CN115079513A - Embedded micro-nano device for substrate structuring treatment and jet printing preparation method thereof - Google Patents
Embedded micro-nano device for substrate structuring treatment and jet printing preparation method thereof Download PDFInfo
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/0002—Lithographic processes using patterning methods other than those involving the exposure to radiation, e.g. by stamping
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B81—MICROSTRUCTURAL TECHNOLOGY
- B81C—PROCESSES OR APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OR TREATMENT OF MICROSTRUCTURAL DEVICES OR SYSTEMS
- B81C1/00—Manufacture or treatment of devices or systems in or on a substrate
- B81C1/00349—Creating layers of material on a substrate
- B81C1/00373—Selective deposition, e.g. printing or microcontact printing
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/16—Coating processes; Apparatus therefor
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
- H05K3/107—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern by filling grooves in the support with conductive material
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
- H05K3/12—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using thick film techniques, e.g. printing techniques to apply the conductive material or similar techniques for applying conductive paste or ink patterns
- H05K3/1208—Pretreatment of the circuit board, e.g. modifying wetting properties; Patterning by using affinity patterns
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
- H05K3/18—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/05—Flexible printed circuits [FPCs]
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/01—Tools for processing; Objects used during processing
- H05K2203/0104—Tools for processing; Objects used during processing for patterning or coating
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/07—Treatments involving liquids, e.g. plating, rinsing
- H05K2203/0736—Methods for applying liquids, e.g. spraying
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/07—Treatments involving liquids, e.g. plating, rinsing
- H05K2203/0756—Uses of liquids, e.g. rinsing, coating, dissolving
- H05K2203/0776—Uses of liquids not otherwise provided for in H05K2203/0759 - H05K2203/0773
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/11—Treatments characterised by their effect, e.g. heating, cooling, roughening
- H05K2203/1173—Differences in wettability, e.g. hydrophilic or hydrophobic areas
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Abstract
The invention belongs to the technical field related to the preparation of flexible electronic devices, and discloses an embedded micro-nano device for substrate structuring treatment and a jet printing preparation method thereof, wherein the method comprises the following steps: (1) providing a nano-imprinting template, wherein a plurality of arched strip-shaped bulges are formed on the surface of the nano-imprinting template; (2) spin-coating a polymer glue solution on a flexible transparent substrate, and continuously pressing the polymer glue solution by adopting a nano-imprint template to obtain a structured substrate, wherein a plurality of channels are formed in the obtained polymer glue layer; (3) performing local hydrophilic/hydrophobic treatment on the structured substrate to enable the bottom surface and the side wall surface of the channel to have hydrophilicity and the upper surface of the side wall of the channel to have hydrophobicity; (4) filling nano metal slurry in a channel of the structured substrate by utilizing an electrofluid spray printing mode, and further obtaining the embedded micro-nano device. The invention realizes large-area and curved surface manufacturing, overcomes the limitation of the prior manufacturing technology, and has the advantages of low cost, high efficiency and the like.
Description
Technical Field
The invention belongs to the technical field related to preparation of flexible electronic devices, and particularly relates to an embedded micro-nano device for substrate structuring treatment and a jet printing preparation method thereof.
Background
With the rapid increase of the demand for large-area flexible electronic devices such as wearable electronic equipment, robot electronic skins, aircraft intelligent skins and the like, the requirements for flexibility, precision, area amplitude, integration level, curved surface conformal attachment and the like of the electronic devices are higher and higher, and correspondingly, higher requirements are provided for the resolution, positioning precision, manufacturing consistency, large-area batch manufacturing and curved surface compatibility of the manufacturing process.
Compared with the existing manufacturing technology, the photoetching technology has strong manufacturing controllability and high resolution, but has complex flow, higher cost and lower efficiency, and can only be suitable for small-area and plane manufacturing. Although the self-assembly technology can be used for manufacturing large-area curved surfaces, the manufacturing controllability is poor and the efficiency is low. In the printing process, the screen/gravure printing can realize the printing and manufacturing of a plane structure, but the pattern resolution is low, the multi-layer overprinting precision is limited, a physical mask is needed, and the manufacturing of a curved surface structure is extremely difficult; the transfer printing technology has very high requirements on ink rheology and is mainly used for plane manufacturing; the jet printing technology does not need a mask plate, and can be used for manufacturing patterns on a plane/curved substrate, wherein the piezoelectric/thermal bubble jet printing technology is limited by low printing resolution (>20 mu m) and narrow ink viscosity range (5-20 cP); the aerosol jet printing technology is limited by the types of ink materials and is difficult to meet the jet printing manufacture of a multilayer heterostructure; the electrofluid spray printing technology is a stretching spray printing technology driven by an electric field, can realize ultrahigh resolution printing, and realize switching printing of three modes of point spraying, direct writing and atomization, has outstanding potential and advantages in the aspect of high-precision manufacturing of large-area micro-nano structures, but still has the problems of poor positioning precision, poor pattern size consistency, limited conductivity due to small height-width ratio of pattern lines, poor adhesion force, reduced reliability and the like.
In view of the above-mentioned problems with large-area flexible curved surface electronic manufacturing techniques, several new composite manufacturing techniques have been proposed. Patent CN202110982869.0 combines nanoimprint lithography and dry etching processes to prepare grid electrode channels and positive electrode window regions with nanometer line width on the surface of the transparent anti-reflection layer, and coats electrode slurry on the surface of the transparent anti-reflection layer by spraying, and then uses a scraper to scrape silver paste into the grid electrode channels and the positive electrode window regions, although a solar cell with nanometer line width grid electrode is obtained, the scraping of silver paste by using the scraper is difficult to avoid the residue and waste of silver paste, and the integrity of channel filling is also difficult to ensure. Patents CN112566365A and CN104009124A also have the above limitations. Patent CN201910585900.X combines electrofluid spray printing technology and hot stamping technology to prepare a double-gate organic thin film transistor, gets rid of the dependence of traditional technologies such as mask and photoetching on precision instruments, but is limited in application in special scenes such as large manufacturing breadth and batch preparation. In the OLED manufacturing flow, inkjet printing technology is commonly used to fill pixel pits at fixed points, as in patent nos. CN110635068A and CN 106601779A, but it is commonly used for rigid substrates and the pixel pits have small aspect ratio, and further research is needed for micro-nano device manufacturing.
In summary, for the requirements of large-area, mass-production and complex curved surface manufacturing of flexible electronic devices, the existing single manufacturing technology and composite manufacturing technology cannot meet all the requirements, so a manufacturing method with the advantages of high resolution, low cost, efficient mass production, strong manufacturing controllability, large area, curved surface manufacturing and the like is urgently needed.
Disclosure of Invention
Aiming at the defects or improvement requirements of the prior art, the invention provides an embedded micro-nano device for substrate structural processing and a jet printing preparation method thereof, which combine the advantages of high precision, large-area manufacturing, high viscosity range and high resolution of an electrofluid jet printing technology, firstly obtain a high-resolution structured substrate by utilizing the roll-to-roll nanoimprint technology, and then fill conductive slurry in a patterned channel of the structured substrate by utilizing the electrofluid jet printing technology, thereby realizing the manufacturing of the embedded micro-nano device. The invention provides a local hydrophilic and hydrophobic treatment method for a structured substrate and a nano-imprint template for realizing directional fluid transmission, realizes self-alignment of slurry during spray printing and directional transportation and self-leveling in a channel, and has wide application prospects in the fields of medical health, aerospace, Internet of things, human-computer interaction and the like, such as wearable electronics, aircraft intelligent skin, structural health monitoring, transparent solar cells, display panels, intelligent artificial limbs and the like.
In order to achieve the above object, according to an aspect of the present invention, there is provided a method for preparing an embedded micro-nano device by inkjet printing, the method comprising the steps of:
(1) providing a nano-imprinting template, wherein a plurality of strip-shaped bulges are formed on the surface of the nano-imprinting template, the strip-shaped bulges are arched, and the thickness of the strip-shaped bulges is gradually increased from two ends to the middle along a smooth curve;
(2) spin-coating a polymer glue solution on a flexible transparent substrate, continuously pressing the polymer glue solution by adopting a nano-imprinting template, and then curing the polymer glue solution to form a polymer glue layer so as to obtain a structured substrate, wherein a plurality of channels are formed in the polymer glue layer and penetrate through the surface of the polymer glue layer away from the flexible transparent substrate; the shape and the position of the channel respectively correspond to the shape and the position of the strip-shaped bulges;
(3) performing local hydrophilic/hydrophobic treatment on the structured substrate, wherein the bottom surface and the side wall surface of the channel after the local hydrophilic/hydrophobic treatment have hydrophilicity, and the region of the surface of the polymer adhesive layer, which is far away from the flexible transparent substrate and is not penetrated by the channel, has hydrophobicity;
(4) and filling nano metal slurry in the channel of the structured substrate by utilizing an electric fluid jet printing mode, thereby obtaining the embedded micro-nano device.
Further, the nano-imprint template is obtained by steps of coating template materials on a silicon mother board, vacuum-assisted degassing, glue homogenizing, curing, demolding and the like, wherein the silicon mother board is obtained by multiple times of alignment and etching.
Further, the nano-imprinting template is basically rectangular, and a plurality of strip-shaped protrusions are formed on one surface of the nano-imprinting template; the strip-shaped protrusions are of a symmetrical structure, and the geometric centers of the strip-shaped protrusions and the geometric centers of the nano-imprinting templates are collinear.
Further, the preparation of the structured substrate by the nanoimprint lithography method comprises the following steps:
s21, spin-coating polymer glue solution on the flexible transparent substrate;
s22, continuously pressing the nano-imprinting template into polymer glue solution coated on the flexible transparent substrate under the action of pressure, then carrying out ultraviolet curing on the polymer glue solution, and finishing the copying of the nano-imprinting template graph through plastic deformation;
and S23, rotationally demolding the primary product obtained in the step S22 to obtain the structured substrate.
Further, the local hydrophilic/hydrophobic treatment of the structured substrate comprises the steps of:
s31, carrying out ultraviolet irradiation hydrophilic modification treatment on the structured substrate;
and S32, spraying the hydrophobic material onto the coating roller in a spraying mode, uniformly coating the hydrophobic material onto the upper surface of the side wall of the trench by using the coating roller, and naturally drying or carrying out auxiliary drying heat treatment at 60-70 ℃ for 20 minutes to obtain the cured hydrophobic material.
Further, after the electrofluid jet printing is finished, sintering post-treatment is needed to endow functionality, and then the embedded micro-nano device is obtained.
Further, after the filling, the obtained device is stored in a control box at normal temperature and predetermined relative humidity for several minutes.
Further, after completion of the filling, the resulting device was stored in a control box at 30 ℃ and 80% relative humidity for 5 minutes.
Further, the structured substrate was irradiated with an ultraviolet irradiator for 10 minutes in an open environment.
Furthermore, after the electrofluid jet printing is finished, sintering post-treatment is needed, and the obtained device is dried for a period of time at a temperature lower than the sintering temperature before sintering, so that the sintering quality is improved.
According to another aspect of the invention, the embedded micro-nano device with the substrate structured treatment is prepared by adopting the jet printing preparation method of the embedded micro-nano device with the substrate structured treatment.
In general, compared with the prior art, the embedded micro-nano device for substrate structuring processing and the jet printing preparation method thereof provided by the invention have the following beneficial effects:
1. the jet printing preparation method combines the advantages of high precision and large-area manufacturing of a roll-to-roll nano-imprinting technology and high viscosity range and high resolution of an electrofluid jet printing technology, obtains a high-resolution structured substrate by utilizing the roll-to-roll nano-imprinting technology, and fills conductive paste in a patterned channel of the structured substrate by utilizing the electrofluid jet printing technology, so that a flexible embedded micro-nano device is manufactured, large-area and curved surface manufacturing is realized, the limitation of the existing manufacturing technology is overcome, and the jet printing preparation method has the advantages of batch manufacturing, low cost, high efficiency and the like.
2. The height of the nano-imprinting template is smoothly increased from two ends to the middle along the length of the nano-imprinting template in a curve mode, so that the depth of the channel of the imprinted structured substrate is increased from two ends to the middle, directional fluid transmission can be achieved, slurry can smoothly flow in the channel, and the uniformity and the integrity of filling are guaranteed.
3. The structured substrate is modified through local hydrophilic and hydrophobic, the channel side wall and the bottom have hydrophilicity, the upper surface of the channel side wall has hydrophobicity, when the alignment is inaccurate, liquid drops dropping on the upper surface of the channel side wall can automatically flow into the hydrophilic channel bottom with high surface energy from the hydrophobic surface with low surface energy, the alignment precision is further improved, the channel subjected to hydrophilic treatment enables slurry to flow more smoothly in the channel, and the problem that the ultra-fine channel is difficult to seep into due to the action of surface tension is solved.
4. The patterned structure prepared by the invention has good dimensional consistency, the structured substrate prepared by the nanoimprint technology has high resolution and small error, and the channel structure limits the transverse flow of the conductive ink, so that the problems of uneven line width profile, uneven thickness, burrs, coffee ring effect and the like are eliminated.
5. The invention can manufacture the embedded micro-nano device with high depth-to-width ratio, the lead obtained by single spray printing of the electrofluid spray printing technology is difficult to reach the nanometer thickness, and the width of the lead can be increased by multiple printing.
6. The manufacturing controllability is strong, the nano-imprinting technology can accurately control the structure size, the error is small, the failure rate is low, the electro-fluidic jet printing technology can realize jet printing according to needs, accurate positioning and control of a printing path, and the yield of device batch production is ensured.
7. The conducting circuit is embedded into the flexible transparent substrate, so that the abrasion of the device in the using process can be reduced, the conducting circuit is not easy to oxidize and fall off, the service life of the device is long, and the reliability is high.
Drawings
FIG. 1 is a schematic diagram of a jet printing preparation method of an embedded micro-nano device for substrate structuring processing provided by the invention;
FIG. 2 is a schematic flow chart of a jet printing preparation method of an embedded micro-nano device for substrate structuring processing provided by the invention;
fig. 3 (a) and (b) are schematic views illustrating different angles of a structured substrate capable of realizing directional fluid transmission;
FIG. 4 is a schematic illustration of a localized hydrophilic/hydrophobic modification of a structured substrate;
fig. 5 is a schematic diagram of an electrofluidic jet-filled structured substrate.
The same reference numbers will be used throughout the drawings to refer to the same or like elements or structures, wherein: 1-flexible transparent substrate, 2-polymer adhesive, 3-nano imprinting template, 4-hydrophobic material, 5-nano metal slurry and 6-electrofluid spray printing equipment.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and do not limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
The invention provides a jet printing preparation method of an embedded micro-nano device for substrate structuralization processing, which comprises the following steps:
providing a nano-imprinting template, wherein a plurality of strip-shaped bulges are formed on the surface of the nano-imprinting template, the strip-shaped bulges are arched, and the thickness of the strip-shaped bulges is gradually increased from two ends to the middle along a smooth curve.
The nano-imprint template is obtained by coating a template material on a silicon mother board, vacuum-assisted degassing, glue homogenizing, curing, demolding and the like, wherein the silicon mother board is obtained by multiple times of alignment and etching. The nano-imprint template is basically rectangular and is subjected to patterning treatment, a plurality of strip-shaped protrusions are formed on one surface of the nano-imprint template, the thickness of each strip-shaped protrusion increases from two ends to the middle along a smooth curve, so that the depth of a channel obtained by imprinting through the nano-imprint template increases from two ends to the middle, and therefore when the nano-metal slurry is filled in an electrofluid jet printing mode, the nano-metal slurry is automatically transported to the middle of the channel directionally.
In this embodiment, the strip-shaped protrusions have a symmetrical structure, and the geometric center of the strip-shaped protrusions is collinear with the geometric center of the nano-imprinting template.
Spin-coating a polymer glue solution on a flexible transparent substrate, continuously pressing the polymer glue solution by adopting a nano-imprinting template, and then curing the polymer glue solution to form a polymer glue layer so as to obtain a structured substrate, wherein a plurality of channels are formed in the polymer glue layer and penetrate through the surface of the polymer glue layer away from the flexible transparent substrate; the shape and the position of the channel respectively correspond to the shape and the position of the strip-shaped bulges.
First, the flexible transparent substrate is sequentially cleaned and dried, and then the flexible transparent substrate is fed into the imprinting mechanism.
The method for preparing the structured substrate by adopting the nano-imprinting mode comprises the following steps:
and S21, spin-coating a polymer glue solution on the flexible transparent substrate.
And S22, continuously pressing the nano-imprinting template into the polymer glue solution coated on the flexible transparent substrate under the action of pressure, then carrying out ultraviolet curing on the polymer glue solution, and finishing the copying of the nano-imprinting template pattern through plastic deformation.
And S23, rotationally demolding the primary product obtained in the step S22 to obtain the structured substrate.
And thirdly, performing local hydrophilic/hydrophobic treatment on the structured substrate, wherein the bottom surface and the side wall surface of the channel after the local hydrophilic/hydrophobic treatment have hydrophilicity, and the region of the surface of the polymer adhesive layer, which is far away from the flexible transparent substrate and is not penetrated by the channel, has hydrophobicity.
The local hydrophilic/hydrophobic treatment of the structured substrate comprises the steps of:
and S31, carrying out ultraviolet irradiation hydrophilic modification treatment on the structured substrate.
And S32, spraying the hydrophobic material onto the coating roller in a spraying mode, uniformly coating the hydrophobic material onto the upper surface of the side wall of the trench by using the coating roller, and naturally drying or carrying out auxiliary drying heat treatment at 60-70 ℃ for 20 minutes to obtain the cured hydrophobic material.
After local hydrophilic/hydrophobic modification, the side wall and the bottom of the channel are ensured to have hydrophilicity, and the upper surfaces of the two side walls of the channel have hydrophobicity. When the alignment is inaccurate, the liquid drops dropping on the upper surface of the side wall of the channel can automatically flow into the bottom of the hydrophilic channel with high surface energy from the hydrophobic surface with low surface energy, so that the alignment precision is further improved.
Filling nano metal slurry in the channel of the structured substrate in an electro-fluid jet printing mode, and further obtaining the embedded micro-nano device.
The metal nano-slurry is conductive printable nano-metal ink, and can be any one of gold, silver, copper, aluminum or liquid metal. The electrofluid spray printing process adopts electrofluid spray printing equipment, and applies direct current or alternating current voltage between a metal or nonmetal spray head and a substrate to pull ink out of the spray head to form a Taylor cone with a pole tip, so that the preparation of submicron or nanometer electronic devices can be realized. The electrofluid spray printing process in the subsequent steps adopts the device.
Different printing paths can be designed for different structured substrates, such as fixed-point interval printing, segmented printing, reciprocating continuous printing and the like, so as to ensure that the channels are completely filled.
And after the electrofluid jet printing is finished, sintering post-treatment is required to endow functionality, and then the embedded micro-nano device is obtained. The sintering mode can be hot plate sintering, oven sintering and photon sintering, and through sintering, metal particles in the nano metal ink are melted and connected together, so that the nano device has conductivity, and the micro-nano device has functionality.
After filling, the obtained device is placed in a control box with normal temperature and high relative humidity for storage for several minutes, so that the solvent is uniformly and slowly volatilized, and more holes caused by too fast volatilization of ink in the channel are avoided. The resulting device is baked for a period of time at a temperature below the sintering temperature before being sintered to improve the quality of the sintering.
The invention also provides the embedded micro-nano device with the substrate structuralized treatment, which is prepared by adopting the jet printing preparation method of the embedded micro-nano device with the substrate structuralized treatment.
The present invention will be described in further detail with reference to specific examples.
The embodiment of the invention provides a jet printing preparation method of an embedded micro-nano device for substrate structuring processing, which is shown in fig. 1 and fig. 2. In a preferred embodiment, the technology is used for manufacturing the metal mesh transparent conductive film, and specifically comprises the following steps:
s1: the flexible transparent substrate 1 is cleaned and dried, the flexible transparent substrate 1 is cleaned by using a detergent, an acetone solution, isopropyl alcohol and deionized water in sequence, and the flexible transparent substrate is dried by using nitrogen after being cleaned.
S2: the method comprises the steps of manufacturing a nano-imprint template 3 capable of realizing directional fluid transmission, coating template materials on a silicon mother board, vacuum-assisted degassing, glue homogenizing, curing, demolding and the like to obtain the nano-imprint template 3, wherein the silicon mother board is obtained after multiple times of alignment and etching. In the embodiment, the grid electrode channels of the metal grid transparent conductive film are distributed and interconnected in a longitude and latitude mode according to a certain interval, the line width is 1-10 mu m, the depth is 1-10 mu m, and the interval can be flexibly adjusted according to actual requirements.
S3: the method for manufacturing the structured substrate by utilizing the nanoimprint technology specifically comprises the following steps:
(1) the UV imprint paste is coated on the flexible transparent substrate 1.
And in the process of roll surface rotating gluing, the polymer glue 2 is transferred from the first-stage glue spreader to the intermediate roll in an adhesion mode and then coated on the substrate, and finally a polymer glue layer with uniform thickness is formed on the flexible transparent substrate 1.
(2) The nano-imprinting template 3 is wound on an imprinting roller, the flexible transparent substrate 1 coated with the UV polymer imprinting adhesive is continuously conveyed between the imprinting roller and a supporting roller, the nano-imprinting template is pressed into a soft polymer adhesive layer under the action of mechanical stress, and the copying of the template pattern is completed through the plastic deformation of the polymer adhesive.
(3) The photoresist is uv cured and demolded by a demolding roller to obtain a structured substrate, as shown in fig. 3.
S4: the local hydrophilic/hydrophobic modification of the structured substrate, as shown in fig. 4, specifically comprises the following steps:
(1) and carrying out ultraviolet irradiation hydrophilic modification treatment on the structured substrate.
And irradiating the structured substrate for 10 minutes in an open environment by using an ultraviolet irradiator, increasing hydrophilic groups including hydroxyl groups of the structured substrate, and improving the hydrophilicity of the structured substrate, the uniformity of droplet deposition and the adhesion of the slurry.
(2) The hydrophobic material 4 is sprayed in a spray pattern to the coating roller.
The hydrophobic material 4 is sprayed to the coating roller in a spraying mode by using a 0.3mm caliber spray gun at a pressure of 0.2Pa and a low flow rate, and a layer of hydrophobic material coating with uniform thickness is formed on the surface of the coating roller.
In the embodiment, the hydrophobic material 4 is a Semlike ZXL-WN super-hydrophobic nano protective coating.
(3) And uniformly coating the hydrophobic material on the upper surface of the side wall of the channel of the structured substrate by using a coating roller, and naturally drying or carrying out auxiliary drying heat treatment at 60-70 ℃ for 20 minutes to finish curing.
After the local hydrophilic/hydrophobic modification of the structured substrate, the side wall and the bottom of the channel are ensured to have hydrophilicity, and the upper surfaces of the two side walls of the channel have hydrophobicity. When the alignment is not accurate, the liquid drops dropping on the upper surface of the side wall of the channel can automatically flow into the bottom of the hydrophilic channel with high surface energy from the hydrophobic surface with low surface energy, so that the alignment precision is further improved.
S5 filling nano metal slurry 5 in the channel on the surface of the structured substrate by using an electrofluid jet printing technology, which specifically comprises the following steps:
(1) according to the pattern of the structured substrate, a printing path is designed in CAD software, aiming at the metal grid channel, a channel in a certain direction is selected, and after the channels in the certain direction are filled in sequence, the channels in the other direction are filled. When filling a certain channel, taking one end of the channel as a starting point, continuously spraying and printing to the other end, and then turning back and repeatedly printing until the channel is completely filled.
(2) The print path in the CAD software is generated into a DXF formatted file and is imported to the electro-fluid jet printing apparatus 6.
(3) The injector is used for absorbing about 0.5ml of nano silver paste as conductive ink, a glass nozzle is adopted, the diameter of the nozzle is 10-30 mu m, and the glass nozzle and the injector are assembled and arranged on a corresponding mechanism of the electrofluid spray printing equipment 6.
(4) Adjusting parameters such as proper air pressure, proper voltage, proper distance between the nozzle and the substrate, and the like, leading the parameters into a printing path, determining a printing starting point, performing jet printing deposition according to the pre-drawn printing path, and filling the patterned channel, as shown in fig. 5.
S6 post-sintering treatment for endowing functionality, specifically comprising the following steps:
(1) after the filling, the device is placed in a control box with 30 ℃ and 80% relative humidity for storage for 5 minutes, so that the solvent is uniformly and slowly volatilized, and more holes are prevented from being generated due to the fact that ink in the channel is volatilized too fast.
(2) Drying for 1 hour in an oven at 100 ℃ to improve the sintering quality.
The flash lamp is sintered for 200 seconds and 300 seconds, so that the nano silver paste has good conductivity and is endowed with functionality.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. A jet printing preparation method of an embedded micro-nano device for substrate structuralization processing is characterized by comprising the following steps:
(1) providing a nano-imprinting template, wherein a plurality of strip-shaped bulges are formed on the surface of the nano-imprinting template, the strip-shaped bulges are arched, and the thickness of the strip-shaped bulges is gradually increased from two ends to the middle along a smooth curve;
(2) spin-coating a polymer glue solution on a flexible transparent substrate, continuously pressing the polymer glue solution by adopting a nano-imprinting template, and then curing the polymer glue solution to form a polymer glue layer so as to obtain a structured substrate, wherein a plurality of channels are formed in the polymer glue layer and penetrate through the surface of the polymer glue layer away from the flexible transparent substrate; the shape and the position of the channel respectively correspond to the shape and the position of the strip-shaped bulges;
(3) performing local hydrophilic/hydrophobic treatment on the structured substrate, wherein the bottom surface and the side wall surface of the channel after the local hydrophilic/hydrophobic treatment have hydrophilicity, and the region of the surface of the polymer adhesive layer, which is far away from the flexible transparent substrate and is not penetrated by the channel, has hydrophobicity;
(4) and filling nano metal slurry in the channel of the structured substrate by utilizing an electric fluid jet printing mode, thereby obtaining the embedded micro-nano device.
2. The jet printing preparation method of the embedded micro-nano device for the substrate structural processing according to claim 1, characterized in that: the nano-imprinting template is basically rectangular, and a plurality of strip-shaped bulges are formed on one surface of the nano-imprinting template; the strip-shaped bulges are of symmetrical structures, and the geometric centers of the strip-shaped bulges are collinear with the geometric center of the nano-imprinting template.
3. The jet printing preparation method of the embedded micro-nano device for the substrate structural processing according to claim 1, characterized in that: the method for preparing the structured substrate by adopting the nano-imprinting mode comprises the following steps:
s21, spin-coating polymer glue solution on the flexible transparent substrate;
s22, continuously pressing the nano-imprinting template into polymer glue solution coated on the flexible transparent substrate under the action of pressure, then carrying out ultraviolet light curing on the polymer glue solution, and finishing the copying of the nano-imprinting template graph through plastic deformation;
and S23, rotationally demolding the primary product obtained in the step S22 to obtain the structured substrate.
4. The jet printing preparation method of the embedded micro-nano device for the substrate structural processing according to claim 1, characterized in that: the local hydrophilic/hydrophobic treatment of the structured substrate comprises the steps of:
s31, carrying out ultraviolet irradiation hydrophilic modification treatment on the structured substrate;
and S32, spraying the hydrophobic material onto the coating roller in a spraying mode, uniformly coating the hydrophobic material onto the upper surface of the side wall of the trench by using the coating roller, and naturally drying or carrying out auxiliary drying heat treatment at 60-70 ℃ for 20 minutes to obtain the cured hydrophobic material.
5. The jet printing preparation method of the embedded micro-nano device for the substrate structural processing according to claim 1, characterized in that: and after the electrofluid jet printing is finished, sintering post-treatment is required to endow functionality, and then the embedded micro-nano device is obtained.
6. The jet printing preparation method of the embedded micro-nano device for the substrate structural processing according to any one of claims 1 to 5, wherein the jet printing preparation method comprises the following steps: after the filling is completed, the obtained device is stored in a control box at normal temperature and with a predetermined relative humidity for several minutes.
7. The jet printing preparation method of the embedded micro-nano device for the substrate structural processing according to claim 6, characterized in that: after completion of the filling, the resulting device was stored in a control box at 30 ℃ and 80% relative humidity for 5 minutes.
8. The jet printing preparation method of the embedded micro-nano device for the substrate structural processing according to any one of claims 1 to 5, wherein the jet printing preparation method comprises the following steps: the structured substrate was irradiated using an ultraviolet irradiator for 10 minutes in an open environment.
9. The jet printing preparation method of the embedded micro-nano device for the substrate structural processing according to any one of claims 1 to 5, wherein the jet printing preparation method comprises the following steps: after the electrofluid spray printing is finished, sintering post-treatment is needed, and the obtained device is dried for a period of time at the temperature lower than the sintering temperature before sintering so as to improve the sintering quality.
10. The embedded micro-nano device with the substrate structured treatment prepared by the jet printing preparation method of the embedded micro-nano device with the substrate structured treatment of any one of claims 1 to 9.
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