CN107579153B - Low-power consumption resistance-variable storing device and preparation method thereof of the one kind based on electrode hafnium (Hf) doping - Google Patents
Low-power consumption resistance-variable storing device and preparation method thereof of the one kind based on electrode hafnium (Hf) doping Download PDFInfo
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Abstract
The present invention discloses a kind of low-power consumption resistance-variable storing device and preparation method thereof based on the doping of electrode hafnium, the laminated construction that the memory is successively made of silicon substrate, hearth electrode, change resistance layer and top electrode, wherein hearth electrode is titanium nitride, with a thickness of 50~300nm, change resistance layer is zirconium oxide, with a thickness of 10~50nm, top electrode is hafnium doped indium tin oxide, with a thickness of 100~300nm；Hafnium doping content is 10%~30%；Top electrode is also possible to hafnium doping FTO, ZTO conductive metallic compound.Preparation method is to sputter to prepare each layer film respectively by magnetron sputtering technique.The invention has the advantages that preparing simple, easily operated, by adulterating Hf element in ITO electrode, it can effectively reduce operation electric current and operation voltage, reduced the power consumption of device to nanowatt rank；Limitation electric current is not needed in operation, and there is good durability.With preferable development potentiality and application value.
Description
Technical field
The present invention relates to microelectronics and resistance-variable storing device technical field, specifically one kind can reduce resistance-variable storing device
The method of power consumption.
Background technique
With the fast development of modern information technologies, the processing capacity of data constantly enhances, data volume sharp increase.Together
When, it is desirable to can obtain function admirable, cheap storage chip to store mass data.Current main-stream it is non-volatile
Property memory technology is based on the floating gate type flash memory (flash storage) based on charge-storage mechanism, with the continuous contracting of size
It is small, floating-gate device operate voltage, power consumption, integrated technique, reliability, in terms of be faced with physics and technical
Bottleneck.In recent years, many ferroelectric memorys (FeRRAM), magnetic storage (MRAM), phase transition storage (PRAM) and resistive are deposited
The extensive concern by all circles such as reservoir (RRAM).Wherein, candidate of the resistance-variable storing device as next-generation nonvolatile memory
The storage potentiality that person is showed substantially exceed other several non-volatile devices, and major advantage has structure simple, erasable
Speed is fast, storage density is high, repeats that erasable number is high, size is small, multistage storage, low-power consumption and easily mutually compatible with CMOS technology etc.
Many merits.
Electrode material influences the performance of resistance-variable storing device very big.In recent years, having to obtain better change resistance performance
Many different electrode materials are applied in resistance-variable storing device.Such as active electrode has Cu, Ag, Ni etc., inert electrode have Pt,
Au, W, Ti, Cr, Al etc., wherein traditional platinum electrode apply the most extensively, but the high cost and high power consumption of Pt electrode make its throwing
Enter production to be restricted.Tin indium oxide (ITO) is a kind of conductor rich in Lacking oxygen, because of its self-limiting, low operation electric current
It is used as electrode material with the characteristic of voltage and low-power consumption to be widely used in resistance-variable storing device.Researcher is exploring improvement
In resistance-variable storing device, resistance-variable storing device change resistance performance is improved by changing electrode.Po-Hsun Chen et al. is in document:
Effects of erbium doping of indium tin oxide electrode in resistive random
Access memory and Improving Performance by Doping Gadolinium Into the Indium-
Tin–Oxide Electrode in HfO2By rare earth element in-Based Resistive Random Access Memory
In erbium (Er) and gadolinium (Ga) incorporation ITO top electrode, lower operation electric current and low-power consumption are obtained but since Ga and Er content is rare,
So in the Research Prospects of industrial circle and uncertain.
Summary of the invention
Technology based on the above background, the present invention provide a kind of that hafnium (Hf) element incorporation tin indium oxide (ITO) is electric as top
The resistance-variable storing device and preparation method of pole, the preparation method is simple, low in cost and Hf is mixed in ITO becomes ITO by conductor
For characteristic of semiconductor, make the present invention that there is the low-power consumption of biggish memory window, high consistency and nanowatt grade, therefore Hf is adulterated
ITO electrode is a kind of electrode material for having very much development potentiality and researching value.
The invention is realized in this way sequentially consisting of the folded of silicon substrate, hearth electrode, change resistance layer and top electrode composition
Layer structure；The hearth electrode is titanium nitride, with a thickness of 50~300nm；Change resistance layer is zirconium oxide, with a thickness of 10~50nm,；Top
Electrode is hafnium doped indium tin oxide, and with a thickness of 100~300nm, hafnium doping content is 10%~30%.
Further, heretofore described hearth electrode is made of the conductive metals magnetron sputtering such as Pt, Au, W, Ti, Cu, Ag；
The hearth electrode is also possible to the metal alloys such as Pt/Ti alloy, Cu/Ti alloy, Cu/Au alloy or Cu/Al alloy
Magnetron sputtering is made
The top electrode is the conductive metallic compounds magnetron sputtering such as hafnium doped ITO or hafnium doping FTO, ZTO, TiN
It is made.
Further, heretofore described resistive layer material is ZrO2、HfO2、TiO2、NiO2Or TaOx。
Further, in the present invention hearth electrode with a thickness of 150nm, top electrode with a thickness of 100~200nm.
The preparation method of resistance-variable storing device as described herein, the specific steps are as follows:
1, silicon substrate is cleaned with Ultrasound Instrument；
2, the target material as hearth electrode is placed on target platform, utilizes magnetron sputtering technique or atomic layer deposition on a silicon substrate
Product prepares hearth electrode, and magnetron sputtered vacuum degree is less than 10‐4Pa, underlayer temperature are room temperature, operating pressure is 0.3~0.8Pa, sputtering
Power is 50~100W；
3, the target material as change resistance layer is placed on target platform, magnetron sputtering technique or atom is utilized on above-mentioned hearth electrode
The method of layer deposition prepares change resistance layer, and magnetron sputtered vacuum degree is less than 10‐4Pa, underlayer temperature are room temperature, operating pressure be 0.3~
0.8Pa, sputtering power are 50~80W；
4, the ITO electrode target material as top electrode is placed on target platform, while doping target material Hf target is placed on target
On platform, selects different capacity ratio to sputter simultaneously Hf target and ITO target, doping is prepared using different proportion sputtering power
The top electrode that content is 10%~30% sputters vacuum degree less than 10‐4Pa, underlayer temperature are room temperature, operating pressure be 0.3~
The sputtering power of 0.8Pa, Hf target is 10W, the sputtering power of ITO target is 100~150W；
Film characterization and device detection
The hafnium doped indium oxide tin thin film of preparation is scanned electron microscope (SEM) analysis.Scanning electron microscope
(SEM) instrument used is JSM-7100F, and surface topography characterization is carried out under the voltage of 15kV.
The electrology characteristic based on hafnium doped indium tin oxide top electrode resistance-variable storing device prepared is tested, tester
Device is Agilent B1500A Semiconductor Parameter Analyzer.Grounded probe is pressed in titanium nitride hearth electrode surface, by another probe
It is pressed in hafnium doped indium tin oxide top electrode surface.
The present invention has the advantages that the resistance-variable storing device preparation method is simple, easily operated, by mixing in ITO electrode
Miscellaneous Hf element can effectively reduce the operation electric current and operation voltage of resistance-variable storing device, reduce the power consumption of device to nanowatt rank；
The resistance-variable storing device does not need limitation electric current in operation, and has good durability.
Detailed description of the invention
Fig. 1 is device junction composition of the present invention；
Wherein 1 is silicon substrate, and 2 be hearth electrode, and 3 be change resistance layer, and 4 be top electrode；
Fig. 2 is two Hf:ITO of the embodiment of the present invention (10W:150W) film scanning electron microscope (SEM) sectional view；
Fig. 3 is the resistance-variable storing device current-voltage cyclic curve (100 circulations) of the embodiment of the present invention one；
Fig. 4 is the resistance-variable storing device current-voltage cyclic curve (100 circulations) of the embodiment of the present invention two；
Fig. 5 is resistance-variable storing device current-voltage circulation correlation curve (10 of the embodiment of the present invention one and embodiment two
Circulation)；
Fig. 6 is the high low resistance state distribution map of resistance-variable storing device of the embodiment of the present invention two.
Specific embodiment
A kind of resistance-variable storing device of low-power consumption of the present invention, it is mainly by silicon substrate, hearth electrode, change resistance layer and top electrode group
At wherein hearth electrode material is titanium nitride (TiN), and resistive layer material is zirconium oxide (ZrO2), top electrode material is Hf doping
ITO, FTO and ZTO conductive metallic compound magnetron sputtering are made, because Hf doped ITO, FTO and ZTO obtain phase as top electrode
As a result, therefore specific embodiment in be specifically described using Hf doped ITO as top electrode.With reference to the accompanying drawing by specific
The present invention will be further described in detail for embodiment.
Embodiment one
A kind of resistance-variable storing device of low-power consumption, it is mainly made of silicon substrate, hearth electrode, change resistance layer and top electrode,
Indsole electrode material is titanium nitride (TiN), and resistive layer material is zirconium oxide (ZrO2), with a thickness of 25nm, top electrode material is oxygen
Change indium tin (ITO), with a thickness of 200nm.
Step 1. cleaning silicon chip
Silicon wafer is placed in Ultrasound Instrument, successively with acetone, dehydrated alcohol, deionized water difference ultrasound 15min；
Step 2. prepares hearth electrode
One layer of titanium nitride hearth electrode is prepared using magnetically controlled sputter method on a silicon substrate, magnetron sputtered vacuum degree is less than 10‐ 4Pa, underlayer temperature are room temperature, operating pressure 0.5Pa, sputtering power 80W, and being passed through argon flow is 30sccm, when
Between be 25min, with a thickness of 150nm.
Step 3. prepares change resistance layer
TiN substrate is placed in magnetic control sputtering device, by the ZrO as change resistance layer2Target is placed in radio-frequency sputtering target platform, and magnetic control splashes
Vacuum degree is penetrated less than 10‐4Pa, underlayer temperature are room temperature, operating pressure 0.3Pa, rf sputtering power 60W, are passed through argon gas stream
Amount is 38sccm, time 14min, with a thickness of 25nm.；
Step 4. prepares top electrode
Non- hafnium doped indium tin oxide top electrode is prepared with magnetic control sputtering device, tin indium oxide target material is placed in d.c. sputtering target position simultaneously
Sputtering, magnetron sputtered vacuum degree is less than 10‐4Pa, underlayer temperature are room temperature, operating pressure 0.3Pa, the sputtering function of tin indium oxide
Rate is 150W, and being passed through argon flow is 30sccm, time 20min, with a thickness of 200nm.
Embodiment two
A kind of resistance-variable storing device of low-power consumption, it is mainly made of silicon substrate, hearth electrode, change resistance layer and top electrode,
Indsole electrode material is titanium nitride (TiN), and resistive layer material is zirconium oxide (ZrO2), with a thickness of 25nm, top electrode material is hafnium
Doped indium tin oxide (Hf:ITO), with a thickness of 200nm.
Step 1. cleaning silicon chip
Silicon wafer is placed in Ultrasound Instrument, successively with acetone, dehydrated alcohol, deionized water difference ultrasound 15min；
Step 2. prepares hearth electrode
One layer of titanium nitride hearth electrode is prepared using magnetically controlled sputter method on a silicon substrate, magnetron sputtered vacuum degree is less than 10‐ 4Pa, underlayer temperature are room temperature, operating pressure 0.5Pa, sputtering power 80W, and being passed through argon flow is 30sccm, when
Between be 25min, with a thickness of 150nm.
Step 3. prepares change resistance layer
TiN substrate is placed in magnetic control sputtering device, by the ZrO as change resistance layer2Target is placed in radio-frequency sputtering target platform, and magnetic control splashes
Vacuum degree is penetrated less than 10‐4Pa, underlayer temperature are room temperature, operating pressure 0.3Pa, rf sputtering power 60W, are passed through argon gas stream
Amount is 38sccm, time 14min, with a thickness of 25nm.；
Step 4. prepares top electrode
Hafnium doped indium tin oxide top electrode is prepared with magnetic control sputtering device, hafnium and tin indium oxide target material are respectively placed in d.c. sputtering
Target position simultaneously sputters simultaneously, and magnetron sputtered vacuum degree is less than 10‐4Pa, underlayer temperature are that room temperature, operating pressure 0.3Pa, hafnium splash
Penetrating power is 10W, and the sputtering power of tin indium oxide is 150W, and being passed through argon flow is 30sccm, time 20min, with a thickness of
200nm, the content of hafnium element are about 12%.
The hafnium doped indium oxide tin thin film of preparation is scanned electron microscope (SEM) analysis.Scanning electron microscope
(SEM) instrument used is JSM-7100F, and surface topography characterization is carried out under the voltage of 15kV, and attached drawing 2 is this example top electricity
Very thin films scanning electron microscope (SEM) sectional view.
Embodiment three
A kind of resistance-variable storing device of low-power consumption, it is mainly made of silicon substrate, hearth electrode, change resistance layer and top electrode,
Indsole electrode material is titanium nitride (TiN), and resistive layer material is zirconium oxide (ZrO2), with a thickness of 25nm, top electrode material is hafnium
Doped indium tin oxide (Hf:ITO), with a thickness of 150nm.
Step 1. cleaning silicon chip
Silicon wafer is placed in Ultrasound Instrument, successively with acetone, dehydrated alcohol, deionized water difference ultrasound 15min；
Step 2. prepares hearth electrode
One layer of titanium nitride hearth electrode is prepared using magnetically controlled sputter method on a silicon substrate, magnetron sputtered vacuum degree is less than 10‐ 4Pa, underlayer temperature are room temperature, operating pressure 0.5Pa, sputtering power 80W, and being passed through argon flow is 30sccm, when
Between be 25min, with a thickness of 150nm.
Step 3. prepares change resistance layer
TiN substrate is placed in magnetic control sputtering device, by the ZrO as change resistance layer2Target is placed in radio-frequency sputtering target platform, and magnetic control splashes
Vacuum degree is penetrated less than 10‐4Pa, underlayer temperature are room temperature, operating pressure 0.3Pa, rf sputtering power 60W, are passed through argon gas stream
Amount is 38sccm, time 14min, with a thickness of 25nm.；
Step 4. prepares top electrode
Hafnium doped indium tin oxide top electrode is prepared with magnetic control sputtering device, hafnium and tin indium oxide target material are respectively placed in d.c. sputtering
Target position simultaneously sputters simultaneously, and magnetron sputtered vacuum degree is less than 10‐4Pa, underlayer temperature are that room temperature, operating pressure 0.3Pa, hafnium splash
Penetrating power is 10W, and the sputtering power of tin indium oxide is 125W, and being passed through argon flow is 30sccm, time 20min, with a thickness of
150nm, the content of hafnium element are about 20%.
Example IV
A kind of resistance-variable storing device of low-power consumption, it is mainly made of silicon substrate, hearth electrode, change resistance layer and top electrode,
Indsole electrode material is titanium nitride (TiN), and resistive layer material is zirconium oxide (ZrO2), with a thickness of 25nm, top electrode material is hafnium
Doped indium tin oxide (Hf:ITO), with a thickness of 100nm.
Step 1. cleaning silicon chip
Silicon wafer is placed in Ultrasound Instrument, successively with acetone, dehydrated alcohol, deionized water difference ultrasound 15min；
Step 2. prepares hearth electrode
One layer of titanium nitride hearth electrode is prepared using magnetically controlled sputter method on a silicon substrate, magnetron sputtered vacuum degree is less than 10‐ 4Pa, underlayer temperature are room temperature, operating pressure 0.5Pa, sputtering power 80W, and being passed through argon flow is 30sccm, when
Between be 25min, with a thickness of 150nm.
Step 3. prepares change resistance layer and TiN substrate is placed in magnetic control sputtering device, by the ZrO as change resistance layer2Target, which is placed in, to be penetrated
RF sputtering target platform, magnetron sputtered vacuum degree is less than 10‐4Pa, underlayer temperature are room temperature, operating pressure 0.3Pa, radio-frequency sputtering function
Rate is 60W, and being passed through argon flow is 38sccm, time 14min, with a thickness of 25nm.
Step 4. prepares top electrode
Hafnium doped indium tin oxide top electrode is prepared with magnetic control sputtering device, hafnium and tin indium oxide target material are respectively placed in d.c. sputtering
Target position simultaneously sputters simultaneously, and magnetron sputtered vacuum degree is less than 10‐4Pa, underlayer temperature are that room temperature, operating pressure 0.3Pa, hafnium splash
Penetrating power is 10W, and the sputtering power of tin indium oxide is 100W, and being passed through argon flow is 30sccm, time 20min, with a thickness of
100nm, the content of hafnium element are about 30%.
The memory that each embodiment is obtained carries out electrology characteristic test, and test equipment is Agilent B1500A semiconductor
Parameter analyzer.Grounded probe is pressed in titanium nitride hearth electrode surface, another probe is pressed in hafnium doped indium tin oxide top electricity
Pole surface.First filament formed (Forming) process using Agilent B1500A test software set scanning voltage as 0V~
10V, it is about 5.8V that limitation electric current, which is 100 μ A, Forming voltages,；Then -1V~0.8V is set by scanning voltage again, infinitely
Electric current processed, scanning voltage, which works one to recycle, is divided into four parts, first scans from 0V to+0.8V, then from+0.8V scanning to 0V,
Then it scans from 0V to -1.0V, finally scans from -1.0V to 0V, set voltage is 0.3~0.6V, and resetting voltage is -0.6V
~-1.0V.
Test result is shown in attached drawing
Attached drawing 3 is one resistance-variable storing device current-voltage cyclic curve of embodiment (100 circulation), is deposited in the present embodiment one
The operation power of reservoir is about 20 μ W.
Attached drawing 4 is memory current-voltage (I-V) cyclic curve (100 circulations) that embodiment two obtains, the present embodiment
The operation power of middle memory is about 800nW；
Attached drawing 5 is the resistance-variable storing device current-voltage circulation correlation curve (10 circulations) of embodiment one and embodiment two；
Attached drawing 6 is the high low resistance state distribution map of memory that embodiment two obtains.
Test result analysis
By comparing undoped with ITO device and Hf doped ITO device (Hf content is 12%), see attached drawing 5, it is known that with do not mix
Miscellaneous ITO device has bigger resistive window, lower operation electric current and more compared to Hf doped ITO device (Hf content be 12%)
Low operation power and, resistive window increases to 100 by 35, and high-impedance state electric current is reduced to 73nA, low resistance state electric current by 2.5 μ A
6.6 μ A are reduced to by 60.8 μ A, operation power is reduced to 800nW by 20 μ W.
Claims (4)
1. low-power consumption resistance-variable storing device of the one kind based on electrode hafnium (Hf) doping, successively by silicon substrate, hearth electrode, change resistance layer and top
The laminated construction of electrode composition；It is characterized in that, the hearth electrode is titanium nitride, with a thickness of 50~300nm；The change resistance layer is
Zirconium oxide, with a thickness of 10~50nm；The top electrode is hafnium doped indium tin oxide, with a thickness of 100~300nm, hafnium doping content
It is 10%~30%；
The low-power consumption resistance-variable storing device based on electrode hafnium (Hf) doping is prepared by following steps:
1), silicon substrate is cleaned with Ultrasound Instrument；
2), the target material as hearth electrode is placed on target platform, utilizes magnetron sputtering technique or atomic layer deposition on a silicon substrate
Prepare titanium nitride hearth electrode；
3), the target material as change resistance layer is placed on target platform, on above-mentioned titanium nitride hearth electrode using magnetron sputtering technique or
The method of atomic layer deposition prepares zirconium oxide change resistance layer；
4), the ITO electrode target material as top electrode is placed on target platform, while doping target material Hf target is placed on target platform
On, it selects different capacity ratio to sputter simultaneously Hf target and ITO target, is contained using different proportion sputtering power to prepare doping
The top electrode that amount is 10%~30%.
2. a kind of low-power consumption resistance-variable storing device based on electrode hafnium (Hf) doping according to claim 1, which is characterized in that
The top electrode is that hafnium doped ITO or hafnium adulterate FTO, ZTO conductive metallic compound magnetron sputtering and be made.
3. a kind of low-power consumption resistance-variable storing device based on electrode hafnium (Hf) doping according to claim 1 or 2, feature exist
In the hearth electrode be conductive metal, metal alloy or conductive metallic compound.
4. according to claim 1 or 2 a kind of based on electrode hafnium (Hf) doping low-power consumption resistance-variable storing device, feature exists
In the change resistance layer is ZrO2、HfO2、TiO2、NiO2Or TaOx。
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| CN103500796A (en) * | 2013-10-14 | 2014-01-08 | 北京大学 | Oxide-based transparent RRAM (Resistive Random Access Memory) and preparation method thereof |
| CN106953007A (en) * | 2017-03-17 | 2017-07-14 | 广东工业大学 | A kind of resistance-variable storing device and the method for improving the erasable voltage stability of resistance-variable storing device |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103500796A (en) * | 2013-10-14 | 2014-01-08 | 北京大学 | Oxide-based transparent RRAM (Resistive Random Access Memory) and preparation method thereof |
| CN106953007A (en) * | 2017-03-17 | 2017-07-14 | 广东工业大学 | A kind of resistance-variable storing device and the method for improving the erasable voltage stability of resistance-variable storing device |
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| "effects of erbium doping of indium tin oxide electrode in resistive random access memory";Po-Hsun Chen等;《Applied Physics Express》;20160218;第9卷;第034202(1-4)页 * |
| "Enhancement of organic light emitting device peroformances with Hf-doped indium tin oxide anodes";T.-H.Chen等;《Applied Physics Letters》;20040913;第85卷(第11期);摘要、第2092页第2栏第9行-第2094页第1栏第24行 * |
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