CN108899418A - A kind of noncrystal membrane device and its preparation method and application - Google Patents
A kind of noncrystal membrane device and its preparation method and application Download PDFInfo
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- CN108899418A CN108899418A CN201810745219.2A CN201810745219A CN108899418A CN 108899418 A CN108899418 A CN 108899418A CN 201810745219 A CN201810745219 A CN 201810745219A CN 108899418 A CN108899418 A CN 108899418A
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- 239000012528 membrane Substances 0.000 title claims abstract description 122
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000000758 substrate Substances 0.000 claims abstract description 52
- 239000007788 liquid Substances 0.000 claims description 51
- 239000002243 precursor Substances 0.000 claims description 50
- 239000010936 titanium Substances 0.000 claims description 33
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 25
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 claims description 24
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 22
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 229910052697 platinum Inorganic materials 0.000 claims description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 8
- 229910052710 silicon Inorganic materials 0.000 claims description 8
- 239000010703 silicon Substances 0.000 claims description 8
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 claims description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- 229910002328 LaMnO3 Inorganic materials 0.000 claims description 4
- 229910002340 LaNiO3 Inorganic materials 0.000 claims description 4
- 229910003387 SrMnO3 Inorganic materials 0.000 claims description 4
- 229910002353 SrRuO3 Inorganic materials 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims description 4
- 230000005611 electricity Effects 0.000 claims description 4
- 239000011521 glass Substances 0.000 claims description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical group [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052737 gold Inorganic materials 0.000 claims description 4
- 239000010931 gold Substances 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 3
- 239000004411 aluminium Substances 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 239000004332 silver Substances 0.000 claims description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 239000010937 tungsten Substances 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims 1
- 230000015654 memory Effects 0.000 abstract description 11
- 239000010409 thin film Substances 0.000 abstract description 10
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 20
- 230000008859 change Effects 0.000 description 14
- 239000010408 film Substances 0.000 description 13
- 239000000463 material Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 7
- 238000000034 method Methods 0.000 description 6
- 238000003860 storage Methods 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 238000000137 annealing Methods 0.000 description 5
- 239000003292 glue Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 206010016256 fatigue Diseases 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000002441 reversible effect Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 229910002554 Fe(NO3)3·9H2O Inorganic materials 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 229910052712 strontium Inorganic materials 0.000 description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- -1 Acyl acetone Chemical compound 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229910002370 SrTiO3 Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 1
- 238000000224 chemical solution deposition Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- HBAGRTDVSXKKDO-UHFFFAOYSA-N dioxido(dioxo)manganese lanthanum(3+) Chemical compound [La+3].[La+3].[O-][Mn]([O-])(=O)=O.[O-][Mn]([O-])(=O)=O.[O-][Mn]([O-])(=O)=O HBAGRTDVSXKKDO-UHFFFAOYSA-N 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005566 electron beam evaporation Methods 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012163 sequencing technique Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- NDTZMEKCGHOCBU-UHFFFAOYSA-N strontium;dioxido(dioxo)manganese Chemical compound [Sr+2].[O-][Mn]([O-])(=O)=O NDTZMEKCGHOCBU-UHFFFAOYSA-N 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N70/00—Solid-state devices having no potential barriers, and specially adapted for rectifying, amplifying, oscillating or switching
- H10N70/20—Multistable switching devices, e.g. memristors
- H10N70/24—Multistable switching devices, e.g. memristors based on migration or redistribution of ionic species, e.g. anions, vacancies
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N70/00—Solid-state devices having no potential barriers, and specially adapted for rectifying, amplifying, oscillating or switching
- H10N70/011—Manufacture or treatment of multistable switching devices
- H10N70/021—Formation of switching materials, e.g. deposition of layers
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N70/00—Solid-state devices having no potential barriers, and specially adapted for rectifying, amplifying, oscillating or switching
- H10N70/011—Manufacture or treatment of multistable switching devices
- H10N70/041—Modification of switching materials after formation, e.g. doping
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N70/00—Solid-state devices having no potential barriers, and specially adapted for rectifying, amplifying, oscillating or switching
- H10N70/801—Constructional details of multistable switching devices
- H10N70/881—Switching materials
- H10N70/883—Oxides or nitrides
- H10N70/8836—Complex metal oxides, e.g. perovskites, spinels
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Semiconductor Memories (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention belongs to thin-film device technical fields more particularly to a kind of noncrystal membrane device and its preparation method and application.Noncrystal membrane device of the present invention includes：Substrate, first electrode structure, noncrystal membrane layer and second electrode structure；First electrode structure setting is in substrate；The side that first electrode structure deviates from substrate is arranged in noncrystal membrane layer；Second electrode structure setting deviates from the side of first electrode structure in noncrystal membrane layer, and first electrode structure contacts with each other with second electrode structure and connect；Noncrystal membrane layer is SrFexTi1‑xO3Noncrystal membrane layer, wherein x is 0.05~0.5.Noncrystal membrane device of the present invention uses SrFexTi1‑xO3Noncrystal membrane layer, the device have the electric conductivity of apparent rectifier diode, and rectification characteristic is significant；The devices switch ratio is greater than 103, when Current Voltage loop test reaches 40 times, on-off ratio has non-volatile memories almost without great changes；The electric current of the device only has small fluctuation, with good stability and fatigue durability at any time.
Description
Technical field
The invention belongs to thin-film device technical field more particularly to a kind of noncrystal membrane device and preparation method thereof and answer
With.
Background technique
Nonvolatile memory currently on the market based on flash memory (Flash), but with science and technology high speed development, respectively
Class novel electronic product emerges one after another, and there has also been more harsh requirements and more excellent to the properties of memory for electronic product
Change the demand of performance, such as read or write speed is fast, storage density is high, low in energy consumption, the service life is long, thinner and volume is smaller.It can show
For the size of the flash storage part in stage in 65nm or less, traditional multi-crystal silicon floating bar structure is there are erasable and writing speed and reliably
Property contradiction and gate medium leak electricity the problems such as limit advanced optimizing for the memory device.Therefore, it develops a kind of novel
Memory device becomes the new trend of E-Science person.Based on different mechanisms and material, existing multiple memorizers part has at present
Greatly it may can replace flash storage part, such as ferroelectric memory (Ferroelectric Random Access
Memory, FeRAM), magnetic memory (Magnetic Random Access Memory, MRAM), phase transition storage (Phase
Change Random Access Memory, PRAM) and resistance-variable storing device (Resistive Random Access Memory,
RRAM).In these memories, RRAM because it have simple process, low in energy consumption, storage density is high, size is small and with biography
System CMOS technology good compatibility etc. advantages and be widely studied.
RRAM is a kind of nonvolatile memory, which is can be in high-impedance state (HRS) and low with the resistance of thin-film material
Realize that reversible transformation is basic functional principle and the mode as memory between resistance state (LRS), therefore, device operates voltage
It is easier obtain, the bigger storage performance to RRAM of change multiplying power of resistance value more has easily, this just operating to thin-film material
Voltage and resistance value, which change the performances such as multiplying power, very big requirement.
Summary of the invention
In view of this, being deposited the present invention provides a kind of noncrystal membrane device and its preparation method and application with meeting resistive
The requirement that operates the performances such as voltage and resistance value change multiplying power of the reservoir to thin-film material.
The specific technical solution of the present invention is as follows：
A kind of noncrystal membrane device, including：Substrate, first electrode structure, noncrystal membrane layer and second electrode structure；
The first electrode structure setting is in the substrate；
The side that the first electrode structure deviates from the substrate is arranged in the noncrystal membrane layer；
The second electrode structure setting deviates from the side of the first electrode structure in the noncrystal membrane layer, and described the
One electrode structure contacts with each other with the second electrode structure and connect；
The noncrystal membrane layer is SrFexTi1-xO3Noncrystal membrane layer, wherein x is 0.05~0.5.
Preferably, the noncrystal membrane layer is SrFe0.1Ti0.9O3Noncrystal membrane layer.
Preferably, the noncrystal membrane layer with a thickness of 150nm~300nm.
Preferably, the substrate be substrate of glass, silicon wafer substrate, single-crystal strontium titanate substrate, niobium-doped strontium titanate substrate or platinum/
Titanium/silica/silicon (100) substrate.
Preferably, the first electrode structure is platinum electrode, LaNiO3Electrode, SrRuO3Electrode, LaRuO3Electrode,
LaMnO3Electrode, SrMnO3Electrode, ITO electrode or FTO electrode.
Preferably, the second electrode structure is gold electrode, platinum electrode, tungsten electrode, silver electrode or aluminium electrode.
The present invention also provides a kind of preparation methods of noncrystal membrane device, including：
After first electrode structure is formed on the substrate, formed in the side that the first electrode structure deviates from the substrate non-
Polycrystalline thin film layer, then second electrode structure is formed away from the side of the first electrode structure in the noncrystal membrane layer；
Wherein, the first electrode structure contacts with each other with the second electrode structure and connect；
The noncrystal membrane layer is SrFexTi1-xO3Noncrystal membrane layer, x are 0.05~0.5.
Preferably, forming noncrystal membrane layer away from the side of the substrate in the first electrode structure includes：
Ferric nitrate precursor liquid is added dropwise in strontium nitrate precursor liquid and obtains the first mixed liquor, then in first mixed liquor
Butyl titanate precursor liquid is added dropwise and forms SrFexTi1-xO3After precursor liquid, using the SrFexTi1-xO3Precursor liquid is described first
Electrode structure is coated away from the side of the substrate, forms noncrystal membrane layer.
Preferably, second electrode structure packet is formed away from the side of the first electrode structure in the noncrystal membrane layer
It includes：
Film layer removal is carried out in the setting position of the noncrystal membrane layer, to expose the first electrode structure；
The second electrode structure is formed away from the side of the first electrode structure in the noncrystal membrane layer, and described
First electrode structure contacts with each other with the second electrode structure and connect.
The present invention also provides preparation method systems described in noncrystal membrane device described in above-mentioned technical proposal or above-mentioned technical proposal
Application of the noncrystal membrane device obtained in resistance-variable storing device.
In conclusion a kind of noncrystal membrane device of the present invention, including：Substrate, first electrode structure, noncrystal membrane layer and
Two electrode structures；The first electrode structure setting is in the substrate；The noncrystal membrane layer is arranged in the first electrode
Structure deviates from the side of the substrate；The second electrode structure setting deviates from the first electrode knot in the noncrystal membrane layer
The side of structure, the first electrode structure contact with each other with the second electrode structure and connect；The noncrystal membrane layer is
SrFexTi1-xO3Noncrystal membrane layer, wherein x is 0.05~0.5.Noncrystal membrane device of the present invention uses SrFexTi1-xO3Amorphous
Film layer, test result show that the device has the electric conductivity of apparent rectifier diode, and rectification characteristic is significant；The devices switch
It is greater than 10 than (ratio of high-impedance state and low resistance state)3, when Current Voltage loop test reaches 40 times, on-off ratio is almost without very big
Variation has non-volatile memories；The electric current of the device only has small fluctuation at any time, with good stability and resistance to
Fatigability.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described.
Fig. 1 is the structural schematic diagram of one of embodiment of the present invention noncrystal membrane device；
Fig. 2 is the Current Voltage figure of one of embodiment of the present invention noncrystal membrane device；
Fig. 3 is that the Current Voltage of one of embodiment of the present invention noncrystal membrane device recycles figure；
Fig. 4 is the current time figure of one of embodiment of the present invention noncrystal membrane device；
It illustrates：1. substrate；2. first electrode structure；3. noncrystal membrane layer；4. second electrode structure.
Specific embodiment
The present invention provides a kind of noncrystal membrane devices and its preparation method and application, to meet resistance-variable storing device to film
The requirement for operating the performances such as voltage and resistance value change multiplying power of material.
The technical scheme in the embodiments of the invention will be clearly and completely described below, it is clear that described implementation
Example 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 field is common
Technical staff's every other embodiment obtained without making creative work belongs to the model that the present invention protects
It encloses.
Referring to Fig. 1, for the structural schematic diagram of one of embodiment of the present invention noncrystal membrane device.
A kind of one embodiment of noncrystal membrane device provided in an embodiment of the present invention, including：Substrate 1, first electrode knot
Structure 2, noncrystal membrane layer 3 and second electrode structure 4；
First electrode structure 2 is set in substrate 1；
The side that first electrode structure 2 deviates from substrate 1 is arranged in noncrystal membrane layer 3；
Second electrode structure 4 be arranged in noncrystal membrane layer 3 deviate from first electrode structure 2 side, first electrode structure 2 with
Second electrode structure 4 contacts with each other connection；
Noncrystal membrane layer 3 is SrFexTi1-xO3Noncrystal membrane layer, wherein x is 0.05~0.5.
In the embodiment of the present invention, noncrystal membrane layer 3 is SrFe0.1Ti0.9O3Noncrystal membrane layer.
In the embodiment of the present invention, noncrystal membrane layer 3 with a thickness of 150nm~300nm, the thickness of noncrystal membrane layer 3 is more excellent
It is selected as 280nm~300nm.The too thin breakdown voltage of noncrystal membrane layer 3 can reduce, and noncrystal membrane layer 3 is too thick to be not easy to form conductance silk.
In the embodiment of the present invention, substrate 1 is substrate of glass, silicon wafer substrate, single-crystal strontium titanate substrate, niobium-doped strontium titanate substrate
Or platinum/titanium/silica/silicon (100) substrate.Wherein, the chemical formula of niobium-doped strontium titanate is SrTiO3:Nb, platinum/titanium/silica/silicon
(100) chemical formula is Pt/Ti/SiO2/Si(100)。
In the embodiment of the present invention, first electrode structure 2 is platinum electrode, LaNiO3Electrode, SrRuO3Electrode, LaRuO3Electrode,
LaMnO3Electrode, SrMnO3Electrode, ITO electrode or FTO electrode.Wherein, ITO is indium doped tin oxide, and FTO is the oxidation of fluorine doped
Tin.
In the embodiment of the present invention, second electrode structure 4 is gold electrode, platinum electrode, tungsten electrode, silver electrode or aluminium electrode.
In the embodiment of the present invention, substrate 1 is substrate of glass；First electrode structure 2 is FTO electrode；Second electrode structure 4 is
Gold electrode.
Referring to Fig. 2, for the Current Voltage figure of one of embodiment of the present invention noncrystal membrane device.Current-voltage graph
Show electric current with the variation of test voltage, which can indicate the output electric property energy of material, and in Fig. 2, test temperature is 500 DEG C,
Test process voltage increases to full test voltage+5V from -10V, and Fig. 2 shows the change of the electric current in -9.9V~region+4.5V
Change value very little, and reverse saturation current is minimum, illustrates that the unilateral diode of noncrystal membrane device of the present invention conducts electricity very well, it is positive
Breakdown voltage reaches+4.5V, and breakdown reverse voltage is even more to reach -9.9V, shows that the diode of noncrystal membrane device of the present invention is special
Property significant, the electric conductivity with apparent rectifier diode, rectification characteristic is significant.
Referring to Fig. 3, the Current Voltage for one of embodiment of the present invention noncrystal membrane device recycles figure.Current Voltage
In cyclic curve, test voltage from 0V to test voltage maximum value (+Vmax) again to 0V, then it is maximum from 0V to test voltage negative sense
It is worth (- Vmin) again to 0V.In Fig. 3, test temperature is 500 DEG C, when voltage increases to+5V from 0V and is reduced to 0V from+5V again, amorphous
Thin-film device is converted to low resistance state (Low Resistance from the high-impedance state (High Resistance State, HRS) of beginning
State, LRS), there is apparent hysteretic phenomenon in Current Voltage cyclic curve, however is reduced to -5V from 0V, finally returns 0V
During this, the obvious hysteretic phenomenon that the Current Voltage cyclic curve of noncrystal membrane device of the present invention is equally shown,
Noncrystal membrane device of the present invention is converted to high-impedance state from low resistance state again.Fig. 3 shows that electric current all occurs not under all test voltages
Symmetry, negative sense maximum current are greater than forward current.By scheming it can be concluded that noncrystal membrane device unilateal conduction of the present invention, has
Apparent diode resistance change effect, rectification characteristic is preferable, and on-off ratio (ratio of high-impedance state and low resistance state) is greater than 103, have
Non-volatile memories.And with the increase of noncrystal membrane device detection cycle-index, Current Voltage loop test reaches 40 times
When, for on-off ratio almost without great changes, change resistance performance is highly stable, and on-off ratio has almost no change.
Referring to Fig. 4, for the current time figure of one of embodiment of the present invention noncrystal membrane device.The inspection of current time figure
Surveying electric current I indicates the fatigue durability of device with the variation of time T, and in Fig. 4, electric current only has small wave with the time
It is dynamic, show noncrystal membrane device of the present invention fatigue durability with good stability.
It is that a kind of one embodiment of noncrystal membrane device provided in an embodiment of the present invention is described in detail above,
It will be retouched below to a kind of one embodiment progress of the preparation method of noncrystal membrane device provided in an embodiment of the present invention is detailed
It states.
A kind of one embodiment of the preparation method of noncrystal membrane device provided in an embodiment of the present invention, including：
Referring to Fig. 1, deviating from the side of substrate 1 in first electrode structure 2 after forming first electrode structure 2 on the base 1
Noncrystal membrane layer 3 is formed, then forms second electrode structure 4 away from the side of first electrode structure 2 in noncrystal membrane layer 3；
Wherein, first electrode structure 2 contacts with each other with second electrode structure 4 and connect；
Noncrystal membrane layer 3 is SrFexTi1-xO3Noncrystal membrane layer, x are 0.05~0.5.
In the embodiment of the present invention, forming noncrystal membrane layer 3 away from the side of substrate 1 in first electrode structure 2 includes：
Ferric nitrate precursor liquid is added dropwise in strontium nitrate precursor liquid and obtains the first mixed liquor, then is added dropwise in the first mixed liquor
Butyl titanate precursor liquid forms SrFexTi1-xO3After precursor liquid, using SrFexTi1-xO3Precursor liquid deviates from first electrode structure 2
The side of substrate 1 is coated, and noncrystal membrane layer 3 is formed.
In the embodiment of the present invention, the configuration of ferric nitrate precursor liquid includes：With nine water ferric nitrates of mass percent 98.5%
(Fe(NO3)3·9H2O it) is used as raw material, ethyl alcohol is as solvent.By Fe (NO3)3·9H2O is dissolved in ethyl alcohol, stirs 3h at 50 DEG C
To abundant dissolution, ferric nitrate precursor liquid is obtained.
The configuration of strontium nitrate precursor liquid includes：With the strontium nitrate Sr (NO of mass percent 99.5%3)2As raw material, second two
Alcohol is as solvent.By Sr (NO3)2It is dissolved in ethylene glycol, 2h is stirred under room temperature to stabilizer is added dropwise while stirring again after completely dissolution
Acetylacetone,2,4-pentanedione stirs 50min, obtains strontium nitrate precursor liquid.
The configuration of butyl titanate precursor liquid includes：With 99% butyl titanate Ti (OC of mass percent4H9)4As raw material, second
Acyl acetone is as solvent.By Ti (OC4H9)4It is dissolved in acetylacetone,2,4-pentanedione, stirring at normal temperature 2h to being added dropwise while stirring again after completely dissolution
Stabilizer acetylacetone,2,4-pentanedione stirs 50min, obtains butyl titanate precursor liquid.
In the embodiment of the present invention, prepared using ferric nitrate precursor liquid, strontium nitrate precursor liquid and butyl titanate precursor liquid
SrFexTi1-xO3Before precursor liquid, further include：Ferric nitrate precursor liquid, strontium nitrate precursor liquid and butyl titanate precursor liquid are distinguished quiet
It sets 2~3 days.Ferric nitrate precursor liquid, strontium nitrate precursor liquid and the butyl titanate precursor liquid generated without precipitating can be used for preparing
SrFexTi1-xO3Precursor liquid.
Ferric nitrate precursor liquid is added dropwise in strontium nitrate precursor liquid and obtains the first mixed liquor and specifically includes：
Ferric nitrate precursor liquid is slowly added dropwise into strontium nitrate precursor liquid, 3h is at the uniform velocity stirred, obtains the first mixed liquor.
Butyl titanate precursor liquid is added dropwise in the first mixed liquor and forms SrFexTi1-xO3Precursor liquid specifically includes：
Butyl titanate precursor liquid is added dropwise in the first mixed liquor, is at the uniform velocity stirred 3h, obtains the second mixed liquor, if second
Mixed liquor is generated without precipitating, then adjusting the concentration of the second mixed liquor with acetylacetone,2,4-pentanedione is 0.25mol/L~0.3mol/L, then will be mixed
The filtering of liquid filter paper is closed to reduce the dust pollution in air, obtains SrFexTi1-xO3Precursor liquid.
In the embodiment of the present invention, noncrystal membrane layer 3 is prepared using chemical solution deposition.
Using SrFexTi1-xO3Precursor liquid is coated in first electrode structure 2 away from the side of substrate 1, and it is thin to form amorphous
Film layer 3 includes：
By SrFexTi1-xO3Precursor liquid is added dropwise to the side that first electrode structure 2 deviates from substrate 1 dropwise, on sol evenning machine
700rpm~800rpm spin coating 10s~15s, subsequent 2800rpm~3000rpm rotation keep 20s~30s, and every one layer of coating will
Wet film on warm table 180 DEG C of drying glue 10min~15min with except the moisture in striping, 300 DEG C of roasting glue 10min~12min so that
Organic matter in film decomposes, and so repeatedly 2~3 times, 400 DEG C~550 DEG C annealing 12min in quick anneal oven, needed for obtaining
The noncrystal membrane layer 3 of thickness.
In the embodiment of the present invention, using SrFexTi1-xO3 precursor liquid first electrode structure 2 away from substrate 1 side into
Row coating, forming noncrystal membrane layer 3 more specifically includes：Ferric nitrate precursor liquid, strontium nitrate precursor liquid and butyl titanate is respectively configured
Then three kinds of precursor liquids are mixed in together by precursor liquid by certain sequencing, at the uniform velocity stirring 5h, adjust mixed liquor with acetylacetone,2,4-pentanedione
Concentration be 0.25mol/L, ultimately form SrFe0.1Ti0.9O3Precursor liquid.By SrFe0.1Ti0.9O3Precursor liquid is spun and coated at
On one electrode structure FTO electrode, the 800rpm spin coating 10s on sol evenning machine, subsequent 3000rpm rotation keeps 20s, every coating one
Layer, by wet film, 180 DEG C of drying glue 10min are on warm table to remove the moisture in striping, and 300 DEG C of roasting glue 10min are so that having in film
Machine object decomposes, and so repeatedly 2~3 times, obtains the precursor film of required thickness, finally in 500 DEG C of annealing 12min, obtains required thickness
The noncrystal membrane layer 3 of degree.
In the embodiment of the present invention, second electrode structure 4 is formed away from the side of first electrode structure 2 in noncrystal membrane layer 3
Including：
Film layer removal is carried out in the setting position of noncrystal membrane layer 3, to expose first electrode structure 2；
Second electrode structure 4, and first electrode structure 2 are formed away from the side of first electrode structure 2 in noncrystal membrane layer 3
It contacts with each other and connect with second electrode structure 4.
In the embodiment of the present invention, film layer removal is carried out in the setting position of noncrystal membrane layer 3, to expose first electrode knot
Structure 2 includes：
Film layer removal is carried out with diluted hydrofluoric acid in the setting position of noncrystal membrane layer 3, and is being revealed after the completion of short annealing
1 surface of substrate out plates first electrode material, to expose first electrode structure 2.
In the embodiment of the present invention, forming first electrode structure 2 on the base 1 includes：
By first electrode material nickel acid lanthanum (LaNiO3) solution, ruthenic acid strontium (SrRuO3) solution, ruthenic acid lanthanum (LaRuO3) molten
Liquid, lanthanum manganate (LaMnO3) solution or strontium manganate (SrMnO3) solution is spin-coated in substrate 1,300 DEG C of drying glues, annealing.
In the embodiment of the present invention, second electrode structure 4 is formed away from the side of first electrode structure 2 in noncrystal membrane layer 3
Including：
Using template encapsulation method, sputtered away from the side of first electrode structure 2 using electron beam evaporation in noncrystal membrane layer 3
The second electrode material that one layer of diameter is 0.25mm~0.5mm forms second electrode structure 4.
It should be noted that the electric property of noncrystal membrane device of the present invention is by atmosphere, base reservoir temperature, vacuum degree etc.
Influence is very big, needs strict control atmosphere, base reservoir temperature and vacuum degree in the production process.Using sky in the embodiment of the present invention
Gas atmosphere, 20 DEG C of base reservoir temperature, normal pressure.
In noncrystal membrane device of the present invention, the ingredient of noncrystal membrane layer 3 is the strontium titanates (SrFe for mixing ironxTi1-xO3), amorphous
Film layer 3 is the Direct precipitation noncrystal membrane layer in first electrode structure 2, in conjunction with suitable annealing process, so that the amorphous is thin
Membrane module has the diode resistance change effect of highly significant.The preparation condition of noncrystal membrane device of the present invention is easy to get, simple process,
It is suitable for mass production, and the diode resistance change stability of characteristics of noncrystal membrane device, thin small light, the structure of the noncrystal membrane device
Simply, it can be widely applied, be applied in resistance-variable storing device, resistance-variable storing device can be met, voltage and electricity are operated to thin-film material
Resistance value changes the requirement of the performances such as multiplying power, and solves the disadvantage that electronic device thin-film material complex manufacturing technology.The present invention is non-
Brilliant thin-film device preparation process is simple and convenient, and diode resistance change effect is excellent, has immeasurable answer in field of electronic devices
Use prospect.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of noncrystal membrane device, which is characterized in that including：Substrate, first electrode structure, noncrystal membrane layer and second electrode
Structure；
The first electrode structure setting is in the substrate；
The side that the first electrode structure deviates from the substrate is arranged in the noncrystal membrane layer；
The second electrode structure setting deviates from the side of the first electrode structure, first electricity in the noncrystal membrane layer
Pole structure contacts with each other with the second electrode structure and connect；
The noncrystal membrane layer is SrFexTi1-xO3Noncrystal membrane layer, wherein x is 0.05~0.5.
2. noncrystal membrane device according to claim 1, which is characterized in that the noncrystal membrane layer is SrFe0.1Ti0.9O3
Noncrystal membrane layer.
3. noncrystal membrane device according to claim 1, which is characterized in that the noncrystal membrane layer with a thickness of 150nm
~300nm.
4. noncrystal membrane device according to claim 1, which is characterized in that the substrate be substrate of glass, silicon wafer substrate,
Single-crystal strontium titanate substrate, niobium-doped strontium titanate substrate or platinum/titanium/silica/silicon (100) substrate.
5. noncrystal membrane device according to claim 1, which is characterized in that the first electrode structure be platinum electrode,
LaNiO3Electrode, SrRuO3Electrode, LaRuO3Electrode, LaMnO3Electrode, SrMnO3Electrode, ITO electrode or FTO electrode.
6. noncrystal membrane device according to claim 1, which is characterized in that the second electrode structure is gold electrode, platinum
Electrode, tungsten electrode, silver electrode or aluminium electrode.
7. a kind of preparation method of noncrystal membrane device, which is characterized in that including：
It is thin away from the side of substrate formation amorphous in the first electrode structure after first electrode structure is formed on the substrate
Film layer, then second electrode structure is formed away from the side of the first electrode structure in the noncrystal membrane layer；
Wherein, the first electrode structure contacts with each other with the second electrode structure and connect；
The noncrystal membrane layer is SrFexTi1-xO3Noncrystal membrane layer, x are 0.05~0.5.
8. preparation method according to claim 7, which is characterized in that in the first electrode structure away from the substrate
Side forms noncrystal membrane layer：
Ferric nitrate precursor liquid is added dropwise in strontium nitrate precursor liquid and obtains the first mixed liquor, then is added dropwise in first mixed liquor
Butyl titanate precursor liquid forms SrFexTi1-xO3After precursor liquid, using the SrFexTi1-xO3Precursor liquid is in the first electrode
Structure is coated away from the side of the substrate, forms noncrystal membrane layer.
9. preparation method according to claim 7, which is characterized in that deviate from the first electrode in the noncrystal membrane layer
The side of structure forms second electrode structure：
Film layer removal is carried out in the setting position of the noncrystal membrane layer, to expose the first electrode structure；
The second electrode structure, and described first are formed away from the side of the first electrode structure in the noncrystal membrane layer
Electrode structure contacts with each other with the second electrode structure and connect.
10. noncrystal membrane device or claim 7 described in claim 1 to claim 6 any one are any to claim 9
Application of the noncrystal membrane device in resistance-variable storing device made from one preparation method.
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