CN109545962A - A kind of environmentally friendly Bi based perovskite resistance-variable storing device and preparation method thereof - Google Patents
A kind of environmentally friendly Bi based perovskite resistance-variable storing device and preparation method thereof Download PDFInfo
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- 239000010408 film Substances 0.000 claims abstract description 41
- 230000008859 change Effects 0.000 claims abstract description 30
- 238000004528 spin coating Methods 0.000 claims abstract description 19
- 239000000463 material Substances 0.000 claims abstract description 13
- 239000010409 thin film Substances 0.000 claims abstract description 5
- 238000007740 vapor deposition Methods 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 39
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 15
- 239000007772 electrode material Substances 0.000 claims description 13
- 239000002243 precursor Substances 0.000 claims description 13
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims description 12
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 7
- 230000001133 acceleration Effects 0.000 claims description 4
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- JTCFNJXQEFODHE-UHFFFAOYSA-N [Ca].[Ti] Chemical compound [Ca].[Ti] JTCFNJXQEFODHE-UHFFFAOYSA-N 0.000 claims 2
- 238000001548 drop coating Methods 0.000 claims 1
- 238000004544 sputter deposition Methods 0.000 abstract description 7
- 230000006870 function Effects 0.000 abstract description 2
- 238000006068 polycondensation reaction Methods 0.000 abstract description 2
- 230000008569 process Effects 0.000 description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 238000001755 magnetron sputter deposition Methods 0.000 description 12
- 230000004087 circulation Effects 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 8
- 229960000935 dehydrated alcohol Drugs 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 7
- 229910001882 dioxygen Inorganic materials 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- 229920000742 Cotton Polymers 0.000 description 4
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 4
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- 239000013077 target material Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
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- 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
- H10N70/20—Multistable switching devices, e.g. memristors
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- H—ELECTRICITY
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- H10N70/00—Solid-state devices having no potential barriers, and specially adapted for rectifying, amplifying, oscillating or switching
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- 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
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Abstract
The invention discloses a kind of environmentally friendly Bi based perovskite resistance-variable storing devices, belong to function element technical field.Memory of the invention includes hearth electrode, Bi based perovskite change resistance layer, the top electrode set on change resistance layer upper surface set on hearth electrode upper surface, in which: the resistive layer material is MA3Bi2I9Film.Memory of the invention is the preparation method is as follows: in pretreated hearth electrode surface spin coating MA3Bi2I9Film layer；In the MA3Bi2I9Thin-film surface vapor deposition or sputtering metallized electrode.The present invention prepares MA on hearth electrode surface using a step low temperature solution polycondensation3Bi2I9Film, the MA prepared3Bi2I9Film surface is fine and close, and preparation process flow is simple, controllability is strong, product repeatability is high.In addition, resistance variation memory structure of the invention is simple, change resistance performance is excellent, has a wide range of application.
Description
Technical field
The present invention relates to function element technical fields, and in particular to a kind of environmentally friendly Bi based perovskite resistance-variable storing device
And preparation method thereof.
Background technique
With the fast development of information technology, the requirement that people store data is higher and higher.Traditional flash memory technology tool
Have that erasable and writing speed is slow, power consumption is high, and the disadvantages of be faced with the size miniature limit, it is difficult to meet the needs of people, therefore develop
The new non-volatility memorizer haveing excellent performance becomes the research hotspot of semicon industry.Resistance-variable storing device has erasable and writing speed
Fastly, storage density is high, and numerous excellent performances such as low in energy consumption and multilevel storage become the candidate's of next-generation non-volatile technology
One, it has broad application prospects.
Currently, there are many material for being used as change resistance layer, such as metal oxide, perovskite material etc..Metal-oxide film is normal
It is prepared using magnetron sputtering technique, this method requires accuracy of instrument high, preparation cost height.Perovskite material, such as
CH3NH3PbI3, it is widely used in the fields such as solar battery, photodetector, light emitting diode, while the material is in voltage
Under the action of show apparent high low resistance state variation, be applied in resistance-variable storing device.But CH3NH3PbI3Material contains
Noxious material Pb constrains its extensive use.
Based on the above reasons, the application is proposed.
Summary of the invention
It is an object of the invention to provide a kind of environmental-friendly for drawbacks described above existing for existing resistance-variable storing device technology
Type Bi based perovskite resistance-variable storing device and preparation method thereof, the present invention prepare environment friend using nontoxic Bi substitution conventional toxic Pb
Good type perovskite MA3Bi2I9, and by MA3Bi2I9Applied to memory area.
In order to realize above-mentioned first purpose of the present invention, the present invention adopts the following technical scheme:
A kind of environmentally friendly Bi based perovskite resistance-variable storing device, the memory include hearth electrode, are set on hearth electrode
Bi based perovskite change resistance layer, the top electrode set on change resistance layer upper surface on surface, in which: the resistive layer material is MA3Bi2I9
Film.
Further, hearth electrode material described in above-mentioned technical proposal be FTO (tin oxide of fluorine doped), ITO, ZTO, TaN or
Any one of TiN.
Preferably, hearth electrode material described in above-mentioned technical proposal is FTO, and the square resistance of the hearth electrode is 14 Ω sq-1。
Further, for the hearth electrode with a thickness of 100~300nm, shape is rectangle, and side length is 1~2cm.
Further, the Bi based perovskite change resistance layer is with a thickness of 200~600nm.
Further, the Bi based perovskite change resistance layer shape is rectangle, and side length is 1~2cm.
Further, the top electrode material is any one of Pt, Au or W.
Further, for the top electrode with a thickness of 60~100nm, shape is that round or rectangle, diameter or side length are
100~900 μm.
Another object of the present invention is to provide the systems of environmentally friendly Bi based perovskite resistance-variable storing device described above
Preparation Method the described method comprises the following steps:
In pretreated hearth electrode surface spin coating MA3Bi2I9Polycrystal film layer；In the MA3Bi2I9Thin-film surface steams
Plating or sputtering metallized electrode.
Further, above-mentioned technical proposal, the spin coating MA3Bi2I9The method of polycrystal film layer is specific as follows: using first
Liquid-transfering gun measures MA3Bi2I9For perovskite forerunner drop-coated on the hearth electrode surface, spin coating instrument revolving speed is 4000r/min, is accelerated
Degree is 200r/s, spin-coating time 40s, and then anneal under the conditions of 100 DEG C 15min, obtains fine and close MA3Bi2I9Polycrystalline is thin
Film.
Preferably, above-mentioned technical proposal, the MA3Bi2I9Perovskite precursor liquid is formulated with the following method:
By CH3NH3I powder and BiI3Powder is added sequentially in methylamine alcohol solution with the ratio of molar ratio 3:2, at room temperature
30min is stirred, the use of diameter is then that 0.22 μm of filter filters, removes the bulky grain in solution, obtain clear perovskite
Precursor liquid, the perovskite Concentration of precursor solution are 0.35mol/L.
Further, above-mentioned technical proposal, the metal electrode are preferably made using direct current magnetron sputtering process: mask plate is covered
It covers in the MA3Bi2I9Film surface is placed in magnetron sputtering apparatus, and using d.c. sputtering, control underlayer temperature is 300K,
Reaction gas is argon gas, and the indoor air pressure of vacuum is 4Torr, sputtering power 100W, in MA3Bi2I9Film surface deposition
Obtain metallic top electrode layer.
Further, above-mentioned technical proposal, the hearth electrode surface pre-treating process include the following steps:
Step 1. cleans hearth electrode substrate
Dehydrated alcohol is dipped using cotton swab first to scrub base conductive face, then is repeatedly rinsed with deionized water；So
Use deionized water, acetone respectively afterwards, dehydrated alcohol is cleaned by ultrasonic 30min；
Step 2. dioxygen water process hearth electrode surface
The substrate drying that step 1 is cleaned up, is immersed in 1min in the aqueous hydrogen peroxide solution that volumetric concentration is 30%,
Then the aqueous hydrogen peroxide solution of the substrate surface is rinsed well using alcohol, is dried up, stick insulating tape, formed reserved
Electrode, and be placed in UV cleaning device and handle 30min with UV ozone.
Compared with prior art, the beneficial effects of the present invention are:
(1) present invention prepares MA on hearth electrode surface using a step low temperature solution polycondensation3Bi2I9Film is prepared
MA3Bi2I9Film surface is fine and close, and preparation process flow is simple, controllability is strong, product repeatability is high；
(2) of the invention based on MA3Bi2I9The resistance-variable storing device of film change resistance layer has excellent change resistance performance, and this hair
Bright resistance variation memory structure is simple, and preparation process is also simple, easy to operate, and the raw material sources that in addition present invention uses are extensive, system
Make at low cost, is conducive to industrialization；
(3) present invention prepares environmentally friendly perovskite MA using nontoxic Bi substitution Pb3Bi2I9, and by MA3Bi2I9It answers
For memory area, the application range of memory is expanded；
(4) present invention makees solvent preparation perovskite precursor liquid using methylamine alcohol, environmentally protective.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of environmentally friendly Bi based perovskite resistance-variable storing device described in the embodiment of the present invention 1,
In: 1-FTO substrate；2-MA3Bi2I9Film change resistance layer；3-W electrode；
Fig. 2 is MA obtained described in the embodiment of the present invention 13Bi2I9Surface topography (SEM) figure of polycrystal film；
Fig. 3 is FTO/MA made from the embodiment of the present invention 13Bi2I9The I-V curve figure of/W resistance-variable storing device；
Fig. 4 is FTO/MA made from the embodiment of the present invention 13Bi2I9/ W resistance-variable storing device is in Vreadout=0.2V condition
Under, the circulation resistance characteristics figure in 150 periods；
Fig. 5 is ITO/MA made from the embodiment of the present invention 23Bi2I9The I-V curve figure of/Pt resistance-variable storing device；
Fig. 6 is ITO/MA made from the embodiment of the present invention 23Bi2I9/ Pt resistance-variable storing device is in Vreadout=0.2V condition
Under, the circulation resistance characteristics figure in 60 periods.
Specific embodiment
Environmentally friendly Bi based perovskite resistance-variable storing device of the invention, the memory include hearth electrode, are set to bottom electricity
Bi based perovskite change resistance layer, the top electrode set on change resistance layer upper surface of pole upper surface, in which: the resistive layer material is
MA3Bi2I9Film.
The hearth electrode material is any one of FTO (tin oxide of fluorine doped), ITO, ZTO, TaN or TiN.
For the hearth electrode with a thickness of 100~300nm, shape is rectangle, and side length is 1~2cm.
For the Bi based perovskite change resistance layer with a thickness of 200~600nm, the Bi based perovskite change resistance layer shape is rectangle,
Side length is 1~2cm.
The top electrode material is any one of Pt, Au or W.
For the top electrode with a thickness of 60~100nm, shape is round or rectangle, and diameter or side length are 100~900 μm.
Environmentally friendly Bi based perovskite resistance-variable storing device described above is made with the following method:
In pretreated hearth electrode surface spin coating MA3Bi2I9Film layer；In the MA3Bi2I9Thin-film surface vapor deposition or
Sputter metallized electrode.
The present invention is described above to be based on MA3Bi2I9The resistance-variable storing device of film change resistance layer has excellent change resistance performance, and
Preparation process is simple, at low cost, is conducive to industrialization.
Technical solution of the present invention is described in detail below by specific embodiment and attached drawing.Following reality
Applying example is only preferred embodiments of the present invention, is not the restriction that other forms are done to the present invention, any skill for being familiar with this profession
Art personnel are changed to the equivalent embodiment changed on an equal basis possibly also with the technology contents of the disclosure above.It is all without departing from this hair
Bright plan content, any simple modification or equivalent variations made according to the technical essence of the invention to following embodiment, falls
Within the scope of the present invention.
Embodiment 1
As shown in Figure 1, a kind of environmentally friendly Bi based perovskite resistance-variable storing device of the present embodiment, the memory include
Hearth electrode, Bi based perovskite change resistance layer, the top electrode set on change resistance layer upper surface set on hearth electrode upper surface, in which:
The hearth electrode material is FTO, and for the hearth electrode with a thickness of 200nm, shape is rectangle, side length 1cm, the bottom
The square resistance of electrode is 14 Ω sq-1；
The resistive layer material is MA3Bi2I9Film；For the change resistance layer with a thickness of 300nm, shape is rectangle, and side length is
1cm；
The top electrode material is W, and for top electrode with a thickness of 100nm, shape is rectangle, and side length is 900 μm.
The preparation method of environmentally friendly Bi based perovskite resistance-variable storing device described above, comprising the following steps:
Step 1. cleans FTO substrate
Dehydrated alcohol is dipped using cotton swab first to scrub FTO conducting surface, then is repeatedly rinsed with deionized water.Then
Deionized water, acetone are used respectively, and dehydrated alcohol is cleaned by ultrasonic 30min；
The surface step 2. dioxygen water process FTO
By the above-mentioned FTO drying cleaned up, it is immersed in 1min in the aqueous hydrogen peroxide solution that volumetric concentration is 30%, so
The aqueous hydrogen peroxide solution on surface is rinsed well using alcohol afterwards, is dried up, insulating tape is sticked, forms reserved electrode, and put
30min is handled with UV ozone in UV cleaning device.The purpose on the surface dioxygen water process FTO is the leaching in order to improve the surface FTO
Profit ability；
Step 3. matches perovskite precursor liquid
By CH3NH3I and BiI3With molar ratio 3:2 ratio mixed dissolution in green solvent methylamine alcohol solution, what is prepared is molten
Liquid stirs 30min at normal temperature, makes CH3NH3I and BiI3Powder is completely dissolved, and the use of diameter is then 0.22 μm of filter mistake
Filter removes the bulky grain in solution, obtains clear perovskite precursor liquid, solution concentration 0.35mol/L；
Step 4. prepares MA3Bi2I9Polycrystal film
MA is prepared using spin-coating method3Bi2I9Polycrystal film.100 μ L perovskite forerunner's drop-coateds are measured using liquid-transfering gun first
On the surface FTO, spin coating instrument revolving speed is 4000r/min, acceleration 200r/s, spin-coating time 40s, then in 100 DEG C of conditions
Lower annealing 15min removes excess of solvent, obtains fine and close MA3Bi2I9Polycrystal film, surface topography map are as shown in Figure 2.
Step 5. prepares top electrode
Utilize the MA of magnetron sputtering technique in step 43Bi2I9Film surface prepares top electrode.It is covered on mask plate
MA3Bi2I9Film surface is placed in magnetron sputtering apparatus, and sputtering target material is W target, and underlayer temperature 300K, reaction gas is argon
Gas, control the indoor air pressure of vacuum be 4Torr, sputtering power 100W, using direct current magnetron sputtering process prepare with a thickness of
100nm, the W electrode that side length is 900 μm.
So far, a kind of environmentally friendly Bi based perovskite resistance-variable storing device preparation is completed.It is partly led using Agilent B1500A
Body parameter analyzer tests device performance.Firstly, removing MA3Bi2I9The insulating tape of resistance-variable storing device exposes hearth electrode, and will
It is placed in probe station, contacts hearth electrode and top electrode respectively using two probes.Application -4V~4V direct current is swept on top electrode
Voltage is retouched, hearth electrode ground connection measures I-V curve, as shown in figure 3, I-V curve reveals apparent bipolarity electric resistance changing spy
Property.One scanning voltage circulation includes four parts: first from 0 scanning to+4V, then from+4V scanning to 0, then reverse scan, from
- 4V is arrived in 0 scanning, then from -4V scanning to 0, that is, completes a scan period, and every partial scan step number is identical, is 101.In order to anti-
Only device is damaged by high current in test process, and a limitation electric current, size 10mA are set in forward scan.When voltage from
When+4V is arrived in 0 scanning, electric current is gradually increased, and resistance is transformed into low resistance state by high-impedance state, this process is known as SET process, from Fig. 3
It is observed that SET process is a progressive formation, and device has self-rectifying ability；When voltage is from 0 scanning to -4V,
Device is able to maintain that low resistance state, and when negative voltage reaches certain value, resistance is transformed into high-impedance state by low resistance state, this process claims
For RESET process.Device is able to maintain original resistance state when power is off, illustrates that the memory is non-volatile.
Meanwhile the circulation tolerance of device is tested using Agilent B1500A, i.e., scanning voltage continuous several times recycle, and read
High low resistance when 0.2V voltage is taken, as shown in Figure 4.In 150 circle circulations, the high low resistance of device maintains same quantity
Grade, and the resistance ratio between high low resistance state is greater than 10, meets the requirement of general memory memory window.
Embodiment 2
A kind of environmentally friendly Bi based perovskite resistance-variable storing device of the present embodiment, the memory include hearth electrode, set
Bi based perovskite change resistance layer, the top electrode set on change resistance layer upper surface in hearth electrode upper surface, in which:
The hearth electrode material is ITO, and for the hearth electrode with a thickness of 100nm, shape is rectangle, side length 1.5cm；
The resistive layer material is MA3Bi2I9Film；For the change resistance layer with a thickness of 200nm, shape is rectangle, and side length is
1.5cm；
The top electrode material is Pt, and for top electrode with a thickness of 60nm, shape is circle, and diameter is 100 μm.
The preparation method of environmentally friendly Bi based perovskite resistance-variable storing device described above, comprising the following steps:
Step 1. cleans ITO substrate
Dehydrated alcohol is dipped using cotton swab first to scrub ITO conducting surface, then is repeatedly rinsed with deionized water.Then
Deionized water, acetone are used respectively, and dehydrated alcohol is cleaned by ultrasonic 30min；
The surface step 2. dioxygen water process ITO
By the above-mentioned ITO drying cleaned up, it is immersed in 1min in the aqueous hydrogen peroxide solution that volumetric concentration is 30%, so
The aqueous hydrogen peroxide solution on surface is rinsed well using alcohol afterwards, is dried up, insulating tape is sticked, forms reserved electrode, and put
30min is handled with UV ozone in UV cleaning device.The purpose on the surface dioxygen water process ITO is the leaching in order to improve the surface ITO
Profit ability；
Step 3. matches perovskite precursor liquid
By CH3NH3I and BiI3With molar ratio 3:2 ratio mixed dissolution in green solvent methylamine alcohol solution, what is prepared is molten
Liquid stirs 30min at normal temperature, makes CH3NH3I and BiI3Powder is completely dissolved, and the use of diameter is then 0.22 μm of filter mistake
Filter removes the bulky grain in solution, obtains clear perovskite precursor liquid, solution concentration 0.35mol/L；
Step 4. prepares MA3Bi2I9Polycrystal film
MA is prepared using spin-coating method3Bi2I9Polycrystal film.100 μ L perovskite forerunner's drop-coateds are measured using liquid-transfering gun first
On the surface ITO, spin coating instrument revolving speed is 4000r/min, acceleration 200r/s, spin-coating time 30s, then in 100 DEG C of conditions
Lower annealing 15min removes excess of solvent, obtains fine and close MA3Bi2I9Polycrystal film.
Step 5. prepares top electrode
Utilize the MA of magnetron sputtering technique in step 43Bi2I9Film surface prepares top electrode.It is covered on mask plate
MA3Bi2I9Film surface is placed in magnetron sputtering apparatus, and sputtering target material is Pt target, and underlayer temperature 300K, reaction gas is
Argon gas, the control indoor air pressure of vacuum are 4Torr, and sputtering power 100W prepares thickness using direct current magnetron sputtering process
For 60nm, the Pt electrode that diameter is 100 μm obtains Bi based perovskite resistance-variable storing device of the present invention.
The performance for the resistance-variable storing device that the present embodiment obtains is tested using Agilent B1500A Semiconductor Parameter Analyzer.It is first
First, MA is removed3Bi2I9The insulating tape of resistance-variable storing device exposes hearth electrode, and places it in probe station, utilizes two probes
Hearth electrode and top electrode are contacted respectively.Application -4V~4V dc sweeps voltage on top electrode, hearth electrode ground connection measure I-V song
Line, as shown in figure 5, I-V curve reveals apparent bipolarity resistance transformation characteristic.One scanning voltage circulation includes four portions
Point: first from 0 scanning to+4V, then from+4V scanning to 0, to 0, i.e., then reverse scan is scanned from 0 scanning to -4V, then from -4V
It completes a scan period, every partial scan step number is identical, is 101.Device is damaged by high current in test process in order to prevent,
A limitation electric current, size 10mA are set in forward scan.When voltage is from 0 scanning to+4V, electric current is anxious in 0.28V
Increase severely big, resistance is transformed into low resistance state by high-impedance state, this process is known as SET process；When voltage is from 0 scanning to -4V, device energy
Low resistance state is enough maintained, when negative voltage arrival -1.2V, electric current is strongly reduced, and resistance is transformed into high-impedance state by low resistance state, this
Process is known as RESET process.Device is able to maintain original resistance state when power is off, illustrates that the memory is non-volatile.
Meanwhile the circulation tolerance of device is tested using Agilent B1500A, i.e., scanning voltage continuous several times recycle, and read
High low resistance when 0.2V voltage is taken, as shown in Figure 6.In 60 circle circulations, the high low resistance of device maintains the same order of magnitude,
And the resistance ratio between high low resistance state is greater than 10, meets the requirement of general memory memory window.
Embodiment 3
A kind of environmentally friendly Bi based perovskite resistance-variable storing device of the present embodiment, the memory include hearth electrode, set
Bi based perovskite change resistance layer, the top electrode set on change resistance layer upper surface in hearth electrode upper surface, in which:
The hearth electrode material is TiN, and for the hearth electrode with a thickness of 300nm, shape is rectangle, side length 2cm；
The resistive layer material is MA3Bi2I9Film；For the change resistance layer with a thickness of 600nm, shape is rectangle, and side length is
2cm；
The top electrode material is Au, and for top electrode with a thickness of 80nm, shape is circle, and diameter is 500 μm.
The preparation method of environmentally friendly Bi based perovskite resistance-variable storing device described above, comprising the following steps:
Step 1. cleans TiN substrate
Dehydrated alcohol is dipped using cotton swab first to scrub TiN conducting surface, then is repeatedly rinsed with deionized water.Then
Deionized water, acetone are used respectively, and dehydrated alcohol is cleaned by ultrasonic 30min；
The surface step 2. dioxygen water process TiN
By the above-mentioned TiN drying cleaned up, it is immersed in 1min in the aqueous hydrogen peroxide solution that volumetric concentration is 30%, so
The aqueous hydrogen peroxide solution on surface is rinsed well using alcohol afterwards, is dried up, insulating tape is sticked, forms reserved electrode, and put
30min is handled with UV ozone in UV cleaning device.The purpose on the surface dioxygen water process TiN is the leaching in order to improve the surface TiN
Profit ability；
Step 3. matches perovskite precursor liquid
By CH3NH3I and BiI3With molar ratio 3:2 ratio mixed dissolution in green solvent methylamine alcohol solution, what is prepared is molten
Liquid stirs 30min at normal temperature, makes CH3NH3I and BiI3Powder is completely dissolved, and the use of diameter is then 0.22 μm of filter mistake
Filter removes the bulky grain in solution, obtains clear perovskite precursor liquid, solution concentration 0.35mol/L；
Step 4. prepares MA3Bi2I9Polycrystal film
MA is prepared using spin-coating method3Bi2I9Polycrystal film.100 μ L perovskite forerunner's drop-coateds are measured using liquid-transfering gun first
On the surface ITO, spin coating instrument revolving speed is 4000r/min, acceleration 200r/s, spin-coating time 90s, then in 100 DEG C of conditions
Lower annealing 15min removes excess of solvent, obtains fine and close MA3Bi2I9Polycrystal film.
Step 5. prepares top electrode
Utilize the MA of magnetron sputtering technique in step 43Bi2I9Film surface prepares top electrode.It is covered on mask plate
MA3Bi2I9Film surface is placed in magnetron sputtering apparatus, and sputtering target material is Au target, and underlayer temperature 300K, reaction gas is
Argon gas, the control indoor air pressure of vacuum are 4Torr, and sputtering power 100W prepares thickness using direct current magnetron sputtering process
For 80nm, the Au electrode that diameter is 500 μm obtains Bi based perovskite resistance-variable storing device of the present invention.
MA made from the embodiment of the present invention 33Bi2I9The pattern of polycrystal film is substantially the same manner as Example 1, Bi base obtained
The I-V curve of perovskite resistance-variable storing device, circulation tolerance and the performance of the resistance-variable storing device of embodiment 1 are also essentially identical.
Claims (10)
1. a kind of environmentally friendly Bi based perovskite resistance-variable storing device, it is characterised in that: the memory includes hearth electrode, is set to
Bi based perovskite change resistance layer, the top electrode set on change resistance layer upper surface of hearth electrode upper surface, in which: the resistive layer material is
MA3Bi2I9Film.
2. environmentally friendly Bi based perovskite resistance-variable storing device according to claim 1, it is characterised in that: the hearth electrode
Material is any one of FTO, ITO, ZTO, TaN or TiN.
3. environmentally friendly Bi based perovskite resistance-variable storing device according to claim 1, it is characterised in that: the hearth electrode
With a thickness of 100~300nm, shape is rectangle, and side length is 1~2cm.
4. environmentally friendly Bi based perovskite resistance-variable storing device according to claim 1, it is characterised in that: the Bi base calcium
Titanium ore change resistance layer is with a thickness of 200~600nm.
5. environmentally friendly Bi based perovskite resistance-variable storing device according to claim 4, it is characterised in that: the Bi base calcium
Titanium ore change resistance layer shape is rectangle, and side length is 1~2cm.
6. environmentally friendly Bi based perovskite resistance-variable storing device according to claim 1, it is characterised in that: the top electrode
Material is any one of Pt, Au or W.
7. environmentally friendly Bi based perovskite resistance-variable storing device according to claim 1, it is characterised in that: the top electrode
With a thickness of 60~100nm, shape is round or rectangle, and diameter or side length are 100~900 μm.
8. the preparation method of the described in any item environmentally friendly Bi based perovskite resistance-variable storing devices of claim 1~7, feature
It is: the described method comprises the following steps:
In pretreated hearth electrode surface spin coating MA3Bi2I9Polycrystal film layer；In the MA3Bi2I9Thin-film surface vapor deposition or
Sputter metallized electrode.
9. the preparation method of environmentally friendly Bi based perovskite resistance-variable storing device according to claim 8, it is characterised in that:
The spin coating MA3Bi2I9The method of polycrystal film layer is specific as follows: measuring MA using liquid-transfering gun first3Bi2I9Perovskite precursor liquid
Drop coating is on the hearth electrode surface, and spin coating instrument revolving speed is 4000r/min, acceleration 200r/s, spin-coating time 40s, then
Anneal 15min under the conditions of 100 DEG C, obtains fine and close MA3Bi2I9Polycrystal film.
10. the preparation method of environmentally friendly Bi based perovskite resistance-variable storing device according to claim 9, feature exist
In: the MA3Bi2I9Perovskite precursor liquid is formulated with the following method:
By CH3NH3I powder and BiI3Powder is added sequentially in methylamine alcohol solution with the ratio of molar ratio 3:2, is stirred at room temperature
Then 30min is that 0.22 μm of filter filters using diameter, removes the bulky grain in solution, obtain clear perovskite forerunner
Liquid, the perovskite Concentration of precursor solution are 0.35mol/L.
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| CN112133836A (en) * | 2020-09-08 | 2020-12-25 | 宁波大学 | Perovskite solar cell prepared by in-situ growth |
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Application publication date: 20190329 |