CN100457292C - (Ba,Zr)TiO3 ferroelectric film with optimized performance and its preparing method - Google Patents
(Ba,Zr)TiO3 ferroelectric film with optimized performance and its preparing method Download PDFInfo
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- CN100457292C CN100457292C CNB2005101109144A CN200510110914A CN100457292C CN 100457292 C CN100457292 C CN 100457292C CN B2005101109144 A CNB2005101109144 A CN B2005101109144A CN 200510110914 A CN200510110914 A CN 200510110914A CN 100457292 C CN100457292 C CN 100457292C
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Abstract
The present invention relates to a method for preparing performance-optimized (Ba,Zr)TiO3 ferroelectric film. Said method includes the following steps: firstly, using sol-gel method to prepare precursor solution, then coating substrate with said precursor solution to prepare seed crystal layer, then coating said seed crystal layer with said precursor solution to prepare film with required thickness, finally making said film undergo the process of heat treatment for 25-35 min, at 650-750 deg.C, and sputtering electrode so as to obtain the invented product.
Description
Technical field
The present invention relates to a kind of ferroelectric thin film, be specifically related to the method and technology field that a kind of employing chemical method prepares zirconia titanate barium (BZT) ferroelectric thin film.
Background technology
Barium strontium titanate (Ba, Sr) TiO
3(BST) focus of ferroelectric thin film international ferroelectric thin film research owing to its application at the integrated scale integrated circuit of super large becomes, but there is the bigger defective of leakage current under the low electric field in bst thin film.Substitution material as BST has (Ba
1-xSr
x) (Ti
1-yZr
y) O
3(BSTZ), Ba (Zr, Ti) O
3(BZT) and Ba (Ti, Sn) O
3(BTS) etc.Barium zirconium phthalate Ba (Ti, Zr) O
3(BZT) ferroelectric thin film is to BaTiO
3(ABO
3) perovskite structure carries out the B position and substitute, the BZT film has lower leakage conductance electric current, and under high frequency, have excellent dielectric properties equally, therefore can be applied to the holding capacitor on the DRAM of future generation, ferroelectric material and the dielectric, nonlinear material of MLCC.
The process that adopts sol-gel process to prepare ferroelectric thin film has many reports.Sol-gel process with its stoichiometric proportion precise control, film forming area big and evenly, advantage such as the technical process temperature is low, equipment is simple and being adopted by people.In recent years, along with going deep into that ferroelectric thin film is studied, its preparation method is also more and more paid close attention to by people.Generally speaking, ferroelectric thin film is that directly preparation is on silicon substrate, and such thin-film dielectric loss that obtains and leakage current are still bigger.
Summary of the invention
One of purpose of the present invention just provides the better Ba of a kind of electric property (Ti, Zr) O
3Ferroelectric thin film, this kind ferroelectric thin film have certain thickness inculating crystal layer between film and substrate.
Another object of the present invention provides above-mentioned this Ba (Ti, Zr or Sn) O with inculating crystal layer
3The preparation method of ferroelectric thin film.
In order to achieve the above object, the technical scheme taked of the present invention is:
A kind of Ba of performance optimization (Zr, Ti) O
3The preparation method of ferroelectric thin film, its concrete steps are: prepare precursor solution with sol-gel process earlier, then precursor solution is coated in and on substrate, prepares inculating crystal layer, on inculating crystal layer, apply the film that precursor solution prepares desired thickness again, at last with film 650～750 ℃ of following heat treatments 25～35 minutes, the sputter top electrode gets final product.
Described employing sol-gel process preparation precursor solution and precursor solution is coated on the substrate all can takes technique known, but sol-gel process preparation precursor solution list of references Jiwei Zhai, Xi Yao.[J] .Applied Phsics letters.2004,84:3136-3138 and Jiwei Zhai, Haydn Chen.[J] .Applied Phsics letters.2004,841162-1164.But on substrate, apply gel mould list of references Jiwei Zhai, Xi Yao.[J] .Applied Phsics letters.2004,84:3136-3138 and Jiwei Zhai, Haydn Chen.[J] .Applied Phsics letters.2004, shown in the 841162-1164.The concentration of used precursor solution, the number of plies of coating and last to obtain the total thickness of film relevant, promptly molar concentration is big more, and its thickness is also just big more; The number of plies is many more, and its thickness is also big more.For ferroelectric thin film, its gross thickness is 600-800nm generally speaking, and then the thickness of inculating crystal layer can be selected in greater than 0, gets final product smaller or equal to 100nm simultaneously.
The preparation of described inculating crystal layer, its concrete method is: with precursor solution apply on the substrate good after, directly put into 650～750 ℃ environment heat treatment 8～12 minutes, be cooled to room temperature then, apply one deck gel mould down, move in circles up to the seed crystal that obtains desired thickness.
Each heat treatment temperature is 450～550 ℃ after rotation applies gel mould on the inculating crystal layer, and heat treatment time is 8～12 minutes.
Beneficial effect of the present invention: Ba (Ti, Zr or the Sn) O that makes with method of the present invention
3Ferroelectric thin film and general ferroelectric thin film relatively generate the seed crystal identical with thin film composition film performance are had optimization function between film and substrate, characteristics such as make it to have higher dielectric constant, lower dielectric loss and leakage current are low.
Description of drawings
Fig. 1 is that preparation is at Pt/Ti/SiO
2The relation of the dielectric constant of BZT ferroelectric thin film and electric field on/the Si substrate.
Fig. 2 is that preparation is at Pt/Ti/SiO
2The relation of the dielectric loss of BZT ferroelectric thin film and electric field on/the Si substrate.
Fig. 3 is that preparation is at Pt/Ti/SiO
2The leakage conductance electric current of BZT ferroelectric thin film and the relation of electric field on/the Si substrate.
The specific embodiment
Embodiment 1～5
The gross thickness that preparation inculating crystal layer thickness is respectively 0nm, 10nm, 20nm, 40nm and 90nm is (Ba, Zr) TiO of 400nm
3Ferroelectric thin film.
In the Zr/Ti ratio is the synthetic preparation of 0.3/0.7 Ba (Zr, Ti) O
3The precursor solution of the film of composition, the chemical raw material that is adopted are barium acetate [Ba (CH
3COO)
2], zirconium iso-propoxide [Zr (OC
3H
7)
4] and isopropyl titanate [Ti (OC
3H
7)
4], solvent is glacial acetic acid and ethylene glycol ethyl ethers mystery, acetylacetone,2,4-pentanedione is as intercalating agent.Earlier barium acetate is dissolved in glacial acetic acid, be heated to boiling be cooled to then 60 ℃ stand-by.With proper amount of glycol ether dissolution isopropyl titanate, and insert an amount of acetylacetone,2,4-pentanedione as intercalating agent, constantly stirring made it become clear solution in 20 minutes, insert quantitative zirconium iso-propoxide afterwards again, constantly stir 20 minutes until abundant mixing, and be heated to 60 ℃ and mix and add an amount of glacial acetic acid with the glacial acetic acid solution of barium acetate solution is adjusted to 0.3M, constantly stirring became transparent colloidal sol in 60 minutes.Using the filter opening diameter at last is to leave standstill behind the membrane filtration of 0.22 μ m to be used for preparing film in 24 hours.
Employed substrate is Pt/Ti/SiO
2/ Si (100), Pt, Ti, SiO
2With the thickness of Si sheet be respectively 150nm, 50nm, 150nm and 3500nm.
The method that adopts rotation to apply prepares film, and rotary speed is 3000 rev/mins, 20 seconds time.The preparation of seed crystal is that gel mould is directly put into 700 ℃ tube furnace, placed 10 minutes, be cooled to room temperature after the taking-up, apply one deck gel mould down, move in circles up to the seed crystal that obtains desired thickness, and then rotation applies gel mould on inculating crystal layer, gel mould is put into tube furnace again and is handled 10 minutes for 500 ℃, is cooled to room temperature after the taking-up, apply one deck gel mould down, move in circles up to the film that obtains desired thickness.
Seed crystal is identical with the precursor solution concentration that the film principal component is adopted, and the ratio of Zr/Ti is identical.Making the gross thickness that inculating crystal layer thickness is respectively 0nm, 10nm, 20nm, 40nm and 90nm altogether is five BZT films of 400nm.At last with all films 700 ℃ of following heat treatments 30 minutes, the method sputter top electrode of d.c. sputtering is adopted on the surface thereon then, its diameter is that 0.5mm, thickness are about 100nm.
The inculating crystal layer thickness of above-mentioned preparation is respectively the BaZr of 0nm, 10nm, 20nm, 40nm and 90nm
0.3Ti
0.7O
3The relation of the dielectric constant of ferroelectric thin film and dielectric loss and extra electric field is seen Fig. 1 and Fig. 2, and the relation of leakage conductance electric current and extra electric field is seen Fig. 3.
As seen from the figure, there is the BZT film of certain seed crystal thickness on performance, to reduce thin-film material loss and leakage conductance, improved voltage endurance than the BZT film that does not have inculating crystal layer.
Claims (4)
1, a kind of Ba of performance optimization (Zr, Ti) O
3The preparation method of ferroelectric thin film, its concrete steps are: prepare precursor solution with sol-gel process earlier, then precursor solution is coated in and on substrate, prepares inculating crystal layer, on inculating crystal layer, apply the film that precursor solution prepares desired thickness again, at last with film heat treatment 25～35 minutes in 650～750 ℃, sputter top electrode, the ratio of described Zr/Ti are 0.3: 0.7, the thickness of inculating crystal layer＞0 and≤100nm.
2, the Ba of performance optimization as claimed in claim 1 (Zr, Ti) O
3The preparation method of ferroelectric thin film, it is characterized in that the preparation method of inculating crystal layer is as follows: precursor solution applying the heat treatment 8～12 minutes in 650～750 ℃ of good back on the substrate, is cooled to room temperature then, apply one deck gel mould down, move in circles up to the seed crystal that obtains desired thickness.
3, as Ba (Zr, Ti) O of the described arbitrary performance optimization of claim 1～2
3The preparation method of ferroelectric thin film is characterized in that, each heat treatment temperature is 450～550 ℃ after rotation applies gel mould on the inculating crystal layer, and heat treatment time is 8～12 minutes.
4, a kind of Ba of performance optimization (Zr, Ti) O
3Ferroelectric thin film is characterized in that it being Ba (Zr, Ti) O that adopts the described arbitrary performance optimization of claim 1～3
3The preparation method of ferroelectric thin film makes.
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|---|---|---|---|
| CNB2005101109144A CN100457292C (en) | 2005-11-29 | 2005-11-29 | (Ba,Zr)TiO3 ferroelectric film with optimized performance and its preparing method |
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|---|---|---|---|
| CNB2005101109144A CN100457292C (en) | 2005-11-29 | 2005-11-29 | (Ba,Zr)TiO3 ferroelectric film with optimized performance and its preparing method |
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| Publication Number | Publication Date |
|---|---|
| CN1978071A CN1978071A (en) | 2007-06-13 |
| CN100457292C true CN100457292C (en) | 2009-02-04 |
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| CN103265288B (en) * | 2013-05-10 | 2015-10-14 | 伊犁师范学院 | Large dielectric constant piezoelectric ceramic and preparation method thereof |
| CN112299845B (en) * | 2020-11-24 | 2023-08-04 | 厦门三行电子有限公司 | High-performance ceramic dielectric material and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1267654A (en) * | 2000-04-06 | 2000-09-27 | 中国科学院上海技术物理研究所 | Preparation of ferroelectric lead zirconate titanate film material |
| CN1537826A (en) * | 2003-10-23 | 2004-10-20 | 同济大学 | Method of preparing leadless calcium titanium ore structure ferroelectric film possessing high orientation |
-
2005
- 2005-11-29 CN CNB2005101109144A patent/CN100457292C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1267654A (en) * | 2000-04-06 | 2000-09-27 | 中国科学院上海技术物理研究所 | Preparation of ferroelectric lead zirconate titanate film material |
| CN1537826A (en) * | 2003-10-23 | 2004-10-20 | 同济大学 | Method of preparing leadless calcium titanium ore structure ferroelectric film possessing high orientation |
Non-Patent Citations (2)
| Title |
|---|
| sol-gel法制备锆钛酸钡薄膜的研究. 胡丹，翟继卫，张良莹，姚熹.电子元件与材料，第23卷第12期. 2004 |
| sol-gel法制备锆钛酸钡薄膜的研究. 胡丹，翟继卫，张良莹，姚熹.电子元件与材料，第23卷第12期. 2004 * |
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