CN103035842B - Organic resistive random access memory based on graphene quantum dot doping and preparation method thereof - Google Patents
Organic resistive random access memory based on graphene quantum dot doping and preparation method thereof Download PDFInfo
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- CN103035842B CN103035842B CN201310000243.0A CN201310000243A CN103035842B CN 103035842 B CN103035842 B CN 103035842B CN 201310000243 A CN201310000243 A CN 201310000243A CN 103035842 B CN103035842 B CN 103035842B
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Abstract
The invention discloses an organic resistive random access memory based on graphene quantum dot doping and a preparation method thereof. The organic resistive random access memory is a three-layer structure component comprising a bottom electrode, an organic functional layer and a top electrode forming on an insulating substrate. The organic functional layer adopts a polymer doped with graphene quantum dots to be dissolved on the bottom electrode to be spin-coated to form a film and adopts a thermal evaporation method to evaporate a cathode metal material to form a film to form the top electrode, and finally the organic resistive random access memory based on graphene quantum dot doping is made. The preparation process of the memory is simple, and the process is easily controlled and has high repeatability. The memory has the advantages of simple structure, stable performance and high response speed, and a flexible device can be made through a flexible substrate. The memory is used in the field of highly integrated high-capacity multi-value memories and has high application vale.
Description
Technical field
The present invention relates to semiconductor storage, belong to organic memory field, be specifically related to a kind of organic resistive random access memory based on graphene quantum dot doping and preparation method thereof.
Background technology
In the digital times of current information explosion, the production of people and life all be unable to do without the memory of high density, high speed.Resistance-variable storing device has brand-new storage concept, it utilizes the controlled resistive effect existed in some inorganic oxides or organic substance/polymer to answer, namely under different voltage drives, resistance-variable storing device can present two kinds of diverse impedance states (low-resistance and high resistants, corresponding "ON" and "Off"), representative data " 1 " and " 0 " respectively, and after voltage removes, state still keeps, and therefore achieves the storage of data.The advantage of resistance-variable storing device is that structure is simple, low in energy consumption, speed is fast, storage density is high, manufacturing process is simple, very likely replaces traditional non-volatility memorizer and captures semiconductor memory market.
Organic resistive random access memory can be applicable to low cost electronic device and flexible electronic device field, compares and also has flexing with inorganic resistance-variable storing device, with low cost, and material molecule structure can design to improve the superior parts such as performance.But resistance-variable storing device just marches toward the starting stage, the organic material that the organic resistive random access memory of current report is chosen shows the problem of chemical stability and poor heat stability mostly, the stability of device resistance state conversion also has problems in addition, the condition causing resistive materials behavior to be changed all can change because of the fluctuation of device, even for same device, high resistance and low-resistance numerical value of the opening and closing voltage that resistive needs and generation also have certain difference.This larger discrete type will make device be difficult to accurate control, and this has become obstruction organic resistive random access memory and has moved towards practical main bugbear.A kind of graphene quantum dot adopted based on the organic resistive random access memory of graphene quantum dot doping provided by the invention has well thermally-stabilised and chemical stability, and obtained device can have stronger reliability and stability.
Summary of the invention
The object of the invention is to provide a kind of organic resistive random access memory based on graphene quantum dot doping and preparation method thereof, the polymer doped with graphene quantum dot is adopted to be dissolved in spin-coating film on hearth electrode, and adopt thermal evaporation evaporation cathodic metal material filming to form top electrode, preparation technology is simple, and repeatability is high, the stable performance of device, fast response time, and make flexible device by flexible substrate, for highly integrated Large Copacity multivalued storage field, there is very high using value.
For achieving the above object, technical scheme of the present invention is:
Based on an organic resistive random access memory for graphene quantum dot doping, adopt the polymer of graphene quantum dot doping as organic function layer, substrate is formed the three-decker device comprising hearth electrode, organic function layer and top electrode.
Graphene quantum dot in described organic function layer is that 1:1 ~ 1:20 hybrid extraction obtains with volume ratio by chlorobenzene from the graphene quantum dot aqueous solution.
Polymer in described organic function layer is polymethyl methacrylate, polystyrene or polyvinylcarbazole.
Described substrate is glass, quartz, pottery or flexible substrates.
Described hearth electrode is a kind of metal electrode in copper, tungsten, nickel, zinc, aluminium or two kinds and two or more clad metal electrode, or indium oxide mixes tin, doped zinc oxide aluminium, silicon materials; Top electrode is aluminium, copper or silver.
A kind of preparation comprises following operating procedure based on the method for the organic resistive random access memory of graphene quantum dot doping as above:
(1) under atmospheric environment, by acetone, alcohol, deionized water successively ultrasonic cleaning, drying obtains clean indium tin oxide-coated glass;
(2) on electro-conductive glass with rotating speed 1500 ~ 5000r/min spin coating graphene quantum dot doping polymer solution, spin-coating time is 20 ~ 50s;
(3) in vacuum degree 1 × 10
-3~ 6 × 10
-3adopt thermal evaporation evaporation cathode material under the environment of Pa, thickness is 70 ~ 200nm, and evaporation rate is 0.5 ~ 3nm/s.
In described step (2), the polymer solution of graphene quantum dot doping is formed by the chlorobenzene solution dissolve polymer containing graphene quantum dot, and the concentration of polymer is 5 ~ 12mg/mL.
Tool of the present invention has the following advantages and beneficial effect:
(1) current most of compound system organic memory adopts heavy metal particles doping, cost is higher and cause environment and to a certain degree pollute, and the invention provides the preparation of device graphene quantum dot used simple, pollution-free, strong mechanical property, the aperture opening ratio of memory is high, fast response time.
(2) graphene quantum dot introduced by chlorobenzene extracting process has consistent nano-grade size, and can adulterate to most of common polymer, ensures repeatability and the stability of device.
(3) because functional layer material all belongs to organic carbon material, graphene quantum dot inherently can flexible bending, can fabricate devices on flexible substrates, realizes flexible device, for highly integrated Large Copacity multivalued storage field.
(4) structure of device is simple, and preparation cost is low, and easy control simple to operate, can realize large-scale production.
Accompanying drawing explanation
Fig. 1 is the structural representation of the organic resistive random access memory based on graphene quantum dot doping provided by the invention, and 1 represents glass substrate; 2 represent anode, and the present embodiment adopts indium oxide to mix tin as anode; The organic function layer that 3 graphene quantum dots representing spin coating adulterate; 4 negative electrodes representing lattice arrangement, the present embodiment adopts aluminium as negative electrode.
Fig. 2 is the I-V curve of the organic resistive random access memory based on graphene quantum dot doping provided by the invention, the write voltage of memory is-0.8v, device jumps to low resistance state from high-impedance state, namely become " 1 " from " 0 ", and keep one state, when the voltage applying+2v is that device jumps back to high-impedance state by low resistance state, namely become " 0 " from " 1 ", the data of write are wiped free of.
Embodiment
Below the technical scheme in the embodiment of the present invention is described in detail.But described embodiment, is only a part of embodiment of the present invention, is not limited thereto.
Organic resistive random access memory based on graphene quantum dot doping of the present invention, the structure that embodiment specifically adopts is ITO/Polymer:GQDs/Al.If do not add to illustrate, the preparation technology in following embodiment carries out all in atmosphere.
With volume ratio 1:1 ~ 1:20 in separatory funnel, be preferably ratio mixing chlorobenzene and the graphene quantum dot aqueous solution of 1:3, namely get 10ml chlorobenzene and add the 30ml graphene quantum dot aqueous solution, abundant concussion also leaves standstill two days, the obvious layering of visible solution, take out lower floor's solution, be the chlorobenzene solution that extraction has graphene quantum dot.
Organic function layer based on the organic resistive random access memory of graphene quantum dot doping can adopt the dissolution of polymer such as polymethyl methacrylate (PMMA), polystyrene (PS) or polyvinylcarbazole (PVK) to have in extraction the solution film forming formed in graphene quantum dot chlorobenzene solvent.Polymethyl methacrylate (PMMA), polystyrene (PS) fabricate devices is have employed respectively in the present embodiment.
Embodiment 1
Polymethyl methacrylate (PMMA) being dissolved in extraction has in the chlorobenzene solvent of graphene quantum dot, be made into the solution that solute concentration is 5 ~ 12mg/ml, be preferably 10mg/ml, namely get 20mg PMMA be dissolved in 2ml extraction have in the chlorobenzene of graphene quantum dot, through magnetic agitation 6 hours wiring solution-formings.
Structure is that the preparation process of the organic resistive random access memory based on graphene quantum dot doping of ITO/Polymer:GQDs/Al is as follows:
(1) under atmospheric environment, to ITO transparent conducting glass by acetone, alcohol, deionized water successively ultrasonic cleaning 20 minutes, dry in drying box.
(2) the above-mentioned polymer chlorobenzene solution doped with graphene quantum dot of spin coating on clean dried ITO transparent conducting glass, need ito glass before spin coating at the vapour that anhydrates higher than 100 DEG C of heat treated, spin coating process adopts rotating speed 1500 ~ 5000r/min, preferably be defined as 3900r/min, time is 30s, without the need to heat treatment after spin coating.
(3) be positioned over by the sheet that spin coating completes in vacuum thermal evaporation coating machine cavity, cover lattice-like mask plate, spot diameter is 1mm, in vacuum degree 1 × 10
-3~ 6 × 10
-3under the environment of Pa, be preferably defined as 3.5 × 10
-3pa, adopt thermal evaporation evaporation cathode material aluminium, thermal source adopts tungsten filament to turn to helical form, and aluminium wire is wrapped on tungsten filament, evaporation Current Control is at 29.8 ~ 31.0A, and evaporation rate is not strict with, and controls at 1nm/s, form the film of 150nm, namely form the three-system active layer organic photovoltaic devices based on graphene quantum dot.
(4) after plated film completes, take out device, remove mask plate, form lattice structure device, under room temperature environment, by probe station and semi-conductor test instrument test component IV curve, device of the present invention has good resistance-change memory characteristic.
Embodiment 2
Polystyrene (PS) being dissolved in extraction has in the chlorobenzene solvent of graphene quantum dot, be made into the solution that solute concentration is 5 ~ 12mg/ml, be preferably 10mg/ml, namely get 20mg PS be dissolved in 2ml extraction have in the chlorobenzene of graphene quantum dot, through magnetic agitation 6 hours wiring solution-formings.Device preparation and test process complete described in embodiment 1, and the device of institute shows stable resistance-change memory characteristic under probe station and semi-conductor test instrument are tested.
Comparative example 1
Being dissolved in by polymethyl methacrylate (PMMA) does not extract in the chlorobenzene solvent of graphene quantum dot, be made into the solution that solute concentration is 5 ~ 12mg/ml, be preferably 10mg/ml, namely get 20mg PMMA be dissolved in 2ml extraction have in the chlorobenzene of graphene quantum dot, through magnetic agitation 6 hours wiring solution-formings.Device preparation and test process complete described in embodiment 1, and the device of institute does not show obvious resistance-change memory characteristic under probe station and semi-conductor test instrument are tested.
Comparative example 2
Being dissolved in by polystyrene (PS) does not extract in the chlorobenzene solvent of graphene quantum dot, be made into the solution that solute concentration is 5 ~ 12mg/ml, be preferably 10mg/ml, namely get 20mg PS be dissolved in 2ml extraction have in the chlorobenzene of graphene quantum dot, through magnetic agitation 6 hours wiring solution-formings.Device preparation and test process complete described in embodiment 1, and the device of institute does not show obvious resistance-change memory characteristic under probe station and semi-conductor test instrument are tested.
Can see from above-described embodiment, compared with the device prepared under similarity condition based on organic resistive random access memory and the polymer of undoped of graphene quantum dot doping that the present invention adopts the polymer doped with graphene quantum dot to prepare as organic function layer, all show obvious and stable resistance-change memory characteristic.
The foregoing is only preferred embodiment of the present invention, all equalizations done according to the present patent application the scope of the claims change and modify, and all should belong to covering scope of the present invention.
Claims (6)
1. based on an organic resistive random access memory for graphene quantum dot doping, it is characterized in that: adopt the polymer of graphene quantum dot doping as organic function layer, substrate is formed the three-decker device comprising hearth electrode, organic function layer and top electrode;
Graphene quantum dot in described organic function layer is that 1:1 ~ 1:20 hybrid extraction obtains with volume ratio by chlorobenzene from the graphene quantum dot aqueous solution.
2. the organic resistive random access memory based on graphene quantum dot doping according to claim 1, is characterized in that: the polymer in described organic function layer is polymethyl methacrylate, polystyrene or polyvinylcarbazole.
3. the organic resistive random access memory based on graphene quantum dot doping according to claim 1, is characterized in that: described substrate is glass, quartz, pottery or flexible substrates.
4. the organic resistive random access memory based on graphene quantum dot doping according to claim 1, it is characterized in that: described hearth electrode is a kind of metal electrode in copper, tungsten, nickel, zinc, aluminium or two kinds and two or more clad metal electrode, or indium oxide mixes tin, doped zinc oxide aluminium, silicon materials; Top electrode is aluminium, copper or silver.
5. prepare as claimed in claim 1 based on a method for the organic resistive random access memory of graphene quantum dot doping, it is characterized in that: comprise following operating procedure:
(1) on the substrate being coated with hearth electrode with rotating speed 1500 ~ 5000r/min spin coating graphene quantum dot doping polymer solution, spin-coating time is 20 ~ 50s;
(2) in vacuum degree 1 × 10
-3~ 6 × 10
-3adopt thermal evaporation evaporation cathode material under the environment of Pa, thickness is 70 ~ 200nm, and evaporation rate is 0.5 ~ 3nm/s.
6. the preparation method of the organic resistive random access memory based on graphene quantum dot doping according to claim 5, it is characterized in that: in described step (2), the polymer solution of graphene quantum dot doping is formed by the chlorobenzene solution dissolve polymer containing graphene quantum dot, and the concentration of polymer is 5 ~ 12mg/mL.
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| CN103618046B (en) * | 2013-11-08 | 2016-08-17 | 武汉工程大学 | The memory device of graphene quantum dot/poly-(3,4-Ethylenedioxy Thiophene)-poly-(styrene sulfonic acid) material and preparation |
| CN104952900B (en) * | 2015-05-13 | 2017-11-21 | 武汉工程大学 | A kind of memory device based on graphene oxide/polystyrene/Au nano composition and preparation method thereof |
| CN105825886B (en) * | 2016-03-31 | 2018-06-01 | 东南大学 | A kind of micro electronmechanical multivalued memory device |
| CN106449974B (en) * | 2016-10-14 | 2019-04-05 | 华南师范大学 | Based on MoS2The resistance-variable storing device and preparation method thereof of quantum dot insertion organic polymer |
| US11034847B2 (en) * | 2017-07-14 | 2021-06-15 | Samsung Electronics Co., Ltd. | Hardmask composition, method of forming pattern using hardmask composition, and hardmask formed from hardmask composition |
| CN107488267B (en) * | 2017-07-18 | 2020-12-29 | 电子科技大学 | High-resistance-change redox graphene material based on small ball modification and preparation method thereof |
| CN108047472A (en) * | 2017-11-13 | 2018-05-18 | 天津宝兴威科技股份有限公司 | A kind of preparation method of the polymer composite film based on graphene quantum dot doping |
| CN111477740B (en) * | 2020-05-14 | 2023-09-26 | 天津理工大学 | Polymer/quantum dot film memristor capable of simulating nerve synapses and preparation method thereof |
| CN112909163A (en) * | 2021-01-08 | 2021-06-04 | 新疆大学 | Nonvolatile memory device based on resistance random memory characteristic of coal-based graphene quantum dot film and preparation method thereof |
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