CN108987569A - A kind of memristor based on bismuth oxyiodide film, preparation method and application - Google Patents
A kind of memristor based on bismuth oxyiodide film, preparation method and application Download PDFInfo
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- CBACFHTXHGHTMH-UHFFFAOYSA-N 2-piperidin-1-ylethyl 2-phenyl-2-piperidin-1-ylacetate;dihydrochloride Chemical compound Cl.Cl.C1CCCCN1C(C=1C=CC=CC=1)C(=O)OCCN1CCCCC1 CBACFHTXHGHTMH-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000002346 layers by function Substances 0.000 claims abstract description 16
- 210000000225 synapse Anatomy 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims description 18
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims description 9
- UOZDOLIXBYLRAC-UHFFFAOYSA-L [2-hydroxy-3-(trimethylazaniumyl)propyl]-trimethylazanium;diiodide Chemical compound [I-].[I-].C[N+](C)(C)CC(O)C[N+](C)(C)C UOZDOLIXBYLRAC-UHFFFAOYSA-L 0.000 claims description 7
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims description 6
- 239000003792 electrolyte Substances 0.000 claims description 6
- 238000004070 electrodeposition Methods 0.000 claims description 5
- 239000000758 substrate Substances 0.000 claims description 4
- 229940005561 1,4-benzoquinone Drugs 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052797 bismuth Inorganic materials 0.000 claims description 3
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 3
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 239000010410 layer Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 239000000428 dust Substances 0.000 claims description 2
- 238000005516 engineering process Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 238000004062 sedimentation Methods 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims 1
- 229910000416 bismuth oxide Inorganic materials 0.000 claims 1
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 claims 1
- 230000005611 electricity Effects 0.000 claims 1
- 229910052740 iodine Inorganic materials 0.000 claims 1
- 239000011630 iodine Substances 0.000 claims 1
- 238000004088 simulation Methods 0.000 abstract description 11
- 210000004556 brain Anatomy 0.000 abstract description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052760 oxygen Inorganic materials 0.000 abstract description 4
- 239000001301 oxygen Substances 0.000 abstract description 4
- 238000011161 development Methods 0.000 abstract description 2
- 230000009191 jumping Effects 0.000 abstract description 2
- 230000007774 longterm Effects 0.000 abstract description 2
- 230000008569 process Effects 0.000 description 8
- 230000006399 behavior Effects 0.000 description 6
- 230000006870 function Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000009826 distribution Methods 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 230000000638 stimulation Effects 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 230000009329 sexual behaviour Effects 0.000 description 2
- 230000003956 synaptic plasticity Effects 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000002929 anti-fatigue Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007087 memory ability Effects 0.000 description 1
- 230000006386 memory function Effects 0.000 description 1
- 230000035772 mutation Effects 0.000 description 1
- 210000005036 nerve Anatomy 0.000 description 1
- 230000001537 neural effect Effects 0.000 description 1
- 230000001242 postsynaptic effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 230000003977 synaptic function Effects 0.000 description 1
- 230000002123 temporal effect Effects 0.000 description 1
- 238000000844 transformation Methods 0.000 description 1
- 230000007704 transition 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
- H10N70/801—Constructional details of multistable switching devices
- H10N70/881—Switching materials
- H10N70/883—Oxides or nitrides
- H10N70/8836—Complex metal oxides, e.g. perovskites, spinels
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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
- H10N70/021—Formation of switching materials, e.g. deposition of layers
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- Manufacturing & Machinery (AREA)
- Semiconductor Memories (AREA)
Abstract
The present invention provides a kind of memristor based on bismuth oxyiodide film, preparation method and applications.Memristor in the present invention includes hearth electrode, and the resistive functional layer being made of bismuth oxyiodide film is formed on the hearth electrode, is formed with top electrode in the resistive functional layer.The present invention uses resistive functional layer of the bismuth oxyiodide film as memristor, bismuth oxyiodide can make the Lacking oxygen in device become more, these Lacking oxygens can be used as conductive channel stable between top electrode and hearth electrode, so that the resistance of device is not in jumping phenomenon when changing.Memristor in the present invention is due to using resistive functional layer of the bismuth oxyiodide film as device, therefore, realize simulation of the device to biological synapse function, learn again including short-term plasticity, long-term plasticity, double pulses laser, Rush Hour plasticity, study-forgetting-, it means that the simulation powerful computing capability of human brain and efficient artificial intelligent chip have optimistic development prospect.
Description
Technical field
The present invention relates to a kind of memory, specifically a kind of memristor based on bismuth oxyiodide film, its preparation side
Method and application.
Background technique
Compared with traditional von Neumann architecture, human brain executes the information of highly-parallel with low-down power
The ability of processing shows whole superior and efficient feature.Therefore, global scientist is making great efforts to develop word audio
Building module.Basic element in human brain is cynapse, and enormous amount (reaches 1015It is a), and be the pass of study and identification
Key factor.Traditional neural form computing hardware with von Neumann framework consumes a large amount of power, and whole efficiency is lower.Most
Closely, IBM develops a kind of hardware approach and simulates millions of a cynapses to realize using Static Random Access Memory (SRAM)
Function.However, it is single to simulate that this method needs six transistors since each sram cell includes six transistors
Cynapse, this makes this method that can not reach brain scale (1015A cynapse).RRAM, which is provided, a kind of carrys out mould using individual equipment
The feasible method of quasi- cynapse behavior.And it is easier to manufacture on a large scale with high density with the RRAM array of wordline and bit line.?
In synapse device, postsynaptic currents need to gradually increase with input pulse, this represents increased learning ability.Therefore, for
For neuromorphic application, multiple states are needed, this requirement with the legacy memory only with " 0 " and one state is completely not
Together.Although the appearance of memristor has huge attraction to neuromorphic application, general resistance-variable storing device is in " SET mistake
In journey " resistance can have unexpected " SET " characteristic to limit the quantity of conductivity state from high to low suddenly.It makes resistive
Memory is difficult to imitate the learning behavior of cynapse, it is therefore desirable to the device that a resistance gradually changes.
Summary of the invention
It is an object of the invention to provide a kind of memristor based on bismuth oxyiodide film, preparation method and applications.
The object of the present invention is achieved like this: a kind of memristor based on bismuth oxyiodide film, including hearth electrode, in institute
The resistive functional layer for being formed on hearth electrode and being made of bismuth oxyiodide film is stated, is formed with top electrode in the resistive functional layer.It is excellent
Choosing, the hearth electrode is FTO layers, and the top electrode is Ti electrode, to form the device of Ti/BiOI/FTO structure.It is described
Bismuth oxyiodide film with a thickness of 56 nm.
In the present invention, resistive functional layer using bismuth oxyiodide film as memristor, bismuth oxyiodide has oxygen good
Adsorption capacity, so that the Lacking oxygen in device becomes more, these Lacking oxygens can be used as conduction stable between top electrode and hearth electrode
Channel so that the resistance of device is not in jumping phenomenon when changing, but makes resistance become larger or become smaller.
Therefore the conductance during " SET " and " RESET " of the memristor in the present invention can all gradually change, it may be assumed that the state of conductance has
Very much, enable the study of the more preferable simulation biological synapse of device, memory function.
The preparation method of memristor provided by the present invention based on bismuth oxyiodide film, includes the following steps:
A, hearth electrode is prepared on substrate；
B, bismuth oxyiodide film is prepared on the hearth electrode as resistive functional layer；
C, top electrode is prepared on the bismuth oxyiodide film.
Bismuth oxyiodide film is prepared using electrochemical deposition method in step b, specific as follows:
B-1, potassium iodide is dissolved in deionized water, forms propiodal solution；
B-2, it is added five nitric hydrate bismuths as bismuth source in propiodal solution, stirring to solution is clarified, and is added dust technology, is made molten
Liquid pH value be 1-2, preferably 1.7；
B-3,1,4-benzoquinone is dissolved in dehydrated alcohol, and be added into step b-2 acquired solution, form electrolyte；
B-4, using electrolyte in step b-3, prepare bismuth oxyiodide film with electrochemical deposition method, operating voltage is -0.1V, is sunk
The product time is 300s.
Memristor in the present invention due to using resistive functional layer of the bismuth oxyiodide film as device, realization
Simulation of the device to biological synapse function, including short-term plasticity, long-term plasticity, double pulses laser, Rush Hour are plastic
Property, study-forgetting-learn again, this means that the simulation powerful computing capability of human brain and efficient artificial intelligent chip
There is optimistic development prospect.
Detailed description of the invention
In Fig. 1, Fig. 1 (a) is the structural schematic diagram of Ti/BiOI/FTO resistive device in the present invention, and FTO is hearth electrode,
BiOI is resistive functional layer, and Ti is top electrode；Fig. 1 (b) is the I/V scanning curve of Ti/BiOI/FTO resistive device in the present invention
Figure.
Fig. 2 is the retention performance curve of memristor in the present invention.
Fig. 3 is the fatigue resistance curve of memristor in the present invention.
Fig. 4 is that memristor recycles 100 times high low resistance accumulated probability distribution map in the present invention.
Fig. 5 is the dependence linearity curve of opposite synapse weight (Δ W) and opposite stimulation time.
In Fig. 6, Fig. 6 (a) is the performance test figure of device double pulses laser during SET in the present invention, Fig. 6
(b) be device double pulses laser during RESET in the present invention performance test figure.
In Fig. 7, Fig. 7 (a) is synapse weight with the increased simulation drawing of continuous impulse stimulation；Fig. 7 (b) is that synapse weight declines
The simulation drawing subtracted, the i.e. relaxation of STP process, this behavior are similar to human brain forgotten memory curve；Fig. 7 (c) is to be based on
The learning process again of intermediate state.
Specific embodiment
Memristor shows the great potential of the artificial synapse as neuromorphic application.Current most of memristors exist
RESET(" is closed ") during resistance can become larger, this make memristor have enough state simulations " forgetting " process.So
And be " unlatching " in SET() during memristor resistance can occur it is unexpected become smaller, therefore enough states cannot be generated and carry out mould
" study " process of quasi- cynapse.The regulation of conductance only is carried out to device during RESET so that device is only capable of simulation life
The inhibition behavior of object cynapse, and enhancing behavior can not be simulated.
In the present invention, by using bismuth oxyiodide film (BiOI) as the resistive functional layer of memristor, bismuth oxyiodide
Film can make the Lacking oxygen in device become more, these Lacking oxygens can be as the conductive channel of top electrode and hearth electrode.Using this
Memristor in invention can realize the enhancing sexual behaviour of cynapse in one single and inhibit sexual behaviour, this makes neuromorphic
It calculates to have and be made great sense in better learning and memory ability.
As shown in Fig. 1 (a), the structure of the memristor provided by the present invention based on bismuth oxyiodide film is: in glass
(Glass) it is formed with hearth electrode FTO on substrate, bismuth oxyiodide (BiOI) film is formed on hearth electrode FTO, in bismuth oxyiodide film
On be formed with top electrode, top electrode is several Ti electrodes, to form the memristor of Ti/BiOI/FTO structure.Positioned at hearth electrode FTO
Resistive functional layer of the BiOI film as memristor between top electrode Ti.The thickness of BiOI film can be from 10 nm ~ 120
nm。
Memristor provided by the present invention the preparation method comprises the following steps: preparing hearth electrode on substrate first；Later at the bottom
Bismuth oxyiodide film is prepared on electrode as resistive functional layer；Then top electrode is prepared on the bismuth oxyiodide film.
The preparation process of bismuth oxyiodide film is specific as follows:
1., using potassium iodide as propiodal, be dissolved in deionized water, formed concentration be 0.4mol/L propiodal solution.
2., using five nitric hydrate bismuths as bismuth source be added to step 1. in propiodal solution in, forming concentration is
The solution of 0.04mol/L；The solution is stirred to clarify, dilute HNO of 1mol/L is added later3Solution makes the pH value of solution exist
Between 1-2, it is preferred that make the pH value 1.7 of solution.
3., 1,4-benzoquinone is dissolved in dehydrated alcohol, form the solution that concentration is 0.23mol/L, which be added step
2. in resulting acid solution, forming electrolyte.
4., using step 3. in electrolyte, prepare bismuth oxyiodide film with electrochemical deposition method.Work in this step
Voltage is -0.1V, sedimentation time 300s.Finally formed bismuth oxyiodide film with a thickness of 56 nm.
I/V curve test is carried out to the memristor in the present invention, acquired results are as shown in Fig. 1 (b).Voltage scanning is according to figure
It is scanned in 1(b) with the arrow direction of numeral mark, when voltage scanning is to 1.25V, device becomes low-resistance from high-impedance state
State, this process are SET process, and device is breakdown in order to prevent, and the present invention is provided with the limitation electric current of a 5mA；When voltage is swept
When retouching to -1.6V, device returns to high-impedance state by low resistance state, this process is RESET process.As can be seen that device from I/V scanning figure
Part resistance during " SET " and " RESET " all gradually changes, and the phenomenon that mutation does not occur.
Retention performance test is carried out to the memristor in the present invention, acquired results are shown in Fig. 2.The holding of resistive memory is special
Property refer to that storage data in the devices are kept the length of time, the longer device performance of data hold time is better.By applying
Device is respectively placed in high and low resistance state by making alive scanning, reads voltage with lesser 0.01V, reads a device every 5 s
Resistance value, to device after test in 4 hours, there is not larger fluctuation in the discovery high and low resistance state of device, shows that the device is kept
Characteristic is relatively preferable.
Another key factor for measuring the storage performance superiority and inferiority of resistance-variable storing device is fatigue resistance.Device is every time in height
Different degrees of damage can be all generated when converting between low resistance state, deviates high low resistance state, even there is no height by serious person
The transformation of resistance state proves that device has damaged, and cannot reuse at this time, this is known as fatigue phenomenon.Therefore, antifatigue test is
Determine one of the whether good key factor of storage characteristics of resistance-variable storing device, the fatigue resistance of device is stronger, and device performance is more steady
It is fixed.Fatigue resistance test is carried out to the memristor in the present invention, acquired results are shown in Fig. 3.From the figure 3, it may be seen that under 1V voltage,
Device is after experience 100 times high and low resistance state transformations, and there is no significant changes for high and low resistance state, this illustrates in the present invention
Device has relatively good fatigue resistance.
Fig. 4 is the accumulated probability of resistance in " unlatching " and " closing " of memristor in the present invention.Pass through the analysis present invention
Transition resistance distribution situation in resistive device 100 times circulation read-write operations of Ti/BiOI/FTO structure, tires out it
Product probability statistics, as a result, it has been found that, resistance under open state (corresponding low resistance state, i.e. LRS) between 537 Ω to 823 Ω with
Machine distribution, dispersion degree is smaller, has good uniformity；The range of resistance under closed state (corresponding high-impedance state, i.e. HRS) is from 4735 Ω
To 5642 Ω, dispersion degree is relatively weaker.
Fig. 5 is simulation of the memristor to synaptic plasticity function in the present invention, the results show that the device in the present invention has
There is synapse weight to change compound bio cynapse characteristic, is demonstrated by good nerve and learns sharp cutting edge of a knife or a sword Temporal dependency synaptic plasticity
(STDP) learning ability.
Fig. 6 is test of the memristor to double pulses laser performance in synaptic function in the present invention, it is seen that when
Between be spaced smaller, PPF ratio is bigger, that is, influences bigger, this result is consistent with the reflection of biological synapse, shows prepared by the present invention
Memristor reproduced double pulses laser function well.
Fig. 7 is the simulation that memristor in the present invention learns this critical function to study-forgetting-of biological synapse again,
Fig. 7 (a) shows with 50 continuous positive pulse deexcitation cynapse devices as a result, the synapse weight of device is with pulse time
Number gradually increases, this is referred to as learning functionality；After application pulse removes, synapse weight will be under no-bias effect
When decaying, as shown in Fig. 7 (b), in its rate of decay of the incipient stage of decaying than very fast, and then rate of decay is slack-off, this
One variation tendency is consistent with human brain forgotten memory curve.It decays to after a stationary value, and is applied with 20 continuously
Positive pulse go stimulation device, shown in acquired results such as Fig. 7 (c), it is found that before the weight of device is returned to decay, this phenomenon class
It is similar to relearning in brain.Fig. 7 is results showed that memristor prepared by the present invention can simulate in biological synapse
Study-forgetting-learns this behavior again.
Claims (10)
1. a kind of memristor based on bismuth oxyiodide film, characterized in that including hearth electrode, be formed on the hearth electrode by iodine
The resistive functional layer that bismuth oxide film is constituted, is formed with top electrode in the resistive functional layer.
2. the memristor according to claim 1 based on bismuth oxyiodide film, characterized in that the hearth electrode is FTO layers,
The top electrode is Ti electrode, to form the device of Ti/BiOI/FTO structure.
3. the memristor according to claim 1 based on bismuth oxyiodide film, characterized in that the bismuth oxyiodide film
With a thickness of 56 nm.
4. a kind of preparation method of the memristor based on bismuth oxyiodide film, characterized in that include the following steps:
A, hearth electrode is prepared on substrate；
B, bismuth oxyiodide film is prepared on the hearth electrode as resistive functional layer；
C, top electrode is prepared on the bismuth oxyiodide film.
5. the preparation method of the memristor according to claim 4 based on bismuth oxyiodide film, characterized in that the bottom electricity
Extremely FTO layers, the top electrode is Ti electrode, and being formed by device architecture is Ti/BiOI/FTO.
6. the preparation method of the memristor according to claim 4 based on bismuth oxyiodide film, characterized in that in step b
Bismuth oxyiodide film is prepared using electrochemical deposition method, specific as follows:
B-1, potassium iodide is dissolved in deionized water, forms propiodal solution；
B-2, it is added five nitric hydrate bismuths as bismuth source in propiodal solution, stirring to solution is clarified, and is added dust technology, is made molten
Liquid pH value is 1-2；
B-3,1,4-benzoquinone is dissolved in dehydrated alcohol, and be added into step b-2 acquired solution, form electrolyte；
B-4, using electrolyte in step b-3, prepare bismuth oxyiodide film with electrochemical deposition method.
7. the preparation method of the memristor according to claim 6 based on bismuth oxyiodide film, characterized in that step b-4
Middle operating voltage is -0.1V, sedimentation time 300s.
8. the preparation method of the memristor according to claim 6 based on bismuth oxyiodide film, characterized in that step b-2
In make solution ph 1.7 obtained.
9. the preparation method of the memristor according to claim 4 based on bismuth oxyiodide film, characterized in that in step b
Prepared bismuth oxyiodide film with a thickness of 56 nm.
10. a kind of application of memristor described in claim 1 in terms of simulating biological synapse behavior.
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| CN108987569B (en) | 2021-10-26 |
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