CN109946331A - The measuring method and quantum dot ink formulation method of quantum dot surface ligand content - Google Patents
The measuring method and quantum dot ink formulation method of quantum dot surface ligand content Download PDFInfo
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Abstract
The present invention proposes the measuring method and quantum dot ink formulation method of quantum dot surface ligand content.The configuration of quantum dot ink is carried out using this method, it can guarantee the homogeneity of quantum dot drop mass, it can guarantee that dissolubility, the rate of drying of the quantum dot ink of different batches are identical with coffee ring effect, the homogeneity that the pixel resolution of quantum dot display panel can be improved, open bright voltage, photoelectric efficiency.
Description
Technical field
The present invention relates to quantum dot technical field of ink more particularly to the measuring methods and amount of quantum dot surface ligand content
Son point ink formulation method.
Background technique
Quantum dot refers to that geometric dimension is less than the semiconductor nano of its Exciton Bohr Radius.Quantum dot is inhaled due to having
The excellent optical properties such as take-up is wide, fluorescent emission band is narrow, quantum efficiency is high, good light stability, in biomedical, environment energy
There is huge potential application in the fields such as source, illumination display.Compared with liquid crystal display and organic light emitting display, it is based on quantum dot
Luminous display technology is in recent years by the great attention of display industry, and quantum dot light emitting colour gamut is wider, excitation purity is higher, structure
Simpler, stability is higher, it is considered to be display technology of new generation.
The technology of preparing of quantum dot displays part includes spraying, inkjet printing, slot coated, intaglio and silk-screen printing
Deng.It is characterized in that the detailed process of inkjet printing be by quantum dot ink injection on the substrate, it is dry after in specific position
Form quantum dot film.Compared with other technologies of preparing, inkjet printing is at low cost, convenient, print quality is high, is suitble to big ruler
The features such as very little panel makes.The preparation of quantum dot ink is that quantum dot is dissolved in specific solvent, and being formed has certain viscosity, surface
The solution of tension and charge transport ability.Viscosity, surface tension and the charge transport ability of quantum dot ink determine that ink-jet is beaten
The photoelectric properties of the wetting ability, rate of drying, coffee ring effect and film of ink droplet when print, therefore, the quality of quantum dot ink
Ink jet printing performance is played a crucial role.In quantum dot ink configuration process, it is incorporated in matching for quantum dot surface
Body has an important influence quantum dot ink, not only influences the photoelectric properties of quantum dot itself, also will affect quantum dot ink
Dissolubility and stability.Common surface ligand is carboxylic acid, amine, alkyl phosphorus, alkylphosphine oxide, alkyl phosphoric acid, mercaptan etc..Match on surface
Influence of the body to quantum dot own optical performance shows themselves in that the size of quantum dot is less than Exciton Bohr Radius, and exciton is in certain journey
Surface is exposed on degree, surface is easy to be affected and reduce its optical property；When quantum dot surface atom number increases, surface
The defects of dangling bonds also can sharply increase, and Atomic coordinate deficiency leads to quantum dot surface there are many defects, electronics or holes
Presence increase the probability of non-radiative recombination, the combined efficiency for causing normal radiation compound substantially reduces.It is appropriate when being added
When surface ligand, quantum dot surface dangling bonds can be effectively reduced, exciton is made to be no longer exposed to surface, improve the optical of quantum dot
Energy.Influence of the surface ligand to quantum dot dissolubility and stability shows themselves in that increasing for quantum dot surface dangling bonds can make its table
Face free energy is very big, and surface becomes abnormal active, this is also resulted in, and system is unstable, and quantum dot can be intended to aggregation to reduce
Surface area, this will lead to the reduction of quantum dot solution dissolubility.After introducing surface ligand, one end of ligand is connected to quantum dot surface
On atom, one end mixes with solution, can reduce the surface energy of quantum dot, improve the dissolubility of quantum dot, the sub- point of effective inhibitory amount
Solution generates precipitating.
In current quantum dot ink jet printing process, there is a problem that one it is universal, that is, same process preparation
Different batches quantum dot of the same race, the property for the ink being configured under the conditions of same ink set is but not quite similar.Study carefully
Caused by its reason, mainly quantum dot surface ligand content be not identical.If quantum dot surface ligand is very few, quantum dot is not easy
It is dissolved in ink solvent, so that inkjet printing can not be carried out.If the quantum dot surface ligand exchange rate of different batches is different, measure
Dissolubility, rate of drying and the coffee ring effect of son point ink are also not quite similar, thus will affect the quality of luminous layer film, this
Directly result in that the panel quality printed is uneven, pixel resolution is low, opens bright voltage, the problems such as photoelectric efficiency is inhomogenous.
Summary of the invention
In view of above-mentioned deficiencies of the prior art, in order to ensure the stability of quantum dot drop mass, present invention firstly provides
A kind of measuring method of quantum dot surface ligand content, further proposes a kind of preparation method of quantum dot ink.
A kind of measuring method of quantum dot surface ligand content, wherein include:
Sample particle is provided, the individual particle of the sample particle includes quantum dot and is incorporated in having for the quantum dot surface
Machine ligand, the organic ligand are selected from aliphatic carboxylic acid ligand, nitrogenous organic ligand, phosphorous organic ligand or containing sulfydryl
Organic ligand, the organic ligand be it is one or more, when the organic ligand is a variety of, between each organic ligand
Molecular mass difference is no more than 5%；
Sample particle is placed in X-ray photoelectron spectroscopic analysis instrument, using X-ray photoelectron spectroscopic analysis instrument, with AlK α line
Sample particle is excited, makees charge correction with C1s spectral line, quantum dot table is calculated in the content of each element in test sample particle
Face ligand content；
Wherein, when the organic ligand of quantum dot surface is aliphatic carboxylic acid ligand, oxygen element is free of in the quantum dot；Work as quantum
When the organic ligand on point surface is nitrogenous organic ligand, not Nitrogen element in the quantum dot；It is organic when quantum dot surface
When ligand is phosphorous organic ligand, not phosphorus element-containing in the quantum dot；When the organic ligand of quantum dot surface is containing sulfydryl
Organic ligand when, element sulphur is free of in the quantum dot.
The measuring method of quantum dot surface ligand content of the invention, method is simple, widely applicable, strong operability, can
For evaluating the synthesis quality of different batches quantum dot, especially for the different batches quantum for guaranteeing to synthesize in same preparation process
The quality of point provides reliable guarantee.
A kind of configuration method of quantum dot ink, wherein include:
Sample particle is provided, the individual particle of the sample particle includes quantum dot and is incorporated in having for the quantum dot surface
Machine ligand, the organic ligand are selected from aliphatic carboxylic acid ligand, nitrogenous organic ligand, phosphorous organic ligand or containing sulfydryl
Organic ligand；Wherein, when the organic ligand of quantum dot surface is aliphatic carboxylic acid ligand, oxygen element is free of in the quantum dot；
When the organic ligand of quantum dot surface is nitrogenous organic ligand, not Nitrogen element in the quantum dot；Work as quantum dot surface
Organic ligand when being phosphorous organic ligand, not phosphorus element-containing in the quantum dot；When the organic ligand of quantum dot surface is
When organic ligand containing sulfydryl, element sulphur is free of in the quantum dot；
Measure the sample particle of different batches respectively by the measuring method of quantum dot surface ligand content of the present invention
Surface ligand content；
One of batch sample particle is selected as benchmark batch sample particle；
When other batch sample size point surface ligand contents differ not with the surface ligand content of the benchmark batch particle
When more than 10%, other batch sample particles are used to configure ink；
When other batch sample size point surface ligand contents differ super with the surface ligand content of the benchmark batch particle
When 10%, other batch quantity point surface ligand contents are adjusted to the surface ligand with the benchmark batch particle
After content difference is within 10%, other batch particles after surface ligand content will be adjusted and be used to configure ink.
In order to ensure that the stability of quantum dot ink, the present invention propose a kind of quantum dot ink formulation method.Specially needle
To the quantum dot of the same race of different batches, determine that authentic specimen quantum dot surface ligand content is denoted as ω1, determine other each batch systems
Standby sample particle (such as can be other sample particles obtained based on method of the same race or same preparation process) surface ligand
Content ω2If ω2=【90%ω1, 110%ω1], then the quantum dot surface ligand content of sample particle is consistent between batch, can be into
Row quantum dot ink formulation；If ω2<90%ω1, first using ligand, exchange process adjusts ω again2To 90% ω1~110%ω1The amount of progress again
Son point ink formulation；If ω2>110%ω1, first use and ligand method gone to adjust ω2To 90% ω1~110%ω1Quantum dot ink is carried out again
Water is prepared.The configuration of quantum dot ink is carried out using this method, can guarantee the homogeneity of quantum dot drop mass, can guarantee different batches
Dissolubility, the rate of drying of secondary quantum dot ink are identical with coffee ring effect, and the pixel for improving quantum dot display panel is differentiated
Rate, the homogeneity for opening bright voltage, photoelectric efficiency.
Specific embodiment
The present invention provides a kind of measuring method of quantum dot surface ligand content, to make the purpose of the present invention, technical solution
And effect is clearer, clear, the present invention is described in more detail below.It should be appreciated that specific implementation described herein
Example is only used to explain the present invention, is not intended to limit the present invention.
A kind of measuring method of quantum dot surface ligand content, wherein include:
S10 provides sample particle, and the individual particle of the sample particle includes quantum dot and is incorporated in the quantum dot surface
Organic ligand, the organic ligand be selected from aliphatic carboxylic acid ligand, nitrogenous organic ligand, phosphorous organic ligand or contain mercapto
The organic ligand of base, the organic ligand be it is one or more, when the organic ligand be it is a variety of when, each organic ligand it
Between molecular mass difference be no more than 5%；
Sample particle is placed in X-ray photoelectron spectroscopic analysis instrument by S20, using X-ray photoelectron spectroscopic analysis instrument, with AlK α
Line excites sample particle, makees charge correction with C1s spectral line, the content of each element, is calculated quantum dot in test sample particle
Surface ligand content；
The present invention is using the characteristic spectrum of each element in X-ray photoelectron spectroscopic analysis instrument test sample particle, with software meter
Calculation obtains the integral area of characteristic peak, and integral area is the relative amount of each element, obtains characteristic element in organic ligand immediately
Account for sample particle percentage composition because the organic ligand be it is one or more, when the organic ligand be it is a variety of when, each institute
It states the molecular mass difference between organic ligand and is no more than 5%, the sample particle percentage that accounts for of characteristic element contains in organic ligand
Amount can be estimated as quantum dot surface ligand content.It is described organic when the organic ligand of quantum dot surface is aliphatic carboxylic acid ligand
Characteristic element in ligand is oxygen element；It is described organic to match when the organic ligand of quantum dot surface is nitrogenous organic ligand
Characteristic element in body is nitrogen；When the organic ligand of quantum dot surface is phosphorous organic ligand, the organic ligand
In characteristic element be P elements；When the organic ligand of quantum dot surface is the organic ligand containing sulfydryl, the organic ligand
In characteristic element be element sulphur.Also, when the organic ligand of quantum dot surface is aliphatic carboxylic acid ligand, in the quantum dot
Without oxygen element；When the organic ligand of quantum dot surface is nitrogenous organic ligand, not Nitrogen element in the quantum dot；When
When the organic ligand of quantum dot surface is phosphorous organic ligand, not phosphorus element-containing in the quantum dot；When quantum dot surface
When organic ligand is the organic ligand containing sulfydryl, element sulphur is free of in the quantum dot.For example, when quantum dot is CdZnSeS,
Surface ligand cannot be mercaptan ligand；When quantum dot is InP/ZnS, surface ligand cannot be for mercaptan and containing Phosphine ligands.
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 particle is first carried out compression process in the step S20, as one of preferred implementation
Mode, comprising: 5-15mg sample particle is weighed, it is levigate with agate mortar, with acetone or isopropanol by 2*2cm2Aluminium foil wiping
Completely, 1*1cm is cut2Double faced adhesive tape be attached to aluminium foil center.Sample particle powder is layered on double faced adhesive tape, and with completely
Stainless steel sample spoon sample particle powder is uniformly paved with entire adhesive tape, it is thin as far as possible.Take another with acetone wiped clean
Aluminium foil covers sample particle powder, is placed among two pieces of smooth stainless steel modules, and it is 5- that pressure is arranged under grease press
15MPa takes out sample after suppressing 5-15s, and sample to be tested is surfacing, the close thin slice of quality at this time.Remove and is covered on sample
Upper layer aluminium foil on product cuts off bottom aluminium foil along the sample surrounding suppressed, 1*1cm is made2Press sheet compression.
The test of press sheet compression carries out on photoelectron spectrograph.Sample (sample particle) is excited with AlK α line, X-ray function
Rate is 10 ~ 20KV*10 ~ 20mA, and the vacuum degree of energy disperse spectroscopy is 1 ~ 10*10-9Mbar makees electricity with C1s spectral line (in conjunction with energy 284.8eV)
Lotus is corrected to eliminate the influence of extraneous contamination.Setting test scope is 0-1200eV, and range intervals are 30- when accurate scan
50eV.The integral area of characteristic peak is calculated with software, obtains member immediately for the characteristic spectrum that each element is obtained after sample test
The relative amount ratio of element.
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, the organic ligand is identical or different, when the organic ligand difference, between each organic ligand
Molecular mass difference 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 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, selectes base using X-ray photoelectron spectroscopic analysis method
Quasi- 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 it
The sample particle of its batch preparation (such as can be other quantum dot tables obtained based on method of the same race or same preparation process
Face organic ligand content ω2, according to ω1With ω2Between relationship judge whether can by other batch sample particles directly with
Other several batch sample particles are mixed for the configuration of ink.If ω2=【90%ω1, 110%ω1] (ω2Value in 90% ω1~
110%ω1Between), then it is believed that the quantum dot surface organic ligand content of other batch sample particles and authentic specimen
The quantum dot surface organic ligand content of grain is consistent, can carry out quantum dot ink formulation.During being somebody's turn to do, by other batches
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.
In the step S105, if ω2<90%ω1, need to using ligand, exchange process adjusts ω again2To 90% ω1~110%ω1Again
Carry out quantum dot ink formulation；If ω2>110%ω1, need to use and ligand method is gone to adjust ω2To 90% ω1~110%ω1The amount of progress again
Son point ink formulation.The configuration of quantum dot ink is carried out using this method, the homogeneity of quantum dot drop mass is can guarantee, can guarantee
Dissolubility, the rate of drying of the quantum dot ink of different batches are identical with coffee ring effect, improve the picture of quantum dot display panel
Plain resolution ratio, the homogeneity for opening bright voltage, photoelectric efficiency.It is described to adjust other batches after surface ligand content
Sample particle includes: that other batch sample particles are directly used in configuration ink for configuring ink；Or it is this is other
(benchmark particle and/or surface ligand content are in 90% ω with other several sample particles for meeting condition for one batch sample particle1~
110%ω1Between sample particle) be mixed for configure ink.
Specifically, the surface ligand content of benchmark batch particle is denoted as ω1, other batch sample size point surface ligands
Content ω2Lower than 90% ω1When, it can increase other batch sample size point surfaces by quantum dot ligand exchange process again and match
Other batch sample particles are dissolved in nonpolar solvent by body content, including step, and original surface ligand is then added in 25-100
It is swapped at DEG C.The nonpolar solvent can selected from chloroform, n-hexane, heptane, octane, toluene, chlorobenzene, dichloro-benzenes,
Carbon tetrachloride, decane, hendecane, dodecane, tridecane, the tetradecane, pentadecane, hexadecane, heptadecane, octadecane, cyclodecane
One or more of with ring hendecane.The amount of the substance for the ligand that the ligand is added in exchange process is (90%
ω1-ω2)n~(110%ω1-ω2) n, wherein n is the amount of the substance for the ligand being added in quantum dot preparation process.
Specifically, the surface ligand content of benchmark batch particle is denoted as ω1, other batch sample size point surface ligands
Content ω2Higher than 110% ω1When, can method by removing ligand, reduce other batch sample size point surface ligands and contain
Amount.It to be acidic treatment that example removes ligand approach as mentioned, i.e., by other batch sample particles and inorganic acid solution
Mixing, sloughs the ligand on other batch sample particle surfaces.Inorganic acid solution ionizes out H at this time+And anion, surface
Ligand and H+In conjunction with weak acid is generated, to slough ligand.Wherein, the inorganic acid type be selected from hydrochloric acid, nitric acid or
Sulfuric acid, inorganic acid solution are aqueous solution, methanol solution or the ethanol solution that the volumetric concentration of the acid is 1.25% ~ 5%.Described
The amount for removing the substance for removing ligand agent being added during ligand is mQ(ω2-110%ω1)/Ml~mQ(ω2-90%ω1)/Ml,
In, mQFor the quality of other batch sample particles, MlIt is characterized the molecular quality of element.
Below by embodiment, the present invention is described in detail.
Embodiment 1
1, it determines in authentic specimen particle, the surface containing n-donor ligand content ω of quantum dot1.Wherein quantum dot is CdSe quantum dot,
Surface ligand is octadecenyl amine, is included the following steps:
5mg sample particle is weighed, it is levigate with agate mortar, with acetone or isopropanol by 2*2cm2Aluminium foil wiped clean, cut~
1*1cm2Double faced adhesive tape be attached to aluminium foil center, sample particle powder is layered on double faced adhesive tape, and with clean stainless
Sample particle powder is uniformly paved with entire adhesive tape by steel sample spoon, takes another to cover sample with the aluminium foil of acetone wiped clean
Particle powder is placed among two pieces of smooth stainless steel modules, and it is 7MPa that pressure is arranged under grease press, is taken out after suppressing 10s
Sample, sample to be tested is surfacing, the close thin slice of quality at this time.Remove the upper layer aluminium foil being covered on sample, along compacting
Good sample surrounding cuts off bottom aluminium foil, and 1*1cm is made2Press sheet compression, on photoelectron spectrograph, sample with AlK α line swash
Hair, x-ray power 14KV*15mA.The vacuum degree of energy disperse spectroscopy is 3*10-9Mbar, extraneous contamination is with C1s spectral line (in conjunction with energy
284.8eV) make charge correction.Setting test scope is 0-1200eV first, and range intervals are 30-50eV when accurate scan.Sample
The characteristic spectrum of each element is obtained after product test, the integral area of characteristic peak is calculated with software, obtains containing for element immediately
Ratio is measured, it is 4.8% that wherein N element content, which is calculated, is calculated as quantum dot surface ligand content.
2, containing for characteristic element in other batch sample particle CdSe quantum dot surface ligands of same preparation process is determined
Measure ω2.By the process of above-mentioned steps 1, N element content ω in another batch CdSe quantum dot surface ligand is obtained2It is 2.5%, meter
For quantum dot surface ligand content.ω2Less than 90% ω1, first quantum dot progress ligand is exchanged again, by N element in surface ligand
It 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 that CdSe quantum dot is added in the preparation contains
Amount is 21 mmol.Sample particle is added in chloroform, the solution of 10mg/ml is configured to, is then charged with 0.45mmol ten
Eight enamines are stirred at 40 DEG C, are cleaned after stirring with the mixed solution of chloroform and ethyl alcohol, are obtained after ligand exchanges again
Sample particle.
4, the content ω of N element in CdSe quantum dot surface ligand in sample particle is determined after ligand exchanges again3.By step
1 test process obtains the content ω of N element in CdSe quantum dot surface ligand after ligand exchanges again3It is 4.6%, is calculated as quantum
Point surface ligand content.ω3In 90% ω1~110%ω1In range, ink formulation can be directly carried out.
Embodiment 2
1, it determines in authentic specimen particle, the surface containing n-donor ligand content ω of quantum dot1.Wherein quantum dot is ZnO quantum dot, table
Face ligand is stearic acid, is included the following steps:
15mg sample particle is weighed, it is levigate with agate mortar.With acetone or isopropanol by 2*2cm2Aluminium foil wiped clean, cut~
1*1cm2Double faced adhesive tape be attached to aluminium foil center.Sample particle powder is layered on double faced adhesive tape, and with clean stainless
Powder is uniformly paved with entire adhesive tape by steel sample spoon.Another is taken to cover sample particle powder with the aluminium foil of acetone wiped clean
And be placed among two pieces of smooth stainless steel modules, it is 15MPa that pressure is arranged under grease press, sample is taken out after suppressing 10s,
Sample to be tested is surfacing, the close thin slice of quality at this time.Remove the upper layer aluminium foil being covered on sample particle powder, along pressure
The sample surrounding made cuts off bottom aluminium foil, and 1*1cm is made2Press sheet compression.Sample test carries out on photoelectron spectrograph.
Sample is excited with AlK α line, x-ray power 20KV*10mA.The vacuum degree of energy disperse spectroscopy is 9*10-9Mbar, extraneous contamination C1s
Spectral line (in conjunction with energy 284.8eV) makees charge correction.Setting test scope is 0-1200eV first, and range intervals are when accurate scan
30-50eV.The characteristic spectrum that each element is obtained after sample test the integral area of characteristic peak is calculated with software, with to obtain the final product
To the content ratio of element, it is 6.3% that O constituent content ratio, which is calculated, is calculated as quantum dot surface ligand content.
2, ZnO quantum dot surface ligand content ω in other batch sample particles of same preparation process is determined2.By step
Test process described in 1 obtains O constituent content ω in another batch ZnO quantum dot surface ligand2It is 9.8%, is calculated as quantum dot
Surface ligand content.ω2Greater than 110% ω1, quantum dot is first spent into ligand agent processing, O element in surface ligand is adjusted to
90%ω1~110%ω1After in range, then carry out ink configuration.
Quantum dot removes ligand.ZnO quantum dot described in 300mg step 1 is taken, ZnO quantum dot is added and contains 0.9mmol H+, the volumetric concentration of hydrochloric acid is is stirred at room temperature in 2% ethanol solution, with the mixed solution of chloroform and ethyl alcohol after stirring
It is cleaned, obtains the quantum dot for removing some ligands.
Determine the content ω of O element in ZnO quantum dot surface ligand after removing ligand3.By the test process of step 1, obtain
Remove the content ω of O element in ZnO quantum dot surface ligand after ligand3It is 6.7%, is calculated as quantum dot surface ligand content.ω3?
90%ω1~110%ω1In range, ink configuration 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 (12)
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 be no more than 5%；
Sample particle is placed in X-ray photoelectron spectroscopic analysis instrument, using X-ray photoelectron spectroscopic analysis instrument, with AlK α line
Sample particle is excited, makees charge correction with C1s spectral line, quantum dot table is calculated in the content of each element in test sample particle
Face ligand content；
Wherein, when the organic ligand of quantum dot surface is aliphatic carboxylic acid ligand, oxygen element is free of in the quantum dot；Work as quantum
When the organic ligand on point surface is nitrogenous organic ligand, not Nitrogen element in the quantum dot；It is organic when quantum dot surface
When ligand is phosphorous organic ligand, not phosphorus element-containing in the quantum dot；When the organic ligand of quantum dot surface is containing sulfydryl
Organic ligand when, element sulphur is free of in the quantum dot.
2. the measuring method of quantum dot surface ligand content according to claim 1, which is characterized in that the test sample
The content of each element, the step of quantum dot surface ligand content is calculated include: to utilize X-ray photoelectron spectroscopic analysis in grain
The characteristic spectrum of each element, the integral area of each element characteristic peak is calculated with software, is had in instrument test sample particle
Characteristic element accounts for sample particle content in machine ligand, is calculated as quantum dot surface ligand content, wherein when having for quantum dot surface
When machine ligand is aliphatic carboxylic acid ligand, the characteristic element in the organic ligand is oxygen element；Organic when quantum dot surface matches
When body is nitrogenous organic ligand, the characteristic element in the organic ligand is nitrogen；When the organic ligand of quantum dot surface
When for phosphorous organic ligand, the characteristic element in the organic ligand is P elements；When the organic ligand of quantum dot surface is
When organic ligand containing sulfydryl, the characteristic element in the organic ligand is element sulphur.
3. the measuring method of quantum dot surface ligand content according to claim 1, which is characterized in that the quantum dot is one
First quantum dot, binary quantum dot, ternary quantum dots or quaternary quantum dot.
4. the measuring method of quantum dot surface ligand content according to claim 3, which is characterized in that the unitary quantum dot
Selected from Au, Ag, Cu, Pt or C quantum dot；
The binary quantum dot is selected from CdSe, ZnSe, PbSe, CdTe, ZnO, MgO, CeO2、NiO、TiO2, InP or CaF2Quantum
Point；
The ternary quantum dots be selected from CdZnS, CdZnSe, CdSeS, PbSeS, ZnCdTe, CdS/ZnS, CdZnS/ZnS,
CdZnSe/ZnSe、CdSeS/ CdSeS /CdS、CdSe/CdZnSe/CdZnSe/ZnSe、CdZnSe/CdZnSe/ZnSe、CdS/
CdZnS/CdZnS/ZnS、NaYF4Or NaCdF4Quantum dot；
The quaternary quantum dot is selected from CdZnSeyS, CdSe/ZnS, CdZnSe/ZnS, CdSe/CdS/ZnS, CdSe/ZnSe/
ZnS, CdZnSe/CdZnS/ZnS or InP/ZnS quantum dot.
5. the measuring method of quantum dot surface ligand content according to claim 1, which is characterized in that
The 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.
6. the measuring method of quantum dot surface ligand content according to claim 1, which is characterized in that sample particle to be placed in
Before in X-ray photoelectron spectroscopic analysis instrument, further include the steps that suppressing sample particle, pressing pressure 5-15MPa,
Suppress 5-15s.
7. the measuring method of quantum dot surface ligand content according to claim 1, which is characterized in that sample particle to be placed in
In X-ray photoelectron spectroscopic analysis instrument, using X-ray photoelectron spectroscopic analysis instrument, sample is excited with AlK α line, with C1s spectral line
Make charge correction, the determination condition of quantum dot surface ligand content is calculated in the content of test sample particle are as follows: X-ray function
Rate is 10 ~ 20KV*10 ~ 20mA, and the vacuum degree of X-ray photoelectron spectroscopic analysis instrument is 1 ~ 10*10-9Mbar, initial testing range
For 0-1200eV, accurate test scope is 30-50eV.
8. 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；Wherein, when the organic ligand of quantum dot surface is aliphatic carboxylic acid ligand, oxygen element 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；When quantum dot surface
When organic ligand is phosphorous organic ligand, not phosphorus element-containing in the quantum dot；When quantum dot surface organic ligand be containing
When the organic ligand of sulfydryl, element sulphur is free of in the quantum dot；
Measure the institute of different batches respectively by the measuring method of the described in any item quantum dot surface ligand contents of claim 1-7
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.
9. the configuration method of quantum dot ink according to claim 8, 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.
10. the configuration method of quantum dot ink according to claim 9, 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.
11. the configuration method of quantum dot ink according to claim 9, which is characterized in that by the substance of the inorganic acid
Amount be mQ(ω2-110%ω1)/Ml~mQ(ω2-90%ω1)/Ml, by other batch sample particles and inorganic acid solution
Mixing, wherein mQFor the quality of other batch sample particles, MlIt is characterized the molecular quality of element；Work as quantum dot
When the organic ligand on surface is aliphatic carboxylic acid ligand, the characteristic element in the organic ligand is oxygen element；Work as quantum dot surface
Organic ligand when being nitrogenous organic ligand, the characteristic element in the organic ligand is nitrogen；When quantum dot surface
When organic ligand is phosphorous organic ligand, the characteristic element in the organic ligand is P elements；When having for quantum dot surface
When machine ligand is the organic ligand containing sulfydryl, the characteristic element in the organic ligand is element sulphur.
12. the configuration method of quantum dot ink according to claim 8, which is characterized in that the sample of the different batches
Particle is prepared by same preparation process.
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| WHITNEY NOWAK WENGER ET AL.: ""Functionalization of Cadmium Selenide Quantum Dots with Poly(ethylene glycol): Ligand Exchange, Surface Coverage, and Dispersion Stability"", 《LANGMUIR》 * |
| 周国华: ""基于纳米材料的植物激素免疫检测及受体分离分析新方法研究"", 《中国博士学位论文全文数据库 工程科技Ⅰ辑》 * |
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