CN102433124A - Nano-crystal fluorescent powder and preparation method thereof - Google Patents
Nano-crystal fluorescent powder and preparation method thereof Download PDFInfo
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- CN102433124A CN102433124A CN2011102595963A CN201110259596A CN102433124A CN 102433124 A CN102433124 A CN 102433124A CN 2011102595963 A CN2011102595963 A CN 2011102595963A CN 201110259596 A CN201110259596 A CN 201110259596A CN 102433124 A CN102433124 A CN 102433124A
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Abstract
The invention relates to nano-crystal fluorescent powder and a preparation method thereof. The invention belongs to the technical field of luminescent materials. The nano-crystal fluorescent powder is Cu-In-Znx-E/ZnS, wherein E=S or Se, and x is no smaller than 0. The preparation method comprises steps that: copper salt, indium salt, alkanethiol and octadecene are isolated from oxygen, mixed, and heated; long-chain alkyl organic acid is added to the product, the mixture is isolated from oxygen and is heated, such that a reaction source is obtained; zinc salt, long-chain alkyl organic amine and octadecene are isolated from oxygen, mixed, and heated, such that a zinc source is obtained; when E=S, the zinc source is added to the reaction source, and the mixture is heated, such that a colloidal solution 1 is obtained; when E=Se, selenium powder is dissolved, and an obtained selenium source is added to the reaction source; the mixture is heated, such that a colloidal solution 2 is obtained; the zinc source is added to the colloidal solution 2, and the mixture is heated, such that a colloidal solution 3 is obtained; the colloidal solution 1 or 3 is washed, and is subject to vacuum drying, such that the nano-crystal fluorescent powder is obtained. According to the invention, the nano-crystal fluorescent powder contains no rare earth element; the luminescence wavelength is adjustable; the nano-crystal fluorescent powder can be uniformly dispersed in an organic solvent; and the application range of the nano-crystal fluorescent powder is wide. The preparation method is advantaged in high yield, low cost, environment-friendliness, easy operation, and suitability for large-scaled productions.
Description
Technical field
The present invention relates to a kind of nanocrystalline fluorescent material and preparation method thereof, specifically, relate to a kind of REE that do not contain, have solution processable, fluorescence quantum yield height, good stability, emission wavelength is adjustable, the brilliant fluorescent material of the core-shell type nano of applied range; Also relate to the preparation method of a kind of cheap, environmental protection, easy to operate, the nanocrystalline fluorescent material according to the invention that can be mass-produced, belong to the luminescent material technical field.
Background technology
Along with the development of nanosecond science and technology, nanometer material science has become an indispensable key areas of present material scientific development.In a sense, the progress of nano materials research certainly will be pushed many subjects such as physics, chemistry, biology, material to a new level, also can bring new opportunity to the 21 century scientific and technical research simultaneously.Nanocrystalline fluorescent material is one type of new function material that development in recent years is got up; Wherein, Semiconductor nano (quantum dot) fluorescent material, because it has synthetic optical property of size and the machinable characteristics of solution, thereby as luminescent material of new generation; Caused people's extensive concern, obtained significant application achievements at present in fields such as photodiode, biomarker and virus detections.Yet the nanocrystalline fluorescent material of having developed at present of high-quality semiconductor mainly is limited to the material that contains heavy metal lead and cadmium, and the equivalent material of the semiconductor nano fluorescent material of the nontoxic or low toxicity that development environment is friendly is one of significant challenge of semiconductor nano fluorescent material application.
The nanocrystalline fluorescent material of ternary semiconductor like copper indium sulphur (Cu-In-S) and CIS (Cu-In-Se) etc., is the photoelectric functional material of excellent performance, based on the efficiency of conversion of the thin film solar cell of the nanocrystalline fluorescent material of ternary semiconductor near 20%.The exciton radius that obtains the nanocrystalline fluorescent material Cu-In-S of ternary semiconductor through Theoretical Calculation is 4.1nm; The exciton radius of the nanocrystalline fluorescent material Cu-In-Se of ternary semiconductor is 10.6nm; Theoretical prediction can show quantum confined effect when the nanocrystalline size of the nanocrystalline fluorescent material of ternary semiconductor is suitable with its exciton radius, being expected to obtain emission wavelength can synthetic nanocrystalline fluorescent material.In addition,, can also obtain copper zinc indium sulphur (Cu-Zn-In-S) and the copper zinc indium selenium nanocrystalline fluorescent materials of quaternary semiconductor such as (Cu-Zn-In-Se), further modulate its emission wavelength and improve its luminescent properties through doping zinc.Do not contain characteristics such as REE and light emitting region be adjustable owing to have, said ternary, the nanocrystalline fluorescent material of quaternary semiconductor become nanocrystalline fluorescent material of new generation.In the recent period, launched a series of researchs around said ternary, the nanocrystalline fluorescent material of quaternary semiconductor, as Xinhua Zhong group adopt hot injection method with ODE-S as the sulphur source, Zn (Ac)
2, OLA and ODE successively be injected into as the zinc source and obtain fluorescence quantum yield in the pyrosol that contains Cu, In and Zn and reach 56% the nanocrystalline fluorescent material of Cu-In-S/ZnS; Xiurong Yang group is same, and to adopt the synthetic fluorescence quantum yield that obtains of one pot of hot injection method be 40% Zn
xCu
yInS
1.5+x+0.5yNanocrystalline fluorescent material; Narayan Pradhan group is doped in the nanocrystalline fluorescent material of Zn-In-Se ternary semiconductor with Cu, and to synthesize fluorescence quantum yield be 25～30% the nanocrystalline fluorescent material of Cu-Zn-In-Se quaternary semiconductor, and preparation method that the above research is adopted is hot injection method.
But there is following defective in existing hot injection method: (1) complicated operating process, and length consuming time is difficult to realize scale operation; (2) can only prepare the Cu-In-Zn of colloidal usually
x-S/ZnS and Cu-In-Zn
x-Se/ZnS nucleocapsid structure semiconductor nano fluorescent material can't directly be prepared pulverous Cu-In-Zn
x-S/ZnS and Cu-In-Zn
x-Se/ZnS nucleocapsid structure semiconductor nano fluorescent material is not seen in the prior art to have directly to prepare Cu-In-Zn yet
x-S/ZnS and Cu-In-Zn
xThe report of-Se/ZnS nucleocapsid structure semiconductor nano fluorescent material, wherein, said x>=0.
Summary of the invention
Fail to prepare Cu-In-Zn to prior art
x-S/ZnS and Cu-In-Zn
xThe defective of-Se/ZnS nucleocapsid structure semiconductor nano fluorescent material, one of the object of the invention is to provide a kind of nanocrystalline fluorescent material, and said nanocrystalline fluorescent material is Cu-In-Zn
x-S/ZnS and Cu-In-Zn
xThe nanocrystalline fluorescent material of-Se/ZnS; Specifically, said nanocrystalline fluorescent material is for respectively with Cu-In-Zn
x-S and Cu-In-Zn
x-Se is nuclear, and coating ZnS is the Cu-In-Zn of shell
x-S/ZnS and Cu-In-Zn
x-Se/ZnS nucleocapsid structure semiconductor nano fluorescent material, said x>=0.Nanocrystalline fluorescent material according to the invention has and does not contain REE, has characteristics such as toxicity is little, band gap is narrow, photoabsorption coefficient is big, the Stokes displacement is big, self-absorption is little, productive rate is high, good stability, emission wavelength is adjustable; Can be dispersed in the organic solvents such as toluene, chloroform, chlorobenzene and normal hexane; But applied range is widely used in fields such as photodiode, solar cell, low toxicity biological mark, photo-electricdetection.
Two of the object of the invention is to provide a kind of preparation method of nanocrystalline fluorescent material, and said method is with low cost, environmental protection, easy to operate and can scale operation prepare Cu-In-Zn of the present invention
x-S/ZnS and Cu-In-Zn
x-Se/ZnS nucleocapsid structure semiconductor nano fluorescent material.
The object of the invention is realized through following technical proposals.
A kind of nanocrystalline fluorescent material, said nanocrystalline fluorescent material is Cu-In-Zn
xThe nanocrystalline fluorescent material of-E/ZnS, wherein, E=S or Se, x>=0; Specifically, said Cu-In-Zn
xThe nanocrystalline fluorescent material of-E/ZnS is represented with Cu-In-Zn
x-E is nuclear, and coating ZnS is the Cu-In-Zn of shell
x-E/ZnS nucleocapsid structure semiconductor nano fluorescent material, wherein, E=S or Se; Said nanocrystalline fluorescent material is photic or electroluminescent, and the emission wavelength scope is 500～900nm; When x＞0, said Cu-In-Zn
xThe emission wavelength scope of the nanocrystalline fluorescent material of-E/ZnS is at 500～610nm.
A kind of preparation method of nanocrystalline fluorescent material according to the invention, said method steps is following:
Step 1, preparation feedback source
Mantoquita, indium salt, alkyl sulfhydryl and octadecylene mixing are obtained mixing solutions 1, under the starvation state, mixing solutions 1 is heated to 100～120 ℃ also mixed >=30 minutes; Add long alkyl organic acid then; Be heated to 100～120 ℃ under the starvation state after dissolving, elevated temperature to 200～230 ℃, isothermal reaction >=30 minute; Stopped reaction before deposition occurring obtains reaction source;
Wherein, the amount of substance of said mantoquita: the amount of substance of indium salt is 8: 1～1: 8;
When E=S: alkyl sulfhydryl and long alkyl organic acid amount of substance sum: the amount of substance sum of mantoquita and indium salt is 16: 1～2: 1;
When E=Se: alkyl sulfhydryl and long alkyl organic acid amount of substance sum: the amount of substance sum of mantoquita and indium salt is 8: 1～2: 1;
Wherein, said mantoquita is that nanocrystalline fluorescent material technical field prepares the employed conventional mantoquita of nanocrystalline fluorescent material, as: cuprous iodide, cuprous acetate or cupric nitrate etc.
Indium salt is that nanocrystalline fluorescent material technical field prepares the employed conventional indium salt of nanocrystalline fluorescent material, as: indium acetate or indium nitrate etc.
Alkyl sulfhydryl is that nanocrystalline fluorescent material technical field prepares the employed conventional alkyl sulfhydryl of nanocrystalline fluorescent material, as: lauryl mercaptan (DDT) or octyl mercaptan etc.
Long alkyl organic acid is that nanocrystalline fluorescent material technical field prepares the long alkyl organic acid of the employed routine of nanocrystalline fluorescent material, as: oleic acid (OA) etc.
Octadecylene is as solvent.
Zinc salt, long alkyl organic amine and octadecylene are mixed the mixing solutions 2 that obtains muddiness; Under the starvation state, mixing solutions 2 is heated to 50～100 ℃ and mixed >=30 minutes, then elevated temperature to 120～160 ℃; Become clarification until mixing solutions 2, prepare the zinc source;
When E=S: said zinc source is joined in the reaction source that step 1 prepares,, prepare colloidal solution 1 200～230 ℃ of isothermal reactions 0.5～3 hour;
When E=Se: selenium powder is dissolved into prepares selenium source in the solvent, selenium source is joined in the reaction source that step 1 prepares, 180～230 ℃ of isothermal reactions, stopped reaction before deposition occurring obtains colloidal solution 2; Again said zinc source is joined in the colloidal solution 2,, prepare colloidal solution 3 200～230 ℃ of isothermal reactions 0.5～3 hour.
Wherein, said solvent is mixed solution or the tri octyl phosphine and the octadecylene mixed solution of tributylphosphine or tri octyl phosphine or tributylphosphine and octadecylene.
Wherein, the amount of substance of said zinc salt: the amount of substance of long alkyl organic amine is 10: 1～0.25: 1;
During E=S, the amount of substance of alkyl sulfhydryl in the step 1: the amount of substance in zinc source is 1: 5～1: 1
During E=Se, the amount of substance of alkyl sulfhydryl in the step 1: the amount of substance of selenium source: the amount of substance in zinc source is 1: 0.5～2: 1～5.
Wherein, said zinc salt is that nanocrystalline fluorescent material technical field prepares the employed conventional zinc salt of nanocrystalline fluorescent material, as: zinc acetate, Zinic stearas or xanthogenic acid zinc etc.
Long alkyl organic amine is that nanocrystalline fluorescent material technical field prepares the long alkyl organic amine of the employed routine of nanocrystalline fluorescent material, as: oleyl amine etc.
Octadecylene is as solvent.
Step 3, prepare nanocrystalline fluorescent material
The product that step 2 is obtained cleans with polar solvent, obtains Cu-In-Zn through centrifugal settling
xThe nanocrystalline fluorescent material of-E/ZnS;
Said product is colloidal solution 1 or 2; When said product is colloidal solution 1, the Cu-In-Zn for preparing
xE=S in the nanocrystalline fluorescent material of-E/ZnS promptly obtains Cu-In-Zn
xThe nanocrystalline fluorescent material of-S/ZnS; When said product is colloidal solution 3, the Cu-In-Zn for preparing
xE=Se in the nanocrystalline fluorescent material of-E/ZnS promptly obtains Cu-In-Zn
xThe nanocrystalline fluorescent material of-Se/ZnS.
Said polar solvent is the routine cleaning polar solvent that nanocrystalline fluorescent material technical field prepares nanocrystalline fluorescent material, like methyl alcohol or acetone etc.
Said cleaning is the conventional cleaning technique that nanocrystalline fluorescent material technical field prepares nanocrystalline fluorescent material.
The Cu-In-Zn that step 3 is obtained
xThe nanocrystalline fluorescent material of-E/ZnS obtains a kind of nanocrystalline fluorescent material of the present invention 40～70 ℃ of following vacuum-drying>=30 minute.
As said Cu-In-Zn
xDuring E=S in the nanocrystalline fluorescent material of-E/ZnS, obtain a kind of Cu-In-Zn of the present invention
xThe nanocrystalline fluorescent material of-S/ZnS; As said Cu-In-Zn
xDuring E=Se in the nanocrystalline fluorescent material of-E/ZnS, obtain a kind of Cu-In-Zn of the present invention
xThe nanocrystalline fluorescent material of-Se/ZnS.
As the Cu-In-Zn of preparation emission wavelength scope at 500～630nm
xDuring the nanocrystalline fluorescent material of-E/ZnS, in step 1, mantoquita, indium salt, zinc salt, alkyl sulfhydryl and octadecylene mixed obtaining mixing solutions 1.
Work as Cu-In-Zn
xDuring E=S among the-E/ZnS, be 100% in zinc salt, indium salt and mantoquita amount of substance sum, the amount of substance of zinc salt is can prepare the Cu-In-Zn that glows at 30～50% o'clock
xThe nanocrystalline fluorescent material of-S/ZnS, wherein, x>=0; The amount of substance of zinc salt is the Cu-In-Zn that can prepare jaundice light at 60～70% o'clock
xThe nanocrystalline fluorescent material of-S/ZnS, wherein, x＞0, the amount of substance of zinc salt is can prepare the Cu-In-Zn of green light at 80～90% o'clock
xThe nanocrystalline fluorescent material of-S/ZnS, wherein, x＞0.
Work as Cu-In-Zn
xDuring E=Se among the-E/ZnS, be 100% in zinc salt, indium salt and mantoquita amount of substance sum, the amount of substance of zinc salt is can prepare near-infrared luminous Cu-In-Zn at 60～80% o'clock
xThe nanocrystalline fluorescent material of-Se/ZnS, wherein, x>=0.
A kind of Cu-In-Zn provided by the present invention
xThe nanocrystalline fluorescent material of-E/ZnS can be applicable to fields such as low toxicity biological mark, photodiode, solar cell and photo-electricdetection.
Beneficial effect
1. Cu-In-Zn provided by the present invention
xThe nanocrystalline fluorescent material of-E/ZnS has and does not contain REE, and toxicity is little; Emission wavelength is adjustable, and the emission wavelength scope is big: 500～900nm; Can be dispersed in the organic solvents such as toluene, chloroform, chlorobenzene and normal hexane; Good stability; Band gap is narrow; Photoabsorption coefficient is big; Characteristics such as the big and self-absorption of Stokes displacement is little;
2. Cu-In-Zn provided by the present invention
xBut the nanocrystalline fluorescent material applied range of-E/ZnS is widely used in fields such as photodiode, solar cell, low toxicity biological mark and photo-electricdetection;
3. Cu-In-Zn provided by the present invention
xPreparing method's productive rate of the nanocrystalline fluorescent material of-E/ZnS is high, can reach 50～70%, and with low cost, environmental protection, easy to operate, can be mass-produced, the simple reaction container just can prepare the above sample of 10g.
Description of drawings
The Cu-In-Zn that Fig. 1 prepares for embodiment 1,4 and 7
xThe uv-visible absorption spectra figure of the nanocrystalline fluorescent material of-S/ZnS.
The Cu-In-Zn that Fig. 2 prepares for embodiment 1,4 and 7
xThe fluorescence spectrum figure of the nanocrystalline fluorescent material of-S/ZnS.
Transmission electron microscope (TEM) figure of the nanocrystalline fluorescent material of Cu-In-Zn-S/ZnS that Fig. 3 prepares for embodiment 4.
The Cu-In-Zn that Fig. 4 prepares for embodiment 1,4 and 7
xThe X-ray diffractogram of the nanocrystalline fluorescent material of-S/ZnS.
The uv-visible absorption spectra figure of the nanocrystalline fluorescent material of near-infrared luminous Cu-In-Se/ZnS that Fig. 5 prepares for embodiment 10.
The fluorescence spectrum figure of the nanocrystalline fluorescent material of near-infrared luminous Cu-In-Se/ZnS that Fig. 6 prepares for embodiment 10.
Embodiment
Embodiment 1
Step 1, preparation feedback source
0.19g cuprous iodide, 1.16g indium acetate, 5mL lauryl mercaptan and 25mL octadecylene are joined in the there-necked flask of 100mL and mix, obtain mixing solutions 1, with mixing solutions 1 heating under vacuum to 120 ℃ and stir 30min; Add 2.5mL oleic acid then, continue to stir 30min down to dissolving fully in 120 ℃ in vacuum, feed nitrogen and keep 30min, be warmed up to 220 ℃ again, solution is from the light yellow scarlet that becomes, and isothermal reaction 1h obtains reaction source.
2.64g zinc acetate, 10mL oleyl amine and the mixing of 10mL octadecylene are obtained muddy mixing solutions 2; With mixing solutions 2 heating under vacuum to 50 ℃ and stirred 30 minutes; Feed nitrogen 30 minutes elevated temperature to 120 ℃ more then, become clarification to muddy mixing solutions 2, prepare the zinc source; Under 220 ℃, said zinc source dropwise joined in the reaction source that step 1 prepares and react, each adding needs 5min, reacts 15min at every turn, repeats four times, prepares colloidal solution.
Step 3, prepare nanocrystalline fluorescent material
The colloidal solution that step 2 is prepared adds in the 100mL centrifuge tube to high half place of pipe, carries out spinning, obtains bottom thing 1 and supernatant 1; 2. after removing bottom thing 1, add the spinning of 3mL toluene, obtain bottom thing 2 and supernatant 2 to supernatant 1; 3. after removing bottom thing 2, in supernatant 2, add the mixed solution spinning of 60mL acetone and 20mL methyl alcohol, obtain bottom thing 3 and supernatant 3; 4. outwell supernatant 3, after the dissolving of bottom thing 3 usefulness 3mL toluene, add 60mL acetone and the spinning of 20mL methyl alcohol mixed liquor, wash twice; 5. use the 60mL washed with methanol one time, supernatant 4 is outwelled in spinning, obtains nanocrystalline fluorescent material.
The nanocrystalline fluorescent material that step 3 is obtained obtains powdery product at 50 ℃ of following vacuum-drying 1h, and productive rate is 62%.Can know that through detecting said powdery product is the nanocrystalline fluorescent material of a kind of Cu-In-S/ZnS of the present invention.
Step 1, preparation feedback source
0.19g cuprous iodide, 1.16g indium acetate, 5mL lauryl mercaptan and 25mL octadecylene are joined in the there-necked flask of 100mL and mix, obtain mixing solutions 1, with mixing solutions 1 heating under vacuum to 100 ℃ and stir 40min; Add 2.5mL oleic acid then, continue to stir 30min down to dissolving fully in 120 ℃ in vacuum, feed nitrogen and keep 30min, be warmed up to 200 ℃ again, solution is from the light yellow scarlet that becomes, and isothermal reaction 1h obtains reaction source.
2.64g zinc acetate, 10mL oleyl amine and the mixing of 10mL octadecylene are obtained muddy mixing solutions 2; With mixing solutions 2 heating under vacuum to 80 ℃ and stirred 30 minutes, fed nitrogen then 30 minutes, again elevated temperature to 140 ℃; To muddy mixing solutions 2 change clarifications, prepare the zinc source; Under 200 ℃, said zinc source dropwise joined in the reaction source that step 1 prepares and react, adding needs 5min, and reaction 15min repeats four times, prepares colloidal solution.
Step 3, prepare nanocrystalline fluorescent material
Carry out according to embodiment one step 3.
The nanocrystalline fluorescent material that step 3 is obtained obtains powdery product at 40 ℃ of following vacuum-drying 30min, and productive rate is 62%.Can know that through detecting said powdery product is the nanocrystalline fluorescent material of a kind of Cu-In-S/ZnS of the present invention.
Embodiment 3
Step 1, preparation feedback source
0.19g cuprous iodide, 1.16g indium acetate, 5mL lauryl mercaptan and 25mL octadecylene are joined in the there-necked flask of 100mL and mix, obtain mixing solutions 1, with mixing solutions 1 heating under vacuum to 110 ℃ and stir 60min; Add 2.5mL oleic acid then, continue to stir 30min down to dissolving fully in 120 ℃ in vacuum, feed nitrogen and keep 30min, be warmed up to 230 ℃ again, solution is from the light yellow scarlet that becomes, and isothermal reaction 1h obtains reaction source.
2.64g zinc acetate, 10mL oleyl amine and the mixing of 10mL octadecylene are obtained muddy mixing solutions 2; With mixing solutions 2 heating under vacuum to 100 ℃ and stirred 30 minutes, fed argon gas then 30 minutes, again elevated temperature to 160 ℃; To muddy mixing solutions 2 change clarifications, prepare the zinc source; Said zinc source dropwise joined in the reaction source that step 1 prepares at 230 ℃, each adding needs 5min, reacts 15min at every turn, repeats four times, prepares colloidal solution.
Step 3, prepare nanocrystalline fluorescent material
Carry out according to embodiment one step 3
The nanocrystalline fluorescent material that step 3 is obtained obtains powdery product at 70 ℃ of following vacuum-drying 50min, and productive rate is 62%.Can know that through detecting said powdery product is the nanocrystalline fluorescent material of a kind of Cu-In-S/ZnS of the present invention.
The powdery product that embodiment 1～3 is prepared carries out check and analysis respectively, and the result is following:
Element characterizes with thing mutually: adopting model is the X-gamma spectrometer test of EDX-GP, and the percentage composition that draws Zn, Cu, In and S is respectively: 36.4%, 12.7%; 18.2%; 32.7%, prove that said powdery product exists Zn, Cu, In and four kinds of elements of S, does not have other impurity element.Adopting model is the x-ray powder diffraction instrument test of SiemensD5000; Obtain X-ray diffractogram; Shown in Fig. 4 curve a: the position of diffraction peak (2 θ) is at 28.3 °, 46.9 ° and 55.9 °; (112), (204) and (116) crystal faces (JCPDS:65-2732) of the corresponding Cu-In-S yellow copper structure of difference, proving has tetragonal Cu-In-S to generate in the said powdery product; The position of diffraction peak (2 θ) in (200) of 33.5 ° of corresponding ZnS zincblende lattce structures (JCPDS:65-0309), proving has ZnS to generate in the said powdery product.Therefore, said powdery product is the Cu-In-S/ZnS crystal powder.
Pattern and characterization of size: said powdery product is dissolved in obtains solution in the chloroform; On copper mesh, the employing model is that the transmission electron microscope (TEM) of JEM-2100F detects, and obtains TEM figure and shows: the about 3nm of the median size of said powdery product with drips of solution; Be shaped as particulate state; From TEM figure, also can find out the existence of nucleocapsid structure, prove that said powdery product is is nuclear with Cu-In-S, ZnS is the nucleocapsid structure Cu-In-S/ZnS nanometer powder of shell.
Absorb with fluorescence property and characterize: said powdery product is dissolved in the toluene, detects, obtain fluorescence spectrum figure through the FP-6600 XRF; Show like Fig. 2 curve a, have maximum emission peak, explain that said powdery product glows at the 617nm place; Detect through V-570 ultraviolet-visible extinction spectrum appearance; Obtain corresponding uv-visible absorption spectra, shown in Fig. 1 curve a, exist band edge to absorb at the 666nm place with said fluorescence spectrum figure; There is the exciton absorption peak at the 529nm place, the spectral range broad that said powdery product can be excited is described.
Electroluminescent characterizes: with said powdery product as luminescent layer; Poly-triphenylamine is as hole transmission layer; Quinoline aluminum is prepared LED device (LED) as electron transfer layer; Adopting model is that the semiconductor test system test of Keithley 4200 draws: electroluminescent spectrum has maximum emission peak at 625nm, than the fluorescence spectrum red shift 8nm, prove said powdery product is glowed.
In sum, can know that it is the nanocrystalline fluorescent material of a kind of Cu-In-S/ZnS of the present invention that embodiment 1～3 prepares powdery product.
Step 1, preparation feedback source
0.19g cuprous iodide, 1.16g indium acetate, 0.44g zinc acetate, 10mL lauryl mercaptan and 25mL octadecylene are joined in the there-necked flask of 100mL and mix, obtain mixing solutions 1, with mixing solutions 1 heating under vacuum to 120 ℃ and stir 30min; Add 2.5mL oleic acid then, continue to stir 30min down to dissolving fully in 120 ℃ in vacuum, feed nitrogen and keep 30min, be warmed up to 230 ℃ again, solution is from the light yellow orange that becomes, and isothermal reaction 30min obtains reaction source.
2.64g zinc acetate, 10mL oleyl amine and the mixing of 10mL octadecylene are obtained muddy mixing solutions 2; With mixing solutions 2 heating under vacuum to 50 ℃ and stirred 40 minutes, fed argon gas then 30 minutes, again elevated temperature to 120 ℃; To muddy mixing solutions 2 change clarifications, prepare the zinc source; Said zinc source dropwise joined in the reaction source that step 1 prepares at 230 ℃, each adding needs 5min, reacts 15min at every turn, repeats four times, prepares colloidal solution.
Step 3, prepare nanocrystalline fluorescent material
Carry out according to embodiment one step 3.
Carry out according to embodiment one step 4, obtain powdery product, productive rate is 58%.Can know that through detecting said powdery product is the nanocrystalline fluorescent material of a kind of Cu-In-Zn-S/ZnS of the present invention.
Embodiment 5
Step 1, preparation feedback source
0.19g cuprous iodide, 1.16g indium acetate, 0.44g zinc acetate, 10mL lauryl mercaptan and 25mL octadecylene are joined in the there-necked flask of 100mL and mix, obtain mixing solutions 1, with mixing solutions 1 in heating under vacuum to 100 ℃ and stir 50min; Add 2.5mL oleic acid then, continue to stir 30min down to dissolving fully in 120 ℃ in vacuum, feed nitrogen and keep 30min, be warmed up to 200 ℃ again, solution is from the light yellow orange that becomes, and isothermal reaction 30min obtains reaction source.
2.64g zinc acetate, 10mL oleyl amine and the mixing of 10mL octadecylene are obtained muddy mixing solutions 2; With mixing solutions 2 heating under vacuum to 80 ℃ and stirred 50 minutes, fed nitrogen then 30 minutes, again elevated temperature to 140 ℃; To muddy mixing solutions 2 change clarifications, prepare the zinc source; Said zinc source dropwise joined in the reaction source that step 1 prepares at 200 ℃, each adding needs 5min, reacts 15min at every turn, repeats four times, prepares colloidal solution.
Step 3, prepare nanocrystalline fluorescent material
Carry out according to embodiment one step 3.
Carry out according to embodiment one step 4, obtain powdery product, productive rate is 58%.Can know that through detecting said powdery product is the nanocrystalline fluorescent material of a kind of Cu-In-Zn-S/ZnS of the present invention.
Embodiment 6
Step 1, preparation feedback source
0.19g cuprous iodide, 1.16g indium acetate, 0.44g zinc acetate, 10mL lauryl mercaptan and 25mL octadecylene are joined in the there-necked flask of 100mL and mix, obtain mixing solutions 1, with mixing solutions 1 heating under vacuum to 110 ℃ and stir 40min; Add 2.5mL oleic acid then, continue to stir 30min down to dissolving fully in 120 ℃ in vacuum, feed nitrogen and keep 30min, be warmed up to 210 ℃ again, solution is from the light yellow orange that becomes, and isothermal reaction 30min obtains reaction source.
2.64g zinc acetate, 10mL oleyl amine and the mixing of 10mL octadecylene are obtained muddy mixing solutions 2; With mixing solutions 2 heating under vacuum to 100 ℃ and stirred 1 hour, fed nitrogen then 1 hour, again elevated temperature to 160 ℃; To muddy mixing solutions 2 change clarifications, prepare the zinc source; Said zinc source dropwise joined in the reaction source that step 1 prepares at 210 ℃, each injection needs 5min, reacts 15min at every turn, repeats four times, prepares colloidal solution.
Step 3, prepare nanocrystalline fluorescent material
Carry out according to embodiment one step 3.
Carry out according to embodiment one step 4, obtain powdery product, productive rate is 58%.Can know that through detecting said powdery product is the nanocrystalline fluorescent material of a kind of Cu-In-Zn-S/ZnS of the present invention.
The powdery product that embodiment 4～6 is prepared carries out check and analysis respectively, and the result is following:
Element characterizes with thing mutually: through model is that the percentage composition that the X-gamma spectrometer test of EDX-GP draws Zn, Cu, In and S is respectively: 53.3%, 9.3%, 13.3% and 24%; Prove that said powdery product exists Zn, Cu, In and four kinds of elements of S, does not have other impurity element.Adopting model is the x-ray powder diffraction instrument test of Siemens D5000; Obtain X-ray diffractogram; Shown in Fig. 4 curve b: the position of diffraction peak (2 θ) is at 28.4 °, 47.6 ° and 56.1 °; (112), (204) and (116) crystal faces (JCPDS:65-2732) of corresponding Cu-In-S yellow copper structure still totally to the high angle skew, prove that in the Cu-In-S crystal, successfully introducing the Zn element generates tetragonal Cu-In-Zn-S crystal respectively; The position of diffraction peak (2 θ) in (200) of 33.5 ° of corresponding ZnS zincblende lattce structures (JCPDS:65-0309), explaining has ZnS to generate in the said powdery product.Therefore, said powdery product is the Cu-In-Zn-S/ZnS crystal powder.
Pattern and characterization of size: said powdery product is dissolved in obtains solution in the chloroform; On copper mesh, the employing model is that the transmission electron microscope of JEM-2100F detects with drips of solution, and it is as shown in Figure 3 to obtain TEM figure: the about 4nm of the median size of said powdery product; Be shaped as particulate state; From TEM figure, also can find out the existence of nucleocapsid structure, prove that said powdery product is for being nuclear with Cu-In-Zn-S, ZnS is the nucleocapsid structure Cu-In-Zn-S/ZnS nanometer powder of shell.
Absorb with fluorescence property and characterize: said powdery product is dissolved in the toluene, detects, obtain fluorescence spectrum figure through the FP-6600 XRF; Shown in Fig. 2 curve b, there is maximum emission peak at the 553nm place, said powdery product jaundice light is described; Detect through V-570 ultraviolet-visible extinction spectrum appearance; Obtain corresponding uv-visible absorption spectra, shown in Fig. 1 curve b, exist band edge to absorb at the 565nm place with said fluorescence spectrum figure; There is the exciton absorption peak at the 462nm place, the spectral range broad that said powdery product can be excited is described.
Electroluminescent characterizes: with said powdery product as luminescent layer; Poly-triphenylamine is as hole transmission layer; Quinoline aluminum is prepared LED device as electron transfer layer; Adopting model is that the semiconductor test system test of Keithley 4200 draws: electroluminescent spectrum has maximum emission peak at 559nm, than the fluorescence spectrum red shift 6nm, prove when excitation energy is electric energy, also to make the said powdery product light that turns to be yellow.
In sum, can know that it is the nanocrystalline fluorescent material of a kind of Cu-In-Zn-S/ZnS of the present invention that embodiment 4～6 prepares powdery product.
Embodiment 7
Step 1, preparation feedback source
0.038g cuprous iodide, 0.232g indium acetate, 0.176g zinc acetate, 4mL lauryl mercaptan and 4mL octadecylene are joined in the there-necked flask of 50mL and mix, obtain mixing solutions 1, with mixing solutions 1 heating under vacuum to 120 ℃ and stir 30min; Add 1mL oleic acid then, continue to stir 30min down to dissolving fully in 120 ℃ in vacuum, feed nitrogen and keep 30min, be warmed up to 230 ℃ again, solution is from the light yellow oyster that becomes, and isothermal reaction 30min obtains reaction source.
1.584g zinc acetate, 2mL oleyl amine and the mixing of 2mL octadecylene are obtained muddy mixing solutions 2; With liquid mixing solutions 2 heating under vacuum to 50 ℃ and stirred 30 minutes, fed argon gas then 30 minutes, again elevated temperature to 120 ℃; To muddy mixing solutions 2 change clarifications, prepare the zinc source; Said zinc source dropwise joined in the reaction source that step 1 prepares at 230 ℃, each adding needs 5min, reacts 15min at every turn, repeats four times, prepares colloidal solution.
Step 3, prepare nanocrystalline fluorescent material
Carry out according to embodiment one step 3.
Carry out according to embodiment one step 4, obtain powdery product, productive rate is 70%.Can know that through detecting said powdery product is the nanocrystalline fluorescent material of a kind of Cu-In-Zn-S/ZnS of the present invention.
Embodiment 8
Step 1, preparation feedback source
0.038g cuprous iodide, 0.232g indium acetate, 0.176g zinc acetate, 4mL lauryl mercaptan and 4mL octadecylene are joined in the there-necked flask of 50mL and mix, obtain mixing solutions 1, with mixing solutions 1 heating under vacuum to 100 ℃ and stir 60min; Add 1mL oleic acid then, continue to stir 30min down to dissolving fully in 120 ℃ in vacuum, feed nitrogen and keep 30min, be warmed up to 200 ℃ again, solution is from the light yellow oyster that becomes, and isothermal reaction 30min obtains reaction source.
2.64g zinc acetate, 10mL oleyl amine and the mixing of 10mL octadecylene are obtained muddy mixing solutions 2; With mixing solutions 2 heating under vacuum to 80 ℃ and stirred 40 minutes, fed argon gas then 40 minutes, again elevated temperature to 140 ℃; To muddy mixing solutions 2 change clarifications, prepare the zinc source; Said zinc source dropwise joined in the reaction source that step 1 prepares at 200 ℃, each adding needs 5min, reacts 15min at every turn, repeats four times, prepares colloidal solution.
Step 3, prepare nanocrystalline fluorescent material
Carry out according to embodiment one step 3.
Carry out according to embodiment one step 4, obtain powdery product, productive rate is 70%.Can know that through detecting said powdery product is the nanocrystalline fluorescent material of a kind of Cu-In-Zn-S/ZnS of the present invention.
Embodiment 9
Step 1, preparation feedback source
0.038g cuprous iodide, 0.232g indium acetate, 0.176g zinc acetate, 4mL lauryl mercaptan and 4mL octadecylene are joined in the there-necked flask of 50mL and mix, obtain mixing solutions 1, with mixing solutions 1 heating under vacuum to 110 ℃ and stir 40min; Add 1mL oleic acid then, continue to stir 30min down to dissolving fully in 120 ℃ in vacuum, feed nitrogen and keep 30min, be warmed up to 210 ℃ again, solution is from the light yellow oyster that becomes, and isothermal reaction 30min obtains reaction source.
2.64g zinc acetate, 10mL oleyl amine and the mixing of 10mL octadecylene are obtained muddy mixing solutions 2; With mixing solutions 2 heating under vacuum to 100 ℃ and stirred 50 minutes, fed nitrogen then 1 hour, again elevated temperature to 160 ℃; To muddy mixing solutions 2 change clarifications, prepare the zinc source; Said zinc source dropwise joined in the reaction source that step 1 prepares at 210 ℃, each injection needs 5min, reacts 15min at every turn, repeats four times, prepares colloidal solution.
Step 3, prepare nanocrystalline fluorescent material
Carry out according to embodiment one step 3.
Carry out according to embodiment one step 4, obtain powdery product, productive rate is 70%.Can know that through detecting said powdery product is the nanocrystalline fluorescent material of a kind of Cu-In-Zn-S/ZnS of the present invention.
The powdery product that embodiment 7～9 is prepared carries out check and analysis respectively, and the result is following:
Element characterizes with thing mutually: through model is that the percentage composition that the X-gamma spectrometer test of EDX-GP draws Zn, Cu, In and S is respectively: 66.0%, 6.8%, 9.7% and 17.5%; Prove that said powdery product exists Zn, Cu, In and four kinds of elements of S, does not have other impurity element.Adopting model is the x-ray powder diffraction instrument test of Siemens D5000; Obtain X-ray diffractogram; Shown in Fig. 4 curve c: the position of diffraction peak (2 θ) is at 28.6 °, 47.7 ° and 56.5 °; (112), (204) and (116) crystal faces (JCPDS:65-2732) of corresponding Cu-In-S yellow copper structure still totally to the high angle skew, prove that in the Cu-In-S crystal, successfully introducing the Zn element generates tetragonal Cu-In-Zn-S crystal respectively; The position of diffraction peak (2 θ) in (200) of 33.5 ° of corresponding ZnS zincblende lattce structures (JCPDS:65-0309), explaining has ZnS to generate in the said powdery product.Therefore, said powdery product is the Cu-In-Zn-S/ZnS crystal powder.
Pattern and characterization of size: said powdery product is dissolved in obtains solution in the chloroform; On copper mesh, the employing model is that the transmission electron microscope of JEM-2100F detects, and obtains TEM figure and shows: the about 5nm of the median size of said powdery product with drips of solution; Be shaped as particulate state; From TEM figure, also can find out the existence of nucleocapsid structure, prove that said powdery product is for being nuclear with Cu-In-Zn-S, ZnS is the nucleocapsid structure Cu-In-Zn-S/ZnS nanometer powder of shell.
Absorb with fluorescence property and characterize: said powdery product is dissolved in the toluene, detects, obtain fluorescence spectrum figure through the FP-6600 XRF; Shown in Fig. 2 curve c, there is maximum emission peak at the 525nm place, said powdery product green light is described; Detect through V-570 ultraviolet-visible extinction spectrum appearance; Obtain corresponding uv-visible absorption spectra, shown in Fig. 1 curve c, exist band edge to absorb at the 479nm place with said fluorescence spectrum figure; There is the exciton absorption peak at the 385nm place, the spectral range broad that said powdery product can be excited is described.
Electroluminescent characterizes: with said powdery product as luminescent layer; Poly-triphenylamine is as hole transmission layer; Quinoline aluminum is prepared LED device as electron transfer layer; Adopting model is that the semiconductor test system test of Keithley 4200 draws: electroluminescent spectrum has maximum emission peak at 532nm, than the fluorescence spectrum red shift 7nm.Proof also can said powdery product green light when excitation energy is electric energy.
In sum, can know that it is the nanocrystalline fluorescent material of a kind of Cu-In-Zn-S/ZnS of the present invention that embodiment 7～9 prepares powdery product.
Embodiment 10
Step 1, preparation feedback source
With 0.038g cuprous iodide, 0.232g indium acetate, 1mL lauryl mercaptan and 10mL octadecylene join in the there-necked flask of 50mL and mix, and obtain mixing solutions 1, be heated to 120 ℃ and stir 30min of mixing solutions 1 vacuum; Add 0.5mL oleic acid then, continue to stir 30min down to dissolving fully, feed nitrogen and keep 30min, be warmed up to 210 ℃ again in 120 ℃ in vacuum; Solution is from the light yellow scarlet that becomes, and isothermal reaction 1h obtains reaction source.
0.528g zinc acetate, 2mL oleyl amine and the mixing of 2mL octadecylene are obtained muddy mixing solutions 2; With mixed solution 2 heating under vacuum to 50 ℃ and stirred 30 minutes, fed argon gas then 30 minutes, again elevated temperature to 120 ℃; To muddy mixing solutions 2 change clarifications, prepare the zinc source; The 1mmol selenium powder is dissolved in prepares selenium source in the tributylphosphine, selenium source is joined in the reaction source that step 1 prepares fast, the color of solution from from the light yellow scarlet that becomes, obtains the colloidal solution 1 of dark red in 30 seconds; At 210 ℃ said zinc source is dropwise joined in the colloidal solution 2, each injection needs 5min, reacts 15min at every turn, repeats four times, prepares colloidal solution 2 again.
Step 3, prepare nanocrystalline fluorescent material
Carry out according to embodiment one step 3.
Carry out according to embodiment one step 4, obtain powdery product, productive rate is 66%.Can know that through detecting said powdery product is the nanocrystalline fluorescent material of a kind of Cu-In-Se/ZnS of the present invention.
Embodiment 11
Step 1, preparation feedback source
0.038g cuprous iodide, 0.232g indium acetate, 1mL lauryl mercaptan and 10mL octadecylene are joined in the there-necked flask of 50mL and mix, obtain mixing solutions 1, be heated to 100 ℃ and stir 40min of mixing solutions 1 vacuum; Add 0.5mL oleic acid then, continue to stir 30min down to dissolving fully in 120 ℃ in vacuum, feed nitrogen and keep 30min, be warmed up to 200 ℃ again, solution is from the light yellow scarlet that becomes, and isothermal reaction 1h obtains reaction source.
2.64g zinc acetate, 10mL oleyl amine and the mixing of 10mL octadecylene are obtained muddy mixing solutions 2; With mixed solution 2 heating under vacuum to 80 ℃ and stirred 30 minutes, fed nitrogen 40 minutes, again elevated temperature to 140 ℃; To muddy mixing solutions 2 change clarifications, prepare the zinc source; The 0.5mmol selenium powder is dissolved in prepares selenium source in the tributylphosphine; Selenium source is added in the reaction source that step 1 prepares fast; The color of solution is in 30 seconds; From the light yellow scarlet that becomes,, obtain the colloidal solution 1 of dark red at 180 ℃ of isothermal reactions stopped reaction before deposition occurring; At 200 ℃ said zinc source is dropwise joined in the colloidal solution 2, each injection needs 5min, reacts 15min at every turn, repeats four times, prepares colloidal solution 2 again.
Step 3, prepare nanocrystalline fluorescent material
Carry out according to embodiment one step 3.
Carry out according to embodiment one step 4, obtain powdery product, productive rate is 66%.Can know that through detecting said powdery product is the nanocrystalline fluorescent material of a kind of Cu-In-Se/ZnS of the present invention.
Embodiment 12
Step 1, preparation feedback source
0.038g cuprous iodide, 0.232g indium acetate, 1mL lauryl mercaptan and 10mL octadecylene are joined in the there-necked flask of 50mL and mix, obtain mixing solutions 1, with mixing solutions 1 heating under vacuum to 110 ℃ and stir 50min; Add 0.5mL oleic acid then, continue to stir 30min down to dissolving fully, feed nitrogen and keep 30min, be warmed up to 200 ℃ again in 120 ℃ in vacuum; Solution is from the light yellow scarlet that becomes, and isothermal reaction 1h obtains reaction source.
2.64g zinc acetate, 10mL oleyl amine and the mixing of 10mL octadecylene are obtained muddy mixing solutions 2; With mixed solution 2 heating under vacuum to 100 ℃ and stirred 1 hour, fed argon gas then 30 minutes, again elevated temperature to 160 ℃; To muddy mixing solutions 2 change clarifications, prepare the zinc source; The 2mmol selenium powder is dissolved in prepares selenium source in the tributylphosphine; Selenium source is added in the reaction source that step 1 prepares fast; The color of solution is in 30 seconds; From the light yellow scarlet that becomes,, obtain the colloidal solution 1 of dark red at 230 ℃ of isothermal reactions stopped reaction before deposition occurring; At 200 ℃ said zinc source is dropwise joined in the colloidal solution 2, each injection needs 5min, reacts 15min at every turn, repeats four times, prepares colloidal solution 2 again.
Step 3, prepare nanocrystalline fluorescent material
Carry out according to embodiment one step 3.
Carry out according to embodiment one step 4, obtain powdery product, productive rate is 66%.Can know that through detecting said powdery product is the nanocrystalline fluorescent material of a kind of Cu-In-Se/ZnS of the present invention.
The powdery product that embodiment 10～12 is prepared carries out check and analysis respectively, and the result is following:
Element characterizes with thing mutually: through model is that the percentage composition that the X-gamma spectrometer test of EDX-GP draws Zn, Cu, In and Se is respectively: 60.0%, 8.8%, 11.5% and 19.7%; Prove that said powdery product exists Zn, Cu, In and four kinds of elements of Se, does not have other impurity element.Adopting model is the x-ray powder diffraction instrument test of Siemens D5000; Obtaining X-ray diffractogram shows: the position of diffraction peak (2 θ) is at 27.4 °, 45.5 ° and 53.6 °; (111), (220) and (311) crystal faces (JCPDS:65-9041) of the corresponding Cu-In-Se yellow copper structure of difference, proving has tetragonal Cu-In-Se crystal to generate in the product; The position of diffraction peak (2 θ) in (200) of 33.5 ° of corresponding ZnS zincblende lattce structures (JCPDS:65-0309), explaining has ZnS to generate in the said powdery product.Therefore, said powdery product is the Cu-In-Se/ZnS crystal powder.
Pattern and characterization of size: said powdery product is dissolved in obtains solution in the chloroform; On copper mesh, the employing model is that the transmission electron microscope of JEM-2100F detects, and obtains TEM figure and shows: the about 4nm of the median size of said powdery product with drips of solution; Be shaped as particulate state; From TEM figure, also can find out the existence of nucleocapsid structure, prove that said powdery product is for being nuclear with Cu-In-Se, ZnS is the nucleocapsid structure Cu-In-Se/ZnS nanometer powder of shell.
Absorb with fluorescence property and characterize: said powdery product is dissolved in the toluene, detects, obtain fluorescence spectrum figure through the FP-6600 XRF; As shown in Figure 6, there is maximum emission peak at the 710nm place, explain that said powdery product is near-infrared luminous; Detect through V-570 ultraviolet-visible extinction spectrum appearance; Obtain corresponding uv-visible absorption spectra with said fluorescence spectrum figure, as shown in Figure 5, exist band edge to absorb at the 760nm place; There is the exciton absorption peak at the 650nm place, the spectral range broad that said powdery product can be excited is described.
Electroluminescent characterizes: with said powdery product as luminescent layer; Poly-triphenylamine is as hole transmission layer; Quinoline aluminum is prepared LED device as electron transfer layer; Adopting model is that the semiconductor test system test of Keithley 4200 draws: electroluminescent spectrum has maximum emission peak at 735nm, than the fluorescence spectrum red shift 25nm.It is near-infrared luminous that proof also can said powdery product when excitation energy is electric energy.
In sum, can know that it is the nanocrystalline fluorescent material of a kind of Cu-In-Se/ZnS of the present invention that embodiment 10～12 prepares powdery product.
Though in conjunction with accompanying drawing embodiment of the present invention has been described, to those skilled in the art, under the prerequisite that does not break away from the principle of the invention, can also make some distortion and improvement, these also should be regarded as belonging to protection scope of the present invention.
Claims (9)
1. nanocrystalline fluorescent material, it is characterized in that: said nanocrystalline fluorescent material is Cu-In-Zn
xThe nanocrystalline fluorescent material of-E/ZnS, wherein, E=S or Se, x>=0.
2. a kind of nanocrystalline fluorescent material according to claim 1 is characterized in that: said nanocrystalline fluorescent material is photic or electroluminescent, and the emission wavelength scope is 500～900nm.
3. a kind of nanocrystalline fluorescent material according to claim 1 is characterized in that: when x＞0, and said Cu-In-Zn
xThe emission wavelength scope of the nanocrystalline fluorescent material of-E/ZnS is at 500～610nm.
4. the preparation method of a nanocrystalline fluorescent material as claimed in claim 1, it is characterized in that: said method steps is following:
Step 1, preparation feedback source
Mantoquita, indium salt, alkyl sulfhydryl and octadecylene mixing are obtained mixing solutions 1, under the starvation state, mixing solutions 1 is heated to 100～120 ℃ also mixed >=30 minutes; Add long alkyl organic acid then; Be heated to 100～120 ℃ under the starvation state after dissolving, elevated temperature to 200～230 ℃, isothermal reaction >=30 minute; Stopped reaction before deposition occurring obtains reaction source;
Step 2, preparation colloidal solution
Zinc salt, long alkyl organic amine and octadecylene are mixed the mixing solutions 2 that obtains muddiness; Under the starvation state, mixing solutions 2 is heated to 50～100 ℃ and mixed >=30 minutes, then elevated temperature to 120～160 ℃; Become clarification until mixing solutions 2, prepare the zinc source;
When E=S: said zinc source is joined in the reaction source that step 1 prepares,, prepare colloidal solution 1 200～230 ℃ of isothermal reactions 0.5～3 hour;
When E=Se: selenium powder is dissolved into prepares selenium source in the solvent, selenium source is joined in the reaction source that step 1 prepares, 180～230 ℃ of isothermal reactions, stopped reaction before deposition occurring obtains colloidal solution 2; Again said zinc source is joined in the colloidal solution 2,, prepare colloidal solution 3 200～230 ℃ of isothermal reactions 0.5～3 hour;
Step 3, prepare nanocrystalline fluorescent material
The product that step 2 is obtained cleans with polar solvent, obtains Cu-In-Zn through centrifugal settling
xThe nanocrystalline fluorescent material of-E/ZnS;
Said product is colloidal solution 1 or 2; When said product is colloidal solution 1, the Cu-In-Zn for preparing
xE=S in the nanocrystalline fluorescent material of-E/ZnS promptly obtains a kind of Cu-In-Zn
xThe nanocrystalline fluorescent material of-S/ZnS; When said product is colloidal solution 3, the Cu-In-Zn for preparing
xE=Se in the nanocrystalline fluorescent material of-E/ZnS promptly obtains a kind of Cu-In-Zn
xThe nanocrystalline fluorescent material of-Se/ZnS;
Step 4, prepare nanocrystalline fluorescent material
The Cu-In-Zn that step 3 is obtained
xThe nanocrystalline fluorescent material of-E/ZnS obtains a kind of nanocrystalline fluorescent material 40～70 ℃ of following vacuum-drying>=30 minute;
Wherein, the amount of substance of mantoquita described in the step 1: the amount of substance of indium salt is 8: 1～1: 8;
When E=S: alkyl sulfhydryl and long alkyl organic acid amount of substance sum: the amount of substance sum of mantoquita and indium salt is 16: 1～2: 1;
When E=Se: alkyl sulfhydryl and long alkyl organic acid amount of substance sum: the amount of substance sum of mantoquita and indium salt is 8: 1～2: 1;
Solvent described in the step 2 is mixed solution or the tri octyl phosphine and the octadecylene mixed solution of tributylphosphine or tri octyl phosphine or tributylphosphine and octadecylene;
The amount of substance of zinc salt: the amount of substance of long alkyl organic amine is 10: 1～0.25: 1;
During E=S, the amount of substance of alkyl sulfhydryl in the step 1: the amount of substance in zinc source is 1: 5～1: 1
During E=Se, the amount of substance of alkyl sulfhydryl in the step 1: the amount of substance of selenium source: the amount of substance in zinc source is 1: 0.5～2: 1～5.
5. the preparation method of a kind of nanocrystalline fluorescent material according to claim 4 is characterized in that: as the Cu-In-Zn of preparation emission wavelength scope at 500～630nm
xDuring the nanocrystalline fluorescent material of-E/ZnS, in the step 1 mantoquita, indium salt, zinc salt, alkyl sulfhydryl and octadecylene mixed obtaining mixing solutions 1.
6. the preparation method of a kind of nanocrystalline fluorescent material according to claim 4 is characterized in that: work as Cu-In-Zn
xDuring E=S among the-E/ZnS, be 100% in zinc salt, indium salt and mantoquita amount of substance sum, the amount of substance of zinc salt is 30～50% o'clock Cu-In-Zn that prepare
xThe nanocrystalline fluorescent material of-S/ZnS glows, wherein, and x>=0.
7. the preparation method of a kind of nanocrystalline fluorescent material according to claim 4 is characterized in that: work as Cu-In-Zn
xDuring E=S among the-E/ZnS, be 100% in zinc salt, indium salt and mantoquita amount of substance sum, the amount of substance of zinc salt is 60～70% o'clock Cu-In-Zn that prepare
xThe nanocrystalline fluorescent material jaundice of-S/ZnS light, wherein, x＞0.
8. the preparation method of a kind of nanocrystalline fluorescent material according to claim 4 is characterized in that: work as Cu-In-Zn
xDuring E=S among the-E/ZnS, be 100% in zinc salt, indium salt and mantoquita amount of substance sum, the amount of substance of zinc salt is 80～90% o'clock Cu-In-Zn that prepare
xThe nanocrystalline fluorescent material green light of-S/ZnS, wherein, x＞0.
9. the preparation method of a kind of nanocrystalline fluorescent material according to claim 4 is characterized in that: work as Cu-In-Zn
xDuring E=Se among the-E/ZnS, be 100% in zinc salt, indium salt and mantoquita amount of substance sum, the amount of substance of zinc salt is 60～80% o'clock Cu-In-Zn that prepare
xThe nanocrystalline fluorescent material of-Se/ZnS is near-infrared luminous, wherein, and x>=0.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102694110A (en) * | 2012-06-08 | 2012-09-26 | 北京理工大学 | Non-rare earth nanocrystalline fluorescent powder-containing packaging material, preparation method and application |
| CN104019922A (en) * | 2014-04-29 | 2014-09-03 | 北京理工大学 | Organic-inorganic hybrid perovskite material for temperature detection |
| CN111285396A (en) * | 2020-03-16 | 2020-06-16 | 常州大学 | Preparation method of Cu-In-Zn-S nanosphere and application of nanosphere In photoresponse detector |
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2011
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Non-Patent Citations (1)
| Title |
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| WENJIN ZHANG ET AL: "Facile Synthesis of ZnS－CuInS2-Alloyed Nanocrystals for a Color-Tunable Fluorchrome and Photocatalyst", 《INORGANIC CHEMISTRY》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102694110A (en) * | 2012-06-08 | 2012-09-26 | 北京理工大学 | Non-rare earth nanocrystalline fluorescent powder-containing packaging material, preparation method and application |
| WO2013181926A1 (en) * | 2012-06-08 | 2013-12-12 | 北京理工大学 | Packaging material containing non-rare-earth nanocrystal phosphor, preparation method and application thereof |
| CN102694110B (en) * | 2012-06-08 | 2015-06-03 | 北京理工大学 | Non-rare earth nanocrystalline fluorescent powder-containing packaging material, preparation method and application |
| CN104019922A (en) * | 2014-04-29 | 2014-09-03 | 北京理工大学 | Organic-inorganic hybrid perovskite material for temperature detection |
| CN104019922B (en) * | 2014-04-29 | 2016-11-23 | 北京理工大学 | Hybrid inorganic-organic perovskite material is used for temperature sensing by one |
| CN111285396A (en) * | 2020-03-16 | 2020-06-16 | 常州大学 | Preparation method of Cu-In-Zn-S nanosphere and application of nanosphere In photoresponse detector |
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