CN109932379A - 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.Display technology based on quantum dot light emitting is shown in recent years
The great attention of industry, compared with liquid crystal display and organic light emitting display, quantum dot light emitting colour gamut is wider, excitation purity is higher, knot
Structure is simpler, and 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.Wherein the detailed process of inkjet printing be by quantum dot ink injection on the substrate, it is dry after in specific position forming amount
Son point film.Compared with other technologies of preparing, inkjet printing is at low cost, convenient, print quality is high, is suitble to large size panel
The features such as production.The preparation of quantum dot ink is that quantum dot is dissolved in specific solvent, formed have certain viscosity, surface tension and
The solution of charge transport ability.Ink when viscosity, surface tension and the charge transport ability of quantum dot ink determine inkjet printing
Wetting ability, rate of drying, the photoelectric properties of coffee ring effect and film of drop, therefore, the quality of quantum dot ink is to ink-jet
Printing effect plays a crucial role.And in quantum dot ink configuration process, quantum dot surface ligand is to quantum dot ink
Water has an important influence, and not only influences the photoelectric properties of quantum dot itself, also will affect the dissolubility and stabilization of quantum dot ink
Property.Common surface ligand is carboxylic acid, amine, alkyl phosphorus, alkylphosphine oxide, alkyl phosphoric acid, mercaptan etc..Surface ligand to quantum dot from
The influence of body optical property shows themselves in that the size of quantum dot is less than Exciton Bohr Radius, and exciton is exposed to table to a certain extent
Face, surface are easy to be affected and reduce its optical property；When quantum dot surface atom number increases, surface dangling bonds also can be anxious
Increase severely more, the presence for the defects of Atomic coordinate deficiency leads to quantum dot surface there are many defects, electronics or holes increases
The probability of non-radiative recombination, the combined efficiency for causing normal radiation compound substantially reduce.When surface ligand appropriate is added, energy
Quantum dot surface dangling bonds are effectively reduced, exciton is made to be no longer exposed to surface, improve the optical property of quantum dot.Surface ligand pair
The influence of quantum dot dissolubility and stability shows themselves in that increasing for quantum dot surface dangling bonds can make its surface free energy very
Greatly, surface becomes abnormal active, this is also resulted in, and system is unstable, and quantum dot can be intended to assemble this meeting to reduce surface area
Lead to the reduction of quantum dot solution dissolubility.After introducing surface ligand, one end of ligand is connected on quantum dot surface atom, one end
It mixes with solution, the surface energy of quantum dot can be reduced, improve the dissolubility of quantum dot, effective inhibitory amount point solution generates heavy
It forms sediment.
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, studies carefully
Caused by its reason, mainly quantum dot surface ligand exchange rate be not identical.If quantum dot surface ligand is very few, quantum dot is not
It is easily soluble 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,
Dissolubility, rate of drying and the coffee ring effect of quantum dot ink are also not quite similar, thus will affect the quality of luminous layer film,
This directly results in that the panel quality printed is uneven, pixel resolution is low, to open bright voltage, photoelectric efficiency inhomogenous etc. asks
Topic.
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 in the sample particle includes quantum dot and is incorporated in containing for the quantum dot surface
The organic ligand of phosphorus, not phosphorus element-containing in the quantum dot, the organic ligand be it is one or more, when the organic ligand is
When a variety of, the molecular mass difference between each organic ligand is no more than 5%；
It is measured to the mass percentage that P element in organic ligand accounts for sample particle with magnetic nuclear resonance analyzer, is calculated as quantum
Point surface ligand content.
The measuring method of particle surface ligand content of the invention, method is simple, strong operability, can be used for evaluating difference
The synthesis quality of batch quantum dot is provided especially for the quality for the different batches quantum dot for guaranteeing to synthesize in same preparation process
It is reliable to guarantee.
The present invention also provides a kind of configuration methods of quantum dot ink, wherein includes:
Sample particle is provided, the individual particle in the sample particle includes quantum dot and is incorporated in containing for the quantum dot surface
The organic ligand of phosphorus, not phosphorus element-containing in the quantum dot, the organic ligand is identical or different, when the organic ligand is different
When, the molecular mass difference between each organic ligand is no more than 5%；
The sample particle of different batches is measured respectively by the measuring method of particle surface ligand content of the present invention
Surface ligand content；
One of batch sample particle is selected as benchmark batch sample particle；
Do not surpass when other batch sample particle surface ligand contents are differed with the surface ligand content of the benchmark batch particle
When 10%, other batch sample particles are used to configure ink；
When other batch sample particle surface ligand contents and the surface ligand content of the benchmark batch particle differ by more than
When 10%, other batch particle surface ligand contents are adjusted to the surface ligand content with the benchmark batch particle
After 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, the organic ligand content of authentic specimen particle surface is determined using nmr analysis
It is denoted as ω1, determine that the sample particle of other each batches preparation (such as can be other based on method of the same race or same preparation process
Obtained sample particle) surface ligand content ω2If ω2=【90%ω1, 110%ω1], then between batch sample particle quantum
Point surface ligand content is consistent, can carry out quantum dot ink formulation；If ω2<90%ω1, first using ligand, exchange process adjusts ω again2
To 90% ω1~110%ω1Quantum dot ink formulation is carried out again；If ω2>110%ω1, first use and ligand method gone to adjust ω2To 90%
ω1~110%ω1Quantum dot ink formulation is carried out again.The configuration of quantum dot ink is carried out using this method, can guarantee quantum dot ink
The homogeneity of quality can guarantee that the dissolubility of the quantum dot ink of different batches, rate of drying are identical with coffee ring effect, improve
The pixel resolution of quantum dot display panel, the homogeneity for opening bright voltage, photoelectric efficiency.
Specific embodiment
The present invention provides a kind of measuring method of particle surface ligand content, for make the purpose of the present invention, technical solution and
Effect is clearer, clear, and the present invention is described in more detail below.It should be appreciated that specific embodiment described herein
It is only used to explain the present invention, be 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 in the sample particle includes quantum dot and is incorporated in the quantum dot surface
Phosphorous organic ligand, not phosphorus element-containing in the quantum dot, the organic ligand is identical or different, when the organic ligand
When different, the molecular mass difference between each organic ligand is no more than 5%；
S20 is measured to the mass percentage that P element in organic ligand accounts for sample particle, the amount of being calculated as with magnetic nuclear resonance analyzer
Son point surface ligand content.
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 phosphorous organic ligand is selected from alkyl phosphorus, alkylphosphine oxide or alkyl phosphoric acid in step S10.It is preferred that
, the alkyl phosphorus be selected from tributylphosphine, three amyl phosphines, three hexyl phosphines, the depth of the night base phosphine, tri octyl phosphine, three nonyl phosphines or three
Decyl phosphine but not limited to this；Preferably, the alkylphosphine oxide is selected from tributylphosphine oxide, TAPO triamylphosphine oxide, trihexylphosphine oxide, three
Heptyl phosphine oxide, trioctylphosphine oxide (TOPO), three nonyl phosphine oxides or tridecylphosphine oxide (TDPO) but not limited to this；Preferably, alkyl phosphoric acid choosing
It is greater than 8 alkyl phosphoric acid, such as ten alkyl phosphoric acids, undecyl phosphoric acid, dodecylphosphoric acid, tridecyl phosphorus from C atomicity
Acid, myristyl phosphoric acid, pentadecyl phosphoric acid, cetyl phosphoric acid or octadecyl phosphoric acid etc. are without being limited thereto.
Specifically, including the following steps: in the S20
S201 provides internal standard substance solution, and the solvent of the internal standard solution is deuterated chloroform, obtains internal standard compound with nuclear magnetic resonance equipment
The PNMR curve of solution；
S202 provides sample particle solution, and the solvent of the sample particle solution is deuterated chloroform, and institute is added in the internal standard solution
Sample particle solution is stated, solution to be measured is prepared, the PNMR curve of solution to be measured is obtained with nuclear magnetic resonance equipment；
S203 carries out integral operation according to the PNMR curve of internal standard substance solution and the PNMR curve of solution to be measured, and sample is calculated
P element concentration in particle solution, conversion obtain the mass percentage that P element in machine ligand accounts for sample particle, are calculated as quantum dot
Surface ligand content.
The present invention use PNMR nmr analysis, according to the internal standard substance solution PNMR curve of known concentration (phosphorus
Nmr Lines), the sample particle solution is added in the internal standard solution, solution to be measured is prepared, with nuclear magnetic resonance
Equipment obtains the PNMR curve of solution to be measured.Integral fortune is carried out according to internal standard substance solution PNMR curve and solution PNMR curve to be measured
It calculates, P element concentration in sample particle solution is calculated, thus P element mass percentage in the sample particle calculated, due to
P element exists only in organic ligand, and the organic ligand be it is one or more, when the organic ligand be it is a variety of when, respectively
Molecular mass difference between the organic ligand is no more than 5%.P element mass percentage can be used as quantum dot table
Face ligand content.
In step S20, internal standard substance solution and sample particle solution are respectively placed in nuclear magnetic resonance equipment, adjustment nuclear-magnetism is total
The working frequency for equipment of shaking is 150-200MHz, and the spectrum width of test temperature 275-325K, PNMR are 64-102Hz, is tested
To the PNMR curve of internal standard substance solution and the NMR curve of sample particle solution.Preferably, baseline scan first is carried out with internal standard compound,
Sample particle solution testing is carried out again.5-10 PNMR curve is obtained to sample particle solution respectively, according to internal standard substance solution
The PNMR curve opposite peak integral area with the PNMR curve of described 5-10 solution to be measured respectively, is averaged and sample is calculated
P element concentration in product particle solution, conversion obtain the mass ratio of P element and sample particle in machine ligand, are calculated as quantum dot surface
Ligand content.It is furthermore preferred that according to the PNMR curve of the internal standard substance solution PNMR curve with described 5-10 solution to be measured respectively
Opposite peak integral area be averaged after casting out maximum value and minimum value, obtain the content ratio of P element.
Preferably, in the internal standard substance solution, the internal standard compound is triphenyl phosphate, tributyl phosphate or Azodrin etc.
Without being limited thereto, the internal standard substance solution concentration is 10-60mg/mL, and the solvent of the internal standard substance solution is deuterated chloroform.
Preferably, in the sample particle solution, the concentration of the sample particle solution is 10-60mg/ml, the sample
The solvent of product particle solution is deuterated chloroform.
Further, a kind of configuration method of quantum dot ink is also provided, comprising:
S301 provides sample particle, and the individual particle in the sample particle includes quantum dot and is incorporated in the quantum dot surface
Phosphorous organic ligand, not phosphorus element-containing in the quantum dot, the organic ligand be it is one or more, organic match when described
When body is a variety of, the molecular mass difference between each organic ligand is no more than 5%；
S302 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；
S303 selectes one of batch sample particle as benchmark batch sample particle；
S304 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；
S305 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 S304, 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 magnetic nuclear resonance 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 S305, 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 (present invention is P element).
Below by embodiment, the present invention is described in detail.
Embodiment 1
(1) quantum dot sample is CdZnSe/CdZnSe/ZnSe quantum dot, and surface ligand is myristyl phosphoric acid.Determine standard volume
In son point sample in surface ligand containing P the step of content, comprising: it is deuterated to weigh 10 mg triphenyl phosphates addition, 1.000 mL
Chloroform is made into 10.0 mg/mL internal standard substance solution.0.500 mL deuterated chloroform of quantum dot sample addition is weighed to be made into
Then 60.0 mg/mL solution is added 0.1 mL internal standard substance solution, obtains sample solution.By internal standard substance solution and sample
Solution is respectively placed in nuclear magnetic resonance equipment, and the working frequency for adjusting nuclear magnetic resonance equipment is 150MHz, test temperature 275K
,31The spectrum width of PNMR is 70Hz.Obtain internal standard substance solution PNMR curve spectrum and 5 width sample solution PNMR curve spectrums；It is accumulated
Partite transport is calculated, and after casting out maximum value and minimum value, is averaged, is obtained integral result, obtains the content of P element in quantum dot sample
Than being 5.43%.
(2) P element in other batches CdZnSe/CdZnSe/ZnSe quantum dot surface ligand of same preparation process is determined
Content ω2.By above-mentioned reaction and test process, obtain in another batch CdZnSe/CdZnSe/ZnSe quantum dot surface ligand
P element content ω2For 5.40%, ω2In 90% ω1~110%ω1In range, quantum dot ink formulation can be directly used for.
Embodiment 2
(1) quantum dot sample is CdZnS/ZnS quantum dot, and surface ligand is cetyl phosphoric acid.Determine standard quantum point sample
In in surface ligand containing P the step of content, comprising: weigh 30 mg tributyl phosphates 1.000 mL deuterated chloroforms be added and be made into
30.0 mg/mL internal standard substance solution.It weighs 0.500 mL deuterated chloroform of quantum dot sample addition and is made into 45 mg/mL
Then solution is added 0.200 mL internal standard substance solution, obtains sample solution.Internal standard substance solution and sample solution are respectively placed in
In nuclear magnetic resonance equipment, adjust nuclear magnetic resonance equipment working frequency be 180 MHz, test temperature 320K,31The spectrum width of PNMR
For 90 Hz.It tests Shi Xianyong internal standard compound and carries out baseline scan, then carry out sample test.Obtain internal standard substance solution PNMR curve graph
Spectrum and 8 width sample solution PNMR curve spectrums；It carries out integral operation to be averaged after casting out maximum value and minimum value, be accumulated
Divide as a result, the content ratio for obtaining P element in quantum dot sample is 6.38%.
(2) other batches CdZnSe/ZnS quantum dot content of surface ligand containing P ω of same preparation process is determined2.By step
Suddenly test process described in (1) obtains P element content ω in another batch CdZnSe/ZnS quantum dot surface ligand2It is 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%ω1
After in range, then carry out ink configuration.
(3) method that quantum dot removes ligand includes: to take CdZnSe/ZnS quantum dot described in 300mg step (2), will
CdZnSe/ZnS quantum dot, which is added, contains 0.15mmol H+, in the ethanol solution that the volumetric concentration of hydrochloric acid is 2% at room temperature into
Row stirring, is cleaned with the mixed solution of chloroform and ethyl alcohol after stirring, obtains the quantum dot for removing some ligands.
(4) the content ω of P element in CdZnSe quantum dot surface ligand after removing ligand is determined3.By the test of step (1)
Journey obtains the content ω of P element in CdZnSe quantum dot surface ligand after ligand3For 6.45%, ω3In 90% ω1~110%ω1
In range, ink configuration can be directly carried out.
Embodiment 3
(1) quantum dot sample is CdZnSe quantum dot, and surface ligand is octadecyl phosphoric acid.It determines and contains in standard quantum point sample
In P surface ligand the step of content, comprising: weigh 30 mg Azodrin addition, 1.000 mL deuterated chloroforms and be made into 30.0 mg
The internal standard substance solution of/mL.It weighs quantum dot sample and the solution that 0.500 mL deuterated chloroform is made into 30mg/mL is added, then
0.05 mL internal standard substance solution is added, obtains sample solution.Internal standard substance solution and sample solution are respectively placed in nuclear magnetic resonance to set
In standby, the working frequency for adjusting nuclear magnetic resonance equipment is 200 MHz, test temperature 300K,31The spectrum width of PNMR is 100 Hz.
Obtain internal standard substance solution PNMR curve spectrum and 10 width sample solution PNMR curve spectrums；Integral operation is carried out, maximum value is cast out
It after minimum value, is averaged, obtains integral result, the content ratio for obtaining P element in quantum dot sample is 7.52%.
(2) content of P element in other batch quantum dot CdZnSe quantum dot surface ligands of same preparation process is determined
ω2.By above-mentioned reaction and test process, P element content ω in another batch CdZnSe quantum dot surface ligand is obtained2It is 5.6%,
ω2Less than 90% ω1, quantum dot progress ligand is exchanged again first, P element in surface ligand is adjusted to 90% ω1~110%ω1Model
Enclose it is interior after, then carry out ink formulation.
(3) quantum dot ligand exchanges again.Take step (2) CdZnSe quantum dot, it is known that quantum dot be added in the preparation ten
Eight alkyl phosphoric acids and trioctylphosphine oxide (TOPO) ligand content are 14 mmol.CdZnSe quantum dot is added in chloroform, 10mg/ is configured to
Then the solution of ml is charged with 0.8mmol octadecyl phosphoric acid and is stirred at 40 DEG C, chloroform and ethyl alcohol are used after stirring
Mixed solution cleaned, obtain the quantum dot after ligand exchanges again.
(4) the content ω of P element in CdZnSe quantum dot surface ligand after ligand exchanges again is determined3.By the survey of step 1)
Examination process obtains the content ω of P element in CdZnSe quantum dot surface ligand after ligand exchanges again3For 7.36%, 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 (14)
1. a kind of measuring method of quantum dot surface ligand content characterized by comprising
Sample particle is provided, the individual particle in the sample particle includes quantum dot and is incorporated in containing for the quantum dot surface
The organic ligand of phosphorus, not phosphorus element-containing in the quantum dot, the organic ligand be it is one or more, when the organic ligand is
When a variety of, the molecular mass difference between each organic ligand is no more than 5%；
It is measured to the mass percentage that P element in organic ligand accounts for sample particle with magnetic nuclear resonance analyzer, is calculated as quantum
Point surface ligand content.
2. the measuring method of particle surface ligand content according to claim 1, which is characterized in that surveyed with magnetic nuclear resonance analyzer
The step of fixed P element into organic ligand accounts for the mass percentage of sample particle, is calculated as quantum dot surface ligand content include:
Internal standard substance solution is provided, the solvent of the internal standard solution is deuterated chloroform, obtains internal standard substance solution with nuclear magnetic resonance equipment
PNMR curve；
Sample particle solution is provided, the solvent of the sample particle solution is deuterated chloroform, and the sample is added in the internal standard solution
Solution to be measured is prepared in product particle solution, and the PNMR curve of solution to be measured is obtained with nuclear magnetic resonance equipment；
Integral operation is carried out according to the PNMR curve of the PNMR curve of internal standard substance solution and solution to be measured, sample particle is calculated
P element concentration in solution, conversion obtain the mass percentage that P element in machine ligand accounts for sample particle, are calculated as quantum dot surface
Ligand content.
3. the measuring method of quantum dot surface ligand content according to claim 2, which is characterized in that in the internal standard solution,
The concentration of the internal standard compound is 10-60mg/mL.
4. the measuring method of quantum dot surface ligand content according to claim 2, which is characterized in that in the internal standard solution,
The internal standard compound is selected from phenyl ester, tributyl phosphate or Azodrin.
5. the measuring method of quantum dot surface ligand content according to claim 2, which is characterized in that the sample solution
In, the concentration of the sample particle is 10-60mg/ml.
6. the measuring method of quantum dot surface ligand content according to claim 2, which is characterized in that set with nuclear magnetic resonance
The determination condition of the standby PNMR curve for obtaining internal standard substance solution or the PNMR curve that solution to be measured is obtained with nuclear magnetic resonance equipment
Are as follows: the spectrum width of working frequency 150-200MHz, test temperature 275-325K, PNMR are 64-102Hz.
7. the measuring method of quantum dot surface ligand content according to claim 6, which is characterized in that set with nuclear magnetic resonance
The standby PNMR curve for obtaining 5-10 solution to be measured, it is to be measured molten with described 5-10 respectively according to the PNMR curve of internal standard substance solution
The PNMR curve of liquid carries out integral operation, is averaged and P element concentration in sample particle solution is calculated, and conversion obtains machine and matches
The mass ratio of P element and sample particle in body, is calculated quantum dot surface ligand content.
8. 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.
9. the measuring method of quantum dot surface ligand content according to claim 8, 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 are selected from CdZnSe, NaYF4、NaCdF4、ZnCdTe、CdZnSe/ZnSe、CdSe/CdZnSe/
CdZnSe/ZnSe or CdZnSe/CdZnSe/ZnSe quantum 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.
10. a kind of configuration method of quantum dot ink characterized by comprising
Sample particle is provided, the individual particle in the sample particle includes quantum dot and is incorporated in containing for the quantum dot surface
The organic ligand of phosphorus, not phosphorus element-containing in the quantum dot, the organic ligand is identical or different, when the organic ligand is different
When, the molecular mass difference between each organic ligand is no more than 5%；
It is measured described in different batches respectively by the measuring method of the described in any item particle surface ligand contents of claim 1-9
The surface ligand content of sample particle；
One of batch sample particle is selected as benchmark batch sample particle；
Do not surpass when other batch sample particle surface ligand contents are differed with the surface ligand content of the benchmark batch particle
When 10%, other batch sample particles are used to configure ink；
When other batch sample particle surface ligand contents and the surface ligand content of the benchmark batch particle differ by more than
When 10%, other batch particle surface ligand contents are adjusted to the surface ligand content with the benchmark batch particle
After difference is within 10%, other batch particles after surface ligand content will be adjusted and be used to configure ink.
11. the configuration method of quantum dot ink according to claim 10, which is characterized in that the surface of benchmark batch particle
Ligand content is denoted as ω1, as other batch sample particle surface ligand content ω2Higher than 110% ω1When, by removing ligand
Method reduces other batch sample particle surface ligand contents, and the method for removing ligand includes: by described other one
Batch sample particle is mixed with inorganic acid solution, sloughs the ligand on other batch sample particle surfaces.
12. the configuration method of quantum dot ink according to claim 11, 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.
13. the configuration method of quantum dot ink according to claim 11, 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, MlFor the molecular quality of P.
14. the configuration method of quantum dot ink according to claim 11, which is characterized in that the sample of different batches
Particle is prepared by same preparation process.
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