CN102157684B - Resistive random access memory (RRAM) using carbon nano tube (CNT) as solid state electrolyte - Google Patents
Resistive random access memory (RRAM) using carbon nano tube (CNT) as solid state electrolyte Download PDFInfo
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- CN102157684B CN102157684B CN201010593266.3A CN201010593266A CN102157684B CN 102157684 B CN102157684 B CN 102157684B CN 201010593266 A CN201010593266 A CN 201010593266A CN 102157684 B CN102157684 B CN 102157684B
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Abstract
The invention provides a resistive random access memory (RRAM) using a carbon nano tube (CNT) as solid state electrolyte, comprising a lower electrode, an upper electrode, an insulating medium and a CNT, wherein the insulating medium is arranged between the lower electrode and the upper electrode and forms a restraint structure; the CNT grows in the restraint structure; the CNT is a single-walled CNT or multi-walled CNT; and an insulating film is made of silicon dioxide. The RRAM has the advantage that common sulfidic material is replaced by the CNT which is taken as the solid state electrolyte, so that metal ions and metal are restrained in the CNT, and connection and disconnection of an electricity-conducting channel take place in the intrinsic CNT, thereby exhibiting the diffusion of the metal and the metal ions, and effectively improving the controllability of the RRAM and the long holding capacity of the RRAM for data at high temperature. Meanwhile, because the sulfidic material with pollution is replaced by the CNT, thus the RRAM is compatible with a traditional silicon plane complementary metal oxide semiconductor (CMOS) technology, which is beneficial to popularization and application.
Description
Technical field
The present invention relates to electronic manufacture and technical field of memory, particularly relate to using a kind of carbon nano-tube that utilizes as the resistance-variable storing device of solid-state electrolytic solution.
Background technology
Along with the needs that multimedia application, mobile communication etc. store Large Copacity, low-power consumption, non-volatility memorizer, particularly flash memory, the market share of shared semiconductor device becomes increasing, also more and more becomes a kind of considerable memory.The main feature of non-volatility memorizer is the information also can preserving storage when not powering up for a long time, and the feature of its existing read-only memory, has again very high access speed.
Currently marketed non-volatility memorizer take flash memory as main flow, but flush memory device exists that operating voltage is excessive, service speed slow, endurance is good not and due to the shortcomings such as excessively thin tunnel oxide will cause memory time not long in period institute's digestion process.Desirable non-volatility memorizer should possess that operating voltage is low, structure is simple, non-destructive reads, service speed is fast, memory time is long, device area is little, the durable condition such as good.A lot of new material and device are studied at present, attempt to reach above-mentioned target, wherein there is the novel memory devices device of considerable part all to adopt the change of resistance value to be used as the mode remembered, comprise the resistance-variable storing device of resistance-variable storing device and employing solid-state electrolytic solution material.
General solid electrolytic solution resistance change memory is mainly based on the formation of metal guide electric bridge under electric field action in solid-state electrolytic solution and disappearance.Its operation principle is: electrode of metal A is oxidized into metal ion A under electric field action
+, metal ion A
+transmit in solid-state electrolytic solution B, finally reach inertia bottom electrode C, at bottom electrode C place metal ion A
+be reduced into as metal A, along with metal is constantly in bottom electrode C place deposition, finally reach top electrode A, form metal guide electric bridge, device resistance is in low resistive state; Under reversed electric field effect, this metal guide electric bridge disconnects, and device returns to great-great-grandfather's state.These two kinds of resistance states can be changed mutually in the effect of extra electric field.
Such as, but current proposed solid-state electrolytic solution material adopts sulfidic material, CuS, AG-Ge-Se, Ge-Se, ZnCdS, AgI and Cu-Ge-S etc. usually.The first, as everyone knows, these sulphur system material pollutions to technique make the CMOS technology of itself and standard, and tool is not compatible.The second, due to poor heat stability, have impact on the stability of device resistance states in high temperature environments, therefore reduce the hold facility of memory to data.3rd, because the metal guide electric bridge formed is in size, quantitatively have great randomness, this causes the fluctuation of device on voltage and current thus have impact on the controllability of memory.
Summary of the invention
The object of the invention is to for above-mentioned existing problems, there is provided a kind of carbon nano-tube that utilizes as the resistance-variable storing device of solid-state electrolytic solution, this resistance-variable storing device utilizes carbon nano-tube as solid-state electrolytic solution, first existing sulfide solid-state electrolytic solution resistance change memory and the incompatible problem of CMOS technology can be overcome, secondly the stability of existing solid-state electrolytic solution resistance change memory resistance states is in high temperature environments improved, improve the hold facility to data, again can control the size and number of metal guide electric bridge, improve the controllability of device.
Technical scheme of the present invention:
A kind of carbon nano-tube that utilizes is as the resistance-variable storing device of solid-state electrolytic solution, comprise bottom electrode, top electrode, dielectric and carbon nano-tube, dielectric is between bottom electrode and top electrode and form limiting structure (confined structure), carbon nano-tube in limiting structure; The material of described bottom electrode and top electrode is the metal of stable in properties under electric field action, conductive compound or be easy to be oxidized to the metal of metal ion under electric field action, but top electrode and bottom electrode can not character of use is identical simultaneously described electrode materials; Described carbon nano-tube is Single Walled Carbon Nanotube or multi-walled carbon nano-tubes; The material of described insulation film is silicon dioxide.
The thickness of described bottom electrode is 5nm ~ 200nm.
The thickness of described top electrode is 5nm ~ 200nm.
The metal of described stable in properties under electric field action is platinum, iridium or ruthenium.
Described conductive compound is titanium oxide, ruthenium-oxide or tin indium oxide.
The described metal being easy to be oxidized to metal ion under electric field action is copper, silver, iron, zinc or nickel.
The aperture width that described dielectric forms limiting structure is 10nm ~ 10um.
Described carbon nano-tube is P type Single Walled Carbon Nanotube, N-type Single Walled Carbon Nanotube, single wall insulating carbon nanotubes, P type multi-walled carbon nano-tubes, N-type multi-walled carbon nano-tubes or many walls insulating carbon nanotubes, and the diameter > 6nm of carbon nano-tube, length are 5nm ~ 5um; The length of the carbon nano-tube after CMP (Chemical Mechanical Polishing) process (CMP) polishing is utilized to be 5nm ~ 5um.
The thickness of described insulating film material silicon dioxide is 10nm ~ 10um.
Working mechanism of the present invention:
In common solid-state electrolytic solution resistance change memory, electrode of metal is oxidized into metal ion A under electric field action
+, A
+ion transmits in solid-state electrolytic solution B, finally reaches inertia bottom electrode C, at C place A
+ion is reduced into as metal A, and along with metal A is constantly in C place deposition, finally reach top electrode A, form metal guide electric bridge, device resistance is in low resistive state.The metal guide electric bridge that this transformation is formed, in size, quantitatively has great randomness.This causes the fluctuation of device on voltage and current thus have impact on the controllability of memory.On the other hand, in common solid-state electrolytic solution resistance change memory, in order to improve the mobility of metal ion, usually adopt the sulfidic material that structure comparison is loose as solid-state electrolytic solution material.But the thermal stability of sulfidic material is poor, under the high temperature conditions, metal ion and metal obtain heat energy more easily movement in the poor sulfidic material of thermal stability.When being in low resistance state, the metal acquisition heat energy that composition is communicated with top electrode and bottom electrode conducting bridge tends to spread towards periphery.This causes the disconnection of the metal guide electric bridge being communicated with top electrode and bottom electrode, and consequently the resistance of device changes high-impedance state into from low resistance state, lost legacy data.Otherwise in like manner.Thus affect the hold facility of memory to data.
Beneficial effect of the present invention:
Based on above consideration, the present invention, by using carbon nano-tube as solid-state electrolytic solution material in solid electrolytic solution resistance change memory, improves the stability that solid-state electrolytic solution resistance change stores, the hold facility to data under controllability and hot conditions effectively.Carbon nano-tube has typical cannulated architectural feature, therefore the carbon nano-tube of hollow can as the passage being communicated with top electrode and bottom electrode, metal ion enters this carbon nano-tube and within it transmits, the metal ion arriving bottom electrode is constantly reduced into metal, finally reach top electrode, form nano metal conducting bridge in the inside of carbon nano-tube like this.Device resistance is in low resistive state: under reversed electric field effect, and this nano metal conducting bridge disconnects, and device returns to great-great-grandfather's state, and the conduction of conductive channel and disconnection occur in intrinsic carbon nano-tube inside.Therefore by controlling the quantity of carbon nano-tube and diameter, can the fluctuation of effective control device voltage and current, the controllability of raising memory.On the other hand, because metal ion or metal are bound in carbon nano-tube.Even if under the high temperature conditions, also metal ion or the peripherad diffusion of metal can effectively be suppressed, be conducive to the maintenance of device to original resistance state, improve memory in high temperature environments to the permanent hold facility of data, finally produce the novel ultra-large non-volatility memorizer of dependable performance.
Accompanying drawing explanation
Accompanying drawing is this solid-state electrolytic solution resistance change memory structural representation, wherein (a) low resistance state (b) high-impedance state.
In figure: 1. bottom electrode .2. dielectric 3. carbon nano-tube 4. top electrode
Embodiment
Embodiment:
This resistance-variable storing device, comprise bottom electrode 1, top electrode 4, carbon nano-tube 3 and dielectric 2, the material selection 50nm platinum of bottom electrode, the material selection 50nm copper metal of top electrode, silicon dioxide insulator dielectric thickness is 500nm, silicon dioxide insulator medium is formed confined structure, aperture width is 150 nanometers, carbon nano-tube in confined structure, carbon nano-tube selects diameter and length to be respectively many walls insulating carbon nanotubes of 100nm and 3um, and the length being controlled carbon nano-tube by CMP is 200nm.
The preparation process of this resistance-variable storing device is as follows:
1) utilize PVD (physical vapor deposition) or CVD (chemical vapor deposition) process deposits bottom electrode, the thickness of bottom electrode is 50nm platinum;
2) utilize PVD (physical vapor deposition) or CVD (chemical vapor deposition) process deposits dielectric film medium silicon dioxide, its thickness is 500nm;
3) form by conventional photoetching and etching technics the limiting structure (confinedstructure) exposing bottom electrode, the aperture width of described limiting structure is 150nm;
4) conventional technique is utilized to plate catalyst film on the bottom electrode;
5) conventional technique carbon nano-tube is utilized; Diameter and the length of described carbon nano-tube are respectively 100nm and 3um;
6) utilize PVD (physical vapor deposition) or CVD (chemical vapor deposition) process deposits dielectric film medium to fill limiting structure;
7) utilize conventional CMP (Chemical Mechanical Polishing) process to carry out polishing to control the length of carbon nano-tube, the length of the carbon nano-tube after polishing is 200nm;
8) utilize PVD (physical vapor deposition) or CVD (chemical vapor deposition) process deposits top electrode, its thickness is 50nm copper metal.
Resistance-variable storing device of the present invention takes full advantage of the stable resistive characteristic of above-mentioned resistive material, reliability is high.Except above-described embodiment resistance-variable storing device is, utilize the material of above-mentioned resistive characteristic, other device architectures can also be constructed
The foregoing is only the preferred embodiment of invention, not in order to limit the present invention, within the spirit and principles in the present invention all, any amendment made, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (9)
1. one kind utilizes carbon nano-tube as the resistance-variable storing device of solid-state electrolytic solution, it is characterized in that: comprise bottom electrode, top electrode, dielectric and carbon nano-tube, dielectric is between bottom electrode and top electrode and form limiting structure (confined structure), carbon nano-tube in limiting structure; The material of described bottom electrode and top electrode is the metal of stable in properties under electric field action, conductive compound or be easy to be oxidized to the metal of metal ion under electric field action, but top electrode and bottom electrode can not character of use is identical simultaneously described electrode materials; Described carbon nano-tube is Single Walled Carbon Nanotube or multi-walled carbon nano-tubes; The material of described insulation film is silicon dioxide.
2. utilize carbon nano-tube as the resistance-variable storing device of solid-state electrolytic solution according to claim 1, it is characterized in that: the thickness of described bottom electrode is 5nm ~ 200nm.
3. utilize carbon nano-tube as the resistance-variable storing device of solid-state electrolytic solution according to claim 1, it is characterized in that: the thickness of described top electrode is 5nm ~ 200nm.
4. utilize carbon nano-tube as the resistance-variable storing device of solid-state electrolytic solution according to claim 1, it is characterized in that: the metal of described stable in properties under electric field action is platinum, iridium or ruthenium.
5. utilize carbon nano-tube as the resistance-variable storing device of solid-state electrolytic solution according to claim 1, it is characterized in that: described conductive compound is titanium oxide, ruthenium-oxide or tin indium oxide.
6. utilize carbon nano-tube as the resistance-variable storing device of solid-state electrolytic solution according to claim 1, it is characterized in that: the described metal being easy to be oxidized to metal ion under electric field action is copper, silver, iron, zinc or nickel.
7. utilize carbon nano-tube as the resistance-variable storing device of solid-state electrolytic solution according to claim 1, it is characterized in that: the aperture width that described dielectric forms limiting structure is 10nm ~ 10um.
8. utilize carbon nano-tube as the resistance-variable storing device of solid-state electrolytic solution according to claim 1, it is characterized in that: described carbon nano-tube is P type Single Walled Carbon Nanotube, N-type Single Walled Carbon Nanotube, single wall insulating carbon nanotubes, P type multi-walled carbon nano-tubes, N-type multi-walled carbon nano-tubes or many walls insulating carbon nanotubes, and the diameter > 6nm of carbon nano-tube, length are 5nm ~ 5um; The length of the carbon nano-tube after CMP (Chemical Mechanical Polishing) process (CMP) polishing is utilized to be 5nm ~ 5um.
9. utilize carbon nano-tube as the resistance-variable storing device of solid-state electrolytic solution according to claim 1, it is characterized in that: the thickness of described insulating film material silicon dioxide is 10nm ~ 10um.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108565337A (en) * | 2018-04-03 | 2018-09-21 | 集美大学 | The resistance-variable storing device preparation method of positioning plasma treatment is carried out with nanometer shielding layer |
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| CN102881651B (en) * | 2012-10-25 | 2015-10-28 | 天津理工大学 | A kind of method improving electrical interconnection characteristic of carbon nano tube |
| CN107634139B (en) * | 2017-08-30 | 2020-01-14 | 西安理工大学 | Preparation method of large-voltage-resistant silicon oxide resistance change film |
| CN107663633B (en) * | 2017-08-30 | 2019-09-27 | 西安理工大学 | A kind of preparation method of the silica resistance changing film of doped carbon nanometer pipe |
| CN110085589B (en) * | 2018-01-26 | 2021-03-26 | 中芯国际集成电路制造（天津）有限公司 | Carbon nanotube module, semiconductor device and manufacturing method |
| CN110400871A (en) * | 2018-04-24 | 2019-11-01 | 中芯国际集成电路制造（天津）有限公司 | The manufacturing method of carbon nanotube storage organization and the manufacturing method of semiconductor devices |
| CN110400872B (en) * | 2018-04-24 | 2024-02-23 | 中芯国际集成电路制造（天津）有限公司 | Method for manufacturing carbon nano tube storage structure and method for manufacturing semiconductor device |
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| US7977667B2 (en) * | 2008-04-11 | 2011-07-12 | Sandisk 3D Llc | Memory cell that includes a carbon nano-tube reversible resistance-switching element and methods of forming the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108565337A (en) * | 2018-04-03 | 2018-09-21 | 集美大学 | The resistance-variable storing device preparation method of positioning plasma treatment is carried out with nanometer shielding layer |
| CN108565337B (en) * | 2018-04-03 | 2021-05-18 | 集美大学 | Method for preparing resistive random access memory by using nano shielding layer to perform positioning plasma processing |
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