CN101807669A - Organic memory - Google Patents
Organic memory Download PDFInfo
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- CN101807669A CN101807669A CN 201010134970 CN201010134970A CN101807669A CN 101807669 A CN101807669 A CN 101807669A CN 201010134970 CN201010134970 CN 201010134970 CN 201010134970 A CN201010134970 A CN 201010134970A CN 101807669 A CN101807669 A CN 101807669A
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Abstract
The invention relates to an organic memory, which is based on self assembly materials and has the non-volatilisation storage effect on the basis of the self assembly materials. The organic memory comprises an upper electrode, a lower electrode and a functional layer, wherein the functional layer is arranged between the upper electrode and the lower electrode, the functional layer comprises an upper organic semiconductor layer, a lower organic semiconductor layer and an alkyl trichlorosilane self assembly molecular layer, the upper organic semiconductor layer and the lower organic semiconductor layer are mutually isolated, and the alkyl trichlorosilane self assembly molecular layer is arranged between the upper organic semiconductor layer and the lower organic semiconductor layer, and is in contact with the upper organic semiconductor layer and the lower organic semiconductor layer. As the preferable technical scheme, the carbon number of the alkyl in the alkyl trichlorosilane is between 3 and 12, more preferably, the carbon number of the alkyl in the alkyl trichlorosilane is between 6 and 12, and most preferably, octyl trichlorosilane is adopted. Because trapped charges at the interface of the alkyl trichlorosilane self assembly molecular layer and the organic semiconductor layers can regulate and control the voltage barrier property of the self assembly material layer, the rate for the charges to pass the barrier layer is changed, and devices with the electric storage effect are finally obtained.
Description
Technical field
The present invention relates to a kind of organic memory of crosspoint structure.
Background technology
In recent years, the self assembly molecule material has been widely used in organic electronic device, plays modification and functionalization to each interface of device, and has obtained the device that performance increases substantially.It should be noted that, the self assembly molecule material can form thickness usually and only be the thin layer of several nanometers, and electric charge can pass through this one deck by the tunnelling or the transmission of jumping, thereby in theory by modulating the barrier properties of this ultra-thin self assembly molecule layer, can realize that memory effect (is under the situation of same applied voltage, device can present the height electricity and lead state, and is defined as " 1 " and " 0 " state respectively).In addition, because the diversity of self assembly molecule material and the controllability of molecular structure make to have the excellent development prospect based on the self assembly molecule material as the device that causes memory effect.
Summary of the invention
The invention provides a kind of organic memory,, have non-volatile storage effect based on self-assembled material.
Described organic memory comprises upper and lower electrode and places functional layer between the upper and lower electrode, described functional layer comprises the upper and lower organic semiconductor layer of mutual isolation and the alkyl trichlorosilane self assembly molecule layer in the middle of the upper and lower organic semiconductor layer, and described alkyl trichlorosilane self assembly molecule layer contacts with upper and lower organic semiconductor layer.
As preferred version, the carbon number of alkyl is 3-12 in the described alkyl trichlorosilane, and more preferably 6-12 most preferably is octyl trichlorosilane (hereinafter to be referred as OTS).
Described organic semiconductor layer and self assembly molecule layer adopt method well known in the art to prepare.Preferred organic semiconductor layer is the rubrene film.The self assembly molecule layer can adopt vaccum gas phase sedimentation method to obtain, and the growth time of preferred self assembly molecule layer is 2-6h.
Rubrene and OTS are public material, and concrete structure is respectively suc as formula shown in the (a) and (b):
Described upper and lower electrode adopts known configurations, as is metal electrode (as gold electrode), and concrete material should be mated with device material.
Described organic memory is a crosspoint structure.In the research field of organic memory, the device with crosspoint structure is one of type of device that receives much concern, and this mainly is because its simple structure, easy preparation method, and is being expected to realize the device of low processing cost from now on.
As common practise, described organic memory also comprises substrate, and substrate is positioned at the bottom electrode below, and backing material can be required to select according to reality by those skilled in the art.
Because alkyl trichlorosilane self assembly molecule layer is very thin, thickness is not more than 5nm, itself and organic semiconductor layer trapped charge at the interface, can play regulation and control to the barrier nature of self-assembled material layer, thereby the probability that makes electric charge pass through this barrier layer changes the device that finally obtains having the electricity storage effect.
As improvement of the present invention, described organic memory also comprises insulation barrier, described insulation barrier is discontinuous film, and between alkyl trichlorosilane self assembly molecule layer and last organic semiconductor layer, the alkyl trichlorosilane contacts with the hole place of last organic semiconductor layer at discontinuous film.Described insulation barrier is preferably the LiF film.As further preferred version, the thick 15nm of described LiF film.
When there is defective in the self assembly molecule layer, in the time of can not covering down organic semiconductor layer fully, when directly forming organic semiconductor layer on the self assembly molecule layer, last organic semiconductor layer may permeate and pass through defect area, directly contact, thereby cause the generation of leakage current with following organic semiconductor layer.Above the self assembly molecule layer, also be provided with insulation barrier, can play the effect of filling up defective in the self assembly layer, the bigger leakage current that causes to prevent defective in the self assembly layer.The successional film of the right and wrong that this insulation barrier forms on the self assembly molecule layer, organic semiconductor layer can permeate in the hole place of film, contact with self-assembled material, thereby form the interfacial structure between self-assembled material and the organic semiconductor layer, pass through by electric charge, realize the electrical storage effect.Our preferred fluorinated lithium LiF conducts insulating material herein can form the discontinuous film that is made of nano particle, and organic semiconducting materials can permeate still between the nano particle.
The applicant as ultra-thin potential barrier, has designed organic memory based on the self assembly molecule layer.The electric bi-stable state effect that is embodied in the device, it is the typical characteristics of electrical storage, and this effect comes from the self assembly molecule layer as ultra-thin barrier layer, can be regulated and control by interface trapped charge: pass through applied voltage, make the trapped charge of generation at the interface of self assembly molecule layer and organic semiconductor layer, thereby reduce the barrier height of self assembly molecule layer, make the current density of passing through device take place obviously to change.The present invention is simple in structure, novel, and device performance is good, and the preparation method is simple and easy, with low cost, and because the diversity of self assembly molecule layer makes this type of device have the excellent development prospect.
Description of drawings
Fig. 1 is atomic force microscope (hereinafter to be referred as AFM) surface topography map and phasor;
Fig. 2 is the structure chart of organic memory;
Fig. 3 be among Fig. 2 in the dashed rectangle shown in the detail view of functional area;
Fig. 4 is the electric property figure of embodiment 1 and 2 gained organic memories;
Fig. 5 is the electric property figure of OTS growth time gained organic memory different among the embodiment 1;
Fig. 6 is the electric property figure of embodiment 4 gained organic memories.
Embodiment
In following examples, the measurement of current-voltage curve is under inert gas shielding, adopts current source meter Keithley2611 to carry out.
1) with the silicon chip of the silicon dioxide of 300nm thickness as substrate, utilize mask plate, the method by vacuum thermal evaporation forms the bar shaped gold electrode of 50nm thickness as bottom electrode on substrate;
2) method by vacuum thermal evaporation, evaporation one layer thickness is that the organic small molecular semiconductor rubrene film of 50nm is as lower semiconductor layer on the substrate that has the bar shaped gold electrode;
3) sample is placed in the cavity of a sealing, puts an ampoule in the cavity in addition, bottle contains self assembly molecule material OTS.Cavity is vacuumized, gas phase volatilization under the low pressure of the meeting of the unimolecule material in the ampoule at this moment, thus be grown on the organic semiconductor layer, form OTS self assembly molecule layer.The growth time of control OTS self assembly molecule layer.
4) LiF of the method deposit 15nm thickness on sample by hot evaporation;
5) the organic small molecular semiconductor rubrene film that evaporation one deck 50nm is thick on sample again is as upper semiconductor layer;
6) pass through mask plate, thermal vacuum evaporation thickness is that the bar shaped gold electrode of 50nm is as top electrode on sample, form cross-like with the electrode in the step 1), the organic memory structure that obtains is furnished with bottom electrode 2, lower semiconductor layer 4, OTS self assembly molecule layer 5, LiF layer 6, upper semiconductor layer 3, top electrode 1 as shown in Figure 2 successively on substrate.
1) with the silicon chip of the silicon dioxide of 300nm thickness as substrate, utilize mask plate, the method by vacuum thermal evaporation forms the bar shaped gold electrode of 50nm thickness as bottom electrode on substrate;
2) method by vacuum thermal evaporation, evaporation one layer thickness is that the organic small molecular semiconductor rubrene film of 50nm is as lower semiconductor layer on the substrate that has the bar shaped gold electrode;
3) sample is placed in the cavity of a sealing, puts an ampoule in the cavity in addition, bottle contains self assembly molecule material OTS.Cavity is vacuumized, gas phase volatilization under the low pressure of the meeting of the unimolecule material in the ampoule at this moment, thus be grown on the organic semiconductor layer, form OTS self assembly molecule layer.Whole process need six hours.
4) the organic small molecular semiconductor rubrene film that evaporation one deck 50nm is thick on sample again is as upper semiconductor layer;
5) pass through mask plate, thermal vacuum evaporation thickness is that the bar shaped gold electrode of 50nm is as top electrode on sample, form cross-like with the electrode in the step 1), the organic memory structure that obtains is: be furnished with bottom electrode, lower semiconductor layer, OTS self assembly molecule layer, upper semiconductor layer, top electrode on substrate successively.
Preparation process is with embodiment 1, and difference is that the thickness of LiF film is 20nm.
Among Fig. 1 (a) and (b) be the AFM surface topography map and the phasor of the organic semiconductor layer rubrene film surface that gained is pure among the embodiment 1-3; (c) and (d) be the AFM surface topography map and the phasor of rubrene film surface, can be clearly seen that OTS self assembly molecule layer forms on the rubrene surface by six hours vacuum gas phase process growth OTS.Simultaneously, can find to have in the OTS layer self assembly molecule to cover incomplete zone, and we are by the LiF of evaporation deposit one deck 15nm, fill up the defective in the OTS layer, promptly self assembly molecule covers incomplete zone, can avoid the generation of device creepage.Figure (e) is the AFM picture of the hot evaporation LiF of embodiment 1 step 4) layer, can find, the LiF layer is made up of nano particle, so the rubrene film of last layer will and form discontinuous island structure at evaporation at the area deposition between the LiF particle gap during initial stage, and (we can't provide the micrograph of corresponding construction here, its size has exceeded accuracy of instrument, and this point can be proved by document).
Fig. 4 has provided the electricity scans I-V electrical performance testing curve of embodiment 1 gained organic memory (the OTS self assembly molecule layer growth time is 6h), and voltage scans 3V and then flyback to 0V from 0V.Wherein, curve 1,2,3,4 is the electrical performance testing curve of six hours vacuum gas phase process growth OTS self assembly molecule layer gained organic memories.Curve 5 is the electricity scans I-V electrical performance testing curve of embodiment 2 gained organic memories.When voltage 0 when between 2V, scanning, embodiment 1 gained organic memory does not present electricity conversion behavior ( scanning curve 1 and 2 among Fig. 4), i.e. electrical storage effect.And when voltage surpasses threshold voltage 2.8V, can be clearly seen that the I-V curve is led state (i.e. " 0 " state) from initial low electricity and transitted to an individual high electricity and lead state (being one state).It is that current density ratio (on-off ratio of device) when reading voltage can reach 450 (scanning curve 3 among Fig. 4) at 1V that height electricity is led state.Current density keeps height to lead state.SAM (the being the self assembly molecule layer) electric property that provides growth in 6 hours among the figure is the most excellent.If scanning once more, current density still remains on this high electricity and leads state (scanning curve 4 among Fig. 4), therefore, device has been realized the process that writes, and kept good electrical stability, the electric bi-stable state effect of this current density and voltage has shown its nonvolatile storage effect.The electricity scans I of embodiment 2 gained organic memories-V electrical performance testing curve is shown in curve among Fig. 45, because there is defective in OTS self assembly molecule layer, remove insulation barrier LiF film, upper and lower semiconductor layer directly contacts at defect area, thereby causes leakage current.
As can be seen from Figure 5, when the growth time of self assembly molecule (15-30 minute) more in short-term, also be not enough to form continuous self assembly molecule layer, the switch behavior that device shows is very faint; And longer when the growth time of self assembly molecule layer, reach 2-6 hour, the self assembly molecule layer forms, and device body reveals very significantly switch behavior.
1) with the silicon chip of the silicon dioxide of 300nm thickness as substrate, utilize mask plate, the method by vacuum thermal evaporation forms the bar shaped aluminium electrode of 50nm thickness as bottom electrode on substrate;
2) by the method for vacuum thermal evaporation, evaporation one layer thickness is the organic small molecular semiconductor 2-amino-4 of 50nm on the substrate that has bar shaped aluminium electrode, and 5-imidazoles dintrile (AIDCN) film is as lower semiconductor layer;
3) sample is placed in the cavity of a sealing, puts an ampoule in the cavity in addition, bottle contains self assembly molecule material OTS.Cavity is vacuumized, gas phase volatilization under the low pressure of the meeting of the unimolecule material in the ampoule at this moment, thus be grown on the organic semiconductor layer, form OTS self assembly molecule layer.The growth time of control OTS self assembly molecule layer is 6h.
4) LiF of the method deposit 15nm thickness on sample by hot evaporation;
5) the organic small molecular semiconductor 2-amino-4 that evaporation one deck 50nm is thick on sample again, 5-imidazoles dintrile (AIDCN) film is as upper semiconductor layer;
6) pass through mask plate, thermal vacuum evaporation thickness is that the bar shaped aluminium electrode of 50nm is as top electrode on sample, form cross-like with the electrode in the step 1), the organic memory structure that obtains is furnished with bottom electrode 2, lower semiconductor layer 4, OTS self assembly molecule layer 5, LiF layer 6, upper semiconductor layer 3, top electrode 1 as shown in Figure 2 successively on substrate.
Fig. 6 (a) is the current-voltage curve of embodiment 4 gained organic memories.In the device of this structure, we have also obtained electricity transition effects (scanning curve 1).And the high electricity state of leading of device can keep surpassing one hour (scanning curve 2) removing under the situation of applied voltage.In addition, reverse by adding-5V voltage, the high electricity state of leading of device can be reduced to another low electricity and lead state (leading high although the low electricity initial with respect to device led its electricity that shows of state).What Fig. 6 (b) showed is circulation " writing-read-wipe-read " process, shows that the current ratio that device is led state at the height electricity is consistent basically.
Claims (10)
1. organic memory, comprise upper and lower electrode and place functional layer between the upper and lower electrode, it is characterized in that described functional layer comprises the upper and lower organic semiconductor layer of mutual isolation and the alkyl trichlorosilane self assembly molecule layer in the middle of the upper and lower organic semiconductor layer, described alkyl trichlorosilane self assembly molecule layer contacts with upper and lower organic semiconductor layer.
2. organic memory as claimed in claim 1, the carbon number that it is characterized in that alkyl in the described alkyl trichlorosilane is 3-12.
3. organic memory as claimed in claim 2, the carbon number that it is characterized in that alkyl in the described alkyl trichlorosilane is 6-12.
4. organic memory as claimed in claim 3 is characterized in that described alkyl trichlorosilane is the octyl trichlorosilane.
5. organic memory as claimed in claim 1 is characterized in that the growth time of described alkyl trichlorosilane self assembly molecule layer is 2-6h.
6. as each described organic memory among the claim 1-5, it is characterized in that also comprising insulation barrier, described insulation barrier is discontinuous film, between alkyl trichlorosilane self assembly molecule layer and last organic semiconductor layer, the alkyl trichlorosilane contacts with the hole place of last organic semiconductor layer at discontinuous film.
7. organic memory as claimed in claim 6 is characterized in that described insulation barrier is the LiF film.
8. organic memory as claimed in claim 7 is characterized in that the thick 15nm of described LiF film.
9. as each described organic memory among the claim 1-5, it is characterized in that described organic semiconductor layer is the rubrene film.
10. as each described organic memory among the claim 1-5, it is characterized in that described organic memory is a crosspoint structure.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109863259A (en) * | 2016-11-03 | 2019-06-07 | Tgo科技株式会社 | Motherboard, the manufacturing method of motherboard, the manufacturing method of mask and OLED pixel evaporation coating method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1543652A (en) * | 2001-08-13 | 2004-11-03 | �Ƚ�װ�ù�˾ | Memory cell |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1543652A (en) * | 2001-08-13 | 2004-11-03 | �Ƚ�װ�ù�˾ | Memory cell |
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| 《半导体学报》 20081231 孙叶丹 等 界面化学反应形成的纳米颗粒对有机交叉点存储器的影响 2398-2401 1-10 第29卷, 第12期 2 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109863259A (en) * | 2016-11-03 | 2019-06-07 | Tgo科技株式会社 | Motherboard, the manufacturing method of motherboard, the manufacturing method of mask and OLED pixel evaporation coating method |
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