CN108493336A - Self-rectifying resistance-variable storing device and preparation method thereof - Google Patents
Self-rectifying resistance-variable storing device and preparation method thereof Download PDFInfo
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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
- H10N70/20—Multistable switching devices, e.g. memristors
- H10N70/24—Multistable switching devices, e.g. memristors based on migration or redistribution of ionic species, e.g. anions, vacancies
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10B—ELECTRONIC MEMORY DEVICES
- H10B63/00—Resistance change memory devices, e.g. resistive RAM [ReRAM] devices
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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
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Abstract
Present disclose provides a kind of self-rectifying resistance-variable storing devices, including：Lower electrode；Resistive material layer is formed on the lower electrode, for being used as storage medium；Barrier layer is formed in the resistive material layer, using semi-conducting material or insulating materials；And top electrode, it is formed on the barrier layer, Schottky contacts is realized with the material on the barrier layer；Wherein, it using the Schottky contacts between the top electrode and the material on the barrier layer, realizes the self-rectifying of self-rectifying resistance-variable storing device, does not need additional gating transistor or diode as gating unit；And since device has self-rectifying characteristic, the reading crosstalk in crossed array can be inhibited.
Description
Technical field
This disclosure relates to micro-electronic manufacturing and memory area more particularly to a kind of self-rectifying resistance-variable storing device and its preparation
Method.
Background technology
Memory occupies an important position in semi-conductor market, can be generally divided into volatile storage and non-volatile
Memory.Volatile storage, which refers to the information of memory, could be kept when power-up, stored when not powered
Information will lose；And non-volatility memorizer be mainly characterized by also keeping for a long time in the case of not powered storage
Information.Continuous with portable electronic device is popularized, and non-volatility memorizer becomes more and more important in Embedded Application.
Due to the explosivity expansion of the emerging markets such as Internet of Things, artificial intelligence, intelligent vehicle and virtual reality, stores and count in electric terminal
It calculates big data and needs high density in-line memory.Resistance-variable storing device is easily integrated, the spies such as low-power consumption because its is simple in structure
Sign, it is considered to be most promise to be the memory of the following Embedded Application.
Resistance-variable storing device is one metal/oxide/metal (MIM) capacitance structure makes device exist by the effect of electric signal
High resistance state (High Resistance State, HRS) and low resistance (Low Resistance State, LRS) state it
Between reversible transformation, realize store function.Since its is simple in structure, it is especially advantageous for realizing highdensity cross array structure.
The three-dimensionally integrated three-dimensional structure and vertical structure including stack of resistance-variable storing device.Wherein three-dimensional perpendicular resistive
For memory (3DVRRAM) while realizing High Density Integration, cost is lower, therefore has better application prospect.But
In the structure of three-dimensional perpendicular resistance-variable storing device, integrated diode of having no idea can only use the structure of list R.The intersecting maneuver of single R structures
Row have reading cross-interference issue since there are the current leakage paths of low resistance state.Solve the problems, such as that this method is must to connect one on R
A gate tube, such as serial transistor constitutes 1T1R structures or series diode constitutes 1D1R structures).Since 1T1R structures need
Additional gating transistor, but transistor needs to occupy the area of substrate silicon, therefore cannot be used for three-dimensionally integrated.Therefore in three-dimensional
In the structure of vertical resistance-variable storing device, needing random access memory unit i.e. has resistive characteristic to have rectification characteristic again simultaneously.
The self-rectifying resistive device reported at present largely can not achieve CMOS technology compatibility.Minority can be in standard technology
The self-rectifying device of lower preparation, operation voltage want the voltage value of matching logic device 5V to mismatch all in 6V or more with memory.
Invention content
(1) technical problems to be solved
Present disclose provides a kind of self-rectifying resistance-variable storing devices and preparation method thereof, set forth above at least partly to solve
The technical issues of.
(2) technical solution
According to one aspect of the disclosure, a kind of self-rectifying resistance-variable storing device is provided, including：Lower electrode；Resistive material
Layer, is formed on the lower electrode, for being used as storage medium；Barrier layer is formed in the resistive material layer, using partly leading
Body material or insulating materials；And top electrode, it is formed on the barrier layer, Xiao is realized with the insulating materials on the barrier layer
Te Ji is contacted；Wherein, using the Schottky contacts between the top electrode and the insulating materials on the barrier layer, self-rectifying is realized
The self-rectifying of resistance-variable storing device.
In the disclosure some embodiments, the barrier layer is a kind of metal oxide.
In the disclosure some embodiments, a kind of metal oxide includes ZrO2、HfO2、TiO2、SiO2、Ta2O5、
Y2O3、NbO3、ZnO、Tb2O3、CuO、La2O3、Ga2O3、Tb2O3、Yb2O3。
In the disclosure some embodiments, the barrier material thickness is 2nm~5nm, the self-rectifying resistance-change memory
Operation voltage between device top electrode and lower electrode is less than 5V.
In the disclosure some embodiments, the top electrode is formed on barrier layer, including simple substance W, Al, Cu, Ru,
Ti, Ta and conductive metallic compound TiN, TaN, IrO2, at least one of ITO, IZO.
In the disclosure some embodiments, barrier layer uses HfO2Material and top electrode use Pd materials.
In the disclosure some embodiments, the resistive material layer material carries out high temperature in oxygen-enriched environment by lower electrode and moves back
Fire is formed, and thickness is 5nm to 60nm.
In the disclosure some embodiments, the lower electrode includes simple substance W, Al, Ti, Ta.Ni, Hf and conductive metallization
Close object TiN, at least one of TaN.
A kind of method preparing self-rectifying resistance-variable storing device as described above another aspect of the present disclosure provides,
Including：
Step S1 forms lower electrode；
Step S2 forms resistive material layer on lower electrode layer；
Step S3 forms barrier layer on resistive material layer；And
Step S4, forms top electrode on barrier layer, and Schottky contacts are realized with the insulating materials on the barrier layer.
In the disclosure some embodiments, the lower electrode is heavy by electron beam evaporation, chemical vapor deposition, pulse laser
A kind of in product, atomic layer deposition, sputtering method preparing completion；The resistive material layer prepared by the way of thermal oxide and
At carrying out high annealing in oxygen-enriched environment using lower electrode；The barrier layer by electron beam evaporation, chemical vapor deposition,
A kind of in pulsed laser deposition, atomic layer deposition, sputtering method preparing completion；The top electrode passes through electron beam evaporation, change
Learn vapor deposition, pulsed laser deposition, atomic layer deposition, a kind of in sputtering method preparing completion.
(3) advantageous effect
It can be seen from the above technical proposal that disclosure self-rectifying resistance-variable storing device and preparation method thereof is at least with following
One of advantageous effect：
(1) by using resistive material layer as storage medium, utilizing the Schottky contacts of barrier layer and upper electrode material reality
Existing self-rectifying, does not need additional gating transistor or diode as gating unit；And since device has self-rectifying
Characteristic can inhibit the reading crosstalk in crossed array；
(2) due to not needing additional gating device, which not only can be adapted for two-dimensional friendship
Array is pitched, is equally applicable to the crossed array of three-dimensional stacking structure, and the crossed array of three-dimensional vertical structure can be integrated in, because
This substantially increases the integration density of memory, reduces cost, simple in structure, easy of integration；
(3) by using the material of completely compatible CMOS technology, barrier layer thickness is reduced, realizes low operating voltage
Self-rectifying device, operation voltage can be controlled in 5V hereinafter, being suitable for Embedded application.
Description of the drawings
Fig. 1 is the structural schematic diagram of embodiment of the present disclosure self-rectifying resistance-variable storing device.
Fig. 2 is that the embodiment of the present disclosure is based on self-rectifying resistance-variable storing device current-voltage characteristic curve figure.
Fig. 3 is flow chart prepared by embodiment of the present disclosure self-rectifying resistance-variable storing device.
Fig. 4 is the schematic diagram of lower electrode in embodiment of the present disclosure self-rectifying resistance-variable storing device preparation process.
Fig. 5 is the schematic diagram that resistive material layer is formed in embodiment of the present disclosure self-rectifying resistance-variable storing device preparation process.
Fig. 6 is the schematic diagram that barrier layer is formed in embodiment of the present disclosure self-rectifying resistance-variable storing device preparation process.
Fig. 7 is the schematic diagram that top electrode is formed in embodiment of the present disclosure self-rectifying resistance-variable storing device preparation process.
【Embodiment of the present disclosure main element symbol description in attached drawing】
101, lower electrode；201, resistive material layer
301, barrier layer；401, top electrode
Specific implementation mode
To make the purpose, technical scheme and advantage of the disclosure be more clearly understood, below in conjunction with specific embodiment, and reference
The disclosure is further described in attached drawing.
Disclosure some embodiments will be done with reference to appended attached drawing in rear and more comprehensively describe to property, some of but not complete
The embodiment in portion will be shown.In fact, the various embodiments of the disclosure can be realized in many different forms, and should not be construed
To be limited to this several illustrated embodiment；Relatively, these embodiments are provided so that the disclosure meets applicable legal requirement.
In first exemplary embodiment of the disclosure, a kind of self-rectifying resistance-variable storing device is provided.Fig. 1 is the disclosure
The structural schematic diagram of first embodiment self-rectifying resistance-variable storing device.As shown in Figure 1, self-rectifying resistance-variable storing device is from bottom to top successively
Including lower electrode 101, resistive material layer 201, barrier layer 301 and top electrode 401, which has the work(of electric resistance changing
Can, while there is self-rectifying characteristic.
Each component part of the present embodiment self-rectifying resistance-variable storing device is described in detail individually below.
Lower electrode 101 can be by simple substance W, Al, Ti, one kind in Ta.Ni, Hf and conductive metallic compound TiN, TaN
Or several compositions, by electron beam evaporation, one in chemical vapor deposition, pulsed laser deposition, atomic layer deposition, sputtering method
Kind prepares completion, and the thickness and shape of lower electrode 101 are not limited by the present embodiment.
The resistive material layer 201 being formed on lower electrode 101, material thickness are 5nm to 60nm, resistive material layer 201
It as storage medium, is prepared by the way of thermal oxide, that is, electrode is descended to pass through in O2Or O3Atmosphere in carry out high temperature move back
Fire, annealing temperature are 200 DEG C to 400 DEG C, and oxidization time is not limited by the present embodiment.
It is formed in the barrier layer 301 on resistive material layer 201, it can be by ZrO2、HfO2、TiO2、SiO2、Ta2O5、Y2O3、
NbO3、ZnO、Tb2O3、CuO、La2O3、Ga2O3、Tb2O3、Yb2O3Equal metal oxides are formed.In some embodiments, the resistance
Barrier 301 uses a kind of metal oxide matched completely, the metal oxide matched completely i.e. metal to be in highest price
The oxide of state, material thickness are 2nm~5nm, pass through electron beam evaporation, chemical vapor deposition, pulsed laser deposition, atomic layer
Deposition, a kind of in sputtering method preparing completion.Since barrier layer thickness is smaller, operation voltage can control in 5V hereinafter,
Suitable for Embedded application.
The top electrode 401 being formed on barrier layer 301, can be by simple substance W, Al, Cu, Ru, Ti, Ta and conductive gold
Belong to compound TiN, TaN, IrO2, one or more of ITO, IZO constitute, pass through electron beam evaporation, chemical vapor deposition, arteries and veins
A kind of in impulse light deposition, atomic layer deposition, sputtering method preparing completion, and the thickness and shape of metal electrode are not implemented by this
Example limitation.
Wherein, Schottky contacts self-rectifying is realized using barrier layer 301 and 401 material of top electrode, due to metal and blocking
There are the differences of work function for the contact of the material of layer, so a schottky junction can be formed, are equivalent to Schottky diode
Effect, therefore rectification may be implemented, additional gating transistor or diode are not needed as gating unit, in addition, due to
The resistive device does not need additional gating device, which not only can be adapted for two-dimensional intersecting maneuver
Row, are equally applicable to the crossed array of three-dimensional stacking structure, which has the integration density of bigger and lower cost.Cause
This, the invention of the device substantially increases the integration density of memory, reduces cost, simple in structure, easy of integration.
As preferred case study on implementation, the lower electrode of self-rectifying resistance-variable storing device provided in this embodiment uses W materials, resistance
Change material layer uses WOxMaterial, barrier layer use HfO2Material and top electrode use Pd materials.
Fig. 2 is that the present embodiment is based on self-rectifying resistance-variable storing device current-voltage characteristic curve figure.As shown in Fig. 2, the W/
WOxThe current-voltage characteristic curve that the resistance-variable storing device that/HfO/Pd is formed obtains under dc sweeps pattern, the resistive are deposited
Memory device is initially located in low resistive state " 1 ", and when applying bias reaches -3V, the resistive memory turns from low resistive state " 1 "
Become high-impedance state " 0 "；When reusing backward voltage scanning, resistive memory is changed into low resistance state from high-impedance state " 0 " again
" 1 ", from can clearly be seen that low resistance state is in symmetrical rectification characteristic under generating positive and negative voltage in curve, in the reading voltage of ± 0.35V
Under, forward current and negative current ratio>100, have the function of rectifier diode, crossed array knot can be effectively inhibited in this way
Reading crosstalk in structure avoids misreading generation.
So far, first embodiment of the present disclosure self-rectifying resistance-variable storing device introduction finishes.
In second exemplary embodiment of the disclosure, a kind of preparation method of self-rectifying resistance-variable storing device is provided.
Fig. 3 is flow chart prepared by embodiment of the present disclosure self-rectifying resistance-variable storing device.Below in conjunction with Fig. 3 to Fig. 7, self-rectifying is described in detail
The preparation process of resistance-variable storing device.
Step S1 forms lower electrode 101.Fig. 4 is lower electricity in embodiment of the present disclosure self-rectifying resistance-variable storing device preparation process
The schematic diagram of pole.
As shown in figure 4, electroless plating may be used for lower electrode 101 or the method for sputtering is formed, preferably, this
Electrode under W is formed using the method for sputtering in embodiment, following process conditions may be used and carry out：Power 25W~500W；Pressure
By force：0.1Pa~100Pa；Ar throughputs：0.5sccm~100sccm, thickness are 10nm~500nm.
Step S2 forms resistive material layer 201 on 101 layers of lower electrode.Fig. 5 is that embodiment of the present disclosure self-rectifying resistive is deposited
The schematic diagram of resistive material layer is formed in reservoir preparation process.
As shown in figure 5, resistive material layer is formed by the way of carrying out thermal annealing in oxygen-enriched environment, as preferred side
Case, the method that using plasma oxygen atmosphere high temperature is annealed in this programme form WOx, carried out using following process conditions：
Power 100W~200W；Temperature：200 DEG C~400 DEG C, thickness is 5nm~30nm.
Step S3 forms barrier layer 301 on resistive material layer 201.Fig. 6 is that embodiment of the present disclosure self-rectifying resistive is deposited
The schematic diagram on barrier layer is formed in reservoir preparation process.
As shown in fig. 6, preferably, HfO is used in the present embodiment2As barrier layer, pass through atomic layer deposition
Method is formed.It is carried out using following process conditions：Growth temperature：250 DEG C, the pressure in reaction chamber：Less than 2mBar, thickness
For 2nm~5nm.
Step S4 forms top electrode 401 on barrier layer 301.Fig. 7 is embodiment of the present disclosure self-rectifying resistance-variable storing device
The schematic diagram of top electrode is formed in preparation process.
As shown in fig. 7, preferably, upper electrode material uses Pd in the present embodiment, is formed by the method for sputtering,
Process conditions are as follows：Power 25W~500W；Pressure：0.1Pa~100Pa；Ar throughputs：0.5sccm~100sccm, thickness
For 10nm~500nm.
So far, prepared by resistance-variable storing device shown in Fig. 1 completes.
Certainly, according to actual needs, the preparation method of disclosure self-rectifying resistance-variable storing device also include other techniques and
Step, since the innovation of the same disclosure is unrelated, details are not described herein again.
In order to achieve the purpose that brief description, in above-described embodiment 1, any technical characteristic narration for making same application is all
And in this, without repeating identical narration.
So far, the preparation method introduction of second embodiment of the present disclosure self-rectifying resistance-variable storing device finishes.
So far, attached drawing is had been combined the embodiment of the present disclosure is described in detail.It should be noted that in attached drawing or saying
In bright book text, the realization method for not being painted or describing is form known to a person of ordinary skill in the art in technical field, and
It is not described in detail.In addition, the above-mentioned definition to each element and method be not limited in mentioning in embodiment it is various specific
Structure, shape or mode, those of ordinary skill in the art simply can be changed or replaced to it.
It should also be noted that, the direction term mentioned in embodiment, for example, "upper", "lower", "front", "rear", " left side ",
" right side " etc. is only the direction of refer to the attached drawing, not is used for limiting the protection domain of the disclosure.Through attached drawing, identical element by
Same or similar reference numeral indicates.When that understanding of this disclosure may be caused to cause to obscure, conventional structure will be omitted
Or construction.
And the shape and size of each component do not reflect actual size and ratio in figure, and only illustrate the embodiment of the present disclosure
Content.In addition, in the claims, any reference mark between bracket should not be configured to the limit to claim
System.
It unless there are known entitled phase otherwise anticipates, the numerical parameter in this specification and appended claims is approximation, energy
Enough required characteristic changings according to as obtained by content of this disclosure.Specifically, all be used in specification and claim
The number of the middle content for indicating composition, reaction condition etc., it is thus understood that repaiied by the term of " about " in all situations
Decorations.Under normal circumstances, the meaning expressed refers to including by specific quantity ± 10% variation in some embodiments, at some
± 5% variation in embodiment, ± 1% variation in some embodiments, in some embodiments ± 0.5% variation.
Furthermore word "comprising" does not exclude the presence of element or step not listed in the claims.Before element
Word "a" or "an" does not exclude the presence of multiple such elements.
In addition, unless specifically described or the step of must sequentially occur, there is no restriction in the above institute for the sequence of above-mentioned steps
Row, and can change or rearrange according to required design.And above-described embodiment can be based on the considerations of design and reliability, that
This mix and match is used using or with other embodiment mix and match, i.e., the technical characteristic in different embodiments can be freely combined
Form more embodiments.
Those skilled in the art, which are appreciated that, to carry out adaptively the module in the equipment in embodiment
Change and they are arranged in the one or more equipment different from the embodiment.It can be the module or list in embodiment
Member or component be combined into a module or unit or component, and can be divided into addition multiple submodule or subelement or
Sub-component.Other than such feature and/or at least some of process or unit exclude each other, it may be used any
Combination is disclosed to all features disclosed in this specification (including adjoint claim, abstract and attached drawing) and so to appoint
Where all processes or unit of method or equipment are combined.Unless expressly stated otherwise, this specification (including adjoint power
Profit requires, abstract and attached drawing) disclosed in each feature can be by providing the alternative features of identical, equivalent or similar purpose come generation
It replaces.Also, in the unit claims listing several devices, several in these devices can be by same hard
Part item embodies.
Similarly, it should be understood that in order to simplify the disclosure and help to understand one or more of each open aspect,
Above in the description of the exemplary embodiment of the disclosure, each feature of the disclosure is grouped together into single implementation sometimes
In example, figure or descriptions thereof.However, the method for the disclosure should be construed to reflect following intention：It is i.e. required to protect
The disclosure of shield requires features more more than the feature being expressly recited in each claim.More precisely, as following
Claims reflect as, open aspect is all features less than single embodiment disclosed above.Therefore,
Thus the claims for following specific implementation mode are expressly incorporated in the specific implementation mode, wherein each claim itself
All as the separate embodiments of the disclosure.
Particular embodiments described above has carried out further in detail the purpose, technical solution and advantageous effect of the disclosure
It describes in detail bright, it should be understood that the foregoing is merely the specific embodiment of the disclosure, is not limited to the disclosure, it is all
Within the spirit and principle of the disclosure, any modification, equivalent substitution, improvement and etc. done should be included in the guarantor of the disclosure
Within the scope of shield.
Claims (10)
1. a kind of self-rectifying resistance-variable storing device, including：
Lower electrode；
Resistive material layer is formed on the lower electrode, for being used as storage medium；
Barrier layer is formed in the resistive material layer, using semi-conducting material or insulating materials；And
Top electrode is formed on the barrier layer, and Schottky contacts are realized with the material on the barrier layer；
Wherein, using the Schottky contacts between the top electrode and the material on the barrier layer, self-rectifying resistance-change memory is realized
The self-rectifying of device.
2. self-rectifying resistance-variable storing device according to claim 1, the barrier layer is a kind of metal oxide.
3. self-rectifying resistance-variable storing device according to claim 2, a kind of metal oxide includes ZrO2、HfO2、
TiO2、SiO2、Ta2O5、Y2O3、NbO3、ZnO、Tb2O3、CuO、La2O3、Ga2O3、Tb2O3、Yb2O3。
4. self-rectifying resistance-variable storing device according to claim 1, the barrier material thickness is 2nm~5nm, it is described from
Operation voltage between rectification resistance-variable storing device top electrode and lower electrode is less than 5V.
5. self-rectifying resistance-variable storing device according to claim 1, the top electrode is formed on barrier layer, including simple substance
W, Al, Cu, Ru, Ti, Ta and conductive metallic compound TiN, TaN, IrO2, at least one of ITO, IZO.
6. self-rectifying resistance-variable storing device according to claim 1, wherein barrier layer uses HfO2Material and top electrode are adopted
With Pd materials.
7. self-rectifying resistance-variable storing device according to claim 1, the resistive material layer material is by lower electrode in oxygen-enriched ring
It carries out high annealing in border to be formed, thickness is 5nm to 60nm.
8. self-rectifying resistance-variable storing device according to claim 1, the lower electrode includes simple substance W, Al, Ti, Ta.Ni, Hf
And conductive metallic compound TiN, at least one of TaN.
9. a kind of method preparing the self-rectifying resistance-variable storing device as described in any one of claim 1 to 8, including：
Step S1 forms lower electrode；
Step S2 forms resistive material layer on lower electrode layer；
Step S3 forms barrier layer on resistive material layer；And
Step S4, forms top electrode on barrier layer, and Schottky contacts are realized with the insulating materials on the barrier layer.
10. preparation method according to claim 9, wherein
The lower electrode passes through in electron beam evaporation, chemical vapor deposition, pulsed laser deposition, atomic layer deposition, sputtering method
A kind of preparing completion；
The resistive material layer is prepared by the way of thermal oxide, and carrying out high temperature in oxygen-enriched environment using lower electrode moves back
Fire；
The barrier layer passes through in electron beam evaporation, chemical vapor deposition, pulsed laser deposition, atomic layer deposition, sputtering method
A kind of preparing completion；
The top electrode passes through in electron beam evaporation, chemical vapor deposition, pulsed laser deposition, atomic layer deposition, sputtering method
A kind of preparing completion.
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