CN111223770A - Patterned thin film electrode material growth method with neat and smooth edge - Google Patents
Patterned thin film electrode material growth method with neat and smooth edge Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 60
- 239000010409 thin film Substances 0.000 title claims abstract description 54
- 239000007772 electrode material Substances 0.000 title claims abstract description 43
- 238000010146 3D printing Methods 0.000 claims abstract description 39
- 238000005516 engineering process Methods 0.000 claims abstract description 19
- 238000001259 photo etching Methods 0.000 claims abstract description 17
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- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- 238000000059 patterning Methods 0.000 claims description 10
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- 238000007641 inkjet printing Methods 0.000 description 2
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- H—ELECTRICITY
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
- H01L21/283—Deposition of conductive or insulating materials for electrodes conducting electric current
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Abstract
The invention relates to a patterned thin film electrode material growth method with neat and smooth edges, and relates to the field of micro-nano electronic device preparation. The technical problem that the boundary of a patterned thin film electrode material is not smooth and neat in the 3D printing method in the prior art is solved. The invention provides a patterned thin film electrode material growth method with neat and smooth edges, which is a new thin film electrode material growth method combining a 3D printing method and a photoetching technology, can realize the preparation of a thin film electrode under a lower temperature condition, reduces the energy consumption in the electrode preparation process of the traditional electronic preparation method and improves the deposition efficiency of the thin film electrode material, and more importantly, the method fundamentally solves the problems that the boundaries of the patterned thin film electrode material formed by 3D printing are not smooth and regular, and the prepared patterned thin film electrode material has neat and smooth edges (as abstract figures) and has wide application prospects.
Description
Technical Field
The invention relates to the field of micro-nano electronic device preparation, in particular to a method for growing a patterned thin film electrode material with neat and smooth edges.
Background
In recent years, the industry of micro-nano electronic device preparation is not in the way, and the appearance of the micro-nano electronic device not only integrates the technologies in the fields of electronic circuits, electronic components, materials, flat panel display, nanotechnology and the like, but also spans the industries of semiconductors, sealing and testing, materials, chemical engineering, printed circuit boards, display panels and the like, and can assist the transformation of the traditional industries, such as plastics, printing, chemical engineering, metal materials and the like. The application importance of the method in various fields of information, energy, medical treatment, manufacturing and the like is increasingly prominent, and the method becomes a leading-edge technology for competitive development of multinational and cross-national enterprises in the world. The united states, european union, uk, japan and the like have successively made development strategies for integrated circuit technologies based on micro-nano electronic device preparation and invested a lot of scientific research expenses, aiming at preempting the first opportunity in future scientific research and industrial development. The integrated circuit technology is also an object of high attention of researchers in China and a project of national key support, and in recent years, researchers in China develop a large amount of basic research work in the aspects of semiconductor material preparation, micro-nano electronic device preparation, application and the like and make certain progress.
At present, in the field of micro-nano electronic device preparation, a vacuum evaporation mode is generally adopted for deposition growth of a thin film electrode material of an electronic device, but the energy consumption of the process is high, and the vacuum degree has strict requirements. Therefore, the deposition growth method which does not need vacuum, has simple process, is environment-friendly and efficient and can deposit and grow the thin film electrode material in a large area is an important technical requirement for the development of the preparation field of the micro-nano electronic device in the future. In addition, the flexible electronic field is also developed vigorously at home and abroad at the present stage, and the flexible electronic technology generally needs to be prepared under a lower temperature condition because of the particularity of a substrate material, so that the application of the 3D printing technology is an extremely important means in the field of micro-nano electronic device preparation and the future flexible electronic field.
The 3D printing method is contact printing, the ink is printed on the substrate through ultrasonic resonance between the needle body and the crystal oscillator plate by utilizing an ultrasonic resonance release mechanism, and the three-dimensional material module with the required thickness can be formed through repeated printing. The 3D printing method has the advantages of high printing speed, direct imaging, single-step printing step, large processing area, high material utilization rate and the like, and has good application in the fields of micro-nano electronic device preparation and flexible electronics. However, in the 3D printing process, since the diffusion degree of the ink cannot be completely consistent, and the line width of the ink ejected by vibration cannot be completely uniform, the printed patterned thin film material is neat with the naked eye, but the boundary under the microscopic view is still not smooth and neat. When electronic components are prepared, the performance of the device can be directly influenced by whether the boundaries of the thin film electrode materials are regular or not. Therefore, how to prepare a thin film electrode material with a neat edge by using a 3D printing technology is an important problem that needs to be solved urgently by those skilled in the art.
Disclosure of Invention
The invention aims to solve the technical problem that the boundary of a patterned thin film electrode material is not smooth and neat in the 3D printing method in the prior art, and provides a patterned thin film electrode material growing method which is prepared by combining the 3D printing method and the photoetching technology and has neat and smooth edges.
In order to solve the technical problems, the technical scheme of the invention is as follows:
the invention provides a patterned thin film electrode material growing method with neat and smooth edges, which adopts a 3D printing method and a photoetching technology to combine to grow the patterned thin film electrode material with neat and smooth edges.
In the above technical solution, it is preferable that: the method for growing the patterned thin film electrode material with the neat and smooth edge specifically comprises the following steps:
step 1, photoetching and patterning an electrode structure on a substrate by utilizing a traditional photoetching technology;
step 2, printing the electrode ink by adopting a 3D printing method and curing to form a film;
and 3, removing the photoresist to obtain the patterned thin film electrode material with neat and smooth edges.
In the above technical solution, it is further preferable that: the step 1 specifically comprises the following steps: placing the substrate in a photoresist uniformizing instrument, dripping photoresist on the substrate, spin-coating and soft-baking; and then covering the substrate with the cured photoresist by using a mask plate, exposing and developing to obtain the patterned electrode structure.
In the above technical solution, it is still further preferable that: in the step 1, the rotating speed of the glue homogenizing instrument is 500r/min, the rotating time is 10s, then the rotating speed is increased to 2000r/min, and the rotating time is 20 s.
In the above technical solution, it is still further preferable that: the soft drying temperature in the step 1 is 65-90 ℃, and the time is 5-30 minutes.
In the above technical solution, it is still further preferable that: the exposure time in step 1 was 15 s.
In the above technical solution, it is still further preferable that: the development time in step 1 was 8 s.
In the above technical solution, it is further preferable that: the step 2 specifically comprises the following steps: utilize 3D printing apparatus, irritate the electrode ink into the needle body, observe through the computer screen and move the needle point to the contact substrate, set up relevant parameter, ultrasonic resonance prints and covers the electrode ink, and the printing area need not accurate alignment, and electrode ink layer cover patterning electrode structure alright, repeated printing is until printing to required electrode thickness.
In the above technical solution, it is still further preferable that: in step 2, setting the parameters of the 3D printing device as: the printing speed is 0.3-0.5mm/s, the printing times are 2-3 times, and the printing thickness is 40-60 nm.
In the above technical solution, it is further preferable that: the step 3 specifically comprises the following steps: and stripping by adopting an acetone solvent, and removing the photoresist and the electrode ink printed and cured on the photoresist to obtain the patterned thin-film electrode material with neat and smooth edges.
The invention has the beneficial effects that:
the invention provides a patterned thin film electrode material growth method with neat and smooth edges, which is a novel thin film electrode material growth method combining a 3D printing method and a photoetching technology, can realize the preparation of a thin film electrode under a lower temperature condition, reduces the energy consumption in the electrode preparation process of the traditional electronic preparation method and improves the deposition efficiency of the thin film electrode material, and more importantly, fundamentally solves the problems of unsmooth and untidy boundaries of the patterned thin film electrode material formed by 3D printing, and the prepared patterned thin film electrode material has neat and smooth edges and has wide application prospects.
Drawings
The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.
FIG. 1 is a schematic diagram of a first step of lithographically patterning an electrode structure of the present invention in which a photoresist is dropped onto a substrate, wherein: a is a schematic view of the substrate from the first step of lithographically patterning the electrode structure, and b is a schematic view of a front cross-section of the substrate from the first step of lithographically patterning the electrode structure.
Fig. 2 is a schematic diagram of a second step spin coating process for lithographically patterning an electrode structure of the present invention, wherein: a is a schematic view of the substrate resulting from the second step of lithographically patterning the electrode structure, and b is a schematic view of a front cross-section of the substrate resulting from the second step of lithographically patterning the electrode structure.
FIG. 3 is a schematic diagram of a third step of the lithographically patterned electrode structure of the present invention, masked with a reticle post exposure on a substrate, wherein: a is a schematic view of a third step exposure step of lithographically patterned electrode structures, and b is a schematic view from above of the third step exposure step of lithographically patterned electrode structures.
Fig. 4 is a schematic diagram of a patterned electrode structure resulting from a fourth step development process of a lithographically patterned electrode structure of the present invention.
Fig. 5 is a schematic diagram of the process of the invention for resonant 3D printing of electrode ink in patterned electrode structure areas after photolithography.
FIG. 6 is a schematic cross-sectional front view of a substrate obtained after printing electrode ink according to the present invention.
Fig. 7 is a schematic structural diagram of a patterned thin film electrode with uniform and smooth edges obtained after photoresist stripping according to the present invention, wherein a is a schematic sectional front view, and b is a schematic top view.
Fig. 8 is a ZEISS microscope image of a conventional 3D printing method directly printing an electrode pattern.
Fig. 9 is a schematic structural diagram of sample 1 prepared according to the first embodiment of the present invention.
FIG. 10 is a schematic top view of a photolithographic reticle used in the present invention.
Fig. 11 is a schematic diagram of a structure of a plurality of patterned electrodes obtained in accordance with an embodiment of the present invention, in which a is a schematic diagram of a front cross section, and b is a schematic diagram of a top view.
Figure 12 is a ZEISS microscope image of the final silver electrode structure obtained in a first example of the invention.
Fig. 13 is a schematic structural view of sample 2 prepared in example two of the present invention.
Fig. 14 is a schematic diagram of a structure of multiple patterned electrode sets obtained in a second embodiment of the present invention, in which a is a schematic diagram of a front cross section, and b is a schematic diagram of a top view.
Figure 15 is a ZEISS microscope image of the final copper electrode structure obtained in example two of the present invention.
The reference numerals in the figures denote:
100-substrate, 110-photoresist, 120-multi-group patterned electrode structure, 130-electrode ink, 140-needle point, 150-patterned thin film electrode with neat and smooth edge, and 160-mask;
101-Corning glass plate substrate, 102-Si/SiO2A substrate.
Detailed Description
The invention idea of the invention is: the 3D printing technology is one of the more advanced methods in the current thin film material deposition growth technology, can directly deposit various functional materials on a substrate, and is widely applied to the field of preparation of micro-nano electronic devices at home and abroad. Compared with the traditional electronic field, the 3D printing mode has the advantages of simple process, small environmental pollution, capability of completing the process under the conditions of normal temperature and low temperature and the like. However, when a 3D printing method is used to deposit a thin film material, even if the nozzle size of the used 3D printing device is finer, the boundary of the printed and formed patterned thin film material is not smooth and regular. In the field of device preparation, whether the boundary of a thin film electrode is clean and neat can directly influence the performance of a device, and the method is very important for solving the problems that the boundary of a patterned thin film electrode material prepared by a 3D printing method is not smooth and tidy. The invention adopts the combination of the 3D printing method and the photoetching technology to prepare the patterned thin-film electrode material with regular and smooth edges, and effectively solves the problems that the boundary of the patterned thin-film electrode material is not smooth and regular in the 3D printing method.
The invention provides a patterned thin film electrode material growth method with neat and smooth edges, which specifically comprises the following steps:
step 1, photoetching a plurality of groups of patterned electrode structures 120; photoetching an electrode pattern with a required structure on a substrate 100 by using a conventional photoetching technology, wherein the steps are schematically shown in the accompanying drawings 1-4; the method comprises the following specific steps: the first step is as follows: placing a substrate 100 in a spin coater, and dropping a photoresist 110 thereon, as shown schematically in fig. 1; the second step is as follows: spin coating and soft baking, wherein the schematic diagram is shown in figure 2; the third step: then, the substrate 100 with the cured photoresist 110 is covered by a mask 160 and exposed, and the schematic diagram is shown in fig. 3; the fourth step: and developed to obtain a plurality of sets of patterned electrode structures 120, schematically illustrated in fig. 4.
Step 2, printing the electrode ink 130 and curing to form a film; filling the electrode ink 130 into a needle body by using a 3D printing device, observing and moving a needle point 140 to contact the substrate 100 in the step 1 through a computer screen, setting relevant parameters, covering the electrode ink 130 by ultrasonic resonance 3D printing, wherein the printing area does not need to be accurately aligned, the electrode ink 130 layer can be covered with a plurality of groups of patterned electrode structures 120, repeatedly printing until the required electrode thickness is printed, the printing process schematic diagram is shown in figure 5, and the front-view section schematic diagram of the substrate 100 after printing the electrode ink 130 is shown in figure 6;
step 3, removing the photoresist; and stripping off the photoresist 110 and the electrode ink 130 printed and cured thereon by using an acetone solvent, so as to obtain a patterned thin-film electrode 150 with neat and smooth edges, which is schematically shown in fig. 7.
It is preferable that: in the step 1, the rotating speed of the glue homogenizing instrument is 500r/min, the rotating time is 10s, then the rotating speed is increased to 2000r/min, and the rotating time is 20 s; in the step 1, the soft drying temperature is 65-90 ℃ and the time is 5-30 minutes; the exposure time was 15 s; the development time was 8 s.
It is preferable that: in step 2, setting the parameters of the 3D printing device as: the printing speed is 0.3-0.5mm/s, the printing times are 2-3 times, and the printing thickness is 40-60 nm.
It is preferable that: the peeling time in step 3 was 30 s.
The technical solution of the present invention will be clearly and completely described below with reference to the accompanying drawings in the implementation examples of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. Wherein fig. 8 is a ZEISS microscope image of an electrode pattern directly printed by a conventional 3D printing method, as a comparative graph, it is apparent that irregular film boundaries are visible in the graph, and thus it can be known that the electrode boundary prepared by the conventional 3D printing method is irregular. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example one
A20 x 20mm Corning glass sheet substrate 101 is placed in a spin coater, and a photoresist 110 is dropped on the substrate and spin-coated. The rotation speed of the spin coater is 500r/min, the rotation time is 10s, then the rotation speed is increased to 2000r/min, and the rotation time is 20 s. The corning glass sheet substrate 101 with the photoresist 110 spin-coated thereon was placed in a 65 ℃ dry box for soft baking and taken out after 30 minutes, at which time the photoresist 110 was cured onto the corning glass sheet substrate 101, as shown in fig. 9, the schematic diagram is labeled as sample 1.
Multiple sets of patterned electrode structures 120 are lithographically patterned. The sample 1 was masked with a reticle 160, a pattern diagram of the reticle 160 used is shown in fig. 10, and then the sample 1 with the reticle 160 masked was exposed to light for 15 seconds in a photolithography machine. After the exposure is completed, the mask 160 is removed, and the exposed sample 1 is placed in a developing solution for development for 8s, so that a plurality of groups of patterned electrode structures 120 can be obtained on the corning glass sheet substrate 101 after the above steps are completed, and the schematic diagram is shown in fig. 11.
By controlling the contact of the needle tip 140 carrying the metallic silver nanoparticle ink with the surface of the photo-etched corning glass sheet substrate 101, the operation of this example is to slowly lower the needle tip 140 of the Sonoplot/micropolotter II micro-nano 3D printing device (Sonoplot, inc. is a manufacturer of inkjet printing devices) to contact the surface of the corning glass sheet substrate 101.
And then setting the printing speed of a machine to be 0.5mm/s, the printing times to be 3 times, printing a silver electrode metal layer with the thickness of 60nm, completely covering the photoetching multiple groups of patterned electrode structures 120 by the metal electrode layer during printing, and finally placing the corning glass sheet substrate 101 printed with the metal electrode layer on a hot plate for drying at 60 ℃ for 5 min.
And finally stripping by adopting an acetone solvent. And putting the dried corning glass sheet substrate 101 into an acetone solution for ultrasonic stripping for 30s, and removing the redundant photoresist 110 part of the metal electrode layer to obtain the patterned silver electrode with neat and smooth edge, which is disclosed by the invention, as shown in the attached figure 12.
Example two
Taking 15 x 15mm Si/SiO2A substrate 102, placed in a spin coater, on which a photoresist 110 is dropped, spin-coated. The rotation speed of the spin coater is 500r/min, the rotation time is 10s, then the rotation speed is increased to 2000r/min, and the rotation time is 20 s. Spin-coating Si/SiO2The substrate 102 is placed in a drying oven at 90 ℃ for soft baking, and is taken out after 5 minutes, at which time the photoresist 110 is cured to Si/SiO2A schematic diagram is shown in fig. 13 on a substrate 102, labeled sample 2.
Multiple sets of patterned electrode structures 120 are lithographed. Sample 2 was masked with a reticle 160, the pattern of the reticle 160 used is schematically shown in fig. 10, and then sample 2 with the reticle 160 masked was exposed to light for 15 seconds in a photolithography machine. After the exposure is completed, the mask 160 is removed, and the exposed sample 2 is placed in a developing solution for development for 8s, so that a plurality of sets of patterned electrode structures 120 can be obtained on the substrate after the above steps are completed, and the schematic diagram is shown in fig. 14.
By regulating and controlling the needle tip 140 carrying the metallic copper nano particle ink and the Si/SiO after photoetching2The substrate 102 is in surface contact, this example operates by slowly lowering the tip 140 of a Sonoplot/microchip II micro-nano 3D printing device (Sonoplot, inc. is a manufacturer of inkjet printing devices) into contact with Si/SiO2A substrate 102 surface.
Setting the printing speed of a machine to be 0.3mm/s, the printing times to be 2 times, printing the copper electrode metal layer with the thickness of 40nm, completely covering the photoetching multiple groups of patterned electrode structures 120 by the metal electrode layer during printing, and finally printing the Si/SiO of the metal electrode layer2The substrate 102 was dried for 5min at 60 ℃ on a hot plate.
And finally stripping by adopting an acetone solvent. Drying the Si/SiO2The substrate 102 is put into acetone solution for ultrasonic stripping for 30s, and the excess photoresist 110 part of the metal electrode layer is removed, so as to obtain the patterned electrode copper electrode with neat and smooth edge according to the invention, as shown in fig. 15.
The invention combines a 3D printing method and a photoetching technology to prepare the thin film electrode, provides a patterned thin film electrode material growth method with neat and smooth edges, can obtain various 3D printing metal electrode structures with neat edges, effectively solves the problem of irregular electrode edges generated in the preparation process of the traditional 3D printing method, and has wide application prospect.
The principle and the implementation mode of the invention are explained by applying specific examples, and the description of the above examples is only used for helping understanding the method and the core idea of the invention; meanwhile, for a person skilled in the art, according to the idea of the present invention, the specific embodiments and the application range may be changed. In view of the above, the present disclosure should not be construed as limiting the invention.
Claims (10)
1. A method for growing patterned thin-film electrode materials with neat and smooth edges is characterized in that a 3D printing method and a photoetching technology are combined to grow patterned thin-film electrode materials with neat and smooth edges.
2. The method for growing the patterned thin-film electrode material with regular and smooth edges according to claim 1, which comprises the following steps:
step 1, photoetching and patterning an electrode structure on a substrate by utilizing a traditional photoetching technology;
step 2, printing the electrode ink by adopting a 3D printing method and curing to form a film;
and 3, removing the photoresist to obtain the patterned thin film electrode material with neat and smooth edges.
3. The method for growing the patterned thin-film electrode material with regular and smooth edges according to claim 2, wherein the step 1 specifically comprises: placing the substrate in a photoresist uniformizing instrument, dripping photoresist on the substrate, spin-coating and soft-baking; and then covering the substrate with the cured photoresist by using a mask plate, exposing and developing to obtain the patterned electrode structure.
4. The method as claimed in claim 3, wherein the spin speed of the spin coater is 500r/min, 10s, then 2000r/min, 20 s.
5. The method for growing a patterned thin film electrode material with regular and smooth edges according to claim 3, wherein the soft baking temperature is 65-90 ℃ and the time is 5-30 minutes.
6. The method for growing a patterned thin film electrode material with regular and smooth edges as claimed in claim 3, wherein the exposure time is 15 s.
7. The method for growing a patterned thin film electrode material with regular and smooth edges as claimed in claim 3, wherein the developing time is 8 s.
8. The method for growing the patterned thin-film electrode material with regular and smooth edges according to claim 2, wherein the step 2 is specifically as follows: utilize 3D printing apparatus, irritate the electrode ink into the needle body, observe through the computer screen and move the needle point to the contact substrate, set up relevant parameter, ultrasonic resonance prints and covers the electrode ink, and the printing area need not accurate alignment, and electrode ink layer cover patterning electrode area alright, repeated printing is until printing to required electrode thickness.
9. The method for growing the patterned thin film electrode material with neat and smooth edges as claimed in claim 8, wherein the parameters of the 3D printing device are set as follows: the printing speed is 0.3-0.5mm/s, the printing times are 2-3 times, and the printing thickness is 40-60 nm.
10. The method for growing the patterned thin-film electrode material with regular and smooth edges according to claim 2, wherein the step 3 is specifically as follows: and stripping by adopting an acetone solvent, and removing the photoresist and the electrode ink printed and cured on the photoresist to obtain the patterned thin-film electrode material with neat and smooth edges.
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| CN107937939A (en) * | 2017-11-16 | 2018-04-20 | 中国科学院宁波材料技术与工程研究所 | Three-dimensional fine metal structure increases the manufacture method and its manufacture device of material |
| WO2018193446A1 (en) * | 2017-04-16 | 2018-10-25 | Precise Bio Inc. | System and method for laser induced forward transfer comprising a microfluidic chip print head with a renewable intermediate layer |
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2020
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