CN105870321A - Nonlinear self-rectifying resistive random access memory and preparation method therefor - Google Patents
Nonlinear self-rectifying resistive random access memory and preparation method therefor 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 without a potential-jump barrier or surface barrier, and specially adapted for rectifying, amplifying, oscillating or switching
- H10N70/801—Constructional details of multistable switching 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 without a potential-jump barrier or surface barrier, and specially adapted for rectifying, amplifying, oscillating or switching
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Abstract
The invention provides a nonlinear self-rectifying resistive random access memory. The nonlinear self-rectifying resistive random access memory comprises a substrate and a bottom electrode- resistive random layer-energy band modifying layer-top electrode structure arranged on the substrate. The invention also provides a preparation method for the nonlinear self-rectifying resistive random access memory; the preparation method comprises the following steps of 1) defining a bottom electrode pattern, and preparing the bottom electrode on the substrate according to the pattern; 2) depositing the resistive random layer on the bottom electrode by adopting a PVD method, an ALD method or a CVD method; 3) depositing the energy band modifying layer on the resistive random layer by adopting the PVD method or the ALD method; 4) defining a bottom electrode lead-out hole pattern, and etching the bottom electrode lead-out holes in the resistive random layer and the energy band modifying layer according to the pattern; and 5) defining a top electrode pattern, and preparing the top electrode on the modifying layer according to the pattern.
Description
Technical field
The invention belongs to quasiconductor and CMOS hybrid-intergated-circuit technique field, be specifically related to a kind of non-linear self-rectifying resistive and deposit
Reservoir (resistive random access memory, RRAM) and preparation method thereof.
Background technology
In recent years, along with the further development of integrated circuit, size reduction, lower power consumption and the Gao Ji to nonvolatile memory
The requirement of Cheng Du etc. improves constantly, and accounts for the flash memory (flash) of Vehicles Collected from Market dominant contribution due in sides such as size reduction, power consumption and speed
The restriction in face, can not fully meet the requirement of nonvolatile memory development.
Emerging resistance-variable storing device has obtained paying close attention to widely in semiconductor integrated circuit field, and resistance-variable storing device is in high integration, low
The advantage of the aspect such as power consumption and read or write speed has made the contenders in memorizer of new generation.Resistance-variable storing device relies on
Realize State Transferring reversible between high-impedance state (" 0 " state) and low resistance state (one state) under different applied voltage excitations, removing
High-impedance state and low resistance state can be kept after voltage drive, thus realize the non-volatile memories of data.Resistance-variable storing device is by structure letter
The sandwich structure of single metal-change resistance layer-metal is constituted, and therefore can realize ultra-large by simple crossbar structure
With the resistance-variable storing device array of very high-density, reducing owing to increasing the area consumption that transistor is brought as selection pipe, it is special
Levy dimensioned area and can be reduced to 4F2.Additionally, integration density can form 3D by stacked multilayer crossbar structure further
Crossbar structure improves.
But, owing in array, reading of device resistance needs reading to flow through the size of current of this device to judge that device is in height
Resistance state or low resistance state.Under worst case, if a device being in high resistant in crossbar array to be read, and its week
When the device enclosed is in low resistance state, when reading the device being in high-impedance state, electric current can walk around this device being in high-impedance state,
And on low-resistance device around, form sneak electric current.Now, the electric current that reads is actual is in low resistance state about for flowing through
The sneak current value of device, causes and misreads.Research shows, the cross-interference issue of array can bring the maloperation of device, limits battle array
The integrated level of row, increases some row problems such as power consumption of array, significantly limit the memory density of crossbar structure.
At present, in order to solve the cross-interference issue in resistance-variable storing device crossbar array, the array element structure master of resistance-variable storing device
It is divided into two kinds: active array, 1T1R (One Transistor One RRAM) construction unit；Passive array, 1S1R (One
Selector One RRAM) construction unit.In the device cell of the 1T1R structure of active array, device area is risen decisive
Factor is the area of transistor, and reset current needs higher in order to meet resistive device in addition, the increase of source and drain area can be entered
One step increases the area of transistor, and this just greatly limit the integration density of storage array, and losing resistance-variable storing device can be highly dense
Spend integrated advantage.1S1R (one selector one RRAM) although structure eliminate the loss of area, but be the increase in
The step of technique, the pipe that selects simultaneously also required that must have good mating with resistance-variable storing device, have one in actual applications
Fixed limitation.
Summary of the invention
In view of above-mentioned deficiency, the present invention proposes a kind of non-linear self-rectifying resistance-variable storing device and preparation method thereof, passes based on using
System CMOS technology realizes having non-linear self-rectifying resistive memory, even eliminates resistance-variable storing device to reducing
Cross-interference issue present in crossbar structure.
In order to solve above-mentioned technical problem, the technical solution used in the present invention is as follows:
A kind of non-linear self-rectifying resistance-variable storing device, including substrate and the hearth electrode-change resistance layer-energy band decorative layer-top being positioned on substrate
Electrode structure.
Further, described hearth electrode-change resistance layer-energy band decorative layer-top electrode structure is metal-insulator-insulator-metal
(Metal-Insulator-Insulator-Metal) capacitance structure or metal-semiconductor-SEMICONDUCTOR-METAL (Metal-Semiconductor-
Semiconductor-Metal) capacitance structure.
Further, described substrate uses silicon or glass；
Described hearth electrode and top electrode use metal material, and thickness is 50nm-200nm；
Described change resistance layer uses the transition metal oxide with resistive characteristic, and thickness is 5nm-50nm；Or employing organic material,
Thickness is 200nm-500nm；
Described energy band decorative layer uses oxide, and thickness is 1-20nm.
Further, described metal material is Ti, Al, Au, W, Cu, Ta, Pt, Ir or TiN, TaN；
Described transition metal oxide is TaOx、HfOx、SiOxOr SrTiO3, described organic material is parylene；
Described oxide is SiO2、TiO2Or HfO2。
The preparation method of a kind of non-linear self-rectifying resistance-variable storing device, comprises the steps:
1) definition hearth electrode figure, prepares hearth electrode according to this figure on substrate；
2) PVD (physical vapor deposition), the method for ALD (atomic layer deposition) or CVD (chemical vapor deposition) is used to exist
Change resistance layer is deposited on hearth electrode；
3) using the method for PVD or ALD to deposit on change resistance layer can band decorative layer；
4) definition hearth electrode fairlead figure, at change resistance layer and can etch hearth electrode fairlead by band decorative layer according to this figure；
5) definition top electrode figure, prepares top electrode according to this figure on decorative layer.
Further, described step 1), 4) and 5) defined in the method for figure be to utilize photoetching technique to define on a photoresist
Figure.
Further, the preparation method of described hearth electrode and top electrode includes PVD and evaporation deposition method.
Further, described change resistance layer uses the transition metal oxide with resistive characteristic, and thickness is 5nm-50nm；Or use
Organic material, thickness is 200nm-500nm；
Further, described energy band decorative layer uses oxide, and thickness is 1-20nm.
The present invention proposes a kind of non-linear self-rectifying resistance-variable storing device and preparation method thereof, can be embedded into resistive and deposit by band decorative layer
In reservoir formed double-decker, utilize can band decorative layer material thickness change, and appropriate design change resistance layer, can band decorative layer and
Band structure coupling between electrode material, it is possible to achieve the I-E characteristic of resistive memory is optimized, makes this resistive
Memorizer shows symmetrical two-way non-linear self-rectifying characteristic.This resistance-variable storing device has symmetrical two-way non-linear self-rectifying characteristic,
The crossbar array of its composition either reads low resistance state or high-impedance state, due to the existence of non-linear rectifying section, script
Resistance on the path of crossfire is significantly larger than resistance to be read, it is possible to effectively suppresses crossfire, thus keeps away
Exempt to misread, the scale of mass production of the integration density and resistance-variable storing device that improve storage array is had great significance.It addition, should
Preparation method is mutually compatible with traditional cmos process, low cost, easily comes into operation.
Accompanying drawing explanation
Fig. 1 is the current-voltage characteristic curve figure of this non-linear self-rectifying resistance-variable storing device.
In figure: by high-impedance state to the transition process of low resistance state under the excitation of S1-forward voltage；S2-low resistance state keeps process；S3-
The non-linear switching process of forward low resistance state；The non-linear switching process of S4-negative sense low resistance state；By low-resistance under the excitation of S5-negative voltage
State is to the transition process of high-impedance state；S6-high-impedance state keeps process.
Fig. 2 (A)-2 (E) is corresponding to the enforcement step of each embodiment.
Fig. 3 is crossbar array and crossfire path schematic diagram.
Detailed description of the invention
Features described above and advantage for making the present invention can become apparent, special embodiment below, and coordinate institute's accompanying drawing to make specifically
Bright as follows.
Embodiment 1
The present embodiment 1 provides a kind of non-linear self-rectifying resistance-variable storing device and preparation method thereof, and this resistance-variable storing device uses silicon substrate,
Use Pt as hearth electrode material, use Ta2O5(or oxide of its non-chemical proportion), as change resistance layer material, uses SiO2
As energy band decorative layer material, use Ta as top electrode material.
Ta2O5And SiO2It is all material compatible with standard CMOS process.Based on Ta2O5Resistance-variable storing device have excellence
Memory performance, including the durability of superelevation, ultrafast switching speed and good retention performance.Additionally, Ta2O5Also have
The features such as heat stability height, chemical property torpescence.SiO2As the gate dielectric material in highly developed CMOS technology, material
Material character and parameter are readily apparent from, and prepare simple and the most controlled.The Dominant Facies of bi-material combines, and adds rational physical machine
The design in preparative layer face, had both met the requirement of CMOS technique compatible, can realize again the two-way non-linear self-rectifying spy of resistance-variable storing device
Property, lifting and large-scale production for resistance-variable storing device crossbar array of structures integration density have great significance.
The preparation method of this non-linear self-rectifying resistance-variable storing device is as follows:
1) utilize photoetching technique to define hearth electrode figure on a photoresist, use PVD method to deposit Pt hearth electrode on a silicon substrate
Material, thickness is 50nm, then removes photoresist, as shown in Fig. 2 (A)；
2) PVD method is used to deposit one layer of Ta on hearth electrode2O5Change resistance layer thin-film material, thickness is 20nm, such as Fig. 2 (B)
Shown in；
3) PVD method is used to deposit one layer of SiO on change resistance layer2Two-way non-linear self-rectifying can be realized by band decorative layer material, thick
Degree is 5nm, as shown in Fig. 2 (C)；
4) the hearth electrode fairlead figure first defining out on a photoresist by photoetching technique, then use the method for dry etching in resistance
Change layer and energy band decorative layer etch hearth electrode fairlead, and remove photoresist, as shown in Fig. 2 (D)；
5) utilize photoetching technique to define top electrode figure on a photoresist, use PVD method can deposit Ta top on band decorative layer
Electrode material, thickness is 200nm, then removes photoresist and i.e. obtain this resistance-variable storing device, as shown in Fig. 2 (E).
Embodiment 2
The present embodiment 2 provides a kind of non-linear self-rectifying resistance-variable storing device and preparation method thereof, and this resistance-variable storing device uses silicon substrate,
Use TaN as hearth electrode material, use SrTiO3As change resistance layer material, use HfO2As energy band decorative layer material,
Use TaN as top electrode material.
The preparation method of this non-linear self-rectifying resistance-variable storing device is as follows:
1) utilize photoetching technique to define hearth electrode figure on a photoresist, use evaporation deposition method to deposit TaN on a silicon substrate
Hearth electrode material, thickness is 200nm, then removes photoresist；
2) PVD method is used to deposit one layer of SrTiO on hearth electrode3Change resistance layer thin-film material, thickness is 50nm；
3) ALD method is used to deposit one layer of HfO on change resistance layer2Two-way non-linear self-rectifying can be realized by band decorative layer material, thick
Degree is 20nm；
4) the hearth electrode fairlead figure first defining out on a photoresist by photoetching technique, then use the method for dry etching in resistance
Change layer and energy band decorative layer etch hearth electrode fairlead, and remove photoresist；
5) utilize photoetching technique to define top electrode figure on a photoresist, use PVD method can deposit TaN on band decorative layer
Top electrode material, thickness is 50nm, then removes photoresist and i.e. obtain this resistance-variable storing device.
Embodiment 3
The present embodiment 3 provides a kind of non-linear self-rectifying resistance-variable storing device and preparation method thereof, and this resistance-variable storing device uses glass lined
The end, use Ir as hearth electrode material, use HfO2As change resistance layer material, use TiO2As energy band decorative layer material,
Use TiN as top electrode material.
The preparation method of this non-linear self-rectifying resistance-variable storing device is as follows:
1) utilize photoetching technique to define hearth electrode figure on a photoresist, use evaporation deposition method to deposit Ir on a glass substrate
Hearth electrode material, thickness is 100nm, then removes photoresist；
2) ALD method is used to deposit one layer of HfO on hearth electrode2Change resistance layer thin-film material, thickness is 5nm；
3) PVD method is used to deposit one layer of TiO on change resistance layer2Two-way non-linear self-rectifying can be realized by band decorative layer material, thick
Degree is 1nm；
4) the hearth electrode fairlead figure first defining out on a photoresist by photoetching technique, then use the method for dry etching in resistance
Change layer and energy band decorative layer etch hearth electrode fairlead, and remove photoresist；
5) utilize photoetching technique to define top electrode figure on a photoresist, use evaporation deposition method can deposit on band decorative layer
TiN top electrode material, thickness is 100nm, then removes photoresist and i.e. obtain this resistance-variable storing device.
Embodiment 4
The present embodiment 4 provides a kind of non-linear self-rectifying resistance-variable storing device and preparation method thereof, the layers of material of this resistance-variable storing device
Composition and thickness are identical with embodiment 1, and its preparation method difference is change resistance layer and can all use ALD by band decorative layer
Method deposit is made.
Embodiment 5
The present embodiment 5 provides a kind of non-linear self-rectifying resistance-variable storing device and preparation method thereof, the change resistance layer material of this resistance-variable storing device
Organic material parylene selected by material, uses CVD method to be prepared, and thickness is 500nm, other composition, preparation method
And parameter is identical with embodiment 1.
Embodiment 6
The present embodiment 6 provides a kind of non-linear self-rectifying resistance-variable storing device and preparation method thereof, the change resistance layer material of this resistance-variable storing device
Organic material parylene selected by material, uses CVD method to be prepared, and thickness is 350nm, other composition, preparation method
And parameter is identical with embodiment 4.
Embodiment 7
The present embodiment 7 provides a kind of non-linear self-rectifying resistance-variable storing device and preparation method thereof, the change resistance layer material of this resistance-variable storing device
Organic material parylene selected by material, uses CVD method to be prepared, and thickness is 200nm, other composition, preparation method
And parameter is identical with embodiment 4.
From above-described embodiment, prepare transition metal oxide change resistance layer thin-film material and energy decorative layer material, both can adopt
Using PVD method, it would however also be possible to employ ALD method, compared with PVD method, ALD method can be prepared thinner；Preparation has
Machine material is made change resistance layer and is used CVD method.
The one non-linear self-rectifying resistance-variable storing device provided for the present invention, uses its resistive mistake that DC Sweep mode obtains
Current-voltage (I-V) characteristic of journey is as it is shown in figure 1, in figure, by high-impedance state to low resistance state under the excitation of S1 forward voltage
Transition process；S2 low resistance state keeps process；The non-linear switching process of S3 forward low resistance state；S4 negative sense low resistance state is non-linear
Switching process；By low resistance state to the transition process of high-impedance state under the excitation of S5 negative voltage；S6 high-impedance state keeps process.Logical
Cross the hearth electrode ground connection making this resistance-variable storing device, then the voltage of top electrode can control the resistance of this resistance-variable storing device so that it is occurs
Conversion between high resistant and low-resistance, i.e. this resistance-variable storing device " 0 ", the conversion between " 1 " two states, it was demonstrated that resistance can be realized
Change effect, under the operation of positively and negatively voltage, its current-voltage characteristic curve can show the Nonlinear Integer of near symmetrical
Stream effect.
By formation double-decker can be embedded in resistance-variable storing device by band decorative layer, utilize the thickness change of energy band decorative layer material,
And the band structure coupling between appropriate design change resistance layer, energy band decorative layer and electrode material, it is possible to achieve to resistive memory
I-E characteristic is optimized.This is because, if the energy gap material more than change resistance layer energy gap can be selected band decorative layer
At the bottom of material, and the conduction band of energy band decorative layer material at the bottom of higher than the conduction band of resistive material, metal electrode selects the material that work function is bigger simultaneously
Material, then can form higher potential barrier with electrode by band decorative layer, if now energy band decorative layer material thickness is relatively thin, electronics is permissible
By the way of tunnelling, arrive change resistance layer, and tunnelling current has nonlinear characteristic, it is thereby achieved that non-linear self-rectifying
Characteristic.
Fig. 3 is crossbar array and crossfire path schematic diagram, as seen from the figure, due to the reading of this device resistance in array,
Need to read and flow through the size of current of this device to judge that device is in high-impedance state or low resistance state.Under worst case, if wanted
Read a device being in high resistant in crossbar array, and when device about is in low resistance state, when reading is in
During the device of high-impedance state, electric current can walk around this device being in high-impedance state, and forms sneak electricity on low-resistance device around
Stream.In this case, in crossbar structure, the shortest path that crossfire can flow through such as unchecked three devices in figure
Part, when i.e. elected middle device (device in dotted line in figure) is Vread voltage, actual point of each device on crosstalk path
Pressure is 1/3rd Vread, and the electric current that reads is actual is the sneak current value flowing through and being in low resistance state device about, causes
Misread.If device uses the non-linear self-rectifying resistance-variable storing device that the present invention provides, can from Fig. 1 i-v curve
Electric current when going out the high-impedance state of Vread reading is greater than the low resistance state electric current that 1/3rd Vread read, i.e. due to low resistance state
Non-linear self-rectification effect, the resistance of read path is less than crosstalk path, so restrained effectively crosstalk, during negative voltage
As the same.It follows that two-way non-linear self-rectification effect can suppress the crosstalk in crossbar array effectively during low resistance state.
Above example is only limited in order to technical scheme to be described, those of ordinary skill in the art can
Technical scheme is modified or equivalent, without departing from the spirit and scope of the present invention, the guarantor of the present invention
The scope of protecting should be as the criterion with described in claim.
Claims (9)
1. a non-linear self-rectifying resistance-variable storing device, it is characterised in that include substrate and the hearth electrode-change resistance layer-energy band decorative layer-top electrode structure being positioned on substrate.
Non-linear self-rectifying resistance-variable storing device the most according to claim 1, it is characterized in that, described hearth electrode-change resistance layer-energy band decorative layer-top electrode structure is metal-insulator-insulator-metal capacitance structure or metal-semiconductor-SEMICONDUCTOR-METAL capacitance structure.
Non-linear self-rectifying resistance-variable storing device the most according to claim 1, it is characterised in that
Described substrate uses silicon or glass；
Described hearth electrode and top electrode use metal material, and thickness is 50nm-200nm；
Described change resistance layer uses the transition metal oxide with resistive characteristic, and thickness is 5nm-50nm；Or employing organic material, thickness is 200nm-500nm；
Described energy band decorative layer uses oxide, and thickness is 1-20nm.
Non-linear self-rectifying resistance-variable storing device the most according to claim 3, it is characterised in that
Described metal material is Ti, Al, Au, W, Cu, Ta, Pt, Ir or TiN, TaN；
Described transition metal oxide is TaOx, HfOx, SiOx or SrTiO3, described organic material is parylene；
Described oxide is SiO2、TiO2Or HfO2。
5. a preparation method for non-linear self-rectifying resistance-variable storing device, comprises the steps:
1) definition hearth electrode figure, prepares hearth electrode according to this figure on substrate；
2) method of PVD, ALD or CVD is used to deposit change resistance layer on hearth electrode；
3) using the method for PVD or ALD to deposit on change resistance layer can band decorative layer；
4) definition hearth electrode fairlead figure, at change resistance layer and can etch hearth electrode fairlead by band decorative layer according to this figure；
5) definition top electrode figure, prepares top electrode according to this figure on decorative layer.
Preparation method the most according to claim 5, it is characterised in that described step 1), 4) and 5) defined in the method for figure be to utilize photoetching technique to define figure on a photoresist.
Preparation method the most according to claim 5, it is characterised in that the preparation method of described hearth electrode and top electrode includes PVD and evaporation deposition method.
Preparation method the most according to claim 5, it is characterised in that described change resistance layer uses the transition metal oxide with resistive characteristic, and thickness is 5nm-50nm；Or employing organic material, thickness is 200nm-500nm.
Preparation method the most according to claim 5, it is characterised in that described energy band decorative layer uses oxide, and thickness is 1-20nm.
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| CN110752293A (en) * | 2019-09-27 | 2020-02-04 | 北京大学 | Bidirectional threshold switch selection device and preparation method thereof |
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