CN105702857B - A kind of non-volatile more bit micro-/ nano resistance-variable storing devices and application method based on trap states regulation and control - Google Patents

A kind of non-volatile more bit micro-/ nano resistance-variable storing devices and application method based on trap states regulation and control Download PDF

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Publication number
CN105702857B
CN105702857B CN201610160435.1A CN201610160435A CN105702857B CN 105702857 B CN105702857 B CN 105702857B CN 201610160435 A CN201610160435 A CN 201610160435A CN 105702857 B CN105702857 B CN 105702857B
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micro
nano
voltage
resistance
variable storing
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CN105702857A (en
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赵婕
程抱昌
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Hengfeng Honglian Aluminum Co ltd
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Nanchang University
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    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10NELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N70/00Solid-state devices without a potential-jump barrier or surface barrier, and specially adapted for rectifying, amplifying, oscillating or switching
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10NELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N70/00Solid-state devices without a potential-jump barrier or surface barrier, and specially adapted for rectifying, amplifying, oscillating or switching
    • H10N70/801Constructional details of multistable switching devices

Abstract

It is a kind of based on trap states regulation and control non-volatile more bit micro-/ nano resistance-variable storing devices and application method, resistance-variable storing device include dielectric substrate, the one-dimensional micro-/ nano lines of ZnO of single Sn element dopings, electrode, encapsulating material etc..The one-dimensional micro-/ nano lines of ZnO of single Sn element dopings are placed in dielectric substrate, and electrode is respectively welded in both ends;Encapsulating material by the one-dimensional micro-/ nano lines of the ZnO of single Sn element dopings, electrode package on an insulating substrate.Apply write-in voltage when information is written between two end electrodes.Apply write-in voltage when non-volatile more bit storages between two end electrodes, then remove write-in voltage and applies reading voltage.Apply write-in voltage when information erasing between two end electrodes, then remove write-in voltage and apply reading voltage, then be placed in 70 DEG C of environment, is subsequently placed in room temperature.The present invention realizes response and storage to electric field information, and simple process, small, light and handy portable, good compatibility can be utilized efficiently.

Description

A kind of non-volatile more bit micro-/ nano resistance-variable storing devices based on trap states regulation and control And application method
Technical field
The present invention relates to micro/nano material technical field, it is related to a kind of utilizing the non-volatile of trap states regulation and control Resistance states More bit micro-/ nano resistance-variable storing devices, can be without constructing gate voltage and particular device structure, will be according to different big Small electric signal is into the reading of row information, write-in, storage and erasing.
Background technology
In recent years, in various novel non-volatile memories, resistance-variable storing device is since it is with simple in structure, energy consumption Low, fast response time, repetitive read-write is good, time information memory is long, non-destructive is read, can expand assembling and CMOS technology can It the advantages that compatible, receives domestic and international scientist and widely pays close attention to.Resistance switch effect is as object crucial in resistance-variable storing device Phenomenon is managed, is widely found in electrolyte, perovskite material, transparent metal oxide.The electricity of resistor switching device Current-voltage characteristic curve can quickly change with voltage change between high-impedance state and low resistance state.Although resistance switch effect is Through clearly being observed, however its mechanism, still in continuous research, studying the possibility obtained at present leads to resistance switch Mechanism have filament effect, Lacking oxygen migration, electron transition conduction, Schottky tunnel modulation, Poole-Frenkel excitation etc. Deng.Nearest researcher observed negative differential resistance effect in the monodimension nanometer material with resistance switch effect.In addition, the back of the body This effect, which is based on, also to be found in the one-dimensional nano structure device that both ends are same metal electrode to the resistance switch effect of the back of the body The local effect to injecting electronics of surface trap state can store charge and electronics for a long time.In order to realize that non-volatile resistance state is deposited Effect is stored up, the both ends of single-walled carbon nanotube are welded on SiO by James M. Tour seminars2On/Si substrates, and in bottom structure Build a gate electrode.Charge is in carbon nanotube and SiO under the action of gate voltage2Interface is captured.It is this based on single one-dimensional The nano-device of single-walled carbon nanotube structure has resistance switch effect and non-volatile memories function.Ting Yu seminars Single one-dimensional ZnO nanowires are welded on ferroelectricity Pb (Zr0.3Ti0.7)O3On film, it is built into the field-effect tube with gate electrode (FET), storage effect can be effectively adjusted by gate voltage.Wooyoung Shim et al. are in single one-dimensional Ge/Si nucleocapsids The gate electrode of two superpositions is constructed on nano wire, the gate electrode of constructed internal layer can control the switch of resistance, outer layer gate electrode Have the function of adjusting resistance state.Constructed device has the effect of more bit resistance-variable storing devices, while its on-off ratio is big, stablizes Time is long, can be integrated applied in logic circuit.Minghui Cao etc. are in GeSe2Incorporation Bi forms orderly superstructure and receives Rice band.Under high voltages, electronics jumps to conduction band from Bi impurity energy levels, under interfacial polarization effect, the electronics of transition out Local is in space-charge region, and electron transition leaves empty trap and is kept always.This makes by single GeSe2:Bi nanometers The two ends welding Ag electrode nano-devices that band is constructed are alternatively arranged as non-volatile resistive while being switched with negative differential resistance Memory.
Although domestic and international researcher has been obtained for some achievements in terms of Nonvolatile resistance variation memory, in order to obtain Non-volatile more bit storage performances are obtained, researcher can build gate voltage or design particular device structure when designing device, few Number need not build the resistance-variable storing device of gate voltage or particular device structure, and also only there are two resistance states, are difficult to realize more bit storages Performance.
Invention content
The present invention provides a kind of non-volatile more bit micro-/ nano resistance-variable storing devices regulated and controled based on trap states, is a kind of Without constructing gate voltage and particular device structure, non-volatile more bit micro-/ nano resistance-variable storing devices can respond different electricity Field signal is simultaneously stored for a long time, it can be achieved that more bit storages of electric field signal and existing non-volatile more bits memory is overcome to deposit Dependence of the reservoir to gate voltage and particular device structure,
The present invention is achieved by the following technical solutions.
A kind of non-volatile more bit micro-/ nano resistance-variable storing devices based on trap states regulation and control of the present invention, including Dielectric substrate(101), single Sn element dopings the one-dimensional micro-/ nano lines of ZnO(102), electrode one(103), electrode two(104)、 Conducting wire one(105), conducting wire two(106), encapsulating material(107).The one-dimensional micro-/ nano lines of ZnO of single Sn element dopings(102)It puts It sets in dielectric substrate(101)On, the one-dimensional micro-/ nano lines of ZnO of single Sn element dopings(102)Electrode one is respectively welded in both ends (103)With electrode two(104), electrode one(103)With electrode two(104)It is separately connected conducting wire one(105)With conducting wire two(106); Encapsulating material(107)By the one-dimensional micro-/ nano lines of ZnO of entire single Sn element dopings(102), electrode one(103)With electrode two (104)It is encapsulated in dielectric substrate(101)On.
Preferably, the one-dimensional micro-/ nano lines of ZnO of the single Sn element dopings are that incorporation Sn elements are miscellaneous in ZnO lattices The one-dimensional micro-/ nano line of matter defect.
Preferably, the dielectric base is aluminium oxide ceramics substrate, aluminium nitride ceramics substrate or silicon nitride ceramics substrate.
Preferably, the metal electrode is aluminium, silver or platinum.
Preferably, the encapsulating material is epoxy resin, urethanes, dimethyl silicone polymer or poly- methyl-prop E pioic acid methyl ester.
It, can be by conducting wire one when micro-/ nano resistance-variable storing device work of the present invention(105)With conducting wire two(106)With letter Number forcing function generator(108)Connection.
Above-mentioned non-volatile more bit micro-/ nano resistance-variable storing devices pair are used it is a further object to provide a kind of The method of response, the storage, erasing of different electric field signals.
(1)A kind of information write-in method of non-volatile more bit micro-/ nano resistance-variable storing devices based on trap states regulation and control, It is characterized in that applying any write-in voltage in 1V-10V between micro-/ nano resistance-variable storing device two end electrodes.
(2)It is a kind of based on trap states regulation and control the non-volatile of non-volatile more bit micro-/ nano resistance-variable storing devices compare more Special storage method, it is characterized in that applying any in 1V-10V write between the micro-/ nano resistance-variable storing device two end electrodes Enter voltage, then removes write-in voltage and apply 0.5V and read voltage.
(3)A kind of information erasing method of non-volatile more bit micro-/ nano resistance-variable storing devices based on trap states regulation and control, It is characterized in that applying any write-in voltage in 1V-10V between micro-/ nano resistance-variable storing device two end electrodes, write-in is then removed Voltage simultaneously applies 0.5V reading voltages, then micro-/ nano resistance-variable storing device is positioned in 70 DEG C of environment, is subsequently placed to room temperature ring In border.
Compared with prior art, the present invention has the following advantages.
(1)Using upper new breakthrough.The present invention utilizes the modulating action of electronics in trap states, realizes to electric field information Response and storage;The micro-/ nano resistance-variable storing device can have any voltage in identification 1V to 12V, according to the size of voltage It is distinguishing to be stored in signal in the micro-/ nano resistance-variable storing device, realize more bit storage performances.
(2)Simple process, small, light and handy portable, good compatibility.The micro-/ nano resistance-variable storing device of the present invention is not necessarily to structure It builds gate voltage and particular device structure is achieved with the storage of non-volatile and more bits, simplify production process, save energy Source consumes;The micro-/ nano resistance variation memory structure of the present invention is simple, small, manufacture craft is simple, of low cost, and is not necessarily to Special working environment has good environment compatibility.
(3)Efficiently utilize.The micro-/ nano resistance-variable storing device of the present invention is without extensive, high intensity energy input, it is only necessary to It places in atmospheric environment;Electric field signal can be repeatedly written-storage-and wiped by the micro-/ nano resistance-variable storing device of the present invention, Keep resistance-variable storing device Ke Xunhuanliyong;The micro-/ nano resistance-variable storing device of the present invention has more bit storage performances, increases storage Density realizes the efficient utilization of the energy.
Description of the drawings
Fig. 1 is a kind of typical structure schematic diagram of the micro-/ nano resistance-variable storing device of the present invention.Wherein, 101 be insulation lining Bottom, 102 for single Sn element dopings the one-dimensional micro-/ nano lines of ZnO, 103 be electrode one, 104 be electrode two, 105 be conducting wire one, 106 be that conducting wire two, 107 is encapsulating material, 108 is function performance generator.
Fig. 2 be the present invention micro-/ nano resistance-variable storing device 2V, 4V, 6V, 8V, 10V voltage write-in after, storage performance survey Examination, the bold portion on picture top are the electric current in test process, and the dotted portion of picture lower part is the operation in test process Voltage.
Fig. 3 be the present invention micro-/ nano resistance-variable storing device 2V, 4V, 6V, 8V, 10V voltage write-in after, electric current is at any time Variation diagram.
Fig. 4 is repetitive read-write performance test curve of the micro-/ nano resistance-variable storing device of the present invention at 2V, picture top Bold portion is the electric current in test process, and the dotted portion of picture lower part is the operation voltage in test process.
Fig. 5 is repetitive read-write performance test curve of the micro-/ nano resistance-variable storing device of the present invention at 4V, picture top Bold portion is the electric current in test process, and the dotted portion of picture lower part is the operation voltage in test process.
Fig. 6 is repetitive read-write performance test curve of the micro-/ nano resistance-variable storing device of the present invention at 6V, picture top Bold portion is the electric current in test process, and the dotted portion of picture lower part is the operation voltage in test process.
Fig. 7 is repetitive read-write performance test curve of the micro-/ nano resistance-variable storing device of the present invention at 8V, picture top Bold portion is the electric current in test process, and the dotted portion of picture lower part is the operation voltage in test process.
Fig. 8 is repetitive read-write performance test curve of the micro-/ nano resistance-variable storing device of the present invention at 10V, picture top Bold portion be electric current in test process, the dotted portion of picture lower part is the operation voltage in test process.
Specific implementation mode
Below in conjunction with embodiment and attached drawing, technical scheme of the present invention is clearly and completely described.Obviously, institute The embodiment of description is only a part of the embodiment of the present invention, instead of all the embodiments, based on the embodiments of the present invention, this The every other embodiment that field those of ordinary skill is obtained without making creative work, belongs to the present invention Protection domain.
Secondly, combination schematic diagram of the present invention is described in detail, when describing the embodiments of the present invention, for purposes of illustration only, institute It is example to state schematic diagram, should not limit the scope of protection of the invention herein.
A kind of micro-/ nano resistance-variable storing device of present invention offer can without grid voltage and particular device structure Respond any voltage in 1V to 10V, according to the size of voltage between two end electrodes it is distinguishing electric signal is stored in it is described In micro-/ nano resistance-variable storing device, non-volatile more bit storage performances are realized.A kind of micro-/ nano resistance-variable storing device of the present invention Using the trap level in the ZnO micro-/ nano lines of single Sn element dopings, electronics in trap level is filled by extra electric field State regulates and controls the resistance of device, realizes non-volatile more bit storage performances to electric signal.
Fig. 1 shows that the micro-/ nano resistance-variable storing device typical structure schematic diagram of the present invention includes dielectric base successively 101, the ZnO micro-/ nanos line 102 of single Sn codopes, electrode 1, electrode 2 104, conducting wire 1, conducting wire 2 106, envelope Package material 107, function performance generator 108.
The dielectric base 101 is by aluminium oxide ceramics substrate, aluminium nitride ceramics substrate, any material of silicon nitride ceramics substrate Material is constituted.The ZnO micro-/ nanos line 102 of the single Sn doping is to contain the one-dimensional of Sn element impurity defects in ZnO lattices Micro-/ nano line, preparation process are.
1, it cleans and dries corundum ceramic substrate and ceramic boat.
2, according to 4:1:2 mass ratio weighs required ZnO powder, SnO2Powder and C powder are as evaporation source, in agate alms bowl It is ground, so that it is sufficiently mixed and hook.Then ceramics of the mixed raw material of 3 g or so as evaporation source charging feedstock cleaning are taken In boat, ceramic boat is slowly pushed into ceramic tube weather, leeward will be then put into equipped with ceramic substrate, and ensure equipped with mixed The ceramic boat for closing object is just aligned at thermocouple, preferably to control temperature, it is allowed effectively to evaporate.
3, first it is passed through the nitrogen of 10 min in advance into ceramic tube, after, tube furnace is set to 1100oC is adjusted Electric current makes furnace temperature with 50oThe rate of C/min starts to warm up, and is continually fed into the mixed gas of nitrogen and hydrogen, in order to Airflow rate need to be controlled by preventing powder to be blown away, and keep stable throughput, and suitable growth is provided for Sn doping zinc oxide nanometer sticks Condition after being raised to assigned temperature, keeps the temperature 3h.Stop heating after to the time, 60 are dropped in temperature oCAir valve can be closed, it is cooling to cause Find that osmanthus on piece deposited a large amount of white product after room temperature.
The metal electrode 1, electrode 2 104, selected from aluminium, silver, platinum, gold.
The encapsulated layer is selected from epoxy resin, urethanes, dimethyl silicone polymer, polymethyl methacrylate In any one.
In conjunction with Fig. 1, a kind of preparation process of micro-/ nano resistance-variable storing device of the invention includes.
1, dielectric base 101 uses specification with absolute ethyl alcohol and to be gone for the aluminium oxide ceramics substrate of 20mm X 10mm X 1mm Ionized water ultrasound is respectively washed 3 times.
2, the one-dimensional micro-/ nano lines of the ZnO of single Sn doping 102 use a diameter of 5 μm of length for 735 μm of micro-/ nano line, Disperse the one-dimensional micro-/ nano lines 102 of ZnO of Sn element dopings and be horizontally placed in dielectric base 101, in the ZnO mono- of Sn element dopings Electrode 1, electrode 2 104 is respectively welded in 102 both ends of dimension micro-/ nano line, and electrode one, electrode two are silver paste.
3, it waits for that silver paste is dried at room temperature, welds copper wire as conducting wire 1 in electrode 1, electrode 2 104 welds copper wire As conducting wire 1, circuit is drawn.
4, good 107 dimethyl silicone polymer of encapsulating material (PDMS) of coating pre-coordination, and it is positioned over heated at constant temperature face On plate, it is warming up to 150 DEG C of 2 h of solidification.
5, the external circuit and function generator 108 that copper wire is drawn is connected, completes the preparation of thermal electric generator.
The micro-/ nano resistance-variable storing device of the present invention is introduced respectively in 2V, 4V, 6V, 8V, 10V electricity with reference to Fig. 2 to Fig. 8 The method of pressure write-in, storage, erasing and cycle read-write
Embodiment 1.
Fig. 2 be the present invention micro-/ nano resistance-variable storing device 2V, 4V, 6V, 8V, 10V voltage write-in after, storage performance survey Examination.The function generator that the micro-/ nano resistance-variable storing device two end electrodes are connected is adjusted to read voltage 0.5V, it then will be electric Pressure is adjusted to write-in voltage, and write-in voltage is 2V, 4V, 6V, 8V, the 10V arbitrarily chosen in 1V-10V, is adjusted after information of voltage write-in It is back to and reads voltage 0.5V.As shown in Fig. 2, after voltage 2V, 4V, 6V, 8V, 10V write-in, the micro-/ nano resistance-change memory Utensil has different resistance states.The ZnO micro-/ nano lines of Sn doping have the trap energies such as impurity energy level, surface state, intrinsic defect Grade, different write-in voltage can fill the trap level of different depth.After trap is filled with electrons, the micro-/ nano The resistance states of resistance-variable storing device change.
Embodiment 2.
Fig. 3 be the present invention micro-/ nano resistance-variable storing device 2V, 4V, 6V, 8V, 10V voltage write-in after, electric current is at any time Variation diagram.Specially first the function generator that the micro-/ nano resistance-variable storing device two end electrodes are connected is adjusted to read voltage Write-in voltage is then adjusted to 2V, 4V, 6V, 8V, 10V by 0.5V respectively, is recalled to after information of voltage write-in to reading voltage 0.5V And the stability of tester electric current increase with time.As shown in figure 3, after voltage 2V, 4V, 6V, 8V, 10V write-in, in trap Hole is filled with electrons, and is removed write-in voltage and is applied reading voltage, the correspondence of the micro-/ nano resistance-variable storing device is specific Write-in voltage has specific resistance states, and resistance states can be kept for a long time.When the hole in trap is filled with electrons Afterwards, electronics receives the effect of trap local and is limited in trap so that after write-in voltage removes, resistance states can be protected for a long time It handles, realizes good storage stability.
Embodiment 3.
Fig. 4 to Fig. 8 be the present invention micro-/ nano resistance-variable storing device in the case that write-in voltage be 2V, 4V, 6V, 8V, 10V Repeated readwrite performance test.Specially:Step 1, the letter that the micro-/ nano resistance-variable storing device two end electrodes are connected Number generator is adjusted to read voltage 0.5V, and voltage is then adjusted to 2V, 4V, 6V, 8V, 10V respectively and is written into row information;Step Two, micro-/ nano resistance-variable storing device both end voltage is recalled to voltage 0.5V and reads information;Step 3 hinders the micro-/ nano Transition storage is positioned over progress signal erase process in 70 DEG C of environment;Step 4 restores room temperature, micro-/ nano resistance-variable storing device Resistance state restPoses;Repetitive cycling step 1 is removed to the repeatability of the step 4 detection micro-/ nano resistance-variable storing device It is written outside voltage, the readings voltage in all steps is the DC voltage of 0.5V, and dotted portion is tested in Fig. 4 to Fig. 8 Operation voltage in journey.If Fig. 4 to Fig. 8 bold portions is respectively the micro-/ nano resistance-change memory being written with 2V, 4V, 6V, 8V, 10V Device recycles readwrite performance figure.Micro-/ nano resistance-variable storing device after voltage is written can preserve resistance state for a long time, until being positioned over 70 Signal is wiped in DEG C environment.The ZnO micro-/ nanos line of Sn element dopings can form a series of trap states.In the case where voltage is written, fall into Hole in trap is filled with electrons, since trap has the function of local electronic, after write-in voltage removes, and micro-/ nano resistive Memory can preserve resistance state for a long time.Micro-/ nano resistance-variable storing device is positioned in 70 DEG C of environment, after the electronics in trap is heated Trap is escaped, the resistance value state of micro-/ nano resistance-variable storing device restores to original state, and storage signal is wiped free of.It is described it is micro-/receive Rice resistance-variable storing device has different write-in voltage the performance of identifiable storage performance and repetitive read-write so that described Micro-/ nano resistance-variable storing device has good recycling performance.

Claims (7)

1. a kind of non-volatile more bit micro-/ nano resistance-variable storing devices based on trap states regulation and control, including dielectric substrate(101)、 The one-dimensional micro-/ nano lines of ZnO of single Sn element dopings(102), electrode one(103), electrode two(104), conducting wire one(105), lead Line two(106), encapsulating material(107);The one-dimensional micro-/ nano lines of ZnO of single Sn element dopings(102)It is placed on dielectric substrate (101)On, the one-dimensional micro-/ nano lines of ZnO of single Sn element dopings(102)Electrode one is respectively welded in both ends(103)With electrode two (104), electrode one(103)With electrode two(104)It is separately connected conducting wire one(105)With conducting wire two(106);Encapsulating material(107) By the one-dimensional micro-/ nano lines of ZnO of entire single Sn element dopings(102), electrode one(103)With electrode two(104)It is encapsulated in absolutely Edge substrate(101)On;It is characterized in that the one-dimensional micro-/ nano lines of ZnO of the single Sn element dopings are to mix Sn in ZnO lattices The one-dimensional micro-/ nano line of element impurity defect.
2. micro-/ nano resistance-variable storing device according to claim 1, it is characterized in that the dielectric base is alumina ceramic-base Bottom, aluminium nitride ceramics substrate or silicon nitride ceramics substrate.
3. micro-/ nano resistance-variable storing device according to claim 1, it is characterized in that the electrode one, electrode two are aluminium, silver Or platinum.
4. micro-/ nano resistance-variable storing device according to claim 1, it is characterized in that the encapsulating material be epoxy resin, Urethanes, dimethyl silicone polymer or polymethyl methacrylate.
5. the information write-in method of micro-/ nano resistance-variable storing device described in claim 1, it is characterized in that being deposited in micro-/ nano resistive Apply any write-in voltage in 1V-10V between reservoir two end electrodes.
6. the storage method of non-volatile more bits of micro-/ nano resistance-variable storing device described in claim 1, it is characterized in that in institute Apply any write-in voltage in 1V-10V between the micro-/ nano resistance-variable storing device two end electrodes stated, then removes write-in voltage simultaneously Apply 0.5V and reads voltage.
7. the information erasing method of micro-/ nano resistance-variable storing device according to claim 1, it is characterized in that being hindered in micro-/ nano Apply any write-in voltage in 1V-10V between transition storage two end electrodes, then removes write-in voltage and apply 0.5V and read electricity Pressure, then micro-/ nano resistance-variable storing device is positioned in 70 DEG C of environment, it is subsequently placed in room temperature environment.
CN201610160435.1A 2016-03-21 2016-03-21 A kind of non-volatile more bit micro-/ nano resistance-variable storing devices and application method based on trap states regulation and control Expired - Fee Related CN105702857B (en)

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