CN109932377A - A kind of measuring method of quantum dot surface ligand coverage rate - Google Patents
A kind of measuring method of quantum dot surface ligand coverage rate Download PDFInfo
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Abstract
The present invention proposes a kind of measuring method of quantum dot surface ligand coverage rate, can be used for the performance rating to quantum dot.If KiLess than 2*10‑10mol/cm2, then quantum dot quality defect need to be by KiValue carries out the application such as solution or ink configuration again after improving.Quantum dot surface ligand coverage rate is determined using this method, as a result accurate, it is easy to operate, further, it can guarantee the stability of quantum dot surface ligand coverage rate by means of the present invention, the dissolubility that can guarantee the quantum dot of different batches, when avoiding quantum dot solution preparation film forming because rate of drying it is different caused by 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 technology of quantum dots field more particularly to a kind of measuring methods of quantum dot surface ligand coverage rate.
Background technique
Quantum dot refers to that geometric dimension is less than the semiconductor nano of its Exciton Bohr Radius.Quantum dot is inhaled due to having
The excellent optical properties such as take-up is wide, fluorescent emission band is narrow, quantum efficiency is high, good light stability, in biomedical, environment energy
There is huge potential application in the fields such as source, illumination display.Display technology based on quantum dot light emitting is shown in recent years
The great attention of industry, compared with liquid crystal display and organic light emitting display, quantum dot light emitting colour gamut is wider, excitation purity is higher, knot
Structure is simpler, and stability is higher, it is considered to be display technology of new generation.
The technology of preparing of quantum dot displays part includes spin coating, inkjet printing etc..The detailed process of both methods be by
Quantum dot solution is injected on basis material, forms quantum dot film in specific position after drying.Viscosity, the table of quantum dot solution
Face tension and charge transport ability determine the wetting ability, rate of drying of quantum dot drop, coffee ring in device fabrication process
The photoelectric properties of effect and film, therefore, the quality of quantum dot solution play a crucial role device preparation.And it is measuring
In the process for preparation of son point solution, quantum dot surface ligand has an important influence quantum dot solution, and surface ligand not only influences
The photoelectric properties of quantum dot itself also will affect the dissolubility and stability of quantum dot solution.Common quantum dot surface ligand
For carboxylic acid, amine, alkyl phosphorus, alkylphosphine oxide, alkyl phosphoric acid, mercaptan etc..Influence of the surface ligand to quantum dot own optical performance
Show themselves in that the size of quantum dot is less than Exciton Bohr Radius, exciton is exposed to surface to a certain extent, and surface is easy by shadow
It rings and reduces its optical property；When quantum dot surface atom number increases, surface dangling bonds also can sharply increase, and Atomic coordinate is not
The presence for the defects of foot leads to quantum dot surface there are many defects, electronics or holes increases the probability of non-radiative recombination,
The combined efficiency for causing normal radiation compound substantially reduces.When surface ligand appropriate is added, quantum dot table can be effectively reduced
Face dangling bonds, make exciton be no longer exposed to surface, improve the optical property of quantum dot.Surface ligand is to quantum dot dissolubility and surely
It qualitatively influences to show themselves in that increasing for quantum dot surface dangling bonds can make its surface free energy very big, surface becomes abnormal living
It sprinkles, 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 quantum dot solution dissolution
Property reduce.After introducing surface ligand, one end of ligand is connected on quantum dot surface atom, and one end mixes with solution, can be reduced
The surface energy of quantum dot, improves the dissolubility of quantum dot, and effective inhibitory amount point solution generates precipitating.
Therefore, the dissolubility of quantum dot influences the preparation of device and performance very big.And the dissolubility of quantum dot in addition to
Other than quantum dot itself and ligand species, another important factor in order is the coverage rate of quantum dot surface ligand.If quantum dot
Surface coverage is low, then the dissolubility of quantum dot is poor, and the uniformity of quantum dot solution is poor, and the rate of drying of quantum dot solution
The quality of luminous layer film is affected with coffee ring effect, this is directly resulted in, and the panel quality that prints is uneven, pixel point
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 coverage rate.
A kind of measuring method of quantum dot surface ligand coverage rate, wherein including
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；
Measure the average grain diameter of particle in the sample particle；
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, the content ratio of each element, is calculated quantum dot in test sample particle
Surface ligand coverage rate Ki;
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 present invention proposes a kind of method for determining quantum dot surface ligand using XPS analysis method as ligand coverage rate.It is logical
Cross the coverage rate K of measurement quantum dot surface organic ligandsi, can be used for the performance rating to quantum dot.If KiLess than 2*10-10mol/
cm2, then quantum dot quality defect need to be by KiValue carries out the application such as solution or ink configuration again after improving.It is determined and is measured using this method
Son point surface ligand coverage rate, it is as a result accurately, easy to operate, further, it can guarantee quantum dot surface by means of the present invention
The stability of ligand coverage rate can guarantee the dissolubility of the quantum dot of different batches, avoid quantum dot solution preparation film forming when because
Coffee ring effect caused by rate of drying is different can improve the pixel resolution of quantum dot display panel, open bright voltage, photoelectricity effect
The homogeneity of rate.
Specific embodiment
The present invention provides a kind of measuring method of quantum dot surface ligand coverage rate, to make the purpose of the present invention, technical side
Case and effect are clearer, clear, and the present invention is described in more detail below.It should be appreciated that specific reality described herein
It applies example to be only used to explain the present invention, be not intended to limit the present invention.
A kind of measuring method of quantum dot surface ligand coverage rate, wherein including
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；
Measure the average grain diameter of particle in the sample particle；
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, the content ratio of each element, is calculated quantum dot in test sample particle
Surface ligand coverage rate Ki;
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 present invention proposes a kind of method for determining quantum dot surface ligand coverage rate using XPS analysis method.Pass through measurement
The coverage rate K of quantum dot surface organic ligandi, can be used for the performance rating to quantum dot.If KiLess than 2*10-10mol/cm2, then
Quantum dot quality defect, need to be by KiValue carries out the application such as solution or ink configuration again after improving.Quantum dot is determined using this method
Surface ligand coverage rate, it is as a result accurately, easy to operate, further, it can guarantee quantum dot surface ligand by means of the present invention
The stability of coverage rate can guarantee the dissolubility of the quantum dot of different batches, avoid quantum dot solution preparation when forming a film because of drying
Coffee ring effect caused by rate is different can improve the pixel resolution of quantum dot display panel, open bright voltage, photoelectric efficiency
Homogeneity.
The quantum dot surface ligand coverage rate test Computing Principle are as follows:
The sample particle is the set of several individual particles, and the individual particle includes quantum dot and is incorporated in quantum dot surface
Ligand.Surface ligand coverage rate K in the present inventioniRefer to the substance of mating surface ligand in quantum dot unit surface area
Amount, surface ligand directly in conjunction with quantum dot, pass through the feature in the specific groups in conjunction with quantum dot by specific functional groups
Surface ligand coverage rate K can be calculated in the amount of the substance of elementi.Surface ligand coverage rate KiIt can be by following public by surface
Formula obtains:
Ki=ml/(0.74MlmQSq/ρQVq) (formula 1)
It provides in sample particle, the quality of weird atom is m in specific functional groups in quantum dot surface ligandl, molecular matter
Amount is Ml, the gross mass of sample particle is mQ, density ρQ, individual particle surface area S in sample particleq, volume Vq, sample
Grain is in closs packing, space utilization rate 0.74, it is assumed that particle is spherical shape, mean particle size d.
Wherein, individual particle volume is Vq , the surface area of individual particle, counted after substituting into formula
Calculation obtains Ki=mlρQd/4.44MlmQ(formula 2), wherein the organic ligand will be divided by 2, when described when being fat carboxylic acid's ligand
When organic ligand is multidentate ligand, the ligand number of teeth need to be removed, when for example, two mercaptan, the ligand number of teeth is 2.
In above-mentioned formula 2, ρQIt can be according to searching related substances density or testing to obtain using Archimedes principle, d can basis
TEM test quantum dot size obtains.Therefore it needs to test to obtain m using suitable methodl/mQQuantum dot surface can be obtained
Ligand coverage rate.
The present invention is using the characteristic spectrum of each element in X-ray photoelectron spectroscopic analysis instrument test sample particle, and use is soft
The integral area of characteristic peak is calculated in part, and integral area is the relative amount of each element, obtains feature in organic ligand immediately
Element accounts for sample particle content than i.e. ml/mQ.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, 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.
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.
When the organic ligand of quantum dot surface is aliphatic carboxylic acid ligand, the characteristic element in the organic ligand is oxygen member
Element；When the organic ligand of quantum dot surface is nitrogenous organic ligand, the characteristic element in the organic ligand is nitrogen；
When the organic ligand of quantum dot surface is phosphorous organic ligand, the characteristic element in the organic ligand is P elements；When
When the organic ligand of quantum dot surface is the organic ligand containing sulfydryl, the characteristic element in the organic ligand is element sulphur.
In a kind of wherein embodiment, in step S20 of the present invention, the sample can be measured using transmission electron microscope analysis instrument
The average grain diameter of particle in product particle.
Specifically, measuring the test condition of the average grain diameter of particle in the sample particle using transmission electron microscope analysis instrument
Are as follows: acceleration voltage 200-300kV, emission current are 7-20 μ A, and operating distance is 10-20 mm, dead time 20%-40%.
The step of measuring the average grain diameter of particle in the sample particle using transmission electron microscope analysis instrument includes: to take sample
Grain is dissolved in the quantum dot solution that preparation concentration is 1-5 mg/mL in nonpolar solvent and takes a small amount of quantum after solution is completely dissolved
Copper mesh is placed in progress test analysis d in transmission electron microscope analysis instrument on copper mesh by point solution drop 5-10 drop.Specifically, first to sample
Product amplify analysis, and amplification factor is 70000-150000 times, and taken amount sub- point is concentrated and finely dispersed region is focused
TEM picture is obtained, then TEM picture is analyzed with software, length of the scale is first set, then 30-80 quantum dot is taken to carry out
Calibration, is finally calculated the average grain diameter d of particle.
Specifically, sample particle is first carried out compression process in the step S30, 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 of element, you can learn that characteristic element accounts for sample particle mass fraction i.e. m in machine ligandl/mQ, formula Ki=ml
ρQd/4.44MlmQ, K is calculatedi。
It has been investigated that the quantum dot surface ligand coverage rate KiIf being less than 2*10-10mol/cm2, then quantum dot is molten
Solution property is not good enough, influences the subsequent film quality for being prepared into film.It need to be by KiValue carries out solution or ink configuration etc. again and answers after improving
With.Improve KiLigand can be used in value, and exchange process carries out again.Detailed process are as follows: quantum dot is first dissolved in nonpolar solvent, then plus
Enter surface ligand of the same race to swap at 25-150 DEG C.The nonpolar solvent include chloroform, n-hexane, heptane, octane,
Toluene, chlorobenzene, dichloro-benzenes, carbon tetrachloride, decane, hendecane, dodecane, tridecane, the tetradecane, pentadecane, hexadecane, 17
Alkane, octadecane, cyclodecane, ring hendecane, octadecylene etc..The amount for the ligand that the ligand is added in exchange process again must not
Less than (2*10-10-K1) n1/K1(formula 3, K0Represent target quantum dot surface ligand coverage rate, K1Represent the quantum dot measured for the first time
Ligand coverage rate, n1 are the amount of ligand being added for the first time in quantum dot preparation process).Using this process by KiValue is increased to greater than 2*
10-10mol/cm2Quantum dot can be carried out to other solution applications.
Below by embodiment, the present invention is described in detail.
Embodiment 1
TEM combination XPS determines CdZnSe/CdZnSe/ZnSe quantum dot surface phosphorus-containing ligand coverage rate
Determine the size d of CdZnSe/CdZnSe/ZnSe quantum dot.Taking surface ligand is the CdZnSe/ of myristyl phosphoric acid
CdZnSe/ZnSe quantum dot is dissolved in hexane solution, the solution of 5 mg/ml of preparation, after solution is completely dissolved, is taken a small amount of
Carbon net is placed in transmission electron microscope analysis instrument on copper mesh and carries out test analysis by 5 drop of quantum dot solution drop.Acceleration voltage, which is arranged, is
200kV, for emission current in 10 μ A, operating distance is set as 15 mm, dead time 20%.Analysis is amplified to sample, is first arranged
Amplification factor is 70000 times, and taken amount sub- point is concentrated and finely dispersed region is focused analysis, shoots its TEM picture.It is right
TEM picture is analyzed, and length of the scale is first arranged, then 30-80 quantum dot is taken to be demarcated, and the size of quantum dot is calculated
D is 12.5 nm.
P element content in CdZnSe/CdZnSe/ZnSe quantum dot surface ligand is determined using XPS.Weigh 5mg quantum dot
Sample, it is levigate with agate mortar.With acetone or isopropanol by 2*2cm2Aluminium foil wiped clean, cut 1*1cm2Double faced adhesive tape patch
In aluminium foil center.Sample is layered on double faced adhesive tape, and is uniformly paved with powder entirely with clean stainless steel sample spoon
Adhesive tape.Another is taken to cover sample with the aluminium foil of acetone wiped clean.Aluminium foil+sample is placed in two blocks of smooth stainless steels
Among module, it is 7MPa that pressure is arranged under grease press, takes out sample after suppressing 10s, and sample to be tested is surfacing, matter at this time
The close thin slice in ground.Remove the upper layer aluminium foil being covered on sample, cuts off bottom aluminium foil along the sample surrounding suppressed, 1* is made
1cm2Press sheet compression.On photoelectron spectrograph, sample is excited with AlK α line, x-ray power 14KV*15mA.Energy disperse spectroscopy
Vacuum degree be 3*10-9Mbar, extraneous contamination make charge correction with C1s spectral line (in conjunction with energy 284.8eV).Setting test model first
It encloses for 0-1200eV, range intervals are 30-50eV when accurate scan.The characteristic spectrum of each element is obtained after sample test, use is soft
The integral area of characteristic peak is calculated in part, obtains the content ratio of element immediately, and it is 4.5% that wherein P element content, which is calculated,.
Determine CdZnSe/CdZnSe/ZnSe quantum dot surface myristyl phosphoric acid ligand coverage rate.Known ml /mQFor
4.5%, quantum dot size d are 12.5 nm, and quantum dot density is 5.8 g/cm3, quantum dot surface ligand is calculated according to formula 2
Coverage rate KiFor 2.35*10-9mol/cm2, this value is greater than 2*10-10mol/cm2, it is not required to progress ligand and exchanges again, can directly carries out
Solution is prepared.
Embodiment 2
TEM combination XPS determines ZnO quantum dot surface stearic acid ligand coverage rate.
Determine the size d of quantum dot.Taking surface ligand is that stearic ZnO quantum dot is dissolved in normal octane solution, is prepared
The solution of 1 mg/ml is obtained, after solution is completely dissolved, takes a small amount of 10 drop of quantum dot solution drop on copper mesh, copper mesh is placed in
Test analysis is carried out in transmission electron microscope analysis instrument.Setting acceleration voltage is 200 kV, and emission current is in 20 μ A, operating distance setting
For 20 mm, dead time 30%.Analysis is amplified to sample, first be arranged amplification factor be 100000 times, taken amount sub- point concentrate and
Finely dispersed region is focused analysis, shoots its TEM picture.TEM picture is analyzed, length of the scale is first set, then
30-80 quantum dot is taken to be demarcated, the size d that quantum dot is calculated is 8.9 nm.
O constituent content in ZnO quantum dot surface ligand is determined using XPS.15mg quantum dot sample is weighed, agate mortar is used
It is levigate.With acetone or isopropanol by 2*2cm2Aluminium foil wiped clean, cut~1*1cm2Double faced adhesive tape be attached to aluminium foil centre bit
It sets.Sample is layered on double faced adhesive tape, and powder is uniformly paved with to entire adhesive tape with clean stainless steel sample spoon.Take another
Sample is covered with the aluminium foil of acetone wiped clean.Aluminium foil+sample is placed among two pieces of smooth stainless steel modules, is being pressed
It is 15MPa that pressure is arranged under oil machine, takes out sample after suppressing 10s, and sample to be tested is that surfacing, quality are closely thin at this time
Piece.Remove the upper layer aluminium foil being covered on sample, cuts off bottom aluminium foil along the sample surrounding suppressed, 1*1cm is made2Tabletting
Sample.Sample test carries out on photoelectron spectrograph.Sample is excited with AlK α line, x-ray power 20KV*10mA.Power spectrum
The vacuum degree of instrument is 9*10-9Mbar, the C1s spectral line (in conjunction with energy 284.8eV) of extraneous contamination are used as charge and correct.Setting is surveyed first
Examination range is 0-1200eV, and range intervals are 30-50eV when accurate scan.The characteristic spectrum of each element is obtained after sample test,
The integral area of characteristic peak is calculated with software, obtains the content ratio of element immediately, O constituent content ratio, which is calculated, is
0.3%。
Calculate quantum dot surface ligand coverage rate K1.The density of ZnO quantum dot is 5.9 g/cm3, according to above-mentioned test knot
Fruit, ZnO quantum dot is having a size of 8.9 nm, and O element is shared with body mass ratio is 0.3% in stearic acid ligand in quantum dot, calculates
K1For 1.05 * 10-10 mol/cm2。K1Value is less than 2*10-10mol/cm2, ligand need to be carried out and exchanged again.
Quantum dot surface ligand exchanges again.It is 4 mmol that stearic acid ligand, which is added, in known ZnO during the preparation process, then is matching
For body in exchange process, stearic additional amount must not be less than 3.61mmol.It takes ZnO quantum dot to be dissolved in hexane solution, adds
Enter 4 mmol stearic acid into ZnO hexane solution, 40 DEG C of 4 h of heating stirring obtain the quantum after ligand exchanges again after cleaning
Point.Method of the ZnO Jing Guo above-mentioned steps 2 after ligand is exchanged again tests and analyzes the content of surface ligand again, obtains K2For
2.05*10-10mol/cm2.Therefore, ZnO can be used for configuring other solution after ligand exchanges again
A kind of method for being provided for the embodiments of the invention determining quantum dot surface ligand coverage rate above has carried out detailed Jie
It continues, for those of ordinary skill in the art, thought according to an embodiment of the present invention, in specific embodiments and applications
There will be changes, in conclusion the contents of this specification are not to be construed as limiting the invention, it is all to think according to present invention design
Want any change made all within protection scope of the present invention.
Claims (11)
1. a kind of measuring method of quantum dot surface ligand coverage rate 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；
Measure the average grain diameter of particle in the sample particle；
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 coverage rate Ki;
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 coverage rate according to claim 1, which is characterized in that utilize X-ray light
The characteristic spectrum of each element, the integral of each element characteristic peak is calculated with software in electron spectroscopy analysis instrument test sample particle
The quantum dot surface ligand coverage rate is calculated in area, the sample particle mass ratio that accounts for for obtaining characteristic element in organic ligand
Ki, wherein when the organic ligand of quantum dot surface is aliphatic carboxylic acid ligand, the characteristic element in the organic ligand is oxygen member
Element；When the organic ligand of quantum dot surface is nitrogenous organic ligand, the characteristic element in the organic ligand is nitrogen；
When the organic ligand of quantum dot surface is phosphorous organic ligand, the characteristic element in the organic ligand is P elements；When
When the organic ligand of quantum dot surface is the organic ligand containing sulfydryl, the characteristic element in the organic ligand is element sulphur.
3. 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, ternary quantum dots or quaternary quantum dot.
4. according to the measuring method of claim 3 quantum dot surface ligand coverage rate, which is characterized in that
The unitary quantum dot 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 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 coverage rate according to claim 1, which is characterized in that described containing sulfydryl
Organic ligand is selected from a mercaptan, two mercaptan, mercaptoalcohol, mercapto-amine or mercaptan acid；
The aliphatic carboxylic acid ligand is that C atomicity is fatty acid between 8 ~ 18；
The phosphorous organic ligand is selected from alkyl phosphorus, alkylphosphine oxide or alkyl phosphoric acid；
The nitrogenous organic ligand is the organic amine that carbon atom number is greater than 8.
6. the measuring method of quantum dot surface ligand coverage rate according to claim 1, which is characterized in that set sample particle
Before in X-ray photoelectron spectroscopic analysis instrument, further include the steps that suppressing sample particle, pressing pressure 5-
15MPa suppresses 5-15s.
7. the measuring method of quantum dot surface ligand coverage rate according to claim 1, which is characterized in that set sample particle
In X-ray photoelectron spectroscopic analysis instrument, using X-ray photoelectron spectroscopic analysis instrument, sample is excited with AlK α line, is composed with C1s
Line makees charge correction, and the measurement strip of quantum dot surface ligand coverage rate is calculated in the content of each element in test sample particle
Part are as follows: x-ray power is 10 ~ 20KV*10 ~ 20mA, and the vacuum degree of X-ray photoelectron spectroscopic analysis instrument is 1 ~ 10*10-9Mbar,
Initial testing range is 0-1200eV, and accurate test scope is 30-50eV.
8. the measuring method of quantum dot surface ligand coverage rate according to claim 1, which is characterized in that use transmission electron microscope
The average grain diameter of particle in sample particle described in analysis-e/or determining.
9. the measuring method of quantum dot surface ligand coverage rate according to claim 8, which is characterized in that use transmission electron microscope
The test condition of the average grain diameter of particle in sample particle described in analysis-e/or determining are as follows: acceleration voltage 200-300kV, transmitting electricity
Stream is 7-20 μ A, and operating distance is 10-20 mm, dead time 20%-40%.
10. the measuring method of quantum dot surface ligand coverage rate according to claim 8 or claim 9, which is characterized in that using transmission
It includes: to amplify analysis to sample that electron microscope analysis instrument, which measures the step of average grain diameter of particle in the sample particle, amplification
Multiple is 70000-150000 times, and taken amount sub- point is concentrated and finely dispersed region is focused to obtain the TEM figure of sample particle
Piece analyzes the TEM picture with software, takes 30-80 quantum dot to be demarcated, the average grain of particle is calculated
Diameter.
11. according to claim 1 to the measuring method of any one of 9 quantum dot surface ligand coverage rates, which is characterized in that if
KiLess than 2*10-10mol/cm2, further comprise the steps of: using ligand again exchange process improve quantum dot surface ligand coverage rate.
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