CN109932285A - The measuring method and quantum dot ink formulation method of quantum dot surface ligand content - Google Patents
The measuring method and quantum dot ink formulation method of quantum dot surface ligand content Download PDFInfo
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Abstract
The present invention proposes the measuring method and quantum dot ink formulation method of quantum dot surface ligand content.The configuration of quantum dot ink is carried out using this method, it can guarantee the homogeneity of quantum dot drop mass, it can guarantee that dissolubility, the rate of drying of the quantum dot ink of different batches are identical with coffee ring effect, the homogeneity that the pixel resolution of quantum dot display panel can be improved, open bright voltage, photoelectric efficiency.
Description
Technical field
The present invention relates to quantum dot technical field of ink more particularly to the measuring methods and amount of quantum dot surface ligand content
Son point ink formulation method.
Background technique
Quantum dot refers to that geometric dimension is less than the semiconductor nano of its Exciton Bohr Radius.Quantum dot is inhaled due to having
The excellent optical properties such as take-up is wide, fluorescent emission band is narrow, quantum efficiency is high, good light stability, in biomedical, environment energy
There is huge potential application in the fields such as source, illumination display.Compared with liquid crystal display and organic light emitting display, it is based on quantum dot
Luminous display technology is in recent years by the great attention of display industry, and quantum dot light emitting colour gamut is wider, excitation purity is higher, structure
Simpler, stability is higher, it is considered to be display technology of new generation.
The technology of preparing of quantum dot displays part includes spraying, inkjet printing, slot coated, intaglio and silk-screen printing
Deng.It is characterized in that the detailed process of inkjet printing be by quantum dot ink injection on the substrate, it is dry after in specific position
Form quantum dot film.Compared with other technologies of preparing, inkjet printing is at low cost, convenient, print quality is high, is suitble to big ruler
The features such as very little panel makes.The preparation of quantum dot ink is that quantum dot is dissolved in specific solvent, and being formed has certain viscosity, surface
The solution of tension and charge transport ability.Viscosity, surface tension and the charge transport ability of quantum dot ink determine that ink-jet is beaten
The photoelectric properties of the wetting ability, rate of drying, coffee ring effect and film of ink droplet when print, therefore, the quality of quantum dot ink
Ink jet printing performance is played a crucial role.In quantum dot ink configuration process, it is incorporated in matching for quantum dot surface
Body has an important influence quantum dot ink, not only influences the photoelectric properties of quantum dot itself, also will affect quantum dot ink
Dissolubility and stability.Common surface ligand is carboxylic acid, amine, alkyl phosphorus, alkylphosphine oxide, alkyl phosphoric acid, mercaptan etc..Match on surface
Influence of the body to quantum dot own optical performance shows themselves in that the size of quantum dot is less than Exciton Bohr Radius, and exciton is in certain journey
Surface is exposed on degree, surface is easy to be affected and reduce its optical property；When quantum dot surface atom number increases, surface
The defects of dangling bonds also can sharply increase, and Atomic coordinate deficiency leads to quantum dot surface there are many defects, electronics or holes
Presence increase the probability of non-radiative recombination, the combined efficiency for causing normal radiation compound substantially reduces.It is appropriate when being added
When surface ligand, quantum dot surface dangling bonds can be effectively reduced, exciton is made to be no longer exposed to surface, improve the optical of quantum dot
Energy.Influence of the surface ligand to quantum dot dissolubility and stability shows themselves in that increasing for quantum dot surface dangling bonds can make its table
Face free energy is very big, and surface becomes abnormal active, this is also resulted in, and system is unstable, and quantum dot can be intended to aggregation to reduce
Surface area, this will lead to the reduction of quantum dot solution dissolubility.After introducing surface ligand, one end of ligand is connected to quantum dot surface
On atom, one end mixes with solution, can reduce the surface energy of quantum dot, improve the dissolubility of quantum dot, the sub- point of effective inhibitory amount
Solution generates precipitating.
In current quantum dot ink jet printing process, there is a problem that one it is universal, that is, same process preparation
Different batches quantum dot of the same race, the property for the ink being configured under the conditions of same ink set is but not quite similar.Study carefully
Caused by its reason, mainly quantum dot surface ligand content be not identical.If quantum dot surface ligand is very few, quantum dot is not easy
It is dissolved in ink solvent, so that inkjet printing can not be carried out.If the quantum dot surface ligand exchange rate of different batches is different, measure
Dissolubility, rate of drying and the coffee ring effect of son point ink are also not quite similar, thus will affect the quality of luminous layer film, this
Directly result in that the panel quality printed is uneven, pixel resolution is low, opens bright voltage, the problems such as photoelectric efficiency is inhomogenous.
Summary of the invention
In view of above-mentioned deficiencies of the prior art, in order to ensure the stability of quantum dot drop mass, present invention firstly provides
A kind of measuring method of quantum dot surface ligand content, further proposes a kind of preparation method of quantum dot ink.
A kind of measuring method of quantum dot surface ligand content, wherein include:
Sample particle is provided, the individual particle of the sample particle includes quantum dot and is incorporated in having for the quantum dot surface
Machine ligand, the organic ligand are selected from aliphatic carboxylic acid ligand, nitrogenous organic ligand, phosphorous organic ligand or containing sulfydryl
Organic ligand, the organic ligand be it is one or more, when the organic ligand is a variety of, between each organic ligand
Molecular mass difference is no more than 5%；
Wherein, when the organic ligand of quantum dot surface is aliphatic carboxylic acid ligand, oxygen element is free of in the quantum dot；Work as quantum
When the organic ligand on point surface is nitrogenous organic ligand, not Nitrogen element in the quantum dot；It is organic when quantum dot surface
When ligand is phosphorous organic ligand, not phosphorus element-containing in the quantum dot；When the organic ligand of quantum dot surface is containing sulfydryl
Organic ligand when, element sulphur is free of in the quantum dot；
The sample particle is placed in energy depressive spectroscopy, the data of each element content in the sample particle are acquired,
Obtain the content curve of contained each element；
Each element type is demarcated, quantum dot surface ligand content is calculated.
The measuring method of quantum dot surface ligand content of the invention, method is simple, widely applicable, strong operability, can
For evaluating the synthesis quality of different batches quantum dot, especially for the different batches quantum for guaranteeing to synthesize in same preparation process
The quality of point provides reliable guarantee.
A kind of configuration method of quantum dot ink, wherein include:
Sample particle is provided, the individual particle of the sample particle includes quantum dot and is incorporated in having for the quantum dot surface
Machine ligand, the organic ligand are selected from aliphatic carboxylic acid ligand, nitrogenous organic ligand, phosphorous organic ligand or containing sulfydryl
Organic ligand；Wherein, when the organic ligand of quantum dot surface is aliphatic carboxylic acid ligand, oxygen element is free of in the quantum dot；
When the organic ligand of quantum dot surface is nitrogenous organic ligand, not Nitrogen element in the quantum dot；Work as quantum dot surface
Organic ligand when being phosphorous organic ligand, not phosphorus element-containing in the quantum dot；When the organic ligand of quantum dot surface is
When organic ligand containing sulfydryl, not element sulphur in the quantum dot；
Measure the sample particle of different batches respectively by the measuring method of quantum dot surface ligand content of the present invention
Surface ligand content；
One of batch sample particle is selected as benchmark batch sample particle；
When other batch sample size point surface ligand contents differ not with the surface ligand content of the benchmark batch particle
When more than 10%, other batch sample particles are used to configure ink；
When other batch sample size point surface ligand contents differ super with the surface ligand content of the benchmark batch particle
When 10%, other batch quantity point surface ligand contents are adjusted to the surface ligand with the benchmark batch particle
After content difference is within 10%, other batch particles after surface ligand content will be adjusted and be used to configure ink.
In order to ensure that the stability of quantum dot ink, the present invention propose a kind of quantum dot ink formulation method.Specially needle
To the quantum dot of the same race of different batches, determine that authentic specimen quantum dot surface ligand content is denoted as ω1, determine other each batch systems
Standby sample particle (such as can be other sample particles obtained based on method of the same race or same preparation process) surface ligand
Content ω2If ω2=【90%ω1, 110%ω1], then the quantum dot surface ligand content of sample particle is consistent between batch, can be into
Row quantum dot ink formulation；If ω2<90%ω1, first using ligand, exchange process adjusts ω again2To 90% ω1~110%ω1The amount of progress again
Son point ink formulation；If ω2>110%ω1, first use and ligand method gone to adjust ω2To 90% ω1~110%ω1Quantum dot ink is carried out again
Water is prepared.The configuration of quantum dot ink is carried out using this method, can guarantee the homogeneity of quantum dot drop mass, can guarantee different batches
Dissolubility, the rate of drying of secondary quantum dot ink are identical with coffee ring effect, and the pixel for improving quantum dot display panel is differentiated
Rate, the homogeneity for opening bright voltage, photoelectric efficiency.
Specific embodiment
The present invention provides a kind of measuring method of quantum dot surface ligand content, to make the purpose of the present invention, technical solution
And effect is clearer, clear, the present invention is described in more detail below.It should be appreciated that specific implementation described herein
Example is only used to explain the present invention, is not intended to limit the present invention.
A kind of measuring method of quantum dot surface ligand content, wherein include:
S10 provides sample particle, and the individual particle of the sample particle includes quantum dot and is incorporated in the quantum dot surface
Organic ligand, the organic ligand be selected from aliphatic carboxylic acid ligand, nitrogenous organic ligand, phosphorous organic ligand or contain mercapto
The organic ligand of base, the organic ligand be it is one or more, when the organic ligand be it is a variety of when, each organic ligand it
Between molecular mass difference be no more than 5%；
The sample particle is placed in scanning electron microscope by S20, selectes sample to be tested particle；
The sample to be tested particle is placed in energy depressive spectroscopy by S30, to the data of each element content in the sample particle
It is acquired, obtains the content curve of contained each element；
S40 demarcates each element type, and quantum dot surface ligand content is calculated.
The method that the present invention uses energy spectrum analysis obtains the content curve of each element in sample particle, to sample to be tested
Particle each element type is demarcated, and is obtained according to the integral area at each element peak in content curve each in sample to be tested particle
The relative amount of element, due to the organic ligand be it is one or more, when the organic ligand be it is a variety of when, it is each described organic
Molecular mass difference between ligand is no more than 5%, and the relative amount of characteristic element can be used as quantum dot surface in machine ligand
Ligand content, wherein the characteristic element when the organic ligand of quantum dot surface is aliphatic carboxylic acid ligand, in the organic ligand
For oxygen element；When the organic ligand of quantum dot surface is nitrogenous organic ligand, the characteristic element in the organic ligand is
Nitrogen；When the organic ligand of quantum dot surface is phosphorous organic ligand, the characteristic element in the organic ligand is phosphorus
Element；When the organic ligand of quantum dot surface is the organic ligand containing sulfydryl, the characteristic element in the organic ligand is sulphur
Element.Also, when the organic ligand of quantum dot surface is aliphatic carboxylic acid ligand, oxygen element is free of in the quantum dot；Equivalent
When the organic ligand on son point surface is nitrogenous organic ligand, not Nitrogen element in the quantum dot；When having for quantum dot surface
When machine ligand is phosphorous organic ligand, not phosphorus element-containing in the quantum dot；When the organic ligand of quantum dot surface is containing mercapto
When the organic ligand of base, not element sulphur in the quantum dot.For example, when quantum dot be CdZnSeS when, surface ligand cannot for containing
Mercaptoalcohol ligand；When quantum dot is InP/ZnS, surface ligand cannot be for containing mercaptoalcohol and containing Phosphine ligands.
The quantum dot includes a kind of known quantum dot A, wherein the quantum dot A include unitary, binary, ternary,
Quaternary quantum dot.
Specifically, the quantum dot can be selected from unitary quantum dot, binary quantum dot, ternary quantum dots or four in step S10
First quantum dot.Such as: the unitary quantum dot is selected from Au, Ag, Cu, Pt or C quantum dot；The binary quantum dot be selected from CdSe,
ZnSe、PbSe、CdTe、ZnO、MgO、CeO2、NiO、TiO2, InP or CaF2Quantum dot；The ternary quantum dots be selected from CdZnS,
CdZnSe、CdSeS、PbSeS、ZnCdTe、CdS/ZnS、CdZnS/ZnS、CdZnSe/ZnSe、CdSeS/ CdSeS /CdS、
CdSe/CdZnSe/CdZnSe/ZnSe、CdZnSe/CdZnSe/ZnSe、CdS/CdZnS/CdZnS/ZnS、NaYF4Or NaCdF4Amount
Sub- point；The quaternary quantum dot includes CdZnSeyS, CdSe/ZnS, CdZnSe/ZnS, CdSe/CdS/ZnS, CdSe/ZnSe/
ZnS, CdZnSe/CdZnS/ZnS or InP/ZnS quantum dot.
Specifically, the organic ligand containing sulfydryl is selected from a mercaptan, two mercaptan, mercaptoalcohol, mercapto-amine in step S10
Or mercaptan acid；Preferably, a mercaptan is selected from hexyl mercaptan, spicy thioalcohol, nonyl mercaptan, decyl mercaptan, undecyl mercaptan, 12 sulphur
Alcohol, 13 mercaptan, tetradecanylthioalcohol, 16 mercaptan or stearylmercaptan but not limited to this；Preferably, two mercaptan are selected from 1,2-
Pungent two mercaptan of dithioglycol, 1,3- dimercaptopropane, 1,4- succinimide mercaptans, 1,5- pentane disulfide thioalcohol, 1,6- ethanthiol, 1,8- or 1,
Two mercaptan of the 10- last of the ten Heavenly stems but not limited to this；Preferably, the mercaptoalcohol is selected from 2 mercapto ethanol, 3- sulfydryl -1- propyl alcohol, 4- sulfydryl -
N-butyl alcohol, 5- sulfydryl -1- amylalcohol or 6- sulfydryl -1- hexanol, 8- sulfydryl -1- octanol but not limited to this；Preferably, the mercapto
Base acid be selected from 2- thioacetic acid, 3- mercaptopropionic acid, 4- mercaptobutyric acid, dimercaptosuccinic acid, 6- mercaptohexanoic acid, 4- mercaptobenzoic acid or
Cysteine but not limited to this；Preferably, the mercapto-amine is selected from 2-MEA, 3- mercaptopropylamine, 4- sulfydryl butylamine, 5-
Sulfydryl amylamine, 6- sulfydryl hexylamine, 2- amino-3-mercaptopropionic acid, 2- aminothiophenol or mercaptoundecylamine but not limited to this.
The aliphatic carboxylic acid ligand is that C atomicity is fatty acid between 8 ~ 18, it is preferred that for example can be selected from stearic acid,
Octadecenic acid, heptadecanoic acid, heptadecenoic acid, hexadecylic acid, gaidic acid, tetradecylic acid, tetradecenoic acid, lauroleic acid or ten olefin(e) acids etc. are no
It is limited to this.
The phosphorous organic ligand is selected from alkyl phosphorus, alkylphosphine oxide or alkyl phosphoric acid.Preferably, alkyl phosphorus choosing
From tributylphosphine, three amyl phosphines, three hexyl phosphines, the depth of the night base phosphine, tri octyl phosphine, three nonyl phosphines or three decyl phosphines but not limited to this；
Preferably, the alkylphosphine oxide is selected from tributylphosphine oxide, TAPO triamylphosphine oxide, trihexylphosphine oxide, triheptylphosphine oxide, trioctylphosphine oxygen
Phosphine, three nonyl phosphine oxides or tridecylphosphine oxide (TDPO) but not limited to this；Preferably, the alkyl phosphoric acid is selected from the alkane that C atomicity is greater than 8
Base phosphoric acid, such as ten alkyl phosphoric acids, undecyl phosphoric acid, dodecylphosphoric acid, tridecyl phosphoric acid, myristyl phosphoric acid, ten
Five alkyl phosphoric acids, cetyl phosphoric acid or octadecyl phosphoric acid etc. are without being limited thereto.
Specifically, taking sample particle in the step S20, conducting resinl or Double-face gummed paper being bonded on specimen holder, uniformly
The sample particle is sprinkling upon on specimen holder by ground, plates one layer of conductive film, and the preferred conductive film is Au conductive film, Ag conduction
Film or Pt conductive film, plated film time are 1-10 min；Sample particle is placed in scanning electron microscope and is observed, setting amplification factor is
200-1500 times, select sample particle concentrated area as analyzed area, analyzed area size is 5*5-20*20um2, analysis area
Sample particle in domain is sample to be tested particle.
Specifically, in the step S30, by sample to be tested particle as in energy depressive spectroscopy to institute in sample to be tested particle
Content data containing each element is acquired, and obtains the content curve of element in quantum dot.
Specifically, in the step S40, each element type in constituent content curve that the step S30 is obtained into
Rower is fixed, takes the opposite of characteristic element in organic ligand to contain according to the relative amount that the integral area at each element peak obtains each element
Amount, as quantum dot surface ligand content.Preferably, 5-10 analyzed area can be selected as 5- the same sample particle
10 groups of sample to be tested particles are analyzed, and the average relative amount of characteristic element in quantum dot surface ligand is calculated, as
Quantum dot surface ligand content.
Further, a kind of configuration method of quantum dot ink is also provided, comprising:
S101 provides sample particle, and the individual particle of the sample particle includes quantum dot and is incorporated in the quantum dot surface
Organic ligand, the organic ligand be selected from aliphatic carboxylic acid ligand, nitrogenous organic ligand, phosphorous organic ligand or contain mercapto
The organic ligand of base；
S102 is measured the table of the sample particle of different batches by the measuring method of above-mentioned quantum dot surface ligand content respectively
Face ligand content；
S103 selectes one of batch sample particle as benchmark batch sample particle；
S104 works as the surface ligand content phase of other batch sample size point surface ligand contents and the benchmark batch particle
When difference is no more than 10%, other batch sample particles are used to configure ink；
S105 works as the surface ligand content phase of other batch sample size point surface ligand contents and the benchmark batch particle
When difference is more than 10%, other batch quantity point surface ligand contents are adjusted to the surface with the benchmark batch particle
After ligand content difference is within 10%, other batch particles after surface ligand content will be adjusted and be used to configure ink.
In the step S104, in order to ensure that the stability of quantum dot ink, the present invention propose that a kind of quantum dot ink is matched
Method processed.It is specially directed to the same sample particle of several different batches, utilizes gravitational thermal analysis method selected reference batch sample
Particle simultaneously determines that the content of the quantum dot surface organic ligand of benchmark batch sample particle is denoted as ω1, determine other batch systems
Standby sample particle (such as can be other quantum dot surface organic ligands obtained based on method of the same race or same preparation process
Content ω2, according to ω1With ω2Between relationship judge whether can by other batch sample particles directly with other several batches
Secondary sample particle is mixed for the configuration of ink.If ω2=【90%ω1, 110%ω1] (ω2Value in 90% ω1~110%ω1It
Between), then it is believed that the quantum of the quantum dot surface organic ligand content of other batch sample particles and authentic specimen particle
Point surface organic ligands content is consistent, can carry out quantum dot ink formulation.During being somebody's turn to do, by other batch sample particles
It include: that other batch sample particles are directly used in configuration ink for configuring ink；Or by other batch samples
(benchmark particle and/or surface ligand content are in 90% ω with other several sample particles for meeting condition for product particle1~110%ω1It
Between sample particle) be mixed for configure ink.
In the step S105, if ω2<90%ω1, need to using ligand, exchange process adjusts ω again2To 90% ω1~110%ω1Again
Carry out quantum dot ink formulation；If ω2>110%ω1, need to use and ligand method is gone to adjust ω2To 90% ω1~110%ω1The amount of progress again
Son point ink formulation.The configuration of quantum dot ink is carried out using this method, the homogeneity of quantum dot drop mass is can guarantee, can guarantee
Dissolubility, the rate of drying of the quantum dot ink of different batches are identical with coffee ring effect, improve the picture of quantum dot display panel
Plain resolution ratio, the homogeneity for opening bright voltage, photoelectric efficiency.It is described to adjust other batches after surface ligand content
Sample particle includes: that other batch sample particles are directly used in configuration ink for configuring ink；Or it is this is other
(benchmark particle and/or surface ligand content are in 90% ω with other several sample particles for meeting condition for one batch sample particle1~
110%ω1Between sample particle) be mixed for configure ink.
Specifically, the surface ligand content of benchmark batch particle is denoted as ω1, other batch sample size point surface ligands
Content ω2Lower than 90% ω1When, it can increase other batch sample size point surfaces by quantum dot ligand exchange process again and match
Other batch sample particles are dissolved in nonpolar solvent by body content, including step, and original surface ligand is then added in 25-100
It is swapped at DEG C.The nonpolar solvent can selected from chloroform, n-hexane, heptane, octane, toluene, chlorobenzene, dichloro-benzenes,
Carbon tetrachloride, decane, hendecane, dodecane, tridecane, the tetradecane, pentadecane, hexadecane, heptadecane, octadecane, cyclodecane
One or more of with ring hendecane.The amount of the substance for the ligand that the ligand is added in exchange process is (90%
ω1-ω2)n~(110%ω1-ω2) n, wherein n is the amount of the substance for the ligand being added in quantum dot preparation process.
Specifically, the surface ligand content of benchmark batch particle is denoted as ω1, other batch sample size point surface ligands
Content ω2Higher than 110% ω1When, can method by removing ligand, reduce other batch sample size point surface ligands and contain
Amount.It to be acidic treatment that example removes ligand approach as mentioned, i.e., by other batch sample particles and inorganic acid solution
Mixing, sloughs the ligand on other batch sample particle surfaces.Inorganic acid solution ionizes out H at this time+And anion, surface
Ligand and H+In conjunction with weak acid is generated, to slough ligand.Wherein, the inorganic acid type be selected from hydrochloric acid, nitric acid or
Sulfuric acid, inorganic acid solution are aqueous solution, methanol solution or the ethanol solution that the volumetric concentration of the acid is 1.25% ~ 5%.Described
The amount for removing the substance for removing ligand agent being added during ligand is mQ(ω2-110%ω1)/Ml~mQ(ω2-90%ω1)/Ml,
In, mQFor the quality of other batch sample particles, MlIt is characterized the molecular quality of element.
Below by embodiment, the present invention is described in detail.
Embodiment 1
Determine characteristic element in the surface ligand of standard particle CdZnSe/CdZnSe/ZnSe quantum dot (surface ligand is spicy thioalcohol)
The relative amount of plain S is ω1.Standard particle is taken, conducting resinl or Double-face gummed paper are bonded on specimen holder, equably standard
Grain is sprinkling upon on specimen holder, plates one layer of Pt conductive film, and plated film time is 2 min, and then standard particle is placed in scanning electron microscope
Observation.It is 500 times that amplification factor, which is arranged, and selection criteria particle concentrated area is analyzed, and analyzed area size is 5*5um2,
Content data acquisition is carried out to each element contained by the standard particle in selected analysis area in energy depressive spectroscopy, obtains containing for each element
Curve is measured, Cd, Zn, Se and S element in constituent content curve are demarcated respectively, obtained according to the integral area at each element peak
To the relative amount of each element.The standard particle for continuing 5 regions of selection criteria particle is analyzed, and each member is then calculated
The average value of cellulose content ratio, so that obtaining S element relative amount in quantum dot surface ligand is 4.7%.
Determine characteristic element S in other batches CdZnSe/CdZnSe/ZnSe quantum dot surface ligand of same preparation process
The relative amount ω of element2.By the process of step 1, another batch CdZnSe/CdZnSe/ZnSe quantum dot surface ligand is obtained
Middle S constituent content ω2For 4.5%, ω2In 90% ω1~110%ω1In range, quantum dot ink formulation can be directly used for.
Embodiment 2
1, characteristic element in the surface ligand of standard particle CdZnSe/ZnS quantum dot (surface ligand is octadecyl phosphoric acid) is determined
The relative amount of plain P is ω1。
Standard particle is taken, conducting resinl or Double-face gummed paper are bonded on specimen holder, standard particle is equably sprinkling upon sample
On seat, layer of Au conductive film is plated, plated film time is 5 min, and then standard particle is placed in scanning electron microscope and is observed, setting is put
Big multiple is 1000 times, is analyzed standard particle concentrated area, and analyzed area size is 8*8um2, using energy depressive spectroscopy
In to each element contained by the standard particle in selected analysis area carry out content data acquisition, obtain the content curve of each element,
Cd, Zn, Se, S and P element are demarcated respectively in constituent content curve, P element is obtained according to the integral area at each element peak
Content.The standard particle for continuing 5 regions of selection criteria particle is analyzed, and the flat of each element content ratio is then calculated
Mean value, so that obtaining P element relative amount in quantum dot surface ligand is 6.4%.
2, the content of feature P element in other batches CdZnSe/ZnS quantum dot surface ligand of same preparation process is determined
ω2.By the test process described in step 1, P element content ω in another batch CdZnSe/ZnS quantum dot surface ligand is obtained2For
7.8%, ω2Greater than 110% ω1, quantum dot is first spent into ligand agent processing, P element in surface ligand is adjusted to 90% ω1~
110%ω1After in range, then carry out ink configuration.
3, quantum dot removes ligand, takes CdZnSe/ZnS quantum dot described in 300mg step 1, by CdZnSe/ZnS quantum dot
It is added and contains 0.15mmol H+, it is stirred in the ethanol solution that the volumetric concentration of hydrochloric acid is 2% at room temperature, chlorine is used after stirring
Imitative and ethyl alcohol mixed solution is cleaned, and the quantum dot for removing some ligands is obtained.
Determine the content ω of P element in CdZnSe/ZnS quantum dot surface ligand after removing ligand3.By the test of step 1
Journey obtains the content ω of P element in CdZnSe/ZnS quantum dot surface ligand after ligand3For 6.9%, ω3In 90% ω1~110%
ω1In range, ink configuration can be directly carried out.
Embodiment 3
1, characteristic element in the surface ligand of standard particle CdS/CdZnS/CdZnS/ZnS quantum dot (surface ligand is oleyl amine) is determined
The relative amount of plain N is ω1。
Standard particle is taken, conducting resinl or Double-face gummed paper are bonded on specimen holder, standard particle is equably sprinkling upon sample
On seat, layer of Au conductive film is plated, plated film time is 10 min, standard particle is placed in scanning electron microscope and is observed, setting amplification
Multiple is 1500 times, and selection criteria particle concentrated area is analyzed, and analyzed area size is 20*20 um2, using power spectrum point
Content data acquisition is carried out to each element contained by the standard particle in selected analysis area in analyzer, the content for obtaining each element is bent
Line demarcates standard particle Cd, Zn, Se, S and N in constituent content curve, obtains each member according to the integral area at each element peak
The content of element.The standard particle for continuing 10 regions of selection criteria particle is analyzed, and each element content ratio is then calculated
Average value, so that obtaining in quantum dot surface ligand N element relative amount is 18.6%.
2, characteristic element in other batches CdS/CdZnS/CdZnS/ZnS quantum dot surface ligand of same preparation process is determined
The content ω of element2.By the test process of step 1, obtain in another batch CdS/CdZnS/CdZnS/ZnS quantum dot surface ligand
N element content ω2For 14.2%, ω2Less than 90% ω1, first quantum dot progress ligand is exchanged again, by N element tune in surface ligand
It is whole to 90% ω1~110%ω1After in range, then carry out ink formulation.
3, quantum dot ligand exchanges again.Take the CdS/CdZnS/CdZnS/ZnS quantum dot in step 2, it is known that quantum dot exists
The ligand content being added when preparation is 14mmol.CdS/CdZnS/CdZnS/ZnS quantum dot is added in chloroform, is configured to
Then the solution of 10mg/ml is charged with 0.6mmol oleyl amine and is stirred at 40 DEG C, with chloroform and ethyl alcohol after stirring
Mixed solution is cleaned, and the quantum dot after ligand exchanges again is obtained.
4, the content ω of N element in CdS/CdZnS/CdZnS/ZnS quantum dot surface ligand after ligand exchanges again is determined3。
By the process of step 1, the content of N element in CdS/CdZnS/CdZnS/ZnS quantum dot surface ligand after ligand exchanges again is obtained
ω3For 18.0%, ω3In 90% ω1~110%ω1In range, ink formulation can be directly carried out.
A kind of method for being provided for the embodiments of the invention quantum dot ink configuration above is described in detail, for
Those of ordinary skill in the art, thought according to an embodiment of the present invention, have in specific embodiments and applications
Change place, in conclusion the contents of this specification are not to be construed as limiting the invention, it is all to be done according to design philosophy of the present invention
Any change all within protection scope of the present invention.
Claims (13)
1. a kind of measuring method of quantum dot surface ligand content characterized by comprising
Sample particle is provided, the individual particle of the sample particle includes quantum dot and is incorporated in having for the quantum dot surface
Machine ligand, the organic ligand are selected from aliphatic carboxylic acid ligand, nitrogenous organic ligand, phosphorous organic ligand or containing sulfydryl
Organic ligand, the organic ligand be it is one or more, when the organic ligand is a variety of, between each organic ligand
Molecular mass difference is no more than 5%；
Wherein, when the organic ligand of quantum dot surface is aliphatic carboxylic acid ligand, oxygen element is free of in the quantum dot；Work as quantum
When the organic ligand on point surface is nitrogenous organic ligand, not Nitrogen element in the quantum dot；It is organic when quantum dot surface
When ligand is phosphorous organic ligand, not phosphorus element-containing in the quantum dot；When the organic ligand of quantum dot surface is containing sulfydryl
Organic ligand when, not element sulphur in the quantum dot；
The sample particle is placed in energy depressive spectroscopy, the data of each element content in the sample particle are acquired,
Obtain the content curve of contained each element；
Each element type is demarcated, quantum dot surface ligand content is calculated.
2. the measuring method of quantum dot surface ligand content according to claim 1, which is characterized in that each element type into
The step of rower is fixed, and quantum dot surface ligand content is calculated includes: to mark to sample to be tested particle each element type
It is fixed, the relative amount of the characteristic element in organic ligand is obtained according to the integral area of each element in content curve, is calculated as
Quantum dot surface ligand content, wherein when the organic ligand of quantum dot surface is aliphatic carboxylic acid ligand, in the organic ligand
Characteristic element be oxygen element；When the organic ligand of quantum dot surface is nitrogenous organic ligand, in the organic ligand
Characteristic element is nitrogen；Spy when the organic ligand of quantum dot surface is phosphorous organic ligand, in the organic ligand
Sign element is P elements；Spy when the organic ligand of quantum dot surface is the organic ligand containing sulfydryl, in the organic ligand
Sign element is element sulphur.
3. the measuring method of quantum dot surface ligand content according to claim 1, which is characterized in that the quantum dot is one
First quantum dot, binary quantum dot, ternary quantum dots or quaternary quantum dot.
4. the measuring method of quantum dot surface ligand content according to claim 1, which is characterized in that the unitary quantum dot
Selected from Au, Ag, Cu, Pt or C quantum dot；
The binary quantum dot is selected from CdSe, ZnSe, PbSe, CdTe, ZnO, MgO, CeO2、NiO、TiO2, InP or CaF2Quantum
Point；
The ternary quantum dots be selected from CdZnS, CdZnSe, CdSeS, PbSeS, ZnCdTe, CdS/ZnS, CdZnS/ZnS,
CdZnSe/ZnSe、CdSeS/ CdSeS /CdS、CdSe/CdZnSe/CdZnSe/ZnSe、CdZnSe/CdZnSe/ZnSe、CdS/
CdZnS/CdZnS/ZnS、NaYF4Or NaCdF4Quantum dot；
The quaternary quantum dot is selected from CdZnSeyS, CdSe/ZnS, CdZnSe/ZnS, CdSe/CdS/ZnS, CdSe/ZnSe/
ZnS, CdZnSe/CdZnS/ZnS or InP/ZnS quantum dot.
5. the measuring method of quantum dot surface ligand content according to claim 1, which is characterized in that the having containing sulfydryl
Machine ligand is selected from a mercaptan, two mercaptan, mercaptoalcohol, mercapto-amine or mercaptan acid；
The aliphatic carboxylic acid ligand is that C atomicity is fatty acid between 8 ~ 18；
The phosphorous organic ligand is selected from alkyl phosphorus, alkylphosphine oxide or alkyl phosphoric acid；
The nitrogenous organic ligand is the organic amine that carbon atom number is greater than 8.
6. the measuring method of quantum dot surface ligand content according to claim 1, which is characterized in that selected sample to be tested
After particle, the sample particle is placed in energy depressive spectroscopy, the data of each element content in sample particle are acquired, are obtained
To the content curve of contained each element, the step of selected sample to be tested particle includes: that the particle is placed in scanning electricity
On specimen holder in mirror, one layer of conductive film is plated in the particle surface, setting amplification factor is 200-1500 times, selects particle
The particle of concentrated area is sample to be tested particle.
7. the measuring method of quantum dot surface ligand content according to claim 6, which is characterized in that the conductive film is selected from
Au conductive film, Ag conductive film or Pt conductive film.
8. the measuring method of quantum dot surface ligand content according to claim 6, which is characterized in that the sample particle of selection
The area size of concentrated area is 25-400um2。
9. a kind of configuration method of quantum dot ink characterized by comprising
Sample particle is provided, the individual particle of the sample particle includes quantum dot and is incorporated in having for the quantum dot surface
Machine ligand, the organic ligand are selected from aliphatic carboxylic acid ligand, nitrogenous organic ligand, phosphorous organic ligand or containing sulfydryl
Organic ligand；Wherein, when the organic ligand of quantum dot surface is aliphatic carboxylic acid ligand, oxygen element is free of in the quantum dot；
When the organic ligand of quantum dot surface is nitrogenous organic ligand, not Nitrogen element in the quantum dot；Work as quantum dot surface
Organic ligand when being phosphorous organic ligand, not phosphorus element-containing in the quantum dot；When the organic ligand of quantum dot surface is
When organic ligand containing sulfydryl, not element sulphur in the quantum dot；
Measure the institute of different batches respectively by the measuring method of the described in any item quantum dot surface ligand contents of claim 1-8
State the surface ligand content of sample particle；
One of batch sample particle is selected as benchmark batch sample particle；
When other batch sample size point surface ligand contents differ not with the surface ligand content of the benchmark batch particle
When more than 10%, other batch sample particles are used to configure ink；
When other batch sample size point surface ligand contents differ super with the surface ligand content of the benchmark batch particle
When 10%, other batch quantity point surface ligand contents are adjusted to the surface ligand with the benchmark batch particle
After content difference is within 10%, other batch particles after surface ligand content will be adjusted and be used to configure ink.
10. the configuration method of quantum dot ink according to claim 9, which is characterized in that the surface of benchmark batch particle
Ligand content is denoted as ω1, as other batch sample size point surface ligand content ω2Higher than 110% ω1When, by removing ligand
Method, reduce other batch sample size point surface ligand contents, the method for removing ligand include: by it is described its
Its batch sample particle is mixed with inorganic acid solution, sloughs the ligand on other batch sample particle surfaces.
11. the configuration method of quantum dot ink according to claim 10, which is characterized in that the inorganic acid solution choosing
From hydrochloric acid solution, nitric acid solution or sulfuric acid solution；
And/or the volumetric concentration of the inorganic acid solution is 1.25% ~ 5%；
And/or the solvent in the inorganic acid solution is water, methanol or ethyl alcohol.
12. the configuration method of quantum dot ink according to claim 10, which is characterized in that by the substance of the inorganic acid
Amount be mQ(ω2-110%ω1)/Ml~mQ(ω2-90%ω1)/Ml, by other batch sample particles and inorganic acid solution
Mixing, wherein mQFor the quality of other batch sample particles, MlIt is characterized the molecular quality of element；Work as quantum dot
When the organic ligand on surface is aliphatic carboxylic acid ligand, the characteristic element in the organic ligand is oxygen element；Work as quantum dot surface
Organic ligand when being nitrogenous organic ligand, the characteristic element in the organic ligand is nitrogen；When quantum dot surface
When organic ligand is phosphorous organic ligand, the characteristic element in the organic ligand is P elements；When having for quantum dot surface
When machine ligand is the organic ligand containing sulfydryl, the characteristic element in the organic ligand is element sulphur.
13. the configuration method of quantum dot ink according to claim 9, which is characterized in that the sample of different batches
Particle is prepared by same preparation process.
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Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070183934A1 (en) * | 2006-02-03 | 2007-08-09 | Institute For Systems Biology | Multiplexed, microfluidic molecular assay device and assay method |
| CN101196461A (en) * | 2007-03-17 | 2008-06-11 | 广西师范大学 | Method for measuring CdTe quantum point grain diameter by resonant vibration scattered spectrum |
| CN101747890A (en) * | 2010-01-21 | 2010-06-23 | 首都医科大学 | Synthesis and purification method of quantum dots wrapped by different ligands and product thereof |
| CN102492068A (en) * | 2011-12-09 | 2012-06-13 | 江苏康纳思光电科技有限公司 | Quantum dots modified by macromolecular monomer, preparation method for quantum dots and application of quantum dots |
| US20120322679A1 (en) * | 2009-12-01 | 2012-12-20 | Oxford Nanopore Technologies Limited | Biochemical analysis instrument |
| CN105289505A (en) * | 2015-11-07 | 2016-02-03 | 长春工业大学 | Cadmium selenide quantum dot and zirconium base coordination polymer composite material and preparation method |
| CN105315792A (en) * | 2015-11-18 | 2016-02-10 | Tcl集团股份有限公司 | Quantum dot printing ink and preparation method thereof and quantum dot light-emitting diode |
| CN105399080A (en) * | 2015-10-15 | 2016-03-16 | 南京工业大学 | Method for preparing graphene-quantum dot composite material |
| CN105907180A (en) * | 2016-05-04 | 2016-08-31 | Tcl集团股份有限公司 | Quantum dot ink and preparation method thereof |
| US20170069813A1 (en) * | 2015-09-08 | 2017-03-09 | The Regents Of The University Of California | Nanostructured layers of thermoelectric materials |
| CN106596486A (en) * | 2016-12-13 | 2017-04-26 | Tcl集团股份有限公司 | Inorganic perovskite quantum dot probe, production method thereof, and mercury ion detection method |
| CN106867526A (en) * | 2017-02-28 | 2017-06-20 | Tcl集团股份有限公司 | The preparation method and applications of graphene quantum dot |
| CN106905497A (en) * | 2017-03-22 | 2017-06-30 | 京东方科技集团股份有限公司 | Quantum dot compound, intermediate and its preparation method and application |
-
2017
- 2017-12-15 CN CN201711350476.8A patent/CN109932285B/en active Active
Patent Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070183934A1 (en) * | 2006-02-03 | 2007-08-09 | Institute For Systems Biology | Multiplexed, microfluidic molecular assay device and assay method |
| CN101196461A (en) * | 2007-03-17 | 2008-06-11 | 广西师范大学 | Method for measuring CdTe quantum point grain diameter by resonant vibration scattered spectrum |
| US20120322679A1 (en) * | 2009-12-01 | 2012-12-20 | Oxford Nanopore Technologies Limited | Biochemical analysis instrument |
| CN101747890A (en) * | 2010-01-21 | 2010-06-23 | 首都医科大学 | Synthesis and purification method of quantum dots wrapped by different ligands and product thereof |
| CN102492068A (en) * | 2011-12-09 | 2012-06-13 | 江苏康纳思光电科技有限公司 | Quantum dots modified by macromolecular monomer, preparation method for quantum dots and application of quantum dots |
| US20170069813A1 (en) * | 2015-09-08 | 2017-03-09 | The Regents Of The University Of California | Nanostructured layers of thermoelectric materials |
| CN105399080A (en) * | 2015-10-15 | 2016-03-16 | 南京工业大学 | Method for preparing graphene-quantum dot composite material |
| CN105289505A (en) * | 2015-11-07 | 2016-02-03 | 长春工业大学 | Cadmium selenide quantum dot and zirconium base coordination polymer composite material and preparation method |
| CN105315792A (en) * | 2015-11-18 | 2016-02-10 | Tcl集团股份有限公司 | Quantum dot printing ink and preparation method thereof and quantum dot light-emitting diode |
| CN105907180A (en) * | 2016-05-04 | 2016-08-31 | Tcl集团股份有限公司 | Quantum dot ink and preparation method thereof |
| CN106596486A (en) * | 2016-12-13 | 2017-04-26 | Tcl集团股份有限公司 | Inorganic perovskite quantum dot probe, production method thereof, and mercury ion detection method |
| CN106867526A (en) * | 2017-02-28 | 2017-06-20 | Tcl集团股份有限公司 | The preparation method and applications of graphene quantum dot |
| CN106905497A (en) * | 2017-03-22 | 2017-06-30 | 京东方科技集团股份有限公司 | Quantum dot compound, intermediate and its preparation method and application |
Non-Patent Citations (2)
| Title |
|---|
| WHITNEY NOWAK WENGER等: "Functionalization of cadmium selenide quantum dots with poly(ethlene glycol)：ligand exchange,surface coverage,and dispersion stability", 《ACS PUBLICATIONS》 * |
| 侯元晖: "表面配体对CdSe量子点发光性质的影响", 《分析材料学报》 * |
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