CN103247758B - Adopt erasable film variable-resistance memory unit of flexible-paper-base and preparation method thereof - Google Patents
Adopt erasable film variable-resistance memory unit of flexible-paper-base and preparation method thereof Download PDFInfo
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- CN103247758B CN103247758B CN201310157318.6A CN201310157318A CN103247758B CN 103247758 B CN103247758 B CN 103247758B CN 201310157318 A CN201310157318 A CN 201310157318A CN 103247758 B CN103247758 B CN 103247758B
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Abstract
The invention belongs to nonvolatile semiconductor memory member technical field, be specially a kind of erasable film RRAM memory cell adopting flexible-paper-base.The present invention with the ink color printing paper of flexible bendable for substrate, SnO 2 thin film is as change resistance layer, Electrochromic Molybdenum Oxide Coatings is as oxygen accumulation layer, concrete structure composition is followed successively by: ink color printing paper base plate, as the metal nickel film of hearth electrode, SnO 2 thin film, Electrochromic Molybdenum Oxide Coatings, as the metal molybdenum film of top electrode.The present invention under cryogenic (~ 100 DEG C) utilizes magnetically controlled DC sputtering technology, prepares metal nickel film, SnO 2 thin film, Electrochromic Molybdenum Oxide Coatings, metal molybdenum film successively at substrate.Variable-resistance memory unit prepared by the present invention has the characteristics such as good bending durability, and in non-volatile memories field, flexible electronic device field has broad application prospects.
Description
Technical field
The invention belongs to nonvolatile semiconductor memory member technical field, be specifically related to a kind of erasable film variable-resistance memory unit and preparation method thereof.
Background technology
Resistor type random access memory (ResistiveRandomAccessMemory, RRAM) mechanism is that external electric field triggers reversible resistance transition effect, namely under alive effect outside, resistance reversible transition between low resistance state (" 0 ") and high-impedance state (" 1 ") of device, and the resistance obtained can keep getting off after external electric field is removed.Based on this effect, scientific circles propose a kind of novel nonvolatile memory concept---resistor type random access memory
.the final goal of RRAM technology becomes single mnemon by changing containing multiple memory device in existing single electronic product.In time several years in future, it will be applied more broadly in the circuit chip with various Novel intelligent function, and even is had a revolutionary change in the field such as electronics and computer science and technology.
Current random asccess memory part (RAM) is mainly divided three classes: static random access memory part (SRAM), dynamic random access memory part (DRAM) and flash memory (FlashMemory).There are pluses and minuses separately: the shortcoming of static random access memory part is that the number of transistors that a memory cell needs is many, expensive, and storage density is low; Dynamic random access memory part needs when being energized constantly to refresh could preserve data, and after power-off, data will be lost; Flash memory is the memory that uniquely can carry out data preservation in cold situation, but speed is slow.RRAM is a kind of brand-new memory device, and its main advantage shows: one is that preparation is simple.Memory cell is metal-oxide-metal sandwich structure, by the thin-film technique preparation that sputtering, vapour deposition etc. are conventional; Two is erasable speed fast
.the pulse duration that erasable speed is changed by trigger resistance determines, is generally less than for 100 nanoseconds, far above flash storage; Three is that storage density is high
.research shows that the region that resistance changes is very little, about several nanometer, therefore memory cell can be very little, in addition, multilevel electric resistance changing phenomenon is also there is in RRAM, utilize these resistance states can store different information, the storage of more information can be realized under the condition not changing memory cell volume; Four is that semiconductor technology compatibility is good
,rRAM can utilize existing semiconductor process techniques to produce, thus greatly reduces development cost.
The existing research report preparing film resistance-variable storing device using metal-oxide semiconductor (MOS)s such as niobium oxide, nickel oxide, zirconia and aluminium oxide as accumulation layer in recent years.But wherein a lot of raw material belong to expensive metal, or need equipment costly to prepare film, increase production cost.
Tin ash (SnO
2) be a kind of sull storage medium getting a good eye value, have nontoxic, harmless, cost is low, wide energy gap and transmission of visible light high.If use this sull RRAM in memory cell matrix, production cost can be reduced to a great extent.Also there is researcher to prepare the metal oxide RRAM of Bendable as substrate with Traditional flexible material such as PET, PES etc. simultaneously.Because paper material has low cost, cheap, green, bent, the advantages such as recovery, obtain the concern of people in the last few years in field of electronic devices, are such as the thin-film transistor of base material with paper, lithium battery etc.The actual application value of the flexible resistance-variable storing device of paper substrate can be predicted.Correlative study also thinks that molybdenum electrode and resistive material interface can form Electrochromic Molybdenum Oxide Coatings, absorbs (storage) layer, contribute to the formation of Lacking oxygen conductive channel when write operation as oxygen, thus reduces write voltage, improves write voltage consistency.
Summary of the invention
The object of the invention is to provide a kind of that have good bending endurance quality, erasable film variable-resistance memory unit and preparation method thereof.
The erasable film variable-resistance memory unit that the present invention proposes, with the ink color printing paper of flexible bendable for base material, tin oxide (SnO
x (0<X≤2)) film as change resistance layer, molybdenum oxide (MoO
x (1.5<X<3)) film is as oxygen accumulation layer, concrete structure composition is followed successively by: ink color printing paper base plate, as the metal nickel film of hearth electrode, tin oxide resistance changing film, Electrochromic Molybdenum Oxide Coatings, as the metal molybdenum film of top electrode.This variable-resistance memory unit can be designated as Mo/MoO
x (1.5<X<3)/ SnO
x (0<X≤2)/ Ni/ ink color printing paper base plate.Specifically as shown in Figure 1.
The preparation method of the above-mentioned erasable film variable-resistance memory unit that the present invention proposes is with the ink color printing paper of flexible bendable for substrate, and adopt magnetron sputtering technique deposition of layers film successively, concrete steps are as follows:
1, adopt W metal target, using Ar gas as working gas, operating pressure is 2.0 × 10
-1pa, on ink color printing paper base plate, sputtering forms W metal film; Wherein, sputtering current is 150 ~ 200mA, and sputtering voltage is 450 ~ 550V, sputtering time 15 ~ 30 minutes;
2, prepare tin oxide resistance changing film, the steps include: to use metallic tin target, first heat the substrate processed through step (1), temperature to 50 ~ 150 DEG C; By O
2reative cell is passed into, control O with Ar gas
2the dividing potential drop of reacting gas is 7 × 10
-2pa ~ 1.5 × 10
-1pa, operating pressure is 3.0 ~ 6.0 × 10
-1pa, sputtering forms tin oxide resistance changing film; Wherein, sputtering current is 50 ~ 200mA, and sputtering voltage is 300 ~ 500V, and sputtering time is 10 ~ 30 minutes, and this film thickness is 100 ~ 250nm;
3, prepare Electrochromic Molybdenum Oxide Coatings, the steps include: to use metal molybdenum target, first heat the substrate processed through step (1), (2), temperature to 50 ~ 150 DEG C, by O
2reative cell is passed into, control O with Ar gas
2the dividing potential drop of reacting gas is 5 × 10
-2pa ~ 1.5 × 10
-1pa, operating pressure is 3.0 ~ 6.0 × 10
-1pa, sputtering forms Electrochromic Molybdenum Oxide Coatings; Wherein, sputtering current is 50 ~ 200mA, and sputtering voltage is 300 ~ 550V, and sputtering time is 5 ~ 20 minutes; This film thickness is 40 ~ 150nm;
4, DC magnetron sputtering method is utilized to prepare molybdenum top electrode finally by mask plate, the steps include: that the method for the mask by being of a size of 200 μm × 200 μm prepares the molybdenum top electrode that thickness is 100 ~ 200nm, sputtering current is 150 ~ 250mA, sputtering voltage is 300 ~ 400V, sputtering time 20 ~ 40 minutes.
In the present invention, prepare the preferred condition of tin oxide resistance changing film as follows:
Substrate temperature is 80 ~ 120 DEG C;
By variable conductance valve by O
2reative cell is passed into, O with Ar gas
2the dividing potential drop of reacting gas is 8 × 10
-2pa ~ 1.2 × 10
-1pa, the operating pressure in reative cell is 5.0 × 10
-1pa;
Sputtering current is 80 ~ 120mA, and sputtering voltage is 350 ~ 450V, and sputtering time is 15 ~ 25 minutes.
Prepare molybdenum oxide (MoO
x (1.5<x<3)) the preferred condition of film is as follows:
Substrate temperature is 80 ~ 120 DEG C;
By variable conductance valve by O
2reative cell is passed into, O with Ar gas
2the dividing potential drop of reacting gas is 8.0 × 10
-2pa ~ 1.2 × 10
-1pa, the operating pressure in reative cell is 5.0 × 10
-1pa;
Sputtering current is 140 ~ 160mA, and sputtering voltage is 400 ~ 450V, and sputtering time is 7 ~ 12 minutes.
In the present invention, preparing thickness by the method for the mask being of a size of 200 μm × 200 μm is the molybdenum top electrode that 100 ~ 150nm is thick, and sputtering current is 150 ~ 200mA, and sputtering voltage is 350 ~ 400V, sputtering time 20 ~ 30 minutes.
The present invention has successfully been prepared by direct current magnetron sputtering process under cryogenic with the tin oxide/Electrochromic Molybdenum Oxide Coatings memory cell of ink printing paper material good bending endurance quality for substrate has.Magnetron sputtering method has that controllability is good, deposition rate is high, can the thin feature of Large-Area-Uniform system, be suitable for applying in the industrial production.
Flexible tin oxide/Electrochromic Molybdenum Oxide Coatings the variable-resistance memory unit of paper substrate that the present invention makes has good change resistance performance, high low resistance state to hold time when bending (radius of curvature 5cm) and smooth time be all greater than 1 × 10
4second, 200 times the erasable Memory windows of dc sweeps is greater than 10, erasable bending durability 10
4more than secondary, state maintains bending durability 10
5above.Store in information, the fields such as flexible electronic are with a wide range of applications.
Accompanying drawing explanation
Fig. 1 is the structure chart of the flexible variable-resistance memory unit of paper substrate tin oxide/molybdenum oxide and test schematic diagram.
Fig. 2 is the erasing writing successive measuring current voltage response of the flexible variable-resistance memory unit of paper substrate tin oxide/molybdenum oxide.
Fig. 3 is that the high low resistance state of the flexible variable-resistance memory unit of paper substrate tin oxide/molybdenum oxide is held time test curve.Wherein, when a is for bending, when b is smooth.
Fig. 4 is the high low-resistance cyclic curve of the flexible variable-resistance memory unit of paper substrate tin oxide/molybdenum oxide.
Fig. 5 is that the bending number of times height of the flexible variable-resistance memory unit of paper substrate tin oxide/molybdenum oxide hinders change curve.
Number in the figure: 1 is ink color printing paper substrates, and 2 is nickel hearth electrode, and 3 is tin oxide resistance changing film, and 4 is Electrochromic Molybdenum Oxide Coatings, and 5 is molybdenum top electrode, and 6 is probe.
Embodiment
The specific embodiment of the present invention is further described below by object lesson.
Select W metal target, first reative cell vacuum is extracted into lower than 3.0 × 10 before thin film deposition
-3pa, then passes into reative cell by variable conductance valve by Ar gas, and the operating pressure controlled in reative cell is 2.0 × 10
-1pa.Sputtering current and sputtering voltage are adjusted to 180mA and 500V respectively, sputtering time 20 minutes, ink paper base plate form metal nickel film as hearth electrode.Electrode square resistance is less than 10 ohm.
Select metal tin target, first reative cell vacuum is extracted into lower than 3.0 × 10 before thin film deposition
-3pa, substrate heating to 100 DEG C, then by variable conductance valve by O
2pass into reative cell successively with Ar gas, and the partial pressure of oxygen controlled in reative cell is 1.1 × 10
-1pa, operating pressure is 5.0 × 10
-1pa.Sputtering current and sputtering voltage are modulated to 110mA and 400V respectively, and sputtering time 20 minutes, hearth electrode is formed SnO 2 thin film change resistance layer.SnO 2 thin film thickness is about 200nm.
Select metal molybdenum target, first reative cell vacuum is extracted into lower than 3.0 × 10 before thin film deposition
-3pa, substrate heating to 100 DEG C, then by variable conductance valve by O
2pass into reative cell successively with Ar gas, and the partial pressure of oxygen controlled in reative cell is 1.0 × 10
-1pa, operating pressure is 5.0 × 10
-1pa.Sputtering current and sputtering voltage are modulated to 100mA and 450V respectively, sputtering time 7 minutes, hearth electrode is formed Electrochromic Molybdenum Oxide Coatings resistive oxygen accumulation layer.Electrochromic Molybdenum Oxide Coatings thickness is about 50nm.
By the mask plate that aperture is 200 microns, adopt direct magnetic control method to prepare thickness and be about the thick metal M o film of 150nm as top electrode, sputtering current and sputtering voltage are respectively 200mA and 380V, and sputtering time is about 25 minutes.
The paper substrate tin oxide prepared/molybdenum oxide flexible variable-resistance memory unit height low resistance state to hold time when bending (radius of curvature 5cm) and smooth time be all greater than 1 × 10
4second, 200 times the erasable Memory windows of dc sweeps is greater than 10, erasable bending durability 10
4more than secondary, state maintains bending durability 10
5above.See shown in Fig. 3, Fig. 4, Fig. 5.
Claims (2)
1. a preparation method for film RRAM memory cell, is characterized in that with the ink color printing paper of flexible bendable for substrate, and adopt magnetron sputtering technique deposition of layers film successively, concrete steps are as follows:
(1) adopt W metal target, using Ar gas as working gas, operating pressure is 2.0 × 10
-1pa, on ink color printing paper base plate, sputtering forms W metal film; Wherein, sputtering current is 150 ~ 200mA, and sputtering voltage is 450 ~ 550V, sputtering time 15 ~ 30 minutes;
(2) prepare tin oxide resistance changing film, the steps include: to use metallic tin target, heat the substrate processed through step (1), temperature to 50 ~ 150 DEG C; By O
2reative cell is passed into, control O with Ar gas
2the dividing potential drop of reacting gas is 7 × 10
-2pa ~ 1.5 × 10
-1pa, operating pressure is 3.0 ~ 6.0 × 10
-1pa, sputtering forms tin oxide resistance changing film; Wherein, sputtering current is 50 ~ 200mA, and sputtering voltage is 300 ~ 500V, and sputtering time is 10 ~ 30 minutes, and this film thickness is 100 ~ 250nm;
(3) prepare Electrochromic Molybdenum Oxide Coatings, the steps include: to use metal molybdenum target, heat the substrate processed through step (1), (2), temperature to 50 ~ 150 DEG C, by O
2reative cell is passed into, control O with Ar gas
2the dividing potential drop of reacting gas is 5 × 10
-2pa ~ 1.5 × 10
-1pa, operating pressure is 3.0 ~ 6.0 × 10
-1pa, sputtering forms Electrochromic Molybdenum Oxide Coatings; Wherein, sputtering current is 50 ~ 200mA, and sputtering voltage is 300 ~ 550V, and sputtering time is 5 ~ 20 minutes; This film thickness is 40 ~ 150nm;
(4) DC magnetron sputtering method is utilized to prepare molybdenum top electrode finally by mask plate, the steps include: that the method for the mask by being of a size of 200 μm × 200 μm prepares the molybdenum top electrode that thickness is 100 ~ 200nm, sputtering current is 150 ~ 250mA, sputtering voltage is 300 ~ 400V, sputtering time 20 ~ 40 minutes.
2. an erasable film RRAM memory cell for the employing flexible-paper-base prepared by method described in claim 1, is characterized in that with the ink color printing paper of flexible bendable for substrate, tin oxide SnO
x, 0 < x≤2, film as change resistance layer, molybdenum oxide MoO
y, 1.5 < y < 3, film is as oxygen accumulation layer, concrete structure composition is followed successively by: ink color printing paper base plate, as the metal nickel film of hearth electrode, and tin oxide resistance changing film, Electrochromic Molybdenum Oxide Coatings, as the metal molybdenum film of top electrode.
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| WO2016092374A1 (en) * | 2014-12-10 | 2016-06-16 | King Abdullah University Of Science And Technology | All-printed paper-based memory |
| WO2016124969A2 (en) | 2014-12-31 | 2016-08-11 | King Abdullah University Of Science And Technology | All-printed paper memory |
| CN112885869A (en) * | 2021-02-03 | 2021-06-01 | 湖北大学 | 1S1R device based on metallic intercalation and preparation method thereof |
| CN117642061B (en) * | 2024-01-26 | 2024-05-07 | 电子科技大学长三角研究院(衢州) | Homojunction and resistive random access memory based on platinum doped tin oxide |
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| CN102260846A (en) * | 2011-07-22 | 2011-11-30 | 复旦大学 | Polycrystalline tin dioxide resistance changing film and preparation method and application thereof |
| CN102368535A (en) * | 2011-11-10 | 2012-03-07 | 复旦大学 | Erasable double layer film structure resistance variation memory cell and preparation method thereof |
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| CN102260846A (en) * | 2011-07-22 | 2011-11-30 | 复旦大学 | Polycrystalline tin dioxide resistance changing film and preparation method and application thereof |
| CN102368535A (en) * | 2011-11-10 | 2012-03-07 | 复旦大学 | Erasable double layer film structure resistance variation memory cell and preparation method thereof |
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