WO2014176845A1 - 有机薄膜的喷墨打印方法 - Google Patents

有机薄膜的喷墨打印方法 Download PDF

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Publication number
WO2014176845A1
WO2014176845A1 PCT/CN2013/081602 CN2013081602W WO2014176845A1 WO 2014176845 A1 WO2014176845 A1 WO 2014176845A1 CN 2013081602 W CN2013081602 W CN 2013081602W WO 2014176845 A1 WO2014176845 A1 WO 2014176845A1
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WIPO (PCT)
Prior art keywords
printing
substrate
film
column
printing substrate
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PCT/CN2013/081602
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English (en)
French (fr)
Inventor
王向华
邱龙臻
刘则
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BOE Technology Group Co Ltd
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BOE Technology Group Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/0041—Digital printing on surfaces other than ordinary paper
    • B41M5/0064—Digital printing on surfaces other than ordinary paper on plastics, horn, rubber, or other organic polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/0011—Pre-treatment or treatment during printing of the recording material, e.g. heating, irradiating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/0041—Digital printing on surfaces other than ordinary paper
    • B41M5/0047—Digital printing on surfaces other than ordinary paper by ink-jet printing
    • 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

Definitions

  • Embodiments of the present invention relate to an inkjet printing method of an organic thin film. Background technique
  • inkjet printing Due to the high efficiency, low cost, non-contact form and flexible processing of inkjet printing technology, patterns formed by inkjet printing are widely used in the processing of organic electronic devices.
  • inkjet printing realizes deposition and patterning of a functional polymer film, and realizes processing of an organic light emitting diode, an organic thin film transistor (OTFT), and an integrated device thereof.
  • OFT organic thin film transistor
  • Inkjet printing generally forms a continuous film by overlapping the ink droplets.
  • the process of forming a large-area continuous film by overlapping multiple lines is likely to cause problems such as uneven thickness of the film, discontinuity, or pattern deformation, as compared with printing a single-point or single-line pattern.
  • the prior art uses a change in the temperature of the substrate to control the drying process of the ink to achieve printing of a continuous organic film.
  • Printing small molecule organic semiconductor inks at too low a substrate temperature the printed pattern will cause pattern distortion during the drying process, and too high substrate temperature will easily lead to film discontinuity, so the appropriate substrate temperature is constant. To the extent that pattern distortion can be reduced, a continuous uniform film is obtained.
  • the printing speed tends to be slow, especially in the case where the substrate temperature is low, and raising the substrate temperature causes a problem of low crystallinity of the film. Therefore, in the inkjet printing process, the adjustment range of the substrate temperature is relatively limited.
  • Ink using a mixed solvent due to the difference in surface tension between the two solvent components, causes Marangoni convection inside the droplet.
  • the movement of the line of contact of the circular ink droplets on the substrate with the substrate is typically an isotropic retraction.
  • the solute concentration reaches a certain threshold, the contact line stops moving, and the solute begins to form a film from the edge to the middle by self-assembly.
  • the shape and morphology of the film are relatively easy to control.
  • the ink droplets overlap each other.
  • Both the rate of solvent evaporation at the initial stage of printing and the rate of crystallization of solute crystals increase due to an increase in the surface area of the liquid.
  • controlling the geometry and microstructure of the film requires dynamic adjustment of the self-assembled environment. For example, in a process of printing a line shape in a single pass, the film near the beginning of the line is thicker than the end, and the crystallinity is generally higher. This is mainly because the rapid crystallization of the solute during the drying of the ink causes a concentration gradient and drives the directional migration of the solute molecules. In different parts of the printed line, variations in assembly speed and even changes in growth mode due to different ink concentrations result in uneven thickness and morphology of the film.
  • Figure 1 shows the existing inkjet printing method.
  • the printing area 14 is an organic semiconductor layer between the source electrode 13 and the drain electrode 15
  • the nozzle 12 at the lower end of the head 11 can continuously eject ink droplets at a certain frequency.
  • the spacing between the drop point of the previous drop and the drop of the next drop is the dot pitch.
  • the lines printed in the Y direction are columns
  • the lines printed in the X direction are lines
  • printing in the Y direction is one stroke.
  • the print head 11 first prints a column in the Y direction, then moves a column pitch in the X direction, and then prints the next column in the Y direction, and thus repeats to form a printed film of a certain area.
  • the movement of the substrate is mostly used to realize the movement in the Y direction and the X direction, and the moving speed and the moving distance of the substrate are determined according to the dot pitch of the ink dots.
  • the dot pitch usually printed is the same in both the X and Y directions.
  • a continuous film can be formed when the dot pitch is sufficiently small.
  • Embodiments of the present invention provide an ink jet printing method for improving the uniformity of film thickness and thereby improving the quality of an ink jet pattern.
  • an inkjet printing method for an organic film comprising: adjusting a surface energy of a printing substrate;
  • the organic film is printed on the printed substrate such that the droplets on the printed substrate are spread.
  • said uniformly spreading the droplets on the printing substrate comprises causing the spread droplet diameter on the printing substrate to be 2-4 times the diameter of the spherical droplets ejected from the printer nozzle.
  • the adjusting the surface energy of the printing substrate comprises forming a surface energy gradient in the printing column direction or perpendicular to the printing column direction on the surface of the printing substrate.
  • the forming a surface energy gradient comprises:
  • the three-dimensional mask comprising a mask substrate having a plurality of openings and a warping sheet disposed at each opening of the mask substrate, the warping
  • the angle between the plane of the film and the plane of the reticle substrate is 10. ⁇ 100.
  • the opening corresponds to printing an area on the bottom of the village where the organic film needs to be printed.
  • the adjusting the printing of the bottom surface energy comprises performing a hydrophobic treatment and/or a hydrophilic treatment on the printing village bottom.
  • the performing hydrophobic treatment and/or hydrophilic treatment on the printing village bottom comprises:
  • the fluorination treatment of the printed village bottom makes the printing village bottom surface hydrophobic; and/or the UV cleaning of the printing village bottom makes the printing village bottom surface hydrophilic.
  • the organic film is formed by variable pitch printing.
  • the column pitch of the variable column pitch printing is decreased in the order of the printing columns.
  • the organic film is formed by one-pass multi-column printing.
  • the one-way multi-column printing is a one-way three-column printing.
  • the organic film is also printed with variable pitch spacing.
  • the inkjet printing method of the present invention can be applied to the production of an organic thin film in a flat panel display, and can also be applied to the production of an organic thin film in a solar cell panel, and can also be applied to the production of an organic thin film in other optoelectronic products. Therefore, the present invention does not Limited to the applications listed above.
  • 1 is a schematic view of a conventional inkjet printing method
  • FIG. 2 is a schematic view showing a first embodiment of an inkjet printing method of the present invention
  • FIG. 3 is a photograph of an organic film printed by a first embodiment of the inkjet printing method of the present invention
  • FIG. 4 is a photograph of an organic film printed by a first comparative example of the conventional inkjet printing method
  • 5 is a photograph of an organic thin film printed by a second comparative example of the conventional ink jet printing method
  • FIG. 6 is a photograph of an organic thin film printed by the second embodiment of the ink jet printing method of the present invention
  • FIG. 8 is a photograph of an organic film printed by a third embodiment of the inkjet printing method of the present invention
  • FIG. 9 is a schematic view showing a fourth embodiment of the inkjet printing method of the present invention.
  • Figure 10 is a schematic view showing a fifth embodiment of the ink jet printing method of the present invention.
  • an embodiment of the present invention provides an ink jet printing method of an organic film.
  • the form of adjusting the surface energy of the printing substrate is used to control the spreading of the ink droplets on the surface of the printing substrate, so that the droplets are uniformly spread on the surface of the printing substrate, thereby making the organic film uniform in thickness and capable of Improve the quality of the pattern formed by the organic film.
  • An inkjet printing method for an organic thin film comprising: adjusting surface energy of a printing substrate; printing an organic thin film on the printing substrate such that droplets on the printing substrate are uniformly spread.
  • said uniformly spreading the droplets on the printed substrate comprises: when the adjusted printed substrate surface enables the spread droplet diameter on the printed substrate to be about 2 diameters of the spherical droplets ejected from the printer nozzle When ⁇ 4 times, the film has the best effect on the hook and shape.
  • the surface energy of the printing substrate is adjusted, so that The droplets that are spread on the bottom of the printing village have a diameter of about 40 to 80 ⁇ m, and such droplet spreading facilitates film formation on the bottom surface of the printing village. Therefore, the surface energy of the printed substrate can be adjusted to overcome the change of the film pattern and the morphology caused by the directional migration of the solute molecules, so that the film thickness is uniform, thereby improving the quality of the inkjet pattern.
  • the adjusting the surface energy of the printing substrate comprises forming a surface energy gradient in the printing column direction or perpendicular to the printing column direction on the printing village bottom surface.
  • the forming the surface energy gradient comprises: performing a fluorination treatment on the printed village bottom surface; and performing ultraviolet ozone cleaning on the printed village bottom surface through the stereo mask.
  • the reticle plate may include a reticle substrate having a plurality of openings and a ridge plate disposed at each opening of the reticle substrate, and an angle between a plane of the ridger and a plane of the reticle substrate may be About 10. ⁇ 100.
  • the opening corresponds to printing an area on the bottom of the village where the organic film is to be printed.
  • a printed mask substrate is treated with a three-dimensional mask having an opening and a warp sheet, and a partial gradient of surface energy is formed on the area where the organic film is to be printed due to the partial blocking effect of the warp sheet on the open area.
  • the adjusting the printing of the bottom surface energy comprises performing a water repellent treatment and/or a hydrophilic treatment on the printing village bottom.
  • the hydrophobic treatment may be performed by a fluorination treatment to form a hydrophobic surface on the surface of the substrate;
  • the hydrophilic treatment may be performed by ultraviolet ozone cleaning to form a hydrophilic surface on the surface of the substrate, according to the inkjet ink and the surface properties of the substrate.
  • the bottom of the village is subjected to hydrophobic treatment and/or hydrophilic treatment, so that the surface of the village and the ink are matched to make the ink spread properly on the surface of the village.
  • the fluorination treatment is used to form a hydrophobic village bottom surface, and then ultraviolet ozone cleaning is used to form a certain hydrophilicity. Print the bottom surface of the organic film.
  • the organic film may be formed by variable pitch printing.
  • the column spacing of the variable column spacing printing is decremented in the order of the printing columns.
  • the column spacing of the multiple lines constituting the film is equal, and usually the dot pitch of the printed single line is controlled.
  • two disadvantages often occur.
  • the drying process of the ink is developed from the periphery to the middle, and finally the film formed in the central portion of the film is of poor quality; the other case is that if the printing direction is from left to right, the film is dried from left to right.
  • the solute migrates from right to left, causing the film thickness to be left high and low right, often accompanied by a sudden change in the morphology of the film. Both of these conditions can lead to a decrease in film properties and material properties, or The effective film area available is greatly reduced.
  • the patterned thin film device can be printed by increasing the print area and offsetting with an appropriate pattern, this has significantly limited the efficiency of the printed pattern film.
  • a variable column spacing printing technique may be employed. For example, in the process of printing a large-area film pattern from left to right, the column pitch of printing from left to right is gradually reduced, which can effectively prevent the film from appearing to be left high and right, and can make the film thickness more uniform. , to make the film more uniform. Moreover, the single-pass multi-column and variable-column spacing printing technology can not only efficiently print a continuous film of a large number of films, but also effectively solve the problem of uneven film thickness.
  • the organic film may be formed by one-pass multi-column printing.
  • the printer that can be used is a printer having a plurality of side-by-side nozzles, and the nozzles of the plurality of side-by-side nozzles simultaneously eject ink droplets to realize multi-column printing.
  • the organic film may also be printed with variable pitch spacing.
  • the stroke interval of one stroke and the next stroke may be the same or different.
  • the stroke pitch is decreased in the order of the printing stroke, it is similar to the variable column spacing, which can effectively solve the problem of uneven film thickness. For example, if the column spacing is N times the droplet diameter and N is a positive integer, the column spacing of the variable column spacing printing can be reduced by N times, N-1 times, N-2 times up to 1 times the droplet diameter.
  • the column spacing of the first column and the second column of the printing is N times the droplet diameter
  • the column spacing of the printed second column and the third column is N-1 times the droplet diameter, etc.
  • the printed lines are The print starts less loosely and is denser at the end of the print.
  • the volume V of a single droplet ejected by the nozzle is 10 picolitres.
  • the single-row multi-column printing has a print column spacing of 5 to 50 micrometers ( ⁇ ), for example, the column spacing may be 5 micrometers, 10 meters, 15 meters, 20 meters, 25 meters, 30 meters, 45 meters, 50 meters. In the case of other printhead sizes, the column spacing can be, for example, proportional to the cube root of a single drop volume.
  • the one-way multi-column printing may be a one-way three-column printing.
  • One-way multi-column printing can print three columns in one stroke, or two columns in one stroke, or four columns in one stroke, or five columns in one stroke. Generally, it is determined according to the stroke of printing. The longer the stroke is required. The number of columns printed in a single pass is greater.
  • the inkjet printing method of the embodiment of the invention can be applied to the production of an organic thin film in a flat panel display, and can also be applied to the production of an organic thin film in a solar panel, and can also be applied to other light.
  • the ink jet printing method of the present invention will be described below by way of an exemplary embodiment.
  • the following examples each take the case of a 10 picoliter print head, i.e., the spherical droplets ejected from the nozzle have a diameter of about 20 ⁇ m.
  • the organic film is printed by a single-pass multi-column printing method, and the surface energy of the printing substrate is adjusted before the organic film is printed, and multi-column printing is realized by using multiple nozzles.
  • the following is an example of an organic thin film transistor with multi-head inkjet printing bottom contact. Be explained.
  • multi-nozzle printing is adopted.
  • the spatial period in which the nozzles 11 are arranged along the X direction is the printing column spacing, and the ejection of the nozzles 12 of each of the nozzles 11 are respectively performed by the same frequency and the determined phase difference.
  • Independent pulse voltage waveform control is adopted.
  • the printing substrate was a silicon wafer prepared with a gold (Au) electrode, and a thermal silicon oxide having a thickness of about 300 nm was previously grown on the surface of the silicon wafer.
  • This embodiment requires printing a poly-3-hexylthiophene (a tube called P3HT, an organic polymer semiconductor) ink solution between the source electrode 13 and the drain electrode 15 in a solvent concentration of o-dichlorobenzene and poly-3-hexylthiophene. It is about 0.25 ⁇ 0.75wt.%.
  • the surface energy of the printing substrate is first adjusted.
  • Step 1 Fluorinating the silicon wafer, preferably using dry fluorination treatment (FDTS), so that the surface of the silicon wafer is hydrophobic;
  • FDTS dry fluorination treatment
  • Step 2 Put the fluorinated silicon wafer into the ultraviolet ozone cleaning machine, set the temperature to 35 ° C, and the time is 8 min. Press the start button to automatically complete the ultraviolet ozone cleaning, so that the surface of the silicon wafer exhibits certain hydrophilicity;
  • Step 3 As shown in FIG. 2, an ink-jet printed P3HT film is formed on the printing region 14 between the source electrode 13 and the drain electrode 15 of the OTFT device at the bottom to form an organic semiconductor layer.
  • the diameter of the spherical droplets ejected from the nozzles 12 of the nozzle 11 is about 20 ⁇ m, after processing the printed substrate, a single droplet is spread on the surface of the printing substrate after a diameter of about 40 to 80 ⁇ m, and the droplets The size is even.
  • three nozzles 11 are used to simultaneously print three columns, the column pitch is set to a single droplet diameter, i.e., about 20 ⁇ m, and the width of the one-pass printing covers just about 45 micrometers of parallel channels.
  • Figure 3 is an optical photograph of a bottom contact OTFT device formed by drying a single pass three-column ink. It can be seen from the photograph that the print area has a good straight line shape, a uniform pattern, and no deformation.
  • FIG 4 is an optical photograph of dried TIPS pentacene (collectively referred to as 6,13-bis(triisopropylsilylethynyl) pentacene) ink using conventional single pass single line printing. As can be seen from the photo, The adjacent columns of the print overlap partially, and the film cannot be formed well.
  • This embodiment prints a rectangular film by varying the pitch of the columns and adjusts the surface energy of the printed substrate before printing the organic film.
  • variable column pitch printing method which is characterized in that the dot pitch along the Y direction is constant, but the column pitch along the X direction is gradual.
  • the surface energy of the silicon oxide substrate is adjusted according to the first step and the second step in the embodiment 1.
  • the diameter of the spherical liquid droplets ejected from the nozzle 12 of the shower head 11 is about 20 ⁇ m, for example, after the printing substrate is processed, a single liquid droplet is processed. After spreading on the surface of the printing substrate, the diameter is between about 40 and 80 ⁇ m, and the droplet size is uniform.
  • Fig. 5 is a three-bar TIPS pentacene film printed by a conventional printing method in which the X-direction and the ⁇ direction dot pitch are the same, and dot pitches of 15 ⁇ m, ⁇ and 5 ⁇ are respectively printed.
  • the three strip films are not regular rectangles, and all have different degrees of pattern variation.
  • the two films printed by the variable column spacing printing method for example, use a Y-direction dot pitch of 15 ⁇ m, the dot pitch is equivalent to the diameter of the spherical droplets ejected from the nozzle, and the column spacing in the X direction is as follows.
  • the order of the print columns is sequentially decreased from 60 ⁇ m, 45 ⁇ m, 30 ⁇ m to 15 ⁇ m.
  • the shape of the film shown in Fig. 6 is a regular rectangle, which is visible in accordance with the set print pattern.
  • a rectangular film is printed by a single-pass multi-column and variable stroke pitch printing method.
  • One-way multi-column printing uses multi-nozzle printing, where the stroke spacing refers to the distance between one stroke and the next stroke in a single pass and multiple columns.
  • print efficiency is proportional to the number of print passes in the ⁇ direction and the number of simultaneously used nozzles.
  • the printing pattern shown in Fig. 7 is characterized in that the dot pitch along the x direction is constant, and the stroke pitch in the X direction is also fixed, but the column pitch along the X direction is periodically changed.
  • the unit pattern includes three segments, each of which includes three rows of ⁇ -direction lattice portions overlapping, each segment adopting three nozzles When printing, each nozzle can print one column of dot matrix lines, and one unit pattern uses three nozzles to print at the same time and needs to print three strokes.
  • FIG. 8 shows a rectangular TIPS pentacene film unit pattern printed on an organic thin film array on a PVP (poly(4-ethoxyphenyl)) insulating substrate, the film being formed by overlapping four lines of three nozzles. Continuous and dense.
  • PVP poly(4-ethoxyphenyl)
  • the solute has a tendency to move to the left, that is, the pattern protrudes to the left.
  • the spacing between the thick lines can also be gradual. Take the three lines shown in Figure 7 as an example. Appropriately increase the distance between the first thick line and the second thick line from left to right, that is, increase the first stroke and the second.
  • the stroke distance of the stroke is beneficial to inhibit the migration of the solute to the left to form a left protrusion.
  • This embodiment employs single pass multi-column printing, and the printing substrate is a non-parallel channel OTFT having a geometric gradient.
  • a trapezoidal finger-shaped source electrode 13 and a trapezoidal finger-shaped drain electrode 14 are used, which are characterized in that the width of the finger is gradually changed, and the printing area 14 between the fingers, that is, the channel width is also gradually changed along the X direction.
  • the printing process of an OTFT device structure having such a non-parallel channel can utilize the geometric gradient of the pattern to control the flow direction of the ink, inhibiting the directional migration of the solute. Therefore, single-pass multi-column printing is used, for example, multi-nozzle printing, and printing is performed using a periodically variable pitch printing pattern as shown in FIG.
  • the organic semiconductor layer functions as a film, in which case the surface of the substrate needs to be processed to form a surface energy gradient.
  • single-row multi-column printing is adopted, that is, multi-column printing is realized by using multiple nozzles, and the surface energy of the printing substrate is first adjusted so that the dispersion component and the polar component of the surface energy vary from about 0 to 50 mN/m. .
  • the diameter of the spherical droplets ejected from the nozzles 12 of the nozzle 11 as about 20 ⁇ m
  • a single droplet is spread on the surface of the printing substrate after a diameter of about 40 to 80 ⁇ m, and the droplets The size is even.
  • the magnitude of the surface energy is the algebraic sum of the dispersion component and the polar component.
  • the print substrate 19 can be selected as a silicon oxide wafer, and a thin film transistor array having a top contact is prepared on the silicon oxide wafer.
  • a thin film transistor array having a top contact is prepared on the silicon oxide wafer.
  • an organic semiconductor layer between the source electrode and the drain electrode is prepared.
  • the surface of the printing village bottom 19 is fluorinated, for example, a self-assembled perfluorododecyltrichlorosilane monolayer on the surface of the printed substrate 19 to obtain a hydrophobic printed substrate surface;
  • the film 16 is provided with a selective ultraviolet odor on the surface of the printing substrate 19 in which the organic semiconductor layer of the thin film transistor is printed.
  • the metal sheet which is lifted up by the three-dimensional mask 16 is warped, and the angle ⁇ with the bottom of the mask can be designed to be about 10. ⁇ 100.
  • An angle within the range such as an angle ⁇ of about 10°, 20°, 30°, 40°, 50°, 80°, 85°, 90° or 100°.
  • the ink for forming the organic semiconductor layer is printed in a single pass and multiple columns in each rectangular projection area by using multiple nozzles, and the surface energy gradient can be used to control the inkjet printed organic semiconductor film.
  • the surface energy of the printed substrate bottom surface from the source electrode to the drain electrode is gradually reduced or gradually increased to form a surface energy gradient, and the surface energy gradient causes the molecular orientation in the ink to form a single orientation, and further The conductivity between the source electrode and the drain electrode is improved.
  • the surface energy gradient formed on the surface of the printed substrate can be adjusted and optimized according to the performance of the thin film device.
  • the method of forming the surface energy gradient using the stereo mask as described in this embodiment is not limited to the combination of the above process steps, and may be a combination of other surface treatment methods.
  • the stereo mask is suitable for dry gas phase treatment (eg UV ozone cleaning, plasma surface treatment) and for optical processing (eg UV light).
  • the gradient of the strength of the dry gas phase surface treatment in the exposed area is adjusted by the angle between the designed blade and the bottom of the mask.
  • the size and shape of the raised blade are variable, and the number of the pieces is
  • the position is also variable. For example, each rectangular through hole can be provided with two symmetrical pieces. This can be applied to patterns that achieve different gradient changes.
  • the above five exemplary embodiments are unconventional inkjet printing methods and combinations thereof, according to ink
  • the physical properties of water, the characteristics of the material and pattern of the substrate, using the above different printing methods and combinations, can overcome the adverse effects of solute migration on the film morphology during ink drying, and improve the uniformity and repeatability of printing large-area continuous film. , Improve printing accuracy and optimize film topography; also enable high-speed printing of large gauge arrays.
  • the form of adjusting the surface energy of the printing substrate is used to control the spreading of the inkjet droplets on the surface of the printing village, so that the droplets spread evenly on the surface of the printing village bottom.
  • the organic film is made uniform in thickness and can improve the quality of the pattern formed by the organic film.

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Abstract

一种有机薄膜的喷墨打印方法，包括：调节打印衬底的表面能；在打印衬底上打印有机薄膜，使得在打印衬底上的液滴均匀铺展。采用这种喷墨打印方法，提高了打印薄膜厚度的均匀性以及喷墨图案的质量。

Description

有机薄膜的喷墨打印方法
技术领域
本发明的实施例涉及一种有机薄膜的喷墨打印方法。 背景技术
由于喷墨打印技术具有高效、 低成本、 非接触形式及柔性的加工过程等 特点， 因此， 采用喷墨打印形成的图案被广泛应用于有机电子器件的加工中。 通过打印功能性高分子溶液， 喷墨打印实现了功能高分子薄膜的沉积和图案 化， 并实现了有机发光二极管、 有机薄膜晶体管（OTFT )及其集成器件的加 工。
喷墨打印一般采用墨滴交叠覆盖的方式形成连续薄膜。 与打印单点或单 线条图案相比， 通过多线条交叠覆盖形成大面积连续薄膜的工艺容易导致薄 膜厚度不均， 不连续或者图案形变等问题。 针对这一问题， 现有技术采用衬 底温度的变化来控制墨水的干燥过程， 实现打印连续的有机薄膜。 在过低的 衬底温度下打印小分子有机半导体墨水， 打印的图案在干燥过程中会导致图 案变形， 而过高的衬底温度则易导致薄膜不连续， 因此采用合适的衬底温度 在一定程度上可以减少图案形变， 同时获得连续均匀的薄膜。 但是利用这种 控制衬底温度方法打印大面积薄膜时， 打印速度往往比较慢， 尤其是在衬底 温度较低的情况下， 而升高衬底温度又会带来薄膜结晶度低的问题。 因此在 喷墨打印工艺中， 衬底温度的调节范围比较有限。
采用混合溶剂的墨水， 由于两种溶剂组分在表面张力上的差异， 会引起 液滴内部的马兰戈尼对流（ Marangoni convection )。 在最筒单的单墨滴打印的 情况下， 随着溶剂挥发， 衬底上的圓形墨滴与衬底的接触线的移动通常是各 向同性的后退。 当溶质浓度达到一定阈值后， 接触线停止移动， 溶质开始从 边缘向中间通过自组装形成薄膜， 这种情况下薄膜的形状和形貌比较容易控 制。 但是在打印线条或者二维薄膜的情况下， 墨滴彼此交叠。 在打印初始阶 溶剂挥发速度和溶质结晶生长的速度均因为液体表面积的增加而增加。 在这 种情况下， 控制薄膜的几何形状和微观形貌需要对自组装环境进行动态调节。 例如在单程打印一个线条形状的工艺中， 线条起始端附近的薄膜比末端要厚， 结晶度一般也比较高。 这主要是因为， 在墨水干燥过程中溶质的快速结晶引 起浓度梯度， 并且驱动溶质分子定向迁移。 在打印线条的不同部位， 由于墨 水浓度不同而引致组装速度的变化甚至是生长模式的改变， 因此导致薄膜的 厚度和形貌不均。
图 1所示为现有的喷墨打印方式。 根据图形打印的需要， 如打印区域 14 为源电极 13和漏电极 15之间的有机半导体层， 喷头 11下端的喷嘴 12可以 按照一定的频率连续喷射墨水液滴。 前一滴液滴的落点和后一滴液滴的落点 之间的间距为点间距。 在此， 沿 Y方向打印的线条为列， 沿 X方向打印的线 条为行， 沿 Y方向打印一次为一个行程。 打印时喷头 11首先沿 Y方向打印 一列， 再沿 X方向移动一个列间距， 再沿 Y方向打印下一列， 如此反复， 形 成一定面积的打印薄膜。 现有技术多采用衬底的移动来实现 Y方向和 X方向 的移动， 衬底的移动速度和移动距离根据墨点的点间距确定。 通常打印的点 间距在 X方向和 Y方向都是相同的。 当点间距足够小的情况下可以形成连续 薄膜。 在打印一定宽度的有机薄膜时， 需要多个行程才可以打印出足够宽度 的薄膜。 在较长行程的打印过程中， 由于墨水的干燥速度相对较快， 常常出 现的问题是相邻的线条之间会出现不连续交叠或不均匀。
由上述分析可知， 通过现有的喷墨打印技术， 会存在薄膜的厚度不均匀、 薄膜不连续或图案形变的问题。 发明内容
本发明的实施例提供一种喷墨打印方法， 用以提高薄膜厚度的均匀性， 进而提高喷墨图案的质量。
根据本发明的一个方面， 提供一种有机薄膜的喷墨打印方法， 其包括： 调节打印衬底的表面能；
在打印衬底上打印有机薄膜， 使得在打印衬底上的液滴均勾铺展。
根据本发明的一个实施例， 所述使得在打印衬底上的液滴均匀铺展包括 使得在打印衬底上的铺展的液滴直径为打印机喷嘴喷出的球形液滴直径的 2-4倍。
根据本发明的一个实施例， 所述调节打印衬底的表面能包括在打印衬底 表面沿打印列方向或者垂直于打印列方向形成表面能梯度。 根据本发明的一个实施例， 所述形成表面能梯度包括：
对打印村底表面进行氟化处理；
通过立体掩膜版， 对打印村底表面进行紫外臭氧清洗， 所述立体掩膜版 包括具有多个开口的掩膜版基底及设置于掩膜版基底每个开口处的翘片， 所 述翘片所在平面与掩膜版基底所在平面的夹角为 10。~100。， 所述开口对应打 印村底上需打印有机薄膜的区域， 当透过所述立体掩膜版对打印村底进行紫 外臭氧清洗时， 打印村底上需打印有机薄膜的区域形成表面能梯度。
根据本发明的一个实施例， 所述调节打印村底表面能包括对打印村底进 行疏水处理和 /或亲水处理。
根据本发明的一个实施例， 所述对打印村底进行疏水处理和 /或亲水处理 包括：
对打印村底进行氟化处理， 使得打印村底表面呈现疏水性； 和 /或 对打印村底进行紫外臭氧清洗， 使得打印村底表面呈现亲水性。
根据本发明的实施例， 对上述喷墨打印方法， 所述有机薄膜采用变列间 距打印形成。
根据本发明的实施例， 所述变列间距打印的列间距按照打印列的先后顺 序递减。
对上述的喷墨打印方法， 所述有机薄膜采用单程多列打印形成。
根据本发明的一个实施例， 所述单程多列打印为单程三列打印。
根据本发明的一个实施例， 所述有机薄膜还采用变行程间距打印。
本发明喷墨打印方法可以应用于平板显示中的有机薄膜的制作， 也可以 应用于太阳能电池板中的有机薄膜的制作， 也可以应用于其它光电子产品中 有机薄膜的制作， 因此， 本发明不限于上面所列举的应用。 附图说明
以下将结合附图对本发明的实施例进行更详细的说明， 以使本领域普通 技术人员更加清楚地理解本发明， 其中：
图 1为现有的喷墨打印方法示意图；
图 2为本发明喷墨打印方法第一实施例示意图；
图 3为本发明喷墨打印方法第一实施例打印的有机薄膜的照片； 图 4为现有的喷墨打印方法第一对比例打印的有机薄膜的照片； 图 5为现有的喷墨打印方法第二对比例打印的有机薄膜的照片； 图 6为本发明喷墨打印方法第二实施例打印的有机薄膜的照片； 图 7为本发明喷墨打印方法第三实施例打印方式的示意图；
图 8为本发明喷墨打印方法第三实施例打印的有机薄膜的照片； 图 9为本发明喷墨打印方法第四实施例示意图；
图 10为本发明喷墨打印方法第五实施例示意图。
附图标记：
11-喷头 12-喷嘴 13-源电极 14-打印区域 15-漏电极
16-立体掩膜版 17-通孔 18-翘片 19-打印衬底 具体实施方式
为使本发明的实施例的目的、 技术方案和优点更加清楚， 下面将结合本 发明实施例的附图对本发明的实施例的技术方案进行清楚、 完整的描述。 显 然， 所描述的实施例仅是本发明的一部分示例性实施例， 而不是全部的实施 例。 基于所描述的本发明的示例性实施例， 本领域普通技术人员在无需创造 性劳动的前提下所获得的所有其它实施例都属于本发明的保护范围。
为了提高打印效率， 提高打印有机薄膜的质量， 本发明的实施例提供了 一种有机薄膜的喷墨打印方法。 在该技术方案中， 采用调节打印衬底表面能 的形式来控制喷墨的液滴在打印衬底表面的铺展， 使得液滴在打印衬底的表 面铺展均匀， 因此使得有机薄膜厚度均匀并且能提高有机薄膜形成的图案的 质量。
根据本发明实施例提供的有机薄膜的喷墨打印方法， 其包括： 调节打印 衬底的表面能； 在打印衬底上打印有机薄膜， 使得在打印衬底上的液滴均匀 铺展。
在本发明的实施例中， 若图案本身具有梯度变化， 比如非平行沟道或者 梯度变化的表面能都可以对其上方的喷墨液滴产生作用。 恰当利用这种作用 可以有效克服溶质分子定向迁移带来的薄膜图形和形貌变化。 例如， 所述使 得在打印衬底上的液滴均匀铺展包括： 当调节的打印衬底表面能使在打印衬 底上的铺展的液滴直径为打印机喷嘴喷出的球形液滴直径的约 2~4倍时， 薄 膜的均勾度和形貌的效果最好。 以 10皮升的打印喷头为例， 即喷头的喷嘴喷 出的单个球形液滴的直径约为 20μηι时，对打印衬底的表面能进行调节后，使 得在打印村底上铺展的液滴的直径为约 40~80μηι, 这样的液滴铺展有利于在 打印村底表面成膜。 因此， 可以采用调节打印村底的表面能来克服溶质分子 定向迁移带来的薄膜图形和形貌的变化， 使得薄膜厚度均匀， 进而提高喷墨 图案的质量。
根据本发明的实施例， 所述调节打印村底的表面能包括在打印村底表面 沿打印列方向或者垂直于打印列方向形成表面能梯度。 例如， 所述形成表面 能梯度包括： 对打印村底表面进行氟化处理； 通过立体掩膜版， 对打印村底 表面进行紫外臭氧清洗。 所述立体掩膜版可以包括具有多个开口的掩膜版基 底及设置于掩膜版基底每个开口处的翘片， 所述翘片所在平面与掩膜版基底 所在平面的夹角可以为约 10。~100。， 所述开口对应打印村底上需打印有机薄 膜的区域。 当透过所述立体掩膜版对打印村底进行紫外臭氧清洗时， 打印村 底上需打印有机薄膜的区域形成表面能梯度。
在本发明的实施例中， 形成表面能梯度的方式可以有多种。 例如， 采用 具有开口和翘片的立体掩膜版对打印村底进行处理， 由于翘片对开口区域的 部分遮挡作用， 使得需打印有机薄膜的区域上形成具有一定梯度的表面能。
根据本发明的实施例， 所述调节打印村底表面能包括对打印村底进行疏 水处理和 /或亲水处理。 所述疏水处理可以采用氟化处理， 使村底表面形成疏 水表面； 所述亲水处理可以采用紫外臭氧清洗， 使村底表面形成亲水表面， 根据喷墨的墨水和村底的表面性能， 对村底进行疏水处理和 /或亲水处理， 使 得村底表面和墨水相配合， 使墨水在村底表面进行合适的铺展。
在本发明实施例中， 由于一些打印村底的表面能不适合直接进行喷墨打 印， 因此采用氟化处理形成疏水性的村底表面， 再采用紫外臭氧清洗形成具 有一定亲水性的适于打印有机薄膜的村底表面。
根据本发明的一些实施例， 所述有机薄膜可以采用变列间距打印形成。 例如， 所述变列间距打印的列间距按照打印列的先后顺序递减。
如果采用的喷墨打印工艺中， 构成薄膜的多线条的列间距相等， 通常也 就是控制打印单线条的点间距， 这样的方式常常出现两种不利的情况。 一种 情况是墨水干燥成膜过程从四周向中间发展， 最终在薄膜的中央区域形成的 薄膜质量较差； 另一种情况是若打印方向自左向右， 则薄膜自左向右干燥成 膜， 但同时溶质会自右向左迁移， 造成薄膜厚度左高右低， 往往还伴随着薄 膜形貌的突变。 这两种情况都会导致薄膜均勾性和材料性能下降， 或者导致 可利用的有效薄膜面积大幅减少。 尽管可以通过增加打印面积和采用适当的 图案偏移印制图案化薄膜器件， 但是这已经明显限制了印制图案薄膜的效率。
在本发明的一些实施例中， 可以采用变列间距的打印技术。 例如， 在自 左向右打印大面积薄膜图案的过程中， 设定自左向右打印的列间距逐渐减小， 这样就能有效防止薄膜出现左高右低的现象， 可以使薄膜厚度更均匀， 使薄 膜的形貌更均匀。 而且采用单程多列以及变列间距的打印技术， 不仅可以高 效率地打印大 莫的连续的薄膜， 而且可以有效解决薄膜厚度不均匀的问题。
在上述的喷墨打印方法中， 所述有机薄膜可以采用单程多列打印形成。 在本发明的一些实施例中， 采用多列打印一个行程的方式， 可以避免采 用单列打印容易出现薄膜厚度不均匀的问题， 并且提高了打印效率。 对于单 程多列打印的方式， 可以采用的打印机为具有多个并排喷头的打印机， 多个 并排喷头的喷嘴同时喷出墨滴来实现多列打印。
根据本发明的一些实施例， 所述有机薄膜还可以采用变行程间距打印。 在本发明的实施例中， 一个行程与下一个行程的行程间距可以相同， 也 可以不同。 当行程间距按照打印行程的先后顺序递减时， 也跟变列间距类似， 可以有效解决薄膜厚度不均匀的问题。例如，假设列间距为 N倍的液滴直径， N为正整数， 则变列间距打印的列间距可以按照液滴直径的 N倍、 N-1倍、 N-2倍直至 1倍的规律递减， 即， 打印的第一列与第二列的列间距为 N倍的 液滴直径， 打印的第二列和第三列的列间距为 N-1倍的液滴直径等， 打印的 线条在打印起始较疏松， 在打印后期较密集。
以采用 10皮升打印喷头为例，即喷头喷出单个液滴的体积 V为 10皮升。 根据本发明的一个实施例， 所述单程多列打印的打印列间距为 5~50 微米 ( μηι ), 例如列间距可以为 5微米、 10 米、 15 米、 20 米、 25 米、 30 米、 45 米、 50 米。 在其他打印喷头尺寸的情况下， 列间距例如可以正 比于单个液滴体积的立方根。
根据本发明的一个实施例， 所述单程多列打印可以为单程三列打印。 单 程多列打印可以一个行程打印三列， 也可以一个行程打印两列， 也可以一个 行程打印四列， 也可以一个行程打印五列， 一般根据打印的行程来确定， 打 印的行程越长需要的单程打印的列数就越多。
本发明实施例的喷墨打印方法可以应用于平板显示中的有机薄膜的制 作， 也可以应用于太阳能电池板中的有机薄膜的制作， 也可以应用于其它光 电子产品中有机薄膜的制作， 但是本发明不限于此。
以下列举示例性的实施例对本发明喷墨打印方法进行说明， 以下实施例 都以采用 10皮升打印喷头为例， 即喷嘴喷出的球形液滴的直径约为 20μηι。
实施例 1
本实施例采用单程多列打印方式打印有机薄膜， 并在打印有机薄膜之前 调节打印衬底的表面能， 采用多喷头实现多列打印， 以下以多喷头喷墨打印 底接触的有机薄膜晶体管为例进行说明。
本实施例采用多喷头打印， 如图 2所示， 喷头 11沿着 X方向排列的空 间周期为打印列间距， 每个喷头 11的喷嘴 12的喷射按照相同的频率和确定 的相位差分别由彼此独立的脉沖电压波形控制。
打印衬底为制备有金（Au ) 电极的硅片， 且硅片表面预先生长厚度为约 300nm的热氧化硅。 本实施例要求在源电极 13和漏电极 15之间打印聚 3-己 基噻吩（筒称为 P3HT,—种有机聚合物半导体）墨水溶液，溶剂为邻二氯苯, 聚 3-己基噻吩的浓度为约 0.25〜 0.75wt.%。
由于热氧化硅衬底的亲水性艮强， 不利于喷墨打印， 因此首先调节打印 衬底的表面能。
步骤一、 氟化处理硅片， 优选采用干法氟化处理（FDTS ), 使得硅片表 面呈现疏水性；
步骤二、 将氟化处理后的硅片放进紫外臭氧清洗机， 设置温度 35°C , 时 间 8min,按启动键自动完成紫外臭氧清洗，使得硅片表面呈现一定的亲水性； 步骤三、 如图 2所示， 喷墨打印 P3HT薄膜于底接触 OTFT 器件的源电 极 13和漏电极 15之间的打印区域 14, 形成有机半导体层。 以喷头 11的喷嘴 12喷出的球形液滴的直径为约 20μηι为例， 经对打印衬底处理后， 单个液滴 在打印衬底表面铺展后直径在约 40~80μηι之间， 并且液滴大小均匀。 在本发 明实施例中采用三个喷头 11同时打印三列， 设定的列间距为单个液滴直径， 即为约 20μηι, 单程打印的宽度刚好覆盖约 45微米的平行沟道。
图 3为采用单程三列打印的墨水干燥后形成的底接触的 OTFT器件的光 学照片。 由该照片可以看出， 打印区域的直线型较好， 图案均匀， 并未发生 形变。
图 4为采用现有的单程单列打印的 TIPS并五苯（全称为 6,13-双（三异 丙基硅烷基乙炔基）并五苯） 墨水干燥后的光学照片。 由该照片可以看到， 打印的相邻两列存在部分交叠， 不能 ^艮好地形成薄膜。
可见， 在采用单列打印的情况下， 需要多个行程才可以打印出足够宽度 的薄膜覆盖沟道区域， 常常出现的问题是相邻的线条之间会出现不连续交叠， 而采用多列打印可以避免线条之间的不连续交叠， 提高薄膜均匀性。
实施例 2
本实施例采用变列间距的方式打印矩形薄膜， 并在打印有机薄膜之前调 节打印衬底的表面能。
当墨水中的溶质分子在衬底上的结晶速度明显高于溶剂挥发速度的情况 下， 溶质分子的结晶引起溶质分子沿着 X方向的反方向迁移， 对薄膜形状和 形貌产生不良影响。 为了克服这种溶质迁移效应， 除了提高温度之外， 还可 以采用变列间距的打印方法， 其特点是沿着 Y方向的点间距不变， 但是沿着 X方向的列间距是渐变的。
按照实施例 1中步骤一和步骤二调节氧化硅衬底的表面能， 以喷头 11的 喷嘴 12喷出的球形液滴的直径为约 20μηι为例， 经对打印衬底处理后， 单个 液滴在打印衬底表面铺展后直径在约 40~80μηι之间， 并且液滴大小均匀。 图 5是采用常规的打印方法， 即 X方向和 Υ方向点间距相同， 分别采用 15μηι, ΙΟμηι和 5μηι的点间距打印的三个条形 TIPS并五苯薄膜。 由照片可以看出三 个条形薄膜都不是规矩的矩形， 都具有不同程度的图形变异。 如图 6所示为 采用变列间距的打印方法打印的两块薄膜， 例如， 采用了 15μηι的 Y方向点 间距， 点间距与喷嘴喷出的球形液滴的直径相当， X方向的列间距按照打印 列的先后顺序从 60μηι, 45μηι, 30μηι到 15μηι依次减小。 图 6所示的薄膜形 状为规则的矩形， 可见与设定的打印图案是一致的。
实施例 3
本实施例采用单程多列并变行程间距的打印方式打印矩形薄膜。 单程多 列打印采用多喷头打印， 这里的行程间距指单程多列打印一个行程与下一个 行程的间距。
大规模重复的阵列图案， 如平板显示的驱动电路 OTFT 阵列的打印效率 与 Υ方向打印行程和同时采用的喷头数量成正比。采用图 7所示的打印图案， 其特点是沿着 Υ方向的点间距不变， X方向的行程间距也是固定的， 但是沿 着 X方向的列间距是周期性变化的。 以图 7所示为例， 单元图案包括三段线 条， 每个线条包括三列 Υ方向的列点阵部分交叠， 每段线条采用三个喷头同 时打印， 每个喷头可以打印一个列点阵线条， 一个单元图案采用三个喷头同 时打印需打印三个行程。 通过增加单元图案在 Y方向的重复周期数， 可以提 高打印效率。 但是重复周期数受到墨水干燥速度和同时使用的喷头数量的制 约。 适当增加同时使用的喷头数量， 可以相应增加单元图案沿着 Y方向的重 复周期数， 从而大幅提高打印大规模阵列的效率。 图 8所示的是打印在 PVP (聚（4-乙婦基苯酚））绝缘衬底上的有机薄膜阵列的矩形 TIPS 并五苯薄膜 单元图案， 薄膜由四条三喷头打印的粗线条交叠形成， 连续而且致密。 但是 仍然可以看到溶质有向左移动的倾向， 即图案左边突出。 粗线条之间的间距 也可以是渐变的， 以图 7所示三根线条为例， 适当增加从左向右的第一条粗 线与第二条粗线的距离， 即增加第一行程和第二行程的行程间距， 有利于抑 制溶质向左迁移形成左边突出。
实施例 4
本实施例采用单程多列打印， 并且打印衬底为具有几何梯度的非平行沟 道 OTFT。
如图 9所示， 采用梯形手指状的源电极 13和梯形手指状的漏电极 14结 构， 其特点是手指的宽度渐变， 手指之间的打印区域 14即沟道宽度也是沿着 X方向渐变的。 具有这种非平行沟道的 OTFT器件结构的打印过程可以利用 图案的几何梯度控制墨水的流动方向， 抑制溶质的定向迁移。 因此， 采用单 程多列打印方式， 例如采用多喷头打印， 并采用如图 7所示的周期性变间距 的打印图案进行打印。
实施例 5
在打印有机薄膜晶体管的有机半导体层的过程中， 有机半导体层的薄膜 性作用， 这种情况下需要对衬底表面进行处理形成表面能梯度。
本实施例采用单程多列打印， 即采用多喷头实现多列打印， 并且首先调 节打印衬底的表面能， 使得表面能的色散分量和极性分量的变化范围为约 0-50毫牛 /米。 以喷头 11的喷嘴 12喷出的球形液滴的直径为约 20μηι为例， 经对打印衬底处理后， 单个液滴在打印衬底表面铺展后直径在约 40~80μηι之 间， 并且液滴大小均匀。 表面能的大小是色散分量和极性分量的代数和。 表 面能的梯度可以是表面能大小或者两个分量中的一个或全部沿 X方向或沿 Υ 方向有梯度变化趋势。 在打印村底表面形成表面能梯度可以如下进行。
如图 10所示， 打印村底 19可以选为氧化硅片， 在该氧化硅片上制备具 有顶接触的薄膜晶体管阵列， 首先需制备位于源电极和漏电极之间的有机半 导体层， 在制备有机半导体之前， 对打印村底 19表面进行氟化处理， 例如， 在打印村底 19表面自组装全氟十二烷基三氯硅烷单分子层， 得到疏水的打印 村底表面； 然后通过立体掩膜版 16,对打印村底 19表面进行选择性的紫外臭 在该矩形投影区域需打印薄膜晶体管的有机半导体层。 立体掩膜版 16上翘起 的金属片， 即翘片 18, 与掩膜 底的夹角 α可以设计为约 10。~100。范围内 的一个角度， 例如夹角 α为约 10°、 20°、 30°、 40°、 50°、 80°、 85°、 90°或 100°。 在通过矩形通孔 17对打印村底上与通孔 17对应的矩形投影区域进行紫外臭 氧表面清洗时， 由于翘片 18的部分遮挡效果， 打印村底 19表面的矩形投影 区域在紫外臭氧清洗后具有梯度变化的表面能。 如图 10所示， 每个矩形投影 区域的从左到右亲水性逐渐增加， 即表面能逐渐升高， 这样就在村底表面的 每个矩形投影区域形成了表面能梯度。
在打印村底上形成表面能梯度后， 采用多喷头在每个矩形投影区域单程 多列打印用于形成有机半导体层的墨水， 可以利用这种表面能梯度对喷墨打 印的有机半导体薄膜进行控制， 提高打印薄膜的工艺稳定性并缩小薄膜性能 的分布范围， 降低工艺成本。 在本发明实施例中， 从源电极到漏电极的打印 村底表面的表面能逐渐减小或逐渐增加， 形成表面能梯度， 这样的表面能梯 度会使得墨水中的分子取向形成单一取向， 进而提高了源电极和漏电极之间 的导电性能。 当然， 在打印村底表面形成的表面能梯度可以根据薄膜器件的 性能进行调整和优化。
该实施例所述的利用立体掩膜版形成表面能梯度的方法不限于上述工艺 步骤的组合， 还可以是其他表面处理方法的组合。 立体掩膜版适用于干法气 相表面处理（如紫外臭氧清洗， 等离子体表面处理）， 也适用于光学处理 （如 紫外光照)。 通过设计的翘片与掩膜 底的夹角来调节干法气相表面处理在 暴露区域的作用强度的变化梯度， 另外， 翘起的翘片的大小和形状是可变的， 翘片的数量和位置也是可变的， 比如每个矩形通孔可以设有左右对称的两个 翘片。 这样就可以应用于实现不同的梯度变化的图案。
以上举出的五个示例性实施例是非常规喷墨打印方式及其组合， 根据墨 水的物理性质， 村底材料和图案的特点， 采用上述不同的打印方式和组合， 可以克服墨水干燥过程中溶质迁移对薄膜形貌的不利影响， 提高打印大面积 连续薄膜的均匀性和重复性， 提高打印精确度并且优化薄膜形貌； 也可以实 现大规摸阵列的高速打印。
在本发明的实施例的喷墨打印方法中， 采用调节打印村底表面能的形式 来控制喷墨的液滴在打印村底表面的铺展， 使得液滴在打印村底的表面铺展 均匀， 因此， 使得有机薄膜厚度均匀并且能提高有机薄膜形成的图案的质量。 发明的精神和范围。 本发明也意图包含属于本发明权利要求范围之内的这些 修改和变形及其任何等同物。

Claims

权利要求书
1、 一种有机薄膜的喷墨打印方法， 其包括：
调节打印衬底的表面能；
在打印衬底上打印有机薄膜， 使得在打印衬底上的液滴均勾铺展。
2、 如权利要求 1所述的喷墨打印方法， 其中所述使得在打印衬底上的液 滴均匀铺展包括使得在打印衬底上铺展的液滴直径为打印机喷嘴喷出的球形 液滴直径的约 2~4倍。
3、 如权利要求 1或 2所述的喷墨打印方法， 其中所述调节打印衬底的表 面能包括在打印衬底表面沿打印列方向或者垂直于打印列方向形成表面能梯 度。
4、 如权利要求 1-3任一项所述的喷墨打印方法， 其中所述形成表面能梯 度包括：
对打印衬底表面进行氟化处理；
通过立体掩膜版， 对打印衬底表面进行紫外臭氧清洗， 所述立体掩膜版 包括具有多个开口的掩膜版基底及设置于掩膜版基底每个开口处的翘片， 所 述翘片所在平面与掩膜版基底所在平面的夹角为约 10。~100。， 所述开口对应 打印衬底上需打印有机薄膜的区域， 当透过所述立体掩膜版对打印衬底进行 紫外臭氧清洗时， 打印衬底上需打印有机薄膜的区域形成表面能梯度。
5、 如权利要求 1-4任一项所述的喷墨打印方法， 其中所述调节打印衬底 表面能包括对打印衬底进行疏水处理和 /或亲水处理。
6、 如权利要求 1-5任一项所述的喷墨打印方法， 其中所述对打印衬底进 行疏水处理和 /或亲水处理包括：
对打印衬底进行氟化处理， 使得打印衬底表面呈现疏水性； 和 /或 对打印衬底进行紫外臭氧清洗， 使得打印衬底表面呈现亲水性。
7、 如权利要求 1~6任一项所述的喷墨打印方法， 其中所述有机薄膜采用 变列间距打印形成。
8、 如权利要求 7所述的喷墨打印方法， 其中所述变列间距打印的列间距 按照打印列的先后顺序递减。
9、 如权利要求 1~8任一项所述的喷墨打印方法， 其中所述有机薄膜采用 单程多列打印形成。
10、 如权利要求 9所述的喷墨打印方法， 其中所述单程多列打印为单程 三列打印。
11、 根据权利要求 1-10任一项所述的喷墨打印方法， 其中所述有机薄膜 还采用变行程间距打印。
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