CN101280054A - Conjugated polymer containing iridium complex and preparation of electrical storage device thereof - Google Patents
Conjugated polymer containing iridium complex and preparation of electrical storage device thereof Download PDFInfo
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- CN101280054A CN101280054A CNA200810025558XA CN200810025558A CN101280054A CN 101280054 A CN101280054 A CN 101280054A CN A200810025558X A CNA200810025558X A CN A200810025558XA CN 200810025558 A CN200810025558 A CN 200810025558A CN 101280054 A CN101280054 A CN 101280054A
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Abstract
The preparation methods for conjugated polymer containing iridium complexes and the related electrical memory component of conjugated polymer comprise the following steps: ITO conductive glass is washed by water, acetone and 2-propanol respectively in ultrasonic wave; the conjugated polymer containing iridium complexes in the patent claim 1 is used as memory material to prepare polymer solution with concentration of 0.1-500mg/mL; the polymer solution is then spin-coated on the ITO conductive glass; the solvent is removed under vacuum to obtain the polymer membrane. Gold, aluminum, copper and other metal are used as the upper electrode after vapor plating, while the ITO conductive glass is used as the lower electrode; the polymer material is used as memory medium to prepare and obtain the monolayer polymer memory component. Such polymer contains donating electron units (fluorine unit and others) and withdrawing electron units (iridium complexes) at the same time. The materials presented in the invention can form membrane through spin-coating, without the problem of uneven disperse of heavy metal complexes; based on needs, other functional groups can be introduced into the polymer molecular chain to be expected to prepare highly-efficient and stable memory components.
Description
Technical field
The present invention relates to a class and contain the conjugated polymers electricity storage medium of complex of iridium and the preparation of electrical storage device thereof.Belong to electricity storage novel material and technical field.
Background technology
The fast development of digital products such as mobile phone, PDA, digital camera, Digital Video, flash disk, MP3 player makes the demand sharp increase of electric storage chip.This shows that electricity storage has become on the semi-conductor market staggering growth point.With the inorganic semiconductor material is the switch and the memory device of medium, because its proven technique has obtained using widely in current message area.But because the restriction and the production cost of photoetching technique are exponential growth with size decreases, and this material has reached the limit of its research and development gradually, the chip manufacturing size can not be gone down ad infinitum for a short time in recent years.Under Moore's Law promoted, semi-conductor industry constantly satisfied the market requirement that cost descends and performance improves with minification to improve integrated level.But Technology is not easy to realize that outstanding performance is the problems such as decrease in yield of chip transistor leakage and device.The main supplier of world's storage market recognizes this technology limitation already, and therefore in order to satisfy more high-performance, more low-cost demand of future, they drop into the new memory technology that the huge fund exploitation is intended to substitute prior art one after another.
In recent years, owing to having characteristics such as switch and information storage, the functional device of organic molecule material is subjected to extensive concern.Because this type of material and element manufacturing are simple, cost is low, and there is the potential ability to break through the dimension limit of silicon integrated circuit, thereby has very big researching value.Before the research of electricity storage medium and device starts from 50 years, scientists has proposed to prepare with organic film the imagination of memory device very early, but at that time because its technology is immature, the principle complexity, be difficult to find good reasons such as organic molecule storage media, make this technology not make a breakthrough always.Along with being that the electrical bistable property of charge-transfer complex of representative and the research of device are in the news with Ag-TCNQ and Cu-TCNQ etc., in addition organic functional material have volume little, in light weight, form good characteristics such as changeable, the easy processing of structure, cost is low, make its concern that has obtained the investigator again, and then obtained developing rapidly.In recent years, reported the organic film material (1013bits/cm that can realize Ultrahigh-Density Data Storage both at home and abroad in succession
2); The single organic film (transition between states time 5-10ns) that is used for supper-fast information storage; Information is wiped, is write number of times and reaches 1,000,000 times metal and organic interlayer thin-film device etc.A large amount of organic materialss include organic dye, charge transfer complex body, conjugation oligomer redox complex body or the like, have been successfully applied to dynamo-electric field of storage.Have the storage of data in the electromechanical memory devices different with silicon-based devices, be by under applied voltage, and data are stored in the high conductivity of organic materials and the variation of low electric conductivity.Replace memory device that traditional inorganic semiconductor makes novel high-density, supper-fast, high stability just in the near future with organic molecule material.
Compare with organic molecule, polymkeric substance has the favorable mechanical processing characteristics, can spin-coating film, cut down finished cost, and obtain large-area high-quality thin film.And polymer thermostable is good, can prolong device lifetime.In addition, polymer architecture is changeable, can the synthesizing new structure and the material of specific function.So on highly integrated, high-impact performance and processing characteristics, have clear superiority.The most outstanding advantage of electrostrictive polymer storage is to obtain very highdensity storage by three-dimensional stacked technology, and its storage potentiality are quite huge.AMD (having annexed Coatue) company has realized the plastics storage antetype device of 32Gbit in the laboratory at present.Another advantage is to make polymer memory not need high temperature, high vacuum, the high-precision expensive device of producing the semi-conductor chip with resembling, and might produce cost polymer memory extremely cheap, jettisonable.Although just just began in these several years the production technique of polymer memory is researched and developed, it becomes the most possible new memory technology that replaces present electric memory technology except that MRAM, FeRAM, OUM gradually.
The polymkeric substance that contains complex of iridium has been successfully applied to photodiode, and number of research projects proves that this is the semiconductor material of a class excellent performance.With the method for copolymerization, complex of iridium is introduced the LARGE CONJUGATE MOLECULES chain, the stability of phosphorescent substance in polymeric matrix is increased, can bring into play the advantage of conjugated polymer material and avoid the shortcoming of co-mixing system.This class conjugate class polymkeric substance has characteristic of semiconductor, can strengthen the flowability of electric charge in system, and expectation can obviously improve the over-all properties of polymer memory device, as reducing read-write voltage, the joule heating that produces when reducing to move, improving device stability etc.But the systematic study of correlated performance is still waiting further to carry out.
Summary of the invention
Technical problem: the object of the present invention is to provide a kind of conjugated polymers electricity storage medium that contains complex of iridium and with the preparation method of this polymkeric substance as the electrical storage device of active material.This base polymer contains simultaneously and pushes away electronic unit (unit such as fluorenes) and draw electronic unit (complex of iridium), has electric bistable character, can realize its application in electrical storage device.But the material spin-coating film that contains among the present invention does not exist heavy metal complex to disperse uneven problem, and can introduce other functional groups as required in polymer molecular chain, is expected to prepare efficient, stable memory device.
Technical scheme: the conjugated polymers that the present invention attempts a class is contained complex of iridium prepares corresponding electrical storage device as electric storage medium, and relates to the preparation technology of corresponding device, improves the efficient and the stability of device.The present invention adopts the Suzuki reaction to synthesize eka-iridium complex polymerisation thing material, and the structural formula of compound is as follows:
Wherein, R is the alkyl that contains 1 to 12 carbon;
Wherein,
For can with Ir coordinate N, N heterogeneous ring compound;
Wherein, L be can with iridium coordinate C, N heterogeneous ring compound;
Wherein, m is the unitary quantity of fluorenes in the polymer chain, and n is the unitary quantity of complex of iridium in the polymer chain.The scope of m and n is 0.1≤m≤100,0.1≤n≤100, n/ (m+n) 〉=0.1%.
According to above-described compound structure, enumerate wherein three kinds as follows:
R is that carbonatoms is 8 alkyl chain;
Be 2,2-dipyridyl unit, L is a 1-phenyl isoquinolin quinoline, the title complex red-emitting.
R is that carbonatoms is 8 alkyl chain;
Be 2,2-dipyridyl unit, L is 1-(9,9-dioctyl fluorene-2)-isoquinoline 99.9, the title complex red-emitting.
R is that carbonatoms is 8 alkyl chain;
Be 2,2-dipyridyl unit, L is a 1-phenyl isoquinolin quinoline, the title complex red-emitting.
Preparation method with above-mentioned any compound memory device that is storage medium is as follows: with the washings such as water, acetone and 2-propyl alcohol respectively in ultrasonic wave of ITO conductive glass.As storage medium, configuration concentration is the polymers soln of 0.1-500mg/mL with the described conjugated polymers that contains complex of iridium of claim 1, and is spun on the ITO conductive glass, removes under the vacuum and desolvates, and obtains polymeric film.Metals such as gold evaporation, aluminium, copper are as top electrode then, and ITO conductive glass etc. is made lower electrode, and described polymer materials prepares the single polymer layer memory device as storage media.
Beneficial effect: polymkeric substance has the favorable mechanical processing characteristics, can spin-coating film, cut down finished cost, and obtain large-area high-quality thin film.And polymer thermostable is good, can prolong device lifetime.In addition, polymer architecture is changeable, can the synthesizing new structure and the material of specific function.So on highly integrated, high-impact performance and processing characteristics, have clear superiority.The most outstanding advantage of electrostrictive polymer storage is to obtain very highdensity storage by three-dimensional stacked technology, and its storage potentiality are quite huge.Another advantage is to make polymer memory not need high temperature, high vacuum, the high-precision expensive device of producing the semi-conductor chip with resembling, and might produce cost polymer memory extremely cheap, jettisonable.Be incorporated into complex of iridium in the conjugated polymers molecular chain and be applied in the electrical storage device, expectation can obviously improve the over-all properties of polymer memory device, as reducing read-write voltage, the joule heating that produces when reducing to move, improve device stability, improve current on/off ratio and having faster the time of response etc.Preliminary result of study shows that with the memory device of this class material as the storage medium preparation, switch current ratio has reached nearly 10
6, " opening " and " pass " state is all very stable, read the circulation reach 10
8The time, " opening ", " pass " electric current all do not have to change.
Description of drawings
Fig. 1. the electrical storage device among the present invention is the current-voltage scanning curve under the state of Kai Heguan respectively,
Fig. 2. the electrical storage device ON/OFF current ratio-voltage curve among the present invention,
Fig. 3. the umber of pulse that the electrical storage device among the present invention is read split with off status under the influence of electric current,
Fig. 4. the time is to the influence of electric current under the electrical storage device open and closed.
Embodiment
In order to understand the content of patent of the present invention better, further specify technical scheme of the present invention below by concrete example and legend.
The conjugated polymers that contains complex of iridium of the present invention is a molecular formula polymkeric substance as follows:
Wherein, R is the alkyl that contains 1 to 12 carbon;
Wherein,
For can with Ir coordinate N, N heterogeneous ring compound;
Wherein, L be can with iridium coordinate C, N heterogeneous ring compound;
Wherein, m is the unitary quantity of fluorenes in the polymer chain, and n is the unitary quantity of complex of iridium in the polymer chain;
The scope of m and n is 0.1≤m≤100,0.1≤n≤100, n/ (m+n) 〉=0.1%;
The alkyl R that contains 1 to 12 carbon is positioned on 9 of fluorenes.
Embodiment 1:
Water, acetone and 2-propyl alcohol washed 15 minutes respectively in ultrasonic wave with the ITO conductive glass.With the following compound of structure is storage medium, and configuration concentration is the toluene solution of 10mg/mL, is spun on the ITO conductive glass.Remove under the vacuum and desolvate the about 50nm of polymkeric substance thickness.Evaporating Al is as top electrode then.The device detection area is 0.4 * 0.4 square millimeter.The device architecture synoptic diagram is as shown below.Measure the current-voltage curve of device and judge whether material has electric bi-stable state, opens and close voltage, erasable repeatedly ability; Survey the difference between current of constant voltage read/write pulsed current assessment device " 0 " and " 1 " signal, and device read, write and wipe stability; The current-responsive of test component under unlatching and closing condition is assessed the read/write speed of device etc. respectively; With accelerated weathering test the life-span of device is assessed.With the ion sputtering method device is carried out Vacuum Package with tetrafluoroethylene.
Embodiment 2:
Water, acetone and 2-propyl alcohol washed 15 minutes respectively in ultrasonic wave with the ITO conductive glass.With the following compound of structure is storage medium, and configuration concentration is the toluene solution of 10mg/mL, is spun on the ITO conductive glass.Remove under the vacuum and desolvate the about 50nm of polymkeric substance thickness.Evaporation Au is as top electrode then.The device detection area is 0.2 * 0.2 square millimeter.Measure the current-voltage curve of device and judge whether material has electric bi-stable state, opens and close voltage, erasable repeatedly ability; Survey the difference between current of constant voltage read/write pulsed current assessment device " 0 " and " 1 " signal, and device read, write and wipe stability; The current-responsive of test component under unlatching and closing condition is assessed the read/write speed of device etc. respectively; With accelerated weathering test the life-span of device is assessed.With the ion sputtering method device is carried out Vacuum Package with tetrafluoroethylene.
Embodiment 3:
Water, acetone and 2-propyl alcohol washed 15 minutes respectively in ultrasonic wave with the ITO conductive glass.With the following compound of structure is storage medium, and configuration concentration is the toluene solution of 10mg/mL, is spun on the ITO conductive glass.Remove under the vacuum and desolvate the about 50nm of polymkeric substance thickness.Evaporation Cu is as top electrode then.The device detection area is 0.15 * 0.15 square millimeter.Measure the current-voltage curve of device and judge whether material has electric bi-stable state, opens and close voltage, erasable repeatedly ability; Survey the difference between current of constant voltage read/write pulsed current assessment device " 0 " and " 1 " signal, and device read, write and wipe stability; The current-responsive of test component under unlatching and closing condition is assessed the read/write speed of device etc. respectively; With accelerated weathering test the life-span of device is assessed.With the ion sputtering method device is carried out Vacuum Package with tetrafluoroethylene.
Claims (6)
1. conjugated polymers that contains complex of iridium is characterized in that this conjugated polymers is a molecular formula polymkeric substance as follows:
Wherein, R is the alkyl that contains 1 to 12 carbon;
Wherein,
For can with Ir coordinate N, N heterogeneous ring compound;
Wherein, L be can with iridium coordinate C, N heterogeneous ring compound;
Wherein, m is the unitary quantity of fluorenes in the polymer chain, and n is the unitary quantity of complex of iridium in the polymer chain;
The scope of m and n is 0.1≤m≤100,0.1≤n≤100, n/ (m+n) 〉=0.1%;
The alkyl R that contains 1 to 12 carbon is positioned on 9 of fluorenes.
2. as the conjugated polymers that contains complex of iridium of claim 1, it is characterized in that the alkyl R that contains 1 to 12 carbon is identical group, or be different groups.
3. the conjugated polymers that contains complex of iridium as claimed in claim 1 is characterized in that described conjugated polymers is:
Wherein R is that carbonatoms is 8 alkyl chain;
Be 2,2-dipyridyl unit, L is a 1-phenyl isoquinolin quinoline, the title complex red-emitting.
4. the conjugated polymers that contains complex of iridium as claimed in claim 1 is characterized in that described conjugated polymers is:
Wherein, R is that carbonatoms is 8 alkyl chain;
Be 2,2-dipyridyl unit, L is 1-(9,9-dioctyl fluorene-2)-isoquinoline 99.9, the title complex red-emitting.
5. the conjugated polymers that contains complex of iridium as claimed in claim 1 is characterized in that described conjugated polymers is:
Wherein, R is that carbonatoms is 8 alkyl chain;
Be 2,2-dipyridyl unit, L is a 1-phenyl isoquinolin quinoline, the title complex red-emitting.
6. the preparation method of the memory device of a conjugated polymers that contains complex of iridium as claimed in claim 1 is characterized in that this conjugated polymers is as follows as the preparation method of the memory device of storage medium:
With the washings such as water, acetone and 2-propyl alcohol respectively in ultrasonic wave of ITO conductive glass; As storage medium, configuration concentration is the polymers soln of 0.1-500mg/mL with the described conjugated polymers that contains complex of iridium, and is spun on the ITO conductive glass, removes under the vacuum and desolvates, and obtains polymeric film; Metals such as gold evaporation, aluminium, copper are as top electrode then, and ITO conductive glass etc. is made lower electrode, and described polymer materials prepares the single polymer layer memory device as storage media.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102344546A (en) * | 2011-07-11 | 2012-02-08 | 南京邮电大学 | Electrical bistable material for conjugated polymer as well as preparation method and application thereof |
| CN104835922A (en) * | 2015-04-27 | 2015-08-12 | 南京邮电大学 | Photochromic compound-based bidirectional heterogenic organic diode electrical storage device and preparation method thereof |
| CN105336859A (en) * | 2015-09-28 | 2016-02-17 | 北京交通大学 | Organic micromolecule thin film electrical bistable device and manufacturing method thereof |
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2008
- 2008-04-29 CN CNA200810025558XA patent/CN101280054A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102344546A (en) * | 2011-07-11 | 2012-02-08 | 南京邮电大学 | Electrical bistable material for conjugated polymer as well as preparation method and application thereof |
| CN102344546B (en) * | 2011-07-11 | 2013-01-02 | 南京邮电大学 | Electrical bistable material for conjugated polymer as well as preparation method and application thereof |
| CN104835922A (en) * | 2015-04-27 | 2015-08-12 | 南京邮电大学 | Photochromic compound-based bidirectional heterogenic organic diode electrical storage device and preparation method thereof |
| CN104835922B (en) * | 2015-04-27 | 2017-06-30 | 南京邮电大学 | The operating method of the two-way different in nature organic diode electrical storage functionalization based on photochromic compound |
| CN105336859A (en) * | 2015-09-28 | 2016-02-17 | 北京交通大学 | Organic micromolecule thin film electrical bistable device and manufacturing method thereof |
| CN105336859B (en) * | 2015-09-28 | 2018-01-02 | 北京交通大学 | A kind of organic molecule film dual stabilization part and preparation method thereof |
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Open date: 20081008 |