CN109705660A - A kind of compound ink and preparation method thereof, device - Google Patents
A kind of compound ink and preparation method thereof, device Download PDFInfo
- Publication number
- CN109705660A CN109705660A CN201711007440.XA CN201711007440A CN109705660A CN 109705660 A CN109705660 A CN 109705660A CN 201711007440 A CN201711007440 A CN 201711007440A CN 109705660 A CN109705660 A CN 109705660A
- Authority
- CN
- China
- Prior art keywords
- nano
- compound ink
- particle
- metal
- sulfydryl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Abstract
The present invention discloses a kind of compound ink and preparation method thereof, device, wherein the compound ink includes being dispersed in alcohols solvent, passes through nano-metal particle and metal oxide nano particles that bridging molecules connect.For the compound ink after solvent anneal volatilization, metal oxide nano particles and the nano-metal particle can not will lead to the optical quenching of luminescent material with split-phase；And the nano-metal particle in the compound ink has surface enhanced resonant effect, can effectively promote the luminous efficiency of LED device；Meanwhile the bridging molecules in the compound ink make nano-metal particle and the obvious split-phase of semiconductor nano metal oxide, to prevent nano-metal particle from contacting semiconductor nano metal oxide, influence the energy level distribution and carrier mobility of device entirety.
Description
Technical field
The present invention relates to LED device fields more particularly to a kind of compound ink and preparation method thereof, device.
Background technique
Surface plasma enhancement effect (surface plasma enhancement, SPE) is the another of inorganic nano material
One special nature.For coin race metal, such as gold, silver or copper, the particle under nano-scale can be to the outer of specific wavelength
The excitation of boundary's electromagnetic wave generates resonance, to achieve the effect that enhance signal.Therefore, the metallic of the Nano grade can
It is widely used in electrooptical device, for example, for luminescence display diode, the nano metal particles bring table
Face enhancement effect can be used for the light of amplification semiconductor material sending, to promote the luminous efficiency of device.
Zinc oxide is as a kind of wide-band gap material, and forbidden energy gap is about 3.37eV at room temperature, and exciton binding energy is high,
Belong to n-type semiconductor.Zinc oxide has the characteristics that light transmittance is high, resistance is small, (such as thin in photoelectric conversion and opto-electronic device
In film solar cell, organic film light emitting diode and quantum dot film light emitting diode) it is used as electron transfer layer, have wide
General and deep application.Similarly, nickel oxide is as wide-band gap material, equally there is outstanding chemical stability and excellent
Light, electricity, magnetic performance；Semiconductor material of the nickel oxide as p-type, is similarly subjected to the attention of semicon industry.Nano oxygen
Change the double grading that zinc has both nano material and macroscopical zinc oxide, the diminution of size is along with Electronic Structure and crystal structure
Variation, produce the skin effect, bulk effect, quantum size effect and macroscopical tunnel effect that macroscopical zinc oxide do not have
It answers, also has the characteristics that polymolecularity, can be dispersed in organic solvent, for the post-production technique carried out based on solution, such as spray
It applies, blade coating, inkjet printing create possibility.
In recent years, have many researchs both at home and abroad to be dedicated to for nano metal particles being supported on nano zine oxide or nickel oxide
In structure, to construct the nanocomposite for taking into account two kinds of material advantages, for manufacturing electron transfer layer or/and hole transport
Layer, to improve photoelectric device efficiency.However, the technique that the prior art uses is the systems such as vapor deposition, vapor deposition or etching mostly
Make at high cost, energy consumption is high, and stock utilization is low and the method that does not meet industrially scalable production requirement；And existing side
Method can't efficiently use the characteristics of nano-particle material is easy to solvation.
Inkjet printing technology has attracted extensive concern in opto-electronic device manufacturing in recent years, especially in film
It is considered as the effective way for solving cost problem and realizing scale in display device manufacturing technology, this technology is in combination with base
Film display screen is made in the functional material of solution and advanced ink jet printing device, can be improved the utilization rate of material, is dropped
Low cost improves production capacity.However, ink jet printing device is higher to the physical property requirements of ink, for example, it is suitable boiling point, viscous
Degree, surface tension and the solute dispersed evenly and stably, bring bigger difficulty to ink formulation；And existing ink pair
The luminous efficiency promotion of device is poor, while must also consider whether ink can be to other knot of device in ink jet printing process
It is configured to change and damage physically or chemically.
Therefore, the existing technology needs to be improved and developed.
Summary of the invention
In view of above-mentioned deficiencies of the prior art, the purpose of the present invention is to provide a kind of compound ink and preparation method thereof,
Device, it is intended to solve existing ink and easily lead to the optical quenching of luminescent material and physics or change easily are caused to the other structures of device
The problem of learning the change and damage of property.
Technical scheme is as follows:
A kind of compound ink, wherein including being dispersed in alcohols solvent, by bridging molecules connect nano-metal particle and receive
Rice metal oxide particle.
The compound ink, wherein the nano-metal particle is that one of gold, silver, copper, aluminium, iron, platinum, nickel are single
The solid granulates of matter or multiple element component alloy.
The compound ink, wherein the nano-metal particle is spheric granules.
The compound ink, wherein the diameter of the spheric granules is 2-100nm.
The compound ink, wherein the nano-metal particle is aspherical particle, the shape of the aspherical particle
For one of nanometer rods, nano wire, nanometer square and nanometer tetrahedron or a variety of.
The compound ink, wherein the partial size of at least one dimension of aspherical particle is 2-100nm.
The compound ink, wherein the bridging molecules are sulfydryl alkanoic acid and sulfydryl acid derivative.
The compound ink, wherein the sulfydryl alkanoic acid be 7- sulfydryl enanthic acid, 8- sulfydryl octanoic acid, 9- sulfydryl n-nonanoic acid,
10- sulfydryl capric acid, 11- Mercaptoundecanoic acid, 12- sulfydryl dodecanoic acid, 13- sulfydryl tridecanoic acid, 14- sulfydryl tetradecanoic acid,
15- sulfydryl pentadecanoic acid or 16- mercaptohexadecanoic acid.
The compound ink, wherein the alkane less than or equal to 6 carbon atoms is connected on the main chain carbon of the sulfydryl alkanoic acid
Base functional group.
The compound ink, wherein the alkyl functional group is ethyl, propyl, isopropyl, butyl, isobutyl group, tertiary fourth
One of base, amyl, isopentyl, neopentyl and phenyl are a variety of.
The compound ink, wherein the metal oxide nano particles are nano nickel oxide particles, nanoscale molybdenum oxide
Particle, nano oxidized tungsten particle, nano granular of zinc oxide, nano titania particle or Nano granules of stannic oxide.
The compound ink, wherein the alcohols solvent is methanol, ethyl alcohol, normal propyl alcohol, isopropanol, n-butanol, 2- fourth
Alcohol, the tert-butyl alcohol or 2- methyl-1-propyl alcohol.
The compound ink, wherein the concentration of the compound ink is 1-100mg/ml.
A kind of preparation method of compound ink, wherein comprising steps of
A kind of nano-metal particle solution is provided；
Metal oxide nano particles are dispersed in alcohols solvent, metal oxide nano particles dispersion liquid is obtained；
It will be added in the nano-metal particle solution containing bridging molecules bifunctional；
The metal oxide nano particles dispersion liquid is added in the nano-metal particle solution containing bridging molecules,
Reaction obtains compound ink.
A kind of LED device, including first electrode, luminescent layer, second electrode and setting are in the first electrode
Carrier blocking layers and/or carrier injection layer between luminescent layer or between second electrode and luminescent layer, wherein the load
It flows sub- transport layer and/or carrier injection layer uses any one compound ink in described to be prepared.
The utility model has the advantages that compound ink prepared by the present invention, the physical properties such as viscosity, surface tension and boiling point can expire
The present ink jet printing device of foot, the compound ink is after solvent anneal volatilization, metal oxide nano particles and nanogold
Metal particles can not will lead to the optical quenching of luminescent material with split-phase；And the nano-metal particle in the compound ink has
Surface enhanced resonant effect can effectively promote the luminous efficiency of LED device；Meanwhile the bridge in the compound ink
Molecule is connect with very strong bonding functional group, which can be with nano-metal particle bonding, the other end
Semiconductor nano metal oxide bonding divides nano-metal particle obviously with semiconductor nano metal oxide after bonding
Phase influences energy level distribution and the current-carrying of device entirety to prevent nano-metal particle from contacting semiconductor nano metal oxide
Transport factor.
Detailed description of the invention
Fig. 1 is a kind of flow chart of the preparation method preferred embodiment of compound ink of the present invention；
Fig. 2 is the device luminescent spectrum figure in the embodiment of the present invention 1 and comparative example 1；
Fig. 3 is the device luminescent spectrum figure in the embodiment of the present invention 2 and comparative example 2.
Specific embodiment
The present invention provides a kind of compound ink and preparation method thereof, device, for make the purpose of the present invention, technical solution and
Effect is clearer, clear, and the present invention is described in more detail below.It should be appreciated that specific embodiment described herein
Only to explain the present invention, it is not intended to limit the present invention.
Referring to Fig. 1, Fig. 1 is a kind of flow chart of the preparation method preferred embodiment of compound ink of the present invention, as schemed institute
Show, including step:
S10, a kind of nano-metal particle solution is provided；
S20, metal oxide nano particles are dispersed in alcohols solvent, obtain metal oxide nano particles dispersion liquid；
S30, it will be added in the nano-metal particle solution containing bridging molecules bifunctional；
S40, that the metal oxide nano particles dispersion liquid is added to the nano-metal particle containing bridging molecules is molten
In liquid, reaction obtains compound ink.
Specifically, inkjet printing technology industrialized as existing thin-film display part, the effective way of large-scale production,
The production capacity that thin-film display part can be significantly improved reduces its production cost.However, since ink jet printing device is to the object of ink
Rationality can and chemical property it is more demanding, such as suitable boiling point, viscosity, surface tension and be uniformly dispersed and stable solute
Deng this brings bigger difficulty to the preparation of ink, and existing ink easily leads to the optical quenching of luminescent material and easily to device
The other structures of part cause change and damage physically or chemically.
To solve the problems of existing ink, present embodiments provide for a kind of preparation methods of compound ink, lead to
It is added after the nano-metal particle solution is first heated to 50-100 DEG C and contains bridging molecules bifunctional, then again will
Metal oxide nano particles dispersion liquid is added in the nano-metal particle solution containing bridging molecules, reacts 20-30h
Afterwards to get arrive compound ink；That is, the compound ink includes being dispersed in alcohols solvent, connected by bridging molecules
Nano-metal particle and metal oxide nano particles.Since the metallic particles under nano-scale can be to the external world of specific wavelength
The excitation of electromagnetic wave generates resonance, to achieve the effect that enhance signal, therefore, when the compound ink for providing present embodiment
When being used to prepare LED device, surface enhanced effect brought by the nano-metal particle in the compound ink is available
In the light that amplifying device luminescent layer issues, to promote the luminous efficiency of device；Bridging molecules in the compound ink simultaneously
With very strong bonding functional group, which can be with nanogold with nano-metal particle bonding, the other end
Belong to oxide bonding, makes nano-metal particle and the obvious split-phase of nano-metal-oxide after bonding, to prevent nano metal
Particle contact nanometer metal oxide influences the energy level distribution and carrier mobility of device entirety；The nano metal oxide
Object is semiconductor nano metal oxide.
The solvent in nano-metal particle solution that present embodiment provides is alcohols solvent, and nano metal simple substance particle is molten
Alcohols solvent in liquid is identical as the alcohols solvent range of choice in metal oxide nano particles dispersion liquid, it is preferable that described
Alcohols solvent is methanol, ethyl alcohol, normal propyl alcohol, isopropanol, n-butanol, 2- butanol, the tert-butyl alcohol or 2- methyl-1-propyl alcohol etc., but not
It is limited to this.
Further, since the coin race metallic particles under nano-scale has the excitation to the external electromagnetic wave of specific wavelength
Resonance is generated, to reach the feature of enhancing signal effect.In one embodiment, the nano metal simple substance particle solution
In nano-metal particle be spheric granules, with isotropism, that is to say, that the identical spheric granules of these shapes is connecing
It receives the resonance wave generated after the excitation of external electromagnetic wave uniformly to dissipate in all directions of space, the light of sending is uniform
's；Simultaneously because nano-metal particle is spheric granules, regular shape is excited by the nano metal simple substance spheric granules
Resonance peak bandwidth will not broaden so that luminescent color is purer.
Further, the position by adjusting the adjustable formant of size of nano metal spherical shape particle spectrally
It sets, the diameter of the preferably described nano metal spherical shape particle of present embodiment is that 2-100nm works as nano metal ball in the range
When the diameter of shape particle is bigger, formant is mobile to long wave direction, when the diameter of nano metal spherical shape particle is smaller, is total to
Vibration peak is mobile to shortwave direction.In practical applications, the nano metal spherical shape particle of suitable size can be selected according to actual needs
To prepare corresponding luminescent device.
In another embodiment, in the actual production process of device, some devices need to be simultaneously emitted by multiband
Light, in order to realize through localized plasmon resonance effect while enhancing the light of different-waveband, what the present invention used
Nano metal is aspherical particle shape, preferably, the aspherical particle shape is nanometer rods, nano wire, nanometer square
Or nanometer tetragonal body etc., but not limited to this.Specifically, the nano metal aspherical particle that the present invention uses has anisotropy
Feature, that is to say, that these different aspherical nano-metal particles can excite different-waveband i.e. different colours simultaneously
Light；By these different aspherical nano-metal particles and the available more waves of metal oxide semiconductor combination collocation
The amplification material of section.
Similarly, present embodiment can also exist by adjusting the adjustable formant of size of nano metal aspherical particle
Position spectrally, the partial size of present embodiment preferably at least one dimension of the nano metal aspherical particle are 2-
100nm, in the range, when the partial size of nano metal aspherical particle is bigger, formant is mobile to long wave direction, when receiving
The partial size of rice metal aspherical particle is got over hour, and formant is mobile to shortwave direction.It in practical applications, can be according to practical need
The nano metal aspherical particle for selecting suitable size is asked to prepare corresponding luminescent device.
Further, the nano-metal particle is one of gold, silver, copper, aluminium, iron, platinum, nickel simple substance or a variety of simple substance
The solid-state aspherical particle of composition or multiple element component alloy.For emitting the device of short-wavelength light (purple light or black light)
Part, it is necessary to use nano aluminum as excitation of plasma body carrier, however due to the chemical stability of the aluminium simple substance under nano-scale
It is poor, cause nanometer rate that cannot be used alone, but need to be combined into alloy with other metallic elements such as gold, silver, copper, platinum,
Excitation of plasma carrier can be used as；Equally, for the device of transmitting long wavelength light (feux rouges or near-infrared), then needing will be chemical
Other metallic element component alloys such as the poor copper metal nano particle of stability and gold, silver, aluminium, platinum, can as etc. from
Son excitation carrier.Therefore, during some special device productions, need the nano metal element component alloy as etc.
Ion excitation carrier.
Specifically, two kinds of carriers, i.e. hole in electronics and valence band in conduction band are usually contained in semiconductor, when half
When the electric conductivity of conductor relies primarily on the hole in valence band, then the based semiconductor is known as P-type semiconductor；When the conduction of semiconductor
When property relies primarily on the hole in valence band, then the based semiconductor is known as N-type semiconductor.In the present invention, the semiconductor gold
Belong to oxide particle include nano nickel oxide particles, nanoscale molybdenum oxide particle, nano oxidized tungsten particle, nano granular of zinc oxide,
Nano titania particle or Nano granules of stannic oxide etc., but not limited to this.
In the metal oxide particle, wherein nano nickel oxide particles, nanoscale molybdenum oxide particle and nanometer tungsten oxide
Grain is P-type semiconductor nano particle；Nano granular of zinc oxide, nano titania particle and Nano granules of stannic oxide are that N-type is partly led
Body.By taking P-type semiconductor nickel oxide as an example, nickel oxide has outstanding chemical stability and excellent as a kind of wide-band gap material
Good light, electricity and magnetic performance shines in thin-film solar cells, organic film light emitting diode and quantum dot film
In diode, there is extensive and deep application as hole transmission layer.By taking N-type semiconductor zinc oxide as an example, zinc oxide is one
Kind wide-band gap material, forbidden energy gap are about 3.37eV at room temperature, and exciton binding energy is high, and light transmittance is high, resistance is small and has
There are excellent light, electricity and a magnetic performance, therefore (such as thin-film solar cells has zinc oxide in photoelectric conversion and opto-electronic device
Machine is thin-film led and quantum dot film light emitting diode) in, also have as electron transfer layer extensive and deep
Using.
Further, nano-nickel oxide (or zinc oxide) particle is with nano material and macroscopical nickel oxide (or zinc oxide)
Double grading, the diminution of size along with Electronic Structure and crystal structure variation, to produce macroscopical nickel oxide
Skin effect, bulk effect, quantum size effect and the macroscopical tunnel-effect not had；Nano-nickel oxide (or zinc oxide)
Grain also has the characteristics that polymolecularity, can be dispersed in organic solvent, for the post-production technique carried out based on solution, such as sprays
It applies, blade coating or inkjet printing create possibility.
In another embodiment, contained by being added after nano-metal particle aqueous solution is first heated to 50-100 DEG C
The bridging molecules of strong bonding functional group；P-type semiconductor metal oxide (nickel oxide) particle dispersion is added to described receive again
In rice metallic particles solution, the P-type semiconductor metal oxide-nanometer connected by bridging molecules is arrived after mixing 20-30h
The compound ink of metal aspherical particle；The preferred heating temperature of present embodiment is 60-80 DEG C, incorporation time 24-26h, this
Compound ink made from part can be used for preparing the hole transmission layer and/or hole injection layer of device；That is, the composite ink
Water can be individually used for preparing the hole transmission layer or hole injection layer of device, or be used to prepare simultaneously device hole injection layer and
Hole transmission layer.The hole transmission layer and/or hole injection layer of compound ink preparation can effectively facilitate hole through the invention
It is compound with electronics, and make the light issued from luminescent layer, after hole transmission layer and/or hole injection layer, light intensity is obtained
Effectively amplification, to promote the luminous efficiency of device.
In another embodiment, contained by being added after nano-metal particle aqueous solution is first heated to 50-100 DEG C
The bridging molecules of strong bonding functional group, then N-type nano-metal-oxide (zinc oxide) particle dispersion is added to the nanometer
In metallic particles solution, received after mixing 20-30h to get to the N-type semiconductor nano-metal-oxide-connected by bridging molecules
The rice compound ink of metallic particles；Present embodiment preferred heating time is 60-80 DEG C, incorporation time 24-26h, under this condition
Compound ink obtained is used to prepare the electron transfer layer and/or electron injecting layer of device；That is, the compound ink can
Be individually used for preparing the electron transfer layer of device and/or electron injecting layer, or be used to prepare simultaneously device electron transfer layer and/
Or electron injecting layer.The electron transfer layer and/or electron injecting layer of compound ink preparation can effectively facilitate sky through the invention
The transmission in cave, and make the light issued from luminescent layer, after electron transfer layer and/or electron injecting layer, light intensity is obtained effectively
Amplification, to promote the luminous efficiency of device.
Further, joined bridging molecules in compound ink provided by the invention, the bridging molecules be containing by force at
The small organic molecule of key functional group, specifically, the bridging molecules are sulfydryl alkanoic acid and sulfydryl acid derivative, the sulfydryl alkane
Acid is 7- sulfydryl enanthic acid, 8- sulfydryl octanoic acid, 9- sulfydryl n-nonanoic acid, 10- sulfydryl capric acid, 11- Mercaptoundecanoic acid, 12- sulfydryl 12
Alkanoic acid, 13- sulfydryl tridecanoic acid, 14- sulfydryl tetradecanoic acid, 15- sulfydryl pentadecanoic acid or 16- mercaptohexadecanoic acid etc., but not
It is limited to this；The alkyl functional group less than or equal to 6 carbon atoms is wherein also connected on the main chain carbon of the sulfydryl alkanoic acid, it is described
It is ethyl less than or equal to the alkyl functional of 6 carbon atoms group, propyl, isopropyl, butyl, isobutyl group, tert-butyl, amyl, different
One of amyl, neopentyl or phenyl are a variety of, but not limited to this.
Mercapto functional group end in the sulfydryl alkanoic acid molecule can be received with nano-metal particle surface bonding to replace
Common stable group (such as citric acid) in rice metallic particles solution, carboxyl functional group in the sulfydryl alkanoic acid molecule can be with
Semiconductor nano metal oxide bonding；That is, the sulfydryl alkanoic acid molecule can bridge simultaneously nano-metal particle with
Semiconductor nano metal oxide particle, to achieve the effect that nano metal and metal oxide semiconductor split-phase；Further
Ground, the bridging molecules can also prevent nano-metal particle from contacting metal oxide semiconductor, and nano metal is avoided to change half
The fermi level of conductor metal oxide to ensure the energy level distribution and carrier mobility of device entirety, while also avoiding
Using harsh conditions by Nano metal particles deposition on metal oxide nano particles surface.
Further, in the present embodiment, the alkyl functional group on the sulfydryl alkanoic acid main chain carbon, which can control, receives
Distribution density and spacing of the rice metallic particles on metal oxide semiconductor, to control the dissolution of composite material in the ink
Property, plasma resonance hot spot quantity with mutually cope with luminous intensity amplification, while can also prevent carrier because quantum tunneling imitate
Electric effect caused by medium should be punctured.
Further, between 1-100mg/ml, the concentration refers to multiple the concentration of the compound ink of present embodiment preparation
All solutes in ink total concentration in a solvent is closed, due to bridging molecules one end and nano metal simple substance particle bonding, separately
One end and semiconductor nano metal oxide particle bonding, therefore, the solute in the compound ink are as follows: connected by bridging molecules
Nano metal simple substance particle and metal oxide nano particles formed composite construction particle；In the compound ink, receive
The ratio between mole of rice metallic particles and semiconductor nano metal oxide particle is 1:(1-1000).Specifically, in order to protect
The semiconductor property of metal oxide itself is not influenced while the compound ink is demonstrate,proved with surface resonance reinforcing effect and, this
The ratio between mole of the preferably described nano-metal particle of embodiment and semiconductor nano metal oxide particle is 1:(10-
400), preferably, being also still exposed to metal oxide nano particles largely in dicyandiamide solution in the proportional region, thus
The dispersibility of compound ink is fully ensured that.
Preferably, the compound ink of various concentration can greatly influence the print performance of ink, the present invention passes through experiment card
Bright, when the concentration of the compound ink is between 10-60mg/ml, print performance is preferable.
Further, in the step S20, semiconductor nano metal oxide particle is dispersed in alcohols solvent,
Obtain nano-metal-oxide dispersion liquid；Specifically, during preparing compound ink, the composition of ink itself is to printing
Technologic performance has a very important influence, and in the present invention, the alcohols solvent in the preferably described compound ink is lower alcohol
Solvent, the lower alcohol solvent are methanol, ethyl alcohol, normal propyl alcohol, isopropanol, n-butanol, 2- butanol, the tert-butyl alcohol or 2- methyl-1-
Propyl alcohol etc., but not limited to this；When the alcohols solvent in the compound ink is lower alcohol solvent, the lower alcohol solvent is half-and-half
Conductor metal oxide nano particles have good peptizaiton, can obtain the solution of clear, and blocking is avoided to print
Machine nozzle can guarantee the stability of prepared compound ink.
Simultaneously as the chain length of lower alcohol is shorter, the surface potential energy between composite material granular will not be increased considerably, and
It is easy to be detached from composite material in film forming, close structure can be constituted between composite material granular molecule, so that multiple
It is preferable to close ink filming performance；
Preferably, since lower alcohol solvent can not dissolve the sull to have formed a film, therefore composite ink prepared by the present invention
Water will not cause to damage when printing multilayer grading structure to understructure.
To advanced optimize InkJet printing processes, in another embodiment, the alcohols solvent is lower alcohol and height
The mixed solvent of grade alcohol is used to prepare compound ink after mixing lower alcohol solvent and higher alcohol solvent, can effectively be promoted multiple
Close the filming performance of ink.Specifically, the higher alcohol and lower alcohol molecule can form part of the constant azeotrope combination, so that compound
Ink be not easy it is too fast can send out, thus effectively contain compound ink condensed at nozzle cause solute be precipitated plug nozzle the problem of,
The azeotropic mixture combination also can avoid compound ink in the drying process simultaneously, because the local turbulence that too fast volatilization is formed disturbs still
The composite material not formed a film.
Further, the higher alcohol molecule can also adjust surface tension and viscosity of compound ink etc. and beat with ink-jet
Print relevant physical property, in the present invention, the higher alcohol solvent be 1,2- butanediol, 1,3-BDO, 1,4-butanediol,
2,3-butanediol, 1,5-PD, glycerine, 1,2,4-butanetriol or 1,2,3- butantriols etc., but not limited to this, pass through control
The surface tension and viscosity of compound ink is adjusted in the dosage of higher alcohol solvent, preferably, present embodiment adjusting is described compound
The viscosity of ink is 3-15cP and/or surface tension is 28-36mN/m, and saturated vapor pressure is lower than 0.02kPa.It is preferred that described compound
The viscosity of ink be 6-12cP, surface tension 29-33mN/m, saturated vapor pressure be lower than 0.01kPa, by compound ink object
Rationality matter is arranged in the range, and it is qualitative to may make that composite ink water can adapt to ink-jet and ink droplet volatilization solidification in printing technology
Demand, and can avoid that compound ink, which can not be sprayed in nozzle, droplet size is uneven, hangover and coffee ring etc. are a variety of is unfavorable for
The phenomenon that printing.
Further, the present invention also provides a kind of LED devices, including first electrode, luminescent layer, second electrode
And carrier blocking layers and/or load between the first electrode and luminescent layer or between second electrode and luminescent layer are set
Flow sub- implanted layer, wherein the carrier injection layer and/or carrier blocking layers are using the compound ink preparation of any one of the above
It forms.
Specifically, the carrier blocking layers include electron transfer layer, hole transmission layer, the carrier injection layer packet
Include electron injecting layer, hole injection layer.Further, electronic work ergosphere (including electron transfer layer and electron injecting layer) and hole
The not ipsilateral of luminescent layer is arranged in functional layer (including hole transmission layer and hole injection layer), as follows:
A kind of LED device provided by the invention is prepared by inkjet printing technology, wherein the light-emitting diodes
Pipe includes first electrode, hole injection layer and/or hole transmission layer, luminescent layer and second electrode, the hole injection layer and/
Or hole transmission layer is prepared using above-mentioned compound ink, that is to say, that the compound ink can be individually used for preparing device
Hole transmission layer or hole injection layer, or be used to prepare the hole injection layer and hole transmission layer of device simultaneously.
The present invention also provides another LED device, the LED device passes through inkjet printing technology system
It is standby to form, wherein the light emitting diode includes first electrode, luminescent layer, electron injecting layer and/or electron transfer layer and the
Two electrodes, wherein the electron injecting layer and/or electron transfer layer are prepared using above-mentioned compound ink, that is to say, that institute
Stating compound ink can be individually used for preparing the electron transfer layer and/or electron injecting layer of device, or be used to prepare device simultaneously
Electron transfer layer and/or electron injecting layer.
The present invention prepares carrier blocking layers and/or carrier injection layer by compound ink, so that luminescent layer passes through spoke
The photon irradiation of transition generation is penetrated when on the carrier blocking layers and/or carrier injection layer, metal nanoparticle surface
Free electron and photon interact, generate local electric field, the effective electric field in the local electric field and LED device
Resonance is generated, promotes the recombination luminescence efficiency of luminescent layer, enhances the luminous intensity of LED device.
Explanation is further explained to a kind of preparation method of compound ink of the present invention below by specific embodiment:
Embodiment 1
A kind of compound ink, including dispersion is in ethanol, the nano-metal particle that is connected by 6- mercaptohexanoic acid and nano oxidized
The preparation method of zinc particle, the compound ink includes:
Prepare the ethanol solution for the nano granular of zinc oxide that 300ml concentration is 30mg/ml；
Prepare the methanol solution that 100mL concentration is the nanogold particle that 2.8mg/ml has citrate to protect；
The methanol solution of the nanogold particle is heated to 60 DEG C, be then added 5 mL concentration be 1 mg/ml 6- sulfydryl oneself
Sour methanol solution is kept for temperature reflux 24 hours, is eventually adding the ethanol solution of the nano granular of zinc oxide, is reacted and is made multiple
Close ink；
Above-mentioned compound ink is deposited into film, tests its UV-Vis spectra figure, measure it has a half-peak at 530nm
Width is the absorption peak of 30nm.
A kind of preparation method of QLED device, including ito anode is provided, quantum dot layer is made on anode, wherein quantum
Point layer material is to emit the green quantum dot that light is 530 nm, and above-mentioned compound ink production electronics is printed on the quantum dot layer
Transport layer；Ag electrode is made, obtains QLED device, the luminescent spectrum figure of the QLED device is as shown in Figure 2.
Comparative example 1
A kind of preparation method of QLED device, difference from example 1 is that, electron transfer layer uses nanogold particle-
The compound ink of nano zine oxide is prepared, wherein nanogold particle and nano zine oxide are bridged without 6- mercaptohexanoic acid.Comparison
The luminescent spectrum figure of QLED device in example 1 is as shown in Figure 2.As can be seen from FIG. 2, the electron-transport prepared by this compound ink
Layer can enhance the luminous intensity of LED device.
QLED device made by embodiment 1 and comparative example 1 is subjected to test comparison under conditions of electric current is 2 mA respectively,
Embodiment 1 rises to 29% by 17%, illustrates nanogold particle and nano zine oxide compared to comparative example 1, conversion quantum efficiency
Particle solves the problems, such as that nano metal gold particle is reunited on nano granular of zinc oxide surface, promotes after small molecule bridges
Carrier mobility, to improve carrier in the recombination luminescence efficiency of luminescent layer.
Embodiment 2
A kind of compound ink, including dispersion in ethanol, by 7- phenyl -16- mercaptohexanoic acid connect nano-metal particle and
The preparation method of nano granular of zinc oxide, the compound ink includes:
Prepare the ethanol solution for the nano granular of zinc oxide that 200ml concentration is 50mg/ml；
Prepare the methanol solution that 100mL concentration is the nanogold particle that 1.8mg/ml has citrate to protect；
The methanol solution of the nanogold particle is heated to 60 DEG C, the 7- phenyl-that 5 mL concentration are 1 mg/ml is then added
16- mercaptohexanoic acid methanol solution is kept for temperature reflux 24 hours, is eventually adding the ethanol solution of the nano granular of zinc oxide,
Compound ink is made in reaction；
Above-mentioned compound ink is deposited into film, tests its UV-Vis spectra figure, measure it has a half-peak at 580nm
Width is the absorption peak of 38nm.
A kind of preparation method of QLED device, including ito anode is provided, quantum dot layer is made on anode, wherein quantum
Point layer material is to emit the yellow quantum dot that light is 580 nm, and above-mentioned compound ink production electronics is printed on the quantum dot layer
Transport layer；Ag electrode is made, obtains QLED device, the luminescent spectrum figure of the QLED device is as shown in Figure 3.
Comparative example 2
A kind of preparation method of QLED device, the difference is that, electron transfer layer uses nanogold particle-with embodiment 2
The compound ink of nano zine oxide is prepared, wherein nanogold particle and nano zine oxide are without 7- phenyl -16- mercaptohexanoic acid
Bridge joint.The luminescent spectrum figure of QLED device prepared by comparative example 2 is as shown in Figure 3.As can be seen from FIG. 3, pass through this compound ink system
Standby electron transfer layer can enhance the luminous intensity of LED device.
QLED device made by embodiment 2 and comparative example 2 is subjected to test comparison under conditions of electric current is 2 mA respectively,
Embodiment 2 rises to 20% by 10%, illustrates nanogold particle and nano zine oxide compared to comparative example 2, conversion quantum efficiency
Particle solves the problems, such as that nano metal gold particle is reunited on nano granular of zinc oxide surface, promotes after small molecule bridges
Carrier mobility, to improve carrier in the recombination luminescence efficiency of luminescent layer.
In conclusion compound ink prepared by the present invention, the physical properties such as viscosity, surface tension and boiling point can expire
The present ink jet printing device of foot, the compound ink after solvent anneal volatilization, semiconductor nano metal oxide with it is described
Nano-metal particle can not will lead to the optical quenching of luminescent material with split-phase；And the nano metal in the compound ink
Grain has surface enhanced resonant effect, can effectively promote the luminous efficiency of LED device；Meanwhile the compound ink
In bridging molecules have very strong bonding functional group, which can be with nano-metal particle bonding, the other end
Nano-metal particle and semiconductor nano metal oxide can be made bright after bonding with semiconductor nano metal oxide bonding
Aobvious split-phase, to prevent nano-metal particle from contacting semiconductor nano metal oxide, influence the energy level distribution of device entirety with
Carrier mobility.
It should be understood that the application of the present invention is not limited to the above for those of ordinary skills can
With improvement or transformation based on the above description, all these modifications and variations all should belong to the guarantor of appended claims of the present invention
Protect range.
Claims (15)
1. a kind of compound ink, which is characterized in that including being dispersed in alcohols solvent, pass through the nano metal of bridging molecules connection
Particle and metal oxide nano particles.
2. compound ink according to claim 1, which is characterized in that the nano-metal particle be gold, silver, copper, aluminium,
The solid granulates of one of iron, platinum, nickel simple substance or multiple element component alloy.
3. compound ink according to claim 1, which is characterized in that the nano-metal particle is spheric granules.
4. compound ink according to claim 3, which is characterized in that the diameter of the spheric granules is 2-100nm.
5. compound ink according to claim 1, which is characterized in that the nano-metal particle is aspherical particle, institute
The shape for stating aspherical particle is one of nanometer rods, nano wire, nanometer square and nanometer tetrahedron or a variety of.
6. compound ink according to claim 5, which is characterized in that the grain of at least one dimension of aspherical particle
Diameter is 2-100nm.
7. compound ink according to claim 1, which is characterized in that the bridging molecules are sulfydryl alkanoic acid or sulfydryl alkanoic acid
Derivative.
8. compound ink according to claim 7, which is characterized in that the sulfydryl alkanoic acid is 7- sulfydryl enanthic acid, 8- sulfydryl
Octanoic acid, 9- sulfydryl n-nonanoic acid, 10- sulfydryl capric acid, 11- Mercaptoundecanoic acid, 12- sulfydryl dodecanoic acid, 13- sulfydryl tridecanoic acid,
14- sulfydryl tetradecanoic acid, 15- sulfydryl pentadecanoic acid or 16- mercaptohexadecanoic acid.
9. compound ink according to claim 7, which is characterized in that be connected with and be less than on the main chain carbon of the sulfydryl alkanoic acid
Equal to the alkyl functional group of 6 carbon atoms.
10. compound ink according to claim 9, which is characterized in that the alkyl functional group is ethyl, propyl, isopropyl
One of base, butyl, isobutyl group, tert-butyl, amyl, isopentyl, neopentyl and phenyl are a variety of.
11. compound ink according to claim 1, which is characterized in that the metal oxide nano particles are nano oxygen
Change nickel particle, nanoscale molybdenum oxide particle, nano oxidized tungsten particle, nano granular of zinc oxide, nano titania particle or nano oxygen
Change tin particles.
12. compound ink according to claim 1, which is characterized in that the alcohols solvent be methanol, ethyl alcohol, normal propyl alcohol,
Isopropanol, n-butanol, 2- butanol, the tert-butyl alcohol or 2- methyl-1-propyl alcohol.
13. compound ink according to claim 1, which is characterized in that the concentration of the compound ink is 1-100mg/ml.
14. a kind of preparation method of compound ink, which is characterized in that comprising steps of
A kind of nano-metal particle solution is provided；
Metal oxide nano particles are dispersed in alcohols solvent, metal oxide nano particles dispersion liquid is obtained；
It will be added in the nano-metal particle solution containing bridging molecules bifunctional；
The metal oxide nano particles dispersion liquid is added in the nano-metal particle solution containing bridging molecules,
Reaction obtains compound ink.
15. a kind of LED device, including first electrode, luminescent layer, second electrode and setting are in the first electrode
Carrier blocking layers and/or carrier injection layer between luminescent layer or between second electrode and luminescent layer, which is characterized in that
The carrier blocking layers and/or carrier injection layer using the compound ink preparation of any one in the claim 1-13 and
At.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711007440.XA CN109705660A (en) | 2017-10-25 | 2017-10-25 | A kind of compound ink and preparation method thereof, device |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711007440.XA CN109705660A (en) | 2017-10-25 | 2017-10-25 | A kind of compound ink and preparation method thereof, device |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109705660A true CN109705660A (en) | 2019-05-03 |
Family
ID=66253231
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711007440.XA Pending CN109705660A (en) | 2017-10-25 | 2017-10-25 | A kind of compound ink and preparation method thereof, device |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109705660A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110299437A (en) * | 2019-06-26 | 2019-10-01 | 东南大学 | A kind of full-inorganic QLEDs device of surface treated NiO film and preparation method thereof |
| WO2020035004A1 (en) * | 2018-08-15 | 2020-02-20 | Tcl集团股份有限公司 | Composite material and quantum dot light-emitting diode and preparation method therefor |
| CN114039002A (en) * | 2020-12-15 | 2022-02-11 | 广东聚华印刷显示技术有限公司 | Electron transport ink, electron transport film, electroluminescent diode, and display device |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102169119A (en) * | 2010-12-31 | 2011-08-31 | 西安交通大学 | Preparation method for nano -gold immune probe |
| CN105810851A (en) * | 2016-05-03 | 2016-07-27 | 深圳市华星光电技术有限公司 | Preparation method of quantum dot light-emitting diode display and quantum dot light-emitting diode display |
| CN106190113A (en) * | 2016-07-18 | 2016-12-07 | 东北师范大学 | Ultraviolet emission ZnO quantum dot and Ag nanoparticle heterojunction structure compound system |
| CN106299159A (en) * | 2016-08-25 | 2017-01-04 | 纳晶科技股份有限公司 | The preparation method of metal oxide nanoparticles and quanta point electroluminescent device |
| CN106380934A (en) * | 2016-08-30 | 2017-02-08 | Tcl集团股份有限公司 | Zinc-oxide-based nanometer particle ink and preparation method thereof |
| CN106972115A (en) * | 2017-05-27 | 2017-07-21 | 深圳市华星光电技术有限公司 | The preparation method and OLED display panel of OLED display panel |
-
2017
- 2017-10-25 CN CN201711007440.XA patent/CN109705660A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102169119A (en) * | 2010-12-31 | 2011-08-31 | 西安交通大学 | Preparation method for nano -gold immune probe |
| CN105810851A (en) * | 2016-05-03 | 2016-07-27 | 深圳市华星光电技术有限公司 | Preparation method of quantum dot light-emitting diode display and quantum dot light-emitting diode display |
| CN106190113A (en) * | 2016-07-18 | 2016-12-07 | 东北师范大学 | Ultraviolet emission ZnO quantum dot and Ag nanoparticle heterojunction structure compound system |
| CN106299159A (en) * | 2016-08-25 | 2017-01-04 | 纳晶科技股份有限公司 | The preparation method of metal oxide nanoparticles and quanta point electroluminescent device |
| CN106380934A (en) * | 2016-08-30 | 2017-02-08 | Tcl集团股份有限公司 | Zinc-oxide-based nanometer particle ink and preparation method thereof |
| CN106972115A (en) * | 2017-05-27 | 2017-07-21 | 深圳市华星光电技术有限公司 | The preparation method and OLED display panel of OLED display panel |
Non-Patent Citations (3)
| Title |
|---|
| 李德娜等: "《水溶性量子点纳米微球的制备、表征及其在生物检测中的应用》", 《高等学校化学学报》 * |
| 赵秀萍等: "《柔性版印刷技术》", 30 April 2003, 中国轻工业出版社 * |
| 郑德海: "《现代网印油墨选择与使用手册》", 31 December 2000, 中国轻工业出版社 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020035004A1 (en) * | 2018-08-15 | 2020-02-20 | Tcl集团股份有限公司 | Composite material and quantum dot light-emitting diode and preparation method therefor |
| CN110838551A (en) * | 2018-08-15 | 2020-02-25 | Tcl集团股份有限公司 | Composite material, quantum dot light-emitting diode and preparation method thereof |
| CN110299437A (en) * | 2019-06-26 | 2019-10-01 | 东南大学 | A kind of full-inorganic QLEDs device of surface treated NiO film and preparation method thereof |
| CN114039002A (en) * | 2020-12-15 | 2022-02-11 | 广东聚华印刷显示技术有限公司 | Electron transport ink, electron transport film, electroluminescent diode, and display device |
| CN114039002B (en) * | 2020-12-15 | 2023-02-17 | 广东聚华印刷显示技术有限公司 | Electron transport ink, electron transport film, electroluminescent diode, and display device |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Yuan et al. | Highly efficient carbon dots with reversibly switchable green–red emissions for trichromatic white light-emitting diodes | |
| Yu et al. | Laser‐Generated Supranano Liquid Metal as Efficient Electron Mediator in Hybrid Perovskite Solar Cells | |
| Tsai et al. | A study of the preparation and properties of antioxidative copper inks with high electrical conductivity | |
| Jeong et al. | Silver‐based nanoparticles for surface plasmon resonance in organic optoelectronics | |
| Topp et al. | Impact of the incorporation of Au nanoparticles into polymer/fullerene solar cells | |
| Lim et al. | Facile synthesis of colloidal CuO nanocrystals for light-harvesting applications | |
| Majumder et al. | Nitrogen‐doped graphene quantum dot‐decorated ZnO nanorods for improved electrochemical solar energy conversion | |
| CN109705664A (en) | A kind of compound ink and preparation method thereof, device | |
| CN109705660A (en) | A kind of compound ink and preparation method thereof, device | |
| Kim et al. | Inkjet printing of transparent InZnSnO conducting electrodes from nano-particle ink for printable organic photovoltaics | |
| Petridis et al. | Laser generated nanoparticles based photovoltaics | |
| Kus et al. | Synthesis of nanoparticles | |
| Subramanian et al. | High-performance photodetector based on a graphene quantum dot/CH3NH3PbI3 perovskite hybrid | |
| Jhuang et al. | Localized surface plasmon resonance of copper nanoparticles improves the performance of quasi-two-dimensional perovskite light-emitting diodes | |
| Wang et al. | Integrated effects of near-field enhancement-induced excitation and surface plasmon-coupled emission of elongated gold nanocrystals on fluorescence enhancement and the applications in pleds | |
| CN109705663A (en) | A kind of compound ink and preparation method thereof, device | |
| Chen et al. | Passivation layer of potassium iodide yielding high efficiency and stable deep red perovskite light-emitting diodes | |
| Payandeh et al. | High-brightness perovskite light-emitting diodes using a printable silver microflake contact | |
| Ahmadian-Yazdi et al. | Fabrication of semiconducting methylammonium lead halide perovskite particles by spray technology | |
| Sun et al. | High performance perovskite LEDs via SPR and enhanced hole injection by incorporated MoS2 | |
| CN109705661A (en) | A kind of compound ink and preparation method thereof, device | |
| CN109980129B (en) | Metal oxide, preparation method thereof and QLED device | |
| CN109705662A (en) | A kind of compound ink and preparation method thereof, device | |
| CN109705659A (en) | A kind of compound ink and preparation method thereof, device | |
| KR101191527B1 (en) | Nano CuO Added Organic Thin Film And Electronic Device Using It |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190503 |