CN109932405A - The measuring method of quantum dot surface ligand content and the preparation method of quantum dot ink - Google Patents
The measuring method of quantum dot surface ligand content and the preparation method of quantum dot ink Download PDFInfo
- Publication number
- CN109932405A CN109932405A CN201711352578.3A CN201711352578A CN109932405A CN 109932405 A CN109932405 A CN 109932405A CN 201711352578 A CN201711352578 A CN 201711352578A CN 109932405 A CN109932405 A CN 109932405A
- Authority
- CN
- China
- Prior art keywords
- quantum dot
- ligand
- particle
- sample particle
- organic ligand
- 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
Abstract
The present invention proposes the measuring method of quantum dot surface ligand content and the preparation method of quantum dot ink.The configuration of quantum dot ink is carried out using the preparation method of quantum dot ink of the present invention, 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 a kind of measuring methods of quantum dot surface ligand content
And the preparation method of quantum dot ink.
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.During quantum dot ink formulation, 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 in the sample particle includes quantum dot and is incorporated in having for the quantum dot surface
Machine ligand, the organic ligand are selected from organic ligand or nitrogenous organic ligand containing sulfydryl, and the organic ligand is one kind
Or it is a variety of, when the organic ligand is a variety of, the molecular mass difference between each organic ligand is no more than 5%；
Element sulphur or nitrogen account for the mass percentage of sample particle in the sample particle described in potentiometric determination, are calculated as
Quantum dot surface ligand content；
Wherein, when the organic ligand of quantum dot surface is the organic ligand containing sulfydryl, element sulphur is free of in the quantum dot；When
When the organic ligand of quantum dot surface is nitrogenous organic ligand, not Nitrogen element in the quantum dot.
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 preparation method of quantum dot ink, wherein include:
Sample particle is provided, the individual particle in the sample particle includes quantum dot and is incorporated in having for the quantum dot surface
Machine ligand, the organic ligand are selected from organic ligand or nitrogenous organic ligand containing sulfydryl, and the organic ligand is one kind
Or it is a variety of, when the organic ligand is a variety of, the molecular mass difference between each organic ligand is no more than 5%；
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；
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 prepare 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 sample particles after surface ligand content will be adjusted and be used to prepare ink.
In order to ensure that the stability of quantum dot ink, the present invention propose a kind of preparation method of quantum dot ink.Specially
For 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 batches
Match on sample particle (such as can be other sample particles obtained based on method of the same race or same preparation process) surface of preparation
Body content ω2If ω2=【90%ω1, 110%ω1], then the quantum dot surface ligand content of sample particle is consistent between batch, can
Carry out quantum dot ink formulation；If ω2<90%ω1, first using ligand, exchange process adjusts ω again2To 90% ω1~110%ω1It carries out again
Quantum dot ink formulation；If ω2>110%ω1, first use and ligand method gone to adjust ω2To 90% ω1~110%ω1Quantum dot is carried out again
Ink formulation.Quantum dot ink formulation is carried out using this method, the homogeneity of quantum dot drop mass is can guarantee, can guarantee difference
Dissolubility, the rate of drying of the quantum dot ink of batch are identical with coffee ring effect, improve the pixel point of quantum dot display panel
Resolution, 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 and the preparation method of quantum dot ink, to make
The purpose of the present invention, technical solution and effect are clearer, clear, and the present invention is described in more detail below.It should be appreciated that
The specific embodiments described herein are merely illustrative of 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 in the sample particle includes quantum dot and is incorporated in the quantum dot surface
Organic ligand, the organic ligand is selected from organic ligand or nitrogenous organic ligand containing sulfydryl, and the organic ligand is
One or more, when the organic ligand is a variety of, the molecular mass difference between each organic ligand is no more than
5%；
S20 in the sample particle described in potentiometric determination element sulphur or nitrogen account for the mass percentage of sample particle,
It is calculated as quantum dot surface ligand content；
Wherein, when the organic ligand of quantum dot surface is the organic ligand containing sulfydryl, element sulphur is free of in the quantum dot；When
When the organic ligand of quantum dot surface is nitrogenous organic ligand, not Nitrogen element in the quantum dot.
The present invention proposes that a kind of percentage for determining that characteristic element accounts for sample particle in organic ligand using potentiometric titration contains
Amount because the organic ligand be it is one or more, when the organic ligand is a variety of, rubbing between each organic ligand
You are no more than 5% at molecular mass difference, and characteristic element, which accounts for sample particle percentage composition, in organic ligand can be estimated as quantum dot surface
Ligand content.Characteristic element when the organic ligand of quantum dot surface is the organic ligand containing sulfydryl, in the organic ligand
For element sulphur；When the organic ligand of quantum dot surface is nitrogenous organic ligand, the characteristic element in the organic ligand is
Nitrogen.Also, when the organic ligand of quantum dot surface is the organic ligand containing sulfydryl, sulfur-bearing is not first in the quantum dot
Element；When the organic ligand of quantum dot surface is nitrogenous organic ligand, not Nitrogen element in the 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
With one of mercaptan acid or a variety of.
Preferably, a mercaptan be selected from hexyl mercaptan, spicy thioalcohol, nonyl mercaptan, decyl mercaptan, undecyl mercaptan, lauryl mercaptan,
One of 13 mercaptan, tetradecanylthioalcohol, 16 mercaptan and stearylmercaptan are a variety of；
Preferably, two mercaptan are selected from 1,2- dithioglycol, 1,3- dimercaptopropane, Isosorbide-5-Nitrae-succinimide mercaptans, 1,5-, penta 2 sulphur
One of pungent two mercaptan of alcohol, 1,6- ethanthiol, 1,8- and two mercaptan of the 1,10- last of the ten Heavenly stems are a variety of；
Preferably, the mercaptoalcohol is selected from 2 mercapto ethanol, 3- sulfydryl -1- propyl alcohol, 4- sulfydryl-n-butyl alcohol, 5- sulfydryl -1-
One of amylalcohol, 6- sulfydryl -1- hexanol and 8- sulfydryl -1- octanol are a variety of；
Preferably, the mercaptan acid is selected from 2- thioacetic acid, 3- mercaptopropionic acid, 4- mercaptobutyric acid, dimercaptosuccinic acid, 6- sulfydryl
One of caproic acid, 4- mercaptobenzoic acid and cysteine are a variety of；
Preferably, the mercapto-amine is selected from 2-MEA, 3- mercaptopropylamine, 4- sulfydryl butylamine, 5- sulfydryl amylamine, 6- sulfydryl
One of hexylamine, 2- amino-3-mercaptopropionic acid, 2- aminothiophenol and mercaptoundecylamine are a variety of.
Specifically, the nitrogenous organic ligand is selected from one of primary amine, secondary amine and tertiary amine or a variety of in step S10.
Preferably, the primary amine be selected from benzylamine, n-butylamine, n-propylamine, cyclohexylamine, phenyl ethylamine, n-hexylamine, isopropylamine,
Aniline, para-totuidine, parachloroanilinum, para-bromoaniline, P-nethoxyaniline, Putriscine and 1, one of 5- pentanediamine or
It is a variety of；
Preferably, the secondary amine is selected from one of dimethylamine, diphenylamines, two octodrines, double tridecyl amines and methylphenylamine
Or it is a variety of；
Preferably, the tertiary amine is selected from dimethyl octylame, dimethyldodecyl amide, dimethyl lauryl amine, dimethyl tetradecy lamine, diformazan
One of base cetylamine, dimethyl octadecylamine, dimethyl oil base amine, double octyl methyl amine, double decyl methyl amines and trioctylamine
Or it is a variety of.
In a kind of wherein embodiment, in step S20 of the present invention, using in the potentiometric determination sample particle
Element sulphur or nitrogen account for the mass percentage of sample particle, are calculated as quantum dot surface ligand content.The potentiometric titration
Test philosophy is to form a work as indicator electrode and reference electrode and sample particle solution using metal-inert electrode
Make battery.It with the addition of titrant, is chemically reacted with by measured ion, ion concentration is tested in titration process and is changed
Become, leads to the potential change between indicator electrode and reference electrode, titration end-point is finally determined with the jumping of indicator electrode current potential.
In titration process, mercaptan sulfur on organic ligand and silver ion are formed as mercaptan sulfur silver precipitating, according to the usage amount of titrant,
To obtain the mass percentage that S element accounts for sample particle；ClO in perchloric acid4 -With the Cl in pH glass electrode-Form electricity
Pole reaction, according to the usage amount of titrant, to obtain the mass percentage that N element accounts for sample particle；
Wherein electrode potential equation are as follows:。
Specifically, in a kind of wherein embodiment, the step S20 includes:
S201 dissolves the sample particle, obtains sample particle solution；
S202 is inserted into indicator electrode, reference electrode in the sample particle solution, and it is molten that titrant is dropped to the sample particle
Constant-current titration is carried out in liquid, and draws E-V titration curve, and the titrant usage amount of titration end-point is obtained according to titration curve, is changed
It is counted as the mass percentage of sulphur or nitrogen and sample particle in sample particle, is calculated as quantum dot surface ligand content, wherein
E is potential, and V is volume consumed by titrant.
Specifically, in step S201, weighs sample particle described in 10-30mg and be placed in 250 mL conical flasks or corresponding range
In the mating titration cup of potentiometric titrimeter, 30-50mL isopropanol is added as solvent, rocking is completely dissolved the sample particle
In the solvent, the sample particle solution is obtained.
Specifically, in step S202, when the organic ligand of quantum dot surface is the organic ligand containing sulfydryl, the titration
Agent is silver nitrate alcohol standard titration solution, and the indicator electrode is silver-sulfide electrode, and the reference electrode is glass reference electricity
Pole.Wherein the process for preparation of the silver nitrate alcohol standard titration solution is as follows: with 10 mL deionized waters in 1000mL volumetric flask
It dissolves 1.7-8.5 g silver nitrate and it is molten to obtain 0.01-0.05mol/L silver nitrate alcohol standardized titration with isopropanol to graduation mark
Liquid.Wherein the preparation process of the silver-sulfide electrode is as follows:
(1) preparation of alkaline titration solvent is drawn 1.6-3.2 g anhydrous sodium acetate and is dissolved in 25 mL anaerobic waters, is then injected into
Into 975 mL isopropanols, 0.02-0.04mol/L alkalinity titration solvent is obtained；
(2) polish silver electrode silver terminal with sand paper first, then the silver electrode silver terminal after polishing be immersed in containing 5-8 mL,
In 100 mL alkalinity titration solvents of 1 wt% sodium sulfide solution, then under agitation, 70- is slowly instilled from buret
100 mL silver nitrate alcohol standard titration solutions, and rotating electrode, make to vulcanize silvering and are equably plated in electrode silver terminal, when titration
Between control in 1-2 min.
Specifically, in step S202, when the organic ligand of quantum dot surface is nitrogenous organic ligand, the titrant
For perchloric acid standard titration solution, the indicator electrode is pH glass electrode, and the reference electrode is glass reference electrode.Wherein
The process for preparation of the perchloric acid standard titration solution is as follows: increase chloric acid (70%) 8.5-17 mL in 1000mL volumetric flask,
Add 100 mL of isopropanol dissolve after, then plus dioxane be diluted to graduation mark, obtain 0.1-0.2mol/L perchloric acid standardized titration
Solution.
In step S202, specific constant-current titration test condition are as follows: setting current potential preset value dE (set)=15-18
MV, potential balance permissible value dE=4-5 mV, potential value record time dt=0.5-1 s, and minimum level value records time dt
(min)=0.5-1 s, maximum potential value record time dt (max)=5-10 s, threshold value=200 mV/mL.Wherein, current potential
After the value record time refers to that every drop titrant drop is entered, it is made to re-record potential value with example reaction 0.5-1s, it is therefore an objective to allow drop
Determine agent and sample sufficiently reacts, reading numerical values again after stablizing potential value.The minimum level value record time refers to that mounting device is inserted
After entering electrode, electrode comes into full contact with sample, and initial minimum level, which reaches, stablizes the required time.Maximum potential value records the time
After the completion of referring to titration, potential value reaches maximum, 5-10 s is waited, until current potential is no longer changed.Specific constant-current titration
Test process are as follows: reference electrode and indicator electrode are inserted into the container equipped with sample particle solution, with the nitric acid of above-mentioned preparation
Silver-colored alcohol standard titration solution or perchloric acid standard titration solution carry out constant-current titration；Appropriate titrant is added, after current potential is constant,
Record millivolt and ml；When close to terminal, it is constant to reach current potential by 5-10 min；To avoid measured object during titration empty
Gas oxidation, should shorten titration time, titration cannot be interrupted；Finally, using E potential as ordinate, volume V consumed by titrant is
Abscissa draws E-V titration curve, and obtains volume consumed by titrant according to titration curve potential break point, then convert
The mass percentage that sample particle is accounted at sulphur in sample particle or nitrogen is calculated as quantum dot surface ligand content.
Further, a kind of preparation method of quantum dot ink is also provided, comprising:
S101 provides sample particle, and the individual particle in the sample particle includes quantum dot and is incorporated in the quantum dot surface
Organic ligand, the organic ligand is selected from organic ligand or nitrogenous organic ligand containing sulfydryl, and the organic ligand is
One or more, when the organic ligand is a variety of, the molecular mass difference between each organic ligand is no more than
5%；
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 prepare 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 prepare 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 potentiometric titration selected reference batch sample
Grain simultaneously determines that the content of the quantum dot surface organic ligand of benchmark batch sample particle is denoted as ω1, determine other batch preparations
Sample particle (such as can be other quantum dot surface organic ligands obtained based on method of the same race or same preparation process and contain
Measure ω2, according to ω1With ω2Between relationship judge whether can by other batch sample particles directly with other several batches
Sample particle is mixed for the preparation 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 preparation ink for preparing 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 prepare 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.Quantum dot ink formulation 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 preparation ink for preparing 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 prepare 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
1, the relative amount of characteristic element S in the surface ligand of standard particle CdSe quantum dot (surface ligand is decyl mercaptan) is determined
For ω1。
1. the preparation of 0.0l mol/L silver nitrate alcohol standard titration solution, with 10 mL deionizations in 1000mL volumetric flask
Water dissolves 1.7 g silver nitrates, with isopropanol to graduation mark；
2. the preparation of alkaline titration solvent is drawn 1.6 g anhydrous sodium acetates and is dissolved in 25 mL anaerobic waters, is then injected into 975
In mL isopropanol；
3. the preparation of silver-sulfide electrode, 1) polish silver electrode silver terminal with sand paper.2) the silver electrode silver terminal after polishing is soaked
7 mL are not being contained, in 100 mL alkalinity titration solvents of 1 wt% sodium sulfide solution.3) under agitation, from buret
It is slowly added into 80 mL, 0.01 mol/L silver nitrate alcohol standard titration solution, and rotating electrode, plates vulcanization silvering equably
In silver electrode silver terminal.Titration time is controlled in 2 min；
4. sample measures, the mating titration of instrument that 20 mg sample particles are placed in 250 mL conical flasks or corresponding range is accurately weighed
In cup, 40 mL isopropanols are added, shaking is dispersed in sample particle in solvent.It is arranged current potential preset value dE (set)=17
MV, minimum titrant additive amount dV (min)=0.01 mL, maximum titrant additive amount dV (max)=0.2 mL, current potential are flat
Weigh the mV of permissible value dE=5, and potential value records the s of time dt=1, and minimum level value records time dt (min)=0.5 s, most
Big potential value records time dt (max)=6 s, threshold value=200 mV/mL.Glass is packed into the container equipped with sample particle
Reference electrode and above-mentioned steps 3) preparation silver-sulfide electrode, with above-mentioned steps 1) prepare 0.01 mol/L silver nitrate alcohol
Standard titration solution is titrated；Appropriate titrant is added, after current potential is constant, record millivolt and ml；When close to terminal,
It is constant to reach current potential by 7 min；To avoid the object oxidation by air that cures during titration, titration time should be shortened, titration is not
It can interrupt；Finally, volume V consumed by titrant is abscissa using E potential as ordinate, E-V titration curve, and root are drawn
Volume consumed by titrant is obtained according to titration curve potential break point, then is converted into element sulphur in sample particle and accounts for sample particle
Mass content be 4.5%.
2, determine that the opposite of characteristic element S element contains in other batch CdSe quantum dot surface ligands of same preparation process
Measure ω2.By the process of step 1, S constituent content ω in another batch CdSe quantum dot surface ligand is obtained2For 4.9%, ω2?
90%ω1~110%ω1In range, quantum dot ink formulation can be directly used for.
Embodiment 2
1, standard particle CeO is determined2The relative amount of characteristic element N in the surface ligand of quantum dot (surface ligand is n-hexylamine)
For ω1。
1. the preparation of 0.1 mol/L perchloric acid titrand, takes perchloric acid (70%) 8.5 in 1000mL volumetric flask
ML, add 100 mL of isopropanol dissolve after, then plus dioxane be diluted to graduation mark；
2. sample test accurately weighs the mating titration of instrument that 30 mg sample particles are placed in 250 mL conical flasks or corresponding range
In cup, 50 mL isopropanols are added, shaking is dispersed in sample particle in solvent.It is arranged current potential preset value dE (set)=16
MV, minimum titrant additive amount dV (min)=0.02 mL, maximum titrant additive amount dV (max)=0.2 mL, current potential
The mV of permissible value dE=5 is balanced, potential value records the s of time dt=0.5, and minimum level value records time dt (min)=1 s,
Maximum potential value records time dt (max)=5 s, threshold value=200 mV/mL.Glass is packed into the container equipped with sample particle
Glass reference electrode and pH glass electrode, with above-mentioned steps 1) calibration 0.1 mol/L perchloric acid standard titration solution titrated；
Appropriate titrant is added, after current potential is constant, record millivolt and ml；When close to terminal, reach current potential perseverance by 6 min
It is fixed；Finally, volume V consumed by titrant is abscissa using E potential as ordinate, E-V titration curve is drawn, and according to drop
Determine curve potential break point and obtain volume consumed by titrant, then is converted into the matter that N element in sample particle accounts for sample particle
Measuring content is 5.1%.
2, other batches CeO of same preparation process is determined2The opposite of characteristic element N element contains in quantum dot surface ligand
Measure ω2.By the process of step 1, another batch CeO is obtained2N element content ω in quantum dot surface ligand2For 4.7%, ω2?
90%ω1~110%ω1In range, quantum dot ink formulation can be directly used for.
It is provided for the embodiments of the invention the measuring method and quantum dot ink of a kind of quantum dot surface ligand content above
The preparation method of water is described in detail, for those of ordinary skill in the art, thought according to an embodiment of the present invention,
There will be changes in specific embodiment and application range, in conclusion the content of the present specification should not be construed as to this hair
Bright limitation, all any changes made according to design philosophy of the present invention are 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 having for the quantum dot surface
Machine ligand, the organic ligand are selected from organic ligand or nitrogenous organic ligand containing sulfydryl, and the organic ligand is one kind
Or it is a variety of, when the organic ligand is a variety of, the molecular mass difference between each organic ligand is no more than 5%；
Element sulphur or nitrogen account for the mass percentage of sample particle in the sample particle described in potentiometric determination, are calculated as
Quantum dot surface ligand content；
Wherein, when the organic ligand of quantum dot surface is the organic ligand containing sulfydryl, element sulphur is free of in the quantum dot；When
When the organic ligand of quantum dot surface is nitrogenous organic ligand, not Nitrogen element in the quantum dot.
2. the measuring method of quantum dot surface ligand content according to claim 1, which is characterized in that described to use constant-current titration
Method measures the mass percentage that element sulphur or nitrogen in the sample particle account for sample particle, is calculated as quantum dot surface ligand
The step of content includes:
The sample particle is dissolved, sample particle solution is obtained；
It is inserted into indicator electrode, reference electrode in the sample particle solution, titrant is dropped in the sample particle solution
Constant-current titration is carried out, and draws E-V titration curve, titrant usage amount is obtained according to titration curve titration end-point, is converted into sample
The mass percentage of element sulphur or nitrogen and sample particle in product particle, is calculated as quantum dot surface ligand content, wherein E
For potential, V is volume used in titrant.
3. the measuring method of quantum dot surface ligand content according to claim 2, which is characterized in that the constant-current titration
Test condition are as follows: setting current potential preset value be 15-18 mV, potential balance permissible value be 4-5 mV, potential value record the time be
0.5-1 s, minimum level value record the time as 0.5-1 s, and maximum potential value is recorded as 5-10 s, threshold value=200 mV/mL.
4. the measuring method of quantum dot surface ligand content according to claim 2, which is characterized in that when quantum dot surface
When organic ligand is the organic ligand containing sulfydryl, the titrant is silver nitrate alcohol standard titration solution, and the indicator electrode is
Silver-sulfide electrode.
5. the measuring method of quantum dot surface ligand content according to claim 2, which is characterized in that when quantum dot surface
When organic ligand is nitrogenous organic ligand, the titrant is perchloric acid standard titration solution, and the indicator electrode is pH glass
Glass electrode.
6. the measuring method of quantum dot surface ligand coverage rate according to claim 1, which is characterized in that the quantum dot is
Unitary quantum dot, binary quantum dot or ternary quantum dots.
7. the measuring method of quantum dot surface ligand coverage rate according to claim 6, which is characterized in that the unitary quantum
Point is 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.
8. the measuring method of quantum dot surface ligand coverage rate according to claim 1, which is characterized in that described containing sulfydryl
Organic ligand is selected from one of a mercaptan, two mercaptan, mercaptoalcohol, mercapto-amine and mercaptan acid or a variety of.
9. the measuring method of quantum dot surface ligand coverage rate according to claim 1, which is characterized in that described nitrogenous has
Machine ligand is selected from one of primary amine, secondary amine and tertiary amine or a variety of.
10. a kind of preparation 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 having for the quantum dot surface
Machine ligand, the organic ligand are selected from organic ligand or nitrogenous organic ligand containing sulfydryl, and the organic ligand is one kind
Or it is a variety of, when the organic ligand is a variety of, the molecular mass difference between each organic ligand is no more than 5%；
Measure the institute of different batches respectively by the measuring method of the described in any item quantum dot surface ligand contents of claim 1-9
State 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 prepare 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 sample particles after surface ligand content will be adjusted and be used to prepare ink.
11. the preparation method of quantum dot ink according to claim 10, which is characterized in that benchmark batch sample particle
Surface ligand content is denoted as ω1, as other batch sample particle surface ligand content ω2Higher than 110% ω1When, pass through deallocation
The method of body, reduces other batch sample particle 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.
12. the preparation 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 preparation 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 S or N.
14. the preparation 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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711352578.3A CN109932405B (en) | 2017-12-15 | 2017-12-15 | Method for measuring content of ligand on surface of quantum dot and method for preparing quantum dot ink |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711352578.3A CN109932405B (en) | 2017-12-15 | 2017-12-15 | Method for measuring content of ligand on surface of quantum dot and method for preparing quantum dot ink |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109932405A true CN109932405A (en) | 2019-06-25 |
| CN109932405B CN109932405B (en) | 2021-08-10 |
Family
ID=66980291
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711352578.3A Active CN109932405B (en) | 2017-12-15 | 2017-12-15 | Method for measuring content of ligand on surface of quantum dot and method for preparing quantum dot ink |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109932405B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111876146A (en) * | 2020-09-01 | 2020-11-03 | 合肥福纳科技有限公司 | Quantum dot with stable ligand, preparation method thereof and QLED (quantum light emitting diode) device |
| CN113049549A (en) * | 2019-12-27 | 2021-06-29 | 浙江大学 | Electrochemical luminescent agent, biological detection reagent and electrochemical immunoassay method |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009076282A (en) * | 2007-09-19 | 2009-04-09 | Seiko Epson Corp | Discharge liquid, discharge liquid set, thin film pattern forming method, thin film, light-emitting device, image display apparatus, and electronic apparatus |
| CN102581298A (en) * | 2012-02-20 | 2012-07-18 | 山东大学 | Gold nanoparticle array with continuously-changed surface charge density |
| CN102608086A (en) * | 2012-01-12 | 2012-07-25 | 吉林大学 | Method for detecting melamine in milk on basis of inner-filter effect of fluorescence between CdTe quantum dots and AuNPs |
| CN105153807A (en) * | 2015-07-21 | 2015-12-16 | 京东方科技集团股份有限公司 | Quantum dot ink |
| CN105218741A (en) * | 2015-11-06 | 2016-01-06 | 武汉理工大学 | A kind of preparation method of Thermo-sensitive magnetic composite microsphere |
| KR20160147526A (en) * | 2015-06-15 | 2016-12-23 | 한국기계연구원 | Passivated quantum dot and method for manufacturing the same |
| CN106566318A (en) * | 2016-11-08 | 2017-04-19 | 厦门世纳芯科技有限公司 | Quantum dot ink and preparation method thereof |
| CN106661229A (en) * | 2014-07-16 | 2017-05-10 | 纳米系统公司 | Silicone ligands for quantum dots |
-
2017
- 2017-12-15 CN CN201711352578.3A patent/CN109932405B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009076282A (en) * | 2007-09-19 | 2009-04-09 | Seiko Epson Corp | Discharge liquid, discharge liquid set, thin film pattern forming method, thin film, light-emitting device, image display apparatus, and electronic apparatus |
| CN102608086A (en) * | 2012-01-12 | 2012-07-25 | 吉林大学 | Method for detecting melamine in milk on basis of inner-filter effect of fluorescence between CdTe quantum dots and AuNPs |
| CN102581298A (en) * | 2012-02-20 | 2012-07-18 | 山东大学 | Gold nanoparticle array with continuously-changed surface charge density |
| CN106661229A (en) * | 2014-07-16 | 2017-05-10 | 纳米系统公司 | Silicone ligands for quantum dots |
| KR20160147526A (en) * | 2015-06-15 | 2016-12-23 | 한국기계연구원 | Passivated quantum dot and method for manufacturing the same |
| CN105153807A (en) * | 2015-07-21 | 2015-12-16 | 京东方科技集团股份有限公司 | Quantum dot ink |
| CN105218741A (en) * | 2015-11-06 | 2016-01-06 | 武汉理工大学 | A kind of preparation method of Thermo-sensitive magnetic composite microsphere |
| CN106566318A (en) * | 2016-11-08 | 2017-04-19 | 厦门世纳芯科技有限公司 | Quantum dot ink and preparation method thereof |
Non-Patent Citations (4)
| Title |
|---|
| 李德亮: "修饰纳米SiO2的表面功能团测定及在尼龙6中的应用", 《万方数据库》 * |
| 林伟: "配体结构对量子点光学性能影响的研究", 《中国优秀硕士学位论文全文数据库（工程科技I辑）》 * |
| 蓝碧瑛: "碱渣中二价硫及硫醇的测定（硝酸银电位法）", 《福建分析测试》 * |
| 薛琪鸿 等: "自动电位滴定法测定馏分燃料中的硫醇硫及银-硫化银电极的制备", 《分析仪器》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113049549A (en) * | 2019-12-27 | 2021-06-29 | 浙江大学 | Electrochemical luminescent agent, biological detection reagent and electrochemical immunoassay method |
| CN111876146A (en) * | 2020-09-01 | 2020-11-03 | 合肥福纳科技有限公司 | Quantum dot with stable ligand, preparation method thereof and QLED (quantum light emitting diode) device |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109932405B (en) | 2021-08-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109932405A (en) | The measuring method of quantum dot surface ligand content and the preparation method of quantum dot ink | |
| KR101451684B1 (en) | Electrically conductive ink and process for production of base material having electrically conductive coating film attached thereto using same | |
| CN104316643B (en) | Three element assay methods of nickel-cobalt-manganese ternary material | |
| Schneider et al. | pH and concentration dependence of the optical properties of thiol-capped CdTe nanocrystals in water and D 2 O | |
| CN116731704B (en) | Luminescent composite nano material, preparation method and application thereof in pH measurement | |
| Milardović et al. | Synthesis and electrochemical characterization of AgNP ink suitable for inkjet printing | |
| Sung-Tsuen et al. | The crystallization of magnesium hydroxide | |
| CN100494309C (en) | Synthesis method of core/shell type cadmium telluride/cadmium sulfide water-soluble quantum dot | |
| CN109932476A (en) | A kind of measuring method of quantum dot surface ligand coverage rate | |
| CN102286226A (en) | Colorless transparent conductive ink as well as preparation method and application thereof | |
| KR102067888B1 (en) | ELECTROCHEMICAL SENSOR DETECTING NITROBENZENE USING Au-Ag ALLOY NANODOTS AND METHOD OF THE SAME | |
| JP5749798B2 (en) | Rare earth element doped yttrium oxide light-emitting film containing conductive oxide and method for preparing the same | |
| CN109932325A (en) | The measuring method and quantum dot ink formulation method of particle surface ligand content | |
| CN100503093C (en) | Metal microparticle, composition containing the same and process for producing metal microparticle | |
| CN110499152B (en) | Colorimetric and fluorescent double-response fluorescent detection probe and sensor | |
| CN109932274A (en) | The measuring method and quantum dot ink formulation method of quantum dot surface ligand content | |
| CN113122233A (en) | Quantum dot composite material, preparation method thereof and quantum dot light-emitting diode | |
| Shiba et al. | Preparation of Eu (III) acetylacetonate-doped well-defined titania particles with efficient photoluminescence properties | |
| CN109932326B (en) | Method for measuring coverage rate of ligand on surface of quantum dot | |
| CA2399295C (en) | Color imparting compositions for ink jet printer inks | |
| CN109932267B (en) | Method for measuring coverage rate of ligand on surface of quantum dot | |
| CN109932285A (en) | The measuring method and quantum dot ink formulation method of quantum dot surface ligand content | |
| CN115128138A (en) | Gold nanoparticle modified nickel molybdate nanocomposite and preparation method thereof | |
| CN109932358A (en) | The measuring method and quantum dot ink formulation method of quantum dot surface ligand content | |
| CN109946331A (en) | The measuring method and quantum dot ink formulation method of quantum dot surface ligand content |
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 | ||
| CB02 | Change of applicant information |
Address after: 516006 TCL science and technology building, No. 17, Huifeng Third Road, Zhongkai high tech Zone, Huizhou City, Guangdong Province Applicant after: TCL Technology Group Co.,Ltd. Address before: 516006 Guangdong province Huizhou Zhongkai hi tech Development Zone No. nineteen District Applicant before: TCL RESEARCH AMERICA Inc. |
|
| CB02 | Change of applicant information | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |