rate of annealing is 5～15 ℃/sec, obtains nickel acid lanthanum bottom electrode.
9. method as claimed in claim 4, it is characterized in that, step c) comprises following operation: under the air pressure of 2.0～3.0Pa that the nickel acid lanthanum bottom electrode that step b) is obtained is 0～30% in oxygen partial pressure, be warming up to 600～700 ℃, adopt radio-frequency magnetron sputter method, sputter 1～3 hour under the power of 60～90W, deposition obtains lanthanum and manganese codoped barium strontium titanate, after sputter, be warming up to 650～800 ℃ with the speed of 1～2 ℃/min, anneal 1～2 hour, finally be cooled to room temperature with the speed of 1～2 ℃/min, obtain take silicon chip as substrate base, lanthanum nitrate is the lanthanum of bottom electrode and manganese codoped barium strontium titanate.
10. the application of the barium strontium titanate described in claim 1 or 2 in dielectric tuning device.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104532186A (en) * | 2014-12-25 | 2015-04-22 | 庞凤梅 | Method for preparing BTS film by virtue of radio frequency magnetron sputtering |
| CN105801112A (en) * | 2016-03-23 | 2016-07-27 | 武汉理工大学 | Nd and Al co-doped substituted Ba0.4Sr0.6TiO3 giant dielectric ceramic and preparation method thereof |
| CN106784279A (en) * | 2016-12-22 | 2017-05-31 | 北京科技大学 | A kind of preparation method of high-performance doped strontium titanates oxide thermoelectricity film |
| CN108023096A (en) * | 2017-12-07 | 2018-05-11 | 北京理工大学 | The preparation method of solid oxide fuel cell densification double-layer ceramic connector |
-
2013
- 2013-12-28 CN CN201310740835.6A patent/CN103820760A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104532186A (en) * | 2014-12-25 | 2015-04-22 | 庞凤梅 | Method for preparing BTS film by virtue of radio frequency magnetron sputtering |
| CN105801112A (en) * | 2016-03-23 | 2016-07-27 | 武汉理工大学 | Nd and Al co-doped substituted Ba0.4Sr0.6TiO3 giant dielectric ceramic and preparation method thereof |
| CN106784279A (en) * | 2016-12-22 | 2017-05-31 | 北京科技大学 | A kind of preparation method of high-performance doped strontium titanates oxide thermoelectricity film |
| CN106784279B (en) * | 2016-12-22 | 2019-06-04 | 北京科技大学 | A kind of preparation method of strontium titanate doping oxide thermoelectricity film |
| CN108023096A (en) * | 2017-12-07 | 2018-05-11 | 北京理工大学 | The preparation method of solid oxide fuel cell densification double-layer ceramic connector |
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Application publication date: 20140528 |