CN106340586A - Preparation method of carbon/nickel oxide resistive memory thin film - Google Patents

Preparation method of carbon/nickel oxide resistive memory thin film Download PDF

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Publication number
CN106340586A
CN106340586A CN201610859007.8A CN201610859007A CN106340586A CN 106340586 A CN106340586 A CN 106340586A CN 201610859007 A CN201610859007 A CN 201610859007A CN 106340586 A CN106340586 A CN 106340586A
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carbon
film
nickel oxide
preparation
nickel
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CN106340586B (en
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李颖
赵高扬
杨志孟
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Xian University of Technology
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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 having no potential barriers, and specially adapted for rectifying, amplifying, oscillating or switching
    • H10N70/801Constructional details of multistable switching devices
    • H10N70/881Switching materials
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10NELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N70/00Solid-state devices having no potential barriers, and specially adapted for rectifying, amplifying, oscillating or switching
    • H10N70/011Manufacture or treatment of multistable switching devices
    • H10N70/021Formation of switching materials, e.g. deposition of layers
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10NELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N70/00Solid-state devices having no potential barriers, and specially adapted for rectifying, amplifying, oscillating or switching
    • H10N70/011Manufacture or treatment of multistable switching devices
    • H10N70/021Formation of switching materials, e.g. deposition of layers
    • H10N70/026Formation of switching materials, e.g. deposition of layers by physical vapor deposition, e.g. sputtering
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10NELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N70/00Solid-state devices having no potential barriers, and specially adapted for rectifying, amplifying, oscillating or switching
    • H10N70/801Constructional details of multistable switching devices
    • H10N70/881Switching materials
    • H10N70/883Oxides or nitrides
    • H10N70/8833Binary metal oxides, e.g. TaOx

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  • Manufacturing & Machinery (AREA)
  • Semiconductor Memories (AREA)
  • Thermistors And Varistors (AREA)

Abstract

The invention discloses a preparation method of a carbon/nickel oxide resistive memory thin film. The method includes the following steps that: a nickel oxide thin film is prepared; and a carbon film is prepared on the nickel oxide thin film, so that a carbon/nickel oxide composite thin film is prepared, top electrode preparation is performed on the carbon/nickel oxide composite thin film through using a sputtering apparatus, and the carbon/nickel oxide resistive memory thin film is obtained. According to the method of the invention, the carbon film and the nickel oxide thin film are composited, and therefore, compared with other materials having resistance variation characteristics, the carbon/nickel oxide composite thin film prepared by the preparation method of the invention has a smooth surface, and the preparation method has the advantages of low preparation cost, simple techniques and easiness in control, and can improve the preparation efficiency of the composite thin film, and the resistance variation performance of the carbon/nickel oxide composite thin film is significantly better than that of a single nickel oxide thin film.

Description

A kind of preparation method of carbon/nickel oxide Memister film
Technical field
The invention belongs to microelectronic material resistance-variable storing device thin-film material technical field is and in particular to a kind of carbon/nickel oxide The preparation method of Memister film.
Background technology
With the raising of people's life requirement, either notebook computer, portable hard drive or smart mobile phone sum code-phase The memory that machine etc. is required to excellent performance ensures people to data, the demand to information Store.Meanwhile, the complexity of data and Pang Substantially make the requirement more and more higher of storage capacity, erasable ability and reading speed to data for the people, low cost, low-power consumption and height The memory of storage density will become the primary trend of future development.Non-volatility memorizer is mainly with " flash memory " memory (flash) based on.Flash memory is non-volatile due to having, and each restarting equipment can save substantial amounts of time cost, Thus be widely used.But its erasable speed slow (more than ms level), and erasing voltage is also higher.These lack Point makes flash be difficult to meet the demand to information Store for the people.When particularly element height is integrated now, tunnel oxide thickness Degree more and more thinner, electric charge tunneling effect makes the bad stability of flash memory.Meanwhile, resistance-type memory is continuous Ground all has each towards low-power consumption, high density, low cost and read or write speed development faster, the resistance-type memory of a new generation Feature.Therefore, how to reduce erasing voltage while improving its erasable speed is a key issue.
Content of the invention
It is an object of the invention to provide a kind of preparation method of carbon/nickel oxide Memister film, solve existing depositing The problem that reservoir erasable speed is slow and erasing voltage is high.
The technical solution adopted in the present invention is, a kind of preparation method of carbon/nickel oxide Memister film, specifically presses Implement according to following steps:
Step 1, prepares nickel oxide film;
Step 2, prepares carbon film on step 1 gained nickel oxide film, obtains carbon/oxidation nickel composite film;
Step 3, carries out top electrode preparation using sputter to step 2 gained carbon/oxidation nickel composite film, obtains final product.
The present invention is further characterized in that,
In step 1, the preparation process of nickel oxide film is:
Step 1.1: prepare oxidation nickel sol;
Step 1.2: at room temperature, using dipping-pulling method by step 1.1 gained oxidation nickel sol in pt platinum electrode base Lift on plate, obtain nickel oxide gel film;
Step 1.3: after the nickel oxide gel film that step 1.2 is obtained is dried at room temperature for, toast at 60~80 DEG C 10~15min, is subsequently heat-treated 20~30min at a temperature of 300~700 DEG C, after cooling, obtains final product on pt platinum electrode substrate Nickel oxide film.
In step 1.1, the process for preparation of oxidation nickel sol is: by nickel acetate, acetylacetone,2,4-pentanedione, acrylic acid and EGME Consumption mixing by 1:1:1:12.
In step 2, the preparation process of carbon/oxidation nickel composite film is:
Step 1 gained nickel oxide film is placed on the supporting spring of vacuum evaporation instrument fixing, then carbon rope is fixed on carbon Evaporation source on;Open vacuum evaporation instrument power supply, the electric current adjusting evaporation instrument, to 50~60a, is deposited with, after carbon fracture of rope, Stop evaporation, after cooling, obtain final product carbon/oxidation nickel composite film.
Carbon rope is made up of the graphite fibre of purity 99%, a diameter of 2 millimeters, and carbon rope length degree is 1 centimetre.
In step 3, using the process that sputter carries out top electrode preparation to carbon/oxidation nickel composite film it is: open sputtering Instrument, carbon/oxidation nickel composite film sample is put into, fixes mask plate (mask), then open sputter power supply, taken out Gas, when vacuum reaches 1*10-3After pa, the sputtering of top electrode is carried out to it.
Sputtering target material is pt, and purity is 99.9%, and sputtering time is 5~7min.
The invention has the beneficial effects as follows, carbon film is combined with nickel oxide film, is compared to other and there is resistive spy The material of property, the smooth surface of carbon/oxidation nickel composite film, preparation cost is low, process is simple, be easily controlled, and improves preparation The preparation efficiency of laminated film, and its change resistance performance is substantially better than single nickel oxide film.
Brief description
Fig. 1 is atomic force (afm) scanned photograph on the embodiment of the present invention 1 gained nickel oxide film surface;
Fig. 2 is atomic force (afm) scanned photograph on the embodiment of the present invention 2 gained nickel oxide film surface;
Fig. 3 is atomic force (afm) scanned photograph on the embodiment of the present invention 3 nickel oxide film surface;
Fig. 4 is nickel oxide film heat treatment cycle curve figure in the inventive method;
Fig. 5 is C-V characteristic (i-v) curve of the embodiment of the present invention 3 gained carbon/nickel oxide Memister thin-film device;
Fig. 6 be the embodiment of the present invention 3 gained carbon/nickel oxide Memister film in each element with etching depth change Curve map.
Specific embodiment
The present invention is described in detail with reference to the accompanying drawings and detailed description.
A kind of preparation method of carbon of the present invention/nickel oxide Memister film, specifically implements according to following steps:
Step 1, prepares nickel oxide film:
Step 1.1: prepare oxidation nickel sol: nickel acetate, acetylacetone,2,4-pentanedione, acrylic acid and EGME are pressed 1:1:1:12 Consumption (herein amount ratio be mol ratio) mixing, during preparation, in glove box, (under room temperature) is prepared;
Step 1.2: at room temperature, using dipping-pulling method by step 1.1 gained oxidation nickel sol in pt platinum electrode base Lift on plate, obtain nickel oxide gel film;
Step 1.3: after the nickel oxide gel film that step 1.2 is obtained is dried at room temperature for, toast at 60~80 DEG C 10~15min, the volatilization that can accelerate liquid phase component promotes intermolecular polymerisation, subsequently at heat at a temperature of 300~700 DEG C Reason 20~30min (heat treatment is carried out in heat-treatment furnace), is finally cooled to room temperature with heat-treatment furnace, that is, heat treatment process is one The process of individual heating and heat preservation cooling, obtains final product the nickel oxide film on pt platinum electrode substrate.
Step 2, step 1 gained nickel oxide film is placed on the supporting spring of vacuum evaporation instrument fixing, then that carbon rope is solid It is scheduled on the evaporation source of carbon;Open vacuum evaporation instrument power supply, the electric current adjusting evaporation instrument, to 50~60a, is deposited with, and carbon rope breaks After splitting, stop evaporation, after cooling, obtain final product carbon/oxidation nickel composite film;Wherein, carbon rope by purity 99%, a diameter of 2 millimeters Graphite fibre is made, and carbon rope length degree is 1 centimetre.
Step 3, carries out top electrode preparation using sputter to step 2 gained carbon/oxidation nickel composite film: open sputtering Instrument, carbon/oxidation nickel composite film sample is put into, fixes mask plate (mask), then open sputter power supply, taken out Gas, when vacuum reaches 1*10-3After pa, the sputtering of top electrode is carried out to it, obtain final product.Sputtering target material is pt, and purity is 99.9%, Sputtering time is 5~7min.
Embodiment 1
Step 1: weigh nickel acetate, acetylacetone,2,4-pentanedione, acrylic acid and EGME respectively by the amount ratio of 1:1:1:12, mix After conjunction, obtain oxidation nickel sol;At room temperature, using dipping-pulling method, carry out oxygen using pulling machine on pt platinum electrode substrate Change the lifting of nickel gel film, after the nickel oxide gel film that lifting is obtained is dried at room temperature, toast at 60 DEG C 10min, is subsequently heat-treated 20min at a temperature of 300 DEG C, then takes out and naturally cool to room temperature, that is, obtain in pt platinum electrode Nickel oxide film on substrate.
Step 2: the preparation of carbon/oxidation nickel composite film: step 1 gained nickel oxide film is placed on vacuum evaporation instrument Fixing on supporting spring, then by purity 99%, a diameter of 2 millimeters, the carbon rope of length 1cm is fixed on the evaporation source of carbon;Open true Empty evaporation instrument power supply, the electric current adjusting evaporation instrument, to 50a, is deposited with, and after carbon fracture of rope, stops evaporation, after cooling, obtains final product Carbon/oxidation nickel composite film.
Step 3: open sputter, the carbon/oxidation nickel composite film sample of preparation on pt platinum electrode is put into, fixing Good mask plate (mask), is evacuated, when vacuum reaches 1*10-3The sputtering of top electrode can be carried out to it after pa.Sputtering target material For pt, purity is 99.9%, and sputtering time is 5 minutes.The pt layer having sputtered is carbon/oxidation nickel composite film Memister Top electrode.One complete carbon/oxidation nickel composite film resistance memory cell is just prepared and is completed.
Using AFM (afm), the present embodiment (300 DEG C of heat treatments) gained nickel oxide film surface is carried out Microexamination, Fig. 1 is the flat scanning figure of nickel oxide film, and scan area is 1*1um2.
Embodiment 2
Step 1: weigh nickel acetate, acetylacetone,2,4-pentanedione, acrylic acid and EGME respectively by the amount ratio of 1:1:1:12, mix After conjunction, obtain oxidation nickel sol;At room temperature, using dipping-pulling method, carry out oxygen using pulling machine on pt platinum electrode substrate Change the lifting of nickel gel film, after the nickel oxide gel film that lifting is obtained is dried at room temperature, toast at 70 DEG C 13min, is subsequently heat-treated 25min at a temperature of 500 DEG C, then takes out natural cooling, that is, obtain on pt platinum electrode substrate Nickel oxide film.
Step 2: the preparation of carbon/oxidation nickel composite film: step 1 gained nickel oxide film is placed on vacuum evaporation instrument Fixing on supporting spring, then by purity 99%, a diameter of 2 millimeters, the carbon rope of length 1cm is fixed on the evaporation source of carbon;Open true Empty evaporation instrument power supply, the electric current adjusting evaporation instrument, to 55a, is deposited with, and after carbon fracture of rope, stops evaporation, after cooling, obtains final product Carbon/oxidation nickel composite film.
Step 3: open sputter, the carbon/oxidation nickel composite film sample of preparation on pt platinum electrode is put into, fixing Good mask plate (mask), is evacuated, when vacuum reaches 1*10-3The sputtering of top electrode can be carried out to it after pa.Sputtering target material For pt, purity is 99.9%, and sputtering time is 6 minutes.The pt layer having sputtered is carbon/oxidation nickel composite film Memister Top electrode.One complete carbon/oxidation nickel composite film resistance memory cell is just prepared and is completed.
Using AFM (afm), the present embodiment (500 DEG C of heat treatments) gained nickel oxide film surface is carried out Microexamination, Fig. 2 is the flat scanning figure of nickel oxide film, and scan area is 1*1um2.
Embodiment 3
Step 1: weigh nickel acetate, acetylacetone,2,4-pentanedione, acrylic acid and EGME respectively by the amount ratio of 1:1:1:12, mix After conjunction, obtain oxidation nickel sol;At room temperature, using dipping-pulling method, carry out oxygen using pulling machine on pt platinum electrode substrate Change the lifting of nickel gel film, after the nickel oxide gel film that lifting is obtained is dried at room temperature, toast at 80 DEG C 15min, is subsequently heat-treated 30min at a temperature of 700 DEG C, then takes out and naturally cool to room temperature, that is, obtain in pt platinum electrode Nickel oxide film on substrate.
Step 2: the preparation of carbon/oxidation nickel composite film: step 1 gained nickel oxide film is placed on vacuum evaporation instrument Fixing on supporting spring, then by purity 99%, a diameter of 2 millimeters, the carbon rope of length 1cm is fixed on the evaporation source of carbon;Open true Empty evaporation instrument power supply, the electric current adjusting evaporation instrument, to 60a, is deposited with, and after carbon fracture of rope, stops evaporation, after cooling, obtains final product Carbon/oxidation nickel composite film.
Step 3: open sputter, the carbon/oxidation nickel composite film sample of preparation on pt platinum electrode is put into, fixing Good mask plate (mask), is evacuated, when vacuum reaches 1*10-3The sputtering of top electrode can be carried out to it after pa.Sputtering target material For pt, purity is 99.9%, and sputtering time is 7 minutes.The pt layer having sputtered is carbon/oxidation nickel composite film Memister Top electrode.One complete carbon/oxidation nickel composite film resistance memory cell is just prepared and is completed.
Using AFM (afm), the present embodiment (700 DEG C of heat treatments) gained nickel oxide film surface is carried out Microexamination, Fig. 3 is the flat scanning figure of nickel oxide film, and scan area is 1*1um2.
The electrology characteristic test at normal temperatures of the embodiment of the present invention 3 gained carbon/oxidation nickel composite film Memister, if Put the testing research that current protection limit (compliance current) is 10ma;Nickel oxide film heat treatment in the inventive method Process curve figure is as shown in Figure 4.
Fig. 5 is C-V characteristic (i-v) curve of carbon/oxidation nickel composite film Memister, and the electric current shown in figure is protected Shield is limited to 1ma, and the curve of in figure is C-V characteristic (i-v) curve after loop test 10 times, shows more stable bipolar Resistance switch performance.The electric resistance changing effect that pt/c/nio/pt device can significantly be found out from figure is bipolarity, and device The initial resistance of part is low resistance state, and therefore pt/c/nio/pt device there occurs reset process.During reset, voltage is little When 1.3v, the resistance value of low resistance state is kept approximately constant.When voltage reaches 1.3v, with the low-resistance of the increase device of voltage The resistance of state is gradually reduced, and resistance state is changed into high-impedance state by low resistance state, and device occurs reset process.
Consult work function respectively 4.8ev, 5ev, 5.6ev that pertinent literature obtains nio, c, pt, because the work function of c is little In pt work function so that the Interfacial Potential Barrier area of c and pt is very thin, carrier tunnelling probability greatly enhances, and has high load Flowing sub- injection effect, so being Ohmic contact between c/pt, being also Ohmic contact in the same manner between nio/c.The interface of Ohmic contact Resistance value is smaller, it is only necessary to the test voltage of a very little or electric current just can promote pt/ when to device applied voltage Nio/c/pt resistive memory be internally formed conductive filament.
Carry out deep etching using x-ray photoelectron spectroscopy (xps) to carbon/oxidation nickel composite film Memister to divide Analysis, obtains Fig. 6.Wherein, curve a is the percentage composition change curve of oxygen element, and b is the percentage composition change curve of carbon, c Percentage composition change curve for ni element.As can be seen from the figure the percentage composition of sample element is with etch period and etching Depth constantly improves generation and significantly changes.Because carbon has good adsorptivity, can adsorb a certain amount of on the surface of carbon Oxygen element, with the increase of etching depth, the oxygen element on surface can constantly be worn away, and constituent content constantly declines.Work as quarter When erosion depth progressivelyes reach the top layer of carbon film, the content of carbon constantly can improve with the increase of etching depth, further Etching, the content of carbon keeps constant.
The preparation based on carbon/oxidation nickel composite film for the present invention, is compared to the material that other have resistive characteristic, binary Metal oxide and amorphous carbon material have the characteristics that structure is simple, material component is easily controlled, and its resistive characteristic is excellent In single nickel oxide film, with traditional cmos technique, there is good compatibility simultaneously.
The present invention is using the preparation carrying out carbon/oxidation nickel composite film on pt platinum electrode and further to carbon/oxidation The electric property of nickel composite film is studied.
Sol-gel process is respectively adopted using the inventive method and vacuum vapour deposition combines, the oxidation nickel sol of configuration Nickel oxide film stable and being obtained on pt platinum electrode using this preparation method, is then made on the surface of nickel oxide film Prepare carbon film with vacuum vapour deposition, just can obtain the excellent carbon of change resistance performance/oxidation nickel composite film.Carbon/nickel oxide THIN COMPOSITE The smooth surface of film, preparation cost is low, process is simple, be easily controlled, and improves the preparation efficiency preparing laminated film, and its Change resistance performance is substantially better than single nickel oxide film.

Claims (7)

1. a kind of preparation method of carbon/nickel oxide Memister film is it is characterised in that specifically implement according to following steps:
Step 1, prepares nickel oxide film;
Step 2, prepares carbon film on step 1 gained nickel oxide film, obtains carbon/oxidation nickel composite film;
Step 3, carries out top electrode preparation using sputter to step 2 gained carbon/oxidation nickel composite film, obtains final product.
2. a kind of preparation method of carbon according to claim 1/nickel oxide Memister film is it is characterised in that walk In rapid 1, the preparation process of nickel oxide film is:
Step 1.1: prepare oxidation nickel sol;
Step 1.2: at room temperature, step 1.1 gained is aoxidized on pt platinum electrode substrate by nickel sol using dipping-pulling method Lifting, obtains nickel oxide gel film;
Step 1.3: by step 1.2 be obtained nickel oxide gel film be dried at room temperature for after, at 60~80 DEG C baking 10~ 15min, is subsequently heat-treated 20~30min at a temperature of 300~700 DEG C, after cooling, obtains final product the oxygen on pt platinum electrode substrate Change nickel film.
3. a kind of preparation method of carbon according to claim 2/nickel oxide Memister film is it is characterised in that walk In rapid 1.1, the process for preparation of oxidation nickel sol is: by nickel acetate, acetylacetone,2,4-pentanedione, acrylic acid and EGME by 1:1:1:12 Consumption mixing.
4. a kind of preparation method of carbon according to claim 1/nickel oxide Memister film is it is characterised in that walk In rapid 2, the preparation process of carbon/oxidation nickel composite film is:
Step 1 gained nickel oxide film is placed on the supporting spring of vacuum evaporation instrument fixing, then carbon rope is fixed on the steaming of carbon On rising;Open vacuum evaporation instrument power supply, the electric current adjusting evaporation instrument, to 50~60a, is deposited with, after carbon fracture of rope, stop Evaporation, after cooling, obtains final product carbon/oxidation nickel composite film.
5. a kind of preparation method of carbon according to claim 4/nickel oxide Memister film is it is characterised in that carbon Rope is made up of the graphite fibre of purity 99%, a diameter of 2 millimeters, and carbon rope length degree is 1 centimetre.
6. a kind of preparation method of carbon according to claim 1/nickel oxide Memister film is it is characterised in that walk In rapid 3, using the process that sputter carries out top electrode preparation to carbon/oxidation nickel composite film it is: open sputter, by carbon/oxygen Change nickel composite film sample to put into, fix mask plate, then open sputter power supply, be evacuated, when vacuum reaches 1* 10-3After pa, the sputtering of top electrode is carried out to it.
7. a kind of preparation method of carbon according to claim 6/nickel oxide Memister film is it is characterised in that splash Material of shooting at the target is pt, and purity is 99.9%, and sputtering time is 5~7min.
CN201610859007.8A 2016-09-28 2016-09-28 A kind of preparation method of carbon/nickel oxide Memister film Expired - Fee Related CN106340586B (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107256924A (en) * 2017-06-09 2017-10-17 京东方科技集团股份有限公司 Resistive device and preparation method thereof, the preparation method of display base plate, display device

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CN104518083A (en) * 2013-09-26 2015-04-15 中国科学院宁波材料技术与工程研究所 Memory cell of resistive random access memory and preparation method thereof
CN105714250A (en) * 2016-02-19 2016-06-29 西安理工大学 Preparation method of N-doped amorphous carbon film resistive random access memory

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Publication number Priority date Publication date Assignee Title
US20140175355A1 (en) * 2012-12-20 2014-06-26 Intermolecular Inc. Carbon Doped Resistive Switching Layers
CN104518083A (en) * 2013-09-26 2015-04-15 中国科学院宁波材料技术与工程研究所 Memory cell of resistive random access memory and preparation method thereof
CN105714250A (en) * 2016-02-19 2016-06-29 西安理工大学 Preparation method of N-doped amorphous carbon film resistive random access memory

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Publication number Priority date Publication date Assignee Title
CN107256924A (en) * 2017-06-09 2017-10-17 京东方科技集团股份有限公司 Resistive device and preparation method thereof, the preparation method of display base plate, display device
CN107256924B (en) * 2017-06-09 2019-10-11 京东方科技集团股份有限公司 Resistive device and preparation method thereof, the production method of display base plate, display device

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