CN109705664A - 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
- CN109705664A CN109705664A CN201711007450.3A CN201711007450A CN109705664A CN 109705664 A CN109705664 A CN 109705664A CN 201711007450 A CN201711007450 A CN 201711007450A CN 109705664 A CN109705664 A CN 109705664A
- Authority
- CN
- China
- Prior art keywords
- nano
- compound ink
- particle
- metal
- compound
- 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 the nano-metal particle and metal oxide nano particles for being dispersed in the mixed solvent, and the mixed solvent includes basic organic solvent and higher alcohol solvent.The physical properties such as viscosity, surface tension and the boiling point of compound ink provided by the invention can satisfy present ink jet printing device, the compound ink is 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 be obviously improved the luminous efficiency of device；Higher alcohol can effectively 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.
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 that the preparation of existing ink is difficult, be difficult to meet the needs of ink jet printing device and existing ink easily leads to hair
The optical quenching of luminescent material and the problem of easily cause change and damage physically or chemically to the other structures of device.
Technical scheme is as follows:
A kind of compound ink, wherein nano-metal particle and metal oxide nano particles including being dispersed in the mixed solvent,
The mixed solvent includes basic organic solvent and higher alcohol solvent.
The compound ink, wherein the basic organic solvent is alkane halogeno-benzene class, halogenated naphthalenes and lower alcohols
One of solvent is a variety of.
The compound ink, wherein the lower alcohol solvent is methanol, ethyl alcohol, normal propyl alcohol, isopropanol, n-butanol, 2-
Butanol, the tert-butyl alcohol or 2- methyl-1-propyl alcohol, the alkane are n-hexane, the isomer of n-hexane, normal heptane, normal heptane
Isomer, normal octane or normal octane isomer, the halogenated benzene kind solvent is chlorobenzene, o-dichlorohenzene, two
Chlorobenzene or paracide.
The compound ink, wherein the higher alcohol is 1,2- butanediol, 1,3-BDO, 1,4-butanediol, 2,3-
Butanediol, 1,5- pentanediol, glycerine, 1,2,4- butantriol or 1,2,3- butantriol.
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 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 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 basic organic solvent, metal oxide nano particles dispersion liquid is obtained；
The metal oxide nano particles dispersion liquid is added in the nano-metal particle solution, after mixing the predetermined time
Higher alcohol is added, compound ink is obtained.
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
Sub- implanted layer and/or carrier blocking layers are flowed to be prepared using any one described compound ink.
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 be obviously improved the luminous efficiency of LED device；Further, higher alcohol can effectively be kept away
Exempt from compound ink and can not spray in nozzle, a variety of the phenomenon that being unfavorable for printing hairs such as droplet size is uneven, hangover and coffee ring
It is raw.
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 of the embodiment of the present invention 1 and comparative example 1；
Fig. 3 is the device luminescent spectrum figure of 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 basic organic solvent, obtain metal oxide nano particles dispersion
Liquid；
S30, the metal oxide nano particles dispersion liquid is added in the nano-metal particle solution, mixes pre- timing
Between after add higher alcohol, obtain 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 crosses and metal oxide nano particles dispersion liquid is added in the nano-metal particle solution, added after mixing the predetermined time
Higher alcohol to get arrive compound ink.Due to the metallic particles under nano-scale can external electromagnetic wave to specific wavelength excitation
Resonance is generated, to achieve the effect that enhance signal, therefore, when the compound ink containing higher alcohol 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；Further, the higher alcohol can effectively avoid
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.
The solvent in nano-metal particle solution that present embodiment provides is basic organic solvent, and nano-metal particle is molten
Basic organic solvent in liquid is identical as the basic organic solvent range of choice in metal oxide nano particles dispersion liquid, preferably
Ground, the basic organic solvent are one of alkane halogeno-benzene class, halogenated naphthalenes and lower alcohols solvent or a variety of.
Specifically, since there is the coin race metallic particles under nano-scale the excitation to the external electromagnetic wave of specific wavelength to produce
Raw resonance, to reach the feature of enhancing signal effect.In one embodiment, receiving in the nano-metal particle solution
Rice metallic particles is spheric granules, with isotropism, that is to say, that the identical spheric granules of these shapes is receiving the external world
The resonance wave generated after the excitation of electromagnetic wave uniformly dissipates in all directions of space, and the light of sending is uniform；Simultaneously
Since nano-metal particle is spheric granules, regular shape, the resonance excited by the nano metal simple substance spheric granules
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,
The diameter of the limited nano metal spherical shape particle of present embodiment is 2-100nm, in the range, when nano metal spherical
When the diameter of grain is bigger, formant is mobile to long wave direction, when the diameter of nano metal spherical shape particle is smaller, formant
It is mobile to shortwave direction.In practical applications, the nano metal spherical shape particle of suitable size can be selected to make according to actual needs
Standby corresponding luminescent device.
In the actual production process of device, some devices need to be simultaneously emitted by multiwave light, in order to realize
Pass through localized plasmon resonance effect enhances the light of different-waveband simultaneously, and the nano metal that present embodiment uses is aspherical
Grain shape, preferably, the aspherical particle shape includes nanometer rods, nano wire, nanometer square and nanometer tetragonal body
Deng, but not limited to this.Specifically, the nano metal aspherical particle that the present invention uses has anisotropic feature, also
It is to say that these different aspherical nano-metal particles can excite the different-waveband i.e. light of different colours simultaneously；By these
Different aspherical nano-metal particle and the available multiwave amplification material of metal oxide semiconductor combination collocation
Material.
Similarly, present embodiment can also exist by adjusting the adjustable formant of size of nano metal aspherical particle
Position spectrally, in the present embodiment, the partial size of 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 metal oxidation
Composition granule includes nano nickel oxide particles, nanoscale molybdenum oxide particle, nano oxidized tungsten particle, nano granular of zinc oxide, nano oxygen
Change titanium particle or Nano granules of stannic oxide etc., but not limited to this.
In the metal oxide semiconductor, wherein nano nickel oxide particles, nanoscale molybdenum oxide particle and nano oxidized
Tungsten particle is P-type semiconductor nano particle；Nano granular of zinc oxide, nano titania particle and Nano granules of stannic oxide are N-type
Semiconductor.By taking P-type semiconductor nickel oxide as an example, nickel oxide as a kind of wide-band gap material, have outstanding chemical stability with
And excellent light, electricity and magnetic performance, in thin-film solar cells, organic film light emitting diode and quantum dot film
In light emitting diode, there is extensive and deep application as hole transmission layer.By taking N-type semiconductor zinc oxide as an example, zinc oxide
It is a kind of wide-band gap material, forbidden energy gap is about 3.37eV at room temperature, and exciton binding energy is high, and light transmittance is high, resistance is small
And there is excellent light, electricity and magnetic performance, therefore zinc oxide is in photoelectric conversion and opto-electronic device (such as thin film solar electricity
Pond, organic film light emitting diode and quantum dot film light emitting diode) in, also have as electron transfer layer extensive and deep
The application entered.
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 one embodiment, by the way that P-type semiconductor metal oxide (nickel oxide) particle dispersion is added to institute
It states in nano-metal particle solution, higher alcohol is added to get the P-type semiconductor metal oxygen containing higher alcohol is arrived after mixing 20-30h
The compound ink of compound-nano-metal particle；The preferred incorporation time of present embodiment is 24-26h, by P made from mixing 24-26h
Type metal oxide semiconductor-compound ink of nano-metal particle is used to prepare hole transmission layer and/or the hole injection of device
Layer, that is to say, that the P-type semiconductor metal oxide-compound ink of nano-metal particle can be individually used for preparing device
Hole transmission layer or hole injection layer, or it is used to prepare the hole injection layer and hole transmission layer of device simultaneously.Through the invention
The hole transmission layer and/or hole injection layer of compound ink preparation can effectively facilitate the compound of hole and electronics, and make from
The light that luminescent layer issues, after hole transmission layer and/or hole injection layer, light intensity is effectively amplified, to promote device
Luminous efficiency.
In another embodiment, by the way that N-type nano-metal-oxide (zinc oxide) particle dispersion is added to institute
It states in nano-metal particle solution, higher alcohol is added to get the N-type semiconductor metal oxygen containing higher alcohol is arrived after mixing 20-30h
The compound ink of compound-nano-metal particle；The preferred incorporation time of present embodiment is 24-26h, by N made from mixing 24-26h
Type metal oxide semiconductor-compound ink of nano-metal particle is used to prepare the electron transfer layer and/or electron injection of device
Layer, that is to say, that the N-type semiconductor metal oxide-compound ink of nano-metal particle can be individually used for preparing device
Electron transfer layer and/or electron injecting layer, or it is used to prepare the electron transfer layer and/or electron injecting layer of device simultaneously.Pass through
The electron transfer layer and/or electron injecting layer of the present invention compound ink preparation can effectively facilitate the transmission in hole, and make from
The light that luminescent layer issues, after electron transfer layer and/or electron injecting layer, light intensity is effectively amplified, to promote device
Luminous efficiency.
Further, in the step S20, semiconductor nano metal oxide particle is dispersed in basic organic solvent
In, obtain nano-metal-oxide dispersion liquid；Specifically, during preparing compound ink, the group of ink itself is pairs of
Performance in printing technology has a very important influence, in the present invention, the basic organic solvent in the preferably described compound ink
Including alkane, halogeno-benzene class, halogenated naphthalenes or lower alcohols solvent etc., but not limited to this.
Specifically, the alkane is the isomerism of n-hexane, the isomer of n-hexane, normal heptane, normal heptane
The isomer of body, normal octane or normal octane；The halogenated benzene kind solvent is chlorobenzene, o-dichlorohenzene, m-dichlorobenzene or to two
Chlorobenzene；The lower alcohol solvent is methanol, ethyl alcohol, normal propyl alcohol, isopropanol, n-butanol, 2- butanol, the tert-butyl alcohol or 2- methyl-1-
Propyl alcohol；The halogenated naphthalenes are chlorinated naphthalene, bromination naphthalene or iodate naphthalene etc..
The basic organic solvent has good peptizaiton to semiconductor metal oxide nano particles, can obtain
The solution for obtaining clear avoids blocking printer nozzle, can guarantee the stability of prepared compound ink；
Further, the basic organic solvent will not increase considerably the surface potential energy between composite material granular, and at
It is easy to be detached from composite material when film, close structure can be constituted between composite material granular molecule, so that composite ink
MJPZ better performances；Simultaneously as the basic organic solvent can not dissolve the sull to have formed a film, therefore this hair
The compound ink of bright preparation will not cause to damage when printing multilayer grading structure to understructure.
To advanced optimize InkJet printing processes, present embodiment adds by the metal oxide nano particles dispersion liquid
Enter into the nano-metal particle aqueous solution and after mixing the predetermined time, joined higher alcohol；By the way that the higher alcohol is added
The filming performance of compound ink can effectively be promoted.Specifically, the higher alcohol and lower alcohol molecule can form partially azeotropic
Object combination so that compound ink be not easy it is too fast can send out, cause solute to be precipitated to effectively contain that compound ink condenses at nozzle
The problem of plug nozzle, while azeotropic mixture combination also can avoid compound ink in the drying process, because too fast volatilization is formed
Local turbulence disturb the composite material that not yet forms 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, containing described in present embodiment adjusting
The viscosity of the compound ink of higher alcohol is 3-15cP and/or surface tension is 28-36mN/m, and saturated vapor pressure is lower than 0.02kPa.
It is preferred that the viscosity of the compound ink containing higher alcohol is 6-12cP, surface tension 29-33mN/m, saturated vapor pressure is lower than
0.01kPa in the range by the physical property setting of the compound ink of contained higher alcohol may make that composite ink water energy is enough suitable
Answer ink-jet and ink droplet volatilization in printing technology to solidify qualitative demand, and can avoid compound ink can not spray in nozzle, ink
A variety of the phenomenon that of being unfavorable for printing such as drop size unevenness, hangover and coffee ring.
Further, the concentration of the compound ink containing higher alcohol of present embodiment preparation is in 1-100mg/
Between ml, the concentration refers to the total concentration in a solvent of all solutes in compound ink, and the solute includes nanometer
Metal oxide particle and nano-metal particle；In the compound ink containing higher alcohol, nano-metal particle and nanometer
The ratio between mole of metal oxide particle is 1:(1-1000).Specifically, in order to guarantee the compound ink have surface
The semiconductor property of metal oxide itself, the present embodiment preferably described nanogold are not influenced while resonant check effect again
The ratio between mole of metal particles and metal oxide nano particles is 1:(10-400), preferably, to receive in the proportional region
Rice metal oxide particle is largely still exposed in dicyandiamide solution, to fully ensure that the dispersibility of compound ink.
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 containing higher alcohol is between 10-60mg/ml, print performance is preferable.
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 use any one of the above to contain higher alcohol
Compound ink is prepared.
Specifically, the carrier blocking layers include electron transfer layer, hole transmission layer, the carrier injection layer packet
Include electron injecting layer, hole injection layer.Electronic work ergosphere (including electron transfer layer and electron injecting layer) and hole functional layer (packet
Include hole transmission layer and hole injection layer) the not ipsilateral of luminescent layer is set, 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 using the compound ink preparation of above-mentioned P-type semiconductor metal oxide-nano-metal particle containing higher alcohol
It forms, that is to say, that the P-type semiconductor metal oxide containing the higher alcohol-compound ink of nano-metal particle can be independent
It is used to prepare the hole transmission layer or hole injection layer of device, or is used to prepare the hole injection layer and hole transport of device simultaneously
Layer.
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 use the above-mentioned N-type semiconductor metal oxygen containing higher alcohol
The compound ink of compound-nano-metal particle is prepared, that is to say, that the N-type semiconductor metal oxide-nano metal
The compound ink of grain 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 should including the nano granular of zinc oxide and nano-Ag particles being dispersed in ethyl alcohol and 1,4-butanediol
The preparation method of compound ink includes:
100ml is prepared, concentration is the ethanol solution of the nano granular of zinc oxide of 20mg/ml；
10ml is prepared, concentration is the ethanol solution of the nano-Ag particles of 3mg/ml；
With vigorous stirring, the ethanol solution of nano-Ag particles is added dropwise into the ethanol solution of nano granular of zinc oxide, and
Continue stirring at room temperature 24 hours to get the compound ink of nano-Ag particles-nano zine oxide；
It washs the compound ink of the nano-Ag particles-nano zine oxide repeatedly with propyl alcohol 3 times, is then dispersed again with ethyl alcohol, by
The 1,4-butanediol of 50ml is added dropwise to get the compound ink of nano-Ag particles-nano zine oxide containing 1,4-butanediol, it is described
The viscosity that compound ink measures at 25 DEG C is 8.32cP.
By the compound ink of above-mentioned nano-Ag particles-nano zine oxide and contain nano-Ag particles-nanometer of 1,4- butanediol
Zinc oxide composite ink water deposits film forming, the compound ink of nano-Ag particles-nano zine oxide containing 1,4-butanediol respectively
Film formation surface roughness Ra is 0.035 μm, and the nano-Ag particles-nano zine oxide composite ink MJPZ surface roughness Ra is
5 μm。
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 blue quantum dot；Above-mentioned nano-Ag particles-nanometer containing 1,4- butanediol is printed on the quantum dot layer
The compound ink of zinc oxide makes electron transfer layer；Ag electrode is made, QLED device, the luminescent spectrum figure of the QLED device are obtained
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 above-mentioned nano silver
The compound ink of grain-nano zine oxide is prepared.The luminescent spectrum figure of QLED device prepared by comparative example 1 is as shown in Figure 2.According to
Fig. 2 is it is found that can enhance the luminous intensity of QLED device by the electron transfer layer of this compound ink preparation.
QLED device made by embodiment 1 and comparative example 1 is carried out test comparison discovery: embodiment 1 is compared to comparison
Example 1, luminescence generated by light conversion quantum efficiency (PLQY) improves 25.4%, and electroluminescence quantum transfer efficiency (EQE) improves
45%；Illustrate that the movement for inhibiting ink solute in volatilization process is added in 1,4-butanediol, promotes the uniform journey that device is made
Degree, prevent mistake closs packing of the metallic particles on shaping membrane and caused by SPE Quenching.
Embodiment 2
A kind of compound ink should including the nano granular of zinc oxide and nanogold particle being dispersed in ethyl alcohol and 1,3-BDO
The preparation method of compound ink includes:
100ml is prepared, concentration is the ethanol solution of the nano granular of zinc oxide of 16mg/ml；
10ml is prepared, concentration is the ethanol solution of the nanogold particle of 20mg/ml；
With vigorous stirring, the ethanol solution of nanogold particle is added dropwise into the ethanol solution of nano granular of zinc oxide, and
Continue stirring at room temperature 24 hours to get the compound ink of nanogold particle-nano zine oxide；
It washs the compound ink of the nanogold particle-nano zine oxide repeatedly with propyl alcohol 3 times, is then dispersed again with ethyl alcohol, by
The 1,3-BDO of 50ml is added dropwise to get the compound ink of nanogold particle-nano zine oxide containing 1,3-BDO, it is described
The viscosity that compound ink measures at 25 DEG C is 8.50cP.
By the compound ink of above-mentioned nanogold particle-nano zine oxide and nanogold particle-nanometer containing 1,3 butylene glycol
Zinc oxide composite ink water deposits film forming, the compound ink of nanogold particle-nano zine oxide containing 1,3-BDO respectively
Film formation surface roughness Ra is 1 μm, and the nanogold particle-nano zine oxide composite ink MJPZ surface roughness Ra is 5 μ
m。
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 blue quantum dot；Above-mentioned nanogold particle-nanometer containing 1,3 butylene glycol is printed on the quantum dot layer
The compound ink of zinc oxide makes electron transfer layer；Ag electrode is made, QLED device, the luminescent spectrum figure of the QLED device are obtained
As shown in Figure 3.
Comparative example 2
A kind of preparation method of QLED device, the difference is that, electron transfer layer uses above-mentioned nanogold with embodiment 2
The compound ink of grain-nano zine oxide is prepared.The luminescent spectrum figure of QLED device prepared by comparative example 2 is as shown in Figure 3.According to
Fig. 3 is it is found that can enhance the luminous intensity of QLED device by the electron transfer layer of this compound ink preparation.
QLED device made by embodiment 2 and comparative example 2 is carried out test comparison discovery: embodiment 2 is compared to comparison
Example 2, luminescence generated by light conversion quantum efficiency (PLQY) improves 25%, and electroluminescence quantum transfer efficiency (EQE) improves
23.9%；Illustrate that the movement for inhibiting ink solute in volatilization process is added in 1,3-BDO, promotes the uniform journey that device is made
Degree, prevent mistake closs packing of the metallic particles on shaping membrane and caused by SPE Quenching.
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 containing higher alcohol is after solvent anneal volatilization, semiconductor nano metal
Oxide and the nano-metal particle can not will lead to the optical quenching of luminescent material with split-phase；And it is described to contain higher alcohol
Compound ink in nano-metal particle have surface enhanced resonant effect, the hair of LED device can be obviously improved
Light efficiency；Further, higher alcohol can effectively avoid compound ink can not be sprayed in nozzle, droplet size is uneven, hangover and
Coffee ring etc. is a variety of to be unfavorable for the phenomenon that printing.
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 (13)
1. a kind of compound ink, which is characterized in that nano-metal particle and nano metal oxygen including being dispersed in the mixed solvent
Compound particle, the mixed solvent include basic organic solvent and higher alcohol solvent.
2. compound ink according to claim 1, which is characterized in that the basic organic solvent be alkane halogeno-benzene class,
One of halogenated naphthalenes and lower alcohols solvent are a variety of.
3. compound ink according to claim 2, which is characterized in that the lower alcohol solvent is methanol, ethyl alcohol, positive third
Alcohol, isopropanol, n-butanol, 2- butanol, the tert-butyl alcohol or 2- methyl-1-propyl alcohol, the alkane be n-hexane, same point of n-hexane it is different
Structure body, normal heptane, the isomer of normal heptane, normal octane or normal octane isomer, the halogenated benzene kind solvent is
Chlorobenzene, o-dichlorohenzene, m-dichlorobenzene or paracide.
4. compound ink according to claim 1, which is characterized in that the higher alcohol is 1,2- butanediol, 1,3- fourth two
Alcohol, 1,4- butanediol, 2,3- butanediol, 1,5- pentanediol, glycerine, 1,2,4- butantriol or 1,2,3- butantriol.
5. 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.
6. compound ink according to claim 1, which is characterized in that the nano-metal particle is spheric granules.
7. compound ink according to claim 6, which is characterized in that the diameter of the spheric granules is 2-100nm.
8. 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.
9. compound ink according to claim 8, which is characterized in that the grain of at least one dimension of aspherical particle
Diameter is 2-100nm.
10. 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.
11. compound ink according to claim 1, which is characterized in that the concentration of the compound ink is 1-100mg/ml.
12. 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 basic organic solvent, metal oxide nano particles dispersion liquid is obtained；
The metal oxide nano particles dispersion liquid is added in the nano-metal particle solution, after mixing the predetermined time
Higher alcohol is added, compound ink is obtained.
13. 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 injection layer and/or carrier blocking layers using the compound ink preparation of any one in the claim 1-11 and
At.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711007450.3A CN109705664A (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 |
|---|---|---|---|
| CN201711007450.3A CN109705664A (en) | 2017-10-25 | 2017-10-25 | A kind of compound ink and preparation method thereof, device |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109705664A true CN109705664A (en) | 2019-05-03 |
Family
ID=66253387
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711007450.3A Pending CN109705664A (en) | 2017-10-25 | 2017-10-25 | A kind of compound ink and preparation method thereof, device |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109705664A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110733178A (en) * | 2019-10-28 | 2020-01-31 | 季华实验室 | aerosol jet printing method and system for volatile ink |
| 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 |
| CN111276623A (en) * | 2020-01-19 | 2020-06-12 | 中国工程物理研究院流体物理研究所 | Modified hole transport layer and blue-light perovskite light-emitting diode based on same |
| CN113054125A (en) * | 2021-03-11 | 2021-06-29 | 武汉华星光电半导体显示技术有限公司 | Display panel, preparation method thereof and display device |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105131712A (en) * | 2015-07-28 | 2015-12-09 | Tcl集团股份有限公司 | Quantum dot printing ink and preparation method thereof, and quantum dot light emitting diode |
| CN105778619A (en) * | 2014-12-17 | 2016-07-20 | 中国科学院苏州纳米技术与纳米仿生研究所 | Polymer-nanometer metal oxide composite ink, and preparation method and application thereof |
| 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 |
| CN106876599A (en) * | 2017-03-10 | 2017-06-20 | 纳晶科技股份有限公司 | Inorganic metal compound, the composition containing it, device and device and preparation method |
| 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 CN201711007450.3A patent/CN109705664A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105778619A (en) * | 2014-12-17 | 2016-07-20 | 中国科学院苏州纳米技术与纳米仿生研究所 | Polymer-nanometer metal oxide composite ink, and preparation method and application thereof |
| CN105131712A (en) * | 2015-07-28 | 2015-12-09 | Tcl集团股份有限公司 | Quantum dot printing ink and preparation method thereof, and quantum dot light emitting diode |
| 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 |
| CN106876599A (en) * | 2017-03-10 | 2017-06-20 | 纳晶科技股份有限公司 | Inorganic metal compound, the composition containing it, device and device and preparation method |
| 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 |
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 |
| CN110733178A (en) * | 2019-10-28 | 2020-01-31 | 季华实验室 | aerosol jet printing method and system for volatile ink |
| CN111276623A (en) * | 2020-01-19 | 2020-06-12 | 中国工程物理研究院流体物理研究所 | Modified hole transport layer and blue-light perovskite light-emitting diode based on same |
| CN113054125A (en) * | 2021-03-11 | 2021-06-29 | 武汉华星光电半导体显示技术有限公司 | Display panel, preparation method thereof and display device |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Xuan et al. | Inkjet-printed quantum dot color conversion films for high-resolution and full-color micro light-emitting diode displays | |
| CN109705664A (en) | A kind of compound ink and preparation method thereof, device | |
| Sarma et al. | Fabrication of Ag/ZnO heterostructure and the role of surface coverage of ZnO microrods by Ag nanoparticles on the photophysical and photocatalytic properties of the metal-semiconductor system | |
| Alamri et al. | Fully inkjet-printed photodetector using a graphene/perovskite/graphene heterostructure | |
| Li et al. | Recent progress in silver nanowire networks for flexible organic electronics | |
| Wang et al. | Original core–shell structure of cubic CsPbBr3@ amorphous CsPbBr x perovskite quantum dots with a high blue photoluminescence quantum yield of over 80% | |
| Zhang et al. | Increasing photoluminescence quantum yield by nanophotonic design of quantum-confined halide perovskite nanowire arrays | |
| CN105062193B (en) | Printing ink composition and electronic device | |
| US8080322B2 (en) | Light emitting device having high luminous efficiency and high stability | |
| Kim et al. | Inkjet printing of transparent InZnSnO conducting electrodes from nano-particle ink for printable organic photovoltaics | |
| CN107275499A (en) | A kind of light emitting diode with quantum dots and preparation method thereof | |
| CN102558954B (en) | Preparation method for nano-copper ink applied to printed electronics | |
| CN109705663A (en) | A kind of compound ink and preparation method thereof, device | |
| CN109705660A (en) | A kind of compound ink and preparation method thereof, device | |
| 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 | |
| CN109387896A (en) | A kind of quantum dot color filter film based on local surface plasma resonance | |
| CN109705661A (en) | A kind of compound ink and preparation method thereof, device | |
| US20200373508A1 (en) | Electroluminescent material ink and electroluminescent device thereof | |
| CN110970569B (en) | Quantum dot light-emitting diode and preparation method thereof | |
| 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 | |
| CN108795154A (en) | Zinc oxide base nano particle ink | |
| CN109705666A (en) | A kind of compound ink and preparation method thereof, device | |
| Lee | Designing of low-cost, eco-friendly, and versatile photosensitive composites/inks based on carboxyl-terminated quantum dots and reactive prepolymers in a mixed solvent: suppression of the coffee-ring strain and aggregation |
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 |