CN102255045A - MgxZn1-xO electrically induced resistance change film and preparation method of asymmetrical structure heterojunction thereof - Google Patents

MgxZn1-xO electrically induced resistance change film and preparation method of asymmetrical structure heterojunction thereof Download PDF

Info

Publication number
CN102255045A
CN102255045A CN2011102240383A CN201110224038A CN102255045A CN 102255045 A CN102255045 A CN 102255045A CN 2011102240383 A CN2011102240383 A CN 2011102240383A CN 201110224038 A CN201110224038 A CN 201110224038A CN 102255045 A CN102255045 A CN 102255045A
Authority
CN
China
Prior art keywords
film
preparation
mgxzn1
substrate
electricity causes
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN2011102240383A
Other languages
Chinese (zh)
Inventor
王�华
高书明
许积文
杨玲
周尚菊
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Guilin University of Electronic Technology
Original Assignee
Guilin University of Electronic Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Guilin University of Electronic Technology filed Critical Guilin University of Electronic Technology
Priority to CN2011102240383A priority Critical patent/CN102255045A/en
Publication of CN102255045A publication Critical patent/CN102255045A/en
Pending legal-status Critical Current

Links

Images

Landscapes

  • Surface Treatment Of Glass (AREA)

Abstract

The invention discloses a MgxZn1-xO electrically induced resistance change film and a preparation method of an asymmetrical structure heterojunction thereof. The preparation method comprises the steps of: using glass plated with ITO (Indium Tin Oxide), AZO and other transparent conductive oxide films as a substrate; dropping prepared MgxZn1-xO sol on the substrate, carrying out spinning-coating and making a wet film, carrying out low-temperature drying treatment; carrying out preheating treatment on the dried film until a MgxZn1-xO film with required thickness is obtained; annealing the MgxZn1-xO to ensure that the film is crystallized; naturally cooling a sample to obtain the MgxZn1-xO electrically induced resistance change film; and preparing a metal top electrode film on the surface of the film by adopting a direct-current magnetron sputtering process to obtain the asymmetrical structure heterojunction of a metal film/MgxZn1-xO/transparent conductive oxide film. The invention has the advantages of capability of realizing large-area film manufacture, low cost, higher high/low resistance ratio and lower setting voltage and resetting voltage and capability of greatly improving anti-fatigue property of the electrically induced resistance change film, and can be applied to the field of transparent electronics.

Description

A kind of Mg＜sub〉x＜/sub〉Zn＜sub〉1-x＜/sub〉the O electricity causes the preparation method of resistive film and unsymmetric structure heterojunction thereof
Technical field
The present invention relates to material and devices field in microelectronics and the optoelectronics, specifically is a kind of Mg xZn 1-xThe O electricity causes the preparation method of resistive film and unsymmetric structure heterojunction thereof.
Background technology
Semiconductor memory array structure can comprise a plurality of interconnected memory cell.For example, the unit storage unit of dynamic random access memory (DRAM) can comprise switch and capacitor.DRAM can have higher integrated level and service speed faster.Yet, when power-off, can from DRAM, wipe the data that all have been stored, promptly volatility makes loss of data.
On the other hand, flash memory can be used as the representative that can preserve the non-volatility memorizer of having stored data (different with volatile storage) when power supply is closed, but integrated speed and service speed are lower than DRAM.Along with the structural development of conventional memory cell has been approached dimension limit, multiple novel nonvolatile memory is researched and developed in existing a large amount of academic research, is wherein arranged most: variable resistance type (RRAM) memory, magnetic memory (MRAM), ferroelectric memory (FRAM) and phase transition storage (PRAM) comprising of market potential.MRAM can utilize the change of tunnel junction polarised direction to store data, but access speed is slower.FRAM can utilize ferroelectric polarization characteristic to store data, and service speed is faster, but data holding ability has much room for improvement.The phase change resistor that PRAM depends on certain material changes stores data, memory cell comprises resistor and switching transistor, yet, when adopting traditional DRAM technology to make PRAM, etching is difficulty more, and can need the longer time cycle, low productivity ratio and high unit cost can reduce the market competitiveness.
Since houston, u.s.a university reported first in 2000 finds that in the Mn oxide film electric pulse triggers reversible resistance (EPIR:Electrical pulse induced resistance-change) effect, shown great attention to based on the exploitation of the novel changable resistance random access memory (RRAM) of this effect.In RRAM, store status manifests by the difference of resistive material resistance.When being equal to or greater than the voltage that voltage (set voltage) is set and being applied to the resistive material, can reduce the resistance of resistive material, this is corresponding with the ON state.When the voltage that will be equal to or greater than resetting voltage is applied to the resistive material, can increase the resistance of resistive material, this is corresponding with the OFF state.That sort memory has is non-volatile, the stability of remember condition, operating voltage is low, cost is low, speed is fast, storage density is high, manufacturing is simple and with current C MOS(complementary metal-oxide-semiconductor) advantage such as ic process compatibility is good.Therefore, the research that a large amount of financial resources and manpower are devoted to RRAM has been cast by a lot of in the world in recent years electronics and semiconductor company.There are Sharp, Sony, Samsung Electronics, LSI Logic, Matssushita Electric Industrial, Winbond Electronics etc. in the company that is being engaged in exploitation RRAM technology.The semiconductor manufacturing facility supplier Tegal that has tame general headquarters to be located at California Petauluma in addition specially provides relevant RRAM equipment.Sharp and University of shizouka cooperate, and have developed the raw product of a high speed RRAM, and its data write speed is faster than three orders of magnitude of NAND type flash memory.
Recently, electric resistance changing and memory characteristic in multiple material system, have all been found, such as rare earth manganese oxide material (Pr 0.7Ca 0.3MnO 3Deng), transition metal perovskite structure material (SrZrTiO 3, SrTiO 3Deng), Dyadic transition metal oxide materials (NiO, TiO 2, Cu xO, Cu-MoO X, ZnO, Mg-ZnO, Co-ZnO, Mn-ZnO, Fe 2O 3, ZrO 2Deng), organic polymer semi-conducting material (pentacene etc.) and some sulfide materials.For the practicability of resistance-type memory, improve the resistance ratio and the stability of the high low resistance state of resistive material, the preparation cost etc. that reduces to be provided with voltage (Vset) and resetting voltage (Vreset), reduction material all is very important.At present, obtain to have that steady resistance changes and the material system of memory characteristic is the key issue that realizes that the RRAM storage further develops.Advantages such as the Dyadic transition metal oxide materials not only has component and crystal structure is simple, preparation temperature is low, good reproducibility, and with the semiconductor CMOS process compatible, help realizing its practicability target.
Summary of the invention
The object of the present invention is to provide and a kind ofly prepare Mg being coated with on the glass substrate of transparent conductive oxide film xZn 1-xThe O electricity causes sol-gel (sol-gel) process and the " metallic film/Mg of resistive film xZn 1-xThe O/ transparent conductive oxide film " preparation method of unsymmetric structure heterojunction.
A kind of Mg that the present invention proposes xZn 1-xThe O electricity causes the preparation method of resistive film and unsymmetric structure heterojunction thereof, comprises the steps:
(1) is substrate with the glass that is coated with transparent conductive oxide film, and substrate is carried out surface treatment and cleaning;
(2) preparation Mg xZn 1-xO colloidal sol;
(3) colloidal sol for preparing is dripped on the substrate, spare glue again, make wet film;
(4) wet film of even good glue carries out the low temperature drying processing under 90 ℃-120 ℃, removes carbon, hydrogen composition in the wet film;
(5) will dry the film of handling and under 320 ℃ of-390 ℃ of temperature, carry out The pre-heat treatment;
(6) repeat above-mentioned steps (3)-(5), determine number of repetition, until the Mg that obtains desired thickness according to the thickness of required film xZn 1-xThe O film;
(7) with Mg xZn 1-xThe O film carries out 30-60 minute annealing in process under air atmosphere, 400 ℃ of-520 ℃ of temperature, make the film crystallization;
(8) can obtain Mg behind the sample natural cooling xZn 1-xThe O electricity causes the resistive film;
(9) at Mg xZn 1-xThe O electricity causes and adopts magnetically controlled DC sputtering prepared electrode of metal film on the resistive film surface, obtains " metallic film/Mg xZn 1-xThe O/ transparent conductive oxide film " the unsymmetric structure heterojunction.
Wherein:
The described transparent conductive oxide film of step (1) can be tin indium oxide (ITO), zinc oxide aluminum (AZO) etc., and is coated with the surface treatment of transparent conductive oxide film glass substrate and cleaning requires and step is:
1. soaked 24 hours with sodium hydroxide solution, remove the attachment that remains in the surface;
2. in the acetone ultrasonic cleaning 10-15 minute, remove the substrate surface organic substance;
3. in the ethanol ultrasonic cleaning 8-15 minute, remove the hydrocarbon of substrate surface;
4. use deionized water ultrasonic cleaning 10 minutes at last, remove residual ethanol.
The described preparation of step (2) Mg xZn 1-xThe raw material of O colloidal sol is: zinc acetate (Zn(CH 3COO) 22H 2O), four water magnesium acetate (Mg(CH 3COO) 24H 2O), EGME (CH 3OCH 2CH 2OH), monoethanolamine, isopropyl alcohol.The mol ratio of four water Yi Suan Mei ︰ zinc acetates is 0.11-0.67 ︰ 1.00, as solute; Monoethanolamine is as stabilizer, and the mol ratio of Rong Zhi ︰ monoethanolamine is 0.80-1.10:1.00; The volume ratio of Yi glycol Jia Mi ︰ isopropyl alcohol is 0.8-1.10 ︰ 1.00, and as solvent, and the 0.25-0.55 mole of solute is joined 1000 milliliters of solvents;
The best proportioning of above-mentioned raw materials is: the mol ratio of solute four water Yi Suan Mei ︰ zinc acetates is 0.25 ︰ 1.00; The mol ratio of Rong Zhi ︰ monoethanolamine is 1.00:1.00; The volume ratio of solvent ethylene glycol Jia Mi ︰ isopropyl alcohol is 1.00 ︰ 1.00; 0.30 mole of solute is joined 1000 milliliters of solvents;
Above-mentioned preparation Mg xZn 1-xThe preparation method of O colloidal sol comprises the steps:
1. in the container of clean dry, add an amount of EGME and isopropyl alcohol;
2. load weighted zinc acetate, four water magnesium acetate powder are put into container;
3. the adequate amount of ethanol amine stabiliser is poured in the container;
4. the temperature of constant temperature blender with magnetic force is set to 25 ℃, aforementioned solution is placed on the magnetic stirring apparatus stirred 12 hours, makes it reaction evenly fully, obtains the Mg of transparent homogeneous xZn 1-xO colloidal sol.
The described electrode of metal film of step (9) can be silver metal materials such as (Ag), and process and requirement that described magnetically controlled DC sputtering prepares the electrode of metal film are:
1. be that the mask of 0.5mm aperture covers Mg with having a lot of diameters xZn 1-xThe O electricity causes above the resistive film, can obtain the point-like metal film electrode behind the plated film;
2. prepared Mg xZn 1-xThe sample substrate temperature of O/ transparent conductive oxide film is 200-300 ℃, and sputtering power is 70-100W, and base vacuum is 3-5 * 10 -3Pa, sputtering atmosphere are Ar gas, and its pressure is 20-30Pa;
3. the about 50-60nm of the thickness of metal electrode film;
Mg xZn 1-xThe O electricity causes resistive film and " metallic film/Mg xZn 1-xThe O/ transparent conductive oxide film " the structure heterojunction preparation technology's flow process as shown in Figure 1.
For to Mg xZn 1-xThe O electricity causes resistive film and " metallic film/Mg xZn 1-xThe O/ transparent conductive oxide film " heterojunction carries out electric performance test, need erode a part of Mg xZn 1-xThe O electricity causes the resistive film and exposes the transparent conductive oxide film hearth electrode." metallic film/the Mg for preparing xZn 1-xThe O/ transparent conductive oxide film " the heterojunction test structure is as shown in Figure 2.
Advantage of the present invention is: (1) adopts Sol-Gel prepared Mg xZn 1-xThe O electricity causes the resistive film, and the control of the component of film accurately and is easy to adjust (doping) component, can large tracts of land system film, and cost is low; (2) adopt repeatedly even glue, the process program of layering preheating can improve degree of crystallinity, reduces the film internal stress, improves the performance of film, particularly has higher high/low resistance ratio and lower voltage and the resetting voltage of being provided with; (3) prepared " metallic film/electricity causes resistive film/transparent conductive oxide film " is the unsymmetric structure heterojunction, can improve the fatigue resistance that electricity causes the resistive film greatly, and can be applicable to transparent electronic applications.
Description of drawings
Fig. 1 is Mg of the present invention xZn 1-xThe O electricity causes resistive film and " metallic film/Mg xZn 1-xThe O/ transparent conductive oxide film " preparation technology's flow chart of structure heterojunction
Fig. 2 is the present invention " metallic film/Mg xZn 1-xO/transparent conductive oxide film " heterojunction test structure schematic diagram
Fig. 3 is the Mg for preparing on the ITO transparent conductive oxide film glass substrate that is coated with of embodiment 1 0.2Zn 0.8The O electricity causes the XRD figure of resistive film
Fig. 4 is the " Ag/Mg of embodiment 1 0.2Zn 0.8O/ITO " feature of heterojunction I- VCurve chart
Fig. 5 is the feature that adopts same sampling technology, do not carry out " Ag/ZnO/ITO " heterojunction of Mg doping I- VCurve chart
Fig. 6 is embodiment 1 " Ag/Mg 0.2Zn 0.8O/ITO " the switch circulation resistance variations figure of heterojunction
Embodiment
Mg xZn 1-xThe O sol formulation is: (a) solute four water magnesium acetate (Mg(CH 3COO) 24H 2O) and zinc acetate (Zn(CH 3COO) 22H 2O) mol ratio is 0.11-0.67 ︰ 1.00; (b) monoethanolamine is as stabilizer, and the mol ratio of Rong Zhi ︰ monoethanolamine is 0.80-1.10:1.00; (c) volume ratio of solvent ethylene glycol Jia Mi ︰ isopropyl alcohol is 0.8-1.10 ︰ 1.00, and the solute of 0.25-0.55 mole is joined 1000 milliliters of solvents.
Embodiment 1:
(1) with the glass that is coated with the ITO transparent conductive film as substrate, glass substrate is carried out surface treatment and cleaning:
1. soaked 24 hours with sodium hydroxide solution, remove the attachment that remains in the surface;
2. acetone ultrasonic cleaning 10-15 minute, remove the substrate surface organic substance;
3. ethanol ultrasonic cleaning 8-15 minute, remove the hydrocarbon of glass surface;
4. use deionized water ultrasonic cleaning 10 minutes at last, remove residual ethanol.
(2) adopt following raw material (its purity is and analyzes pure 99.99%) preparation Mg 0.2Zn 0.8O colloidal sol:
Zinc acetate (Zn (CH 3COO) 22H 2O) 52.68 grams
Four water magnesium acetate (Mg(CH 3COO) 24H 2O) 12.867 grams
20.00 milliliters of monoethanolamines
500 milliliters of EGMEs
500 milliliters of isopropyl alcohols
Wherein: (a) solute four water magnesium acetate (Mg(CH 3COO) 24H 2O the mol ratio of) ︰ zinc acetate is 0.25 ︰ 1.00, and stabilizer alcohol amine is 20.00 milliliters; (b) 0.30 mole of solute is joined 1000 milliliters of solvents (wherein containing: 500 milliliters of EGMEs, 500 milliliters of isopropyl alcohols).
(3) with the Mg for preparing 0.2Zn 0.8O colloidal sol drips 1-2 and drips on the glass substrate that is coated with ito thin film, starts sol evenning machine and spares glue, forms wet film;
(4) wet film of even good glue carries out the low temperature drying processing under 100 ℃, removes carbon, hydrogen composition in the wet film;
(5) film that will dry carries out The pre-heat treatment on 350 ℃ constant temperature heat dish;
(6) repeat above-mentioned steps (3)-(5) 4 times, obtain Mg 0.2Zn 0.8The O film;
(7) with Mg 0.2Zn 0.8The O film is annealed in air ambient, and annealing temperature is 500 ℃, and the time is 30 minutes, makes the film crystallization;
(8) can obtain Mg behind the sample natural cooling 0.2Zn 0.8The O electricity causes the resistive film;
(9) at Mg 0.2Zn 0.8The O electricity causes and adopts magnetically controlled DC sputtering prepared Ag upper electrode film on the resistive film surface, obtains " Ag/Mg 0.2Zn 0.8O/ITO " the unsymmetric structure heterojunction:
1. be that the mask of 0.5mm aperture covers Mg with having a lot of diameters 0.2Zn 0.8The O electricity causes above the resistive film;
2. underlayer temperature is 250 ℃ during sputter, and sputtering power is 80W, and base vacuum is 4 * 10 -3Pa, sputtering atmosphere are Ar gas, and its pressure is 25Pa;
3. the thickness of metal electrode film is 50nm.
Mg 0.2Zn 0.8The O electricity causes resistive film and " Ag/Mg 0.2Zn 0.8O/ITO " the structure heterojunction preparation technology's flow process as shown in Figure 1.
For to " Ag/Mg 0.2Zn 0.8O/ITO " heterojunction carries out electric performance test, need erode a part of Mg 0.2Zn 0.8The O film exposes the ITO hearth electrode.The Ag/Mg for preparing 0.2Zn 0.8O/ITO heterojunction test structure as shown in Figure 2.
Embodiment 2:
(1) with the glass that is coated with the AZO transparent conductive film as substrate, glass substrate is carried out surface treatment and cleaning:
1. soaked 24 hours with sodium hydroxide solution, remove the attachment that remains in the surface;
2. acetone ultrasonic cleaning 10-15 minute, remove the substrate surface organic substance;
3. ethanol ultrasonic cleaning 8-15 minute, remove the hydrocarbon of glass surface;
4. use deionized water ultrasonic cleaning 10 minutes at last, remove residual ethanol.
(2) adopt following raw material (its purity is and analyzes pure 99.99%) preparation Mg 0.2Zn 0.8O colloidal sol:
Zinc acetate (Zn (CH 3COO) 22H 2O) 87.80 grams
Four water magnesium acetate (Mg(CH 3COO) 24H 2O) 21.445 grams
30.00 milliliters of monoethanolamines
500 milliliters of EGMEs
500 milliliters of isopropyl alcohols
Wherein: (a) solute four water magnesium acetate (Mg(CH 3COO) 24H 2O mol ratio 0.25 ︰ 1.00 of) ︰ zinc acetate, stabilizer alcohol amine is 30.00 milliliters; (b) 0.50 mole of solute is joined 1000 milliliters of solvents (wherein containing: 500 milliliters of EGMEs, 500 milliliters of isopropyl alcohols).
(3) with the Mg for preparing 0.2Zn 0.8O colloidal sol drips 1-2 and drips on the glass substrate that is coated with the AZO film, starts sol evenning machine and spares glue, forms wet film;
(4) wet film of even good glue carries out the low temperature drying processing under 100 ℃, removes carbon, hydrogen composition in the wet film;
(5) film that will dry carries out The pre-heat treatment on 380 ℃ constant temperature heat dish;
(6) repeat above-mentioned steps (3)-(5) 5 times, obtain Mg 0.2Zn 0.8The O film;
(7) with Mg 0.2Zn 0.8The O film is annealed in air ambient, and annealing temperature is 480 ℃, and the time is 40 minutes, makes the film crystallization;
(8) can obtain Mg behind the sample natural cooling 0.2Zn 0.8The O electricity causes the resistive film;
All the other are with embodiment 1.Mg 0.2Zn 0.8The O electricity causes resistive film and " Ag/Mg 0.2Zn 0.8O/AZO " the structure heterojunction preparation technology's flow process as shown in Figure 1, the Ag/Mg for preparing 0.2Zn 0.8O/AZO heterojunction test structure as shown in Figure 2.
 
Embodiment 3:
(1) with the glass that is coated with the ITO transparent conductive film as substrate, glass substrate is carried out surface treatment and cleaning:
1. soaked 24 hours with sodium hydroxide solution, remove the attachment that remains in the surface;
2. acetone ultrasonic cleaning 10-15 minute, remove the substrate surface organic substance;
3. the super shake of ethanol is 8-15 minute, removes the hydrocarbon of glass surface;
4. at last with the super shake of deionized water 10 minutes, remove residual ethanol.
(2) adopt following raw material (its purity is and analyzes pure 99.99%) preparation Mg 0.1Zn 0.9O colloidal sol:
Zinc acetate (Zn (CH 3COO) 22H 2O) 59.265 grams
Four water magnesium acetate (Mg(CH 3COO) 24H 2O) 6.4335 grams
20.00 milliliters of monoethanolamines
500 milliliters of EGMEs
500 milliliters of isopropyl alcohols
Wherein: (a) solute four water magnesium acetate (Mg(CH 3COO) 24H 2O mol ratio 0.11 ︰ 1.00 of) ︰ zinc acetate, stabilizer alcohol amine is 20.00 milliliters; (b) 0.30 mole of solute is joined 1000 milliliters of solvents (wherein containing: 500 milliliters of EGMEs, 500 milliliters of isopropyl alcohols).
(3) with the Mg for preparing 0.1Zn 0.9O colloidal sol drips 1-2 and drips on the glass substrate that is coated with ito thin film, starts sol evenning machine and spares glue, forms wet film;
(4) wet film of even good glue carries out the low temperature drying processing under 100 ℃, removes carbon, hydrogen composition in the wet film;
(5) film that will dry carries out The pre-heat treatment on 350 ℃ constant temperature heat dish;
(6) repeat above-mentioned steps (3)-(5) 5 times, obtain Mg 0.1Zn 0.9The O film;
(7) with Mg 0.1Zn 0.9The O film is annealed in air ambient, and annealing temperature is 500 ℃, and the time is 30 minutes, makes the film crystallization;
(8) can obtain Mg behind the sample natural cooling 0.1Zn 0.9The O electricity causes the resistive film;
(9) at Mg 0.1Zn 0.9The O electricity causes and adopts magnetically controlled DC sputtering prepared Ag upper electrode film to obtain " Ag/Mg on the resistive film surface 0.2Zn 0.8O/ITO " the unsymmetric structure heterojunction:
1. be that the mask of 0.5mm aperture covers Mg with having a lot of diameters 0.1Zn 0.9The O electricity causes above the resistive film;
2. underlayer temperature is 300 ℃ during sputter, and sputtering power is 100W, and base vacuum is 5 * 10 -3Pa, sputtering atmosphere are Ar gas, and its pressure is 20Pa;
3. the about 60nm of the thickness of metal electrode film.
All the other are with embodiment 1.Mg 0.1Zn 0.9The O electricity causes resistive film and " Ag/Mg 0.1Zn 0.9O/ITO " the structure heterojunction preparation technology's flow process as shown in Figure 1, " the Ag/Mg for preparing 0.1Zn 0.9O/ITO " the heterojunction test structure is as shown in Figure 2.
In above-mentioned all embodiment, step (1) can move to step (2) and carry out afterwards.
To typical Mg xZn 1-xThe O electricity causes resistive film and " Ag/Mg xZn 1-xO/ITO " structure and the performance test of heterojunction be as follows:
On the glass substrate that is coated with the ITO transparent conductive film, Mg 0.2Zn 0.8The XRD that the O electricity causes the resistive film as shown in Figure 3, " Ag/Mg 0.2Zn 0.8O/ITO " feature of heterojunction I- VCurve as shown in Figure 4, its electric resistance changing process can be described as: film is initially in a high-impedance state, current value is extremely low, when applying forward voltage and reach 0.8V, film changes low resistance state into, electric current sharply rises, reach when applying negative voltage then ,-during 1.8V, film returns to high-impedance state, a circulation like this, when applying voltage, top electrode Ag is a positive direction, and hearth electrode ITO is a negative direction, the voltage that applies when making film become low resistance state is called voltage is set, and the voltage that is applied when making film return to high-impedance state is called resetting voltage.Do not carry out the feature of " Ag/ZnO/ITO " heterojunction that Mg mixes with Fig. 5 I- VCurve is compared as can be seen, and Mg mixes and obviously improved Mg 0.2Zn 0.8The O electricity causes the high low resistance state ratio of resistive film, Mg after Mg mixes simultaneously 0.2Zn 0.8The O film be provided with that the 1.8V of voltage when not mixing is reduced to 0.8V, resetting voltage is reduced to 1.8V by 2.5V.Fig. 6 is " Ag/Mg 0.2Zn 0.8O/ITO " the resistance variations figure of No. 160 switches circulations of heterojunction experience; visible high-impedance state is at 250 Ω～1500 Ω; the resistance variations space that the switching of low resistance state between 40 Ω～60 Ω Gao ∕ low resistance states is 6～40 times; and show good repeatability and stability, illustrate to have good fatigue resistance.
Though the present invention is with preferred embodiment openly as above, and non-limiting the present invention.

Claims (10)

1. Mg xZn 1-xThe O electricity causes the preparation method of resistive film and unsymmetric structure heterojunction thereof, it is characterized in that comprising the steps:
(1) is substrate with the glass that is coated with transparent conductive oxide films such as ITO, AZO, and substrate is carried out surface treatment and cleaning;
(2) preparation Mg xZn 1-xO colloidal sol;
(3) colloidal sol for preparing is dripped on the substrate, spare glue again, make wet film;
(4) wet film to even good glue carries out the low temperature drying processing, removes carbon, hydrogen composition in the wet film;
(5) will dry the film of handling and carry out The pre-heat treatment;
(6) repeat above-mentioned steps (3)-(5), determine number of repetition, until the Mg that obtains desired thickness according to the thickness of required film xZn 1-xThe O film;
(7) to above-mentioned Mg xZn 1-xThe O film carries out annealing in process under air ambient, uniform temperature, make the film crystallization;
(8) can obtain Mg behind the sample natural cooling xZn 1-xThe O electricity causes the resistive film;
(9) at Mg xZn 1-xThe O electricity causes and adopts magnetically controlled DC sputtering prepared electrode of metal film on the resistive film surface, obtains " metallic film/Mg xZn 1-xThe O/ transparent conductive oxide film " the unsymmetric structure heterojunction.
2. preparation method according to claim 1 is characterized in that: the surface treatment and the cleaning step of transparent conductive oxide film glass substrate such as the described ITO of being coated with of step (1), AZO are:
1. soaked 24 hours with sodium hydroxide solution, remove the attachment that remains in the surface;
2. in the acetone ultrasonic cleaning 10-15 minute, remove the substrate surface organic substance;
3. in the ethanol ultrasonic cleaning 8-15 minute, remove the hydrocarbon of substrate surface;
4. at last with the super shake of deionized water 10 minutes, remove residual ethanol.
3. preparation method according to claim 1 is characterized in that: the described preparation of step (2) Mg xZn 1-xThe raw material of O colloidal sol is: zinc acetate (Zn (CH 3COO) 22H 2O), four water magnesium acetate (Mg(CH 3COO) 24H 2O), EGME (CH 3OCH 2CH 2OH), monoethanolamine, isopropyl alcohol; The mol ratio of four water Yi Suan Mei ︰ zinc acetates is 0.11-0.67 ︰ 1.00, as solute; Monoethanolamine is as stabilizer, and the mol ratio of Rong Zhi ︰ monoethanolamine is 0.80-1.10:1.00; The volume ratio of Yi glycol Jia Mi ︰ isopropyl alcohol is 0.8-1.10 ︰ 1.00, and as solvent, and the 0.25-0.55 mole of solute is joined 1000 milliliters of solvents.
4. according to claim 1 or 3 described preparation methods, it is characterized in that: the described preparation of step (2) Mg xZn 1-xThe optimum proportion of materials of O colloidal sol is: the mol ratio of solute four water Yi Suan Mei ︰ zinc acetates is 0.25 ︰ 1.00; The mol ratio of Rong Zhi ︰ monoethanolamine is 1.00:1.00; The volume ratio of solvent ethylene glycol Jia Mi ︰ isopropyl alcohol is 1.00 ︰ 1.00; 0.30 mole of solute is joined 1000 milliliters of solvents.
5. according to claim 1 or 3 described preparation methods, it is characterized in that: Mg described in the step (2) xZn 1-xThe preparation method of O colloidal sol comprises the steps:
1. in the container of clean dry, add an amount of EGME and isopropyl alcohol;
2. load weighted zinc acetate, four water magnesium acetate powder are put into container;
3. the adequate amount of ethanol amine solvent is poured in the container;
4. the temperature of constant temperature blender with magnetic force is set to 25 ℃, aforementioned solution is placed on the magnetic stirring apparatus stirred 12 hours, makes it reaction evenly fully, obtains the Mg of transparent homogeneous xZn 1-xO colloidal sol.
6. preparation method according to claim 1 is characterized in that:
Mg in step (4), (5) and (7) xZn 1-xThe heat-treat condition of O film is: dry under 90-120 ℃ of temperature earlier, The pre-heat treatment is carried out in the back under 320-390 ℃ of temperature, is annealing 30-60 minute under 400-520 ℃, air ambient in temperature at last.
7. preparation method according to claim 1 is characterized in that: the described electrode of metal film of step (9) is silver.
8. preparation method according to claim 1 is characterized in that: the process that the described magnetically controlled DC sputtering of step (9) prepares the electrode of metal film is:
1. be that the mask of 0.5mm aperture covers Mg with having a lot of diameters xZn 1-xThe O electricity causes above the resistive film, can obtain the point-like metal film electrode behind the plated film;
2. prepared Mg xZn 1-xThe sample substrate temperature of O/ transparent oxide film is 200-300 ℃, and sputtering power is 70-100W, and base vacuum is 3-5 * 10 -3Pa, sputtering atmosphere are Ar gas, and its pressure is 20-30Pa;
3. the about 50-60nm of the thickness of metal electrode film.
9. use a kind of Mg of the described preparation method's preparation of one of claim 1-6 xZn 1-xThe O electricity causes the resistive film.
10. use a kind of Mg of the described preparation method's preparation of one of claim 1-8 xZn 1-xThe O electricity causes resistive film unsymmetric structure heterojunction.
CN2011102240383A 2011-09-20 2011-09-20 MgxZn1-xO electrically induced resistance change film and preparation method of asymmetrical structure heterojunction thereof Pending CN102255045A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN2011102240383A CN102255045A (en) 2011-09-20 2011-09-20 MgxZn1-xO electrically induced resistance change film and preparation method of asymmetrical structure heterojunction thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN2011102240383A CN102255045A (en) 2011-09-20 2011-09-20 MgxZn1-xO electrically induced resistance change film and preparation method of asymmetrical structure heterojunction thereof

Publications (1)

Publication Number Publication Date
CN102255045A true CN102255045A (en) 2011-11-23

Family

ID=44982150

Family Applications (1)

Application Number Title Priority Date Filing Date
CN2011102240383A Pending CN102255045A (en) 2011-09-20 2011-09-20 MgxZn1-xO electrically induced resistance change film and preparation method of asymmetrical structure heterojunction thereof

Country Status (1)

Country Link
CN (1) CN102255045A (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103014686A (en) * 2012-12-06 2013-04-03 桂林电子科技大学 Method for preparing Mn-Zn oxide electrogenerated resistive thin films and asymmetric light-pervious resistive capacitors thereof
CN103236498A (en) * 2013-04-25 2013-08-07 桂林电子科技大学 Nonpolar resistive random-access memory and preparation method thereof
CN103730572A (en) * 2014-01-03 2014-04-16 华南师范大学 Complementary type resistance random access memory and manufacturing method thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1967848A (en) * 2006-11-21 2007-05-23 华中科技大学 Ferroelectric film capacity used for ferroelectric memorizer and its manufacturing method
CN102180704A (en) * 2011-03-04 2011-09-14 桂林电子科技大学 Preparation method of Bi3TiNbO9-Bi4Ti3O12 natural superlattice ferroelectric film on Si substrate

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1967848A (en) * 2006-11-21 2007-05-23 华中科技大学 Ferroelectric film capacity used for ferroelectric memorizer and its manufacturing method
CN102180704A (en) * 2011-03-04 2011-09-14 桂林电子科技大学 Preparation method of Bi3TiNbO9-Bi4Ti3O12 natural superlattice ferroelectric film on Si substrate

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
《phys. stat. sol. (c)》 20040930 T. Murakawa et al. 《Structural and optical properties of MgxZn1-xO thin films formed by sol-gel method》 第1卷, 第10期 *
DONGXU ZHAO ET AL.: "《Photoluminescence properties of MgxZn1-xO alloy thin films fabricated by the sol-gel deposition method》", 《J. APPL. PHYS.》 *
LEI SHI ET AL.: "《Bipolar Resistance Switching in Fully Transparent ZnO:Mg-Based Devices》", 《APPLIED PHYSICS EXPRESS》 *
T. MURAKAWA ET AL.: "《Structural and optical properties of MgxZn1-xO thin films formed by sol–gel method》", 《PHYS. STAT. SOL. (C)》 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103014686A (en) * 2012-12-06 2013-04-03 桂林电子科技大学 Method for preparing Mn-Zn oxide electrogenerated resistive thin films and asymmetric light-pervious resistive capacitors thereof
CN103236498A (en) * 2013-04-25 2013-08-07 桂林电子科技大学 Nonpolar resistive random-access memory and preparation method thereof
CN103236498B (en) * 2013-04-25 2015-10-28 桂林电子科技大学 A kind of nonpolar resistance-variable storing device and preparation method thereof
CN103730572A (en) * 2014-01-03 2014-04-16 华南师范大学 Complementary type resistance random access memory and manufacturing method thereof
CN103730572B (en) * 2014-01-03 2016-04-13 华南师范大学 A kind of complementary type resistance-variable storing device and preparation method thereof

Similar Documents

Publication Publication Date Title
Carlos et al. Recent progress in solution‐based metal oxide resistive switching devices
Kim et al. Nanofilamentary resistive switching in binary oxide system; a review on the present status and outlook
Lee et al. Tailored 2D/3D halide perovskite heterointerface for substantially enhanced endurance in conducting bridge resistive switching memory
CN103035842B (en) Organic resistive random access memory based on graphene quantum dot doping and preparation method thereof
He et al. Impact of chemical doping on resistive switching behavior in zirconium-doped CH3NH3PbI3 based RRAM
CN103280525B (en) Transparent resistance random access memory and manufacturing method thereof
CN105720195B (en) A kind of inorganic halogen perovskite resistance-variable storing device and preparation method thereof
CN101826598B (en) Polymorphic organic resistive random access memory and preparation method
CN103311434B (en) Transparent resistive random access memory and production method thereof
CN102255045A (en) MgxZn1-xO electrically induced resistance change film and preparation method of asymmetrical structure heterojunction thereof
CN103219466B (en) Organic resistive random access memory and preparation method thereof
CN104425712B (en) The all-transparent resistance-variable storing device of a kind of rare earth oxide as accumulation layer and preparation method thereof
CN103474571B (en) Resistance memory component and manufacturing method thereof
CN101894908A (en) Resistive random access memory and preparation method thereof
CN103187527B (en) A kind of Ce doping Bi 4-xce xti 3o 12the preparation method of electroluminescent resistance changing film and resistive electric capacity thereof
CN103014686A (en) Method for preparing Mn-Zn oxide electrogenerated resistive thin films and asymmetric light-pervious resistive capacitors thereof
CN103236498B (en) A kind of nonpolar resistance-variable storing device and preparation method thereof
Shi et al. Flexible resistance memory devices based on Cu/ZnO: Mg/ITO structure
CN109659431A (en) The flash memories of coordination polymer film and preparation method thereof based on benzene tetramine
Zhao et al. Resistive switching characteristics of Dy 2 O 3 film with a Pt nanocrystal embedding layer formed by pulsed laser deposition
Wang et al. Solution processed resistive random access memory devices for transparent solid-state circuit systems
CN109037440A (en) A kind of resistance-variable storing device and its preparation method and application
CN103346257A (en) Metallic oxide resistor storage unit and low-temperature photochemical preparation method thereof
CN103296206A (en) Organic non-volatile ferroelectric three-bit memory and manufacturing method thereof
CN107768518B (en) A kind of Al/Ge for phase transition storage10Sb90Class superlattices phase change film material and preparation method

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C02 Deemed withdrawal of patent application after publication (patent law 2001)
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20111123