CN109054804A - Nuclear shell structured nano crystalline substance and preparation method thereof - Google Patents

Nuclear shell structured nano crystalline substance and preparation method thereof Download PDF

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CN109054804A
CN109054804A CN201810934092.9A CN201810934092A CN109054804A CN 109054804 A CN109054804 A CN 109054804A CN 201810934092 A CN201810934092 A CN 201810934092A CN 109054804 A CN109054804 A CN 109054804A
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shell
nanocrystal
zinc
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王允军
朱凯文
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Suzhou Xingshuo Nanotech Co Ltd
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Abstract

It is brilliant that this application discloses a kind of nuclear shell structured nanos, and the first shell of the Zn doping including nanocrystal, the cladding nanocrystal, the second shell for coating first shell, the composition of the nanocrystal is Ag2S, the composition of first shell are ZnxAg2(1‑x)S, the composition of second shell are ZnS, wherein 0 < x < 1.The nuclear shell structured nano trichite light efficiency of the application preparation is high, and fluorescence emission peak is continuous controllable between 1000-1200nm, solves existing Ag2S nanocrystalline stability is weak, is easy the problem reunited, luminous efficiency is lower.

Description

Nuclear shell structured nano crystalline substance and preparation method thereof
Cross reference to related applications
This application claims entitled " a kind of nuclear shell structured nano crystalline substance and preparation method thereof " for submitting on September 20th, 2017 The priority of Chinese patent application " 201710851197.3 ", all the contents of the application are herein incorporated by reference.
Technical field
This application involves technical field of nanometer material preparation more particularly to a kind of nuclear shell structured nano crystalline substance and its preparation sides Method.
Background technique
Nanocrystalline is a kind of semiconductor nano material of three-dimensional dimension all between 1-20 nanometers, with half-peak width, The advantages that good light stability, controllable wavelength.Due to its special photoelectric property and excellent optical physics stability, pass through adjusting Nanocrystalline size adjusts nanocrystalline corresponding band gap, can adjust significantly its electricity, optical characteristics, therefore, only Emission wavelength can be adjusted by only adjusting nanocrystalline size, and it is made to show its excellent excitation purity and high shine Efficiency etc..
As a kind of outstanding fluorescence luminescent material, and nanocrystalline surface has the characteristics that be easy to modify, it is nanocrystalline Last century end, which is just attempted, to be applied in biomarker field.But with going deep into for research, the fluorescence of common transmitting visible region is received Meter Jing is shallow to tissue penetration depths and scattering is strong, is not able to satisfy the demand of biomarker, these disadvantages worker of advancing science opens Send out the nanocrystalline of the transmitting near infrared light strong to tissue penetration.The material of more common near-infrared nanocrystalline include PbS, CdHgTe、PbSe、Ag2S etc., but wherein most material all contains toxic heavy metal ingredient such as Cd, Pb and Hg, these are all limited Further applying for they is made.In comparison, Ag2S nanocrystalline is a kind of less toxic or even nontoxic ideal near-infrared material, Ag2The forbidden bandwidth of S is 0.9-1.1eV, it shows very excellent fluorescence in the launch window region of 1000-1400nm Property.
However due to Ag2S nanocrystalline size is smaller, and the coordination of surface atom is insufficient, unsaturated bond and dangling bond are more, So that Ag2S nanocrystalline fluorescence quantum efficiency is lower.
Summary of the invention
The application's is designed to provide a kind of nuclear shell structured nano crystalline substance and preparation method thereof, to solve existing Ag2S receives The lower problem of the brilliant fluorescence quantum efficiency of rice.
According to the one aspect of the application, it is brilliant to provide a kind of nuclear shell structured nano, including is received described in nanocrystal, cladding First shell of the Zn doping of meter Jing He, the second shell for coating first shell, the composition of the nanocrystal is Ag2S, The composition of first shell is ZnxAg2(1-x)S, the composition of second shell are ZnS, wherein 0 < x < 1.
Preferably, first shell passes through cation exchange by the Zn element in alkyl zinc or alkyl zinc complex Mode replaces Ag element in nanocrystal and is prepared.
Preferably, the nanocrystalline emission peak is in 1000-1200nm.
Preferably, contain ligand outside second shell, include at least one sulfydryl in the molecular structure of the ligand With at least one hydrophilic chain.
According to further aspect of the application, a kind of preparation method of nuclear shell structured nano crystalline substance is comprised the following processes: step Rapid 1, nanocrystal is prepared in oily phase；Step 2 is added the first zinc precursor into the nanocrystal, before first zinc The Zn element driven in body exchanges Ag element in the nanocrystal by cation, obtains the Zn being coated on outside the nanocrystal First shell of doping；Step 3, in the second shell of the first shell outer cladding；The composition of the nanocrystal is Ag2S, institute The composition for stating the first shell is ZnxAg2(1-x)S, the composition of second shell are ZnS, wherein 0 < x < 1.
Preferably, the process for preparing the nanocrystal includes: step 11, will contain Ag presoma and non-complexing solvent mixes It closes, makes the dissolution of presoma containing Ag, form solion containing Ag；Step 12 will contain S presoma and mix with the first ligand, it It is injected at 100-160 DEG C in the solion containing Ag afterwards, reacts 1-60min, obtain the nanocrystal；It is described to contain Ag Presoma includes at least one of silver carboxylate, the complex compound of silver；The presoma containing S includes S simple substance, the first ligand packet Include at least one of sulfhydryl compound, fatty acid, fatty amine, phosphine, phosphine oxide.
Preferably, the process for preparing first shell includes: to mix first zinc precursor with non-complexing solvent, First zinc precursor is dissolved, is injected at 100-160 DEG C in the nanocrystal later, 1-30min is reacted, it is described Zn element exchanges Ag element in the nanocrystal by cation in first zinc precursor, obtains being coated on the nanocrystal First shell of outer zinc doping；First zinc precursor includes alkyl zinc or alkyl zinc complex.
Preferably, the Ag element exchanged accounts for the molar ratio of total Ag element in the nanocrystal less than 0.2.
Preferably, the process for preparing second shell includes: to prepare the precursor solution of second shell, will be described The nanocrystal for coating the first shell is warming up to 180-300 DEG C, injects the precursor solution of second shell later, reacts 1- 30min obtains the second shell being coated on outside first shell；Contain the second zinc in the precursor solution of second shell Presoma, second zinc precursor include xanthopone, zinc diethyl dithiocarbamate, cetyl xanthic acid At least one of zinc, olefin(e) acid zinc.
It preferably, further include that the surface of second shell prepared in the step 3 by ligand exchange reaction is repaired The step of adoring hydrophilic ligand.
The utility model has the advantages that the application passes through in Ag2S nanocrystal outer cladding ZnxAg2(1-x)The first shell of S and ZnS second shell Layer, the nuclear shell structured nano for being prepared into high-luminous-efficiency is brilliant, and fluorescence emission peak is continuous controllable between 1000-1200nm, solves Existing Ag2S nanocrystalline stability is weak, is easy the problem reunited, luminous efficiency is lower.
Detailed description of the invention
Fig. 1 is the fluorescence emission spectrogram of compound of nuclear shell structured nano crystalline substance in the embodiment of the present application 1；
Fig. 2 is the fluorescence emission spectrogram of compound of nuclear shell structured nano crystalline substance in the embodiment of the present application 2；
Fig. 3 is Ag in nuclear shell structured nano crystalline substance and comparative example 1 in the embodiment of the present application 32S nanocrystalline fluorescence emission Spectrogram；
Fig. 4 is the transmission electron microscope figure of nuclear shell structured nano crystalline substance in the embodiment of the present application 3.
Specific embodiment
Below in conjunction with the application embodiment, technical solutions in the embodiments of the present application is described in detail, and is shown So, described embodiment is only a part of embodiment of the application, rather than whole embodiments.Based in the application Embodiment, those of ordinary skill in the art's every other implementation obtained without making creative work Mode belongs to the application protection scope.
The application provides a kind of nuclear shell structured nano crystalline substance, and first of the Zn doping including nanocrystal, cladding nanocrystal Shell, the second shell for coating the first shell, the composition of nanocrystal are Ag2S, the composition of the first shell are ZnxAg2(1-x)S, the The composition of two shells is ZnS, wherein 0 < x < 1.Nuclear shell structured nano crystalline substance with above structure can effectively solve Ag2S Defect caused by lattice match difference between nanocrystal and ZnS shell, the nuclear shell structured nano crystalline substance of the application preparation have height Quantum yield, and have preferable air stability, temperature stability and optical stability.
In one preferred embodiment, the size of nanocrystal be 1.5-10.0nm, the first shell with a thickness of 0.3-1.5nm, the second shell with a thickness of 1.5-4.5nm.By adjust the size of nanocrystal, the first shell thickness, the The parameters such as doping content of Zn element in the thickness of two shells and the first shell, can preferably adjust above-mentioned core-shell structure copolymer The position of structure nano crystalline substance emission peak, optimizes its fluorescence quantum yield and stability.
In order to improve Ag2The luminescent properties of S nanocrystal, in one preferred embodiment, Ag2S nanocrystal is to mix Miscellaneous nanocrystal, the element for doping preferably include at least one of Mn, CO, Ni, Fe, In, Cu, Au, I, Cl.
The application nuclear shell structured nano crystalline substance in, it is therein it is critical that, first in Ag2The surface of S nanocrystal Prepare ZnxAg2(1-x)Then the first shell of S recycles surface epitaxial growth method to realize ZnS shell in the height of the first shell layer surface Quality epitaxial growth.In one preferred embodiment, the first shell is by the Zn member in alkyl zinc or alkyl zinc complex Element replaces Ag element in nanocrystal by way of cation exchange and is prepared.
In one preferred embodiment, nanocrystalline launch wavelength is in 1000-1200nm.
In order to increase dispersibility and stability of the nuclear shell structured nano crystalline substance in water phase, in a preferred embodiment party In formula, contains ligand outside the second shell, include at least one sulfydryl and at least one hydrophilic chain in the molecular structure of ligand.Parent Water chain preferably includes polyglycol chain.
In another typical embodiment of the application, a kind of preparation method of nuclear shell structured nano crystalline substance is provided, is wrapped Include following process: step 1 prepares nanocrystal in oily phase；Step 2 is added the first zinc precursor into nanocrystal, and first Zn element in zinc precursor exchanges Ag element in nanocrystal by cation, obtains being coated on the Zn doping outside nanocrystal The first shell；Step 3, in first the second shell of shell outer cladding；Wherein, the composition of nanocrystal is Ag2S, the first shell Composition be ZnxAg2(1-x)S, the composition of the second shell are ZnS, wherein 0 < x < 1.
Step 1 is the preparation process of nanocrystal, compared to synthesis in water Ag2S nanocrystal, oil can mutually provide higher Reaction temperature effectively reduce Ag to improve nanocrystalline nucleation rate and crystallinity2The lattice of S nanocrystal lacks It falls into and surface defect, Ag in the application2S nanocrystal nanocrystal is prepared in oily phase.
In one preferred embodiment, Ag is prepared in the application2The process of S nanocrystal includes: step 11, will contain Ag presoma is mixed with non-complexing solvent, dissolves presoma containing Ag, forms solion containing Ag；Step 12 will contain S presoma It is mixed with the first ligand, is injected at 100-160 DEG C in the solion containing Ag later, reacts 1-60min, obtain Ag2S Nanocrystal.
Non-complexing solvent refers to preferably to be wrapped with the poor solvent of coordination abilities, non-complexing solvents such as metallic element such as Ag, Zn Include at least one of alkene, alkane, ethers.Specifically, alkene includes but is not limited to ten alkene of 1-, 1- endecatylene, 1- 12 Carbene, 1- tridecylene, tetradecene, 1- pentadecane alkene, cetene, 1- heptadecene, 1- octadecene, 1- 19 Carbene, 1- eicosylene；Alkane includes but is not limited to the alkane that carbon atom number is 6-20 including n-hexane, normal heptane, just pungent Alkane, n -nonane, n-decane, n-undecane, n-dodecane, n-tridecane, n-tetradecane, n-pentadecane, hexadecane, positive 17 Alkane, n-octadecane, NSC 77136, n-eicosane；Ethers includes but is not limited to the aliphatic ether that carbon atom number is 6-20.
Presoma containing Ag preferably includes at least one of silver carboxylate, complex compound of silver.Specifically, silver carboxylate preferably includes The saturation or unsaturated silver carboxylate that carbon atom number is 2-18；The complex compound of silver preferably includes diethyl-dithio amino first At least one of sour silver-colored, silver ion and complex compound, silver ion and the complex compound of amine of mercaptan.Silver carboxylate or silver in the application Complex compound the inorganic salts of silver can be dissolved in corresponding carboxylic acid or complexing agent and are prepared, silver-colored inorganic salts preferably wrap Include silver nitrate.
Presoma containing S preferably includes at least one of S simple substance, mercaptan, sulfur dioxide.In a specific embodiment In, S presoma is S simple substance.
First ligand preferably includes at least one of sulfhydryl compound, fatty acid, fatty amine, phosphine, phosphine oxide.Specifically, Sulfhydryl compound preferably includes at least one of n- dodecyl mereaptan, positive tetradecanylthioalcohol, spicy thioalcohol, trioctylphosphine mercaptan；Fatty acid Preferably include capric acid, hendecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, Heptadecanoic acide, At least one of stearic acid, arachic acid；Fatty amine preferably include ten amine, lauryl amine, tetradecy lamine, cetylamine, in octadecylamine At least one；Phosphine preferably includes tri octyl phosphine, tributylphosphine；Phosphine oxide preferably includes trioctylphosphine oxide (TOPO), tributylphosphine oxide.
In above-mentioned steps 11, in order to increase and promote Ag presoma in the dispersion of non-complexing solvent, Ag presoma it is molten Solution is preferably carried out in the condition of heating, ultrasound or stirring.It is excellent after the dissolution of Ag presoma will be contained in order to purify presoma containing Ag Choosing further includes the water removal deoxygenation to the solion containing Ag.
In above-mentioned steps 12, in order to increase Ag2The stability of S nanocrystal reduces hot environment to its optical property Influence, Ag2S nanocrystal is synthesized under the conditions of 100-160 DEG C.It can be effective by adjusting reaction temperature and reaction time Control Ag2The emission peak positions of S nanocrystal, in one preferred embodiment, reaction temperature are 100-120 DEG C, instead Preferably in 2-20min between seasonable.
Step 2 is the process in nanocrystal outer cladding Zn the first shell adulterated, in the specific embodiment of the application, First shell is to exchange Ag element in the nanocrystal by cation by the Zn element in the first zinc precursor to obtain.
In one preferred embodiment, the process for preparing the first shell includes: by the first zinc precursor and non-complexing Solvent mixing, dissolves the first zinc precursor, is injected into the nanocrystal at 100-160 DEG C later, reacts 1- 30min, Zn element exchanges Ag element in the nanocrystal by cation in the first zinc precursor, obtains being coated on nanocrystalline First shell of the zinc doping outside core.
In order to increase Ag2The stability of S nanocrystal reduces influence of the hot environment to its optical property, the first shell And it is prepared under lower temperature conditions.Ag is realized at low temperature in order to reach2Taking for Zn element occurs for S nanocrystal surface Generation, the first zinc precursor are selected from the higher substance of activity.In one preferred embodiment, the first zinc precursor includes alkyl Zinc or alkyl zinc complex；Specifically, zinc alkyl preferably include zinc methide, diethyl zinc, dipropyl zinc, dibutyl zinc, At least one of diaryl zine, alkyl zinc complex preferably include alkyl zinc and tetramethylethylenediamine or Isosorbide-5-Nitrae-dioxane Complex compound.
Since the first zinc precursor is the higher alkyl zinc of activity or alkyl zinc complex, as substitution Ag2S nanocrystal When middle Ag element, the first excessive zinc precursor will be quickly by Ag2S nanocrystal is substituted by ZnS completely.It is preferred at one In embodiment, the Ag element exchanged accounts for the molar ratio of total Ag element in nanocrystal less than 0.2, can be added by control The mole and Ag of Zn element in first zinc precursor2The mole of Ag element controls above-mentioned molar ratio in S nanocrystal.? In one preferred embodiment, the first shell is gradient-structure in the application, and gradient-structure refers to Ag2S nanocrystal Middle Ag element is gradually replaced by Zn element, from nanocrystal toward the direction of the second shell on, the concentration of Ag element is gradually reduced, and The concentration of Zn element gradually increases.
Step 3 is the process in first the second shell of shell outer cladding, in the specific embodiment of the application, the second shell For ZnS.By in Ag2The first shell of Zn doping is prepared outside S nanocrystal, is had between ZnS and the first shell in the application Preferable lattice.
In one preferred embodiment, the process of the second shell of preparation includes: that the presoma of the second shell of preparation is molten The nanocrystal for coating the first shell is warming up to 180-300 DEG C, injects the precursor solution of the second shell later, reacted by liquid 1-30min obtains the second shell being coated on outside the first shell.The presoma of second shell can be sulfur-containing compound containing zinc, It is also possible to the combination of the compound containing sulphur, the compound containing zinc respectively.
In order to guarantee the synthesis quality of the second shell presoma, the preparation temperature of the second shell is higher than first shell in the application The synthesis temperature of layer, the active activity less than the first zinc precursor of the second zinc precursor.In one preferred embodiment, The synthesis temperature of second shell is 180-230 DEG C.In one preferred embodiment, the second zinc precursor includes ethyl xanthan At least one of sour zinc, zinc diethyl dithiocarbamate, cetyl xanthic acid zinc, olefin(e) acid zinc.Activity lower the Two zinc precursors can preferably coat the first shell, while will not be to Ag2S nanocrystal damages.
After having coated the second shell, further include to nanocrystalline purifying, thus remove extra unreacted raw material and Surface ligand etc..In one preferred embodiment, nanocrystalline purifying includes adding ethyl alcohol or methanol isopolarity solvent After entering in former reaction product liquid, precipitated nanocrystals are brilliant, separate nanocrystalline process.
In one preferred embodiment, be prepared it is nanocrystalline after, further include being existed by ligand exchange reaction The step of surface modification hydrophilic ligand of second shell.In one preferred embodiment, the molecule knot of hydrophilic ligand It include at least one sulfydryl and at least one hydrophilic chain in structure, so that in nanocrystalline equal preferable dispersion in water phase.This It is nanocrystalline by can be adapted for the fields such as bio-imaging after ligand exchange reaction in application, in a preferred embodiment In, can further include in the molecular structure of hydrophilic ligand can with the specific position in conjunction with target molecule, such as when When target molecule is antibody, specific position is can be with the particular functional group in conjunction with antibody.
The application is described further below in conjunction with embodiment and comparative example.
Embodiment 1
(1) step 1: nanocrystal is prepared in oily phase:
170 milligrams of silver nitrates, 1 milliliter of oleic acid, 10 milliliters of n- dodecyl mereaptans, 30 milliliters of octadecylenes are added 100 milliliters In three-necked flask, deoxygenation is stirred and removed water, forms solion containing Ag.
S powder is mixed with oleyl amine solution, stirring dissolves S powder, obtains the S precursor solution that concentration is 1M.130 degrees Celsius Under, by 500 microlitres of S precursor solution heat injection solion containing Ag, 10min is reacted, Ag is obtained2S nanocrystal.
(2) step 2: diethyl zinc is mixed with octadecylene, obtains the diethyl zinc octadecene solution that concentration is 1M.130 Under degree Celsius, 0.2 milliliter of diethyl zinc octadecene solution heat is injected into Ag2In S nanocrystal solution, 30min is reacted, is obtained To being coated on Ag2Zn outside S nanocrystalxAg2(1-x)The first shell of S.
(3) under 3:220 degrees Celsius of step, the xanthopone heat that 5 milliliters of concentration is 1M is injected into and is coated with ZnxAg2(1-x)The Ag of the first shell of S2In S nanocrystal solution, 20min is reacted, obtains being coated on ZnxAg2(1-x)The first shell of S Outer the second shell of ZnS.
Embodiment 2
(1) step 1: nanocrystal is prepared in oily phase:
170 milligrams of silver nitrates, 1 milliliter of oleic acid, 10 milliliters of n- dodecyl mereaptans, 30 milliliters of octadecylenes are added 100 milliliters In three-necked flask, deoxygenation is stirred and removed water, forms solion containing Ag.
S powder is mixed with oleyl amine solution, stirring dissolves S powder, obtains the S precursor solution that concentration is 1M.130 degrees Celsius Under, by 500 microlitres of S precursor solution heat injection solion containing Ag, 10min is reacted, Ag is obtained2S nanocrystal.
(2) step 2: diethyl zinc is mixed with octadecylene, obtains the diethyl zinc octadecene solution that concentration is 1M.140 Under degree Celsius, 0.2 milliliter of diethyl zinc octadecene solution heat is injected into Ag2In S nanocrystal solution, 30min is reacted, is obtained To being coated on Ag2Zn outside S nanocrystalxAg2(1-x)The first shell of S.
(3) under 3:220 degrees Celsius of step, the xanthopone heat that 5 milliliters of concentration is 1M is injected into and is coated with ZnxAg2(1-x)The Ag of the first shell of S2In S nanocrystal solution, 25min is reacted, obtains being coated on ZnxAg2(1-x)The first shell of S Outer the second shell of ZnS.
Embodiment 3
(1) step 1: nanocrystal is prepared in oily phase:
170 milligrams of silver nitrates, 1 milliliter of oleic acid, 10 milliliters of n- dodecyl mereaptans, 30 milliliters of octadecylenes are added 100 milliliters In three-necked flask, deoxygenation is stirred and removed water, forms solion containing Ag.
S powder is mixed with oleyl amine solution, stirring dissolves S powder, obtains the S precursor solution that concentration is 1M.130 degrees Celsius Under, by 500 microlitres of S precursor solution heat injection solion containing Ag, 10min is reacted, Ag is obtained2S nanocrystal.
(2) step 2: diethyl zinc is mixed with octadecylene, obtains the diethyl zinc octadecene solution that concentration is 1M.150 Under degree Celsius, 0.2 milliliter of diethyl zinc octadecene solution heat is injected into Ag2In S nanocrystal solution, 30min is reacted, is obtained To being coated on Ag2Zn outside S nanocrystalxAg2(1-x)The first shell of S.
(3) under 3:220 degrees Celsius of step, the xanthopone heat that 5 milliliters of concentration is 1M is injected into and is coated with ZnxAg2(1-x)The Ag of the first shell of S2In S nanocrystal solution, 30min is reacted, obtains being coated on ZnxAg2(1-x)The first shell of S Outer the second shell of ZnS.
Comparative example 1
Preparation does not contain the Ag of shell2S is nanocrystalline:
170 milligrams of silver nitrates, 1 milliliter of oleic acid, 10 milliliters of n- dodecyl mereaptans, 30 milliliters of octadecylenes are added 100 milliliters In three-necked flask, deoxygenation is stirred and removed water, forms solion containing Ag.
S powder is mixed with oleyl amine solution, stirring dissolves S powder, obtains the S precursor solution that concentration is 1M.150 degrees Celsius Under, by 500 microlitres of S precursor solution heat injection solion containing Ag, 10min is reacted, Ag is obtained2S nanocrystal.
Fig. 1 is the launching light spectrogram of nuclear shell structured nano crystalline substance in embodiment 1, and fluorescence emission peak is near 1020nm；Figure 2 be the launching light spectrogram of nuclear shell structured nano crystalline substance in embodiment 2, and fluorescence emission peak is near 1080nm；Fig. 3 is embodiment 3 The Ag of shell is not contained in middle nuclear shell structured nano crystalline substance and comparative example 12S nanocrystalline launching light spectrogram shows corresponding hair respectively Peak value is penetrated near 1200nm and 1285nm；Fig. 4 is the transmission electron microscope figure of nuclear shell structured nano crystalline substance in embodiment 3.
It can be seen that the nanometer with nucleocapsid structure prepared using the technical solution of the application from above-mentioned characterization result Crystalline substance, has the characteristics that even size distribution, and fluorescence emission wavelengths are continuously adjusted within the scope of 1000-1200nm.From the knot of Fig. 3 Fruit can be seen that and the Ag without containing shell2S is nanocrystalline to be compared, the nuclear shell structured nano trichite light efficiency prepared in the application It significantly increases, the fluorescence intensity under the same terms improves at least 5 times.
The application passes through in Ag2S nanocrystal outer cladding ZnxAg2(1-x)The second shell of the first shell of S and ZnS, is prepared into height The nuclear shell structured nano of luminous efficiency is brilliant, meanwhile, fluorescence emission spectrum is unchanged after a long time placement for room temperature, shows good Physics and chemical stability.Since the nuclear shell structured nano crystalline substance of the application preparation does not contain heavy metal, while emission peak is located at Near infrared region can be widely used in the fields such as biological living imaging, biomarker.
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 It changes among still in the protection scope of the application.

Claims (10)

1. a kind of nuclear shell structured nano is brilliant, the first shell, the packet of the Zn doping including nanocrystal, the cladding nanocrystal The second shell of first shell is covered, the composition of the nanocrystal is Ag2The composition of S, first shell is ZnxAg2(1-x)S, the composition of second shell are ZnS, wherein 0 < x < 1.
2. nuclear shell structured nano according to claim 1 is brilliant, which is characterized in that first shell by alkyl zinc or Zn element in alkyl zinc complex replaces Ag element in nanocrystal by way of cation exchange and is prepared.
3. nuclear shell structured nano according to claim 1 is brilliant, which is characterized in that the nanocrystalline emission peak is in 1000- 1200nm。
4. nuclear shell structured nano according to claim 1 is brilliant, which is characterized in that contain ligand outside second shell, institute State in the molecular structure of ligand includes at least one sulfydryl and at least one hydrophilic chain.
5. a kind of preparation method of nuclear shell structured nano crystalline substance, which is characterized in that comprise the following processes:
Step 1 prepares nanocrystal in oily phase；
The first zinc precursor is added into the nanocrystal for step 2, the Zn element in first zinc precursor by sun from Son exchanges Ag element in the nanocrystal, obtains the first shell of the Zn being coated on outside nanocrystal doping；
Step 3, in the second shell of the first shell outer cladding；
The composition of the nanocrystal is Ag2S, the composition of first shell are ZnxAg2(1-x)S, the composition of second shell For ZnS, wherein 0 < x < 1.
6. preparation method according to claim 5, which is characterized in that the process for preparing the nanocrystal includes:
Step 11 will contain Ag presoma and mix with non-complexing solvent, make the dissolution of presoma containing Ag, and formation ion containing Ag is molten Liquid；
Step 12 will contain S presoma and mix with the first ligand, be injected into the solion containing Ag at 100-160 DEG C later In, 1-60min is reacted, the nanocrystal is obtained；
The presoma containing Ag includes at least one of silver carboxylate, the complex compound of silver；
The presoma containing S includes S simple substance, first ligand include sulfhydryl compound, fatty acid, fatty amine, phosphine, in phosphine oxide At least one.
7. preparation method according to claim 5, which is characterized in that the process for preparing first shell includes: by institute It states the first zinc precursor to mix with non-complexing solvent, is injected into institute at 100-160 DEG C after dissolving first zinc precursor It states in nanocrystal, reacts 1-30min, Zn element is exchanged in the nanocrystal by cation in first zinc precursor Ag element obtains the first shell of the zinc doping being coated on outside the nanocrystal；
First zinc precursor includes alkyl zinc or alkyl zinc complex.
8. preparation method according to claim 7, which is characterized in that the Ag element exchanged accounts for the nanocrystal In total Ag element molar ratio less than 0.2.
9. preparation method according to claim 5, which is characterized in that the process for preparing second shell includes: to prepare The nanocrystal of the first shell of the cladding is warming up to 180-300 DEG C, injected later by the precursor solution of second shell The precursor solution of second shell reacts 1-30min, obtains the second shell being coated on outside first shell；
Contain the second zinc precursor in the precursor solution of second shell, second zinc precursor includes ethoxy-dithioformic acid At least one of zinc, zinc diethyl dithiocarbamate, cetyl xanthic acid zinc, olefin(e) acid zinc.
10. preparation method according to claim 5, which is characterized in that further include by ligand exchange reaction in the step The step of surface modification hydrophilic ligand of second shell prepared in rapid 3.
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