CN108485645A - Titanium dioxide skeleton quantum dot, preparation method and its application - Google Patents
Titanium dioxide skeleton quantum dot, preparation method and its application Download PDFInfo
- Publication number
- CN108485645A CN108485645A CN201810210819.9A CN201810210819A CN108485645A CN 108485645 A CN108485645 A CN 108485645A CN 201810210819 A CN201810210819 A CN 201810210819A CN 108485645 A CN108485645 A CN 108485645A
- Authority
- CN
- China
- Prior art keywords
- quantum dot
- titanium dioxide
- ligand
- skeleton
- dioxide skeleton
- 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.)
- Granted
Links
Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
- H10K50/115—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising active inorganic nanostructures, e.g. luminescent quantum dots
-
- 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
- C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
- C09K11/025—Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
Abstract
The present invention provides a kind of titanium dioxide skeleton quantum dot, preparation method and its applications.The titanium dioxide skeleton quantum dot includes：Multiple surfaces have the quantum dot of ligand；Titanium dioxide skeleton including multiple chain structures, at least partly connected by titanium dioxide key between chain structure, chain structure includes at least one A structures and at least one B structure, the chemical formula of A structures is (R NHOC R '), B structure chemical formula be (R ' COOX), each A and each B structure by respectively in R ' chemical bonds connect；R is connect at least partly ligand by intermolecular force, and micro-cavity structure is formed, and the X in R ' COOX chains is titanium elements or H, is connected by titanium dioxide skeleton between each quantum dot, R, R ' it is respectively hydrocarbyl chain.Chain structure length in the skeleton of the titanium dioxide skeleton quantum dot is longer and uniformity is preferable, realizes the effect of the membrane uniformity and planarization that improve solwution method film forming.
Description
Technical field
The present invention relates to technical field of quantum dot preparation, in particular to a kind of titanium dioxide skeleton quantum dot, its system
Preparation Method and its application.
Background technology
Quantum dot (Quantum Dots, abbreviation QD) is extremely small inorganic nanocrystal.Quantum dot is generally
The semi-conductor nano particles of II-VI group and iii-v element, mostly nucleocapsid.Because have quantum size effect, display,
Illumination, solar cell, laser, biological fluorescent labelling etc. have broad application prospects.
In the device containing quantum dot film, the uniformity of quantum dot film directly affects device performance.Using solwution method
Film forming is most commonly seen technique there is the quantum dot of surface ligand to be easy to reunite, and also during forming quantum film
There is the influence of the factors such as coffee ring effect, more uniform film can not be formed, these have all directly influenced the efficiency and hair of device
Optical uniformity.
It can be seen from the above, the problem of existing quantum dot is easily reunited when solwution method forms a film.
Invention content
The main purpose of the present invention is to provide a kind of titanium dioxide skeleton quantum dot, preparation method and its apply, with
It solves quantum dot in the prior art when solwution method forms a film easily to reunite, form a film non-uniform problem.
To achieve the goals above, according to an aspect of the invention, there is provided a kind of titanium dioxide skeleton quantum dot,
It is characterized in that, including：The surface of multiple quantum dots, the quantum dot has ligand；Titanium dioxide skeleton, including multiple links
Structure is connected with each other by titanium dioxide key between at least partly described chain structure, and each chain structure includes at least
The chemical formula of one A structure and at least one B structure, the A structures is (R-NHOC-R '), and the B structure chemical formula is (R '-
COOX), be located at the same chain structure in each A structures and each B structure by the R ' in each self-structure each other
Between chemical bond connect；In each chain structure, the R is connected at least partly described ligand by intermolecular force
It connects, the chain structure and the ligand form the micro-cavity structure around the quantum dot, at least partly described in the chain structure
X in R '-COOX chains is titanium elements, and the X in R '-COOX chains described in remainder is H, is formed in each quantum dot periphery
The titanium dioxide skeleton so that connected by the titanium dioxide skeleton between each quantum dot, wherein R, R ' it is respectively hydrocarbon
Base chain.
Further, the hydrocarbyl chain is intertwined and connected at least partly described ligand by intermolecular force.
Further, the ligand selected from mercaptan, TOP, TOPO group in groups in it is one or more.
To achieve the goals above, according to an aspect of the invention, there is provided a kind of titanium dioxide skeleton quantum dot
Preparation method, which is characterized in that include the following steps：Chemical formula is R-NH by S12Alkylamine be with chemical structural formulaPolymerization of carboxylic acid occur dehydration, obtain chemical formula be (R-NHOC-R ')n1-(R’-COOH)n2-(R’-NHOC-
R)n3Compound, wherein R and R ' is respectively alkyl, m >=2, n1 >=1, n2 >=1, n3 >=0；S2, by (R-NHOC-R ') n1-
The quantum dot of (R '-COOH) n2- (R '-NHOC-R) n3 compounds and surface with ligand, which is added in the first solvent, to be mixed, and is obtained
The first solution containing micro-cavity structure quantum dot, it is isolated described to contain micro-cavity structure quantum dot, wherein the micro-cavity structure
Quantum dot includes quantum dot and surrounds the compound of the quantum dot, and the R chains of the compound are logical at least partly described ligand
Cross intermolecular force connection；S3, will be dissolved in the second solvent containing the micro-cavity structure quantum dot, then with the solution containing titanium source
It mixes under certain condition, reacts, obtain the second solution containing titanium dioxide skeleton quantum dot.
Further, in the S2, the reaction temperature is 5~35 DEG C, described to be mixed into agitating mode mixing centainly
Time.
Further, first solvent includes chloroform, tetrahydrofuran, and second solvent includes ethyl alcohol, butanol, isopropyl
Alcohol.
Further, the titanium source includes titanate ester, and the preferably described titanate ester is selected from metatitanic acid fourth fat, metatitanic acid isopropyl
Ester, tetraethyl titanate group in groups in it is one or more.
Further, the value range of the m is：2~20.
Further, after the second solution for obtaining the titanium dioxide skeleton quantum dot, the preparation method is also wrapped
It includes：The second solution containing the titanium dioxide skeleton quantum dot is detached, titanium dioxide skeleton quantum dot is obtained.
According to another aspect of the present invention, a kind of preparation method of quantum dot film is additionally provided, which includes：
The solution of quantum dot is set on substrate using solwution method, quantum dot film is obtained after dry, wherein the quantum dot is above-mentioned
Titanium dioxide skeleton quantum dot.
According to a further aspect of the invention, a kind of quantum dot film is additionally provided, quantum dot film includes quantum dot, wherein
The quantum dot is above-mentioned titanium dioxide skeleton quantum dot.According to a further aspect of the invention, a kind of quantum is additionally provided
Point device, which is characterized in that the quantum dot device includes above-mentioned quantum dot film, wherein the quantum dot film is for sending out
The luminescent layer of light or functional layer for shining and transmitting electronics.
It applies the technical scheme of the present invention, provide a kind of titanium dioxide skeleton quantum dot, preparation method and its answers
With due to forming titanium dioxide skeleton in quantum dot surface, for the existing quantum dot with organic ligand, this two
Titanium oxide matrix quantum dot includes the skeleton for being looped around multiple links of Internal Quantum point periphery and being configured to, the chain structure length compared with
Long and uniformity is preferable, can more steadily be connect with quantum dot surface ligand, increase the stability of quantum dot entirety, avoid
The phenomenon that easily reuniting when existing quantum dot film forming with uneven organic ligand, solves existing quantum dot in solution
Realize the effect of the membrane uniformity and planarization that improve solwution method film forming the problem of method is easily reunited when forming a film.
Other than objects, features and advantages described above, the present invention also has other objects, features and advantages.
Below with reference to figure, the present invention is described in further detail.
Description of the drawings
The Figure of description for constituting the part of the present invention is used to provide further understanding of the present invention, and of the invention shows
Meaning property embodiment and its explanation are not constituted improper limitations of the present invention for explaining the present invention.In the accompanying drawings：
Fig. 1 shows that a kind of principle of the preparation method of optional titanium dioxide skeleton quantum dot provided by the present invention is shown
It is intended to.
Reference numeral：
10, quantum dot；20, ligand；30, chemical formula is (R-NHOC-R ')n1-(R’-COOH)n2-(R’-NHOC-R)n3's
Compound；301, hydrocarbyl chain R.
Specific implementation mode
It should be noted that in the absence of conflict, the feature in embodiment and embodiment in the present invention can phase
Mutually combination.The present invention will be described in detail below with reference to the accompanying drawings and embodiments.
In order to enable those skilled in the art to better understand the solution of the present invention, below in conjunction in the embodiment of the present invention
Attached drawing, technical scheme in the embodiment of the invention is clearly and completely described, it is clear that described embodiment is only
The embodiment of a part of the invention, instead of all the embodiments.Based on the embodiments of the present invention, ordinary skill people
The every other embodiment that member is obtained without making creative work should all belong to the model that the present invention protects
It encloses.
It should be noted that term " first " in description and claims of this specification and above-mentioned attached drawing, "
Two " etc. be for distinguishing similar object, without being used to describe specific sequence or precedence.It should be appreciated that using in this way
Data can be interchanged in the appropriate case, so as to the embodiment of the present invention described herein.In addition, term " comprising " and " tool
Have " and their any deformation, it is intended that cover it is non-exclusive include, for example, containing series of steps or unit
Process, method, system, product or equipment those of are not necessarily limited to clearly to list step or unit, but may include without clear
It is listing to Chu or for these processes, method, product or equipment intrinsic other steps or unit.
As described in background technology, quantum dot is easy to reunite in the prior art, the quantum for causing solwution method to prepare
Point film is susceptible to non-uniform phenomenon, these have all directly influenced the efficiency and uniformity of luminance of device.The hair of the application
A person of good sense studies regarding to the issue above, it is proposed that a kind of titanium dioxide skeleton quantum dot, preparation method and its application.It should
Titanium dioxide skeleton quantum dot includes：The surface of multiple quantum dots, quantum dot has ligand；Titanium dioxide skeleton, including it is multiple
Chain structure is at least partly connected with each other between chain structure by titanium dioxide key, and each chain structure includes at least one A
The chemical formula of structure and at least one B structure, A structures is (R-NHOC-R '), and B structure chemical formula is (R '-COOX), is located at same
Each A structures and each B structure in one chain structure are connected to chemical bond to each other by the R ' in each self-structure；In each link
In structure, R is connect at least partly ligand by intermolecular force, and chain structure and ligand form the microcavity knot around quantum dot
Structure, the X in chain structure at least partly in R '-COOX chains is titanium elements, and the X in remainder R '-COOX chains is H, in each amount
Son point periphery forms titanium dioxide skeleton so that is connected by titanium dioxide skeleton between each quantum dot, wherein R, R ' respectively
For hydrocarbyl chain.
Using the application, due to forming titanium dioxide skeleton in quantum dot surface, the titanium dioxide skeleton is by each quantum
Point connects at each interval, thus for the existing quantum dot with organic ligand, the titanium dioxide skeleton quantum
Point includes being looped around the skeleton that multiple links of Internal Quantum point periphery are configured to, the chain structure length is longer and uniformity compared with
It is good, it can more steadily connect with quantum dot surface ligand, to increase the stability of quantum dot entirety, avoid existing
The phenomenon that quantum dot with uneven organic ligand is easily reunited when forming a film, solves existing quantum dot when solwution method forms a film
The problem of easily reuniting realize the effect of the membrane uniformity and planarization that improve solwution method film forming.In an optional implementation
In mode, the C number of above-mentioned hydrocarbyl chain R is preferably 6~20.The C number of above-mentioned hydrocarbyl chain R ' is preferably 2~10.One
In a preferred embodiment, hydrocarbyl chain is intertwined and connected at least partly ligand by intermolecular force.
The hydrocarbyl chain being intertwined and connected by intermolecular force at least ligand in this preferred embodiment can be upper
State the hydrocarbyl chain that R or R ' or R and R ' are represented, the hydrocarbyl chain that preferably R is represented.In some alternative embodiments, ligand selects
From mercaptan, tri octyl phosphine (being abbreviated as TOP), trioctylphosphine (being abbreviated as TOPO) organize in groups in it is one or more.
According to a further aspect of the invention, a kind of preparation method of titanium dioxide skeleton quantum dot, the preparation side are additionally provided
Method includes the following steps：
Chemical formula is R-NH by S12Alkylamine be with chemical structural formulaPolymerization of carboxylic acid occur dehydration,
It is (R-NHOC-R ') to obtain chemical formulan1-(R’-COOH)n2-(R’-NHOC-R)n3Compound, wherein R and R ' is respectively hydrocarbon
Base, m >=2, n1 >=1, n2 >=1, n3 >=0；
In this step, the value range of above-mentioned m is 2~20.In an optional embodiment, above-mentioned hydrocarbyl chain R
C number be preferably 6~20.The C number of above-mentioned hydrocarbyl chain R ' is preferably 2~10.
S2, by (R-NHOC-R ')n1-(R’-COOH)n2-(R’-NHOC-R)n3Compound and surface have the quantum of ligand
Point is added in the first solvent and mixes, and obtains the first solution containing micro-cavity structure quantum dot, wherein micro-cavity structure quantum dot includes
Quantum dot and the compound for surrounding quantum dot, R chains are connect at least partly ligand by intermolecular force in compound；
Fig. 1 shows that a kind of principle of the preparation method of optional titanium dioxide skeleton quantum dot provided by the present invention is shown
It is intended to, as shown in Fig. 1 left figures, it is (R-NHOC-R ') that 10 surface of quantum dot, which has ligand 20, the chemical formula that step S1 is generated,n1-
(R’-COOH)n2-(R’-NHOC-R)n3Compound 30 in hydrocarbyl chain can be connect with ligand 20 by intermolecular force,
The micro-cavity structure around 10 surface of quantum dot is formed, the micro-cavity structure is as shown in Fig. 1 right figures.
In the present embodiment, micro-cavity structure can also be referred to as micro-sphere structure, and above compound is that alkyl is amine-modified
Polymerization of carboxylic acid, similar to a kind of chain structure with multiple branches, Fig. 1 illustrates only a kind of form of optional chain structure, should
Chain structure includes multiple hydrocarbyl chain R (as shown in Figure 1 301) and multiple (portions being connect as shown in Figure 1 with COOH hydrocarbyl chain R '
Point), wherein hydrocarbyl chain R (as shown in Figure 1 301) is connect by intermolecular force with quantum dot surface ligand 20, and alkyl
Carboxyl (COOH) on chain R ' is then located remotely from the side of quantum dot, and the structure for one layer of compound having outside such quantum dot is i.e.
For micro-cavity structure, in an alternative embodiment, R (as shown in Figure 1 301) in multiple compounds separately with not
Same ligand correspondence is intertwined, and forms the micro-cavity structure that compound surrounds quantum dot.
In the present embodiment, it can be various structures that surface, which has the quantum-dot structure in the quantum dot of ligand, be formed
Material can also include the various existing materials for being used to form quantum dot.
In an optional embodiment, above-mentioned quantum dot can be selected from the semi-conducting material shape for the group that following material is constituted
At：II-VI group semiconducting compound, III-V semiconductor compound, group IV-VI semiconducting compound, IV races semiconductor chemical combination
Object and combinations thereof.Above-mentioned ligand includes mercaptan, tri octyl phosphine (being abbreviated as TOP), trioctylphosphine (being abbreviated as TOPO) ligand
In it is one or more.The ligand of quantum dot surface be not limited to it is above-mentioned enumerate several, can meet can twine with hydrocarbyl chain
It can be used around ligand together.
In an optional embodiment, the reaction temperature in this step S2 is 5~35 DEG C, and it is mixed to be mixed into agitating mode
Unification is fixed time, and preferably stirring includes but not limited to magnetic agitation, and preferably mixing time is 0.5 to 3.5h.
In one preferred embodiment, the first solvent includes but not limited to chloroform, tetrahydrofuran in this step S2
(THF), those skilled in the art can select suitable solvent as the first solvent as needed.
S3 will be dissolved in the second solvent containing micro-cavity structure quantum dot, then be mixed under certain condition with the solution containing titanium source
It closes, reaction obtains titanium dioxide skeleton quantum dot.
As shown in Figure 1, the surface ligand 20 of quantum dot 10, is being (R-NHOC-R ') with chemical formulan1-(R’-COOH)n2-
(R’-NHOC-R)n3Compound 30 in hydrocarbyl chain R (as shown in Figure 1 301) connected by intermolecular force after, then
The solution (Ti as shown in Figure 1) of the compound containing titanium elements is added, compound and compound 30 containing titanium elements are at least
Part carboxy CO OH reacts, and forms the structure as shown in Fig. 1 right figures, i.e. the H in hydroxyl in carboxy CO OH is replaced by Ti, and Ti is former
Son is connect with the oxygen atom in the hydroxyl in hydroxyl COOH, so that passes through titanium dioxide key between each quantum dot 10
Ground connects, and obtains titanium dioxide skeleton quantum dot, each quantum dot is embedded in titanium dioxide skeletal internal, as shown in Fig. 1 right figures.
In this step S3, the second solvent includes but not limited to ethyl alcohol, butanol, isopropanol, and those skilled in the art can select to close as needed
Suitable solvent is as the second solvent.
Using the application, due to forming titanium dioxide skeleton in quantum dot surface, thus relative to existing with organic
For the quantum dot of ligand, which includes being looped around multiple links of Internal Quantum point periphery to be configured to
Skeleton, the chain structure length is longer and uniformity is preferable, can more steadily be connect with quantum dot surface ligand, to increase
The stability of quantum dot entirety solves the phenomenon that easily reunion when avoiding existing quantum dot film forming with organic ligand
Realize the membrane uniformity peace for improving solwution method film forming the problem of existing quantum dot is easily reunited when solwution method forms a film
The effect of whole property.In one preferred embodiment, the mixing time in this step S3 can be controlled in 0.5~3.5h, be stirred
The purpose mixed is that the carboxyl of the quantum dot surface of micro-cavity structure is allowed fully to be reacted with titanium source, wherein mixing time is most preferably 2h.
In one preferred embodiment, titanium source includes but not limited to titanate ester, and preferably titanate ester is selected from metatitanic acid
Fourth fat, isopropyl titanate, tetraethyl titanate group in groups in it is one or more.
Purer titanium dioxide skeleton quantum dot in order to obtain is obtaining two in an optional embodiment
After second solution of titanium oxide matrix quantum dot, which further includes：Detach the of the quantum dot of skeleton containing titanium dioxide
Two solution obtain titanium dioxide skeleton quantum dot.The filtering may be used filter progress, can also use other filter plants into
Row filtering.
According to the application third aspect, a kind of preparation method of quantum dot film, the preparation side of the quantum dot film are additionally provided
Method includes：The solution of quantum dot is set on substrate using solwution method, quantum dot film is obtained after dry, wherein quantum dot is
Above-mentioned titanium dioxide skeleton quantum dot.
In the present embodiment, solwution method is such as, but not limited to inkjet printing, printing, spin coating, slot coated, spraying, this
Field technology personnel can select suitable solwution method film-forming process as needed.
In the present embodiment, before obtaining quantum dot film, after being set on substrate, which also wraps
It includes：The solution for the quantum dot of skeleton containing titanium dioxide being set on substrate is dried and is either cured or other can make
The technique of the volatizable materials such as the solvent in solution removal.
Using above-described embodiment, the titanium dioxide skeleton quantum dot of preparation is obtained using solwution method setting on substrate
Quantum dot film, since titanium dioxide skeleton quantum dot is not easy to reunite, to which solwution method film forming is uniform, smooth.
According to the fourth aspect of the application, a kind of quantum dot film is additionally provided, quantum dot film includes quantum dot, wherein amount
Son point be titanium dioxide skeleton quantum dot in above-described embodiment or above-mentioned quantum dot film for according to above-mentioned preparation method system
At.Quantum dot film made of being prepared has uniformly, and surface roughness is low, more smooth advantage.
According to the 5th of the application aspect, a kind of quantum dot device is additionally provided, quantum dot device includes quantum as above
Point film, wherein quantum dot film is the functional layer for luminous luminescent layer or for shining and transmitting electronics.
In the present embodiment, above-mentioned quantum dot device includes electroluminescent device, photo luminescent devices, electroluminescent photic hair
Optical mixer part, solar cell either including quantum dot film or other include quantum dot film film layer device.
The quantum dot device formed using above-mentioned quantum dot film, due to even film layer, when the quantum dot film is luminescent layer,
The uniformity of luminance of quantum dot device is good at this time；Since the quantum dot film includes the quantum dot for having titanium dioxide skeleton,
Quantum dot can be used for luminescent material, and titanium dioxide itself can also be used as electron transport material, also to the quantum dot film
It can be used as luminescent layer and electron transfer layer, one layer of electron transfer layer can be saved in this way, simplify manufacture craft；In addition, ability
Field technique personnel can also need, and select suitable electron transfer layer, and the injection and transmission of electronics are adjusted by matching energy level.
Below in conjunction with embodiment and comparative example further explanation titanium dioxide skeleton quantum dot provided by the present application, its system
Preparation Method and its application.
Embodiment 1
The preparation method of titanium dioxide skeleton quantum dot film provided in this embodiment includes the following steps：
1) titanium dioxide skeleton quantum dot is prepared.
It is R-NH by chemical formula2Alkylamine and monomer be R '-COOH polymerization of carboxylic acid carry out dehydration, obtain chemistry
Formula is (R-NHOC-R ')n1-(R’-COOH)n2-(R’-NHOC-R)n3Compound to get to the amine-modified polymerization of carboxylic acid of alkyl,
Wherein, R and R ' is respectively alkyl, n1 >=1, n2 >=1, n3 >=0；Using the compound and quantum dot (ligand is mercaptan) in chloroform
Reaction is thoroughly mixed in solution, alkylamine will be looped around quantum dot surface after the completion of reaction, form a kind of micro-cavity structure,
The hydrocarbyl chain R of above compound (the amine-modified polymerization of carboxylic acid of alkyl) can be wrapped in one with the initial ligand of quantum dot surface at this time
Rise, at the same carboxyl can the amount of swimming in point microcavity outermost.
Then it is dissolved in ethanol solution processed quantum dot is obtained, adds butyl titanate room temperature, inert conditions
Lower stirring two hours, the carboxylic acid on quantum dot microcavity surface will be reacted with butyl titanate, finally obtained using titanium dioxide as bone
The quantum dot of frame (matrix).
2) quantum dot film and quanta point electroluminescent device are prepared.
Titanium dioxide skeleton quantum dot solution is filtered with filter；
PVK hole transmission layers are arranged in the ito glass substrate for providing surfacing on ito glass substrate；Then using rotation
Above-mentioned titanium dioxide skeleton quantum dot solution is set on substrate, will obtain quantum dot by coating, printing or the mode of coating
Film；
Ag electrodes are deposited on quantum dot film, form the quantum that structure is ITO/PVK/ titanium dioxide skeleton quantum dot/Ag
Point electroluminescent device.
Comparative example 1
With above-described embodiment difference lies in：
1) titanium dioxide skeleton quantum dot is prepared.
Prepare the quantum dot solution of quantum dot (ligand is mercaptan), wherein quantum dot is consistent with the type in embodiment 1.
2) quantum dot film and quanta point electroluminescent device are prepared.
Quantum dot solution is filtered with filter；
The ito glass substrate for providing surfacing is arranged PVK layers on ito glass substrate；Then spin-coating method is used, it will
Above-mentioned quantum dot solution is set on substrate, will obtain quantum dot film；
Ag electrodes are deposited on quantum dot film, form the quanta point electroluminescent device that structure is ITO/PVK/ quantum dots/Ag
Part.
Test method：Luminescence Uniformity test to the electroluminescent device of embodiment 1 and comparative example 1, test method and
As a result as follows：
Using PR670 spectral luminosities/coloration/radiancy meter of PHOTO RESEARCH companies production, it is in current density
2mA/cm2Under conditions of, brightness (the unit Cd/m of 21 points of mean allocation in the luminescent device in testing example2), and lead to
It crosses calculation formula and calculates luminance uniformity=(Max-Min)/(2Ave), and Ave=(L1+L2+L3+ ...+L20+L21)/21,
Wherein Max refers to the maximum value of brightness in 21 data, and Min refers to the value of wherein brightness minimum, and Ave refers to that the brightness of each point is average
Value, L1, L2 ... L21 represent the brightness value of each point.The value of luminance uniformity is smaller, indicates its more uniform, thickness of film layer that shines
It is better to spend the uniformity.
It is as follows to survey result：The brightness uniformity of the quanta point electroluminescent device prepared in embodiment 1 is 97.8%, comparison
The brightness uniformity of the quanta point electroluminescent device prepared in example 1 is 86.2%, and is learnt by electron-microscope scanning observation, right
There is the pattern of apparent protrusion in quantum dot film pattern out-of-flatness in ratio 1, and roughness is high, and the quantum dot film in embodiment 1
Overall flat is uniform.
From the foregoing, it will be observed that the electroluminescent of the luminescent layer formed using the titanium dioxide skeleton quantum dot in above-described embodiment 1
Quantum dot device, luminance uniformity is higher, and the bed roughness that shines is small, and flatness is high, and film layer is evenly.
Using titanium dioxide skeleton quantum dot provided by the present application, preparation method and its application, may be implemented to imitate as follows
Fruit：
(1) it uses titanium dioxide skeleton quantum dot made from the application preparation method to be not easy to reunite, can be formed more uniform
Film layer.
(2) the quantum dot film for using titanium dioxide skeleton quantum dot to be formed, quantum dot is well dispersed, does not have apparent reunion
Occur, and surface roughness is low, it is very smooth.
(3) the quantum dot film and quantum dot device for using titanium dioxide skeleton quantum dot to be formed, due to titanium dioxide itself
Electron transport material is can also be used as, one layer of electron transfer layer can be saved, simplifies manufacture craft.
It these are only the preferred embodiment of the present invention, be not intended to restrict the invention, for those skilled in the art
For member, the invention may be variously modified and varied.Any modification made by all within the spirits and principles of the present invention,
Equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (11)
1. a kind of titanium dioxide skeleton quantum dot, which is characterized in that including：
The surface of multiple quantum dots, the quantum dot has ligand；
Titanium dioxide skeleton, including multiple chain structures, by titanium dioxide key phase between at least partly described chain structure
It connects, each chain structure includes at least one A structures and at least one B structure, and the chemical formula of the A structures is (R-
NHOC-R '), the B structure chemical formula is (R '-COOX), is located at each A structures in the same chain structure and each institute
B structure is stated to connect to chemical bond to each other by the R ' in each self-structure；In each chain structure, the R and at least portion
The ligand is divided to be connected by intermolecular force, the chain structure and the ligand form the microcavity knot around the quantum dot
Structure, the X in the chain structure at least partly described the R '-COOX chains are titanium elements, the X in R '-COOX chains described in remainder
For H, the titanium dioxide skeleton is formed in each quantum dot periphery so that pass through the titanium dioxide between each quantum dot
Titanium skeleton connects, wherein R, R ' it is respectively hydrocarbyl chain.
2. titanium dioxide skeleton quantum dot according to claim 1, which is characterized in that the hydrocarbyl chain and at least partly institute
Ligand is stated to be intertwined and connected by intermolecular force.
3. titanium dioxide skeleton quantum dot according to claim 1, which is characterized in that the ligand be selected from mercaptan, TOP,
TOPO groups in groups in it is one or more.
4. a kind of preparation method of titanium dioxide skeleton quantum dot, which is characterized in that include the following steps：
Chemical formula is R-NH by S12Alkylamine be with chemical structural formulaPolymerization of carboxylic acid occur dehydration, obtain
It is (R-NHOC-R ') to chemical formulan1-(R’-COOH)n2-(R’-NHOC-R)n3Compound, wherein R and R ' is respectively alkyl,
M >=2, n1 >=1, n2 >=1, n3 >=0；
S2, by (R-NHOC-R ')n1-(R’-COOH)n2-(R’-NHOC-R)n3There is the quantum dot of ligand to add for compound and surface
Enter and mixed in the first solvent, obtains the first solution containing micro-cavity structure quantum dot, it is isolated described to contain micro-cavity structure amount
Sub- point, wherein the micro-cavity structure quantum dot includes the quantum dot and surrounds the compound of the quantum dot, describedization
The R chains for closing object are connect at least partly described ligand by intermolecular force；
S3 will be dissolved in the second solvent containing the micro-cavity structure quantum dot, then be mixed under certain condition with the solution containing titanium source
It closes, reaction obtains the second solution containing titanium dioxide skeleton quantum dot.
5. preparation method according to claim 4, which is characterized in that in the S2, the reaction temperature is 5~35
DEG C, it is described to be mixed into agitating mode mixing certain time.
6. preparation method according to claim 4, which is characterized in that first solvent includes chloroform, tetrahydrofuran, institute
It includes ethyl alcohol, butanol, isopropanol to state the second solvent.
7. preparation method according to claim 4, which is characterized in that the titanium source includes titanate ester, the preferably described titanium
Esters of gallic acid selected from metatitanic acid fourth fat, isopropyl titanate, tetraethyl titanate group in groups in it is one or more.
8. preparation method according to claim 4, which is characterized in that the value range of the m is：2~20.
9. a kind of preparation method of quantum dot film, which is characterized in that including：
The solution of quantum dot is set on substrate using solwution method, quantum dot film is obtained after dry, wherein the quantum dot is
Titanium dioxide skeleton quantum dot described in any one of claims 1 to 3.
10. a kind of quantum dot film, which is characterized in that the quantum dot film includes quantum dot, wherein the quantum dot is wanted for right
Seek the titanium dioxide skeleton quantum dot described in any one of 1 to 3.
11. a kind of quantum dot device, which is characterized in that the quantum dot device includes quantum dot as claimed in claim 10
Film, wherein the quantum dot film is the functional layer for luminous luminescent layer or for shining and transmitting electronics.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810210819.9A CN108485645B (en) | 2018-03-14 | 2018-03-14 | Titanium dioxide framework quantum dot, preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810210819.9A CN108485645B (en) | 2018-03-14 | 2018-03-14 | Titanium dioxide framework quantum dot, preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108485645A true CN108485645A (en) | 2018-09-04 |
| CN108485645B CN108485645B (en) | 2020-10-27 |
Family
ID=63339154
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810210819.9A Active CN108485645B (en) | 2018-03-14 | 2018-03-14 | Titanium dioxide framework quantum dot, preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108485645B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105985774A (en) * | 2015-02-09 | 2016-10-05 | 纳晶科技股份有限公司 | Nanocrystalline-ligand compound, preparation method of nanocrystalline-ligand compound, printing material and use of printing material |
| CN107633951A (en) * | 2017-09-26 | 2018-01-26 | 哈尔滨工业大学 | A kind of method and its application that homogeneity barrier layer/skeleton structure is prepared using titanium tetrachloride hydrolysis |
| CN107680815A (en) * | 2017-09-18 | 2018-02-09 | 哈尔滨工业大学 | A kind of preparation method and applications of homogeneity barrier layer/skeleton titania structure |
| CN107722184A (en) * | 2016-08-11 | 2018-02-23 | 三星电子株式会社 | Quantum dot aggregate particle, its manufacture method and include its composition, compound and electronic installation |
-
2018
- 2018-03-14 CN CN201810210819.9A patent/CN108485645B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105985774A (en) * | 2015-02-09 | 2016-10-05 | 纳晶科技股份有限公司 | Nanocrystalline-ligand compound, preparation method of nanocrystalline-ligand compound, printing material and use of printing material |
| CN107722184A (en) * | 2016-08-11 | 2018-02-23 | 三星电子株式会社 | Quantum dot aggregate particle, its manufacture method and include its composition, compound and electronic installation |
| CN107680815A (en) * | 2017-09-18 | 2018-02-09 | 哈尔滨工业大学 | A kind of preparation method and applications of homogeneity barrier layer/skeleton titania structure |
| CN107633951A (en) * | 2017-09-26 | 2018-01-26 | 哈尔滨工业大学 | A kind of method and its application that homogeneity barrier layer/skeleton structure is prepared using titanium tetrachloride hydrolysis |
Non-Patent Citations (2)
| Title |
|---|
| JUNG-HO JO等: "Effective surface passivation of multi-shelled InP quantum dots through a simple complexing with titanium species", 《APPLIED SURFACE SCIENCE》 * |
| YAN ZHAO等: "Photoluminescent Properties of Novel Rare Earth Organic–Inorganic Nanocomposite with TiO2 Modified Silica via Double Crosslinking Units", 《PHOTOCHEMISTRY AND PHOTOBIOLOGY》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108485645B (en) | 2020-10-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108251117B (en) | Core-shell quantum dot, preparation method thereof and electroluminescent device containing core-shell quantum dot | |
| CN104302572B (en) | Include the luminaire and its manufacture method of the flat colloidal semiconductor nanocrystal of anisotropy | |
| CN105932039B (en) | OLED display | |
| JP2020184544A (en) | Semiconductor particles in electronic element | |
| CN110534655A (en) | A kind of perovskite quantum dot film and preparation method thereof and device | |
| CN109065740A (en) | Oled display substrate and preparation method thereof, display device | |
| CN1957058A (en) | Improved color-converting photoluminescent film | |
| CN108219792A (en) | Quantum dot purification process and quantum dot, device and quantum dot composition | |
| US10347836B2 (en) | QLED device and manufacturing method thereof, QLED display panel and QLED display device | |
| JP2017504078A (en) | Compensation film and organic dot for compensation film | |
| CN106098905A (en) | The method of the synthesis of stream continuously of the polymer pad that core-shell structure copolymer is quantum dot-doped and the method for the emission spectrum of correction light-emitting device | |
| US20180273843A1 (en) | Quantum dot film and method of preparing the same | |
| CN110265557A (en) | A kind of flexible white light device and preparation method thereof | |
| CN112993198A (en) | Germanium-based perovskite photoelectric material, application, preparation method, device and device preparation method | |
| CN112961669A (en) | Preparation method of solid-phase carbon quantum dot, solid-phase carbon quantum dot prepared by same and light-emitting device | |
| CN111384302A (en) | Full-solution preparation method of fibrous inorganic perovskite quantum dot light-emitting diode | |
| CN108485645A (en) | Titanium dioxide skeleton quantum dot, preparation method and its application | |
| CN109860379A (en) | A kind of full-inorganic perovskite quantum dot polychrome luminescent film and preparation method thereof | |
| CN110551502A (en) | Yellow-red waveband quantum dot, and synthesis method and application thereof | |
| CN102130301A (en) | White organic electroluminescence device based on color conversion and manufacturing method thereof | |
| CN111662715B (en) | Core-shell quantum dot and preparation method thereof, quantum dot film and light-emitting diode | |
| Lee et al. | High-Resolution Multicolor Patterning of InP Quantum Dot Films by Atomic Layer Deposition of ZnO | |
| CN106784391A (en) | Quantum dot light emitting device and preparation method thereof, liquid crystal display device | |
| CN113122258A (en) | Quantum dot, preparation method thereof and quantum dot light-emitting diode | |
| Chen et al. | One-step spray coating strategy toward a highly uniform large-area CsPbBr 3@ PMMA composite film for backlit display |
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 |