CN114523780A - Nanoparticle self-assembly deposition method based on magnetic field regulation - Google Patents
Nanoparticle self-assembly deposition method based on magnetic field regulation Download PDFInfo
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- CN114523780A CN114523780A CN202210256641.8A CN202210256641A CN114523780A CN 114523780 A CN114523780 A CN 114523780A CN 202210256641 A CN202210256641 A CN 202210256641A CN 114523780 A CN114523780 A CN 114523780A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/0041—Digital printing on surfaces other than ordinary paper
- B41M5/0047—Digital printing on surfaces other than ordinary paper by ink-jet printing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
- B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
- B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
- B41J2/01—Ink jet
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
- B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
- B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
- B41J2/01—Ink jet
- B41J2/17—Ink jet characterised by ink handling
- B41J2/175—Ink supply systems ; Circuit parts therefor
- B41J2/17503—Ink cartridges
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
- B41J3/00—Typewriters or selective printing or marking mechanisms characterised by the purpose for which they are constructed
- B41J3/407—Typewriters or selective printing or marking mechanisms characterised by the purpose for which they are constructed for marking on special material
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/24—Vacuum evaporation
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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
- H05K3/1241—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 ink-jet printing or drawing by dispensing
- H05K3/125—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 ink-jet printing or drawing by dispensing by ink-jet printing
Abstract
The invention provides a magnetic field regulation-based nanoparticle self-assembly deposition method, and belongs to the technical field of nanoparticle self-assembly. The method comprises the following steps: the method comprises the following steps: building an ink-jet printing deposition device based on magnetic field regulation; step two: placing ink in inkjet printing equipment, wherein the ink is magnetic fluid ink or magnetic nanoparticle ink; step three: designing a printing line for printing or coating a dot matrix and a line by using a pipettor, starting a Helmholtz coil to electrify and apply a magnetic field, placing a printing substrate on a constant-temperature heating base, and depositing a single-layer microstructure magnetic chain pattern on the substrate by ink-jet printing; step four: and fusing and superposing the microstructure magnetic chains by changing the direction of the magnetic field to form a multilayer microstructure pattern. According to the method, a horizontal magnetic field is applied through the Helmholtz coil, the evaporation speed of liquid drops is controlled by heating the base at a constant temperature, and the preparation of uniform deposition patterns and dense parallel chain-shaped microstructure deposition patterns can be realized.
Description
Technical Field
The invention belongs to the technical field of nanoparticle self-assembly, and particularly relates to a nanoparticle self-assembly deposition method based on magnetic field regulation.
Background
The evaporation and deposition of the liquid drops on the surface of the substrate are a research field with wide application, the regulation and control of the liquid drop deposition are the key research directions, and the liquid drop deposition method has wide application in the fields of ink-jet printing, biomedical detection and the like. In many cases (e.g. ink jet printing for the preparation of printed electronic circuits, components) it is desirable to obtain a uniform or near uniform deposition pattern, however the internal flow (e.g. capillary flow, marangoni flow) transport during droplet evaporation can produce a coffee ring effect, which severely affects droplet deposition quality. Therefore, various control techniques have been developed for artificially interfering with the evaporation of the droplets and the transport of the nanoparticles, thereby obtaining a high-quality deposition pattern. For magnetic fluid or ink containing magnetic nano particles, the magnetic field active regulation technology is an effective regulation means, and the self-assembly effect of the magnetic nano particles under a horizontal magnetic field provides possibility for preparing microstructure deposition patterns on the basis of uniform deposition.
The internal flow (such as capillary flow and Marangoni flow) transportation in the droplet evaporation process can cause uneven deposition of particles, and the droplet deposition quality is seriously influenced, so that a regulating and controlling means is required to intervene in the evaporation and deposition of the droplets. For magnetic fluid or ink containing magnetic nano particles, the active magnetic field regulation and control technology is an effective regulation and control means. Under a horizontal magnetic field, magnetic nano particles are combined into a dense long chain along a magnetic induction line (namely, self-assembly effect), the structure can be reserved to be completely deposited by setting evaporation parameters, and under the condition of multi-layer printing combination, the technology can realize the manufacturing of deposition patterns with approximate uniform deposition and complex microstructures.
Disclosure of Invention
The invention aims to provide a nanoparticle self-assembly deposition method based on magnetic field regulation. Horizontal magnetic field is applied through a Helmholtz coil, the constant-temperature heating base controls the evaporation speed of liquid drops, and the technology can realize the preparation of uniform deposition patterns and dense parallel chain-shaped microstructure deposition patterns.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a nanoparticle self-assembly deposition method based on magnetic field regulation, which comprises the following steps:
the method comprises the following steps: building an ink-jet printing deposition device based on magnetic field regulation; the device comprises:
the device comprises Helmholtz coils, ink-jet printing equipment and a constant-temperature heating base, wherein the Helmholtz coils are arranged on two sides of the constant-temperature heating base, and the ink-jet printing equipment is arranged on the constant-temperature heating base;
step two: placing ink in inkjet printing equipment, wherein the ink is magnetic fluid ink or magnetic nanoparticle ink;
step three: designing a printing circuit to print or coating a dot matrix and a circuit by using a pipettor, starting a Helmholtz coil to electrify and apply a magnetic field, setting the magnetic field strength to be more than 20mT, placing a printing substrate on a constant-temperature heating base, setting the temperature of the constant-temperature heating base to be 50-70 ℃ lower than the boiling point of an ink solvent, and depositing a single-layer microstructure magnetic chain pattern on a substrate by ink-jet printing;
step four: and fusing and superposing the microstructure magnetic chains by changing the direction of the magnetic field to form a multilayer microstructure pattern.
Preferably, the magnetic fluid ink comprises a water-based ferrofluid ink or a kerosene-based ferrofluid ink.
Preferably, the magnetic nanoparticle ink is obtained by mixing magnetic particles and a dispersion solvent, wherein the magnetic particles are iron, cobalt, nickel or nanoparticles doped and coated with iron, cobalt and nickel.
Preferably, the magnetic particles have a particle size of less than 50 nm.
Preferably, the dispersing solvent is one or more selected from deionized water, ethylene glycol, terpineol, cyclohexane or isopropanol.
Preferably, the mass fraction of the ink is 2% -20%.
Preferably, a stabilizer is added into the ink, the stabilizer is PVP or xanthan gum, and the adding amount of the stabilizer is preferably 0.05-1% by mass.
Preferably, the printing substrate is silicon carbide, aluminum nitride, aluminum oxide, glass, bakelite plate, tissue paper or PI film.
Preferably, the multilayer microstructure pattern formed in the fourth step is sintered in a tube furnace, the maximum sintering heating temperature is set to 700 ℃, the temperature rise time is 30min, and the constant temperature time is preferably 10min, so that the crossed microstructure conductive circuit is obtained.
Principle of the invention
The invention provides a nanoparticle self-assembly deposition method based on magnetic field regulation, wherein Helmholtz coils are selected for applying a magnetic field and consist of two groups of coils, the distance between the coils is the radius of the coils, and after the coils are electrified, a uniform magnetic field can be generated in the center of the coils. The helmholtz coil needs to be compatible with the inkjet printing apparatus in order to be able to apply the magnetic field during the printing process. The magnetic nanometer particle liquid drop is placed on the surface of a constant temperature heating base, the liquid drop can be evaporated and deposited, and the magnetic field is applied in the evaporation process, so that the magnetic nanometer particle in the liquid drop can generate a self-assembly effect. The principle of the self-assembly effect is shown in fig. 1. When two paramagnetic particles are aligned perpendicular to the magnetic induction lines, they repel each other (FIG. 1a), and when they are aligned parallel to the magnetic induction lines, they attract each other and form a chain (FIG. 1 b).
By controlling the heating temperature and the magnetic field strength, the ink can obtain different deposition forms: in the absence of magnetic field application, the droplets will evaporate in a pattern of coffee ring deposition, resulting in a ring-like uneven deposition pattern (see fig. 2 a); at low magnetic field strength (10mT and below) and high substrate temperature (specific temperature is related to the boiling point of the ink solvent), the droplet will obtain an approximately uniform deposition pattern, but its internal microstructure cannot be resolved (see fig. 2 b); under the condition of high magnetic field strength (more than 10 mT) and low substrate temperature, the magnetic chain microstructure formed by self-assembly in the liquid drop can resist internal flow and remain until complete evaporation, so that a clear dense parallel chain microstructure deposition pattern is obtained (as shown in figure 2 c).
On the basis of a single-layer microstructure, a complex microstructure pattern can be prepared by changing the direction of a magnetic field and the position of each liquid drop. The preparation of large-scale complex microstructures relies on two effects: (1) and fusing the microstructure magnetic chains. As shown in fig. 3a, the microstructure patterns deposited before and after the deposition are fused with each other under the action of the magnetic field, so as to form an uninterrupted flux linkage pattern; (2) and (4) superposing the microstructure magnetic chains. As shown in fig. 3b, when multiple droplets are deposited by changing the magnetic field direction, the microstructure patterns deposited in front and back are overlapped with each other, thereby forming an intersecting complex microstructure.
The invention has the advantages of
The invention provides a magnetic field regulation-based nanoparticle self-assembly deposition method, which intervenes in the evaporation deposition process of droplets by utilizing a magnetic field, has strong regulation and control effects and wide application range compared with the traditional regulation and control droplet deposition means for regulating ink properties, substrate properties and particle morphology, can be matched with passive regulation and control, and has incomparable advantages compared with the traditional passive regulation and control. In addition, the magnetic field regulation and control can be used for manufacturing parallel chain-shaped microstructure deposition patterns, the patterns can further manufacture complex microstructures in a multi-droplet fusion and superposition mode, and the patterns can be applied to various preparation scenes, such as preparation of flexible extension circuits, preparation of light-transmitting conductive films and the like.
Drawings
FIG. 1 is a diagram illustrating the effect of self-assembly effect of nanoparticles of the present invention under the action of a magnetic field;
FIG. 2 is a deposition pattern of a dense parallel chain microstructure prepared under high magnetic field strength in accordance with the present invention;
FIG. 3 is a diagram illustrating the fusion of the microstructure flux linkage and the superposition effect of the microstructure flux linkage according to the present invention;
FIG. 4 is a flow chart of a process for fabricating a conductive circuit of an intersecting microstructure according to embodiment 1 of the present invention;
FIG. 5 is a microscopic view of an actual circuit printed with the conductive circuits of the crossed microstructure in example 1 of the present invention;
FIG. 6 is a schematic structural diagram of an inkjet printing deposition apparatus based on magnetic field regulation according to the present invention;
FIG. 7 is a partially enlarged view of the displacement mechanism and the constant temperature heating base of the ink-jet printing deposition apparatus based on magnetic field regulation according to the present invention;
FIG. 8 is a schematic diagram of the construction of the X-axis displacement mechanism and the Y-axis displacement mechanism of the present invention;
fig. 9 is a schematic diagram of a rotatable printing substrate according to the present invention.
In the figure: 1. a top observation camera; 2. a Helmholtz coil; 3. an ink supply conduit; 4. a printing nozzle; 5. a side view camera; 6. an X-axis displacement mechanism; 7. heating the base at a constant temperature; 8. a Y-axis displacement mechanism; 9. a rotatable printing substrate; 10. a frame unit; 11. a device driving power supply; 12. a gas source; 13. an ink storage tank; 14. an inkjet printing driving module; 15. a stepping motor; 16. a guide rail; 17. a sliding table; 18. a lead screw; 19. an upper rotating sleeve; 20. the lower part is fixed with a sleeve.
Detailed Description
A nanoparticle self-assembly deposition method based on magnetic field regulation, which comprises the following steps:
the method comprises the following steps: building an ink-jet printing deposition device based on magnetic field regulation; the device comprises:
the device comprises Helmholtz coils, ink-jet printing equipment and a constant-temperature heating base, wherein the Helmholtz coils are arranged on two sides of the constant-temperature heating base, and the ink-jet printing equipment is arranged on the constant-temperature heating base; the Helmholtz coil is used for manufacturing a horizontal magnetic field with uniform strength, the ink-jet printing equipment drives the nozzle to manufacture printing liquid drops as required through a pulse electric signal, the heating base controls the temperature to be constant at a set temperature through a PID algorithm, and the heating temperature range can reach up to 180 ℃;
step two: placing ink in inkjet printing equipment, wherein the ink is magnetic fluid ink or magnetic nanoparticle ink, the magnetic fluid ink preferably comprises water-based ferrofluid ink or kerosene-based ferrofluid ink, the magnetic nanoparticle ink is obtained by mixing magnetic particles and a dispersion solvent, the magnetic particles are preferably iron, cobalt, nickel or doped iron-cobalt-nickel-coated nanoparticles, the particle size of the magnetic particles is less than 50nm, the source is commercially available, and the dispersion solvent is preferably selected from one or more of deionized water, ethylene glycol, terpineol, cyclohexane or isopropanol; the mass fraction of the ink is preferably 2-20%. The ink can also be added with a stabilizer preferably, the stabilizer is PVP or xanthan gum, and the adding amount of the stabilizer is preferably 0.05-1% by mass; after the magnetic nanoparticle ink is prepared, the magnetic nanoparticle ink is preferably placed in an ultrasonic crusher for ultrasonic depolymerization for 2 to 3 hours, the power of the ultrasonic crusher is preferably 240w, and the ink is taken out and filtered;
step three: designing a printing circuit to print or coating a dot matrix and a circuit by using a pipettor, starting a Helmholtz coil to electrify and apply a magnetic field, setting the magnetic field strength to be more than 20mT, placing a printing substrate on a constant-temperature heating base, setting the temperature of the constant-temperature heating base to be 50-70 ℃ lower than the boiling point of an ink solvent, and depositing a single-layer microstructure magnetic chain pattern on a substrate by ink-jet printing; the printing base is preferably silicon carbide, aluminum nitride, aluminum oxide, glass, bakelite board, tissue paper or PI film;
step four: and fusing and superposing the microstructure magnetic chains by changing the direction of the magnetic field to form the multilayer microstructure pattern.
After the multilayer microstructure pattern is obtained in the embodiment, the pattern obtained by printing is preferably sintered in a tubular furnace, and helium is introduced to prevent the circuit from being oxidized in the sintering process; for printing materials with poor substrate temperature resistance, laser sintering can be used, and finally conducting circuits or corresponding sensors or components can be obtained. The maximum sintering heating temperature is set to be 700 ℃, the temperature rise time is preferably 30min, and the constant temperature time is preferably 10 min. And after heating, naturally cooling the substrate to room temperature in a tube furnace to finally obtain the crossed microstructure conductive circuit.
The inkjet printing deposition apparatus based on magnetic field control according to this embodiment, as shown in fig. 6 and 7, includes:
the Helmholtz printing device comprises a frame unit 10, wherein a Helmholtz coil 2, a rotatable printing substrate 9, a displacement mechanism, a constant-temperature heating base 7, an observation system, an ink supply pipeline 3 and a printing nozzle 4 are arranged in the frame unit 10;
the Helmholtz wire 2 is arranged at two sides of a rotatable printing substrate 9, a displacement mechanism is arranged above the rotatable printing substrate 9, a constant-temperature heating base 7 is arranged above the displacement mechanism, a printing nozzle 4 is arranged above the constant-temperature heating base 7, an ink supply pipeline 3 is arranged above the printing nozzle 4, and a piezoelectric ceramic driving signal circuit of the printing nozzle is integrated on the ink supply pipeline 3;
the ink supply pipeline 3 and the observation system are respectively connected with the frame unit 10; the observation system includes a top observation camera 1 and a side observation camera 5, the top observation camera 1 is disposed above the printing nozzle 4 and connected to the top of the frame unit 10, and the side observation camera 5 is disposed on the side of the printing nozzle and connected to the side of the frame unit 10.
As shown in fig. 9, the rotatable printing substrate 9 according to the present embodiment is composed of an upper rotating sleeve 19 and a lower fixed sleeve 20, and the upper rotating sleeve 19 is sleeved with the lower fixed sleeve 20. The upper rotating sleeve 19 can be manually adjusted, can rotate in any direction and be fixed at any angle, and therefore the direction of the magnetic field can be changed in the printing process.
As shown in fig. 8, the displacement mechanism according to this embodiment includes an X-axis displacement mechanism 6 and a Y-axis displacement mechanism 8, the X-axis displacement mechanism 6 is disposed above the Y-axis displacement mechanism 8, the X-axis displacement mechanism 6 and the Y-axis displacement mechanism 8 have the same structure, and respectively include a stepping motor 15, a guide rail 16, a sliding table 17 and a lead screw 18, the stepping motor 15 is disposed on one side of the guide rail 16 and connected to the lead screw 18, and the sliding table 17 and the lead screw 18 are both disposed on the guide rail 16; the motor 15 drives the lead screw 18 to rotate, and the lead screw 18 drives the sliding table 17 to reciprocate in the length direction of the guide rail 16.
The frame unit 10 of the present embodiment includes an upper platform, a lower platform, and a four-sided frame, and the material of the frame unit 10 is aluminum alloy.
The structure of the constant temperature heating base 7 in the embodiment is not particularly limited, and the existing heating base 7 can be adopted, and the constant temperature heating function is realized by arranging the heating sheet made of the copper block in the base.
The ink supply pipe 3, the printing nozzle 4 and the ink storage tank 13 are coated with a layer of magnetic flexible material, and a high-strength magnetic field generated by the helmholtz coil 2 can interfere with the normal operation of the ink-jet printer equipment, so that the equipment which is easily interfered needs to be coated with a magnetic shielding material, the interference of the magnetic field on the equipment is avoided, and the source of the magnetic flexible material is commercially available.
The device driving power supply 11 according to this embodiment can realize fast switching of a magnetic field and fast adjustment of the magnetic field intensity, the inkjet printing device needs to regulate and control the current and voltage of the helmholtz coil 2 to manufacture a constant magnetic field, and the device driving power supply 11 is MP2005D in model.
The present invention will be described in further detail with reference to specific examples.
Example 1a cross-microstructure conductive circuit was prepared by magnetic ink-jet printing of nickel nanoparticles with ink, the preparation process being shown in figure 4,
the method comprises the following steps: building an ink-jet printing deposition device based on magnetic field regulation;
step two: nickel nanoparticle ink formulation
Purchasing nickel nanoparticles with the particle size of less than 50nm and mixing the nickel nanoparticles with an ethylene glycol solvent, wherein the mass fraction of the nickel nanoparticles is 10%; putting the ink into an ultrasonic crusher for ultrasonic depolymerization for 2 hours, wherein the power of the ultrasonic crusher is 240 w; taking out the ink and filtering the ink by using a filter with the pore diameter of 50 mu m to finally obtain the nickel nanoparticle ink for printing;
step three: printing single layer lines using a magnetic field ink jet printer
The ink is placed in the ink-jet printing equipment, and the air pressure of an ink supply pipeline and the driving waveform of nozzle piezoelectric ceramics are adjusted, so that the ink-jet printing equipment can generate stable ink drops; placing a printing substrate on a constant-temperature heating base, and setting the heating temperature to be 80 ℃; switching on a Helmholtz coil power supply, setting the magnetic field intensity to be 30mT, wherein the magnetic field direction forms +45 degrees with the printing line direction; printing a circuit to obtain a single-layer microstructure deposition pattern;
step four: printing multilayer microstructure patterns
Changing the direction of the magnetic field to be minus 45 degrees with the direction of the printing line, and printing again to obtain a double-layer crossed microstructure line;
step five: sintering to make the circuit conductive
Placing the printed circuit and the constant-temperature heating base inside a tubular furnace, and introducing helium to prevent the circuit from being oxidized in the sintering process; setting the highest heating temperature at 700 ℃, the temperature rise time at 30min and the constant temperature time at 10 min; and after the addition is finished, naturally cooling the substrate to room temperature in a tube furnace to finally obtain the crossed microstructure conductive circuit.
The circuit has better conductivity and interface stress resistance due to the existence of the microstructure. The actual line micrographs obtained by printing are shown in fig. 5, where fig. 5a represents the micrographs with one layer printed at +45 degrees in the magnetic field direction, 5b represents the micrographs with one layer printed with the magnetic field direction and line +45, and then-45 prints one layer with two layers of micrographs.
Claims (9)
1. A nanoparticle self-assembly deposition method based on magnetic field regulation is characterized by comprising the following steps:
the method comprises the following steps: building an ink-jet printing deposition device based on magnetic field regulation; the device comprises:
the device comprises Helmholtz coils, ink-jet printing equipment and a constant-temperature heating base, wherein the Helmholtz coils are arranged on two sides of the constant-temperature heating base, and the ink-jet printing equipment is arranged on the constant-temperature heating base;
step two: placing ink in inkjet printing equipment, wherein the ink is magnetic fluid ink or magnetic nanoparticle ink;
step three: designing a printing circuit to print or coating a dot matrix and a circuit by using a pipettor, starting a Helmholtz coil to electrify and apply a magnetic field, setting the magnetic field strength to be more than 20mT, placing a printing substrate on a constant-temperature heating base, setting the temperature of the constant-temperature heating base to be 50-70 ℃ lower than the boiling point of an ink solvent, and depositing a single-layer microstructure magnetic chain pattern on a substrate by ink-jet printing;
step four: and fusing and superposing the microstructure magnetic chains by changing the direction of the magnetic field to form a multilayer microstructure pattern.
2. The magnetic field regulation-based nanoparticle self-assembly deposition method according to claim 1, wherein the magnetic fluid ink comprises a water-based ferrofluid ink or a kerosene-based ferrofluid ink.
3. The magnetic field regulation-based nanoparticle self-assembly deposition method according to claim 2, wherein the magnetic nanoparticle ink is obtained by mixing magnetic particles and a dispersion solvent, and the magnetic particles are iron, cobalt, nickel or nanoparticles doped with iron, cobalt and nickel.
4. The magnetic field regulation-based nanoparticle self-assembly deposition method according to claim 3, wherein the magnetic particles have a particle size of less than 50 nm.
5. The magnetic field regulation-based nanoparticle self-assembly deposition method according to claim 3, wherein the dispersion solvent is one or more selected from deionized water, ethylene glycol, terpineol, cyclohexane or isopropanol.
6. The magnetic field regulation-based nanoparticle self-assembly deposition method according to claim 1, wherein the mass fraction of the ink is 2% -20%.
7. The magnetic field regulation-based nanoparticle self-assembly deposition method according to claim 1, wherein a stabilizer is added to the ink, the stabilizer is PVP or xanthan gum, and the addition amount of the stabilizer is preferably 0.05-1% by mass.
8. The magnetic field regulation-based nanoparticle self-assembly deposition method according to claim 1, wherein the printing substrate is silicon carbide, aluminum nitride, aluminum oxide, glass, bakelite plate, tissue paper or PI film.
9. The magnetic field regulation-based nanoparticle self-assembly deposition method according to claim 1, wherein the multilayer microstructure pattern obtained in the fourth step is sintered in a tube furnace, the sintering heating temperature is set to be 700 ℃ at most, the temperature rise time is 30min, and the constant temperature time is preferably 10min, so as to obtain the crossed microstructure conductive circuit.
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