CN103241025A - Ink jet printing method of organic thin film - Google Patents

Ink jet printing method of organic thin film Download PDF

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Publication number
CN103241025A
CN103241025A CN2013101562482A CN201310156248A CN103241025A CN 103241025 A CN103241025 A CN 103241025A CN 2013101562482 A CN2013101562482 A CN 2013101562482A CN 201310156248 A CN201310156248 A CN 201310156248A CN 103241025 A CN103241025 A CN 103241025A
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China
Prior art keywords
printed substrate
substrate
printing
print
inkjet printing
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CN2013101562482A
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Chinese (zh)
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CN103241025B (en
Inventor
王向华
邱龙臻
刘则
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京东方科技集团股份有限公司
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Priority to CN201310156248.2A priority Critical patent/CN103241025B/en
Publication of CN103241025A publication Critical patent/CN103241025A/en
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B41PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41MPRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00Duplicating or marking methods; Sheet materials for use therein
    • B41M5/0041Digital printing on surfaces other than ordinary paper
    • B41M5/0064Digital printing on surfaces other than ordinary paper on plastics, horn, rubber, or other organic polymers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B41PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41JTYPEWRITERS; SELECTIVE PRINTING MECHANISMS, e.g. INK-JET PRINTERS, THERMAL PRINTERS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
    • B41J11/00Devices or arrangements of selective printing mechanisms, e.g. ink-jet printers, thermal printers, for supporting or handling copy material in sheet or web form
    • B41J11/0015Devices or arrangements of selective printing mechanisms, e.g. ink-jet printers, thermal printers, for supporting or handling copy material in sheet or web form for treating before, during or after printing or for uniform coating or laminating the copy material before or after printing
    • B41J11/002Curing or drying the ink on the copy materials, e.g. by heating or irradiating
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B41PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41MPRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00Duplicating or marking methods; Sheet materials for use therein
    • B41M5/0011Pre-treatment or treatment during printing of the recording material, e.g. heating, irradiating
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B41PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41MPRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00Duplicating or marking methods; Sheet materials for use therein
    • B41M5/0041Digital printing on surfaces other than ordinary paper
    • B41M5/0047Digital printing on surfaces other than ordinary paper by ink-jet printing
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L51/00Solid state devices using organic materials as the active part, or using a combination of organic materials with other materials as the active part; Processes or apparatus specially adapted for the manufacture or treatment of such devices, or of parts thereof
    • H01L51/0001Processes specially adapted for the manufacture or treatment of devices or of parts thereof
    • H01L51/0002Deposition of organic semiconductor materials on a substrate
    • H01L51/0003Deposition of organic semiconductor materials on a substrate using liquid deposition, e.g. spin coating
    • H01L51/0004Deposition of organic semiconductor materials on a substrate using liquid deposition, e.g. spin coating using printing techniques, e.g. ink-jet printing, screen printing
    • H01L51/0005Deposition of organic semiconductor materials on a substrate using liquid deposition, e.g. spin coating using printing techniques, e.g. ink-jet printing, screen printing ink-jet printing

Abstract

The invention relates to the technical field of ink jet printing, and discloses an ink jet printing method of an organic thin film. The ink jet printing method comprises the following steps of: regulating the surface energy of a printing substrate; and printing the organic thin film on the printing substrate so that liquid drops positioned on the printing substrate are uniformly spread. The technical scheme is as follows: the surface energy of the printing substrate is regulated so that the printing substrate is suitable for the spreading of the liquid drops, so that the thickness uniformity of the printed thin film is enhanced, and the quality of an ink jet pattern is greatly enhanced. Besides, the invention also provides a column gap changed print mode, and the column gap changed print mode solves the problem of nonuniform thickness of the printed thin film.

Description

A kind of inkjet printing methods of organic film
Technical field
The present invention relates to the inkjet technology field, particularly relate to a kind of inkjet printing methods of organic film.
Background technology
Inkjet technology is owing to have efficient, low-cost, noncontact form and flexible characteristics such as process, therefore, the pattern that adopts inkjet printing to form is widely used in the processing of organic electronic device, by the printing function Polymer Solution, inkjet printing has been realized functional polymer depositing of thin film and patterning, and realized the processing of Organic Light Emitting Diode, OTFT (Organic Thin Film Transistor is called for short OTFT) and integrated device thereof.
Inkjet printing generally adopts the mode of the overlapping covering of ink droplet to form continuous film.Compare with printing single-point or single line bar pattern, the technology that forms the large tracts of land continuous film by the overlapping covering of multi-line causes uneven film thickness easily, problems such as discontinuous or pattern deformation.At this problem, prior art adopts the variation of underlayer temperature to control the dry run of ink, realizes printing continuous organic film.Under low excessively underlayer temperature, print the small molecule organic semiconductor ink, the pattern of printing can cause pattern deformation in dry run, too high underlayer temperature then easily causes film discontinuous, therefore adopt suitable underlayer temperature can reduce pattern deformation to a certain extent, obtain continuously film uniformly simultaneously.But when utilizing this control underlayer temperature method to print large area film, print speed is often slow, and especially under the lower situation of underlayer temperature, and the rising underlayer temperature can bring the low problem of thin film crystallization degree.Therefore in inkjet printing technology, the scope of regulating underlayer temperature is more limited.
The difference of two kinds of solvent compositions on surface tension adopts the ink of mixed solvent, owing to can cause the kalimeris dagger-axe Buddhist nun convection current (Marangoni convection) of drop inside.Under the situation that the simplest single ink droplet is printed, along with solvent evaporates, the movement of the circular ink droplet on the substrate and the contact wire of substrate is isotropic retreating normally, after solute concentration reaches certain threshold value, contact wire stops mobile, solute begins to form film to the centre by self assembly from the edge, and the shape of film and pattern ratio is easier to control in this case.But under the situation of printing lines or two-dimensional film, ink droplet overlaps each other.Printing the starting stage, the solvent on the substrate passes through to print additional speed greater than the speed of solvent evaporates, and is printing the later stage, and the speed of solvent evaporates speed and solute crystalline growth all increases because of the increase of liquid surface area.In this case, geometry and the microscopic appearance of control film need carry out dynamic adjustments to the self assembly environment.For example print in the technology of a lines shape in one way, near the lines initiating terminal film is thicker than terminal, and degree of crystallinity is generally also than higher, mainly be because, the rapid crystallization of solute causes concentration gradient in the ink dried process, and drives the solute molecule directional migration.At the different parts of printing lines, cause the variation of assembling speed or even the change of growth pattern owing to body is different, therefore, cause thickness and the pattern inequality of film.
As shown in Figure 1, the inkjet printing mode of prior art, needs according to graphic printing, be organic semiconductor layer between source electrode 13 and the drain electrode 15 as print area 14, the nozzle 12 of shower nozzle 11 lower ends can be according to certain frequency continuous injection ink droplets, spacing between the drop point that the drop point that last dropping liquid drips and back one dropping liquid drip is dot spacing, in this explanation, the lines of printing along Y-direction are row, the lines of printing along directions X are row, and printing along Y-direction once is a stroke, and shower nozzle 11 is at first printed row along Y-direction during printing, move a column pitch along directions X again, print next column along Y-direction again, so repeatedly, form the printing film of certain area, prior art adopts the movement of substrate to realize the movement of Y-direction and directions X more, and the translational speed of substrate and displacement are determined according to the dot spacing of ink dot.Usually the dot spacing of printing all is identical in directions X and Y-direction.Under the enough little situation of dot spacing, can form continuous film.When printing the organic film of certain width, need a plurality of strokes just can print the film of enough width, in the print procedure of longer stroke, because the rate of drying of ink is very fast relatively, usually the problem of Chu Xianing is can appearance between the adjacent lines discontinuous overlapping or inhomogeneous.
As the above analysis, by existing inkjet technology, can exist film in uneven thickness, film is discontinuous or the problem of pattern deformation.
Summary of the invention
The purpose of this invention is to provide a kind of inkjet printing methods, in order to improving the uniformity of film thickness, and then improve the quality of ink-jetting pattern.
The inkjet printing methods of organic film of the present invention comprises:
The surface of regulating printed substrate can;
Print organic film in printed substrate, make drop uniform spreading on printed substrate.
Preferably, describedly make the drop uniform spreading on printed substrate be specially, make that the liquid-drop diameter of sprawling on printed substrate is 2~4 times of spherical droplets diameter of printer nozzle ejection.
Preferably, the surface of described adjusting printed substrate can be specially on the printed substrate surface and form surface energy gradient along the print line direction or perpendicular to the print line direction.
Preferable, described formation surface can gradient comprise:
Carry out fluorination treatment to printing substrate surface;
By the stereo mask version, carry out the UV ozone cleaning to printing substrate surface, described stereo mask version comprises the mask version substrate with a plurality of openings and is arranged at the fin of each opening part of mask version substrate, the angle on plane, described fin place and plane, mask version substrate place is 10 °~100 °, the zone that needs to print organic film on the corresponding printed substrate of described opening, when through described stereo mask version printed substrate being carried out the UV ozone cleaning, the zone that needs on the printed substrate to print organic film forms surface energy gradient.
Preferably, described adjusting printed substrate surface can be specially printed substrate is carried out hydrophobic treatment and/or hydrophilic treated.Described hydrophobic treatment can adopt fluorination treatment, makes substrate surface form hydrophobic surface; Described hydrophilic treated can adopt UV ozone to clean, make substrate surface form water-wetted surface, according to the ink of ink-jet and the surface property of substrate, substrate is carried out hydrophobic treatment and/or hydrophilic treated, make substrate surface and ink match, make ink carry out suitable sprawling at substrate surface.
Preferable, described printed substrate is carried out hydrophobic treatment and/or hydrophilic treated is specially:
Printed substrate is carried out fluorination treatment, make the printed substrate surface present hydrophobicity; And/or
Printed substrate is carried out UV ozone clean, make the printed substrate surface present hydrophily.
Preferably, to above-mentioned inkjet printing methods, described organic film adopts and becomes column pitch printing formation.
Preferable, the column pitch that described change column pitch is printed successively decreases according to the sequencing of print line.For example, suppose that column pitch is N liquid-drop diameter doubly, N is positive integer, then become column pitch that column pitch prints can according to the N of liquid-drop diameter doubly, N-1 doubly, N-2 doubly successively decreases until 1 times rule, that is, first row of printing are N liquid-drop diameter doubly with the column pitch of secondary series, and the secondary series of printing and tertial column pitch are N-1 liquid-drop diameter doubly etc., the lines of printing are initial more loose in printing, printing the later stage comparatively dense.
To above-mentioned inkjet printing methods, described organic film adopts the one way multiple row to print and forms.
Be example to adopt 10 skins to rise printing head, be that the volume V that shower nozzle sprays single drop is 10 skin liters, about 20 microns of diameter, the print line spacing that described one way multiple row is printed is 5~50 microns (μ m), for example column pitch can be 5 microns, 10 microns, 15 microns, 20 microns, 25 microns, 30 microns, 45 microns, 50 microns, and the print line spacing can equate with the dot spacing of printing, also can not wait with the print point spacing, preferably, column pitch equates with dot spacing.Under the printing head printing situation of other sizes, dot spacing is proportional to the cubic root of the spherical droplets volume of nozzle ejection, perhaps is proportional to the diameter of the spherical droplets of nozzle ejection.Preferably, the dot spacing of printing lines is equal at directions X and Y-direction, and suitable with the diameter of spherical droplets.
Preferably, described one way multiple row prints to one way three row printings.
Preferable, described organic film also adopts and becomes the printing of stroke spacing.
Inkjet printing methods of the present invention can be applied to the making of the organic film in the FPD, also can be applied to the making of the organic film in the solar panel, also can be applied to the making of organic film in other photoelectron product.
In inkjet printing methods of the present invention, adopt the form of regulating printed substrate surface energy to control drop the sprawling on the printed substrate surface of ink-jet, make drop even at the surface spreading of printed substrate, therefore, make organic film thickness evenly and can improve the quality of the pattern that organic film forms.
Description of drawings
Fig. 1 is the inkjet printing methods schematic diagram of prior art;
Fig. 2 is the inkjet printing methods first embodiment schematic diagram of the present invention;
Fig. 3 is the photo of the organic film of inkjet printing methods first embodiment printing of the present invention;
Fig. 4 is the photo of the organic film of existing inkjet printing methods first Comparative Examples printing;
Fig. 5 is the photo of the organic film of existing inkjet printing methods second Comparative Examples printing;
Fig. 6 is the photo of the organic film of inkjet printing methods second embodiment printing of the present invention;
Fig. 7 is the schematic diagram of inkjet printing methods the 3rd embodiment printing type of the present invention;
Fig. 8 is the photo of the organic film of inkjet printing methods the 3rd embodiment printing of the present invention;
Fig. 9 is inkjet printing methods the 4th embodiment schematic diagram of the present invention;
Figure 10 is inkjet printing methods the 5th embodiment schematic diagram of the present invention.
Reference numeral:
11-shower nozzle 12-nozzle 13-source electrode 14-print area 15-drain electrode
16-stereo mask version 17-through hole 18-fin 19-printed substrate
The specific embodiment
In order to improve printing effect, improve the quality of printing organic film, the invention provides a kind of inkjet printing methods of organic film.In this technical scheme, adopt the form of regulating printed substrate surface energy to control drop the sprawling on the printed substrate surface of ink-jet, make drop even at the surface spreading of printed substrate, therefore, make organic film thickness evenly and can improve the quality of the pattern that organic film forms.For making the purpose, technical solutions and advantages of the present invention clearer, by the following examples the present invention is described in further detail.
The inkjet printing methods of embodiment of the invention organic film comprises:
The surface of regulating printed substrate can;
Print organic film in printed substrate, make drop uniform spreading on printed substrate.
In embodiments of the present invention, if pattern itself has graded, surface such as non-parallel raceway groove or graded can be to the ink-jet drop generation effect of its top, appropriately utilize this effect can effectively overcome film pattern and pattern variation that the solute molecule directional migration brings, preferably, describedly make the drop uniform spreading on printed substrate be specially, when the printed substrate surface of regulating can make the liquid-drop diameter of sprawling on printed substrate be 2~4 times of spherical droplets diameter of printer nozzle ejection, the uniformity of film and the effect of pattern are best, the printing head that rises with 10 skins is example, the diameter of single spherical droplets that is the nozzle ejection of shower nozzle is about 20 μ m, after regulating the surface of printed substrate, make that the diameter of the drop sprawled in printed substrate is 40~80 μ m, such drop is sprawled and is conducive at the printed substrate surface filming, therefore, can adopt the surface of regulating printed substrate can overcome film pattern and pattern variation that the solute molecule directional migration brings, make film thickness even, and then improve the quality of ink-jetting pattern.
Preferably, the surface of described adjusting printed substrate can be specially on the printed substrate surface and form surface energy gradient along the print line direction or perpendicular to the print line direction.Preferable, described formation surface can gradient comprise:
Carry out fluorination treatment to printing substrate surface;
By the stereo mask version, carry out the UV ozone cleaning to printing substrate surface, described stereo mask version comprises the mask version substrate with a plurality of openings and is arranged at the fin of each opening part of mask version substrate, the angle on plane, described fin place and plane, mask version substrate place is 10 °~100 °, the zone that needs to print organic film on the corresponding printed substrate of described opening, when through described stereo mask version printed substrate being carried out the UV ozone cleaning, the zone that needs on the printed substrate to print organic film forms surface energy gradient.
In embodiments of the present invention, the mode that forms surface energy gradient has multiple, the preferred stereo mask version with opening and fin that adopts is handled printed substrate, because to the partial occlusion effect of open area, making, fin needs to form on the zone of printing organic film the surface energy with certain gradient.
Preferably, described adjusting printed substrate surface can be specially printed substrate is carried out hydrophobic treatment and/or hydrophilic treated.Described hydrophobic treatment can adopt fluorination treatment, makes substrate surface form hydrophobic surface; Described hydrophilic treated can adopt UV ozone to clean, make substrate surface form water-wetted surface, according to the ink of ink-jet and the surface property of substrate, substrate is carried out hydrophobic treatment and/or hydrophilic treated, make substrate surface and ink match, make ink carry out suitable sprawling at substrate surface.
In embodiments of the present invention, because the surface of some printed substrate can be not suitable for directly carrying out inkjet printing, therefore, adopt fluorination treatment to form hydrophobic substrate surface, adopt UV ozone to clean again and form to have certain hydrophilic substrate surface that is suitable for printing organic film.
Preferably, described organic film adopts and becomes column pitch printing formation.Preferable, the column pitch that described change column pitch is printed successively decreases according to the sequencing of print line.
In the existing inkjet printing technology, the column pitch that constitutes the multi-line of film equates, just controls the dot spacing of printing list lines usually, two kinds of disadvantageous situations usually occur.A kind of situation be the ink dried film forming procedure from around to the centre development, finally the film quality that forms at the middle section of film is relatively poor; Another kind of situation be if Print direction from left to right, film drying and forming-film from left to right then, but the migration that solute can right-to-left simultaneously causes a film thickness left side high right low, is accompanied by the sudden change of film morphology toward contact.Both of these case all can cause uniformity of film and material property to descend, and perhaps causes available effective film area significantly to reduce.Although can be by increasing print area and adopt suitable pattern shift impressing pattern thin-film device, significant limitation the efficient of impressing pattern film.
In embodiments of the present invention, can adopt the printing technique that becomes column pitch, for example, in the process of printing the large area film pattern from left to right, setting the column pitch of printing from left to right reduces gradually, so just can prevent effectively that the high right low phenomenon in a left side from appearring in film, can make film thickness more even, make the pattern of film more even.Adopt the printing technique of one way multiple row and change column pitch, not only can print extensive continuous film expeditiously, and can effectively solve the even problem of uneven film thickness.
To above-mentioned inkjet printing methods, described organic film adopts the one way multiple row to print and forms.
In embodiments of the present invention, adopt multiple row to print the mode of a stroke, avoided existing single-row printing to occur the even problem of uneven film thickness easily, and improved printing effect.For the mode that the one way multiple row is printed, the printer that can adopt is the printer with a plurality of shower nozzles side by side, and the nozzle of a plurality of shower nozzles side by side sprays ink droplet simultaneously and realizes the multiple row printing.
Preferably, described organic film also adopts and becomes the printing of stroke spacing.
In embodiments of the present invention, the stroke spacing of stroke and next stroke can be identical, also can be different, and also similar with becoming column pitch when the stroke spacing is successively decreased according to the sequencing of printing stroke, can effectively solve the even problem of uneven film thickness.
Be example to adopt 10 skins to rise printing head, be that the volume V that shower nozzle sprays single drop is 10 skin liters, preferably, the print line spacing that described one way multiple row is printed is 5~50 microns (μ m), and for example column pitch can be 5 microns, 10 microns, 15 microns, 20 microns, 25 microns, 30 microns, 45 microns, 50 microns.Under the situation of other printing head sizes, column pitch is proportional to the cubic root of single droplet size.
Preferably, described one way multiple row prints to one way three row printings.The one way multiple row is printed and can be printed three row by a stroke, also can print two row by a stroke, also can print four row by a stroke, also can print five row by a stroke, determine according to the stroke of printing that generally the columns that the one way of the more long needs of the stroke of printing is printed is just more many.
Inkjet printing methods of the present invention can be applied to the making of the organic film in the FPD, also can be applied to the making of the organic film in the solar panel, also can be applied to the making of organic film in other photoelectron product.
Below enumerate specific embodiment inkjet printing methods of the present invention is described, following examples are example to adopt 10 skins to rise printing head all, i.e. the diameter of the spherical droplets of nozzle ejection is about 20 μ m.
Embodiment 1
Present embodiment adopts one way multiple row printing type to print organic film, and the surface of regulating printed substrate before printing organic film can, adopting many shower nozzles to realize that multiple rows print, below is that example describes with the OTFT of contact at the bottom of many shower nozzles inkjet printing.
Present embodiment adopts many shower nozzles to print, as shown in Figure 2, the space periodic that shower nozzle 11 is arranged along directions X is the print line spacing, and the injection of the nozzle 12 of each shower nozzle 11 is controlled by pulse voltage waveform independent of each other respectively according to identical frequency and definite phase difference.
Printed substrate has the silicon chip (silicon chip surface growth thickness in advance is the thermal oxidation silicon of 300nm) of gold (Au) electrode for preparation, requirement is printed poly-3-hexyl thiophene and (is abbreviated P3HT as between source electrode 13 and drain electrode 15, a kind of organic polymer semiconductor) ink solution, solvent is o-dichlorohenzene, and the concentration of poly-3-hexyl thiophene is 0.25~0.75wt.%.
Because the hydrophily of thermal oxidation silicon substrate is very strong, is unfavorable for inkjet printing, therefore at first regulate the surface energy of printed substrate:
Step 1, fluorination treatment silicon chip preferably adopt dry fluorination process to handle (FDTS), make silicon chip surface present hydrophobicity;
Step 2, put the silicon chip after the fluorination treatment into the UV ozone cleaning machine, 35 ℃ of temperature are set, time 8min finishes UV ozone automatically by start key and cleans, and makes silicon chip surface present certain hydrophily;
Step 3, as shown in Figure 2, inkjet printing P3HT film forms organic semiconductor layer in the source electrode 13 of end contact OTFT device and the print area 14 between the drain electrode 15.Diameter with the spherical droplets of nozzle 12 ejection of shower nozzle 11 is that 20 μ m are example, and through to after printing substrate processing, between 40~80 μ m, and the drop size is even at diameter behind the printed substrate surface spreading for single drop.Adopt three shower nozzles 11 to print three row simultaneously in embodiments of the present invention, the column pitch of setting is single liquid-drop diameter, is 20 μ m, and the width that one way is printed just covers 45 microns parallel channel.
The optical photograph of the OTFT device of the end contact that forms after the ink dried of Fig. 3 for the three row printings of employing one way.By this photo as can be seen, the linear pattern of print area is better, and pattern is even, and deformation does not take place.
Fig. 4 is the optical photograph after TIPS pentacene (full name is 6, two (the tri isopropyl silane ethyl-acetylene base) pentacenes of the 13-) ink dried that adopts the single-row printing of prior art one way.Can be seen that by this photo adjacent two row of printing exist part overlapping, can not form film well.
As seen, under the situation that adopts single-row printing, need the film that a plurality of strokes just can print enough width to cover channel region, usually the problem of Chu Xianing be can occur between the adjacent lines discontinuous overlapping, and adopt multiple row to print can to avoid discontinuous overlapping between the lines, improve uniformity of film.
Embodiment 2
Present embodiment adopts the mode that becomes column pitch to print rectangular film, and regulates the surface energy of printed substrate before printing organic film.
When the solute molecule in the ink in the crystallization rate on the substrate under the situation of solvent evaporates speed, the crystallization of solute molecule causes that solute molecule along the migration of the opposite direction of directions X, produces harmful effect to film shape and pattern.In order to overcome this solute migration effect, except improving temperature, can also adopt the Method of printing that becomes column pitch, be characterized in constant along the dot spacing of Y-direction, still the column pitch along directions X is gradual change.
The surface of regulating silicon oxide substrate according to step 1 and step 2 among the embodiment 1 can, diameter with the spherical droplets of nozzle 12 ejection of shower nozzle 11 is that 20 μ m are example, after to the printing substrate processing, between 40~80 μ m, and drop size evenly at diameter behind the printed substrate surface spreading for single drop.Fig. 5 adopts conventional Method of printing, and namely directions X is identical with the Y-direction dot spacing, adopts 15 μ m respectively, three bar shaped TIPS pentacene thin film that the dot spacing of 10 μ m and 5 μ m is printed.By photo as can be seen three strip films be not the rectangle of rule, and all have figure variation in various degree.Be illustrated in figure 6 as two films that adopt the Method of printing printing that becomes column pitch, specifically adopted the Y-direction dot spacing of 15 μ m, the diameter of the spherical droplets of dot spacing and nozzle ejection is suitable, the column pitch of directions X according to the sequencing of print line from 60 μ m, 45 μ m, 30 μ m reduce successively to 15 μ m.Film shape shown in Figure 6 is the rectangle of rule, is consistent with the print pattern of setting as seen.
Embodiment 3
Present embodiment adopts the one way multiple row and becomes the printing type printing rectangular film of stroke spacing.Wherein the one way multiple row is printed and is adopted many shower nozzles to print, and the stroke spacing here refers to the spacing of an one way multiple row stroke of printing and next stroke.
The extensive array pattern that repeats is directly proportional with the shower nozzle quantity that Y-direction is printed stroke and employing simultaneously as the printing effect of the drive circuit OTFT array of FPD.Adopt print pattern shown in Figure 7, be characterized in constant along the dot spacing of Y-direction, the stroke spacing of directions X is also fixed, but the column pitch along directions X is periodically variable, and Figure 7 shows that example, unit pattern is made up of three sections lines, each lines constitutes by the row dot matrix part of three row Y-directions is overlapping, every section lines adopt three shower nozzles to print simultaneously, and each shower nozzle can be printed row dot matrix lines, and a unit pattern adopts three shower nozzles to print simultaneously needs to print three strokes.By increasing unit pattern at the repetition period of Y-direction number, can improve printing effect.But the repetition period number is subjected to ink dried speed and the restriction of the shower nozzle quantity of use simultaneously.Suitably increase the shower nozzle quantity of using simultaneously, can corresponding increase unit pattern along the repetition period number of Y-direction, thereby significantly improve the efficient of printing large scale array.Shown in Figure 8 is is printed on PVP(poly-(4-vinylphenol)) the rectangle TIPS pentacene thin film unit pattern of organic film array on the dielectric substrate, the overlapping formation of thick lines that film is printed by four three shower nozzles, continuous and fine and close.But can see that still solute has the tendency that is moved to the left, namely the pattern left side is outstanding.Spacing between the thick lines also can be gradual change, be example with three lines shown in Figure 7, suitably increase from left to right article one thick line and the distance of second thick line, namely increase the stroke spacing of first stroke and second stroke, be conducive to suppress solute and move left and form the left side and give prominence to.
Embodiment 4
Present embodiment adopts the one way multiple row to print, and printed substrate is the non-parallel raceway groove OTFT with how much gradients.
As shown in Figure 9, adopt the source electrode 13 of trapezoidal finger-shaped and drain electrode 14 structures of trapezoidal finger-shaped, be characterized in the width gradual change pointed, the print area 14 between the finger is that channel width is also along the directions X gradual change.Print procedure with OTFT device architecture of this non-parallel raceway groove can utilize the flow direction of the geometry gradient control ink of pattern, suppresses the directional migration of solute.Therefore, adopt one way multiple row printing type, be specially and adopt many shower nozzles to print, and adopt the print pattern of periodicity change spacing as shown in Figure 7 to print.
Embodiment 5
In the process of the organic semiconductor layer of printing OTFT, the direction that the film of organic semiconductor layer is grown in being parallel to the plane of substrate surface has decisive role to the performance of OTFT device, and needing that in this case substrate surface is handled the formation surface can gradient.
Present embodiment adopts the one way multiple row to print, namely adopt many shower nozzles to realize the multiple row printing, and the surface of at first regulating printed substrate can, make that the dispersive component of surface energy and the excursion of polar component are 0~50 milli ox/rice, diameter with the spherical droplets of nozzle 12 ejection of shower nozzle 11 is that 20 μ m are example, through to after printing substrate processing, between 40~80 μ m, and the drop size evenly at diameter behind the printed substrate surface spreading for single drop.The size of surface energy is the algebraical sum of dispersive component and polar component.The surface can gradient can be the surface can size or two components in one or all along directions X or along Y-direction graded trend is arranged.
Forming the surface on the printed substrate surface can gradient specifically comprise:
As shown in figure 10, printed substrate 19 can be elected oxidized silicon chip as, prepare the thin film transistor (TFT) array with top contact at this oxidized silicon chip, at first need prepare the organic semiconductor layer between source electrode and drain electrode, before the preparation organic semiconductor, fluorination treatment is carried out on printed substrate 19 surfaces, be specially in printed substrate 19 surperficial self assembly perfluor dodecyl trichlorosilane monolayers, obtain hydrophobic printed substrate surface; Then by stereo mask version 16, optionally UV ozone cleaning is carried out on printed substrate 19 surfaces, rectangular through-hole 17 projections of stereo mask version 16 form rectangular projection region in printed substrate 19, need print the organic semiconductor layer of thin film transistor (TFT) in this rectangular projection region, the sheet metal of perk on the stereo mask version 16, it is fin 18, can be designed as a angle in 10 °~100 ° scopes with the angle α of mask version substrate, for example angle α is 10 °, 20 °, 30 °, 40 °, 50 °, 80 °, 85 °, 90 ° or 100 °.When the rectangular projection region corresponding with through hole 17 carried out the UV ozone surface clean on by 17 pairs of printed substrate of rectangular through-hole, because the partial occlusion effect of fin 18, the rectangular projection region on printed substrate 19 surfaces has the surface energy of graded after UV ozone is cleaned, as shown in figure 10, the from left to right hydrophily of each rectangular projection region increases gradually, be that the surface can raise gradually, so just each rectangular projection region at substrate surface has formed surperficial energy gradient.
After printed substrate forms surface energy gradient, adopt many shower nozzles to print the ink that is used to form organic semiconductor layer in each rectangular projection region one way multiple row, can utilize this surface gradient to be controlled by the organic semiconductor thin-film of inkjet printing, improve the technology stability of printing film and the distribution of dwindling film performance, reduce the technology cost.In embodiments of the present invention, the surface on the printed substrate surface from the source electrode to drain electrode can reduce gradually or increase gradually, form surface energy gradient, it is single-orientated that such surface can gradient can make that the molecularly oriented in the ink forms, and then improved the electric conductivity between source electrode and the drain electrode.Certainly, the surface that forms on printed substrate surface can gradient can be adjusted and optimizes according to the performance of thin-film device.
The described method of utilizing the stereo mask version to form surface energy gradient of this embodiment is not limited to the combination of above-mentioned processing step, can also be the combination of other surface treatment methods.The stereo mask version is applicable to dry method gas phase surface treatment (cleaning plasma surface treatment as UV ozone), also is applicable to optical treatment (as ultraviolet lighting).Regulate the surface treatment of dry method gas phase at the variable gradient of the action intensity of exposed region by the fin of design and the angle of mask version substrate, in addition, the size of the fin of perk and shape are variable, the quantity of fin and position also are variable, can be provided with symmetrical two fins such as each rectangular through-hole.So just can be applied to realize the pattern of different graded.
Five embodiment that more than enumerate are unconventional inkjet printing mode and combination thereof, physical property according to ink, the characteristics of backing material and pattern, adopt above-mentioned different printing type and combination, can overcome in the ink dried process solute migration to the adverse effect of film morphology, improve uniformity and the repeatability of printing the large tracts of land continuous film, improve and print accuracy and optimize film morphology; Also can realize the flying print of large scale array.
Obviously, those skilled in the art can carry out various changes and modification to the present invention and not break away from the spirit and scope of the present invention.Like this, if of the present invention these are revised and modification belongs within the scope of claim of the present invention and equivalent technologies thereof, then the present invention also is intended to comprise these changes and modification interior.

Claims (11)

1. the inkjet printing methods of an organic film is characterized in that, comprising:
The surface of regulating printed substrate can;
Print organic film in printed substrate, make drop uniform spreading on printed substrate.
2. inkjet printing methods as claimed in claim 1 is characterized in that, describedly makes the drop uniform spreading on printed substrate be specially, and makes that the liquid-drop diameter of sprawling in printed substrate is 2~4 times of spherical droplets diameter of printer nozzle ejection.
3. inkjet printing methods as claimed in claim 1 is characterized in that, the surface of described adjusting printed substrate can be specially on the printed substrate surface and form surface energy gradient along the print line direction or perpendicular to the print line direction.
4. inkjet printing methods as claimed in claim 3 is characterized in that, described formation surface can gradient comprise:
Carry out fluorination treatment to printing substrate surface;
By the stereo mask version, carry out the UV ozone cleaning to printing substrate surface, described stereo mask version comprises the mask version substrate with a plurality of openings and is arranged at the fin of each opening part of mask version substrate, the angle on plane, described fin place and plane, mask version substrate place is 10 °~100 °, the zone that needs to print organic film on the corresponding printed substrate of described opening, when through described stereo mask version printed substrate being carried out the UV ozone cleaning, the zone that needs on the printed substrate to print organic film forms surface energy gradient.
5. inkjet printing methods as claimed in claim 1 is characterized in that, described adjusting printed substrate surface can be specially carries out hydrophobic treatment and/or hydrophilic treated to printed substrate.
6. inkjet printing methods as claimed in claim 5 is characterized in that, described printed substrate is carried out hydrophobic treatment and/or hydrophilic treated is specially:
Printed substrate is carried out fluorination treatment, make the printed substrate surface present hydrophobicity; And/or
Printed substrate is carried out UV ozone clean, make the printed substrate surface present hydrophily.
7. as each described inkjet printing methods of claim 1~6, it is characterized in that described organic film adopts and becomes column pitch printing formation.
8. inkjet printing methods as claimed in claim 7 is characterized in that, the column pitch that described change column pitch is printed successively decreases according to the sequencing of print line.
9. as each described inkjet printing methods of claim 1~6, it is characterized in that described organic film adopts the one way multiple row to print and forms.
10. inkjet printing methods as claimed in claim 9 is characterized in that, described one way multiple row prints to one way three row and prints.
11. inkjet printing methods according to claim 9 is characterized in that, described organic film also adopts and becomes the printing of stroke spacing.
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