CN103236498B - A kind of nonpolar resistance-variable storing device and preparation method thereof - Google Patents
A kind of nonpolar resistance-variable storing device and preparation method thereof Download PDFInfo
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- CN103236498B CN103236498B CN201310145858.2A CN201310145858A CN103236498B CN 103236498 B CN103236498 B CN 103236498B CN 201310145858 A CN201310145858 A CN 201310145858A CN 103236498 B CN103236498 B CN 103236498B
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Abstract
The invention discloses a kind of nonpolar resistance-variable storing device and preparation method thereof, comprise conductive substrates and to hold concurrently bottom electrode, resistance-change memory medium, electrode of metal.Conductive substrate material is p
+type silicon chip substrate, resistance-change memory dielectric film is ZnMn
2o
4and alloy, doped chemical comprises Y, Sc, Mg, Si, Sn and In, and thickness is 20nm to 1200nm.Electrode of metal material comprises Al, Ag, Au, Cu, Ni, Pt and Ti, and its thickness is 50nm to 200nm.Advantage of the present invention is: the resistance-variable storing device of same structure possesses bipolarity and unipolar storage characteristics simultaneously.According to the resistance-change memory characteristic of opposed polarity, the application prospect of easily extensible resistance-variable storing device.
Description
Technical field
The invention belongs to memory area, particularly relate to a kind of nonpolar resistance-variable storing device and preparation method thereof.
Background technology
The performance of develop rapidly to memory of Information technology proposes requirements at the higher level, is widely used in the flash storage of the mobile devices such as mobile phone, MP3 player, digital camera, closelys follow CMOS equal proportion convergent-divergent paces in the past in vicennial development.But after semiconductor industry enters 22nm technology node, further developing of flash storage receives severe challenge.Flash stores the development constantly reducing Flash along with device size based on charge-storage mechanism and is restricted, and along with the continuous reduction of tunneling layer thickness, the leakage of electric charge will become more and more serious, and this will directly affect the performance of flash storage.Semiconductor industry is generally estimated, flash storage will halt 45nm technology node.Therefore find a kind of feasible non-novel memory devices based on charge-storage mechanism to substitute flash storage and become inevitable choice.Under these circumstances, all kinds of novel memory technology is arisen at the historic moment, and as the representative of non-volatility memorizer, flash memory exists the technology barriers such as read or write speed is slow, storage density is low, also faces serious convergent-divergent problem simultaneously.Along with conventional memory cell structural development approaches dimension limit, various new nonvolatile memory has been widely studied and has developed, wherein the comprising of most potentiality to be exploited: electroluminescent resistance-variable storing device (RRAM), magnetic memory (MRAM), ferroelectric memory (FRAM) and phase transition storage (PRAM).
RRAM utilizes the resistance of resistive dielectric material high resistance and low-resistance conversion to occur under electric field action to realize the storage of digital information " 0 " and " 1 ".Because of its have structure simple, can contractility good, storage density is high, low in energy consumption, read or write speed fast, repeatable operation tolerance is strong, data hold time is long, with the advantage such as Si integrated technique is compatible, cause the extensive concern of international community, very likely become the replacer of traditional flash nonvolatile memory.
RRAM research and development in, the exploitation of high-performance electroluminescent resistive material and the design of unit component structure the most noticeable.Nearly ten, in multiple material system, all found that electroluminescent resistive effect is answered, 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
xo, Cu-MoOx, ZnO and alloy, Fe
2o
3, ZrO
2deng), organic polymer semi-conducting material (PI, PEI, PS etc.) and sulfide material.For reaching the practical target of RRAM, improving resistance ratio and the stability of resistive material high and low resistance state, reducing to arrange voltage (Vset) and resetting voltage (Vreset), the preparation cost etc. of reduction material is all very important.At present, obtaining the material system with steady resistance transformation and good fatigue resistance is the key that promotion RRAM memory further develops.
In the resistance-variable storing device of these oxides as resistive dielectric film, its resistive behavior or be bipolarity saltus step, or be unipolarity saltus step, the memory that simultaneously there are two kinds of polarity saltus step behaviors in a kind of structure lacking very.J.M. Luo reports and to adulterate BiFeO with Mn
3make resistance-variable storing device and present nonpolar memory property.The existence (being called nonpolar) of two kinds of storage polarity, can conveniently select wherein a kind of saltus step polarity to meet the requirement of memory to memory property, by playing the advantage of the resistance-variable storing device of different saltus step polarity, will there is very important practical significance and potential economic worth in semiconductor technology application.
Summary of the invention
The object of the present invention is to provide one to possess bipolarity and unipolar resistance-variable storing device and preparation method thereof, this memory can use wherein a kind of polarity transformation behavior according to memory requirement simultaneously.
The object of the invention is to be achieved through the following technical solutions:
A kind of nonpolar resistance-variable storing device, comprises the conductive substrates stacked from bottom to up and to hold concurrently bottom electrode, resistance-change memory medium and electrode of metal on a storage medium, unlike the prior art:
(1) resistance-change memory medium is the ZnMn simultaneously possessing bipolarity and unipolar resistive behavior
2o
4and alloy;
(2) conductive substrate material is p
+type silicon chip substrate, its direction of growth is (100) direction, p
+type silicon chip is simultaneously also as the bottom electrode of memory;
(3) electrode of metal material comprises Al, Ag, Au, Cu, Ni, Pt and Ti, and its thickness is 50nm to 200nm.
The alloy of described resistance-change memory medium comprises Y, Sc, Mg, Si, Sn and In, and its form is film, and thickness is 20nm to 1200nm.
The structure of described resistance-variable storing device is metal/insulator/semiconductor (MIS) structure, metal specifically/resistance-change memory medium/p
+the structure of type silicon.
A preparation method for nonpolar resistance-variable storing device, comprises the steps:
(1) with the RCA cleaning cleaning silicon chip of standard, and drying and processing is carried out;
(2) ZnMn is prepared on the bottom electrode
2o
4and alloy resistive dielectric film;
(3) at ZnMn
2o
4and electrode of metal prepared by alloy resistive dielectric film.
Step (2) uses chemical solution depositing technology to prepare ZnMn
2o
4and alloy resistive dielectric film, coating number of times is 1 to 14 times, and the annealing temperature of film is higher than 620 DEG C, and annealing time 1 ~ 4h, carries out rapid thermal treatment (RTP) with Halogen lamp LED better.
Step (3) uses evaporation process to prepare electrode of metal, and background vacuum is better than 4.0 × 10
-4pa; Use metal mask version, the diameter of circular hole is 500 μm to 30 μm.
The invention has the beneficial effects as follows: the resistance-variable storing device of same structure possesses bipolarity and unipolar storage characteristics simultaneously.According to the resistance-change memory characteristic of opposed polarity, the application prospect of easily extensible resistance-variable storing device.
Accompanying drawing explanation
Fig. 1 is the three-decker schematic diagram of resistance-variable storing device of the present invention;
Fig. 2 is Ag/ZnMn of the present invention
2o
4/ p
+the X-ray diffractogram of-Si;
Fig. 3 surface topography map;
Fig. 4 cross-section morphology figure;
Fig. 5 is Ag/ZnMn of the present invention
2o
4/ p
+the bipolarity resistive characteristic of-Si resistance-variable storing device;
Fig. 6 is Ag/ZnMn of the present invention
2o
4/ p
+the unipolarity resistive characteristic of-Si resistance-variable storing device.
Embodiment
Below, reference example describes nonpolar resistance-variable storing device of one of the present invention and preparation method thereof.But, the invention is not restricted to these embodiments.
With reference to Fig. 1, a kind of nonpolar resistance-variable storing device to be held concurrently bottom electrode 1, ZnMn by the substrate spliced from below to up
2o
4film 2, top electrode 3 form.ZnMn
2o
4film 2 and top electrode 3 are sequentially positioned at substrate holds concurrently the top of bottom electrode 1, ZnMn
2o
4film 2 is clipped between top electrode 3 and bottom electrode 1, forms MIS capacitance structure.Described ZnMn
2o
4film 2 is polycrystalline structure, and thickness is at 20nm to 1200nm, and preferred thickness is at 50nm to 500nm.Described bottom electrode 1 is p
+the resistance of type silicon chip substrate be 2 Ω to 200 Ω, the direction of growth is (100) crystal face.Described top electrode 3 is metal electrode, and comprise Al, Ag, Au, Cu, Ni, Pt and Ti, its thickness is 50nm to 200nm, preferred 80nm.
The preparation method of above-mentioned nonpolar resistance-variable storing device, comprises the steps:
(1) p is provided
+type silicon chip, as substrate and lower electrode material, with standard RCA clean technique cleaning silicon chip, and carries out drying and processing.In one embodiment, selection resistance is the p of 2 Ω
+type silicon chip, as substrate, after the cleaning of RCA technique, with infrared lamp is dried after drying up the globule with the nitrogen of drying again.
(2) on the substrate of step (1) holds concurrently bottom electrode, ZnMn is formed
2o
4and the resistive dielectric film of doping, doped chemical comprises Y, Sc, Mg, Si, Sn and In.The pure chemicals of selection analysis, as the raw material of chemical solution deposition, comprises manganese acetate, zinc acetate, EGME, diethanol amine, acetylacetone,2,4-pentanedione.Manganese acetate, zinc acetate are as the raw material solute of Zn and Mn, and EGME is as solvent, and diethanol amine to be held concurrently stabilizer as chaotropic agent, and acetylacetone,2,4-pentanedione is as chelating agent.Use the spin coating mode of chemical solution precipitation, low speed controls at 300 ~ 500rpm, and High-speed Control is at 3000 ~ 4000rpm, and the baking temperature of wet film controls at 90 ~ 120 DEG C, and the time is 10 ~ 20min, and the pre-heat treatment temperature is 200 ~ 350 DEG C, and the time is 10 ~ 30min.According to the demand of resistive dielectric film thickness, repeatedly repeat spin coating plated film.Finally, film is carried out rapid thermal treatment in air or oxygen atmosphere, heat treatment temperature is higher than 620 DEG C, and the time is 1 ~ 4h, is naturally cooled by sample, can obtain the ZnMn of crystalline state
2o
4resistive dielectric film.In one embodiment, the mol ratio of Zn and Mn element is 1:2, and the mol ratio of solute and triethanolamine is 1:1, and concentration is 0.4mol/L, finally adds 1ml acetylacetone,2,4-pentanedione.The presoma prepared is dripped to p
+in silicon chip substrate, low speed 300rpm, high speed 3000rpm, start spin coater and carry out spin coating, form wet film, wet film is carried out low temperature drying process at 120 DEG C, and the time is 10min, then heat-treat at 350 DEG C, time is 15min, finally film is carried out rapid thermal treatment in air atmosphere, and temperature is 650 DEG C, time is 60min, naturally obtains the ZnMn of polycrystalline state after cooling
2o
4electroluminescent resistance changing film, film thickness is 400nm.
(3) in the ZnMn of step (2)
2o
4and electrode of metal prepared by the resistive dielectric film of doping.Prepare electrode of metal with evaporation process, described metal electrode material comprises Al, Ag, Au, Cu, Ni, Pt and Ti, and its thickness is 50nm to 200nm.In one embodiment, with metal A g as top electrode, diameter is that the stainless steel mask plate of 500 μm blocks, and the background vacuum of cavity is 4.0 × 10
-4pa, film thickness is 88nm.
Fig. 2 is the ZnMn of one embodiment of the present of invention
2o
4the X-ray diffractogram of resistive dielectric film, this diffraction pattern shows ZnMn
2o
4resistive dielectric film is the polycrystal film of crystalline state.
Fig. 3 is the ZnMn of one embodiment of the present of invention
2o
4the surface topography map of the scanning electron microscopy (SEM) of resistive dielectric film.As seen from the figure, film is polycrystalline structure, and crystallite dimension is between 5 ~ 20nm, and grain shape is spherical structure.
Fig. 4 is the ZnMn of one embodiment of the present of invention
2o
4the cross-section morphology figure of the scanning electron microscopy (SEM) of resistive dielectric film.As seen from the figure, the thickness of film is about 400nm, and surfacing is combined closely with silicon chip.
Fig. 5 is the ZnMn of one embodiment of the present of invention
2o
4the bipolarity resistive behavior of resistance-variable storing device, the initial state of device is high-impedance state, and in the process of the positive and negative particles of applying bias, device shows the resistance transformation characteristic of bipolarity (Bipolar).Voltage is when forward is increased to Vset, and device is converted to low resistance state from high-impedance state, and now device current obviously increases, and keeps always, until when reaching Vreset, the electric current of device sharply declines, and the transformation from low resistance state to high-impedance state occurs.As can be seen from Figure 4, HRS and LRS is more stable, and the ratio of high low resistance is greater than 102, for the write and reading storing data leaves very large operating space.
Fig. 6 is the ZnMn of one embodiment of the present of invention
2o
4the unipolarity resistive behavior of resistance-variable storing device, the initial state of device is high-impedance state, and in the process of applying bias scanning, device shows the resistance transformation characteristic of unipolarity (Unipolar).Voltage is when forward is increased to Vset, and device is converted to low resistance state from high-impedance state, and now device current obviously increases, and keeps always.When carrying out second time scanning, when reaching Vreset, the electric current of device sharply declines, and the transformation from low resistance state to high-impedance state occurs.
Although the present invention is with preferred embodiments openly as above, and non-limiting the present invention, any those skilled in the art without departing from the spirit and scope of the present invention, can do suitable improvement, and therefore, the scope that scope defines with claim is as the criterion.
Claims (1)
1. a nonpolar resistance-variable storing device, comprise the conductive substrates of splicing from bottom to up and to hold concurrently bottom electrode, resistance-change memory medium and electrode of metal three-decker on a storage medium, is characterized in that: described resistance-change memory medium is ZnMn
2o
4and alloy, doped chemical comprises Y, Sc, Mg, Si, Sn and In, and its form is film, and thickness is 20nm to 1200nm; Resistance-variable storing device possesses bipolarity and unipolar resistive behavior simultaneously, i.e. nonpolar storage behavior, and described conductive substrate material is p
+type silicon chip substrate, p
+type silicon chip is simultaneously also as the bottom electrode of memory;
The preparation method of this nonpolar resistance-variable storing device is: (1) uses RCA standard cleaning technique cleaning silicon chip substrate, and carries out drying and processing;
(2) chemical solution deposition technique is adopted to prepare ZnMn on the bottom electrode
2o
4and alloy resistive dielectric film; Film quick thermal treatment process, coating number of times be 1 to 14 times, the annealing temperature of film higher than 620 DEG C, annealing time 1 ~ 4h;
(3) at ZnMn
2o
4and on alloy resistive dielectric film, adopt evaporation process to prepare metal electrode, base vacuum is better than 4.0 × 10
-4pa; Use metal mask version, the diameter of circular hole is 500 μm to 30 μm.
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| CN110752289A (en) * | 2018-07-23 | 2020-02-04 | 天津理工大学 | Based on MnZn codoped BiFeO3Resistive random access memory of thin film and preparation method thereof |
| CN110752290A (en) * | 2018-07-23 | 2020-02-04 | 天津理工大学 | Based on BiFeO3Resistive random access memory and preparation method thereof |
| CN113120960B (en) * | 2021-03-05 | 2023-02-17 | 广东轻工职业技术学院 | Nitrogen-doped and oxygen vacancy-modified zinc manganate nanotube array material and preparation method and application thereof |
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| CN101894908A (en) * | 2010-06-01 | 2010-11-24 | 中山大学 | Resistive random access memory and preparation method thereof |
| 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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| CN101894908A (en) * | 2010-06-01 | 2010-11-24 | 中山大学 | Resistive random access memory and preparation method thereof |
| 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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