CN100456514C - Single-layer organic memory and mfg. method thereof - Google Patents
Single-layer organic memory and mfg. method thereof Download PDFInfo
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- CN100456514C CN100456514C CNB2005100167227A CN200510016722A CN100456514C CN 100456514 C CN100456514 C CN 100456514C CN B2005100167227 A CNB2005100167227 A CN B2005100167227A CN 200510016722 A CN200510016722 A CN 200510016722A CN 100456514 C CN100456514 C CN 100456514C
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Abstract
The present invention belongs to an organic memory and a manufacture thereof, which relates to the single layer organic memory and the manufacture method thereof. An organic film NPB or NPB doped with dye is clamped between two crossed electrodes by adopting a sandwich structure, wherein one electrode is a metal Ag electrode. A voltage is added between two electrodes, and a device is changed from one state to another state. Thus, the stored information can be read, written and rubbed off by changing the voltage, and the stored process has close relation with a selected organic material and the Ag electrode. The single layer organic memory has the characteristics of simple manufacturing technique, low cost, small size, big memory capacity, low power consumption, fast read-write and high stability.
Description
Technical field
The present invention relates to a kind of memory and manufacture method thereof with the organic material preparation.
Background technology
Memory is an important electron device in the semiconductor electronics field, in fields such as information and electronics industries wide application prospect is arranged.Memory not only will have small size, ultra-high capacity and fast reading and writing ability, and the characteristics of low-power consumption, low cost and high reliability will be arranged.Though the silicon memory of extensive use at present has the characteristics of quick storage, but the manufacturing cost that the photoetching process of expensive manufacturing equipment, complexity and peripheral transistor drive circuit have increased it, and area that silicon chip is limited and two-dimentional process technology limit its memory capacity, can not satisfy information age big capacity information storage and portable requirement.
Organic memory is a kind of brand-new electronic device, and its research starts from the seventies in 20th century, because device performance difference and do not cause people's attention at that time.In recent years, organic memory has more and more caused people's attention, and has obtained significant progress.2002, the Y.Yang group of california university was being delivered the organic memory of switch more than 1,000,000 times on the appliedphysics letters.What sort memory adopted is a kind of three-layer sandwich structure, is about to organic layer/nano metal layer/organic layer and is clipped between the metal electrode of two intersections.By change two voltages between the electrode just can make device from a status switch to another state, thereby reach memory function to the reading and writing and the wiping of information.The device manufacturing processes of this sandwich requires relatively strictness, particularly Zhong Jian nano metal layer, and its film morphology thickness is very big to the memory property influence.
Summary of the invention
In order to solve the problem that the three-decker organic memory exists, the present invention takes new process to produce single-layer organic memory.One of purpose of the present invention provides a kind of organic memory of individual layer; Another object of the present invention provides the manufacture method of sort memory.
The present invention is clipped in the organic film of individual layer between the electrode of two intersections, makes the single-layer organic memory of structure shown in attached Fig. 1 and 2.Wherein electrode adopts indium tin oxide (ITO), gold (Au), silver (Ag), copper (Cu) and aluminium (Al), but at least one electrode is Ag; Organic film adopts hole mobile material N, N '-two (1-naphthyl)-N, and N '-diphenyl-1,1 '-diphenyl-4,4 '-diamines, hereinafter to be referred as NPB, or the NPB of organic dyestuff doping.Wherein dye adulterated dose is 5,6,11,12-tetraphenyl-naphthonaphthalene (rubrene), the 2-{2-tert-butyl group-6-[2-(1,1,7,7-tetramethyl-2,3,6,7-tetrahydrochysene-1H, 5H-pyrido [3,2,1-ij] quinoline-9-yl)-vinyl]-pyrans-4-inner salt alkene }-malononitrile (DCJTB), 2-{2-isopropyl-6-[2-(1,1,7,7-tetramethyl-2,3,6,7-tetrahydrochysene-1H, 5H-pyrido [3,2,1-ij] quinoline-9-yl)-vinyl]-pyrans-4-inner salt alkene }-malononitrile (DCJTI), 4-(dicyano methylene)-2-methyl-6-[is right-(dimethylamino) styryl]-4H-pyrans (DCM), 10-(2-[4-morpholinodithio base)-2,3,6,7-tetrahydrochysene-1,1,7,7-tetramethyl-1H, 5H, 11H-(1)-benzo give a tongue-lashing the ketone group of muttering-(6,7,8-ij) quinolizine-11-ketone (C545T) and quinacridine.Apply voltage between two electrodes, device will be from a status switch to another state.Like this, by changing voltage, canned data just can be realized the process of reading and writing and wiping.
The preparation method of organic memory of the present invention is: when electrode 2 adopts ITO, earlier ITO is photo-etched into the electrode of fine strip shape, cleans then, nitrogen dries up, and uses oxygen plasma treatment 2 minutes; When electrode 2 adopts metal, should be 1-5 * 10 in vacuum degree
-4In the filming equipment of handkerchief, the metal electrode of fine strip shape on evaporation on the substrate, and then be 1-5 * 10 in vacuum degree
-4In the filming equipment of handkerchief, successively with organic layer 3, electrode 4 evaporations on electrode 2.Wherein two electrodes intersect mutually, and the thickness of electrode is the 100-500 nanometer, and the thickness of organic layer is the 50-500 nanometer.The evaporation rate of NPB is controlled at 0.1-0.5 nanometer per second in the organic layer, and dye adulterated dose evaporation rate is controlled at 0.001-0.05 nanometer per second, and the evaporation rate of electrode is controlled at 0.5-5 nanometer per second.When organic layer mixed, dyestuff and NPB be evaporation simultaneously, and the weight ratio of doping is between 0%-10%.
Advantage of the present invention is to adopt individual layer sandwich structure, promptly the individual layer organic film is clipped between two crossed electrodes, has simplified the design and implementation technology of memory greatly, has reduced cost.The single-layer organic memory of making has the good stability of forging a good relationship, and at normal temperatures and pressures, but unpackaged device switch is more than 1,000,000 times.
In addition, the rete of single-layer organic memory has only hundreds of nanometers, can do on same substrate layer by layer, and each accumulation horizon can be independently from peripheral circuit or end circuit addressing, the true three-dimensional memory technology is provided, and this three dimensional constitution has improved memory capacity greatly.And organic memory does not need transistor, this design feature make we can peripheral circuit do the outside of memory array or below, simplified the design and implementation technology of memory, further reduced cost.In a word, organic memory, particularly single-layer organic memory will have wide application prospect in message area and electronics industry.
Description of drawings
Fig. 1 is the structural representation of organic memory.1-glass or flexible substrate among the figure, 2-electrode, 3-organic layer, 4-electrode.Fig. 1 also is the specification digest accompanying drawing.
Fig. 2 is the generalized section of Fig. 1.
Fig. 3 is the voltage-to-current bistable behavior curve of organic memory embodiment 1, and promptly under same voltage, device exists two different electricity to lead state, and the starting voltage of scanning is-12 volts.
Fig. 4 is the voltage-to-current bistable behavior curve of organic memory embodiment 2, and the starting voltage of scanning is-12 volts.
Fig. 5 is that organic memory embodiment 1 " writes-read-wipe-read " circulation.The voltage of wherein writing, reading and wipe is respectively-12,8 and 20 volts.Write voltage after read voltage through one, memory is in high electricity and leads state, wipes voltage after read voltage through one again, and memory is in and hangs down electricity and lead state.High electricity is led and is hanged down electricity and lead the state Kai Heguan of instruction memory respectively.
Fig. 6 be among the organic memory embodiment 1 the ON/OFF electric current with the change curve of " writing-read-wipe-read " cycle-index.At normal temperatures and pressures, unpackaged devices switch 1,000,000 primary currents do not have significant change.
Embodiment
Embodiment 1:
Earlier the ITO on the ito glass is photo-etched into the electrode of 4 mm wides, 30 millimeters long, cleans then, nitrogen dries up, and uses oxygen plasma treatment 2 minutes.In vacuum degree is 1-5 * 10
-4In the filming equipment of handkerchief, the NPB of evaporation 200 nanometer thickness on the ITO electrode of handling well, that evaporation and ITO intersect on NPB again is wide 4 millimeters, long 30 millimeters, the metal A g electrode of thick 200 nanometers, is prepared into the organic memory that structure is ITO/NPB/Ag.The effective area of memory is 16 square millimeters.The evaporation rate of NPB is controlled at 0.2 nanometer per second, and the evaporation rate of Ag electrode is controlled at 1 nanometer per second.It is anodal that accompanying drawing 3 has provided with Ag, and ITO is the voltage-to-current bistable behavior curve of negative pole, and the starting voltage of scanning is-12 volts.What accompanying drawing 5 had provided organic memory writes-reads-wipe-read circulation.Wherein write, read and wipe voltage to be respectively-12,8 and 20 volts.Write voltage after read voltage through one, memory is in high electricity and leads state, wipes voltage after read voltage through one again, and memory is in and hangs down electricity and lead state.High electricity is led and is hanged down electricity and lead the state Kai Heguan of instruction memory respectively, and its switch current ratio is 20.At normal temperatures and pressures, unpackaged storage switch 1,000,000 primary currents do not have obvious variation, and this can be authenticated from accompanying drawing 6.
Embodiment 2:
Earlier the ITO on the ito glass is photo-etched into the electrode of 4 mm wides, 30 millimeters long, cleans then, nitrogen dries up, and handles 2 minutes with the contour daughter of oxygen.In vacuum degree is 1-5 * 10
-4In the filming equipment of handkerchief, on the ITO electrode of handling well, organic dyestuff rubrene is doped in the mode of steaming altogether forms organic layer among the NPB.The weight ratio of NPB and rubrene is 100: 5, and the thickness of doped organic layer is 200 nanometers.That at last evaporation and ITO intersect on the organic layer that mixes is wide 4 millimeters, grow 30 millimeters, the metal A g electrode of thick 200 nanometers, is prepared into the organic memory that structure is ITO/NPB:rubrene/Ag.The effective area of memory is 16 square millimeters.The evaporation rate of NPB is controlled at 0.2 nanometer per second, and the evaporation rate of rubrene is controlled at 0.01 nanometer per second, and the evaporation rate of Ag electrode is controlled at 1 nanometer per second.It is anodal that accompanying drawing 4 has provided with Ag, and ITO is the voltage-to-current bistable behavior curve of negative pole, and the starting voltage of scanning is-12 volts.The switch current ratio of device memory when writing, reading and wiping voltage and be respectively-12,8 and 20 volts is 60.At normal temperatures and pressures, unpackaged storage switch 1,000,000 primary currents do not have obvious variation.
Embodiment 3:
In vacuum degree is 1-5 * 10
-4In the filming equipment of handkerchief, the Ag electrode of wide 4 millimeters, long 30 millimeters of evaporation one deck, thick 300 nanometers on glass substrate is doped to organic dyestuff rubrene and forms organic layer among the NPB in the mode of steaming altogether.The weight ratio of NPB and rubrene is 100: 5, and the thickness of doped organic layer is 200 nanometers.At last on the organic layer that mixes evaporation and former Ag electrode crossing wide 4 millimeters, grow 30 millimeters, the metal A g electrode of thick 200 nanometers, be prepared into the organic memory that structure is Ag/NPB:rubrene/Ag.The effective area of memory is 16 square millimeters.The evaporation rate of NPB is controlled at 0.2 nanometer per second, and the evaporation rate of rubrene is controlled at 0.01 nanometer per second, and the evaporation rate of Ag electrode is controlled at 1 nanometer per second.The switch current ratio of memory is 100 when the voltage of writing, reading and wipe is respectively-10,4 and 12 volts.At normal temperatures and pressures, unpackaged storage switch 1,000,000 primary currents do not have obvious variation.
Embodiment 4:
Earlier the ITO on the ito glass is photo-etched into the electrode of 4 mm wides, 30 millimeters long, cleans then, nitrogen dries up, and uses oxygen plasma treatment 2 minutes.In vacuum degree is 1-5 * 10
-4In the filming equipment of handkerchief, on the ITO electrode of handling well, organic dyestuff DCJTB is doped in the mode of steaming altogether forms organic layer among the NPB.The weight ratio of NPB and DCJTB is 100: 5, and the thickness of doped organic layer is 200 nanometers.That at last evaporation and ITO intersect on the organic layer that mixes is wide 4 millimeters, grow 30 millimeters, the metal A g electrode of thick 200 nanometers, is prepared into the organic memory that structure is ITO/NPB:DCJTB/Ag.The effective area of memory is 16 square millimeters.The evaporation rate of NPB is controlled at 0.2 nanometer per second, and the evaporation rate of DCJTB is controlled at 0.01 nanometer per second, and the evaporation rate of Ag electrode is controlled at 1 nanometer per second.The switch current ratio of device memory when writing, reading and wiping voltage and be respectively-12,8 and 20 volts is 40.At normal temperatures and pressures, unpackaged storage switch 1,000,000 primary currents do not have obvious variation.
Embodiment 5:
Earlier the ITO on the ito glass is photo-etched into the electrode of 4 mm wides, 30 millimeters long, cleans then, nitrogen blow in, with oxygen plasma treatment 2 minutes.In vacuum degree is 1-5 * 10
-4In the filming equipment of handkerchief, on the ITO electrode of handling well, organic dyestuff DCM is doped in the mode of steaming altogether forms organic layer among the NPB.The weight ratio of NPB and DCM is 100: 5, and the thickness of doped organic layer is 200 nanometers.That at last evaporation and ITO intersect on the organic layer that mixes is wide 4 millimeters, grow 30 millimeters, the metal A g electrode of thick 200 nanometers, is prepared into the organic memory that structure is ITO/NPB:DCM/Ag.The effective area of memory is 16 square millimeters.The evaporation rate of NPB is controlled at 0.2 nanometer per second, and the evaporation rate of DCM is controlled at 0.01 nanometer per second, and the evaporation rate of Ag electrode is controlled at 1 nanometer per second.The switch current ratio of device memory when writing, reading and wiping voltage and be respectively-12,8 and 20 volts is 40.At normal temperatures and pressures, unpackaged storage switch 1,000,000 primary currents do not have obvious variation.
Embodiment 6:
Earlier the ITO on the ito glass is photo-etched into the electrode of 4 mm wides, 30 millimeters long, cleans then, nitrogen dries up, and uses oxygen plasma treatment 2 minutes.In vacuum degree is 1-5 * 10
-4In the filming equipment of handkerchief, on the ITO electrode of handling well, organic dyestuff C545T is doped in the mode of steaming altogether forms organic layer among the NPB.The weight ratio of NPB and C545T is 100: 5, and the thickness of doped organic layer is 200 nanometers.That at last evaporation and ITO intersect on the organic layer that mixes is wide 4 millimeters, grow 30 millimeters, the metal A g electrode of thick 200 nanometers, is prepared into the organic memory that structure is ITO/NPB:C545T/Ag.The effective area of memory is 16 square millimeters.The evaporation rate of NPB is controlled at 0.2 nanometer per second, and the evaporation rate of C545T is controlled at 0.01 nanometer per second, and the evaporation rate of Ag electrode is controlled at 1 nanometer per second.The switch current ratio of device memory when writing, reading and wiping voltage and be respectively-12,8 and 20 volts is 30.At normal temperatures and pressures, unpackaged storage switch 1,000,000 primary currents do not have obvious variation.
Embodiment 7:
In vacuum degree is 1-5 * 10
-4In the filming equipment of handkerchief, go up evaporation one deck wide 4 millimeters, long 30 millimeters, the Ag electrode of thick 300 nanometers, organic dyestuff rubrene is doped in the mode of steaming altogether forms organic layer among the NPB at flexible substrate polyester (PET).The weight ratio of NPB and rubrene is 100: 5, and the thickness of doped organic layer is 200 nanometers.At last on the organic layer that mixes evaporation and former Ag electrode crossing wide 4 millimeters, grow 30 millimeters, the metal A g electrode of thick 200 nanometers, be prepared into the organic memory that structure is Ag/NPB:rubrene/Ag.The effective area of memory is 16 square millimeters.The evaporation rate of NPB is controlled at 0.2 nanometer per second, and the evaporation rate of rubrene is controlled at 0.01 nanometer per second, and the evaporation rate of Ag electrode is controlled at 1 nanometer per second.The switch current ratio of memory is 100 when the voltage of writing, reading and wipe is respectively-10,4 and 12 volts.At normal temperatures and pressures, unpackaged storage switch 1,000,000 primary currents do not have obvious variation.
Claims (4)
1, a kind of single-layer organic memory is characterized in that its structural group of device becomes: glass of Lian Jieing or flexible substrate (1) successively, an electrode (2), the NPB organic layer (3) that hole mobile material NPB or organic dyestuff mix, another electrode (4); Wherein having an electrode in two electrodes at least is silver, and two electrodes intersect.
2, single-layer organic memory as claimed in claim 1 it is characterized in that an electrode (2) adopts indium tin oxide ITO or Ag, and another electrode (4) is Ag; Organic layer (3) adopts hole mobile material X, X '-two (1-naphthyl)-N, N '-diphenyl-1,1 '-diphenyl-4,4 '-diamines (NPB), or the NPB of organic dyestuff doping, wherein dye adulterated dose is 5,6,11,12-tetraphenyl-naphthonaphthalene (rubrene), the 2-{2-tert-butyl group-6-[2-(1,1,7,7-tetramethyl-2,3,6,7-tetrahydrochysene-1H, 5H-pyrido [3,2,1-ij] quinoline-9-yl)-vinyl]-pyrans-4-inner salt alkene }-malononitrile (DCJTB), 2-[2-isopropyl-6-[2-(1,1,7,7-tetramethyl-2,3,6,7-tetrahydrochysene-1H, 5H-pyrido [3,2,1-ij] quinoline-9-yl)-vinyl]-pyrans-4-inner salt alkene }-malononitrile (DCJTI), 4-(dicyano methylene)-2-methyl-6-[is right-(dimethylamino) styryl]-4H-pyrans (DCM), 10-(2-[4-morpholinodithio base)-2,3,6,7-tetrahydrochysene-1,1,7,7-tetramethyl-1H, 5H, 11H-(1)-benzo give a tongue-lashing the ketone group of muttering-(6,7,8-ij) quinolizine-11-ketone (C545T) and quinacridine.
3, a kind of method for preparing single-layer organic memory is characterized in that an electrode (2) adopts ITO, and IT0 is photo-etched into the electrode of fine strip shape, cleans then, and nitrogen dries up, with oxygen plasma treatment 2 minutes; And then be 1-5 * 10 in vacuum degree
-4In the filming equipment of handkerchief, evaporation organic layer (3) and another electrode silver (4) successively on an electrode (2), wherein the thickness of silver electrode (4) is the 100-500 nanometer, and intersects with electrode (2), the thickness of organic layer is the 50-500 nanometer; The evaporation rate of NPB is controlled at 0.1-0.5 nanometer per second in the organic layer, and dye adulterated dose evaporation rate is controlled at 0.001-0.05 nanometer per second, and the evaporation rate of electrode is controlled at 0.5-5 nanometer per second; Organic layer adopts dye adulterated NPB, and dyestuff and NPB steam altogether, and the dyestuff of doping and the weight ratio of NPB are between 0%-10%.
4, a kind of method for preparing single-layer organic memory is characterized in that an electrode (2) adopts silver, is 1-5 * 10 in vacuum degree earlier
-4In the filming equipment of handkerchief, the silver electrode of fine strip shape on evaporation on the substrate; And then be 1-5 * 10 in vacuum degree
-4In the filming equipment of handkerchief, evaporation organic layer (3) and another electrode silver (4) successively on an electrode (2), wherein the thickness of two electrodes is the 100-500 nanometer, and intersects mutually, and the thickness of organic layer is the 50-500 nanometer; The evaporation rate of NPB is controlled at 0.1-0.5 nanometer per second in the organic layer, and dye adulterated dose evaporation rate is controlled at 0.001-0.05 nanometer per second, and the evaporation rate of two electrodes is controlled at 0.5-5 nanometer per second; Organic layer adopts dye adulterated NPB, and dyestuff and NPB steam altogether, and the dyestuff of doping and the weight ratio of NPB are between 0%-10%.
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Citations (4)
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| CN1239329A (en) * | 1999-06-16 | 1999-12-22 | 复旦大学 | Organical electric bistable device with superhigh-speed phase change |
| JP2002026277A (en) * | 2000-06-30 | 2002-01-25 | Seiko Epson Corp | Memory device and method for driving the same |
| CN1392564A (en) * | 2001-06-05 | 2003-01-22 | 惠普公司 | Non-volatile memory |
| CN1481034A (en) * | 2002-07-12 | 2004-03-10 | 日本先锋公司 | Organic film switching memory and memory appliance |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1239329A (en) * | 1999-06-16 | 1999-12-22 | 复旦大学 | Organical electric bistable device with superhigh-speed phase change |
| JP2002026277A (en) * | 2000-06-30 | 2002-01-25 | Seiko Epson Corp | Memory device and method for driving the same |
| CN1392564A (en) * | 2001-06-05 | 2003-01-22 | 惠普公司 | Non-volatile memory |
| CN1481034A (en) * | 2002-07-12 | 2004-03-10 | 日本先锋公司 | Organic film switching memory and memory appliance |
Non-Patent Citations (1)
| Title |
|---|
| 薄膜聚合物存储器. 申功烈. 电子产品世界，邮发代号82-552. 2003 * |
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