CN105185903B - A kind of preparation method of resistor-type memory cell - Google Patents
A kind of preparation method of resistor-type memory cell Download PDFInfo
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- CN105185903B CN105185903B CN201510503866.9A CN201510503866A CN105185903B CN 105185903 B CN105185903 B CN 105185903B CN 201510503866 A CN201510503866 A CN 201510503866A CN 105185903 B CN105185903 B CN 105185903B
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Abstract
A kind of preparation method of resistor-type memory cell, it is related to nonvolatile semiconductor memory member technical field, first, with conductive material formation lower electrode layer on substrate, deposition or one layer of insulating medium layer of spin coating on lower electrode layer, groove is formed on insulating medium layer by photoetching process, the bottom land of groove passes to lower electrode layer；Then, the functional layer of resistor-type memory cell is formed in groove, the functional layer is upper and lower two layers of laminated construction, and it is by amorphous SnOxLayer and nitrogen oxides MnOxNyLayer laminate is constituted, amorphous SnOxMiddle x span is 0<x<2, nitrogen oxides MnOxNyIn x and y span be respectively 1<x<2,0.001<y<2；Finally, the flush of upper electrode layer and insulating medium layer is made using flatening process with conductive material formation upper electrode layer on a functional, you can.Resistor-type memory cell prepared by the present invention can stably realize multilevel storage, it is possible to increase the storage density and stability of memory cell.
Description
Technical field
The present invention relates to nonvolatile semiconductor memory member technical field, and in particular to a kind of resistive formula of high density thin membrane structure
The preparation method of memory cell.
Background technology
Developed rapidly recently as computer technology, Internet technology, nonvolatile semiconductor memory member is in semiconductor row
Play the part of more and more important role in industry.In nonvolatile semiconductor memory member, though when power supply be cut off, the elementary cell of device
Still keep the data stored in elementary cell.Resistive random access memory (RRAM)（Resistive Random Access Memory,
RRAM）It is a kind of new nonvolatile memory, the mechanism of its work is to trigger reversible resistance transition effect in external electric field, that is, is existed
In the presence of applied voltage, the resistance of device is in low resistance state（“0”）And high-impedance state（“1”）Between reversible transition, it is and resulting
Resistance external electric field removal after can remain behind.Resistor-type memory due to high read or write speed, high integration and
The features such as multilevel storage ability, and as the focus studied at this stage.
Resistive memory is usually metal-oxide-metal sandwich structure, can pass through conventional filming technology
Such as sputter, prepared by the technique that is vapor-deposited；Meanwhile, be present multilevel electric resistance changing phenomenon in resistive memory, do not changing
The storage of more information can be realized under conditions of unit volume, and it is good with semiconductor technology compatibility, it is possible to use it is existing
Some semiconductor process technique production, can reduce development cost significantly.
On the premise of performance is ensured, the focus that storage density is existing research how is improved, storage density ability is improved
Reduce cost and improve the market competitiveness.In general, the storage density for improving memory mainly has following two modes：The first
It is, come the size of reduction unit area, typically to use cross array structure with realization theory by technique or device architecture
Minimum unit area；Second is to use multilevel memory cell, can improve storage face in the case where not increasing storage area
Product, lowers the cost of position/area, and multilevel storage refers to binary number of the record more than a bit on a node of memory
According to, so that increase the storage density of memory, raising memory capacity.
At present, researcher obtains multilevel storage and mainly obtained by improving individual layer change resistance layer, such as applies different
Reset voltages obtain the resistance of different high-impedance states, or pass through and apply different programmings electricity to one-off programming memory
The program current of pressure or different current strength, makes one-time programming memory program different low resistance states from high-impedance state, to realize
Multilevel storage.But be due to individual layer change resistance layer structures shape during reset, not no stable intermediate state, just
Cause the uniformity of the multilevel storage of individual layer resistive Rotating fields it is difficult to ensure that.
The content of the invention
It is an object of the invention to provide a kind of resistor-type memory cell for the membrane structure that change resistance performance is good, stability is good and
Its preparation method.
To achieve the above object, the technical scheme is that：A kind of resistor-type memory cell, its functional layer becomes for resistance
Change type accumulation layer, the functional layer is upper and lower two layers of laminated construction, and it is by amorphous SnOxLayer and nitrogen oxides MnOxNyLayer
Lamination is constituted, wherein, amorphous SnOxMiddle x span is 0<x<2, nitrogen oxides MnOxNyIn x and y value model
Enclose respectively 1<x<2,0.001<y<2.
The resistor-type memory cell includes substrate, lower electrode layer, functional layer, upper electrode layer and insulating medium layer, lower electricity
Pole layer is covered on substrate, and insulating medium layer is covered on lower electrode layer, and insulating medium layer passes to lower electrode layer provided with bottom land
Groove, upper electrode layer and functional layer are sequentially provided with from top to bottom in groove, functional layer is directly contacted with lower electrode layer, Top electrode
Layer is set with insulating medium layer flush.
The lower electrode layer and upper electrode layer are conducting metal, conductive metal alloy or conductive metallic compound, wherein
Conducting metal be Cu, Ag, Ti, Pt or Ni, conductive metal alloy be Pt/Ti, Cu/Ti or Cu/Au, conductive metallic compound
For TiN, TaN or ITO.
The material of the insulating medium layer is SiO2Or SiN.
The thickness of the lower electrode layer and upper electrode layer is amorphous SnO in 80-150nm, functional layerxThe thickness of layer
For 20-45nm, nitrogen oxides MnOxNyThe thickness of layer is 50-80nm, and the thickness of insulating medium layer is 300nm ~ 5000nm.
The substrate is the substrate of glass substrate, semiconductor substrate or other suitable materials.
The preparation method of the resistor-type memory cell of the present invention, comprises the following steps：
（1）, on substrate with conductive material formation lower electrode layer；
（2）, on lower electrode layer deposition or one layer of insulating medium layer of spin coating, then by photoetching process in insulating medium layer
Upper formation groove, the bottom land of groove passes to lower electrode layer；
（3）, using the method for magnetron sputtering or ald the resistor-type memory cell is formed in groove
Functional layer, the functional layer is upper and lower two layers of laminated construction, and it is by amorphous SnOxLayer and nitrogen oxides MnOxNyLayer laminate
Constitute, wherein, amorphous SnOxMiddle x span is 0<x<2, nitrogen oxides MnOxNyIn x and y span point
Wei 1<x<2,0.001<y<2；
（4）, on a functional with conductive material formation upper electrode layer, using flatening process make upper electrode layer with insulation be situated between
The flush of matter layer, you can.
Above-mentioned steps（3）In, the formation of double-decker functional layer includes amorphous SnOxFilm forming step and nitrogen oxygen
Compound MnOxNyFilm forming step, can first form amorphous SnO in groovexFilm layer, then in amorphous SnOxIt is thin
Nitrogen oxides MnO is formed in film layerxNyFilm layer, can also first form nitrogen oxides MnO in groovexNyFilm layer, then in nitrogen
Oxide M nOxNyAmorphous SnO is formed in film layerxFilm layer.
Amorphous SnOxFilm forming method：Using metallic tin as target, the reaction of magnetic-controlled sputtering coating equipment is controlled
Chamber indoor temperature is 180 DEG C ~ 200 DEG C, and O is passed through into reaction chamber2With Ar gases, metallic tin target is sent out under Ar Ions Bombardments
Raw sputtering, and with the O in reaction chamber2Collide and react, so as to form amorphous SnOxFilm.
Nitrogen oxides MnOxNyThe forming method of film layer：First, two-step method：First, using metal Mn as target, control is anti-
It is 100 ~ 400 DEG C to answer chamber indoor temperature, and O is passed through into reaction chamber2With Ar gases, metal Mn targets are sent out under Ar Ions Bombardments
Raw sputtering, and with the O in reaction chamber2Collide and react, so as to be initially formed one layer of MnOxFilm layer；Then, to MnOxLayer
N~+ implantation is carried out with by MnOxLayer is changed into nitrogen oxides MnOxNyLayer.2nd, one-step method：Using metal Mn as target, control
Reaction chamber indoor temperature is 100 ~ 400 DEG C, and O is passed through into reaction chamber2With Ar gases, while into reaction chamber inject nitrogen from
Component, metal Mn targets are sputtered under Ar Ions Bombardments, with the O in reaction chamber2Collide and the generation MnO that reactsx,
MnOxCombined with the Nitrogen ion of injection, so as to form one layer of nitrogen oxides MnOxNyFilm layer.In two methods, by controlling oxygen
X and y value are controlled with the intake of Nitrogen ion, finally makes the nitrogen oxides MnO to be formedxNyX and y span point
Wei 1<x<2,0.001<y<2.
In the preparation process in accordance with the present invention, even if amorphous Sn OxA surface part for layer is being passed through O2During absorb
Oxygen formation SnO2, the storage characteristics of this layer is not interfered with yet, because the main component or the SnO of amorphous of this layerx, 0<x<2.
Beneficial effect：
1st, the store function layer of resistor-type memory cell prepared by the present invention is by amorphous SnOxLayer and nitrogen oxides
MnOxNyThe double-decker of layer laminate formation, the store function layer of this double-decker, in the presence of current impulse, can stablize
Realize multilevel storage in ground.
2nd, resistor-type memory cell prepared by the present invention has low resistance state, stable intermediate state and high-impedance state, realizes many
The stability and uniformity of resistance state, it is possible to increase the storage density and stability of memory cell.
3rd, wherein, amorphous SnOx, can under low current operation with a very brief current impulse in stable state
To realize reset processes, current power dissipation can be reduced in storing process.Nitrogen oxides MnOxNyIn N+Movement can be real
The formation and fracture of existing room conductive channel, can also reduce the resistive voltage in storing process, reduce electric current work(during storage
Consumption.
Brief description of the drawings
The structural representation for the resistor-type memory cell that accompanying drawing 1 is prepared for the present invention；
The test chart of the I-E characteristic for the resistor-type memory cell that accompanying drawing 2 is prepared for the present invention；
The test chart of the resistance state retentivity for the resistor-type memory cell that accompanying drawing 3 is prepared for the present invention.
The drawing reference numeral of accompanying drawing 1：1st, substrate, 2, lower electrode layer, 3, insulating medium layer, 4 and 5 represent the non-of functional layer respectively
Crystalline state SnOxLayer and nitrogen oxides MnOxNyLayer, or nitrogen oxides MnO is represented respectivelyxNyLayer and amorphous Sn OxLayer, 6, upper electricity
Pole layer.
Embodiment
As shown in figure 1, resistor-type memory cell prepared by the present invention includes substrate 1, lower electrode layer 2, functional layer, Top electrode
Layer 6 and insulating medium layer 3, lower electrode layer 2 are covered on substrate 1, and insulating medium layer 3 is covered on lower electrode layer 2, dielectric
Layer 3 passes in the groove of lower electrode layer 2, groove provided with bottom land and is sequentially provided with upper electrode layer 6 and functional layer, function from top to bottom
Layer is directly contacted with lower electrode layer 2, and upper electrode layer 6 is set with the flush of insulating medium layer 3.Functional layer therein becomes for resistance
Change type accumulation layer, the functional layer is upper and lower two layers of laminated construction, and it is by amorphous SnOxLayer and nitrogen oxides MnOxNyLayer
Lamination is constituted, wherein, amorphous SnOxMiddle x span is 0<x<2, nitrogen oxides MnOxNyIn x and y value model
Enclose respectively 1<x<2,0.001<y<2.Functional layer can be that upper strata is amorphous SnOxLayer, lower floor is nitrogen oxides MnOxNy
Layer or upper strata are nitrogen oxides MnOxNyLayer, lower floor is amorphous SnOxLayer.
Using analyzing parameters of semiconductor tester test prepared by the present invention based on double-decker resistance-change memory functional layer
The I-E characteristic of resistor-type memory cell（Namely I-V characteristic）, resistor-type is tested under the continuous scan pattern of voltage
The I-E characteristic of memory cell, current-voltage test result are as shown in fig. 2, it can be seen that in certain voltage and electricity
Flow down, resistor-type memory cell of the invention can stably realize the circulation of erasing and write-in, can realize the characteristic of storage.
The resistance state for the resistor-type memory cell based on double-decker resistance-change memory functional layer that accompanying drawing 3 is prepared for the present invention is protected
The test chart of holding property, as can be seen from the figure：Resistor-type memory cell prepared by the present invention has stable low resistance state, intermediate state
And high-impedance state, resistance state has good retention performance.
Two embodiments are set forth below to illustrate the preparation method of resistor-type memory cell of the present invention, can be according to the present invention's
The difference of each tunic material in resistor-type memory cell, the appropriate section in two embodiment preparation methods is changed or
Replacement can just prepare the different resistor-type memory cell in the scope of the present invention.
Embodiment 1
A kind of preparation method of resistor-type memory cell, its step is as follows：
（1）, lower electrode layer formed on substrate using magnetron sputtering coating method：Using Ni metal target, using Ar gas as
Working gas, on the glass substrate sputtering forms Cu films, wherein operating pressure during sputtering is 5 × 10-1Pa~10×10- 1Pa, sputtering time is 20 ~ 25min, and sputtering voltage is 300 ~ 380V, and sputtering current is 120 ~ 180mA, finally in glass substrate
It is upper to form the Cu lower electrode layers that thickness is about 80-150nm；
（2）, on Cu lower electrode layers formed one layer of insulating medium layer：The mode for forming insulating medium layer can be atomic layer
Deposition process or the mode of spin coating, the thickness for forming insulating medium layer is 300nm ~ 5000nm, and the material of insulating medium layer can be with
For SiO2Or SiN, after insulating medium layer is formed, groove is formed on insulating medium layer using traditional photoetching process,
For forming other follow-up Rotating fields；
（3）, amorphous SnO is formed in the groove of formationxFilm：Using metallic tin target, in reaction chamber internal control
Temperature processed is 180 DEG C ~ 200 DEG C, and O is passed through into reaction chamber2With Ar gases, O is controlled2The partial pressure of gas is 5 × 10-2Pa~1×
10-1Pa, operating pressure is 5 × 10-1Pa~10×10-1Pa, metallic tin target is sputtered under Ar Ions Bombardments, and with reaction
O in chamber2Collide and react, so as to form amorphous SnOxFilm, wherein, the reaction time（That is sputtering time）For
40 ~ 100 minutes, 50 ~ 200mA of sputtering current, sputtering voltage was 300 ~ 380V, the amorphous Sn O of formationxThe thickness of film is 20
~45nm；
（4）, nitrogen oxides MnOxNyThe preparation of film：Nitrogen oxides MnOxNyFilm is prepared in two steps, first, using Mn
Target, the temperature for keeping substrate is 100 ~ 400 DEG C, and O is passed through into reaction chamber2With Ar gases, O is controlled2The partial pressure of gas is 5
×10-2Pa~1×10-1Pa, metal Mn targets are sputtered under Ar Ions Bombardments, and with the O in reaction chamber2Collide and send out
Raw reaction, so as to be initially formed one layer of MnOxLayer, wherein, the reaction time（That is sputtering time）For 20 ~ 150 minutes, sputtering current 30 ~
400mA, sputtering voltage is 200 ~ 380V；Then, to MnOxLayer carries out N~+ implantation, and the ion implanting time is 10 ~ 80 minutes,
So as to by MnOxLayer is changed into nitrogen oxides MnOxNyLayer.Wherein, control x's and y by controlling the intake of oxygen and Nitrogen ion
Value, finally makes the nitrogen oxides MnO to be formedxNyX and y span be respectively 1<x<2,0.001<y<2, the thickness of formation
Spend for 50-80nm；
（5）, in nitrogen oxides MnOxNyPass through the method formation Ag metal levels of magnetron sputtering or ald on film
As upper electrode layer, the Ag metal levels and dielectric as upper electrode layer are made by flatening process after formation Ag metal levels
Layer surface is flushed, that is, the functional layer and upper electrode layer of the double-decker ultimately formed are located in the groove of insulating medium layer.
Embodiment 2
A kind of preparation method of resistor-type memory cell, its step is as follows：
（1）, using Pt metal target, using Ar gas as working gas, on a semiconductor substrate sputtering form Pt films, wherein
Semiconductor substrate can be Si substrates, operating pressure during sputtering is 5 × 10-1Pa~10×10-1Pa, sputtering time be 20 ~
45min, sputtering voltage is 300 ~ 380V, and sputtering current is 120 ~ 180mA, forms the Pt bottom electrodes that thickness is about 80-150nm
Layer；
（2）, on Pt lower electrode layers formed one layer of insulating medium layer, is formed insulating medium layer mode can for deposit or
The mode of spin coating, the thickness for forming insulating medium layer is 300nm ~ 5000nm, and the material of insulating medium layer can be SiO2Or
SiN materials, after insulating medium layer is formed, groove is formed for shape using traditional photoetching process on insulating medium layer
Into other follow-up Rotating fields；
（3）, nitrogen oxides MnO is formed in the groove of formationxNyFilm：Forming nitrogen oxides MnOxNyAdopted during film
Formed with a step, using Mn targets, the temperature for keeping substrate is 100 ~ 400 DEG C, and O is passed through into reaction chamber2With Ar gases, together
When Nitrogen ion source is injected into reaction chamber, control O2The partial pressure of gas is 5 × 10-2Pa~1×10-1Pa, sputtering current 30 ~
400mA, sputtering voltage is 200 ~ 380V, and the reaction time is 50 ~ 180 minutes, and metal Mn targets splash under Ar Ions Bombardments
Penetrate, with the O in reaction chamber2Collide and the generation MnO that reactsx, MnOxCombined with the Nitrogen ion of injection, so as to form one layer
Nitrogen oxides MnOxNyFilm layer；Wherein, x and y value are controlled by controlling the intake of oxygen and Nitrogen ion, finally makes shape
Into nitrogen oxides MnOxNyX and y span be respectively 1<x<2,0.001<y<2, the thickness of formation is about 50-80nm；
（4）, in nitrogen oxides MnOxNyAmorphous SnO is formed on filmxFilm：Using metallic tin target, in reaction chamber
It is indoor to control temperature to be 180 DEG C ~ 200 DEG C, O is passed through into reaction chamber2With Ar gases, O is controlled2The partial pressure of gas is 5 × 10- 2Pa~1×10-1Pa, operating pressure is 5 × 10-1Pa~10×10-1Pa, forms amorphous SnOxFilm；Wherein, the reaction time
For 40 ~ 100 minutes, 50 ~ 200mA of sputtering current, sputtering voltage was 300 ~ 380V, the amorphous Sn O of formationxThe thickness of film is
20~45nm；
（5）, in amorphous Sn OxUpper electricity is used as by magnetron sputtering or ald formation Ti metal levels on film
Made after pole layer, formation Ti metal levels by flatening process neat as the Ti metal levels and dielectric layer surface of upper electrode layer
Flat, the double-deck resistive functional layer and upper electrode layer ultimately formed is located in the groove of insulating medium layer.
Claims (6)
1. a kind of preparation method of resistor-type memory cell, it is characterised in that：Comprise the following steps：
（1）, on substrate with conductive material formation lower electrode layer；
（2）, on lower electrode layer deposition or one layer of insulating medium layer of spin coating, then by photoetching process on insulating medium layer shape
Into groove, the bottom land of groove passes to lower electrode layer；
（3）, the function of the resistor-type memory cell is formed using the method for magnetron sputtering or ald in groove
Layer, the functional layer is upper and lower two layers of laminated construction, and it is by amorphous SnOxLayer and nitrogen oxides MnOxNyLayer laminate is constituted,
Wherein, amorphous SnOxMiddle x span is 0<x<2, nitrogen oxides MnOxNyIn x and y span be respectively 1<
x<2,0.001<y<2；
（4）, on a functional with conductive material formation upper electrode layer, make upper electrode layer and insulating medium layer using flatening process
Flush, you can.
2. a kind of preparation method of resistor-type memory cell as claimed in claim 1, it is characterised in that：Step（3）In, utilize
The method that magnetic-controlled sputtering coating equipment forms the functional layer is：First, using metallic tin as target, magnetron sputtering plating is controlled
The reaction chamber indoor temperature of equipment is 180 DEG C ~ 200 DEG C, and O is passed through into reaction chamber2With Ar gases, the gold under Ar Ions Bombardments
Category tin target sputter, and with the O in reaction chamber2Collide and react, so as to form amorphous SnOxFilm；So
Afterwards, using metal Mn as target, it is 100 ~ 400 DEG C to control reaction chamber indoor temperature, and O is passed through into reaction chamber2With Ar gases,
Metal Mn targets are sputtered under Ar Ions Bombardments, and with the O in reaction chamber2Collide and react, so that in amorphous
The SnO of statexMnO is formed on filmxLayer, to MnOxLayer carries out N~+ implantation with by MnOxLayer is changed into nitrogen oxides MnOxNy
Layer.
3. a kind of preparation method of resistor-type memory cell as claimed in claim 1, it is characterised in that：Step（1）And step
（4）Described in conductive material be conducting metal, conductive metal alloy or conductive metallic compound, conducting metal therein is
Cu, Ag, Ti, Pt or Ni, conductive metal alloy be Pt/Ti, Cu/Ti or Cu/Au, conductive metallic compound be TiN, TaN or
ITO。
4. a kind of preparation method of resistor-type memory cell as claimed in claim 1, it is characterised in that：The insulating medium layer
Material be SiO2Or SiN.
5. a kind of preparation method of resistor-type memory cell as claimed in claim 1, it is characterised in that：The lower electrode layer and
The thickness of upper electrode layer is amorphous SnO in 80-150nm, functional layerxThe thickness of layer is 20-45nm, nitrogen oxides
MnOxNyThe thickness of layer is 50-80nm, and the thickness of insulating medium layer is 300nm ~ 5000nm.
6. a kind of preparation method of resistor-type memory cell as claimed in claim 1, it is characterised in that：Step（1）Described in
Substrate be glass substrate or semiconductor substrate.
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| US8274065B2 (en) * | 2009-10-19 | 2012-09-25 | Macronix International Co., Ltd. | Memory and method of fabricating the same |
| CN102867911A (en) * | 2011-07-07 | 2013-01-09 | 复旦大学 | Resistance memory and preparation method thereof |
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