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CN101426639B - Post-deposition encapsulation of nanostructures: compositions, devices and systems incorporating same - Google Patents

Post-deposition encapsulation of nanostructures: compositions, devices and systems incorporating same Download PDF

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CN101426639B
CN101426639B CN2005800187089A CN200580018708A CN101426639B CN 101426639 B CN101426639 B CN 101426639B CN 2005800187089 A CN2005800187089 A CN 2005800187089A CN 200580018708 A CN200580018708 A CN 200580018708A CN 101426639 B CN101426639 B CN 101426639B
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nanostructured
coating
combination thing
nano
ligand combination
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CN101426639A (en
Inventor
J·A·怀特佛德
R·部鲁尔
M·布勒堤
陈建
K·C·克鲁登
段镶锋
W·P·弗里曼
D·希尔德
F·利昂
刘超
A·麦瑟
K·S·闵
J·W·帕斯
E·西尔
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Walden Technology Co ltd
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Nanosys Inc
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Priority to CN201210344519.2A priority Critical patent/CN102945800B/en
Priority claimed from PCT/US2005/020100 external-priority patent/WO2005123373A2/en
Publication of CN101426639A publication Critical patent/CN101426639A/en
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Abstract

本发明提供了用来制备离散的涂覆纳米结构的配体组合物，以及涂覆纳米结构本身和包含它们的器件。还提供了在纳米结构上形成后沉积壳和对纳米结构进行可逆改性的方法。本发明的配体和涂覆的纳米结构特别适用于密堆积的纳米结构组合物，这种组合物能改善量子约束和/或减少纳米结构之间的交叉干扰。The present invention provides ligand compositions for making discrete coated nanostructures, as well as coated nanostructures themselves and devices comprising them. Also provided are methods of forming post-deposited shells on nanostructures and reversibly modifying nanostructures. The ligands and coated nanostructures of the invention are particularly useful in close-packed nanostructure compositions that improve quantum confinement and/or reduce crosstalk between nanostructures.

Description

The back deposition of nanostructured is sealed: composition, device and comprise their system
The cross reference of related application
The application is a non-interim application patent application; The priority and the rights and interests of original temporary patent application below it requires: Jeffery A.Whiteford equals the USSN60/578236 that is entitled as " POST-DEPOSITION ENCAPSULATION OF NANOCRYSTALS:COMPOSITIONS; DEVICES AND SYSTEMS INCORPORATING SAME " of submission on June 8th, 2004; And Jeffery A.Whiteford equals the USSN 60/632570 that is entitled as " POST-DEPOSITION ENCAPSULATION OF NANOSTRUCTURES:COMPOSITIONS; DEVICES AND SYSTEMS INCORPORATING SAME " of submission on November 30th, 2004; Their draw at this in full and are reference, to satisfy various purposes.
Invention field
The present invention relates generally to field of nanometer technology.More specifically, the present invention relates to and discrete relevant composition, the Apparatus and method for of coated with nano structure.
Background of invention
Single nanostructured and be embedded in the other materials nanostructured that forms nano composite material and have many promising application comprises the optics that utilizes them and the application of electrical properties.A useful especially purposes will be based on the field of storage of complexing nano thing, and wherein nanostructured can be used for the store high-density electric charge.
Can be used for preparing in the synthetic method of nanostructured, usually employing becomes the figure method from top to bottom, like chemical vapor deposition (CVD) or molecular beam epitaxial growth method (MBE), next life nucleation and nuclear: the shell nanostructured.These methods are general to produce bigger and/or unordered and/or low-density accumulation nanostructured, and needs the treatment step of expensive (high temperature, high vacuum).The solution-based synthetic method also can be used to synthesized semiconductor nanocrystal (nuclear or nuclear/shell), and said semiconductor nanocrystal more adapts to the solution-based sedimentation, like spin coating or other method of evaporating.For example; The nanostructured that comprises CdSe nuclear (or nucleus) and ZnS shell can be through the solution deposition techniques preparation [for example; See Murray etc. (1993) " Synthesis and characterization of nearlymonodisperse CdE (E=S; Se, Te) semicondutor nanocrystals " J.Am.Chem.Soc.115:8706-8715].Yet the nanostructured that is generated by these and other standard nuclear-shell synthetic technology does not possess enough thick shell usually, so that enough electric charges are constrained in the nuclear, prevents that electric charge is diffused in other nanostructureds apart from several nanometers of first nanostructured.
Perhaps, can produce based on the nanostructured synthesis technique of chemical self-organizing method and to obtain optimally-controlled crystal habit and crystalline size, but the nanostructured that these synthetic methods produce has extra organic and/or surfactant compounds.Though the regulation and control that in building-up process, can be used for improving the dissolubility of nanostructured and help nanostructured; But organic pollution is combined in nanostructured surface consumingly, thus the further regulation and control that suppressed new synthetic nanostructured also/or be incorporated in device and the terminal applies.
Even can processing, the diameter of these CdSe:ZnS structures allow high density to pile up (for example about 1x10 12/ centimetre 2Or higher), the ZnS shell can not provide enough quantum confinement, so that at microelectronics and photonic device, includes but not limited to effectively utilize nanostructured in storage or the charge accumulator.
Therefore, the coated with nano structure that need disperse in this area, they can easily be integrated into various manufacturing process, need not further handle.The coated with nano structure optimization is tightly packed, keeps the CdSe/ZnS nuclear of its quantum confinement overgauge simultaneously: shell structure.Through discrete coated with nano structure is provided, apply discrete nanostructured part, combined the device of coated with nano structure and prepared the method for coated with nano structure, the present invention has satisfied above-mentioned and other demands.Through studying following content, can obtain complete understanding of the present invention.
Summary of the invention
One type of general embodiments provides discrete coated with nano structure.Said discrete coated with nano structure comprises the single nanostructured with first surface, and with associate first coating of (associate) of the first surface of single nanostructured.First coating has first optics, electricity, physics or structural property, and can change into second coating with one or more optics that are different from first coating, electricity, physics or structural property.In some embodiments, first coating is sealed nanostructured; In other embodiments, first coating covers the part (for example nanostructured do not associate with substrate surface part) of nanostructured.In one embodiment, the electrical properties of second coating is a dielectric property; Exemplary second coating of this embodiment comprises Si oxide, boron oxide compound and their combination.
Can be used to prepare the present invention and include, but are not limited to the nanostructured of nanocrystal, nano dot, nano wire, nanometer rods, nanotube, various nano particle, nanometer four leg structures, nanometer three-prong structure, nano double leg structure, branch, the nanocrystal of branch and four leg structures of branch through the nanostructured of the composition of discontinuous coating; Said various nano particle for example comprises metal, semiconductor or insulating nano particle, metal nanoparticle such as palladium, gold, platinum, silver, titanium, iridium, cobalt, tin, zinc, nickel, iron or ferrite nano particles or their alloy; Inorganic or the organic nano particle of amorphous, crystal and polycrystalline; And polymer nano-particle; Like those polymer nano-particles commonly used in the combinatorial chemistry synthesis technique, for example can be available from BangsLaboratories (Fishers, those polymer nano-particles IN).In a preferred implementation, nanostructured comprises sphere, almost spherical and/or isotropic nano particle, like nano dot and/or quantum dot.The nanostructured that applies preferably has at least one size (the for example diameter of coated with nano structure), and this size is less than about 10 nanometers, and is optional less than about 8 nanometers, 5 nanometers or 4 nanometers.In embodiments more of the present invention, the diameter of the nanostructured of coating is about the 2-6 nanometer, for example between the 2-4 nanometer.
Many ligand combination things can be used as the coating of nanostructured.In one type of embodiment, second coating comprises oxide (SiO for example 2).In some embodiments, first coating has first component that comprises silica cage modle complex compound and second component that comprises one or more nanostructured bound fractions (binding moiety).The bound fraction of exemplary nano structure comprises with the protonated of lower part or deprotonation form: phosphonate ester, phosphinate, carboxylate, sulphonic acid ester, sulfinic acid ester, amine, alcohol, acid amides and/or thiol moiety.The bound fraction of preferred nanostructured comprises the ester moiety of phosphonate ester, phosphinate, carboxylate, sulphonic acid ester and sulfinic acid ester.Usually, the bound fraction of nanostructured is connected on the silica cage modle complex compound independently of one another, for example connects via oxygen atom on the cage or silicon atom.
In specific embodiment, the nanostructured of coating comprises the silsesquioxane composition as first coating.Silsesquioxane can be the cagelike structure of sealing or the cagelike structure that part is opened wide.The available one or more boron of silica cage modle complex compound (for example silsesquioxane), methyl, ethyl, the side chain that contains 3-22 (or more) carbon atom or linear paraffin or alkene, isopropyl, isobutyl group, phenyl, cyclopenta, cyclohexyl, suberyl, iso-octyl, norborny and/or trimethyl silyl, electron-withdrawing group, donor residues or their combination are derived.In another embodiment, in first coating composition, adopt discrete esters of silicon acis.The discrete esters of silicon acis that can be used as first coating is the phosphorus esters of silicon acis.During curing, silica cage modle complex compound first coating is converted into silicon oxide-containing (SiO for example usually 2) the second rigidity coating.
The coating that adopts in the present composition reveals first character at its initial (before promptly transforming or before solidifying) state table usually, and transform or curing after second state table reveal the different second qualities.For example, for transform or solidify before and after have the coating of different electrical properties, first electrical properties can comprise electric conductivity and second electrical properties is non-conductive (vice versa).Similarly, the material that is in first attitude can be electron type conductor or neutral material, and the material that is in second attitude can be the cavity type conductor.Perhaps, for the embodiment of relevant optical property, first and second optical properties can be opacity and transparency, for example to the opacity and the transparency of visible light.Perhaps, first optical property can be included in the light absorption (or transmission or emission) of first wavelength, and second optical property is included in the light absorption (or transmission or emission) of second wavelength.Perhaps, for the embodiment of relevant structural property, the material that is in first attitude can be a flexible molecule, and second attitude can comprise the shell of rigidity (porous or solid).In one type of embodiment, first physical property comprises (for example) solubility in selected solvent, and that second electrical properties comprises is non-conductive.The conversion of coating can be heated and/or apply radiation and accomplished through (for example).
The present invention also provides the array that comprises many discrete coated with nano structures.In a preferred implementation, the unit nanostructured exist density greater than about 1 * 10 10/ centimetre 2, greater than about 1 * 10 11/ centimetre 2, more preferably greater than about 1 * 10 12/ centimetre 2, even greater than about 1 * 10 13/ centimetre 2Randomly, unit nanostructured and base material are like the surface association of silicon wafer.In some embodiments; The unit nanostructured was sealed before associating with substrate surface; And in other embodiments, the first of unit nanostructured and base material associate, and the second portion of unit nanostructured combines with first coating or second coating.Randomly, substrate surface comprises the surperficial binding partner that is connected the second nanostructured bound fraction, for example, is used for associating mutually with the part of nanostructured surface.For example, for silicon wafer, silane moiety can be brought into play the function of binding partner on base material or surface.
The device that comprises many discrete coated with nano structures constitutes another characteristic of the present invention.The exemplary means that can comprise the nanostructured of discrete applications of the present invention includes but not limited to charge accumulator, memory (for example flash memories) and photoelectric device.
Another aspect the invention provides the composition that contains the coated with nano structure, the coating that said composition has many nanostructureds and each unit nanostructured is separated.Said coating comprises the bound fraction of many nanostructureds that link to each other with the unit nanostructured surface; After the surface association of the bound fraction of nanostructured and unit nanostructured, coating can be converted into second coating (insulation shell for example; First coating is also optional to be insulating coating).Second coating or " shell " are preferably rigid structure, and (distance of for example selected or appointment, or fixed intervals) is provided between the adjacent cells nanostructured at interval.For example, according to the coating that is adopted, the diameter of given coated with nano structure (or in piling up array the distance between the center of adjacent nanostructured) can (for example) be about the 1-100 nanometer, or optionally is about 1-50 nanometer.Some preferred aspect, need higher bulk density, thereby the distance between the nanostructured is optional is about 1-10 nanometer, about 3-10 nanometer, more preferably about 2-6 nanometer, 3-5 nanometer according to appointment, perhaps about 2-4 nanometer.In some aspects, preferred thickness should provide acceptable insulation or coating layer thickness, keeps high-bulk-density simultaneously again, this moment the coated with nano structure diameter in about 2-6 nanometer range, choose wantonly and be about 3.5 nanometers (or littler).
In some embodiments, insulation shell can reduce or prevent between the unit nanostructured of adjacent or adjacency, or nanostructured is adjacent with another or adjacent material or base material between the electric charge diffusion or shift (for example horizontal proliferation or transmission).Perhaps, shell can reduce or prevent the transmission of other types, like the transmission of light or heat.In one type of embodiment; Insulation shell has reduced the electric charge diffusion rate between the unit nanostructured; Thereby electronics average time of jumping to another unit nanostructured from a unit nanostructured is greater than the scheduled time (for example surpass 1 millisecond, 1 second, 1 minute, 1 hour, 1 day, January, even 1 year or longer).
The bound fraction that can be used for the nanostructured of the present composition includes but not limited to one or more phosphonate esters, phosphonic acids, carboxylic acid or carboxylate, amine, phosphine, phosphine oxide, sulphonic acid ester, sulfinic acid ester, alcohol, epoxides, acid amides or thiol moiety.The coating that is used for forming insulation shell can be organic/inorganic composition organic and inorganic or that mix.In embodiments more of the present invention, the coating that nanostructured combines comprises Si oxide cage modle complex compound, like one or more silsesquioxanes or discrete esters of silicon acis.
Nearly all characteristic of above-mentioned embodiment all is applicable to the embodiment that these are relevant; For example, in the type of nanostructured, the density of unit nanostructured, association, inclusion and/or other similar aspect in the device with base material.The optional topcoat compositions, the topcoat compositions that for example contained material is identical with coating or insulation shell of comprising of composition.
In another embodiment, the present invention also provides many by rigidity SiO 2Shell seal discrete nanostructured; Unit nanostructured wherein: the diameter of shell structure (the unit nanostructured that its shell is promptly arranged) is (perhaps optional less than about 8 nanometers less than 10 nanometers approximately; Less than about 6 nanometers; Less than about 4 nanometers, or less than about 3.5 nanometers), and/or the density of unit nanostructured is greater than 1 * 10 10/ centimetre 2, optional greater than about 1 * 10 11/ centimetre 2, about 1 * 10 12/ centimetre 2, even be equal to or greater than about 1 * 10 13/ centimetre 2Unit nanostructured optional arrangement becomes array, for example orderly or unordered array.Nearly all characteristic of above-mentioned embodiment all is applicable to the embodiment that these are relevant; For example, in the type of nanostructured, association, inclusion, top coat and/or other similar aspect in the device with base material.
The present invention also provides the device that contains many discrete coated with nano structures, system, composition, film etc.Can adopt the exemplary means of the coated with nano structure that the present invention disperses is memory, for example flash memories.In a preferred implementation, flash memories comprises many rigidity SiO that are wrapped in 2The discrete nanostructured of shell, wherein the diameter of unit nanostructured is approximately less than 6 nanometers, and the density of nano structured unit is greater than about 1 * 10 10/ centimetre 2, perhaps its density is more preferably greater than about 1 * 10 12/ centimetre 2Other exemplary means comprise charge accumulator and photoelectric device.
On the other hand, the invention provides the method that on nanostructured, forms back deposition shell.Said method comprising the steps of: the one or more nanostructureds with the ligand combination thing that associates with first surface are provided; Wherein the ligand combination thing can be converted into rigid crust; Transform then or curing ligand combination thing; On the first surface of nanostructured, produce rigid crust, thereby behind deposition ligand combination thing, formed shell.The ligand combination thing can be any ligand combination thing that (for example) this specification is introduced.
Can adopt numerous technology known in the art, nanostructured is provided through synthetic one or more nano wires, nanometer rods, nanotube, branch's nanostructured, branch's nanocrystal, nanometer four leg structures, nanometer three-prong structure, nano double leg structure, nanocrystal, nano dot, quantum dot, nano particle or branch's four leg structures (or their combination in any).For some embodiment, providing one or more nanostructureds to relate to provides semiconductor nanocrystal or metal nanocrystal, and they have a size at least less than 10 nanometers, less than about 5 nanometers, or between the 2-4 nanometer, or littler.
In one type of embodiment; Through the one or more nanostructureds with surfactant that one or more and first surface associate are provided; And make surfactant and the exchange of ligand combination thing, can obtain having the nanostructured of the ligand combination thing that associates with first surface.The step of exchange surface activating agent can realize through the whole bag of tricks.For example; Surfactant (for example carboxylic acid, aliphatic acid, phosphine and/or phosphine oxide) can exchange through " mass action " effect; Promptly; Nanostructured is suspended or is dissolved in the organic solvent, then the nanostructured that suspends is mixed with the ligand combination thing, thereby surfactant and ligand combination thing on first surface are exchanged.The adoptable organic solvent of this step includes but not limited to toluene, chloroform, chlorobenzene and their combination.Perhaps; Surfactant can be removed through various technological original positions (after for example being deposited on the base material); As carry out the organic desorb of low temperature (orgnic striping) earlier, utilize the material (for example providing) that contains active oxygen to carry out oxidation then through the generation of UV ozone, RF antozone generating process or oxygen base generating process.Then, the ligand combination thing can associate with the nanostructured of desorb.In another kind of embodiment, synthesis of nano structure in the presence of the ligand combination thing, thereby need not carry out the surfactant exchange step.
The inventive method is included on the first surface through the nanostructured of ligand exchange, and the ligand combination thing is transformed or solidifies, and produces the step of second coating (for example, in some embodiments, rigidity and/or insulation shell).In a preferred implementation, curing schedule is through non-degradable or destroy under the temperature of nanostructured through other modes, and heating has the nanostructured of the ligand combination thing of association and carries out.For the composition of nanostructure-containing of the present invention, solidify usually being lower than about 500 ℃ temperature and carry out.In some embodiments, heating process is carried out between 200-350 ℃.The result of solidification process forms second coating or shell (for example on the nanostructured first surface, forming thin solid matrix).For example, shell can comprise electrically conductive composition, electrical insulation composition, optical clear composition, the opaque composition of optics, even these combination of features.In a preferred implementation, second coating is the rigid insulation shell, and it comprises the composition of glass or category of glass, like SiO 2
Curing schedule is optional to carry out through heating nanostructured in oxidizing atmosphere.Comprise in the embodiment of metal in nanostructured, the heating nanostructured can make metal be converted into metal oxide in oxidizing atmosphere.Metal oxide can be chosen wantonly and be converted into metal; For example (for example handling nanostructured; Said processing can comprise nanostructured is in about 200-750 ℃, even is higher than in 750 ℃ the temperature environment) back is in reducing atmosphere heating nanostructured, and/or on nanostructured, apply dielectric.
The nanostructured of using in the inventive method is optional to be connected on the base material, for example, connects through second nanostructured surface.Although can adopt various base materials, a kind of exemplary substrate is a silicon substrate, for example silicon wafer (for example containing or the oxygen-free silicon coating).Another kind of exemplary substrate is a silicon nitride surface, and this surface is positioned on silicon wafer, transmission electron microscope(TEM) (TEM) grid or other suitable substrates.In some embodiments, the nanostructured of coating connects (surface portion that does not for example contact with the ligand combination thing) through second nanostructured surface.
Also optional being included on the one or more nanostructureds that link to each other with base material of the inventive method used planarization composition, for example the spin-coating glass planarization composition.Though this optional step can be carried out before or after curing schedule, the graduation composition is preferably used after part is solidified into rigid crust.
Another aspect the invention provides the nanostructured of the rigid crust with back deposition formation, as adopts the nanostructured of the said method preparation of this specification.In some preferred implementations, rigid crust comprises silicon (SiO for example 2) and/or boron (B 2O 3).
The present invention also provides the method for nanostructured being carried out reversible modification.These methods provide one or more nanostructureds that comprise metal.Metal is carried out oxidation, produce metal oxide, and nanostructured is processed.Then, with the metal oxide reduction, obtain metal.Can come the oxidized metal through heating nanostructured in oxidizing atmosphere (for example oxygen containing atmosphere).Usually nanostructured is heated to about 200-700 ℃ temperature (for example about 200-500 ℃).Similarly, can come reducing metal oxide through heating nanostructured in reducing atmosphere, said reducing atmosphere for example is hydrogeneous atmosphere, for example forming gas.
After describing in detail below the combination advantages, can understand above-mentioned and other targets and characteristic of the present invention more fully.
Definition
Before describing the present invention in detail, be to be understood that particular device or the system of the invention is not restricted to, because they naturally can change.It is also understood that the used term of this specification just in order to describe specific embodiment, rather than be used for restriction.Only if clear in addition pointing out, this specification requires used singulative " ", " a kind of " and " being somebody's turn to do " etc. to comprise that its plural number points to, and gets the odd number meaning of a word only if related content clearly shows with Rights attached thereto.Therefore, for example, " nanostructured " comprises the combination of two or more nanostructureds; " a kind of ligand combination thing " comprises the mixture of part, or the like.
Only if qualification is arranged in addition, all technology and scientific terminology that this specification uses all have the common implication of understanding of those skilled in the art.All can in practical operation, be used for testing the present invention though be similar to or be equivalent to any method and the material that this specification introduces, what this specification was introduced is preferable material and method.In explanation of the present invention and claim, will use following term according to following definitions.
Term used herein " nanostructured " refers to have the structure of at least one zone or characteristic size, and said characteristic size is less than about 500 nanometers, for example less than about 100 nanometers, and less than about 50 nanometers, even less than about 10 nanometers or about 5 nanometers.Described zone or characteristic size are normally along the zone or the size of the minimum axle of this structure.This example of structure comprises nanocrystal, nanometer four leg structures, nanometer three-prong structure, nano double leg structure, nanocrystal, nano dot, quantum dot, the nano particle of nano wire, nanometer rods, nanotube, branch, nanometer four leg structures (for example inorganic dendritic macromole (dendrimer)) of branch etc.The material character of nanostructured is uniformly basically, perhaps can be (for example inhomogeneous structure) heterogeneous in some embodiments.For example, nanostructured can be basically crystalline state, be the monocrystalline attitude, the polycrystalline attitude, metallic state, polymer state, unbodied or their combination basically.For example, nanostructured can comprise metal, semiconductor, insulator or their combination.An aspect, a size in three sizes of nanostructured be less than about 500 nanometers, for example less than about 200 nanometers, and less than about 100 nanometers, less than about 50 nanometers, less than about 10 nanometers, even less than about 5 nanometers.
When being used for describing nanostructured, term " crystalline state " or " being crystalline state basically " are meant such practical work, and promptly nanostructured shows long-range order usually along one or more sizes of this structure.Those skilled in the art can understand, and term " long-range order " will depend on the absolute dimension of concrete nanostructured, because the order of monocrystalline can not exceed the border of this crystal.In this case, " long-range order " is meant that on most of at least size of this nanostructured be orderly basically.In some cases, nanostructured possibly contain oxide or other coatings, perhaps possibly be made up of a nuclear and at least one shell.In this case, should be appreciated that oxide, shell or other coatings need not show this order (for example, it can be unbodied, polycrystalline attitude, or the like).In this case, word " crystalline state ", " being crystalline state basically ", " being the monocrystalline attitude basically " or " monocrystalline attitude " are meant the situation (not comprising coating or shell) of nanostructured centronucleus.Term used herein " crystalline state " or " being crystalline state basically " mean and also comprise such structure; Promptly can comprise various defectives, pile up shortcoming, the structure of atom replacement etc., as long as this structure show basically long-range order (for example nanostructured or its nuclear at least one at least about on 80% length in order).In addition, should be appreciated that between the nuclear and the outside of nanostructured, or between nuclear and the adjacent shell, or the interface between the shell and the second adjacent shell can comprise amorphous areas, even can be unbodied.This does not hinder nanostructured is included into the crystalline state of definition here or is crystalline state basically.
When being used for describing nanostructured, term " monocrystalline attitude " shows that on this nanostructured basically be crystalline state, and comprises monocrystalline basically.When being used for describing the heterojunction structure of the nanostructured that comprises a nuclear and one or more shells, " monocrystalline attitude " is meant that its nuclear is crystalline state basically, and comprises monocrystalline basically.
" nanocrystal " is the nanostructured that is the monocrystalline attitude basically.Therefore, nanocrystal has at least one zone or characteristic size, and its size is less than about 500 nanometers, for example less than about 200 nanometers, and less than about 100 nanometers, less than about 50 nanometers, even less than about 20 nanometers.Term " nanocrystal " is intended to comprise the nanostructured that is the monocrystalline attitude basically, and this structure can comprise various defectives, pile up shortcoming, atom replacement etc., and does not comprise this defective, shortcoming or the substituted nanostructured that is the monocrystalline attitude basically.For the heterojunction structure of the nanocrystal that comprises a nuclear and one or more shells, the nuclear of nanocrystal is the monocrystalline attitude usually basically, but shell needn't be like this.On the one hand, each size in three sizes of nanocrystal is less than about 500 nanometers, for example less than about 200 nanometers, and less than about 100 nanometers, less than about 50 nanometers, even less than about 20 nanometers.The example of nanocrystal includes but not limited to nanocrystal spherical in shape basically, the nanocrystal of branch, and four leg structures (for example inorganic dendritic macromole) that are nano wire, nanometer rods, nano dot, quantum dot, nanometer four leg structures, nanometer three-prong structure, nano double leg structure and the branch of monocrystalline attitude basically.
" nanocrystal spherical in shape basically " is the nanocrystal that draw ratio is about 0.8-1.2.
" nanometer rods " is a nanostructured that main shaft is longer than other two main shafts.Therefore, the draw ratio of nanometer rods is greater than 1.The draw ratio of nanometer rods of the present invention is for about 1.5-10, but can be greater than about 10, greater than about 20, and greater than about 50 with greater than about 100, even greater than about 100000.Long nanometer rods (for example draw ratio is greater than about 10) is called nano wire sometimes.The diameter of nanometer rods preferably less than about 200 nanometers, is more preferably less than about 150 nanometers usually less than about 500 nanometers, most preferably less than about 100 nanometers, and about 50 nanometers, about 25 nanometers, even less than about 10 nanometers or about 5 nanometers.Nanometer rods can have different diameters, also can have basic diameter uniformly, that is to say that variation in the maximum variable scope of diameter is less than about 20% (for example, less than about 10%, less than about 5%, or less than about 1%).Nanometer rods is crystalline state usually basically and/or is the monocrystalline attitude basically, but can be (for example) polycrystal or amorphous.
" nanostructured of branch " is the nanostructured with three or more a plurality of arms, and wherein each arm all has the characteristic of nanometer rods; Or have the nanostructured of two or more a plurality of arms, wherein each arm all has the characteristic of nanometer rods, and disperses from the central area with the crystal structure that is different from said arm and to come.Example includes but not limited to nano double leg structure (double-legged structure), nanometer three-prong structure (three-prong structure) and nanometer four leg structures (four leg structures), and they have two, three and four arms respectively.
" nanometer four leg structures " are the nanostructured of tetrahedron branch normally, its four arms from the central area or nuclear emission come, the angle of wherein any two arms be about 109.5 the degree.Usually nuclear is a kind of crystal structure, and arm is another kind of crystal structure.
" nano particle " is draw ratio less than any nanostructured of about 1.5.Nano particle can have Any shape, comprises (for example) nanocrystal, particle (draw ratio is about 0.9-1.2) and erose particle spherical in shape basically.Nano particle can be unbodied, crystalline state, the part crystalline state, polycrystalline attitude or other forms.The material character of nano particle is uniformly basically, perhaps is (for example heterojunction structure) heterogeneous in some embodiments.Nano particle is gone up basically can be by any made of conveniently obtaining.
" draw ratio " is length and nanostructured second and the 3rd of first of nanostructured the ratio of average length, and wherein second and the 3rd is immediate each other two axles of length.For example, the draw ratio of perfect rod is the length of its major axis and diameter ratio perpendicular to the cross section of (being orthogonal to) this major axis.
" diameter " of the used nanostructured of the present invention is meant the diameter of the cross section that is orthogonal to first of nanostructured, wherein first length and second and the 3rd difference maximum (second and the 3rd is immediate each other two axles of length).First is not necessarily the longest axle of nanostructured; For example, for the dish type nanostructured, cross section is the rounded basically cross section that is orthogonal to vertical minor axis of dish.If cross section is not circular, diameter is the mean value of this cross section main shaft and countershaft.For elongation or the nanostructured of high length-diameter ratio, like nano wire or nanometer rods, on the cross section of major axis, record diameter usually perpendicular to nano wire or nanometer rods.For such as the such spherical nanostructure of quantum dot, diameter is to pass the center from a side of ball to record to opposite side.
Term used herein " coating " is meant and is applied to the surface, like the part on the nanostructured surface.Coating can be sealed the structure that applies this coating wholly or in part.In addition, coating can be porous or solid.
Term " optical property " is meant the transmission that relates to photon or the physical characteristic of generation.
Similarly, term " electrical properties " is meant the transmission that relates to electronics (or hole) or the physical characteristic of generation.
Term " high density accumulation " or " high density " are meant about 10 12Individual nanostructured/centimetre 2Or higher density.
" organic group " is the chemical group that comprises at least one carbon-hydrogen bond.
The chemical group that " alkyl " is made up of carbon atom and hydrogen atom.
" alkyl " is meant straight chain, side chain or cyclic saturated hydrocarbon part, comprises all position isomers, for example methyl, ethyl, propyl group, 1-Methylethyl, butyl, 1-methyl-propyl, 2-methyl-propyl, 1; 1-dimethyl ethyl, amyl group, 1-methyl butyl, 2-methyl butyl, 3-methyl butyl, 2,2-dimethyl propyl, 1-ethyl propyl, hexyl, 1,1-dimethyl propyl, 1; 2-dimethyl propyl, 1-methyl amyl, 2-methyl amyl, 3-methyl amyl, 4-methyl amyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1; 3-dimethylbutyl, 2; 2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethyl-butyl, 2-ethyl-butyl, 1; 1; 2-trimethyl propyl group, 1,2,2-trimethyl propyl group, 1-ethyl-1-methyl-propyl and 1-ethyl-2-methyl-propyl, cyclopenta, cyclohexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, positive decyl etc.Alkyl can be for example substituted or unsubstituted.
" thiazolinyl " is meant straight chain, side chain or the ring-type unsaturated hydrocarbon moiety that comprises the two keys of one or more carbon-carbon.Exemplary alkenyl groups comprises vinyl, 2-acrylic, 2-cyclobutenyl, 3-cyclobutenyl, 1-methyl-2-acrylic, 2-methyl-2-acrylic, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-2-butene base, 2-methyl-2-butene base, 3-methyl-2-butene base, 1-methyl-3-cyclobutenyl, 2-methyl-3-cyclobutenyl, 3-methyl-3-cyclobutenyl, 1; 1-dimethyl-2-acrylic, 1; 2-dimethyl-2-acrylic, 1-ethyl-2-acrylic, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-2-pentenyl, 2-methyl-2-pentenyl, 3-methyl-2-pentenyl, 4-methyl-2-pentenyl, 1-methyl-3-pentenyl, 2-methyl-3-pentenyl, 3-methyl-3-pentenyl, 4-methyl-3-pentenyl, 1-methyl-4-pentenyl, 2-methyl-4-pentenyl, 3-methyl-4-pentenyl, 4-methyl-4-pentenyl, 1; 1-dimethyl-2-cyclobutenyl, 1; 1-dimethyl-3-cyclobutenyl, 1; 2-dimethyl-2-cyclobutenyl, 1; 2-dimethyl-3-cyclobutenyl, 1,3-dimethyl-2-cyclobutenyl, 1,3-dimethyl-3-cyclobutenyl, 2; 2-dimethyl-3-cyclobutenyl, 2; 3-dimethyl-2-cyclobutenyl, 2,3-dimethyl-3-cyclobutenyl, 3,3-dimethyl-2-cyclobutenyl, 1-ethyl-2-cyclobutenyl, 1-ethyl-3-cyclobutenyl, 2-ethyl-2-cyclobutenyl, 2-ethyl-3-cyclobutenyl, 1; 1,2-trimethyl-2-acrylic, 1-ethyl-1-methyl-2-acrylic, 1-ethyl-2-methyl-2-acrylic etc.Thiazolinyl can be substituted or unsubstituted.
" alkynyl " is meant straight chain, side chain or the ring-type unsaturated hydrocarbon moiety that comprises one or more carbon-carbon triple bond.For example; Representational alkynyl comprises 2-propynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl, valerylene base, 3-pentynyl, 4-pentynyl, 1-methyl-2-butynyl, 1-methyl-3-butynyl, 2-methyl-3-butynyl, 1; 1-dimethyl-2-propynyl, 1-ethyl-2-propynyl, 2-hexyn, 3-hexyn, 4-hexyn, 5-hexyn, 1-methyl-valerylene base, 1-methyl-3-pentynyl, 1-methyl-4-pentynyl, 2-methyl-3-pentynyl, 2-methyl-4-pentynyl, 3-methyl-4-pentynyl, 4-methyl-valerylene base, 1; 1-dimethyl-2-butynyl, 1; 1-dimethyl-3-butynyl, 1; 2-dimethyl-3-butynyl, 2; 2-dimethyl-3-butynyl, 3,3-dimethyl-1-butynyl, 1-ethyl-2-butynyl, 1-ethyl-3-butynyl, 2-ethyl-3-butynyl, 1-ethyl-1-methyl-2-propynyl etc.Alkynyl can be substituted or unsubstituted.
Term " aryl " is meant the chemical substituting group that comprises aromatic group or be made up of aromatic group.Exemplary aryl comprises, for example phenyl, benzyl, tolyl, xylyl, alkylaryl etc.Aryl is optional to comprise a plurality of aromatic rings (for example xenyl etc.).For example, aryl can be substituted or unsubstituted.In " substituted aryl ", at least one hydrogen atom is replaced by one or more other atoms.
Term " alkylaryl " is meant the group that comprises alkyl and aryl moiety.
" hetero atom " is meant the atom beyond carbon and the hydrogen.Example includes but not limited to oxygen, nitrogen, sulphur, phosphorus and boron.
" surfactant " be can with the molecule of one or more surface interactions of nanostructured (no matter be weak effect or pretend usefulness).
Term " about " used herein represent given value can this value+/-10% change, perhaps choose wantonly this value+/-5%, perhaps in some embodiments, said value+/-1% change.
This paper also defines or has characterized other many terms.
The accompanying drawing summary
Shown in Figure 1 is the structure that is used as the example silicon sesquioxyalkane of nanostructured part of the present invention.
Shown in Figure 2 is exemplary discrete esters of silicon acis part, and it contains the bound phosphate groups that combines headgroup of a conduct and nanostructured.
Shown in Figure 3 for prepare the sketch map of base material with the quantum dot that has applied part.Go up most a row, applying the surfactant (crystal synthetic ligands) on CdSe nano dot surface with phosphorus esters of silicon acis ligand exchange.A middle row, apply SiO with the silane part 2The surface, the individual layer that the self aggregation of formation surface aggregation (assembly) part (SAL) forms.Next row, the nano dot that will pass through ligand exchange is administered on the base material that SAL applies, through behind assembling, washing and the curing schedule, at SiO 2Stay the individual layer that tightly packed CdSe is ordered on the base material, SiO 2Between said point.
Side view (last figure) and the vertical view (figure below) that is converted into second coating for first coating on many contiguous quantum dots shown in Figure 4.Left side figure is SiO 2The closs packing individual layer that CdSe is ordered on the base material, SiO 2Part is between said point.Part changes SiO in curing process 2Dielectric.Right figure is depicted as heat cure SiO afterwards 2The closs packing individual layer that CdSe is ordered on the base material, SiO 2Part is between said point.
Shown in Figure 5 for the example of the present invention's first coating composition.
Shown in Figure 6 for producing the exemplary synthetic schemes of silsesquioxane part seven cyclopenta POSS disilane alcohol diethoxy phosphate.
Detailed Description Of The Invention
Many electronic application will have benefited from providing the technology and the composition of the nanostructured of having improved energy barrier height and/or quantum confinement.For example, have storage and/or transfer that these nanostructureds of improving character can be used for the quantization electric charge at microelectronic, perhaps be used for the generation and the transfer of photon in the photon field.For example, the storage medium that such solid-state memory utilization has discontinuous read-write character such as flash memories.Charge storage in closelypacked discrete nanostructured such as quantum dot, can be improved memory capacity.Especially; Under high density, pile up the nanostructured (nanostructured that for example has sphere, almost spherical and/or isotropic structure good and that quantum confinement character is improved; Like nano dot or quantum dot) be hopeful to be used for the discrete of electric charge and/or quantization storage especially, and the generation and the transfer that are used for photon.
Cross interference between the nano dot (signal that promptly produces owing to the electron interaction between nanostructured disturbs) causes device performance relatively poor.Yet; Through the distance between the control nanostructured; And/or around discrete nanostructured, add insulation or dielectric coat material such as silica, composition provided by the invention, method and device can make the charge storage cell of nanostructured can be tightly packed (for example density is 1 * 10 10/ centimetre 2Or higher, even reach 1 * 10 12/ centimetre 2Or higher), keep simultaneously or improve quantum confinement character.
For example, when nanostructured was used as charge storage cell, two subject matters that need to consider were to introduce suitable surface nature, and selected nanostructured is piled into orderly or unordered individual layer.Storage is used for high density data, and nanostructured preferably provides with the orderly form of single sheet of one or more closs packings.For the semiconduction nanocrystal, this area has prepared the CdSe individual layer that six sides pile up, and its method has been utilized being separated between aliphatic surfactant and the aromatics conjugated organic materials on the nanocrystal, and deposits through spin coating.Yet in the manufacture process of memory, it is disadvantageous embedding nanocrystal at organic substrate inner (or top).For this reason, the present invention provides the individual layer quantum dot with silsesquioxane or esters of silicon acis ligand surface part through various self-assembling methods in one embodiment, and these quantum dots are fit to charge storage and use.
Part that utilization and nanostructured surface associate or coating can keep selected spacing between nanostructured.For different application, can change the size of part-nanostructured complex compound, thereby change the distance between the adjacent nanostructured through changing the composition of association part.Therefore, in the process of base material or the matrix of preparation nanostructure-containing, part size capable of using come the control point-spacing.
In addition, the physical property of nanostructured composition also can be regulated through introducing the part coating, and this part coating can be transformed into second coating with required second kind of character (for example dielectricity).For example, in embodiments more provided by the invention, the nanocrystal that is in the coating of " post processing " or cure states can be reached insulation by silica containing second coating or shell, for example, reduces the cross interference between the nanocrystal thus.Other required character include but not limited to ductility, rigidity, hear resistance, electric conductivity, transparency and opacity (opacity), specifically depend on related application.In addition, also comprise the ligand combination thing in the composition of the present invention, after said common composition is transformed into second coating, can influence the HOMO or the valence link energy level of nanostructured composition.
Yet; Though the present invention mainly uses (for example) charge storage; Electric charge insulation and/or nanostructured spacing like nonvolatile memory are launched to describe; But those skilled in the art read to will be understood that after this specification, the present invention with and various formation aspect independent or combination have more than these application-specific of mentioning wide many applications.Especially, provide or introduce can be when needed (after for example associating) to change the character of nanostructured with nanostructured but the ability of converted in-situ or the conversion coating that transforms through other modes be with a wide range of applications.For example, utilizable energy provides the coating material depositing optical layers of first optical property, but this character can be converted into second optical property after deposition.In addition; Separately coating is associated on nanostructured; This coating is regulation and control more easily under a kind of form; But after being coated on the nanostructured equably or otherwise as required, can transform, this ability compares to the nanostructured coating processes of introducing the front and has significant advantage.
Discrete coated with nano structure
The invention provides the method and composition that relates to discrete coated with nano structure.These nanostructureds are different from the nanostructured that is embedded in the matrix, and difference is that each nanostructured that applies when synthetic or after subsequent applications, has the border that is limited coating, and this coating is with matrix is non-conterminous on every side.For ease of discussing, coating is generally called work " part " in this article, because the molecule that this coating comprises interacts with nanostructured surface individually, for example forms covalent bond, ionic bond, Van der Waals force or other specific interactions of molecules.The present invention also provides many discrete coated with nano structures, and wherein first coating has changed second coating into, and each single like this nanostructured is directly contact not, and other disadvantageous contact, for example electric connections do not take place yet.In addition, with typical case's nuclear known in the art: the core-shell type nanometer structure is different, and second coating (shell) component of the nanostructured of coating usually is an amorphous state.Randomly, the diameter of the nanostructured of coating (for example " nanostructured: coating " structure) is less than about 10 nanometers, and is optional less than about 5 nanometers, less than about 4 nanometers, even less than about 3.5 nanometers.
The nanostructured of discrete applications of the present invention comprises single nanostructured; First coating that this structure has first surface and associates with single nanostructured first surface; And have first optics, electricity, physics or structural property, wherein first coating can change second coating with electricity, optics, structure and/or other physical propertys of being different from first coating into.In some embodiments, first coating has been sealed nanostructured (being that it encases its coated nanostructured fully).In other embodiments, nanostructured is by partially encapsulated.For example, first coating can cover in the nanostructured not the part of associating with another composition, said another composition such as substrate surface.
The nanostructured of polynary coating
The present invention also provides the composition of the nanostructured that contains coating, and said composition has many nanostructureds, and first coating of these nanostructureds separates each unit nanostructured.Usually, coating has the part of many combining nano structures, and these parts are used for coating is connected to the surface of unit nanostructured.Can change first coating into second coating or shell then; Said second coating or shell have a kind of different in kind at least in primary coat; Different coatings on electrical properties, optical property, chemical property and/or structural property for example; For example insulation and non-conductive (or nonisulated at least), but perhaps rigidity but not ductility.Insulating coating as herein described (or insulation shell) comprises non-conductive material (for example dielectric material).Insulation shell can prevent at least that usually electric charge from shifting within a short period of time basically; For example insulation shell can reduce the electric charge diffusion rate between the unit nanostructured, thereby electronics is at least 1 millisecond from the average time that a unit nanostructured jumps on another unit nanostructured, perhaps optional at least 10 milliseconds; At least 100 milliseconds, at least 1 second, at least 1 minute; At least 1 hour; At least 1 day, January at least, or at least 1 year or longer.Electric charge shift optional by basically by retardance (device that for example comprises the insulating nano structure can be kept the electric charge that applies) from 1 millisecond at least 1 second, 1 minute, 1 hour, 1 day, 1 year or the longer scheduled time.According to the present invention reversible coating mechanism is provided, for example is different from the synthesis of nano crystal that contains the shell component, we can obtain many benefits, comprise that (for example) provides littler nuclear-shell structure, and the shell of higher adhesion possibly is provided; When this nanostructured is arranged in a layer, in the time of for example in individual layer, can obtain higher bulk density.Some embodiment is enough to be about 1 * 10 for nanostructured provides density 10/ centimetre 2Density.Yet in a preferred embodiment, the density of nanostructured is about 1 * 10 in the composition layer of nanostructure-containing 11/ centimetre 2Or higher, perhaps be about 1 * 10 12/ centimetre 2Or higher, be more preferably 1 * 10 13/ centimetre 2Or it is higher.
The optional nanostructured (for example with selected density) that many discrete applications are provided with the form of an individual layer.Yet in some embodiments, many nanostructureds comprise a plurality of individual layers, and each individual layer has unit nanostructured selected or that need density independently.
One preferred embodiment in, many nanostructureds that apply are used as charge storage cell in various high density datas storages are used.To in these are used, utilizing integrated coated with nano structure that two key requests are arranged, one is the selection of suitable surface nature, and another is the closs packing of nanostructured in monolayer array, and said monolayer array is optional to be the good monolayer array of the degree of order.Like and colleague .2002 " Electroluminescence from single monolayers of nanocrystalsin molecular organic devices " Nature 420:800-803 such as () Coe that introduced, the aliphatic surfactant on the individual layer CdSe type semiconduction nanocrystal nanocrystal capable of using of six sides accumulation and be deposited on being separated between the aromatics conjugated organic materials on the nanocrystal through spin-coating method and prepare.Yet the nanocrystal composition that is embedded in the organic substrate inner (or top) of 40 nanometer thickness is not suitable for the manufacture process of memory.Except that other problems, the thickness of (electric conductivity is good) organic substrate can not provide enough quantum confinement, and can reduce the read/write ability and the predictability of device.In addition, organic layer is incompatible with typical memory manufacturing technology.For this reason, more being adapted to the coated with nano structure that charge storage uses can provide through the present invention.In a concrete preferred implementation, many coated with nano structures of the present invention comprise one or more individual layer nano dots, and said individual layer nano dot contains the surface ligand of silsesquioxane or esters of silicon acis part.For example, these nanostructureds can prepare through the various self-assembling methods that this paper introduces; After the curing, the gained nanostructured reaches insulation through second coating of silica containing part.Except other advantages, second oxide coating has reduced the cross interference between the nanostructured.
Coating and relevant nature
Be prepared in the part that is used as first coating in the present composition, the Apparatus and method for, as a kind of intermediary, second coating can be generated by it with selected or required character (or multiple character).Second coating provides electricity, optics, physics or the configuration state that is different from first coating, like rigidity, solubility and/or optical property (refractive index, emission and/or absorbent properties) variation has taken place.Many coating compositions all can consider to be used for the present invention.For example, coating can be organic composite, and like various polymer precursors, these precursors can be transformed into another kind (second kind) coating composition through chemistry or irradiance method, for example through crosslinked, further polymerization etc.Exemplary organic composite includes but not limited to dendritic macromole PAMAM (amine dendritic macromole); The methyl methacrylate (polymethyl methacrylate precursor) of amine (or other connect the headgroup of nanocrystal) end-blocking; The polymer that contains the phosphonate ester headgroup; Carboxylic acid-terminated diene or diacetylene composition; Can be converted into any of polymer contains the hetero atom monomer down in chemistry, heat or optical excitation, and the part described in the USSN 10/656910 that is entitled as " Organic Species that Facilitate Charge Transferto/from Nanostructures " of submission on September 4th, 2003 such as White.
Perhaps, said coating can be inorganic compositions.Optional silicon or the Si oxide part of comprising of said coating.It will be apparent to one skilled in the art that used term " silica " can be regarded as the silicon that refers to be oxidized to any degree here.Therefore, term " silica " can refer to chemical constitution SiO x, wherein x (comprises end value) between 1-2.Be used for inorganic coating of the present invention and include but not limited to that tin oxide, oxidation alum, manganese oxide, titanium oxide, zirconia, tungsten oxide, niobium oxide, carborundum, silicon nitride and other contain silicon coating and/or contain boron dope.In some preferred implementations, coating comprises the composition of hydridization organic/inorganic thing, and some embodiments of the relevant silica cage modle complex compound that provides like this specification are said.The composition that also can provide referring to following document: Schubert (2001) " Polymers Reinforced by Covalently BondedInorganic Clusters " Chem.Mater.13:3487-3494; Feher and Walzer (1991) " Synthesis and characterization of vanadium-containing silsesquioxanes " Inorg. Chem.30:1689-1694; Coronado and Gomez-Garc í a (1998) " Polyoxometalate-BasedMolecular Materials " Chem.Rev.98:273-296; Katsoulis (1998) " A Survey ofApplication of Polyoxometalates " Chem.Rev.98:359-387; Muller and Peters (1998) " Polyoxometalates:Very Large Clusters-Nanoscale Magnets " Chem.Rev.98:239-271; Rhule etc. (1998) " Polyoxometalates in Medicine " Chem.Rev.98:327-357; Weinstock (1998) " Homogeneous-Phase Electron-Transfer Reactions ofPolyoxometalates " Chem.Rev.98:113-170; Suzuki (1999) " Recent Advancedin the Cross-Coupling Reactions of Organoboron Derivatives with OrganicElectrophiles 1995-1998 " J.Organomet.Chem.576:147-168; Sellier etc. (2003) " Crystal structure and charge order below the metal-insulator transition in thevanadium bronze β-SrV 6O 15" Solid State Sciences5:591-599; Bulgakov etc. (2000) " Laser ablation synthesis of zinc oxide clusters:a new family of fullerenes? " Chem.Phys.Lett.320:19-25; Citeau etc. (2001) " A novel cage organotellurate (IV) macrocyclic host encapsulating a bromide anion guest " Chem.Commun.Pp.2006-2007; Gigant etc. (2001) " Synthesis and Molecular Structures of SomeNew Titanium (IV) Aryloxides " J.Am.Chem.Soc.123:11623-11637; Liu etc. (2001) " A novel bimetallic cage complex constructed from six V 4Co pentatomicrings:hydrothermal synthesis and crystal structure of [(2,2 '-Py 2NH) 2Co] 3V 8O 23" Chem.Commun.Pp.1636-1637; And Ai Yinhuofen (Eindhoven) the Rob W.J.M.Hanssen of technology university paper in 2003 " On the formation and reactivity of multinuclearsilsesquioxane metal complexes ".
In a preferred implementation, coating is to contain silicon coating (for example inorganic compositions or hybrid inorganic/organic composition), and deposition coating and with after the association of nanostructured bound fraction and unit nanostructured surface contains silicon coating and can be converted into rigidity SiO 2Insulation shell.The invention provides the nanostructured of coating, wherein second coating comprises rigidity SiO 2Shell, the diameter of discrete coated with nano structure is optional to be less than or equal to 50 nanometers, is less than or equal to 20 nanometers, is less than or equal to 10 nanometers, is less than or equal to 6 nanometers, perhaps is less than or equal to 3.5 nanometers.
In some embodiments, for example in the process of the nanostructured composition that is connected with base material of preparation (for example, can referring to Fig. 3 and 4 illustrated embodiment), coating can be used between the adjacent cells nanostructured, provide the interval.Coating part of the present invention is chosen wantonly has such size; The nanostructured that promptly applies can be piled up; At the interval (between the center to center) that provides between the nanostructured less than about 10 nanometers; Perhaps the interval between the nanostructured center is optional less than about 8 nanometers, less than about 5 nanometers, or less than about 4 nanometers.In many embodiments, coating is that the interval that provides between the nanostructured surface (for example, the long approximately 1-2 nanometer of part) is about the 8-10 nanometer, about 4-8 nanometer, or preferably about 2-4 nanometer.
In preferred embodiment, coating composition or rigid crust can reduce or prevent the diffusion of electric charge between the unit nanostructured.This embodiment especially preferably can be converted into the coating composition of Si oxide and/or boron oxide compound second coating.
The part coating is converted into second coating (its character is different from first coating usually) afterwards, and the nanostructured of coating is chosen wantonly with the base material association and/or covered with the top coat material.Optional first coating or second coating of being similar to of the composition of top coat material.For example, around discrete nanostructured, form rigidity SiO 2After the shell, can on many nanostructureds, cover and also can change SiO into 2Composition, thereby nanostructured is embedded in the silicon matrix.
Be prepared in the part that is used as first coating in the present composition, the Apparatus and method for,, generate second coating with selected or required character (or multiple character) through it as a kind of media.For example, the quantum dot that is used for flash memories need keep discrete border between adjacent nanostructured.This can realize that this part can be converted into the rigid crust (second coating) with given diameter through a kind of part is provided, thus the distance between the control point.In addition, if second coating can also play the function of improving quantum confinement and reducing cross interference between the quantum dot, the performance of device can improve; Also need to produce the part of second coating with dielectric property.The invention provides the ligand combination thing that can be used as first coating, with generating discrete coated with nano structure, this nanostructured for example has improved energy barrier height and/or quantum confinement.
First coating has different physical propertys usually with second coating.For example, first coating can be electroneutral (first electrical properties), and second coating has dipole moment (second electrical properties); Similarly, first coating can have dipole moment and second coating is electroneutral.In another embodiment, first coating is nonisulated or (for example conjugation conduction organic-metal hybrid thing) of electric conductivity, and second coating is insulation or dielectric (for example metal oxide).In another embodiment, first coating is insulation or dielectric, and second coating is nonisulated or electric conductivity.Interestedly especially be, first coating has ductility, and it can be converted into rigidity second coating (particularly those have the coating of semiconduction or insulating properties).A preferred composition embodiment sealing selected nanostructured as the rigid insulation shell is silica (SiO 2), this rigidity SiO 2Second coating optional by comprising Si oxide cage modle complex compound (for example silsesquioxane) but first production of coatings of extension.
Perhaps, first and second coatings can have different optical properties.For example, first optical property is included in the light absorption or the light emissivity of first wavelength, and second optical property is included in light absorption or the light emissivity (for example coating through containing lanthanide etc.) of second wavelength.Perhaps, first optical property can be weakened or is (opacity) of non-transmitted light, and second optical property is the transparency (vice versa).Another related embodiment comprises first and second coatings with different band-gap energies, for example, can be used to change the electronics and/or the conduction property of coated with nano structure.
As another example, first and second coatings can have different physical propertys, like the solubility in selected solvent.For example, first coating can make the coated with nano structure be dissolved in selected solvent, is beneficial to the dispersion, deposition of nanostructured etc., and it is less to comprise the dissolving of nanostructured in selected solvent of second coating.Obviously, first and second coatings above-mentioned character capable of being combined; For example, the solubility of first coating in selected solvent can increase, and second coating is non-conductive.
Silica cage modle complex compound
In a preferred implementation, being used for the part coating of coated with nano structure is silica cage modle complex compound.Many rings silicon-containing compound of silsesquioxane by name, polyhedral oligomeric silsesquioxane (POSS) for example is one type of soluble discrete silica cage modle complex compound (for example, can be referring to Hanssen, the same).The example silicon sesquioxyalkane comprises hydrogen silsesquioxane (HSQ) and methyl silsesquioxane (MSQ); Other silsesquioxane structures are shown in Fig. 1, and (wherein the R group comprises various chemical groups, includes but not limited to short-chain alkyl, like methyl, ethyl, isopropyl, isobutyl group; Chain alkyl is like iso-octyl and norborny; And aryl and non-aromatic ring structure, like phenyl, cyclopenta, cyclohexyl and suberyl).Silsesquioxane can be that (for example, wherein some epoxy atom is not connected to contiguous silicon atom simultaneously for the cagelike structure of sealing or cagelike structure that part is opened wide; For example, can be referring to Fig. 5 B).The non-esters of silicon acis organic group that is positioned on cage modle complex compound edge or the angle can pass through functionalization, part is attached on the face that exposes of nanostructured.The optional effect of playing electrophilic (or giving electronics) group of non-esters of silicon acis group.The functional group that can introduce the silsesquioxane part includes but not limited to: alkyl, alcohol, phosphine, phosphonate ester, mercaptan, ether, carboxylate, amine, epoxides, alkene and alkyl, and other relevant nanostructured bound fractions, hydrotropy part or electrophilic/electron donating group.
A preferred deriving method is in silica cage modle monomer, to introduce boron, after the heat treated generation is comprised second coating of boron oxide compound and Si oxide.
Example silicon sesquioxyalkane structure is shown in Fig. 1.Silsesquioxane was both commercially available, also can synthesize, and for example passed through RSiCl 3Or RSi (OR) 3The hydrolytic condensation of monomer is synthesized [for example, referring to (1998) such as Feher J.Am.Chem.Soc.111:1741; Brown etc. (1964) J.Am.Chem.Soc.86:1120; Brown etc. (1965) J.Am.Chem.Soc.87:4313-4323].Comprise the reaction condition of type of solvent, pH, temperature through regulation and control, and select the R substituted radical, can control character (for example polyhedron type, sealing are still the opened wide) [Feher etc. (1995) of the cagelike structure that forms in the building-up process Polyhedron14:3239-3253].More silsesquioxane structure (for example assigning to derive with the nanostructured joint portion) can be from Hybrid Plastics (Fountain Valley, CA; Network address is hybridplastics.com) obtain.
Usually, as composition or before being used for the inventive method, the silsesquioxane structure is connected to one or more nanostructured bound fractions.Any standard coupling reaction known in the art all can be used to the silsesquioxane structure of deriving, and for example has the connection headgroup of one or more nanostructureds.For example, can be referring to (1995) such as Feher PolyhedronThe reaction of describing among the 14:3239-3253.(well known by persons skilled in the art) can be referring to (for example) Fessendon and Fessendon about other information of general synthetic technology, (1982) Organic Chemistry, the 2nd edition, Willard Grant Press, Boston Mass; Carey & Sundberg, (1990) Advanced Organic Chemistry, the 3rd edition, Parts A and B, Plenum Press, New York; And March, (1985) Advanced Organic Chemistry, the 3rd edition, John Wileyand Sons, New York.Can choose wantonly said standard chemical reaction is improved, to improve reaction efficiency, productive rate and/or convenience degree.
Silsesquioxane composition as the present invention's first coating includes, but is not limited to the composition that Fig. 5 and table 1 provide.
Other discrete esters of silicon acis also can derive the nanostructured bound fraction, to form the present composition.For example, cyclopenta trimethoxy silane (CAS 143487-47-2) can with the water condensation, be then assembled in the basket structure.Then, the connection headgroup of nanostructured can be connected to one or more free hydroxyl position before or after forming cage.
Phosphorus esters of silicon acis part is another preferred implementation that is applicable to composition described herein and method.As shown in Figure 2, the bound phosphate groups on the phosphorus esters of silicon acis part can be used to part is connected on the nanostructured.The preferred employing can thermal decomposition be SiO in the method and composition of the present invention 2Phosphorus esters of silicon acis part; Comprise SiO 2Shell can obtain the energy barrier height higher than ZnS, and in subsequent treatment or manufacturing step, possibly have higher temperature tolerance.Exemplary phosphorus esters of silicon acis part is seen Fig. 5 A and 5B.
Be shown in Fig. 5 D-5I with thiol moiety as other parts that nanostructured connects headgroup.Obviously, to the preferred specific nanostructured bound fraction of specific nanostructured composition; For example, containing mercaptan (for example aryl mercaptan) part partly is the preferred part of some metal Nano structure (for example Pd nanostructured).
Exemplary nano structure bound fraction includes but not limited to: phosphate, phosphonate ester, carboxylate, sulphonic acid ester, sulfinic acid ester, amine, alcohol, acid amides and/or the thiol moiety of protonated or deprotonation form; The ester moiety of phosphate, phosphonate ester, carboxylate, sulphonic acid ester and sulfinic acid ester; Phosphine, phosphine oxide and epoxides, one or more in them often are connected on the cage modle complex compound of silica through oxygen atom or silicon atom independently.
Polyoxometallate
In other embodiments of the present invention, being used for the part coating of coated with nano structure is polyoxometallate.Polyoxometallate is metal-oxygen cluster anions, and the early transition metal (V, N, Ta, Mo and W) by highest oxidation state forms usually.Many derivatives be can prepare from the polyoxometallic acid salt composite, halide derivative, alkoxyl derivatives, thiol derivative, phosphorus derivant and Organosilyl derivative comprised; For better comprehensive, can be referring to Gouzerh and Proust (1990) Chem.Rev.98:77-111.For example, many alum oxygen acid salt derivant can be used as first coating in the present composition and the method.Change first part into contain the oxidation alum second coating then, its character may be compared with silica.
Polyoxometallate can be used as first coating on the nanostructured, is converted into subsequently to have second coating of different nature.Some polyoxometallate (the for example sour form of molybdenum base and tungsten Quito oxometallate) has photochromism or electrochromism; After said polyoxometallate is converted into second coating [for example; Handle with organic reducing agent; Perhaps letting it accept the extra electric field effect (for example, can be referring to Yamse (1998) Chem. Rev.98:307-325)], these character can descend or change.
Other ligand combination things
Second part is optional to comprise catechol functional group, and this functional group can be used to regulate the electrochemical properties of second coating.Can be used for catechol group of the present invention and include but not limited to pyrocatechol, salicylic acid and 2, the 2-xenol [for example, can be referring to (2001) such as Gigant J.Am.Chem.Soc.123:11632-11637].
In many embodiments of the present invention, second coating is a kind of insulation compsn (for example being used for around nanostructured, forming insulation shell).In a preferred implementation, second coating is to form the polyhedral metal oxide of oxide, or glass, or glassy composition.Silica (SiO 2), boron oxide (B 2O 3) and titanium dioxide (TiO 2) be preferred second coating ingredients, they can be by the present invention's first coating through generations (though also can adopt other oxidation state) such as (for example) thermal degradations.Other relevant second coating include but not limited to comprise the composition of following component: GeO 2, P 2O 5, AsO 5, P 2O 3, As 2O 3, Sb 2O 3, V 2O 5, Nb 2O 5, Ta 2O 5, SnO 2And WO 3And the oxide of other oxidation state of the metal oxide of giving.
Exemplary composition
Be listed in the table below 1 and Fig. 5 and 6 as the exemplary composition of the present invention's first coating.
Table 1
Figure G05818708920061213D000221
Figure G05818708920061213D000231
Figure G05818708920061213D000241
Figure G05818708920061213D000251
Other exemplary composition that can be used as first coating include but not limited to be similar to the compound of compound 1-3,5-6 and 8-13, but R wherein is organic group or hydrogen atom.For example, R can be an alkyl.In some embodiments, R is alkyl (for example cycloalkyl, or carbon atom is less than 20 even less than 10 short-chain alkyl), aryl, alkylaryl, alkenyl or alkynyl.For example, in some embodiments, R is isobutyl group, methyl, hexyl, cyclopenta or cyclohexyl.
An aspect, the present invention also provides the single composition that applies dielectric coat for discrete nanostructured.Said composition comprises first component that contains silica cage modle complex compound and second component that contains one or more nanostructured bound fractions, and wherein each nanostructured bound fraction is connected on the silica cage modle complex compound through (for example) oxygen atom or silicon atom independently.The present composition is converted into dielectric coat after depositing on the nanostructured surface.
Nanostructured
Nanostructured with any synthetic technology preparation known in the art can be used to prepare the coated with nano structure that the present invention disperses, and for example, has both comprised nanometer semiconductor structure, also comprises metal Nano structure.Usually, accomplish after nanostructured synthetic, after taking out in any solvent that for example nanostructured is used or the synthetic material, first coating is converted into second coating from building-up process.First coating preferably can easily shift from nanostructured surface.
Nanostructured substrate surface optional and like silicon wafer or TEM grid associates.In some embodiments, use the compositions-treated base material, to associate individual layer (SAM) part of said composition such as functionalization self assembly with nanostructured.The exemplary composition of reason functionalization substrate surface comprises silicon nitride coating, contains the silane part of nanostructured bound fraction, or other can provide or accept proton so that be incorporated into the chemical group (for example amine, alcohol, phosphonate ester, fluorine or other non-carbon hetero atoms) on the nanostructured of coating through hydrogen bond.For example, the silane part can comprise having chemical formula [X 3Si-spacer groups-conjugated group] structure, wherein X is the combination of Cl, OR, alkyl, aryl, other alkyl, hetero atom or these groups, spacer groups is alkyl, aryl and/or hetero atom combination.Through introducing the group of Photocrosslinkable, the structure of part is optional to have response to optical excitation, makes part that crosslinked (for example each other, or with the surface of SAL coated substrate) take place.Can be used for example surface part of the present invention (among Fig. 4 generally be called it " SAL ") can be available from Gelest Inc. (Tullytown, PA; Network address: gelest.com).
The single nanostructured that adopts in the composition includes but not limited to the nanocrystal of nanocrystal, nano dot, nano wire, nanometer rods, nanotube, quantum dot, nano particle, nanometer four leg structures, three-prong structure, double-legged structure, branch or four leg structures of branch.The invention is not restricted to nanometer semiconductor structure or metal Nano structure; The type of used nanostructured partly depends on the purpose of its requirement.Though any in these nanostructured embodiments all can be used for the present invention, set forth for convenient, with sphere, almost spherical and/or isotropism nanocrystal, be used as typical nanostructured like nano dot and/or quantum dot.For many embodiments, the nano dot of coating or the diameter of quantum dot (for example first size) are less than about 10 nanometers, and be optional less than about 8 nanometers, 6 nanometers, 5 nanometers or 4 nanometers.In some embodiments, the diameter range of nanostructured (for example nano dot or quantum dot) is about the 2-4 nanometer.In the preferred implementation that is used for the closs packing nano-structure array, the diameter that applies quantum dot or nano dot is less than or equal to about 6 nanometers, or optionally is less than or equal to about 3.5 nanometers.
Nanostructured is like nanocrystal, quantum dot, nano particle etc., available many mechanism manufacturings well known by persons skilled in the art.In addition, can adopt many methods to control the size of nanostructured easily, and these methods through the adjustment after also applicable to material different.The optionally washing nanostructured is to remove residual unnecessary surfactant and/or unnecessary part in synthetic.For example, can equal the U.S. Patent application USSN 10/796832 that is entitled as " Process for producing nanocrystals and nanocrystals producedthereby " of submission on March 10th, 2004 referring to Scher; Scher equals the USSN 60/544285 that is entitled as " Methods of processing nanocrystals, compositions, devices and systemsusing same " of submission on February 11st, 2004; Scher equals the USSN 60/628455 that is entitled as " Process for group III-V semiconductor nanostructure synthesis and compositionsmade using same " of submission on November 15th, 2004; Whiteford equals the USSN 60/637409 that is entitled as " Process for group 10metal nanostructure synthesis and compositions madeusing same " of submission on December 16th, 2004; And the list of references in the middle of them.
The nanostructured that is adopted in the composition of nanostructure-containing of the present invention goes up basically can be by any material preparation that is easy to get.For example, nanocrystal can comprise inorganic material, for example is selected from II-VI family, the semi-conductive various semi-conducting materials of III-V family or IV family; Comprise that also (for example) contain the material of first element and second element; Wherein first element is selected from periodic table of elements II family, and second element is selected from VI family (for example materials such as ZnS, ZnO, ZnSe, ZnTe, CdS, CdSe, CdTe, HgS, HgSe, HgTe, MgS, MgSe, MgTe, CaS, CaSe, CaTe, SrS, SrSe, SrTe, BaS, BaSe, BaTe); The material that comprises first and second elements, wherein first element is selected from III-th family, and second element is selected from V family (for example materials such as GaN, GaP, GaAs, GaSb, InN, InP, InAs, InSb); The material (materials such as Ge, Si) that comprises IV family element; Material such as PbS, PbSe, PbTe, AlS, AlP and AlSb; Perhaps their alloy or mixture.Metal such as Pd, Pt, Au, Ag, Ni, Fe, Sn, Zn, Ti, Ir and Co and metal oxide also can be used to the synthetic nanostructured of the present invention that is used for.For example; Relevant other details that can be used for crystalline state nanometer structure of the present invention can be illustrated in the U.S. Patent application sequence that is entitled as " Nanocomposite Based PhotovoltaicDevices " submitted on September 4th, 2003 No. 10/656802; Its complete content is incorporated into this paper by reference, to satisfy various purposes.
In a preferred implementation; The nanostructured that device of the present invention adopts comprises CdSe roughly spherical in shape or Pd nanocrystal, perhaps can synthesize other Metal Substrate of sphere, almost spherical and/or isotropism nano particle (like nano dot and/or quantum dot) or semiconductor-based nanostructured.
On nanostructured, form the method for back deposition shell
Through sedimentation on the conduction organic material layer or inner preparation nuclear/shell CdSe/ZnS method for semiconductor and this semi-conductive this area that is applied in be known, but there are some problems in these methods.For example, the energy barrier height that had of the thin ZnS shell in " nanostructured: shell " structure is not enough to prevent that electric charge from leaking from nanostructured.Though this problem can solve through the very thick ZnS shell of growth; But the method is unrealistic on synthesizing; Because after synthetic several individual layers, tension force will cause forming defective, nanocrystal becomes insoluble; Interval between the nanocrystal will be too big, can not satisfy storage and use the requirement to bulk density.In theory, this problem can contain first shell (ZnS) and other shell (SiO through growth 2) nuclear structure (CdSe) solve, but there is same deficiency in the method in the formation of defective, solubility with at interval.The present invention has overcome these problems; Both can part be switched directly on the selected nanostructured; Can to be converted into second part (for example oxide) after used part solidifies but will to keep the solubility (for example purpose in order deposit) of nanostructured in organic solvent, also can be in the presence of this part growth of nanostructures.
The invention provides the method that on nanostructured, forms back deposition shell.These methods comprise some steps: 1) one or more nanostructureds with the ligand combination thing that associates with first surface are provided, and ligand combination thing wherein can change second coating (for example changing rigid crust into) with different electricity, optics, physics or structural property into; 2) the ligand combination thing is cured, on the nanostructured first surface, forms second coating (for example rigid crust), thereby, on nanostructured, form shell through back deposition ligand combination thing on nanostructured.The inventive method is preferably carried out not destroying or weaken under the temperature of structure and/or physical property of nanostructured.
In one type of embodiment, the nanostructured that contains the ligand combination thing that associates with it forms through the exchange surface part.In this type of embodiment; Provide one or more steps that contain the nanostructured of the ligand combination thing that associates with first surface to comprise one or more nanostructureds that contains one or more surfactants that associate with first surface are provided, and exchange at this first surface upper surface activating agent and ligand combination thing.In another kind of embodiment, nanostructured is synthetic in the presence of the ligand combination thing, and need not to exchange part.
Nanostructured is provided
The inventive method can be used on any one of numerous nanostructureds, generate the shell or second coating, and said nanostructured includes but not limited to the nanostructured of nanocrystal, nano dot, nano wire, nanometer rods, nanotube, quantum dot, nano particle, nanometer four leg structures, nanometer three-prong structure, nano double leg structure, branch etc.In addition, the inventive method is not limited to the nanostructured with specific route of synthesis preparation.For example; Usually adopt various surfactants and/or aliphatic acid [for example, can disclose 2002/0066401 based on the synthetic Pd of organic metal solution, CdSe, CdTe and CdS nanocrystal referring to the United States Patent (USP) that Peng etc. is entitled as " Synthesis of colloidal nanocrystals " as cosolvent; The United States Patent (USP) that Peng etc. are entitled as " Colloidal nanocrystals with highphotoluminescence quantum yields and methods of preparing the same " discloses 2003/173541; (2001) NanoLetters 1:333-337 such as Kim etc. (2003) NanoLetters 3:1289-1291 and Qu, they this draw be with reference to].Nanostructured with the organic composite preparation that combines a little less than these or other can be used for method of the present invention.
The exchange surface part
In some embodiments of the inventive method, nanostructured is to provide through preparation in the presence of the organic composite (" growth part ") of weak combination or growth initial configuration (the for example nuclear part of nanostructured).Therefore the association of part and the nanostructured of growth exchanges than with a little less than generating the part (" displaced ligands ") of first coating easily, for example passes through mass action and exchanges.
The nanostructured that the inventive method adopts has one or more organic composites or growth part usually, and they and nanostructured surface associate (for example in building-up process, being used to dissolve nanostructured).Typical growth part comprises surfactant, and for example phosphine or phosphine oxide are like tri octyl phosphine (TOP), tri-n-butyl phosphine (TBP) or trioctylphosphine oxide (TOPO) (TOPO); Perhaps acid is like cetyl phosphonic acids (HDPA) or octadecyl phosphonic acids (ODPA).As substituting or in addition; Between synthesis phase, can adopt various long-chain carboxylic acids; Aliphatic acid for example; Like stearic acid, palmitic acid, myristic acid, laurate, capric acid, sad, caproic acid and butyric acid, and other saturated or unsaturated type resin acids, and let their keep associating with nanostructured surface.In the methods of the invention, the growth part exchanges with changing second part with different electricity, optics, physics or structural property or the ligand combination thing of second coating into, thereby formation is through the nanostructured composition of ligand exchange.In a preferred embodiment, the growth part with can change the rigid insulation shell into, exchange like the ligand combination thing of oxide.
The surfactant that associates with nanostructured surface exchanges with the endocrine part or first coating, can be through many mechanism completion known in the art.In one embodiment, exchange surface activating agent step relates to the nanostructured suspension or is dissolved in the organic solvent, and the nanostructured that suspends is mixed with the ligand combination thing.The solvent that can be used for this exchange process is included in any solvent that adopts usually in the process of synthetic and processing nanostructured, like toluene, chloroform, chlorobenzene etc.The temperature of carrying out exchange step depends on related part, can be from room temperature to the higher temperature that is equal to or greater than 100 ℃, 200 ℃, 300 ℃ etc.For example, the surface ligand that comprises the sulfonic acid part can exchange under situation about not heating basically, chooses wantonly and at room temperature carries out.
In another embodiment, nanostructured and substrate surface (for example a kind of solid phase embodiment but not in solution) associate.Organic surface active agent on the nanostructured can original position be removed, and for example removes (temperature＜500 ℃, choose wantonly between 200-350 ℃) through the organic desorption process of low temperature.After desorption process is accomplished, choose wantonly and carry out oxidation, for example carry out oxidation with reactive oxygen species.Subsequently, adopt any technology known in the art (vapour deposition, injection, dip-coating etc.) that displaced ligands (the for example first coating part) is administered on the nanostructured.
The self aggregation of individual layer
Randomly, because intermolecular self aggregation active force brings out the nanostructured that has applied part and forms individual layer.For example, in a preferred implementation, the invention provides the nanocrystal of regulating with silsesquioxane or esters of silicon acis part, to be used for the charge storage field.Nanostructured is preferably lined up closely packed array, perhaps more preferably lines up high density and/or orderly closely packed array.The controlled self aggregation of closs packing array can be accomplished through various wet processings, and as nanostructured-first ligand combination thing is deposited on self-assembled monolayer (SAM) or other functionalization base materials or the oxide, the self assembly that perhaps drives through evaporation is accomplished.
The component of self aggregation individual layer is associated with substrate surface and nanostructured simultaneously, thereby between the two, forms bridge joint or connection.Be applicable to that various SAM composition of the present invention includes but not limited to organosilan, phosphonic acids, phosphine, mercaptan, amine, hetero atom etc.In a preferred implementation, SAM is made up of the silane part, and this part has one and is used for the headgroup that links to each other with silsesquioxane or esters of silicon acis part.In another preferred implementation, base material can be directly with being fit to carry out functionalization with the headgroup that is connected of nanocrystals.Through for example spin coating, dip-coating, spraying or traditional printing technology, use nanostructured with solution, be deposited on then on SAM or the functionalization base material.Use organic solvent such as toluene or chloroform with the nanostructured of unnecessary (combine) flush away from the base material subsequently, obtained applying the individual layer nanocrystal of siliceous part.
Perhaps, said individual layer also can prepare through the aggregation method that evaporation drives, and need not the base material through specially treated.Through spin coating, dip-coating, spraying or traditional printing technology, nanocrystal is deposited on the base material from solution.The process of drying through the control solvent can obtain arranging orderly nanocrystal array.
No. the 60/671134th, the U.S. Patent application sequence that is entitled as " Methods and devices for forming nanostructure monolayers and devicesincluding such monolayers " that other details of relevant formation individual layer can equal to submit on April 3rd, 2005 referring to (for example) Heald; It is in full with reference to being incorporated into this paper, to satisfy various purposes.
Solidify the ligand combination thing and generate second coating
Deposition and forming after the individual layer can be carried out thermal annealing to base material, to solidify first coating (thereby on the nanostructured first surface, form the second layer, this layer is the rigid insulation shell in some embodiments).Which kind of technology curing schedule adopts depend on the ligand combination thing type that this method is used.Curing can as carrying out in argon gas or the nitrogen, also can be carried out in atmosphere such as oxygen at inert atmosphere.Solidification temperature can be regulated according to surface ligand.For example, the hardening composition step possibly relate to the nanostructured that heating contains the ligand combination thing that associates with it, on nanostructured surface, to form rigid crust.Heating can one step or branch multistep carry out, can adopt various device, [see (2001) such as Yang like hot plate or quartzy stove Proc.Natl.Acad.Sci.25:339-343].In some embodiments, heating part: the nanostructured complex compound is to being lower than about 500 ℃, between optional heat arrives 200-350 ℃.The heat cure of silsesquioxane be usually directed to heat contain silsesquioxane composition to being lower than about 500 ℃, preferably be lower than about 350 ℃, thereby change cagelike structure into network structure.Relate in the embodiment of siliceous part at other, curing process resolves into SiO with first coating 2Second coating.For example, FTIR spectrometer capable of using, through thermogravimetric analysis monitor first be coated with course second coating (or shell) conversion [referring to top Yang (2001), its content is with reference to being incorporated into this paper].
In another embodiment, the ligand combination thing from first be coated with course second coating or shell transformation can comprise composition is carried out radiation that this transformation has changed electronics or optical property.For example, for the embodiment that adopts PMMA precursor or carboxylate diene or diacetylene part, polymerisation is photoactivation, and it is crosslinked to cause first coating to take place, and is formed with casing (second coating).
In some embodiments, one or more nanostructureds of providing of the inventive method are connected on the base material through second nanostructured surface.This base material is optional to be silicon wafer.In some embodiments, the unit nanostructured was sealed before associating with substrate surface, and in other embodiments, the first of unit nanostructured and base material associate, and the second portion of unit nanostructured and first coating or second coating are associated.The optional silane part that combines with the second nanostructured bound fraction that comprises of silicon wafer surface is for example so that base material and the association of a part of nanostructured surface.
After the curing, choose on the coated with nano structure that links to each other with base material another layer (for example) first coating esters of silicon acis of spin coating etc. wantonly, heat cure then, thus top coat or cover layer are provided.In some embodiments, top layer is an insulation oxide layer.The optional step that applies planarization composition that further comprises of the inventive method is as cover layer or the topcoat compositions on paint and the nanostructured that base material links to each other.Optional planarization composition can apply before or after the step of solidifying the ligand combination thing.Planarization composition has been filled any narrow gap that stays, and produces (relatively) flat surface in the treated part of wafer and/or nanostructured composition.Top coat or planarisation material are preferably complied with the rigidity shell facies of the nanostructured that applies.Planarization composition is optional to be dielectric material (identical or different with second coating composition on forming).
The exemplary planar formed material includes but not limited to various esters of silicon acis, phosphorus esters of silicon acis and is called spin-coating glass (Spin On Glass) siloxanes (SOG).Ligand combination thing of the present invention can be chosen wantonly as planarization composition.
The present invention also provides the nanostructured with rigid crust of the back deposition formation of adopting method preparation as herein described.In a preferred implementation, rigid crust comprises silicon or Si oxide, nanostructured: the diameter of shell composition is less than or equal to about 6 nanometers.
Reduce the method that electric charge spreads between polynary quantum dot
On the other hand, the invention provides and reduce the method that electric charge spreads between the polynary nanometer structure, said nanostructured for example is nano dot, particularly quantum dot.Said method comprising the steps of: the ligand combination thing that will contain electron withdraw group links to each other with the surface of unit nano dot (or quantum dot or other nanostructureds); On nano dot surface, unit, form dipole; Improve the electron affinity of nano dot, thereby reduce the electric charge diffusion (like the lateral charge diffusion) between the nano dot.Optional composition and the method that is used for formation described herein back deposition shell of the nanostructured that forms like this.
Many ligand combination things of the present invention have the electrophilic characteristic, can be used as electrophilic composition in this method (for example silica cage modle complex compound, like silsesquioxane).In some embodiments, the electrophilic composition comprises fluorine atom (F for example -, SiF, SiF derivative, or fluoropolymer is like polytetrafluoroethylene (PTFE)).In other embodiments, the ligand combination thing is boron-containing compositions (for example aryl-boron oligomer or a boric acid composition).The electrophilic composition is optional to comprise the conjugated group of the nanostructured that is used for linking to each other with nanostructured surface, as phosphonic acids partly, phosphonate ester or other nanostructured bound fractions, those that introduce like this specification.
First and second character of ligand combination thing of the present invention are optional to be the character relevant with photic color development (for example, relate in external irritant, like light or other incidence electromagnetic radiation, the variable color of in coating, inducing).In some embodiments, the electrophilic composition comprises photoactivation molecule inner salt, for example spiro-pyrans.The example molecule inner salt that can be used for the inventive method and composition includes but not limited to HOOCCH 2CH (NH (CH 3) 2) CH 2CH 2PO 3H 2Also can be referring to (2001) " Photochromism of cationic spiropyran-doped silica gel " such as L é austic New.J.Chem.25:1297-1301, its content is with reference to being incorporated into this paper.
In one type of embodiment, many nano dots (or quantum dot or other nanostructureds) comprise the medium that produces and shift discrete quantization photon, perhaps discrete quantization charge storage or charge transfer medium.
One or more (for example many) nano dot (for example quantum dot) or other nanostructureds that the present invention also provides the electric charge diffusion to reduce, their available method preparations as herein described.This nanostructured is optional to be comprised by depositing the rigid crust that forms behind the ligand combination thing, for example comprises the rigid crust of silicon or silica.It can be any material that this nanostructured goes up basically, has virtually any size and/or shape.One type preferred embodiment in, the diameter of nanostructured is less than 6 nanometers, for example, less than 3.5 nanometers.
Other details of the relevant ligand combination thing that is fit to be used for to improve nanostructured character can equal the U.S. Patent application 60/635799 that is entitled as " Compositions and methods formodulation of nanostructure energy levels " submitted on December 13rd, 2004 referring to for example Whiteford.
Make the method for memory
The present invention also provides and has made the method based on the memory of nanostructured, and said memory utilizes the nanocrystal stored charge.Of (2002, the same) such as Coe, CdSe/ZnS nuclear/shell semiconductor can be deposited on the conduction organic material layer above/inside.Yet there are some problems in this method of originally introducing.At first, the thin ZnS shell that this method produces does not have sufficiently high energy barrier, is difficult to prevent that electric charge from leaking from nanocrystal.Although this problem can solve through the very thick ZnS shell of growth in theory, the method is unpractical on synthesizing.After having deposited some individual layer shells, its tension force can cause the formation of defective, and/or nanocrystal become insoluble, thereby possible thickness of the shell has been constituted physical constraints.In addition, it will be too big that the spacing between the nanocrystal of thick coating is arranged, and can't satisfy storage and use the requirement to bulk density.This problem also might be passed through growth cores (CdSe) shell (ZnS) and the 3rd shell (SiO 2) solve, this method has possibility on synthetic, but also exists and top similar problem.The present invention has adopted new method, and the ligand combination thing (for example modification silsesquioxane part) that provides with this paper is directly with ligand exchange (for example, roughly spherical in shape CdSe or Pd nanometer small crystals) on nanostructured.(perhaps as stated, nanostructured can be grown in the presence of the ligand combination thing).The first part coating preferably transforms or is cured as oxide, keeps the dissolubility of nanostructured in organic solvent simultaneously, so that deposit.
Based on nanostructured, utilize the manufacturing approach of the memory of nanocrystal stored charge may further comprise the steps: 1) many nanostructureds are provided, and said nano structured unit all associates with the weak part of growth that combines; 2) the growth part combines with displaced ligands, and on the unit nanostructured, forms first coating; Unit nanostructured and the substrate surface that 3) will pass through coating associate; 4) change first coating into second coating, two kinds of coatings are different on one or more electricity, optics, physics or structural property, thereby obtain the memory based on nanostructured.In one type of related embodiment, the 1st) and the 2nd) step changed a step into, this moment, nanostructured was synthesized in the presence of part, part forms first coating on the unit nanostructured.What preferably, can form the closs packing nanostructured most effectively is the nano particle (like nano dot and/or quantum dot) with sphere, almost spherical and/or isotropic geometry.The displaced ligands of first coating can be accomplished through the exchange of (for example) mass action the exchange of growth part or surfactant.For helping the carrying out of this process, the binding constant of weak combination growth part is preferably less than the binding constant of used part in first coating.
The advantage that method had of this synthesis of nano structure is that the contained organic impurities of nanostructured product is less than the nanostructured through existing method preparation.Another advantage is that the length of displaced ligands can be regulated, so that the diameter of control coated with nano structure separates suitable distance thereby make between the nanocrystal, to reduce and/or to prevent that electric charge from leaking, still can realize the high density accumulation simultaneously.
Device
Utilize the composition of nanostructure-containing of the present invention, can make many electronics and optical applications device.Especially, the device of any employing (or after design, can adopt) nano dot nanostructured can both have benefited from the compositions and methods of the invention.For example, various electronic devices such as transistor and memory can use the composition manufacturing of nanostructure-containing of the present invention.Luminescent device like LED, the backboard light source that is used for LCD, phosphor body, PV, photodetector and photodiode, and other opto-electronic devices such as photovoltaic device, also can adopt the composition of nanostructure-containing of the present invention.In addition, the nanostructured of coating can be used for the signal attenuation composition and/or as detectable label (for example based on second optical property with specific emission wavelength).
The composition of nanostructure-containing of the present invention is specially adapted to the manufacturing of flash memory structure body.Flash memory is the read-only storage (EEPROM) of one type of electro-erasable programmable, can fast erasing and programming again.Utilize the device of the constant power supply of this type, non-volatile memory characteristic, have the speed of service more efficiently, change because this storage is a subregion, rather than only change a byte at every turn than standard EEPROM device.
Usually at bit of each memory cell coding, each memory cell comprises two transistors that separated by thin oxide layer (control gate and a floating gate) to flash memory.The characteristic of this unit is the specific limiting voltage between two grid.Program control on floating gate/stored charge, these grid are also controlled two kinds of possible voltage levvls (open/close state of memory cell) between the transistor.Also developed manyly than trick, wherein memory cell has two or more voltage limits (be on each memory cell voltage be divided into plural level).Other details of relevant memory, transistor etc. based on nanostructured can referring to, for example Xiangfeng Duan equals the U.S. Patent application 11/018572 that is entitled as " Nano-enabled memory devices andanisotropic charge carrying arrays " submitted on December 21st, 2004.
As mentioned here, uncontrolled signal transmission (cross interference) can reduce the performance/efficiency of given device between the adjacent signals carrier.Reduce the cross interference between the nanostructured in the device of nanostructure-containing, a kind of mechanism is the distance that increases between the nanostructured.When what relate to is nanoscale structures, and during like quantum dot, the method is particularly useful.The distance that increases between the adjacent quantum dot can realize through forming the rigid crust that each quantum dot is sealed, and can control the distance between the said point like this.On discrete nanostructured, can form rigid crust after deposition first coating, thereby keep discrete (physical separation) characteristic of single nanostructured.If (for example dielectric or the non-conductive) material with suitable is processed, rigid crust also can provide another to reduce the mechanism of cross interference between nanostructured.
The composition of nanostructure-containing of the present invention can 10 10/ centimetre 2, 10 11/ centimetre 2, 10 12/ centimetre 2Or the preparation of higher density, and can not lose quantum confinement or increase the cross interference between the quantum dot.
The invention provides the novel method of making nanocrystal with heterojunction structure, the nanocrystal that said heterogeneous structural nano crystal is made up of two kinds or more kinds of different component in this way, wherein different elements are given the nanocrystal useful properties jointly.As mentioned here, this heterojunction structure is embodied on nuclear-shell orientation usually, and wherein the nuclear of first material is surrounded by the shell of second material.Be worth pointing out; First material can comprise conductor material, semi-conducting material or insulating materials (for example dielectric material); Second material can comprise conductor material, semi-conducting material or insulating materials (for example dielectric material) similarly; They can form combination in any (for example two all is conductive material, and is conductive material and another is an insulating materials, or the like).The inventive method provides operational flexibility, promoting making these nanocrystals easily, and the control special parameter, for example with size Control in scope less than 10 nanometers, this former not accomplishing.Therefore can expect that any application that common nuclear-the shell nanocrystal is had all is the potential use of the present composition, for example, according to those nanocrystal compositions of method preparation as herein described.In addition, these novel methods can also provide other many application.
Nanostructured is carried out the method for reversible modification
Use for some, for example make some device based on nanostructured, nanostructured must withstand high temperatures be handled, for example can not melt and with contiguous nanostructured fusion.For can be used in this application, though can select to comprise the nanostructured of materials with high melting point, the fusing point of all material all can be reduced to nanometer range because of their physical size and descend; Therefore, even if for materials with high melting point, high temperature processing step still has problems.
The invention provides nanostructured, for example the parts of the nanostructured of semiconductor devices carry out the novel method of reversible modification, so that in subsequent processing steps, protect nanostructured.As an object lesson, the inventive method can be used to the palladium quantum dot is carried out oxidation (for example through in oxidizing atmosphere high annealing), thereby when in the process of making flash memories, being encapsulated in quantum dot in the dielectric material that covers it, improves its anti-fusion ability.This oxidizing process is reversible (for example through in reducing atmosphere high annealing), can palladium oxide be reduced to pure palladium (or pure basically palladium) conversely, so that utilize the character of Metal Palladium during the device operation.Be worth pointing out that the inventive method can include but not limited to the nanostructured of any material of protection, shape and size in the high-temperature operation in various subsequent operations.
Therefore, one type of general embodiments provides the method for nanostructured being carried out reversible modification.These methods can provide one or more metallic nanostructureds.With burning, obtain metal oxide earlier, again nanostructured is handled.Reducing metal oxide obtains metal then.
Through heating nanostructured in oxidizing atmosphere (for example oxygen-containing atmosphere), can be with burning.Usually nanostructured is heated to the temperature (between for example about 200 ℃-500 ℃) between about 200-700 ℃.Similarly, through at reducing atmosphere, for example hydrogeneous atmosphere, for example synthesis gas (is N 2In contain 5% H 2) middle heating nanostructured, can metal oxide be reduced.Obviously, reacting gas preferably can pass nanostructured any material on every side and touch nanostructured.Perhaps, nanostructured can be through heating partial reduction at least in nitrogen atmosphere.Usually nanostructured is heated to the temperature (for example about 200-500 ℃) between about 200-700 ℃.
Wanting the nanostructured of modification to go up basically can be virtually any size and/or shape.Therefore; For example, nanostructured can comprise nanocrystal, nanometer four leg structures, three-prong structure, double-legged structure, nanocrystal, nano dot, quantum dot, nano particle, four leg structures of branch or their combination in any of one or more nano wires, nanometer rods, nanotube, branch.In one type of embodiment, nanostructured is a spherical nanostructure on basically.
Said method is applicable to and comprises any nanostructured that the metal of reversible oxidation can take place.For example, said metal can be noble metal (for example Au, Ag or Pt) or transition metal (for example Ni, Fe, Sn or Zn).One type preferred embodiment in, metal is Pd; In this type of embodiment, metal oxide is PdO.What oxidation took place can be nanostructured whole or its a part of (for example superficial layer).For example, can be the metal generation oxidation more than 10% in all nanostructureds, for example greater than 20%, greater than 50%, greater than 75%, even greater than 90% metal.Can monitor (conversely too) to oxidizing process, for example pass through such as the such technology of energy dissipation spectroscopic methodology (EDS) to reduction process.
Treatment step as mentioned above, that this reversible oxidation can be carried out at high temperature is for example protected nanostructured in some device fabrication steps.Therefore; For example; In one type of embodiment, the treatment step of nanostructured comprise with nanostructured place temperature between about 200-750 ℃ (for example be higher than about 250 ℃, be higher than about 500 ℃ or be higher than about 600 ℃ temperature), even be higher than under about 750 ℃ temperature.For example, when on nanostructured, applying dielectric material, just possibly run into such high temperature.
Can protect nanostructured through reversible oxidation, for example prevent that them from high temperature fusing.In addition (or as substituting), utilize and also can protect nanostructured such as coating as herein described.Therefore, in one type of embodiment, one or more nanostructureds that provided have first coating of associating with each nanostructured first surface.First coating has first optics, electricity, physics or structural property, can change second coating with different optical, electricity, physics or structural property into.For example, first and/or second coating can be any coating as herein described.Therefore, for example, second coating can comprise oxide, for example SiO 2, it is optional by forming such as silsesquioxane composition as herein described.Through this nanostructured of heating in oxidizing atmosphere, can change first coating into second coating; Obviously, this transition process can be carried out with the burning process simultaneously.Coating (SiO for example 2) help to keep the separation state between the nanostructured, thereby reduce the possibility that adjacent nanostructured at high temperature fuses.The silsesquioxane part comprises the not enough SiO of formation 2Required stoichiometric oxygen; Therefore, in oxidizing atmosphere, solidify first coating that contains silsesquioxane and can form the better SiO of quality 2Second coating, this coating also help (or help as alternative) to stop the nanostructured fusion.
Embodiment
Following examples be used for the explanation and unrestricted of the present invention.Should be appreciated that said embodiment and embodiment only are used for illustration purpose, their various improvement or version are included in the application's spirit and scope and the scope that Rights attached thereto require for a person skilled in the art.
Embodiment 1: the preparation of closely packed nanostructured individual layer
The method that preparation has the base material of closely packed nanostructured is shown in Fig. 3 and 4.The synthetic nano dot (representing) that has surfactant with a ball, said surfactant-coated nano dot surface.Surfactant and silsesquioxane or other esters of silicon acis parts (L) carry out ligand exchange.
Silane part with the combination headgroup (B) that has nanostructured applies selected base material (for example silica wafers).The individual layer surface aggregation part (SAL) of self aggregation interacts and association on silane part and the substrate surface, and the interface (shown in vertical arrow) that connects nanostructured is provided.Example surface is assembled part and is comprised ring dimethylamino base section and SiMe 2Group, they connect base (ring dimethylamino-organic spacer group-SiMe through one 2) link together.
Through spin coating or the solvent-laden nano dot of dip-coating, the nano dot that will pass through ligand exchange is applied on the SAL substrate then.The unnecessary nano dot of flush away from this substrate obtains by the individual layer nano dot of silica containing part insulation.Because the individual layer character of surface aggregation part, tightly packed (shown in side view among Fig. 4) takes place in nano dot.The base material that combines with nanostructured carries out thermal annealing then, solidifying said layer, thereby first coating (for example phosphorus esters of silicon acis part) is converted into the second coating (SiO 2Shell).Choose wantonly the annealing surface of gained is handled, another layer (top layer or cover layer) esters of silicon acis of spin coating also carries out heat cure, obtains the nano dot memory.
Synthesizing of 2: seven cyclopenta POSS of embodiment disilane alcohol diethoxy phosphate
(Fig. 6) as described herein synthetic exemplary polyhedral oligomeric silsesquioxane (POSS) part seven cyclopenta POSS disilane alcohol diethoxy phosphate 2.Institute all carries out under inert atmosphere with the Schlenk technology in steps.Solvent carries out drying with
Figure G05818708920061213D000381
molecular sieve, through three freezing-vacuumize-thawing cycle outgases.With the static vacuum drying of phosphorus pentoxide 12 hours, before the use, (Cl-P (O) (OEt) for the chloro diethyl phosphonate in drier for seven cyclopenta POSS, three silanols 1 2) carry out vacuum transfer.Measure mass spectrum in the Scripps of La Jolla research institute, on Bruker FT NMR, use 31P measures 31P{ 1The H}NMR spectrum, frequency is 162MHz.
Be reflected in 50 milliliters of Schlenk flasks and carry out.Seven cyclopenta POSS, three silanols 1 (1.00 grams, 1.14 mMs) are dissolved in the mixture of toluene (10 milliliters) and triethylamine (15 milliliters), obtain settled solution.Add Cl-P (O) (OEt) with syringe then 2(0.650 gram, 0.545 milliliter, 3.77 mMs) stirred 1 minute simultaneously.After about 5 minutes, it is muddy that settled solution becomes.Stirred overnight in argon gas atmosphere.
Add Cl-P (O) (OEt) 2After about 20 hours, remove volatile materials through vacuum transfer.(3 * 8mL), vacuum transfer is removed volatile materials once more with hexane extraction with residue.Residue is dissolved in 1.25 milliliters of toluene, it is separated out from solution, be oily with 6 milliliters of acetonitriles.Abandon the upper strata phase, repeat twice of precipitation process.Then gained grease is dissolved in 6 milliliters of THF, 2 milliliters of toluene are in about 6 milliliters of acetonitriles at last.Last a kind of solvent under agitation slowly adds, and is muddy up to solution becomes.Then mixture is cooled to-35 ℃ and spends the night, at this moment produce some white micro-crystals bodies.Remove supernatant, remove volatile solvent through vacuum transfer, until remaining initial body long-pending 1/3rd, this is to obtain more white micro-crystals body.Remove remaining supernatant, product is stayed in the flask.Dry white crystallized product 2 under vacuum then, up to pressure reach＜0.010 torr kept 1 hour.Separated product obtains white micro-crystals body 0.320 gram, and 0.313 mM, productive rate are 27.5%.Mass spectrum: ESI-TOF (-) m/z 1034 [M-H+Na], ESI-TOF (-) m/z1011 [M-H].NMR 31P{ 1H}NMR(162MHz，Tol-d 8，25C)δ-11.3(s，1P)。
With 2.0 equivalent Cl-P (O) (OEt) 2With 2.0 equivalent Et 3N or pyridine also can be accomplished this reaction in toluene.Course of reaction comprises and uses hexane wash as stated.Through-35 ℃ of crystallizations, from the mixed solvent system that THF, toluene and acetonitrile are formed, isolate product.
Other silsesquioxane derivatives of the present invention comprise:
1) closed esters of silicon acis cage modle POSS molecule list silanol, it has an organic spacer group that is attached on the alcohol, obtains ether (aryl or alkyl derivative), and the carbon bond on the spacer groups other end is connected on the combination headgroup of nanostructured.
2) open type esters of silicon acis cage modle POSS molecule three silanols, it has three organic spacer groups that are attached on the alcohol, obtains three ethers, and the carbon bond on the spacer groups other end is connected on the bound fraction of nanostructured.
3) the esters of silicon acis dimer (or bigger oligomer) through condensation prepared.Difunctional silane and single heteroatom functional POSS have one to combine headgroup, and this combination headgroup is centered close to the middle part of difunctional silane bay unit.
4) open this cage (for example on a limit) through selection (Si-O-Si), and the glycol that exposes is carried out modification, change closed esters of silicon acis cage into external form from interior type, so that connect or crosslinked caged molecule from side with connecting headgroup.
Embodiment 3: on SAM, generate the single layer coating nanostructured
Through various wet processings, as deposit on the individual layer (SAM) of self aggregation, reach with silsesquioxane or esters of silicon acis part the individual layer nanocrystal is regulated with the self aggregation of controlled way, use to be used for charge storage.The method can be used to prepare the individual layer with closely packed nano-structure array, is preferably orderly closely packed nano-structure array.
Apply the individual layer of the self aggregation of being made up of the silane part at substrate surface, the silane part has one to connect headgroup, is used for being connected with silsesquioxane or esters of silicon acis part.Utilize spin coating, dip-coating or spraying, perhaps the traditional printing technology is deposited on nanocrystal on the SAM from solution.The unnecessary nano dot of flush away from the base material obtains the individual layer nanocrystal that is insulated by silica containing part.
Embodiment 4: drive through evaporation and assemble the orderly coated with nano structure of generation individual layer
The individual layer of nanostructure-containing of the present invention also can drive the method preparation of assembling through evaporation.In this embodiment, need not carry out functionalization or stratification to base material with chemical part through specially treated, be used for associating with nanostructured.The CdSe nanocrystal dropwise is cast on the silicon nitride base material.The process of drying can be inhaled through the composition of surface ligand and with the cleaning cloth of ability lyosoption and gone lip-deep liquid to control.Through the process of drying of control solvent, can obtain the good nanocrystal array of arranging in order.
Embodiment 5: be used for the preparation of the array nanostructured of memory
The present invention has introduced the universal method of preparation memory, and said memory is used the nanocrystal stored charge.This method is simplified to and adopts the CdSe nanocrystal that does not have shell, carries out ligand exchange with the silsesquioxane part then, and wherein the silsesquioxane part carries out modification with the phosphonate ester headgroup, in order to connect nanocrystal.On the base material that applies oxide, these nanocrystals are deposited as individual layer then.
Yet used same general method is easy to be applied on the metal nanocrystal equally, as long as improve the synthetic of nanocrystal, prepares metal nanocrystal roughly spherical in shape, as to have weak binding partner, for example the Pd nanocrystal.Can clean these nanocrystals then, and characterize through for example NMR.Part can be through connecting different headgroups on silsesquioxane, for example mercaptan or sulfonate ester group carry out modification, so that be connected on the nanocrystal better.Part can carry out purifying, characterizes with NMR and mass spectrum then.Ligand exchange to nanocrystal, is monitored exchange process with VT-NMR.Cleaning is through the nanocrystal of exchange, to remove unnecessary part then.Then nanocrystal is deposited on the base material that has prepared (SAM coating, functionalization or not the oxide base material of functionalization) through spin coating or evaporation.
Can change to various aspects of the present invention easily or change, still can accomplish the synthetic of discrete coated with nano structure simultaneously.The type of used nanocrystal can change: CdSe, any II-VI, III-V or IV semiconductor, any metal (including but not limited to Pd, Pt, Au, Ag, Ni, Fe, Sn, Zn and Co).Narrow size distribution both can obtain in initial synthesizing, and also can obtain through follow-up size Selection step.In addition, being used for the weak part conjugated group of growth part or first coating (for example relevant with oxide) part that combines can change: mercaptan, sulphonic acid ester, sulfinic acid ester, phosphinate, carboxylate, phosphonate radical, phosphonate ester, amine, phosphine etc.Can generate (solidifying the back) various monoxide ligands according to the selection and the target purposes of first coating, like SiO x, TiO x, VnO xOr other oxides.Deposition process also can be made and be different from variation recited above.
The another kind of method that forms oxide is with controlled manner oxidation nanometer plane of crystal (for example, with the bubbling form oxygen being blasted in the weak solution of nanocrystal), obtains having the oxide (the Co nuclear that the oxidation crust of cobalt is for example arranged) of certain energy barrier.The first coating part of the present invention still can apply by solution, and after deposited monolayers, solidifies.Be applicable to that the method that this storage is used also can be used for being embedded in the nanocrystal such as in tagant or this matrix of phosphor body.
Embodiment 6: based on the preparation of the charge accumulator of nanostructured
Can prepare capacitor, for example, can this explanation prepare charge accumulator, like the feasibility of flash memories based on nanocrystal based on nanocrystal.For making such exemplary means, prepared a silicon wafer, the raceway groove oxide layer of 3-6 nanometer thickness is arranged above it.Through surfactant exchange or synthetic in the presence of part, preparation has the palladium quantum dot that associates with ligand combination thing of the present invention (for example POSS part shown in Fig. 5 F), and it is suspended in organic solvent such as the toluene.With the nanocrystal spin coating or drip and to be coated onto on the wafer that applies oxide, wetting, dry then then.Unnecessary nanocrystal is removed in rinsing, on wafer, stays to be the nanocrystal of individual layer basically.This wafer in 250 ℃ of roasting 10-30 minutes, to solidify the ligand combination thing, forms second coating (SiO for example in oxygen-containing atmosphere 2Shell).On nanocrystal, deposit another oxide skin(coating) (SiO for example through chemical vapour deposition (CVD) 2Layer), vapor deposition chromium and gold on this oxide skin(coating) form electrode.Be determined at and apply before programming and the erasing voltage and afterwards CV curve, characterize obtained device thus.
From the clear purpose of understanding, though in front the present invention has been carried out comparatively detailed description, those skilled in the art should be appreciated that in not deviating from true scope of the present invention after reading this specification, can make various changes in form and details.For example, above-mentioned all technology and equipments can various combining forms use.All publications that the application quotes, patent, patent application and/or other documents are all in full with reference to incorporated herein; To satisfy various purposes, just reference is the same respectively in order to satisfy various purposes as every part of publication, patent, patent application and/or other documents.

Claims (38)

1. one kind forms the method that the back deposits shell on nanostructured, and said method comprises:
One or more nanostructureds with the ligand combination thing that associates with first surface are provided, and said ligand combination thing can change rigid crust into, and said ligand combination thing comprises many nanostructured bound fractions that are connected on the silica cage modle complex compound;
The ligand combination thing is cured, on the first surface of nanostructured, produces rigid crust, thereby form the shell of back deposition.
2. the method for claim 1 is characterized in that, provides one or more steps that contain the nanostructured of the ligand combination thing that associates with first surface to comprise:
Provide one or more to contain the nanostructured of one or more surfactants that associate with first surface;
With the surfactant on the ligand combination thing exchange first surface.
3. method as claimed in claim 2 is characterized in that one or more surfactants comprise one or more carboxylic acids.
4. method as claimed in claim 2 is characterized in that one or more surfactants comprise one or more aliphatic acid.
5. method as claimed in claim 2 is characterized in that one or more surfactants comprise one or more phosphines or phosphine oxide.
6. method as claimed in claim 2 is characterized in that, the step of exchange surface activating agent comprises:
Nanostructured is suspended or is dissolved in the organic solvent;
The nanostructured that suspends is mixed with the ligand combination thing, thereby surfactant is exchanged with the ligand combination thing on first surface.
7. method as claimed in claim 6 is characterized in that, organic solvent is selected from toluene, chloroform, chlorobenzene and their combination.
8. method as claimed in claim 2 is characterized in that, the step of exchange surface activating agent comprises:
Carry out the organic desorb of low temperature, form the nanostructured of desorb;
Material with containing active oxygen carries out oxidation to the nanostructured through desorb;
Ligand combination thing and the nanostructured through desorb are associated, thus with the surfactant on the ligand combination thing exchange first surface.
9. method as claimed in claim 8 is characterized in that, the material that contains active oxygen provides through UV ozone generating process, RF antozone generating process or oxygen radical generating process.
10. the method for claim 1 is characterized in that, provides one or more steps that contain the nanostructured of the ligand combination thing that associates with first surface to be included in the ligand combination thing and has down synthetic one or more nanostructureds.
11. the method for claim 1; It is characterized in that, provide the step of one or more nanostructureds to comprise in the synthetic structure one or more: the nanocrystal of nano wire, nanometer rods, nanotube, branch, nanometer four leg structures, nanometer three-prong structure, nano double leg structure, nanocrystal, nano dot, quantum dot, nano particle, four leg structures of branch or their combination in any.
12. the method for claim 1 is characterized in that, provides the step of one or more nanostructureds to comprise providing to have the semiconductor nanocrystal of a size less than 10 nanometers at least.
13. the method for claim 1 is characterized in that, provides the step of one or more nanostructureds to comprise providing to have the metal nanocrystal of a size less than 10 nanometers at least.
14. the method for claim 1 is characterized in that, curing schedule comprises heating, and one or more contain the nanostructured of the ligand combination thing that associates with first surface.
15. method as claimed in claim 14 is characterized in that, heating is carried out being lower than 500 ℃.
16. method as claimed in claim 14 is characterized in that, heating is carried out between 200-350 ℃.
17. method as claimed in claim 14 is characterized in that, heating is carried out in oxidizing atmosphere.
18. the method for claim 1 is characterized in that, silica cage modle complex compound comprises silsesquioxane and forms.
19. the method for claim 1 is characterized in that, the ligand combination thing is selected from:
Figure FSB00000842269800021
Figure FSB00000842269800031
Figure FSB00000842269800041
Wherein R is organic group or hydrogen atom.
20. method as claimed in claim 19 is characterized in that, R is an alkyl.
21. method as claimed in claim 19 is characterized in that, R is alkyl, cycloalkyl, aryl or alkylaryl.
22. method as claimed in claim 21 is characterized in that, R is isobutyl group, methyl, hexyl, cyclopenta or cyclohexyl.
23. the method for claim 1 is characterized in that, the ligand combination thing is selected from:
Figure FSB00000842269800051
Wherein R is alkyl, hetero atom or electron-withdrawing group; With
Figure FSB00000842269800052
Wherein R is a halide.
24. the method for claim 1 is characterized in that rigid crust comprises electrically conductive composition.
25. the method for claim 1 is characterized in that rigid crust comprises electrical insulation composition.
26. the method for claim 1 is characterized in that, rigid crust comprises the optical clear composition.
27. the method for claim 1 is characterized in that, provides the step of one or more nanostructureds to comprise through second nanostructured surface nanostructured is linked to each other with base material.
28. method as claimed in claim 27 is characterized in that base material comprises silicon substrate.
29. method as claimed in claim 27, this method also comprises:
With planarization composition be administered to one or more with nanostructured that base material links to each other on.
30. method as claimed in claim 29 is characterized in that, uses the step of planarization composition and before solidifying ligand combination thing step, carries out.
31. method as claimed in claim 29 is characterized in that, uses the step of planarization composition and after solidifying ligand combination thing step, carries out.
32. the rigidity SiO of the back deposition formation that is prepared according to the described method of claim 1 2The many discrete nanostructured of shell parcel is characterized in that, unit nanostructured and its shell diameter together are less than 6 nanometers, and the density that the unit nanostructured exists is greater than 1 * 10 12/ centimetre 2
33. many nanostructureds as claimed in claim 32 is characterized in that the unit nanostructured is arranged in array.
34. many nanostructureds as claimed in claim 32 is characterized in that, unit nanostructured and substrate surface associate.
35. many nanostructureds as claimed in claim 34, said nanostructured also comprises top coat.
36. many nanostructureds as claimed in claim 35 is characterized in that top coat comprises the silica top coat.
37. device comprises the described many nanostructureds of claim 32.
38. device as claimed in claim 37 is characterized in that, said device comprises charge accumulator.
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