CN105573002A - Display member with information storage function and preparation method for same - Google Patents
Display member with information storage function and preparation method for same Download PDFInfo
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- CN105573002A CN105573002A CN201410528715.4A CN201410528715A CN105573002A CN 105573002 A CN105573002 A CN 105573002A CN 201410528715 A CN201410528715 A CN 201410528715A CN 105573002 A CN105573002 A CN 105573002A
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Abstract
The invention provides a display member with an information storage function and a preparation method for the same. The display member is formed by a transparent substrate, a transparent base electrode layer, a transparent polymer electrolyte layer, a transparent dielectric layer and a transparent top electrode layer; the transparent base electrode layer, the transparent polymer electrolyte layer, the transparent dielectric layer and the transparent top electrode layer are formed on the surface of the transparent substrate; the transparent polymer electrolyte layer has great conductive performance; the transparent dielectric layer has DRAM property and electrochromism property; when different voltage is applied, the display member shows different resistance state and has an information storage function; light transmissivity can be changed and different colors are displayed; the display member has the electrochromism property; the display member with the information storage function can be widely applied to the fields of multifunctional storage, multifunctional display and transparent electronics; and an effective path is provided for display member and storage member integration.
Description
Technical field
The invention belongs to memory device and display device technical field, particularly relate to a kind of display device with information storage function and preparation method thereof.
Background technology
DRAM (DynamicRandomAccessMemory, i.e. dynamic RAM) as one of the important composition of storer, there is the integrated and high speed operation of height, be widely used in the mobile device such as computer system, mobile phone, data recording equipment, printer, control system etc.;
Electrochromism is a kind of important display technique, refers to the phenomenon that the optical properties (reflectivity, transmitance, absorptivity etc.) of material changes under the effect of extra electric field show as the reversible change of color and transparency in appearance.The material with electrochromic property is called electrochromic material, is called electrochromic device with the device that electrochromic material is made.
Electrochromic device has the features such as optical property continuously adjustabe, low-work voltage, low-power consumption, radiationless, wide viewing angle, open circuit memory, mainly comprises electrochromic, electrochromism reservoir, electrochromic display device (ECD), intelligent dimming automobile rearview mirror, electron beam printing technology and sensor, camouflage clothes etc. at present.
But, study at present about DRAM and electrochromic crossing domain and still seldom relate to.
The device of current development can't have storage characteristics and electrochromic property simultaneously.And there is the device of DRAM characteristic and electrochromic property simultaneously, to be used widely in optics, electricity, storer, display, photoelectricity storage, photoelectric display, Transparence Display and crossing domain thereof, and effective way can be provided for memory device and the integrated of display device.
Such as, along with sweeping over of the third time world information industry tide after computing machine, internet, the radio frequency mainly relied between storage chip, antenna and plug-in reader based on the Intelligent Recognition of RFID is mutual, by receiving radiofrequency signal that plug-in reader sends, the energy that obtains by means of induction current send out prestore in the chips Item Information, utilize plug-in reader to read after carry out decoding and process, to realize the information communication between computing machine and article; If resistance-change memory, intelligent display and radio-frequency technique can be combined, while utilizing radiofrequency signal to read storage information, it is directly presented on label, then can realize eye recognition and machine recognition simultaneously, really reach the object realizing man-machine interaction, have broad application prospects.
Summary of the invention
Technical purpose of the present invention is to provide a kind of display device with information storage function, this device not only has the electrology characteristic of DRAM, and has electrochromic property, when applying different voltage, show the change of high low resistance state, present different colors simultaneously.
A kind of display device with information storage function, as shown in Figure 1, comprise transparent substrates, form clear bottom electrode layer on a transparent substrate, be formed in the transparent polymer dielectric substrate on clear bottom electrode layer, be formed in the transparency dielectric layer on transparent polymer dielectric substrate, and be formed in the transparent top electrode layer on transparency dielectric layer; And described transparent substrates is insulator, and transparent polymer dielectric substrate has good electric conductivity, and transparency dielectric layer has DRAM character and electrochromism property.
Described transparent substrates is for ultraviolet (UV), infrared ray (IR), near infrared ray (NIR) and/or limit of visible spectrum printing opacity, its material is not limit, and comprises a kind of material in the materials such as glass, jewel, transparent oxide material, transparent nitride material, transparent polymer material or two or more combined materials.When selecting two or more combined materials, multiple different materials can be formed transparent substrates with single layer structure, also can be formed transparent substrates with sandwich construction, and the material in every layer can be homogenous material or combined material.Described transparent oxide includes but not limited to the oxide of Ti, the oxide of Zn, the oxide of Zr, the oxide of Mg, the oxide of Al and alloyed oxide etc., such as SrTiO
3, LiAlO
3, LaAlO
3, GGG, MgO, Sapphire, BaTiO
3, ZrO
2(YSZ), LiGaO
2deng.Described transparent nitride includes but not limited to nitride, the nitride of Si, the oxide of Al, the nitride etc. of Ga of Ti.
Described clear bottom electrode layer and transparent top electrode layer are transparent conductive material, include but not limited to transparent conductive oxide, transparent conducting nitride material etc.Described transparent conductive oxide includes but not limited to FTO, ITO etc., described transparent conductive nitride include but not limited to containing Ti and/or Zr, the conductive nitride of good heat resistance, or the conductive nitride etc. of good heat resistance containing Al, Si, Mo, Cr, Nb, Hf, Ni, Co, Fe, Pd, Ag, Au, Pt, Ce.
Described transparent polymer dielectric substrate can be made up of following bi-material:
I () comprises the material of ionic liquid and organic polymer insulator, the salt that described ionic liquid is made up of kation and negative ion:
Described kation is including, but not limited to one or several kations in lithium ion, ammonium ion, imidazoles, oxazole, piperidines, pyrazine, pyrazoles, pyridazine, pyridine, pyrimidine, pyrrolidine, pyrrolin, pyrroles, thiazole, triazole, 4,4'-Bipyridine etc.
Described negative ion is including, but not limited to F
-, Cl
-, Br
-, I
-, NO
3 -, N (CN)
2 -, BF
4 -, ClO
4 -, RSO
3 -, RCOO
-(wherein, R is alkyl or phenyl), PF
6 -, (CF
3)
2pF
4 -, (CF
3)
3pF
3 -, (CF
3)
4pF
2 -, (CF
3)
5pF
-, (CF
3)
6pF
-, (CF
3sO
3 -)
2, (CF
3cF
2sO
3 -)
2, (CF
3sO
3 -)
2n
-, CF
3cF
2(CF
3)
2cO
-, (CF
3sO
2)
2cH
-, (SF
5)
3c
-, (CF
3sO
3 -)
3c
-, CF
3(CF
2 -)
7sO
3 -, CF
3cO
2 -and CH
3cO
2 -in one or more mixed anion.
Described organic polymer insulator is including, but not limited to ethene, vinyl cyanide, methyl methacrylate, hydroxyethyl methylacrylate, methyl acrylate, methacrylonitrile, methyl styrene, vinyl esters, vinyl chloride, 1, the polymeric material that one or more mix monomer in the vinyl monomers such as 1-dichloroethylene, vinylidene fluoride, acrylamide, tetrafluoroethene, vinyl acetate, methyl-vinyl ketone, ethene, styrene, p-methoxystyrene, p-cyano styrene and acrylate and oxirane is polymerized.
(ii) monomer is by the obtained polymeric material of polyreaction, and described monomer comprises kation and negative ion;
Described polymeric material includes but not limited to one or more the combination in methyl methacrylate (PMMA), poly-inclined vinylidene fluoride (PVDF), Polyvinylchloride (PVC), polyethylene oxide (PEO) and poly hydroxy ethyl acrylate (PHEMA) etc.
Described kation is including, but not limited to one or several kations in lithium ion, ammonium ion, imidazoles, oxazole, piperidines, pyrazine, pyrazoles, pyridazine, pyridine, pyrimidine, pyrrolidine, pyrrolin, pyrroles, thiazole, triazole, 4,4'-Bipyridine etc.
Described negative ion is including, but not limited to F
-, Cl
-, Br
-, I
-, NO
3 -, N (CN)
2 -, BF
4 -, ClO
4 -, RSO
3 -, RCOO
-(wherein, R is alkyl or phenyl), PF
6 -, (CF
3)
2pF
4 -, (CF
3)
3pF
3 -, (CF
3)
4pF
2 -, (CF
3)
5pF
-, (CF
3)
6pF
-, (CF
3sO
3 -)
2, (CF
3cF
2sO
3 -)
2, (CF
3sO
3 -)
2n
-, CF
3cF
2(CF
3)
2cO
-, (CF
3sO
2)
2cH
-, (SF
5)
3c
-, (CF
3sO
3 -)
3c
-, CF
3(CF
2 -)
7sO
3 -, CF
3cO
2 -and CH
3cO
2 -in one or more mixed anion.
Described monomer is preferably vinyl monomer.Described vinyl monomer includes but not limited to the combination of a kind of monomer in vinyl cyanide, methyl methacrylate, methyl acrylate, methacrylonitrile, methyl styrene, vinyl esters, vinyl chloride, vinylidene chloride, acrylamide, tetrafluoroethene, vinyl acetate, methyl-vinyl ketone, ethene, styrene, p-methoxystyrene, p-cyano styrene and acrylate etc. or various of monomer.
Described transparency dielectric layer has DRAM and electrochromic property, and this type of material comprises: the one in organic and metallo organic material, inorganic material, polymeric material or its any combination.
Wherein, described organic and metallo organic material can be selected from following a few class material:
(i) poly methylene imine and derivant thereof;
(ii) viologen (4,4'-bipyridine salt) or derivatives thereof;
As preferably, described viologen is methyl viologen (MV);
(iii) azole compounds or derivatives thereof;
As preferably, described azole compounds is two (4,1-phenylene)-bis-(diazene-2,1-bis-base)-bis-(N, the N xylidin) of 4,4'-(1E, 1'E)-4,4'-sulphonyl;
(iv) arylamine race or derivatives thereof;
(v) carbazole quinoline or derivatives thereof;
(vi) cyanine or derivatives thereof;
(vii) methoxyl biphenyl or derivatives thereof;
(viii) quinones and derivant thereof;
(ix) thiazine or derivatives thereof;
(x) pyrazoline or derivatives thereof;
(xi) four cyano quinoline promise bismethane (TCNQ);
(xii) tetrathiafulvalene (TTF);
(xiii) [M
iI(the two pyridine of 2,2'-)]
2+or [M
iI(the two pyridine of 2,2'-)
2(the two pyridine-pyridine of 4 monomethyl-2,2'-)
2+, wherein said M is iron, ruthenium, osmium, nickel, chromium, copper, rhodium, iridium, cobalt or polypyridine Base Metal misfit thing;
Described polypyridine Base Metal misfit thing includes but not limited to three (4-[2-(4-pyridine radicals) vinyl]-4'-methyl-2, 2'-dipyridine starves (II) two (hexafluorophosphoric acid), three (4-[2-(4-pyridine radicals) vinyl]-4'-methyl 2, 2'-dipyridine cobalt (II) two (hexafluorophosphoric acid), three (4-[2-(4-pyridine radicals) vinyl]-4'-methyl 2, 2'-dipyridine) ruthenium (II) two (hexafluorophosphoric acid), two (2, 2'-dipyridine) [4'-methyl-4-(2-(4-pyridine radicals) vinyl)-2, 2'-dipyridine] starve (II) [two (hexafluorophosphoric acid)/diiodo-], two (2, 2'-dipyridine) [4'-methyl-4-(2-(4-pyridine radicals) vinyl)-2, 2'-dipyridine] ruthenium (II) [two (hexafluorophosphoric acid)/diiodo-], two (2, 2'-dipyridine) [4'-methyl-4-(2-(4-(3-propyl trimethoxy silicane) pyridine) vinyl)-2, 2'-dipyridine] osmium (II) [three (hexafluorophosphoric acid)/diiodo-s] or two (2, 2'-dipyridine) [4'-methyl-4-(2-(4-(3-propyl trimethoxy silicane) pyridine) vinyl)-2, 2'-dipyridine] ruthenium (II) [three (hexafluorophosphoric acid)/diiodo-s] etc.,
(xiv) in monomer, the metallophthalocyanine of clamping or polymerized form or porphyrin;
(xv) metal six ammonobase compound;
(xvi) the dithiole misfit thing of nickel, palladium or platinum;
(xvii) to starve or the dioxy alkene misfit thing of ruthenium;
(xviii) the mixed valence misfit thing of ruthenium, osmium or iron;
Described inorganic material includes but not limited to tungsten oxide, yttrium oxide, vanadium oxide, nickel oxide, molybdena, titanium dioxide, manganese oxide, niobium oxide, cupric oxide, be oxidized smooth, rheium oxide, rhodium oxide, ruthenium-oxide, iron oxide, chromium oxide, cobalt oxide, cerium oxide, bismuth oxide, tin oxide, praseodymium, bismuth, plumbous, silver, hydrogenation lanthanum (LaH2/LaH3), nickel doping SrTiO3, indium nitride, dithiole ruthenium, phosphotungstic acid, ferrocene-naphthalimide two compound, one or more potpourri in organic ruthenium misfit thing.
Described polymeric material is conducting polymer, include but not limited to polypyrrole, poly-(3, 4-ethylene dioxythiophene) (PEDOT), poly-(3, 4-propylene dioxy base) blind fen PProDOT, poly-(2, the two dodecyloxy benzene of 4-ethylene dioxythiophene), poly-dioxypyrrole, poly-(3, 4-ethylene dioxythiophene): poly-(styrene sulphonate) (PEDOT:PSS), polythiophene, polyaniline, polyacetylene, poly-(to sub-benzene sulphur), poly-(to phenylenevinylenes) (PPV), poly-indoles, poly-pyrene, polycarbazole, poly-azulenes, poly-azatropylidene, polyfluorene, poly-naphthalene, poly-furans, based on the potpourri of one or more in the metallized polymer film of polypyridine misfit thing or polymerization viologen system etc. and derivant thereof.
The described metallized polymer film based on polypyridine misfit thing or polymerization viologen system comprise pyridine replacement viologen, pyridine two replaces viologen, two (3-pyrroles-1-base propyl group)-4,4'-dipyridines and the derivant etc. thereof of N, N'-.
The preparation method that the present invention has the display device of information storage function is: in transparent substrates through method cleaning that is chemical or physics, then the depositing system of physics or chemistry is put into, clear bottom electrode is formed at transparent substrates surface deposition, then transparent polymer dielectric substrate is formed in clear bottom electrode surface deposition, form transparency dielectric layer in transparent polymer electrolyte layer surface deposition, finally form transparent top electrode at transparency dielectric layer surface deposition.
Described depositing system includes but not limited to PVD (physical vapour deposition (PVD)), ALD (ald), CVD (chemical vapor deposition) etc.
Described transparent dielectric layer thickness can from a few nm to hundreds of um.
Experiment confirms, when the display device having an information storage function to the present invention applies different voltage, this device shows information storage function on the one hand, that is, when applying different voltage, device shows different resistance states (being called for short high-impedance state and low resistance state), and high low resistance state is more stable, on-off ratio is stablized, can erasing writing successive tens of time, the cyclicity of device is better; Meanwhile, this device shows electrochromic property, and the change of this color changes synchronous with resistance states.Namely, under electric field action, electronics in transparent polymer dielectric substrate and negative ion or kation (when comprising negative ion, kation in transparent polymer dielectric substrate) embed in transparent dielectric layer material, the transmitance of device is changed, thus makes device show different colors; When polarity of voltage changes, the ion embedded in dielectric layer can be deviate from from dielectric layer, and device returns to again the color of intrinsic.
When comprising negative ion, kation in transparent polymer dielectric substrate, as a kind of implementation, display device the present invention to information storage function does not apply voltage, applies forward voltage, and applies reverse voltage, and its resistance state and color change as follows:
(1) voltage is not applied
Described device is in high-impedance state, shows its intrinsic color, i.e. color one.
(2) forward voltage scanning (0 → V
max→ 0)
When voltage is from 0 forward scan, the electronics in transparent polymer dielectric substrate, negative ion or kation embed in transparent dielectric layer material gradually, and device is changed to low resistance state by high-impedance state, and device color is changed to color two by intrinsic color one simultaneously.
(3) negative voltage scanning (0 → V
min→ 0)
When voltage scans constantly from 0 negative sense, the electronics in transparent polymer dielectric substrate, negative ion or kation embed in transparent dielectric layer material gradually, and device is changed to low resistance state by high-impedance state, and device color is changed to color three by intrinsic color one simultaneously.
Therefore, this device has memory function and Presentation Function simultaneously, can be used in optics or photoelectricity device or product.In addition, this device has good light transmission in ultraviolet-visible light-near infrared range, certainly will be used widely in optics, electricity, storer, display, photoelectricity storage, photoelectric display, Transparence Display and crossing domain thereof, for optics, electricity, storer, display, photoelectricity storage, photoelectric display, Transparence Display and the integrated of crossing domain thereof provide effective way.
Accompanying drawing explanation
Fig. 1 is cross-sectional view, shows the structural representation that the present invention has the display device of information storage function;
Fig. 2 is photo figure, shows the change that the embodiment of the present invention 1 has display device color under electric field action of information storage function;
Fig. 3 is curve map, shows light transmission rate when display device that the embodiment of the present invention 1 has an information storage function does not apply electric field;
Fig. 4 .1 is curve map, shows the light transmission rate of display device under positive field effect that the embodiment of the present invention 1 has information storage function;
Fig. 4 .2 is curve map, shows the light transmission rate of display device under negative sense electric field action that the embodiment of the present invention 1 has information storage function;
Fig. 5 is curve map, shows the I-V curve that the embodiment of the present invention 1 has the display device of information storage function;
Fig. 6 is curve map, shows the high low resistance state transformation test result figure of display device in loop test that the embodiment of the present invention 1 has information storage function.
Embodiment
Below with reference to drawings and Examples, the present invention will be further described.It is pointed out that the following stated embodiment is intended to be convenient to the understanding of the present invention, and any restriction effect is not play to it.Accompanying drawing is intended to the general characteristic that the method, structure and/or the material that adopt in embodiment are shown, and supplements the following written description provided.But these accompanying drawings are not in proportion and can not reflect precision architecture or the Performance Characteristics of any given embodiment accurately, and should not be interpreted as limiting or the restriction numerical value contained of embodiment or performance range.Such as, clear in order to state, the relative thickness of layer, region and/or structural detail, shape and position can be reduced, exaggerate or change.
Embodiment 1:
In the present embodiment, there is the structure of the display device of information storage function as shown in Figure 1, comprise transparent substrates, be formed in the clear bottom electrode layer on transparent substrates surface, be formed in the transparent polymer dielectric substrate of clear bottom electrode layer surface, be formed in the transparency dielectric layer of transparent polymer electrolyte layer surface, and be formed in the transparent top electrode layer on transparency dielectric layer surface.
Non-transparent substrate material is quartz, and clear bottom electrode material and transparent top electrode material are all ITO, and transparent dielectric layer material is poly methylene imine, and transparent polymer dielectric substrate is lithium perchlorate (LiClO
4), the potpourri of polymethylmethacrylate (PMMA), ethylene carbonate (EC) and carbonic allyl ester (PC).
Transparent polymer dielectric substrate is formed on clear bottom electrode layer by the mode of polymerization, spin coating, LB or self assembly.Transparency dielectric layer is formed on organic transparent polymer dielectric substrate by the mode of electrochemical polymerization, spin coating, LB or self assembly.
In the present embodiment, the molecular structure of poly methylene imine is as shown below:
Carry out transmission measurement to the display device with information storage function in the present embodiment, as shown in Figure 2, before not applying voltage, device has very high permeability at 400nm to 1100nm to result, and transmitance is more than 85%.
Constant voltage is applied to the display device with information storage function in the present embodiment.As shown in Figure 3, when voltage be 0V or do not apply voltage time, device shows as color one, and this is the color of poly methylene imine intrinsic; When applying voltage and being about 2V, device shows as color two; When applying voltage and being about-2.2V, device shows as color three.Although do not illustrate concrete color in Fig. 3, color one, color two, color three are all different.
Carry out continuous print transmission measurement to the display device with information storage function in the present embodiment, result is as shown in Fig. 4 .1 and Fig. 4 .2.As can be seen from Fig. 4 .1 and Fig. 4 .2, along with forward executes alive increase, transmittance curve has engendered new peak, and when voltage is about 2V, device shows as color two; Along with negative sense executes alive increase, transmittance curve has engendered new peak, and when voltage is about-2.2V, device shows as color three.Color one, color two and color three and the solid colour shown with Fig. 3 respectively.
Carry out voltage scanning to the above-mentioned display device with information storage function, sweep limit is-3V-+3V, and scanning step is 0.01V, Limited Current be 1mA, I-V curve as shown in Figure 5.
(1) forward voltage scanning (0 → 3V → 0)
When voltage increases gradually from 0 forward, electric current remains unchanged substantially along curve 1, and now device is in high-impedance state, and resistance is about 10
7-10
8Ω, device is color one, i.e. the color of its intrinsic.
When voltage forward is increased to voltage V
1(V
1be about 1.83V) time, electric current increases along curve 2 jumping characteristic, and continuing increases voltage, and electric current linearly increases along curve 3, and now device is in low resistance state, and resistance is about 10
4Ω; Meanwhile, in this stage, due to ClO
4 -be combined with the imine linkage of poly methylene imine in a large amount of embedding poly methylene imine film, cause poly methylene imine variable color, thus device is color two.
After voltage is increased to 3V, reduce voltage gradually, electric current linearly reduces along curve 4, now embeds the ClO of poly methylene imine
4 -reverse migration, poly methylene imine changes to intrinsic color gradually, and when voltage is 0, device becomes intrinsic color.
(2) negative voltage scanning (0 →-3V → 0)
When voltage increases gradually from 0 negative sense, electric current remains unchanged substantially along curve 5, and now device is in high-impedance state, and resistance is about 10
7-10
8Ω, device is color one.
When voltage negative is to being increased to voltage V
2time (V
2be about-2.28V), electric current increases along curve 6 jumping characteristic, and continuing increases voltage, and electric current linearly increases along curve 7, and now device is in low resistance state, and resistance is about 10
4Ω; Meanwhile, in the devices due to Li
+be combined with the nitrogen-atoms of poly methylene imine in a large amount of embedding poly methylene imine film, cause poly methylene imine variable color, device shows as color three.
Voltage negative reduces gradually to negative sense after being increased to-3V, and electric current linearly reduces along curve 8, now embeds the Li of poly methylene imine
+can oppositely move, poly methylene imine changes to the color of intrinsic again gradually, and when voltage is 0, device becomes intrinsic color one.
Carry out anti-fatigue performance test to the display device with information storage function in the present embodiment, result as shown in Figure 6, shows the circulation more than 50 times that this device can be stable.
Embodiment 2:
In the present embodiment, the structure with the display device of information storage function is substantially identical with the structure in embodiment 1, and difference is transparent dielectric material is viologen (4,4'-bipyridine salt).This transparent dielectric material is formed on transparent polymer dielectric substrate by the mode of electrochemical polymerization, spin coating, LB or self assembly.
Carry out transmission measurement to the display device with information storage function in the present embodiment, before result is presented at and does not apply voltage, this device has high permeability in visible region.
In the present embodiment, based on the electrochromism of the display device of the information storage function of viologen (4,4'-bipyridine salt) and resistive process as follows:
Before making alive, viologen is in oxidized state, and now device is in high-impedance state, Show Color one, i.e. the color of its intrinsic.
(1) forward voltage scanning (0 → V
max→ 0)
When voltage increases gradually from 0 forward, negative ion in transparent polymer dielectric substrate embeds in viologen film gradually, viologen starts to lose electronics, changed to semi-oxidation state by oxidized state gradually, device has high-impedance state to change to low resistance state, and device color is changed to color two by intrinsic color one simultaneously.
Increase when voltage continues forward, the electronics trend of viologen all loses, and finally become reduction-state, device gets back to high-impedance state again, now device Show Color three.
(2) negative voltage scanning (0 → V
min→ 0)
When voltage increases gradually from 0 negative sense, kation in transparent polymer dielectric substrate embeds in viologen film gradually, and viologen starts to obtain electronics, is changed gradually by reduction-state to semi-oxidation state, device is changed to low resistance state by high-impedance state, and device color is changed by color three-dimensional color two simultaneously.
Increase when voltage continues negative sense, viologen obtains maximum electronics gradually, and finally become oxidized state, device gets back to low resistance state again, now device Show Color one.
Embodiment 3:
In the present embodiment, the structure with the display device of information storage function is substantially identical with the structure in embodiment 1, and difference is transparent dielectric material is WO
3metal oxide.This transparent dielectric material is deposited on organic transparent polymer dielectric substrate by physics or chemical deposition.
Carry out transmission measurement to the display device with information storage function in the present embodiment, before result is presented at and does not apply voltage, this device has high permeability in visible region.
Before making alive, device is in high-impedance state, Show Color one, i.e. the color of its intrinsic.
(1) forward voltage scanning (0 → V
max→ 0)
When voltage increases gradually from 0 forward, the electronics in transparent polymer dielectric substrate and kation inject sull simultaneously, and device is changed to low resistance state by high-impedance state, and device color is changed to color two by intrinsic color one simultaneously.
(2) negative voltage scanning (0 → V
min→ 0)
When voltage increases gradually from 0 negative sense, electronics and kation are deviate from simultaneously from the sull transparent polymer dielectric substrate, and device is changed to high-impedance state by low resistance state again, and device color is changed to intrinsic color one by color two simultaneously.
Embodiment 4:
In the present embodiment, the structure with the display device of information storage function is substantially identical with the structure in embodiment 1, and difference is transparent dielectric material is metal phthalocyanine.This transparent dielectric material is formed on organic transparent polymer dielectric substrate by the mode of electrochemical polymerization, spin coating, LB or self assembly.
In the present embodiment, the molecular structure of metal phthalocyanine is as follows:
This metal phthalocyanine molecule can form chelate with many metal ion species, has electrochromism and change resistance performance.Metal phthalocyanine is the electrochromic material of chelate type, and metallic ion is positioned at the center of Phthalocyanine, also has metallic ion to be positioned at the middle sandwich structure of two phthalocyanine rings.
Carry out transmission measurement to the display device with information storage function in the present embodiment, before result is presented at and does not apply voltage, this device has high permeability in visible region.
Before making alive, this device is in high-impedance state, Show Color one, i.e. the color of its intrinsic.
(1) forward voltage scanning (0 → V
max→ 0)
When voltage increases gradually from 0 forward, negative ion in transparent polymer dielectric substrate embeds in Metal phthalocyanine film gradually, and metal phthalocyanine loses electronics, and oxidation reaction occurs, device is changed to low resistance state by high-impedance state, and device color is changed to color two by intrinsic color one simultaneously.
(2) negative voltage scanning (0 → V
min→ 0)
When voltage increases gradually from 0 negative sense, kation in transparent polymer dielectric substrate embeds in Metal phthalocyanine film gradually, and metal phthalocyanine obtains electronics, and reduction reaction occurs, device is changed to low resistance state by high-impedance state, and device color is changed to color one by color two simultaneously.
Embodiment 5:
In the present embodiment, the structure with the display device of information storage function is substantially identical with the structure in embodiment 3, and difference is transparent dielectric material is MoO
3metal oxide.
Carry out transmission measurement to the display device with information storage function in the present embodiment, before result is presented at and does not apply voltage, this device has high permeability in visible region.
Before making alive, this device is in high-impedance state, Show Color one, i.e. the color of its intrinsic.
(1) forward voltage scanning (0 → V
max→ 0)
When voltage increases gradually from 0 forward, the electronics in transparent polymer dielectric substrate and kation inject sull simultaneously, and device is changed to low resistance state by high-impedance state, and device color is changed to color two by intrinsic color one simultaneously.
(2) reverse voltage scanning (0 → V
min→ 0)
When voltage increases gradually from 0 negative sense, electronics and kation are deviate from simultaneously from the sull transparent polymer dielectric substrate, and device is changed to high-impedance state by low resistance state again, and device color is changed to intrinsic color one by color two simultaneously.
Embodiment 6:
In the present embodiment, the structure with the display device of information storage function is substantially identical with the structure in embodiment 3, and difference is transparent dielectric material is V
2o
5metal oxide.
Carry out transmission measurement to the display device with information storage function in the present embodiment, before result is presented at and does not apply voltage, this device has high permeability in visible region.
Before making alive, this device is in high-impedance state, Show Color one, i.e. the color of its intrinsic.
(1) forward voltage scanning (0 → V
max→ 0)
When voltage increases gradually from 0 forward, the electronics in transparent polymer dielectric substrate and kation inject sull simultaneously, and device is changed to low resistance state by high-impedance state, and device color is changed to color two by intrinsic color one simultaneously.
(2) reverse voltage scanning (0 → V
min→ 0)
When voltage increases gradually from 0 negative sense, electronics and kation are deviate from simultaneously from the sull transparent polymer dielectric substrate, and device is changed to high-impedance state by low resistance state again, and device color is changed to intrinsic color one by color two simultaneously.
Embodiment 7-22:
In the present embodiment, the structure with the display device of information storage function is substantially identical with the structure in embodiment 1, and difference is transparent dielectric material is azole respectively, arylamine race, carbazole quinoline, cyanine, methoxyl biphenyl, quinones, thiazine, pyrazoline, four cyano quinoline promise bismethane (TCNQ), tetrathiafulvalene (TTF), [M
iI(the two pyridine of 2,2'-)]
2+or [M
iI(the two pyridine of 2,2'-)
2(the two pyridine-pyridine of 4 monomethyl-2,2'-)
2+, in monomer, the metallophthalocyanine of clamping or polymerized form or porphyrin, metal six ammonobase compound, the dithiole misfit thing of nickel, palladium or platinum, starves or the dioxy alkene misfit thing of ruthenium, the mixed valence misfit thing of ruthenium, osmium or iron.
Carry out transmission measurement to the display device with information storage function in above-described embodiment 7-22, before result is presented at and does not apply voltage, this device has high permeability in visible region.
When applying different voltage to the display device with information storage function in above-described embodiment 7-22, device not only has different resistance states, has color change simultaneously, and can erasing writing successive tens times, has very high transmitance.Therefore can be used in optics, electricity, storer, display, photoelectricity storage, photoelectric display, Transparence Display and crossing domain thereof, effective way can be provided for memory device and the integrated of display device.
Above-described embodiment is used for explaining and the present invention is described, instead of limits the invention, and in the protection domain of spirit of the present invention and claim, any amendment make the present invention and change, all fall into protection scope of the present invention.
Claims (12)
1. one kind has the display device of information storage function, it is characterized in that, comprise transparent substrates, be formed in the clear bottom electrode layer on transparent substrates surface, be formed in the transparent polymer dielectric substrate of clear bottom electrode layer surface, be formed in the transparency dielectric layer of transparent polymer electrolyte layer surface, and be formed in the transparent top electrode layer on transparency dielectric layer surface; Further, described transparent substrates is insulator, and transparent polymer dielectric substrate has good electric conductivity, and transparency dielectric layer has DRAM character and electrochromism property.
2. there is the display device of information storage function as claimed in claim 1, it is characterized in that, described transparent substrates is one or more combined material of glass, jewel, transparent oxide material, transparent nitride material, transparent macromolecular material.
3. have the display device of information storage function as claimed in claim 1, it is characterized in that, described clear bottom electrode layer and transparent top electrode layer are formed by transparent conductive oxide or transparent conductive nitride.
4. there is the display device of information storage function as claimed in claim 1, it is characterized in that, described transparent polymer electrolyte layer comprises ionic liquid and organic polymer insulator, the salt that described ionic liquid is made up of kation and negative ion.
5. there is the display device of information storage function as claimed in claim 4, it is characterized in that, described kation comprises one or several kations in lithium ion, ammonium ion, imidazoles, oxazole, piperidines, pyrazine, pyrazoles, pyridazine, pyridine, pyrimidine, pyrrolidine, pyrrolin, pyrroles, thiazole, triazole, 4,4'-Bipyridine;
Described negative ion comprises F
-, Cl
-, Br
-, I
-, NO
3 -, N (CN)
2 -, BF
4 -, ClO
4 -, RSO
3 -, RCOO
-(wherein, R is alkyl or phenyl), PF
6 -, (CF
3)
2pF
4 -, (CF
3)
3pF
3 -, (CF
3)
4pF
2 -, (CF
3)
5pF
-, (CF
3)
6pF
-, (CF
3sO
3 -)
2, (CF
3cF
2sO
3 -)
2, (CF
3sO
3 -)
2n
-, CF
3cF
2(CF
3)
2cO
-, (CF
3sO
2)
2cH
-, (SF
5)
3c
-, (CF
3sO
3 -)
3c
-, CF
3(CF
2 -)
7sO
3 -, CF
3cO
2 -and CH
3cO
2 -in one or more mixed anion.
6. there is the display device of information storage function as claimed in claim 4, it is characterized in that, described organic polymer insulator comprises vinyl cyanide, methyl methacrylate, hydroxyethyl methylacrylate, methyl acrylate, methacrylonitrile, methyl styrene, vinyl esters, vinyl chloride, 1, 1-dichloroethylene, 1, 1-difluoroethylene, acrylamide, tetrafluoroethene, vinyl acetate, methyl-vinyl ketone, ethene, styrene, p-methoxystyrene, the polymeric material that one or more mix monomer in the vinyl monomers such as p-cyano styrene and acrylate and oxirane is polymerized.
7. have the display device of information storage function as claimed in claim 1, it is characterized in that, described transparent polymer electrolyte layer is the polymeric material that monomer is obtained by polyreaction, and described monomer comprises kation and negative ion.
8. there is the display device of information storage function as claimed in claim 7, it is characterized in that, described kation comprises one or several kations in lithium ion, ammonium ion, imidazoles, oxazole, piperidines, pyrazine, pyrazoles, pyridazine, pyridine, pyrimidine, pyrrolidine, pyrrolin, pyrroles, thiazole, triazole, 4,4'-Bipyridine;
Described negative ion comprises F
-, Cl
-, Br
-, I
-, NO
3 -, N (CN)
2 -, BF
4 -, ClO
4 -, RSO
3 -, RCOO
-(wherein, R is alkyl or phenyl), PF
6 -, (CF
3)
2pF
4 -, (CF
3)
3pF
3 -, (CF
3)
4pF
2 -, (CF
3)
5pF
-, (CF
3)
6pF
-, (CF
3sO
3 -)
2, (CF
3cF
2sO
3 -)
2, (CF
3sO
3 -)
2n
-, CF
3cF
2(CF
3)
2cO
-, (CF
3sO
2)
2cH
-, (SF
5)
3c
-, (CF
3sO
3 -)
3c
-, CF
3(CF
2 -)
7sO
3 -, CF
3cO
2 -and CH
3cO
2 -in one or more mixed anion.
9. have the display device of information storage function as claimed in claim 7, it is characterized in that, described transparent dielectric layer material is selected from the combination of one or more in organic and metallo organic material, inorganic material, polymeric material;
Described organic and metallo organic material is selected from the one in following material:
(i) poly methylene imine and derivant thereof;
(ii) viologen (4,4'-bipyridine salt) or derivatives thereof;
(iii) azole compounds or derivatives thereof;
(iv) arylamine race or derivatives thereof;
(v) carbazole quinoline or derivatives thereof;
(vi) cyanine or derivatives thereof;
(vii) methoxyl biphenyl or derivatives thereof;
(viii) quinones and derivant thereof;
(ix) thiazine or derivatives thereof;
(x) pyrazoline or derivatives thereof;
(xi) four cyano quinoline promise bismethane (TCNQ);
(xii) tetrathiafulvalene (TTF);
(xiii) [M
iI(the two pyridine of 2,2'-)]
2+or [M
iI(the two pyridine of 2,2'-)
2(the two pyridine-pyridine of 4-methyl-2,2'-)
2+, wherein said M is iron, ruthenium, osmium, nickel, chromium, copper, rhodium, iridium, cobalt or polypyridine Base Metal misfit thing;
(xiv) in monomer, the metallophthalocyanine of clamping or polymerized form or porphyrin;
(xv) metal six ammonobase compound;
(xvi) the dithiole misfit thing of nickel, palladium or platinum;
(xvii) to starve or the dioxy alkene misfit thing of ruthenium;
(xviii) the mixed valence misfit thing of ruthenium, osmium or iron;
Described inorganic material is selected from tungsten oxide, yttrium oxide, vanadium oxide, nickel oxide, molybdena, titanium dioxide, manganese oxide, niobium oxide, cupric oxide, be oxidized smooth, rheium oxide, rhodium oxide, ruthenium-oxide, iron oxide, chromium oxide, cobalt oxide, cerium oxide, bismuth oxide, tin oxide, praseodymium, bismuth, plumbous, silver, hydrogenation lanthanum, nickel doping SrTiO3, indium nitride, dithiole ruthenium, phosphotungstic acid, ferrocene-naphthalimide two compound, one or more potpourri in organic ruthenium misfit thing,
Described polymeric material is selected from polypyrrole, poly-(3, 4-ethylene dioxythiophene) (PEDOT), poly-(3, 4-propylene dioxy base) blind fen PProDOT, poly-(2, the two dodecyloxy benzene of 4-ethylene dioxythiophene), poly-dioxypyrrole, poly-(3, 4-ethylene dioxythiophene): poly-(styrene sulphonate) (PEDOT:PSS), polythiophene, polyaniline, polyacetylene, poly-(to sub-benzene sulphur), poly-(to phenylenevinylenes) (PPV), poly-indoles, poly-pyrene, polycarbazole, poly-azulenes, poly-azatropylidene, polyfluorene, poly-naphthalene, poly-furans, based on the potpourri of one or more in the metallized polymer film of polypyridine misfit thing or polymerization viologen system and derivant thereof.
10. have the display device of information storage function as claimed in claim 9, it is characterized in that, described viologen is methyl viologen (MV);
Described azole compounds is two (4,1-phenylene)-bis-(diazene-2,1-bis-base)-bis-(N, the N-dimethyl-aniline) of 4,4'-(1E, 1'E)-4,4'-sulphonyl;
Described polypyridine Base Metal misfit thing comprises three (4-[2-(4-pyridine radicals) vinyl]-4'-methyl-2, (II) two (hexafluorophosphoric acid) starved by 2' pyridine, three (4-[2-(4-pyridine radicals) vinyl]-4'-methyl 2, 2'-dipyridine cobalt (II) two (hexafluorophosphoric acid), three (4-[2-(4-pyridine radicals) vinyl]-4'-methyl-2, 2'-dipyridine) ruthenium (II) two (hexafluorophosphoric acid), two (2, 2'-dipyridine) [4'-methyl-4-(2-(4-pyridine radicals) vinyl)-2, 2'-dipyridine] starve (II) [two (hexafluorophosphoric acid)/diiodo-], two (2, 2'-dipyridine) [4'-methyl-4-(2-(4-pyridine radicals) vinyl)-2, 2'-dipyridine] ruthenium (II) [two (hexafluorophosphoric acid)/diiodo-], two (2, 2'-dipyridine) [4'-methyl-4-(2-(4-(3-propyl trimethoxy silicane) pyridine) vinyl)-2, 2'-dipyridine] osmium (II) [three (hexafluorophosphoric acid)/diiodo-s] or two (2, 2'-dipyridine) [4'-methyl-4-(2-(4-(3-propyl trimethoxy silicane) pyridine) vinyl)-2, 2'-dipyridine] combination of one or more in ruthenium (II) [three (hexafluorophosphoric acid)/triiodos] etc.,
The described metallized polymer film based on polypyridine misfit thing or polymerization viologen system comprise that pyridine replaces viologen, pyridine two replaces viologen, two (3-pyrroles-1-base propyl group)-4, the 4'-dipyridines of N, N'-and derivant thereof.
11. display devices with information storage function as described in claim 4 or 7, is characterized in that, do not apply voltage, apply forward voltage, and when applying negative voltage, the resistance state of described display device and color change as follows:
(1) voltage is not applied
Described device is in high-impedance state, Show Color one;
(2) forward voltage scanning (0 → V
max→ 0)
When voltage is from 0 forward scan, the electronics in transparent polymer dielectric substrate, negative ion or kation embed in transparent dielectric layer material gradually, and device is changed to low resistance state by high-impedance state, and device color is changed to color two by intrinsic color one simultaneously;
(3) negative voltage scanning (0 → V
min→ 0)
When voltage is from 0 negative sense scanning, the electronics in transparent polymer dielectric substrate, negative ion or kation embed in transparent dielectric layer material gradually, and device is changed to low resistance state by high-impedance state, and device color is changed to color three by intrinsic color one simultaneously.
The method with the display device of information storage function of 12. preparations as described in claim arbitrary in claim 1 to 11, it is characterized in that, in transparent substrates through method cleaning that is chemical or physics, then the depositing system of physics or chemistry is put into, clear bottom electrode is formed at transparent substrates surface deposition, then transparent polymer dielectric substrate is formed in clear bottom electrode surface deposition, form transparency dielectric layer in transparent polymer electrolyte layer surface deposition, finally form transparent top electrode at transparency dielectric layer surface deposition.
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