CN1849718A - Memory device and methods of using and making the device - Google Patents
Memory device and methods of using and making the device Download PDFInfo
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- CN1849718A CN1849718A CN 200480025672 CN200480025672A CN1849718A CN 1849718 A CN1849718 A CN 1849718A CN 200480025672 CN200480025672 CN 200480025672 CN 200480025672 A CN200480025672 A CN 200480025672A CN 1849718 A CN1849718 A CN 1849718A
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Abstract
A memory cell (104) made of two electrodes(106, 202, 108, 204) with a controllably conductive media between the two electrodes is disclosed. The controllably conductive media (110) contains an active low conductive layer (112) and passive layer (114). The controllably conductive media (110) changes its impedance when an external stimuli such as an applied electric field is imposed thereon. Methods of making the memory devices/cells, methods of using the memory devices/cells, and devices such as computers containing the memory devices/cells are also disclosed.
Description
Technical field
The present invention is generally speaking about the method for memory device and manufacturing and the described memory device of use.Particularly the present invention is about containing the memory device of may command conductive layer.
Background technology
The basic function of computer and memory device comprises process information and storage.In general computer system, these algorithms, logic and storage operation are to carry out by being often referred to the device that reversibly switches between the state that is called " 0 " and " 1 " at two.These switching devices are by the semiconductor device institute assembly that can carry out these multiple functions and can switch with high speed between two states.。
Electronically addressing or logical device for example are used for storing or deal with data, are to use inorganic solid state, and particularly crystalline silicon devices is made.Metal oxide semiconductor field-effect answers transistor (MOSFET) to be one of main important devices.
Many for make faster, the littler and more cheap progress of computer and memory device relate to more multiple transistor or other electronic structure is integrated, clamp-on on the silicon of postage-stamp-sized.The silicon chip of postage-stamp-sized may comprise tens million of transistors, and each transistor is little of being the hundreds of nanometer.Yet, based on the device of silicon just near their the basic dimension of object limit.
Inorganic solid-state devices can't be used labyrinth usually, because this can cause expensive and loss of data storage density.Based on the circuit of the volatile semiconductor memory of inorganic semiconductor material must the sustainable supply electric current to keep store information, the result causes heat and high power consumption.Nonvolatile semiconductor device has the data rate (data rate) of reduction and high relatively energy loss and complexity highly.
Moreover, owing to inorganic solid state device sizes reduction and integrated level rising, the susceptibility of aiming at feasible value is improved, thereby it is more difficult significantly to cause manufacturing to have.On behalf of minimum dimension, form feature with little minimum dimension to be used to make operating circuit.Must have aligning feasible value, for example 1/4th of minimum dimension much smaller than little minimum dimension.
Dwindle inorganic solid-state devices and cause the problem of dopant diffusion lengths.When the dimension reduction, the dopant diffusion lengths in the silicon causes the difficulty of making design.In this relation, then use many adjustings to reduce the alloy mobility and reduce the time be in high temperature.Yet, and uncertain these adjustings can continue and unrestricted.
Crossing semiconductor junction (in reverse-bias direction) imposes voltage and can produce depleted region near connecing face.The width of depleted region is to decide according to semi-conductive doping level.If depleted region is extended and contacted with another depleted region, then may produce break-through (punch through) or uncontrollable electric current.
The higher-doped degree trends towards making avoids the required interval of break-through to minimize.Yet if the change in voltage of per unit distance is very big, can produces other difficulty and be: the big change in voltage of per unit distance causes the intensity of electric field big.Electronics by sharp gradient like this may accelerate to significantly the energy level greater than minimum conduction band (conduction band) energy.So electronics is known as hot electron, and may have enough energy by insulator, causes expendable semiconductor device to damage.
Dwindle and the integrated insulating properties of monolithic semiconductor substrate that causes has more challenge.Particularly device lateral isolation each other has difficulty in some situation.Another difficulty is that leakage current dwindles.Another difficulty is the diffusion of charge carrier at substrate again; Be free carrier can spread surpass tens of microns and in and store charge.
Summary of the invention
For the present invention is provided the basic understanding of some aspects, aspect, following is summary description of the present invention.This summary description and be not used in definition of the present invention main/key factor or be used to describe scope of the present invention.Its sole purpose is for showing notions more of the present invention in simplified form as preface in greater detail afterwards.
The invention provides new memory device, its have following one or more: little size, the information that can store multidigit (multiple bits), short resistance/impedance switching time, low operating voltage, low cost, high-reliability, Changshou life (thousands of/millions of circulations) than conventional memory device but three-dimension packaging, relatively low temperature (or high temperature) handle, in light weight, high density/integrated level, and the memory conservation degree that prolongs.
An aspect of of the present present invention is about containing the memory device of at least one memory cell, this memory cell is to be made of two electrodes, has the may command conducting medium between these two electrodes, this may command conducting medium contains low conductive layer and passive layer, and wherein this passive layer has the valence band Fermi level (Fermi level) that approaches low conductive layer.Others of the present invention are about using (for example programming) described memory device/unit to make memory device/unit, and about the device of for example computer that contains described memory device/unit.
In order to address relevant purpose before finishing, the feature that the present invention includes complete below description and in claims, point out especially.Following explanation and accompanying drawing describe some aspect of the present invention and execution mode in detail.Yet these only are representational, and rule of the present invention can use some modes to change.Other purpose of the present invention, advantage or novel feature will and become more remarkable with reference to the accompanying drawings by following detailed description of the present invention.
Description of drawings
Fig. 1 describes the perspective view of the two-dimentional microelectronic component that contains a plurality of memory devices for according to an aspect of the present invention.
Fig. 2 describes the perspective view of the three dimensional microelectronic device that contains a plurality of memory devices for according to a further aspect in the invention.
Embodiment
The present invention relates to the memory cell that constitutes by two electrodes, have the may command conducting medium between these two electrodes.The may command conducting medium contains conductive layer and passive layer.This medium can be organic and inorganic or organic mixing inorganic material.Memory cell can randomly contain other layer, and for example other electrode, electric charge keep layer and/or chemical active layer.The impedance meeting of may command conducting medium changes when applying electric field imposing environmental stimuli.A plurality of memory cell, it can be described as array, forms a new memory device.In this relation, memory cell can form new memory device and operate in the mode that is similar to the mos field effect transistor (MOSFET) in the conventional semiconductor storage unit.Yet, in memory device, use new memory cell to replace conventional MOSFET and have advantage.
With reference to figure 1, the concise and to the point microelectronic memory device of describing according to an aspect of the present invention that contains a plurality of memory cell 100, and decomposition Figure 102 of exemplary memory cell 104.Microelectronic memory device 100 contains requisite number purpose memory cell, by the number decision of the row that occurred, row and layer (three-dimensional as described later).First electrode 106 and second electrode 108 show with the direction of perpendicular, though other direction also may reach the structure of decomposing Figure 102.Each memory cell 104 contains first electrode 106 and second electrode 108, and the may command conducting medium 110 between two electrodes.May command conducting medium 110 contains low conductive layer 112 and passive layer 114.Peripheral circuit and device do not show for simplification.
Memory cell contains at least two electrodes, can be arranged at two centres of clamping the electrode of may command conducting medium as one or more electrodes.Electrode can for example conducting metal, conductive metal alloy, conducting metal oxide, conducting polymer thin film, semi-conducting material etc. be made by electric conducting material.
The example of electrode comprises one or more in the following material: aluminium, chromium, copper, germanium, gold, magnesium, manganese, indium, iron, nickel, palladium, platinum, silver, titanium, zinc and alloy thereof; Tin indium oxide (ITO); Polysilicon; Doped amorphous silicon; Metal silicide etc.Alloy electrode is particularly including Hastelloy (Hastelloy ), kovar alloy (Kovar ), invar alloy (Invar), monel alloy (Monel ), Ying Kenaier alloy (Inconel ), brass, stainless steel, magnesium-silver alloy and multiple other alloy.
In one embodiment, the thickness of each electrode is about 0.01 Φ m or bigger and for about 10 μ m or littler independently.In another specific embodiment, the thickness of each electrode is independently for being about 0.05 μ m or bigger and be about 5 μ m or littler.In another specific embodiment, the thickness of each electrode is about 0.1 μ m or bigger and for about 1 μ m or littler independently.
The may command conducting medium is arranged between two electrodes, can use environmental stimuli to show as conductivity, semiconduction or non-conductive with controllable way.Usually when not having environmental stimuli, the may command conducting medium is non-conductive or has high impedance.Moreover, in some specific embodiments, can set up the conductivity/resistivity of a plurality of degree to the may command conducting medium by controllable way.For example, the conductivity/resistivity that is used for a plurality of degree of may command conducting medium can comprise non-conductive state, high conduction state and semiconductive state.
The may command conducting medium can show as conductivity, the non-conductive or state of any mediate (conductivity degree) with controllable way by environmental stimuli (extraneous expression is from the outside of may command medium).For example, externally under electric field, the radiation etc., originally be converted to conductivity may command conducting medium for non-conductive may command conducting medium.
The may command conducting medium contains one or more low conductive layers and one or more passive layer.In one embodiment, the may command conducting medium contains at least one organic semiconductor layer that is adjacent to passive layer (without any the intermediate layer between organic semiconductor layer and passive layer).In another specific embodiment, the may command conducting medium contains at least one inorganic low conductive layer that is adjacent to passive layer (without any the intermediate layer between inorganic layer and passive layer).In another specific embodiment, the mixture that the may command conducting medium contains organic and inorganic material is adjacent to passive layer (without any the intermediate layer between low conductive layer and passive layer) as low conductive layer.
Organic semiconductor layer contains at least a organic polymer (as the conjugation organic polymer), organo-metallic compound (as the conjugation organo-metallic compound), organometallic polymer (as the conjugation organometallic polymer), buckyballs (Buckyball), carbon nano-tube (as C6 to C60 carbon nano-tube) etc.Therefore organic semiconductor has carbon is main structure, and being generally carbon-hydrogen is main structure, and it is different from conventional MOSFET.The characteristic feature of organic semiconducting materials has the p track of overlapping for them, and/or they have at least two stable oxidation state.The feature of organic semiconducting materials is that also they can present two or more resonant structures.Overlapping p track provides the controlled electrical conductivity matter of may command conducting medium.The amount of electric charge injection organic semiconductor layer also influences the conductivity degree of organic semiconductor layer.
Carbon nano-tube is generally the seamless cylinder that the hexagon net of carbon atom (usually from about 6 to about 60 carbon atoms) is rolled into.Each end can be divided subcovering by half fullerene (fullerence).Carbon nano-tube can be by the laser evaporation effect (carbon-Raney nickel can quicken to grow up) or the carbon-arc method preparation of carbon target, to grow into the similar array of single-walled nanotube.Buckyballs is more specific to be buckminsterfullerence (Buckminster Fullerene), is the pure carbon of 60 atoms of football-shaped bunch.
Organic polymer contains the conjugation organic polymer usually.The polymer backbone of conjugation organic polymer extends (essence is perpendicular to the inside of electrode, opposed face usually) along its length between electrode.The conjugation organic polymer can be a linearity or a chain, as long as this polymer keeps its conjugated nature.Conjugated polymer be characterized as the p track that they have overlapping.The feature of conjugated polymer is that also they present two or more resonant structures.The conjugated nature of conjugation organic polymer provides the controlled electrical conductivity matter of may command conducting medium.
In this relation, low conductive layer or organic semiconductor layer as the conjugation organic polymer, have the ability that gives or accept electric charge.Usually, the atom/part in organic semiconductor or the polymer has at least two metastable oxidation state.Two metastable oxidation state make organic semiconductor can give and accept electric charge and promote that with conductivity compound interacts electrically.Organic semiconductor layer gives and accepts electric charge and also promotes the characteristic of compound to decide according to conductivity with the synergistic electrically ability of passive layer.Can be from the iunjected charge of passive layer by limitation (trap) at organic semiconductor layer and the interface that is adjacent to passive layer.This can change the conductivity of low conductive layer and cause the storage effect.
The organic polymer organic monomer of organic polymer (or constitute) can be ring-type or non-annularity.Between formation or depositional stage, organic polymer is self assembly between electrode.The example of conjugation organic polymer comprises one or more polyacetylene; Polyphenylacetylene; Poly-tolans; Polyaniline; Poly-(right-phenyl-vinyl); Polythiophene; Poly-porphyrin; The big ring of porphyrin; The poly-porphyrin that mercaptan is derived; Poly-class of metallocenes such as poly-ferrocene, poly-phthalocyanine; The polyethylene base system; Polystyrene (polystiroles); Poly-(tert-butyl group) tolans; Poly-(trifluoromethyl) tolans; Poly-two (trifluoromethyl) acetylene; Poly-two (tert-butyl diphenyl) acetylene; Poly-(trimethyl silyl) tolans; Poly-(carbazole) tolans; Polydiacetylene; Polypyridine acetylene; The polymethoxy phenylacetylene; Polymethyl-benzene acetylene; Poly-(tert-butyl group) phenylacetylene; Poly-nitro-phenylacetylene; Poly-(trifluoromethyl) phenylacetylene; Poly-(trimethyl silyl) phenylacetylene; Poly-dipyrryl methane; Poly-istain (polyindoqiunone); Poly-dihydroxy indole; Poly-trihydroxyindole; Furans-poly-dihydroxy indole; Poly-istain-2-carboxyl; Poly-istain; Polyphenyl and dithiazole; Poly-(right-phenyl sulfide); Polypyrrole; Polystyrene; Poly-furans; Poly-indoles; Poly-azulenes; Polyphenylene; Polypyridine; Poly-two pyridines; Poly-six thiophene; Poly-(silicone base half porphyrazine) [poly (siliconoxoporphyrazine)]; Poly-(germanium ketone group half porphyrazine); Poly-(vinyl dioxy base thiophene); Polypyridine metal complex etc.
The chemical constitution example of the repetitive/part of manufacturing conjugation organic polymer and conjugation organometallic polymer comprises one or more in the formula (I) to (XIII):
Wherein each R is hydrogen or alkyl independently; Each M is metal independently; Each E is O, N, S, Se, Te or CH independently; Each L is independently for containing or the continuous group of conjugation (unsaturation); And each n is about 1 or bigger and about 25,000 or littler independently.In another specific embodiment, each n is about 2 or bigger and about 10,000 or littler independently.In another specific embodiment, each n is about 20 or bigger and about 5,000 or littler independently.The example of metal comprises Ag, Al, Au, B, Cd, Co, Cu, Fe, Ga, Hg, Ir, Mg, Mn, Ni, Pb, Pd, Pt, Rh, Sn and Zn.The example of L group comprises the alkyl that has conjugacy or have the ability that forms resonant structure, for example phenyl, the phenyl that is substituted, acetenyl etc.
Any described chemical formula can have one or more side chain substituents, and it is not presented in the chemical formula.For example, phenyl can appear on the polythiophene structure, as on 3 of each thiophene part.In another example, alkyl, alkoxyl, cyano group, amido and/or hydroxyl substituent can appear on the phenyl ring of any polyphenylacetylene, poly-tolans and poly-(right-phenyl vinyl) conjugated polymer.
Noun " alkyl " comprises hydrocarbon and is substituted the hydrocarbon group of (substantially).Alkyl contains 1 or more carbon atoms and common about 60 or carbon atom still less.In another specific embodiment, alkyl contains 2 or more carbon atoms and about 30 or carbon atom still less.The hydrocarbon group that is meant that is substituted contains hetero atom substituents or hetero-atom and main organic character that can impact polymer, and does not hinder organic polymer to form the ability of conjugated structure.The example of alkyl comprises following:
(1) hydrocarbon substituent, be fatty group (as alkyl or alkenyl), alcyl (as cycloalkyl, cycloalkenyl group) substituting group, acyl group, phenyl, through aromatic radical-, fatty group-and the aromatic substituents of alcyl-replacement etc., and cyclic substituents, wherein said ring be fully another part by molecule (that is, for example, the substituting group of any two appointments can form an alcyl together);
(2) hydrocarbon substituent that is substituted, promptly those contain the substituting group of non-hydrocarbon group, and in the present invention in full, it can't change substituent main organic character; One skilled in the art will recognize that these groups (as halogen (particularly chlorine and fluorine, for example perfluoroalkyl, perfluor aryl), cyano group, thiocyano, amido, alkylamino radical, sulfonyl, hydroxyl, sulfhydryl, nitro, nitroso, sulphur oxygen base (sulfoxy) etc.);
(3) hetero atom substituents promptly has main organic character in the present invention in full, contain atom except carbon, appear in the ring or in the chain and the other parts substituting group (as alkoxyl, alkylthio group) that to be carbon atom form.Suitably hetero-atom, comprises for apparent and easy to know those skilled in the art, for example, and sulphur, oxygen, nitrogen, fluorine, chlorine and those substituting groups such as pyridine radicals, furyl, thienyl, imidazole radicals, imido grpup, amide groups, amido formoxyl etc.
Except organic material or as the substitute of organic material, active low conductive layer can contain organic and/or inorganic materials.Inorganic material comprises, low electric conductivity chalcogen compound (chalcogenide) or transition metal oxide.Transition metal oxide has low electric conductivity usually, with formula M
xO
yExpression, wherein M is a transition metal, and x and y are from about 0.25 to about 5 independently.Similar transient metal sulfide also can use.The transition metal that is in the oxide allows a plurality of oxidation state, causes externally changing after the match conductivity.Example comprises Cu oxide (CuO, Cu
2O), ferriferous oxide (FeO, Fe
3O
4), Mn oxide (MnO
2, Mn
2O
3Deng), titanium oxide (TiO
2).This material can hot evaporation, CVD or plasma form.An advantage using inorganic material is to have the bigger elasticity of using high temperature to make, makes and its purposes can be combined with deposited top layer such as electrode with routine techniques.Another advantage is that inorganic material has high heat diffusion capabilities.This makes the high current practice of obtained device have high reliability.
Active low conductive layer can be organic and mixture inorganic material.Inorganic material (transition metal oxide/sulfide) embeds in the organic semiconducting materials usually.Example comprises polyphenylacetylene and Cu
2S mixing, polyphenylacetylene and Cu
2O mixing etc.This layer can economic mode form.For example, can rotary coating be dissolved with Cu as styrene 4-sulfonic acid copper
+The polyphenylacetylene of salt.Substrate can be passive layer or promoting layer.Then use the CVD method to import as H
2The reactant gas of S, with and Cu
+React and the even Cu that embeds of generation
2S.This kind organic and inorganic composite material can have controllable initial conductivity by adjusting copper ion concentration.Another advantage than pure organic materials can be in some instances because the existence of inorganic material has good heat diffusion capabilities for the organic-inorganic composite material.Therefore, it can allow the high current practice of obtained device to have good reliability.
In a specific embodiment, new memory cell contains inorganic Cu
2O and organic semiconducting materials both as active low conductive layer.In this specific embodiment, Cu
2O is just on passive layer and have about 1 nanometer to the thickness of about 3 nanometers.Organic semiconducting materials is at Cu
2O is last and have about 0.001 micron or about 1 micron or thickness still less of as many as more.
In one embodiment, low conductive layer contains the thin layer that is designed to promote or prolong charge retention time.This thin layer can be arranged at low conductive layer Anywhere, but approaching usually layer centre.Thin layer contains the compound of any electrode material or following heterocyclic/aromatic compound layer.In one embodiment, thin layer has about 50 dusts () or about 0.1 micron or thickness still less of as many as more.In another specific embodiment, thin layer has about 100 dusts or about 0.05 micron or thickness still less of as many as more.For example, memory cell can contain first electrode of copper, the passive layer of copper sulfide, the low conductive layer of poly-(phenyl vinyl) and second electrode of aluminium, and wherein poly-(phenyl vinyl) low conductive layer contains the thick copper layer of 250 dusts therein.
In one embodiment, organic semiconducting materials does not contain organic metallic compound.In another specific embodiment, organic semiconducting materials contains the organic polymer that mixes with organo-metallic compound.In another specific embodiment, memory cell randomly contains the organo-metallic compound layer.In a specific embodiment again, low conductive layer contains organo-metallic compound.The chemical constitution example of multiple organo-metallic compound comprises formula (XIV) to (XVII):
M and E are for as defined above in the formula.
In one embodiment, low conductive layer is not with salt dopping.In another specific embodiment, low conductive layer is with salt dopping.Described salt is for having anion and cationic ionic compound.The general example of salt of low conductive layer of can be used for mixing comprises alkaline earth metal halogen, sulfate, persulfate, nitrate, phosphate etc.; Alkali metal halogen, sulfate, persulfate, nitrate, phosphate etc.; Transition metal halogen, sulfate, persulfate, nitrate, phosphate etc.; Ammonium halogen, sulfate, persulfate, nitrate, phosphate etc.; Quaternary alkyl ammonium halogen, sulfate, persulfate, nitrate, phosphate etc.
In one embodiment, low conductive layer has about 0.001 micron or about 5 microns or thickness still less of as many as more.In another specific embodiment, low conductive layer has about 0.01 micron or more 2.5 microns of as many as or thickness still less.In another specific embodiment, low conductive layer has about 0.05 micron or about 1 micron or thickness still less of as many as more.
Low conductive layer can use the rotary coating technology to form (mixture of deposited polymer/polymer precursor and solvent then removes solvent from substrate/electrode), uses the optional chemical vapor deposition (CVD) formation that comprises gas reaction, vapour deposition etc.CVD comprises low-pressure chemical vapor deposition (LPCVD), plasma gain chemical vapour deposition (CVD) (PECVD) and the vapour deposition (HDCVD) of high density chemistry.Between formation or depositional stage, low electric conducting material can self assembly between electrode.Usually do not need one or more terminal functional groupization with organic polymer so that it is appended to electrode/passive layer.
Feasiblely between low electric conducting material and passive layer become covalent bond.Perhaps, need closely contact to be provided at the good charge charge carrier/electron exchange between low conductive layer and passive layer.Low conductive layer and passive layer are that electrical couplings makes at two interlayers charge carrier/electron exchange is arranged.
Passive layer contains at least a conduction and promotes compound, and it provides the controlled electrical conductivity matter of may command conducting medium.Conduction promotes that compound has the ability that gives or accept electric charge (electric hole and/or electronics).Therefore passive layer can and hang down conductive layer/passive layer is transported, promoted electric charge/charge carrier to be injected into low conductive layer and/or is increased in low conductive layer between the interface electric charge carrier concentration at electrode.In some instances, passive layer can store the charge balance that opposite charges provides the global storage device thus.Store charge/electric charge carrier is to promote the existence of two relatively stable oxidation state of compound to promote by conduction.
In other example, passive layer has ferroelectric behavior (ferroelectric behavior), as the ion exchange under at impressed field.This usually occurs in the face that connects of active layer." ferroelectric " character causes the polarity that influenced by impressed field, and it revises interface state significantly, then changes the conductivity of memory cell.Memory cell by this class passive layer material has the ion-electron conductive mechanism, and because in the displacement of the metal ion at interface, so the data retention time of memory cell is longer relatively usually.Yet, have shortcoming in some instances, because need the long period that memory cell is switched to another state by a state sometimes.
Usually, conduction promotes compound or promotes the atom in the compound to have at least two metastable oxidation state in conduction.Two relatively stable oxidation state allow conduction promote compound can give or accept electric charge and interact electrically with low conductive layer.Employed particular conductivity promotes compound to select through certain in given memory cell, so that two relatively stable oxidation state couplings of two relatively stable oxidation state and low electric conducting material.Make conduction promote being with of two relatively stable oxidation state of compound and low electric conducting material to be complementary, promote the reservation of electric charge carrier at low conductive layer.
Coupling can be with the Fermi level that is meant passive layer to approach the valence band of active low conductive layer.As a result, when being with when not changing in fact of the low conductive layer of charging, the electric charge carrier of injection (to active layer) can be again and the charge bonded that is in passive layer.Coupling can be with and comprise erasing and the length of electric charge (data) retention time of the electric charge injection of trading off.
In one embodiment, when coupling can be with, the Fermi level of passive layer was in about 0.7 electron-volt (eV) of the valence band of low conductive layer.In another specific embodiment, the Fermi level of passive layer is in about 0.5 electron-volt of the valence band of low conductive layer.In another specific embodiment, the Fermi level of passive layer is in about 0.3 electron-volt of the valence band of low conductive layer.In a specific embodiment again, the Fermi level of passive layer is in about 0.15 electron-volt of the valence band of low conductive layer.In some instances, valence band is the highest occupied molecular orbit (HOMO) of material.
Impose impressed field according to field direction and can reduce energy barrier (energybarrier) between passive layer and low conductive layer.Therefore, can obtain in programming operation, to strengthen electric charge and inject, and in erase operation for use, also strengthen charge bonded in reverse field at normal field.
In some instances, when electric conducting material was hanged down in formation, particularly when low conductive layer contained the conjugation organic polymer, passive layer can be used as catalyst.In this relation, the polymer backbone of conjugation organic polymer can form in abutting connection with passive layer at the beginning, and away from reaching growth or combination perpendicular to the passive layer surface in fact.As a result, the polymer backbone of conjugation organic polymer is self aligned in the two interelectrode directions of crossing.
The conduction that can form passive layer promotes the example of compound to comprise one or more ketone sulfide (Cu
xS, wherein x is about 0.5 to about 3), silver-colored sulfide (Ag
2S, AgS), golden sulfide (Au
2S, AuS) etc.In these materials, Cu
2S and Ag
2S can have ferroelectric property, refers to that metal ion externally has displacement under the manipulation fields.Passive layer can contain two-layer or more multi-layered sub-passive layer (sub-passive layers), and each sublayer is contained, and identical, different or multiple conduction promotes compound.
Oxidation technology is used in the growth of passive layer, forms via gas-phase reaction or deposition between electrode.In some instances, in order to promote long charge retention time (in low conductive layer), can plasma treatment after passive layer forms.Plasma treatment has been modified the energy barrier of passive layer.
In one embodiment, containing thickness that conduction promotes the passive layer of compound is about 2 dusts or about 0.1 micron or still less of as many as more.In another specific embodiment, it is about 10 dusts or about 0.01 micron or still less of as many as more that passive layer has thickness.In another specific embodiment, it is about 50 dusts or about 0.005 micron or still less of as many as more that passive layer has thickness.
For manufacturing and the operation that promotes new memory cell, active low conductive layer is than passive bed thickness.In one embodiment, the thickness of low conductive layer than the thickness thick about 10 of passive layer to about 500 times.In another specific embodiment, the thickness of low conductive layer than the thickness thick about 25 of passive layer to about 250 times.
In one embodiment, new memory cell randomly contains heterocyclic/aromatic compound layer.In another specific embodiment, low conductive layer is doped with heterocyclic/aromatic compound.If exist, the thickness of this heterocyclic/aromatic compound layer is about 0.001 micron or about 1 micron or still less of as many as more.The example of the chemical constitution of multiple heterocyclic/aromatic compound specifically comprises nitrogen heterocyclic ring, comprises formula (XVIII) to (XXIII):
The area size of single memory cell (measuring the surface area of two electrodes that directly overlap mutually) is less based on the memory cell such as the MOSFET of silicon than routine.In one embodiment, the area of memory cell of the present invention size is about 0.0001 square micron or about 4 square microns of as many as or littler more.In another specific embodiment, the area of memory cell of the present invention size is about 0.001 square micron or about 1 square micron of as many as or littler more.
Use outside stimulus to promote the operation of new memory spare/unit to reach the switching effect.Outside stimulus comprises external electrical field and/or light radiation.Under multiple situation, memory cell is conduction (Low ESR or " opening " state) or non-conductive (high impedance or " pass " state).
Memory cell can have conduction or the low impedance state more than again, for example very high conduction state (very low impedance state), high conduction state (low impedance state), conduction state (moderate impedance state) and non-conductive state (high impedance status), making thus can be with the information storage of multidigit in single memory cell, and for example 2 or bits of data or 4 or the data of multidigit more more.
When outside stimulus surpasses threshold values as the electric field that applies, memory cell then takes place switch to " opening " state from " pass ".When outside stimulus does not surpass threshold values or do not exist, memory cell then takes place switch to " pass " state from " opening ".Threshold values changes according to multiple factor, comprises the material character that constitutes memory cell, low conductive layer and passive layer, the thickness of multiple layer etc.
Generally speaking, when the outside stimulus that exist to surpass threshold values during as the electric field that applies (" opening " state), then make the voltage apply with the information write storage unit or from the memory cell information of erasing, and when having the outside stimulus be lower than threshold values, make that then the voltage that applies reads information from memory cell as the electric field that applies; Otherwise, when not having the environmental stimuli above threshold values (" pass " state), then avoid the voltage that applies with the information write storage unit or from the memory cell information of erasing.
For writing information to memory cell, then apply voltage or pulse signal above valve.For reading the information of write storage unit, then apply the voltage or the electric field of any polarity.Measuring impedance is to be in low impedance state or high impedance status (therefore being " opening " or " pass ") with the decision memory cell.For the information of erasing and writing, then impose above the negative voltage of threshold values or polarity in contrast to the polarity that writes signal from memory cell.
Memory device described here can be used for forming logical device, as central processing unit (CPU); Volatile memory device such as DRAM device, SRAM device etc.; I/O device (I/O chip); And nonvolatile semiconductor memory member such as EEPROM, EPROM, PROM etc.Memory device can in-plane (two dimension) be made, or with the three-dimensional manufacturing of the planar array that contains at least two memory cell.
With reference to figure 2, according to an aspect of the present invention, show the three dimensional microelectronic memory device 200 that contains a plurality of memory cell.Three dimensional microelectronic memory device 200 contains a plurality of first electrodes 202, a plurality of second electrode 204 and a plurality of memory cell layers 206.It between each first and second electrode may command conducting medium (not shown).A plurality of first electrodes 202 and a plurality of second electrode 204 show with the direction of perpendicular, but other direction is also possible.Three dimensional microelectronic memory device can contain the memory cell of very high number, therefore promotes device density.Show peripheral circuit and device for simplicity and not.
Described memory cells/devices can be used for the device of any needs storage.For example, memory device is used for computer, equipment, industrial equipment, hand-held device, communication equipment, media device, research and research and development equipment, haulage vehicle, radar/satellite device etc.Hand-held device, and hand-held electronic devices particularly are because the volume of new memory spare is little and in light weight, so can reach the enhancement of Portability.The example of hand-held device comprises mobile phone and other two places communication device, personal digital assistant, hand held omniselector, calling set, notebook computer, remote controllers, register (film and sound), broadcast receiver, micro television and web browser, camera etc.
Following embodiment describes the present invention.Unless otherwise noted, otherwise the other parts of following embodiment and specification and claims, all parts and percentage are calculation by weight, and all temperature are Celsius temperature, and pressure is atmospheric pressure or near atmospheric pressure.
Embodiment 1
Use has the top electrode of 2,000 dust thickness ITO and has the bottom electrode formation memory cell of 1,000 dust thickness silver.Silver sulfide passive layer with 50 dust thickness is provided on bottom electrode.The organic semiconductor layer that will contain polyphenylacetylene and have 800 dust thickness is formed on the passive layer with the CVD technology.Then again top electrode is fixed on the polymeric layer.
Embodiment 2
Use has the top electrode of 1,000 dust thickness copper and has the bottom electrode formation memory cell of 1,000 dust thickness copper.Passive layer of copper sulfide with 70 dust thickness is provided on bottom electrode.Use hot heating technique on copper sulfide, to form and have the Cu of 2 nano thickness as first active layer
2O.The organic polymer layers that will contain polyphenylacetylene and have conduct second active layer of 900 dust thickness is formed on the Cu of first active layer with the CVD technology
2On the O.Then again top electrode is fixed on the polymeric layer.
Embodiment 3
Use has the top electrode of 1,500 dust thick aluminium and has the bottom electrode formation memory cell of 1,000 dust thickness copper.Passive layer of copper sulfide with 65 dust thickness is provided on bottom electrode.The organic semiconductor layer that will contain polyphenylacetylene and have 700 dust thickness is formed on the passive layer with the CVD technology.Then again top electrode is fixed on the polymeric layer.
Embodiment 4
Use has the top electrode of 1,500 dust thickness copper and has the bottom electrode formation memory cell of 1,000 dust thickness copper.Passive layer of copper sulfide with 25 dust thickness is provided on bottom electrode.Polythiophene and Cu will have wherein been embedded
2S nanoparticle and the organic semiconductor layer with 700 dust thickness are formed on the passive layer with rotary coating and CVD technology.Then again top electrode is fixed on the polymeric layer.
Though the present invention shows with certain preferred specific embodiment or specific embodiment and describes that those of ordinary skills can understand when reading and understanding this specification and accompanying drawing, and the replacement and the modification of equivalence can take place.The multiple function that is had for said modules (assembly, device, circuit etc.) particularly, unless otherwise, otherwise noun (comprise any denotion for " meaning ") is to be used to describe the specific function (that is function equivalent) that any assembly relevant with these assemblies implemented described assembly, even and the structure that disclosed for equal on the structure but have the described function of illustrative embodiments of the present invention.In addition, though special characteristic of the present invention may only use a kind of open among several embodiment, these features can be in conjunction with one or more further features of other embodiment, to help any given or specific application.
Claims (17)
1. a memory cell (104) comprising:
First electrode (106,202);
Second electrode (108,204); And
May command conducting medium (110) between first electrode and second electrode, this may command conducting medium comprises:
Low conductive layer (112), it comprises at least a conjugation organic polymer, conjugation organo-metallic compound, conjugation organometallic polymer, buckyballs, carbon nano-tube, low electric conductivity chalcogen compound, reaches transition metal oxide, and
Passive layer (114), it comprises the conduction promoting layer.
2. memory cell as claimed in claim 1, wherein said low conductive layer (112) comprises at least a conjugation organic polymer, described conjugation organic polymer is selected from polyacetylene; Polyphenylacetylene; Poly-tolans; Polyaniline; Poly-(right-phenyl-vinyl); Polythiophene; Poly-porphyrin; The big ring of porphyrin; The mercaptan poly-porphyrin of deriving; Poly-class of metallocenes, poly-phthalocyanine; Polyethylene base system or polystyrene.
3. memory cell as claimed in claim 1, wherein said conduction promote compound (110) to comprise to be selected from least a in copper sulfide, silver-colored sulfide and/or the golden sulfide.
4. memory cell as claimed in claim 1, the thickness of wherein said low conductive layer (112) are about 0.001 micron or more and about 5 microns or still less, and the thickness of described passive layer (114) is about 2 dusts or more and 0.1 micron or still less.
5. memory cell as claimed in claim 1, the thickness of wherein said low conductive layer (112) are about 0.01 micron or more and 1 micron or still less, and the thickness of described passive layer (114) is about 10 dusts or more and 0.01 micron or still less.
6. memory cell as claimed in claim 1, wherein said low conductive layer (112) comprise at least a conjugation organo-metallic compound or the conjugation organometallic polymer that is selected from the cohort of being made up of following formula:
7. memory cell as claimed in claim 1, wherein said first electrode (106,202) and second electrode (108,204) comprise independently and are selected from aluminium, chromium, copper, germanium, gold, magnesium, manganese, indium, iron, nickel, palladium, platinum, silver, titanium, zinc or its alloy; Tin indium oxide; Polysilicon; Doped amorphous silicon; Or at least a in the metal silicide.
8. memory cell as claimed in claim 1, wherein said conduction promote compound (110) to comprise to be selected from least a in copper sulfide or the silver-colored sulfide, and described low conductive layer comprises conjugated polymer, and this conjugated polymer comprises following repetitive:
9. memory cell as claimed in claim 1, wherein said conduction promotes compound (110) to comprise to be selected from least a in copper sulfide or the silver-colored sulfide, and described low conductive layer (112) comprises conjugated polymer, and this conjugated polymer comprises following repetitive:
10. memory cell as claimed in claim 1, wherein said conduction promotes compound (110) to comprise to be selected from least a in copper sulfide or the silver-colored sulfide, and described low conductive layer (112) comprises conjugated polymer, and this public affairs conjugated polymer comprises following repetitive:
Be selected from least a in copper sulfide or the silver-colored sulfide 11. memory cell as claimed in claim 1, wherein said conduction promote compound (110) to comprise, and described low conductive layer (112) comprises the conjugation organic polymer with following repetitive:
12. one kind with the method for information storage in memory cell (104), this memory cell (104) comprises first electrode (106,202), second electrode (108,204), may command conducting medium (110) between described first electrode and second electrode, this may command conducting medium comprises low conductive layer (112) and passive layer (114), should comprise the conjugation organic polymer by low conductive layer, the conjugation organo-metallic compound, the conjugation organometallic polymer, buckyballs, carbon nano-tube, the low electric conductivity chalcogen compound, and transition metal oxide at least a, and described passive layer comprises the conduction promoting layer, and this method comprises:
Provide the outside stimulus that surpasses threshold values so that may command conducting medium (110) shows as conduction; And
Input writes signal.
13. as the method for claim 12, wherein said outside stimulus comprises at least one in external electrical field and the light radiation.
14. as the method for claim 12, wherein after writing, described memory cell comprises 2 or the information of multidigit more.
15. as the method for claim 12, wherein said passive layer (114) has the Fermi level in about 0.7 electron-volt of described low conductive layer (112) valence band.
16. a method of making memory cell (104) comprises:
First electrode (106) is provided;
On described first electrode, form and comprise that conduction promotes the passive layer (114) of compound;
Go up formation in described passive layer (114) and comprise conjugation organic polymer, conjugation organo-metallic compound, conjugation organometallic polymer, buckyballs, carbon nano-tube, low electric conductivity chalcogen compound, reach at least a low conductive layer (112) in the transition metal oxide, the conduction of wherein said passive layer promotes compound through selecting; And
Second electrode (108) is provided on described low conductive layer (112).
17. as the method for claim 16, wherein said low conductive layer (112) forms with chemical vapour deposition (CVD) or rotary coating technology.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
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| US48569903P | 2003-07-09 | 2003-07-09 | |
| US60/485,699 | 2003-07-09 | ||
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101329701B (en) * | 2008-07-09 | 2010-06-09 | 清华大学 | TMO material applied to CeRAM |
| CN101681921B (en) * | 2007-03-27 | 2013-03-27 | 桑迪士克3D公司 | Memory cell comprising a carbon nanotube fabric element and a steering element and methods of forming the same |
| CN103403905A (en) * | 2011-03-24 | 2013-11-20 | 株式会社东芝 | Organic molecular memory |
-
2004
- 2004-05-21 CN CN 200480025672 patent/CN1849718A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101681921B (en) * | 2007-03-27 | 2013-03-27 | 桑迪士克3D公司 | Memory cell comprising a carbon nanotube fabric element and a steering element and methods of forming the same |
| CN101329701B (en) * | 2008-07-09 | 2010-06-09 | 清华大学 | TMO material applied to CeRAM |
| CN103403905A (en) * | 2011-03-24 | 2013-11-20 | 株式会社东芝 | Organic molecular memory |
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