CN101252042B - Nanometer line bottom electrode and dielectric medium composite film of capacitor and preparing method thereof - Google Patents
Nanometer line bottom electrode and dielectric medium composite film of capacitor and preparing method thereof Download PDFInfo
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- CN101252042B CN101252042B CN2008100599953A CN200810059995A CN101252042B CN 101252042 B CN101252042 B CN 101252042B CN 2008100599953 A CN2008100599953 A CN 2008100599953A CN 200810059995 A CN200810059995 A CN 200810059995A CN 101252042 B CN101252042 B CN 101252042B
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- CN
- China
- Prior art keywords
- bottom electrode
- line bottom
- composite film
- titanium silicide
- nanometer line
- Prior art date
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- Expired - Fee Related
Links
- 239000003990 capacitor Substances 0.000 title claims abstract description 43
- 239000002131 composite material Substances 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims description 20
- 239000000758 substrate Substances 0.000 claims abstract description 27
- 229910021341 titanium silicide Inorganic materials 0.000 claims abstract description 27
- 239000002070 nanowire Substances 0.000 claims abstract description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 24
- 229910008484 TiSi Inorganic materials 0.000 claims description 20
- 239000002243 precursor Substances 0.000 claims description 16
- 239000012528 membrane Substances 0.000 claims description 13
- 239000010936 titanium Substances 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 10
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 8
- ITHZDDVSAWDQPZ-UHFFFAOYSA-L barium acetate Chemical compound [Ba+2].CC([O-])=O.CC([O-])=O ITHZDDVSAWDQPZ-UHFFFAOYSA-L 0.000 claims description 8
- 238000005229 chemical vapour deposition Methods 0.000 claims description 8
- 239000011521 glass Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- 229910052788 barium Inorganic materials 0.000 claims description 7
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 claims description 7
- 229910052712 strontium Inorganic materials 0.000 claims description 7
- 229910000018 strontium carbonate Inorganic materials 0.000 claims description 7
- 229910021421 monocrystalline silicon Inorganic materials 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 5
- 229910021420 polycrystalline silicon Inorganic materials 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 2
- 239000003989 dielectric material Substances 0.000 abstract description 5
- 238000003980 solgel method Methods 0.000 abstract description 4
- 239000010408 film Substances 0.000 description 31
- 238000000151 deposition Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 4
- 229910021332 silicide Inorganic materials 0.000 description 4
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 229910008479 TiSi2 Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- DFJQEGUNXWZVAH-UHFFFAOYSA-N bis($l^{2}-silanylidene)titanium Chemical compound [Si]=[Ti]=[Si] DFJQEGUNXWZVAH-UHFFFAOYSA-N 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Landscapes
- Fixed Capacitors And Capacitor Manufacturing Machines (AREA)
- Inorganic Insulating Materials (AREA)
Abstract
The invention discloses a nano wire bottom electrode and a dielectric compound film capacitor, wherein, a titanium silicide conductive film layer, a titanium silicide nano wire bottom electrode layer and a dielectric film layer are deposited on a substrate from the top down. The capacitor is prepared by adoption of the sol-gel method, has low requirements on equipment, and is convenient to operate and easy to realize. The dielectric compound film capacitors utilizes the high specific surface area of the titanium silicide nano wire bottom electrode, greatly increases the contact area of dielectrics and the electrode, and improves the capacitance of the film composite structure which is over three times of the capacitance of a common electrode film with the same scale.
Description
Technical field
The present invention relates to the application of conducting nanowires and the operation technique of dielectric hearth electrode material.Especially the compound high capacitance film capacitor structure of nanometer line bottom electrode/dielectric that on the nanometer line bottom electrode substrate, forms by sol-gel process.
Background technology
Since finding carbon nano-tube, the research of monodimension nanometer material has caused the great interest of people.Compare with carbon nano-tube, the composition of nano wire is easy to control, and therefore, the research of nano wire has caused the great interest of people especially.Along with the development of nano wire research, various silicide nano wire is produced out.Yet, up to the present, the research of the application of silicide nano wire also is in the starting stage, great majority all concentrate on its preparation research the research of silicide nano wire, and fewer to the research of its application, obviously, the application prospect of silicide nano wire needs further developing.
Along with improving constantly that the device miniaturization degree requires, the miniaturization of the capacitor that plays an important role in circuit has become the key of electronic instrument miniaturization, and the film capacitor of big capacity small size will have bigger application space.Analyze theoretically, improve electric capacity and can reduce dielectric thickness from increasing the contact area between electrode and the dielectric, set about aspects such as use high dielectric constant material.Because reducing of dielectric layer thickness is limited, and the method for contact area increases limited to electric capacity on the one hand between traditional increase electrode and the dielectric, be easy to again on the other hand make device volume huge, therefore, at present, the use of high dielectric constant material becomes a very important selection that improves electric capacity.Yet the dielectric constant of material is not infinitely to improve, and is more and more higher along with condenser capacity is required, and obviously only can not really deal with problems by single high dielectric constant dielectric material yet.So provide a kind of brand-new thinking and invent a kind of new structure and will become the key that high capacitance film capacitor makes a breakthrough.
Titanium silicide is owing to its high-melting-point low-resistivity is widely used as contact and interconnection in the circuit.The titanium silicide nano line is because the conductivity of itself, if be prepared into the integrative-structure of titanium silicide hearth electrode and conduction titanium silicide nano wire, form the nano line electrode layer, and with this hearth electrode as film capacitor, composite dielectric material layer in the above again occupies same that the contact area of its dielectric and electrode will greatly increase under the yardstick.With this as can be known, when the titanium silicide nano line that uses the high conductivity bigger serface during as the dielectric hearth electrode, same dielectric substance and same occupying under the yardstick, the capacitance of its film capacitor will greatly improve thereupon, this provides new method for the ultra-high capacity development of Film Capacitors, also provides novel thin-film capacitor device for device miniaturization; Because this composite construction manufacture craft and semiconductor technology are mated fully, be convenient to very much the application of nano wire in field of electronic devices on the other hand, this will provide a kind of new thinking for the application of titanium silicide nano line and other conducting nanowires.
Summary of the invention
The object of the present invention is to provide a kind of nanometer line bottom electrode of high capacity capacitor and dielectric medium composite film and preparation method thereof.
The nanometer line bottom electrode of capacitor of the present invention and dielectric medium composite film deposit titanium silicide conductive membrane layer, titanium silicide nano line bottom electrode layer and thin dielectric rete from bottom to top successively on substrate.
Above-mentioned substrate can be glass substrate, monocrystalline silicon substrate or polycrystalline silicon substrate.
Said titanium silicide conductive membrane layer is Ti
5Si
3Crystalline phase or TiSi
2Crystalline phase, or by Ti
5Si
3And TiSi
2Crystalline phase is formed.Said titanium silicide nano line bottom electrode layer is that form is the TiSi crystalline phase or the TiSi of nano line cluster or rocket shape nano wire
2Crystalline phase.Said thin dielectric rete is Ba
xSr
1-xTiO
3Thin dielectric film, x=0.3～1.
The preparation method of nanometer line bottom electrode and dielectric medium composite film, employing be sol-gel process, may further comprise the steps:
1) powder barium acetate and strontium carbonate are dissolved in the acetic acid, the mol ratio of Sr and Ba is 0～2.33, is stirred to whole dissolvings, obtains the solution first;
2) metatitanic acid four fourth fat are dissolved in the EGME, obtain solution second;
3) be mixing in 1: 1 in molar ratio with two kinds of solution of first, second, compound concentration is the transparent precursor sol Ba of 0.3～0.6mol/l
xSr
1-xTiO
3, x=0.3～1;
4) cleaning base plate deposits titanium silicide conductive membrane layer and titanium silicide nano line bottom electrode layer successively with chemical vapour deposition technique on substrate;
5) on titanium silicide nano line bottom electrode layer, apply Ba with czochralski method
xSr
1-xTiO
3Precursor sol;
6) at 580～640 ℃ of heat treatment 30～60min, obtain nanometer line bottom electrode and dielectric medium composite film.
Ba
xSr
1-xTiO
3The thickness of thin dielectric film is determined by pull rate.Generally, pull rate is controlled at 2cm/min～6cm/min.
The present invention compares the beneficial effect that has to be had with background technology:
1, adopt sol-gel process to prepare nanometer line bottom electrode and dielectric medium composite film, low for equipment requirements, easy to operate, be easy to realize.
2, by on titanium silicide nano line bottom electrode layer, preparing Ba
xSr
1-xTiO
3Thin dielectric film utilizes the high-specific surface area of titanium silicide nano line hearth electrode, and it is long-pending to increase dielectric and electrode contact surface greatly, has improved the capacitance of this film composite structure, and its capacitance is more than 3 times of same scale ordinary electrode thin-film electro capacity.
Description of drawings
Fig. 1 nanometer line bottom electrode of the present invention and dielectric medium composite film capacitor schematic diagram;
Embodiment
Further specify the present invention below in conjunction with drawings and Examples.
With reference to Fig. 1, nanometer line bottom electrode of the present invention and dielectric medium composite film capacitor deposit titanium silicide conductive membrane layer 2 from bottom to top, titanium silicide nano line bottom electrode layer 3 and thin dielectric rete 4 successively on substrate 1.
Embodiment 1
1) with powder barium acetate Ba (CH
3COO)
2With strontium carbonate SrCO
3Be dissolved in the acetic acid, the mol ratio of Sr and Ba is 0.667, is stirred to whole dissolvings, obtains the solution first;
2) with metatitanic acid four fourth fat Ti (OC
4H
9)
4Be dissolved in EGME CH
3OCH
2CH
2Among the OH, obtain solution second;
3) be mixing in 1: 1 in molar ratio with two kinds of solution of first, second, compound concentration is the transparent precursor sol Ba of 0.35mol/l
xSr
1-xTiO
3, x=0.6;
4) clean glass substrate, with chemical vapour deposition technique depositing Ti successively on glass substrate
5Si
3Conductive membrane layer and TiSi nanometer line bottom electrode layer;
5) on TiSi nanometer line bottom electrode layer, apply Ba with the speed of 4cm/min with czochralski method
0.6Sr
0.4TiO
3Precursor sol;
6) at 580 ℃ of heat treatment 60min, obtain nanometer line bottom electrode and dielectric medium composite film capacitor.
With the electric capacity of electric impedance analyzer test compound film capacitor, test result shows that bifilm capacitor capacitance of the present invention is 3 times of same scale ITO/ dielectric medium composite film capacitor capacitance.
Embodiment 2
1) the powder barium acetate is dissolved in the acetic acid, is stirred to whole dissolvings, obtain the solution first;
2) metatitanic acid four fourth fat are dissolved in the EGME, obtain solution second;
3) be mixing in 1: 1 in molar ratio with two kinds of solution of first, second, compound concentration is the transparent precursor sol Ba of 0.5mol/l
xSr
1-xTiO
3, x=1;
4) clean glass substrate, with chemical vapour deposition technique depositing Ti successively on glass substrate
5Si
3Conductive membrane layer and TiSi
2The nanometer line bottom electrode layer;
5) with czochralski method with the speed of 4cm/min at TiSi
2Apply BaTiO on the nanometer line bottom electrode layer
3Precursor sol;
6) at 640 ℃ of heat treatment 30min, obtain nanometer line bottom electrode and dielectric medium composite film capacitor.
Test result shows that bifilm capacitor capacitance of the present invention is 3.2 times of same scale ITO/ dielectric medium composite film capacitor capacitance.
Embodiment 3
1) with powder barium acetate Ba (CH
3COO)
2With strontium carbonate SrCO
3Be dissolved in the acetic acid, the mol ratio of Sr and Ba is 2.33, is stirred to whole dissolvings, obtains the solution first;
2) with metatitanic acid four fourth fat Ti (OC
4H
9)
4Be dissolved in the EGME, obtain solution second;
3) be mixing in 1: 1 in molar ratio with two kinds of solution of first, second, compound concentration is the transparent precursor sol Ba of 0.4mol/l
xSr
1-xTiO
3, x=0.3;
4) clean monocrystalline silicon substrate, with chemical vapour deposition technique depositing Ti Si successively on monocrystalline silicon substrate
2Conductive membrane layer and TiSi nanometer line bottom electrode layer;
5) on TiSi nanometer line bottom electrode layer, apply Ba with the speed of 4cm/min with czochralski method
0.3Sr
0.7TiO
3Precursor sol;
6) at 600 ℃ of heat treatment 45min, obtain nanometer line bottom electrode and dielectric medium composite film capacitor.
Test result shows that bifilm capacitor capacitance of the present invention is 3.1 times of same scale ITO/ dielectric medium composite film capacitor capacitance.
Embodiment 4
1) with powder barium acetate Ba (CH
3COO)
2With strontium carbonate SrCO
3Be dissolved in the acetic acid, the mol ratio of Sr and Ba is 1.5, is stirred to whole dissolvings, obtains the solution first;
2) with metatitanic acid four fourth fat Ti (OC
4H
9)
4Be dissolved in the EGME, obtain solution second;
3) be mixing in 1: 1 in molar ratio with two kinds of solution of first, second, compound concentration is the transparent precursor sol Ba of 0.3mol/l
xSr
1-xTiO
3, x=0.4;
4) clean glass substrate, with chemical vapour deposition technique depositing Ti successively on glass substrate
5Si
3, TiSi
2Conductive membrane layer and TiSi nanometer line bottom electrode layer;
5) on TiSi nanometer line bottom electrode layer, apply Ba with the speed of 4cm/min with czochralski method
0.4Sr
0.6TiO
3Precursor sol;
6) at 590 ℃ of heat treatment 60min, obtain nanometer line bottom electrode and dielectric medium composite film capacitor.
Test result shows that bifilm capacitor capacitance of the present invention is 3.3 times of same scale ITO/ dielectric medium composite film capacitor capacitance.
Embodiment 5
1) with powder barium acetate Ba (CH
3COO)
2With strontium carbonate SrCO
3Be dissolved in the acetic acid, the mol ratio of Sr and Ba is 1, is stirred to whole dissolvings, obtains the solution first;
2) with metatitanic acid four fourth fat Ti (OC
4H
9)
4Be dissolved in the EGME, obtain solution second;
3) be mixing in 1: 1 in molar ratio with two kinds of solution of first, second, compound concentration is the transparent precursor sol Ba of 0.5mol/l
xSr
1-xTiO
3, x=0.5;
4) clean monocrystalline silicon substrate, with chemical vapour deposition technique depositing Ti Si successively on monocrystalline silicon substrate
2Conductive membrane layer and TiSi
2The nanometer line bottom electrode layer;
5) on TiSi2 nanometer line bottom electrode layer, apply Ba with the speed of 4cm/min with czochralski method
0.5Sr
0.5TiO
3Precursor sol;
6) at 620 ℃ of heat treatment 40min, obtain nanometer line bottom electrode and dielectric medium composite film capacitor.
Test result shows that bifilm capacitor capacitance of the present invention is 3.3 times of same scale ITO/ dielectric medium composite film capacitor capacitance.
Embodiment 6
1) with powder barium acetate Ba (CH
3COO)
2With strontium carbonate SrCO
3Be dissolved in the acetic acid, the mol ratio of Sr and Ba is 0.667, is stirred to whole dissolvings, obtains the solution first;
2) with metatitanic acid four fourth fat Ti (OC
4H
9)
4Be dissolved in the EGME, obtain solution second;
3) be mixing in 1: 1 in molar ratio with two kinds of solution of first, second, compound concentration is the transparent precursor sol Ba of 0.6mol/l
xSr
1-xTiO
3, x=0.6;
4) clean polycrystalline silicon substrate, with chemical vapour deposition technique depositing Ti Si successively on polycrystalline silicon substrate
2Conductive membrane layer and TiSi
2The nanometer line bottom electrode layer;
5) with czochralski method with the speed of 4cm/min at TiSi
2Apply Ba on the nanometer line bottom electrode layer
0.6Sr
0.4TiO
3Precursor sol;
6) at 590 ℃ of heat treatment 50min, obtain nanometer line bottom electrode and dielectric medium composite film capacitor.
Test result shows that bifilm capacitor capacitance of the present invention is 3.1 times of same scale ITO/ dielectric medium composite film capacitor capacitance.
Claims (6)
1. the nanometer line bottom electrode of a capacitor and dielectric medium composite film is characterized in that: deposit titanium silicide conductive membrane layer (2), titanium silicide nano line bottom electrode layer (3) and thin dielectric rete (4) from bottom to top successively on substrate (1).
2. the nanometer line bottom electrode of capacitor according to claim 1 and dielectric medium composite film, it is characterized in that: substrate (1) is glass substrate, monocrystalline silicon substrate or polycrystalline silicon substrate;
3. the nanometer line bottom electrode of capacitor according to claim 1 and dielectric medium composite film, it is characterized in that: titanium silicide conductive membrane layer (2) is Ti
5Si
3Crystalline phase or TiSi
2Crystalline phase or by Ti
5Si
3And TiSi
2Crystalline phase is formed.
4. the nanometer line bottom electrode of capacitor according to claim 1 and dielectric medium composite film, it is characterized in that: said titanium silicide nano line bottom electrode layer (3) is that form is the TiSi crystalline phase or the TiSi of nano line cluster or rocket shape nano wire
2Crystalline phase.
5. the nanometer line bottom electrode of capacitor according to claim 1 and dielectric medium composite film, it is characterized in that: said thin dielectric rete (4) is Ba
xSr
1-xTiO
3Thin dielectric film, x=0.3～1.
6. the preparation method of the nanometer line bottom electrode of capacitor according to claim 1 and dielectric medium composite film is characterized in that may further comprise the steps:
1) powder barium acetate and strontium carbonate are dissolved in the acetic acid, the mol ratio of Sr and Ba is 0～2.33, is stirred to whole dissolvings, obtains the solution first;
2) metatitanic acid four fourth fat are dissolved in the EGME, obtain solution second;
3) be mixing in 1: 1 in molar ratio with two kinds of solution of first, second, compound concentration is the transparent precursor sol Ba of 0.3～0.6mol/l
xSr
1-xTiO
3, x=0.3～1;
4) cleaning base plate deposits titanium silicide conductive membrane layer and titanium silicide nano line bottom electrode layer successively with chemical vapour deposition technique on substrate;
5) on titanium silicide nano line bottom electrode layer, apply Ba with czochralski method
xSr
1-xTiO
3Precursor sol;
6), obtain the nanometer line bottom electrode and the dielectric medium composite film of capacitor at 580～640 ℃ of heat treatment 30～60min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100599953A CN101252042B (en) | 2008-03-07 | 2008-03-07 | Nanometer line bottom electrode and dielectric medium composite film of capacitor and preparing method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100599953A CN101252042B (en) | 2008-03-07 | 2008-03-07 | Nanometer line bottom electrode and dielectric medium composite film of capacitor and preparing method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101252042A CN101252042A (en) | 2008-08-27 |
| CN101252042B true CN101252042B (en) | 2010-06-23 |
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| CN102655176B (en) * | 2012-05-10 | 2015-09-09 | 复旦大学 | Capacitor with nano thread structure and preparation method thereof |
| CN108335781A (en) * | 2018-02-11 | 2018-07-27 | 无锡博硕珈睿科技有限公司 | Composite conductive thin film, preparation method, its application, product with heating film |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1872662A (en) * | 2006-04-24 | 2006-12-06 | 浙江大学 | Nano line cluster of titanium silicide prepared by chemical vapor deposition under normal pressure, and preparation method |
| CN1979705A (en) * | 2005-12-06 | 2007-06-13 | 佳能株式会社 | Nano-wire capacitor and circuit device therewith |
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2008
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1979705A (en) * | 2005-12-06 | 2007-06-13 | 佳能株式会社 | Nano-wire capacitor and circuit device therewith |
| CN1872662A (en) * | 2006-04-24 | 2006-12-06 | 浙江大学 | Nano line cluster of titanium silicide prepared by chemical vapor deposition under normal pressure, and preparation method |
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