CN107170883A - A kind of flexible TiO2The preparation method of resistance-variable storing device array - Google Patents
A kind of flexible TiO2The preparation method of resistance-variable storing device array Download PDFInfo
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- CN107170883A CN107170883A CN201710564097.2A CN201710564097A CN107170883A CN 107170883 A CN107170883 A CN 107170883A CN 201710564097 A CN201710564097 A CN 201710564097A CN 107170883 A CN107170883 A CN 107170883A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 61
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims abstract description 60
- 239000000243 solution Substances 0.000 claims abstract description 47
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 44
- 238000000034 method Methods 0.000 claims abstract description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000000758 substrate Substances 0.000 claims abstract description 18
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims abstract description 7
- -1 isopropoxy titanate esters Chemical class 0.000 claims abstract description 7
- 125000000468 ketone group Chemical group 0.000 claims abstract description 7
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000007864 aqueous solution Substances 0.000 claims abstract description 6
- 239000002243 precursor Substances 0.000 claims abstract description 6
- 230000014759 maintenance of location Effects 0.000 claims abstract description 5
- 239000012528 membrane Substances 0.000 claims description 27
- 238000003491 array Methods 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 14
- 239000010936 titanium Substances 0.000 claims description 14
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 13
- 229910052753 mercury Inorganic materials 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 11
- 150000002500 ions Chemical class 0.000 claims description 11
- 229910052708 sodium Inorganic materials 0.000 claims description 11
- 239000011734 sodium Substances 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 238000002791 soaking Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 238000002493 microarray Methods 0.000 abstract 1
- 238000005516 engineering process Methods 0.000 description 10
- 238000003860 storage Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 4
- 238000005452 bending Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005289 physical deposition Methods 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 238000004847 absorption spectroscopy Methods 0.000 description 1
- 230000006399 behavior Effects 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 238000001312 dry etching Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 108010025899 gelatin film Proteins 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
Classifications
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N70/00—Solid-state devices having no potential barriers, and specially adapted for rectifying, amplifying, oscillating or switching
- H10N70/011—Manufacture or treatment of multistable switching devices
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N70/00—Solid-state devices having no potential barriers, and specially adapted for rectifying, amplifying, oscillating or switching
- H10N70/011—Manufacture or treatment of multistable switching devices
- H10N70/021—Formation of switching materials, e.g. deposition of layers
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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Semiconductor Memories (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The present invention relates to a kind of flexible TiO2The preparation method of resistance-variable storing device array, this method is as follows：By double (levulinic ketone group) ethyoxyl isopropoxy titanate esters, acetylacetone,2,4-pentanedione according to 1：1 molar ratio is dissolved in ethylene glycol monomethyl ether mixing, obtains the precursor aqueous solution that titanium ion concentration is 0.5mol/L.In the PET/ITO substrates that the solution is coated in flexibility by czochralski method, by 365nm ultraviolet irradiations, ethanol dissolves and washes away acquisition TiO2After gel mould microarray, 254nm and 185nm ultraviolet irradiation is further used at 150 DEG C 35 hours, further prepared by Pt electrodes, can both obtain the flexible PET/ITO/TiO with good retention performance and cycle characteristics2Memory array.
Description
Technical field
The present invention relates to information recording device manufacturing technology field, and in particular to a kind of flexible TiO2Resistance-variable storing device array
Preparation method.
Background technology
In the current information explosion epoch, information content is skyrocketed through, along with computer technology, internet and various new
The fast development of popular electronic product such as mobile phone, digital camera, notebook computer etc., people will to the performance of memory
Also more and more higher is sought, not only requires that it has high density, high speed, low cost, low-power consumption, but also it is non-volatile to want it to have
Property.Therefore new non-volatile storage technologies are researched and developed and have become one of focus of current science and technology and industry development.According to storage letter
The keeping quality energy of breath, memory can be divided into two major classes：Volatile memory (the Volatile that data can lose after power-off
Memory), such as dynamic memory (DRAM) and static memory (SRAM)；Non-volatile deposited with what data after power-off will not lose
Reservoir (Non-volatile memory), such as flash memory (Flash memory).
At present, although flash memory Flash technology commercially obtains immense success, limited by itself Ultrahigh
System, as characteristic size further reduces, the development of the technology is faced with many problems.On the one hand its program voltage can not be by
Ratio reduces；On the other hand constantly reduce with device size, the charge holding performance of device declines, make it in a computer
Using being very limited.In light of this situation, numerous semiconductor company Intel, Samsung and IBM etc. are competitively being researched and developed
Based on the nonvolatile storage technologies of new Ultrahigh, to possess market and technical advantage in following keen competition.
2000, scientist Liu of houston, U.S.A university et al. was found that one in huge magnetic resistance sull device
Plant new physical effect --- electric pulse triggering resistive effect is answered, i.e., in the presence of outer Ghana second level width voltage pulse, device
Resistance between low resistance state (" 0 ") and high-impedance state (" l ") reversible transition.Based on this discovery, scientific circles propose one kind
New nonvolatile storage concept --- resistive random access memory, abbreviation resistance-variable storing device (RRAM).Subsequent scientific research personnel
This resistance switch effect is found that in many metal oxide materials.As a kind of brand-new storage concept, RRAM's is excellent
Gesture is mainly manifested in the following aspects：One is to prepare simply；Two be that erasable speed is fast, and generally less than 100ns is far above
Flash storage；Three be that storage density is high；Four be its manufacture craft with the compatibility of traditional CMOS technology very well, it is easy to
Realize that high-volume, low cost are manufactured.Therefore RRAM research is just attracting the concern of more and more scientific research personnel, is considered as
It is the most contenders of nonvolatile memory of future generation.
Suitable material is selected, it is crucial factor that suitable method, which prepares flexible device,.TiO2It is Deng oxide material
Good resistive dielectric material.If but the preparation of this kind of oxide material is prepared using physical deposition techniques, although easily
Low temperature preparation is formed on flexible substrates, but subsequently also needs to etching to form memory cell；If using lower-cost
Prepared by wet chemical method, this kind of oxide material often also needs to the high-temperature heat treatment by more than 400 DEG C, destroys organic lining
Bottom.Therefore, either physical deposition or chemical method prepare this kind of flexible device and all also have certain predicament.Invention is a kind of both
It can be prepared under low temperature, and the device by straightforward procedure formation memory cell can be used, be that flexible electronic device is badly in need of solution
Problem.
The content of the invention
The invention provides a kind of flexible TiO2The preparation method of resistance-variable storing device array, by two step photochemical methods,
Obtain TiO2Flexible resistive device array.
The technical solution adopted in the present invention is：
A kind of flexible TiO2The preparation method of resistance-variable storing device, flexibility is coated in using czochralski method by titanium ion precursor aqueous solution
In PET/ITO substrates TiO is formed on its surface2Gel mould, then to PET/ITO/TiO2Sequentially pass through under high-pressure sodium lamp irradiation and
Irradiation obtains amorphous TiO under low pressure mercury lamp2Membrane array, finally in PET/ITO/TiO2Deposited over arrays Pt electrodes, are obtained
Flexible PET/ITO/TiO with good retention performance and cycle characteristics2Memory array.
Specifically include following steps：
Step 1), double (levulinic ketone group) ethyoxyl isopropoxy titanate esters are mixed with ethylene glycol monomethyl ether solution, acquisition Ti4+
Ion is 0.5mol/L solution A；
Step 2), into solution A add acetylacetone,2,4-pentanedione solution so that acetylacetone,2,4-pentanedione and Ti4+Mol ratio be 1:1, obtained after stirring
Obtain solution B；
Step 3), using step 2）The solution B of gained, using PET/ITO as substrate, using czochralski method, is lifted with 2mm/s speed
Plated film, obtains TiO2Gel mould；
Step 4), in step 3）The PET/ITO/TiO of acquisition2On, mask plate C is placed, is placed in being irradiated under high-pressure sodium lamp,
After irradiation terminates, sample is taken out；
Step 5), by step 4）Sample after irradiation, is immersed in ethanol solution, after soaking 1 minute, takes out sample, uses
Nitrogen is dried up, and obtains TiO2Gel membrane array；
Step 6), by step 5）The TiO2 gel membrane arrays of gained, are put in heating plate, are subsequently placed under low pressure mercury lamp and irradiate；
After irradiation terminates, amorphous TiO is obtained2Membrane array；
Step 7), in step 6）The amorphous TiO obtained2In membrane array, mask plate C is placed again, then using small-sized
Ion sputtering instrument, in PET/ITO/TiO2Deposited over arrays Pt electrodes, are finally obtained using flexible PET as substrate, and ITO is bottom electricity
Pole, Pt is the TiO of Top electrode2Resistance-variable storing device array.
Step 1）Described in solution A concentration control in 0.4-0.5mol/l.
Step 4）Described in high-pressure sodium lamp dominant wavelength be 365nm, exposure time be 30-60 minutes.
Step 5）Described in low pressure mercury lamp dominant wavelength be 185nm and 254nm, heating-up temperature is 150oC exposure times
It is 150 DEG C to control temperature of heating plate all the time for 3-5 hours, in irradiation process.
The flexibility TiO according to made from above-mentioned preparation method2Resistance-variable storing device.
Compared with prior art, the present invention has advantages below：
1. the present invention is by the ultraviolet lithographic method of wet-chemical, a step completes TiO2The preparation of gel membrane array, it is to avoid tradition
The high cost that wet-chemical chamber or other dry etchings are brought, the complicated shortcoming of technology path；
2. the present invention is by deep ultraviolet irradiance method, in low temperature, 150 DEG C just obtain amorphous TiO2Film, it is achieved thereby that
The preparation of flexible device, it is to avoid destruction problem of the high-temperature heat treatment to flexible substrates；
3. pass through specific presoma and complexing agent of the invention so that precursor aqueous solution has sensitivity characteristic to 365nm ultraviolet lights,
There is absorption to 254nm deep ultraviolet again, so that prepared by the step for realizing array, low temperature amorphous state is completed again
TiO2Preparation, significantly reduce cost；
4. obtaining flexible resistive device array by preparation method of the present invention has good memory retention properties and cycle characteristics, curved
Still good resistive behavior can be kept bent more than 1000 times.
Brief description of the drawings
Fig. 1 is flexibility PET/ITO/TiO of the invention2The syntheti c route figure of/Pt resistance-variable storing devices；
Fig. 2 is TiO of the present invention2The uv-visible absorption spectroscopy figure of precursor aqueous solution；
Fig. 3 is PET/ITO/TiO after being bent 1000 times under the conditions of different curvature (K)2The guarantor of/Pt flexibility resistance-variable storing device arrays
Hold performance plot；Wherein,（a）K=0 m-1；(b) 36.2m-1；(c) 49.1m-1；(d) 79.7m-1；
Fig. 4 is PET/ITO/TiO after being bent 1000 times under the conditions of different curvature (K)2/ Pt flexibility transition storage arrays are followed
Ring spy's figure；Wherein,（a）K=0 m-1；(b) 36.2m-1； (c) 49.1m-1；(d) 79.7m-1。
Embodiment
With reference to embodiment, the present invention will be described in detail.
A kind of flexible TiO2The preparation method of resistance-variable storing device, flexibility is coated in using czochralski method by titanium ion precursor aqueous solution
PET/ITO substrates on its surface formed TiO2Gel mould, then to PET/ITO/TiO2Sequentially pass through and irradiated under high-pressure sodium lamp
Amorphous TiO is obtained with irradiation under low pressure mercury lamp2Membrane array, finally in PET/ITO/TiO2Deposited over arrays Pt electrodes, are obtained
There must be the flexible PET/ITO/TiO of good retention performance and cycle characteristics2Memory array.
Specifically include following steps：
Step 1), double (levulinic ketone group) ethyoxyl isopropoxy titanate esters are mixed with ethylene glycol monomethyl ether solution, acquisition Ti4+
Ion is 0.5mol/L solution A；
Step 2), into solution A add acetylacetone,2,4-pentanedione solution so that acetylacetone,2,4-pentanedione and Ti4+Mol ratio be 1:1, obtained after stirring
Obtain solution B；
Step 3), using step 2）The solution B of gained, using PET/ITO as substrate, using czochralski method, is lifted with 2mm/s speed
Plated film, obtains TiO2Gel mould；
Step 4), in step 3）The PET/ITO/TiO of acquisition2On, mask plate C is placed, is placed in being irradiated under high-pressure sodium lamp,
After irradiation terminates, sample is taken out；
Step 5), by step 4）Sample after irradiation, is immersed in ethanol solution, after soaking 1 minute, takes out sample, uses
Nitrogen is dried up, and obtains TiO2Gel membrane array；
Step 6), by step 5）The TiO2 gel membrane arrays of gained, are put in heating plate, are subsequently placed under low pressure mercury lamp and irradiate；
After irradiation terminates, amorphous TiO is obtained2Membrane array；
Step 7), in step 6）The amorphous TiO obtained2In membrane array, mask plate C is placed again, then using small-sized
Ion sputtering instrument, in PET/ITO/TiO2Deposited over arrays Pt electrodes, are finally obtained using flexible PET as substrate, and ITO is bottom electricity
Pole, Pt is the TiO of Top electrode2Resistance-variable storing device array.
Step 1）Described in solution A concentration control in 0.4-0.5mol/l.
Step 4）Described in high-pressure sodium lamp dominant wavelength be 365nm, exposure time be 30-60 minutes.
Step 5）Described in low pressure mercury lamp dominant wavelength be 185nm and 254nm, heating-up temperature is 150oC exposure times
It is 150 DEG C to control temperature of heating plate all the time for 3-5 hours, in irradiation process.
The flexibility TiO according to made from above-mentioned preparation method2Resistance-variable storing device.
The syntheti c route of above-mentioned preparation process is as shown in figure 1, wherein, (a) lifts plated film；(b) under mask plate obstruction conditions
365nm ultraviolet irradiations；(c) ethanol is dissolved and washed away；(d) TiO is obtained2Gel membrane array；(e) the dark purple external irradiations of 185+254nm；(f)Pt
It is prepared by electrode；(h) flexible PET/ITO/TiO is obtained2/ Pt resistance-variable storing device arrays.
The present invention is further detailed below by several embodiments：
Embodiment 1：
By double (levulinic ketone group) ethyoxyl isopropoxy titanate esters, mixed with ethylene glycol monomethyl ether solution, obtain Ti4+Ion is
0.5mol/L solution；Add acetylacetone,2,4-pentanedione solution so that acetylacetone,2,4-pentanedione and Ti4+Mol ratio be 1:1, clarified after stirring
Solution；Using the solution, by czochralski method, using PET/ITO as substrate, plated film is lifted with 2mm/s speed, TiO is obtained2Gel
Film；In the PET/ITO/TiO of acquisition2Upper placement mask plate, is placed in carrying out irradiation 30 under the high-pressure sodium lamp that dominant wavelength is 365nm
Minute, after irradiation terminates, by PET/ITO/TiO2It is immersed in ethanol solution, after soaking 1 minute, takes out, blown with nitrogen
It is dry, obtain TiO2Gel membrane array；Then it is put in 150 DEG C of heating plates, is placed in the low-pressure mercury that wavelength is 185nm and 254nm
Under lamp, irradiation 3 hours is carried out.All the time it is 150 DEG C that temperature of heating plate is controlled in irradiation process.After irradiation terminates, amorphous state is obtained
TiO2Membrane array；In amorphous TiO2In membrane array, identical mask plate is placed, is then splashed using small ion
Instrument is penetrated, in PET/ITO/TiO2Deposited over arrays Pt electrodes, are finally obtained using flexible PET as substrate, ITO is hearth electrode, and Pt is
Top electrode, structure is " PET/ITO/TiO2/ Pt " flexible resistance-variable storing device array.The height resistance ratio of the device can reach
To more than 1000, alternating bending more than 1000 times is without significant change.
Referring to Fig. 2, in solution made from embodiment 1, titanium ion is complexed with acetylacetone,2,4-pentanedione.There is a suction in 360nm
Peak is received, this shows, acetylacetone,2,4-pentanedione is complexed with titanium ion, forms network-like complex compound；The generation of this complex compound, because
To be main peak in 360nm, therefore there is sensitivity characteristic for the ultraviolet light of dominant wavelength to 365nm, after 365nm ultraviolet irradiations,
This complex compound can be caused to decompose, polymerisation can occur for the titanium organic matter after decomposition, so as to form titanium oxide amorphous
State gel mould.Because mask plate has been covered on film in advance, therefore by illumination partly because foring titanium oxide amorphous state gel
Film, it is impossible to dissolved and washed away by ethanol, and organic titanium gel mould is not still by ultraviolet light irradiation part, then it can be dissolved and washed away by ethanol
Fall, so as to form Fig. 1（d）Shown TiO2Gel membrane array.
It can further be seen that TiO from Fig. 22Gel mould, also there is absorption to 254nm, therefore in follow-up 185nm+254nm
In irradiation process, 254nm ultraviolet is further absorbed, and ozone is generated with 185nm reactions, so that TiO2Gel mould battle array
The elements such as the C in row, H are volatilized, and obtain the C that is free of truly, amorphous titanium oxide battle array of the impurity element such as H
Row, shown in such as Fig. 1 (e).Fig. 3 and Fig. 4 are respectively with regard to the flexible PET/ITO/TiO under differently curved curvature2/ Pt devices are protected
The test of characteristic and cycle characteristics is held, is as a result shown, after continuous bend 1000 times, device still has good resistive characteristic,
The ratio of high-impedance state and low resistance state maintains more than 1000 always, with good memory effect.
Embodiment 2：
By double (levulinic ketone group) ethyoxyl isopropoxy titanate esters, mixed with ethylene glycol monomethyl ether solution, obtain Ti4+Ion is
0.5mol/L solution；Add acetylacetone,2,4-pentanedione solution so that acetylacetone,2,4-pentanedione and Ti4+Mol ratio be 1:1, clarified after stirring
Solution；Using the solution, by czochralski method, using PET/ITO as substrate, plated film is lifted with 2mm/s speed, TiO is obtained2Gel
Film；In the PET/ITO/TiO of acquisition2Upper placement mask plate, is placed in carrying out irradiation 60 under the high-pressure sodium lamp that dominant wavelength is 365nm
Minute, after irradiation terminates, by PET/ITO/TiO2It is immersed in ethanol solution, after soaking 1 minute, takes out, blown with nitrogen
It is dry, obtain TiO2Gel membrane array；Then it is put in 150 DEG C of heating plates, is placed in the low-pressure mercury that wavelength is 185nm and 254nm
Under lamp, irradiation 5 hours is carried out.All the time it is 150 DEG C that temperature of heating plate is controlled in irradiation process.After irradiation terminates, amorphous state is obtained
TiO2Membrane array；In amorphous TiO2In membrane array, identical mask plate is placed, is then splashed using small ion
Instrument is penetrated, in PET/ITO/TiO2Deposited over arrays Pt electrodes, are finally obtained using flexible PET as substrate, ITO is hearth electrode, and Pt is
Top electrode, structure is " PET/ITO/TiO2/ Pt " flexible resistance-variable storing device array.The height resistance ratio of the device can reach
To more than 1000, alternating bending more than 1400 times is without significant change.
Embodiment 3：
By double (levulinic ketone group) ethyoxyl isopropoxy titanate esters, mixed with ethylene glycol monomethyl ether solution, obtain Ti4+Ion is
0.4mol/L solution；Add acetylacetone,2,4-pentanedione solution so that acetylacetone,2,4-pentanedione and Ti4+Mol ratio be 1:1, clarified after stirring
Solution；Using the solution, by czochralski method, using PET/ITO as substrate, plated film is lifted with 2mm/s speed, TiO is obtained2Gel
Film；In the PET/ITO/TiO of acquisition2Upper placement mask plate, is placed in carrying out irradiation 60 under the high-pressure sodium lamp that dominant wavelength is 365nm
Minute, after irradiation terminates, by PET/ITO/TiO2It is immersed in ethanol solution, after soaking 1 minute, takes out, blown with nitrogen
It is dry, obtain TiO2Gel membrane array；Then it is put in 150 DEG C of heating plates, is placed in the low-pressure mercury that wavelength is 185nm and 254nm
Under lamp, irradiation 4 hours is carried out.All the time it is 150 DEG C that temperature of heating plate is controlled in irradiation process.After irradiation terminates, amorphous state is obtained
TiO2Membrane array；In amorphous TiO2In membrane array, identical mask plate is placed, is then splashed using small ion
Instrument is penetrated, in PET/ITO/TiO2Deposited over arrays Pt electrodes, are finally obtained using flexible PET as substrate, ITO is hearth electrode, and Pt is
Top electrode, structure is " PET/ITO/TiO2/ Pt " flexible resistance-variable storing device array.The height resistance ratio of the device can reach
To more than 800, alternating bending more than 2000 times is without significant change.
Present disclosure is not limited to cited by embodiment, and those of ordinary skill in the art are by reading description of the invention
And any equivalent conversion taken technical solution of the present invention, it is that claim of the invention is covered.
Claims (6)
1. a kind of flexible TiO2The preparation method of resistance-variable storing device, it is characterised in that applied titanium ion precursor aqueous solution using czochralski method
Apply in flexible PET/ITO substrates in its surface formation TiO2Gel mould, then to PET/ITO/TiO2Sequentially pass through high-pressure mercury
Under lamp the amorphous TiO of acquisition is irradiated under irradiation and low pressure mercury lamp2Membrane array, finally in PET/ITO/TiO2Deposited over arrays
Pt electrodes, obtain the flexible PET/ITO/TiO with good retention performance and cycle characteristics2Memory array.
2. flexible TiO according to claim 12The preparation method of resistance-variable storing device, it is characterised in that specifically include following
Step：
Step 1), double (levulinic ketone group) ethyoxyl isopropoxy titanate esters are mixed with ethylene glycol monomethyl ether solution, acquisition Ti4+From
Son is 0.5mol/L solution A；
Step 2), into solution A add acetylacetone,2,4-pentanedione solution so that acetylacetone,2,4-pentanedione and Ti4+Mol ratio be 1:1, obtained after stirring
Obtain solution B；
Step 3), using step 2）The solution B of gained, using PET/ITO as substrate, using czochralski method, is lifted with 2mm/s speed
Plated film, obtains TiO2Gel mould；
Step 4), in step 3）The PET/ITO/TiO of acquisition2On, mask plate C is placed, is placed in being irradiated under high-pressure sodium lamp,
After irradiation terminates, sample is taken out；
Step 5), by step 4）Sample after irradiation, is immersed in ethanol solution, after soaking 1 minute, takes out sample, uses
Nitrogen is dried up, and obtains TiO2Gel membrane array；
Step 6), by step 5）The TiO2 gel membrane arrays of gained, are put in heating plate, are subsequently placed under low pressure mercury lamp and irradiate；
After irradiation terminates, amorphous TiO is obtained2Membrane array；
7), in step 6）The amorphous TiO obtained2In membrane array, mask plate C is placed again, is then splashed using small ion
Instrument is penetrated, in PET/ITO/TiO2Deposited over arrays Pt electrodes, are finally obtained using flexible PET as substrate, ITO is hearth electrode, and Pt is
The TiO of Top electrode2Resistance-variable storing device array.
3. a kind of flexible TiO according to claim 22The preparation method of resistance-variable storing device array, it is characterised in that step
1）Described in solution A concentration control in 0.4-0.5mol/l.
4. the flexible TiO according to Claims 2 or 32The preparation method of resistance-variable storing device array, it is characterised in that step 4）
Described in high-pressure sodium lamp dominant wavelength be 365nm, exposure time be 30-60 minutes.
5. flexible TiO according to claim 42The preparation method of resistance-variable storing device array, it is characterised in that step 5）In
The dominant wavelength of described low pressure mercury lamp is 185nm and 254nm, and heating-up temperature is 150oC exposure times are 3-5 hours, irradiated
All the time it is 150 DEG C that temperature of heating plate is controlled in journey.
6. flexibility TiO made from the preparation method according to above-mentioned any one claim2Resistance-variable storing device.
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|---|---|---|---|
| CN201710564097.2A CN107170883B (en) | 2017-07-12 | 2017-07-12 | A kind of flexibility TiO2The preparation method of resistance-variable storing device array |
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| CN201710564097.2A CN107170883B (en) | 2017-07-12 | 2017-07-12 | A kind of flexibility TiO2The preparation method of resistance-variable storing device array |
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| Publication Number | Publication Date |
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| CN107170883A true CN107170883A (en) | 2017-09-15 |
| CN107170883B CN107170883B (en) | 2019-06-25 |
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Cited By (3)
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| CN109473547A (en) * | 2018-10-29 | 2019-03-15 | 江苏师范大学 | Bionical device of a kind of flexibility cynapse and preparation method thereof |
| CN110707211A (en) * | 2019-09-29 | 2020-01-17 | 西安理工大学 | Preparation method of cerium oxide memristor film |
| CN112071979A (en) * | 2020-08-26 | 2020-12-11 | 西安理工大学 | Preparation method of grid array composite electrode resistance memory film |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109473547A (en) * | 2018-10-29 | 2019-03-15 | 江苏师范大学 | Bionical device of a kind of flexibility cynapse and preparation method thereof |
| CN109473547B (en) * | 2018-10-29 | 2022-03-15 | 江苏师范大学 | Flexible synapse bionic device and preparation method thereof |
| CN110707211A (en) * | 2019-09-29 | 2020-01-17 | 西安理工大学 | Preparation method of cerium oxide memristor film |
| CN110707211B (en) * | 2019-09-29 | 2023-02-17 | 西安理工大学 | Preparation method of cerium oxide memristor film |
| CN112071979A (en) * | 2020-08-26 | 2020-12-11 | 西安理工大学 | Preparation method of grid array composite electrode resistance memory film |
| CN112071979B (en) * | 2020-08-26 | 2023-07-14 | 西安理工大学 | Preparation method of grid array composite electrode resistance memory film |
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