CN109932274A - 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 the ligand content of particle surface mercaptan ligand, further proposes a kind of preparation side of quantum dot ink
Method.
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 is identical or different, mole when the organic ligand difference, between each organic ligand
Molecular mass difference is no more than 5%；
The particle and reference are placed in thermogravimetric analyzer, under inert gas conditions, according to the sample particle in institute
It states the weightless ratio occurred at the volatilization temperature of organic ligand and 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:
Particle is provided, the individual particle of the sample particle includes quantum dot and is incorporated in the organic of the quantum dot surface and matches
Body, the organic ligand are selected from aliphatic carboxylic acid ligand, nitrogenous organic ligand, phosphorous organic ligand or containing the organic of sulfydryl
Ligand, the organic ligand are one or more, when the organic ligand is a variety of, between each organic ligand moles
Molecular mass difference 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；
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 particle and reference are placed in thermogravimetric analyzer by S20, under inert gas conditions, are existed according to the sample particle
Quantum dot surface ligand content is calculated in the weightless ratio occurred at the volatilization temperature of the organic ligand.
The present invention heats sample particle under the inert atmosphere conditions such as nitrogen, argon gas, and test sample particle becomes with temperature
The mass-change curve of change, since quantum dot surface ligand is organic matter in sample particle, the boiling point of this type organic is 100-
300 DEG C, when being increased to the boiling point of the quantum dot surface ligand with temperature, quantum dot surface ligand volatilizees rapidly and loses
Reconstructed image.Containing for quantum dot surface ligand in sample particle can be calculated according to the weightless ratio occurred at ligand volatilization temperature
Amount.
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, sample preparation weighs the reference and sample particle of phase homogenous quantities respectively in step S20, preferably claim respectively
It takes the reference of 5-10mg and sample particle to be placed in two crucibles, is placed on the left and right side of thermogravimetric analyzer furnace body thermocouple
Carry out test analysis.Preferably, the reference is aluminium oxide, and the crucible is corundum crucible, silica crucible or platinum earthenware
Crucible.
Specific test analysis condition is: under the inert gas environments such as nitrogen, argon gas, will test pressure and is transferred to 0.1-
15MPa, in 30-40 mm/min or so, it is 50-800 DEG C that heating temperature section, which is arranged, for gas flow control, heating rate is 2 ~
10 DEG C/min, data acquisition intervals 1-5pt/s heats reference and sample particle, test sample granular mass with
The curve of temperature change.By due in sample particle quantum dot surface ligand be organic matter, the boiling point of this type organic is 100-
300 DEG C, when being increased to the boiling point of the quantum dot surface ligand with temperature, quantum dot surface ligand volatilizees rapidly and loses
Reconstructed image.Containing for quantum dot surface ligand in sample particle can be calculated according to the weightless ratio occurred at ligand volatilization temperature
Measure (ml /mQ) %, that is, match the percentage of weight and sample particle quality.
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, MlFor the molecular quality of surface ligand.
Below by embodiment, the present invention is described in detail.
Embodiment 1
1, it determines in authentic specimen particle, the surface mercaptan ligand content ω of quantum dot1.Wherein quantum dot is CdZnSe/
CdZnSe/ZnSe quantum dot, surface ligand are spicy thioalcohol, are included the following steps:
5 mg of reference aluminium oxide and sample particle is weighed respectively, is placed in silica crucible, and thermogravimetric analyzer furnace body heat is placed on
The left and right sides of galvanic couple.It will test pressure under Ar gaseous environment and be transferred to 5MPa, gas flow is controlled in 30 mm or so.Setting adds
Hot temperature range is 50-800 DEG C, and heating rate is 2 DEG C/min, data acquisition intervals 1pt/s.To benchmark under atmospheric condition
Sample particle and reference are heated, and test quantum point mass changes the curve varied with temperature, obtain thermogravimetric analysis map.
The weightless ratio that sample occurs at ~ 200 DEG C as can be seen from the results is 17.3%, and weight loss is caused by the volatilization of mercaptan ligand herein.Cause
Mercaptan ligand content is 17.3% in this quantum dot.
2, other batch sample particle CdZnSe/CdZnSe/ZnSe quantum dot surface ligands of same preparation process are determined
Middle spicy thioalcohol ligand content.By above-mentioned reaction and test process, another batch CdZnSe/CdZnSe/ZnSe quantum dot table is obtained
Face ligand content is 17.5%, ω2In 90% ω1~110%ω1In range, quantum dot ink formulation can be directly used for.
Embodiment 2
1, it determines in authentic specimen particle, the surface phosphoric acid ligand content ω of quantum dot1.Wherein quantum dot is CdZnSe/ZnS amount
Sub-, surface ligand is octadecyl phosphoric acid, is included the following steps:
5 mg of reference aluminium oxide and sample particle is weighed respectively, is placed in silica crucible, and thermogravimetric analyzer furnace body heat is placed on
The left and right sides of galvanic couple.Pressure is transferred to 8MPa under Ar gaseous environment, gas flow is controlled in 35 mm or so.Setting heating temperature
Spending section is 50-800 DEG C, and heating rate is 5 DEG C/min, data acquisition intervals 1pt/s.To sample and mark under atmospheric condition
Quasi- sample is heated, and test quantum point mass changes the curve varied with temperature, obtains thermogravimetric analysis map.Sample as can be seen from the results
Product are weightless in ~ 200 DEG C of appearance, weightless ratio 20.4%, and weight loss is caused by ligand volatilization herein.Therefore match in quantum dot
Body content is 20.4%.
2, special elements in other batch samples CdZnSe/ZnS quantum dot surface ligand of same preparation process are determined
Content ω2.By the test process described in step 1, another batch CdZnSe/ZnS quantum dot surface ligand content ω is obtained2For
24.7%, ω2Greater than 110% ω1, quantum dot is first spent into ligand agent processing, content in surface ligand is adjusted to 90% ω1~
110%ω1After in range, then carry out ink configuration.
3, quantum dot removes ligand.Sample particle described in 300mg step 2 is taken, sample particle addition is contained into 0.15mmol
H+, for the volumetric concentration of hydrochloric acid to be stirred at room temperature in 2% ethanol solution, the mixing after stirring with chloroform and ethyl alcohol is molten
Liquid is cleaned, and the quantum dot for removing some ligands is obtained.
Determine that sample particle CdZnSe/ZnS quantum dot surface ligand content is ω after removing ligand3.By the test of step 1
Journey obtains CdZnSe/ZnS quantum dot surface ligand content ω after ligand3For 21.5%, ω3In 90% ω1~110%ω1Range
It is interior, it can directly carry out ink configuration.
Embodiment 3
1, it determines in authentic specimen particle, the surface fatty acid ligand content ω of quantum dot1.Wherein quantum dot is CdS/CdZnS/
CdZnS/ZnS quantum dot, surface ligand are octadecenic acid, are included the following steps:
10 mg of reference aluminium oxide and sample particle is weighed respectively, is placed in corundum crucible, and thermogravimetric analyzer furnace body heat is placed on
The left and right sides of galvanic couple.Pressure is transferred to 10MPa under Ar gaseous environment, gas flow is controlled in 30 mm or so.Setting heating temperature
Spending section is 50-800 DEG C, and heating rate is 10 DEG C/min, data acquisition intervals 1pt/s.Under atmospheric condition to sample and
Standard sample is heated, and test quantum point mass changes the curve varied with temperature, obtains thermogravimetric analysis map.As can be seen from the results
Sample is weightless in ~ 200 DEG C of appearance, weightless ratio 16.5%, and weight loss is caused by ligand volatilization herein.Thus what is calculated arrives
Quantum dot surface ligand content is 16.5%.
2, other batch sample particle CdS/CdZnS/CdZnS/ZnS quantum dot surface ligands of same preparation process are determined
Content ω2.By above-mentioned reaction and test process, obtains another batch CdS/CdZnS/CdZnS/ZnS quantum dot surface ligand and contain
Measure ω2For 12.3%, ω2Less than 90% ω1, quantum dot progress ligand is exchanged again first, O element in surface ligand is adjusted to 90%
ω1~110%ω1After in range, then carry out ink formulation.
3, quantum dot ligand exchanges again, takes step 2 sample particle, it is known that the ligand content that quantum dot is added in the preparation is
18mmol.CdS/CdZnS/CdZnS/ZnS quantum dot is added in chloroform, the solution of 10mg/ml is configured to, is then added thereto
Enter 0.4 mmol octadecenic acid to be stirred at 40 DEG C, is cleaned, obtained with the mixed solution of chloroform and ethyl alcohol after stirring
Ligand exchange again after quantum dot.
Determine CdS/CdZnS/CdZnS/ZnS quantum dot surface ligand content ω after ligand exchanges again3, by the survey of step 1
Examination process obtains CdS/CdZnS/CdZnS/ZnS quantum dot surface surface ligand content ω after ligand exchanges again3For 15.4%, ω3
In 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.It should be understood that the application of the present invention is not limited to the above,
For those of ordinary skills, it can be modified or changed according to the above description, and all these modifications and variations are all
It should belong to the protection scope of appended claims of the present invention.
Claims (11)
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%；
The particle and reference are placed in thermogravimetric analyzer, under inert gas conditions, according to the sample particle in institute
It states the weightless ratio occurred at the volatilization temperature of organic ligand and 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 the quantum dot is one
First quantum dot, binary quantum dot, ternary quantum dots or quaternary quantum dot；And/or the sample particle is by same preparation process system
It is standby to obtain.
3. the measuring method of quantum dot surface ligand content according to claim 2, 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 includes CdZnSeyS, CdSe/ZnS, CdZnSe/ZnS, CdSe/CdS/ZnS, CdSe/ZnSe/
ZnS, CdZnSe/CdZnS/ZnS or InP/ZnS quantum dot.
4. the measuring method of quantum dot surface ligand content according to claim 1, which is characterized in that
The organic ligand containing sulfydryl 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.
5. the measuring method of quantum dot surface ligand content according to claim 1, which is characterized in that in inert gas conditions
Under, quantum dot surface is calculated according to the weightless ratio that the sample particle occurs at the volatilization temperature of the organic ligand
The test condition of ligand content are as follows: in an inert atmosphere, detection pressure is 0.1-15MPa, and gas flow is 30-40 mm/
Min, heating temperature section are 50-800 DEG C, and heating rate is 2 ~ 10 DEG C/min, data acquisition intervals 1-5pt/s.
6. the measuring method of quantum dot surface ligand content according to claim 1, which is characterized in that the reference is oxygen
Change aluminium.
7. 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 the organic of the quantum dot surface
Ligand, the organic ligand are selected from aliphatic carboxylic acid ligand, nitrogenous organic ligand, phosphorous organic ligand or having containing sulfydryl
Machine ligand, the organic ligand is identical or different, when the organic ligand difference, between each organic ligand mole point
Protonatomic mass difference is no more than 5%；
Measure the institute of different batches respectively by the measuring method of quantum dot surface ligand content described in any one of claims 1-6
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.
8. the configuration method of quantum dot ink according to claim 7, which is characterized in that match on the surface of benchmark batch particle
Body content is denoted as ω1, as other batch sample size point surface ligand content ω2Higher than 110% ω1When, by removing ligand
Method reduces other batch sample size point surface ligand contents, and the method for removing ligand includes: will be described other
One batch sample particle is mixed with inorganic acid solution, sloughs the ligand on other batch sample particle surfaces.
9. the configuration method of quantum dot ink according to claim 8, which is characterized in that the inorganic acid solution is selected 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.
10. the configuration method of quantum dot ink according to claim 8, 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 surface ligand.
11. the configuration method of quantum dot ink according to claim 7, which is characterized in that the sample of different batches
Particle is prepared by same preparation process.
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