CN108944050B - Surface treatment method for nozzle - Google Patents
Surface treatment method for nozzle Download PDFInfo
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- CN108944050B CN108944050B CN201711158498.4A CN201711158498A CN108944050B CN 108944050 B CN108944050 B CN 108944050B CN 201711158498 A CN201711158498 A CN 201711158498A CN 108944050 B CN108944050 B CN 108944050B
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- nozzle
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
- B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
- B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
- B41J2/01—Ink jet
- B41J2/135—Nozzles
- B41J2/16—Production of nozzles
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- Manufacturing & Machinery (AREA)
- Particle Formation And Scattering Control In Inkjet Printers (AREA)
Abstract
The invention relates to a surface treatment method of a nozzle, wherein the nozzle comprises an outer surface and an ink ejection channel, the nozzle is made of silicon dioxide, and the method comprises the following steps: filling the ink ejecting channel with filler; treating the filled nozzle with a silane solution comprising a silane containing hydrophobic groups; carrying out heat treatment on the treated nozzle to enable the silane to form a compact hydrophobic self-assembled molecular layer on the outer surface; and removing the filler in the ink ejecting channel. The outer surface of the nozzle after surface treatment is hydrophobic, and the inner surface (inner wall of an ink ejection channel) is hydrophilic, so that stable ink ejection is facilitated; the hydrophobic property of the outer surface of the nozzle reduces and even inhibits the ink flowing out from the inner diameter from wetting on the front surface of the nozzle, and the size of the liquid drop jet can be effectively reduced so as to improve the printing resolution.
Description
Technical Field
The invention relates to the technical field of semiconductor electronic device manufacturing, in particular to a nozzle processing method of an ink-jet printer.
Background
In recent years, high resolution patterning has been widely studied in the preparation of high performance micro semiconductors, electronic devices, and biofunctional materials. Compared with the traditional patterning technology, such as photoetching, electron beam etching, micro-contact transfer printing and the like, the ink-jet printing technology can realize the direct writing of large-area complex patterns, has simple process and low cost, and becomes one of the most promising patterning methods.
At present, ink jet printing technology has been widely used in the preparation of displays, sensors, and other devices. The resolution with which inkjet printing achieves patterning depends primarily on the size of the ejected droplets and the stability of the droplets. Under the same conditions, the smaller the size of the ejected droplets, the higher the resolution of the printed pattern, and the scatter, misalignment, etc. caused by the instability of the droplets all reduce the resolution of the printed pattern. In order to improve the printing resolution, the common methods include reducing the diameter of the nozzle of the print head, adjusting the print pulse signal, changing the physical properties of the printing ink, adjusting the wettability of the substrate, and the like, but these methods have certain limitations on the printing conditions, the ink, the substrate properties, and the like.
Inkjet printing systems typically include one or more printheads with nozzles from which ink is ejected as droplets that are deposited on corresponding substrate locations. During drop formation, ink tends to wet, run, and spill over the front face of the print head nozzle. The greater this wetting of the ink at the nozzle, the greater the surface tension that the solution needs to overcome to disengage from the nozzle, and the resulting drop size to print the nozzle diameter; furthermore, contamination of the ink on the front face of the printhead nozzles can cause or contribute to clogging of the ink jet nozzles and channels, reducing ink printing stability, and such clogging alone or in combination with wetted, contaminated front faces of the nozzles can cause problems with non-ejection of ink or variations in droplet size, droplet tailing, flight direction drift, etc., greatly reducing the resolution of the printed pattern. Therefore, it is desirable to perform an anti-wetting treatment on the front surface of the nozzle of the print head to reduce or inhibit wetting of the ink on the front surface of the nozzle, and to improve the resolution of inkjet printing without changing the dimensions of the print head, the properties of the ink and the substrate, and other external conditions.
The hydrophobic coating is prepared on the surface of the nozzle by using methods such as laminating, chemical vapor deposition and the like, so that the wetting degree of the nozzle can be reduced, and the hydrophobic coating has better chemical stability. More importantly, the technology is difficult to realize the selective deposition of the coating on the surface of the nozzle, and the hydrophobic coating is simultaneously deposited on the inner hole of the nozzle, so that the hydrophilic printing ink is difficult to spray under the repulsion of the hydrophobic capillary tube, thereby causing a series of printing process problems.
Disclosure of Invention
Based on this, it is an object of the present invention to provide a method of surface treatment of nozzles that improves the resolution of inkjet printing.
The specific technical scheme is as follows:
a surface treatment method of a nozzle, wherein the nozzle comprises an outer surface and an ink ejecting channel, the nozzle is made of silicon dioxide, and the method comprises the following steps:
filling the ink ejecting channel with filler;
treating the outer surface of the nozzle with a silane solution comprising a silane containing hydrophobic groups;
carrying out heat treatment on the treated nozzle to enable the silane to form a compact hydrophobic self-assembled molecular layer on the outer surface;
and removing the filler in the ink ejecting channel.
In some of these embodiments, the silane solution further comprises a catalyst selected from n-butylamine.
In some of these embodiments, the silane is selected from an alkylsilane, a perfluoroalkylsilane, a chlorosilane, or an alkoxysilane.
In some of these embodiments, the silane is selected from octadecylethoxysilane, octadecyltrichlorosilane, or tridecafluorooctyltriethoxysilane.
In some embodiments, the method of filling the ink ejection channel with the filler includes:
filling the ink ejecting channel with positive photoresist solution, curing the positive photoresist solution, exposing under UV light, and developing to remove the photoresist on the outer surface.
In some of these embodiments, the process parameters of the UV light illumination are: the UV light power is 15-17mW/cm3。
In some of these embodiments, the process parameters of the UV light illumination are: the exposure time is 2-4 s.
In some of these embodiments, the process parameters of the UV light illumination are: the UV light power is 15-17mW/cm3The exposure time is 2-4 s.
In some of these embodiments, the process parameters of the curing process are: the curing temperature is 100-130 ℃.
In some of these embodiments, the process parameters of the curing process are: the curing time is 1-10 min.
In some of these embodiments, the process parameters of the curing process are: the curing temperature is 100 ℃ and 130 ℃, and the curing time is 1-10 min.
In some of these embodiments, the method of treating the outer surface of the nozzle with the silane solution is: and soaking the nozzle in the silane solution for 24-36 h.
In some of these embodiments, the process parameters of the heat treatment are: the heat treatment temperature is 100-200 ℃.
In some of these embodiments, the process parameters of the heat treatment are: the heat treatment time is 1-2 h.
In some of these embodiments, the process parameters of the heat treatment are: the heat treatment temperature is 100-.
The surface treatment method of the nozzle is based on a molecular self-assembly method, an ink ejection channel of the nozzle is filled and leveled by adopting a filling agent, then the nozzle is soaked in a silane solution containing hydrophobic groups, and then heat treatment is carried out, so that silane molecules are coupled with hydroxyl groups on the surface of the nozzle to form Si-O-Si bonds (the principle is shown in figure 1), and compact hydrophobic self-assembly molecular layers (SAMs) are formed on the outer surface of the nozzle, namely selective anti-wetting treatment is carried out on the surface of the nozzle. The outer surface of the nozzle after surface treatment is hydrophobic, and the inner surface (inner wall of an ink ejection channel) is hydrophilic, so that stable ink ejection is facilitated; the hydrophobic property of the outer surface of the nozzle reduces and even inhibits the ink flowing out from the inner diameter from wetting on the front surface of the nozzle, and the size of the liquid drop jet can be effectively reduced so as to improve the printing resolution.
Meanwhile, the hydrophobic coating on the surface of the nozzle is a self-assembled molecular layer formed on the basis of chemical bonds of Si-O-Si, and has good physical stability. And the invention is based on the whole solution processing technology, the processing technology is simple, and the cost is low.
Drawings
FIG. 1 is a schematic diagram illustrating the basic principle of molecular self-assembly in this embodiment;
FIG. 2 is a schematic structural view of a nozzle;
FIG. 3 is a schematic view of the nozzle after the ink ejection channel has been filled;
FIG. 4 is a schematic representation of the outer surface of the nozzle after formation of a hydrophobic self-assembled molecular layer;
FIG. 5 is a schematic view of the ink ejection channel of the nozzle with the filler removed
FIG. 6 is a schematic illustration of Si-O-Si bonding.
Detailed Description
In order that the invention may be more fully understood, reference will now be made to the following description. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
Examples
Referring to fig. 2, the ink jet print head for processing of the present embodiment is provided with a nozzle 10 including an outer surface 101 and an ink ejection channel 103.
When the surface treatment is not performed, the wettability of the outer surface of the nozzle and the inner wall of the ink ejection channel is generally the same, and the ink for printing is hydrophilic, so that the ink ejected from the ink ejection channel 103 of the nozzle during ink jet printing is easy to wet, flow and overflow on the outer surface of the nozzle, and the resolution and stability of ink printing are reduced.
The surface treatment method of the nozzle (the material is silicon dioxide) comprises the following steps:
s1, filling the ink ejection channel of the nozzle with the filler 104: referring to fig. 3, the nozzle was vertically placed above the positive photoresist solution SJR7540, ensuring that the nozzle was in surface contact with the solution. Since the diameter of the ink ejection channel of the nozzle is usually in the range of 10 to 50 μm, when the nozzle is placed in a photoresist solution, the solution enters the inner wall of the nozzle to fill the nozzle by capillary force. The nozzle filled with the photoresist solution was then set at a power of 16.6mW/cm2Is exposed for 3s, and then developed in a developing solution for 60s to remove the photoresist on the outer diameter of the nozzle. And then heating the nozzle at 120 ℃ for 2min to solidify the filled photoresist and protect the ink ejection channel.
And S2, soaking the filled nozzle in a silane solution. This example uses a solution of Octadecylethoxysilane (OTES). 0.5mL of OTES was dissolved in 7mL of toluene, and 0.1mL of n-butylamine (catalyst) was added to the solution, followed by uniform mixing with stirring. The filled nozzle is soaked in the OTES solution for 24 hours.
S3, after soaking, the nozzle was taken out and placed on a hot stage at 110 ℃ to heat for 1 hour to complete Si-O-Si bonding, and a dense hydrophobic self-assembled molecular layer 105 was formed on the outer surface of the nozzle (as shown in fig. 4).
In this embodiment, the molecular self-assembly is completed by three steps:
firstly, butylamine is adsorbed on-OH groups on the surface of a nozzle to generate a strong nucleophilic grid structure, and the grid structure can adsorb OTES;
in the second step, OTES will take a proton from butylamine and form OH with this proton, i.e. the first step in FIG. 6a (hydrolysis process), the by-products of this step include intermediate (R-Si- (OH)3) and ethanol;
thirdly, the intermediate product is dehydrated with-OH on the surface of the nozzle under the action of butylamine to form a dense hydrophobic self-assembled layer SAMs 4, as shown in FIG. 6. In the whole chemical reaction process, the butylamine is used as a catalyst and does not participate in substantial reaction.
S4, the self-assembled nozzle is repeatedly washed with toluene to remove OTES molecules remaining on the nozzle surface. The nozzles are placed in a resist stripping solution corresponding to the SJR7540 resist for stripping, and the resist in the ink ejection channels of the nozzles is removed to expose the hydrophilic inner wall 102, as shown in fig. 5.
The surface treatment method of the nozzle is based on a molecular self-assembly method, an ink ejection channel of the nozzle is filled and leveled by adopting a filling agent, then the nozzle is soaked in a silane solution containing hydrophobic groups, and then heat treatment is carried out, so that silane molecules are coupled with hydroxyl groups on the surface of the nozzle to form Si-O-Si bonds (the principle is shown in figure 1), and compact hydrophobic self-assembly molecular layers (SAMs) are formed on the outer surface of the nozzle, namely selective anti-wetting treatment is carried out on the surface of the nozzle. The outer surface of the nozzle after surface treatment is hydrophobic, and the inner surface (inner wall of an ink ejection channel) is hydrophilic, so that stable ink ejection is facilitated; the hydrophobic property of the outer surface of the nozzle reduces and even inhibits the ink flowing out from the inner diameter from wetting on the front surface of the nozzle, and the size of the liquid drop jet can be effectively reduced so as to improve the printing resolution.
Meanwhile, the hydrophobic coating on the surface of the nozzle is a self-assembled molecular layer formed on the basis of chemical bonds of Si-O-Si, and has good physical stability. And the invention is based on the whole solution processing technology, the processing technology is simple, and the cost is low.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (7)
1. A surface treatment method of a nozzle is characterized in that the nozzle comprises an outer surface and an ink ejecting channel, the nozzle is made of silicon dioxide, and the method comprises the following steps:
filling the ink ejecting channel with filler; the method for filling the filler in the ink ejecting channel comprises the following steps: filling a positive photoresist solution into the ink ejection channel, curing the positive photoresist solution, then exposing under UV light, and developing to remove the photoresist on the outer surface;
treating the outer surface of the nozzle with a silane solution comprising a silane containing hydrophobic groups; the silane solution further comprises a catalyst selected from the group consisting of n-butylamine;
carrying out heat treatment on the treated nozzle to enable the silane to form a compact hydrophobic self-assembled molecular layer on the outer surface;
and removing the filler in the ink ejecting channel.
2. A method for treating the surface of a nozzle as claimed in claim 1, wherein said silane is selected from the group consisting of alkylsilanes, perfluoroalkylsilanes, chlorosilanes and alkoxysilanes.
3. The method for surface treatment of a nozzle as claimed in claim 2, wherein said silane is selected from octadecylethoxysilane, octadecyltrichlorosilane or tridecafluorooctyltriethoxysilane.
4. The method for treating the surface of a nozzle according to claim 1, wherein the process parameters of the UV light irradiation are: the UV light power is 15-17mW/cm3And/or the exposure time is 2-4 s.
5. The method for treating the surface of a nozzle according to claim 1, wherein the curing process comprises the following process parameters: the curing temperature is 100-130 ℃, and/or the curing time is 1-10 min.
6. The method for surface treatment of a nozzle according to any one of claims 1 to 3, wherein the method for treating the outer surface of the nozzle with the silane solution is: and soaking the nozzle in the silane solution for 24-36 h.
7. A method for treating the surface of a nozzle according to any one of claims 1 to 3, wherein the heat treatment comprises the following process parameters: the heat treatment temperature is 100-200 ℃, and/or the heat treatment time is 1-2 h.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201711158498.4A CN108944050B (en) | 2017-11-20 | 2017-11-20 | Surface treatment method for nozzle |
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| CN201711158498.4A CN108944050B (en) | 2017-11-20 | 2017-11-20 | Surface treatment method for nozzle |
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| CN108944050A CN108944050A (en) | 2018-12-07 |
| CN108944050B true CN108944050B (en) | 2020-03-20 |
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| EP4135984A4 (en) * | 2020-04-14 | 2024-01-17 | Hewlett Packard Development Co | Fluid-ejection die with stamped nanoceramic layer |
| CN115569826A (en) * | 2022-10-21 | 2023-01-06 | 九久胜新流体科技(苏州)有限公司 | CNC machine tool surface treatment method |
| CN116197099B (en) * | 2023-03-10 | 2023-11-07 | 厦门金诺花科学仪器有限公司 | Preparation method of nano-upgrading reusable needle |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1847001A (en) * | 2005-04-12 | 2006-10-18 | 精工爱普生株式会社 | Liquid-repellent member, nozzle plate, liquid-jet head using the same, and liquid-jet apparatus |
| CN1906253A (en) * | 2004-04-29 | 2007-01-31 | 惠普发展公司 | UV curable coating composition |
| CN103895347A (en) * | 2012-12-27 | 2014-07-02 | 精工爱普生株式会社 | Nozzle plate, liquid ejecting head, and liquid ejecting apparatus |
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- 2017-11-20 CN CN201711158498.4A patent/CN108944050B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1906253A (en) * | 2004-04-29 | 2007-01-31 | 惠普发展公司 | UV curable coating composition |
| CN1847001A (en) * | 2005-04-12 | 2006-10-18 | 精工爱普生株式会社 | Liquid-repellent member, nozzle plate, liquid-jet head using the same, and liquid-jet apparatus |
| CN103895347A (en) * | 2012-12-27 | 2014-07-02 | 精工爱普生株式会社 | Nozzle plate, liquid ejecting head, and liquid ejecting apparatus |
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