CN108929690A - A kind of preparation method of alloy nanometer crystals - Google Patents
A kind of preparation method of alloy nanometer crystals Download PDFInfo
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- CN108929690A CN108929690A CN201710392318.2A CN201710392318A CN108929690A CN 108929690 A CN108929690 A CN 108929690A CN 201710392318 A CN201710392318 A CN 201710392318A CN 108929690 A CN108929690 A CN 108929690A
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Abstract
The present invention provides a kind of preparation methods of alloy nanometer crystals, including step：S1, the cation precursor solution including at least two metal cations is provided；S2, anionic pre-cursors solution is provided, anion includes chalcogen；S3, cation precursor solution and anionic pre-cursors solution are reacted in the solution system containing secondary phosphine or secondary phosphine oxide, forms alloy nanometer crystals.The present invention additionally provides a kind of method of regulation alloy nanometer crystals fluorescence emission wavelengths blue shift simultaneously：By adding secondary phosphine or secondary phosphine oxide in the preparation of alloy nanometer crystals, make alloy nanometer crystals fluorescence emission wavelengths blue shift.Preparation method of the invention, it can be under conditions of all precursor dosages of fixation, reaction temperature and reaction time, only by adusting the type and dosage of secondary phosphine added when preparing alloy nanometer crystals or secondary phosphine oxide, the regulation of alloy nanometer crystals level structure and fluorescent characteristic is realized.
Description
Technical field
The present invention relates to nanocrystal preparation technical field more particularly to a kind of preparation methods of alloy nanometer crystals.
Background technique
Semiconductor nano is a kind of classical semiconductor nano material with excellent physical characteristic and chemical characteristic, flat
The fields such as plate shows, biomarker, light emitting diode, photovoltaic device and catalysis have huge application prospect, have sent out at present
It transforms into as one of most active research field of many subjects such as physics, chemistry and materialogy.In order to realize semiconductor nano
Brilliant value, either basic research or practical application require accurately to adjust its level structure and optical property
Control.Different from the nanocrystalline dependence particle size adjustment of binary semiconductor, the control measures of ternary and the above semiconductor nano of ternary
More, and it is alloy type it is nanocrystalline in terms of luminance purity, quantum efficiency, stability and flashing all have more outstanding table
It is existing, it has been increasingly becoming the Research Emphasis in nanocrystalline material field.
Level structure determines nanocrystalline band edge absorption and wavelength of fluorescence, can also be to nanocrystalline fluorescence half-peak breadth, amount
Sub- yield, stability, bio-toxicity etc. have an impact, these characteristics have codetermined nanocrystalline in opto-electronic device and biology doctor
The application value and performance in field.For example, using the difference of CdS and ZnS level structure, in the CdZnS nanometer of its alloying
In crystalline substance, can by adjust Cd/Zn ratio, realize nanocrystalline luminescent color adjusting (J.Phys.Chem.C 2012,116,
15167).For another example, Cu can be reduced by increasing the amount of Se2ZnSn(S1-xSex)4The band gap of alloy nanometer crystals, and then improve it
Electric conductivity (J.Am.Chem.Soc.2011,133,15272).
The method of conventional control alloy nanometer crystals level structure mainly has：Regulate and control the degree of interface alloying, ion is set
It changes and feeds intake by a certain percentage.In general, the limitation of interface alloying, is not particularly suited for all elements；From
New defect may be introduced in sub- replacement process, cause the negative influences such as quantum yield reduction；And it feeds intake by a certain percentage
Mode must change the feed ratio of presoma every time when needing that nanocrystalline energy level, luminous position is adjusted,
Technique is relatively cumbersome.And since active natural differences of presoma etc. influence, it also not can solve all problems.For example, by
In Cd (OA)2Activity be much higher than Zn (OA)2, and be difficult to select and Cd (OA) again in organic system2The comparable Zn of activity
Source is still difficult to synthesize broad-band gap transmitting blue light even if this allows for increasing substantially the ratio of Zn/Cd in solution system
CdZnSe nanocrystalline (Chem.Mater 2008,20,531).
Therefore, there is an urgent need to find a kind of simple process and can quickly and effectively prepare the adjustable conjunction of level structure at present
The method of gold nanocrystals.
Summary of the invention
For the above-mentioned problems in the prior art, the purpose of the present invention is to provide a kind of preparations of alloy nanometer crystals
A kind of method, to realize the regulation of alloy nanometer crystals level structure and fluorescent characteristic by simple and efficient mode.
According to an aspect of the invention, there is provided a kind of preparation method of alloy nanometer crystals, including step：S1, offer
Cation precursor solution including at least two metal cations；S2, anionic pre-cursors solution is provided, anion includes sulfur family member
Element；S3, cation precursor solution and anionic pre-cursors solution are mixed to form alloy nanometer crystals；Preparation method further includes that addition is secondary
Phosphine perhaps secondary phosphine oxide the step of so that cation precursor and anionic pre-cursors molten containing secondary phosphine or secondary phosphine oxide
It reacts to form alloy nanometer crystals of the invention in liquid system.
Preferably, secondary phosphine or secondary phosphine oxide are added in S1 step in cation precursor solution.
Preferably, secondary phosphine or secondary phosphine oxide are added in S2 step in anionic pre-cursors solution.
Preferably, secondary phosphine or secondary phosphine oxide and cation precursor solution, anionic pre-cursors solution synchronized mixes.
Preferably, it is added again after secondary phosphine or the mixing of at least one of secondary phosphine oxide and following substance：Alkane, alkene
Hydrocarbon, halogenated hydrocarbons, aromatic hydrocarbon, ethers, amine, ketone, esters.
Preferably, the general formula of secondary phosphine is PHR2, the general formula of secondary phosphine oxide is R2P(O)H。
Wherein, R includes the alkyl or carbon atom of the substitution of carbon atom number 1-12 or the straight-chain or branching that do not replace
The substitution of number 5-18 or the aryl not replaced.
Preferably, secondary phosphine includes dimethyl phosphine, diethyl phosphine, dipropyl phosphine, dibutyl phosphine, di-t-butyl phosphine, dihexyl
At least one of phosphine, dicyclohexylphosphontetrafluoroborate, dioctyl phosphine, di-n-octyl phosphine, diisooctyl phosphine, diphenylphosphine, xylyl phosphine.
Preferably, secondary phosphine oxide includes dimethyl phosphine oxide, diethyl phosphine oxide, dipropyl phosphine oxide, two
Butyl phosphine oxide, di-t-butyl phosphine oxide, dihexyl phosphine oxide, dicyclohexyl phosphine oxide, dioctyl phosphine oxide,
At least one of di-n-octyl phosphine oxide, diisooctyl phosphine oxide, diphenyl phosphorus oxygen, xylyl phosphorus oxygen.
Preferably, metal cation includes at least one of following metallic element：Zn,Cd,Hg,Mg,Mn,Ni,In,
Ga、Pb、Sn、Bi、Cu、Ag。
Preferably, chalcogen includes at least one of S, Se, Te.
Preferably, cation precursor solution is dissolved in the first solvent by least two metal front salts and is formed.
Preferably, the first solvent include in alkane, alkene, halogenated hydrocarbons, aromatic hydrocarbon, ethers, amine, ketone and esters extremely
Few one kind.
Preferably, metal front salt includes at least one of following compound：Fluoride, chloride, bromide, iodate
Object, sulfonated bodies, salicylate, phosphate, lactate, sulfate, carbonate, nitrate, nitrite, borate, citric acid
Salt, arsenate, arsenite, thiosulfate, sulphite, bisulfites, tartrate, oxalates, formates, acetic acid
Salt, propionate, butyrate, valerate, caproate, enanthate, caprylate, pelargonate, caprate, undecylate, dodecanoate,
Tridecanoic acid salt, tetradecanoate, pentadecanoic acid salt, palmate, margarate, octadecanoate, acrylates, butenoate, amylene
Hydrochlorate, hexene hydrochlorate, heptene hydrochlorate, octene hydrochlorate, nonenoate, decenoate, undecylenate salt, laurylene hydrochlorate, 13
Olefin(e) acid salt, tetradecene hydrochlorate, pentadecylenic acid salt, hexadecylene hydrochlorate, heptadecenoic acid salt and Monoethanolamine Oleate.
Preferably, anionic pre-cursors solution is dissolved in the second solvent by sulfur family precursor and is formed.
Preferably, the second solvent includes tertiary phosphine, and the general formula of tertiary phosphine is PR3。
Wherein, R includes the alkyl or carbon atom of the substitution of carbon atom number 1-12 or the straight-chain or branching that do not replace
The substitution of number 5-18 or the aryl not replaced.
Preferably, tertiary phosphine includes trimethyl-phosphine, triethyl phosphine, tripropyl phosphine, tributylphosphine, tri-n-butyl phosphine, three tertiary fourths
At least one of base phosphine, three hexyl phosphines, tricyclohexyl phosphine, tri octyl phosphine, tri-n-octyl phosphine, triphenylphosphine, trimethylphenyl phosphine.
Preferably, the molar ratio of the secondary phosphine or secondary phosphine oxide and the tertiary phosphine is no more than 0.5.
Preferably, sulfur family precursor includes at least one of following substance：Elemental sulfur, alkyl hydrosulfide, vulcanization trialkyl phosphine,
Vulcanize trialkenyl phosphine, alkyl amino sulfide, alkenyl amino sulfide, hydrogen sulfide, elemental selenium, selenizing trialkyl phosphine, selenizing three
Alkenyl phosphine, alkyl amino selenides, alkenyl amino selenides, hydrogen selenide, simple substance tellurium, telluride trialkyl phosphine, telluride trialkenyl phosphine,
Alkyl amino tellurides and alkenyl amino tellurides, hydrotelluric acid.
Preferably, the second solvent further includes at least one of following substance：Alkane, alkene, halogenated hydrocarbons, aromatic hydrocarbon, ether
Class, amine, ketone, esters.
Preferably, the range of reaction temperature in step S3 is 180-350 DEG C.
Preferably, the reaction time range in step S3 is 0.01-48h.
According to another aspect of the present invention, a kind of alloy nanometer crystals are provided, are made by any of the above-described preparation method.
According to the third aspect of the present invention, a kind of side of regulation alloy nanometer crystals fluorescence emission wavelengths blue shift is provided
Method, alloy nanometer crystals therein are prepared by the following steps：S1, offer include that the cation precursor of at least two metal cations is molten
Liquid；S2, anionic pre-cursors solution is provided, anion includes chalcogen；It is S3, cation precursor solution and anionic pre-cursors is molten
Liquid is mixed to form alloy nanometer crystals；Further include the steps that adding secondary phosphine or secondary phosphine oxide in the preparation of alloy nanometer crystals, with
Cation precursor and anionic pre-cursors are made to react to form this hair in the solution system containing secondary phosphine or secondary phosphine oxide
Bright alloy nanometer crystals；Make alloy nanometer crystals fluorescence emission wavelengths blue shift by addition secondary phosphine or secondary phosphine oxide.
It applies the technical scheme of the present invention, secondary phosphine or secondary phosphine oxide is added in the preparation of alloy nanometer crystals, it can be with
Under conditions of all precursor dosages of fixation, reaction temperature and reaction time, only by adjusting secondary phosphine or secondary phosphine be added
The type and dosage of oxide realize the quick regulation of alloy nanometer crystals level structure and fluorescent characteristic.The preparation method technique
Simply, effective and rapid, it is a kind of universal method for efficiently quickly preparing regulatable alloy nanometer crystals.Preparation through the invention
The size for the alloy nanometer crystals that method obtains, pattern are uniform, and monodispersity is good, and fluorescence quantum yield is high, can be widely applied to
The fields such as opto-electronic device and biomedicine.
Detailed description of the invention
The accompanying drawings constituting a part of this application is used to provide further understanding of the present invention, and of the invention shows
Examples and descriptions thereof are used to explain the present invention for meaning property, does not constitute improper limitations of the present invention.In the accompanying drawings：
Fig. 1 be the nanocrystalline sample I, II of metal chalcogenide compound alloy nanometer crystals-ZnCdSe prepared by the present invention, III,
The UV-visible absorption spectrum of IV；
Fig. 2 be the nanocrystalline sample I, II of metal chalcogenide compound alloy nanometer crystals-ZnCdSe prepared by the present invention, III,
The fluorescence emission spectrogram of compound of IV；
Fig. 3 be the nanocrystalline sample I, II of metal chalcogenide compound alloy nanometer crystals-ZnCdSe prepared by the present invention, III,
The transmission electron microscope figure of IV.
Specific embodiment
Below in conjunction with a specific embodiment of the invention, technical solution in the embodiment of the present invention is retouched in detail
It states, it is clear that described embodiment is only a part of embodiment of the invention, rather than whole embodiments.It is based on
Embodiment in the present invention, those of ordinary skill in the art are obtained all without making creative work
Other embodiments belong to the scope of the present invention.
The present invention provides a kind of preparation methods of alloy nanometer crystals, including step：S1, it provides including at least two metals
The cation precursor solution of cation；S2, anionic pre-cursors solution is provided, anion includes chalcogen；S3, will be before cation
Liquid solution and anionic pre-cursors solution are mixed to form alloy nanometer crystals；Preparation method further includes addition secondary phosphine or secondary phosphine oxide
The step of, so that cation precursor and anionic pre-cursors react in the solution system containing secondary phosphine or secondary phosphine oxide
Form alloy nanometer crystals of the invention.
In the present invention, in the step of preparing alloy nanometer crystals, secondary phosphine or secondary phosphine oxide are added to reaction system
In step, there are numerous embodiments.
In first preferred embodiment, it is molten that secondary phosphine or secondary phosphine oxide are added to cation precursor in S1 step
In liquid.The preparation method of alloy nanometer crystals includes step：S1, secondary phosphine or secondary phosphine oxide are added to including at least two gold medals
In the cation precursor solution for belonging to cation；S2, the anionic pre-cursors solution including chalcogen is added into above-mentioned solution, makes
Cation precursor and anionic pre-cursors react to form the present invention in the solution system containing secondary phosphine or secondary phosphine oxide
Alloy nanometer crystals.
In second preferred embodiment, it is molten that secondary phosphine or secondary phosphine oxide are added to anionic pre-cursors in S2 step
In liquid.The preparation method of alloy nanometer crystals includes step：S1, secondary phosphine or secondary phosphine oxide are added to including including sulfur family member
The anionic pre-cursors solution of element；S2, the cation precursor including at least two metal cations will to be added in above-mentioned solution molten
In liquid, cation precursor and anionic pre-cursors is made to react to be formed in the solution system containing secondary phosphine or secondary phosphine oxide
Alloy nanometer crystals of the invention.
In third preferred embodiment, before secondary phosphine or secondary phosphine oxide and cation precursor solution, anion
Liquid solution synchronized mixes.The preparation method of alloy nanometer crystals includes step：By secondary phosphine or secondary phosphine oxide including at least two
The cation precursor solution of metal cation, the anionic pre-cursors solution mixing including chalcogen, make cation precursor and yin
Ion precursor reacts to form alloy nanometer crystals of the invention in the solution system containing secondary phosphine or secondary phosphine oxide.
In addition, in the present invention, added secondary phosphine or secondary phosphine oxide in the step of preparing alloy nanometer crystals can be with
It is then added in reaction system with after the mixing of at least one of following substance, including：Alkane, alkene, halogenated hydrocarbons, aromatic hydrocarbon,
Ethers, amine, ketone, esters.
Wherein, alkane includes at least one of following substance：1- octadecane, 1- heptadecane, 1- hexadecane, 1- 12
Alkane, the 1- tetradecane, 1- tridecane, 1- pristane, 1- phytane, 1- pentadecane, paraffin, 1- eicosane, 1- octacosane, 1- 20
Four alkane；The alkene includes at least one of following substance：1- octadecene, 1- dodecylene, cetene, 1- 14
Carbene, 1- heptadecene, 19 carbene of 1-, 1- eicosylene, 1- tridecylene, 1- pentadecane alkene；The amine includes as follows
At least one of substance：Hexadecylamine, octadecylamine, tetradecylamine, decyl amine, lauryl amine, hendecane
Base amine, tridecyl amine, 1,12- diamino dodecane, 1,18- diamino octadecane, 1,16- diamino hexadecane, 1,14- bis-
Amino tetradecylamine, oleyl amine；The lipid includes at least one of following substance：Stearyl, acetic acid dodecyl ester, second
Sour cetyl ester, acetic acid eicosane base ester, pentadecane base ester, heptadecane base ester.
In one preferred embodiment, secondary phosphine or secondary phosphine oxide are dissolved in 1- octadecene in advance, then will
It is added in reaction system, keeps cation precursor and anionic pre-cursors molten in the 1- octadecene of secondary phosphine or secondary phosphine oxide
It reacts to form alloy nanometer crystals of the invention in liquid.
The general formula of secondary phosphine in the present invention is PHR2, the general formula of secondary phosphine oxide is R2P(O)H.Wherein, R includes carbon atom
The substitution of the alkyl or carbon atom number 5-18 of the substitution or straight-chain or branching that do not replace of number 1-12 or not
Aryl.In one preferred embodiment, secondary phosphine includes dimethyl phosphine, diethyl phosphine, dipropyl phosphine, dibutyl phosphine, two uncles
Butyl phosphine, dihexyl phosphine, dicyclohexylphosphontetrafluoroborate, dioctyl phosphine, di-n-octyl phosphine, diisooctyl phosphine, diphenylphosphine, xylyl phosphine
At least one of, secondary phosphine oxide includes dimethyl phosphine oxide, diethyl phosphine oxide, dipropyl phosphine oxide, two fourths
Base phosphine oxide, di-t-butyl phosphine oxide, dihexyl phosphine oxide, dicyclohexyl phosphine oxide, dioctyl phosphine oxide, two
At least one of n-octyl phosphine oxide, diisooctyl phosphine oxide, diphenyl phosphorus oxygen, xylyl phosphorus oxygen.
Cation precursor solution in the present invention is dissolved in the first solvent by least two metal front salts to be formed, metal
Metal cation in precursor salt includes at least one of following metallic element：Zn,Cd,Hg,Mg,Mn,Ni,In,Ga,Pb,
Sn, Bi, Cu, Ag, metal front salt include at least one of following compound：Fluoride, chloride, bromide, iodide,
Sulfonated bodies, salicylate, phosphate, lactate, sulfate, carbonate, nitrate, nitrite, borate, citrate,
Arsenate, arsenite, thiosulfate, sulphite, bisulfites, tartrate, oxalates, formates, acetate,
Propionate, butyrate, valerate, caproate, enanthate, caprylate, pelargonate, caprate, undecylate, dodecanoate, ten
Trisalt, tetradecanoate, pentadecanoic acid salt, palmate, margarate, octadecanoate, acrylates, butenoate, penetenoic acid
Salt, hexene hydrochlorate, heptene hydrochlorate, octene hydrochlorate, nonenoate, decenoate, undecylenate salt, laurylene hydrochlorate, tridecylene
Hydrochlorate, tetradecene hydrochlorate, pentadecylenic acid salt, hexadecylene hydrochlorate, heptadecenoic acid salt and Monoethanolamine Oleate, the first solvent include alkane
At least one of hydrocarbon, alkene, halogenated hydrocarbons, aromatic hydrocarbon, ethers, amine, ketone and esters.
In one preferred embodiment, metal front salt includes zinc chloride, zinc bromide, zinc iodide, zinc sulfate, carbonic acid
Zinc, zinc nitrate, zinc acetate, zinc stearate, zinc oleate, ten sour zinc, zinc undecylenate, tetradecylic acid zinc, hexadecylic acid zinc, caddy,
Cadmium sulfate, cadmium carbonate, cadmium nitrate, cadmium oxalate, cadmium acetate, cadmium stearate, cadmium oleate, mercury chloride, mercuric sulfate, carbonic acid mercury, nitric acid
Mercury, mercuric acetate, mercuric stearte, magnesium chloride, magnesium sulfate, magnesium carbonate, magnesium nitrate, magnesium acetate, magnesium stearate, tetradecylic acid magnesium, chlorination
Manganese, manganous bromide, manganese iodide, manganese sulfate, manganese carbonate, manganese nitrate, manganese acetate, nickel chloride, nickelous bromide, nickel iodide, nickel sulfate, carbonic acid
Nickel, nickel nitrate, nickel acetate, nickel stearate, oleic acid nickel, indium acetate, carbonic acid indium, indium nitrate, inidum chloride, indium bromide, indium iodide, height
Chloric acid indium, stearic acid indium, tetradecylic acid indium, gallium chloride, gallium nitrate, acetic acid gallium, oleic acid gallium, stearic acid gallium, lead chloride, lead bromide,
Lead iodide, carboxylic acids of lead, lead borate, plumbi nitras, lead phosphate, lead oxalate, lead sulfate, sulfonic acid lead, stannic chloride, STANNOUS SULPHATE CRYSTALLINE, carbonic acid tin,
Nitric acid tin, bismuth chloride, bismuth sulfate, waltherite, bismuth nitrate, copper chloride, copper sulphate, copper carbonate, copper nitrate, copper acetate, silver chlorate,
At least one of silver bromide and silver iodide.
Anionic pre-cursors solution in the present invention is dissolved in the second solvent by sulfur family precursor to be formed, the sulphur in sulfur family precursor
Race's element includes at least one of S, Se, Te.In one preferred embodiment, sulfur family precursor includes elemental sulfur, alkyl
Mercaptan, vulcanization trialkyl phosphine, vulcanization trialkenyl phosphine, alkyl amino sulfide, alkenyl amino sulfide, hydrogen sulfide, elemental selenium, selenium
Change trialkyl phosphine, selenizing trialkenyl phosphine, alkyl amino selenides, alkenyl amino selenides, hydrogen selenide, simple substance tellurium, three alkane of telluride
Base phosphine, telluride trialkenyl phosphine, alkyl amino tellurides and at least one of alkenyl amino tellurides and hydrotelluric acid.Second solvent
Including tertiary phosphine, the general formula of tertiary phosphine is PR3, wherein R includes the substitution of carbon atom number 1-12 or the straight-chain or branching that do not replace
Alkyl or carbon atom number 5-18 substitution or the aryl that does not replace.In one preferred embodiment, tertiary phosphine includes
Trimethyl-phosphine, triethyl phosphine, tripropyl phosphine, tributylphosphine, tri-n-butyl phosphine, tri-tert-butylphosphine, three hexyl phosphines, thricyclohexyl
At least one of phosphine, tri octyl phosphine, tri-n-octyl phosphine, triphenylphosphine, trimethylphenyl phosphine.
In one preferred embodiment, the second solvent in the present invention only includes tertiary phosphine.
In another preferred embodiment, the present invention in the second solvent include in tertiary phosphine and following substance at least
It is a kind of：Alkane, alkene, halogenated hydrocarbons, aromatic hydrocarbon, ethers, amine, ketone, esters.
It should be noted that according to a preferred embodiment of the invention, during preparing alloy nanometer crystals, instead
The molar ratio of secondary phosphine or secondary phosphine oxide and tertiary phosphine in system is answered to be no more than 0.5.Within this range, alloy nanometer crystals
Level structure can be regulated and controled well, and the product obtained is still able to maintain preferable photoluminescent property.
By solvent used in the above-mentioned preparation step of observation it can be found that the first solvent in cation precursor solution
For at least one of alkane, alkene, halogenated hydrocarbons, aromatic hydrocarbon, ethers, amine, ketone, esters；In anionic pre-cursors solution
Second solvent includes tertiary phosphine, can also include alkane, alkene, halogenated hydrocarbons, aromatic hydrocarbon, ethers, amine, ketone, in esters extremely
Few one kind；Added secondary phosphine or secondary phosphine oxide in the preparation of alloy nanometer crystals, can be with alkane, alkene, halogenated hydrocarbons, virtue
It is then added in reaction system after the mixing of at least one of fragrant hydrocarbon, ethers, amine, ketone, esters.Therefore, alloy is being prepared
In nanocrystalline process, solvent-alkane in solution system, alkene, halogenated hydrocarbons, aromatic hydrocarbon, ethers, amine, ketone, esters
At least one of, cation precursor solution can be derived from, or can be before cation precursor solution and anion
Liquid solution or/and added secondary phosphine or secondary phosphine oxide.
In a preferred embodiment of the invention, cation precursor solution is that zinc oleate and cadmium oleate are dissolved in 1-
Solution in octadecene, anionic pre-cursors solution are the Se solution of tri-n-octyl phosphine dissolution, and that adds into reaction system is secondary
Phosphine or secondary phosphine oxide are diphenyl phosphorus oxygen, the Se for dissolving zinc oleate/cadmium oleate -1- octadecene and tri-n-octyl phosphine,
It reacts in the 1- octadecene solution containing diphenyl phosphorus oxygen, it is nanocrystalline to obtain ZnCdSe.In another of the invention
In preferred embodiment, cation precursor solution is that zinc acetate and cadmium oxalate are dissolved in the solution in 1- octadecene, yin from
Sub- precursor solution is the S solution that tri-tert-butylphosphine and oleyl amine dissolve, the secondary phosphine added into reaction system or secondary phosphine oxide
For the 1- octadecene solution of dioctyl phosphine, dissolve zinc acetate/cadmium oxalate -1- octadecene and tri-tert-butylphosphine and oleyl amine
S reacts in the solution containing dioctyl phosphine, it is nanocrystalline to obtain ZnCdSe.
It should be noted that " cation precursor solution is dissolved in the first solvent by least two metal front salts to the present invention
In the step of middle formation ", " anionic pre-cursors solution is dissolved in the second solvent by sulfur family precursor and is formed ", keep metal front salt molten
Solution is dissolved in the dissolution mechanism in the second solvent in the first solvent, sulfur family precursor, including but not limited to stirring, ultrasound, heating etc.
Means.
In the present invention, cation precursor and anionic pre-cursors are sent out in the solution system containing secondary phosphine or secondary phosphine oxide
The range of reaction temperature that raw reaction forms the alloy nanometer crystals is 180-350 DEG C, reaction time range 0.01-48h.For
The selection of more specific reaction temperature and reaction time, can synthesis condition, selected solvent according to different alloy nanometer crystals
Boiling point, desired target product the parameters such as partial size wavelength carry out adjustment appropriate.
In one preferred embodiment, the alloy nanometer crystals of desired preparation are ZnCdSe, the fluorescence of target product
Launch wavelength is 560nm, and selected solvent is 1- octadecene in reaction.In order to obtain target product, by the temperature of reaction
Control makes reaction keep the temperature 20min at such a temperature in the range of 280-320 DEG C.In another preferred embodiment,
The alloy nanometer crystals of desired preparation are CdSeS, and the fluorescence emission wavelengths of target product are 490nm, selected solvent in reaction
It is similarly 1- octadecene.In order to obtain target product, the temperature of reaction is controlled in the range of 200-240 DEG C, and is made anti-
10min should be kept the temperature at such a temperature.
In the present invention, secondary phosphine or secondary phosphine oxide are added in the preparation of alloy nanometer crystals, can increase sulfur family precursor
Activity, improve nanocrystalline alloying level, and finally change nanocrystalline level structure.Technical side through the invention
Case, by different amounts of secondary phosphine or secondary phosphine oxide or secondary phosphine or secondary phosphine oxide and alkane, alkene, halogenated hydrocarbons, fragrance
The mixture obtained after the mixing of at least one of hydrocarbon, ethers, amine, ketone, esters, it is molten with the cation precursor of fixed amount
Liquid, fixed amount anionic pre-cursors solution mix in an identical manner, and reacted, can be obtained under identical experiment condition
Obtain the different alloy nanometer crystals of fluorescence emission wavelengths.
In one preferred embodiment, by the 1- octadecene containing diphenyl phosphorus oxygen of 0.1 equivalent, 2 equivalents
The mixing of the tri-n-octyl phosphine solution of Zn/Cd metal precursor and 1 equivalent Se, reacts, the ZnCdSe of acquisition under conditions of 300 DEG C
Nanocrystalline fluorescence emission peak is at 520nm.In another preferred embodiment, 0.3 equivalent is contained into diphenylphosphine
The tri-n-octyl phosphine solution of the 1- octadecene of oxygen, the Zn/Cd metal precursor of 2 equivalents and 1 equivalent Se mixes, at 300 DEG C
Under the conditions of react, the ZnCdSe of acquisition nanocrystalline fluorescence emission peak is at 500nm.Contain hexichol be only added 0.1 equivalent
The 1- octadecene of base phosphorus oxygen is compared the step of preparing alloy nanometer crystals, and the 1- containing diphenyl phosphorus oxygen of 0.3 equivalent is added
Blue shift has occurred in the fluorescence emission wavelengths of the preparation step of octadecene alloy nanometer crystals obtained.
It further include removing unreacted raw material after preparing alloy nanometer crystals to improve the optical property of alloy nanometer crystals
And the step of other impurities, specifically include separation, purification.In one preferred embodiment, end reaction liquid is cooled to
Room temperature, is added extractant, and isolated extract liquor adds acetone precipitation, obtains the higher alloy nanometer crystals of purity.
In addition, in the present invention, for different applications, it can choose and continue various have on the surface of alloy nanometer crystals
Machine or inorganic coating.Cladding process reacts item with required when preparing organic or inorganic coating nanocrystalline in the prior art
Part is identical, and the application does not do further specific limit to this.
According to another aspect of the present invention, a kind of alloy nanometer crystals are provided, size, pattern are uniform, and monodispersity is good,
Fluorescence quantum yield is high, can be widely applied to the fields such as opto-electronic device and biomedicine.In addition, the present invention also provides one
The method of kind regulation alloy nanometer crystals fluorescence emission wavelengths blue shift is certain by adding in the preparation of above-mentioned alloy nanometer crystals
The secondary phosphine or secondary phosphine oxide of amount can make alloy nanometer crystals fluorescence emission wavelengths blue shift.Regulation method of the invention, can be with
The photoluminescent property for quickly adjusting alloy nanometer crystals, without changing other reaction raw materials proportions and reaction condition.
Below the present invention will be further illustrated by specific embodiments and the drawings.Its purpose, which is only that, more fully understands this
The content of invention, the protection scope being not intended to limit the present invention.It should be noted that in the absence of conflict, in the application
Feature in embodiment and embodiment can be combined with each other.
The present embodiment is implemented based on technology of the invention, gives detailed embodiment and operating procedure, but this
The protection scope of invention is not limited to following embodiments.If without specified otherwise, technological means used in the embodiment of the present invention is
Conventional means well known to those skilled in the art.The present embodiment only by taking ZnCdSe alloy nanometer crystals as an example, provides one kind
ZnCdSe nanocrystalline preparation method analyzes products therefrom by adjusting the dosage of added secondary phosphine or secondary phosphine oxide
The situation of change of fluorescent characteristic.According to band theory, synchronous variation is had occurred in ZnCdSe nanocrystalline level structure.In fact,
Preparation method and control measures of the invention is same to alloy nanometer crystals such as Hg, Mg, Mn, Ni, In, Ga, Pb, Sn, Bi, Cu, Ag
It is applicable in.
Comparative example 1
S1, cation precursor solution is prepared：
Zn(OA)2-Cd(OA)2Mix precursor solution：
Take the 1- octadecene of 0.1 mM of (mmol) CdO, 1 mM of (mmol) ZnO, 2mL oleic acid (OA) and 8mL in
It is mixed in glass container, under inert atmosphere, is heated to 300 DEG C and stirs, make it completely dissolved, Zn (OA) is prepared2-Cd
(OA)2Precursor solution is mixed, is stored in spare in nitrogen inert atmosphere；
S2, anionic pre-cursors solution is prepared：
Se-TOP sulfur family precursor solution：
10 mMs of (mmol) Se and 5mL tri-n-octyl phosphines (TOP) are taken to mix in glass container, ultrasound is molten after mixing
Solution, obtains Se-TOP sulfur family precursor solution；
S3, ZnCdSe nanocrystalline preparation：
The Se-TOP sulfur family precursor solution prepared in 0.8mL S2 is taken to be injected into the Zn (OA) prepared in S12-Cd(OA)2It is mixed
It closes in precursor solution, is heated to 300 DEG C and stirs, react 10min, cooling terminates reaction, obtains the nanocrystalline sample 1 of ZnCdSe
(I), its transmission electron microscope (TEM) of sampling and testing, ultraviolet-visible absorption spectroscopy (UV-Vis) and fluorescence emission spectrum (PL).
Embodiment 1
On the basis of comparative example 1, embodiment 1 is added to secondary phosphine oxide into reaction system.Wherein, in embodiment 1
Step S1, step S2 it is identical as step S1, the step S2 in comparative example 1.
S3, solution of the preparation containing secondary phosphine oxide：
Diphenyl phosphorus oxygen solution：
It takes the 1- octadecene of 5 mMs of (mmol) diphenyl phosphorus oxygens and 10mL to mix in glass container, surpasses after mixing
Sound dissolution, obtains diphenyl phosphorus oxygen solution；
S4, ZnCdSe nanocrystalline preparation：
The diphenyl phosphorus oxygen solution prepared in 0.1mL S3 is taken, the Zn (OA) prepared in S1 is added drop-wise to2-Cd(OA)2Before mixing
In liquid solution, then the Se-TOP sulfur family precursor prepared in 0.8mL S2 is taken to be injected into above-mentioned mixed liquor, is heated to 300 DEG C and stirs
It mixes, reacts 10min, cooling terminates reaction, obtains the nanocrystalline sample 2 (II) of ZnCdSe, its transmission electron microscope of sampling and testing
(TEM), ultraviolet-visible absorption spectroscopy (UV-Vis) and fluorescence emission spectrum (PL).
Embodiment 2
It is substantially the same manner as Example 1, it is different in, the additional amount of the secondary phosphine oxide added into reaction system.Its
In, the step S1, step S2, step S3 in embodiment 2 are identical as step S1, step S2, the step S3 in embodiment 1.
S4, ZnCdSe nanocrystalline preparation：
The diphenyl phosphorus oxygen solution prepared in 0.3mL S3 is taken, the Zn (OA) prepared in S1 is added drop-wise to2-Cd(OA)2Before mixing
In liquid solution, then the Se-TOP sulfur family precursor prepared in 0.8mL S2 is taken to be injected into above-mentioned mixed liquor, is heated to 300 DEG C and stirs
It mixes, reacts 10min, cooling terminates reaction, obtains the nanocrystalline sample 3 (III) of ZnCdSe, its transmission electron microscope of sampling and testing
(TEM), ultraviolet-visible absorption spectroscopy (UV-Vis) and fluorescence emission spectrum (PL).
Embodiment 3
It is substantially the same manner as Example 1, it is different in, the additional amount of the secondary phosphine oxide added into reaction system.Its
In, step S1, step S2, step S3 in embodiment 3 and step S1, step S2, the step S3 in embodiment 1 are also identical.
S4, ZnCdSe nanocrystalline preparation：
The diphenyl phosphorus oxygen Solutions Solution prepared in 1mL S3 is taken, the Zn (OA) prepared in S1 is added drop-wise to2-Cd(OA)2Mixing
In precursor solution, then the Se-TOP sulfur family precursor prepared in 0.8mL S2 is taken to be injected into above-mentioned mixed liquor, is heated to 300 DEG C simultaneously
Stirring, reacts 10min, and cooling terminates reaction, obtains the nanocrystalline sample 4 (IV) of ZnCdSe, its transmission electron microscopy of sampling and testing
Mirror (TEM), ultraviolet-visible absorption spectroscopy (UV-Vis) and fluorescence emission spectrum (PL).
Embodiment 4
S1, cation precursor solution is prepared：
Zinc acetate-cadmium oxalate mixing precursor solution：
It takes cadmium oxalate, zinc acetate, oleyl amine and 1- octadecene to mix in glass container, under inert atmosphere, is heated to 320
DEG C and stir, make it completely dissolved, obtain zinc acetate-cadmium oxalate mixing precursor solution, be stored in spare in nitrogen inert atmosphere；
S2, anionic pre-cursors solution is prepared：
S-TPP sulfur family precursor solution：
Alkyl hydrosulfide and triphenylphosphine is taken to mix in glass container, ultrasonic dissolution after mixing obtains S-TPP sulfur family precursor
Solution；
S3, ZnCdSe nanocrystalline preparation：
1 mM of (mmol) di-n-octyl phosphine is added drop-wise in the S-TPP sulfur family precursor solution prepared in S2, then is taken in S1
The zinc acetate of preparation-cadmium oxalate mixing precursor solution is injected into above-mentioned mixed liquor, is heated to 320 DEG C and is stirred, reaction
20min, cooling terminate reaction, obtain the nanocrystalline sample of ZnCdSe.
Nanocrystalline sample I, II, III, IV sampling and testing of ZnCdSe that Fig. 1 is comparative example 1, is prepared in embodiment 1 to 3
UV-visible absorption spectrum.Fig. 2 be comparative example 1, the nanocrystalline sample I, II of ZnCdSe prepared in embodiment 1 to 3, III,
The fluorescence emission spectrogram of compound of IV sampling and testing.
Wherein, comparative example 1, the first absorption peak of the nanocrystalline sample I-IV of 1 to 3 gained ZnCdSe of embodiment and emission peak be such as
Under：
| Sample ID | First absorption peak (nm) | Emission peak (nm) |
| I | 550 | 559 |
| II | 513 | 520 |
| III | 499 | 507 |
| IV | 467 | 479 |
As " diphenyl phosphorus oxygen solution " additional amount increases, blue shift is had occurred in the nanocrystalline fluorescence spectrum of ZnCdSe：By Huang
Green (PL=559nm) blue shift blue light (PL=479nm) is arrived, and maintains good half-peak breadth and quantum yield.
Nanocrystalline sample I, II, III, IV sampling and testing of ZnCdSe that Fig. 3 is comparative example 1, is prepared in embodiment 1 to 3
Transmission electron microscope figure.It can be seen from the figure that the size of ZnCdSe nanocrystalline sample I, II, III, IV, pattern are uniform, and
Dispersity is good, without apparent agglomeration.
In addition, the operating procedure of embodiment 4 is similarly obtained the nanocrystalline sample of ZnCdSe.With no addition " di-n-octyl phosphine "
The test data of experiment of secondary phosphine is compared, and apparent blue shift also has occurred in the fluorescence emission wavelengths of nanocrystalline sample obtained.
The above result shows that under identical reaction conditions, the dosage of fixed cation precursor, anionic pre-cursors is only led to
Addition secondary phosphine or secondary phosphine oxide are crossed, blue shift occurs for the fluorescence emission wavelengths that obtained ZnCdSe can be made nanocrystalline, and
It is able to maintain good half-peak breadth and quantum yield.During practical operation, as Cd, Zn, Se in further regulation raw material
When the ratio and secondary phosphine of three and the type and dosage of secondary phosphine oxide, alloy nanometer crystals fluorescence spectrum may be implemented entire
The adjusting of visible light region.
Obviously, the above embodiments are merely examples for clarifying the description, and does not limit the embodiments.It is right
For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of variation or
It changes.There is no necessity and possibility to exhaust all the enbodiments.And it is extended from this it is obvious variation or
Variation is still in the protection scope of this invention.In addition, the term occurred in the present invention is used for technical solution of the present invention
It illustrates and understands, can not be construed as limiting the invention.
Claims (18)
1. a kind of preparation method of alloy nanometer crystals, the preparation method include step：
S1, the cation precursor solution including at least two metal cations is provided；
S2, anionic pre-cursors solution is provided, the anion includes chalcogen；
S3, the cation precursor solution and the anionic pre-cursors solution are mixed to form alloy nanometer crystals；
It is characterized in that, the preparation method further includes the steps that adding secondary phosphine or secondary phosphine oxide, so that the cation
Precursor and the anionic pre-cursors react in the solution system containing the secondary phosphine or secondary phosphine oxide to be formed it is described
Alloy nanometer crystals.
2. preparation method according to claim 1, it is characterised in that：The secondary phosphine or secondary phosphine oxide are added to S1 step
In cation precursor solution described in rapid.
3. preparation method according to claim 1, it is characterised in that：The secondary phosphine or secondary phosphine oxide are added to S2 step
In anionic pre-cursors solution described in rapid.
4. preparation method according to claim 1, it is characterised in that：The secondary phosphine or secondary phosphine oxide and the sun from
Sub- precursor solution, the anionic pre-cursors solution synchronized mixes.
5. according to claim 1, preparation method described in 2,3,4, it is characterised in that：The secondary phosphine or secondary phosphine oxide and with
It is added again after the mixing of at least one of lower substance：Alkane, alkene, halogenated hydrocarbons, aromatic hydrocarbon, ethers, amine, ketone, esters.
6. preparation method according to claim 1, it is characterised in that：The general formula of the secondary phosphine is PHR2, the secondary phosphine oxidation
The general formula of object is R2P (O) H, wherein R includes the alkyl of carbon atom number 1-12 or the aryl of carbon atom number 5-18.
7. preparation method according to claim 6, it is characterised in that：The secondary phosphine includes dimethyl phosphine, diethyl phosphine, two
Propyl phosphine, dibutyl phosphine, di-t-butyl phosphine, dihexyl phosphine, dicyclohexylphosphontetrafluoroborate, dioctyl phosphine, di-n-octyl phosphine, diisooctyl
At least one of phosphine, diphenylphosphine, xylyl phosphine, the secondary phosphine oxide include dimethyl phosphine oxide, diethyl phosphine
Oxide, dipropyl phosphine oxide, dibutyl phosphine oxide, di-t-butyl phosphine oxide, dihexyl phosphine oxide, dicyclohexyl
Phosphine oxide, dioctyl phosphine oxide, di-n-octyl phosphine oxide, diisooctyl phosphine oxide, diphenyl phosphorus oxygen, xylyl
At least one of phosphorus oxygen.
8. preparation method according to claim 1, it is characterised in that：The metal cation includes in following metallic element
At least one：Zn,Cd,Hg,Mg,Mn,Ni,In,Ga,Pb,Sn,Bi,Cu,Ag.
9. preparation method according to claim 1, it is characterised in that：The chalcogen include in S, Se, Te at least
It is a kind of.
10. preparation method according to claim 1, it is characterised in that：The cation precursor solution is by least two gold medals
Category precursor salt, which is dissolved in the first solvent, to be formed, and first solvent includes alkane, alkene, halogenated hydrocarbons, aromatic hydrocarbon, ethers, amine
At least one of class, ketone and esters, the metal front salt include at least one of following compound：Fluoride, chlorine
Compound, bromide, iodide, sulfonated bodies, salicylate, phosphate, lactate, sulfate, carbonate, nitrate, nitrous acid
Salt, borate, citrate, arsenate, arsenite, thiosulfate, sulphite, bisulfites, tartrate, grass
Hydrochlorate, formates, acetate, propionate, butyrate, valerate, caproate, enanthate, caprylate, pelargonate, caprate, ten
One hydrochlorate, dodecanoate, tridecanoic acid salt, tetradecanoate, pentadecanoic acid salt, palmate, margarate, octadecanoate, acrylic acid
Salt, butenoate, pentenoic acid salt, hexene hydrochlorate, heptene hydrochlorate, octene hydrochlorate, nonenoate, decenoate, undecylenate salt,
Laurylene hydrochlorate, tridecylene hydrochlorate, tetradecene hydrochlorate, pentadecylenic acid salt, hexadecylene hydrochlorate, heptadecenoic acid salt and octadecenic acid
Salt.
11. preparation method according to claim 1, it is characterised in that：The anionic pre-cursors solution is molten by sulfur family precursor
Solution is formed in the second solvent, and second solvent includes tertiary phosphine, and the general formula of the tertiary phosphine is PR3, wherein R indicates carbon atom
The alkyl of number 1-12 or the aryl of carbon atom number 5-18.
12. preparation method according to claim 11, it is characterised in that：The tertiary phosphine include trimethyl-phosphine, triethyl phosphine,
Tripropyl phosphine, tributylphosphine, tri-n-butyl phosphine, tri-tert-butylphosphine, three hexyl phosphines, tricyclohexyl phosphine, tri octyl phosphine, three n-octyls
At least one of phosphine, triphenylphosphine, trimethylphenyl phosphine.
13. preparation method according to claim 11, it is characterised in that：The secondary phosphine or secondary phosphine oxide and the uncle
The molar ratio of phosphine is no more than 0.5.
14. preparation method according to claim 11, it is characterised in that：Second solvent further includes in following substance
It is at least one：Alkane, alkene, halogenated hydrocarbons, aromatic hydrocarbon, ethers, amine, ketone, esters.
15. preparation method according to claim 1, it is characterised in that：Range of reaction temperature in step S3 is 180-350
℃。
16. preparation method according to claim 1, it is characterised in that：Reaction time range in step S3 is 0.01-
48h。
17. a kind of alloy nanometer crystals, it is characterised in that：It is made by the preparation method any in claim 1-16.
18. a kind of method of regulation alloy nanometer crystals fluorescence emission wavelengths blue shift, the alloy nanometer crystals are prepared by the following steps：
S1, the cation precursor solution including at least two metal cations is provided；
S2, anionic pre-cursors solution is provided, the anion includes chalcogen；
S3, the cation precursor solution and the anionic pre-cursors solution are mixed to form alloy nanometer crystals；
It is characterized in that, further include the steps that adding secondary phosphine or secondary phosphine oxide in the preparation of the alloy nanometer crystals, so that
The cation precursor and the anionic pre-cursors occur anti-in the solution system containing the secondary phosphine or secondary phosphine oxide
The alloy nanometer crystals should be formed, keep the alloy nanometer crystals fluorescence emission wavelengths blue by addition secondary phosphine or secondary phosphine oxide
It moves.
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| CN111909698B (en) * | 2019-05-07 | 2023-02-10 | 纳晶科技股份有限公司 | Copper-doped alloy quantum dot, preparation method thereof and quantum dot photoelectric device |
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