CN103014686A - Method for preparing Mn-Zn oxide electrogenerated resistive thin films and asymmetric light-pervious resistive capacitors thereof - Google Patents

Method for preparing Mn-Zn oxide electrogenerated resistive thin films and asymmetric light-pervious resistive capacitors thereof Download PDF

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CN103014686A
CN103014686A CN2012105189167A CN201210518916A CN103014686A CN 103014686 A CN103014686 A CN 103014686A CN 2012105189167 A CN2012105189167 A CN 2012105189167A CN 201210518916 A CN201210518916 A CN 201210518916A CN 103014686 A CN103014686 A CN 103014686A
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film
preparation
resistive
znmno
thin film
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王�华
高书明
许积文
周尚菊
杨玲
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Guilin University of Electronic Technology
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Guilin University of Electronic Technology
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Abstract

The invention discloses a method for preparing Mn-Zn oxide electrogenerated resistive thin films and asymmetric light-pervious resistive capacitors thereof, which comprises the following steps of: preparing an Mn-Zn oxide electrogenerated resistive thin film by taking glass plated with a transparent conductive oxide thin film as a substrate and using a CSD (chemical solution deposition) technique, and then by using a direct-current magnetron sputtering technique, preparing a metal thin film upper electrode and obtaining a corresponding asymmetric light-pervious resistive capacitor. The method disclosed by the invention has the advantages that (1) the components of the thin film are controlled accurately, and the components are adjusted (doped) easily, so that an effect of large area film making can be achieved, and the cost is low; (2) because a process scheme of multiple spin coating and layered preheating is adopted, the crystallinity can be improved, the internal stress of the thin film can be reduced, and the properties, especially higher high/low resistance ratio and lower setting voltage and reset voltage, of the thin film can be increased; and (3) the prepared thin film is a capacitor with an asymmetric structure, so that the anti-fatigue properties of the electrogenerated resistive thin film can be greatly improved, and the thin film can be applied to the field of transparent electronics.

Description

A kind of Mn-Zn oxide compound electricity causes the preparation method of resistance changing film and asymmetric printing opacity resistive electric capacity thereof
Technical field
The present invention relates to material and devices field in microtronics and the photoelectronics, specifically a kind of glass substrate being coated with transparent conductive oxide film prepares Mn-Zn oxide compound (ZnMnO 3, ZnMn 2O 4) electricity causes the preparation method of resistance changing film and asymmetric printing opacity resistive electric capacity thereof.Prepared ZnMnO 3, ZnMn 2O 4Electricity causes resistance changing film and asymmetric printing opacity resistive electric capacity can be realized the reversible resistance transformation and can be applicable to transparent electrical causing resistance-variable storing device (RRAM).
Background technology
The semiconductor dynamic random access storer (DRAM) of generally using at present has higher integrated level and storage speed faster, and its defective is volatility, namely when power-off, can wipe the data that all have been stored from DRAM, makes loss of data.
As the representative of non-volatility memorizer, there are the technology barriers such as read or write speed is slow, storage density is low in flash memory, also faces simultaneously serious convergent-divergent problem.Along with the conventional memory cell structural development has been approached dimension limit, the various new nonvolatile memory is widely studied and develops, wherein comprising of tool potentiality to be exploited: electricity causes resistance-variable storing device (RRAM), magneticstorage (MRAM), ferroelectric memory (FRAM) and phase transition storage (PRAM).MRAM utilizes the change of tunnel junction direction of polarization to store data, but access speed is slower; FRAM then utilizes ferroelectric polarization characteristic to store data, deposit read rate fast, but data holding ability has much room for improvement; The phase change resistor that PRAM depends on certain material changes to store data, and memory cell structure and manufacturing process are complicated, and cost is higher.
RRAM is that the variation that utilizes electricity to cause the resistive material resistance realizes storing, because of it has that but contractility simple in structure is good, storage density is high, low in energy consumption, read or write speed fast, the repeatable operation tolerance is strong, data hold time is long, with the advantage such as Si integrated technique compatibility, cause the extensive concern of international community, very likely become the replacer of traditional flash nonvolatile memory.The research that a large amount of financial resources and manpower are devoted to RRAM has been cast by a lot of electronics and semiconductor company in the world in recent years, comprises Sharp, Sony, Samsung Electronics, LSI Logic, Matssushita Electric Industrial, Winbond Electronics etc.Sharp and University of shizouka cooperate, and have developed the raw product of a high speed RRAM, and the read or write speed of its data is faster than three orders of magnitude of NAND type flash memory.
In RRAM research and development, it is the most noticeable that high-performance electric causes the design of the exploitation of resistive material and unit component structure.Nearly ten, in the multiple material system, all found electricity cause resistive effect should, such as rare earth manganese oxide material (Pr 0.7Ca 0.3MnO 3Deng), transition metal perovskite structure material (SrZrTiO 3, SrTiO 3Deng), transiton metal binary oxides material (NiO, TiO 2, Cu x O, Cu-MoO x , ZnO, Mg-ZnO, Co-ZnO, Mn-ZnO, Fe 2O 3, ZrO 2Deng), organic polymer semiconductor material (pentacene etc.) and some sulfide materials.For reaching the practical target of RRAM, improve resistance ratio and the stability of the high and low resistance state of resistive material, reduce to arrange voltage (Vset) and resetting voltage (Vreset), reduction material preparation cost etc. and all be very important.At present, obtain to have that steady resistance changes and the material system of good fatigue resistance is to promote the key that the RRAM storer further develops.
In addition, in recent years, transparent electronic technology obtains important breakthrough, successively successfully prepares transparent high-performance transistor and transparent unicircuit, makes transparent electronics become rapidly one of emerging focus subject.The transparent transistors that utilizes transparent electrode, transparent semi-conductor and consisted of by them and " the transparent electronic technology " of transparent circuitry, from the windshield glass of automobile transparent in one's handsly mechanical, electrically look, duplicating machine, solar cell, sun glasses and toy etc. can be applied.The development in this field is very fast, and approximately in the time in Future Ten year, transparent unicircuit may will be used in very wide scope.Except the U.S., Japan, a lot of countries and international electronics giant have included transparent electronics in its scientific development emphasis planning.
Summary of the invention
The object of the present invention is to provide a kind of glass substrate being coated with transparent conductive oxide film to prepare Mn-Zn oxide compound (ZnMnO 3, ZnMn 2O 4) electricity causes chemical solution deposition (CSD) processing method of resistance changing film and the preparation method of " metallic film/Mn-Zn sull/transparent conductive oxide film " asymmetric printing opacity resistive electric capacity.The method technique is simple and can satisfy the requirement of unicircuit planar technology.
The technical scheme that realizes the object of the invention is:
A kind of Mn-Zn oxide compound electricity causes the preparation method of resistance changing film and asymmetric printing opacity resistive electric capacity thereof, comprises the steps:
(1) adopt chemical solution deposition (CSD) technique to prepare Mn-Zn oxide compound (ZnMnO 3, ZnMn 2O 4) electricity causes resistance changing film;
(2) preparation Mn-Zn oxide compound (ZnMnO 3, ZnMn 2O 4) need multiple spin coating, layering thermal pretreatment during film;
(3) Mn-Zn oxide compound (ZnMnO 3, ZnMn 2O 4) film needs through anneal, and annealing is carried out under air atmosphere;
Specifically comprise the steps:
(1) carries out surface treatment and cleaning take the glass that is coated with transparent conductive oxide film as substrate, and to substrate;
(2) preparation ZnMnO 3, ZnMn 2O 4Precursor solution;
(3) precursor solution for preparing is dripped on the substrate, carry out again spin coating, make wet film;
(4) wet film that spin coating is good carries out oven drying at low temperature under 90-120 ℃ processes, and removes carbon, hydrogen composition in the wet film;
(5) film of drying and processing being crossed carried out under 320-350 ℃ of temperature thermal pretreatment 8-10 minute;
(6) repeat above-mentioned steps (3)-(5), determine multiplicity according to the thickness of required film, until obtain the ZnMnO of desired thickness 3, ZnMn 2O 4Film;
(7) with ZnMnO 3Film under 400-500 ℃ of temperature, ZnMn 2O 4Film carries out 40-60 minute anneal in the air atmosphere under 450-550 ℃ of temperature, make the film crystallization;
(8) can obtain ZnMnO behind the sample naturally cooling 3, ZnMn 2O 4Electricity causes resistance changing film;
(9) at Mn-Zn oxide compound (ZnMnO 3, ZnMn 2O 4) electricity causes on the resistance changing film surface and to adopt magnetically controlled DC sputtering technique to prepare the electrode of metal film, obtains " metallic film/Mn-Zn sull/transparent conductive oxide film " asymmetric printing opacity resistive electric capacity.
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 dirt settling that remains in the surface;
2. in the acetone ultrasonic cleaning 10-15 minute, remove the substrate surface organism;
3. in the ethanol ultrasonic cleaning 8-15 minute, remove the hydrocarbon polymer of substrate surface;
4. use at last deionized water ultrasonic cleaning 10 minutes, remove residual ethanol.
The described preparation of step (2) ZnMnO 3The raw material of precursor solution is: zinc acetate (Zn (CH 3COO) 22H 2O), four water manganous acetate (Mn (CH 3COO) 24H 2O), ethylene glycol monomethyl ether (CH 3OCH 2CH 2OH), thanomin.The mol ratio of four water Yi Suan Meng ︰ zinc acetates is 1.00-1.08:1.00, as solute; Thanomin is as stablizer, and the mol ratio of Rong Zhi ︰ thanomin is 0.80-1.10:1.00; Ethylene glycol monomethyl ether is solvent, and the 0.30-0.45 mole of solute is joined 1000 milliliters of solvents.Its preparation method comprises the steps:
1. in the container of clean dry, add an amount of ethylene glycol monomethyl ether;
2. load weighted zinc acetate, four water manganous acetate powder are put into container;
3. an amount of thanomin is poured in the container;
4. the temperature setting 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 ZnMnO of brown homogeneous 3Precursor solution;
The best proportioning of above-mentioned raw materials is: the mol ratio of solute four water Yi Suan Meng ︰ zinc acetates is 1.04:1.00; The mol ratio of Yi glycol Jia Mi ︰ thanomin is 1.00:1.00; 0.40 mole of solute is joined 1000 milliliters of solvents.
The described preparation of step (2) ZnMn 2O 4The raw material of precursor solution is: zinc acetate (Zn (CH 3COO) 22H 2O), four water manganous acetate (Mn (CH 3COO) 24H 2O), ethylene glycol monomethyl ether (CH 3OCH 2CH 2OH), thanomin.The mol ratio of four water Yi Suan Meng ︰ zinc acetates is 2.00-2.14:1.00, as solute; Thanomin is as stablizer, and the mol ratio of Rong Zhi ︰ thanomin is 0.80-1.10:1.00; Ethylene glycol monomethyl ether is solvent, and the 0.30-0.45 mole of solute is joined 1000 milliliters of solvents.Its preparation method comprises the steps:
1. in the container of clean dry, add an amount of ethylene glycol monomethyl ether;
2. load weighted zinc acetate, four water manganous acetate powder are put into container;
3. an amount of thanomin is poured in the container;
4. the temperature setting 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 ZnMn of brown homogeneous 2O 4Precursor solution;
The best proportioning of above-mentioned raw materials is: the mol ratio of solute four water Yi Suan Meng ︰ zinc acetates is 2.06:1.00; The mol ratio of Yi glycol Jia Mi ︰ thanomin is 1.00:1.00; 0.40 mole of solute is joined 1000 milliliters of solvents.
The described electrode of metal film of step (9) can be the metallic substance such as silver (Ag), platinum (Pt), and processing method 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 Mn-Zn oxide compound (ZnMnO with having a lot of diameters 3, ZnMn 2O 4) electricity causes above the resistance changing film, can obtain the point-like metal film electrode behind the plated film;
2. the sample substrate temperature that has prepared Mn-Zn sull/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;
Mn-Zn oxide compound (ZnMnO 3, ZnMn 2O 4) electricity cause resistance changing film and " metallic film/Mn-Zn sull/transparent conductive oxide film " asymmetric printing opacity resistive electric capacity preparation technology's flow process as shown in Figure 1.
For to Mn-Zn oxide compound (ZnMnO 3, ZnMn 2O 4) electricity causes resistance changing film and " metallic film/Mn-Zn sull/transparent conductive oxide film " electric capacity carries out electric performance test, need to erode a part of Mn-Zn oxide compound (ZnMnO 3, ZnMn 2O 4) electricity causes resistance changing film and expose the transparent conductive oxide film bottom electrode.Test Constructure of as shown in Figure 2 for " metallic film/Mn-Zn sull/transparent conductive oxide film " prepared.
Advantage of the present invention is: (1) adopts chemical solution deposition (CSD) technique to prepare Mn-Zn oxide compound (ZnMnO 3, ZnMn 2O 4) electricity causes resistance changing film, the component control of film accurately and is easy to adjust (doping) component, can the big area masking, and cost is low; (2) adopt multiple spin coating, the process program of layering preheating can improve degree of crystallinity, reduces stress in thin films, improves the performance of film, particularly has higher high/low resistance ratio and lower voltage and the resetting voltage of arranging; (3) prepared " metallic film/electricity causes resistance changing film/transparent conductive oxide film " is unsymmetric structure electric capacity, can greatly improve the fatigue resistance that electricity causes resistance changing film, and can be applicable to transparent electronic applications.
Description of drawings
Fig. 1 is Mn-Zn oxide compound (ZnMnO of the present invention 3, ZnMn 2O 4) electricity causes preparation technology's schema of resistance changing film and " metallic film/Mn-Zn sull/transparent conductive oxide film " asymmetric printing opacity resistive electric capacity;
Fig. 2 is the present invention's " metallic film/Mn-Zn sull/transparent conductive oxide film " Test Constructure of schematic diagram;
Fig. 3 is that the present invention is coated with the ZnMnO for preparing on the ITO transparent conductive oxide film glass substrate 3Electricity causes the X-ray diffraction (XRD) of resistance changing film;
Fig. 4 is the present invention " Ag/ZnMnO 3/ ITO " feature of asymmetric printing opacity resistive electric capacity I- VCurve;
Fig. 5 is the present invention " Ag/ZnMn 2O 4/ ITO " feature of asymmetric printing opacity resistive electric capacity I- VCurve.
Embodiment
ZnMnO 3The precursor solution prescription is: (a) solute four water manganous acetate (Mn (CH 3COO) 24H 2O) and zinc acetate (Zn(CH 3COO) 22H 2O) mol ratio is 1.00-1.08:1.00; (b) thanomin is as stablizer, and the mol ratio of Rong Zhi ︰ thanomin is 0.80-1.10:1.00; (c) solvent is ethylene glycol monomethyl ether, and the solute of 0.30-0.45 mole is joined 1000 milliliters of solvents.
ZnMn 2O 4The precursor solution prescription is: (a) solute four water manganous acetate (Mn (CH 3COO) 24H 2O) and zinc acetate (Zn(CH 3COO) 22H 2O) mol ratio is 2.00-2.14:1.00; (b) thanomin is as stablizer, and the mol ratio of Rong Zhi ︰ thanomin is 0.80-1.10:1.00; (c) solvent is ethylene glycol monomethyl ether, and the solute of 0.30-0.45 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 dirt settling that remains in the surface;
2. acetone ultrasonic cleaning 10-15 minute, remove the substrate surface organism;
3. ethanol ultrasonic cleaning 8-15 minute, remove the hydrocarbon polymer of glass surface;
4. use at last deionized water ultrasonic cleaning 10 minutes, remove residual ethanol.
(2) adopt following raw material (its purity is analytical pure 99.99%) preparation ZnMnO 3Precursor solution:
Zinc acetate (Zn (CH 3COO) 22H 2O) 87.80 grams
Four water manganous acetate (Mn (CH 3COO) 24H 2O) 101.96 grams
21.35 milliliters of thanomins
1000 milliliters of ethylene glycol monomethyl ether
Wherein: (a) solute four water manganous acetate (Mn (CH 3COO) 24H 2O) ︰ zinc acetate (Zn (CH 3COO) 22H 2O) mol ratio is 1.04:1.00, and stabilizer alcohol amine is 21.35 milliliters; (b) 0.40 mole of solute is joined 1000 milliliters of solvents and (is wherein contained: 1000 milliliters of ethylene glycol monomethyl ether).
(3) with the ZnMnO for preparing 3Precursor solution drips 1-2 and drips on the glass substrate that is coated with ito thin film, starts spin coater and carries out spin coating, forms wet film;
(4) wet film that spin coating is good carries out oven drying at low temperature under 100 ℃ processes, and removes carbon, hydrogen composition in the wet film;
(5) film that will dry carried out thermal pretreatment 10 minutes at 330 ℃ constant temp. heating dish;
(6) repeat above-mentioned steps (3)-(5) 4 times, obtain ZnMnO 3Film;
(7) with ZnMnO 3Film is annealed in air ambient, and annealing temperature is 500 ℃, and the time is 50 minutes, makes the film crystallization;
(8) can obtain ZnMnO behind the sample naturally cooling 3Electricity causes resistance changing film;
(9) at ZnMnO 3Electricity causes and adopts magnetically controlled DC sputtering technique to prepare the Ag upper electrode film on the resistance changing film surface, obtains " Ag/ ZnMnO 3/ ITO " asymmetric printing opacity resistive electric capacity:
1. be that the mask of 0.5mm aperture covers ZnMnO with having a lot of diameters 3Electricity causes above the resistance changing 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.
ZnMnO 3Electricity causes resistance changing film and " Ag/ZnMnO 3/ ITO " asymmetric printing opacity resistive electric capacity preparation technology's flow process as shown in Figure 1.
For to " Ag/ZnMnO 3/ ITO " electric capacity carries out electric performance test, need to erode a part of ZnMnO 3Film exposes the ITO bottom electrode." the Ag/ZnMnO for preparing 3/ ITO " Test Constructure of is as shown in Figure 2.
Embodiment 2:
(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 dirt settling that remains in the surface;
2. acetone ultrasonic cleaning 10-15 minute, remove the substrate surface organism;
3. ethanol ultrasonic cleaning 8-15 minute, remove the hydrocarbon polymer of glass surface;
4. use at last deionized water ultrasonic cleaning 10 minutes, remove residual ethanol.
(2) adopt following raw material (its purity is analytical pure 99.99%) preparation ZnMn 2O 4Precursor solution:
Zinc acetate (Zn (CH 3COO) 22H 2O) 87.80 grams
Four water manganous acetate (Mn (CH 3COO) 24H 2O) 201.95 grams
21.35 milliliters of thanomins
1000 milliliters of ethylene glycol monomethyl ether
Wherein: (a) solute four water manganous acetate (Mn (CH 3COO) 24H 2O): zinc acetate (Zn (CH 3COO) 22H 2O) mol ratio 2.06:1.00, stabilizer alcohol amine are 30.00 milliliters; (b) 0.40 mole of solute is joined 1000 milliliters of solvents and (is wherein contained: 1000 milliliters of ethylene glycol monomethyl ether).
(3) with the ZnMn for preparing 2O 4Precursor solution drips 1-2 and drips on the glass substrate that is coated with ito thin film, starts spin coater and carries out spin coating, forms wet film;
(4) wet film that spin coating is good carries out oven drying at low temperature under 100 ℃ processes, and removes carbon, hydrogen composition in the wet film;
(5) film that will dry carried out thermal pretreatment 10 minutes at 350 ℃ constant temp. heating dish;
(6) repeat above-mentioned steps (3)-(5) 5 times, obtain ZnMn 2O 4Film;
(7) with ZnMn 2O 4Film is annealed in air ambient, and annealing temperature is 550 ℃, and the time is 40 minutes, makes the film crystallization;
(8) can obtain ZnMn behind the sample naturally cooling 2O 4Electricity causes resistance changing film;
All the other are with embodiment 1.ZnMn 2O 4Electricity causes resistance changing film and " Ag/ZnMn 2O 4/ ITO " asymmetric printing opacity resistive electric capacity preparation technology's flow process as shown in Figure 1, " the Ag/ZnMn for preparing 2O 4/ ITO " Test Constructure of is as shown in Figure 2.
Embodiment 3:
(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 dirt settling that remains in the surface;
2. acetone ultrasonic cleaning 10-15 minute, remove the substrate surface organism;
3. ethanol ultrasonic cleaning 8-15 minute, remove the hydrocarbon polymer of glass surface;
4. use at last deionized water ultrasonic cleaning 10 minutes, remove residual ethanol.
(2) adopt following raw material (its purity is analytical pure 99.99%) preparation ZnMnO 3Precursor solution:
Zinc acetate (Zn (CH 3COO) 22H 2O) 65.85 grams
Four water manganous acetate (Mn (CH 3COO) 24H 2O) 73.527 grams
28.75 milliliters of thanomins
1000 milliliters of ethylene glycol monomethyl ether
Wherein: (a) solute four water manganous acetate (Mn (CH 3COO) 24H 2O): zinc acetate (Zn (CH 3COO) 22H 2O) mol ratio 1.00:1.00, stabilizer alcohol amine are 28.75 milliliters; (b) 0.30 mole of solute is joined 1000 milliliters of ethylene glycol monomethyl ether solvents.
(3) with the ZnMnO for preparing 3Precursor solution drips 1-2 and drips on the glass substrate that is coated with the AZO film, starts spin coater and carries out spin coating, forms wet film;
(4) wet film that spin coating is good carries out oven drying at low temperature under 100 ℃ processes, and removes carbon, hydrogen composition in the wet film;
(5) film that will dry carried out thermal pretreatment 8 minutes at 350 ℃ constant temp. heating dish;
(6) repeat above-mentioned steps (3)-(5) 5 times, obtain ZnMnO 3Film;
(7) with ZnMnO 3Film is annealed in air ambient, and annealing temperature is 450 ℃, and the time is 60 minutes, makes the film crystallization;
(8) can obtain ZnMnO behind the sample naturally cooling 3Electricity causes resistance changing film;
(9) at ZnMnO 3Electricity causes and adopts magnetically controlled DC sputtering technique to prepare Pt upper electrode film acquisition " Pt/ ZnMnO on the resistance changing film surface 3/ AZO " asymmetric printing opacity resistive electric capacity:
1. be that the mask of 0.5mm aperture covers ZnMnO with having a lot of diameters 3Electricity causes above the resistance changing 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.ZnMnO 3Electricity causes resistance changing film and " Pt/ZnMnO 3/ AZO " asymmetric printing opacity resistive electric capacity preparation technology's flow process as shown in Figure 1, " the Pt/ZnMnO for preparing 3/ AZO " Test Constructure of is as shown in Figure 2.
In above-mentioned all embodiment, step (1) can move to step (2) and carry out afterwards.
To typical Mn-Zn oxide compound (ZnMnO 3, ZnMn 2O 4) electricity causes resistance changing film and " Ag/ZnMnO 3/ ITO, Ag/ZnMn 2O 4/ ITO " structure and the performance test of electric capacity be as follows:
On the glass substrate that is coated with the ITO transparent conductive film, ZnMnO 3The X-ray diffraction (XRD) that electricity causes resistance changing film as shown in Figure 3, " Ag/ ZnMnO 3/ ITO " feature of asymmetric printing opacity resistive electric capacity I- VCurve as shown in Figure 4, " Ag/ZnMnO 3/ ITO " the electric resistance changing process of asymmetric printing opacity resistive electric capacity 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; then, reach when applying negative voltage-during 1.8V, film returns to high-impedance state, and a circulation like this is when applying voltage, upper current conducting cap Ag is positive dirction, bottom electrode ITO is negative direction, and the voltage that applies when making film become low resistance state is called voltage is set, and the voltage that applies when making film return to high-impedance state is called resetting voltage.Fig. 5 " Ag/ZnMn 2O 4/ ITO " feature of asymmetric printing opacity resistive electric capacity I- VCurve is compared and can be found out, because of with Fig. 4 I- VThe ordinate zou of curve is different, can significantly find out ZnMn 2O 4Electricity causes the high low resistance state ratio of having of resistance changing film, but resetting voltage is increased to-3.0V by-1.8V." Ag/ZnMnO 3/ ITO " the resistance change experiment of No. 240 switches circulations of asymmetric printing opacity resistive electric capacity experience; visible high-impedance state is at 250 Ω-2000 Ω; low resistance state is at 40 Ω-60 Ω; the resistance change space doubly of the switching 6-50 between the high/low resistance state; and show good repeatability and stability, illustrate to have good fatigue resistance.
Although the present invention is with preferred embodiment openly as above, and non-limiting the present invention, any those skilled in the art can do suitable improvement without departing from the spirit and scope of the present invention, and therefore, protection domain of the present invention is as the criterion with the scope that claim was defined.

Claims (8)

1. a Mn-Zn oxide compound electricity causes the preparation method of resistance changing film and asymmetric printing opacity resistive electric capacity thereof, it is characterized in that: the glass that the method comprises being coated with transparent conductive oxide film is substrate, adopt the chemical solution deposition processing method to prepare Mn-Zn oxide compound electricity and cause resistance changing film, adopt the magnetically controlled DC sputtering processing method to prepare the metallic film top electrode and obtain corresponding asymmetric printing opacity resistive electric capacity, specifically comprise the steps:
(1) carries out surface treatment and cleaning take the glass that is coated with ITO, AZO transparent conductive oxide film as substrate, and to substrate;
(2) prepare the Mn-Zn oxide compound ZnMnO of different Mn, Zn composition proportion 3, ZnMn 2O 4Precursor solution;
(3) precursor solution for preparing is dripped on the substrate, carry out again spin coating, make wet film;
(4) the good wet film of spin coating is carried out oven drying at low temperature and process, remove carbon, hydrogen composition in the wet film;
(5) film of drying and processing being crossed carries out thermal pretreatment;
(6) repeat above-mentioned steps (3)-(5), determine multiplicity according to the thickness of required film, until obtain the Mn-Zn sull of desired thickness;
(7) above-mentioned Mn-Zn sull is carried out anneal under air ambient, certain temperature, make the film crystallization;
(8) can obtain Mn-Zn oxide compound electricity behind the sample naturally cooling and cause resistance changing film;
(9) cause the resistance changing film surface at Mn-Zn oxide compound electricity and adopt magnetically controlled DC sputtering technique to prepare the electrode of metal film, obtain " metallic film/Mn-Zn sull/transparent conductive oxide film " asymmetric printing opacity resistive electric capacity.
2. preparation method according to claim 1 is characterized in that:
The surface treatment of the transparent conductive oxide film glass substrate such as the described ITO of being coated with of step (1), AZO and cleaning require and step is:
1. soaked 24 hours with sodium hydroxide solution, remove the dirt settling that remains in the surface;
2. in the acetone ultrasonic cleaning 10-15 minute, remove the substrate surface organism;
3. in the ethanol ultrasonic cleaning 8-15 minute, remove the hydrocarbon polymer of substrate surface;
4. use at last deionized water ultrasonic cleaning 10 minutes, remove residual ethanol.
3. preparation method according to claim 1 is characterized in that:
The described preparation of step (2) ZnMnO 3The raw material of precursor solution is: zinc acetate, four water manganous acetates, ethylene glycol monomethyl ether, thanomin; The mol ratio of four water Yi Suan Meng ︰ zinc acetates is 1.00-1.08:1.00, as solute; Thanomin is as stablizer, and the mol ratio of Rong Zhi ︰ thanomin is 0.80-1.10:1.00; Ethylene glycol monomethyl ether is solvent, and the 0.30-0.45 mole of solute is joined 1000 milliliters of solvents;
The described preparation of step (2) ZnMn 2O 4The raw material of precursor solution is: zinc acetate, four water manganous acetates, ethylene glycol monomethyl ether, thanomin; The mol ratio of four water Yi Suan Meng ︰ zinc acetates is 2.00-2.06:1.00, as solute; Thanomin is as stablizer, and the mol ratio of Rong Zhi ︰ thanomin is 0.80-1.10:1.00; Ethylene glycol monomethyl ether is solvent, and the 0.30-0.45 mole of solute is joined 1000 milliliters of solvents.
4. it is characterized in that according to claim 1 or 3 described preparation methods:
ZnMnO described in the step (2) 3The preparation of precursor solution comprises the steps:
1. in the container of clean dry, add an amount of ethylene glycol monomethyl ether;
2. load weighted zinc acetate, four water manganous acetate powder are put into container;
3. an amount of thanomin is poured in the container;
4. the temperature setting 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 ZnMnO of homogeneous 3Precursor solution;
ZnMn described in the step (2) 2O 4The preparation of precursor solution comprises the steps:
1. in the container of clean dry, add an amount of ethylene glycol monomethyl ether;
2. load weighted zinc acetate, four water manganous acetate powder are put into container;
3. an amount of thanomin is poured in the container;
4. the temperature setting 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 ZnMn of homogeneous 2O 4Precursor solution.
5. preparation method according to claim 1 is characterized in that:
ZnMnO in step (4), (5) and (7) 3, ZnMn 2O 4The heat-treat condition of film is: dry under 90-120 ℃ of temperature first, then carry out thermal pretreatment under 320-350 ℃ of temperature, last ZnMnO 3Film is 400-500 ℃, ZnMn in temperature 2O 4Film is annealing 40-60 minute in 450-550 ℃ the air ambient in temperature.
6. preparation method according to claim 1 is characterized in that:
The described electrode of metal film of step (9) can be the metallic substance such as silver, platinum, and processing method 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 Mn-Zn oxide compound electricity and causes above the resistance changing film with having a plurality of diameters, can obtain the point-like metal film electrode behind the plated film;
2. the sample substrate temperature that has prepared Mn-Zn sull/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.
7. a kind of Mn-Zn oxide compound electricity with the described preparation method's preparation of one of claim 1-5 causes resistance changing film.
8. a kind of Mn-Zn oxide compound electricity with the described preparation method's preparation of one of claim 1-6 causes the asymmetric printing opacity resistive of resistance changing film electric capacity.
CN2012105189167A 2012-12-06 2012-12-06 Method for preparing Mn-Zn oxide electrogenerated resistive thin films and asymmetric light-pervious resistive capacitors thereof Pending CN103014686A (en)

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CN104264115A (en) * 2014-09-04 2015-01-07 兰州空间技术物理研究所 Antistatic method for film surface
CN114685314A (en) * 2022-03-28 2022-07-01 桂林理工大学 Steady-state alpha-phase FAPBI3Is manufactured by

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CN101431144A (en) * 2007-11-07 2009-05-13 中国科学院微电子研究所 Method for producing self-isolation resistor transformation type memory unit
CN102255045A (en) * 2011-09-20 2011-11-23 桂林电子科技大学 MgxZn1-xO electrically induced resistance change film and preparation method of asymmetrical structure heterojunction thereof

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CN101431144A (en) * 2007-11-07 2009-05-13 中国科学院微电子研究所 Method for producing self-isolation resistor transformation type memory unit
CN102255045A (en) * 2011-09-20 2011-11-23 桂林电子科技大学 MgxZn1-xO electrically induced resistance change film and preparation method of asymmetrical structure heterojunction thereof

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104264115A (en) * 2014-09-04 2015-01-07 兰州空间技术物理研究所 Antistatic method for film surface
CN104264115B (en) * 2014-09-04 2016-08-17 兰州空间技术物理研究所 A kind of method of coating surface antistatic
CN114685314A (en) * 2022-03-28 2022-07-01 桂林理工大学 Steady-state alpha-phase FAPBI3Is manufactured by

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