CN115003045B - Method for micro-nano 3D printing ceramic-based circuit based on electric field driven jet deposition - Google Patents
Method for micro-nano 3D printing ceramic-based circuit based on electric field driven jet deposition Download PDFInfo
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- CN115003045B CN115003045B CN202210595870.2A CN202210595870A CN115003045B CN 115003045 B CN115003045 B CN 115003045B CN 202210595870 A CN202210595870 A CN 202210595870A CN 115003045 B CN115003045 B CN 115003045B
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- 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
- H05K3/1275—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 by other printing techniques, e.g. letterpress printing, intaglio printing, lithographic printing, offset printing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
- B22F10/20—Direct sintering or melting
- B22F10/22—Direct deposition of molten metal
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
- B22F10/60—Treatment of workpieces or articles after build-up
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
- B22F10/60—Treatment of workpieces or articles after build-up
- B22F10/64—Treatment of workpieces or articles after build-up by thermal means
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y10/00—Processes of additive manufacturing
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- 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
- H05K3/1283—After-treatment of the printed patterns, e.g. sintering or curing methods
- H05K3/1291—Firing or sintering at relative high temperatures for patterns on inorganic boards, e.g. co-firing of circuits on green ceramic sheets
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- 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
- H05K3/188—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 by direct electroplating
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/25—Process efficiency
Abstract
The application discloses a manufacturing method of a micro-nano 3D printing high-precision ceramic-based circuit based on electric field driving spray deposition, which comprises the steps of firstly, spreading a layer of sacrificial layer material on a pretreated ceramic substrate, and curing the sacrificial layer; then, according to a design line, conductive ink is used as a printing material, electric field driving jet deposition micro-nano 3D printing is adopted, and a conductive structure is printed on a ceramic substrate coated with a sacrificial layer; then, using a high-temperature sintering process to remove various organic solvents in the sacrificial layer and the conductive ink, and combining the conductive circuit and the ceramic substrate into a whole through the conductive ink; and finally, carrying out post-treatment on the sintered ceramic circuit board, and drying the finished product. The application utilizes three strategies of spreading a sacrificial layer and electric field driven jet deposition micro-nano 3D printing and high-temperature sintering of a printing circuit, and realizes high-efficiency and low-cost manufacturing of a high-precision ceramic-based circuit by organic combination.
Description
Technical Field
The application belongs to the field of ceramic-based circuit manufacturing and micro-nano scale 3D printing, and particularly relates to a manufacturing method of a micro-nano 3D printing high-precision ceramic-based circuit based on electric field driving jet deposition, which can realize high-efficiency and low-cost manufacturing of a large-size and high-precision ceramic-based circuit board.
Background
Compared with the traditional organic circuit board and metal-based circuit board, the ceramic-based circuit board (ceramic-based circuit) has a plurality of outstanding characteristics and unique advantages, and mainly comprises: (1) Excellent heat conductivity, good temperature cycling performance and high-temperature impact resistance; (2) high insulation resistance and dielectric strength, high reliability; (3) Low dielectric coefficient, excellent high-frequency characteristics and lower dielectric loss, so that the signal delay time is effectively reduced, and the transmission efficiency is improved; (4) The thermal expansion coefficient is low, and especially, the thermal expansion coefficient is good in matching with semiconductor silicon chips, chips and the like; (5) The electronic device is little influenced by extremely harsh environments such as high air tightness, high humidity, high temperature, strong radiation, corrosion and the like; (6) The rigidity and the strength are high, and the effect of effectively supporting and protecting the circuit and the chip is good; (7) The bonding force between the circuit patterns and the ceramic substrate is strong, and the high-density wiring and the high insulation resistance are easy to realize; (8) The mechanical property is good, the warping degree is low, the hardness is high, and the scale precision is high; (9) has both excellent bond strength and electrical properties; (10) has a very low secondary electron emission coefficient; (11) is nontoxic and has good chemical stability; (12) high stability, high thermo-mechanical properties. Therefore, the ceramic-based circuit board has many excellent characteristics such as high thermal conductivity, high heat resistance, low thermal expansion coefficient, high dimensional stability, and the like, and has been widely applied in many fields such as power electronics, high-power LED package substrates, multi-chip modules (MCM), IGBT modules, high-frequency antennas, microwave wireless communication, high-temperature semiconductor packages, and the like, especially in fields such as aerospace, national defense and military, deep sea deep space, high-frequency high-speed communication, and the like.
With the recent popularization of strategic emerging industries such as 5G communication, artificial intelligence, cloud technology, unmanned operation, internet of things and the like and industrial application, high-frequency, high-speed and high-density integration has become an important development trend and direction of current electronic products, and the requirements on the performances such as dielectric constant, dielectric loss, heat resistance and corrosion resistance of a circuit substrate are increasingly high. Therefore, there is an increasing demand for ceramic-based circuit boards, and there is an increasing demand for their performance. This presents a number of new challenges for high performance ceramic-based circuit board fabrication: (1) The precision is higher, namely the line width and the line distance of the circuit are smaller, so that the requirements of high density, high integration level and miniaturization are met; (2) The interconnection density of the ceramic substrate is continuously improved, 3D integration is realized, three-dimensional manufacturing and curved surface conformal manufacturing of a ceramic circuit are realized, and the requirements of high integration level, high precision and high conductivity are met; (3) The manufacturing technology has the characteristics of lower cost, higher efficiency, simpler manufacturing process, green and environment-friendly production, and solves the serious problems of environmental pollution caused by the production of a large amount of waste liquid, waste gas, waste residues and the like generated by the traditional photoetching and etching and the like.
At present, the manufacturing technology of the industrial ceramic circuit board (ceramic surface metal imaging) mainly comprises the following steps: screen printing, direct copper plating (DPC), direct copper plating (DBC), laser activated metallization, inkjet printing of activated materials + selective electroless plating, and the like. Screen printing technology is widely applied to high temperature co-fired ceramic (HTCC) and low temperature co-fired ceramic (LTCC), but the precision of manufacturing thick film circuits by screen printing is low, the line width is generally larger than 60 μm, and the thickness deviation of the manufactured circuits is large due to the rough surface of the ceramic, especially for large-size substrates, the consistency is worse, and the requirements of manufacturing high-precision ceramic-based circuit boards cannot be met. Whether it is a direct copper plating process or a direct copper plating process, they generally need to deposit a layer of copper on a ceramic substrate, and then use photolithography, etching and other processes to realize metal copper patterning (manufacturing of conductive lines), while photolithography and etching processes can realize manufacturing of high-precision line (circuit), the manufacturing cost is high, the process is complex (copper plating or copper plating, photoresist spreading, photolithography, etching, photoresist removal, post-treatment and the like on the ceramic substrate), the efficiency is low, the requirements on the production conditions are high, and especially, a great deal of copper waste is caused, and a great deal of waste liquid, waste gas, waste residue and the like are generated, so that environmental pollution is serious, and future application is more and more limited, especially in the civil engineering field of wide application. In addition, the technology can only manufacture high-precision circuits on planar ceramic substrates, and cannot realize high-precision wiring and conformal ceramic circuit manufacture on three-dimensional curved surfaces and non-planar ceramic substrates, which limits the wide application of ceramic-based circuit boards in many fields such as electronic packaging and the like. The laser activation metallization technology is to scan the ceramic substrate by laser to generate active center with catalytic capability on the surface of the ceramic substrate, and then deposit high-conductivity metal wires by combining with the electroless plating technology. The process of laser modification of the ceramic substrate surface is to decompose the precursor and generate catalytic activity using the high energy of the laser beam, which is mainly induced by thermal action. During electroless plating, only the modified sites catalyze the deposition of metal particles. The width and edge quality of the modified region thus determine the fineness of the final shaped wire. In order to obtain finer metal wires, laser beams with shorter wavelengths in ultraviolet and deep ultraviolet bands or ultra-short pulse laser beams with smaller heat affected zones are adopted or parameters of an optical system are optimized to obtain smaller spot diameters, but the methods cannot fundamentally solve the problem that the heat affected zone at the edge of a laser spot is generated, and the width of a modified zone is enlarged due to the decomposition of a precursor in the heat affected zone. On the other hand, the energy distribution of the laser beam is uneven and is in axisymmetric Gaussian distribution, so that only the energy of the central area of a laser spot can reach the decomposition threshold of a precursor, the precursor near the decomposition threshold cannot be sufficiently decomposed, the edges of the metal wire formed by subsequent electroless plating are sparse and have more burrs, and the electrical property is seriously affected. In addition, the deposition of metal in the electroless plating process is an isotropic process, and the metal wires on the surface of the substrate grow laterally while thickening, which can lead to a final formed circuit width significantly greater than the laser active area width. Thus, laser activated metallization has currently been difficult to meet the manufacturing requirements of high precision ceramic-based circuits. Although the process of ink-jet printing of the activated material and selective electroless plating is simple, the precision is very poor, the line edge roughness of the conductive circuit is poor, the bonding force between the conductive circuit and the ceramic substrate is poor, the efficiency is low, and the method cannot be used for manufacturing a high-precision ceramic circuit board.
Therefore, the existing various ceramic-based circuit board manufacturing technologies cannot meet the industrial manufacturing requirements of low cost, high precision, high efficiency, green environmental protection and large-scale manufacturing of the high-precision ceramic-based circuit board, the ceramic is different from the flat surfaces of glass, PET (polyethylene terephthalate) substrates and the like, the rough surface structure is difficult to realize direct forming of conductive circuits with fine line width and good surface morphology on the surfaces of the ceramic-based circuit boards, particularly the manufacturing of high-precision conformal circuits cannot be realized on the non-flat ceramic surfaces and the three-dimensional curved ceramic surfaces, and the manufacturing of special-shaped ceramic-based circuit boards and oversized high-precision ceramic-based circuit boards is urgent to develop new technologies and new processes for manufacturing new high-precision ceramic-based circuits.
The above information disclosed in this background section is only for enhancement of understanding of the background section of the application and therefore it may not form the prior art that is already known to those of ordinary skill in the art.
Disclosure of Invention
In order to achieve the above purpose, the present application adopts the following technical scheme:
a micro-nano 3D printing high-precision ceramic-based circuit manufacturing method based on electric field driven jet deposition comprises the following steps:
step 1: pretreatment of a ceramic substrate: cleaning, drying and the like are carried out on the printed ceramic substrate, so that the ceramic substrate is ensured to be clean and free from oil stains, dirt and the like;
step 2: coating a sacrificial layer: uniformly spreading a layer of sacrificial layer material on the surface of the pretreated ceramic substrate and curing the sacrificial layer;
step 3: micro-nano 3D printing conductive structure: according to the geometric pattern and the size of the designed conductive structure, selecting conductive ink as a material for printing the conductive structure, and adopting an electric field driven jet deposition micro-nano 3D printing process to print the required conductive structure on the ceramic substrate coated with the sacrificial layer;
step 4: pre-curing the conductive structure: drying and pre-curing the conductive structure on the printed ceramic substrate sacrificial layer;
step 5: treatment of the conductive structure after pre-curing: cleaning and air-drying the conductive structure after pre-curing, and removing dust and impurities attached to the substrate in the printing and pre-curing process;
step 6: sintering of the conductive structure: placing the printed conductive structure into a sintering furnace, performing high-temperature sintering according to a set sintering temperature, time and sintering curve, completely removing the sacrificial layer on one hand, performing sintering conductive treatment (completely removing the organic solvent in the conductive ink) on the printed conductive structure on the other hand, and simultaneously realizing that the printed conductive structure and the ceramic are sintered into a whole (the high-temperature sintering enables the bonding phase in the conductive ink to be combined with the ceramic into a whole, so that the circuit and the ceramic have high bonding strength);
step 7: post-treatment of the sintered conductive structure: and cleaning and drying the sintered conductive structure to ensure that residues on the ceramic substrate and the conductive structure are removed completely in the sintering process.
In some embodiments of the application, the conductive structures are conductive traces, intralevel and interlevel connection circuits, or passive devices including resistors, inductors, capacitors, etc.
In some embodiments of the present application, the ceramic substrate in step 1 includes, but is not limited to, aluminum oxide ceramic, aluminum nitride ceramic, zirconium oxide ceramic, beryllium oxide ceramic, boron nitride ceramic, and the like.
In some embodiments of the present application, the coated sacrificial layer material in step 2 includes, but is not limited to, the following materials: aqueous coating liquids, polydimethylsiloxane (PDMS), polyvinyl alcohol (PVA), and other materials that can improve the surface quality of ceramics and can be removed at high temperatures are also within the scope of the claims of the present application, with aqueous coating liquids being preferred.
In some embodiments of the present application, the method of applying the sacrificial layer material in step 2 includes, but is not limited to, the following processes: spin coating, slot coating, spray coating, pull-up coating, knife coating, and casting coating. Slot coating is preferred.
In some embodiments of the application, the thickness of the plated sacrificial layer in step 2 is 500nm-20 microns.
In some embodiments of the present application, the sacrificial layer curing method in step 2 includes, but is not limited to: heat curing, ultraviolet curing, infrared curing, laser curing, etc.
In some embodiments of the present application, the electric field driven spray deposition micro-nano 3D printing technology in the step 3 includes a contact electric field driven spray deposition micro-nano 3D printing technology, a non-contact electric field driven spray deposition micro-nano 3D printing technology, and a single plate electrode electric field driven spray deposition micro-nano 3D printing technology.
In some embodiments of the present application, the printing material conductive ink used in step 3 includes, but is not limited to, the following materials: the nano silver paste, the nano copper paste and other conductive paste containing nano metal materials are preferably selected to enhance the bonding force between the conductive structure and the ceramic base, wherein the nano silver paste contains a bonding phase, and the bonding phase is glass, oxide or a mixture of the glass and the oxide. Preferably nano silver paste.
In some embodiments of the present application, in the step 3, accurate control of the precision (line width, line spacing) of the printed circuit, the morphology and quality (line edge roughness) of the printed circuit is achieved by controlling the printing process parameters of the electric field driven jet deposition micro-nano 3D printing, where the printing process parameters mainly include: printing nozzles (including but not limited to stainless steel nozzles, wuzang nozzles, glass nozzles, silicon nozzles, plastic nozzles, etc.), inside diameter size, voltage, printing speed, printing height (distance of nozzle from ceramic substrate), back pressure, etc. Depending on the printing material and the accuracy and shape of the printed circuit, a suitable printing process window is preferred.
In some embodiments of the application, the printing nozzle used in step 3 has an inner diameter of 1-300 μm; printing voltage is 300-3000V; the printing speed is 5-100mm/s; printing the printing high end 50-500 mu m; the back pressure is 100-800 kpa.
In some embodiments of the present application, in the step 3, the thickness of the circuit may be obtained by using single printing or repeated printing multiple times according to the thickness dimension of the circuit.
In some embodiments of the present application, the pre-curing of the print circuit in step 4 includes, but is not limited to, the following: heat curing, ultraviolet curing, infrared curing, laser curing, etc.
In some embodiments of the application, the sintering in step 5 includes, but is not limited to, the following processes: sintering in a drying furnace; vacuum sintering; sintering by inert gas; in the sintering process, flowing inert gas is preferably introduced, and the sacrificial layer material and the organic solvent material in the conductive ink are timely discharged out of the sintering furnace. The sintering temperature is 600-2200 ℃. Sintering time is 10-50 minutes.
In some embodiments of the present application, the drying methods in step 1 and step 7 include, but are not limited to, oven drying.
In some embodiments of the present application, the cleaning solution used in the cleaning in the step 1, the step 5 and the step 7 is deionized water, and the air-drying gas is inert gas such as nitrogen.
Compared with the prior art, the application has the following beneficial effects:
the application combines the ceramic substrate spreading sacrificial layer and the electric field driven jet deposition micro-nano 3D printing technology to realize the high-efficiency and low-cost manufacture of the large-size high-precision ceramic-based circuit board, and provides a subversion technical solution for the manufacture and large-scale production of the high-precision ceramic-based circuit board.
The ceramic is different from the flat surfaces of glass, PET base materials and the like, and the rough surface structure is difficult to realize that the conductive circuit with fine line width and good surface appearance is directly formed on the surface of the ceramic, so that the method provided by the application uses a sacrificial layer material to create a good printing environment, and the conductive circuit and the rough ceramic surface form strong bonding force while the sacrificial layer material is removed in the subsequent high-temperature sintering process.
(1) High precision. The application realizes the manufacture of the high-precision ceramic-based circuit, can realize the manufacture of the high-precision ceramic-based circuit with the line width smaller than 10 microns, and particularly has the potential of manufacturing the submicron high-precision ceramic-based circuit. At present, other than the photoetching and etching process, which has the process capability of manufacturing the high-precision ceramic-based circuit with the line width smaller than 10 microns, no other technology can realize the manufacturing of the high-precision ceramic-based circuit with the line width smaller than 10 microns. According to the application, high-precision ceramic-based circuit manufacturing is realized by organically combining three strategies, firstly, the flatness of the ceramic surface is improved by spreading the sacrificial layer, so that the polarized charges on the surface of the substrate are more uniformly distributed, the electric field is more stable, the printing quality, especially the consistency of a large-size substrate printed circuit, is realized, and on the other hand, the sacrificial layer is made of a hydrophobic material, so that the precision of the subsequent printed circuit can be improved. And then, using nano conductive ink, adopting electric field driven jet deposition micro-nano 3D printing to realize high-precision circuit manufacture (the electric field driven jet deposition micro-nano 3D printing has the process capability of sub-micro scale and nano scale characteristic printing), and realizing printing of micro-scale and even sub-micro scale circuits. Finally, through the high-temperature sintering process, the printed circuit contracts (the organic solvent in the conductive ink is removed), if the sacrificial layer is not coated, the conductive ink can infiltrate into the ceramic substrate in the printing process, so that the whole contraction cannot be realized in the sintering process, the contraction rate in the sintering process is only about 10%, the contraction rate coated with the sacrificial layer can at least reach more than 20%, if the whole contraction cannot be realized, the local contraction can cause breakpoint phenomenon after sintering, further the circuit after sintering is discontinuous, the conductivity of the ceramic-based circuit is seriously influenced, and even the phenomenon of non-conduction occurs. The application further improves the precision (line width) of the printed circuit, and can realize the high-precision ceramic-based circuit manufacture by the organic set of the strategies.
(2) Oversized. The application can realize the manufacture of the oversized high-precision ceramic-based circuit. The application adopts an electric field driven jet deposition micro-nano 3D printing process, has the process capability of m-level scale printing, and ensures the printing consistency of a large-size ceramic substrate circuit by combining with the height self-adaptive adjustment of a spray head and a coated sacrificial layer.
(3) And (3) printing the ceramic-based curved surface conformal circuit with high precision. The application can realize the high-precision ceramic-based circuit manufacture on the non-flat ceramic substrate and the curved ceramic substrate and combines the five-axis linkage printing technology. This is a unique technical advantage of the present application, and none of the various existing fabrication techniques can achieve printing of high precision conformal circuits on non-planar ceramic substrates, particularly on curved ceramic substrates.
(4) High production efficiency and short production flow. The existing high-precision ceramic-based circuit manufacturing method requires a plurality of process steps such as copper plating or copper plating, photoresist spreading, photoetching, etching, photoresist removal, post-treatment and the like on a ceramic substrate, and has the advantages of complex process, long period and low production efficiency. The application mainly adopts the process steps of coating the sacrificial layer, printing, sintering and the like, and has short process flow and high production efficiency.
(5) Low cost. On one hand, the traditional high-precision ceramic-based circuit manufacturing method based on photoetching is adopted, and on the other hand, more than 90% of copper is finally wasted; on the other hand, expensive photolithography equipment, sputtering equipment, etc. are required; in addition, the production conditions such as clean room, vacuum, high temperature and the like are required, the production environment is harsh, the production cost is very high, and the production cost is the greatest advantage.
(6) The printed high-precision circuit has high bonding strength with the ceramic substrate. After the conductive sintering, the sacrificial layer is removed, and the circuit is embedded into the roughened surface of the ceramic substrate to form an interlocking structure. If the printing material conductive ink contains glass powder, the glass powder and the ceramic are connected into a whole after sintering, so that the printing material conductive ink has higher connection strength.
(7) In the manufacturing process, waste liquid, waste gas, waste residue and the like are few, so that the method has little pollution to the environment and belongs to green manufacturing. The traditional high-precision ceramic-based circuit manufacturing method based on photoetching and etching can generate a large amount of waste liquid, waste gas, waste residue and the like, has serious environmental pollution and severely restricts the wide utilization of the technology.
(8) The production flexibility is high, and the method is suitable for manufacturing requirements of different batches.
(9) The application can be used for manufacturing high-precision low-temperature co-fired ceramic (LTCC).
(10) The material utilization rate is high. The utilization rate of the material exceeds 95%, and more than 95% of the material is wasted in the existing photoetching and etching processes.
(11) By combining multi-nozzle multi-material printing, the application can realize the integrated manufacture of ceramic structures and electronics and the integrated manufacture of multi-layer ceramic circuits.
Drawings
The accompanying drawings, which are included to provide a further understanding of the application and are incorporated in and constitute a part of this specification, illustrate embodiments of the application and together with the description serve to explain the application.
FIG. 1 is a schematic diagram of a manufacturing method of an electric field driven jet deposition micro-nano 3D printing high-precision ceramic-based circuit;
FIG. 2 is a grid electron microscope image of a multi-layer fine line width circuit according to example 1;
FIG. 3 is a real photograph and an electron microscope of the micro PCB-like conductive pattern of example 2;
wherein 1-a ceramic substrate; 2-a sacrificial layer; 3-printing a spray head; 4-print circuitry.
Detailed Description
It should be noted that the following detailed description is illustrative and is intended to provide an illustration of the application in some embodiments thereof. 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 application belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the present application. As used herein, the singular is also intended to include the plural unless the context clearly indicates otherwise, and furthermore, it is to be understood that the terms "comprises" and/or "comprising" when used in this specification are taken to specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof.
The application will be further described with reference to the drawings and examples.
Example 1
The manufacturing method of the micro-nano 3D printing high-precision ceramic-based circuit based on electric field driven jet deposition comprises the following steps: (1) According to the actual use requirement, adopting alumina ceramic, aluminum nitride ceramic, zirconia ceramic, boron nitride ceramic, beryllium oxide ceramic and the like as the base materials for bearing the circuit; (2) The water-based coating liquid is used as a sacrificial layer, so that a good printing environment is created; (3) The electric field driven jet deposition micro-nano 3D printing technology is used, and the manufacturing of conductive circuits with various shapes, line widths and aspect ratios is realized by utilizing the necking effect of a Taylor cone; (4) And (3) using a high-temperature atmosphere furnace to sinter the printed sample at a high temperature, removing the sacrificial layer and improving the adhesive force of the conductive circuit and the ceramic substrate. (5) And the high-precision ceramic-based circuit is manufactured at low cost by combining an electric field driven jet deposition micro-nano 3D printing high-precision patterning technology and a larger shrinkage effect of a circuit after sintering. In addition, through high temperature sintering, on the one hand, remove the sacrificial layer, especially remove organic components etc. of printing circuit completely, realize circuit and rough ceramic substrate surface and be structural interlocking to and glass powder and ceramic sintering are integrative, the powerful joint strength who promotes circuit and ceramic substrate.
In the embodiment, based on an electric field driven jet deposition micro-nano 3D printing technology, conductive silver paste is selected to print a conductive pattern structure on a ceramic substrate, and the manufactured pattern structure is a multi-layer fine line wide grid structure. The preparation method comprises the following specific preparation steps:
step 1: and (5) pretreatment of the ceramic substrate. The printing ceramic substrate is cleaned by deionized water, and the ceramic substrate is air-dried by nitrogen, so that the ceramic substrate is ensured to be clean and free of dust, impurities and the like. The ceramic substrate is a 99 alumina ceramic plate with the size of 120mm multiplied by 1 mm.
Step 2: and (5) coating a sacrificial layer. And placing 20g of the aqueous coating liquid in a beaker, uniformly spin-coating the coating liquid on a ceramic wafer by using a spin coater, setting the spin-coating speed to be 3000r/min, and spin-coating time to be 50s to obtain the sacrificial layer with the thickness of 1 mu m. And finally, placing the ceramic substrate coated with the sacrificial layer in a vacuum drying oven, and curing for 5min at 70 ℃.
Step 3: micro-nano 3D printing two-layer micro-line width conductive grid structure.
3-1: 200g of conductive silver paste is put into a beaker, 10g of diluent is added, and the mixture is put into a printer feeding module after ultrasonic stirring and low-temperature placement;
3-2: writing a printing program, wherein the effective printing pattern structure of the embodiment is a multi-layer grid structure with the length of 100mm multiplied by 100mm and the period of 0.25mm, the printing nozzle is a glass nozzle with the inner diameter of 60 mu m, the setting printing parameters are the printing height (the distance between the nozzle and the substrate) of 100 mu m, the moving speed of a workbench is 40mm/s, the printing voltage is 1000V, and the back pressure is 200kPa;
3-3: and fixing a printing substrate, setting a printing origin, starting a printing program, and finishing printing.
Step 4: the printed circuit is pre-cured. And (5) placing the printed sample into a vacuum drying oven for pre-curing, wherein the pre-curing temperature is set to be 70 ℃, and the curing time is set to be 15 minutes.
Step 5: cleaning and air-drying a printing circuit: and cleaning the pre-cured sample by using deionized water, and then air-drying the sample by using nitrogen gas to remove dust and impurities attached to the substrate in the printing and pre-curing process.
Step 6: high-temperature sintering of the printed ceramic-based circuit: placing the printed ceramic-based circuit into a sintering furnace, setting the sintering temperature to be 800 ℃ and the sintering time to be 15min, completely removing the sacrificial layer on one hand, and performing sintering conduction treatment (completely removing the organic solvent in the conductive silver paste) on the printed circuit on the other hand, and simultaneously realizing good combination of the printed circuit and the ceramic substrate (high-temperature sintering to enable the conductive silver paste and the rough ceramic surface to form a tenon-and-mortise-like structure);
step 7: post-processing of a printing ceramic-based circuit: and cleaning the sintered ceramic-based circuit by using deionized water, and then air-drying by using nitrogen gas to ensure that residues, dust impurities and the like remained on the ceramic substrate and the circuit in the sintering process are completely removed.
The final product is shown in fig. 2, wherein the left image is a 27X multi-layer grid electron microscope image, and the right image is a 600X grid cross point electron microscope image.
Example 2
In the embodiment, based on an electric field driven jet deposition micro-nano 3D printing technology, conductive silver paste is selected to print a conductive pattern structure on a ceramic substrate, and the manufactured pattern structure is a miniature PCB-like conductive pattern. The preparation method comprises the following specific preparation steps:
step 1: and (5) pretreatment of the ceramic substrate. The printing ceramic substrate is cleaned by deionized water, and the ceramic substrate is air-dried by nitrogen, so that the ceramic substrate is ensured to be clean and free of dust, impurities and the like. The ceramic substrate is a 99 alumina ceramic plate with the size of 10mm multiplied by 100mm multiplied by 1 mm.
Step 2: and (5) coating a sacrificial layer. 5g of aqueous coating liquid is put in a beaker, the coating liquid is uniformly spin-coated on a ceramic wafer by a spin coater, the spin coating speed is set to 1500r/min, the spin coating time is set to 30s, and the thickness of the sacrificial layer is 1.5 mu m. And finally, placing the ceramic substrate coated with the sacrificial layer in a vacuum drying oven, and curing at 70 ℃ for 5min.
Step 3: micro-nano 3D printing 5 layers of fine line width conductive grid structures.
3-1: putting 50g of conductive silver paste into a beaker, adding 0.2g of diluent, carrying out ultrasonic stirring, placing at a low temperature, and then putting into a printer feeding module;
3-2: writing a printing program, wherein the printing nozzle is a glass nozzle with an inner diameter of 20 mu m, the printing parameters are set to be the printing height (the distance between the nozzle and the substrate) of 30 mu m, the moving speed of a workbench is 2mm/s, the printing voltage is 800V, and the back pressure is 200kPa;
3-3: and fixing a printing substrate, setting a printing origin, starting a printing program, and finishing printing.
Step 4: the printed circuit is pre-cured. And (5) placing the printed sample into a vacuum drying oven for pre-curing, wherein the pre-curing temperature is set to be 70 ℃, and the curing time is set to be 15 minutes.
Step 5: cleaning and air-drying a printing circuit: and cleaning the pre-cured sample by using deionized water, and then air-drying the sample by using nitrogen gas to remove dust and impurities attached to the substrate in the printing and pre-curing process.
Step 6: high-temperature sintering of the printed ceramic-based circuit: placing the printed ceramic-based circuit into a sintering furnace, setting the sintering temperature to be 800 ℃ and the sintering time to be 15min, completely removing the sacrificial layer on one hand, and performing sintering conduction treatment (completely removing the organic solvent in the conductive silver paste) on the printed circuit on the other hand, and simultaneously realizing good combination of the printed circuit and the ceramic substrate (high-temperature sintering to enable the conductive silver paste and the rough ceramic surface to form a tenon-and-mortise-like structure);
step 7: post-processing of a printing ceramic-based circuit: and cleaning the sintered ceramic-based circuit by using deionized water, and then air-drying by using nitrogen gas to ensure that residues, dust impurities and the like remained on the ceramic substrate and the circuit in the sintering process are completely removed.
And the final product is shown in fig. 3, wherein the left image is a real shot image of the miniature PCB-like conductive pattern, and the right image is a 36X miniature PCB-like conductive pattern electron microscope image.
The above description is only of the preferred embodiments of the present application and is not intended to limit the present application, but various modifications and variations can be made to the present application by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application should be included in the protection scope of the present application.
Claims (16)
1. The manufacturing method of the micro-nano 3D printing high-precision ceramic-based circuit based on electric field driven jet deposition is characterized by comprising the following steps of:
step 1: pretreatment of a ceramic substrate: cleaning and drying the ceramic substrate for printing;
step 2: coating a sacrificial layer: uniformly spreading a layer of sacrificial layer material on the surface of the pretreated ceramic substrate and curing the sacrificial layer;
step 3: micro-nano 3D printing conductive structure: according to the geometric pattern and the size of the designed conductive structure, selecting conductive ink as a material for printing the conductive structure, and adopting an electric field driven jet deposition micro-nano 3D printing process to print the required conductive structure on the ceramic substrate coated with the sacrificial layer;
step 4: pre-curing the conductive structure: drying and pre-curing the conductive structure on the printed ceramic substrate sacrificial layer;
step 5: treatment of the conductive structure after pre-curing: cleaning and drying the pre-cured conductive structure, and removing pollutants attached to the base material in the printing and pre-curing process;
step 6: sintering of the conductive structure: then placing the conductive structure into a sintering furnace, and performing high-temperature sintering according to the set sintering temperature, sintering time and sintering curve, so that on one hand, the sacrificial layer is completely removed, and on the other hand, the printed conductive structure is subjected to sintering conductive treatment, and meanwhile, the printed conductive structure and the ceramic substrate are sintered into a whole;
step 7: post-treatment of the sintered conductive structure: and cleaning and drying the sintered conductive structure to ensure that residues on the ceramic substrate and the conductive structure are removed completely in the sintering process.
2. The method for manufacturing the micro-nano 3D printing high-precision ceramic-based circuit based on electric field driven jet deposition according to claim 1, wherein the conductive structure is a conductive line or a passive device, and the passive device comprises a resistor, an inductor and a capacitor.
3. The method for manufacturing the micro-nano 3D printing high-precision ceramic-based circuit based on electric field driven jet deposition according to claim 1, wherein the ceramic substrate in the step 1 comprises aluminum oxide ceramic, aluminum nitride ceramic, zirconium oxide ceramic, beryllium oxide ceramic and boron nitride ceramic.
4. The method for manufacturing the micro-nano 3D printing high-precision ceramic-based circuit based on electric field driven spray deposition according to claim 1, wherein the plated sacrificial layer material in the step 2 comprises: aqueous coating liquid, polydimethylsiloxane and polyvinyl alcohol.
5. The method for manufacturing the micro-nano 3D printing high-precision ceramic-based circuit based on electric field driven spray deposition according to claim 1, wherein the method for paving the sacrificial layer material in the step 2 comprises the following steps: spin coating, slot coating, spray coating, pull-up coating, knife coating, and casting coating.
6. The method for manufacturing the micro-nano 3D printing high-precision ceramic-based circuit based on electric field driven jet deposition according to claim 1, wherein the thickness of the coated sacrificial layer in the step 2 is 500nm-20 μm.
7. The method for manufacturing the micro-nano 3D printing high-precision ceramic-based circuit based on electric field driven jet deposition according to claim 1, wherein the conductive ink used in the step 3 is a conductive paste containing nano metal materials.
8. The method for manufacturing the micro-nano 3D printing high-precision ceramic-based circuit based on electric field driven spray deposition according to claim 1, wherein in the step 3, the printing process parameters of the micro-nano 3D printing are controlled to realize the precise control of the line width, the line distance, the shape and the quality of the printing circuit, and the printing process parameters comprise: printing nozzle material, nozzle inner diameter size, printing voltage, printing speed, printing height and back pressure.
9. The method for manufacturing the micro-nano 3D printing high-precision ceramic-based circuit based on electric field driven jet deposition according to claim 1, wherein in the step 3, single printing or repeated printing is selected according to the size of the required conductive structure.
10. The method for manufacturing the micro-nano 3D printing high-precision ceramic-based circuit based on electric field driven jet deposition according to claim 1, wherein the sintering atmosphere in the step 6 is as follows: one of air sintering, vacuum sintering, and inert gas sintering; the sintering temperature is 600-2200 ℃ and the sintering time is 10-50 minutes.
11. The method for manufacturing the micro-nano 3D printing high-precision ceramic-based circuit based on electric field driven spray deposition according to claim 4, wherein the coated sacrificial layer material in the step 2 is aqueous coating liquid.
12. The method for manufacturing the micro-nano 3D printing high-precision ceramic-based circuit based on electric field driven spray deposition according to claim 5, wherein the method for spreading the sacrificial layer material in the step 2 is slot coating.
13. The method for manufacturing the micro-nano 3D printing high-precision ceramic-based circuit based on electric field driven jet deposition according to claim 7, wherein the conductive ink used in the step 3 comprises nano silver paste and nano copper paste.
14. The method for manufacturing the micro-nano 3D printing high-precision ceramic-based circuit based on electric field driven jet deposition according to claim 7, wherein the conductive ink used in the step 3 is nano-slurry containing a bonding phase, and the bonding phase is glass, oxide or a mixture of the glass and the oxide.
15. The method for manufacturing the micro-nano 3D printing high-precision ceramic-based circuit based on electric field driven jet deposition according to claim 8, wherein the inner diameter size of the printing nozzle used in the step 3 is 1-300 μm; printing voltage is 300-3000V; the printing speed is 5-100mm/s; printing height is 50-500 mu m; the back pressure is 100-800 kpa.
16. The method for manufacturing the micro-nano 3D printing high-precision ceramic-based circuit based on electric field driven jet deposition according to claim 10, wherein flowing inert gas is introduced to timely discharge organic solvent materials in sacrificial layer materials and conductive ink out of a sintering furnace.
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