CN103553081A - Preparation method for monodisperse Er-Ho codoped core-shell-structured nanometer crystal - Google Patents
Preparation method for monodisperse Er-Ho codoped core-shell-structured nanometer crystal Download PDFInfo
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Abstract
The invention provides a preparation method for a monodisperse Er-Ho codoped core-shell-structured nanometer crystal, which relates to a preparation method for a core-shell-structured nanometer crystal. The invention aims to overcome the problems of incapable application of both Er<3+> and Ho<3+> in a same matrix and low up-conversion efficiency of a solar cell. The method comprises the following steps: preparing a reaction solution from YCl3 and ErCl3, preparing a raw material liquid from NaOH and NH4F and adding the raw material liquid into the reaction solution to produce a core-structured crystal; putting the core-structured crystal into a reaction solution prepared from YCl3 and HoCl3 so as to obtain a mixed reaction solution, adding the raw material liquid prepared from NaOH and NH4F into the mixed reaction solution so as to obtain a first layer core-shell crystal, adding the first layer core-shell crystal into a reaction solution prepared from YCl3 and adding the raw material liquid prepared from NaOH and NH4F into the reaction solution so as to prepare the codoped core-shell-structured nanometer crystal. The method provided by the invention dopes both Er<3+> and Ho<3+> ions into a same system and enables up-conversion efficiency to be improved.
Description
Technical field
The present invention relates to a kind of preparation method of nano-crystal with core-shell structure body.
Background technology
Photovoltaic solar cell, as renewable pollution-free energy source, can solve the energy and environment two hang-ups well simultaneously, has very vast potential for future development.At present, silica-based (monocrystalline, amorphous, polycrystalline) solar cell accounts for tool dominant position on market; It is higher that yet current photovoltaic efficiency of conversion makes the expense of silica-based solar cell kilowatt-hour compare with conventional energy resources, limits its universalness and practical.Further improve the efficiency of its solar cell, will reduce silica-based solar cell cost, thereby whole photovoltaic clean renewable resources development is played to huge pushing effect.But because sun emmission spectrum and silica-base material absorb mismatch, cause inefficient shortcoming, seriously limited the application of solar cell.According to relevant, at present, in annual energy consumption, sun power only accounts for 1% proportion, for the dependency of traditional Nonrenewable energy resources, does not obtain effective solution.Theoretical Calculation shows that the top efficiency under single-crystal mass silicon solar cell ideal conditions is 30% (the Shockley-Queisser limit), so be very important for the research that improves sun power transformation efficiency.
A major cause of restriction solar cell transformation efficiency is that solar spectral and solar cell absorption spectrum are not mated.Solar spectrum under AM1.5 solar spectrum irradiates, wherein only has a very little part to be absorbed by silicon solar cell.The relaxation loss that the main loss of solar cell has two kinds of (1) high energy solar photon to produce hot carrier, according to estimates nearly 149W/m
2solar energy so kind mode and be depleted.(2) solar photon lower than silicon band gap energy can directly see through silica-base material and not be absorbed nearly 164W/m
2solar energy is because direct transmission is depleted.
In order to improve the transformation efficiency of solar cell, upper conversion, two kinds of modes of quantum-cutting are suggested.Because the 4f-4f transition of electron of rare earth ion inner shell is owing to being subject to the shielding effect of its outside 5s and 5p filled shell, make its fluorescent emission as atom, become very sharp-pointed, also there is the longer life-span simultaneously.The stepped level structure of rare earth ion and wide spectral range (therefrom infrared to soft X-ray) make rare earth ion have unique quantum-cutting ability and upper transfer capability.
Australia T.Trupke professor's seminar and Switzerland H.U.G ü del professor's seminar cooperate to make in 2005 pioneering research; Utilize first hexagonal phase NaYF
4: Er
3+the upper crystallite of changing has improved 2.5%(power under 5 irradiations of milliwatt wavelength into 1523 nanometer lasers by two-sided silica-based solar cell efficiency).The scientist such as the scientist such as Dutch J.Wild in 2010 and German S.Fischer utilizes respectively NaYF subsequently
4: Er
3+, Yb
3+and NaYF
4: Er
3+upper conversion crystallite increases the infrared corresponding of non-crystalline silicon and crystal silicon solar energy battery, has improved its efficiency of conversion.With regard to domestic, also do not see the relevant report of utilizing up-conversion to strengthen solar battery efficiency at present; Even if be just directed to the exploitation of the up-conversion that improves solar battery efficiency, also rarely has report.
At present, by upper conversion, improve solar battery efficiency both at home and abroad and generally all concentrate on Er
3+and Ho
3+two kinds of ions, but the amount of adulterating in matrix due to two kinds of ions is very high, so be difficult to Er
3+and Ho
3+two kinds of ions are applied in same matrix jointly.If can be by Er
3+and Ho
3+in two kinds of ion co-doped to matrix, the efficiency for upper conversion raising solar cell has very large benefit so.
Summary of the invention
The object of the invention is at present cannot be by Er in order to solve
3+and Ho
3+two kinds of ions are jointly applied in same matrix and are applied in the low problem of efficiency of conversion on solar cell, and the preparation method who provides single Er of dispersion and Ho to mix altogether nano-crystal with core-shell structure body.
The preparation method that list of the present invention disperses Er and Ho to mix altogether nano-crystal with core-shell structure body carries out according to the following steps:
One, at room temperature by YCl
3and ErCl
3be dissolved in the solvent of oleic acid and octadecylene, obtain mixed solution;
Two, mixed solution step 1 being obtained, under the stirring velocity of 800r/min, is heated to 130～170 ℃, keeps naturally cooling to room temperature after 30～60 minutes, obtains reaction solution;
Three, by NaOH and NH
4f is dissolved in methyl alcohol, is stirred to dissolving, obtains stock liquid; Wherein NaOH and NH
4the mol ratio of F is 1:1～3;
Four,, under nitrogen protection, the stock liquid that step 3 is obtained joins in the reaction solution that step 2 obtains, and stirs 30～60 minutes under the rotating speed of 800r/min, then increases the temperature to 300 ℃, reacts after 1 hour and is cooled to room temperature, obtains reaction soln;
Five, reaction soln step 4 being obtained is put into centrifuge tube, add dehydrated alcohol, sonic oscillation 10～20min, and with the rotating speed centrifuge washing 10min of 10000r/min, collect solid formation, then add dehydrated alcohol sonic oscillation 10～20min, repeated centrifugation washing, supersound process operation 3 times, the solid formation regathering is distributed in cyclohexane solvent, and the nuclear structure nanocrystal obtaining is stand-by;
Six, at room temperature by YCl
3and HoCl
3be dissolved in the solvent of oleic acid and octadecylene, obtain mixed solution;
Seven, by the mixed solution obtaining in step 6, under the stirring velocity of 800r/min, be heated to 130～170 ℃, keep naturally cooling to 60～80 ℃ after 30～60 minutes, obtain reaction solution;
Eight, nuclear structure nanocrystal step 5 being obtained joins in the reaction solution of step 7 gained, stirs and after 30 minutes, increases the temperature to 100 ℃ except hexanaphthene 10～20 minutes, obtains mixed reaction solution;
Nine, by NaOH and NH
4f is dissolved in methyl alcohol, is stirred to dissolving, obtains stock liquid; Wherein NaOH and NH
4the mol ratio of F is 1:1～3;
Ten,, under nitrogen protection, the stock liquid that step 9 is obtained joins in the mixed reaction solution that step 8 obtains, and stirs 30～60 minutes under the rotating speed of 800r/min, then increases the temperature to 300 ℃, reacts after 1 hour and is cooled to room temperature, obtains reaction soln;
11, reaction soln step 10 being obtained is put into centrifuge tube, add dehydrated alcohol, sonic oscillation 10～20min, and with the rotating speed centrifuge washing 10min of 10000r/min, collect solid formation, then add dehydrated alcohol sonic oscillation 10～20min, repeated centrifugation washing, supersound process operation 3 times, the solid formation regathering is distributed in cyclohexane solvent, and the first layer nano-crystal with core-shell structure body obtaining is stand-by;
12, at room temperature by YCl
3be dissolved in the solvent of oleic acid and octadecylene, obtain mixed solution;
13, mixed solution step 12 being obtained, under the stirring velocity of 800r/min, is heated to 130～170 ℃, keeps naturally cooling to 60～80 ℃ after 30～60 minutes, obtains reaction solution;
14, the first layer nano-crystal with core-shell structure body step 11 being obtained joins in the reaction solution of step 13 gained, stirs and after 30 minutes, increases the temperature to 100 ℃ except hexanaphthene 10～20 minutes, obtains mixed reaction solution;
15, by NaOH and NH
4f is dissolved in methyl alcohol, is stirred to dissolving, obtains stock liquid; Wherein NaOH and NH
4the mol ratio of F is 1:1～3;
16, under nitrogen protection, the stock liquid that step 15 is obtained joins in the mixed reaction solution that step 14 obtains, and stirs 30～60 minutes under the rotating speed of 800r/min, then increases the temperature to 300 ℃, react and be cooled to room temperature after 1 hour, obtain reaction soln;
17, reaction soln step 10 six being obtained is put into centrifuge tube, add dehydrated alcohol, sonic oscillation 10～20min, and with the rotating speed centrifuge washing 10min of 10000r/min, collect solid formation, then add dehydrated alcohol sonic oscillation 10～20min, repeated centrifugation washing, supersound process operation 3 times, the solid formation regathering is distributed in cyclohexane solvent, obtains single Er of dispersion and Ho and mixes altogether nano-crystal with core-shell structure body.
It is white powder NaYF that single dispersion Er of gained of the present invention and Ho mix nano-crystal with core-shell structure body altogether
4: Er
3+@NaYF
4: Ho
3+@NaYF
4nanocrystal, nuclear structure six side's phase NaYF that wherein step 5 obtains
4: Er
3+nanocrystal size is about 23nm, the first layer nucleocapsid structure six side's phase NaYF that step 11 obtains
4: Er
3+@NaYF
4: Ho
3+nanocrystal size is about 35nm, and the single Er of dispersion and the Ho that finally obtain mix nucleocapsid structure six side's phase NaYF altogether
4: Er
3+@NaYF
4: Ho
3+@NaYF
4nanocrystal size is approximately 60nm.The 4th step in synthesis step, the tenth step and the 16 step are the committed steps of nanocrystal growth after forming nucleus, if it is improper that condition is controlled, resulting nanocrystal there will be size inhomogeneous, not of uniform size, or there is the phenomenon of reuniting, illumination effect is produced to considerable influence.
To sum up the present invention has following advantage aspect upper conversion nano crystal raising solar cell transformation efficiency:
(1) successfully by Er
3+and Ho
3+ion co-doped is in an individual system, and the single Er of dispersion and the Ho that obtain mix nano-crystal with core-shell structure body size uniform altogether, jointly by upper switching process, improve solar energy converting rate;
(2) pass through the coated of " nucleocapsid shell " structure, reduced surperficial defect, reduced specific surface area simultaneously, improved respectively Er
3+and Ho
3+the upper efficiency of conversion of two kinds of ions.
Accompanying drawing explanation
Fig. 1 is the nuclear structure NaYF that embodiment mono-step 5 obtains
4: Er
3+the transmission electron microscope picture of nanocrystal;
Fig. 2 is the first layer nucleocapsid structure NaYF that embodiment mono-step 11 obtains
4: Er
3+@NaYF
4: Ho
3+the transmission electron microscope picture of nanocrystal;
Fig. 3 is that single Er of dispersion and the Ho that embodiment mono-obtains mixes nucleocapsid structure NaYF altogether
4: Er
3+@NaYF
4: Ho
3+@NaYF
4the transmission electron microscope picture of nanocrystal;
Fig. 4 is the emmission spectrum of three kinds of nanocrystal tests under the exciting of the laser of 1157nm, and wherein a is the NaYF that embodiment mono-obtains
4: Er
3+@NaYF
4: Ho
3+@NaYF
4" nucleocapsid shell " structure nano is brilliant, and b is NaYF
4: Er
3+@NaYF
4: Ho
3+" nucleocapsid " structure nano is brilliant, and c is the NaYF4:Er that Er and Ho mix altogether
3+, Ho
3+nanocrystal, wherein Er
3+doping volumetric molar concentration be 10%, Ho
3+doping volumetric molar concentration be 10%;
Fig. 5 is the emmission spectrum of three kinds of nanocrystal tests under the exciting of the laser of 1523nm, and wherein a is the NaYF that embodiment mono-obtains
4: Er
3+@NaYF
4: Ho
3+@NaYF
4" nucleocapsid shell " structure nano is brilliant, and b is NaYF
4: Er
3+@NaYF
4: Ho
3+" nucleocapsid " structure nano is brilliant, and c is the NaYF4:Er that Er and Ho mix altogether
3+, Ho
3+nanocrystal, wherein Er
3+doping volumetric molar concentration be 10%, Ho
3+doping volumetric molar concentration be 10%;
Fig. 6 is to be the transmitting collection of illustrative plates that excites two kinds of nanocrystals under 1523nm laser at power, the NaYF that wherein 1-embodiment mono-obtains
4: Er
3+@NaYF
4: Ho
3+@NaYF
4the transmitting collection of illustrative plates of " nucleocapsid shell " structure nano crystalline substance, 2-LiYF
4: Er
3+the transmitting collection of illustrative plates of nanocrystalline particle.
Embodiment
Embodiment one: the preparation method that present embodiment list disperses Er and Ho to mix altogether nano-crystal with core-shell structure body carries out according to the following steps:
One, at room temperature by YCl
3and ErCl
3be dissolved in the solvent of oleic acid and octadecylene, obtain mixed solution;
Two, mixed solution step 1 being obtained, under the stirring velocity of 800r/min, is heated to 130～170 ℃, keeps naturally cooling to room temperature after 30～60 minutes, obtains reaction solution;
Three, by NaOH and NH
4f is dissolved in methyl alcohol, is stirred to dissolving, obtains stock liquid; Wherein NaOH and NH
4the mol ratio of F is 1:1～3;
Four,, under nitrogen protection, the stock liquid that step 3 is obtained joins in the reaction solution that step 2 obtains, and stirs 30～60 minutes under the rotating speed of 800r/min, then increases the temperature to 300 ℃, reacts after 1 hour and is cooled to room temperature, obtains reaction soln;
Five, reaction soln step 4 being obtained is put into centrifuge tube, add dehydrated alcohol, sonic oscillation 10～20min, and with the rotating speed centrifuge washing 10min of 10000r/min, collect solid formation, then add dehydrated alcohol sonic oscillation 10～20min, repeated centrifugation washing, supersound process operation 3 times, the solid formation regathering is distributed in cyclohexane solvent, and the nuclear structure nanocrystal obtaining is stand-by;
Six, at room temperature by YCl
3and HoCl
3be dissolved in the solvent of oleic acid and octadecylene, obtain mixed solution;
Seven, by the mixed solution obtaining in step 6, under the stirring velocity of 800r/min, be heated to 130～170 ℃, keep naturally cooling to 60～80 ℃ after 30～60 minutes, obtain reaction solution;
Eight, nuclear structure nanocrystal step 5 being obtained joins in the reaction solution of step 7 gained, stirs and after 30 minutes, increases the temperature to 100 ℃ except hexanaphthene 10～20 minutes, obtains mixed reaction solution;
Nine, by NaOH and NH
4f is dissolved in methyl alcohol, is stirred to dissolving, obtains stock liquid; Wherein NaOH and NH
4the mol ratio of F is 1:1～3;
Ten,, under nitrogen protection, the stock liquid that step 9 is obtained joins in the mixed reaction solution that step 8 obtains, and stirs 30～60 minutes under the rotating speed of 800r/min, then increases the temperature to 300 ℃, reacts after 1 hour and is cooled to room temperature, obtains reaction soln;
11, reaction soln step 10 being obtained is put into centrifuge tube, add dehydrated alcohol, sonic oscillation 10～20min, and with the rotating speed centrifuge washing 10min of 10000r/min, collect solid formation, then add dehydrated alcohol sonic oscillation 10～20min, repeated centrifugation washing, supersound process operation 3 times, the solid formation regathering is distributed in cyclohexane solvent, and the first layer nano-crystal with core-shell structure body obtaining is stand-by;
12, at room temperature by YCl
3be dissolved in the solvent of oleic acid and octadecylene, obtain mixed solution;
13, mixed solution step 12 being obtained, under the stirring velocity of 800r/min, is heated to 130～170 ℃, keeps naturally cooling to 60～80 ℃ after 30～60 minutes, obtains reaction solution;
14, the first layer nano-crystal with core-shell structure body step 11 being obtained joins in the reaction solution of step 13 gained, stirs and after 30 minutes, increases the temperature to 100 ℃ except hexanaphthene 10～20 minutes, obtains mixed reaction solution;
15, by NaOH and NH
4f is dissolved in methyl alcohol, is stirred to dissolving, obtains stock liquid; Wherein NaOH and NH
4the mol ratio of F is 1:1～3;
16, under nitrogen protection, the stock liquid that step 15 is obtained joins in the mixed reaction solution that step 14 obtains, and stirs 30～60 minutes under the rotating speed of 800r/min, then increases the temperature to 300 ℃, react and be cooled to room temperature after 1 hour, obtain reaction soln;
17, reaction soln step 10 six being obtained is put into centrifuge tube, add dehydrated alcohol, sonic oscillation 10～20min, and with the rotating speed centrifuge washing 10min of 10000r/min, collect solid formation, then add dehydrated alcohol sonic oscillation 10～20min, repeated centrifugation washing, supersound process operation 3 times, the solid formation regathering is distributed in cyclohexane solvent, obtains single Er of dispersion and Ho and mixes altogether nano-crystal with core-shell structure body.
The object of 130～170 ℃ of being heated to described in present embodiment step 2, step 7 and step 13 is in order to dewater.
Present embodiment is by the two-layer coated NaYF that synthesized
4: Er
3+@NaYF
4: Ho
3+@NaYF
4nanocrystal, has realized Er
3+and Ho
3+ion co-doped is in an individual system, and efficiency of conversion on simultaneously strengthening two kinds.Because the absorption spectrum of solar cell material does not mate with solar spectrum, cause a large amount of sun power not to be utilized and slattern, so by this NaYF
4: Er
3+@NaYF
4: Ho
3+@NaYF
4synthesizing of " nucleocapsid shell " nanocrystal, Er
3+and Ho
3+two kinds of ions can be worked simultaneously, have significantly improved upper efficiency of conversion.
Embodiment two: present embodiment is different from embodiment one is the YCl described in step 1
3and ErCl
3integral molar quantity and the volume ratio of oleic acid be 1mmol:3～10ml, YCl
3and ErCl
3integral molar quantity and the volume ratio of octadecylene be 1mmol:12～20ml.Other step and parameter are identical with embodiment one.
Embodiment three: present embodiment is different from embodiment one or two is the YCl described in step 1
3and ErCl
3middle ErCl
3molecular fraction account for 5～30%.Other step and parameter are identical with embodiment one.
Embodiment four: present embodiment is different from one of embodiment one to three be NaOH described in step 3 with the molecular volume of methyl alcohol than being 1mmol:1～4ml, NH
4f is 1mmol:2～10ml with the molecular volume ratio of methyl alcohol.Other step and parameter are identical with one of embodiment one to three.
Embodiment five: present embodiment is different from one of embodiment one to four is NaOH and the NH described in step 3
4the mol ratio of F is 1:2.Other step and parameter are identical with one of embodiment one to four.
Embodiment six: what present embodiment was different from one of embodiment one to five is that step 4 stirs 45 minutes under the rotating speed of 800r/min.Other step and parameter are identical with one of embodiment one to five.
Embodiment seven: present embodiment is different from one of embodiment one to six is the YCl described in step 6
3and HoCl
3integral molar quantity and the volume ratio of oleic acid be 1mmol:3～10ml, YCl
3and HoCl
3integral molar quantity and the volume ratio of octadecylene be 1mmol:12～20ml.Other step and parameter are identical with one of embodiment one to six.
Embodiment eight: present embodiment is different from one of embodiment one to seven is the YCl described in step 6
3and HoCl
3middle HoCl
3molecular fraction account for 5～30%.Other step and parameter are identical with one of embodiment one to seven.
Embodiment nine: present embodiment is different from one of embodiment one to eight is that oleic acid described in step 6 and the volume ratio of octadecylene are 1:3.Other step and parameter are identical with one of embodiment one to eight.
Embodiment ten: what present embodiment was different from one of embodiment one to nine is that step 7 naturally cools to 70 ℃.Other step and parameter are identical with one of embodiment one to nine.
Embodiment 11: what present embodiment was different from one of embodiment one to ten is that in step 9, NaOH is 1mmol:1～4ml with the molecular volume ratio of methyl alcohol, NH
4f is 1mmol:2～10ml with the molecular volume ratio of methyl alcohol.Other step and parameter are identical with one of embodiment one to ten.
Embodiment 12: present embodiment is different from one of embodiment one to 11 is the YCl described in step 12
3compare for 1mmol:3～10ml YCl with the molecular volume of oleic acid
3compare for 1mmol:12～20ml with the molecular volume of octadecylene.Other step and parameter are identical with one of embodiment one to 11.
Embodiment 13: present embodiment is different from embodiment one to 12 is that step 14 stirs and increases the temperature to 100 ℃ after 30 minutes except hexanaphthene 15 minutes.Other step and parameter are identical with one of embodiment one to 12.
Embodiment 14: present embodiment is different from embodiment one to 13 be NaOH described in step 15 with the molecular volume of methyl alcohol than being 1mmol:1～4ml, NH
4f is 1mmol:2～10ml with the molecular volume ratio of methyl alcohol.Other step and parameter are identical with one of embodiment one to 13.
Embodiment 15: present embodiment is different from embodiment one to 13 is the NH described in step 15
4f is 1mmol:8ml with the molecular volume ratio of methyl alcohol.Other step and parameter are identical with one of embodiment one to 13.
Embodiment 16: present embodiment is different from one of embodiment one to 15 be solid formation described in step 5, step 11 and step 10 seven with the molecular volume of hexanaphthene than being 1mmol:4～10mL.Other step and parameter are identical with one of embodiment one to 15.
Embodiment mono-: the preparation method that the present embodiment list disperses Er and Ho to mix altogether nano-crystal with core-shell structure body carries out according to the following steps:
One, at room temperature by 0.9mmolYCl
3and 0.1mmolErCl
3be dissolved in the solvent of 6ml oleic acid and 15ml octadecylene, obtain mixed solution;
Two, mixed solution step 1 being obtained, under the stirring velocity of 800r/min, is heated to 150 ℃, keeps naturally cooling to room temperature after 60 minutes, obtains reaction solution;
Three, by 2.5mmolNaOH and 4mmol NH
4f is dissolved in 10ml methyl alcohol, is stirred to dissolving, obtains stock liquid;
Four,, under nitrogen protection, the stock liquid that step 3 is obtained joins in the reaction solution that step 2 obtains, and stirs 30 minutes under the rotating speed of 800r/min, then increases the temperature to 300 ℃, reacts after 1 hour and is cooled to room temperature, obtains reaction soln;
Five, reaction soln step 4 being obtained is put into centrifuge tube, add dehydrated alcohol, sonic oscillation 10min, and with the rotating speed centrifuge washing 10min of 10000r/min, collect solid formation, then add dehydrated alcohol sonic oscillation 10min, repeated centrifugation washing, supersound process operation 3 times, the solid formation of collecting is distributed in 10ml cyclohexane solvent, and the nuclear structure obtaining is nanocrystalline stand-by;
Six, at room temperature by 0.9mmolYCl
3and 0.1mmolHoCl
3be dissolved in the solvent of 6ml oleic acid and 15ml octadecylene, obtain mixed solution;
Seven, by the mixed solution obtaining in step 6, under the stirring velocity of 800r/min, be heated to 150 ℃, keep naturally cooling to 70 ℃ after 60 minutes, obtain reaction solution;
Eight, nuclear structure nanocrystal step 5 being obtained joins in the reaction solution of step 7 gained, stirs and after 30 minutes, increases the temperature to 100 ℃ except hexanaphthene 20 minutes, obtains mixed reaction solution;
Nine, by 2.5mmolNaOH and 4mmolNH
4f is dissolved in 10ml methyl alcohol, is stirred to dissolving, obtains stock liquid;
Ten,, under nitrogen protection, the stock liquid that step 9 is obtained joins in the mixed reaction solution that step 8 obtains, and stirs 30 minutes under the rotating speed of 800r/min, then increases the temperature to 300 ℃, reacts after 1 hour and is cooled to room temperature, obtains reaction soln;
11, reaction soln step 10 being obtained is put into centrifuge tube, add dehydrated alcohol, sonic oscillation 10min, and with the rotating speed centrifuge washing 10min of 10000r/min, collect solid formation, then add dehydrated alcohol sonic oscillation 10min, repeated centrifugation washing, supersound process operation 3 times, the solid formation regathering is distributed in 10ml cyclohexane solvent, and the first layer nano-crystal with core-shell structure body obtaining is stand-by;
12, at room temperature by 1mmolYCl
3be dissolved in the solvent of 6ml oleic acid and 15ml octadecylene, obtain mixed solution;
13, mixed solution step 12 being obtained, under the stirring velocity of 800r/min, is heated to 150 ℃, keeps naturally cooling to 70 ℃ after 60 minutes, obtains reaction solution;
14, the first layer nano-crystal with core-shell structure body step 11 being obtained joins in the reaction solution of step 13 gained, stirs and after 30 minutes, increases the temperature to 100 ℃ except hexanaphthene 20 minutes, obtains mixed reaction solution;
15, by 2.5mmolNaOH and 4mmolNH
4f is dissolved in 10ml methyl alcohol, is stirred to dissolving, obtains stock liquid;
16,, under nitrogen protection, the stock liquid that step 15 is obtained joins in the mixed reaction solution that step 14 obtains, and stirs 30 minutes under the rotating speed of 800r/min, then increases the temperature to 300 ℃, reacts after 1 hour and is cooled to room temperature, obtains reaction soln;
17, reaction soln step 10 six being obtained is put into centrifuge tube, add dehydrated alcohol, sonic oscillation 10min, and with the rotating speed centrifuge washing 10min of 10000r/min, collect solid formation, then add dehydrated alcohol sonic oscillation 10min, repeated centrifugation washing, supersound process operation 3 times, the solid formation regathering is distributed in 10ml cyclohexane solvent, obtains single Er of dispersion and Ho and mixes altogether nano-crystal with core-shell structure body.
In the present embodiment step 5, step 11 and step 10 seven, the amount of the volume of added dehydrated alcohol does not require, on the not impact of the result of this test.
Nuclear structure that the present embodiment step 5 obtains is nanocrystalline is six side's phase NaYF
4: Er
3+nanocrystal, size is about 23nm, and its transmission electron microscope picture is as shown in Figure 1; The first layer nano-crystal with core-shell structure body that step 11 obtains is six side's phase NaYF
4: Er
3+@NaYF
4: Ho
3+nanocrystal, size is about 35nm, and its transmission electron microscope picture is as shown in Figure 2; It is six side's phase NaYF that the single Er of dispersion finally obtaining and Ho mix nano-crystal with core-shell structure body altogether
4: Er
3+@NaYF
4: Ho
3+@NaYF
4nanocrystal, size is approximately 60nm, and its transmission electron microscope picture is as shown in Figure 3.From Fig. 1 to Fig. 3, can demonstrate prepared nanocrystal and be six side's phases, and synthetic along with nucleocapsid structure, size increases gradually, and crystalline phase is also more and more obvious.Illustrate that this nanocrystal has good application prospect aspect sun power.
The NaYF that the present embodiment obtains
4: Er
3+@NaYF
4: Ho
3+@NaYF
4the emmission spectrum of nanocrystal test under the exciting of the laser of 1157nm as shown in Figure 4, NaYF
4: Er
3+@NaYF
4: Ho
3+@NaYF
4the emmission spectrum of nanocrystal test under the exciting of the laser of 1523nm as shown in Figure 5.NaYF in Fig. 4
4: Er
3+@NaYF
4: Ho
3+@NaYF
4the peak area value of nanocrystal is 46757.03, NaYF
4: Er
3+@NaYF
4: Ho
3+the peak area value of " nucleocapsid " structure nano crystalline substance is 4593.21, strengthens 10 times more than; NaYF in Fig. 5
4: Er
3+@NaYF
4: Ho
3+@NaYF
4the peak area value of nanocrystal is 71098.29, NaYF
4: Er
3+@NaYF
4: Ho
3+the peak area value of " nucleocapsid " structure nano crystalline substance is 23239.26, has strengthened 3 times more than.
Power be under 1523nm laser, excite two kinds of nanocrystals transmitting collection of illustrative plates as shown in Figure 6, NaYF as we know from the figure
4: Er
3+@NaYF
4: Ho
3+@NaYF
4the upper conversion quantum yield of nanocrystal.Upper conversion quantum yield refers to the ratio of the number of photons that number of photons that material inspires and material absorb, i.e. QY=E/A, and wherein QY represents quantum yield, the number of photons of E material transmitting, A represents the number of photons of absorbed.The present embodiment adopts the method for calculation of Relative quantum yields to try to achieve the present embodiment NaYF
4: Er
3+@NaYF
4: Ho
3+@NaYF
4the quantum yield of nanocrystal, adopt Guanying Chen, the people such as Tymish Y Ohulchanskyy are called " Intense visible and near-infrared upconversion photoluminescence in colloidal LiYF < < ACS nano > > the 5th volume 4981-4986 page name in 2011
4: Er
3+nan ocrystals under excitation at1490nm " the middle LiYF recording
4: Er
3+nanocrystal is as a comparison sample, according to the known LiYF of this document
4: Er
3+the quantum yield of nanocrystal is in 1.2% left and right.Then use QY
s=E
s/ A
swith QY
rEF=E
rEF/ A
rEFremove mutually two equation left and right, obtains calculating formula QY
s=(E
s/ E
rEF) * (A
rEF/ A
s) * QY
rEF, QY in its formula
sthe quantum yield of representative sample, QY
rEFrepresent the quantum yield of comparative sample, E
sthe number of photons of representative sample transmitting, E
rEFrepresent the number of photons of comparative sample transmitting, A
sthe number of photons that representative sample absorbs, A
rEFrepresent the number of photons that comparative sample absorbs.Demarcate again its absorption value, make sample NaYF
4: Er
3+@NaYF
4: Ho
3+@NaYF
4nanocrystal and contrast sample LiYF
4: Er
3+nanocrystal is consistent at the absorption peak height of 1523nm, then to the sample of demarcating and contrast sample, adopts the laser of the 1523nm of equal-wattage to excite it, thereby obtains Fig. 6.Because the absorption of sample and contrast sample was demarcated, the A in formula shown
rEF/ A
s=1, QY
rEFknownly equal 1.2%, and E
s/ E
rEFbe exactly in figure all peak-to-peak area values and ratio, by measuring, known NaYF
4: Er
3+@NaYF
4: Ho
3+@NaYF
4the quantum yield of nanocrystal is about 2.4% left and right, far away higher than the quantum yield that contrasts sample nanoparticle.
Claims (10)
1. single preparation method who disperses Er and Ho to mix altogether nano-crystal with core-shell structure body, is characterized in that single Er of dispersion and Ho mix that the preparation method of nano-crystal with core-shell structure body carries out according to the following steps altogether:
One, at room temperature by YCl
3and ErCl
3be dissolved in the solvent of oleic acid and octadecylene, obtain mixed solution;
Two, mixed solution step 1 being obtained, under the stirring velocity of 800r/min, is heated to 130～170 ℃, keeps naturally cooling to room temperature after 30～60 minutes, obtains reaction solution;
Three, by NaOH and NH
4f is dissolved in methyl alcohol, is stirred to dissolving, obtains stock liquid; Wherein NaOH and NH
4the mol ratio of F is 1:1～3;
Four,, under nitrogen protection, the stock liquid that step 3 is obtained joins in the reaction solution that step 2 obtains, and stirs 30～60 minutes under the rotating speed of 800r/min, then increases the temperature to 300 ℃, reacts after 1 hour and is cooled to room temperature, obtains reaction soln;
Five, reaction soln step 4 being obtained is put into centrifuge tube, add dehydrated alcohol, sonic oscillation 10～20min, and with the rotating speed centrifuge washing 10min of 10000r/min, collect solid formation, then add dehydrated alcohol sonic oscillation 10～20min, repeated centrifugation washing, supersound process operation 3 times, the solid formation regathering is distributed in cyclohexane solvent, and the nuclear structure nanocrystal obtaining is stand-by;
Six, at room temperature by YCl
3and HoCl
3be dissolved in the solvent of oleic acid and octadecylene, obtain mixed solution;
Seven, by the mixed solution obtaining in step 6, under the stirring velocity of 800r/min, be heated to 130～170 ℃, keep naturally cooling to 60～80 ℃ after 30～60 minutes, obtain reaction solution;
Eight, nuclear structure nanocrystal step 5 being obtained joins in the reaction solution of step 7 gained, stirs and after 30 minutes, increases the temperature to 100 ℃ except hexanaphthene 10～20 minutes, obtains mixed reaction solution;
Nine, by NaOH and NH
4f is dissolved in methyl alcohol, is stirred to dissolving, obtains stock liquid; Wherein NaOH and NH
4the mol ratio of F is 1:1～3;
Ten,, under nitrogen protection, the stock liquid that step 9 is obtained joins in the mixed reaction solution that step 8 obtains, and stirs 30～60 minutes under the rotating speed of 800r/min, then increases the temperature to 300 ℃, reacts after 1 hour and is cooled to room temperature, obtains reaction soln;
11, reaction soln step 10 being obtained is put into centrifuge tube, add dehydrated alcohol, sonic oscillation 10～20min, and with the rotating speed centrifuge washing 10min of 10000r/min, collect solid formation, then add dehydrated alcohol sonic oscillation 10～20min, repeated centrifugation washing, supersound process operation 3 times, the solid formation regathering is distributed in cyclohexane solvent, and the first layer nano-crystal with core-shell structure body obtaining is stand-by;
12, at room temperature by YCl
3be dissolved in the solvent of oleic acid and octadecylene, obtain mixed solution;
13, mixed solution step 12 being obtained, under the stirring velocity of 800r/min, is heated to 130～170 ℃, keeps naturally cooling to 60～80 ℃ after 30～60 minutes, obtains reaction solution;
14, the first layer nano-crystal with core-shell structure body step 11 being obtained joins in the reaction solution of step 13 gained, stirs and after 30 minutes, increases the temperature to 100 ℃ except hexanaphthene 10～20 minutes, obtains mixed reaction solution;
15, by NaOH and NH
4f is dissolved in methyl alcohol, is stirred to dissolving, obtains stock liquid; Wherein NaOH and NH
4the mol ratio of F is 1:1～3;
16, under nitrogen protection, the stock liquid that step 15 is obtained joins in the mixed reaction solution that step 14 obtains, and stirs 30～60 minutes under the rotating speed of 800r/min, then increases the temperature to 300 ℃, react and be cooled to room temperature after 1 hour, obtain reaction soln;
17, reaction soln step 10 six being obtained is put into centrifuge tube, add dehydrated alcohol, sonic oscillation 10～20min, and with the rotating speed centrifuge washing 10min of 10000r/min, collect solid formation, then add dehydrated alcohol sonic oscillation 10～20min, repeated centrifugation washing, supersound process operation 3 times, the solid formation regathering is distributed in cyclohexane solvent, obtains single Er of dispersion and Ho and mixes altogether nano-crystal with core-shell structure body.
2. single preparation method who disperses Er and Ho to mix altogether nano-crystal with core-shell structure body according to claim 1, is characterized in that the YCl described in step 1
3and ErCl
3integral molar quantity and the volume ratio of oleic acid be 1mmol ︰ 3～10ml, YCl
3and ErCl
3integral molar quantity and the volume ratio of octadecylene be 1mmol ︰ 12～20ml.
3. single preparation method who disperses Er and Ho to mix altogether nano-crystal with core-shell structure body according to claim 1, is characterized in that the YCl described in step 1
3and ErCl
3middle ErCl
3molecular fraction account for 5%～30%.
4. single preparation method who disperses Er and Ho to mix altogether nano-crystal with core-shell structure body according to claim 1, it is characterized in that NaOH described in step 3 with the molecular volume of methyl alcohol than being 1mmol ︰ 1～4ml, NH
4f is 1mmol ︰ 2～10ml with the molecular volume ratio of methyl alcohol.
5. single preparation method who disperses Er and Ho to mix altogether nano-crystal with core-shell structure body according to claim 1, is characterized in that NaOH and NH described in step 3
4the mol ratio of F is 1 ︰ 2.
6. single preparation method who disperses Er and Ho to mix altogether nano-crystal with core-shell structure body according to claim 1, is characterized in that the YCl described in step 6
3and HoCl
3middle HoCl
3molecular fraction account for 5%～30%.
7. single preparation method who disperses Er and Ho to mix altogether nano-crystal with core-shell structure body according to claim 1, is characterized in that the YCl described in step 6
3and HoCl
3integral molar quantity and the volume ratio of oleic acid be 1mmol ︰ 3～10ml, YCl
3and HoCl
3integral molar quantity and the volume ratio of octadecylene be 1mmol ︰ 12～20ml.
8. single preparation method who disperses Er and Ho to mix altogether nano-crystal with core-shell structure body according to claim 1, is characterized in that in step 9, NaOH is 1mmol ︰ 1～4ml with the molecular volume ratio of methyl alcohol, NH
4f is 1mmol ︰ 2～10ml with the molecular volume ratio of methyl alcohol.
9. single preparation method who disperses Er and Ho to mix altogether nano-crystal with core-shell structure body according to claim 1, is characterized in that the YCl described in step 12
3compare for 1mmol ︰ 3～10ml YCl with the molecular volume of oleic acid
3compare for 1mmol ︰ 12～20ml with the molecular volume of octadecylene.
10. single preparation method who disperses Er and Ho to mix altogether nano-crystal with core-shell structure body according to claim 1, it is characterized in that NaOH described in step 15 with the molecular volume of methyl alcohol than being 1mmol ︰ 1～4ml, NH
4f is 1mmol ︰ 2～10ml with the molecular volume ratio of methyl alcohol.
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| CN104974758A (en) * | 2015-07-24 | 2015-10-14 | 哈尔滨汇工科技有限公司 | Preparation method of NaYF4:Er<3+>@NaYF4@TiO2 nanocrystalline dye-sensitized solar cell photo-anode material |
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| CN102391874A (en) * | 2011-09-21 | 2012-03-28 | 中国科学院上海硅酸盐研究所 | NaYF4-based fluorescent nano particles with double effects and preparation method thereof |
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2013
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102391874A (en) * | 2011-09-21 | 2012-03-28 | 中国科学院上海硅酸盐研究所 | NaYF4-based fluorescent nano particles with double effects and preparation method thereof |
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| HAI-SHENG QIAN ET AL.: "Synthesis of Hexagonal-Phase Core-Shell NaYF4 Nanocrystals with Tunable Upconversion Fluorescence", 《LANGMUIR》 * |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104974758A (en) * | 2015-07-24 | 2015-10-14 | 哈尔滨汇工科技有限公司 | Preparation method of NaYF4:Er<3+>@NaYF4@TiO2 nanocrystalline dye-sensitized solar cell photo-anode material |
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