CN108727902A - Inorganic nano material prints ink and preparation method thereof - Google Patents
Inorganic nano material prints ink and preparation method thereof Download PDFInfo
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- CN108727902A CN108727902A CN201710264442.0A CN201710264442A CN108727902A CN 108727902 A CN108727902 A CN 108727902A CN 201710264442 A CN201710264442 A CN 201710264442A CN 108727902 A CN108727902 A CN 108727902A
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
- C09D11/36—Inkjet printing inks based on non-aqueous solvents
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Abstract
The present invention provides a kind of inorganic nano materials to print ink, including at least one inorganic nano material and at least one thio-alcohol organic solvent, the boiling point of the thio-alcohol organic solvent is 100 DEG C -350 DEG C, and the general structure of the thio-alcohol organic solvent is R- (SH)x, wherein the R is selected from C2‑25Aliphatic, aromatic group, the x be positive integer.
Description
Technical field
The invention belongs to electroluminescent diode display technology fields more particularly to a kind of inorganic nano material to print ink
And preparation method thereof.
Background technology
In recent years, quantum dot (QD) luminescent material has played prodigious effect in fields such as LED illumination, liquid crystal displays, amount
Son point substitutes traditional fluorescent powder, is effectively improved the colour gamut of LED and liquid crystal display.Recently, quantum dot light emitting material is made
For the light emitting diode with quantum dots (QLED) of luminescent layer preferable application prospect is shown in fields such as solid-state lighting, FPD,
Receive the extensive concern of academia and industrial circle.
The solution processing properties of quantum dot allow quantum dot light emitting layer to pass through spin coating, blade coating, injection, inkjet printing etc.
It is prepared by various ways.Opposite front several method, inkjet printing technology can be accurately in the desired amount by quantum dot light emitting material
Deposit it is in place, allow semi-conducting material uniform deposition formed film layer.Quantum dot light emitting layer, material are prepared using which
Utilization rate is very high, and simplifies manufacture craft, is easy universal volume production, reduces whole production cost.Ink-jet printing technology is current
The generally acknowledged effective ways that can solve light emitting diode with quantum dots (QLED) device large scale manufacture problem.
But the quantum dot ink currently used for inkjet printing is essentially all that quantum dot is directly dispersing in solvent to make
At.However the solvent that relative distribution is good, such as toluene, chloroform, obtained quantum dot ink viscosity is very small, and boiling point is also very
It is low.When quantum dot is dissolved in the larger solvent of some viscosity, when such as long alkane alcohols solvent, the dispersion effect of quantum dot is again very
Difference causes the quantum dot film thickness prepared inconsistent, and uniformity is very poor.And since quantum dot ink is different from traditional ink, tool
There is the introducing of the polymeric additive (such as long alkane alcohols solvent) of insulating property (properties) often to reduce the charge transport ability of film,
There is negative effect to the photoelectric properties of device, limit its extensive use in the opto-electronic device.In addition, quantum dot ligand exists
It is this complexity solvent environment under can carry out a degree of dissociation equilibrium, upon storage between one timing, it is possible to due to outside
Environment, which changes, causes dissociation equilibrium to destroy so that storage stability wrecks.In order to ensure having for charge between quantum layer
Effect transmission, the unnecessary organic material of introducing that quantum dot film material will be few as possible.Therefore, there is an urgent need to research and develop one kind can
It improves viscosity and there is the solvent of preferably dispersibility and storage stability, so that quantum dot ink disclosure satisfy that ink-jet is beaten
Print requires, and stablizes out of ink, stable to sprawl, uniform drying, and film forming is uniform.
Invention content
The purpose of the present invention is to provide a kind of inorganic nano materials to print ink and preparation method thereof, it is intended to solve existing
Inorganic nano material viscosity of printing ink, boiling point and dispersion effect the problem of being difficult to take into account.
The invention is realized in this way a kind of inorganic nano material prints ink, including at least one inorganic nano material
Boiling point at least one thio-alcohol organic solvent, the thio-alcohol organic solvent is 100 DEG C -350 DEG C, and the thio-alcohol is organic
The general structure of solvent is R- (SH)x, wherein the R is selected from C2-25Aliphatic, aromatic group, the x be positive integer.
And a kind of preparation method of inorganic nano material film, include the following steps：
The formula that ink is printed according to above-mentioned inorganic nano material weighs each component；
Inorganic nano material is dissolved in organic solvent and forms inorganic nano material printing ink, wherein is described organic molten
At least contain a kind of thio-alcohol organic solvent in agent；
Ink is printed in deposited on supports inorganic nano using inkjet printing, by being dried, obtains inorganic nano material
Expect film.
Inorganic nano material printing ink provided by the invention can not only make nothing using thio-alcohol as organic solvent
Machine nano-material surface ligand dissociates in mercaptan solvent reaches balance with absorption, to make inorganic nano material in printing ink
In be uniformly dispersed, storage-stable.Moreover, the inorganic nano material off-set oil of the thio-alcohol organic solvent containing above-mentioned specific structure
Ink, for surface tension within the scope of 20-80mN/m, viscosity under the conditions of 25-35 DEG C is 0.5-60.0mPa.s, be disclosure satisfy that
Requirement of the ink-jet printer to viscosity and surface tension at present is realized the inkjet printing mode of inorganic nano material layer, is had
There is the inorganic nano material luminescent layer of pixel-matrix, high-resolution, electroexcitation.Meanwhile inorganic nano material provided by the invention
Material printing ink has volatile performance appropriate (boiling point is 100 DEG C -350 DEG C), the inorganic nano material that printing can be made to prepare
Organic molecule volatilization in the bed of material is complete, forms the film layer of fine and close arrangement, is passed to which charge between inorganic nano material be effectively ensured
It is defeated, threshold voltage is reduced, efficiency is improved.To sum up, inorganic nano material printing ink provided by the invention has proper viscosity, table
Face tension, dispersion performance, volatile performance, particularly suitable inkjet printing prepares inorganic nano material layer, such as by inkjet printing side
Inorganic nano material luminescent layer in legal system preparation optical diode.
The preparation method of inorganic nano material film provided by the invention, only need to be by inorganic nano material in organic solvent
It is fully dispersed, inorganic nano material is made and prints ink, and then progress inkjet printing, drying can be obtained on carrier, method
Simply, it is easy to accomplish standardization control.
Specific implementation mode
In order to make technical problems, technical solutions and advantageous effects to be solved by the present invention be more clearly understood, below in conjunction with
Embodiment, the present invention will be described in further detail.It should be appreciated that specific embodiment described herein is only used to explain
The present invention is not intended to limit the present invention.
An embodiment of the present invention provides a kind of inorganic nano material print ink, including at least one inorganic nano material and
The boiling point of at least one thio-alcohol organic solvent, the thio-alcohol organic solvent is 100 DEG C -350 DEG C, and the thio-alcohol is organic molten
The general structure of agent is R- (SH)x, wherein the R is selected from C2-25Aliphatic, aromatic group, the x be positive integer.
Specifically, inorganic nano material of embodiment of the present invention printing ink contains organic solvent, the organic solvent can be with
Contain only thio-alcohol organic solvent, or the mixed solvent that thio-alcohol organic solvent is formed with other secondary organic solvents.
The thio-alcohol organic solvent may be used it is one or more, meanwhile, the inorganic nano material can also use a kind of or more
Kind.
Specifically, the boiling point of the thio-alcohol organic solvent is 100 DEG C -350 DEG C.In the embodiment of the present invention, it is based on ink-jet
The needs of printing, the too high or too low film layer for being all unfavorable for forming fine and close arrangement of solvent temperature.Specifically, when solvent boiling point is too low
When, printing ink is during inkjet printing prepares film layer, solvent volatilization, to influence the overall performance of printing ink (such as
Dispersion performance, viscosity, surface tension), it cannot be satisfied inkjet printing requirement；When solvent boiling point is excessively high, in follow-up film forming procedure
In need to could be removed by high temperature, can influence in this way print ink in solute component such as inorganic nano material performance, such as make
At the fluorescent quenching of quantum dot.The thio-alcohol organic solvent of suitable boiling point provided in an embodiment of the present invention has and is suitable for spray
Black printing prepares suitable volatile performance when inorganic nano material layer, to advantageously form the film layer of fine and close arrangement.
In the embodiment of the present invention, range of viscosities of the thio-alcohol organic solvent at 25 DEG C is 0.5cPs-60cPs,
Surface tension at 25 DEG C is 20-80mN/m, disclosure satisfy that requirement of the current ink-jet printer to viscosity and surface tension, is realized
The inkjet printing mode of inorganic nano material layer, obtains the inorganic nano material with pixel-matrix, high-resolution, electroexcitation
Luminescent layer.
Specifically, in the embodiment of the present invention, the R includes C2-25Alkyl, naphthenic base, at this point, x value ranges meet 1
≤x≤25.The C2-25Alkyl, naphthenic base include butyl, cyclobutyl, amyl, cyclopenta, hexyl, cyclohexyl, heptyl, ring
Heptyl, octyl, cyclooctyl, nonyl, cyclononyl, decyl, cyclodecyl, undecyl, ring undecyl, dodecyl, hexadecane
Base, octadecyl.
In the embodiment of the present invention, the C2-25Aliphatic, aromatic group can contain or not contain substituent group, when
The C2-25Aliphatic, aromatic group is when containing substituent group, one or more substituent groups can be contained.The substituent group
Including alkyl, aryl, nitro, cyano, amino ,-N (R ') (R "), halogen, hydroxyl, carboxyl, ester group, ether, carbonyl, alkenyl, alkynes
Base, naphthenic base, alkoxy, aryl, heteroaryl, aryloxy group, heteroaryloxy, alkoxy carbonyl group, perfluoroalkyl, perfluoro alkoxy, sulphur
For alkoxy ,-S (O)2- N (R ') (R ") ,-C (=O)-N (R ') (R "), (R ') (R ") alkyl, (R ') (R ") positive alkoxy,
(R ') (R ") alkyl, aryloxy alkyl ,-S (O)sAryl ,-S (O)sHeteroaryl, silyl-group, wherein the s's
Value range is 0-2, and the R ' and R " is independently chosen from alkyl, naphthenic base, aryl, substitution alkyl, substituted cycloalkyl, substitution virtue
Base.
Further, the alkyl includes branched alkyl, straight chained alkyl, naphthenic base.Preferably, the branched alkyl, straight chain
Alkyl, naphthenic base C1-25Alkyl, i.e., carbon atom number be 1-25.Containing alkyl substituent group, the thio-alcohol can be increased
The dissolubility of organic solvent.
Wherein, the alkyl include but not limited to methyl, ethyl, propyl, isopropyl, isobutyl group, sec-butyl, tertiary butyl,
Amyl, isopentyl, neopentyl, cyclopenta, hexyl, cyclohexyl, isohesyl.
The aryl include but not limited to phenyl, xenyl, triphenyl, benzo naphthalene, anthryl, phenalene, phenanthryl,
Fluorenyl, pyrenyl, Qu Ji, base, azulenyl.
It the heteroaryl but is not limited to include dibenzothiophenes, dibenzofurans, furans, thiophene, benzofuran, benzo thiophene
Pheno, pyrazoles, imidazoles, triazole, isoxazole, thiazole, oxadiazoles, oxatriazole, dioxazole, thiadiazoles, pyridine, is rattled away at carbazole
Piperazine, pyrimidine, pyrazine, triazine, oxazines, oxathiazine, oxadiazine, indoles, benzimidazole, indazole, indoxazine,
Benzoxazoles, benzisoxazole, benzothiazole, quinoline, isoquinolin, cinnoline, quinazoline, quinoxaline, naphthalene, phthalein,
Pteridine, xanthene, acridine, azophenlyene, phenthazine, phenoxazine, dibenzoselenophene, benzoselenophene,
benzofuropyridine、indolocarbazole、pyridylindole、pyrrolodipyridine、
furodipyridine、benzothienopyridine、thienodipyridine、benzoselenophenopyridine
The substituent group formed with selenophenodipyridine.
As particular preferred embodiment, the thio-alcohol organic solvent includes 2- naphthalenes methyl mercaptan, 4- methyl mercapto azoles -2- sulphur
Alcohol, 2,5- dimethyl -3- furanthiols, furfuryl mercaptan, thiophene -2- mercaptan, 4- chloro benzyl mercaptans, 1- hexadecanethiols, positive 15
Alkyl hydrosulfide, n-tetradecane base mercaptan, tertiary tetradecyl mercaptan, 1- tridecane thiols, tert-dodecylmercaotan, 1- hendecane sulphur
Alcohol, 1- nonyls mercaptan, tertiary nonyl mercaptan, 2- methyl -3- tetrahydrofurans mercaptan, 1- Foxlene -8- mercaptan, isopentene group mercaptan, 2-
Methylbenzyl mercaptan, tetra- oxa- tridecane -13- mercaptan of 2,5,8,11-, cyclohexylmercaptan, trimethyl silicon substrate methyl mercaptan, oxinane -
4- mercaptan, (2- mercaptos ethyl) hexamethylene alkanethiol, 2- [(phenyl mercaptan) methyl] -2- cyclopentene-1-ones, 2- trifluoromethylbenzene sulphur
Alcohol, 2- methyl -3- furanthiols acetic acid esters, 3- [(2- methoxyl group -2- oxygen ethyl) is thio] methyl propionate, methyl mercaptan -1 3-,
2- glycol propane, 2- methyl -3- furanthiols, the chloro- 6- luorobenzyls mercaptan of 2-, 4- luorobenzyls mercaptan, 5- heptyl -2- furans sulphur
Alcohol, 2- methyl -2- pentanes mercaptan, 3- ethyl -3- pentanes mercaptan, 2- (diisopropylaminoethyl)-ethane thiol, 3- bromobenzyl sulphur
Alcohol, 4- methylbenzyls mercaptan, 2,3- dimethyl -2- butane thiols, tri isopropyl silane mercaptan, 3- phenyl -1- propane mercaptan, 3-
Methyl -4- pyridines mercaptan, 2- phenyl-propane -1- mercaptan, thiogeraniol, double mercapto ethyl thioethers, 1- (9- mercaptoethanols) -3,6,
Tri- oxygen decane -11- alcohol of 9-, 3- sulfydryl -1- hexanols, 3 methyl mercapto 1 hexanol, 8- sulfydryl -1- octanols, 4- iodobenzene -1- mercaptan,
(tetrahydrofuran -3- bases) methyl mercaptan, morpholine -4- ethanethios, oleyl mercaptan, 2,3- ethylene oxide diformazans alkanethiol, 3-
N-Propyl Bromide -1- mercaptan, 11- (1H- pyrroles -1- bases) hendecane -1- mercaptan, 4- methyl butyl ether -1- mercaptan, 2- (pyrrolidines -1-
Base) ethane thiol, five oxa- hexadecane -1- mercaptan of 3,6,9,12,15-.
In the embodiment of the present invention, in order to assign the suitable dispersion performance of inorganic nano material printing ink, viscosity and
Surface tension, so that obtained inorganic nano material printing ink is more suitable for inkjet printing and prepares inorganic nano material film
Layer.Preferably, it is in terms of 100% to print the weight percentage of ink by the inorganic nano material, and the thio-alcohol is organic molten
The weight percentage of agent is 0.01%-99.9%.Specifically, the weight percentage of the thio-alcohol organic solvent can be
0.01%, 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 99.9%.
The inorganic nano material prints the matrix component of ink as the inorganic nano material, can be IV races, II-
VI races, II-V races, iii-v, III-VI races, group IV-VI, I-III-VI races, II-IV-VI races, II-IV-V races binary or more
At least one of element, semiconductor compound.Specifically, the inorganic nano material can be selected from but not limited to CdSe, CdS,
At least one of CdTe, ZnO, ZnSe, ZnS, ZnTe, HgS, HgSe, HgTe, CdZnSe；It is also selected from but is not limited to
InAs、InP、InN、GaN、InSb、InAsP、InGaAs、GaAs、GaP、GaSb、AlP、AlN、AlAs、AlSb、CdSeTe、
At least one of ZnCdSe.In addition, the inorganic nano material can also be perovskite nanometer particle material, particularly preferably send out
Light perovskite nano-particle, metal nano particle material, metal oxide nanoparticles material and combinations thereof.
The composition form of the inorganic nano material is unrestricted, can be doped or non-doped inorganic nano material,
Wherein, doping refers to that other doped chemicals are also contained in the inside of the inorganic nano material.Specifically, the inorganic nano material
Material can be quanta point material.Wherein, the ligand of the quantum dot include sour ligand, mercaptan ligand, amine ligand, (oxygen) Phosphine ligands,
At least one of phosphatide, soft phosphatide, polyvinylpyridine etc..As specific embodiment, the acid ligand is ten acid, hendecene
At least one of acid, tetradecylic acid, oleic acid, stearic acid；The mercaptan ligand is eight alkyl hydrosulfides, lauryl mercaptan, 18
At least one of alkyl hydrosulfide；The amine ligand includes at least one of oleyl amine, octadecylamine, eight amine；(oxygen) phosphine is matched
Body is at least one of tri octyl phosphine, trioctylphosphine oxide (TOPO).
In the embodiment of the present invention, the structure type of the quantum dot is unrestricted, and it is mixed that uniform mixed type, gradient can be used
Close type, core-shell structure copolymer type or union type.
Inorganic nano material printing described in the embodiment of the present invention is suitable for inkjet printing quantum dot light emitting layer, when described inorganic
When water content is higher in nano material printing ink, since shipwreck is in volatilization or removal, it is easy residual in the quantum dot ink
It stays, and then influences the performance of the quantum dot light emitting layer formed.In view of this, quantum dot described in the embodiment of the present invention is preferably
Oil-soluble quantum dot.
As particular preferred embodiment, the average-size of the quantum dot is 1-20nm.
It is in terms of 100% by the gross weight of the quantum dot ink, the preferred weight percentage composition of the quantum dot is 0.01-
20.0%, as specific embodiment, the dosage of the quantum dot can be 0.01%, 0.1%, 0.2%, 0.5%, 0.8%,
1.0%, the concrete numerical values such as 2.0%, 4.0%, 5.0%, 8.0%, 10.0%, 12.0%, 15.0%, 18.0%, 20.0% contain
Amount.Further, as a preferred embodiment, the weight percentage of the quantum dot is 4-15%.
In the embodiment of the present invention, only ink can be printed using the thio-alcohol organic solvent as inorganic nano material only
One solvent, can also be on the basis of using thio-alcohol organic solvent, and addition secondary organic solvent forms mixed solvent, to adjust
Inorganic nano material prints the balance of the dispersion performance and viscosity of ink.
The viscosity of inorganic nano material printing ink provided in an embodiment of the present invention, passes through the thio-alcohol organic solvent
Dosage and concrete type are regulated and controled.Inorganic nano material provided in an embodiment of the present invention prints ink, under the conditions of 25-35 DEG C
Viscosity be 0.5-60.0mPa.s, concretely 1mPa.s, 5mPa.s, 10mPa.s, 15mPa.s, 20mPa.s, 25mPa.s,
30mPa.s,35mPa.s,40mPa.s,45mPa.s,50mPa.s,55mPa.s,60mPa.s；Further, the quantum dot oil
The viscosity of ink is preferably that 25 DEG C of viscosity is preferably 1-30.0mPa.s, and more preferably viscosity under the conditions of 25-35 DEG C is 1-
15.0mPa.s.The surface tension of the inorganic nano material printing ink is 20.0-80.0mN/m, in inkjet printing mistake
It can be discharged glibly from printing head in journey, and there is preferable film forming characteristics.Specifically, stating inorganic nano material off-set oil
The surface tension of ink can be 20.0mN/m, 30.0mN/m, 40.0mN/m, 50.0mN/m, 60.0mN/m, 70.0mN/m, 80.0mN/
m。
Inorganic nano material provided in an embodiment of the present invention prints ink, and the thio-alcohol organic solvent is in inkjet printing
It can be removed by heating and/or pressure reducing mode in last handling process, not interfere with the inorganic nano that inkjet printing is prepared
Film layer, such as quantum dot light emitting layer.
Inorganic nano material printing ink provided in an embodiment of the present invention not only may be used using thio-alcohol as organic solvent
So that inorganic nano material surface ligand dissociates in mercaptan solvent reaches balance with absorption, to make inorganic nano material print
It is uniformly dispersed in brush ink, storage-stable.Moreover, the inorganic nano material of the thio-alcohol organic solvent containing above-mentioned specific structure
Ink is printed, for surface tension within the scope of 20-80mN/m, viscosity under the conditions of 25-35 DEG C is 0.5-60.0mPa.s, energy
Enough meet requirement of the current ink-jet printer to viscosity and surface tension, realize the inkjet printing mode of inorganic nano material layer,
Obtain the inorganic nano material luminescent layer with pixel-matrix, high-resolution, electroexcitation.Meanwhile it is provided by the invention inorganic
Nano material, which prints ink, has volatile performance appropriate (boiling point is 100 DEG C -350 DEG C), and printing can be made to prepare inorganic
Organic molecule volatilization in layer of nanomaterial is complete, the film layer of fine and close arrangement is formed, to be effectively ensured between inorganic nano material
Charge transmits, and reduces threshold voltage, improves efficiency.To sum up, inorganic nano material printing ink provided by the invention has appropriate
Viscosity, surface tension, dispersion performance, volatile performance, particularly suitable inkjet printing prepare inorganic nano material layer, such as pass through ink-jet
Method of printing prepares the inorganic nano material luminescent layer in light emitting diode.
And the embodiment of the present invention additionally provides a kind of preparation method of inorganic nano material film, includes the following steps：
S01. the formula that ink is printed according to above-mentioned inorganic nano material weighs each component；
S02. inorganic nano material is dissolved in organic solvent and forms inorganic nano material printing ink, wherein is described to have
At least contain a kind of thio-alcohol organic solvent in solvent；
S03. it uses inkjet printing to print ink in deposited on supports inorganic nano, is dried, obtains inorganic by adding
Nano material film.
Specifically, in above-mentioned steps S01, the formula and its preferred ingredient, content of the inorganic nano material printing ink
It has hereinbefore stated, in order to save length, details are not described herein again.
In above-mentioned steps S02, inorganic nano material is dissolved in organic solvent, discrete form is unrestricted, can be used and stirs
The mode of mixing is realized.
In above-mentioned steps S03, by selecting suitable ink-jet printer to carry out inkjet printing, receive deposited on supports is inorganic
Then processing solvent flashing is dried to inorganic nano printing ink in rice printing ink.Specifically, the inkjet printing
It is preferred that being realized using piezoelectric ink jet printing or thermal inkjet-printing.The drying process includes dry heating, cooling and drying and decompression
It is dry.Preferably, the temperature of the heat treatment is 30-180 DEG C, heating time 0-30min；The temperature of the cooling processing
It is 0-20 DEG C；The vacuum degree of the reduced pressure treatment is 1 × 10-6Torr is to normal pressure.Through being dried to obtain inorganic nano material film, such as
Quantum dot film.It is suitable to be dried mode, it can ensure institute under the premise of efficiently removing the thio-alcohol organic solvent
Inorganic nano material such as quanta point material is stated not to be damaged.
The inorganic nano material film dry film formed through inkjet printing, thickness is preferably 10-100nm；Further, through spray
The inorganic nano material film thickness of dry film that ink printing is formed is 20-50nm.
The preparation method of inorganic nano material film provided in an embodiment of the present invention, only need to be by inorganic nano material organic
It is fully dispersed in solvent, inorganic nano material is made and prints ink, and then progress inkjet printing, drying can obtain on carrier
, method is simple, it is easy to accomplish standardization control.
It is illustrated with reference to specific embodiment.
Embodiment 1
A kind of inorganic nano material printing ink, the weight percentage that ink is printed with the inorganic nano material are
100% meter, includes each component of following weight percentage：The red CdSe/ZnS quantum dots and 88% that 12% oleyl amine is stablized
Mixed solvent, the in the mixed solvent, including weight percentage are 10% dodecane solvent, 78%1- Foxlene -8- mercaptan.
A kind of preparation method of inorganic nano material film, includes the following steps：
S11. the formula that ink is printed according to above-mentioned inorganic nano material weighs each component；Wherein, mixed solvent is by 12
Alkane and 1- Foxlene -8- mercaptan composition, various solvents are all made of corresponding method water removal, deoxygenation is refined to purity and is more than
99.9%.
S12., 500mL single-necked flasks are provided, in the case of stirring, add the red CdSe/ZnS amounts that oleyl amine is stablized successively
Sub- point, dodecane and 1- Foxlene -8- mercaptan, are stirred 30min, obtain quantum dot printing ink composition；
S13. by the quantum dot printing ink composition by ink-jet printer the inkjet printing on carrier, be printed as 20 ×
The red quantum dot layer of 30um, 200 × 200ppi of resolution ratio.145 DEG C, nitrogen stream volatile dry 30min are heated on hot plate,
Obtain monochromatic quantum dot luminescent layer.
Embodiment 2
A kind of inorganic nano material printing ink, the weight percentage that ink is printed with the inorganic nano material are
100% meter, includes each component of following weight percentage：The green CdZnSe/CdZnS's and 90% that 10% oleyl amine is stablized is mixed
Bonding solvent, the in the mixed solvent, including weight percentage are 23% tridecane, 40% decahydronaphthalenes, 27%1- nonyl mercaptan.
A kind of preparation method of inorganic nano material film, includes the following steps：
S21. the formula that ink is printed according to above-mentioned inorganic nano material weighs each component；Wherein, mixed solvent is by 13
Alkane, decahydronaphthalenes and 1- nonyl mercaptan composition, various solvents are all made of corresponding method water removal, deoxygenation is refined to purity and is more than
99.9%.
S22., 500mL high-density polyethylene bottles are provided, in the case of stirring, add the green that oleyl amine is stablized successively
CdZnSe/CdZnS, tridecane, decahydronaphthalenes and 1- nonyl mercaptan, are stirred 30min, obtain quantum dot printing ink composition；
S23. by the quantum dot printing ink composition by ink-jet printer the inkjet printing on carrier, be printed as 20 ×
The green quantum dot layer of 30um, 200 × 200ppi of resolution ratio.110 DEG C, vacuum 1 × 10 are heated on hot plate-6It volatilizees under Torr
Dry 30min, obtains monochromatic quantum dot luminescent layer.
Embodiment 3
A kind of inorganic nano material printing ink, the weight percentage that ink is printed with the inorganic nano material are
100% meter, includes each component of following weight percentage：Blue CdS/CdZnS, the green CdZnSe/ that 10% oleyl amine is stablized
CdZnS contains with red CdSe/ZnS quantum azeotropic mixture and 90% mixed solvent, the in the mixed solvent, including weight percent
Amount is 40% cyclohexyl benzene, 40% decahydronaphthalenes, 10%3- phenyl -1- propane mercaptan.
A kind of preparation method of inorganic nano material film, includes the following steps：
S31. the formula that ink is printed according to above-mentioned inorganic nano material weighs each component；Wherein, mixed solvent is by hexamethylene
Base benzene, decahydronaphthalenes and 3- phenyl -1- propane mercaptan composition, various solvents are all made of corresponding method water removal, deoxygenation is refined to
Purity is more than 99.9%.
S32., 500mL high-density polyethylene bottles are provided, in the case of stirring, add the blue CdS/ that oleyl amine is stablized successively
CdZnS, green CdZnSe/CdZnS, red CdSe/ZnS quantum dots, cyclohexyl benzene, decahydronaphthalenes and 3- phenyl -1- propane sulphur
Alcohol is stirred 30min, obtains quantum dot printing ink composition；
S33. by the quantum dot printing ink composition by ink-jet printer the inkjet printing on carrier, be printed as 20 ×
Blue, green, the red side-by-side quantum dot layers of 30um, 200 × 200ppi of resolution ratio.Be cooled to 18 DEG C, vacuum degree 1 ×
10-6Volatile dry 30min under Torr obtains three primary colours quantum dot light emitting layer.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
All any modification, equivalent and improvement etc., should all be included in the protection scope of the present invention made by within refreshing and principle.
Claims (10)
1. a kind of inorganic nano material prints ink, which is characterized in that including at least one inorganic nano material and at least one
The boiling point of thio-alcohol organic solvent, the thio-alcohol organic solvent is 100 DEG C -350 DEG C, the structure of the thio-alcohol organic solvent
General formula is R- (SH)x, wherein the R is selected from C2-25Aliphatic, aromatic group, the x be positive integer.
2. inorganic nano material as described in claim 1 prints ink, which is characterized in that the R includes C2-25Alkyl, ring
Alkyl, the C2-25Alkyl, naphthenic base include butyl, cyclobutyl, amyl, cyclopenta, hexyl, cyclohexyl, heptyl, cycloheptyl
Base, octyl, cyclooctyl, nonyl, cyclononyl, decyl, cyclodecyl, undecyl, ring undecyl, dodecyl, cetyl,
Octadecyl.
3. inorganic nano material as claimed in claim 1 or 2 prints ink, which is characterized in that the C2-25Aliphatic, virtue
Fragrant race's group contains one or more substituent groups, and the substituent group includes alkyl, aryl, nitro, cyano, amino ,-N (R ')
(R "), halogen, hydroxyl, carboxyl, ester group, ether, carbonyl, alkenyl, alkynyl, naphthenic base, alkoxy, aryl, heteroaryl, fragrant oxygen
Base, heteroaryloxy, alkoxy carbonyl group, perfluoroalkyl, perfluoro alkoxy, thio alkoxy ,-S (O)2- N (R ') (R ") ,-C (=O)-
N (R ') (R "), (R ') (R ") alkyl, (R ') (R ") positive alkoxy, (R ') (R ") alkyl, aryloxy alkyl ,-S (O)sVirtue
Base ,-S (O)sHeteroaryl, silyl-group, wherein the value range of the s is 0-2, and the R ' and R " is independently chosen from alkane
Base, naphthenic base, aryl, substitution alkyl, substituted cycloalkyl, substituted aryl.
4. inorganic nano material as claimed in claim 3 prints ink, which is characterized in that the alkyl includes C1-25Branch
Alkyl, straight chained alkyl, naphthenic base.
5. inorganic nano material as claimed in claim 3 prints ink, which is characterized in that the alkyl include methyl, ethyl,
Propyl, isopropyl, isobutyl group, sec-butyl, tertiary butyl, amyl, isopentyl, neopentyl, cyclopenta, hexyl, cyclohexyl, dissident
Base；And/or
The aryl includes phenyl, xenyl, triphenyl, benzo naphthalene, anthryl, phenalene, phenanthryl, fluorenyl, pyrenyl, bends
Base, base, azulenyl；And/or
The heteroaryl includes dibenzothiophenes, dibenzofurans, furans, thiophene, benzofuran, benzothiophene, carbazole, pyrrole
Azoles, imidazoles, triazole, isoxazole, thiazole, oxadiazoles, oxatriazole, dioxazole, thiadiazoles, pyridine, pyridazine, pyrimidine, pyrrole
Piperazine, triazine, oxazines, oxathiazine, oxadiazine, indoles, benzimidazole, indazole, indoxazine, benzoxazoles,
Benzisoxazole, benzothiazole, quinoline, isoquinolin, cinnoline, quinazoline, quinoxaline, naphthalene, phthalein, pteridine, oxa-
Anthracene, acridine, azophenlyene, phenthazine, phenoxazine, dibenzoselenophene, benzoselenophene,
benzofuropyridine、indolocarbazole、pyridylindole、pyrrolodipyridine、
furodipyridine、benzothienopyridine、thienodipyridine、benzoselenophenopyridine
The substituent group formed with selenophenodipyridine.
6. inorganic nano material as claimed in claim 1 or 2 prints ink, which is characterized in that the thio-alcohol organic solvent
Including 2- naphthalenes methyl mercaptan, 4- methyl mercapto azoles -2- mercaptan, 2,5- dimethyl -3- furanthiols, furfuryl mercaptan, thiophene -2- mercaptan,
4- chloro benzyl mercaptans, 1- hexadecanethiols, n-pentadecane base mercaptan, n-tetradecane base mercaptan, tertiary tetradecyl mercaptan, 1- tridecanes
Mercaptan, tert-dodecylmercaotan, 1- undecane thiols, 1- nonyls mercaptan, tertiary nonyl mercaptan, 2- methyl -3- tetrahydrofurans mercaptan, 1-
Foxlene -8- mercaptan, isopentene group mercaptan, 2- methylbenzyls mercaptan, tetra- oxa- tridecane -13- mercaptan of 2,5,8,11-, hexamethylene sulphur
Alcohol, trimethyl silicon substrate methyl mercaptan, oxinane -4- mercaptan, (2- mercaptos ethyl) hexamethylene alkanethiol, 2- [(phenyl mercaptan) methyl] -
2- cyclopentene-1-ones, 2- trifluoromethyls benzenethiol, 2- methyl -3- furanthiols acetic acid esters, 3- [(2- methoxyl group -2- oxygen ethyl)
It is thio] methyl propionate, 3- methyl mercaptan -1,2- glycol propane, 2- methyl -3- furanthiols, the chloro- 6- luorobenzyls mercaptan of 2-, 4-
Luorobenzyl mercaptan, 5- heptyl -2- furanthiols, 2- methyl -2- pentanes mercaptan, 3- ethyl -3- pentanes mercaptan, 2- (diisopropyls
Amino)-ethane thiol, 3- bromobenzylthiols, 4- methylbenzyls mercaptan, 2,3- dimethyl -2- butane thiols, tri isopropyl silane
Mercaptan, 3- phenyl -1- propane mercaptan, 3- methyl -4- pyridines mercaptan, 2- phenyl-propane -1- mercaptan, thiogeraniol, double mercapto second
Base thioether, three oxygen decane -11- alcohol of 1- (9- mercaptoethanols) -3,6,9-, 3- sulfydryl -1- hexanols, 3 methyl mercapto 1 hexanol, 8- mercaptos
Base -1- octanols, 4- iodobenzene -1- mercaptan, (tetrahydrofuran -3- bases) methyl mercaptan, morpholine -4- ethanethios, oleyl mercaptan,
2,3- ethylene oxide diformazans alkanethiol, 3- N-Propyl Bromide -1- mercaptan, 11- (1H- pyrroles -1- bases) hendecane -1- mercaptan, 4- methoxies
Base butane -1- mercaptan, 2- (pyrrolidin-1-yl) ethane thiol, five oxa- hexadecane -1- mercaptan of 3,6,9,12,15-.
7. inorganic nano material as claimed in claim 1 or 2 prints ink, which is characterized in that the inorganic nano material accounts for
Inorganic nano material prints the 0.01-20% of total weight of printing ink；And/or
The thio-alcohol organic solvent accounts for the 0.01-99.9% of inorganic nano material printing total weight of printing ink.
8. inorganic nano material as claimed in claim 1 or 2 prints ink, which is characterized in that the thio-alcohol organic solvent
Range of viscosities at 25 DEG C is 0.5cPs-60cPs, and the surface tension at 25 DEG C is 20-80mN/m.
9. a kind of preparation method of inorganic nano material film, includes the following steps：
The formula for printing ink according to any inorganic nano materials of claim 1-8 weighs each component；
Inorganic nano material is dissolved in organic solvent and forms inorganic nano material printing ink, wherein in the organic solvent
At least contain a kind of thio-alcohol organic solvent；
Ink is printed in deposited on supports inorganic nano using inkjet printing, by being dried, it is thin to obtain inorganic nano material
Film.
10. the preparation method of inorganic nano material film as claimed in claim 9, which is characterized in that the drying process
Mode includes heating dry, cooling and drying and is dried under reduced pressure, wherein the temperature of the heat drying is 30-180 DEG C, when heating
Between be 0-30min；
The temperature of the cooling and drying is 0-20 DEG C；
The vacuum degree of the drying process is 1 × 10-6Torr is to normal pressure.
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