CN101359592B - Manufacturing method of FeRAM - Google Patents
Manufacturing method of FeRAM Download PDFInfo
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- CN101359592B CN101359592B CN2007100443315A CN200710044331A CN101359592B CN 101359592 B CN101359592 B CN 101359592B CN 2007100443315 A CN2007100443315 A CN 2007100443315A CN 200710044331 A CN200710044331 A CN 200710044331A CN 101359592 B CN101359592 B CN 101359592B
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- coated
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- ferroelectric polymers
- hearth electrode
- plastic substrate
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 30
- 229920000642 polymer Polymers 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 31
- 238000007639 printing Methods 0.000 claims abstract description 11
- 239000000758 substrate Substances 0.000 claims description 20
- 229920003023 plastic Polymers 0.000 claims description 19
- 229920001940 conductive polymer Polymers 0.000 claims description 17
- 238000013459 approach Methods 0.000 claims description 15
- 239000007772 electrode material Substances 0.000 claims description 13
- 239000002322 conducting polymer Substances 0.000 claims description 12
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 10
- 239000011248 coating agent Substances 0.000 claims description 9
- 238000000576 coating method Methods 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- 238000000137 annealing Methods 0.000 claims description 8
- 239000002131 composite material Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 229920000767 polyaniline Polymers 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 4
- MIZLGWKEZAPEFJ-UHFFFAOYSA-N 1,1,2-trifluoroethene Chemical group FC=C(F)F MIZLGWKEZAPEFJ-UHFFFAOYSA-N 0.000 claims description 3
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 239000012535 impurity Substances 0.000 claims description 3
- 239000000178 monomer Substances 0.000 claims description 3
- 229920006254 polymer film Polymers 0.000 claims description 3
- 239000002002 slurry Substances 0.000 claims description 3
- FJLUATLTXUNBOT-UHFFFAOYSA-N 1-Hexadecylamine Chemical compound CCCCCCCCCCCCCCCCN FJLUATLTXUNBOT-UHFFFAOYSA-N 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- HKOOXMFOFWEVGF-UHFFFAOYSA-N phenylhydrazine Chemical compound NNC1=CC=CC=C1 HKOOXMFOFWEVGF-UHFFFAOYSA-N 0.000 claims description 2
- 229940067157 phenylhydrazine Drugs 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 claims description 2
- 229940071536 silver acetate Drugs 0.000 claims description 2
- 239000004094 surface-active agent Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 239000004020 conductor Substances 0.000 abstract description 3
- 230000003628 erosive effect Effects 0.000 abstract 1
- 229920002521 macromolecule Polymers 0.000 abstract 1
- 239000011159 matrix material Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 239000010409 thin film Substances 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 4
- 230000010287 polarization Effects 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 230000003679 aging effect Effects 0.000 description 3
- 238000010924 continuous production Methods 0.000 description 3
- 239000010408 film Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 238000012536 packaging technology Methods 0.000 description 2
- 229920002239 polyacrylonitrile Polymers 0.000 description 2
- 229920005644 polyethylene terephthalate glycol copolymer Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- UXGNZZKBCMGWAZ-UHFFFAOYSA-N dimethylformamide dmf Chemical compound CN(C)C=O.CN(C)C=O UXGNZZKBCMGWAZ-UHFFFAOYSA-N 0.000 description 1
- 238000010017 direct printing Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005669 field effect Effects 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 238000001259 photo etching Methods 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
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Abstract
The invention provides a method for fabricating an RAM chip which is capable of printing ferroelectric polymers. The method takes conducting macromolecules as electrode and contact to assemble a data memory totally based on polymer. The circuit of the data memory can be made by directly printing conducting material on a thin polymer layer, thus dispensed with the indispensable techniques of vacuum process and mechanical erosion in conventional fabrication of an inorganic transistor and greatly simplifying assembling process. The invention is suitable for mass production and can reduce production cost.
Description
Technical field
The invention relates to a kind of manufacturing approach of random access chip, particularly relevant for a kind of manufacturing approach of printing the all-polymer ferro-electric random access chip.
Background technology
Traditional information storage system be with data storing in the circuit that monocrystalline silicon and multiple metal, insulating material etc. are processed, circuit forms two-dimensional array on silicon chip.Utilize photoetching technique, through exposure and many steps such as selective etch, with the figure transfer that designs on the mask to silicon chip.Step is various, complex process, long processing time.
Development along with memory system technologies; Use on functional material based on the deposition of solution and direct printing technique, a kind of possibility of new manufacturing electronic device is provided, for example organic field effect tube (FET); Can be applied to low cost, large-area flexible electronic device.Therefore the random access message storage (FeRAM) based on the ferroelectric thin film of solution deposition receives increasing concern; Even break off because the memory characteristic of this type systematic is a power supply; Remember condition does not disappear or changes, and only when storage or reading of data, needs power supply.Early stage ferro-electric random access technology mainly is the ferroelectric random memory technology that adopts based on ferroelectric ceramic thin film, on silicon substrate, deposits ferroelectric ceramic thin film, and silicon is as grid, and ferroelectric ceramic thin film and metal electrode are as source electrode and drain electrode.But to the ferroelectric ceramic thin film Study on Technology only is the research of some basic aspects, but fails to obtain the breakthrough of large-scale application.
Had [Pb (Zr, Ti) O afterwards with PZT
3] be dielectric ferroelectric random storage chip; Like the chip for cell phone of the 1T/1C framework of Japanese fujitsu and Korea S three magnitude companies, the toxicity of the lead (Pb) in the PZT dielectric and PZT must limit further developing of it in high temperature (usually more than 1000 ℃) processing then.
Summary of the invention
The manufacturing approach that the purpose of this invention is to provide a kind of ferro-electric random access chip, but its simplified assembling process, and can carry out large-scale continuous production, reduce production costs.
According to above-mentioned purpose, the present invention proposes a kind of manufacturing approach of ferro-electric random access chip, and at first the coating conducting polymer composite forms hearth electrode on plastic substrate; Back to be dried is coated with ferroelectric polymers on hearth electrode; Elder generation anneals in baking oven in drying at room temperature then after being coated with ferroelectric polymers; After treating that ferroelectric polymers is cooled to room temperature, on ferroelectric polymers, be coated with top electrode; Drying forms the finished product element in atmosphere then.
According to the manufacturing approach of ferro-electric random access chip of the present invention, wherein forming hearth electrode at coating conducting polymer composite on the plastic substrate is through regulating the conductive polymer solution prescription line that on plastic substrate, prints electrode.
According to the manufacturing approach of ferro-electric random access chip of the present invention, wherein forming hearth electrode at coating conducting polymer composite on the plastic substrate is on plastic substrate, to be coated with conductive polymer film.
According to the manufacturing approach of ferro-electric random access chip of the present invention, be on the plastic substrate that is coated with hearth electrode, to print ferroelectric polymer film wherein at the ferroelectric polymers that is coated with on the hearth electrode.
According to the manufacturing approach of ferro-electric random access chip of the present invention, the ferroelectric polymers that wherein on hearth electrode, is coated with is for gathering (vinylidene-trifluoro-ethylene), and wherein the monomer mole ratio of vinylidene and trifluoro-ethylene is 90:10～50:50.
According to the manufacturing approach of ferro-electric random access chip of the present invention, the step of the ferroelectric polymers that wherein on hearth electrode, is coated with also is included in gathers (vinylidene-trifluoro-ethylene) and is dissolved in the solvent back filtering solution to remove the step of mechanical impurities.
According to the manufacturing approach of ferro-electric random access chip of the present invention, annealing temperature is 120～150 ℃ in the step of wherein in baking oven, annealing, and annealing time is 10～60 minutes.
According to the manufacturing approach of ferro-electric random access chip of the present invention, wherein top electrode is identical with the hearth electrode material, processes by conducting polymer.
According to the manufacturing approach of ferro-electric random access chip of the present invention, wherein upper electrode material is mixed by polystyrolsulfon acid (PSSH, Aldrich company produces) and silver powder (production of Aldrich company).
According to the manufacturing approach of ferro-electric random access chip of the present invention, wherein upper electrode material is a conductive nano silver slurry.
According to the manufacturing approach of ferro-electric random access chip of the present invention, wherein top electrode is printed on the ferroelectric polymers with method of printing, and upper electrode material is prepared with commodity electrically conductive polyaniline (production of Finland Panipol company).
For reaching aforementioned purpose, a kind of ferro-electric random access chip of the present invention, it comprises a matrix, is formed at hearth electrode on the matrix, is formed at the ferroelectric polymers on the hearth electrode and is formed at the top electrode on the ferroelectric polymers.
The present invention is electrode and contact with the conducting polymer; Assembling is all based on the information-storing device of polymer; Its " circuit " can have been broken away from the vacuum process and the lithographic technique that must use in traditional mineral crystal pipe manufacturer with electric conducting material direct " printing " on polymer foil, greatly simplified packaging technology; Can carry out large-scale continuous production, reduce production cost.
Description of drawings
Fig. 1 is the structural representation according to chip of the present invention.
Fig. 2 is the chip structure sketch map of another embodiment of the present invention.
Fig. 3 is the memory unit structure sketch map of chip of the present invention.
Fig. 4 is a manufacturing method of chip flow chart of the present invention.
Fig. 5 a is the polarization performance resolution chart of the ferroelectric properties of chip of the present invention.
Fig. 5 b is the ageing properties resolution chart of the ferroelectric properties of chip of the present invention.
Embodiment
See also shown in Figure 1, its chip 10 structural representations for having single mnemon according to the first embodiment of the present invention, it comprises matrix 11 and is formed at the mnemon 12 on the matrix 11.This chip has single mnemon in the present embodiment, but is not to be used for limiting the present invention, and is as shown in Figure 2, and chip 10 ' of the present invention in other embodiments can have some mnemons 12 '.
See also shown in Figure 3, the mnemon of chip of the present invention 12 it comprise the bottom hearth electrode 21, be formed at the ferroelectric polymers 22 on the hearth electrode 21 and be formed at the top electrode 23 on the ferroelectric polymers 22.
See also shown in Figure 4ly, it shows manufacturing method of chip flow chart of the present invention, and this method comprises the steps:
Step 41: at first on the plastic substrate of smooth, be coated with conducting polymer composite to form hearth electrode (BE).Wherein be coated with conducting polymer composite, can be to use water-soluble poly aniline, through the regulator solution prescription, line prints electrode on plastic substrate.Live width is at 50 microns, at interval at 50 to 100 microns.The end of line is widened.Also can be with the metal or the precursor solution that are suitable for printing or printing.On the plastic substrate of smooth, like polyacrylonitrile (PAN), PETG (PET), conductive polymer film in the coating, like polyaniline PANi, polypyrrole Ppy gathers enedioxy thiophene (PEDOT), waits as hearth electrode.
Step 42: after treating to be coated with the plastic substrate drying of hearth electrode, on the plastic substrate that is coated with hearth electrode, print ferroelectric polymers.Wherein this ferroelectric polymers is that ferroelectric polymers gathers (vinylidene-trifluoro-ethylene) (P (VDF/TrFE)).Wherein the monomer mole ratio scope of vinylidene and trifluoro-ethylene is 90:10～50:50, and adopting mol ratio in the present embodiment is the ratio of 70:30.The method of its coating is dissolved in the solvent for ferroelectric polymers is gathered (vinylidene-trifluoro-ethylene), and solvent has dimethyl formamide DMF, cyclohexane, diethyl carbonate etc.Concentration of ordinary dissolution in the present embodiment is that 100ml dissolution with solvents 5g gathers (vinylidene-trifluoro-ethylene).
Also comprise filtering solution to remove the step of mechanical impurities after (vinylidene-trifluoro-ethylene) dissolves fully gathering, wherein the filter pore size is between 0.1 to 0.45 micron.
Utilize then and be dissolved with the solvent that gathers (vinylidene-trifluoro-ethylene) and on the plastic substrate that is coated with hearth electrode, be coated with ferroelectric polymers and gather (vinylidene-trifluoro-ethylene), i.e. printing formation ferroelectric polymer film.
Step 43: will be coated with the present drying at room temperature of plastic substrate that ferroelectric polymers gathers (vinylidene-trifluoro-ethylene), in baking oven, anneal then.Wherein annealing temperature is 120～150 ℃, and annealing time is 10～60 minutes.
Step 44: after treating that ferroelectric polymers is cooled to room temperature, on ferroelectric polymers, be coated with top electrode.Wherein the material of top electrode is identical with the material of hearth electrode in the present embodiment.
Step 45: drying is 2～30 minutes in 50～80 ℃ of atmosphere, forms the finished product element.
Like this, top electrode of the present invention and hearth electrode are interlaced, and " activity " information memory cell is promptly by spontaneous generation between the electrode " line " that intersects up and down.
See also shown in Fig. 5 a and Fig. 5 b; It is respectively the element made according to the method for first embodiment of the invention in room temperature through the polarization performance of ferroelectric properties test and the resolution chart of ageing properties; Wherein operating voltage is 20V in this example by the thickness decision that gathers (vinylidene-trifluoro-ethylene).PUND measures through polarization, and Fig. 5 a has shown the rapid polarization counter-rotating performance that element of the present invention is good, for the fast access of mnemon provides maybe.Fig. 5 b shows that chip of the present invention has good ageing properties.
Matrix in the second embodiment of the present invention; Hearth electrode is identical with first embodiment with preparation with the material that gathers (vinylidene-trifluoro-ethylene); Different with first embodiment is that upper electrode material is mixed by polystyrolsulfon acid (PSSH, Aldrich company produces) and silver powder (production of Aldrich company) among second embodiment.Prescription fully stirs in room temperature for PSSH (5% aqueous solution) 10 grams, silver powder 0.4 gram, stirs before each the use again.
Matrix in the third embodiment of the present invention, hearth electrode is identical with first embodiment with preparation with the material that gathers (vinylidene-trifluoro-ethylene), and different with first embodiment is that upper electrode material is a conductive nano silver slurry among the 3rd embodiment.The Nano Silver prescription is: 0.34g (2mmol) silver acetate, 4.82g (20mmol) hexadecylamine, 80ml toluene, 0.22g phenylhydrazine (PhNHNH
2), reaction is 1 hour under 60 ℃ of temperature.
Matrix in the third embodiment of the present invention; Hearth electrode is identical with first embodiment with preparation with the material that gathers (vinylidene-trifluoro-ethylene); Different with first embodiment is that top electrode is to be printed on method of printing to gather on (vinylidene-trifluoro-ethylene) film in the 4th embodiment. upper electrode material is prepared with commodity electrically conductive polyaniline (production of Finland Panipol company); Prescription is: the polystyrolsulfon acid aqueous solution 5 grams of percentage by weight 8%Panipol12 gram, 5% percentage by weight, surfactant Zonyl FS-300 (du pont company, percentage by weight 30% aqueous solution) 0.5 gram, deionized water 15 grams.
The present invention is electrode and contact with the conducting polymer; Assembling is all based on the information-storing device of polymer; Its " circuit " can have been broken away from the vacuum process and the lithographic technique that must use in traditional mineral crystal pipe manufacturer with electric conducting material direct " printing " on polymer foil, greatly simplified packaging technology; Can carry out large-scale continuous production, reduce production cost.
Claims (11)
1. the manufacturing approach of a ferro-electric random access chip is characterized in that comprising the steps: at first coating conducting polymer composite formation hearth electrode on plastic substrate; Back to be dried is coated with ferroelectric polymers on hearth electrode; Elder generation anneals in baking oven in drying at room temperature then after being coated with ferroelectric polymers; After treating that ferroelectric polymers is cooled to room temperature, on ferroelectric polymers, be coated with top electrode; Drying forms the finished product element in atmosphere then; Wherein:
The ferroelectric polymers that on hearth electrode, is coated with is Kynoar-trifluoro-ethylene, and wherein the monomer mole ratio of vinylidene and trifluoro-ethylene is 90: 10～50: 50;
Annealing temperature is 120～150 ℃ in the step of in baking oven, annealing, and annealing time is 10～60 minutes.
2. the method for claim 1 is characterized in that: the step that forms hearth electrode at coating conducting polymer composite on the plastic substrate is through regulating the conductive polymer solution prescription line that on plastic substrate, prints electrode.
3. the method for claim 1 is characterized in that: the step that forms hearth electrode at coating conducting polymer composite on the plastic substrate is on plastic substrate, to be coated with conductive polymer film.
4. the method for claim 1 is characterized in that: the step at coating ferroelectric polymers on the hearth electrode is on the plastic substrate that is coated with hearth electrode, to print ferroelectric polymer film.
5. method as claimed in claim 4 is characterized in that: the step of the ferroelectric polymers that on hearth electrode, is coated with also is included in Kynoar-trifluoro-ethylene and is dissolved in the solvent back filtering solution to remove the step of mechanical impurities.
6. the method for claim 1, it is characterized in that: top electrode is identical with the hearth electrode material, processes by conducting polymer.
7. the method for claim 1, it is characterized in that: upper electrode material is mixed by polystyrolsulfon acid and silver powder.
8. method as claimed in claim 7 is characterized in that: the prescription of upper electrode material be weight percentage 5% polystyrolsulfon acid aqueous solution 8-12 gram, silver powder 0.2-0.6 gram, fully stir in room temperature, and stir again before each the use.
9. the method for claim 1; It is characterized in that: upper electrode material is a conductive nano silver slurry; The prescription of upper electrode material Nano Silver is: 0.3-0.4g silver acetate, 4-6g hexadecylamine, 70-100ml toluene, 0.2-0.3g phenylhydrazine, reaction is 1 hour under 60 ℃ of temperature.
10. the method for claim 1, it is characterized in that: top electrode is printed on the ferroelectric polymers with method of printing, and upper electrode material is prepared with the commodity electrically conductive polyaniline.
11. method as claimed in claim 10 is characterized in that: the prescription of top electrode is: the polystyrolsulfon acid aqueous solution 5 grams of the electrically conductive polyaniline 10-13 gram of percentage by weight 8%, percentage by weight 5%, the surfactant Zonyl FS-300 aqueous solution 0.25-0.75 gram of percentage by weight 30%, deionized water 12-18 gram.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007100443315A CN101359592B (en) | 2007-07-30 | 2007-07-30 | Manufacturing method of FeRAM |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007100443315A CN101359592B (en) | 2007-07-30 | 2007-07-30 | Manufacturing method of FeRAM |
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| Publication Number | Publication Date |
|---|---|
| CN101359592A CN101359592A (en) | 2009-02-04 |
| CN101359592B true CN101359592B (en) | 2012-05-30 |
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| CN2007100443315A Expired - Fee Related CN101359592B (en) | 2007-07-30 | 2007-07-30 | Manufacturing method of FeRAM |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006135246A1 (en) * | 2005-06-14 | 2006-12-21 | Thin Film Electronics Asa | A method in the fabrication of a ferroelectric memory device |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006135246A1 (en) * | 2005-06-14 | 2006-12-21 | Thin Film Electronics Asa | A method in the fabrication of a ferroelectric memory device |
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