CN109461813A - A kind of resistance-variable storing device and preparation method thereof based on tungsten sulfide nanometer sheet - Google Patents
A kind of resistance-variable storing device and preparation method thereof based on tungsten sulfide nanometer sheet Download PDFInfo
- Publication number
- CN109461813A CN109461813A CN201811172693.7A CN201811172693A CN109461813A CN 109461813 A CN109461813 A CN 109461813A CN 201811172693 A CN201811172693 A CN 201811172693A CN 109461813 A CN109461813 A CN 109461813A
- Authority
- CN
- China
- Prior art keywords
- zro
- resistance
- layer
- substrate
- nanometer sheet
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- ITRNXVSDJBHYNJ-UHFFFAOYSA-N tungsten disulfide Chemical compound S=[W]=S ITRNXVSDJBHYNJ-UHFFFAOYSA-N 0.000 title abstract description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000000758 substrate Substances 0.000 claims abstract description 39
- 230000008859 change Effects 0.000 claims abstract description 35
- 238000004544 sputter deposition Methods 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 5
- 229920002120 photoresistant polymer Polymers 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims 6
- 239000011787 zinc oxide Substances 0.000 claims 3
- 238000001514 detection method Methods 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 61
- 238000005457 optimization Methods 0.000 description 16
- 238000000034 method Methods 0.000 description 12
- 230000015654 memory Effects 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- 239000000463 material Substances 0.000 description 10
- 238000003860 storage Methods 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000011368 organic material Substances 0.000 description 5
- 230000009471 action Effects 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 150000001768 cations Chemical class 0.000 description 3
- 230000005684 electric field Effects 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 229960004756 ethanol Drugs 0.000 description 3
- 238000007689 inspection Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 230000002929 anti-fatigue Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 239000007784 solid electrolyte Substances 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 1
- 229910052774 Proactinium Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001548 drop coating Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000012010 growth Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000002346 layers by function Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 230000034655 secondary growth Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
- H10N70/026—Formation of switching materials, e.g. deposition of layers by physical vapor deposition, e.g. sputtering
-
- 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
- H10N70/882—Compounds of sulfur, selenium or tellurium, e.g. chalcogenides
- H10N70/8822—Sulfides, e.g. CuS
-
- 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
- H10N70/8833—Binary metal oxides, e.g. TaOx
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Semiconductor Memories (AREA)
Abstract
The present invention provides a kind of resistance-variable storing device and preparation method thereof based on tungsten sulfide nanometer sheet, the first ZrO that the structure of the memristor successively includes Pt substrate from top to bottom, formed on the Pt substrate2Change resistance layer, in the first ZrO2The WS formed on change resistance layer2Nanometer sheet dielectric layer, in the WS2The 2nd ZrO formed on nanometer sheet dielectric layer2Change resistance layer and in the 2nd ZrO2The Ag electrode layer formed on change resistance layer.Resistance-variable storing device passage capacity detection provided by the invention proves that it, with good resistive characteristic, shows relatively stable change in resistance, differ larger between high resistance and low-resistance value, it is not easy to cause to misread, and the WS2Fatigue resistance of the nanometer sheet resistance-variable storing device under high-impedance state and low resistance state is more excellent.
Description
Technical field
The present invention relates to resistance-variable storing device technical fields, and in particular to a kind of resistance-variable storing device based on tungsten sulfide nanometer sheet
And preparation method thereof.
Background technique
In recent years, the size of integrated circuit technology has been deep into 20 nanometers hereinafter, traditional Nonvolatile Memory Device
Already close to physics limit, the popular domain that non-volatility memorizer of new generation has become scientists from all over the world's research is developed.Currently,
The main Types of non-volatility memorizer have magnetic memory, phase transition storage and resistance-variable storing device.Wherein resistance-variable storing device has
Low in energy consumption, read or write speed is fast, and data holding ability is good, and it is new the one of great application prospect the advantages that being easily integrated that production is simple
For memory.
The general structure of resistance-variable storing device is typical sandwich structure, has upper/lower electrode and is arranged between upper/lower electrode
The varistor material of resistive phenomenon can be generated.Under the action of applying bias, it can make the resistance states of device that high low resistance state occur
Transformation, thus realize 0 and 1 storage.For resistance-variable storing device, select different resistive layer materials for device
It can produce bigger effect, it may be said that resistive layer material is the core of resistance-variable storing device.
Scientific investigations showed that can as change resistance layer material category it is various, mainly have four major class at present.First is that perovskite
Oxide.Many shows bipolarity storage characteristics based on the device of the material, but this kind of material preparation process difficulty is big, with
Traditional device is incompatible.Second is that transition-metal oxide, transition metal binary oxide have ingredient it is simple, it is low in cost,
It is easily prepared, manufacture it is mutually compatible with CMOS technology the advantages that, although the resistive memory based on transition metal binary oxide
It has many good qualities, but its resistive mechanism is not completely clear, and the reliability of device also requires study, this is to a certain extent
Its development and application are hindered, the development prospect of this kind of resistive device is not very bright and clear.Third is that solid electrolyte, this kind of resistive
Memory has typical sandwich structure, including electrochemical activity electrode (Ag, Cu etc.), electrochemicaUy inert electrode (W, Pt etc.)
The resistive functional layer constituted with solid electrolyte material.Their resistive characteristic is since electrification occurs for active metal electrode material
Learn react caused by metal cation migrate under electric field action caused by metallic conduction filament formation be broken led
It causes.When active metal electrode applies forward voltage appropriate, which can occur oxidation reaction, become corresponding gold
Belong to cation, migrated through solid-state electrolytic solution material to inert electrode under electric field action, reaches inert electrode surface and obtain later
Electronics occurs reduction reaction and generates metallic atom.Metallic atom is deposited on cathode, and filament is raw in inert electrode side first
It is long, after filament is grown completely and connects the active electrode of metal, conductive channel is formed, memory becomes low-resistance from high-impedance state
State, break-over of device.After applying backward voltage, electrochemical dissolution phenomenon can occur for metallic conduction filament, form the gold of conductive channel
Category be oxidized to metal cation, and under the action of electric field to active electrode migrate, at this time conductive channel be broken, memory by
Low resistance state is changed into high-impedance state, and device switching is in off state.Fourth is that organic material, organic material production at present is simple, cost
Cheap, the research using the bistable characteristic production resistance-variable storing device of organic material is relatively broad.It is organic compared with inorganic material
The maximum advantage of material is many kinds of, and selectable leeway is big.Although organic material has lot of advantages, mostly organic
The stability and storage performance of material itself are poor, non-refractory, and durability and data memory characteristic are also bad, and reading and writing, wiping
Except etc. service speeds it is slow, this affects organic material in the application in resistive memory field to a certain extent.Therefore,
The operations such as further research change in resistance is stable, storage performance is good, memory characteristic is good, antifatigue durability is good, reading and writing, erasing
Fireballing memory device is the project tried to explore in industry.
Summary of the invention
One of the objects of the present invention is to provide a kind of resistance-variable storing devices, to solve existing resistance-variable storing device resistive stability
The undesirable problem with antifatigue durability.
The second object of the present invention is to provide a kind of preparation method of resistance-variable storing device.
An object of the present invention is achieved through the following technical solutions: a kind of resistance-variable storing device, structure from it is lower to
On successively include Pt substrate, the first ZrO that is formed on the Pt substrate2Change resistance layer, in the first ZrO2It is formed on change resistance layer
WS2Nanometer sheet dielectric layer, in the WS2The 2nd ZrO formed on nanometer sheet dielectric layer2Change resistance layer and described second
ZrO2The Ag electrode layer formed on change resistance layer.
The WS2Nanometer sheet dielectric layer with a thickness of 10 ~ 100nm.
First ZrO2Change resistance layer and the 2nd ZrO2The thickness of change resistance layer is 5 ~ 50nm.
The Ag electrode layer is evenly distributed on the 2nd ZrO by several2The circular electric that diameter on change resistance layer is 80 ~ 300 μm
Pole is constituted.
The circular electrode with a thickness of 50 ~ 200nm.
The present invention also provides the preparation methods of above-mentioned resistance-variable storing device, comprising the following steps:
(a) Pt substrate is successively used in acetone, alcohol and deionized water to ultrasonic cleaning, uses N after taking-up2Drying；
(b) the Pt substrate of dried and clean is fixed on the substrate table of magnetron sputtering apparatus cavity, and cavity is evacuated to 1 ×
10-4~6×10-4Pa is passed through the O of Ar and 10 ~ 40sccm that flow is 20 ~ 75sccm into cavity2, adjusting interface valve makes cavity
Interior pressure maintains 1 ~ 6Pa, opens control ZrO2The radio frequency source of target build-up of luminance, adjustment RF source power are 60 ~ 100W, are made
ZrO2Target build-up of luminance, 1 ~ 5min of pre-sputtering；10 ~ 30min of formal sputtering later forms the first ZrO on Pt substrate2Change resistance layer；
(c) the first ZrO will be formed with2The Pt substrate of change resistance layer is placed on the pallet of photoresist spinner, draws WS with needle tubing2Solution is added dropwise
Onto substrate, setting revolving speed is 300 ~ 2000 r/min, makes WS2Solution gets rid of even on Pt substrate, makes WS later2Solution steams naturally
Hair, that is, form the WS of stratiform2Nanometer sheet dielectric layer；
(d) the first ZrO will be formed with2Change resistance layer and WS2The Pt substrate of nanometer sheet dielectric layer is fixed to magnetron sputtering apparatus cavity
Substrate table on, and cavity is evacuated to 1 × 10-4~6×10-4Pa, be passed through into cavity flow be 20 ~ 75sccm Ar and
The O of 10 ~ 40sccm2, adjusting interface valve makes the intracorporal pressure of chamber maintain 1 ~ 6Pa, opens control ZrO2The radio frequency of target build-up of luminance
Source, adjustment RF source power are 60 ~ 100W, make ZrO2Target build-up of luminance, 1 ~ 5min of pre-sputtering；10 ~ 30min of formal sputtering later,
In WS2The 2nd ZrO is formd on nanometer sheet dielectric layer2Change resistance layer；
(e) it is being formed with the first ZrO2Change resistance layer, WS2Nanometer sheet dielectric layer and the 2nd ZrO2It places and covers on the Pt substrate of change resistance layer
Cavity is evacuated to 1 × 10 by film version-4~4×10-4Pa is passed through the Ar that flow is 20 ~ 30sccm into cavity, adjusts interface
Valve makes the intracorporal pressure of chamber maintain 1 ~ 6Pa, opens the DC source of control Ag target build-up of luminance, and adjustment direct current source power is 8 ~ 11W, makes
Ag target build-up of luminance, 4 ~ 6min of pre-sputtering；6 ~ 10min of formal sputtering later, in the 2nd ZrO2Ag electrode layer is formed on change resistance layer.
The first ZrO in step (b)2The 2nd ZrO in change resistance layer and step (d)2The thickness of change resistance layer is 5 ~ 50nm.
In step (c), the WS2Solution is by WS2It is dissolved in ethanol solution and is sufficiently mixed and be made, WS2: ethanol solution=
1mg : 1mL；The WS2Nanometer sheet dielectric layer with a thickness of 10 ~ 100nm.
In step (e), the round hole that diameter is 80 ~ 300 μm is evenly equipped on the mask plate.
In step (e), the Ag electrode layer is evenly distributed on the 2nd ZrO by several2Diameter on change resistance layer is 80 ~ 300 μ
The circular electrode of m is constituted, the circular electrode with a thickness of 50 ~ 200nm.
WS provided by the invention2Nanometer sheet resistance-variable storing device, which passes through drop coating and gets rid of even method with photoresist spinner, forms WS2Nanometer
Piece dielectric layer, and with magnetron sputtering method diauxic growth ZrO2Change resistance layer, the detection of gained resistance-variable storing device passage capacity prove its tool
There is good resistive characteristic, show relatively stable change in resistance, differs larger between high resistance and low-resistance value, do not allow
It easily causes and misreads, and the WS2Fatigue resistance of the nanometer sheet resistance-variable storing device under high-impedance state and low resistance state is more excellent.
Provided by the invention preparation method is simple, good operability, optimizes device performance, is different from traditional use
The memory device of oxide preparation, structure novel is unique, and performance is good, make resistance-variable storing device storage performance it is more stable,
Durability is strong, and application prospect is more wide.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of resistance-variable storing device.
Fig. 2 is embodiment 2 in preparation WS2The structural representation of the magnetron sputtering apparatus used when nanometer sheet resistance-variable storing device
Figure.
Fig. 3 is WS prepared by embodiment 22Nanometer sheet resistance-variable storing device WS2Dielectric layer scanning electron microscope (SEM) picture.
Fig. 4 is that embodiment 2 adds WS2The current-voltage characteristic forming curve comparison figure of nanometer sheet optimization front and back.
Fig. 5 is that embodiment 2 adds WS2The high low resistance state retention performance curve comparison figure of nanometer sheet optimization front and back.
Fig. 6 is that embodiment 2 adds WS2The repeat property curve comparison figure of nanometer sheet optimization front and back.
Fig. 7 is that embodiment 2 adds WS2The high low resistance state durability line comparison diagram of nanometer sheet optimization front and back.
Specific embodiment
Following example is for present invention be described in more detail, but embodiment does not do any type of limit to the present invention
It is fixed.Unless stated otherwise, the present invention uses reagent, method and apparatus is the art conventional reagents, method and apparatus.
Embodiment 1
WS prepared by the present invention2The structure of nanometer sheet resistance-variable storing device is as shown in Figure 1, include the substrate 1 of the bottom, in substrate 1
First ZrO of upper growth2Change resistance layer 2, in the first ZrO2The WS bonded on change resistance layer 22Nanometer sheet dielectric layer 3, in WS2Nanometer sheet
The 2nd ZrO grown on dielectric layer 32Change resistance layer 4 and in the 2nd ZrO2The Ag electrode layer 5 grown on change resistance layer 4.
Wherein substrate 1 is Pt substrate, WS2Nanometer sheet dielectric layer 3 with a thickness of 10-100nm；First ZrO2Change resistance layer 2 and
Two ZrO2The thickness of change resistance layer 4 is 5 ~ 50nm.
Wherein the thickness of Ag electrode layer 5 can be within the scope of 50nm ~ 200nm；Ag electrode layer 5 includes several is evenly distributed on
2nd ZrO2The circular electrode that diameter on change resistance layer 4 is 80 ~ 300 μm.
Embodiment 2
WS of the present invention2The preparation method of nanometer sheet resistance-variable storing device includes the following steps:
(1) surface attachment is wiped into first with the sub absorbent cotton wiping for successively dipping acetone, dehydrated alcohol is taken the photograph in the surface of Pt substrate
The little particles such as dust tentatively remove the greasy dirt on its surface, then put Pt substrate in acetone with ultrasonic cleaning 10 minutes, so
After be put into alcohol with ultrasonic cleaning 10 minutes, then be put into deionized water with clip taking-up with ultrasonic cleaning 5 minutes, it
After take out, use N2Drying；
(2) the first ZrO2The preparation of change resistance layer: magnetron sputtering apparatus as shown in Figure 2 is used, Pt substrate is fixed on magnetic control and is splashed
It penetrates on tabletting platform 8, and tabletting platform 8 is put into cavity on substrate table 9, fix, close cavity and cavity is vacuumized；
5 × 10 are extracted into the intracorporal pressure of chamber-4Pa hereinafter, open intake valve 6, to cavity in be passed through the Ar and 25sccm of 50sccm
O2, by adjusting the switch size of gate valve 7, the intracorporal pressure of adjusting cavity makes cavity air pressure maintain 3Pa；Radio frequency source is opened,
Make ZrO2Target build-up of luminance, the power for adjusting radio frequency source is 80W, pre-sputtering 3min, then formal sputtering 10min, on Pt substrate
Form the first ZrO with a thickness of 10nm2Change resistance layer；
(3) WS2The preparation of nanometer sheet dielectric layer: by the WS of 1mg2It is dissolved in the ethanol solution (75%) of 1mL, mixes, obtain WS2It is molten
Liquid；Treated that Pt substrate is placed in photoresist spinner for step (2)；Prepared WS is drawn with disposable needle tubing2Solution is dripped in Pt substrate
Middle position, solution can be extended to Pt substrate perimeter, whole surface finally be covered, later under the revolving speed of 300-2000 r/min
By WS2Solution gets rid of even, forms the WS of the stratiform with a thickness of 65nm2Nanometer sheet dielectric layer；
(4) the 2nd ZrO2The preparation of change resistance layer: using magnetron sputtering apparatus as shown in Figure 2, carries out ZrO2Change resistance layer it is secondary
Growth, the same step of process conditions (2), finally in WS2The 2nd ZrO with a thickness of 10nm is formd on nanometer sheet dielectric layer2Resistive
Layer；
(5) preparation of Ag electrode layer: in the 2nd ZrO that step (4) are formed2Placing on change resistance layer and being evenly equipped with diameter is 90 μm
The mask plate of round hole puts tabletting platform 8 in order, is put on the intracorporal substrate table 9 of chamber, closes cavity after fixing, to cavity and
Gas circuit is evacuated to 2 × 10-4Pa or so；The DC source of control Ag target build-up of luminance is opened, adjustment direct current source power is 10W, makes Ag
Target can build-up of luminance, then pre-sputtering 6min；Formal sputtering 10min later, in the 2nd ZrO2Formd on change resistance layer with a thickness of
The Ag electrode layer of 60nm.
The structure of resistance-variable storing device before being optimized by this method is represented by Ag/ZrO2/ Pt, the WS after optimization2Nanometer sheet
The structure of resistance-variable storing device is represented by Ag/ ZrO2/ WS2/ZrO2/ Pt, the device are a kind of novel resistive memories,
Key point is in ZrO2Between be additionally arranged WS2Nanometer sheet dielectric layer.
Embodiments described above is one embodiment in the preparation method that the present invention is protected, as long as in right
It is required that and the range of technological parameter described in this description (the chamber vacuum degree of such as its magnetron sputtering, splashes RF source power in advance
Penetrate time and formal sputtering time etc.) in can get the claimed resistance-variable storing device of the present invention, and prepared resistive is deposited
Device prepared by reservoir and the present embodiment 2 has substantially similar performance.
3 performance test of embodiment
Optimize the preceding resistance-variable storing device (Ag/ZrO prepared by being added in embodiment 22/ Pt) scanning voltage measure its Current Voltage
As a result forming characteristic curve is shown in Fig. 4 a.By known to Fig. 4 a darker curve when apply for the first time forward scan voltage from 0V to
During 1.5V is gradually increased, this device is in high-impedance state (electric current is smaller), in 1.2V or so, its electricity at the beginning
Resistance state is slowly changed to low resistive state from high resistant, and with the increase of voltage, low resistive state reaches stationary value；Reach maximum scan
After voltage, scanning voltage starts to be gradually reduced, the 0V when scanning voltage continues to be reduced to, then start negative sense ask scanning to-
When 0.23V or so, reach closing voltage, high-resistance state is slowly gradually converted by low resistance state, and device is always held at
High resistance state, until voltage scanning returns to 0V.Apply forward scan voltage from 0V when second known to Fig. 4 a lighter curve
During being gradually increased to 1.5V, this device is in high-impedance state (electric current is smaller) at the beginning, in 0.5V or so, it
Resistance states are slowly changed to low resistive state from high resistant, and with the increase of voltage, low resistive state reaches stationary value；Reach maximum to sweep
After retouching voltage, scanning voltage starts to be gradually reduced, the 0V when scanning voltage continues to be reduced to, and then starts negative sense and scanning is asked to arrive
In -0.15V or so, reach closing voltage, high-resistance state is slowly gradually converted by low resistance state, and device is always maintained at
In high resistance state, until voltage scanning returns to 0V.
By being added in the WS prepared after the optimization of embodiment 22The scanning voltage of nanometer sheet resistance-variable storing device measures its electric current electricity
Forming characteristic curve is pressed, as a result sees Fig. 4 b.When forward scan voltage gradually increases from 0V to 0.6V known to Fig. 4 b darker curve
In big process, this device is in high-impedance state (electric current is smaller) at the beginning, and in 0.5V or so, its resistance states are by height
Resistance slowly changes to low resistive state, and with the increase of voltage, low resistive state reaches stationary value；After reaching maximum scan voltage, sweep
It retouches voltage to start to be gradually reduced, the 0V when scanning voltage continues to be reduced to, then starts negative sense and ask scanning in -0.13V or so
When, reach closing voltage, high-resistance state is slowly gradually converted by low resistance state, and device is always held at high resistance shape
State, until voltage scanning returns to 0V.When the mistake that forward scan voltage is gradually increased from 0V to 0.6V known to Fig. 4 b lighter curve
Cheng Zhong, this device is in high-impedance state (electric current is smaller) at the beginning, and in 0.18V or so, its resistance states are slow by high resistant
Slowly change to low resistive state, with the increase of voltage, low resistive state reaches stationary value；After reaching maximum scan voltage, scanning electricity
Pressing off the beginning is gradually reduced, the 0V when scanning voltage continues to be reduced to, and then starts negative sense and asks scanning in -0.06 V or so,
Reach closing voltage, high-resistance state is slowly gradually converted by low resistance state, and device is always held at high resistance state, directly
0V is returned to voltage scanning.Forming process switching voltage decreases after obviously showing optimization.
As a result the retention performance of resistance-variable storing device before inspection optimization is shown in Fig. 5 a.Resistance after detecting the preparation optimization of embodiment 2
As a result the retention performance of transition storage is shown in Fig. 5 b.From figure 5 it can be seen that the WS after the optimization based on this method preparation2Nanometer
Piece resistance-variable storing device has good retention performance, and high low resistance state is obvious, is maintaining 4 × 104S still has apparent height
Low resistance state.
The repeat property of resistance-variable storing device before inspection optimization, is as a result shown in Fig. 6 a, and the resistive after the preparation optimization of embodiment 2 is deposited
As a result the repeat property of reservoir is shown in Fig. 6 b.The WS prepared after this method optimization2Nanometer sheet resistance-variable storing device electric property is more steady
Fixed, repeatability is more preferably.
As a result the durability of resistance-variable storing device before inspection optimization is shown in Fig. 7 a, the resistance-change memory after the preparation optimization of embodiment 2
As a result the durability of device is shown in Fig. 7 b.The WS prepared after this method optimization2Nanometer sheet resistance-variable storing device durability is 1 × 109, stablize
Property is more preferably.
Examples detailed above is the preferable embodiment of the present invention, but embodiments of the present invention are not by the limit of the embodiment
System, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (10)
1. a kind of resistance-variable storing device, which is characterized in that its structure successively includes Pt substrate, the shape on the Pt substrate from top to bottom
At the first ZrO2Change resistance layer, in the first ZrO2The WS formed on change resistance layer2Nanometer sheet dielectric layer, in the WS2Nanometer sheet
The 2nd ZrO formed on dielectric layer2Change resistance layer and in the 2nd ZrO2The Ag electrode layer formed on change resistance layer.
2. resistance-variable storing device according to claim 1, which is characterized in that the WS2Nanometer sheet dielectric layer with a thickness of 10 ~
100nm。
3. resistance-variable storing device according to claim 1, which is characterized in that the first ZrO2Change resistance layer and the 2nd ZrO2Resistance
The thickness of change layer is 5 ~ 50nm.
4. resistance-variable storing device according to claim 1, which is characterized in that the Ag electrode layer is evenly distributed on by several
Two ZrO2The circular electrode that diameter on change resistance layer is 80 ~ 300 μm is constituted.
5. resistance-variable storing device according to claim 4, which is characterized in that the circular electrode with a thickness of 50 ~ 200nm.
6. a kind of preparation method of resistance-variable storing device, which comprises the following steps:
(a) Pt substrate is successively used in acetone, alcohol and deionized water to ultrasonic cleaning, uses N after taking-up2Drying；
(b) the Pt substrate of dried and clean is fixed on the substrate table of magnetron sputtering apparatus cavity, and cavity is evacuated to 1 ×
10-4~6×10-4Pa is passed through the O of Ar and 10 ~ 40sccm that flow is 20 ~ 75sccm into cavity2, adjusting interface valve makes cavity
Interior pressure maintains 1 ~ 6Pa, opens control ZrO2The radio frequency source of target build-up of luminance, adjustment RF source power are 60 ~ 100W, are made
ZrO2Target build-up of luminance, 1 ~ 5min of pre-sputtering；10 ~ 30min of formal sputtering later forms the first ZrO on Pt substrate2Change resistance layer；
(c) the first ZrO will be formed with2The Pt substrate of change resistance layer is placed on the pallet of photoresist spinner, draws WS with needle tubing2Solution is added dropwise
Onto substrate, setting revolving speed is 300 ~ 2000 r/min, makes WS2Solution gets rid of even on Pt substrate, makes WS later2Solution steams naturally
Hair, that is, form the WS of stratiform2Nanometer sheet dielectric layer；
(d) the first ZrO will be formed with2Change resistance layer and WS2The Pt substrate of nanometer sheet dielectric layer is fixed to magnetron sputtering apparatus cavity
On substrate table, and cavity is evacuated to 1 × 10-4~6×10-4Pa is passed through the Ar and 10 that flow is 20 ~ 75sccm into cavity
The O of ~ 40sccm2, adjusting interface valve makes the intracorporal pressure of chamber maintain 1 ~ 6Pa, opens control ZrO2The radio frequency source of target build-up of luminance,
Adjustment RF source power is 60 ~ 100W, makes ZrO2Target build-up of luminance, 1 ~ 5min of pre-sputtering；10 ~ 30min of formal sputtering later, in WS2
The 2nd ZrO is formd on nanometer sheet dielectric layer2Change resistance layer；
(e) it is being formed with the first ZrO2Change resistance layer, WS2Nanometer sheet dielectric layer and the 2nd ZrO2It places and covers on the Pt substrate of change resistance layer
Cavity is evacuated to 1 × 10 by film version-4~4×10-4Pa is passed through the Ar that flow is 20 ~ 30sccm into cavity, adjusts interface
Valve makes the intracorporal pressure of chamber maintain 1 ~ 6Pa, opens the DC source of control Ag target build-up of luminance, and adjustment direct current source power is 8 ~ 11W, makes
Ag target build-up of luminance, 4 ~ 6min of pre-sputtering；6 ~ 10min of formal sputtering later, in the 2nd ZrO2Ag electrode layer is formed on change resistance layer.
7. the preparation method of resistance-variable storing device according to claim 6, which is characterized in that the first ZrO in step (b)2Resistance
The 2nd ZrO in change layer and step (d)2The thickness of change resistance layer is 5 ~ 50nm.
8. the preparation method of the memristor according to claim 6 based on zinc oxide, which is characterized in that in step (c), institute
State WS2Solution is by WS2It is dissolved in ethanol solution and is sufficiently mixed and be made, WS2: ethanol solution=1mg: 1mL；The WS2Nanometer
Piece dielectric layer with a thickness of 10 ~ 100nm.
9. the preparation method of the memristor according to claim 6 based on zinc oxide, which is characterized in that in step (e), institute
It states and is evenly equipped with the round hole that diameter is 80 ~ 300 μm on mask plate.
10. the preparation method of the memristor according to claim 6 based on zinc oxide, which is characterized in that in step (e),
The Ag electrode layer is evenly distributed on the 2nd ZrO by several2The circular electrode that diameter on change resistance layer is 80 ~ 300 μm is constituted, institute
State circular electrode with a thickness of 50 ~ 200nm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811172693.7A CN109461813B (en) | 2018-10-09 | 2018-10-09 | Resistive random access memory based on tungsten sulfide nanosheet and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811172693.7A CN109461813B (en) | 2018-10-09 | 2018-10-09 | Resistive random access memory based on tungsten sulfide nanosheet and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109461813A true CN109461813A (en) | 2019-03-12 |
| CN109461813B CN109461813B (en) | 2022-08-19 |
Family
ID=65607396
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811172693.7A Active CN109461813B (en) | 2018-10-09 | 2018-10-09 | Resistive random access memory based on tungsten sulfide nanosheet and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109461813B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111275177A (en) * | 2020-01-16 | 2020-06-12 | 北京大学 | Full memristor neural network and preparation method and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104810477A (en) * | 2015-05-07 | 2015-07-29 | 河北大学 | Misunderstanding prevention resistance random access memory and production method thereof |
| CN105810817A (en) * | 2016-05-31 | 2016-07-27 | 天津理工大学 | A Two-Dimensional Nanosheet MoS2 Vertical Structure Resistive Switching Device |
| CN106025065A (en) * | 2016-05-30 | 2016-10-12 | 天津理工大学 | Two-dimensional nano molybdenum sulfide sheet layer/binary oxide laminated structure type resistive random access memory |
| CN106654009A (en) * | 2016-12-19 | 2017-05-10 | 中国科学院宁波材料技术与工程研究所 | Memristor and application thereof |
| CN106684242A (en) * | 2015-11-05 | 2017-05-17 | 华邦电子股份有限公司 | Conductive bridge type random access memory |
| CN107681049A (en) * | 2017-09-01 | 2018-02-09 | 河北大学 | A kind of resistance-variable storing device for avoiding misreading and preparation method |
-
2018
- 2018-10-09 CN CN201811172693.7A patent/CN109461813B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104810477A (en) * | 2015-05-07 | 2015-07-29 | 河北大学 | Misunderstanding prevention resistance random access memory and production method thereof |
| CN106684242A (en) * | 2015-11-05 | 2017-05-17 | 华邦电子股份有限公司 | Conductive bridge type random access memory |
| CN106025065A (en) * | 2016-05-30 | 2016-10-12 | 天津理工大学 | Two-dimensional nano molybdenum sulfide sheet layer/binary oxide laminated structure type resistive random access memory |
| CN105810817A (en) * | 2016-05-31 | 2016-07-27 | 天津理工大学 | A Two-Dimensional Nanosheet MoS2 Vertical Structure Resistive Switching Device |
| CN106654009A (en) * | 2016-12-19 | 2017-05-10 | 中国科学院宁波材料技术与工程研究所 | Memristor and application thereof |
| CN107681049A (en) * | 2017-09-01 | 2018-02-09 | 河北大学 | A kind of resistance-variable storing device for avoiding misreading and preparation method |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111275177A (en) * | 2020-01-16 | 2020-06-12 | 北京大学 | Full memristor neural network and preparation method and application thereof |
| CN111275177B (en) * | 2020-01-16 | 2022-10-21 | 北京大学 | A kind of full memristor neural network and its preparation method and application |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109461813B (en) | 2022-08-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102810634B (en) | Resistor type random access memory of a kind of high stability and preparation method thereof | |
| CN108831992B (en) | A resistive memory with hafnium-doped zinc oxide resistive switching layer and preparation method thereof | |
| CN101621114A (en) | Oxide multilayered gradient film and RRAM component structured thereby | |
| CN111009608B (en) | A solid electrolyte memristor and its preparation method and application | |
| JP2011124511A (en) | Storage element and storage device | |
| CN104659208A (en) | Non-volatile resistive memory device and preparation method thereof | |
| CN101577308A (en) | A doped ZrO2 resistive variable memory and its manufacturing method | |
| CN108328565A (en) | A kind of device based on controllable nano crackle and preparation method thereof and control method | |
| CN103500701B (en) | A method for preparing nano-devices | |
| CN105514268A (en) | Resistive random access memory with high on-off ratio and preparation method thereof | |
| CN105552220A (en) | Silicon oxide thin film based low power consumption resistive random access memory and preparation method therefor | |
| CN101872836A (en) | Resistive nonvolatile memory device and manufacturing method thereof | |
| CN116017989A (en) | A resistive memory device and its preparation method and atomic point contact construction method | |
| CN109461813A (en) | A kind of resistance-variable storing device and preparation method thereof based on tungsten sulfide nanometer sheet | |
| CN109411600A (en) | A kind of method and its resistance-variable storing device reducing resistance-variable storing device operation voltage | |
| CN109494301A (en) | A kind of method and its resistance-variable storing device improving resistance-variable storing device stability | |
| CN109065711A (en) | A kind of solid electrolyte resistance-variable storing device and preparation method thereof | |
| CN106601910B (en) | A kind of organic electrode resistance-variable storing device and preparation method thereof | |
| CN103247758B (en) | Adopt erasable film variable-resistance memory unit of flexible-paper-base and preparation method thereof | |
| CN105679933B (en) | A kind of multilevel memory cell controlled altogether based on conductive filament and polarization | |
| CN107579153B (en) | A low-power resistive memory based on electrode hafnium (Hf) doping and its preparation method | |
| CN102723435A (en) | Method for preparing resistance random access memory device realizing multiple-valued storage performance based on interface oxygen vacancy | |
| CN106887519B (en) | Preparation method of resistive random access memory for realizing multi-value storage | |
| CN103915565B (en) | A kind of multistage random access memory unit and preparation method thereof | |
| CN115458680B (en) | A defect-controllable monolayer amorphous gallium oxide single- and bipolar coexisting resistive switching memory and its fabrication method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |