CN102239107A - Methods for preparing nanocrystals using electron transfer agents - Google Patents

Abstract

Compositions and methods for the preparation of core nanocrystals are provided, using mismatched precursors and two or more electron transfer agents to independently control the nucleation and growth phases of particle formation.

Description

Use electron transfer agent to prepare nanocrystalline method

The cross reference of related application

The application requires the priority of the U.S. Provisional Application sequence number 61/102,589 of submission on October 3rd, 2008, and its content is incorporated into by reference in full.

To the federal government sponsored research statement of the inventor's patent right of generation down

The part of embodiment disclosed herein is to carry out under the government with the cooperation agreement No. 70NANB4H3053 of national standard and the Institute for Research and Technology and the US Department of Commerce supports.Government has certain right in the embodiment of the disclosure.

Technical field

The disclosure provides the method for using two kinds of electron transfer agent synthesizing nano-particles.More particularly, the disclosure provides to make and can be used for a plurality of fields, comprises the method for the nano particle of biology, analysis and combinatorial chemistry, medical diagnosis, genetic analysis, solar energy conversion and display.

Background technology

Semiconductor nano has between individual molecule and the optical property that becomes the uniqueness between the piece material, and for more and more important for detecting, follow the tracks of and observe individual molecule and microcosmic biology and biological chemical structure in the kinds of experiments method in biology, chemistry, medical science and the science of heredity.They provide and are easy to observe and the enough bright fluorescence signal of observing conscientiously with single nanocrystalline realization with activation.

Forming the nanocrystalline several different methods of nuclear by metal-anion binary salt is known in this area.These methods can be classified according to the type of used reactant and the mechanism of the supposition how relatively oxidation state of reactant produces based on usually.

In first kind of approach, Fan Ying metal and nonmetallic ingredient all provide with its neutral atomic form each other.For example, people such as Murray, J. Am. Chem. Soc., 1993,115:8706 has described dimethyl cadmium (Me ₂Cd) with the reaction of trioctylphosphine selenizing phosphine (TOPSe), these two kinds of reactants discharge neutral cadmium (Cd respectively in solution ⁰) and selenium (Se ⁰) atom, so that do not need electronics to shift so that make their oxidation state coupling.Because this reactant is in the form that is fit to react to each other, this situation is regarded as " coupling " of oxidation state: neither need oxidation or reduction just can react, also can not cause the unbalance of clean electronics.This type of reaction is carried out usually very fast, because cadmium and selenium atom immediate response when collision forms cadmium selenide (CdSe).

In second class, this metal and nonmetallic ingredient all provide with their ionic species.For example, people such as Peng, J Am. Chem. Soc., 2001,123:183 has described at TOPO and phosphonic acids part, uses cadmium oxide (CdO) to prepare CdSe and cadmium telluride (CdTe) as the cadmium ion source down as the existence of hexyl phosphonic acids (HPA), myristyl phosphonic acids (TDPA) or octyl phosphonic acid (OPA).Cadmium salt discharges Cd in solution ²⁺Ion.Simultaneously two (trimethyl silyl) sulfide (TOPSe) discharge Se in solution ^2-These reactions are also carried out very fast, because the same immediate response of this cadmium and sulphion forms cadmium sulfide (CdSe).This reaction type is considered to " coupling ", because also do not need oxidation or reduce each thing class, and they can be with suitable stoichiometric reaction to make neutral products.

In these kinds separately, intermediate makes to each other high reactivity and is difficult to control granularity, particle productive rate and granularity dispersiveness.In a single day the reactant class discharges in solution, will be with the speed of diffusion-controlled or very near so fast speed response.In some cases, use part or solvent can slightly slow down this reaction, but these approach can not provide the control general way that particle generates.

Especially, for example, can not prevent that usually this type of reaction from forming new nanocrystalline (be called nucleation, it makes to be difficult to control and is intended to the reaction of adding shell on nanocrystalline existing).Usually need on nanocrystalline, form shell to be used for some purposes, because this shell has greatly improved the chemistry and the photostability of this nanocrystal.This shell is usually by making with the nanocrystalline different and complementary semi-conducting material of the nuclear of below; Therefore, if hull shape becomes reaction to cause nucleation, then can form newly nanocrystalline with those different compositions that have Yu want that mix of wanting.In case and they form with form of mixtures, extremely difficultly separate that these are nanocrystalline.

In the third approach, can select the precursor of mismatch, make a kind of precursor that neutral atom is provided in solution under reaction condition, another kind of precursor provides ion simultaneously.For example, (it is Cd to the alkyl phosphonic acid cadmium ²⁺The source of ion) and selenizing tri octyl phosphine (TOPSe) (it is Se ⁰The source) mixture can be as the precursor of mismatch.This type of precursor can not react and form the neutrals class, unless there be the oxidation state of electron transfer agent with one of conditioned reaction thing class, provides " coupling " thing that can react class thus.For example, reducing agent can be used for to Cd ²⁺Adding electronics (is Cd so that two kinds of nonionic thing classes to be provided ⁰And Se ⁰), or can be to Se ⁰Adding electronics (is Cd so that two kinds of ionic species to be provided ²⁺And Se ^2-).Arbitrary approach, in case atom thing class is " coupling ", their reaction can be carried out, but this is reflected under the situation that does not have this type of electron transfer agent and can not carries out.Perhaps, the two kinds of ionic species (i.e. two kinds of cations or two kinds of anion) with identical charges also will be " mismatches ".For example, can use the precursor of the mismatch that two kinds of cationic species are provided, wherein a kind of thing class is reduced the anionic species that can stand " coupling " reaction to provide.For example, Se ²⁺Or Se ⁴⁺Can be reduced so that selenium anion Se to be provided ^2-, it can take place and metal cation thing class, as Cd ²⁺Reaction.In another example, two kinds of cationic species all can be reduced to the neutrals class.How the incremental process that Fig. 1 has described nucleation and growth participates in the explanation reducing agent.

In another example, in the reaction between neutrals class and anionic species, oxidant can be used as this electron transfer agent.For example, Cd ⁰And Se ^-2Can wherein use oxidant so that with Se as the precursor of mismatch ^-2Be oxidized to Se ⁰, obtain two kinds of neutrals classes that " coupling " reaction can take place.Needs to this electronic transfer process and reagent are greatly ignored: because the small-scale and the complexity of the reaction that comprises, the effect of electron transfer agent is realized by the impurity that is present in the raw material or generate accidentally in position usually.

Reported some reactions of the electron transfer agent with adding: for example, Zehnder and Treadway, U.S. Pat 7,147,712 have described use promoter (it can be oxygen or reducing agent) to promote and to control nucleation and promote crystal growth.Add single reducing agent causing nucleation, or nanocrystalline initial formation, in case and nucleation take place then promote nanocrystalline growth.This method provides to the particle productive rate with to the control of final size.But,, only can realize the separation in two stages by indirect means because identical reducing agent is used for this nucleation and growth stage.

Still need make the method for nanocrystalline product with high product yield with to the height control level of granularity and particle dispersiveness, and need control the nanocrystalline nucleation and growth stage respectively.

Summary of the invention

Provide herein and avoiding or reducing as far as possible and use two kinds of electron transfer agents temporarily to separate nucleation and growth phase under the condition of nucleation to control and to promote the method for nanocrystalline growth.These methods provide the nanocrystalline preparation method who shows product repeatability and controlled performance and this type of nanocrystalline new compositions.Method of the present invention can independently be controlled the nucleation and growth stage of nanocrystalline preparation.

The embodiment that provides herein has the nanocrystalline of reproducible product feature by using the electron transfer agent of controlling nanocrystalline formation and growth independently to advantageously provide.This method applicability is strong because they in addition when the speed that adds reagent in nanocrystalline preparation feedback exists some to change, also can reproducibly provide nanocrystalline.In certain embodiments, use two kinds of reducing agents to control the process of nanocrystalline formation.

In one aspect, make the method for nanocrystalline colony, comprising: mixture is provided, and this mixture comprises: first precursor; Second precursor, wherein this first precursor and this second precursor have the oxidation state of mismatch; Present in an amount at least sufficient to produce the sub-transfer agent of forceful electric power of required nucleation amount; With the sub-transfer agent of light current that is different from the sub-transfer agent of this forceful electric power; And this mixture is heated to is enough to cause temperature a period of time that nanocrystalline colony forms.

In yet another aspect, make nanocrystalline method, comprising: the mixture that comprises first precursor and second precursor is provided, and wherein this first precursor and this second precursor have the oxidation state of mismatch; In this mixture, add the sub-transfer agent of forceful electric power that is lower than stoichiometry with the amount that is enough to produce required nucleation amount; Choose wantonly mixture is heated together to produce required nucleation amount; In this mixture, add the sub-transfer agent of light current with the amount that is enough to produce required nanocrystalline increment; And optional a period of time that this mixture heating is enough to produce required nanocrystalline increment.

Aspect another, make nanocrystalline method, comprise: the mixture that comprises first precursor, second precursor and the 3rd precursor is provided, and wherein this first and second precursor has the oxidation state of mismatch, and wherein the 3rd precursor has the oxidation state that is matched with this first precursor or this second precursor; And optional this mixture is heated to the temperature a period of time that is enough to cause nanocrystalline formation.

With reference to its specific embodiment, and further consider the example that is included in herein, the others of this method and composition and advantage will be apparent by following more detailed description.It being understood that term used herein only is used to describe specific embodiment, rather than in order to limit.

Description of drawings

Fig. 1 has shown that two kinds of independent reducing agents are used in promotion nucleation and growth subsequently in the nanocrystalline formation of ZnTe.

Fig. 2 has shown that weak reductant is used for nanocrystalline growth phase, and this in this embodiment weak reductant comes from this precursor compound itself.Zinc undecylenate is that the example of weak reductant as the precursor compound of unsaturated carboxylic acid ester group also is provided.As shown in the higher level of absorbance in right side among Fig. 2 like that, for zinc undecylenate, the particle productive rate is higher than zinc stearate.Zinc undecylenate has promoted crystal growth by the weak reductant group is provided.

The specific embodiment

Following detailed description and the embodiment included with reference to this paper can more easily understand embodiment as herein described.It being understood that the term that this paper adopts only is used to describe specific embodiment, and be not intended to limit.

Unless otherwise defined, the identical implication that has of all technology used herein and scientific terminology and embodiment one skilled in the art disclosed herein institute common sense.

" one " used herein or " a kind of " are meant " at least a " or " one or more ".

" pact " used herein is meant that this numerical value is similar to, and the enforcement that little change can appreciable impact the disclosed embodiments.When using numerical limits, unless context illustrate separately, " pact " be meant this numerical value can change ± 10% and remain in the scope of disclosed embodiment.

" nano particle " used herein is meant any particle of at least one key dimension in the nanoscale scope.Nano particle has at least one key dimension in about 1 to 1000 nanometer range usually.

The example of nano particle comprises nanocrystalline, and is nanocrystalline as nuclear/shell, adds the organic coating of any firm association or other material that can be on this nanocrystal surface.Nano particle can also comprise that exposed nuclear/shell is nanocrystalline, and it is nanocrystalline or nuclear/shell is nanocrystalline to have the nuclear of layer of other material that for example TDPA, OPA, TOP, TOPO maybe can not remove from this surface by conventional solvation.Nano particle can have in its surface can be by further crosslinked ligand layer; And nano particle can have the other or another face coat that can change these particle properties (for example improve or be reduced in dissolubility in water or other solvent).This layer from the teeth outwards is included in the term " nano particle ".

" nanocrystalline " used herein is meant the nano particle of being made by the inorganic substances that have the ordered crystalline structure usually.It can be meant have the nuclei of crystallization (examining nanocrystalline) nanocrystalline, or refers to that nuclear/shell is nanocrystalline.Nanocrystalline to have full-size usually be the 1-100 nanometer, and preferred maximum dimension is the nuclear diameter of about 1 to 50 nanometer.

Examining nanocrystalline is it not to be applied the nanocrystalline of shell; It is semiconductor nano normally, and it is made by single semi-conducting material usually.It can have homogeneous forms, or its composition can change with the degree of depth of this nanocrystalline inside.The nanocrystalline of many types is known, prepares nanocrystal and is known to its method that applies shell in this area.Disclosed herein nanocrystalline usually be the fluorescence nano that becomes clear, and the nano particle by their preparations also becomes clear usually, for example has at least about 10%, sometimes at least about 20%, sometimes at least about 30%, sometimes at least about 40% and sometimes at least about 50% or bigger quantum yield.Concerning nanocrystalline, advantageously have protection they in use or in storage process, exempt from the surface ligand layer of deterioration.

" quantum dot " used herein is meant the nanocrystalline particle of being made by the material that when the body is semiconductor or insulating materials, and it has adjustable photophysical property near ultraviolet (UV) to far infrared (IR) scope.

" water-soluble " is used in reference to this material (item) at this paper and dissolves in maybe can be suspended in and contain group water solution, in water or group water solution or cushioning liquid (comprising those of biology or molecular detection system of being used for well known by persons skilled in the art).Although water soluble nanometer particles is used to describe on the micromolecular meaning of independent solvation at this term be not genuine " dissolving ", their solvations and be suspended in the compatible solvent of their extexine in, thus, the nano particle that is easy to be dispersed in the water is considered to water miscible or water dispersible.It is hydrophilic that water soluble nanometer particles can also be considered to, because its surface can and have water-soluble with water compatible.

" hydrophobic nano particle " used herein is meant and can easily is dispersed in or is dissolved in and the immiscible solvent of water, as the nano particle in hexane, the toluene etc.This nano particle is not easy to be dispersed in the water usually.

" hydrophily " used herein is meant the surface nature of solid, or the bulk property of liquid, and wherein this solid or liquid show in high dielectric media than higher miscibility or dissolubility in low dielectric media.For example, in methyl alcohol than varsol for example in the decane the higher material of dissolubility be considered to hydrophilic.

Nano particle can synthesize with the shape of different complexities, as sphere, clavate, plate-like, triangle, nano-rings, nanoshell, quadrangle, nano wire etc.These geometries have different character separately: the orientation dependence of the spatial distribution of surface charge, incident light wave polarization and electric field space scope.In certain embodiments, disclosed herein nanocrystalline be subsphaeroidal.

In certain embodiments, nano particle provided herein can be that to have a nuclear/shell of the nanocrystal that is covered by the semiconductor shell nanocrystalline.Can make the thickness of shell be suitable for providing required particle properties.The thickness of shell can influence wavelength of fluorescence, quantum yield, fluorescent stability and other photostability characteristic.

This nanocrystal and shell can be made by metal and non-metallic atom that any suitable becoming known for forms semiconductor nano.The semi-conducting material that is suitable for this nuclear and/or shell includes but not limited to comprise the material of 2-16 family, 12-16 family, 13-15 family and the 14th family's element base semiconductor, as ZnS, ZnSe, ZnTe, CdS, CdSe, CdTe, HgS, HgSe, HgTe, MgS, MgSe, MgTe, CaS, CaSe, CaTe, SrS, SrSe, SrTe, BaS, BaSe, BaTe, GaN, GaP, GaAs, GaSb, InP, InAs, InSb, AlS, AlP, AlSb, PbS, PbSe, Ge and Si with and ternary and quaternary mixture.Usually, the nanocrystalline nuclear of this nuclear/shell is made up of different semi-conducting materials with shell, and at least a atomic type of binary semiconductor material that this means the nuclear of nuclear/shell is different from the atomic type in the nanocrystalline shell of this nuclear/shell.This nanocrystal and shell can be made by any suitable known metal and non-metallic atom that forms semiconductor nano.Can use technology known in the art to make semiconductor nano.Referring to for example United States Patent(USP) Nos. 6,048,616,5,990,479,5,690,807,5,505,928 and 5,262, on May 27th, 357 and 1999 disclosed International Patent Publication No. WO 99/26299.The common manufacturing of these methods has protection in its surface, and they exempt from hydrophobicity part coating nanocrystalline of quick deterioration.

Nanocrystalline can the sign by its radiative percentage quantum productive rate.For example, nanocrystalline quantum yield disclosed herein can for greater than about 10%, greater than about 20%, greater than about 30%, greater than about 40%, greater than about 50%, greater than about 60%, greater than about 70%, greater than about 80%, greater than about 90% and any two of these values between scope.This quantum yield greater than about 30%, is preferably greater than 50% usually, greater than 70% and sometimes greater than 80%.

In certain embodiments, the metallic atom of the shell on the nanocrystal is selected from Cd, Hg, Zn, Be, Al, Ga, Mn, Cu and Mg.Second element in these semiconductor shells can be selected from S, Se, Te, O, P, As, N and Sb.

This nano particle can have any suitable dimensions; Usually, its size can be provided in the fluorescence of the UV-visible part of electromagnetic spectrum, because this scope is easily for and biochemistry activity biological in monitoring in the associated media.Relation between size and the wavelength of fluorescence is known, makes nano particle that more I can need be chosen in the certain material that provides suitable wavelength under the small size thus, as InP as the nanocrystalline nuclear of the nuclear/shell that designs especially for a short time.

In common embodiment, nanocrystalline diameter described herein can for about 1 nanometer to about 100 nanometers, diameter is about 1 to about 50 nanometers sometimes, diameter is about 1 to about 25 nanometers sometimes.The more specifically scope of nanocrystalline size can include but not limited to: about 0.5 nanometer to about 5 nanometers, about 1 nanometer to about 50 nanometers, about 2 nanometers to about 50 nanometers, about 1 nanometer to about 20 nanometers, about 2 nanometers to about 20 nanometers or about 2 to about 10 nanometers.The nanocrystalline example of size more specifically can include but not limited to: about 0.1 nanometer, about 0.5 nanometer, about 1 nanometer, about 2 nanometers, about 3 nanometers, about 4 nanometers, about 5 nanometers, about 6 nanometers, about 7 nanometers, about 8 nanometers, about 9 nanometers, about 10 nanometers, about 11 nanometers, about 12 nanometers, about 13 nanometers, about 14 nanometers, about 15 nanometers, about 16 nanometers, about 17 nanometers, about 18 nanometers, about 19 nanometers, about 20 nanometers, about 25 nanometers, about 30 nanometers, about 35 nanometers, about 40 nanometers, about 45 nanometers, about 50 nanometers, and the scope between any two of these values.For basic and aspheric nanocrystalline, clavate for example, its minimum dimension can be for about 1 to about 100 nanometers, or be about 1 nanometer to about 50 nanometers, or be extremely about 25 nanometers of about 1 nanometer, be about 1 nanometer about 10 nanometers or be about 1 nanometer to 5 nanometer sometimes extremely.

In certain embodiments, provide herein diameter less than about 10 nanometers or diameter less than about 7 nanometers or diameter nanocrystal less than about 5 nanometers.These nanocrystalline small sizes are favourable in many application, particularly because disclosed herein nanocrystalline bright unexpectedly under their size.

The monochromatic goods of typical nano particle have the preferred substantially the same crystal of size and dimension.In fact the nanocrystalline sphere or subglobose that is considered to usually can be Any shape still.What perhaps, this nanocrystalline shape can the right and wrong sphere.For example, for redder color, nanocrystalline shape variable is oblate sphere.Preferably at least about 60%, at least about 70%, at least about 80%, at least about 90%, have identical size with this particle of about 100% ideally at least about 95%.Can be with root mean square (" rms ") the measurement size deviation of diameter, it preferably less than about 20%rms, is more preferably less than about 10%rms less than about 30%rms.Dimensional discrepancy can be less than about 10%rms, less than about 9%rms, less than about 8%rms, less than about 7%rms, less than about 6%rms, less than about 5%rms or the scope between any two of these values.It is " monodispersed " that the colony of this particle is sometimes referred to as.Those of ordinary skills will appreciate that, and are nanocrystalline, obtain with the size distribution form usually as the specific dimensions of semiconductor nano.

Be well known that the color of this semiconductor nano (emission light) can be by changing this nanocrystalline size and forming to come " tuning ".The nanocrystalline wavelength that can absorb wide spectrum, and launch the light of narrow wavelength.This excites different usually with emission wavelength, and not overlapping.Single nano particle of colony that disperses can be characterized by the fluorescent emission that their generations have narrow relatively wavestrip.The example of luminous width (FWHM) comprises less than about 200 nanometers, less than about 175 nanometers, less than about 150 nanometers, less than about 125 nanometers, less than about 100 nanometers, less than about 75 nanometers, less than about 60 nanometers, less than about 50 nanometers, less than about 40 nanometers, less than about 30 nanometers, less than about 20 nanometers with less than about 10 nanometers.The emission width is located preferably less than about 50 nanometers at the full width at half maximum (FWHM) of emission band, and is more preferably less than about 35 nanometers.This emission light preferably has the emission wavelength of symmetry.This luminous maximum is usually at any wavelength place of about 200 nanometers to about 2,000 nanometers.Luminous peaked example includes but not limited to: about 200 nanometers, about 400 nanometers, about 600 nanometers, about 800 nanometers, about 1,000 nanometer, about 1,200 nanometers, about 1,400 nanometers, about 1,600 nanometers, about 1,800 nanometers, about 2,000 nanometers, and the scope between any two of these values.In certain embodiments, green is desirable, therefore is chosen in the wavelength in the green area.

This nano particle can have the face coat that increases various functionalities.For example, this nanocrystallinely can scribble lipid, phosphatide, aliphatic acid, polynucleotide, polyethylene glycol, first antibody, SA, antibody fragment, protein or nucleic acid base aptamers, biotin, streptavidin, protein, peptide, organic molecule, organic or inorganic dyestuff, precious metal or noble-metal-cluster.

The spectral characteristic of nano particle can use any suitable photo measure or light gathering unit to monitor usually.The example of this device is the CCD(charge-coupled image sensor) camera, video equipment, CTT imaging, be contained in digital camera, photomultiplier, fluorescence photometer and the photometer on the fluorescence microscope, the microscope of various structures, and even human eye.Luminously can monitor continuously or monitor at one or more discontinuous time points.The photostability of nano particle and sensitivity allow the variation of non-volatile recording electromotive force.

In certain embodiments, the nano particle that provides herein can be a member that the nano particle list of similar composition disperses colony.This monodisperse particle colony be characterised in that in certain embodiments its show aspect the diameter of this nuclear or the minimum dimension less than about 30%rms, preferably less than about 20%rms, be more preferably less than the deviation of about 10%rms.In certain embodiments, this monodisperse particle colony is showing aspect the diameter of this nuclear or the minimum dimension less than about 5% or less than the deviation of about 3%rms.Those of ordinary skills will appreciate that, and are nanocrystalline, in fact obtain with the size distribution form as the specific dimensions of semiconductor nano.

Single nano particle of colony that disperses is characterised in that they produce the fluorescence radiation with narrow relatively wavelength band.In certain embodiments, this monodisperse particle colony is characterised in that when by radiation, and this colony's transmitted bandwidth is less than about 60 nanometer full width at half maximum (FWHM), or less than about 50 nanometer FWHM and sometimes less than the light of about 40 nanometer FWHM.

In certain embodiments, described in this article ligand-modified before, by adding outer covering layer or shell, will examine efficient and the stability of semiconductor nano modification thus to improve its fluorescence radiation to this semiconductor nano nucleus.It can be preferred having shell, because the blemish of this semiconductor nano nucleus surface can produce the trap (it damages the electricity and the optical property of this semiconductor nano nucleus) in electronics or hole or other non-radiative energy loss mechanism (its dissipated photon energy that absorbs or the wavelength of affects fluorescence radiation at least), thereby causes widening of emission band.Insulating barrier in this semiconductor nano nucleus surface can provide the atomic energy hop of chemical potential at the interface, and this has eliminated the energy state that can serve as the trap in electronics and hole.This has obtained higher efficient in luminescence process.

Suitable shell material comprises the semi-conducting material with band-gap energy higher than this semiconductor nano nucleus.Except having than the higher band-gap energy of this semiconductor nano nucleus, suitable shell material should have with respect to good conduction band and the valence band offset of nuclear semiconductor nano.Therefore, this conduction band can desirably be higher than this nuclear semiconductor nano and valence band can desirably be lower than this nuclear semiconductor nano.Semiconductor nano nucleus for the energy of launching visible (for example CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, GaP, GaAs, GaN) or near-infrared (for example InP, InAs, InSb, PbS, PbSe) can use the shell material of band-gap energy in ultraviolet region.Exemplary shell material includes but not limited to: CdS, CdSe, InP, InAs, ZnS, ZnSe, ZnTe, GaP, GaN and chalcogen magnesium, for example MgS, MgSe and MgTe.For at the nearly luminous semiconductor nano nucleus of IR, also can use the shell material of band-gap energy in visibility region light, as CdS or CdSe.The preparation of the semiconductor nano that applies for example is found in people (1997) J. Phys. Chem. B 101:9463 such as Dabbousi, people such as Hines (1996) J. Phys. Chem. 100:468-471, people (1997) J. Phys. Chem. 106:9869 such as people such as Peng (1997) J. Am. Chem. Soc. 119:7019-7029 and Kuno.What it is also understood that in the art is, the actual wavelength of fluorescence of specific nanocrystal depends on the size and the composition thereof of this nuclear, therefore above-mentioned classification is similar to, and be described as nanocrystal luminous in visible or near infrared region in fact can be luminous with longer or shorter wavelength according to the size of this nuclear.

When using nuclear/shell fluorescence semiconductor nanocrystalline, advantageously make this nano particle as far as possible little sometimes; Thus in certain embodiments, this nanocrystalline diameter can be less than about 20 nanometers, and usually less than about 8 nanometers, sometimes diameter is less than about 6 nanometers, and in certain embodiments, diameter that this is nanocrystalline or size be less than about 5 nanometers, or diameter or size are less than 4 nanometers.

Nanocrystalline precursor can be described as first precursor and second precursor sometimes.This first precursor can be metallic salt, as halide, carboxylate, phosphonate, carbonate, hydroxide or the diketone (diketonate) of metal or its salt-mixture (halogenated carboxylic acid salt for example, as (halo) (oleic acid) Cd), wherein this metal can be for example Cd, Zn, Mg, Be, Mn, Cu, Co, Pb Hg, Al, Ga, In or Tl.This second precursor can be for example O, S, Se, Te, N, P, As or Sb.This second precursor mixture can comprise amine, as primary amine (C for example ₈-C ₂₀Alkylamine).This second precursor can comprise for example phosphine chalcogenide, two (silicyl) chalcogenide, dioxygen thing class, ammonium salt or three (silicyl) phosphine or the like.

In one embodiment, this first precursor can contact the combination to form metallic precursor by making metal or metalline with this second precursor with reducing agent.This reducing agent can comprise alkylphosphines, 1, and 2-glycol or aldehyde are as C ₆-C ₂₀Alkyl diol or C ₆-C ₂₀Aldehyde.

The example of suitable metalline can include but not limited to the acetylacetone,2,4-pentanedione cadmium, cadmium iodide, cadmium bromide, caddy, cadmium hydroxide, cadmium carbonate, cadmium acetate, cadmium oxide, zinc acetylacetonate, zinc iodide, zinc bromide, zinc chloride, zinc hydroxide, zinc carbonate, zinc acetate, zinc oxide, magnesium acetylacetonate, magnesium iodide, magnesium bromide, magnesium chloride, magnesium hydroxide, magnesium carbonate, magnesium acetate, magnesia, acetylacetone,2,4-pentanedione mercury, mercuric iodixde, mercuric bromide, mercury chloride, mercuric hydroxide, carbonic acid mercury, mercuric acetate, aluminium acetylacetonate, silver iodide, aluminium bromide, aluminium chloride, aluminium hydroxide, aluminium carbonate, aluminium acetate, the acetylacetone,2,4-pentanedione gallium, gallium iodide, gallium bromide, gallium chloride, gallium hydroxide, the carbonic acid gallium, the acetate gallium, Indium Tris acetylacetonate, indium iodide, indium bromide, inidum chloride, indium hydroxide, the carbonic acid indium, indium acetate, the acetylacetone,2,4-pentanedione thallium, thallium iodide, thallium bromide, thallium chloride, thallium hydroxide, thallium carbonate or thallium acetate.Suitable metalline also comprises for example carboxylate, as oleate, stearate, myristate and palmitate, mixing halogenation carboxylate, and as M (halogenation) (oleic acid) salt, and phosphonate.

Alkyl can be the side chain or the non-branched-chain saturated hydrocarbon group of 1 to 100 carbon atom, preferred 1 to 30 carbon atom, as methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, the tert-butyl group, octyl group, decyl, myristyl, cetyl, eicosyl, tetracosyl or the like, and cycloalkyl, as cyclopenta, cyclohexyl or the like.Randomly, alkyl can contain 1 to 6 and be selected from-O-,-S-,-M-and-NR-be connected base, wherein R is a hydrogen, or C1-C8 alkyl or low-grade alkenyl.

With this metalline with before this second precursor mixes, this metalline can contact with ligand solvent to form metallic precursor.Typical ligand solvent comprises alkylphosphines, alkylphosphine oxide, alkyl phosphonic acid, alkyl phosphinic acid or contains the carboxylic acid solvent; But other ligand solvent also is applicable to this nanocrystalline production as pyridine, furans and amine.The example of suitable ligand solvent comprises pyridine, tri-n-octyl phosphine (TOP) and TOPO (TOPO).Also comprise the solvent that contains acid, as oleic acid, stearic acid, myristic acid, palmitic acid, TDPA, OPA or the like.This ligand solvent can comprise 1,2-glycol or aldehyde.This 1,2-glycol or aldehyde can promote the reaction between the metalline and second precursor, improve the nanocrystalline quality that obtains in growth course and this process.

This second precursor normally chalcogenide is given body or V group element, as phosphine chalcogenide, two (silicyl) chalcogenide, dioxygen, ammonium salt or three (silicyl) phosphine.The second suitable precursor comprises dioxygen, elementary sulfur, two (trimethyl silyl) selenides ((TMS) ₂Se), trialkyl selenizing phosphine, as selenizing (tri-n-octyl phosphine) (TOPSe) or selenizing (tri-n-butyl phosphine) (TBPSe), trialkyl tellurium phosphine, as telluriumization (tri-n-octyl phosphine) (TOPTe) or six propyl group phosphorus triamide tellurides (HPPTTe), two (trimethyl silyl) tellurides ((TMS) ₂Te), sulphur, two (trimethyl silyl) sulfide ((TMS) ₂S), the trialkyl phosphine sulfide, as sulfuration (tri-n-octyl phosphine) (TOPS), three (dimethylamino) arsine, ammonium salt is as ammonium halide (NH for example ₄Cl), phosphatization three (trimethyl silyl) ((TMS) ₃P), three (trimethyl silyl) arsenide ((TMS) ₃As) or three (trimethyl silyl) antimonide ((TMS) ₃Sb).In certain embodiments, this first precursor and this second precursor can be with the part in a part.

" ligand solvent " used herein is meant that effectively coordination is to the solvent of nanocrystal surface, as TOP, TOPO, TDPA, OPA, carboxylic acid and amine." ligand solvent " also comprises phosphine, phosphine oxide, phosphonic acids, phosphinic acids, amine and the carboxylic acid that is generally used for nanocrystalline somatomedin and forms coating or layer in this nanocrystal surface.They got rid of do not have duplet that bonding is provided in case with the heteroatomic varsol of this nanocrystal surface coordination, as hexane, toluene, hexadecane, octadecylene etc.Do not contain the hetero atom of coordination, be referred to herein as non-ligand solvent as the varsol of O, S, N or P to nanocrystal surface.Be noted that, term " solvent " is used for these terms with its usual manner: it is meant the medium of load, dissolving or dispersion and the reaction between them, but it does not participate in the reaction of this reaction material or usually not by the modification of the reaction of this reaction material institute.

Precursor

The formation of nano particle generally includes two different stages: the phase I, nucleation needs the coalescent nucleation of a large amount of precursors (being nucleation), and second stage, growth comprises that precursor adds on the existing nuclear.When the precursor atom mates (promptly be non-ionic (neutrality), or one be cationic, another is anionic) on type, they are reaction very apace usually.This type of fast reaction usually produces a large amount of nucleation, even also like this when being unacceptable when nucleation, and can cause forming the particle colony that lacks uniform particle size because growth takes place simultaneously with nucleation.

To these two the independence controls that form the stage is valuable, because nucleation stage has determined the nano particle productive rate, and growth phase has determined the final size of nano particle.

Importantly in nanocrystalline formation, nucleation stage is separated with growth phase, make all this nanocrystallinely roughly form simultaneously, subsequently all together growth phase with time quantum to obtain the even distribution of nano-particles size, provide nuclear nanocrystalline single colony that disperses.If formed and formed new small nuclear after a period of time of growing at other particle, will be difficult to obtain uniform size.

The method in this nucleation and growth stage of separation that the control of each separate phases is strengthened is provided herein.

Two stages that this method control particle forms realize by using " mismatch " precursor." mismatch " precursor can not react under the situation that does not have adding or lost electrons, makes that the precursor in the solution all exists with the ionic state or the middle condition of complementation; Otherwise they can not be in conjunction with forming neutral products.By controlling quantity and the character that is present in the electron transfer agent in this reactant mixture with the precursor of mismatch, can utilize and not have electron transfer agent, the reactivity of " mismatch " precursor shortcoming under the situation as reducing agent or oxidant is with the nucleation and growth stage of temporary transient control particle formation.

If a kind of precursor is provided for the neutrals class of nanocrystalline formation in solution, and other precursor provides ionic species in solution under used reaction condition, if perhaps this precursor provide separately have identical charges ionic species (promptly, two kinds of cations or two kinds of anion), the precursor that provides herein will be considered to " mismatch ".The example of the precursor of mismatch comprises and the precursor that a kind of cationic species is provided that a kind of nonionic (promptly neutral) thing class or another kind of cationic precursor pairing are provided, perhaps the precursor that a kind of anionic species is provided that matches with the precursor that a kind of nonionic (i.e. neutrality) thing class or another kind of anionic species are provided.The correlative class is to be present in this hull shape to become reactant class under the reaction condition.

In certain embodiments, can use the binary oxidizer system.In further embodiments, can use binary reducing agent system.In further embodiments, can use mixed electronic transfer agent system (being a kind of oxidant and a kind of reducing agent).In some such embodiment, can use one group of precursor, wherein a kind of neutrals class that provides, another kind provides cationic species.In this system, can add reducing agent so that this neutrals class is reduced to anion, or cationic species is reduced to neutral oxidation state.

In certain embodiments, this first precursor can comprise metallic atom M, and this second precursor can comprise non-metallic atom X, wherein selects this precursor so that their oxidation state is a mismatch.

This nanocrystal and shell can be made by any suitable known metal and non-metallic atom that forms semiconductor nano.The semi-conducting material that is suitable for this nuclear and/or shell includes but not limited to comprise the material of 2-16 family, 12-16 family, 13-15 family and the 14th family's element base semiconductor, as ZnS, ZnSe, ZnTe, CdS, CdSe, CdTe, HgS, HgSe, HgTe, MgS, MgSe, MgTe, CaS, CaSe, CaTe, SrS, SrSe, SrTe, BaS, BaSe, BaTe, GaN, GaP, GaAs, GaSb, InN, InP, InAs, InSb, AlAs, AlP, AlSb, PbS, PbSe, Ge and Si with and binary, ternary and quaternary mixture.

The selection of the composition of this semi-conductor nano particles influences the characteristic spectrum emission wavelength of this particle.Thus, the specific composition of the nano particle that can provide herein based on the spectral regions selection of monitoring.For example, the semiconductor nano of the energy in the visible emitting scope includes but not limited to CdS, CdSe, CdTe, ZnSe, ZnTe, GaP and GaAs.The semiconductor nano of emission near infrared range self-energy includes but not limited to InP, InAs, InSb, PbS and PbSe.At last, emission blue light to the example of the semiconductor nano of near ultraviolet energy includes but not limited to ZnS and GaN.In each case, can realize additional tuning this wavelength of fluorescence extremely to a certain degree by the shell that on this nanocrystal, increases.

The precursor that can in method disclosed herein, be used as this " first " precursor comprise the element (for example Zn, Cd, Hg, Mg, Ca, Sr, Ba or the like) that contains the 2nd family that is selected from the periodic table of elements and the 12nd family compound, contain the compound of the element (Al, Ga, In or the like) of the 13rd family that is selected from the periodic table of elements, and the compound that contains the element (Si, Ge, Pb or the like) of the 14th family that is selected from the periodic table of elements.This precursor of many forms can be used for method disclosed herein.

The examples for compounds that can be used as first precursor can be an organo-metallic compound, as metal alkyl thing class, or salt, as metal halide, metal acetate, metal carboxylate, metal phosphinate hydrochlorate, metal phosphinates, metal oxide or other salt.In certain embodiments, this first precursor provides the neutrals class in solution.For example, metal alkyl thing class is as diethyl zinc (Et ₂Zn) or dimethyl cadmium be considered to neutral zinc atom (Zn in the solution usually ⁰) the source.In further embodiments, this first precursor provides ionic species (being metal cation) in solution.For example, zinc chloride (ZnCl ₂) and other zinc halide, zinc acetate (Zn (OAc) ₂) and zinc polycarboxylate be considered to Zn in the solution usually ²⁺Cationic source.

Only as an example, suitable first precursor that neutral metal thing class is provided comprises the metal diaikyl source, as dimethyl cadmium (Me ₂Cd), diethyl zinc (Et ₂Zn) or the like.Suitable first precursor that metal cation is provided in solution comprises for example cadmium salt, as cadmium acetate (Cd (OAc) ₂), cadmium nitrate (Cd (NO ₃) ₂), cadmium oxide (CdO) and other cadmium salt; And zinc salt, as zinc chloride (ZnCl ₂), zinc acetate (Zn (OAc) ₂), zinc oleate (Zn (oleic acid) ₂), chloro (oleic acid) zinc, zinc undecylenate, zinc salicylate and other zinc salt.In certain embodiments, this first precursor salt that is Cd or Zn.In certain embodiments, it is halide, acetate, carboxylate or the oxide salt of Cd or Zn.In further embodiments, this first precursor is M (O ₂CR) salt of X-shaped formula, wherein M is Cd or Zn; X is halogen or O ₂CR; And R is the optional undersaturated C that is ₄-C ₂₄Alkyl.Other suitable form that can be used as the 2nd, 12,13 and 14 family's elements of first precursor is known in this area.

The precursor that can be used as " second " precursor in the method disclosed herein comprise the element (for example S, Se, Te or the like) that contains the 16th family that is selected from the periodic table of elements compound, contain the element (N, P, As, Sb or the like) of the 15th family that is selected from the periodic table of elements compound, contain the 14th family that is selected from the periodic table of elements element (Ge, Si or the like) compound and contain the compound of the element (halide) of the 17th family that is selected from the periodic table of elements.This precursor of many forms can be used for method disclosed herein.It being understood that in certain embodiments this second precursor will provide the neutrals class in solution, and in further embodiments, this second precursor will provide ionic species in solution.

It should be understood that in certain embodiments nanoparticle core and/or shell can comprise and surpass two kinds of precursors.For example, can adopt the same procedure of describing to use three kinds of precursors herein, use four kinds of precursors with formation quaternary nano particle to form the ternary nano particle, or the like.

When this first precursor comprises metal cation, that this second precursor will preferably provide in solution will be uncharged (i.e. neutrality) non-metallic atom.In common embodiment, when this first precursor comprises metal cation, this second precursor is contributed neutral chalcogen, and the most common is S ⁰, Se ⁰Or Te ⁰

Be suitable for providing second precursor of neutral chalcogen for example to comprise the trialkyl phosphine adduct of elementary sulfur (be generally at amine, for example decyl amine, oleyl amine or dioctylamine, or alkene are as the solution form in the octadecylene) and S, Se and Te.This type of trialkyl phosphine adduct is described as R in this article sometimes ₃P=X, wherein X is S, Se or Te, and each R is that H maybe can and can be undersaturated C1-C24 alkyl for straight chain, side chain, ring-type or its combination independently.Exemplary this type of second precursor comprises three (normal-butyl phosphine) selenides (TBP=Se), three (n-octyl phosphine) selenides (TOP=Se) and corresponding sulphur and tellurium reagent, TBP=S, TOP=S, TBP=Te and TOP=Te.These reagent are usually by with required element, and as Se, S or Te and suitable ligand solvent, for example TOP or TBP mix and form.Under this reaction condition, provide the precursor of anionic species to use with first precursor that the neutral metal atom is provided (as alkyl metal cpd and above-mentioned or known in the art other compound) usually.

In certain embodiments, this second precursor provides electronegative nonmetallic ion (S for example in solution ^-2, Se ^-2Or Te ^-2).The example of suitable second precursor that ionic species is provided comprises silyl compound, as two (trimethyl silyl) selenides ((TMS) ₂Se), two (trimethyl silyl) sulfide ((TMS) ₂S) and two (trimethyl silyl) tellurides ((TMS) ₂Te).What included equally is the compound of hydrogenation, as H ₂Se, H ₂S, H ₂Te; And slaine, as NaHSe, NaSH or NaHTe.In this case, can use oxidant that neutral metal thing class is oxidized to can be in " coupling " reaction and the cationic species of anion precursors reaction, maybe can use oxidant to improve the oxidation state of this anion precursor, can stand the neutrals class that " coupling " reacts with neutral metal thing class to provide.

Other exemplary organic precursor is described in the U.S. Patent number 6 of authorizing people such as Bawendi, 207,299 and 6, in 322,901, use weak acid as the synthetic method of precursor material by people such as Qu, (2001), Nano Lett., 1 (6): 333-337 is open, its separately disclosure incorporate in full this paper by reference into.

This first and this second precursor can mix with appropriate solvent to be formed for the solution of method disclosed herein.The solvent or the solvent mixture that are used to form first precursor solution can be identical or different with solvent that is used to form second precursor solution or solvent mixture.This precursor can dissolve separately, or they can be mixed together in the single solution.

Can be before or after precursor is admixed together and with this solvent and/or precursor with before or after this weak reductant mixes, carry out the heating of mixture.In certain embodiments, first precursor, second precursor and weak reductant are all chosen wantonly and are mixed in suitable solvent or solvent mixture with the formation reactant mixture, and before adding strong reductant this reactant mixture are heated to suitable temperature subsequently.

The order and the speed of adding precursor are not most important to method disclosed herein usually.

In certain embodiments, add this precursor with the speed that only is subjected to the practical considerations restriction relevant thus, and can under the situation that temperature control allows, add this precursor as quickly as possible with keeping desired reaction temperature.Similarly, this precursor can all be present in this reactant mixture, when it is heated to desired reaction temperature, and can add one or both these electron transfer agents after reaching operating temperature.In certain embodiments, before reaching desired reaction temperature, the sub-transfer agent of this forceful electric power is not joined in the reactant mixture at least.

Ligand solvent

Suitable ligand solvent comprises (as illustration and unrestricted) hydro carbons, amine, alkylphosphines, alkylphosphine oxide, carboxylic acid, ether, furans, phosphonic acids (phospho-acids), pyridine and composition thereof.In fact this solvent can comprise the mixture of solvent, is called " dicyandiamide solution " usually in the art.In a preferred embodiment, this solvent comprises at least a ligand solvent.In certain embodiments, this dicyandiamide solution comprises secondary amine and trialkyl phosphine (for example TBP or TOP), phosphonic acids (for example TDPA, OPA) or trialkyl phosphine oxide (for example TOPO).

Ligand solvent can be the solvent (as alkane) of non-coordination basically and the mixture of the part of definition hereinafter.

Suitable hydro carbons comprises 10 alkanes to about 30 carbon atoms, alkene and aromatic hydrocarbon; Example comprises octadecylene and saualane.This hydro carbons can comprise alkane, alkene and aromatics part, as the mixture of alkylbenzene (for example mesitylene).

Suitable amine includes but not limited to monoalkylamine, dialkylamine and trialkylamine, for example trioctylamine, dioctylamine, octylame, oleyl amine, decyl amine, dodecyl amine, cetylamine or the like.The alkyl of these amine each alkyl usually contains 6-24 the carbon atom of having an appointment, and can comprise undersaturated carbon-carbon bond, and each amine has the total number of carbon atoms that amounts to about 10-30 carbon atom usually in its all alkyl.

The exemplary alkyl phosphine includes but not limited to trialkyl phosphine, tri-n-butyl phosphine (TBP), tri-n-octyl phosphine (TOP) or the like.Each alkyl of the alkyl of these phosphines contains 6-24 the carbon atom of having an appointment, and can contain undersaturated carbon-carbon bond, and each phosphine has the total number of carbon atoms that amounts to about 10-30 carbon atom in its all alkyl.

Suitable alkylphosphine oxide includes but not limited to the trialkyl phosphine oxide, TOPO (TOPO) or the like.Each alkyl of the alkyl of these phosphine oxides contains 6-24 the carbon atom of having an appointment, and can contain undersaturated carbon-carbon bond, and each phosphine oxide has the total number of carbon atoms that amounts to about 10-30 carbon atom in its all alkyl.

Exemplary aliphatic acid includes but not limited to stearic acid, oleic acid, palmitic acid, myristic acid and laurate, and other carboxylic acid of formula R-COOH, and wherein R is C ₆-C ₂₄Alkyl and can contain undersaturated carbon-carbon bond.

Exemplary ether and furans include but not limited to oxolane and the form that methylates, glyme or the like.

Suitable phosphonic acids and phosphinic acids include but not limited to hexyl phosphonic acids (HPA), myristyl phosphonic acids (TDPA) and octyl phosphonic acid (OPA), and usually with alkylphosphine oxide, be used in combination as TOPO.Suitable phosphonic acids and phosphinic acids have formula RPO ₃H ₂Or R ₂PO ₂H, wherein each R is the C6-C24 alkyl independently, and can contain undersaturated carbon-carbon bond.

Exemplary pyridines includes but not limited to pyridine, alkylation pyridine, nicotinic acid or the like.

Suitable alkene comprises for example octadecylene, squalene and other undersaturated C4-C30 hydro carbons.

Solvent can separately or be used in combination.The TOP-TOPO dicyandiamide solution is usually used in this area, and other relevant (for example butyl) system is also like this.For example, TOP can be used in combination with the formation cadmium solution with TOPO, and TOP can be used to form selenium solution (for example TOP+cadmium acetate or TOP+cadmium nitrate) separately.

The technical grade solvent can be used, and the existence of useful impurity in this kind solvent (for example TOP and/or TOPO) can be had benefited from.In certain embodiments, this solvent comprises at least a ligand solvent.In a kind of preferred embodiment, this solvent is pure.Usually, this means that this solvent contains is less than 10 volume % and more preferably less than the impurity that can be used as electron transfer agent of 5 volume %.Therefore, be that 90% or 97% TOPO and purity are that the solvent of 90% TOP is specially adapted to method disclosed herein as purity, and purity to be higher than 99% solvent be preferred.

Exist small amount of impurities that the source of expecting outer electron transfer agent can be provided, if they promote the nucleation of the shell precursor of mismatch, this can cause realizing the target of embodiment disclosed herein.In addition, particular agent can be weak reducing/oxidizing agent in a kind of system, or be strong reducing/oxidizing agent in different systems, or invalid reducing/oxidizing agent: weak and must depend on that by force being used for this nanocrystal forms the concrete shell precursor of reaction and the solvent and the temperature of employing.

For example, in some systems, the unsaturated bond that is provided by one of solvent or precursor can as described hereinly be weak reducing/oxidizing agent like that; In other systems, it can't be used as weak reducing/oxidizing agent effectively, and will add weak reducing/oxidizing agent to promote nanocrystalline growth, even there is unsaturated bond, as in containing the slaine of unsaturated group (as oleate).

In order accurately to control two stages of nanocrystalline formation, therefore, desirable sometimes is to differentiate and measure to be used for the solvent of these methods and any strong or weak reducing/oxidizing agent that reagent exists.Therefore, in certain embodiments, the reagent of the method that be used for describing is estimated its effect in specific system herein.Be used for this method reagent, solvent, reducing agent or precursor applicability can by it is tested with observe this material in described system whether as strong reducing/oxidizing agent or contain as the impurity of strong reducing/oxidizing agent and determine.When reagent is used as strong reducing/oxidizing agent or contains the impurity that is used as strong reducing/oxidizing agent, should remove, substitute or this reagent of further purifying method disclosed herein.

Part

In a kind of preferred embodiment, part is included in this reaction.Part is the compound with precursor and/or nano particle complexing.Suitable part comprises (as illustration and unrestricted) phosphonic acids, as hexyl phosphonic acids and myristyl phosphonic acids (TDPA), octyl phosphonic acid (OPA), carboxylic acid, and as the isomers of octadecanoid acid, amine, acid amides, pure and mild ether.In some cases, this part can be identical with this solvent.

Electron transfer agent: reducing agent

Among the disclosed in this article embodiment, the nucleation and growth stage that the control particle forms can realize by the precursor that uses the mismatch that can not react under the situation without electron transfer agent interpolation or lost electrons.Use two kinds of independent electron transfer agents, particularly one or more reducing agents, make it possible to promote nucleation independently or grow to required degree, and improve these two the temporary transient separation that form the stage.This method makes it possible to independent control particle productive rate and granularity, also may produce to have the more particle of narrow size distribution.

The reducing agent (going back original reagent) of " by force " used herein or " stronger " is meant and can promotes nucleation or promote to cause the reducing agent that particle forms under the actual conditions of the reaction of using this reducing agent.The reducing agent of " weak " or " more weak " is meant and can not promotes actual nucleation or promote to cause particle to form under used actual conditions, still can promote the original reagent of going back of particle growth under these conditions.

What it will be understood by those skilled in the art that is that specific reductant is that strong reductant or weak reductant depend on the circumstances, and depends on the special reaction condition of using this reducing agent.As nucleation was desired, the particle surface place (promptly in growth phase process) of electronics transfer in growth was than easier carrying out on the dissociated ion in solution.For given system (nanocrystalline formation reaction), can by determine this to be tried reducing agent to show as strong reductant under these conditions still be weak reductant that this is tried that reducing agent is divided into by force or a little less than.By under appropriate reaction conditions do not have any elementary nanocrystalline (what add is nanocrystalline) in the initial action mixture situation under make described specific precursor and this be tried reducing agent to contact and determine so that if nucleation takes place and can be observed, can determine whether the specific reducing agent that tried is strong reductant: usually, if nucleation is with remarkable speed, for example take place at least about 50% speed with the nucleation rate height when not existing this to be tried reducing agent, this is tried reducing agent and is promoted nucleation, and is regarded as strong reductant in this system.If this existence that is tried reducing agent does not significantly improve nucleation rate, then it is not the strong reductant in this system.

Under becoming reaction condition at hull shape, with nanocrystalline by elementary (adding) of the formed same type of this precursor in the presence of make described specific precursor be tried reducing agent to contact with this, can determine whether the specific reducing agent that tried is weak reductant: usually, if nanocrystalline growth takes place with the speed that improves, for example with the speed of twice at least of the growth rate height when not existing this to be tried reducing agent, this is tried the reducing agent that reducing agent can be considered to be suitable for promoting nanocrystalline growth.It can be suitable weak reductant thus, as long as it is not used as strong reductant in described system.

Be suitable for promoting nanocrystalline growth if try reducing agent by above-mentioned test, but be not the strong reductant in the described specific system that this is tried reducing agent can be considered to weak reductant.Because the relative intensity of reducing agent depends on these factors, this function classification of reducing agent is to can be used for method weak or that strong reductant is sorted out, and it can be applied to any specific reducing agent that tried by routine test.

Because the particle surface place (promptly in growth phase process) of electronics transfer in growth is than can more easily carrying out on dissociated ion in solution, as nucleation was desired, nucleation need be than the stronger reducing agent of growing.The difference of reactive aspect makes it possible to by providing the sub-transfer agent of a small amount of forceful electric power (it consumes in nucleation process fast) to make two stages separate with more substantial more weak electron transfer agent (it makes it possible to continuous growth).This is examined nanocrystalline size and can come by the wavelength of fluorescence in the monitoring growth phase process easily to determine.

Among the embodiment that provides in this article, can regulate the degree of nucleation by the amount of the strong reductant of use in the control reaction.In certain embodiments, can be to be enough to promoting aequum nucleation amount to add strong reductant.In further embodiments, can be to add strong reductant with respect to the stoichiometric amount of being lower than of precursor to be restored.In some such embodiment, the addition of strong reductant can for the stoichiometric reaction aequum of nanocrystalline precursor less than about 1/10th, about 1/10th, less than about 2/10ths, less than about 3/10ths or less than about 4/10ths.In some specific embodiments, the amount of the strong reductant of adding can be about 1/10th of stoichiometric reaction aequum.

In case strong reductant exhausts (this can take place fast) under suitable reaction temperature, stop the extra little nuclear that forms substantially.Thus, the amount of restriction strong reductant makes it possible to nucleation stage is separated with growth phase.This method makes it possible to independent control particle productive rate and granularity, and can also make the particle with narrower Size Distribution potentially.Because this precursor keeps mismatch, the lasting growth needs of nanocrystal adds second electron transfer agent.Add weak reductant and make particle grow, but can not promote further nucleation, the particle of uniform-dimension is provided thus.

Because can pass through the use control reaction of electron transfer agent, it is also unnecessary to control the speed (as among some nanocrystalline preparation method) that adds precursor in reaction carefully.This nanocrystalline precursor can quick as required disposable interpolation under the situation that does not cause the sub-cooled reactant mixture; Needn't slowly add precursor in many embodiment of these methods becomes to prevent unwanted new karyomorphism.In fact, this precursor can mix in suitable solvent with the weak reductant of choosing wantonly and be heated to required reaction condition, and nanocrystalline formation (this can cause by adding strong reductant) can not take place.

In a preferred embodiment, this strong reductant can add under the running temperature of nucleation being enough to take place.Under this temperature, it is believed that when adding strong reductant quick explosion type nucleation takes place, consume this reducing agent thus fast.Under these conditions, all nuclears are nanocrystalline roughly to be formed simultaneously, all common subsequently growth phase with time quantum to cause the even distribution of granularity, monodispersed particle colony is provided.

It will be understood by those skilled in the art that specific reductant is that strong reductant or weak reductant depend on the special reaction condition of wherein using this reducing agent.

Appropriate reductant can comprise (as illustration and unrestricted) chemical compound, as tertiary phosphine, secondary phosphine, uncle's phosphine (for example diphenylphosphine, dicyclohexylphosphontetrafluoroborate and dioctyl phosphine); Amine (for example decyl amine and cetylamine); Hydrazine; Hydroxyphenyl compound (for example hydroquinones and phenol); Hydrogen; Hydride (for example sodium borohydride, lithium triethylborohydride, sodium hydride and lithium aluminium hydride reduction or the like); Metal (for example mercury and potassium); Borine (THF:BH for example ₃And B ₂H ₆); Aldehyde (for example benzaldehyde and butyraldehyde); Pure and mild mercaptan (for example ethanol and sulfo-ethanol); Reproducibility halide (I for example ^-And I ₃ ^-); Alkene (for example oleic acid); Alkyne; With multifunctional reducing agent, promptly contain the single chemical species that surpasses a reducing agent part, each reducing agent partly has identical or different reducing power, as three-(hydroxypropyl) phosphine and monoethanolamine); Or the like.

Usually, hydride (metal hydride of similar aluminum hydride, or metallic boron hydrides) and borine are as strong reductant.Other reducing agent can be used as strong reductant or weak reductant, depends on concrete reaction condition.For example, alkylphosphines can be used as strong reductant in CdSe synthetic, but will be weak reductant in ZnTe synthetic.Other reducing agent is generally weak reductant as alkene, alkyne, amine or the like.

In certain embodiments, can provide this weak reductant by the component of one of precursor.For example, the unsaturated carboxylic acid ester group as oleate, can be used as the weak reductant of embodiment disclosed herein.Fig. 2 has described a kind of reaction, wherein Zn ²⁺The tellurium precursor of thing class and mismatch, the TOPTe reaction.Among first width of cloth figure of on the left side, Zn ²⁺Salt is saturated salt, does not therefore have weak reductant.In second width of cloth figure on right side, this salt comprises undersaturated hydroxy-acid group, and it provides reducing agent.The particle productive rate of two kinds of reactions is all low, and showing needs strong reductant to promote effective nucleation; But, adopt this salt unsaturated carboxylic acid to cause nanocrystalline faster formation as the significant reaction of weak reductant.

In certain embodiments, provide weak reductant to promote nanocrystalline growth, sometimes can be with M (O ₂C-R ') _nThe carboxylate metal salt form of form provides this containing metal precursor, and wherein M is this metal, and n is the integer by the definite 1-3 of this metallic atom oxidation state, and R ' is C ₄-C ₁₀₀Unsaturated alkyl.In further embodiments, this salt can comprise these type of salt unsaturated carboxylic acid counter ion counterionsl gegenions and one or more other counter ion counterionsl gegenions, for example halide ion.These provide under the situation that does not add additional materials in reactant mixture the approach that makes things convenient for of weak reductant are provided, and have guaranteed that the reactive chemistry metering can provide every precursor atom at least one weak reductant molecule.But, in some systems, must determine that these are to serve as weak reductant rather than serve as strong reductant.

In further embodiments, solvent can serve as weak reductant as alkene, alkyne or amine solvent.When greatly excessive weak reductant was used in hope, this method was particularly useful.But, must determine that in some systems this solvent is to serve as weak reductant rather than serve as strong reductant.

Estimate existence and use electro-chemical systems (K-A system) as the relevant certain benefits of this reducing agent, promptly negative electrode serves as electron source.By utilizing the source of electrode, calculate the enclosed pasture equivalent easily, and directly control their transfer rate as the reduction equivalent.The use of electrode can also be controlled the physical positioning of reduction activity, and the electromotive force that directly forms array of particles at the electrode surface place.Because this negative electrode will be placed in the reative cell, material is selected to be preferably not the material with this precursor, part or ligand solvent reaction.Anode is placed on the reaction vessel outside usually, so the material selection is unrestricted, and can use any known anode material.Exemplary cathode materials comprises platinum, silver or carbon.Carry the illustrative methods of reproducibility equivalent to be included in bipolar electrode (working electrode with to electrode) or three electrodes (working electrode, to electrode and the reference electrode) structure to negative electrode and use constant current or potentiostat.

Be applicable to being chosen in those skilled in the art's limit of power of reducing agent of specific combination of precursors.

Electron transfer agent: oxidant

Among the disclosed in this article embodiment, the nucleation and growth stage that the control particle forms can realize by the precursor that uses the mismatch that can not react under the situation without electron transfer agent interpolation or lost electrons.Use two kinds of independent electron transfer agents, particularly one or more oxidants, make it possible to promote nucleation independently or grow to required degree, and improve these two the temporary transient separation that form the stage.This method makes it possible to independent control particle productive rate and granularity, also may produce to have the more particle of narrow size distribution.

" by force " used herein or " stronger " oxidant (oxidising agent) are meant and can promote nucleation or promote to cause the oxidant that particle forms under the actual conditions of the reaction of using this oxidant." weak " or " more weak " oxidant is meant and can not promotes nucleation or promote to cause particle to form under the actual conditions that uses, still can promote the oxidant of particle growth under these conditions.

What it will be understood by those skilled in the art that is that specific oxidant is that strong oxidizer or weak oxidant depend on the circumstances, and depends on the special reaction condition of using this oxidant.As nucleation was desired, the particle surface place (promptly in growth phase process) of electronics transfer in growth was than can more easily carrying out on the dissociated ion in solution.For given system (nanocrystalline formation reaction), can be by determining that this be tried oxidant and show as strong oxidizer or weak oxidant under these conditions, thereby with this tried oxidant be categorized as strong or a little less than.By under appropriate reaction conditions do not have any elementary nanocrystalline (what add is nanocrystalline) in the initial action mixture situation under make described specific precursor and this be tried oxidant to contact and determine so that if nucleation takes place and can be observed, can determine whether the specific oxidant that tried is strong oxidizer: usually, if nucleation is with remarkable speed, for example take place at least about 50% speed with the nucleation rate height when not existing this to be tried oxidant, this is tried oxidant and is promoted nucleation, and is regarded as strong oxidizer in this system.If this existence that is tried oxidant fails to significantly improve this nucleation rate, then it is not the strong oxidizer in this system.

Under becoming reaction condition at hull shape, with nanocrystalline by elementary (adding) of the formed same type of this precursor in the presence of make described specific precursor be tried oxidant to contact with this, can determine whether the specific oxidant that tried is weak oxidant: usually, if nanocrystalline growth takes place with the speed that improves, for example with the speed of twice at least of the growth rate height when not existing this to be tried oxidant, this is tried oxidant can be the oxidant that is suitable for promoting nanocrystalline growth.It can be suitable weak oxidant thus, as long as it is not used as strong oxidizer in described system.

Be suitable for promoting nanocrystalline growth if try oxidant by above-mentioned test, but be not the strong oxidizer in the described specific system that this is tried oxidant can be weak oxidant.Because the relative intensity of oxidant depends on these factors, this function classification of oxidant is to can be used for method weak or that strong oxidizer is sorted out, and it can be applied to any specific oxidant that tried by routine test.

Because electronics shifts usually the particle surface place (promptly in the growth phase process) in growth than can more easily carrying out on dissociated ion in solution, as nucleation is desired, the oxidant that nucleation need be stronger than growth.The difference of reactive aspect makes it possible to by providing the sub-transfer agent of a small amount of forceful electric power (it consumes in nucleation process fast) to make two stages separate with more substantial more weak electron transfer agent (it makes it possible to continuous growth).This is examined nanocrystalline size and can come by the wavelength of fluorescence in the monitoring growth phase process easily to determine.

In the method that provides in this article, can regulate the degree of nucleation by the amount of the strong oxidizer of use in the control reaction.In certain embodiments, can be to be enough to the promoting amount of required nucleation amount to add strong oxidizer.In a preferred embodiment, can be to add strong oxidizer with respect to the stoichiometric amount of being lower than of precursor to be restored.In some such embodiment, the amount of the strong oxidizer of adding can for the stoichiometric reaction aequum of this nanocrystalline precursor less than about 1/10th, about 1/10th, less than about 2/10ths, less than about 3/10ths or less than about 4/10ths.In specific embodiment, the amount of the strong oxidizer of adding can be about 1/10th of stoichiometric reaction aequum.

In case strong oxidizer exhausts (this can take place fast) under suitable reaction temperature, stop the extra little nuclear that forms substantially.Thus, the amount of restriction strong oxidizer makes it possible to nucleation stage is separated with growth phase.This method makes it possible to independent control particle productive rate and granularity, and can also make the particle with narrower Size Distribution potentially.Because this precursor keeps mismatch, the continued growth of nanocrystal need be added second electron transfer agent.Add weak oxidant and make particle grow, but can not promote further nucleation, the particle of uniform-dimension is provided thus.

Owing to the control that can realize by the use of electron transfer agent (being generally oxidant) reaction, it is also unnecessary to control the speed (as among some nanocrystalline preparation method) that adds precursor in reaction carefully.This nanocrystalline precursor can quick as required disposable interpolation under the situation that does not cause the sub-cooled reactant mixture; Needn't slowly add precursor in many embodiment of these methods becomes to prevent unwanted new karyomorphism.In fact, this precursor can mix in suitable solvent with the weak oxidant of choosing wantonly and be heated to required reaction condition, and nanocrystalline formation (this can cause by adding strong oxidizer) can not take place.

In a preferred embodiment, this strong oxidizer can add under the running temperature of nucleation being enough to take place.Under this temperature, it is believed that when adding strong oxidizer quick explosion type nucleation takes place, consume this oxidant thus fast.Under these conditions, all nuclears are nanocrystalline roughly to be formed simultaneously, all common subsequently growth phase with time quantum to cause the even distribution of granularity, monodispersed particle colony is provided.

It will be understood by those skilled in the art that specific oxidant is that strong oxidizer or weak oxidant depend on the special reaction condition of wherein using this oxidant.Suitable oxidant can comprise (as illustration and unrestricted) chemical compound, as: potassium nitrate; The salt of hypochlorous acid, chlorous acid, chloric acid, perchloric acid and other similar halogen compounds; T-butyl hypochlorate; Halogen is as fluorine, chlorine, bromine and iodine; Permanganate and compound; Ammonium ceric nitrate; Hexavalent chromium compound, as chromic acid and dichromic acid, and chromium trioxide, PCC

(PCC) and chromate/bichromate compound; Peroxide compound; Tollens reagent; Oxysulfide; Persulfuric acid; Oxygen; Ozone; Osmium tetroxide; Nitric acid; Nitrous oxide; Silver (I) compound; Copper (II) compound; Molybdenum (IV) compound; Iron (III) compound; Manganese (IV) compound; N-methylmorpholine-N-oxide and other N-oxide; The trimethyl amine n-oxide; 3-chlorine benzylhydroperoxide and other peroxy acid; Or peracetic acid.

In certain embodiments, can provide this weak oxidant by the component of one of precursor.

Estimate existence and use electro-chemical systems (K-A system) as the relevant certain benefits of this oxidant, promptly negative electrode serves as electron source.By utilizing the source of electrode, calculate the enclosed pasture equivalent easily, and directly control their transfer rate as the oxidation equivalent.The use of electrode can also be controlled the physical positioning of oxidation activity, and the electromotive force that directly forms array of particles at the electrode surface place.Because this negative electrode will be placed in the reative cell, material is selected to be preferably not the material with this precursor, part or ligand solvent reaction.Anode is placed on the reaction vessel outside usually, so the material selection is unrestricted, and can use any known anode material.Exemplary cathode materials comprises platinum, silver or carbon.Be included in bipolar electrode (working electrode with to electrode) or three electrodes (working electrode, to electrode and the reference electrode) structure to the illustrative methods of negative electrode delivery of oxygen voltinism equivalent and use constant current or potentiostat.

Use strong and/or the nanocrystalline method of the sub-transfer agent manufacturing of light current

Provide the precursor that in the presence of the electron transfer agent that adds, uses mismatch herein and make nanocrystalline method.In certain embodiments, the nucleation and growth stage of using two kinds of different electron transfer agents to form with independent control particle.

In one aspect, provide the method for making nanocrystalline or its colony herein, this method comprises: (a) provide to comprise first precursor, second precursor, first (promptly strong) electron transfer agent (for example, amount with the nucleation that is enough to form desired level), the mixture of second (promptly weak) the electron transfer agent amount of the nanocrystalline growth that is enough to form desired level (for example, with) and optional solvent (as ligand solvent); (b) this mixture is heated to the temperature a period of time that is enough to cause nanocrystalline formation.

In certain embodiments, this nanocrystalline formation is reflected in the continuous flow reactor system and takes place.In further embodiments, this nanocrystalline formation is reflected in the batch reactor system and takes place.

In certain embodiments, this first and second electron transfer agent is an oxidant.In further embodiments, this first and second electron transfer agent is a reducing agent.In certain embodiments, this first electron transfer agent is an oxidant, and this second electron transfer agent is reducing agent, or opposite.

In certain embodiments, the strong and sub-transfer agent of light current is changed into middle condition with the oxidation state of this first precursor or this second precursor by this.In further embodiments, by this oxidation state strong and the sub-transfer agent of light current mates this first precursor and this second precursor.

In certain embodiments, this method further comprises step (c), cools off this mixture to stop nanocrystalline further growth or to dilute this mixture to stop nanocrystalline further growth.In certain embodiments, this method further comprises and separates the nanocrystalline step that method thus makes.In further embodiments, this method further be included in separate or unseparated situation under to the step of this nanocrystalline interpolation shell.

The component of this reactant mixture (i.e. first precursor, second precursor, first reducing agent and second reducing agent) can be chosen wantonly in solvent or solvent mixture with any order and add, and can be before one or more components of adding this mixture or adding this reaction of heating in the process of one or more components of this mixture.This precursor usually mixes to be formed for the solution of method disclosed herein with appropriate solvent or solvent mixture.The solvent that is used for this first precursor and second precursor can be identical or different.

In certain embodiments, form the mixture that comprises first precursor, second precursor, first electron transfer agent, second electron transfer agent and optional solvent, subsequently this mixture is heated to the temperature a period of time that is enough to cause nanocrystalline formation.

In common embodiment, as further describing herein, under the reaction condition that is adopted, this first electron transfer agent is the sub-transfer agent of forceful electric power, and this second electron transfer agent is the sub-transfer agent of light current.

In further embodiments, heating comprises the mixture of first precursor, second precursor, the sub-transfer agent of light current and optional solvent; The sub-transfer agent of forceful electric power adds to be enough to promote nucleation to the amount of required degree, and heats this reactant mixture with the temperature and time that is enough to cause nanocrystalline formation.

In a further embodiment, heating comprises the mixture of first precursor, the sub-transfer agent of light current and optional first solvent; Second precursor that to choose wantonly in second solvent (it can be identical or different with first solvent) joins in the mixture of heating; Add the sub-transfer agent of forceful electric power with the amount that is enough to promote nucleation subsequently, and continue heating a period of time being enough to cause under the temperature of nanocrystalline formation.

In further embodiments, be enough to heat the mixture that comprises first precursor, second precursor, the sub-transfer agent of forceful electric power and optional solvent under the temperature that promotes the nucleation crystal to form; In this mixture, add the sub-transfer agent of light current subsequently promoting the particle growth, and be enough to cause under the temperature of nanocrystalline formation further this reactant mixture a period of time of heating.

In other embodiment again, the mixture that will comprise first precursor, second precursor and optional solvent is heated to be enough to have the temperature that issues product nucleus at the sub-transfer agent of forceful electric power, in the mixture of heating, add the sub-transfer agent of forceful electric power and the sub-transfer agent of light current simultaneously subsequently, then continue to heat a period of time being enough to cause under the temperature of nanocrystalline formation.

In a preferred embodiment, this first electron transfer agent is different with second electron transfer agent.In particularly preferred embodiment, as further describing herein, this first electron transfer agent is strong oxidizer/reducing agent, and this second electron transfer agent is weak oxidant/reducing agent.This first electron transfer agent and this second electron transfer agent can be chemical oxidizing agent/reducing agent or negative electrode independently.

In yet another aspect, provide the method for making nanocrystalline or its colony; This method comprises: the mixture that comprises first precursor and second precursor is provided, and wherein this first precursor and this second precursor have the oxidation state of mismatch; In this mixture, add the sub-transfer agent of forceful electric power that is lower than stoichiometry with the amount that is enough to produce required nucleation amount; Choose wantonly mixture is heated together to produce required nucleation amount; In this mixture, add the sub-transfer agent of light current with the amount that is enough to produce required nanocrystalline increment; And this mixture of optional heat a period of time of being enough to produce required nanocrystalline increment.

In certain embodiments, this strong and sub-transfer agent of light current is an oxidant.In further embodiments, this strong and sub-transfer agent of light current is a reducing agent.In certain embodiments, the sub-transfer agent of this forceful electric power is that oxidant and the sub-transfer agent of this forceful electric power are reducing agents, or opposite.

In certain embodiments, provide this forceful electric power transfer agent with the amount that is enough to form required nucleation level.In certain embodiments, provide this light current transfer agent with the amount that is enough to form required nanocrystalline level of growth.

In certain embodiments, the strong and sub-transfer agent of light current is changed into middle condition with the oxidation state of this first precursor or this second precursor by this.In further embodiments, by this oxidation state strong and the sub-transfer agent of light current mates this first precursor and this second precursor.

In yet another aspect, provide the method for examining nanocrystalline or its colony of making; This method comprises:

(a) provide first mixture that comprises first precursor, second precursor and optional solvent; (b) in the presence of the sub-transfer agent of forceful electric power, this first mixture is heated to enough height to promote the temperature of nucleation; (c) add the sub-transfer agent of forceful electric power so that second mixture to be provided, wherein to be enough to the promoting amount of nucleation to add the sub-transfer agent of this forceful electric power; (d) this second mixture is heated to the temperature a period of time that is enough to cause nanocrystalline formation.

In certain embodiments, this method further comprises step (e), cools off this second mixture stoping this nanocrystalline further growth, or dilutes this reactant mixture to stop further growth.This method is separated this nanocrystalline step optional further comprising from reactant mixture.This method is also optional to be comprised to going up or to the nanocrystalline step of adding shell that goes up of the nuclear that separates from the nuclear of this reactant mixture is nanocrystalline.

In a preferred embodiment, in the process of adding the sub-transfer agent of this forceful electric power, this first mixture is remained on enough height with under the temperature that promotes nucleation.

In a preferred embodiment, this method further comprises and adds the sub-transfer agent of light current, wherein before adding the sub-transfer agent of forceful electric power, simultaneously or add the sub-transfer agent of this light current afterwards.

In certain embodiments, this first mixture further comprises the sub-transfer agent of light current.In some such embodiment, provide this light current transfer agent by solvent or by the unsaturated group that is present on one of precursor.

In further embodiments, step (c) further is included in before the sub-transfer agent of adding forceful electric power or adds the sub-transfer agent of light current simultaneously.In some such embodiment, add the sub-transfer agent of this light current discretely simultaneously and with the sub-transfer agent of this forceful electric power.

In a further embodiment, step (c) adds the sub-transfer agent of light current after further being included in and adding the sub-transfer agent of this forceful electric power.In some such embodiment, be enough to add the sub-transfer agent of this light current after a period of time that makes the nucleation crystal form.In further embodiments, after the sub-transfer agent of forceful electric power but before nucleation stage is finished, add the sub-transfer agent of this light current.

In certain embodiments, this strong and sub-transfer agent of light current is an oxidant.In further embodiments, this strong and sub-transfer agent of light current is a reducing agent.In certain embodiments, the sub-transfer agent of this forceful electric power is an oxidant, and the sub-transfer agent of this forceful electric power is a reducing agent, or opposite.

In certain embodiments, the strong and sub-transfer agent of light current is changed into middle condition with the oxidation state of this first precursor or this second precursor by this.In further embodiments, by this oxidation state strong and the sub-transfer agent of light current mates this first precursor and this second precursor.

More on the one hand, provide the method for making nanocrystalline or its colony herein, comprising: mixture (a) is provided, and it comprises: (i) first precursor; (ii) second precursor, wherein this first precursor and this second precursor have the oxidation state of mismatch; The (iii) sub-transfer agent of forceful electric power; The sub-transfer agent of light current that (iv) is different from the sub-transfer agent of this forceful electric power; (v) Ren Xuan one or more solvents; (b) this mixture is heated to the temperature a period of time that is enough to cause nanocrystalline formation.

Further, can be with being suitable for after nucleation takes place, keeping a large amount of mismatch of growth to using a small amount of " coupling " precursor.Should " coupling " precursor can immediate response, under the situation that does not have the sub-transfer agent of forceful electric power, cause nucleation thus.In case " coupling " precursor exhausts, the existence of the sub-transfer agent of light current can be used for keeping growth in the reactant mixture, and does not have extra nucleation.For example, a small amount of reactive higher zinc precursor, as diethyl zinc can with R ₃P=Se together, with more substantial Zn ²⁺Precursor is used in combination.This Zn ⁰Precursor, for example diethyl zinc can use to cause the nucleation of aequum with abundant amount.In case it exhausts (this can take place fast), this Zn under the appropriate reaction temperature ²⁺Precursor is to exist the enough amounts of required extent of growth, so that produce required nanocrystalline size in the presence of the sub-transfer agent of light current.Can in this growth phase process, easily determine this nanocrystalline size by the monitoring wavelength of fluorescence.

In one aspect, provide the method for making nanocrystalline or its colony herein, this method comprises: the mixture that comprises first precursor, second precursor, the 3rd precursor and optional solvent (a) is provided, wherein this first and second precursor has the oxidation state of mismatch, and wherein the 3rd precursor has the oxidation state that is matched with this first precursor or second precursor; (b) this mixture is heated to the temperature a period of time that is enough to cause nanocrystalline formation.

In certain embodiments, this mixture further comprises the sub-transfer agent of light current.In some such embodiment, before adding the 3rd precursor, simultaneously or add this weak reductant afterwards.

In certain embodiments, the sub-transfer agent of this light current is an oxidant.In further embodiments, the sub-transfer agent of this light current is a reducing agent.

In certain embodiments, this nanocrystalline formation is reflected in the continuous flow reactor system and takes place.In further embodiments, this nanocrystalline formation is reflected in the batch reactor system and takes place.

In yet another aspect, provide the method for examining nanocrystalline or its colony of making herein, this method comprises: first mixture that comprises first precursor, second precursor and optional solvent (a) is provided, and wherein this first and second precursor has the oxidation state of mismatch; (b) this first mixture is heated to enough height in the presence of the 3rd precursor to promote the temperature of nucleation, wherein the 3rd precursor has the oxidation state with this first precursor or this second precursor match; (c) to be enough to the promoting amount of nucleation to add the 3rd precursor; (d) this second mixture is heated to the temperature a period of time that is enough to cause nanocrystalline formation.

In some embodiment of methods described herein, the sub-transfer agent of this forceful electric power is a chemical reducing agent, is selected from tertiary phosphine; Secondary phosphine; Uncle's phosphine; Amine; Hydrazine; The hydroxyphenyl compound; Hydrogen; Hydride; Metal; Borine; Aldehyde; Alcohol; Mercaptan; Reproducibility halide; With multifunctional reducing agent.

In some embodiment of methods described herein, the sub-transfer agent of this forceful electric power is a chemical oxidizing agent, as: potassium nitrate; The salt of hypochlorous acid, chlorous acid, chloric acid, perchloric acid and other similar halogen compounds; T-butyl hypochlorate; Halogen is as fluorine, chlorine, bromine and iodine; Permanganate and compound; Ammonium ceric nitrate; Hexavalent chromium compound, as chromic acid and dichromic acid, and chromium trioxide, PCC

(PCC) and chromate/bichromate compound; Peroxide compound; Tollens reagent; Oxysulfide; Persulfuric acid; Oxygen; Ozone; Osmium tetroxide; Nitric acid; Nitrous oxide; Silver (I) compound; Copper (II) compound; Molybdenum (IV) compound; Iron (III) compound; Manganese (IV) compound; N-methylmorpholine-N-oxide and other N-oxide; The trimethyl amine n-oxide; 3-chlorine benzylhydroperoxide and other peroxy acid; Or peracetic acid.

In other embodiment of methods described herein, this strong oxidizer/reducing agent is a negative electrode.In some such embodiment, this negative electrode is made by the material that is selected from platinum, silver and carbon.

In the common embodiment of this method, add this strong oxidizer/reducing agent to be lower than stoichiometry.In some such embodiment, the amount of the strong oxidizer/reducing agent of adding be the stoichiometric reaction aequum less than about 1/10th, about 1/10th, less than about 2/10ths, less than about 3/10ths or less than about 4/10ths.In a preferred embodiment, the amount of the strong oxidizer/reducing agent of adding is less than about 1/10th of the stoichiometric reaction aequum.In a preferred embodiment, be enough to take place to add this strong oxidizer/reducing agent under the running temperature of nucleation.

In some embodiment of this method, this reactant mixture is heated to the temperature that is enough to promote nucleation, and remains under the steady temperature, add this strong oxidation/reducing agent simultaneously.

In some embodiment of methods described herein, the sub-transfer agent of this light current is a chemical reducing agent, and it is selected from: tertiary phosphine; Secondary phosphine; Uncle's phosphine; Amine; Hydrazine; The hydroxyphenyl compound; Hydrogen; Hydride; Metal; Borine; Aldehyde; Alcohol; Mercaptan; Reproducibility halide; With multifunctional reducing agent.

In some embodiment of methods described herein, the sub-transfer agent of this light current is a chemical oxidizing agent, as: potassium nitrate; The salt of hypochlorous acid, chlorous acid, chloric acid, perchloric acid and other similar halogen compounds; T-butyl hypochlorate; Halogen is as fluorine, chlorine, bromine and iodine; Permanganate and compound; Ammonium ceric nitrate; Hexavalent chromium compound, as chromic acid and dichromic acid, and chromium trioxide, PCC (PCC) and chromate/bichromate compound; Peroxide compound; Tollens reagent; Oxysulfide; Persulfuric acid; Oxygen; Ozone; Osmium tetroxide; Nitric acid; Nitrous oxide; Silver (I) compound; Copper (II) compound; Molybdenum (IV) compound; Iron (III) compound; Manganese (IV) compound; N-methylmorpholine-N-oxide and other N-oxide; The trimethyl amine n-oxide; 3-chlorine benzylhydroperoxide and other peroxy acid; Or peracetic acid.

In other embodiment of methods described herein, this weak oxidant/reducing agent is a negative electrode.In some such embodiment, this negative electrode is made by the material that is selected from platinum, silver and carbon.

In some embodiment of method provided herein, this solvent is selected from hydro carbons, amine, alkylphosphines, alkylphosphine oxide, carboxylic acid, ether, furans, phosphonic acids, pyridine and composition thereof.In some such embodiment, this solvent comprises solvent mixture.In common embodiment, this reactant mixture comprises at least a solvent, preferred at least a ligand solvent.

In specific embodiment, use to comprise alkylphosphines and alkylphosphine oxide, as the solvent mixture of TOP/TOPO.In further embodiments, use the solvent mixture that comprises amine, particularly secondary amine and alkylphosphines or alkylphosphine oxide.For example, dioctylamine can be used in combination with TBP, TOP or TOPO.The example of concrete solvent comprises for example TOPO, TOP, tributylphosphine, decyl amine, dioctylamine, oleyl amine, octadecane, saualane, oleic acid, stearic acid, myristyl phosphonic acids and composition thereof.

In certain embodiments, this first precursor comprises metallic atom, and this second precursor is the containing metal atom not.In specific embodiment, when in the reactant mixture of heating, this first precursor can become the contribution metal cation to karyomorphism.In some such embodiment, this first precursor can be the salt of Cd or Zn.In specific embodiment, halide, acetate, carboxylate, phosphonate or oxide salt that this first precursor can be Cd, Zn, In or Ga.

In certain embodiments, when its in reactant mixture of heating the time, this second precursor can be contributed and be used for uncharged non-metallic atom that karyomorphism becomes.In specific embodiment, this second precursor can be R ₃The group of P=X form, wherein X is S, Se or Te, and each R is H or C independently ₁-C ₁₀₀Alkyl.In specific embodiment, this second precursor is three-(normal-butyl phosphine) selenides (TBP=Se), three-(n-octyl phosphine) selenides (TOP=Se), (butyl phosphine) sulfide (TBP=S), three-(n-octyl phosphine) sulfide (TOP=S), (butyl phosphine) tellurides (TBP=Te) or three-(n-octyl phosphine) tellurides (TOP=Te).

In common embodiment, except this first precursor and second precursor, there is not other precursor.

In certain embodiments, except this first precursor and second precursor, there is the 3rd precursor.In some such embodiment, the 3rd precursor provides the reactive species that has with the oxidation state of this first precursor or second precursor match.In some such embodiment, the 3rd precursor provides neutral metal thing class.For example, the 3rd precursor can provide neutral metal thing class, for example Zn ⁰Or Cd ⁰Metal diaikyl precursor (Et for example ₂Zn or Me ₂Cd).In further embodiments, the 3rd precursor can become the charged non-metallic atom of contribution to karyomorphism.For example, the 3rd precursor can provide S ^2-Or Se ^2-

As described herein, this nanocrystal can be made by any suitable known metal and non-metallic atom that forms semiconductor nano.In certain embodiments, this is endorsed to comprise CdSe, CdS, CdTe, InP, InAs, ZnS, ZnSe, ZnTe, GaP or its mixture.

Further, it is nanocrystalline to provide the nuclear of making by one of described method herein herein.

In the described in this article method, heating steps carries out being enough to cause under the temperature of temporary transient discrete homogeneous nucleation usually, and this causes forming single nanocrystalline single colony that disperses.Usually, this heating steps more preferably from about carries out under the temperature in 220-350 ℃ of scope in about 150-350 ℃ scope.In addition, mixing and heating steps can carry out in emptying and in the container of filling and/or purging as the inert gas of nitrogen.This filling can be regular, or can purge the fixed time continuously after filling.In certain embodiments, this blend step can comprise cooling step before being exposed to this first or second reducing agent, for example, was cooled to the temperature in about 50 to 150 ℃ of scopes.

The actual temperature scope it being understood that above-mentioned scope only for exemplary, and is not to limit by any way, owing to can change with the relative stability of reducing agent, precursor, part and solvent.Higher or lower temperature can be suitable for specific reaction.Be suitable for providing the time of nano particle and temperature conditions to fix on really in the those skilled in the art's that adopt normal experiment the limit of power.

Advantageously under the situation of getting rid of oxygen and moisture, carry out described nanocrystalline formation reaction herein.In certain embodiments, this is reflected in the inert atmosphere, as carrying out in glove box.Also common strict purification of solvent and reagent with removal moisture and oxygen and other impurity, and common with being designed to method and apparatus processing and the transfer that minimizing as far as possible is exposed to moisture and/or oxygen.In addition, this mixing and heating steps can carry out in emptying and in the container of filling and/or purging as the inert gas of nitrogen.This filling can be regular, or can purge the fixed time continuously after filling.If solvent realizes that with reagent required hull shape becomes reaction not introduce strong reductant in reaction, their purity is enough.

The solvent that is used for these reactions often comprises amine, and exemplary such as hexadecylamine, dioctylamine are another suitable examples.Amine solvent is difficult to fully purify being used for especially sensitive system, as is used for ZnTe nanocrystal reaction (because this reactive component and product show the especially high sensitivity to moisture and air).When usually under inert atmosphere, carrying out nanocrystalline preparation, carry out further special precautionary measures and step and be used to prepare the nanocrystalline amine solvent of ZnTe with purification with solvent of purifying and reagent.The amine that is used as the solvent of these reactions is placed on emptying repeatedly and also uses immediately in the flask of anhydrous inert atmosphere filling.Add in this amine solvent subsequently and surpassing 100 ℃ of down dry anhydrous Na OH or KOH that cross in a vacuum, suspension stirred 8 hours at least.This amine filters to remove solid under inert atmosphere, distills under inert atmosphere subsequently, and stores under inert atmosphere.

Synthetic ZnTe is for realizing that method disclosed herein is good especially example, because Zn ²⁺With Te ⁰All extremely difficult free reduction in solution causes extremely difficult nucleation under the situation that does not add strong reductant.Under the situation that does not have the sub-transfer agent of forceful electric power, at ZnCl ₂With Bu ₃Do not observe nucleation (promptly not forming particle) in the mixture of P=Te.This is because the mismatch between the oxidation state of used tellurium and zinc precursor: zinc chloride is+2 oxidation state under this reaction condition, but tellurium precursor Bu ₃P=Te provides Te under this reaction condition ⁰It is believed that uncharged tellurium thing class can not be easily and Zn ^{+ 2}Reaction, the reaction that take place requires Te ⁰Be reduced to Te ^2-, or with Zn ^{+ 2}Be reduced to Zn ⁰Adding the sub-transfer agent of forceful electric power (being reducing agent) passes through probably with Te ⁰Be reduced to Te ^2-Make it possible to react.The method that provides in the example 1 adopts lithium triethylborohydride (LiEt ₃BH) as the strong nucleation reducing agent that promotes.Oleic acid as weak reductant, causes at LiEt in the method ₃Energy continued growth after BH exhausts, even when adding LiEt significantly to be lower than the stoichiometry level ₃Also like this during BH.

Except the control that improves to granularity and productive rate, the further benefit of the inventive method come from embodiment disclosed herein intrinsic scale and the improvement of manufacturability.The synthetic example of most popular chalcogen zinc particles adopts diethyl zinc (to produce the Zn of a large amount of gases ⁰The source), increased mutability and limited manufacturability.When using zinc salt, their reducing resistance requires to use the strong reductant that produces gas usually.This method can be used this type of reducing agent to be lower than stoichiometry.In the example below, the addition of strong reductant is 1/10th of a stoichiometric reaction aequum.In addition, as mentioned above, this method makes nanocrystalline synthetic more reliable, because it does not depend on so that similar nanocrystalline precursor adds the situation of speed (because this reducing agent provides controlled reaction rate).

The nanocrystalline method that provides herein is provided

Nanocrystalline to can be used for utilizing condition well known by persons skilled in the art to form nuclear/shell nanocrystalline by the nuclear of the method manufacturing that provides herein.

In addition, by these method manufacturings nanocrystalline can be as known in the art like that the modification by the part that exists on the nanocrystal surface come further modification.For example, the part on the nanocrystal surface can be exchanged for other part so that to the new character of this nanocrystalline introducing, as water-soluble.The nanocrystalline method that manufacturing has the water soluble ligand coating is known in this area.For example, people such as Adams provide by applying the method that amphipathic polymerization material coating is made water-solubility nanocrystalline, U.S. Patent No. 6,649,138 to the brilliant surface of hydrophobic nano.This method is from the hydrophobic nano crystalline substance, as the described herein nanocrystalline beginning with hydrophobicity part (as trialkyl phosphine, trialkyl phosphine oxide, alkylamine or alkyl phosphoric acid) coating.Add the skin of forming by a plurality of amphipathic dispersant molecules that comprise at least two water repellent regions and at least two hydrophilic regions to it.In certain embodiments, this amphipathic nature polyalcohol comprises the acrylic or methacrylic acid polymer, and this polymer has some and uses the hydrophobicity amido, has at least the monoalkylamine of 4-12 carbon or the acrylic acid groups that dialkylamine is converted into acid amides as each alkyl; And it is water-soluble to improve to have some free hydroxy-acid groups.Be applicable to that these and other suitable amphipathic dispersant of this purposes is described in the 14-18 hurdle of the patent of Adams, its content is incorporated herein by this reference.

Thus in one aspect, disclosed embodiment provides and has had as herein described nanocrystalline as amphipathic dispersant coating as described in the people such as Adams.This is nanocrystalline to have water-solublely thus, makes them be applicable to the nanocrystalline method of multiple known use such as quantum dot.Nanocrystalline and the method for making them of dissolving is disclosed in herein.

Cover with paint, lacquer, colour wash, etc. other nanocrystalline method and be described in United States Patent (USP) 6,955 by people such as Naasani, 855 with U.S. Patent No. 7,198,847 in.These methods comprise with little water soluble ligand, and this is nanocrystalline as imidazo-containing compounds (for example dipeptides) coating.Suitable imidazo-containing compounds has been described on the 7th hurdle in ' 855 Naasani patent.

Term " imidazo-containing compounds " is meant that for this specification and claims having at least one can be used for the bonding metal, as zinc or other metal cation, or contains the molecule of the imidazole group (for example imidazole ring) of this type of cationic substrate.That part of what pay close attention to, preferably at least one imidazoles part is in the end portion with respect to this molecular structure.Usually, imidazole ring nitrogen usually as ligand so that bonding metal ion effectively, as zinc or cadmium.In one embodiment, this imidazo-containing compounds comprises amino acid, or the two or more amino acid that link together (for example this area is called " peptidyl " or " oligopeptides "), it can include but not limited to histidine, carnosine, anserine, baleen (baleine), homocarnosine, 1-Methyl histidine, 3-Methyl histidine, imidazoles lysine, contain the ornithine (for example 5-methylimidazole ketone) of imidazoles, the alanine (for example (β)-(2-imidazole radicals)-L (α) alanine) that contains imidazoles, β-alanyl histamine (carcinine), histamine or the like.The amino acid that contains imidazoles can be synthetic with methods known in the art (referring to people such as for example Stankova, 1999, J. Peptide Sci. 5:392-398, its disclosure is incorporated herein by this reference).

Term " amino acid " is meant the compound that contains at least one amino and at least one carboxyl as known in the art like that and for this specification and claims.As known in the art, amino can be positioned at the carboxyl position adjacent on.Such as known in the art, amino can be positioned at the carboxyl position adjacent on, or may reside in any position along amino molecule.Except at least one imidazoles part, this amino acid can further comprise one or more additional reactive functional groups (for example amino, mercaptan, carboxyl, carboxylic acid amides or the like).This amino acid can be D(dextrorotation) configuration or L(be left-handed) naturally occurring amino acid, synthesizing amino acid, modified amino acid, amino acid derivativges, the amino acid precursor of configuration.Such as known in the art, the example of derivative can include but not limited to N-methylate derivative, acid amides or ester, and the composition that wherein has an aminoacid functional as coating as herein described (for example give water-soluble, the abundant buffering of about pH 6 to the pH scope of about pH 10, as the sense of the coating that improves fluorescence intensity and have one or more reactive functional of bonding molecular probe effectively that can be used for).The amino acid of aforementioned amino acids can use in a preferred embodiment, and preferred amino acids can be used for the composition of disclosed embodiment separately, and gets rid of the amino acid outside the preferred amino acid.Histidine is particularly preferredly to be used to be coated with that this is functionalized, the imidazo-containing compounds of fluorescence nano.

Part on nanocrystalline disclosed herein can also be crosslinked with the stability that improves this nanocrystalline composition and improve its characteristic.The method that surface ligand coating on nanocrystalline disclosed herein can be described with Naasani, crosslinked with various crosslinking agents.The preferred crosslinking agent that is used for disclosed embodiment comprises those that people such as Naasani describes, comprises three (methylol) phosphine (THP) and three (methylol) phosphino--propionic ester (THPP).Having the nanocrystalline of crosslinked water soluble ligand coating is another kind of embodiment disclosed herein thus.

The nanocrystalline method that can be used for tracking molecule known in the art by these method manufacturings.For example, they can be connected on the plurality of target molecule by known method.Usually, they are connected on the affinity molecule or are used for further transformation.This type of further transformation can be used for introducing selected interested target (or goods) molecule on nanocrystal surface, as antibody or other concrete affinity molecule.The method that this type of affinity molecule is connected on the fluorescence carrier is known in this area, and can easily adjust: referring to for example U.S. Patent No. 6 to be used for this method, 423,551, it has also been described and can be used for nanocrystal surface is connected to target molecule and some difunctionality reagent that are connected to nanocrystal surface.These methods also are used in introduces a large amount of or one deck functionalized molecule on the nanocrystal surface, wherein this functionalized molecule can provide new surface nature to this nano particle, as water dispersible.In certain embodiments, provide can be used for detecting required target compound, cell or organelle modification to connect the nanocrystalline of affinity molecule.

The nanocrystalline of this modification can be connected to the affinity molecule that is used to follow the trail of, discern or locate the method for molecule (s) of interest, and described affinity molecule can be bonded on this molecule (s) of interest, proves that molecule (s) of interest exists and its distribution or where be positioned at.This nanocrystalline also can be used in conjunction with test to show the distribution of the molecule that this affinity molecule is admitted.In case determine target compound, in the general ability scope that is chosen in those skilled in the art of suitable affinity molecule; For example, conventional method can be used for making or discerning the antibody that is suitable for being bonded to specifically on the interested target molecule.This antibody can be connected to thus disclosed herein nanocrystalline on, use this nanocrystalline as fluorescence labeling, it can be used for the existence, position of recognition objective compound subsequently or moves.In certain embodiments, provide by can selectivity be bonded to suitable affinity molecule on the target molecule be connected to nanocrystalline on, and make the nanocrystalline and target molecule that is connected to affinity molecule contact method with the identification or the molecule that follows the trail of the objective.Follow the trail of or detect and to realize by adopting the conventional method of following the trail of the fluorescence labeling part, as using fluorescence imaging system, microscope or camera.

In certain embodiments, provide described functionalized nanocrystalline herein.This nanocrystalline can being connected on the affinity molecule, this affinity molecule are to select to be bonded to specifically on the interested target molecule.Be connected to nanocrystalline optional being bonded on the interested target molecule on this affinity molecule to form fluorescently-labeled compound.Interested target molecule comprises the cell surface antigen feature of protein, enzyme, acceptor, nucleic acid, hormone and concrete cell type.

The described herein or many technology quoted and method are that those skilled in the art fully understand and generally use with conventional method.In appropriate circumstances, unless otherwise specified, carry out the program that comprises use commercial reagent box and reagent according to the rules and/or the parameter of manufacturer's regulation usually.

The argumentation of the conventional method that provides herein only is used for illustration purpose.Other alternative approach and embodiment are conspicuous for the those skilled in the art of the present invention that read.

Unless offer some clarification on separately, with conjunction " or " one group of project connecting should not be construed as requirement and repels mutually in this group, but be interpreted as " and/or ".Although can or advocate project, key element or the component of embodiment disclosed herein with the singulative description, unless clear and definite prescribed limits is an odd number, plural number is also considered in its scope.

All patents of quoting herein, patent application, patent disclosure, journal of writings and other list of references are all incorporated this paper into through this incorporated.

As using in claims and the specification, word " comprises " (and any type of comprising, as " comprise " and " comprises " and " comprised "), " have " and (and any type ofly have, as " have " and " has "), " comprise " (and any type of comprising, as " includes " and " include ") or " containing " (and any type of containing, as " contains " and " contain ") be to comprise end points or open end points, and do not get rid of additional, key element of not enumerating or method step.

Provide the following example as about making and use the further guide of method disclosed herein, and it should not be construed as the restriction to the various embodiment of these methods.

Example 1

It is nanocrystalline to form ZnTe nuclear

Unless otherwise specified, all used reagent are anhydrous, and all operations carries out under inert atmosphere.Zinc chloride (685 milligrams, 5 mMs) is weighed in 250 milliliters of round-bottomed flasks with two 14/20 joints and ground glass plug.Add dioctylamine (35 milliliters) and oleic acid (1.6 milliliters, 5 mMs), and magnetic stirring bar is installed on flask.With glass plug fat liquoring and close, an adapter glass rubber septum jam-pack, installation adapter and stainless steel hot galvanic couple on a joint, it is connected on the temperature controller of regulating 180 watts of heating jackets.This flask is placed in the heating jacket, and is connected to plug on the flowing nitrogen source and opens it.Temperature controller is set, so that flask is heated to 115 ℃ and keeping this temperature to dissolve up to zinc salt under this temperature under gentle agitation.Subsequently this flask is found time and recharge nitrogen three times.

This temperature is increased to 230 ℃ subsequently, and by the 1M tellurium solution in the tributylphosphine of 15 milliliters of syringe addings, cool off flask contents through partition slightly this moment.When temperature turns back to 220 ℃, the 1M lithium triethylborohydride solution in the oxolane of 1 milliliter of the quick adding of syringe.This temperature is increased to 240 ℃ and kept 15 seconds to 30 minutes, up to reaching desired particle size, and cooling fast subsequently.

Claims (39)

1. make the method for nanocrystalline colony, comprising:

Mixture is provided, and described mixture comprises:

First precursor;

Second precursor, wherein said first precursor and described second precursor have the oxidation state of mismatch;

The sub-transfer agent of forceful electric power presents in an amount at least sufficient to produce required nucleation amount; With

The sub-transfer agent of light current that is different from the sub-transfer agent of described forceful electric power; And

Described mixture is heated to the temperature a period of time that is enough to cause the formation of nanocrystalline colony.

2. the method for the nanocrystalline colony of manufacturing according to claim 1, wherein nanocrystalline formation is reflected in the batch reactor system and takes place.

3. the method for the nanocrystalline colony of manufacturing according to claim 1, wherein nanocrystalline formation is reflected in the continuous flow reactor system and takes place.

4. the method for the nanocrystalline colony of manufacturing according to claim 1 is wherein changed into middle condition by sub-transfer agent of described forceful electric power and the sub-transfer agent of described light current with the described oxidation state of described first precursor or described second precursor.

5. the method for the nanocrystalline colony of manufacturing according to claim 1, the wherein described oxidation state of mating described first precursor and described second precursor by sub-transfer agent of described forceful electric power and the sub-transfer agent of described light current.

6. the method for the nanocrystalline colony of manufacturing according to claim 1, sub-transfer agent of wherein said forceful electric power and the sub-transfer agent of described light current are reducing agents.

7. the method for the nanocrystalline colony of manufacturing according to claim 1, sub-transfer agent of wherein said forceful electric power and the sub-transfer agent of described light current are oxidants.

8. the method for the nanocrystalline colony of manufacturing according to claim 1, wherein one or more described precursor and electron transfer agents of heating before mixing.

9. the method for the nanocrystalline colony of manufacturing according to claim 6, wherein said strong reductant and described weak reductant are selected from: tertiary phosphine, secondary phosphine, uncle's phosphine, amine, hydrazine, hydroxyphenyl compound, hydrogen, hydride, metal, borine, aldehyde, alcohol, mercaptan, reproducibility halide, multifunctional reducing agent and composition thereof.

10. the method for the nanocrystalline colony of manufacturing according to claim 7, wherein said strong oxidizer and described weak oxidant are selected from potassium nitrate; Hypochlorite, chlorite, chlorate, perchlorate and other similar halogen compounds; T-butyl hypochlorate; Halogen; Permanganate and compound; Ammonium ceric nitrate; Hexavalent chromium compound; Peroxide compound; Tollens reagent; Oxysulfide; Persulfuric acid; Oxygen; Ozone; Osmium tetroxide; Nitric acid; Nitrous oxide; Silver (I) compound; Copper (II) compound; Molybdenum (IV) compound; Iron (III) compound; Manganese (IV) compound; N-methylmorpholine-N-oxide; The trimethyl amine n-oxide; 3-chlorine benzylhydroperoxide, peroxy acid; Peracetic acid, and composition thereof.

11. the method for the nanocrystalline colony of manufacturing according to claim 1, wherein said strong reductant is a negative electrode.

12. the method for the nanocrystalline colony of manufacturing according to claim 1, wherein said weak reductant is a negative electrode.

13. the method for the nanocrystalline colony of manufacturing according to claim 1 further comprises solvent in described mixture.

14. the method for the nanocrystalline colony of manufacturing according to claim 13, wherein said solvent is selected from hydro carbons, amine, alkylphosphines, alkylphosphine oxide, carboxylic acid, ether, furans, phosphonic acids, pyridine and composition thereof.

15. the method for the nanocrystalline colony of manufacturing according to claim 13, wherein said solvent is a ligand solvent.

16. the method for the nanocrystalline colony of manufacturing according to claim 1 further comprises the described mixture of cooling.

17. the method for the nanocrystalline colony of manufacturing according to claim 1, wherein said first precursor is selected from the salt of being made up of Cd, Zn, Ga, In, Al, Pb, Ge, Si, Hg, Mg, Ca, Sr, Ba and composition thereof.

18. the method for the nanocrystalline colony of manufacturing according to claim 1, wherein said second precursor is R ₃P=X, wherein X is S, Se or Te, and each R is H or C independently ₁-C ₂₄Alkyl.

19. the method for the nanocrystalline colony of manufacturing according to claim 1, wherein said second precursor are S, Se or the Te that is dissolved in alkylphosphines, alkene or the amine.

20. the method for the nanocrystalline colony of manufacturing according to claim 1, wherein said second precursor is dissolved in tributylphosphine or the tri octyl phosphine.

21. the method for the nanocrystalline colony of manufacturing according to claim 1 further comprises:

The described nanocrystalline colony of optional separated; With

Apply shell to each described nanocrystalline colony.

22. the method for the nanocrystalline colony of manufacturing according to claim 21, wherein said shell material is selected from ZnS, ZnSe, ZnTe, CdS, CdSe, CdTe, HgS, HgSe, HgTe, MgS, MgSe, MgTe, CaS, CaSe, CaTe, SrS, SrSe, SrTe, BaS, BaSe, BaTe and composition thereof.

23. the method for the nanocrystalline colony of manufacturing according to claim 21, wherein said shell material is selected from GaN, GaP, GaAs, GaSb, InP, InAs, InSb, AlS, AlP, AlSb, PbS, PbSe, Ge, Si and composition thereof.

24. the method for the nanocrystalline colony of manufacturing according to claim 1, wherein said first precursor or described second precursor can serve as the sub-transfer agent of described light current.

25. the method for the nanocrystalline colony of manufacturing according to claim 1 wherein provides described light current transfer agent with the amount that is enough to be used in required nanocrystalline growth.

26. make nanocrystalline method, comprising:

The mixture that comprises first precursor and second precursor is provided, and wherein said first precursor and described second precursor have the oxidation state of mismatch;

In described mixture, add the sub-transfer agent of forceful electric power that is lower than stoichiometry with the amount that is enough to produce required nucleation amount;

Choose wantonly mixture is heated together to produce required nucleation amount;

In described mixture, add the sub-transfer agent of light current with the amount that is enough to produce required nanocrystalline increment; With

Optional a period of time that described mixture heating is enough to produce required nanocrystalline increment.

27. the method that manufacturing according to claim 26 is nanocrystalline, wherein said nanocrystalline formation is reflected in the batch reactor system and takes place.

28. the method that manufacturing according to claim 26 is nanocrystalline, wherein said nanocrystalline formation is reflected in the continuous flow reactor system and takes place.

29. the method that manufacturing according to claim 26 is nanocrystalline is wherein changed into middle condition by sub-transfer agent of described forceful electric power and the sub-transfer agent of described light current with the described oxidation state of described first precursor or described second precursor.

30. the method that manufacturing according to claim 26 is nanocrystalline is wherein by described strong and described oxidation state that the sub-transfer agent of light current mates described first precursor and described second precursor.

31. the method that manufacturing according to claim 26 is nanocrystalline, sub-transfer agent of wherein said forceful electric power and the sub-transfer agent of described light current are reducing agents.

32. the method that manufacturing according to claim 26 is nanocrystalline, sub-transfer agent of wherein said forceful electric power and the sub-transfer agent of described light current are oxidants.

33. make nanocrystalline method, comprising:

The mixture that comprises first precursor, second precursor and the 3rd precursor is provided, and wherein said first precursor and described second precursor have the oxidation state of mismatch, and wherein said the 3rd precursor has the oxidation state that is matched with described first precursor or described second precursor; With

Choose wantonly described mixture is heated to the temperature a period of time that is enough to cause nanocrystalline formation.

34. the method that manufacturing according to claim 33 is nanocrystalline, wherein said mixture further comprise the sub-transfer agent of light current.

35. the method that manufacturing according to claim 34 is nanocrystalline, the sub-transfer agent of wherein said light current is a reducing agent.

36. the method that manufacturing according to claim 34 is nanocrystalline, the sub-transfer agent of wherein said light current is an oxidant.

37. the method that manufacturing according to claim 33 is nanocrystalline, wherein said the 3rd precursor is to be enough to the promoting amount of required nucleation amount to add.

38. the method that manufacturing according to claim 34 is nanocrystalline, the sub-transfer agent of wherein said light current is to be enough to the promoting amount of required nanocrystalline increment to add.

39. the method that manufacturing according to claim 33 is nanocrystalline further comprises:

Before adding described the 3rd precursor, form the premix that contains described first precursor and described second precursor; With

Choose the described premix of heating before adding described the 3rd precursor wantonly.

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