CN101556986A - Multi-state resistive switching material, thin film prepared therewith, multi-sate resistive switching memory element and application of memory element in memory device - Google Patents
Multi-state resistive switching material, thin film prepared therewith, multi-sate resistive switching memory element and application of memory element in memory device Download PDFInfo
- Publication number
- CN101556986A CN101556986A CNA2009100277672A CN200910027767A CN101556986A CN 101556986 A CN101556986 A CN 101556986A CN A2009100277672 A CNA2009100277672 A CN A2009100277672A CN 200910027767 A CN200910027767 A CN 200910027767A CN 101556986 A CN101556986 A CN 101556986A
- Authority
- CN
- China
- Prior art keywords
- film
- state
- resistive switching
- storage unit
- state resistive
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Abstract
The invention relates to a multi-state resistive switching material which has the performances of two memories: PCRAM and RRAM and can not only realize the resistance change in the amorphous-crystalline transition, but also realize the formation of metal nanorods and the resistance change caused by disintegration at a stable crystal shape, thereby being capable of being applied in the manufacture of multi-state resistive switching memories. The invention also relates to a thin film prepared by the multi-state resistive switching material. The invention further relates to a multi-sate resistive switching memory element prepared by the thin film. The invention further relates to an application of the multi-sate resistive switching memory element in a memory device. The chemical formula of the multi-state resistive switching material is AgxGeyTez, wherein x is more than 5 and less than 15, y is more than 10 and less than 25, z is equal to 100-x-y, the melting point of the multi-state resistive switching material is 330-400 DEG C, and the crystallization temperature is 180-280 DEG C. The invention can be applied in the manufacture of the multi-state resistive switching memories and greatly increase the memory density of the memories.
Description
Technical field
The invention belongs to microelectronic component and material field thereof, be specifically related to a kind of multi-state resistive switching material, with its film that makes, multi-state resistive storage unit and the application of described storage unit in storage device.
Background technology
In order to satisfy the requirement of ever-increasing information processings in field such as the Internet, multimedia and three-dimensional animation and storage, people wish to obtain the record carrier of vast capacity.Follow the fast development of computer communication technology, the development of information storage media is also advanced by leaps and bounds.As the storage density of disc driver, since the nineties in 20th century, promptly with 60% speed increment, in recent years, its storage density growth rate was more up to 100%.The charge storage of considering present extensive use is near its physics limit, and scientists is being tried to explore new memory technology theory and storage medium always, in the hope of breaking through the storage limit.The development of some novel nonvolatile memory-phase transition storages (PCRAM) and resistance-variable storing device (RRAM) in recent years is noticeable, is considered to the feasibility height and the less nanoscale memory spare of risk.Be different from traditional nonvolatile memory technology based on charge storage, such as hard disk (HDD) and flash memory (Flash), novel non-volatile memory technology is based on the change of resistance.In addition, RRAM also receives much concern as candidate's device of memristor (Memristor).RRAM is under effect of electric field, and based on the electrochemistry of solids reaction mechanism, metal ion can freely transmit in medium, causes the formation of nano metal silk or nano-metal particle cluster and disappearance to realize bistable resistive.And PCRAM utilizes the chalcogenide compound semiconductor to carry out the nonvolatile memory of reversible transition and the stable characteristic preparation that keeps between amorphous state and two kinds of crystal structures of crystalline state.The speed of the read-write operation of PCRAM is very fast, and is suitable with DRAM (dynamic random access memory), but the number of operations height; Simple in structure, area is little, is easy to realize the high density storage; Good with the CMOS processing compatibility, because these outstanding advantages, comprised Intel in nearly 2 years, Samsung drops into strength in succession in interior major company and research institution and studies this phase transition storage.But,, the requirement of storage medium is also fallen far short because the storage principle of PCRAM and RRAM is completely different, as RRAM when operating, the crystal habit of material will remain unchanged, otherwise can impact resistance value, can't realize accurately writing, wiping and read operation.Therefore, up to the present, also there is not a kind of material can have the performance of PCRAM and two kinds of memories of RRAM concurrently, thereby both can change and realize that resistance changed at amorphous state-crystalline state, can realize under stable crystal habit that again the metal nano silk forms and disintegrates the resistance that causes and changes, be applied to the manufacturing of multi-state resistive memory, also therefore, the performance of these two kinds of novel memories has been subjected to certain restriction.
Goal of the invention
The invention provides a kind of multi-state resistive switching material, can have the performance of PCRAM and two kinds of memories of RRAM concurrently, thereby both can change and realize that resistance changed at amorphous state-crystalline state, can realize under stable crystal habit that again the metal nano silk forms and disintegrates the resistance that causes and changes, thereby can be applied to the manufacturing of multi-state resistive memory.
The present invention also provides the film that makes with described multi-state resistive switching material.
The present invention also provides the multi-state resistive that makes with above-mentioned film memory element.
The present invention also provides the application of above-mentioned multi-state resistive memory element in storage device.
The chemical formula of described multi-state resistive switching material is Ag
xGe
yTe
z, 5＜x＜15,10＜y＜25 wherein, z=100-x-y, the fusing point of described multi-state resistive switching material are 330-400 ℃, crystallization temperature is 180-280 ℃.
Described multi-state resistive switching material is used in less than 1.0 * 10
-2The vacuum under pressure levitation melting method of Pa makes: be smelted into Ag-Ge alloy at the 550-700 ℃ of mixture with Ag, Ge, then Ag-Ge alloy and Te continued melting formation alloy block at 400-550 ℃, obtain multi-state resistive switching material.
With the film that described multi-state resistive switching material makes, adopt the impulse laser deposition system preparation, method is as follows:
A) block of multi-state resistive switching material is made target;
B) less than 5.0 * 10
-4Under the pressure of Pa, laser beam is focused on the target, in 100-180 ℃ on substrate deposit thickness be the thick film of 30～2000nm, described film is an amorphous state.
As improvement of the present invention, the film that step b is obtained carries out the in-situ annealing processing under 250-300 ℃, obtain the film of crystalline state.
Wherein, impulse laser deposition system uses the KrF excimer laser.
Multi-state resistive storage unit with described film makes comprises film, nonreactive electrode and reaction electrode, and wherein reaction electrode is a silver.
Described nonreactive electrode adopts various well known materials, is preferably platinum or gold.
Those of ordinary skills can be as requested, determine every physical size of multi-state resistive storage unit, as preferred version, described nonreactive electrode thickness is 100～1000nm, film thickness is 100～500nm, and the thickness of reaction electrode is 200～800nm.
In order to control the effective dimensions of storage unit, also comprise the insulating barrier between nonreactive electrode and film in the above-mentioned multi-state resistive storage unit, in the middle of the insulating barrier through hole is arranged, film closely contacts in described via regions with nonreactive electrode.As preferred version, described insulating layer material is a silicon dioxide, and thickness is 30～300nm, and the size of described through hole is 30～10000nm.
The preparation method of above-mentioned multi-state resistive storage unit is as follows:
A) depositing insulating layer on nonreactive electrode;
B) etching through hole on insulating barrier;
C) insulating barrier top deposit film;
D) deposition reaction electrode on the film.
Described film is preferably crystalline state, and its preparation method is as follows:
A) depositing insulating layer on nonreactive electrode;
B) etching through hole on insulating barrier;
C) insulating barrier top deposited amorphous attitude film;
D) deposition reaction electrode on the film;
E) carrying out in-situ annealing under 250-300 ℃ handles.
When the multi-state resistive storage unit is applied to storage device, pick out lead-in wire respectively by reaction electrode and nonreactive electrode.Operation principle is as follows:
When storage unit is realized the phase transformation switching effect, need avoid anodal silver ion to enter film in order to distinguish two kinds of operation principles, need make reaction electrode not participate in reaction as negative pole, nonreactive electrode is as positive electrode, utilize electric energy (heat) to make material change writing and wiping of realization information mutually between crystalline state (low-resistance) and amorphous state (high resistant), the variation of reading by measuring resistance of information realizes.We make film be in crystalline state after 250 ℃ of annealing, and this state is made as OFF state, are initial state.And ablation process is meant and adds a weak point and strong potential pulse, and electric energy is transformed into heat energy, and the chalcogenide compound temperature is elevated to more than the fusion temperature, through cooling fast, the long-range order of polycrystalline is destroyed, thereby realizes by the conversion of polycrystalline to amorphous; Erase process then refers to apply a potential pulse long and intensity is medium, and the temperature of chalcogenide compound is elevated to more than the crystallization temperature, below the fusion temperature, and keeps the regular hour, makes chalcogenide compound be converted into polycrystalline by amorphous state; Reading of data is that resistance value by measuring chalcogenide compound realizes that the intensity of pulse voltage that add this moment is very weak, and the heat energy of generation can only make the temperature of chalcogenide compound be elevated to below the crystallization temperature, does not cause that material undergoes phase transition.
When storage unit was realized the resistive switching effect, reaction electrode connect positive source, and nonreactive electrode connects power cathode.After reaction electrode added positive voltage, the metallic atom in the reaction electrode was oxidized, formed cation and entered film, and the metal ion in the film is reduced, and was deposited on and formed metal nano silk structure on the nonreactive electrode; After reaction electrode added negative voltage, the metal nano silk that deposits on the nonreactive electrode was disintegrated and is entered film with cationic form, and simultaneously the cation in the film will be reduced into metallic atom, broke away from film and was deposited on the reaction electrode.This OR threshold voltage is decided by the ionic oxide formation energy and the ionic conduction potential barrier of thin-film material, and after reaction electrode added malleation greater than threshold value, the resistance of film sharply reduced.
The resistive storage unit that uses described film preparation to have phase transformation switching effect and resistive switching effect concurrently carries out following performance test:
The instrument that carries out the performance test of phase transformation switching effect for storage unit is: Keithley 2400 source measurement units and Agilent81104A pulse signal generator.Main test component is respectively to high and short and the low and response of long electrical wave pulse.Promptly utilize Agilent 81104A pulse signal generator to change the state (amorphous state or crystalline state) of resistive memory cell, the back uses Keithley2400 source measurement unit to record the current-voltage correlation (U-I) of resistive memory cell.
The instrument that carries out the performance test of resistive switching effect for storage unit is: Keithley 2400 source measurement units; The Agilent33250A function; LeCroy WaveRunner 62Xi oscilloscope.Main test component to one-period change the response of voltage and device to read-write-read-response of erasing voltage periodic signal.Measuring circuit is shown in Fig. 3 schematic diagram, in the drawings, need to give resistance 15 of AGT film mnemon sample 16 series connection of preparation, resistance is 100 Ω, oscilloscope C1 and C2 are connected on series resistance 15 and the function 17, are used for testing the voltage signal that is added in mnemon sample 16 and series resistance 15 two ends.
Test result shows, uses this storage unit to have following beneficial effect:
(1) film and the film after 250 ℃ of annealing without annealing are carried out X-ray diffraction analysis (XRD), the result as shown in Figure 4.Diffraction maximum does not appear in the film without annealing, illustrates that film is an amorphous state; And the film after 250 ℃ of annealing forms GeTe
4(222), main diffraction maximum such as (311), (321), film is crystalline state.
(2) differential thermal analysis (DSC) is used to test the transformation temperature and the fusing point of noncrystalline membrane, and its result as shown in Figure 5.Film amorphous-crystalline transition peak occurs in 221 ℃, the fusion peaks occur in 331 ℃; Its crystallization enthalpy and melting enthalpy be respectively 36.19J/g and-47.92J/g.
(3) film is crystallization in the storage unit after 250 ℃ of annealing, and device is in OFF state " 0 ".Make reaction electrode not participate in reaction as negative pole, nonreactive electrode is as positive electrode.Apply one high and lack that (1mA, curtage pulse 50ns) make the film in the storage unit change amorphous state into by crystalline state, and storage unit is in open mode " 1 " at this moment, and resistance is about 10 at the storage unit two ends
5Ω; If use again one low and grow the curtage pulse of (0.2mA, 50 μ s), make film change crystalline state into by amorphous state, OFF state " 0 " is returned in the device shutoff, resistance is about 10
3Ω finishes once circulation thus, and its typical current voltage pattern as shown in Figure 6.Black line represents that device is in crystalline state; Red line represents that device is in amorphous state, and changes crystalline state in 4.4V into owing to thermal effect.
(4) the resistive memory cell of finishing the phase transformation switch still is in crystalline state, applies a positive voltage on the reaction electrode of storage unit, and when this voltage reaches certain threshold value (0.15V), memory cell is by high-resistance state " 0 " (10
5Ω) change low resistance state " 2 " (being about 10 Ω) suddenly into, the voltage that applies progressively reduces and becomes negative value, the resistance of memory cell remains on low resistance state, the absolute value that applies negative voltage on reaction electrode film 14 reaches certain threshold value, and (0.3V), memory cell changes high-resistance state " 0 " suddenly into by low resistance state.Fig. 7 has at length shown the response to voltage of the storage unit that is in crystalline state.The storage unit that this test result explanation is in crystalline state has significant resistive switching effect, and the ratio of its crystalline state resistive memory cell switch resistance surpasses 4 orders of magnitude.
(5) owing to the above-mentioned good switching characteristic of resistive storage unit, it has the function that reads-write-read-wipe of resistance-variable storing device fully.We might as well be defined as low resistance state " writing " or " 1 ", high-resistance state are defined as " wiping " or " 0 "; Fig. 8 shows this storage unit under the high-frequency test condition, to read-write-read-response of erasing voltage periodic signal, when reading pulse a and be added on the element, the response current of memory cell is zero substantially, is in high-resistance state (2.08 * 10
4Ω), write when pulse b is applied on the memory cell and make device switch to low resistance state, (corresponding resistance is 1.34 * 10 to occur bigger response current 0.52mA simultaneously
3Ω), next immediately when reading pulse c and being added on the memory cell response current of element be that (corresponding resistance is 1.82 * 10 to 0.034mA
3Ω), erasing pulse d acts on the result of memory cell and makes element occur switching to high-resistance state behind the big electric current of a transient state; Thereby to the read pulse no current response (corresponding resistance is at least 104 ohm) of next cycle following closely.This explanation, reading-write-read-effect of erasing voltage periodic signal under, high-resistance state and low resistance state all can exist after electric field is removed for a long time, this storage unit has the basic function of non-volatile resistance-variable storing device fully.
(6) seasonable in above-mentioned storage unit performance resistive effect, because the power (about 0.03-0.04mW) that forms nano wire is less than the required power of its phase transformation (about 5-6mW), can when being in amorphous state, film carry out, and can not make film be converted into crystalline state from amorphous state, be resistive effect should and cholesteric-nematic transition between can not interfere with each other, therefore storage unit can be write by cholesteric-nematic transition earlier, change amorphous state into, and then under amorphous state, should write, thereby can increase its storage density greatly by resistive effect.
In sum, apply the present invention to storage device, the basic function that not only has nonvolatile memory, and can have the performance of PCRAM and two kinds of memories of RRAM concurrently, thereby both can change and realize that resistance changed at amorphous state-crystalline state, can realize under stable crystal habit that again the metal nano silk forms and disintegrates the resistance that causes and changes, thereby can be applied to the manufacturing of multi-state resistive memory, increase the storage density of memory greatly.
Description of drawings
Fig. 1: the structural representation of the pld (pulsed laser deposition) growing system of preparation film;
The 1-KrF excimer laser; The 2-condenser lens; The 3-target; 4-target platform; The 5-growth room; The interface valve of 6-mechanical pump and molecular pump; The 7-substrate; The 8-substrate table; The 9-resistance-heated furnace.
Fig. 2: the storage unit structural representation that has phase transformation switching effect and resistive switching effect concurrently of based thin film preparation
The 10-silicon substrate; The 11-nonreactive electrode; The 12-insulating barrier; The 13-film; The 14-reaction electrode;
Fig. 3: storage unit electrical performance testing schematic diagram
The 15-series resistance; The 16-storage unit; The 17-function;
Fig. 4: embodiment 2 gained film X-ray diffraction analysis figure.The x axle is represented the angle of diffraction of X ray, and the y axle is represented the intensity of X ray.
The amorphous film differential thermal analysis curve of Fig. 5: embodiment 2 gained.The x axle is represented temperature, and the y axle is represented heat flow rate.
The phase-change characteristic current-voltage figure of Fig. 6: embodiment 3 gained storage units, wherein the x axle is represented the suffered voltage of device (unit is volt), the y axle is represented the response current (unit is ampere) of device.Black line represents that device is in crystalline state; Red line represents that device is in amorphous state, and changes crystalline state in 4.4V.
Resistive characteristic voltage-current characteristics the figure of Fig. 7: embodiment 3 gained crystalline state storage units, wherein the x axle is represented the suffered voltage of device (unit is volt), the y axle is represented the response current (unit is ampere) of device.The process that voltage applies is from 0V to+0.5V, to 0V, to-2.0V, to 0V.Voltage signal is the step pattern, and the time width of step is about 100ms.
The read write attribute of Fig. 8: embodiment 3 gained crystalline state storage units, x axle express time (unit is a microsecond) wherein, the y axle in the Lower Half component are the suffered voltage signal of device (unit is volt); A, b, c, d refer to read pulse, write pulse, read pulse, erasing pulse respectively.
The amorphous film differential thermal analysis curve of Fig. 9: embodiment 5 gained.The x axle is represented temperature, and the y axle is represented heat flow rate.
The amorphous film differential thermal analysis curve of Figure 10: embodiment 8 gained.The x axle is represented temperature, and the y axle is represented heat flow rate.(Fig. 9 and Figure 10 please revise, as long as differential thermal curve is just passable)
The phase-change characteristic current-voltage figure of Figure 11: embodiment 9 gained storage units, wherein the x axle is represented the suffered voltage of device (unit is volt), the y axle is represented the response current (unit is ampere) of device.Black line represents that device is in crystalline state; Red line represents that device is in amorphous state, and changes crystalline state in 1.45V.
Resistive characteristic voltage-current characteristics the figure of Figure 12: embodiment 9 gained crystalline state storage units, wherein the x axle is represented the suffered voltage of device (unit is volt), the y axle is represented the response current (unit is ampere) of device.The process that voltage applies is from 0V to+0.5V, to 0V, to-0.5V, to 0V.Voltage signal is the step pattern, and the time width of step is about 100ms.
Embodiment
The preparation of embodiment 1. multi-state resistive switching material
1.0 * 10
-2Pa adopts down the floating smelting process of vacuum to make: at the 550-700 ℃ of melting proportioning Ag that is 10mol, the mixture of the Ge of 15mol forms Ag-Ge alloy, Te with Ag-Ge alloy and 75mol continues melting formation block at 400-550 ℃ then, obtains multi-state resistive switching material, and its chemical formula is Ag
10Ge
15Te
75
The preparation of embodiment 2. thin-film materials
Preparation process is as follows:
(a) the multi-state resistive switching material polishing that embodiment 1 is obtained cuts into circle, as target 3;
(b) target 3 is fixed on the target platform 4 of deposition film making system of pulse laser, substrate 7 is fixed on the substrate table 8, and they are placed in the growth room 5 of deposition film making system of pulse laser;
(c) with the interface valve 6 of vacuum pump by mechanical pump and molecular pump growth room 5 is evacuated down to 5.0 * 10
-4Pa is with downforce;
(d) start KrF excimer laser 1, wavelength 248nm, pulse duration 30ns, single pulse energy 210mJ, energy density is 2.0J/cm
2, laser beam is focused on the target 3 by condenser lens 2; According to single pulse energy, determined sedimentation time 3 minutes, in 150 ℃ on substrate 7 deposit thickness be the thick film of 30nm;
(f) after the thin film deposition, be heated by resistive stove 9 heated substrate platforms 8, make substrate 7 temperature be set in 250 ℃, carry out annealing in process, can obtain the film of crystalline state.
(7) film and the film after 250 ℃ of annealing without annealing are carried out X-ray diffraction analysis (XRD), the result as shown in Figure 4.Diffraction maximum does not appear in the film without annealing, illustrates that film is an amorphous state; And the film after 250 ℃ of annealing forms GeTe
4(222), main diffraction maximum such as (311), (321), film is crystalline state.Differential thermal analysis (DSC) is used to test the transformation temperature and the fusing point of noncrystalline membrane, and its result as shown in Figure 5.Film amorphous-crystalline transition peak occurs in 221 ℃, the fusion peaks occur in 331 ℃; Its crystallization enthalpy and melting enthalpy be respectively 36.19J/g and-47.92J/g.
Preparation process is as follows:
(a), on silicon substrate 10 with pulsed laser deposition deposition nonreactive electrode film 11, its material is a platinum, the thickness of nonreactive electrode 11 is 200 nanometers, laser intensity is 240mJ, deposition pressure is 5.0 * 10
-4Pa, underlayer temperature are 80 ℃;
(b), on nonreactive electrode 11, utilize radio frequency magnetron sputtering method to deposit a layer insulating 12, the material of insulating barrier is a silicon dioxide, its thickness is 100 nanometers; Using the SiO 2-ceramic target during sputter, is that the argon gas of 5-15Pa is a sputter gas with pressure, and underlayer temperature is 80 ℃;
(c) in insulating barrier 12, utilize the focused particle beam etching method, process the micropore that diameter is 100 nanometers, expose the nonreactive electrode 11 of bottom;
(d) be that the metal mask plate of 0.5mm hole covers on the insulating barrier that processes micropore with being carved with diameter, the hole of mask plate is aimed at the hole on the insulating barrier;
(e) will put into the pulsed laser deposition chamber through the silicon substrate 10 after above-mentioned steps (a) and (b), (c), (d) mask film covering, and utilize pulsed laser deposition technique deposit film 13 on insulating barrier, deposition process is with embodiment 2, and the thickness of film 13 is 200nm;
(f) by the metal mask plate pulse laser sediment method, at film 13 surface deposition reaction electrodes 14, its material is a silver, and thickness is 200 nanometers, and growth room's 5 internal pressures are 10
-4The low vacuum of Pa;
(g) after reaction electrode 14 deposition, carry out in-situ annealing 1 hour in 250 ℃, obtain the storage unit of crystalline state;
(h) pick out the spun gold lead-in wire by reaction electrode 14 and nonreactive electrode 11 respectively at last.
The preparation multi-state resistive switching material, its chemical formula is Ag
15Ge
25Te
60, method is with embodiment 1, and difference is that proportioning is Ag 15mol, Ge 25mol, Te 60mol.
The preparation thin-film material, method is with embodiment 2, and difference is to use embodiment 4 gained multi-state resistive switching material as target 3, in 120 ℃ on substrate 7 deposit thickness be the thick noncrystalline membrane of 2000nm, at 250 ℃, carry out in-situ annealing and handle, obtain the film of crystalline state.Its DSC curve as shown in Figure 9, unannealed noncrystalline membrane amorphous-crystalline transition peak occurs in 210 ℃, the fusion peaks occur in 332 ℃.
Preparation has the storage unit of phase transformation switching effect and resistive switching effect concurrently, method is with embodiment 2, difference is to use in the step (e) embodiment 4 gained multi-state resistive switching material as target, in 120 ℃ on insulating barrier deposit thickness be the thick noncrystalline membrane of 500nm, in the step (g) at 250 ℃, carry out in-situ annealing and handle, obtain the storage unit of crystalline state.
The preparation multi-state resistive switching material, its chemical formula is Ag
5Ge
10Te
85, method is with embodiment 1, and difference is that proportioning is Ag5mol, Ge 10mol, Te 85mol.
Embodiment 8
The preparation thin-film material, method is with embodiment 2, and difference is to use embodiment 6 gained multi-state resistive switching material as target 3, in 100 ℃ on substrate 7 deposit thickness be the thick noncrystalline membrane of 200nm, at 280 ℃, carry out in-situ annealing and handle, obtain the film of crystalline state.Its DSC curve as shown in figure 10, unannealed noncrystalline membrane amorphous-crystalline transition peak occurs in 180 ℃, the fusion peaks occur in 340 ℃.
Embodiment 9.
Preparation has the storage unit of phase transformation switching effect and resistive switching effect concurrently, method is with embodiment 2, difference is to use in the step (e) embodiment 6 gained multi-state resistive switching material as target, in 100 ℃ on insulating barrier deposit thickness be the thick noncrystalline membrane of 200nm, in the step (g) at 280 ℃, carry out in-situ annealing and handle, obtain the storage unit of crystalline state.
The phase-change characteristic of embodiment 9 gained storage units as shown in figure 11.Film is crystallization in the storage unit after 250 ℃ of annealing, and device is in OFF state " 0 ".Make reaction electrode not participate in reaction as negative pole, nonreactive electrode is as positive electrode.Apply one high and lack that (1mA, curtage pulse 50ns) make the film in the storage unit change amorphous state into by crystalline state, and storage unit is in open mode " 1 " at this moment, and resistance is about 10 at the storage unit two ends
6Ω; If use again one low and grow the curtage pulse of (0.2mA, 50 μ s), make film change crystalline state into by amorphous state, OFF state " 0 " is returned in the device shutoff, resistance is about 10
3Ω finishes once circulation thus, and changes crystalline state in 1.45V into owing to thermal effect.
The resistive memory cell that embodiment 9 gained storage units are finished the phase transformation switch still is in crystalline state, applies a positive voltage on the reaction electrode of storage unit, and when this voltage reaches certain threshold value (0.06V), memory cell is by high-resistance state " 0 " (10
5Ω) change low resistance state " 2 " (being about 10 Ω) suddenly into, the voltage that applies progressively reduces and becomes negative value, the resistance of memory cell remains on low resistance state, the absolute value that applies negative voltage on reaction electrode film 14 reaches certain threshold value (0.36V), memory cell changes high-resistance state " 0 " suddenly into by low resistance state, and its i-v curve as shown in figure 12.
Claims (12)
1. a multi-state resistive switching material is characterized in that chemical formula is AgxGeyTez, 5＜x＜15,10＜y＜25 wherein, and z=100-x-y, the fusing point of described multi-state resistive switching material are 330-400 ℃, crystallization temperature is 180-280 ℃.
2. multi-state resistive switching material as claimed in claim 1 is characterized in that being used in less than 1.0 * 10
-2The vacuum under pressure levitation melting method of Pa makes: be smelted into Ag-Ge alloy at the 550-700 ℃ of mixture with Ag, Ge, then Ag-Ge alloy and Te continued melting formation alloy block at 400-550 ℃, obtain multi-state resistive switching material.
3. the film that makes with claim 1 or 2 described multi-state resistive switching material is characterized in that adopting the impulse laser deposition system preparation, and method is as follows:
A) block of multi-state resistive switching material is made target;
B) less than 5.0 * 10
-4Under the pressure of Pa, laser beam is focused on the target, in 100-180 ℃ on substrate deposit thickness be the thick film of 30～2000nm, described film is an amorphous state.
4. film as claimed in claim 3 is characterized in that the film that step b is obtained carries out in-situ annealing and handles under 250-300 ℃, obtains the film of crystalline state.
5. the multi-state resistive storage unit that makes with claim 3 or 4 described films is characterized in that comprising film, nonreactive electrode and reaction electrode, and wherein reaction electrode is a silver.
6. multi-state resistive storage unit as claimed in claim 5 is characterized in that described nonreactive electrode is platinum or gold.
7. multi-state resistive storage unit as claimed in claim 5 is characterized in that also comprising the insulating barrier between nonreactive electrode and film, in the middle of the insulating barrier through hole is arranged, and film closely contacts in described via regions with nonreactive electrode.
8. multi-state resistive storage unit as claimed in claim 7 is characterized in that described insulating layer material is a silicon dioxide, and thickness is 30～300nm, and the size of described through hole is 30～10000nm.
9. multi-state resistive storage unit as claimed in claim 7 is characterized in that the preparation method is as follows:
A) depositing insulating layer on nonreactive electrode;
B) etching through hole on insulating barrier;
C) insulating barrier top deposit film;
D) deposition reaction electrode on the film.
10. as each described multi-state resistive storage unit among the claim 7-9, it is characterized in that described film is a crystalline state.
11. the multi-state resistive storage unit described in claim 10 is characterized in that the preparation method is as follows:
A) depositing insulating layer on nonreactive electrode;
B) etching through hole on insulating barrier;
C) insulating barrier top deposited amorphous attitude film;
D) deposition reaction electrode on the film;
E) carrying out in-situ annealing under 250-300 ℃ handles.
12. as each described multi-state resistive storage unit application in storage device among the claim 5-11.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100277672A CN101556986B (en) | 2009-05-20 | 2009-05-20 | Multi-state resistive switching material, thin film prepared therewith, multi-sate resistive switching memory element and application of memory element in memory device |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100277672A CN101556986B (en) | 2009-05-20 | 2009-05-20 | Multi-state resistive switching material, thin film prepared therewith, multi-sate resistive switching memory element and application of memory element in memory device |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101556986A true CN101556986A (en) | 2009-10-14 |
| CN101556986B CN101556986B (en) | 2010-08-25 |
Family
ID=41175017
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009100277672A Expired - Fee Related CN101556986B (en) | 2009-05-20 | 2009-05-20 | Multi-state resistive switching material, thin film prepared therewith, multi-sate resistive switching memory element and application of memory element in memory device |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101556986B (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102487123A (en) * | 2010-12-06 | 2012-06-06 | 中国科学院微电子研究所 | Nanoscale non-volatile resistive random access memory unit and preparation method thereof |
| CN102542334A (en) * | 2012-01-14 | 2012-07-04 | 中国人民解放军国防科学技术大学 | Hamming network circuit based on memristors |
| CN104733610A (en) * | 2013-12-23 | 2015-06-24 | 杭州华为数字技术有限公司 | Metal-doped germanium tellurium base resistance change storage material, preparation method and resistance change unit device |
| CN105112882A (en) * | 2015-07-27 | 2015-12-02 | 河南科技大学 | Method for applying pre-stress to promote separation for silver particles on surface of silver alloy film |
| CN106098923A (en) * | 2016-07-21 | 2016-11-09 | 同济大学 | A kind of argyrodite thermoelectric material and preparation method thereof |
| CN106289329A (en) * | 2015-06-05 | 2017-01-04 | 华为技术有限公司 | A kind of memristor and sensor |
| CN112864185A (en) * | 2019-11-12 | 2021-05-28 | 华邦电子股份有限公司 | Bridge type random access memory and manufacturing method thereof |
| CN113724759A (en) * | 2021-09-01 | 2021-11-30 | 哈尔滨工程大学 | Optical fiber memristor unit based on evanescent field |
| CN113724758A (en) * | 2021-09-01 | 2021-11-30 | 哈尔滨工程大学 | Multi-core optical fiber memristor and erasing, writing and reading scheme |
| WO2021254241A1 (en) * | 2020-06-16 | 2021-12-23 | International Business Machines Corporation | Phase change device |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1269243C (en) * | 2003-09-10 | 2006-08-09 | 中国科学院物理研究所 | Nanometer metal or alloy composite material and preparation and usage thereof |
| JP2006013430A (en) * | 2004-05-28 | 2006-01-12 | Fujitsu Ltd | Magnetoresistance effect element, magnetic head, and magnetic storage device |
-
2009
- 2009-05-20 CN CN2009100277672A patent/CN101556986B/en not_active Expired - Fee Related
Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102487123B (en) * | 2010-12-06 | 2013-11-06 | 中国科学院微电子研究所 | Nanoscale non-volatile resistive random access memory unit and preparation method thereof |
| CN102487123A (en) * | 2010-12-06 | 2012-06-06 | 中国科学院微电子研究所 | Nanoscale non-volatile resistive random access memory unit and preparation method thereof |
| CN102542334A (en) * | 2012-01-14 | 2012-07-04 | 中国人民解放军国防科学技术大学 | Hamming network circuit based on memristors |
| CN102542334B (en) * | 2012-01-14 | 2014-05-21 | 中国人民解放军国防科学技术大学 | Hamming network circuit based on memristors |
| CN104733610A (en) * | 2013-12-23 | 2015-06-24 | 杭州华为数字技术有限公司 | Metal-doped germanium tellurium base resistance change storage material, preparation method and resistance change unit device |
| CN104733610B (en) * | 2013-12-23 | 2017-12-15 | 杭州华为数字技术有限公司 | Metal-doped germanium telluro resistance-change memory material and preparation method and resistive element device |
| CN106289329A (en) * | 2015-06-05 | 2017-01-04 | 华为技术有限公司 | A kind of memristor and sensor |
| CN105112882B (en) * | 2015-07-27 | 2017-11-03 | 河南科技大学 | It is a kind of to apply the method that prestressing force promotes silver alloy film surface to separate out Argent grain |
| CN105112882A (en) * | 2015-07-27 | 2015-12-02 | 河南科技大学 | Method for applying pre-stress to promote separation for silver particles on surface of silver alloy film |
| CN106098923A (en) * | 2016-07-21 | 2016-11-09 | 同济大学 | A kind of argyrodite thermoelectric material and preparation method thereof |
| CN112864185A (en) * | 2019-11-12 | 2021-05-28 | 华邦电子股份有限公司 | Bridge type random access memory and manufacturing method thereof |
| CN112864185B (en) * | 2019-11-12 | 2024-03-12 | 华邦电子股份有限公司 | Bridge type random access memory and manufacturing method thereof |
| WO2021254241A1 (en) * | 2020-06-16 | 2021-12-23 | International Business Machines Corporation | Phase change device |
| US11355703B2 (en) | 2020-06-16 | 2022-06-07 | International Business Machines Corporation | Phase change device with interfacing first and second semiconductor layers |
| GB2611679A (en) * | 2020-06-16 | 2023-04-12 | Ibm | Phase change device |
| CN113724759A (en) * | 2021-09-01 | 2021-11-30 | 哈尔滨工程大学 | Optical fiber memristor unit based on evanescent field |
| CN113724758A (en) * | 2021-09-01 | 2021-11-30 | 哈尔滨工程大学 | Multi-core optical fiber memristor and erasing, writing and reading scheme |
| CN113724758B (en) * | 2021-09-01 | 2023-07-14 | 哈尔滨工程大学 | Multicore fiber memristor device and scheme of erasing, writing and reading |
| CN113724759B (en) * | 2021-09-01 | 2023-07-14 | 哈尔滨工程大学 | Optical fiber memristor unit based on evanescent field |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101556986B (en) | 2010-08-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101556986B (en) | Multi-state resistive switching material, thin film prepared therewith, multi-sate resistive switching memory element and application of memory element in memory device | |
| CN102227015B (en) | Phase transition storage material and preparation method thereof | |
| US9276202B2 (en) | Phase-change storage unit containing TiSiN material layer and method for preparing the same | |
| WO2018205915A1 (en) | Vox gating tube-based phase change storage unit | |
| CN103794723A (en) | Phase change memory unit and method for manufacturing phase change memory unit | |
| CN102361063B (en) | Thin film material for phase change memory and preparation method thereof | |
| Liu et al. | Universal memory based on phase-change materials: From phase-change random access memory to optoelectronic hybrid storage | |
| CN100477318C (en) | Phase change film material of silicon-adulterated sulfur series for phase change memory | |
| CN110148668B (en) | Al-Sc-Sb-Te phase-change material, phase-change memory unit and preparation method thereof | |
| CN101521260B (en) | Nano composite phase-change material and preparation method thereof | |
| CN111320145A (en) | Phase change material, phase change memory unit and manufacturing method thereof | |
| CN101488557A (en) | Si-Sb-Se phase changing thin-film material used for phase changing memory | |
| US7884345B2 (en) | Phase-change material, memory unit and method for electrically storing/reading data | |
| CN110635033A (en) | B-Sb-Te phase-change material, phase-change storage unit and preparation method thereof | |
| CN101916823B (en) | Phase change storage device based on antimony telluride composite phase change material and preparation method thereof | |
| CN102097585A (en) | Preparation method of quasi-edge contact nano phase-change memory cell | |
| CN100364132C (en) | Silicon-contained series surfur-family compound phase transformation film material for phase transformation memory | |
| CN102544355B (en) | Phase-change storage material and preparation method thereof as well as storage device provided therewith and preparation method thereof | |
| CN102769101A (en) | GeTe4 phase-change memory element and preparation method thereof | |
| CN102130297B (en) | Resistive random access memory based on P/N type oxide laminated structure and preparation method thereof | |
| CN102610745B (en) | Si-Sb-Te based sulfur group compound phase-change material for phase change memory | |
| CN111244271B (en) | Phase change material, phase change memory unit and preparation method thereof | |
| WO2017104577A1 (en) | Phase-change material and phase-change type memory element | |
| CN109119534B (en) | A kind of 1S1R type phase-change memory cell structure and preparation method thereof | |
| CN111463345B (en) | Ta-Ge-Sb-Te phase-change material, preparation method thereof and phase-change memory unit |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20100825 Termination date: 20130520 |