CN1815771A - Erasable, readable molecular-base electric double-stable negative-resistance component - Google Patents
Erasable, readable molecular-base electric double-stable negative-resistance component Download PDFInfo
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- CN1815771A CN1815771A CN 200510111831 CN200510111831A CN1815771A CN 1815771 A CN1815771 A CN 1815771A CN 200510111831 CN200510111831 CN 200510111831 CN 200510111831 A CN200510111831 A CN 200510111831A CN 1815771 A CN1815771 A CN 1815771A
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Abstract
The invention is related to technical areas of molecules based electronic device and ferroelectric thin film. Structure of the disclosed device is in structure of metal- Organic-metal (M1-Organic-M2). Two ends of metal layer are as electrodes, and the middle organic layer (including interface of metal-organic) is as function layer. Using external electric signal, the molecules based electronic device carries out writing in, erasing, and reading out operations. The device possesses unusual negative resistance characteristic. The disclosed thin film device possesses extensive use value in areas of information storage, information processing and logic operation. Moreover, the disclosed device is suitable particular to situation negative resistance characteristic being required.
Description
Technical field
The invention belongs to molecular-based electronic device and ferroelectric thin-film technology field, the molecular-base electric double-stable negative-resistance component that be specifically related to a kind of electrically-erasable, can read.
Technical background
Utilizing organic molecule to make electronic device as dielectric layer is one of developing direction of functional material and areas of information technology.This be because: on the one hand organic molecule has multiple functional character, can cut the performance of control device by molecular structure; The size of organic molecule is at nanoscale on the other hand, and size of devices may diminish to nanoscale in principle.
Metal-organic-metallic (M-Organic-M) structure is the simplest a kind of device, and the simplicity of structure and manufacture craft is very favourable for practical application and industrialization.Usually, but that this device will be realized the electricity inverse conversion is very difficult, and many purposes are the devices (write-once read-many-times memory is called for short WORM) that repeatedly reads as write-once, and therefore, its application has been subjected to very big restriction.([1]W.Xu，G.R.Chen，R.J.Li，Z.Y.Hua，Appl.Phys.Lett.1995，67：2241；[2]S.Moller，C.Perlov，W.Jackson，et?al.，Nature?2003，426：166)
Adopt simple M-Organic-M structure to realize that reversible translation function is the target that scientific circles and industrial circle are being pursued always.The present invention on the basis of previous invention, but but adopt simple M-Organic-M structure to realize the inverse conversion and the read out function of thin-film device high-resistance state and low resistance state, and disclosed uncommon negative resistance charactertistic.([3] xuwei, Lv Yinxiang, Central China one, a kind of molecular based bi-stable electric organic film device and manufacture craft thereof of electrically-erasable, application for a patent for invention number 01132374.4)
Summary of the invention
The objective of the invention is to the molecular-base electric double-stable negative-resistance component that proposes a kind of electrically-erasable, can read.
The molecular-base electric double-stable negative-resistance component that the present invention proposes is made of hearth electrode, organic molecular film and top electrode, is M
1-Organic-M
2Sandwich, as shown in Figure 1.Wherein, M
1, M
2Represent two metal electrodes, Organic is the organic functions dielectric layer.
The electrode material that the present invention proposes thin-film device can adopt multiple metal, such as Ag, Cu, Al etc.Hearth electrode (M
1) and top electrode (M
2) can adopt different metal, also can adopt identical metal.Reasonable combination has: Ag-Organic-Al, Al-Organic-Ag, Cu-Organic-Al, Al-Organic-Cu, Cu-Organic-Cu, Ag-Organic-Ag, Cu-Organic-Ag and Ag-Organic-Cu etc.
The molecular material that the present invention proposes to be used to make organic function medium layer (Organic) adopts and contains 1 of heterocycle, 1-dicyano ethene derivatives, and structural formula is shown below:
Wherein, R1 is hydrogen atom, methyl, ethyl, phenyl or benzyl; R2 and R3 are hydrogen atom, chlorine atom, fluorine atom, bromine atoms, methyl, ethyl, phenyl, aromatic radical or methoxyl group; R1, R2, R3 can be identical, also can be different.
The organic functions dielectric layer of the electric double-stable negative-resistance component that the present invention proposes can adopt a kind of of following molecular material to make:
(1) 3-hydrogenated benzimidazoles-2-subunit-1,1-dicyano methane, structural formula is as shown in the formula shown in (MS-1):
(2) 2-(1-phenyl-1,3-dihydro-benzimidazolyl-2 radicals-subunit)-malononitrile, structural formula is as shown in the formula shown in (MS-2):
(3) 2-(5-methyl isophthalic acid, 3-dihydrobenzo imidazoles)-malononitrile, structural formula is as shown in the formula shown in (MS-3):
(4) 2-(5-chloro-1,3-dihydrobenzo imidazoles)-malononitrile, structural formula is as shown in the formula shown in (MS-4):
(5) 2-(1H, 3H-perimidine-2-subunit) malononitrile, structural formula is as shown in the formula shown in (MS-5):
(6) 2-(2 '-dicyano methylene-1,3,2 ', 3 '-tetrahydrochysene-1 ' H-[5,5 '] connection (benzimidazole)-2-subunit) malononitrile, structural formula is as shown in the formula shown in (MS-6):
Above-mentioned molecular material has very high fusing point and heat-resistant stability.This quasi-molecule material can enough vacuum thermal evaporation method film forming.
The performance of molecular-based electronic device is relevant with the purity and the process conditions of molecular material with rate of finished products.In previous patent of invention, employed organic molecule material is obtained by chemical synthesis, and is directly used in the making device.Owing to do not pass through strict purification process, there is inconsistency to a certain degree in the performance of device.
The present invention proposes to be used for the organic molecule material of electric double-stable negative-resistance component through strict purification.Before the organic functions dielectric layer of making device, molecular material carries out purification process earlier, and purification process is as follows: by the molecular material that chemical synthesis obtains, use DMF (N, TMSDMA N dimethylamine base formamide) and ethyl alcohol recrystallization earlier; Do post with silica G then and carry out column chromatography purification; At last, with vacuum sublimation method purifying organic molecule material, obtain highly purified organic molecule material.
Adopt highly purified organic molecule material to make rate of finished products, electrical property and stability and useful life that organic function medium layer can obviously improve device.
Its manufacture method of electric double-stable negative-resistance component that the present invention proposes is as follows:
The metal film that evaporation one deck is thicker on smooth substrate surface is done hearth electrode, and then evaporation molecule organic layer and metal roof electrode successively.The thickness of top hearth electrode is in 80～200 nanometer range, and the thickness of molecule organic layer is in 50～120 nanometer range.So just constituted molecular-base electric double-stable negative-resistance component, as shown in Figure 1.
The electric double-stable negative-resistance component that the present invention proposes possesses two kinds of different Resistance states (high-resistance state and low resistance state), but can enough signal of telecommunication inverse conversion that adds between high-impedance state and the low resistance state.Higher applied voltage (such as: 3～8 volts) effect under, device is in high resistance state; Lower applied voltage (such as: 1～3 volt) effect under, device is in low resistance state; The resistance value of two states compares more than 1000 times, even can meet or exceed 100,000 times.These two kinds of high low resistance states, can also with a small voltage (such as: 0.1～0.8 volt) read, in the process of reading, the state of device does not change.Reversible conversion times between high-impedance state and the low resistance state can be above 2000 times.
Adopt through the molecular material of purification process and make the function medium layer of electric double-stable negative-resistance component and control the process conditions of element manufacturing well, the rate of finished products of device can reach more than 95%, and the consistency of electrical characteristics is also better between the different components.The device of un-encapsulated is preserved in atmospheric environment after 1 year and is measured, but electric bistable negative resistance charactertistic and erasable read operation still keep.
Adopt different molecular materials, different metal electrode and different thickness and process conditions, the numerical value of device electrical characteristic parameter can change, but crucial erasable characteristic is consistent with negative resistance charactertistic.
Therefore, the logic element that the molecular-based electronic device that the present invention proposes can be used as in switch element, electric memory and information processing and the computing uses, and needing also to be particularly suitable for the occasion of negative resistance device.
Description of drawings
Fig. 1 electric double-stable negative-resistance component structural diagrams of the present invention.
The measuring circuit schematic diagram of Fig. 2 thin-film device (sample).
The continuous reversible transfer characteristic of Fig. 3 high-impedance state and low resistance state
Fig. 4 high-impedance state and the low resistance state current curve of 0.2V voltage effect more than 3 hours.
(a) be the read current curve of low resistance state; (b) be the read current curve of high-impedance state
Fig. 5 thin-film device is " writing-read-wipe-read " characteristic continuously.Wherein, write (2V)-read (0.5V)-wipe (6V)-read (0.5V)
Number in the figure: 1 is substrate; 2 is hearth electrode (M
1); 3 is molecule organic layer (Organic); 4 is top electrode (M
2).
Embodiment
Be that example further describes the present invention with Ag-(MS-1)-Al electric double-stable negative-resistance component below:
Molecular material (MS-1) is through purification process.
The preparation of device Ag-(MS-1)-Al: the wave carrier piece with cleaning is substrate, 2 * 10
-3Adopt vacuum thermal evaporation method evaporation hearth electrode (Ag), organic MS-1 film and top electrode (Al) successively under the Pa pressure.About 100 nanometers of the thickness of top hearth electrode, the about 80-100 nanometer of organic layer MS-1 thickness.The organic layer evaporation rate is 0.5～3 /s.The area of top electrode and hearth electrode juxtaposition part is 0.1mm
2
The electrical characteristics of device Ag-(MS-1)-Al:
With thin-film device Ag-(MS-1)-Al and current-limiting resistance (1k Ω) series connection, and be connected in the measuring circuit, utilize the HP33120 function generator to produce various potential pulses as pumping signal, gather the change in voltage at current-limiting resistance two ends with the HP54645A digital oscilloscope, thereby understand the variation of sample state.This method of measurement can avoid owing to sample resistance with the comparable measure error of bringing of oscillographic internal resistance.Measuring circuit as shown in Figure 2; The I-t curved measurement of device adopts Keithley 2400 digital source tables, when giving the device input voltage, measures the electric current of the device of flowing through.
Fig. 3 employing-7.5V is to this thin-film device of scanning voltage effect of 7.5V.In the zone of absolute value less than 3.0 ± 1.0V of voltage, device is low resistance state (one state), and resistance is about 10
3Ω; When absolute value of voltage during greater than 3.0 ± 1.0V, thin-film device is in high-resistance state (" 0 " attitude), and resistance is about 10
7Ω; The resistance value ratio of two states about 10
4The reversible conversion of two states can continuous several times be carried out.Thisly be the characteristic that low resistance state, high voltage region are high-impedance state at low-voltage area, just in time opposite with common bi-stable electric organic characteristic, be a kind of typical negative resistance device.
After removing extra electric field, the high-impedance state of device and low configuration can be in atmospheric environment stable existence.Research is also found, acts on this device with a less potential pulse (100mV-500mV), can not change the original residing state of device, as shown in Figure 4." 0 " and " 1 " two states of this explanation device can " be read " to go out with a less voltage.
To be this device writing (2V)-read (0.5V)-wipe (6V)-read current response under the impulse action of (0.5V) continuous voltage to Fig. 5.Illustrating that this device is erasable can read again.
Claims (6)
1, a kind of molecular-base electric double-stable negative-resistance component is characterized in that adopting M
1-Organic-M
2Structure, wherein, the metal level M of two ends
1And M
2Be electrode, middle organic layer Organic is as the function medium layer; The molecular-based electronic device employing adds the signal of telecommunication and writes, wipes and read; Wherein, metal electrode M
iAnd M
2Adopt Ag, Cu or Al; The molecular material of function medium layer adopts and contains 1 of heterocycle, 1-dicyano ethene derivatives, and structural formula is shown below:
Wherein, R1 is hydrogen atom, methyl, ethyl, phenyl or benzyl; R2 and R3 are hydrogen atom, chlorine atom, fluorine atom, bromine atoms, methyl, ethyl, phenyl, aromatic radical or methoxyl group; R1, R2, P3 can be identical, also can be different.
2, molecular-base electric double-stable negative-resistance component according to claim 1 is characterized in that:
Device architecture is one of the following kind: Ag-Organic-Al, Al-Organic-Ag, Cu-Organic-Al, Al-Organic-Cu, Cu-Organic-Cu, Ag-Organic-Ag, Cu-Organic-Ag and Ag-Organic-Cu.
3, molecular-base electric double-stable negative-resistance component according to claim 1 and 2 is characterized in that thin-film device exists high-resistance state and low resistance state, and these two kinds of states are controlled with applied voltage: under the high voltage effect, be in high-resistance state; Under the low voltage effect, be in low resistance state; But the inverse conversion of two kinds of states realizes by changing applied voltage; Two kinds of states come " reading " with very low voltage signal.
4,, it is characterized in that the material of described organic functions dielectric layer adopts a kind of of following organic compound according to the described molecular-base electric double-stable negative-resistance component of one of claim 1～3:
(1) 3-hydrogenated benzimidazoles-2-subunit-1,1-dicyano methane, structural formula is as shown in the formula shown in (MS-1):
(2) 2-(1-phenyl-1,3-dihydro-benzimidazolyl-2 radicals-subunit)-malononitrile, structural formula is as shown in the formula shown in (MS-2):
(3) 2-(5-methyl isophthalic acid, 3-dihydrobenzo imidazoles)-malononitrile, structural formula is as shown in the formula shown in (MS-3):
(4) 2-(5-chloro-1,3-dihydrobenzo imidazoles)-malononitrile, structural formula is as shown in the formula shown in (MS-4):
(5) 2-(1H, 3H-perimidine-2-subunit) malononitrile, structural formula is as shown in the formula shown in (MS-5):
(6) 2-(2 '-dicyano methylene-1,3,2 ', 3 '-tetrahydrochysene-1 ' H-[5,5 '] connection (benzimidazole)-2-subunit) malononitrile, structural formula is as shown in the formula shown in (MS-6):
5,, it is characterized in that described organic functions dielectric layer adopts the molecular material of purified processing to make according to the described molecular-base electric double-stable negative-resistance component of claim 1～4.
6, a kind of molecular-base electric double-stable negative-resistance component as claimed in claim 1 is as the application in information processing and logical operation field of switch element and electric memory.
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| CN105336854A (en) * | 2015-09-29 | 2016-02-17 | 北京交通大学 | Silver symmetric electrode polymer electrical bistable device based on whole-wet method |
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| CN1139998C (en) * | 2001-11-30 | 2004-02-25 | 复旦大学 | Electrically erasable molecular base organic electric bistable film device and its producing technology |
| JP2003309307A (en) * | 2002-02-08 | 2003-10-31 | Matsushita Electric Ind Co Ltd | Organic electronic device and manufacturing method thereof |
| CN1282259C (en) * | 2003-03-03 | 2006-10-25 | 中国科学院长春应用化学研究所 | Organic semiconductor FET with protecting layer and its making process |
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| CN105336854A (en) * | 2015-09-29 | 2016-02-17 | 北京交通大学 | Silver symmetric electrode polymer electrical bistable device based on whole-wet method |
| CN105336854B (en) * | 2015-09-29 | 2018-05-18 | 北京交通大学 | One kind is based on Whote-wet method silver symmetry electrode electrostrictive polymer bistable device |
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