CN109651882A - A kind of inkjet printing hole injection layer ink and its application in organic light emitting display - Google Patents
A kind of inkjet printing hole injection layer ink and its application in organic light emitting display Download PDFInfo
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- CN109651882A CN109651882A CN201811580156.6A CN201811580156A CN109651882A CN 109651882 A CN109651882 A CN 109651882A CN 201811580156 A CN201811580156 A CN 201811580156A CN 109651882 A CN109651882 A CN 109651882A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/17—Carrier injection layers
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/10—Deposition of organic active material
- H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
- H10K71/13—Deposition of organic active material using liquid deposition, e.g. spin coating using printing techniques, e.g. ink-jet printing or screen printing
- H10K71/135—Deposition of organic active material using liquid deposition, e.g. spin coating using printing techniques, e.g. ink-jet printing or screen printing using ink-jet printing
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/10—Organic polymers or oligomers
- H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
- H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
- H10K85/1135—Polyethylene dioxythiophene [PEDOT]; Derivatives thereof
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Abstract
The invention discloses a kind of inkjet printing hole injection layer ink and its applications in organic light emitting display.The ink is mixed with by PEDOT aqueous solution and isopropanol.The ink becomes PEDOT film since the region of ink-jet printer organic light emitting display pixel on the substrate by oxygen plasma treatment and carbon tetrafluoride plasma treatment carries out inkjet printing.PEDOT ink composition of the invention and preparation method are simple, and auxiliary solvent nature is stablized, and content is low and volatility is stronger, and removings is easily dried after printing-filming, and will not cause PEDOT film surface coarse since drying time is too long and electric property changes etc..PEDOT film uniformity with higher avoids the generation of coffee ring effect without apparent intermediate thin, the phenomenon of edge thickness.And improve the insulated column height of etching and the matching of multiple functional layers.It has a good application prospect.
Description
Technical field
The invention belongs to inkjet printing organic light emitting display technical fields.It is related to a kind of inkjet printing hole injection layer ink
Water and its application in organic light emitting display.
Background technique
Organic light-emitting diode display (OLED) has the characteristics that ultrathin flexible, wide viewing angle, high contrast, low energy consumption, quilt
It is considered to substitute the next-generation flat panel display of liquid crystal.The processing cost of inkjet printing organic light emitting display is low and production efficiency
Height is that industrial circle generally acknowledges most potential advanced lines organic light emitting display panel volume production processing technology.
OLED is generally included: substrate, the hole injection layer on anode, is set to hole note at the anode on substrate
Enter the hole transmission layer on layer, the luminescent layer on hole transmission layer, the electron transfer layer on luminescent layer and is set to electricity
Cathode (as shown in Fig. 1) in sub- transport layer, includes multiple functional layers.The principle of luminosity of OLED display device is semiconductor
Material and luminous organic material pass through carrier injection and composite guide photoluminescence under electric field driven.OLED display device is usual
Using ITO pixel electrode and metal electrode respectively as the anode and cathode of device, under certain voltage driving, electrons and holes
It is injected into electron transfer layer and hole transmission layer from cathode and anode respectively, electrons and holes pass through electron transfer layer and sky respectively
Cave transport layer moves to luminescent layer, and meets in luminescent layer, forms exciton and excites light emitting molecule, the latter relaxes through overshoot
Henan and issue visible light.
OLED device is most common the preparation method comprises the following steps: hole injection layer, hole transmission layer and luminescent layer use inkjet printing
Method preparation.Inkjet printing methods are that functional material ink is instilled scheduled pixel region using single or multiple spray heads,
Later by film needed for dry obtain, this method has many advantages, such as that stock utilization is high, at low cost.
I.e. inkjet printing organic light emitting display is using the picture that shines in inkjet printing technology processing organic light emitting display panel
Plain unit.The high performance organic light emitting display panel of inkjet printing, it is important to guarantee the thickness of function film in print pixel unit
Spend uniformity, such as hole injection layer, three primary colours organic luminous layer, electron injecting layer.Film in homogeneous thickness is to improve display
The efficient lighting area of panel pixel improves the uniformity of panel luminance and the key of service life.
In the actual operation process, usually there is coffee ring effect in the film of inkjet printing, form that thin film center is thin and side
The non-uniform phenomenon of edge thickness.In inkjet printing organic light emitting display, generallys use insulated column limit ink and freely sprawl, to drop
The size of low print pixel structure, improves the resolution ratio of display panel.Meniscus effect of the ink under insulated column limitation is injected,
Also uneven film thickness can be caused even.And insulated column height while cannot meet multiple functional layer marking inks simultaneously
Match.
In order to improve the uniformity of film in inkjet printing pixel unit under insulated column restrictive condition, the patent No.
The U.S. patent Nos of US7102280, it was recently reported that the side to be matched by insulated column height and printing high molecular material quantity of ink
Method, make in marking ink drying process occur gelation when with horizontal meniscus, to obtain thickness after ink dried
Uniform film.Although the technology solves the non-uniformity problem of film to a certain extent, insulated column height cannot
Matching while meeting multiple functional layer marking inks simultaneously.When the type slug of insulated column height and printing hole injection layer ink
When part matches, uniform organic light emitting film is obtained in order to guarantee to continue on hole injection layer printing, it is necessary to organic light emission
The composition and print conditions of material ink carry out necessary adjustment, to increase the matching of itself and insulated column height.This leads to this
Technical application is difficult, and process complexity is high, and it is small to produce adoptable process tolerance.
Summary of the invention
The present invention for the technical issues of be: the prior art is using hole injection layer ink used in inkjet printing methods
Obtained hole injection layer uneven film thickness is even, influences the uniformity and service life of efficient lighting area and panel luminance,
And meniscus effect of the ink under insulated column limitation is injected, further result in the uneven of film thickness.And isolation pillar height
Matching while degree cannot meet multiple functional layer marking inks simultaneously, will affect the uniformity of film of other function layer.Therefore
In ink jet printing process not only by ink-jet printing ink prepare hole injection layer uneven film thickness it is even, as well as every
Multiple functional layers cannot be met simultaneously from pillar height degree and cause the uneven film thickness of other function layer even, further increased pair
The influence of display panel pixel efficient lighting area and panel luminance.
This is to the above problem, and the present invention provides a kind of inkjet printing hole injection layer ink, which has wide
Insulated column height suitability can lead to that is, in the proportional region of broader insulated column height and stamping ink water layer average thickness
It crosses printing and obtains thickness and rise and fall small film.The uniformity that can either be avoided coffee ring effect, guarantee film, but also insulated column
Height can match with multiple functional layers.
Application (i.e. ink the present invention also provides inkjet printing with hole injection layer ink in organic light emitting display
Application in inkjet printing hole injection layer film forming.), this is used, and the uniformity of film obtained after the ink printed is good, makes
The matching degree of insulated column height and multiple functional layers is high, can significantly improve the efficient lighting area of display panel pixel, improves
The uniformity of panel luminance prolongs its service life.
The present invention is achieved by the following technical solutions
A kind of inkjet printing hole injection layer ink, the ink mainly by following volumes percentage raw material preparation and
At: PEDOT aqueous solution 90~97.5%, auxiliary solvent 2.5~10%.
The inkjet printing hole injection layer ink, the auxiliary solvent are isopropanol；
Preferably, the percent by volume of the isopropanol in the ink is 2.5~5%.
The inkjet printing hole injection layer ink, the surface tension of the ink are 40~51mN/m；
Preferably, the surface tension of the ink is 45~51mN/m.
A kind of inkjet printing hole injection layer PEDOT film, the above-mentioned inkjet printing hole injection layer ink of the film
Inkjet printing forms.
The inkjet printing hole injection layer PEDOT film, it is described to be carried out by inkjet printing hole injection layer with ink
The method of inkjet printing the following steps are included:
(1) ratio as requested prepares raw material isopropanol and PEDOT aqueous solution, and isopropanol and PEDOT aqueous solution are mixed
It closes uniformly, that is, forms PEDOT ink；
(2) insulated column figure is processed on substrate；
(3) oxygen plasma treatment is carried out first to the substrate that machined insulated column figure, then carry out carbon tetrafluoride etc. from
Subprocessing obtains region (region i.e. between insulated column, the anode region of insulated column surface hydrophobicity and organic light emitting display pixel.)
Hydrophilic substrate；
(4) it will be packed into ink-jet print system after PEDOT ink filter that step (1) obtains, then plays PEDOT ink
The region of organic light emitting display pixel hydrophilic on substrate is printed to, PEDOT ink is by obtaining thickness after evaporation gel, drying
Uniform PEDOT film, completes the inkjet printing of the ink.
The inkjet printing hole injection layer PEDOT film processes the tool of insulated column figure on step (2) described substrate
Body process are as follows: use sol evenning machine spin coating photoresist on ito glass substrate, carry out uv-exposure processing using litho machine, then
Develop, rinsed using deionized water, is dried with nitrogen, insulated column pattern can be obtained；
Specifically: sol evenning machine spin coating photoresist on ito glass substrate is used, heats 4min in 165 DEG C of thermal station, room temperature is cold
But after, uv-exposure processing, time for exposure 65s are carried out using litho machine；It is placed in 110 DEG C of thermal station again and heats 4min, room temperature is cold
But after, develop, 30~40s of developing time is rinsed using deionized water, is dried with nitrogen, and insulated column pattern can be obtained；
Preferably, the revolving speed in spin coating process is 1500~2500rpm, and revolving speed changes at room temperature in different.
The inkjet printing hole injection layer PEDOT film, the width of gained insulated column are 50 μm, between insulated column
Groove width is 200 μm, and the height of the insulated column is 2.0~2.5 μm.
The inkjet printing hole injection layer PEDOT film, oxygen flow when step (3) described oxygen plasma treatment
28sccm/s, power 100w, time 150s-210s；Carbon tetrafluoride flow 98sccm/s when carbon tetrafluoride plasma treatment, function
Rate 150w, time 60s-90s；
After plasma treatment, the height of gained insulated column is 1.5~2.0 μm；
After step (3) graphics process to insulated column, the water contact angle on gained insulated column surface is greater than 90 °；On substrate
Less than 25 ° (water contact angles in the region i.e. between insulated column of the water contact angle in the region of organic light emitting display pixel.)；
Preferably, the water contact angle on gained insulated column surface is greater than 110 ° after processing.
The inkjet printing hole injection layer PEDOT film, when step (4) the PEDOT ink filter use 0.2
μm nylon micro porous filter membrane is filtered；Hydrophilic organic light emitting display pixel in step (4) the PEDOT ink printed to substrate
Region when, ink layer thickness and the insulated column height ratio after plasma treatment printed in region is (3~7): 1；
Drying described in step (4) is to heat 4min in 200 DEG C of thermal station.
Above-mentioned inkjet printing hole injection layer ink and the inkjet printing hole injection layer PEDOT film are organic
Application in luminescence display.
PEDOT ink of the present invention by the method for inkjet printing, print on substrate insulated column and insulated column it
Between organic light emitting display pixel region, by drying and forming-film (gained film have good uniformity, avoid centre
The generation of coffee ring effect thin, edge is thick), obtain hole injection layer, i.e., hole injection layer material is poly- (3,4- enedioxies
Thiophene)-polystyrolsulfon acid (English name: Poly (3,4-ethylenedioxythiophene) Polystyrene
Sulfonate, abbreviation PEDOT).
Compared with prior art, the present invention has following positive beneficial effect
PEDOT ink of the invention can obtain in the proportional region of bigger insulated column height and ink layer average thickness
Thickness rises and falls smaller PEDOT film, gained film uniformity with higher, and without apparent intermediate thin, edge is thick shows
As avoiding the generation of coffee ring effect.
And in fixed insulated column height, the thickness range for obtaining uniform PEDOT film is bigger.Or identical
Under the thickness condition of PEDOT film, selectable insulated column altitude range is wider.Therefore, need to design insulated column height with
Printing organic luminous layer ink it is flux matched to realize organic luminous layer in homogeneous thickness printing when, using PEDOT ink of the invention
Water can relax the restriction to the optional range of insulated column height, increase the matching of insulated column height and luminous organic material ink,
The tolerance of whole printing technology design is improved, efficiently solving insulated column height cannot ask with what multiple functional layers matched
Topic；
Meanwhile PEDOT ink composition and preparation method of the invention is simple, auxiliary solvent nature is stablized, and content is low and volatilizees
Property is stronger, removing is easily dried after printing-filming, and will not cause PEDOT film surface coarse and electric since drying time is too long
The problems such as learning performance change.
Detailed description of the invention
Fig. 1 is common OLED structure figure；
Fig. 2 is the molecular structure of PEDOT；
Inkjet printing PEDOT ink film forming procedure when Fig. 3 is matched height needed for insulated column height is equal to PEDOT ink
Schematic diagram；Wherein (a) is the pixel electrode surface process schematic that printed droplets alignment deposits between insulated column, is (b) ink
The dry schematic diagram for forming PEDOT film of water.
The meaning of symbol in figure are as follows: 1 is substrate, and 2 be insulated column, and 3 be the meniscus for printing PEDOT ink, and 4 be PEDOT
Height when gelation occurs for ink, and 5 be the height of dry PEDOT film；H indicates insulated column height；
Fig. 4 is ink film forming procedure schematic diagram when insulated column height is greater than PEDOT ink match height, wherein (a) is pure
Water is the commercial PEDOT ink of solvent, (b) is PEDOT ink of the present invention.Relative to commercialization ink, ink of the present invention it is curved
Month face curvature is small, and the smaller PEDOT film of thickness fluctuating can be obtained in greater area of ratio；
Fig. 5 is ink film forming procedure schematic diagram when insulated column height is less than PEDOT ink match height, wherein (a) is pure
Water is the commercial PEDOT ink of solvent, (b) is PEDOT ink of the present invention.Relative to commercialization ink, ink of the present invention it is curved
Month face curvature is small, and the smaller PEDOT film of thickness fluctuating can be obtained on bigger area ratio；
Fig. 6 is the collecting method schematic diagram for printing the fluctuating measurement of PEDOT film thickness；
Fig. 7 is the thickness test data that the embodiment of the present invention and comparative example print PEDOT film.
Specific embodiment
The present invention is described in more details below by specific embodiment, but be not intended to restrict the invention
Protection scope.
Print system used in following embodiment is the AD-P- of Microdrop Technologies company, Germany
8000 professional print systems.The photoresist is the negative photoresist of U.S. Futurrex company, model NR71-
1500PY.The PEDOT aqueous solution is purchased from Heraeus company, Germany, model CleviosTM(PEDOT's P VP AI 4083 exists
Content in aqueous solution is 1.3~1.7wt%), the molecular structure of PEDOT material is as shown in Fig. 1.
The process that inkjet printing PEDOT ink forms PEDOT film is as shown in Fig. 2: PEDOT ink passes through inkjet printing
System forms the drop of micron-scale and is aligned the region for depositing to the pixel of the organic light emitting display on substrate 1 between insulated column 2
Surface (i.e. anode surface) is then isolated the limitation of column 2 and only sprawls in anode surface, forms the ink bent moon with certain curvature
Face 3.When printing PEDOT quantity of ink and when insulated column matched, with marking ink evaporation and gelation occurs, gel is high
Degree 4 is contour with insulated column 2, can dry and (heat 4min in 200 DEG C of thermal station) the smooth PEDOT film 5 of formation under this condition.
Attached drawing 3 and attached drawing 4 are respectively matched height required for PEDOT ink of the insulated column height larger and smaller than printing
When the case where.PEDOT ink of the invention has lower surface tension, therefore the meniscus relative to commercialization PEDOT water
Curvature is smaller, and the smaller PEDOT film of thickness fluctuating can be obtained on bigger area ratio, improves printing PEDOT film
Uniformity.
Attached drawing 5 gives the collecting method of printing PEDOT uniformity of film characterization:
Wherein w1 is the width for printing PEDOT film.
A point is PEDOT thin film center point, and the distance w2 to PEDOT film edge is equal to 0.5w1.
The distance of B1 point and B2 point to A point is w3, numerically equal to 0.4w1.
In the present invention, PEDOT film with a thickness of the film thickness numerical value at A point, film height relief is A dot thickness
The difference of the average value of numerical value and B1 and B2 point PEDOT film thickness.With the size characterization film thickness of film height relief
Uniformity.
The present invention provides a kind of inkjet printing hole injection layer inks, and the ink is mainly by following volumes percentage
Raw material is prepared: PEDOT aqueous solution 90~97.5%, auxiliary solvent 2.5~10%；The auxiliary solvent is isopropanol.
Preferably, the percent by volume of the isopropanol in the ink is 2.5~5%.
The surface tension of the gained ink jet ink for printing is 40~51mN/m；
Preferably, the surface tension of the ink jet ink for printing is 45~51mN/m.
The present invention also provides a kind of inkjet printing hole injection layer PEDOT film, the above-mentioned inkjet printing of the film is empty
Cave implanted layer is printed with ink jet.
The present invention also provides a kind of inkjet printing hole injection layer PEDOT films to be carried out using above-mentioned ink-jet printing ink
The method of inkjet printing, comprising the following steps:
(1) ratio as requested prepares raw material isopropanol and PEDOT aqueous solution, and isopropanol and PEDOT aqueous solution are mixed
It closes uniformly, that is, forms PEDOT ink；
(2) insulated column figure is processed on substrate；
Specifically: sol evenning machine spin coating photoresist on ito glass substrate is used, heats 4min in 165 DEG C of thermal station, room temperature is cold
But after, uv-exposure processing, time for exposure 65s are carried out using litho machine；It is placed in 110 DEG C of thermal station again and heats 4min, room temperature is cold
But after, develop, 30~40s of developing time is rinsed using deionized water, is dried with nitrogen, and insulated column pattern can be obtained；
Preferably, the revolving speed in spin coating process is 1500~2500rpm；Since photoetching adhesiveness is related with temperature, this turn
Speed changes at room temperature in different.
More there is choosing, the revolving speed in spin coating process is 2100rpm.
The width of gained insulated column is 50 μm, and the groove width between insulated column is 200 μm, and the height of the insulated column is
2.0~2.5 μm；
Preferably, the height of gained insulated column is 2.3 μm.
(3) oxygen plasma treatment is carried out first to the substrate that machined insulated column figure, then carry out carbon tetrafluoride etc. from
Subprocessing obtains region (region i.e. between insulated column, the anode region of insulated column surface hydrophobicity and organic light emitting display pixel.)
Hydrophilic substrate；
Oxygen flow 28sccm/s when the oxygen plasma treatment, power 100w, time 150s-210s；Carbon tetrafluoride
Carbon tetrafluoride flow 98sccm/s, power 150w, time 60s-90s when plasma treatment；
After plasma treatment, the height of gained insulated column is 1.5~2.0 μm；
Preferably, after plasma treatment, the height of gained insulated column is 1.8 μm.
After insulated column graphics process, the water contact angle on gained insulated column surface is greater than 90 °；Organic light emitting display on substrate
Less than 25 ° (water contact angles in the region i.e. between insulated column of the water contact angle in the region of pixel.)；
Preferably, the water contact angle on gained insulated column surface is greater than 110 ° after processing.
(4) it will be packed into ink-jet print system after PEDOT ink filter that step (1) obtains, then plays PEDOT ink
The region of organic light emitting display pixel hydrophilic on substrate is printed to, PEDOT ink is by obtaining thickness after evaporation gel, drying
Uniform PEDOT film, completes the inkjet printing of the ink.
The 0.2 μm of nylon micro porous filter membrane used when the PEDOT ink filter is filtered；The PEDOT ink printed
On to substrate when the region of hydrophilic organic light emitting display pixel, in region print ink layer thickness with pass through plasma treatment
The ratio of gained insulated column height is (3~7) afterwards: 1；
The drying is to heat 4min in 200 DEG C of thermal station.
Above-mentioned inkjet printing hole injection layer ink and the inkjet printing hole injection layer PEDOT film are organic
Application in luminescence display.
Specific embodiment is as follows:
Embodiment 1
A kind of inkjet printing hole injection layer ink, the PEDOT aqueous solution which is 97.5% by percent by volume
The isopropanol for being 2.5% with percent by volume is prepared；
The surface tension of gained ink is 51mN/m.
The ink is mixed evenly by PEDOT aqueous solution and isopropanol and be can be obtained.
Embodiment 2
A kind of inkjet printing hole injection layer ink, the ink by percent by volume be 95% PEDOT aqueous solution and
The isopropanol that percent by volume is 5% is prepared；
The surface tension of gained ink is 45mN/m.
The ink is mixed evenly by PEDOT aqueous solution and isopropanol and be can be obtained.
Embodiment 3
A kind of inkjet printing hole injection layer ink, the PEDOT aqueous solution which is 92.5% by percent by volume
The isopropanol for being 7.5% with percent by volume is prepared；
The surface tension of gained ink is 42mN/m.
The ink is mixed evenly by PEDOT aqueous solution and isopropanol and be can be obtained.
Embodiment 4
A kind of inkjet printing hole injection layer ink, the ink by percent by volume be 90% PEDOT aqueous solution and
The isopropanol that percent by volume is 10% is prepared；
The surface tension of gained ink is 40mN/m.
The ink is mixed evenly by PEDOT aqueous solution and isopropanol and be can be obtained.
The present invention also provides the PEDOT films that the PEDOT ink as described in Examples 1 to 4 carries out inkjet printing formation
(as hole injection layer).
Embodiment 5
Using PEDOT ink described in embodiment 1 carry out inkjet printing formed PEDOT film inkjet printing methods it
One, method includes the following steps:
(1) isopropanol for measuring 0.25 milliliter, is added in 9.75 milliliters of PEDOT aqueous solution, is uniformly mixed, shape
At printable PEDOT ink；
(2) insulated column figure is processed on the substrate of print system: using sol evenning machine spin coating photoresist on ito glass substrate
(revolving speed in spin coating process is 2100rpm), heats 4min in 165 DEG C of thermal station, after room temperature is cooling, is carried out using litho machine purple
Outer exposure-processed, time for exposure 65s；It is placed in 110 DEG C of thermal station again and heats 4min, after room temperature is cooling, developed, developing time
30~40s is rinsed using deionized water, is dried with nitrogen, and insulated column pattern can be obtained；
The width of gained insulated column is 50 μm, groove width between insulated column be 200 μm (highly for plasma etching before
2.3 μm, 1.8 μm after plasma etching)；
(3) oxygen plasma treatment is first carried out to the substrate that machined insulated column figure, then carries out carbon tetrafluoride plasma
Processing, oxygen plasma treatment treatment conditions are as follows: oxygen flow 28sccm/s, power 100w, time 180s, carbon tetrafluoride plasma
Treatment conditions are as follows: carbon tetrafluoride flow 98sccm/s, power 150w, time 60s；
It is 100 ° that insulated column surface water contact angle is obtained after the completion of processing, the region the ITO (anode of organic light emitting display pixel
Region) contact angle of water is 20 ° of substrate；
(4) ink-jet is packed into after filtering the PEDOT ink prepared in step (1) using 0.2 μm of nylon micro porous filter membrane to beat
Then the alignment of PEDOT ink is printed to organic light emitting display pixel region hydrophilic on substrate, controls the ink of printing by print system
The ratio of water layer thickness and insulated column height is (3~7): 1；Gel occurs after marking ink evaporation, is then dried (200
DEG C thermal station heats 4min), dry complete that PEDOT film can be obtained；
Detect according to the film that collecting method described in attached drawing 5 obtains the embodiment: PEDOT film is thick
Degree rises and falls within 9nm, and (ratio of ink layer thickness and insulated column height that control prints is (3 as shown in curve 1 in attached drawing 6
~7): 1 makees curve).
Embodiment 6
Using PEDOT ink as described in example 2 carry out inkjet printing formed PEDOT film inkjet printing methods it
Three, method includes the following steps:
(1) isopropanol for measuring 0.50 milliliter, is added in 9.50 milliliters of PEDOT aqueous solution, is uniformly mixed, shape
At printable PEDOT ink；
(2) insulated column figure is processed on the substrate of print system: using sol evenning machine spin coating photoresist on ito glass substrate
(revolving speed in spin coating process is 2100rpm), heats 4min in 165 DEG C of thermal station, after room temperature is cooling, is carried out using litho machine purple
Outer exposure-processed, time for exposure 65s；It is placed in 110 DEG C of thermal station again and heats 4min, after room temperature is cooling, developed, developing time
30~40s is rinsed using deionized water, is dried with nitrogen, and insulated column pattern can be obtained；
The width of gained insulated column is 50 μm, groove width between insulated column be 200 μm (highly for plasma etching before
2.3 μm, 1.8 μm after plasma etching)；
(3) oxygen plasma treatment is first carried out to the substrate that machined insulated column figure, then carries out carbon tetrafluoride plasma
Processing, oxygen plasma treatment treatment conditions are as follows: oxygen flow 28sccm/s, power 100w, time 150s, carbon tetrafluoride plasma
Treatment conditions are as follows: carbon tetrafluoride flow 98sccm/s, power 150w, time 90s；
It is 110 ° that insulated column surface water contact angle is obtained after the completion of processing, the region the ITO (anode of organic light emitting display pixel
Region) contact angle of water is 25 ° of substrate；
(4) ink-jet is packed into after filtering the PEDOT ink prepared in step (1) using 0.2 μm of nylon micro porous filter membrane to beat
Then the alignment of PEDOT ink is printed to organic light emitting display pixel region hydrophilic on substrate, controls the ink of printing by print system
The ratio of water layer thickness and insulated column height is (3~7): 1；Gel occurs after marking ink evaporation, is then dried (200
DEG C thermal station heats 4min), dry complete that PEDOT film can be obtained；
Detect according to the film that collecting method described in attached drawing 5 obtains the embodiment: PEDOT film is thick
Degree rises and falls within 10nm, and (the ink layer thickness of control printing and the ratio of insulated column height are as shown in curve 2 in attached drawing 6
(3~7): 1 makees curve).
Embodiment 7
Using PEDOT ink described in embodiment 3 carry out inkjet printing formed PEDOT film inkjet printing methods it
Three, method includes the following steps:
(1) isopropanol for measuring 0.75 milliliter, is added in 9.25 milliliters of PEDOT aqueous solution, is uniformly mixed, shape
At printable PEDOT ink；
(2) insulated column figure is processed on the substrate of print system: using sol evenning machine spin coating photoresist on ito glass substrate
(revolving speed in spin coating process is 2100rpm), heats 4min in 165 DEG C of thermal station, after room temperature is cooling, is carried out using litho machine purple
Outer exposure-processed, time for exposure 65s；It is placed in 110 DEG C of thermal station again and heats 4min, after room temperature is cooling, developed, developing time
30~40s is rinsed using deionized water, is dried with nitrogen, and insulated column pattern can be obtained；
The width of gained insulated column is 50 μm, groove width between insulated column be 200 μm (highly for plasma etching before
2.3 μm, 1.8 μm after plasma etching)；
(3) oxygen plasma treatment is first carried out to the substrate that machined insulated column figure, then carries out carbon tetrafluoride plasma
Processing, oxygen plasma treatment treatment conditions are as follows: oxygen flow 28sccm/s, power 100w, time 150s, carbon tetrafluoride plasma
Treatment conditions are as follows: carbon tetrafluoride flow 98sccm/s, power 150w, time 90s；
It is 110 ° that insulated column surface water contact angle is obtained after the completion of processing, the region the ITO (anode of organic light emitting display pixel
Region) contact angle of water is 25 ° of substrate；
(4) ink-jet is packed into after filtering the PEDOT ink prepared in step (1) using 0.2 μm of nylon micro porous filter membrane to beat
Then the alignment of PEDOT ink is printed to organic light emitting display pixel region hydrophilic on substrate, controls the ink of printing by print system
The ratio of water layer thickness and insulated column height is (3~7): 1；Gel occurs after marking ink evaporation, is then dried (200
DEG C thermal station heats 4min), dry complete that PEDOT film can be obtained；
Detect according to the film that collecting method described in attached drawing 5 obtains the embodiment: PEDOT film is thick
Degree rises and falls within 8nm, and (ratio of ink layer thickness and insulated column height that control prints is (3 as shown in curve 3 in attached drawing 6
~7): 1 makees curve).
Embodiment 8
Using PEDOT ink as described in example 4 carry out inkjet printing formed PEDOT film inkjet printing methods it
One, method includes the following steps:
(1) isopropanol for measuring 1.00 milliliters, is added in 9.00 milliliters of PEDOT aqueous solution, is uniformly mixed, shape
At printable PEDOT ink；
(2) insulated column figure is processed on the substrate of print system: using sol evenning machine spin coating photoresist on ito glass substrate
(revolving speed in spin coating process is 2100rpm), heats 4min in 165 DEG C of thermal station, after room temperature is cooling, is carried out using litho machine purple
Outer exposure-processed, time for exposure 65s；It is placed in 110 DEG C of thermal station again and heats 4min, after room temperature is cooling, developed, developing time
30~40s is rinsed using deionized water, is dried with nitrogen, and insulated column pattern can be obtained；
The width of gained insulated column is 50 μm, groove width between insulated column be 200 μm (highly for plasma etching before
2.3 μm, 1.8 μm after plasma etching)；
(3) oxygen plasma treatment is first carried out to the substrate that machined insulated column figure, then carries out carbon tetrafluoride plasma
Processing, oxygen plasma treatment treatment conditions are as follows: oxygen flow 28sccm/s, power 100w, time 150s, carbon tetrafluoride plasma
Treatment conditions are as follows: carbon tetrafluoride flow 98sccm/s, power 150w, time 90s；
It is 110 ° that insulated column surface water contact angle is obtained after the completion of processing, the region the ITO (anode of organic light emitting display pixel
Region) water contact angle be 25 ° of substrate；
(4) ink-jet is packed into after filtering the PEDOT ink prepared in step (1) using 0.2 μm of nylon micro porous filter membrane to beat
Then the alignment of PEDOT ink is printed to organic light emitting display pixel region hydrophilic on substrate, controls the ink of printing by print system
The ratio of water layer thickness and insulated column height is (3~7): 1；Gel occurs after marking ink evaporation, is then dried (200
DEG C thermal station heats 4min), dry complete that PEDOT film can be obtained；
Detect according to the film that collecting method described in attached drawing 5 obtains the embodiment: PEDOT film is thick
Degree rises and falls within 9nm, and (ratio of ink layer thickness and insulated column height that control prints is (3 as shown in curve 4 in attached drawing 6
~7): 1 makees curve).
Comparative example
(1) take commercialization PEDOT aqueous solution as ink；
(2) oxygen plasma treatment is first carried out to the substrate that machined insulated column figure, then carries out carbon tetrafluoride plasma
Processing, oxygen plasma treatment condition are as follows: oxygen flow 28sccm/s, power 100w, time 210s；Carbon tetrafluoride plasma treatment
Condition are as follows: carbon tetrafluoride flow 98sccm/s, power 150w, time 60s, obtaining insulated column surface water contact angle is 90 °, organic
The substrate that the contact angle of the ITO regional water of light emitting display pixels is 15 °；
(3) ink-jet is packed into after filtering the PEDOT ink prepared in step (1) using 0.2 μm of nylon micro porous filter membrane to beat
The alignment of PEDOT ink, is then printed to the region ITO of organic light emitting display pixel hydrophilic on substrate by print system, and control is beaten
The amount of printing ink and the insulated column height ratio after plasma treatment are (3~7): 1, PEDOT film thickness rises and falls as the result is shown
Within 22nm, as shown in curve 5 in attached drawing 6, height relief is significantly greater than ink result obtained of the present invention.
Therefore, ink of the present invention inkjet printing prepare film obtained in hole injection layer process rise and fall it is small,
Thickness is uniform, efficiently solves the problems, such as to prepare the generation that the uneven film thickness is even, avoids coffee ring effect, and make
Insulated column height can match with multiple functional layers, avoid the thickness offset problem of other function layer film.Preparation
Simply, easily controllable, stability is good, have a good application prospect.
Claims (10)
1. a kind of inkjet printing hole injection layer ink, which is characterized in that the ink is mainly by the original of following volumes percentage
Material is prepared: PEDOT aqueous solution 90~97.5%, auxiliary solvent 2.5~10%.
2. inkjet printing hole injection layer ink according to claim 1, which is characterized in that the auxiliary solvent is different
Propyl alcohol；
Preferably, the percent by volume of the isopropanol in the ink is 2.5~5%.
3. inkjet printing hole injection layer ink according to claim 1 or 2, which is characterized in that the table of the ink
Face tension is 40~51mN/m；
Preferably, the surface tension of the ink is 45~51mN/m.
4. a kind of inkjet printing hole injection layer PEDOT film, which is characterized in that film ink-jet as described in claim 1 is beaten
Print hole injection layer is printed with ink jet.
5. inkjet printing hole injection layer PEDOT film according to claim 4, which is characterized in that described to be beaten by ink-jet
Print hole injection layer with ink carry out inkjet printing method the following steps are included:
(1) ratio as requested prepares raw material isopropanol and PEDOT aqueous solution, and isopropanol is mixed with PEDOT aqueous solution
It is even, that is, form PEDOT ink；
(2) insulated column figure is processed on substrate；
(3) oxygen plasma treatment is carried out to the substrate that machined insulated column figure first, is then carried out at carbon tetrafluoride plasma
Reason obtains the substrate of insulated column surface hydrophobicity and the region hydrophilic of organic light emitting display pixel；
(4) it will be packed into ink-jet print system after PEDOT ink filter that step (1) obtains, then arrives PEDOT ink printed
Hydrophilic machine light emitting display pixels region on substrate, PEDOT ink are in homogeneous thickness by obtaining after evaporation gel, drying
PEDOT film completes the inkjet printing of the ink.
6. inkjet printing hole injection layer PEDOT film according to claim 5, which is characterized in that step (2) described base
The detailed process of insulated column figure is processed on plate are as follows: use sol evenning machine spin coating photoresist on ito glass substrate, use litho machine
Uv-exposure processing is carried out, then develops, is rinsed using deionized water, is dried with nitrogen, insulated column pattern can be obtained.
7. inkjet printing hole injection layer PEDOT film according to claim 6, which is characterized in that gained insulated column
Width is 50 μm, and the groove width between insulated column is 200 μm；The height of the insulated column is 2.0~2.5 μm.
8. inkjet printing hole injection layer PEDOT film according to claim 5, which is characterized in that step (3) described oxygen
Oxygen flow 28sccm/s when plasma treatment, power 100w, time 150s-210s；When carbon tetrafluoride plasma treatment
Carbon tetrafluoride flow 98sccm/s, power 150w, time 60s-90s；
After step (3) graphics process to insulated column, the water contact angle on gained insulated column surface is greater than 90 °；It is organic on substrate
The water contact angle in the region of light emitting display pixels is less than 25 °；
Preferably, after plasma treatment, the height of gained insulated column is 1.5~2.0 μm.
9. inkjet printing hole injection layer PEDOT film according to claim 5, which is characterized in that step (4) is described
The 0.2 μm of nylon micro porous filter membrane used when PEDOT ink filter is filtered；Step (4) the PEDOT ink printed is to substrate
When the region of upper hydrophilic machine light emitting display pixels, the ink layer thickness of printing and being isolated after plasma treatment in region
Pillar height degree ratio is (3~7): 1；
Drying described in step (4) is to heat 3~5min in 200 DEG C of thermal station.
10. inkjet printing hole injection layer described in inkjet printing hole injection layer ink and claim 4 described in claim 1
Application of the PEDOT film in organic light emitting display.
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| CN201811580156.6A CN109651882B (en) | 2018-12-24 | 2018-12-24 | Hole injection layer ink for ink-jet printing and application thereof in organic light-emitting display |
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| WO2021031247A1 (en) * | 2019-08-20 | 2021-02-25 | 深圳市华星光电半导体显示技术有限公司 | Ink composition |
| CN112786471A (en) * | 2020-12-30 | 2021-05-11 | 广东聚华印刷显示技术有限公司 | Display panel and method for detecting thickness of display panel |
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