CN104409629A - Resistance random access memory based on graphene oxides - Google Patents
Resistance random access memory based on graphene oxides Download PDFInfo
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- CN104409629A CN104409629A CN201410702503.3A CN201410702503A CN104409629A CN 104409629 A CN104409629 A CN 104409629A CN 201410702503 A CN201410702503 A CN 201410702503A CN 104409629 A CN104409629 A CN 104409629A
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Abstract
The invention provides a resistance random access memory based on graphene oxides. An active area of a transistor of the resistance random access memory is formed by doped graphene materials, a storage unit comprises an upper electrode, a lower electrode and a resistance layer between the upper and lower electrodes, and the resistance layer is made of the graphene oxides. Due to the fact that the resistance layer of the resistance random access memory is made of the graphene oxides, rate of the memory is increased while power consumption is reduced owing to high migration rate of graphene.
Description
technical field
The invention belongs to field of semiconductor devices, be specifically related to a kind of resistive random asccess memory based on graphene oxide.
background technology
This year, due to the difficulty that conventional flash memory (flash) is scaled, novel nonvolatile storage is called current study hotspot, wherein resistive random asccess memory (RRAM) is owing to having the advantages such as storage density is high, low in energy consumption, read or write speed is fast, data retention over time is long, becomes one of the most promising type of memory.
Resistive random asccess memory utilizes the resistance of thin-film material can under the signal of telecommunication effects such as voltage, at high-impedance state (High Resistance State, and to realize reversible transformation between low resistance state (Low Resistance State, LRS) be basic functional principle HRS).Traditional resistive material layer is oxide material, comprises perovskite oxide as SrZrO
3, SrTiO
3deng, transition metal oxide as NiO, TiO
2, ZrO etc., solid electrolyte material and organic material etc.
What draw along with Nobel Prize in physics in 2010 makes known, and Graphene (Graphene) has been called the focus that everybody discusses.Graphene is the strongest by the peace moral of Univ Manchester UK as far back as 2004. and extra large nurse and Constantine. Nuo Woxiaoluofu utilize normal tape successfully to peel off from graphite and obtain.Graphene is the thinnest known material at present, and it has excellent conductivity.And the oxide of Graphene (Graphene Oxide, GO) is functionalized Graphene, namely with the single-layer graphene of oxygen functional moieties sp3 bonding.GO is very easily water-soluble, makes it easy to spin coating molding, and the bonding of oxygen functional group can increase the thickness of Graphene, makes the thickness of Graphene increase to about 1nm from 0.34nm.Research shows, GO is different with Graphene, and be a kind of medium relatively with insulation characterisitic, the GO of thermal reduction has then acted on the advantage of the high carrier mobility of Graphene and excessive heat conductance.Because the resistance of GO has controllability, it is made to become a kind of very promising RRAM change resistance layer material.
summary of the invention
The object of the present invention is to provide a kind of can be compatible and can the resistive random asccess memory based on GO of large-scale production with CMOS technology.
The invention provides a kind of resistive random asccess memory based on GO, comprising: the substrate with insulating surface; Be formed in substrate surface grid; The gate oxide of cover gate and at least part of substrate; Formed and the source electrode on gate oxide and drain electrode; Active layer, it covers source electrode and drain electrode and the gate oxide between source electrode and drain electrode; Interlayer insulating film, is coated with active layer and at least part of substrate; Be formed at the conductive plunger in interlayer insulating film, it is connected to drain electrode; Be formed at the bottom electrode on conductive plunger; Be formed at the graphene oxide layer on bottom electrode; And the upper electrode layer be formed on graphene oxide layer.
In this resistance-variable storing device, substrate is the one in Si, Ge, insulating material, SOI; The material of active layer is Graphene; The material of bottom electrode and top electrode is respectively at least one in metal, alloy, metal nitride or transparent oxide material, wherein the material of bottom electrode is preferably the one in Cu, W, Ni, Zr, Ta, Ti, Zn, Al, TaN, TiN, ITO or AZO, and the material of top electrode is preferably Pd, Ta, Ti, TaN, TiN, Cu, Al, Pt, W, Ni, Ru, Ru-Ta alloy, Pt-Ti alloy, at least one of Ni-Ta alloy or at least both composite bed; Conductive plunger is Cu or W.
The present invention also provides a kind of manufacture method of the resistive random asccess memory based on GO, and the method specifically comprises: provide dielectric substrate; Substrate forms gate electrode; Form the gate oxide of covering grid electrode; Gate oxide is formed source electrode and the drain electrode layer of patterning; Form the graphene layer of patterning covering substrate, it covers source electrode and drain electrode and the gate oxide between source electrode and drain electrode; Form the interlayer insulating film covering graphene layer and substrate; Interlayer insulating film forms through hole, and it exposes the Graphene in drain electrode; Adopt filled with conductive material through hole, form conductive plunger; Interlayer insulating film forms the first metal layer; Patterned first metal layer, forms the bottom electrode directly contacted with conductive plunger; Spin coating one deck graphene oxide layer; Patterned Graphene oxide skin(coating), forms the graphene oxide layer covering bottom electrode, as resistive material layer; Form the second metal level; Patterning second metal level forms top electrode.
Wherein the step of spin coating formation graphene oxide layer comprises: weigh dry graphene oxide material, add deionized water, magnetic agitation is extremely without particle; Ultrasonic 1 hour of 150W, keeps temperature lower than 50 DEG C in process; By the graphene oxide aqueous solution after ultrasonic as in centrifuge tube, 14000rpm centrifugal treating 30 minutes; Get the graphene oxide aqueous solution after centrifugal treating, it is the film of 2nm that spin coating forms thickness.
Wherein graphene oxide material manufacturing method comprises: graphite is slowly added the dense H stirred
2sO
4, K
2s
2o
8and P
2o
5mixed solution in, 75 DEG C of magnetic agitation 5 hours; Be cooled to room temperature, with deionized water dilution, place 24 hours; Filter the solution after placing, dry, form the graphite powder of pre-oxidation; The graphite powder of above-mentioned pre-oxidation is added the dense H of 0 DEG C
2sO
4in, stir, under condition of ice bath, slowly add KMnO subsequently
4, and magnetic agitation; KMnO will be added
4solution stir 2 hours at 35-45 DEG C of lower magnetic force; Add deionized water dilution under ice bath, maintain the temperature at less than 50 DEG C; 35-45 DEG C of lower magnetic force stirs 2 hours; Under normal temperature, the solution again stirring 2 hours is diluted, slowly add H subsequently
2o
2, leave standstill more than 20 hours; The above-mentioned solution of suction filtration process, suction funnel slowly adds the mixed liquor of deionized water and concentrated hydrochloric acid, and wherein the mixed liquor of deionized water and concentrated hydrochloric acid is volume ratio 9:1; Add deionization who, make filtrate occur swelling; Get swelling solution in centrifuge tube, add appropriate amount of deionized water, 12000rpm centrifugal treating 2 hours, it is neutral for repeating to founding new rear supernatant; Viscous fluid bottom centrifuge tube is poured in container, dry at 50 DEG C, form graphene oxide powder.
Accompanying drawing explanation
Fig. 1 shows SRAM structure of the present invention;
Fig. 2 is the flow chart of manufacture method of the present invention.
embodiment
Hereafter will specifically describe the preferred embodiments of the present invention by reference to the accompanying drawings, and it will be appreciated by those skilled in the art that this description and should not limitation of the present invention be considered to.
As shown in Figure 1, on the substrate 1 with insulating surface, be formed with the grid structure 2 of patterning.Having the substrate of insulating surface, can be formed with insulating barrier, as silica or silicon nitride, Semiconductor substrate, as Si, Ge etc., can be also dielectric substrate, as glass, or other be usually used in the backing material of flexible base, board, as resin etc.When adopting flexible base, board, be all membrane structure by structure thereon, it can form flexible memory.The material of grid structure 2 can be the common material in this area, as metal, and alloy, metal oxide, doped semiconductor etc.The gate oxide 6 of cover gate and at least part of substrate, gate oxide 6 material can be hafnium.Insulating surface is formed with source electrode 3 and the drain electrode 4 of patterning, and source electrode 3 and drain electrode 4 are metal material or alloy material.Active layer 5, it covers source electrode and drain electrode and the gate oxide between source electrode and drain electrode, and active layer 5 be the grapheme material of doping, to improve the carrier mobility of transistor, raising read or write speed.Be coated with the interlayer insulating film 7 of active layer 5 and at least part of substrate 1, it can be organic insulating material, or inorganic insulating material.Be formed at the conductive plunger 8 in interlayer insulating film 7, it is connected to drain electrode 4, and conductive plunger 8 can be metal or organic conductive material.Be formed at the memory cell on conductive plunger 8, it is for comprising bottom electrode 9, change resistance layer 11 and top electrode 10, and wherein change resistance layer 11 is graphene oxide material.The material of bottom electrode 9 and top electrode 10 is respectively at least one in metal, alloy, metal nitride or transparent oxide material, wherein the material of bottom electrode 9 is preferably the one in Cu, W, Ni, Zr, Ta, Ti, Zn, Al, TaN, TiN, ITO or AZO, and the material of top electrode 10 is preferably Pd, Ta, Ti, TaN, TiN, Cu, Al, Pt, W, Ni, Ru, Ru-Ta alloy, Pt-Ti alloy, at least one of Ni-Ta alloy or at least both composite bed.
Structure shown in Fig. 1 is the structure of a memory cell, can form memory cell array on substrate, for adjacent memory cell, in order to improve integrated level, can adopt common-source technology.
Fig. 2 shows the formation method of the memory cell shown in Fig. 1.
Step S1: provide the substrate 1 with insulating surface can be formed with insulating barrier, as silica or silicon nitride, Semiconductor substrate, as Si, Ge etc., can be also dielectric substrate, as glass, or other be usually used in the backing material of flexible base, board, as resin etc.
Step S2: form gate electrode 2 on substrate.The material of gate electrode can be metal, alloy, metal oxide or doped semiconductor materials.Gate electrode 2 can adopt the methods such as sputtering, CVD or PECVD to be formed, and is formed the figure needed by chemical wet etching.
Step S3: form gate oxide 6.The material of gate oxide 6 can be silica, silicon nitride, silicon oxynitride or other high-k dielectric material materials.
Step S4: the source electrode 3 and the drain electrode 4 that form patterning.Gate oxide 6 forms metal material layer, forms source electrode 3 and drain electrode 4 figures by chemical wet etching.
Step S5: be formed with active layer 5 on substrate.The material of active layer 5 can be the Graphene of doping.This grapheme material can adopt to be formed and cover the graphene layer of substrate surface, then photoetching forms the mode needing pattern, or the normal method such as the method for nano impression is formed.
Step S6: the interlayer insulating film 7 of formation covering source electrode 3, drain 4 and active layer 5 on substrate, can adopt the method for deposition or the method for spin coating to be formed.By photoetching, form through hole, it exposes the active layer 5 in drain electrode 4.By depositing or the mode such as plating, filling vias, forms conductive plunger 8.
Step S7: form memory element.Memory element comprises top electrode 9, change resistance layer 11 and bottom electrode 10.Wherein, bottom electrode 9 and top electrode 10 are by deposit or sputtering mode is formed.The material of change resistance layer 11 is the oxide of Graphene, and it is formed by spin coating, and concrete grammar is: weigh dry graphene oxide material, add deionized water, and magnetic agitation is extremely without particle; Ultrasonic 1 hour of 150W, keeps temperature lower than 50 DEG C in process; By the graphene oxide aqueous solution after ultrasonic as in centrifuge tube, 14000rpm centrifugal treating 30 minutes; Get the graphene oxide aqueous solution after centrifugal treating, it is the film of 2nm that spin coating forms thickness.
Wherein, dry graphene oxide material is formed by the following method:
Graphite is slowly added the dense H stirred
2sO
4, K
2s
2o
8and P
2o
5mixed solution in, 75 DEG C of magnetic agitation 5 hours; Be cooled to room temperature, with deionized water dilution, place 24 hours;
Filter the solution after placing, dry, form the graphite powder of pre-oxidation;
The graphite powder of above-mentioned pre-oxidation is added the dense H of 0 DEG C
2sO
4in, stir, under condition of ice bath, slowly add KMnO subsequently
4, and magnetic agitation;
KMnO will be added
4solution stir 2 hours at 35-45 DEG C of lower magnetic force; Add deionized water dilution under ice bath, maintain the temperature at less than 50 DEG C; 35-45 DEG C of lower magnetic force stirs 2 hours;
Under normal temperature, the solution again stirring 2 hours is diluted, slowly add H subsequently
2o
2, leave standstill more than 20 hours; The above-mentioned solution of suction filtration process, suction funnel slowly adds the mixed liquor of deionized water and concentrated hydrochloric acid, and wherein the mixed liquor of deionized water and concentrated hydrochloric acid is volume ratio 9:1;
Add deionization who, make filtrate occur swelling;
Get swelling solution in centrifuge tube, add appropriate amount of deionized water, 12000rpm centrifugal treating 2 hours, it is neutral for repeating to founding new rear supernatant;
Viscous fluid bottom centrifuge tube is poured in container, dry at 50 DEG C, form graphene oxide powder.
More than show and describe general principle of the present invention and principal character and advantage of the present invention.The technical staff of the industry should understand; the present invention is not restricted to the described embodiments; what describe in above-described embodiment and specification just illustrates principle of the present invention; without departing from the spirit and scope of the present invention; the present invention also has various changes and modifications, and these changes and improvements all fall in the claimed scope of the invention.Application claims protection range is defined by appending claims and equivalent thereof.
Claims (10)
1. a resistive random asccess memory, comprises
There is the substrate of insulating surface;
Be formed in substrate surface grid;
The gate oxide of cover gate and at least part of substrate;
Be formed at the source electrode on gate oxide and drain electrode;
Active layer, it covers source electrode and drain electrode and the gate oxide between source electrode and drain electrode;
Interlayer insulating film, is coated with active layer and at least part of substrate;
Be formed at the conductive plunger in interlayer insulating film, it is connected to drain electrode;
Be formed at the bottom electrode on conductive plunger;
Be formed at the graphene oxide layer on bottom electrode; And
Be formed in the upper electrode layer on graphene oxide layer.
2. resistive random asccess memory, wherein substrate insulating material as claimed in claim 1.
3. resistive random asccess memory as claimed in claim 1, wherein, the material of active layer is Graphene.
4. resistive random asccess memory as claimed in claim 1, wherein the material of bottom electrode and top electrode is respectively at least one in metal, alloy, metal nitride or transparent oxide material.
5. resistive random asccess memory as claimed in claim 4, wherein the material of bottom electrode can be the one in Cu, W, Ni, Zr, Ta, Ti, Zn, Al, TaN, TiN, ITO or AZO, and the material of top electrode is Pd, Ta, Ti, TaN, TiN, Cu, Al, Pt, W, Ni, Ru, Ru-Ta alloy, Pt-Ti alloy, at least one of Ni-Ta alloy or at least both composite bed.
6. resistive random asccess memory as claimed in claim 1, wherein conductive plunger is Cu or W.
7. a manufacture method for resistive random asccess memory, comprising:
The substrate with insulating surface is provided;
Substrate forms gate electrode;
Form the gate oxide of covering grid electrode;
Gate oxide is formed source electrode and the drain electrode of patterning;
Form the graphene layer of patterning covering substrate, it covers source electrode and drain electrode and the gate oxide between source electrode and drain electrode;
Form the interlayer insulating film covering graphene layer and substrate;
Interlayer insulating film forms through hole, and it exposes the Graphene in drain electrode;
Adopt filled with conductive material through hole, form conductive plunger;
Interlayer insulating film forms the first metal layer;
Patterned first metal layer, forms the bottom electrode directly contacted with conductive plunger;
Spin coating one deck graphene oxide layer;
Patterned Graphene oxide skin(coating), forms the graphene oxide layer covering bottom electrode, as resistive material layer;
Form the second metal level;
Patterning second metal level forms top electrode.
8. manufacture method as claimed in claim 7, wherein the step of spin coating formation graphene oxide layer comprises:
Weigh dry graphene oxide material, add deionized water, magnetic agitation is extremely without particle;
Ultrasonic 1 hour of 150W, keeps temperature lower than 50 DEG C in process;
By the graphene oxide aqueous solution after ultrasonic as in centrifuge tube, 14000rpm centrifugal treating 30 minutes;
Get the graphene oxide aqueous solution after centrifugal treating, it is the film of 2nm that spin coating forms thickness.
9. manufacture method as claimed in claim 8, wherein graphene oxide material manufacturing method comprises:
Graphite is slowly added the dense H stirred
2sO
4, K
2s
2o
8and P
2o
5mixed solution in, 75 DEG C of magnetic agitation 5 hours;
Be cooled to room temperature, with deionized water dilution, place 24 hours;
Filter the solution after placing, dry, form the graphite powder of pre-oxidation;
The graphite powder of above-mentioned pre-oxidation is added the dense H of 0 DEG C
2sO
4in, stir, under condition of ice bath, slowly add KMnO subsequently
4, and magnetic agitation;
KMnO will be added
4solution stir 2 hours at 35-45 DEG C of lower magnetic force;
Add deionized water dilution under ice bath, maintain the temperature at less than 50 DEG C;
35-45 DEG C of lower magnetic force stirs 2 hours;
Under normal temperature, the solution again stirring 2 hours is diluted, slowly add H subsequently
2o
2, leave standstill more than 20 hours;
The above-mentioned solution of suction filtration process, suction funnel slowly adds the mixed liquor of deionized water and concentrated hydrochloric acid;
Add deionization who, make filtrate occur swelling;
Get swelling solution in centrifuge tube, add appropriate amount of deionized water, 12000rpm centrifugal treating 2 hours, it is neutral for repeating to founding new rear supernatant;
Viscous fluid bottom centrifuge tube is poured in container, dry at 50 DEG C, form graphene oxide powder.
10. manufacture method as claimed in claim 9, wherein the mixed liquor of deionized water and concentrated hydrochloric acid is volume ratio 9:1.
Priority Applications (1)
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|---|---|---|---|
| CN201410702503.3A CN104409629A (en) | 2014-11-29 | 2014-11-29 | Resistance random access memory based on graphene oxides |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107681048A (en) * | 2017-09-01 | 2018-02-09 | 河北大学 | A kind of memristor and preparation method and application with neurobionics function |
| CN109860390A (en) * | 2019-02-28 | 2019-06-07 | 西交利物浦大学 | RRAM device and preparation method thereof based on graphene oxide |
| CN110911409A (en) * | 2018-09-18 | 2020-03-24 | 联华电子股份有限公司 | Non-volatile memory and forming method thereof |
-
2014
- 2014-11-29 CN CN201410702503.3A patent/CN104409629A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107681048A (en) * | 2017-09-01 | 2018-02-09 | 河北大学 | A kind of memristor and preparation method and application with neurobionics function |
| CN110911409A (en) * | 2018-09-18 | 2020-03-24 | 联华电子股份有限公司 | Non-volatile memory and forming method thereof |
| CN110911409B (en) * | 2018-09-18 | 2022-05-03 | 联华电子股份有限公司 | Non-volatile memory and forming method thereof |
| CN109860390A (en) * | 2019-02-28 | 2019-06-07 | 西交利物浦大学 | RRAM device and preparation method thereof based on graphene oxide |
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Application publication date: 20150311 |