CN114350364B - Preparation method of high fluorescence yield all-inorganic colloid nano crystal - Google Patents
Preparation method of high fluorescence yield all-inorganic colloid nano crystal Download PDFInfo
- Publication number
- CN114350364B CN114350364B CN202210047192.6A CN202210047192A CN114350364B CN 114350364 B CN114350364 B CN 114350364B CN 202210047192 A CN202210047192 A CN 202210047192A CN 114350364 B CN114350364 B CN 114350364B
- Authority
- CN
- China
- Prior art keywords
- nanocrystals
- metal salt
- solution
- ligand
- organic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/88—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing selenium, tellurium or unspecified chalcogen elements
Abstract
The invention belongs to the technical field of nano materials, and particularly relates to a preparation method of an all-inorganic colloid nano crystal with high fluorescence yield.
Description
Technical Field
The invention belongs to the technical field of nano materials, and particularly relates to a preparation method of an all-inorganic colloid nano crystal with high fluorescence yield.
Background
The main body of the nanocrystalline device is colloidal Nanocrystals (NCs), which are usually composed of inorganic nanostructures and surface ligands, and the physical and chemical properties (thermal stability, ductility, optical, electrical, magnetic properties and the like) of the nanocrystalline device are determined by the composition, morphology and structure of the nanocrystalline device and the surface ligands, so that the functional precise design of the nanomaterial can be realized through the regulation and control of the crystals and the ligand parts. At present, a large amount of organic molecules are attached to the surface of the nano crystal synthesized by a solution method, and are used for controlling the morphology of the crystal and keeping the colloid stability of the crystal. However, long chain organic molecules severely hinder the transport of charge or heat between crystals, while also reducing the packing concentration of nanocrystals in the device. Therefore, the device is directly constructed by using the organic-inorganic hybrid nanocrystals, and the device has high energy consumption, poor thermal stability and low working efficiency. The all-inorganic nano material can effectively shorten the inter-crystal distance, thereby improving the coupling between nano crystals, improving the charge transfer speed and enhancing the performances of the material such as conductivity, electron mobility and the like.
At present, the preparation methods of all-inorganic nanocrystals include the following two methods: (1) ligand exchange. The original organic ligand on the surface of the nano crystal is replaced by an inorganic ligand, so that the surface of the nano crystal is changed into negatively charged from electric neutrality and stably exists in a common polar solvent, and the inorganic ligand comprises: chalcogenide ligands (S) 2- ,Se 2- ,Sn 2 S 6 4- ,In 2 Se 4 2- Etc.), halogen-like ligands (Br) - ,CdCl 3 - ,N 3 - ,CN - Etc.) and an oxyanion ligand etc. (PO) 4 3- ,OCN - ,WO 4 2- ,[PMo 12 O 40 ] 3- Etc.); yang (Yang)The ionic portion being typically Na + ，K + ，NH 4 + ，N 2 H 5 + Etc. (2) ligand stripping. Removing the organic ligand on the surface of the nanocrystal to expose the metal atoms which do not form covalent bonds, changing the original electrically neutral nanocrystal surface to be positively charged, and stably existing in a common polar solvent, wherein the stripping ligand comprises: HX (x=cl, br, NO) 3 Etc.), NOBF 4 , 9 Et 3 OBF 4 And Et 2 OBF 3 。
However, the existing preparation method of all-inorganic nanocrystals still has the following disadvantages:
(1) For the traditional inorganic ligand, the hetero atoms are introduced while the original organic ligand is replaced, so that the composition of the nano crystal is changed. (2) For protonic acids and NOBF in the stripping ligand 4 And (3) a ligand and strong acid etch the surface of the nanocrystal to change the morphology of the nanocrystal. (3) For Et in the stripping ligand 3 OBF 4 And Et 2 OBF 3 The ligand, mild lewis acid, is too narrow to handle all nanocrystals and Et 3 OBF 4 The treated nanocrystals lack long-range stability and thus have limited applicability.
A common disadvantage of all ligands present at present is, however: in the ligand exchange process, a large number of defects are inevitably generated on the surface of the nanocrystalline crystal, so that the luminous performance of the crystal is seriously damaged, and the development of all-inorganic nano materials in the field of optical sensors is limited. For example, the fluorescence quantum efficiency (PLQY) of the core-shell nanocrystals protected by conventional organic ligands is above 60%, and can even reach 100%, and then the luminescent efficiency of pure inorganic materials prepared by conventional inorganic ligands and exchange means is only 10% or even lower (< 2%) of the original luminescent efficiency.
Disclosure of Invention
Aiming at the technical problems of low charge transmission efficiency, poor thermal stability, more surface defects, low luminous efficiency, limited application range and the like of the traditional organic-inorganic hybrid nanocrystals, the invention provides a preparation method of the all-inorganic nanocrystals with high fluorescence quantum yield.
The technical scheme of the invention is as follows:
a method for preparing an all-inorganic colloid nano crystal with high fluorescence yield, which comprises the following steps:
And 2, fully contacting the nanocrystals with the organic ligands attached to the surfaces with the metal salt ligand solution to obtain the high fluorescence yield all-inorganic colloid nanocrystals.
Preferably, in the step 1, the metal salt is: m (NO) 3 ) x ，M(BF 4 ) x Or M (OTf) x Wherein m=pb, cd, zn or In; when m=pb, cd, zn, x=2; when m=in, x=3; OTf = triflic acid anion.
Preferably, the M (BF 4 ) x 、M(OTf) x The preparation method of (2) comprises the following steps:
dispersing oxide or hydroxide of metal M in ethanol to obtain white suspension, dropwise adding tetrafluoroboric acid or trifluoromethanesulfonic acid to obtain clear and transparent solution, and distilling under reduced pressure to remove ethanol to obtain white solid which is the required metal salt.
Preferably, in the step 1, the polar solvent is any one of Dimethylformamide (DMF), methylformamide (NMF), formamide (FA), and Dimethylsulfoxide (DMSO).
Preferably, in the step 2, the nanocrystals with the organic ligand attached to the surface are core-shell semiconductor nanocrystals, oxide nanoparticles, or metal nanocrystals.
Preferably, in the step 2, the nanocrystals with the organic ligand attached to the surface are 2-dimensional nanomaterial (e.g., nanoplatelets, nanoribbons, nanodiscs), 1-dimensional nanomaterial (e.g., nanowires, nanorods, etc.), or 0-dimensional nanomaterial.
Preferably, in the preparation method, the nanocrystals with the organic ligands attached to the surface and the metal ions of the metal salt ligand solution are as follows:
wherein, the CdSe (zb) is a CdSe nano sheet of a sphalerite crystal form, and the CdSe (wz) is a CdSe nano sheet of a wurtzite crystal form.
Preferably, said step 2 is carried out in an inert environment, in an anhydrous solvent.
Preferably, the specific steps of the step 2 are as follows:
step 2.1, dispersing nanocrystals with organic ligands attached to the surface in an organic solvent to prepare NCs solution;
and 2.2, mixing the NCs solution with the metal salt ligand solution, and stirring or shaking vigorously to obtain NCs precipitate, namely the high fluorescence yield all-inorganic colloidal nanocrystals.
Preferably, in the step 2.1, the organic solvent is any one of toluene, n-hexane, n-octane, cyclohexane and chloroform.
Preferably, in the step 2.2, the mass ratio of the nanocrystals with the organic ligand attached to the surface to the metal salt ligand is 0.2-1.0.
Preferably, in the step 2.2, the concentration of the NCs solution is 5-10mg/mL, the concentration of the metal salt ligand solution is 0.2-0.5M, and the volume ratio of the NCs solution to the metal salt ligand solution is 10:1; or the concentration of the NCs solution is 5-10mg/mL, the concentration of the metal salt ligand solution is 0.02-0.05M, and the volume ratio of the NCs solution to the metal salt ligand solution is 1:1.
Preferably, in said step 2.2, the NCs precipitate is subjected to a post-treatment: washing NCs precipitate with toluene and hexane mixture, centrifuging to obtain precipitate, dissolving in polar solvent, mixing with hexane/acetone mixture, centrifuging to obtain precipitate, and dispersing in anhydrous polar solvent.
The advantages of the present invention over the prior art are as follows,
the invention establishes a general surface modification strategy by introducing a metal salt ligand which is low in cost and easy to prepare, and realizes the preparation of various all-inorganic colloid nanocrystals.
The invention introduces inorganic metal salt to gently peel off organic ligand, the obtained all-inorganic nanocrystalline keeps absorption and emission spectrum, the shape and size are unchanged, PLQY can reach 97%, which is the highest record of all-inorganic nanocrystalline PLQY. For blue QDs and InP core-shell QDs, the invention discloses an all-inorganic nanocrystal with stronger fluorescence for the first time. By exploring the mechanism, it is clear that the process follows the HSAB theory, and for crystal faces with non-metal anions exposed, the added metal cations can act as weak ligands, and play a role in repairing the surface. In a word, the invention solves the problem of low luminous efficiency of the existing all-inorganic nanocrystals, and simultaneously realizes the coexistence of high charge transfer efficiency and high quantum yield for the first time in all-inorganic nanocrystal materials. The nanocrystals prepared by the method of the invention are expected to find wide application in the field of electro-and photoluminescent quantum dot displays.
Drawings
FIG. 1 is a schematic view of a surface treatment process according to the present invention.
FIG. 2 shows nanocrystals, pristine ligands, and useful metal salts useful in the methods of the invention.
FIG. 3 is a comparison of infrared spectra of nanocrystals before and after processing.
FIG. 4 is a thermogravimetric analysis of nanocrystals before and after processing.
Fig. 5 is a TEM image of nanocrystals before and after processing.
FIG. 6 shows the absorption/emission spectra of core-shell nanocrystals before and after treatment (a, c, e, upper and lower curves before and after treatment, respectively) and fluorescence lifetime decay (b, d, f).
FIG. 7 is a graph showing the comparison of luminescence properties before and after surface treatment of red, green and blue three cadmium core-shell nanocrystals.
FIG. 8 is a graph of ultraviolet absorption spectra (top, left), infrared absorption spectra (top, middle), XRD spectra (top, right) of other nanocrystals treated with the present method, cdSe quantum dots (bottom, left), cdSe nanowires (bottom, middle), cdSe nanoplatelets (bottom, right) of various all-inorganic nanocrystals.
FIG. 9 is a schematic diagram of a surface treatment reaction mechanism, wherein M represents a metal atom on the surface of a nanocrystal, M' represents a metal ion for stripping a ligand, E represents a non-metal atom, X represents an original organic ligand, and L represents L-type organic ligands such as oleylamine and dodecyl mercaptan.
Detailed Description
Screening and preparation of metal salt ligands
The metal salt related by the method is as follows: m (NO) 3 ) x ,M(BF 4 ) x ,M(OTf) x Wherein m=pb, cd, zn, in; when m=pb, cd, zn, x=2; when m=in, x=3. OTf = triflic acid anion. Wherein M (NO) 3 ) x The material is a commercial material, can be purchased directly, and the rest needs to be synthesized by oneself. The specific synthesis process is as follows:
the oxide or hydroxide of the metal is white suspension in ethanol, and the white suspension is gradually changed into clear and transparent solution by dropwise adding tetrafluoroboric acid or trifluoromethanesulfonic acid. After ethanol is removed by distillation under reduced pressure, a white solid is obtained, namely the required metal salt, and the yield is generally 90% -95%.
Preparation of ligand solutions based on metal salts
The corresponding metal salts were dissolved in polar solvents, e.g., DMF, NMF, FA, DMSO, and formulated as colorless solutions of 10mg/mL,20mg/mL, and 40 mg/mL. The solvent is anhydrous solvent, and the preparation process is completed in a glove box filled with nitrogen, so that the metal salt ligand is ensured to be stored in an anhydrous and anaerobic environment.
Example 1: preparation of red-light-emitting all-inorganic CdSe/ZnS core-shell nanocrystals (quantum dots)
All ligand exchanges were performed in a nitrogen filled glove box (O 2 And H 2 Less than 0.01ppm O) with an anhydrous solvent. The surface treatment is achieved by a one-phase system, and the metal salt used for the surface treatment is indium nitrate.
In a one-phase system, cdSe/ZnS core-shell nanocrystals with oleic acid ligands on the surface were dispersed in toluene, while a metal ligand solution was prepared in DMF. For a typical ligand treatment, 1mL of NCs solution (5-10 mg/mL) is mixed with 100. Mu.L of indium nitrate solution (0.2-0.5M). The resulting mixture was vigorously stirred or shaken until precipitation of NCs was observed. The precipitate was further washed (volume 1:0.8) with a toluene and hexane mixture to remove the remaining organic ligands and unreacted metal salts. After centrifugation, the precipitate is redissolved into a polar solvent, such as DMF, NMF, etc. Subsequently, the solution was again mixed with a hexane/acetone mixture (volume ratio 1:0.8) and the precipitate was separated by centrifugation. Subsequently, the precipitate was dispersed again in an anhydrous polar solvent to form a high concentration colloidal stable solution (10-60 mg/mL). A schematic diagram of the surface treatment process is shown in fig. 1.
The infrared spectrum, thermogravimetric analysis and transmission electron microscope images of the prepared all-inorganic nanocrystalline are shown in fig. 3, 4 and 5, and the absorption and emission spectrum pairs before and after treatment are shown in fig. 6a and the fluorescence attenuation data are shown in fig. 6b. FIG. 3 is an infrared spectrum comparison of nanocrystals before and after treatment, demonstrating the removal of organic ligands; FIG. 4 is a thermogravimetric analysis of nanocrystals before and after treatment, further demonstrating that the treated nanocrystals are all inorganic materials; FIG. 5 is a TEM image of nanocrystals before and after processing, demonstrating successful ligand exchange from a substantial shortening of the inter-crystal distance; meanwhile, the size and morphology of the nanocrystals can be seen to be unchanged;
to fully demonstrate the versatility of this method, we surface treated various nanocrystals, as listed in the table of fig. 2. According to a hard-soft-acid-base (HSAB) theory, the acid-base reaction follows the empirical rule of hard-philic-soft-philic. In the organic ligand of the nanocrystal, the carboxylate and phosphonate are both hard bases, while the amine is a softer base. The hardness (hardness, η, in eV) of several metal cations we use is: in (In) 3+ (13)>Zn 2+ (10.88)>Cd 2+ (10.29) the affinities of the carboxylate and the phosphonate are gradually decreased. Therefore, the difficulty of three metal cations for preparing all-inorganic nanocrystals is also increasing in sequence. In judging which metal cations are adequate to convert the nanocrystals to fully inorganic with HSAB theory, except for considering the affinities of cations and ligandsAnd force, also compared to the metallic element of the nanocrystalline body. For example, the ligands are InP NCs and PbS NCs of OA, the former can only use In 3+ Salt stripping ligands, the latter with In 3+ 、Zn 2+ 、Cd 2+ All inorganic nanocrystals can be obtained because the hardness of all three cations is greater than Pb 2+ The extraction of oleic acid coordinated with the latter is naturally not a problem.
Example 2: preparation of green light-emitting all-inorganic InP/ZnSe/ZnS core-shell nanocrystals (quantum dots)
All ligand exchanges were performed in a nitrogen filled glove box (O 2 And H 2 Less than 0.01ppm O) with an anhydrous solvent. The surface treatment is achieved by a one-phase system, and the metal salt used for the surface treatment is indium nitrate.
In a one-phase system, inP/ZnSe/ZnS core-shell nanocrystals with oleic acid ligands on the surface were dispersed in toluene, and an indium nitrate solution was prepared in DMF. For a typical ligand treatment, 1mL of NCs solution (5-10 mg/mL) is mixed with 100. Mu.L of indium nitrate solution (0.2-0.5M). The resulting mixture was vigorously stirred or shaken until precipitation of NCs was observed. The precipitate was redispersed in 0.2mL DMF and precipitated with 1mL toluene to remove the remaining organic ligand and unreacted metal salt. After centrifugation, the precipitate was redissolved in a polar solvent DMF to form a high concentration colloidal stable solution (10-60 mg/mL). The absorption and emission spectra before and after the nanocrystalline treatment are shown in fig. 6c, and the fluorescence attenuation data are shown in fig. 6d.
Example 3: preparation of blue light-emitting all-inorganic CdZnS/ZnS core-shell nanocrystalline (quantum dot)
All ligand exchanges were performed in a nitrogen filled glove box (O 2 And H 2 Less than 0.01ppm O) with an anhydrous solvent. The surface treatment is achieved by a one-phase system, and the metal salt used for the surface treatment is zinc tetrafluoroborate.
In a one-phase system, cdZnS/ZnS core-shell nanocrystals with oleic acid ligands on the surface were dispersed in toluene and zinc tetrafluoroborate solution was prepared in DMF. For a typical ligand treatment, 1mL of NCs solution (5-10 mg/mL) is mixed with 100. Mu.L of zinc tetrafluoroborate solution (0.2-0.5M). The resulting mixture was vigorously stirred or shaken until precipitation of NCs was observed. The precipitate was redispersed in 0.2mL DMF and precipitated with 1mL toluene to remove the remaining organic ligand and unreacted metal salt. After centrifugation, the precipitate was redissolved in a polar solvent DMF to form a high concentration colloidal stable solution (10-60 mg/mL). The absorption and emission spectra before and after nanocrystalline processing are shown in fig. 6e, and fluorescence attenuation data are shown in fig. 6f.
The comparison of the luminescence properties before and after the treatment of the red, green and blue three cadmium core-shell nano crystal faces and the treatment results by the conventional method is shown in the table of figure 7.
Example 4: preparation of all-inorganic CdSe two-dimensional nanosheets
The surface treatment is achieved by a two-phase system, and the metal salt used for the surface treatment is indium nitrate. In a two-phase system, cdSe nanocrystals (CdSe two-dimensional nanoplatelets) are dissolved in n-hexane (5-10 mg/mL), and indium nitrate is dissolved in a polar solvent that is not miscible with hexane, such as DMF (0.02-0.05M). Subsequently, NCs hexane solution (1 mL) was lightly loaded onto polar solvent (1 mL) to form a two-phase mixture. After stirring for ten minutes, the hexane layer changed from dark to colorless and the polar solvent layer changed to dark, indicating complete transfer of the nanocrystals to the polar phase after ligand exchange. NCs were then purified with hexane and separated from the polar solvent by adding the nonpolar solvent toluene. After centrifugation, the nanocrystals were redispersed in a polar solvent DMF to form a 10mg/mL colloidal solution.
Of the six surfaces of CdSe Nanoplatelets (NPLs) of zinc-blende (zb) crystal form, the upper, lower and side surfaces belong to polar surfaces, and the end surface with the smallest area belongs to a nonpolar surface, which is negligible, so Cd atoms are mainly exposed. The surface of CdSe NPLs of wurtzite (wz) crystal forms is mainly a nonpolar surface, and the Cd and Se ratio of the surface is approximately the same. The two nanocrystals were each treated with In (NO) 3 ) 3 After the treatment, the presence or absence of In atom bonding on the surface of the nanocrystals was investigated using inductively coupled plasma emission spectroscopy (ICP-OES). Because NPLs have poor solubility, zb and wz are modified again together with oleylamine and repeatedly washed with a solvent In order to prevent the measurement result from being influenced by free In salt, so that the free In salt does not exist when the material is digested. Zb NPL with almost only metal cation sites exposeds, the presence of In element was not detected after the treatment with In salt. For wz NPLs, an In element was detected at approximately a 1:5 molar ratio to Cd, indicating that In can bind to the surface for NPLs with Se exposure. Next we wash the bound In with methanol, a strongly polar protic solvent instead of DMF 3+ The content of In element is found to be reduced to be extremely small at one time, which indicates that the binding force between In and nonmetallic sites on the surface of the nanocrystalline is not strong, and the nano-crystalline is a weak ligand. The interaction mechanism of the nanocrystals with metal cations of two different crystal planes is shown in fig. 9, and the chemical equation is as follows:
n[(ME) a (MX m ) b ]+(bm+cn)(M’Y n )→n[(ME) a M b M’ c Y (bm+cn) ]+bm(M’X n )
wherein (ME) a (MX m ) b And M' Y n Representing the original NCs and the added metal salt, respectively. This suggests that the surface exposed nonmetallic atoms are more charged due to the dissatisfaction of coordination, and will attract the relatively charged M' to bind to them.
It should be noted that the above-mentioned embodiments are merely preferred embodiments of the present invention, and are not intended to limit the scope of the present invention, and the equivalents or alternatives made on the basis of the above description are all included in the scope of the present invention.
Claims (6)
1. The preparation method of the all-inorganic colloid nano crystal with high fluorescence yield is characterized by comprising the following steps:
step 1, dissolving metal salt in a polar solvent to prepare a metal salt ligand solution; the cation of the metal salt is Pb 2+ ，Cd 2+ ，Zn 2+ Or In 3+ The method comprises the steps of carrying out a first treatment on the surface of the In the step 1, the polar solvent is any one of dimethylformamide, methylformamide, formamide and dimethyl sulfoxide;
step 2, fully contacting the nanocrystals with the organic ligands attached to the surfaces with the metal salt ligand solution to prepare the full inorganic colloid nanocrystals with high fluorescence yield; the step 2 is completed in an inert environment and an anhydrous solvent;
the specific steps of the step 2 are as follows:
step 2.1, dispersing nanocrystals with organic ligands attached to the surface in an organic solvent to prepare NCs solution; the organic solvent is any one of toluene, n-hexane, n-octane, cyclohexane and chloroform;
step 2.2, mixing the NCs solution with the metal salt ligand solution, and vigorously stirring or shaking to prepare NCs precipitate, thus preparing the full inorganic colloid nano crystal with high fluorescence yield;
in the step 1, the metal salt is as follows:
M(NO 3 ) x ，M(BF 4 ) x or M (OTf) x Wherein m=pb, cd, zn or In; when m=pb, cd, zn, x=2; when m=in, x=3; OTf = triflic acid anion.
2. The method of claim 1, wherein said M (BF 4 ) x 、M(OTf) x The preparation method of (2) comprises the following steps:
dispersing oxide or hydroxide of metal M in ethanol to obtain white suspension, dropwise adding tetrafluoroboric acid or trifluoromethanesulfonic acid to obtain clear and transparent solution, and distilling under reduced pressure to remove ethanol to obtain white solid which is the required metal salt.
3. The method according to claim 1, wherein in the step 2, the nanocrystals having the organic ligand attached to the surface are core-shell semiconductor nanocrystals, oxide nanoparticles, or metal nanocrystals.
4. The method according to claim 1, wherein in the step 2, the nanocrystals having the organic ligands attached to the surface are 2-dimensional nanomaterial, 1-dimensional nanomaterial, or 0-dimensional nanomaterial.
5. The method of claim 1, wherein the nanocrystals with organic ligands attached to their surfaces and the metal ions of the metal salt ligand solution are shown in the following table:
wherein, the CdSe (zb) is a CdSe nano sheet of a sphalerite crystal form, and the CdSe (wz) is a CdSe nano sheet of a wurtzite crystal form.
6. The method of claim 1, wherein,
in the step 2.2, the mass ratio of the nanocrystals with the organic ligands attached to the surface to the metal salt ligands is 0.2-1.0.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210047192.6A CN114350364B (en) | 2022-01-17 | 2022-01-17 | Preparation method of high fluorescence yield all-inorganic colloid nano crystal |
| PCT/CN2023/071840 WO2023134714A1 (en) | 2022-01-17 | 2023-01-12 | Preparation method for high fluorescence yield all-inorganic colloidal nanocrystal |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210047192.6A CN114350364B (en) | 2022-01-17 | 2022-01-17 | Preparation method of high fluorescence yield all-inorganic colloid nano crystal |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114350364A CN114350364A (en) | 2022-04-15 |
| CN114350364B true CN114350364B (en) | 2023-04-21 |
Family
ID=81090989
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210047192.6A Active CN114350364B (en) | 2022-01-17 | 2022-01-17 | Preparation method of high fluorescence yield all-inorganic colloid nano crystal |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN114350364B (en) |
| WO (1) | WO2023134714A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114350364B (en) * | 2022-01-17 | 2023-04-21 | 南京大学 | Preparation method of high fluorescence yield all-inorganic colloid nano crystal |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103055954B (en) * | 2013-01-16 | 2015-03-04 | 中国科学院理化技术研究所 | Method for carrying out surface modification on quantum dot/rod, preparation of photosynthetic catalyst as well as system and method |
| CN105940081B (en) * | 2014-02-04 | 2020-06-09 | 亮锐控股有限公司 | Complex inorganic ligands based on coordinated oxygen and hydroxyl for quantum dots |
| US20150298988A1 (en) * | 2014-04-18 | 2015-10-22 | Brett A. Helms | Ionic nanocrystalline materials with high surface charge density and composites of the same |
| CN105369358A (en) * | 2015-11-04 | 2016-03-02 | 北京理工大学 | Method for performing ligand exchange on surface of semiconductor nanocrystalline material |
| KR102596387B1 (en) * | 2017-04-18 | 2023-10-30 | 더 유니버서티 오브 시카고 | Photoactive Inorganic Ligand-capped Inorganic Nanocrystals |
| CN108276986A (en) * | 2017-12-19 | 2018-07-13 | 上海科技大学 | Quanta point material and its preparation with mineral ligand and application |
| CN110386886B (en) * | 2018-04-16 | 2021-12-07 | 中国科学院理化技术研究所 | Rapid, efficient and versatile method for exchanging colloidal nanocrystal surface ligands |
| CN110452681A (en) * | 2018-05-08 | 2019-11-15 | Tcl集团股份有限公司 | Quantum dot solution and preparation method thereof |
| CN110396407B (en) * | 2019-07-31 | 2022-05-24 | 深圳市联宝威科技有限公司 | Preparation method of infrared quantum dot fluorescent powder and prepared infrared quantum dot fluorescent powder |
| CN112239419A (en) * | 2020-11-11 | 2021-01-19 | 江西国化实业有限公司 | Preparation process of zinc trifluoromethanesulfonate |
| CN114350364B (en) * | 2022-01-17 | 2023-04-21 | 南京大学 | Preparation method of high fluorescence yield all-inorganic colloid nano crystal |
-
2022
- 2022-01-17 CN CN202210047192.6A patent/CN114350364B/en active Active
-
2023
- 2023-01-12 WO PCT/CN2023/071840 patent/WO2023134714A1/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| WO2023134714A1 (en) | 2023-07-20 |
| CN114350364A (en) | 2022-04-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Dey et al. | State of the art and prospects for halide perovskite nanocrystals | |
| CN107338048B (en) | InP/GaP/ZnS core-shell quantum dot and preparation method thereof | |
| JP7070826B2 (en) | Semiconductor nanoparticles and their manufacturing methods and light emitting devices | |
| Karar et al. | Structure and photoluminescence studies on ZnS: Mn nanoparticles | |
| Pu et al. | Highly reactive, flexible yet green Se precursor for metal selenide nanocrystals: Se-octadecene suspension (Se-SUS) | |
| JP5682902B2 (en) | High luminous efficiency nanoparticles with water dispersibility | |
| Chang et al. | Strategies for photoluminescence enhancement of AgInS 2 quantum dots and their application as bioimaging probes | |
| JP5519091B2 (en) | Method for producing metal sulfide nanocrystal using thiol compound as sulfur precursor | |
| CN111440607B (en) | Quantum dot with ionic liquid bonded by ions and preparation method thereof | |
| JP5162742B2 (en) | Semiconductor nanoparticles and manufacturing method thereof | |
| KR101941299B1 (en) | Highly luminescent semiconductor nanocrystals | |
| JP2010535692A (en) | Method for forming cadmium and selenium-containing nanocrystalline composites and nanocrystalline composites obtained therefrom | |
| US11247914B2 (en) | Colloidal ternary group III-V nanocrystals synthesized in molten salts | |
| CN114350364B (en) | Preparation method of high fluorescence yield all-inorganic colloid nano crystal | |
| JP2008540304A (en) | Method for preparing chalcopyrite type compounds and other inorganic compounds | |
| Lesiak et al. | pH-dependent fluorescence of thiol-coated CdSe/CdS quantum dots in an aqueous phase | |
| Parani et al. | Thiolated selenium as a new precursor for the aqueous synthesis of CdSe/CdS core/shell quantum dots | |
| KR102071688B1 (en) | Quantum dot particles comprising quantum dot ligands having thiol group and, hydroxy group or carboxyl group, and composition comprising the quantum dot particles, and preparation method of the quantum dot ligands | |
| Madhu et al. | Synthesis and investigation of photonic properties of surface modified ZnO nanoparticles with imine linked receptor as coupling agent-for application in LEDs | |
| Jun et al. | Alkyl thiols as a sulfur precursor for the preparation of monodisperse metal sulfide nanostructures | |
| US8435635B2 (en) | Chemical modification of nanocrystal surfaces | |
| KR102207329B1 (en) | Quantum dot particles comprising quantum dot ligands having thiol group and, hydroxy group or carboxyl group, and composition comprising the quantum dot particles, and preparation method of the quantum dot ligands | |
| KR102220957B1 (en) | Quantum dots in which ionic liquids are ion-bonded and their preparation method | |
| JP7269591B1 (en) | Semiconductor nanoparticles made of AgAuS-based multinary compound | |
| CN110753734A (en) | Semiconductor nano structure and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |