CN105742060B - A kind of high energy storage density solid film integrated-circuit capacitor and preparation method thereof - Google Patents
A kind of high energy storage density solid film integrated-circuit capacitor and preparation method thereof Download PDFInfo
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- CN105742060B CN105742060B CN201610196562.7A CN201610196562A CN105742060B CN 105742060 B CN105742060 B CN 105742060B CN 201610196562 A CN201610196562 A CN 201610196562A CN 105742060 B CN105742060 B CN 105742060B
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- 239000003990 capacitor Substances 0.000 title claims abstract description 80
- 238000004146 energy storage Methods 0.000 title claims abstract description 38
- 239000007787 solid Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 claims abstract description 84
- 239000000758 substrate Substances 0.000 claims abstract description 13
- 239000010936 titanium Substances 0.000 claims description 49
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 39
- 238000000034 method Methods 0.000 claims description 28
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 27
- 229910052712 strontium Inorganic materials 0.000 claims description 25
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 25
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 25
- 238000003756 stirring Methods 0.000 claims description 24
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 22
- 238000007254 oxidation reaction Methods 0.000 claims description 22
- 238000012545 processing Methods 0.000 claims description 22
- 230000037427 ion transport Effects 0.000 claims description 21
- 229960000583 acetic acid Drugs 0.000 claims description 19
- 239000012362 glacial acetic acid Substances 0.000 claims description 18
- 229910052788 barium Inorganic materials 0.000 claims description 15
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 15
- 239000002243 precursor Substances 0.000 claims description 15
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 13
- 230000000694 effects Effects 0.000 claims description 13
- 229910052719 titanium Inorganic materials 0.000 claims description 13
- 238000000576 coating method Methods 0.000 claims description 12
- 230000005611 electricity Effects 0.000 claims description 12
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 11
- 230000008020 evaporation Effects 0.000 claims description 10
- 238000001704 evaporation Methods 0.000 claims description 10
- 238000006703 hydration reaction Methods 0.000 claims description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 9
- 229910052710 silicon Inorganic materials 0.000 claims description 9
- 239000010703 silicon Substances 0.000 claims description 9
- RXSHXLOMRZJCLB-UHFFFAOYSA-L strontium;diacetate Chemical compound [Sr+2].CC([O-])=O.CC([O-])=O RXSHXLOMRZJCLB-UHFFFAOYSA-L 0.000 claims description 9
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 7
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 230000005684 electric field Effects 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 238000000137 annealing Methods 0.000 claims description 5
- LYCAIKOWRPUZTN-NMQOAUCRSA-N 1,2-dideuteriooxyethane Chemical compound [2H]OCCO[2H] LYCAIKOWRPUZTN-NMQOAUCRSA-N 0.000 claims description 2
- 238000013459 approach Methods 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000007711 solidification Methods 0.000 claims description 2
- 230000008023 solidification Effects 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- 239000003792 electrolyte Substances 0.000 abstract description 3
- 239000010408 film Substances 0.000 description 200
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 23
- 230000007547 defect Effects 0.000 description 20
- 239000010410 layer Substances 0.000 description 18
- 238000011282 treatment Methods 0.000 description 18
- 230000003647 oxidation Effects 0.000 description 13
- 229910052697 platinum Inorganic materials 0.000 description 11
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 11
- 150000002500 ions Chemical class 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 239000004411 aluminium Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000002609 medium Substances 0.000 description 3
- 239000006163 transport media Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000008439 repair process Effects 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- -1 Acyl acetone Chemical compound 0.000 description 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 1
- 239000010407 anodic oxide Substances 0.000 description 1
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/33—Thin- or thick-film capacitors
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/002—Details
- H01G4/005—Electrodes
- H01G4/015—Special provisions for self-healing
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Semiconductor Integrated Circuits (AREA)
Abstract
The present invention relates to a kind of high energy storage density solid film integrated-circuit capacitors and preparation method thereof, the capacitor includes substrate base, lower electrode and upper electrode, the lower electrode is coated on substrate base, the capacitor further includes active strontium titanate film, the active strontium titanate film is between upper electrode and lower electrode, the upper electrode is Ti films, and one layer of anode oxide film with self-repair function is equipped between active strontium titanate film and upper electrode.Compared with prior art, the present invention has many advantages, such as that energy storage density is high, can realize selfreparing, electrolyte is not present.
Description
Technical field
The invention belongs to technical field of capacitor preparation, and in particular to a kind of high energy storage density solid film integrated circuit electricity
Container and preparation method thereof.
Background technology
Microelectric technique is one of information age most representative new and high technology, its core technology is semiconductor collection
At circuit engineering.Microelectric technique is based on the advantageous features such as itself integration degree is high, and reaction is quick, occupied space is smaller in electricity
It is widely applied in sub- industry.High integration, low-power consumption, high-performance, high reliability, micromation are microelectric technique development
Direction.In order to reach demand of the development to microelectric technique of social economy, realize that social economy is quick under technical support
Stable development, it is necessary to constantly microelectric technique be optimized and be improved, energetically explore deeper microelectronics skill
Art knowledge, makes microelectric technique preferably serve socio-economic development.And capacitor is as essential in integrated circuit
Important devices, it is also desirable to preferably be optimized and be improved.It is inevitable in medium during the preparation of capacitor and use
Ground will appear various defects, therefore, realize that selfreparing of the defects of the medium under high field is very necessary.
Chinese patent CN103971933A discloses a kind of solid film capacitor and preparation method thereof, has invented a kind of tool
There are the aluminium oxide solid film capacitor of self-repair function, this capacitor active under high field using active oxidation aluminium film
Ion transport (ion near especially at dielectric defect is more active), by the electrode interface near ion transport to defect
It realizes anodic oxidation, and then realizes the selfreparing of fault location.It is different from aluminium electrolutic capacitor, liquid is not present in such capacitor
State electrolyte, but the activated alumina with dielectric effect is used to avoid electrolysis as the provider of oxygen in anodic oxidation
Liquid there are problems that bringing, but the dielectric constant of aluminum oxide film is relatively low, therefore limit further increasing for energy storage density.
Invention content
It is solid that it is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide a kind of high energy storage densities
State thin film integrated circuit capacitor and preparation method thereof.
The purpose of the present invention can be achieved through the following technical solutions:
A kind of high energy storage density solid film integrated-circuit capacitor, including substrate base, lower electrode and upper electrode,
The lower electrode is coated on substrate base, which is characterized in that the capacitor further includes active strontium titanate film, described
For active strontium titanate film between upper electrode and lower electrode, the upper electrode is Ti films, and active strontium titanates is thin
One layer of anode oxide film with self-repair function is equipped between film and upper electrode.
One layer of anode oxide film with self-repair function between active strontium titanate film and upper electrode is anode two
Thin film of titanium oxide.
The lower electrode includes Ti films, Pt films, Au films, Cu films or Ag films.
When lower electrode is Ti films, the capacitor further include one layer be located at active strontium titanate film and lower electrode it
Between the anode oxide film with self-repair function.
At this point, one layer of anode oxide film with self-repair function between active strontium titanate film and lower electrode is sun
Pole titanium deoxid film.
The thickness of the lower electrode is 150~250nm, and the thickness of the upper electrode is 150~250nm, institute
The thickness for the active strontium titanate film stated is 200~350nm, and the thickness of the anode oxide film is 10~50nm.
The substrate base is silicon chip.
A kind of preparation method of high energy storage density solid film integrated-circuit capacitor, this approach includes the following steps:
(1) active strontium titanates sol precursor is prepared:
(1-1) prepares barium source:In glacial acetic acid by strontium acetate dissolving, 0.5~2h is stirred in 70~90 DEG C, temperature slowly drops
The glacial acetic acid solution of PVP is added after to 40~60 DEG C, continues 20~60min of stirring at 40~60 DEG C, obtains barium source, wherein
The amount ratio of strontium acetate and PVP are 1mol:(3~8) g;The ratio of the total amount of strontium acetate and glacial acetic acid in barium source is 1mol:
(1.5~2.5) L;
(1-2) prepares titanium source:Titanium tetraisopropylate is dissolved in ethylene glycol monomethyl ether, 20~60min is stirred at 40~60 DEG C,
Acetylacetone,2,4-pentanedione is added, maintains the temperature at 40~60 DEG C and continues 0.5~2h of stirring, obtain titanium source, wherein titanium tetraisopropylate, second
The amount ratio of glycol methyl ether and acetylacetone,2,4-pentanedione is 1mol:(2~3) L:(0.08~0.12) L;
(1-3) titanium source is slowly added dropwise to barium source, and 5~30min is stirred at 40~60 DEG C, and ethylene glycol is added, and keeps
Temperature stirs 2~4h at 40~60 DEG C, is cooled to room temperature, and after clarified solution is filtered, obtains active strontium titanates sol precursor,
Wherein Sr in the dosage and barium source of ethylene glycol2+Amount ratio be (0.1~0.3) L:1mol;
(2) magnetron sputtering or evaporation coating method is used to prepare layer of conductive film on sinking to the bottom substrate, as lower electrode;
(3) active strontium titanates sol precursor is coated in the surface of lower electrode, carries out this process 5~9 times, is applied every time
It is heat-treated after covering, leads to oxygen annealing 2~4h of processing at a temperature of 450~520 DEG C after reaching required thickness, activity is made
Strontium titanate film;
(4) evaporation coating method or magnetron sputtering method is used to prepare one layer of Ti film on active strontium titanate film, as upper
Portion's electrode is subsequently placed in 10~30min in humid air of the humidity more than 90%, and active strontium titanate film is made be hydrated instead
It answers;
(5) electrochemical process for treating is used, anodic oxidation is carried out on the interface of active strontium titanate film and upper electrode
Reaction generates anode TiO2Solid film capacitor unit is made in film;
(6) it is combined by the capacitor unit prepared or by capacitor unit, solidification is packaged by dielectric, then
Both ends lead is carried out, high energy storage density solid film integrated-circuit capacitor is made.
Preferably, the Ti for the titanium source being added in step (1-3)4+With the Sr in barium source2+Molar ratio be 1:1.Both meet
Chemical reaction proportioning and strontium titanates stoichiometric ratio, save raw material.
Viscosity of the ethylene glycol being added in step (1-3) for adjusting the active strontium titanates sol precursor generated, and glue
The viscosity of body is related with the thickness of each layer of dielectric film and the smoothness of film, under the ethylene glycol dosage, coating
Convenient and film smoothness is good, more properly.
The condition of heat treatment in step (3) is 180~220 DEG C of 3~7min of processing, is warming up to 330~370 DEG C of processing 3
~7min is continuously heating to 480~520 DEG C of 3~7min of processing, is then cooled to 330~370 DEG C of 3~7min of processing, continues to drop
Temperature to 180~220 DEG C processing 3~7min.
Make the abundant combustion decomposition of the organic matter in strontium titanate film in heat treatment process so that the finer and close light of the film
It is sliding.
The electrochemical process for treating of step (5) is used using upper electrode as anode, and lower electrode is as cathode, access electricity
Road is powered, and applies the increased voltage of rate according to 0.1~0.5V/s, until applying voltage is higher than capacitor unit nominal operation
Voltage 5~10% is acted on using the ion transport of active strontium titanate film under the electric field, in active strontium titanate film and top electricity
Anodic oxidation reactions occur on the interface of pole, one layer of anode oxide film is generated in anode.
The anode oxide film is anode TiO2Film, since fault location ionic conductance is higher, the anode TiO that is formed in its vicinity2
Film is also thicker, to realize the selfreparing of fault location.
Similarly, have certainly to form one layer by electrochemical process for treating between active strontium titanate film and lower electrode
When the anode oxide film of repair, change direction of an electric field, using lower electrode as anode, is accessed upper electrode as cathode
Circuit adds the increased voltage of rate according to 0.1~0.5V/s, until applying voltage is higher than capacitor unit rated operational voltage
5~10%, it is acted on using active strontium titanate film ion transport under the electric field, in active strontium titanate film and lower electrode
Anodic oxidation reactions occur on interface, one layer of anode oxide film is generated in anode.
The present invention uses active strontium titanate film as dielectric, while active under high field using active strontium titanate film
Ion transport (ion near especially at dielectric defect is more active, and the strontium titanates in electrochemical treatment process
Ti in film4+It can appraise at the current rate as Ti3+, the transfer of electronics can promote transporting for ion), near ion transport to defect
Electrode interface realize anodic oxidation, and then realize defect selfreparing.This is the technological core and key of the present invention.With oxidation
Aluminium solid film capacitor is compared, and the dielectric constant of capacitor dielectric of the present invention is larger, and the anodic oxidation generated
The dielectric constant of film is also larger, and then promotes the raising of energy storage density, and due to the ion transport function of strontium titanate film
It is stronger, it is more preferable to the repairing effect of defect.
The dielectric film of the present invention is strontium titanates, and strontium titanates belongs to paraelectrics, traditional dielectric oxides with some
(SiO2、Ta2O5、Al2O3Deng) compare, strontium titanates has relatively high dielectric constant, and therefore, it has become high density capacitors
The candidate of medium.In addition, good dielectric properties are but also the capacitance of strontium titanates capacitor increases.But both at home and abroad
Scholar is typically all to improve the energy storage density of capacitor by improving the dielectric constant of strontium titanates.But we are close from energy storage is influenced
Another parameter, that is, disruptive field intensity of degree is started with, and the disruptive field intensity of strontium titanates is improved by selfreparing means, and then improve capacitance
The energy storage density of device has achieved the effect that relatively good.The calculation formula of the energy storage density of strontium titanates is U=1/2 ε E2,
Middle U indicates that energy storage density, ε indicate that dielectric constant, E indicate disruptive field intensity.Therefore energy storage density is directly proportional to dielectric constant, and hits
Wear the square directly proportional of field strength.And as one layer of anode TiO of generation in strontium titanate film2When film, this layer of anode TiO2Film can rise
To repair strontium titanate film in defect effect so that the disruptive field intensity of strontium titanate film increase substantially (improve 60~
80%), to further improve energy storage density.
The present invention not only solves the problems, such as aluminum electrolytic capacitor electrolyte, and due to the dielectric constant of strontium titanate film
Anodic oxide (anode TiO that is very high, being formed between Ti films (upper electrode)2Film) dielectric constant it is also very big, and
The TiO of generation2Film has repaired the defects of strontium titanate film, to improve the disruptive field intensity of strontium titanate film, Jin Erti
The high energy storage density of capacitor, can substantially increase the energy storage density of capacitor through the invention.
Compared with prior art, the present invention has the following advantages:
1, structure, preparation process are simple, are easy to produce in batches.
2, low raw-material cost significantly reduces production cost.
3, internal to be free of liquid dielectric, improve safety and reliability.
4, dielectric permittivity is higher, and energy storage density is higher, Miniaturized, minimizes and is applied to integrated circuit.
5, capacitor has self-reparing capability, greatly improves the service life of capacitor.
Description of the drawings
Fig. 1 is the schematic cross-section of the capacitor unit without electrochemical treatments and carries out the circuit of electrochemical treatments to it
Schematic diagram;
Fig. 2 is the schematic cross-section of the capacitor unit obtained after electrochemical treatments;
In figure, 1 is silicon chip, and 2 be lower electrode, and 3 be active strontium titanate film, and 4 be Ti films, and 5 be anode TiO2Film.
Specific implementation mode
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings.
Embodiment 1
As shown in Figure 1, for capacitor unit schematic cross-section and circuit diagram of the invention without electrochemical treatments, it should
Capacitor unit includes silicon chip 1 (substrate base), lower electrode 2, active strontium titanate film 3 and Ti films 4 (upper electrode);Such as
Shown in Fig. 2, for capacitor unit schematic cross-section of the present invention after electrochemical treatments, the capacitor unit include silicon chip 1, under
Portion's electrode 2, active strontium titanate film 3, Ti films 4 and anode TiO2Film 5, wherein active strontium titanate film 3 is arranged in lower part
Between electrode 2 and Ti films 4,4 interface of active strontium titanate film 3 and Ti films is one layer and is formed by electrochemical method processing
The anode TiO with self-repair function2Film 5.In defect expressivity and reparing process, by the capacitor without electrochemical treatments
Unit both ends apply the voltage being stepped up by certain amplitude, until nominal operation electricity of the voltage applied higher than capacitor unit
Pressure, and kept for a period of time, and then form stable anode TiO2Film 5 obtains high energy storage density solid film integrated circuit electricity
Container unit.The lower electrode 2 is platinum film.2 thickness of lower electrode of single-layer capacitor unit is 200nm, Ti film 4
Thickness be 200nm, 3 thickness of active strontium titanate film be 300nm;Anode TiO25 thickness of film is 50nm, and capacitance is
6.01nF。
The preparation of high energy storage density solid film integrated-circuit capacitor unit includes the following steps:
A, in glacial acetic acid by strontium acetate dissolving, 1h is stirred in 80 DEG C, PVP (0.5g) is added after being slowly dropped to 50 DEG C in temperature
Glacial acetic acid solution, continue at 50 DEG C stir 30min, wherein the glacial acetic acid being added twice altogether be 20ml.It weighs again
The titanium tetraisopropylate of 0.01mol is dissolved in 24ml ethylene glycol monomethyl ethers, stirs 0.5h at 50 DEG C, is added 1ml acetylacetone,2,4-pentanediones, 50 DEG C
Under continue stir 1h.Above-mentioned titanium source is slowly added dropwise to barium source, and stirs 15min at 50 DEG C, addition 2ml ethylene glycol, 50 DEG C
Lower stirring 3h, is cooled to room temperature, clarified solution is filtered, obtain sol precursor;
B, platinum film is prepared on silicon chip 1 using evaporation coating method or magnetron sputtering method, forms lower electrode 4;
C, active strontium titanates sol precursor made from step a is coated on platinum film surface made from step b, is gone forward side by side
Row heat treatment, the condition of the heat treatment are 200 DEG C of processing 5min, 350 DEG C of processing 5min, 500 DEG C of processing 5min, 350 DEG C
5min is handled, 200 DEG C handle 5min, are made annealing treatment 3 hours under last 500 DEG C of logical oxygen, and activity strontium titanate film 3 is made;
D, Ti films are prepared on the active strontium titanate film 3 made from step c using evaporation coating method or magnetron sputtering method
4, it is subsequently placed in humid air, active strontium titanate film 3 is made to carry out hydration reaction;Hydration reaction condition is more than for relative humidity
90% humid air atmosphere, reaction time 10min;
E, using electrochemical treatment, it is anti-that anodic oxidation is carried out on the interface of active strontium titanate film 3 and Ti films 4
It answers, generates anode TiO2High energy storage density solid film integrated-circuit capacitor unit is made in film 5.Electrochemical treatment, specifically
Step is:It is used as anode, platinum film power on circuitry to be accessed, using active strontium titanate film 3 in electricity as cathode Ti films 4
On the interface of active strontium titanate film 3 and Ti films 4 anodic oxidation reactions occur for ion transport off field, are generated in anode
One layer of new anode TiO2Film 5.Since fault location ionic conductance is higher, the anode TiO that is formed in its vicinity2Film 5 is also thicker, from
And realize the selfreparing of fault location.
When work, solid film capacitor, as the dielectric in capacitor, is utilized simultaneously using active strontium titanate film 3
The ion transport active under high field of active strontium titanate film 3, especially at the dielectric defect near ion it is more active,
Electrode interface near ion transport to defect is realized anodic oxidation, and then realized by the effect for realizing ion transport medium
The selfreparing of defect.
Embodiment 2:
In the present embodiment, in glacial acetic acid by strontium acetate dissolving, 50min is stirred in 90 DEG C, after temperature is slowly dropped to 50 DEG C
The glacial acetic acid solution of PVP (0.5g) is added, continues to stir 30min at 50 DEG C, wherein the glacial acetic acid being added twice is altogether
20ml.The butyl titanate for weighing 0.01mol again is dissolved in 24ml ethylene glycol monomethyl ethers, and 0.5h is stirred at 50 DEG C, and 1ml second is added
Acyl acetone continues at 50 DEG C to stir 1h.Above-mentioned titanium source is slowly added dropwise to barium source, and stirs 30min at 50 DEG C, 2ml is added
Ethylene glycol stirs 3h at 50 DEG C, is cooled to room temperature, clarified solution is filtered, obtain sol precursor;The hydration reaction time is
20min, remaining experimental procedure condition is the same as embodiment 1.
Embodiment 3:
A kind of high energy storage density solid film integrated-circuit capacitor, including substrate base, lower electrode and upper electrode,
Lower electrode is coated on substrate base, which further includes active strontium titanate film, and active strontium titanate film is located at top
Between electrode and lower electrode, upper electrode and lower electrode are Ti films, active strontium titanate film respectively with upper electrode
One layer of TiO with self-repair function between lower electrode to be formed by electrochemical process for treating2Film.
The preparation process of the high energy storage density solid film integrated-circuit capacitor unit of the present embodiment is basic with embodiment 1
It is identical, the difference is that, in the present embodiment, Ti films are prepared on silicon chip using magnetron sputtering method, by active titanium obtained
Sour strontium sol precursor is coated on Ti film surfaces, and is heat-treated, and activity strontium titanate film is made;Using magnetron sputtering
Method prepares Ti films on the active strontium titanate film made from step c, is subsequently placed in humid air, makes active strontium titanate film
Carry out hydration reaction;Hydration reaction condition is 100% humid air atmosphere, reaction time 30min, using electrochemical treatments
Method carries out anodic oxidation reactions on the interface of active strontium titanate film and Ti films (upper electrode and lower electrode), raw
At anode TiO2High energy storage density solid film integrated-circuit capacitor unit is made in film.Electrochemical treatment comprises the concrete steps that:
Using the Ti films of upper electrode as anode, power on circuitry is accessed, using the ion transport of active strontium titanate film under the electric field,
Anodic oxidation reactions occur on the interface of active strontium titanate film and the Ti films of upper electrode, new one layer is generated in anode
Anode TiO2Film.Since fault location ionic conductance is higher, the anode TiO that is formed in its vicinity2Film is also thicker, scarce to realize
Fall into the selfreparing at place.By changing direction of an electric field, on the interface of active strontium titanate film and the Ti films of lower electrode
It is also the same to generate anode TiO2Film, to which active strontium titanate film in solid film capacitor unit be better achieved
Selfreparing.
(capacitor surface accumulates 0.1cm to high energy storage density solid film integrated-circuit capacitor unit2, Strontium titanate films dielectric
Constant is 25, anode TiO220) film dielectric constant is
Capacitor unit parameter is as shown in table 1:
Table 1
Embodiment 4:
In the present embodiment, lower part platinum electrode thickness is that the thickness of 200nm, Ti film is 200nm, active strontium titanates
Film thickness is 200nm;Anode TiO2Film thickness is 50nm, and capacitance is that (capacitor surface accumulates 0.1cm to 8.43nF2, strontium titanates
Film dielectric constant is 25, anode TiO220) film dielectric constant is that remaining experimental procedure condition is the same as embodiment 1.
Embodiment 5
The kind high energy storage density solid film integrated-circuit capacitor of the present embodiment is substantially the same manner as Example 1, difference
It is in the preparation process of the capacitor of the present embodiment includes the following steps:
A, in glacial acetic acid by strontium acetate dissolving, 2h is stirred in 70 DEG C, PVP (0.5g) is added after being slowly dropped to 40 DEG C in temperature
Glacial acetic acid solution, continue at 40 DEG C stir 60min, wherein the glacial acetic acid being added twice altogether be 15ml.It weighs again
The titanium tetraisopropylate of 0.01mol is dissolved in 30ml ethylene glycol monomethyl ethers, stirs 4h at 40 DEG C, is added 0.8ml acetylacetone,2,4-pentanediones, 40 DEG C
Under continue stir 2h.Above-mentioned titanium source is slowly added dropwise to barium source, and stirs 30min at 40 DEG C, addition 2ml ethylene glycol, 40 DEG C
Lower stirring 4h, is cooled to room temperature, clarified solution is filtered, obtain sol precursor;
B, platinum film is prepared on silicon chip 1 using evaporation coating method or magnetron sputtering method, forms lower electrode 4;
C, active strontium titanates sol precursor made from step a is coated on platinum film surface made from step b, is gone forward side by side
Row heat treatment, the condition of the heat treatment are 180 DEG C of processing 7min, 330 DEG C of processing 7min, 480 DEG C of processing 7min, 330 DEG C
7min is handled, 180 DEG C handle 7min, are made annealing treatment 4 hours under last 480 DEG C of logical oxygen, and activity strontium titanate film 3 is made;
D, Ti films are prepared on the active strontium titanate film 3 made from step c using evaporation coating method or magnetron sputtering method
4, it is subsequently placed in humid air, active strontium titanate film 3 is made to carry out hydration reaction;Hydration reaction condition is more than for relative humidity
90% humid air atmosphere, reaction time 30min;
E, using electrochemical treatment, it is anti-that anodic oxidation is carried out on the interface of active strontium titanate film 3 and Ti films 4
It answers, generates anode TiO2High energy storage density solid film integrated-circuit capacitor unit is made in film 5.Electrochemical treatment, specifically
Step is:It is used as anode, platinum film power on circuitry to be accessed, using active strontium titanate film 3 in electricity as cathode Ti films 4
On the interface of active strontium titanate film 3 and Ti films 4 anodic oxidation reactions occur for ion transport off field, are generated in anode
One layer of new anode TiO2Film 5.Since fault location ionic conductance is higher, the anode TiO that is formed in its vicinity2Film 5 is also thicker, from
And realize the selfreparing of fault location.
When work, solid film capacitor, as the dielectric in capacitor, is utilized simultaneously using active strontium titanate film 3
The ion transport active under high field of active strontium titanate film 3, especially at the dielectric defect near ion it is more active,
Electrode interface near ion transport to defect is realized anodic oxidation, and then realized by the effect for realizing ion transport medium
The selfreparing of defect.
Embodiment 6
The kind high energy storage density solid film integrated-circuit capacitor of the present embodiment is substantially the same manner as Example 1, difference
It is in the preparation process of the capacitor of the present embodiment includes the following steps:
A, in glacial acetic acid by strontium acetate dissolving, 30min is stirred in 90 DEG C, PVP is added after being slowly dropped to 60 DEG C in temperature
The glacial acetic acid solution of (0.6g) continues to stir 20min at 60 DEG C, wherein the glacial acetic acid being added twice is 25ml altogether.It weighs again
The titanium tetraisopropylate of 0.01mol is dissolved in 20ml ethylene glycol monomethyl ethers, stirs 2h at 60 DEG C, is added 1.2ml acetylacetone,2,4-pentanediones, 60 DEG C
Under continue stir 0.5h.Above-mentioned titanium source is slowly added dropwise to barium source, and stirs 5min at 60 DEG C, addition 2ml ethylene glycol, 60 DEG C
Lower stirring 2h, is cooled to room temperature, clarified solution is filtered, obtain sol precursor;
B, platinum film is prepared on silicon chip 1 using evaporation coating method or magnetron sputtering method, forms lower electrode 4;
C, active strontium titanates sol precursor made from step a is coated on platinum film surface made from step b, is gone forward side by side
Row heat treatment, the condition of the heat treatment are 220 DEG C of processing 3min, 370 DEG C of processing 3min, 520 DEG C of processing 3min, 370 DEG C
3min is handled, 220 DEG C handle 3min, are made annealing treatment 2 hours under last 520 DEG C of logical oxygen, and activity strontium titanate film 3 is made;
D, Ti films are prepared on the active strontium titanate film 3 made from step c using evaporation coating method or magnetron sputtering method
4, it is subsequently placed in humid air, active strontium titanate film 3 is made to carry out hydration reaction;Hydration reaction condition is that relative humidity is
100% humid air atmosphere, reaction time 10min;
E, using electrochemical treatment, it is anti-that anodic oxidation is carried out on the interface of active strontium titanate film 3 and Ti films 4
It answers, generates anode TiO2High energy storage density solid film integrated-circuit capacitor unit is made in film 5.Electrochemical treatment, specifically
Step is:It is used as anode, platinum film power on circuitry to be accessed, using active strontium titanate film 3 in electricity as cathode Ti films 4
On the interface of active strontium titanate film 3 and Ti films 4 anodic oxidation reactions occur for ion transport off field, are generated in anode
One layer of new anode TiO2Film 5.Since fault location ionic conductance is higher, the anode TiO that is formed in its vicinity2Film 5 is also thicker, from
And realize the selfreparing of fault location.
When work, solid film capacitor, as the dielectric in capacitor, is utilized simultaneously using active strontium titanate film 3
The ion transport active under high field of active strontium titanate film 3, especially at the dielectric defect near ion it is more active,
Electrode interface near ion transport to defect is realized anodic oxidation, and then realized by the effect for realizing ion transport medium
The selfreparing of defect.
Embodiment 7
The present embodiment is substantially the same manner as Example 1, the difference is that, the upper electrode of the capacitor of the present embodiment is under
The thickness of portion's electrode is identical, is 150nm, and the thickness of active strontium titanate film is 260nm, TiO2The thickness of anode oxide film is
20nm。
Embodiment 8
The present embodiment is substantially the same manner as Example 1, the difference is that, the upper electrode of the capacitor of the present embodiment is under
The thickness of portion's electrode is identical, is 250nm, and the thickness of active strontium titanate film is 340nm, TiO2The thickness of anode oxide film is
50nm。
Embodiment 9
The present embodiment is substantially the same manner as Example 1, the difference is that, the upper electrode of the capacitor of the present embodiment is under
The thickness of portion's electrode is identical, is 190nm, and the thickness of active strontium titanate film is 280nm, TiO2The thickness of anode oxide film is
25nm。
Embodiment 10
The present embodiment is substantially the same manner as Example 1, the difference is that, the upper electrode of the capacitor of the present embodiment is under
The thickness of portion's electrode is identical, is 160nm, and the thickness of active strontium titanate film is 320nm, TiO2The thickness of anode oxide film is
40nm。
Embodiment 11
The present embodiment is substantially the same manner as Example 1, the difference is that the lower electrode of the present embodiment is Au films.
Embodiment 12
The present embodiment is substantially the same manner as Example 1, the difference is that the lower electrode of the present embodiment is Cu films.
Embodiment 13
The present embodiment is substantially the same manner as Example 1, the difference is that the lower electrode of the present embodiment is Ag films.
Claims (5)
1. a kind of high energy storage density solid film integrated-circuit capacitor, including substrate base, lower electrode and upper electrode, institute
The lower electrode stated is coated on substrate base, which is characterized in that the capacitor further includes active strontium titanate film, the work
Property strontium titanate film between upper electrode and lower electrode, the upper electrode and lower electrode are Ti films, living
Property strontium titanate film and upper electrode between and active strontium titanate film and lower electrode between be equipped with one layer and have and review one's lessons by oneself
The thickness of the anode oxide film acted on again, the lower electrode is 150~250nm, and the thickness of the upper electrode is 150
~250nm, the thickness of the active strontium titanate film are 200~350nm, the thickness of the anode oxide film is 10~
50nm。
2. a kind of high energy storage density solid film integrated-circuit capacitor according to claim 1, which is characterized in that described
Substrate base be silicon chip.
3. a kind of preparation method of high energy storage density solid film integrated-circuit capacitor as described in claim 1, feature
It is, this approach includes the following steps:
(1) active strontium titanates sol precursor is prepared:
(1-1) prepares barium source:In glacial acetic acid by strontium acetate dissolving, 0.5~2h is stirred in 70~90 DEG C, temperature is slowly dropped to 40
The glacial acetic acid solution of PVP is added after~60 DEG C, continues 20~60min of stirring at 40~60 DEG C, obtains barium source, wherein acetic acid
The amount ratio of strontium and PVP are 1mol:(3~8) g;The ratio of the total amount of strontium acetate and glacial acetic acid in barium source is 1mol:(1.5~
2.5)L;
(1-2) prepares titanium source:Titanium tetraisopropylate is dissolved in ethylene glycol monomethyl ether, 20~60min is stirred at 40~60 DEG C, is added
Acetylacetone,2,4-pentanedione maintains the temperature at 40~60 DEG C and continues 0.5~2h of stirring, obtains titanium source, wherein titanium tetraisopropylate, ethylene glycol
The amount ratio of methyl ether and acetylacetone,2,4-pentanedione is 1mol:(2~3) L:(0.08~0.12) L;
(1-3) titanium source is slowly added dropwise to barium source, and 5~30min is stirred at 40~60 DEG C, and ethylene glycol is added, and keeps temperature
2~4h is stirred at 40~60 DEG C, is cooled to room temperature, after clarified solution is filtered, is obtained active strontium titanates sol precursor, wherein
Sr in the dosage and barium source of ethylene glycol2+Amount ratio be (0.1~0.3) L:1mol;
(2) magnetron sputtering or evaporation coating method is used to prepare layer of conductive film on substrate base, as lower electrode;
(3) active strontium titanates sol precursor is coated in the surface of lower electrode, carries out this process 5~9 times, every time after coating
It is heat-treated, leads to oxygen annealing 2~4h of processing at a temperature of 450~520 DEG C after reaching required thickness, activity metatitanic acid is made
Strontium film;
(4) evaporation coating method or magnetron sputtering method is used to prepare one layer of Ti film on active strontium titanate film, as top electricity
Pole is subsequently placed in 10~30min in humid air of the humidity more than 90%, active strontium titanate film is made to carry out hydration reaction;
(5) electrochemical process for treating is used, anodic oxidation reactions are carried out on the interface of active strontium titanate film and upper electrode,
Generate anode TiO2Solid film capacitor unit is made in film;
(6) it is combined by the capacitor unit prepared or by capacitor unit, solidification is packaged by dielectric, then carry out
High energy storage density solid film integrated-circuit capacitor is made in both ends lead.
4. a kind of preparation method of high energy storage density solid film integrated-circuit capacitor according to claim 3, special
Sign is, the condition of the heat treatment in step (3) is 180~220 DEG C of 3~7min of processing, be warming up to 330~370 DEG C of processing 3~
7min is continuously heating to 480~520 DEG C of 3~7min of processing, is then cooled to 330~370 DEG C of 3~7min of processing, continues to cool down
To 180~220 DEG C of 3~7min of processing.
5. a kind of preparation method of high energy storage density solid film integrated-circuit capacitor according to claim 3, special
Sign is that the electrochemical process for treating of step (5) is used using upper electrode as anode, and lower electrode is as cathode, access electricity
Road is powered, and applies the increased voltage of rate according to 0.1~0.5V/s, until applying voltage is higher than capacitor unit nominal operation
Voltage 5~10% is acted on using the ion transport of active strontium titanate film under the electric field, in active strontium titanate film and top electricity
Anodic oxidation reactions occur on the interface of pole, one layer of anode oxide film is generated in anode.
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CN110379632B (en) * | 2019-07-02 | 2021-11-30 | 佛山科学技术学院 | Solid-state film capacitor and preparation method thereof |
CN111223669B (en) * | 2020-01-10 | 2021-08-03 | 河南理工大学 | Solid dielectric film capacitor with high energy storage density and preparation method thereof |
WO2022040987A1 (en) * | 2020-08-26 | 2022-03-03 | 中国科学院深圳先进技术研究院 | Preparation method for thin-film capacitor, and thin-film capacitor |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH09102590A (en) * | 1995-10-05 | 1997-04-15 | Ricoh Co Ltd | Thin film capacitor |
CN1851502A (en) * | 2006-05-26 | 2006-10-25 | 中国科学院上海技术物理研究所 | Strontium barium titanate Bragg mirror and its preparing method |
CN1880253A (en) * | 2005-06-16 | 2006-12-20 | 同济大学 | Thick film material and its ferroelectric(Ba,Sr)TiO3 microcrystalline glass ceramic |
CN101717067A (en) * | 2009-11-28 | 2010-06-02 | 桂林电子科技大学 | Barium strontium titanate-porous silicon composite material and preparation method thereof |
CN101728089A (en) * | 2009-12-22 | 2010-06-09 | 西安交通大学 | Film capacitor with high energy storage density and preparation method thereof |
CN102509743A (en) * | 2012-01-04 | 2012-06-20 | 吉林大学 | Ultraviolet detector based on titanium dioxide/strontium titanate heterojunction and preparation method |
CN103219153A (en) * | 2013-03-26 | 2013-07-24 | 欧阳俊 | High-voltage-resistant and high-energy-density capacitor and preparation method thereof |
CN103971933A (en) * | 2014-05-12 | 2014-08-06 | 同济大学 | Solid state thin film capacitor and preparation method thereof |
-
2016
- 2016-03-31 CN CN201610196562.7A patent/CN105742060B/en not_active Expired - Fee Related
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH09102590A (en) * | 1995-10-05 | 1997-04-15 | Ricoh Co Ltd | Thin film capacitor |
CN1880253A (en) * | 2005-06-16 | 2006-12-20 | 同济大学 | Thick film material and its ferroelectric(Ba,Sr)TiO3 microcrystalline glass ceramic |
CN1851502A (en) * | 2006-05-26 | 2006-10-25 | 中国科学院上海技术物理研究所 | Strontium barium titanate Bragg mirror and its preparing method |
CN101717067A (en) * | 2009-11-28 | 2010-06-02 | 桂林电子科技大学 | Barium strontium titanate-porous silicon composite material and preparation method thereof |
CN101728089A (en) * | 2009-12-22 | 2010-06-09 | 西安交通大学 | Film capacitor with high energy storage density and preparation method thereof |
CN102509743A (en) * | 2012-01-04 | 2012-06-20 | 吉林大学 | Ultraviolet detector based on titanium dioxide/strontium titanate heterojunction and preparation method |
CN103219153A (en) * | 2013-03-26 | 2013-07-24 | 欧阳俊 | High-voltage-resistant and high-energy-density capacitor and preparation method thereof |
CN103971933A (en) * | 2014-05-12 | 2014-08-06 | 同济大学 | Solid state thin film capacitor and preparation method thereof |
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