CN104072769B - The poly-naphthalimide of the wide in range adjustable ternary polymerization type of a kind of information storage behavior and preparation thereof - Google Patents
The poly-naphthalimide of the wide in range adjustable ternary polymerization type of a kind of information storage behavior and preparation thereof Download PDFInfo
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Abstract
The invention belongs to polymer information storage material technical field, adopt the method for multicomponent copolycondensation, with 4,4 '-diaminourea triphenylamine is electron donor, with Isosorbide-5-Nitrae, 5,8-naphthalenetetracarbacidic acidic acid anhydride is electron acceptor, with 9,9 '-bis-(aminophenyl) fluorenes is the 3rd copolymerization units, by regulating the composition of copolymerization units, successfully prepared the poly-naphthalimide of the wide in range adjustable ternary polymerization type of a kind of information storage behavior, structure is as shown in figure (I).
Description
Technical field: the invention belongs to polymer information storage material technical field, be specifically related to the wide in range adjustable ternary polymerization type of a kind of information storage behaviorPoly-naphthalimide and preparation thereof.
Background technology
21 century is the era of knowledge-driven economy taking information industry as core. Various information technologies and information equipment have become can not in people's daily lifeThe part lacking. But along with the mankind enter " nano-electron " epoch from " microelectronics " epoch, traditional information storage material, comprise magnetic storage,Optical storage and semiconductor storage material (as silicon, germanium) have all moved closer to the upper of its application in the live width of device or the size of memory pointLimit. Taking semiconductor storage as example, the integrated level of current computer one single chip has reached the level of 32nm live width, and laboratory has reached 22nm,Substantially, approach its theoretic upper limit 20nm. Therefore, develop the information material of new realized high density quick storage and storage accordinglyTechnology becomes the current key issue urgently to be resolved hurrily of people.
In numerous materials, the polymer information storage material with electric bistable performance is that current high density snap information field of storage can be expectedOne of select. This class material is to rely on the different electric stable state (being low state and high-impedance state) of its two kinds of presenting under electric field action to realize informationStorage, have advantages of that voltage drives, read or write speed is fast; And the size of its functional unit is at nanoscale, the size of memory point can in theoryLittle of even molecular level of nanometer level, and can make the memory device with three-dimensional structure by the method for stack, thereby can realize VHDLarge capacity snap information storage. In addition, compare with traditional magnetic, light and semiconductor storage, memory material of polymer also has flexible and can arbitrarily cut outThe feature of cutting, can meet instantly people for the demand of flexibility storage. In this field, polyimide material is because of its excellent high and low temperature resistance, powerLearn performance, chemistry and dimensional stability, become the important development direction in high density snap information storage medium field, be expected the flexible information in a new generationIn storage medium, obtain important application.
Realize information storage merit by metal nano particle-doped in polyimides, fullerene, CNT, Graphene, graphene oxide etc.It can be the early stage main method adopting. But because different component is difficult to be uniformly distributed in laminated film, the memory device of preparation is often because dividing mutuallyFrom or particle assemble and contain more defect. So people are devoted to by MOLECULE DESIGN, the unit that contains electron donor and acceptor is introducedAmong polyimides macromolecular structure, the electric charge between dependence electron donor-acceptor (EDA) shifts to realize electric bi-stable and the information storage of material. At this neckTerritory, binary polycondensation,, by the polyamine that contains electron donor unit and the multi-anhydride polycondensation with electron acceptor function, is current preparationThe main path of polyimides information storage material. But MOLECULE DESIGN is limited to the kind of monomer structure, in the research of the method, effectively,Alternative electron donor unit and electron acceptor unit are little, and this makes the alternative of its structure and the controllability of performance be subject to great limitSystem. In the polyimides of binary system, in order to realize different information storage behaviors and more excellent memory property, must change electron donor andBe subject to body unit, or the more complicated electron donor-acceptor (EDA) structure of design, and this often will be through complicated and loaded down with trivial details chemical synthesis process. With expection phaseLeft, this extremely have the regulating action of material storage behavior and performance by changing to acceptor specy and the novel way to receptor structure of designLimit, many times, the redesign of structure can not bring the adjusting of material storage behavior and the optimization of memory property, and sometimes also can cause depositingThe reduction of storage behavior even disappears. For this reason, find a kind of method easily and effectively, realization has the polyimides information of different information storage behaviors and depositsThe preparation of storage material and the adjusting of its storage behavior and performance, be of great significance tool to the development in this field.
Prepared in the research of polymer information storage material by early stage doping method, by regulating the content of Nano filling to control material storage behavior, this grindsStudy carefully the enlightenment of result, in the present invention, we changed in the past by MOLECULE DESIGN then binary polycondensation prepare polyimides information storage materialThinking, the method for employing copolycondensation, has different information storage behaviors by several specific electroactive monomers being combined successfully preparedThe polyimide-based information storage material of copoly type. Regulate by the details to each constituent content in copoly type polyimides, successfully realized itThe adjusting of storage behavior and performance. Emphasis of the present invention has reported to have 4 of electron donor function, 4 '-diaminourea triphenylamine (DATPA), has electricityThe Isosorbide-5-Nitrae of sub-function of receptors, 5,8-naphthalenetetracarbacidic acidic acid anhydride (NTDA) and there are 9,9 '-bis-(ammonia of large non-coplanar structure and weak electron function of receptorsBase phenyl) fluorenes (BAPF) be comonomer the poly-naphthalimide of ternary polymerization type and telecommunications breath storage behavior thereof, by regulating DATPA and BAPFBetween ratio between 0% to 10%, change, the performance of material has realized from without electric bi-stable (0% and 1%), to having dynamic random storage(DRAM type) behavior (2%), to thering is static random storage (SRAM type) behavior (5%) and read-only to having (WORM type)The wide in range adjusting of information storage behavior (10%). From in the past need to by change to acceptor specy and design novel realize to receptor structure differentThe way of information memory property is compared, and the method preparation process is simple, synthetic without special monolithic design, adopts the combinations matches of existing monomerCan realize material preparation, raw material sources are extensive, and structure is various, the most important thing is that performance controllability is strong, only changes by composition, can prepareThe flexible information storage material of the wide in range adjustable polyimides of information storage behavior, has extremely strong actual application value, for the flexible information of polyimides is depositedThe exploitation of storage material provides a kind of simple and effective new way.
Summary of the invention
The present invention is by the method for multicomponent copolycondensation, to have 4 of electron donor function, 4 '-diaminourea triphenylamine (DATPA), has electron acceptorThe Isosorbide-5-Nitrae of function, 5,8-naphthalenetetracarbacidic acidic acid anhydride (NTDA) and there are 9,9 '-bis-(aminophenyls) of large non-coplanar structure and weak electron function of receptorsFluorenes (BAPF) is comonomer, has prepared the poly-naphthalimide of ternary polymerization type with electric bi-stable information memory property. What is more important,Only, based on a kind of polyimide material, by the simple adjustment to its copolymerization component ratio, realize the wide in range adjustable of information storage behavior, and becomePrepare to merit the there are different storage behaviors polyimides information storage material of (comprising DRAM type, SRAM type and WORM type). HaveEffect ground has overcome the current binary condensation methods extensively adopting in the time preparing polyimides information storage material, needs the synthetic specific monomer knot of designStructure, process complexity, optional structure are few and to the very limited drawback of material storage behavior regulating power. The method preparation process that this invention adoptsSimply, synthetic without special monolithic design, only form change by copolymerization, can realize the wide in range adjustable, practical of information storage behavior,It is a kind of simple and effective new way of preparing the flexible information storage material of polyimides.
The chemical structural formula of the poly-naphthalimide of ternary polymerization type of synthesized of the present invention is as follows:
In the present invention, the poly-building-up process of naphthalimide of ternary polymerization type and the preparation method of its memory device are as follows:
(1) synthesizing of the poly-naphthalimide of ternary polymerization type
By 4,4 '-diaminourea triphenylamine (DATPA) and 9,9 '-bis-(aminophenyl) fluorenes (BAPF) difference 1:99,2:98,5:95 in molar ratioBe dissolved in organic solvent with 10:90, then add the Isosorbide-5-Nitrae of equivalent, 5,8-naphthalenetetracarbacidic acidic acid anhydride (NTDA) stirs 2～3 in nitrogen protection atmosphereHour, then add after catalyst and continue, 190 DEG C～200 DEG C reactions 12～15 hours, to adopt after cooling methanol extraction, and repeatedly wash with methyl alcoholCan obtain target to the rear filtration drying of solution clarification and gather naphthalimide; Course of reaction is as shown in figure below (I):
Wherein, the catalyst adopting is pyridine/acetic anhydride or isoquinolin.
(2) preparation of the poly-naphthalimide memory device of ternary polymerization type
To gather naphthalimide and be dissolved in organic solvent, be spun on the substrate of conductive egative film electrode, after vacuum drying desolvation, steam with vacuumThe mode of plating or ion sputtering is prepared into top electrode on polyimide layer, and the shape of electrode and area can be by mask plate controls; Wherein in this stepThe organic solvent adopting is 1-METHYLPYRROLIDONE, metacresol, and the electrode adopting comprises indium tin oxide films, silver, aluminium, gold.
Compare with material with existing method, the present invention has following beneficial effect:
1) multicomponent copolycondensation of the present invention is prepared the method for polyimides information storage material, and preparation process is simple, establishes without special monomerMeter is synthetic, adopts the combinations matches of existing monomer can realize material preparation, and raw material sources are extensive, and structure is various, has overcome binary condensation methodsNeed the synthetic specific monomer structure of design, process is complicated and to the very limited drawback of material storage behavior regulating power.
2) the prepared material memory property controllability of the present invention is extremely strong, only by the change of copolymer composition, can prepare information storage behavior wide in rangeThe flexible information storage material of adjustable polyimides, simple to operate efficient, be beneficial to very much the information that design as required has different storage behaviors and depositStorage material, is of very high actual application value.
Brief description of the drawings
Fig. 1. in embodiment 1 preparation 4,4 '-diaminourea triphenylamine, 9,9 '-bis-(aminophenyl) fluorenes, Isosorbide-5-Nitrae, 5,8-naphthalenetetracarbacidic acidic acid anhydride mol ratio is 0:100:100The infrared spectrum of the poly-naphthalimide of ternary polymerization type
Fig. 2. in embodiment 2 preparation 4,4 '-diaminourea triphenylamine, 9,9 '-bis-(aminophenyl) fluorenes, Isosorbide-5-Nitrae, 5,8-naphthalenetetracarbacidic acidic acid anhydride mol ratio is 1:99:100The infrared spectrum of the poly-naphthalimide of ternary polymerization type
Fig. 3. in embodiment 3 preparation 4,4 '-diaminourea triphenylamine, 9,9 '-bis-(aminophenyl) fluorenes, Isosorbide-5-Nitrae, 5,8-naphthalenetetracarbacidic acidic acid anhydride mol ratio is 2:98:100The infrared spectrum of the poly-naphthalimide of ternary polymerization type
Fig. 4. in embodiment 4 preparation 4,4 '-diaminourea triphenylamine, 9,9 '-bis-(aminophenyl) fluorenes, Isosorbide-5-Nitrae, 5,8-naphthalenetetracarbacidic acidic acid anhydride mol ratio is 5:95:100The poly-naphthalimide of ternary polymerization type infrared spectrum
Fig. 5. in embodiment 5 preparation 4,4 '-diaminourea triphenylamine, 9,9 '-bis-(aminophenyl) fluorenes, Isosorbide-5-Nitrae, 5,8-naphthalenetetracarbacidic acidic acid anhydride mol ratio is 10:90:100The poly-naphthalimide of ternary polymerization type infrared spectrum
Fig. 6. in embodiment 6 preparation taking indium tin oxide films as hearth electrode, aluminium is 4 of top electrode, 4 '-diaminourea triphenylamine, 9,9 '-bis-(aminophenyls)Fluorenes, Isosorbide-5-Nitrae, the current-voltage curve of the memory device of the poly-naphthalimide of ternary polymerization type that 5,8-naphthalenetetracarbacidic acidic acid anhydride mol ratio is 0:100:100
Fig. 7. in embodiment 7 preparation taking indium tin oxide films as hearth electrode, aluminium is 4 of top electrode, 4 '-diaminourea triphenylamine, 9,9 '-bis-(aminophenyls)Fluorenes, Isosorbide-5-Nitrae, the current-voltage curve of the memory device of the poly-naphthalimide of ternary polymerization type that 5,8-naphthalenetetracarbacidic acidic acid anhydride mol ratio is 1:99:100
Fig. 8. in embodiment 8 preparation taking indium tin oxide films as hearth electrode, aluminium is 4 of top electrode, 4 '-diaminourea triphenylamine, 9,9 '-bis-(aminophenyls)Fluorenes, Isosorbide-5-Nitrae, the current-voltage curve of the memory device of the poly-naphthalimide of ternary polymerization type that 5,8-naphthalenetetracarbacidic acidic acid anhydride mol ratio is 2:98:100
Fig. 9. in embodiment 9 preparation taking indium tin oxide films as hearth electrode, aluminium is 4 of top electrode, 4 '-diaminourea triphenylamine, 9,9 '-bis-(aminophenyls)Fluorenes, Isosorbide-5-Nitrae, the current-voltage curve of the memory device of the poly-naphthalimide of ternary polymerization type that 5,8-naphthalenetetracarbacidic acidic acid anhydride mol ratio is 5:95:100
Figure 10. in embodiment 10 preparation taking indium tin oxide films as hearth electrode, aluminium is 4 of top electrode, 4 '-diaminourea triphenylamine, 9,9 '-bis-(aminobenzenesBase) fluorenes, Isosorbide-5-Nitrae, the current-voltage curve of the memory device of the poly-naphthalimide of ternary polymerization type that 5,8-naphthalenetetracarbacidic acidic acid anhydride mol ratio is 10:90:100
Specific embodiment
Embodiment 1
4,4 '-diaminourea triphenylamine, 9,9 '-bis-(aminophenyl) fluorenes, Isosorbide-5-Nitrae, the poly-naphthalene of ternary polymerization type that 5,8-naphthalenetetracarbacidic acidic acid anhydride mol ratio is 0:100:100Imido preparation:
Under nitrogen protection by 2.68g (10.0mmol) Isosorbide-5-Nitrae, 5,8-naphthalenetetracarbacidic acidic acid anhydride, 3.48g (10.0mmol) 9,9 '-bis-(aminophenyl) fluorenes,Add in 100mL there-necked flask, add subsequently 50ml metacresol (treated) at room temperature in closed environment, to stir 2 hours, treat that solution stirsEvenly time, under nitrogen protection, add dehydrating agent isoquinolin, be warming up to 200 DEG C of successive reactions 12 hours simultaneously. After cooling, repeatedly use methanol extractionPolymer, and dried, can obtain 4,4 '-diaminourea triphenylamine, 9,9 '-bis-(aminophenyl) fluorenes, Isosorbide-5-Nitrae, 5,8-naphthalenetetracarbacidic acidic acid anhydride mol ratio isThe poly-naphthalimide solid of ternary polymerization type of 0:100:100.
Infrared (KBr compressing tablet): 1712cm-1(C-O asymmetric stretching vibration peak), 1679cm-1(C-O symmetrical stretching vibration peak), 1342cm-1(C-N vibration peak), 746cm-1(C-N-C vibration peak). Number-average molecular weight Mn＝2.03×104, weight average molecular weight Mw＝3.94×104, many pointsLoose coefficient is 1.94.
Embodiment 2
4,4 '-diaminourea triphenylamine, 9,9 '-bis-(aminophenyl) fluorenes, Isosorbide-5-Nitrae, the poly-naphthalene of ternary polymerization type that 5,8-naphthalenetetracarbacidic acidic acid anhydride mol ratio is 1:99:100Imido preparation:
Under nitrogen protection by 2.68g (10.0mmol) Isosorbide-5-Nitrae, 5,8-naphthalenetetracarbacidic acidic acid anhydride, 3.45g (9.9mmol) 9,9 '-bis-(aminophenyl) fluorenes,0.03g (0.1mmol) 4,4 '-diaminourea triphenylamine adds in 100mL there-necked flask, adds subsequently 50ml metacresol (treated) in room temperatureIn lower closed environment, stir 2 hours, in the time that solution stirs, under nitrogen protection, add dehydrating agent isoquinolin, be warming up to 200 DEG C continuously simultaneouslyReact 12 hours. After cooling, repeatedly use methanol extraction polymer, and dried, can obtain 4,4 '-diaminourea triphenylamine, 9,9 '-bis-(aminoPhenyl) fluorenes, Isosorbide-5-Nitrae, the poly-naphthalimide solid of ternary polymerization type that 5,8-naphthalenetetracarbacidic acidic acid anhydride mol ratio is 1:99:100.
Infrared (KBr compressing tablet): 1712cm-1(C-O asymmetric stretching vibration peak), 1680cm-1(C-O symmetrical stretching vibration peak), 1342cm-1(C-N vibration peak), 746cm-1(C-N-C vibration peak). Number-average molecular weight Mn＝2.15×104, weight average molecular weight Mw＝4.13×104, many pointsLoose coefficient is 1.92.
Embodiment 3
4,4 '-diaminourea triphenylamine, 9,9 '-bis-(aminophenyl) fluorenes, Isosorbide-5-Nitrae, the poly-naphthalene of ternary polymerization type that 5,8-naphthalenetetracarbacidic acidic acid anhydride mol ratio is 2:98:100Imido preparation:
Under nitrogen protection by 2.68g (10.0mmol) Isosorbide-5-Nitrae, 5,8-naphthalenetetracarbacidic acidic acid anhydride, 3.41g (9.8mmol) 9,9 '-bis-(aminophenyl) fluorenes,0.06g (0.2mmol) 4,4 '-diaminourea triphenylamine adds in 100mL there-necked flask, adds subsequently 30ml metacresol (treated) in room temperatureIn lower closed environment, stir 2 hours, in the time that solution stirs, under nitrogen protection, add dehydrating agent isoquinolin, be warming up to 200 DEG C continuously simultaneouslyReact 12 hours. After cooling, repeatedly use methanol extraction polymer, and dried, can obtain 4,4 '-diaminourea triphenylamine, 9,9 '-bis-(aminoPhenyl) fluorenes, Isosorbide-5-Nitrae, the poly-naphthalimide solid of ternary polymerization type that 5,8-naphthalenetetracarbacidic acidic acid anhydride mol ratio is 2:98:100.
Infrared (KBr compressing tablet): 1712cm-1(C-O asymmetric stretching vibration peak), 1679cm-1(C-O symmetrical stretching vibration peak), 1342cm-1(C-N vibration peak), 746cm-1(C-N-C vibration peak). Number-average molecular weight Mn＝2.2×104, weight average molecular weight Mw＝4.22×104, polydispersionCoefficient is 1.92.
Embodiment 4
4,4 '-diaminourea triphenylamine, 9,9 '-bis-(aminophenyl) fluorenes, Isosorbide-5-Nitrae, the poly-naphthalene of ternary polymerization type that 5,8-naphthalenetetracarbacidic acidic acid anhydride mol ratio is 5:95:100Imido preparation:
Under nitrogen protection by 2.68g (10.0mmol) Isosorbide-5-Nitrae, 5,8-naphthalenetetracarbacidic acidic acid anhydride, 3.31g (9.5mmol) 9,9 '-bis-(aminophenyl) fluorenes,0.14g (0.5mmol) 4,4 '-diaminourea triphenylamine adds in 100mL there-necked flask, adds subsequently 30ml metacresol (treated) in room temperatureIn lower closed environment, stir 2 hours, in the time that solution stirs, under nitrogen protection, add dehydrating agent isoquinolin, be warming up to 200 DEG C continuously simultaneouslyReact 12 hours. After cooling, repeatedly use methanol extraction polymer, and dried, can obtain 4,4 '-diaminourea triphenylamine, 9,9 '-bis-(aminoPhenyl) fluorenes, Isosorbide-5-Nitrae, the poly-naphthalimide solid of ternary polymerization type that 5,8-naphthalenetetracarbacidic acidic acid anhydride mol ratio is 5:95:100.
Infrared (KBr compressing tablet): 1712cm-1(C-O asymmetric stretching vibration peak), 1678cm-1(C-O symmetrical stretching vibration peak), 1342cm-1(C-N vibration peak), 746cm-1(imide ring in plane vibration peak). Number-average molecular weight Mn＝2.1×104, weight average molecular weight Mw＝4.1×104，Polydispersity coefficient is 1.93.
Embodiment 5
4,4 '-diaminourea triphenylamine, 9,9 '-bis-(aminophenyl) fluorenes, Isosorbide-5-Nitrae, the poly-naphthalene of ternary polymerization type that 5,8-naphthalenetetracarbacidic acidic acid anhydride mol ratio is 10:90:100Imido preparation:
Under nitrogen protection by 1.34g (5.0mmol) Isosorbide-5-Nitrae, 5,8-naphthalenetetracarbacidic acidic acid anhydride, 1.57g (9.5mmol) 9,9 '-bis-(aminophenyl) fluorenes,0.14g (0.5mmol) 4,4 '-diaminourea triphenylamine adds in 50mL there-necked flask, adds subsequently 20ml metacresol (treated) at room temperatureIn closed environment, stir 2 hours, in the time that solution stirs, under nitrogen protection, add dehydrating agent isoquinolin, be warming up to 200 DEG C continuously instead simultaneouslyAnswer 12 hours. After cooling, repeatedly use methanol extraction polymer, and dried, can obtain 4,4 '-diaminourea triphenylamine, 9,9 '-bis-(aminobenzenesBase) fluorenes, Isosorbide-5-Nitrae, the poly-naphthalimide solid of ternary polymerization type that 5,8-naphthalenetetracarbacidic acidic acid anhydride mol ratio is 5:95:100.
Infrared (KBr compressing tablet): 1712cm-1(C-O asymmetric stretching vibration peak), 1681cm-1(C-O symmetrical stretching vibration peak), 1342cm-1(C-N vibration peak), 746cm-1(C-N-C vibration peak). Number-average molecular weight Mn＝2.1×104, weight average molecular weight Mw＝4.0×104, polydispersionCoefficient is 1.91.
Embodiment 6
Taking indium tin oxide films as hearth electrode, aluminium is 4 of top electrode, 4 '-diaminourea triphenylamine, 9,9 '-bis-(aminophenyl) fluorenes, Isosorbide-5-Nitrae, 5,8-naphthalene tetramethylAcid anhydrides mol ratio is the semiconductor parametric test of the poly-naphthalimide memory device of ternary polymerization type of 0:100:100:
To taking indium tin oxide films as hearth electrode, aluminium is 4 of top electrode, 4 '-diaminourea triphenylamine, 9,9 '-bis-(aminophenyl) fluorenes, Isosorbide-5-Nitrae, 5,8-naphthalene fourFormic anhydride mol ratio is that the poly-naphthalimide device of the ternary polymerization type of 0:100:100 carries out current-voltage curve test. At forward voltage scanning and negative senseIn the process of voltage, electric current maintains lower conduction state always, illustrates taking indium tin oxide films as hearth electrode, aluminium is 4 of top electrode, 4 '-diaminoBase triphenylamine, 9,9 '-bis-(aminophenyl) fluorenes, Isosorbide-5-Nitrae, the poly-naphthalimide of ternary polymerization type that 5,8-naphthalenetetracarbacidic acidic acid anhydride mol ratio is 0:100:100 belongs toInsulating materials.
Embodiment 7
Taking indium tin oxide films as hearth electrode, aluminium is 4 of top electrode, 4 '-diaminourea triphenylamine, 9,9 '-bis-(aminophenyl) fluorenes, Isosorbide-5-Nitrae, 5,8-naphthalene tetramethylAcid anhydrides mol ratio is the semiconductor parametric test of the poly-naphthalimide memory device of ternary polymerization type of 1:99:100:
To taking indium tin oxide films as hearth electrode, aluminium is 4 of top electrode, 4 '-diaminourea triphenylamine, 9,9 '-bis-(aminophenyl) fluorenes, Isosorbide-5-Nitrae, 5,8-naphthalene fourFormic anhydride mol ratio is that the poly-naphthalimide device of the ternary polymerization type of 1:99:100 carries out current-voltage curve test. At forward voltage scanning and negative sense electricityIn the process of pressing, electric current maintains lower conduction state always, illustrates taking indium tin oxide films as hearth electrode, aluminium is 4 of top electrode, 4 '-diaminoureaTriphenylamine, 9,9 '-bis-(aminophenyl) fluorenes, Isosorbide-5-Nitrae, the poly-naphthalimide of ternary polymerization type that 5,8-naphthalenetetracarbacidic acidic acid anhydride mol ratio is 1:99:100 belongs to insulationMaterial.
Embodiment 8
Taking indium tin oxide films as hearth electrode, aluminium is 4 of top electrode, 4 '-diaminourea triphenylamine, 9,9 '-bis-(aminophenyl) fluorenes, Isosorbide-5-Nitrae, 5,8-naphthalene tetramethylAcid anhydrides mol ratio is the semiconductor parametric test of the poly-naphthalimide memory device of ternary polymerization type of 2:98:100:
To taking indium tin oxide films as hearth electrode, aluminium is 4 of top electrode, 4 '-diaminourea triphenylamine, 9,9 '-bis-(aminophenyl) fluorenes, Isosorbide-5-Nitrae, 5,8-naphthalene fourFormic anhydride mol ratio is that the poly-naphthalimide device of the ternary polymerization type of 2:98:100 carries out current-voltage curve test. In the scanning of forward voltage for the first timeIn process, electric current maintains lower conduction state always, and in backward voltage scanning process subsequently, device is the state in low conducting first, andWhen voltage be-when 4.7V, device has produced larger current jump, the process writing corresponding to information. In continuous sweep process subsequently, deviceThe high conducting state of part is all maintained. Cut off the electricity supply after 5 seconds, carry out negative sense scanning discovery device-4.7V place has represented good writing againProcess, finds that device presents good reading property and carry out negative sense read test again. Device shows to cut off the electricity supply in said process very easily to be lostThe feature of information illustrates taking indium tin oxide films as hearth electrode, aluminium is 4 of top electrode, 4 '-diaminourea triphenylamine, 9,9 '-bis-(aminophenyl) fluorenes, Isosorbide-5-Nitrae, 5,8-The poly-naphthalimide device of ternary polymerization type that naphthalenetetracarbacidic acidic acid anhydride mol ratio is 2:98:100, meets performance volatibility dynamic random storage (DRAM) typeStorage characteristics.
Embodiment 9
Taking indium tin oxide films as hearth electrode, aluminium is 4 of top electrode, 4 '-diaminourea triphenylamine, 9,9 '-bis-(aminophenyl) fluorenes, Isosorbide-5-Nitrae, 5,8-naphthalene tetramethylAcid anhydrides mol ratio is the semiconductor parametric test of the poly-naphthalimide memory device of ternary polymerization type of 5:95:100:
To taking indium tin oxide films as hearth electrode, aluminium is 4 of top electrode, 4 '-diaminourea triphenylamine, 9,9 '-bis-(aminophenyl) fluorenes, Isosorbide-5-Nitrae, 5,8-naphthalene fourFormic anhydride mol ratio is that the poly-naphthalimide device of the ternary polymerization type of 5:95:100 carries out current-voltage curve test. In the scanning of forward voltage for the first timeIn process, electric current maintains lower conduction state always, and in backward voltage scanning process subsequently, device is the state in low conducting first, andWhen voltage be-when 2.0V, device has produced larger current jump, the process writing corresponding to information. In continuous sweep process subsequently, deviceThe high conducting state of part is all maintained. Cut off the electricity supply after 15 minutes, carry out negative sense scanning discovery device-1.8V place has represented good writing againEnter process, find that device presents good reading property and carry out again negative sense read test. Device still can after showing in said process and cutting off the electricity supplyThe feature of maintenance information illustrates taking indium tin oxide films as hearth electrode, aluminium is 4 of top electrode, 4 '-diaminourea triphenylamine, 9,9 '-bis-(aminophenyl) fluorenes,Isosorbide-5-Nitrae, the poly-naphthalimide device of ternary polymerization type that 5,8-naphthalenetetracarbacidic acidic acid anhydride mol ratio is 5:95:100, meets the storage of performance volatibility dynamic random(SRAM) storage characteristics of type.
Embodiment 10
Taking indium tin oxide films as hearth electrode, aluminium is 4 of top electrode, 4 '-diaminourea triphenylamine, 9,9 '-bis-(aminophenyl) fluorenes, Isosorbide-5-Nitrae, 5,8-naphthalene tetramethylAcid anhydrides mol ratio is the semiconductor parametric test of the poly-naphthalimide memory device of ternary polymerization type of 10:90:100:
To taking indium tin oxide films as hearth electrode, aluminium is 4 of top electrode, 4 '-diaminourea triphenylamine, 9,9 '-bis-(aminophenyl) fluorenes, Isosorbide-5-Nitrae, 5,8-naphthalene fourFormic anhydride mol ratio is that the poly-naphthalimide device of the ternary polymerization type of 10:90:100 carries out current-voltage curve test. In forward voltage scanning for the first timeProcess in, electric current maintains lower conduction state always, in backward voltage scanning process subsequently, device is the state in low conducting first,And when voltage be-when 2.0V, device has produced larger current jump, the process writing corresponding to information. In scanning process subsequently, deviceHigh conducting state be all maintained. The feature that device shows irreversible maintenance information in said process illustrates taking indium tin oxide films as end electricityThe utmost point, aluminium are top electrode 4,4 '-diaminourea triphenylamine, 9, and 9 '-bis-(aminophenyl) fluorenes, Isosorbide-5-Nitrae, 5,8-naphthalenetetracarbacidic acidic acid anhydride mol ratio is 10:90:100Ternary polymerization type gathers naphthalimide device, meets the storage characteristics of (WORM) type of repeatedly reading of the non-volatile write-once of performance.
Claims (2)
1. the poly-naphthalimide of the wide in range adjustable ternary polymerization type of information storage behavior, its structure is as follows:
2. the wide in range adjustable ternary polymerization type of a kind of information storage behavior gathers naphthalimide according to claim 1, it is characterized in that, it synthesizes and depositsMemory device preparation process is as follows:
(1) synthesizing of the poly-naphthalimide of ternary polymerization type
By 4,4 '-diaminourea triphenylamine (DATPA) and 9,9 '-bis-(aminophenyl) fluorenes (BAPF) difference 1:99,2:98,5:95 in molar ratioBe dissolved in organic solvent with 10:90, then add the Isosorbide-5-Nitrae of equivalent, 5,8-naphthalenetetracarbacidic acidic acid anhydride (NTDA) stirs 2～3 in nitrogen protection atmosphereHour, then add after catalyst and continue, 190 DEG C～200 DEG C reactions 12～15 hours, to adopt after cooling methanol extraction, and repeatedly wash with methyl alcoholCan obtain target to the rear filtration drying of solution clarification and gather naphthalimide; Course of reaction is as shown in figure below (I):
Wherein, the catalyst adopting is pyridine/acetic anhydride or isoquinolin;
(2) preparation of the poly-naphthalimide memory device of ternary polymerization type
To gather naphthalimide and be dissolved in organic solvent, be spun on the substrate of conductive egative film electrode, after vacuum drying desolvation, steam with vacuumThe mode of plating or ion sputtering is prepared into top electrode on polyimide layer, and the shape of electrode and area can be by mask plate controls; Wherein in this stepThe organic solvent adopting is 1-METHYLPYRROLIDONE, metacresol, and the electrode adopting is selected from the one in indium tin oxide films, silver, aluminium, gold.
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