CN1631843A - Preparation method of barium strontium titanate film material - Google Patents
Preparation method of barium strontium titanate film material Download PDFInfo
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- CN1631843A CN1631843A CN 200410065775 CN200410065775A CN1631843A CN 1631843 A CN1631843 A CN 1631843A CN 200410065775 CN200410065775 CN 200410065775 CN 200410065775 A CN200410065775 A CN 200410065775A CN 1631843 A CN1631843 A CN 1631843A
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- strontium titanate
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Abstract
The invention adds little sensitizer and nucleation agent in the raw material for preparing target, which can be transmitted averagely into the film in the magnetron sputtering course and can strengthen lots of micro crystal deposited from amorphous state (dielectric constant) solid of the film and help them grow, the method can remarkably increase amorphous state (dielectric constant) of the film made. The nucleation agent is for promoting the formation of crystal nucleus and sensitizer for inducing recrystallization of amorphous state, nucleation agent can use noble metal oxide or noble metal salts, such as cupric oxide, silver nitrate and so on and the sensitizer can use oxide which can increase light sensitivity and promote crystal nucleus forming, such as ceric oxide; the heat procession can use low vacuum heat processing method, which can decrease the temperature, as well as increase the effect of crystallization .
Description
Technical field
The invention belongs to the electronic ceramics technical field, be mainly used in the microwave integrated circuit occasion that requires high-k, low-loss, good stability.
Background technology
Ferroelectric thin-flim materials has good ferroelectric, piezoelectricity, characteristics such as pyroelectricity, electric light and nonlinear optics, it can be widely used in fields such as microtronics, photoelectronics, integrated optics and microelectromechanical systems, and it is one of the forward position of present research in new high-tech and focus.
Wherein the barium strontium titanate medium material is one of more kind of research at present, it fatigue do not occur with excellent dielectric, pyroelectric property, non-linear, high-breakdown-voltage, paraelectric phase, and Curie temperature can be regulated and can be made into characteristics such as film and ic process compatibility and be subjected to generally favoring of people and become one of microwave dielectric material of present tool development prospect by changing component.
Because thin-film material is convenient to and the unicircuit compatibility, it is little to make device volume, so in semiconductor process techniques, usually the barium strontium titanate medium material is made film and use.
Technologies such as pulsed deposition method, magnetron sputtering method, sol-gel method, metal organic chemical vapor deposition are arranged in the preparation method of film.And wherein magnetron sputtering method because simple and efficient, good reproducibility, cost is low, can be made into the high-quality thin-film of high Q, is applicable to the mass production of semiconducter device and unicircuit and is used usually.
In the ordinary course of things, with the strontium-barium titanate bulk ceramic material of high temperature sintering synthesis method preparation, at room temperature its specific inductivity can reach thousands of orders of magnitude; But after in a single day making film by magnetron sputtering technique, the specific inductivity of its film can descend sharp, traces it to its cause, and mainly is that the crystallization effect is damaged, and shows the non-crystalline state characteristic remarkable of film; And the dielectric constant values of wanting to improve the film finished product compares difficulty usually, main way is to select the substrate material in suitable crystalline size and crystal orientation as sedimentary carrier at present, and strengthen the crystallization effect improving the dielectric constant values of thin-film material by the way of pyroprocessing, but these method final effects are subjected to the restriction of its substrate material performance and thermal treatment temp.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art part, adopt new technological method to prepare target, and pass through the transfer of target component structure advantage, strengthen the crystallization effect of magnetron sputtering barium strontium titanate, improve the dielectric constant values of film significantly.
Its know-why and method are as follows:
For reaching above purpose, the present invention is at preparation strontium-barium titanate (Ba
xSr
1-xTiO
3) add the sensitizing agent and the nucleator of trace in the starting material of target, this class additive is transferred in the film equably to be gone, handle to strengthen by suitable crystallization and in the non-crystalline solids of film, separate out a large amount of micritization crystal equably, and making its growth, this method can improve the dielectric constant values of institute's made membrane significantly.Wherein the effect of nucleator mainly is the formation that promotes nucleus, and the effect of sensitizing agent mainly is to induce the amorphous phase crystallization.Nucleator can use metal oxide containing precious metals or precious metal salt, and as cupric oxide, Silver Nitrate etc., sensitizing agent can adopt and can increase photosensitivity, promotes the oxide compound that nucleus forms, as cerium dioxide etc.And thermal treatment can be adopted rough vacuum thermal treatment way, both can further reduce thermal treatment temp, can further improve the crystallization effect effectively again.
Purpose of the present invention can reach by following technical measures:
A kind of preparation method of barium strontium titanate film material is characterized in that this preparation method comprises:
A. prepare the barium strontium titanate medium material on request, and grind to form the ultrafine powder of particle diameter≤1 micron;
B. the sensitizing agent of crystallization will be induced and the ultrafine powder that micritization crystalline nucleator grinds to form particle diameter≤1 micron respectively can be produced, and be doped in the strontium-barium titanate parent powder by 1～8 mol ratio, by being embossed in sintering premolding in 1200～1250 ℃, 2～4 hours;
C. the strontium-barium titanate regrinding of above mixed sensitizing agent and nucleator is made the ultrafine powder of particle diameter≤1 micron, finally become target by being embossed in 1250～1300 ℃, 4～6 hours sinter moldings;
D. adopt magnetron sputtering method to make film, contain sensitizing agent and nucleator in this thin-film material non-crystalline solids composition, by ultraviolet ray intensity 15～20mW/cm
2, 10～30 minutes irradiation and rough vacuum 10～10
-1Pa and thermal treatment in 300～400 ℃, 15～30 minutes form the high-k barium strontium titanate film material.
Advantage of the present invention:
The present invention is by in system target technology, at Ba
xSr
1-xTiO
3Add sensitizing agent and nucleator in the starting material, prepare in the process of film at magnetron sputtering, these doping agents are transferred to equably in institute's made membrane and are gone, by suitable ultraviolet lighting and rough vacuum heat treated, wherein sensitizing agent has promoted the formation of nucleus, induce film amorphous phase crystallization, nucleator can separated out a large amount of crystal under the effect of sensitizing agent equably in the film amorphous phase, and under suitable heating condition, grow, above synthesis result, can strengthen the crystallization effect of film greatly, thereby improve and control the dielectric constant values of film significantly.Evidence: barium strontium titanate medium target material of under same condition, producing and film thereof by method of the present invention and need not be of the present invention the method contrast, dielectric constant values can improve about 40% under the normal temperature.
The present invention can improve the dielectric constant values of barium strontium titanate significantly because the use of sensitizing agent and nucleator, provides very advantageous conditions to the consistency of the design and processes of discrete device and unicircuit.
Use technology of the present invention can make the dielectric constant values of made barium strontium titanate bring up to a new height, thereby for expanding the use range of film, or it is all significant to dwindle the unicircuit size.
Embodiment
Embodiment 1: the Ba that makes ф 80mm * 4mm
0.6Sr
0.4Tio
3Target, wherein the cerium dioxide additive is 1% mol ratio, the cupric oxide additive is 1% mol ratio.
Processing step:
1. by molecular formula Ba
0.6Sr
0.4Tio
3Mol ratio preparation target starting material, grind to form the ultrafine powder of particle diameter≤1 micron, pulverize the ultrafine powder that grinds to form particle diameter≤1 micron after synthetic once more through mold pressing and high temperature presintering in 1200 ℃, 2 hours.
2. grind to form the ultrafine powder of particle diameter≤1 micron by 1% mol ratio cerium dioxide and 1% mol ratio cupric oxide equally, and be incorporated into uniform mixing in the above-mentioned basic powder and after mold pressing and 1200 ℃, 2 hours high temperature sinterings are synthetic, pulverize the ultrafine powder that grinds to form particle diameter≤1 micron once more.
3. pass through mold pressing and finally made the target that ф 80mm * 4mm contains sensitizing agent cerium dioxide and nucleator cupric oxide behind the high temperature sintering in 1250 ℃, 4 hours.
4. utilizing above-mentioned target to make thickness by magnetron sputtering method is 4000 films, uses ultraviolet ray intensity 20mW/cm
2Shone 30 minutes, and in rough vacuum 10～10
-1Pa, temperature is 400 ℃ of following thermal treatments 30 minutes.
Embodiment 2: the Ba that makes ф 80mm * 4mm
0.6Sr
0.4Tio
3Target, wherein the cerium dioxide additive is 5% mol ratio, the cupric oxide additive is 5% mol ratio.
Processing step:
Process is with embodiment 1.But the cerium dioxide additive is 5% mol ratio, and the cupric oxide additive level is 5% mol ratio.
Embodiment 3: the Ba that makes ф 80mm * 4mm
0.6Sr
0.4Tio
3Target, wherein the cerium dioxide additive is 3% mol ratio, the Silver Nitrate additive level is 3% mol ratio.
Processing step:
Technological process is with embodiment 1.But the cerium dioxide additive is 3% mol ratio, and the Silver Nitrate additive level is 3% mol ratio.
Embodiment 4: the Ba that makes ф 80mm * 4mm
0.6Sr
0.4Tio
3Target, wherein the cerium dioxide additive is 8% mol ratio, the Silver Nitrate additive level is 8% mol ratio.
Processing step:
Technological process is with embodiment 1.But the cerium dioxide additive is 8% mol ratio, and the Silver Nitrate additive level is 8% mol ratio.
Claims (3)
1, a kind of preparation method of barium strontium titanate film material is characterized in that this preparation method comprises:
A. prepare the barium strontium titanate medium material on request, and grind to form the ultrafine powder of particle diameter≤1 micron;
B. the sensitizing agent of crystallization will be induced and the ultrafine powder that micritization crystalline nucleator grinds to form particle diameter≤1 micron respectively can be produced, and be doped in the strontium-barium titanate parent powder by 1～8 mol ratio, by being embossed in sintering premolding in 1200～1250 ℃, 2～4 hours;
C. the strontium-barium titanate regrinding of above mixed sensitizing agent and nucleator is made the ultrafine powder of particle diameter≤1 micron, finally become target by being embossed in 1250～1300 ℃, 4～6 hours sinter moldings;
D. adopt magnetron sputtering method to make film, contain sensitizing agent and nucleator in this thin-film material non-crystalline solids composition, by ultraviolet ray intensity 15～20mW/cm
2, 10～30 minutes irradiation and rough vacuum 10～10
-1Pa and thermal treatment in 300～400 ℃, 15～30 minutes form the high-k barium strontium titanate film material.
2, the preparation method of barium strontium titanate film material according to claim 1 is characterized in that inducing the sensitizing agent of crystallization is cerium dioxide.
3, the preparation method of barium strontium titanate film material according to claim 1, it is characterized in that producing micritization crystalline nucleator is cupric oxide or Silver Nitrate.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100657753A CN100341817C (en) | 2004-11-18 | 2004-11-18 | Preparation method of barium strontium titanate film material |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100657753A CN100341817C (en) | 2004-11-18 | 2004-11-18 | Preparation method of barium strontium titanate film material |
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| Publication Number | Publication Date |
|---|---|
| CN1631843A true CN1631843A (en) | 2005-06-29 |
| CN100341817C CN100341817C (en) | 2007-10-10 |
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|---|---|---|---|
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100372803C (en) * | 2006-10-08 | 2008-03-05 | 浙江大学 | Seepage flow type silver/strontium barium titanate/nonex composite material and manufacture method |
| CN103880414A (en) * | 2014-02-25 | 2014-06-25 | 电子科技大学 | Preparation method for cerium-doped barium strontium titanate (BST) thin film |
| CN109912304A (en) * | 2019-03-21 | 2019-06-21 | 清华大学 | A kind of ferrous acid bismuthino ternary solid solution dielectric film material and preparation method thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3129233B2 (en) * | 1997-05-09 | 2001-01-29 | 三菱マテリアル株式会社 | Sputtering target for forming a high dielectric film comprising a composite oxide sintered body of Ba, Sr and Ti |
| JPH10310471A (en) * | 1997-05-09 | 1998-11-24 | Mitsubishi Materials Corp | Sputtering target for forming high dielectric film |
| JPH11131223A (en) * | 1997-10-24 | 1999-05-18 | Mitsubishi Materials Corp | Dielectric sputtering target |
| CN1250482C (en) * | 2003-05-08 | 2006-04-12 | 上海交通大学 | Prep. of strontium titanate barium ceramic target |
-
2004
- 2004-11-18 CN CNB2004100657753A patent/CN100341817C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100372803C (en) * | 2006-10-08 | 2008-03-05 | 浙江大学 | Seepage flow type silver/strontium barium titanate/nonex composite material and manufacture method |
| CN103880414A (en) * | 2014-02-25 | 2014-06-25 | 电子科技大学 | Preparation method for cerium-doped barium strontium titanate (BST) thin film |
| CN103880414B (en) * | 2014-02-25 | 2015-10-21 | 电子科技大学 | A kind of preparation method of cerium dopping barium strontium titanate |
| CN109912304A (en) * | 2019-03-21 | 2019-06-21 | 清华大学 | A kind of ferrous acid bismuthino ternary solid solution dielectric film material and preparation method thereof |
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| Publication number | Publication date |
|---|---|
| CN100341817C (en) | 2007-10-10 |
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