KR102345450B1 - pulsed-mode direct-write laser metallization - Google Patents

Abstract

A method for manufacturing involves coating a substrate 22 with a matrix comprising a material to be patterned on the substrate. A pattern is anchored in the matrix by directing a pulsed energy beam to impinge on the location of the pattern so that adhesion of the material to the substrate occurs along the pattern without sintering the material completely within the pattern. The matrix remaining on the substrate outside the fixed pattern is removed, and after removing the matrix, the material in the pattern is sintered.

Description

pulsed-mode direct-write laser metallization

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method and system for manufacturing printed wiring, in particular for direct writing of metallic features, on circuit boards.

Direct laser sintering of metallic inks is a known technique in printed wiring metallization. For example, US Patent Application Publication 2008/0286488 describes a method for forming a conductive film based on depositing a non-conductive film on a substrate surface. The film includes a plurality of copper nanoparticles, and light sintering or fusing the copper nanoparticles by exposing at least a portion of the film to light makes the exposed portions conductive.

Kumpulainen et al. describe a direct laser sintering technique in "Low Temperature Nanoparticle Sintering with Continuous Wave and Pulse Lasers," Optics & Laser Technology 43 (2011), pages 570-576. This document is about "printable electronics" in which nanoparticle inks printed on a substrate surface contain additives, such as dispersants and carrier liquids, which alter the viscosity and provide good printing properties by separating the nanoparticles of the ink. In the sintering process, the ink particles are heated to a constant, ink-specific temperature, and the carrier liquid and dispersant are evaporated from the ink. Additional heating after evaporation allows the nanoparticles to begin to agglomerate. Laser sintering is known to allow for short sintering times and selective sintering, allowing print structures to contain fragile active ingredients produced by other techniques. This document describes tests carried out with two different types of lasers: pulsed lasers and continuous wave lasers.

After the priority date of this patent application, Theodorakos et al. described another laser sintering technique in "Selective Laser Sintering of Ag Nanoparticles Ink for Applications in Flexible Electronics," Applied Surface Science 336 (2015), pages 157-162. This document describes an efficient tool for selective laser sintering of Ag nanoparticle ink layers on flexible substrates, operating at 532 and 1064 nm, from three different laser sources: continuous wave (CW) or pulsed nanosecond and picosecond lasers. Investigate the potential for Theoretical simulations indicate that the picosecond laser pulse limits the heat-affected area to a few micrometers only around the irradiated area of the ink layer. This prediction was confirmed experimentally.

Embodiments of the present invention provide an improved method and system for laser-based direct writing to a substrate.

In accordance with one embodiment of the present invention, a substrate is coated with a matrix containing a material to be patterned on the substrate, and pulse energy is applied so that adhesion of the material to the substrate occurs along the pattern without sintering the material completely into the pattern. A method of manufacturing is provided which includes fixing a pattern in a matrix by directing a beam to impinge on the location of the pattern. The matrix remaining on the substrate outside the fixed pattern is removed, and after removing the matrix, the material in the pattern is sintered.

In certain embodiments, the material to be patterned comprises nanoparticles. In this embodiment, the material in the nanoparticles is electrically conductive, and the trace resistance after the pulsed energy beam immobilizes the pattern is selected to be at least ten times greater than the final resistance to be achieved by complete sintering of the material in the pattern after removing the matrix. Includes radiation pulses with energy fluence and repetition rate.

In general, directing a pulsed energy beam includes directing a pulse sequence of energy beams to impinge each position in a position on a substrate.

In this embodiment, the pulsed energy beam has a pulse repetition rate of 1 MHz or higher, preferably 10 MHz or higher.

Generally, the matrix contains organic compounds in addition to the material from which the pattern will be made, and directing the pulsed energy beam fluences per pulse selected to cause evaporation of the organic compound from the matrix without completely sintering the material within the pattern. and directing a pulse sequence of an energy beam with For each pulse applied to hold the pattern, a fluence is selected such that the material remains sufficiently porous and the organic compound evaporates through the pores in the material without removal or delamination of the material due to evaporation of the organic compound.

In some embodiments, sintering of the material includes applying a bulk sintering process to the pattern fixed on the substrate. Optionally, sintering the material comprises directing additional pulses of the pulsed energy beam to sinter the fixed pattern on the substrate.

In this embodiment, coating the substrate includes drying the matrix on the substrate prior to irradiating the coated substrate. Additionally or alternatively, removing the matrix includes applying a solvent to remove the matrix remaining on the substrate outside the fixed pattern.

In accordance with one embodiment of the present invention, the substrate is coated with a matrix containing the material to be patterned on the substrate, and a transient profile ramped to a fluence sufficient to anchor the material to the substrate and sinter the material in point. A method is provided comprising directing a pulsed energy beam comprising a pulse such that a ramped temporal profile impinges on a point on a coated substrate.

In this embodiment, the matrix contains an organic compound in addition to the material fixed to the substrate, and the ramped transient profile and fluence sinter the material without causing removal or delamination of the material due to evaporation of the organic compound. Prior to this, it is selected to cause evaporation of organic compounds from the matrix. In certain embodiments, the material comprises nanoparticles, and sintering the material causes fusion of the nanoparticles at a point.

In this embodiment, the pulse has a duration of 20 ns or less.

In some embodiments, directing a beam of pulsed energy includes creating a pattern of material on the substrate by directing the pulses to impinge on a sequence of points that creates a pattern on the coated substrate. Sequence points do not overlap each other. Generally, such methods include, after creating the pattern, removing the matrix remaining on the substrate outside the location of the pattern.

In accordance with an embodiment of the present invention, there is further provided a manufacturing system comprising a coating machine configured to coat a substrate with a matrix containing a material to be patterned on the substrate. A writing machine is configured to fix a pattern in a matrix by directing a beam of pulsed energy to impinge on the location of the pattern so that adhesion of the material to the substrate occurs along the pattern without sintering the material completely into the pattern. . The matrix removal machine is configured to remove the matrix remaining on the substrate outside the fixed pattern. The sintering machine is configured to sinter the material in the pattern after removing the matrix.

According to another embodiment of the present invention, there is further provided a manufacturing system comprising a coating machine configured to coat a substrate with a matrix containing a material to be patterned on the substrate. The writing machine directs a pulsed energy beam comprising pulses that cause a ramped temporal profile to strike a point on the coated substrate with sufficient fluence to fix the material to the substrate and sinter the material at the point ( direct).

BRIEF DESCRIPTION OF THE DRAWINGS The invention will be fully understood from the following detailed description with reference to the drawings.

1 is a schematic diagram illustrating a system for laser-based direct writing and steps in system operation, according to an embodiment of the present invention.
2A-2E are schematic plan views of a substrate on which a trace pattern has been recorded, shown as successive stages of the pattern formation process, in accordance with an embodiment of the present invention.
3A and 3B are schematic cross-sectional views of a substrate on which traces have been recorded, shown as successive stages of the trace formation process, in accordance with an embodiment of the present invention.
4A-4D are schematic cross-sectional views of a substrate on which a trace has been written, shown in successive steps during fixation of the trace, in accordance with an embodiment of the present invention.
4E is a schematic cross-sectional view of the substrate and traces of FIGS. 4A-4D following annealing of the traces, in accordance with an embodiment of the present invention.
5 is a diagram illustrating a correlation between pulse energy thresholds for fixing and damage to a trace recorded on a substrate according to an embodiment of the present invention.
6A is a schematic plan view of a substrate in which dots are written to an array of points by a pulsed beam with variable pulse parameters, in accordance with an embodiment of the present invention.
6B is a schematic plan view of a pattern formed on a substrate by applying a pulsed beam to a series of points in accordance with an embodiment of the present invention.

survey

As described in the previously described PCT patent application PCT/IL2014/000014, direct laser sintering in one step on metallic inks and other nanoparticle sinterable inks does not provide sufficiently uniform results. (The term “nanoparticle” is used in the description and claims herein to mean fine particles having a one-dimensional size of 100 nm or less.) This problem arises, at least in part, from heat transfer that occurs during the local sintering process. do. Non-uniform heat diffusion under these conditions causes thermal variations, which in turn result in inconsistent sintering. This impact is most severe when dealing with high-resolution patterning with metallic features as small as a few microns. At the same time, direct sintering of metallic inks is tens to hundreds of J/cm ² of high laser fluence.

In an embodiment of the present invention, the recording and sintering steps are separated to improve trace uniformity and reliability of the result. The substrate is coated with a suitable matrix and can be dried after coating to remove excess solvent. (Such a matrix includes an ink, paste, or suspension comprising nanoparticles, and is referred to herein as “NP ink” for convenience.) A pulsed energy beam source, such as a laser, scans over the substrate and completely encapsulates the nanoparticles. Record the requested pattern without sintering. As used herein and in the claims, the term "completely not sintered" means that the nanoparticles in the matrix bulk are significantly separated from each other, and in the case of metal nanoparticles, the resistance of the traces at this stage is It is meant to be at least 10 times the final resistance that can be achieved after full sintering.

At this stage of the process, an energy beam records a pattern, referred to herein as “fixing” the pattern in the matrix. In an embodiment, the beam scans the position of the pattern to be written on the substrate, and a sequence (or "burst") of pulses is sufficient to cause adhesion of the material to the substrate along the pattern, but not below the threshold for complete sintering. Mitch to have fluence. This fixation step, in relation to the unirradiated matrix, stabilizes the matrix against subsequent removal of the matrix. The use of pulsed irradiation in this step improves the pattern trace quality by reducing the potential for damage due to the rapid expansion of the gas trapped within the matrix.

During this immobilization step, before the nanoparticles are completely sintered, the material is sufficiently porous to allow the organic compounds in the matrix to evaporate through the pores in the material, which would otherwise be caused by excessively rapid evaporation of the organic compounds. Prevents material removal or delamination. To ensure this kind of controlled evaporation, a laser (or other energy source) is directed at a pulse sequence so that it strikes each position in the pattern at a high repetition rate - such as at least 1 MHz, and possibly at least 10 MHz, at a repetition rate. do. The luens per pulse is chosen such that the required porosity of the matrix is maintained until immobilization is complete.

After the pattern is fixed in this way, the matrix is removed from all unfixed areas, leaving only the stable pattern. This removal can be achieved, for example, by application of a chemical solvent or by radiation removal. In general, the substrate is uniformly heated in the bulk sintering process to sinter the remaining nanoparticles in the pattern. This method achieves uniform metallization in contrast to the non-uniformities typically encountered when direct laser sintering is used. This method is also particularly useful for printing thick lines, since the laser fixing step is less sensitive to thickness than full laser sintering, eg bulk sintering in an oven works well on thick ink traces.

Accordingly, these embodiments provide a simple and fast metallization process with fewer steps than conventional methods. The first step of this process involves only a relatively low laser power. Then the actual metallization step - the bulk sintering process - requires high fluence and high power with large area coverage, such as high power flash lamps or high power lasers or heat sources or light strip illumination by laser arrays. This can be done using the source. Because these embodiments avoid the high local temperatures associated with one-step direct laser sintering, they are suitable for use in the patterning of delicate and flexible substrates, such as plastics and foils.

In another embodiment, a pulsed laser or other energy beam is used for sintering and immobilization. In this case, the inventors have found that pulses with a ramped temporal profile achieve significantly better results than conventional pulses, with nearly uniform intensity over time (such as square wave pulses). A ramped transient profile is desirable in that it causes evaporation of organic compounds from the matrix coated on the substrate prior to sintering the nanoparticle material. The temporal profile and fluence of the pulses are chosen to enhance this effect and thus for removal or exfoliation of the patterned material due to evaporation of organic compounds. These single-step embodiments are particularly suitable (if not the only solution) for creating individual sintering dots on a substrate and creating patterns made from such dots.

The use of a pulsed laser for direct writing (for fixed or direct sintering) in an embodiment of the present invention achieves high resolution, with the possibility of adaptive registration, as in digital image technology. do. Metal lines and other features created by published techniques can achieve widths as small as a few microns. This resolution is limited only to the size of the laser spot that can be focused in the range of 1-2 μm or less. This resolution and quality of the line definition can be improved by tuning the parameters of the laser during the scan. Arbitrary patterns are created in this way and worked directly from computer-aided design and manufacturing (CAD/CAM) data.

In some embodiments, the entire cycle of writing and sintering is performed without contacting the substrate. This feature is particularly beneficial for applications such as the manufacture of solar cells and electronic plastics electronic foils.

Other applications of the techniques described herein include, for example, display back-end metallization for liquid crystal and organic light emitting diode (OLED) displays, touch screen metallization, shunting of OLED lighting devices, and printed electronic circuits and devices on plastic foils. includes The techniques described herein are particularly useful for recording patterns in various NP materials on various dielectric, ceramic, semiconductor, polymer, paper and metal substrates - including metal as well as semiconductor and dielectric particles (such as ceramic particles). It can be applied similarly where

Although embodiments of the present invention refer to the formation of a single metal layer, in alternative embodiments, traces may be written in multiple layers by appropriate repetition of the inventive technique using the same or different inks used in each layer. do.

System Description

1 and 2A-2E schematically illustrate a laser-based direct writing system 20 and processing, in accordance with an embodiment of the present invention. 1 is a diagram illustrating component arrangements and steps in the processing performed by system 20 . 2A-2E are schematic plan views of a substrate 22 onto which a trace pattern is written in the system 20, shown in successive stages of the process. As noted above, substrate 22 may comprise, for example, glass or other dielectric, ceramic, semiconductor, plastic foil or other polymeric material, paper or metal.

Initially, coating machine 24 coats substrate 22 (FIG. 2A) with a matrix layer 28 of uniform thickness, such as a metal nanoparticle (NP) ink, metal NP paste, or metal complex ink or paste. (Fig. 2B). Such inks or pastes include, for example, silver, copper, nickel, palladium, and/or gold nanoparticles, and alloys of such metals, or non-metallic nanoparticles such as silicon or nano-ceramic particles. The matrix layer 28 can vary in thickness from about 0.2 μm to 10 μm or more, depending on the desired end result. Coating machine 24 may apply any suitable area coating technique known in the art, such as screen printing, slot-die or bar coating, spray coating, gravure printing, or spin coating.

Optionally, drying machine 26 dries the matrix applied to substrate 22 . The ink or paste applied by the coating machine 24 contains a large amount of solvent, and the metal volumetric content at this stage is only about 40%. It is therefore desirable, if not compulsory, to dry the matrix prior to the laser scanning step in order to increase the stability of the matrix and reduce the loss of laser energy to the solvent. Possible drying methods include low temperature baking (by convection or radiation), air flow, vacuum drying, or a combination of these techniques.

A laser writing machine 30 fixes a pattern of traces 42 to a matrix 28, as shown in FIG. 2C. In a typical implementation, a substrate 22 having a matrix coated thereon is mounted on a suitable table 34, and a beam scanner 36 beams a pulsed laser 32 (or other suitable pulsed energy source) beam onto the substrate. scan

Laser 32 "writes" the desired pattern into the matrix by exposing the matrix to a well-defined sequence of laser pulses at defined locations on the film. The pattern is determined by the controller 38 based on the appropriate CAD/CAM data stored in the memory 40 . Pulse parameters including wavelength, spot size, fluence, duration, pulse shape, scan rate and repetition rate are selected to best suit the quality of the pattern as further described below. For high throughput, multiple laser beams (generated by multiple lasers, as shown in Figure 1, or by splitting a single high-power pulsed laser beam into subbeams) can be scanned simultaneously over different areas of the substrate. and each beam is independently controlled.

Various types of lasers and laser systems may be used in the laser recording machine 30 . In an embodiment, the laser diode source is directly modulated at a high rate to emit pulses of the desired shape on a time scale of 1 to tens of nanoseconds. In such an embodiment, the pulse shape is ramped (as described further below), and the ramping time is adjusted to match the trace thickness. The pulse parameters are also adjusted according to the trace width, short pulses are used when very narrow lines are required. The choice of pulse parameters also depends on whether machine 30 is used only for fixation, followed by bulk sintering, or whether laser 32 is used to completely sinter the trace.

Optionally, a CW laser source, such as a CW filter laser, may be modulated at the desired high repetition rate to provide the desired pulsed beam. Fast external modulators such as electro-optical and acousto-optic modulators can be used for this purpose.

3A is a schematic cross-sectional view showing one trace 42 secured in matrix 28 by recording machine 30, in accordance with one embodiment of the present invention. Traces 42 do not contain large amounts of sintered metal in this step, and are more attached to substrate 22 than surrounding matrix 28 due to laser exposure (as a result of light and thermal effects) and ) and is stable against removal from

As explained above, the laser parameters of the writing machine 30 are selected to provide the desired local change in matrix properties. The optimal parameters will vary depending on the exact matrix material and size and the recording method chosen, and will be determined in each case by actual testing and evaluation. In any case, the power applied in this step is much less than that required for complete sintering of the nanoparticles in the matrix.

After irradiation, the matrix removal machine 44 removes the unfixed matrix 28 from the entire area of the substrate 22, leaving only the traces 42 (FIG. 2D). Machine 44 may include a solvent bath, eg, immersing the substrate in such a solvent bath to remove the matrix outside the pattern. Alternatively or additionally, machine 44 may apply other types of removal techniques, such as chemical or physical removal of the unfixed matrix.

3B is a schematic cross-sectional view of traces 42 remaining on substrate 22 after removal of matrix 28 by superstition 44 .

Finally, the traces 42 remaining on the substrate 22 after matrix removal are sintered in a sintering machine 46, providing sintered traces 50 as shown in FIG. 2E. The sintering machine 46 may include a conventional sintering oven, provided the substrate 22 is suitable for such processing (eg, as in the case of a glass substrate). Optionally, the sintering machine 46 may use optical sintering, suitable for sensitive substrates such as plastic foil. More optionally, other sintering methods, such as plasma sintering or micro-sintering, are suitable for sensitive substrates, and both plasma sintering or micro-sintering can sinter the metal ink pattern without damaging the raised plastic substrate below. can

In general, when processing copper inks, optical sintering (or microwave or plasma sintering) is preferred after oven sintering because of the tendency of copper to oxidize easily, as well as inks containing other metals that are susceptible to oxidation. Oven sintering of copper ink may be used in a suitable atmosphere (ie, a non-oxidizing atmosphere and/or a reducing atmosphere).

A sintering machine 46 as shown in FIG. 1 uses optical sintering, wherein a high intensity optical source 48 is scanned over the surface of the substrate 22 . Source 48 includes a collection of laser diode bars arranged, for example, in rows or stacks, thus providing the required fluence even over large areas. Average powers of several kilowatts can be achieved using commercially available laser diodes in the near infrared range (approximately 800-1000 nm). Commercially available laser diodes are manufactured by Oclaro Inc. (San Jose, California), Coherent Inc. (Santa Clara, California), or Jenoptik (Jena, Germany).

The following section of this specification describes a method that may be applied by the writing machine 30 to fix the desired pattern in the matrix 28 . 6A and 6B, the writing machine 30 may perform sintering by applying sufficient energy to target points on the substrate making the pattern. In this case, a separate sintering machine 46 is not required. The techniques described herein may be applied in connection with the materials and methods described in the aforementioned PCT patent application PCT/IL2014/000014, as well as other suitable materials and methods known to those skilled in the art.

pulsed laser pattern fixation

4A-4E are schematic cross-sectional views of a substrate 22 for successive steps of writing traces 52 to the substrate in accordance with an embodiment of the present invention. Figures 4A-4D show the matrix 28 continuously during fixation of the traces, and Figure 4E shows the traces 52 following annealing. show

In particular, FIGS. 4A-4D show the cumulative effect of a burst of pulses sent by the laser 32 to a given location in the matrix 28 . At the beginning of the process, nanoparticles 50 are suspended in a significant amount of volatile, organic component matrix 28 . Each successive laser pulse heats the matrix and evaporates additional organic components, causing the density of nanoparticles 50 in matrix 28 to increase from one pulse to the next. However, due to diffusion of heating within the matrix and substrate, the increase in density is almost uniform in the matrix volume. Thus, as shown in FIG. 4D , pores remain between the nanoparticles 50 in the matrix 28 , through which evaporative material can disappear even after almost all of the organic material has been removed from the matrix. During the subsequent sintering step, the nanoparticles are melted to create traces 52, as shown in FIG. 4E.

In contrast, the inventors found that when a CW laser is used for pattern immobilization, the nanoparticle density increases especially in the upper layer of the matrix, and the organic material is trapped underneath. Heating these trapped organic materials can cause rapid and explosive evaporation, removing or exfoliating the surrounding nanoparticle material, thus degrading the quality of the traces formed on the substrate.

In contrast, when pulsed radiation is used for immobilization, the pulse parameters are chosen to promote gradual evaporation of the organic components of matrix 28 during pulse bursts, so as to avoid solidifying the top layer of nanoparticles 50 . The inventors found short pulses with pulse widths ranging from about 1 ns to tens of nanoseconds to give the best results. Fast fixation of traces A high repetition rate - at least 1 MHz, possibly 10 MHz or higher is therefore desirable to achieve high throughput. Pulse fluence and other parameters are chosen to maximize throughput as much as possible without damage to the trace.

5 is a diagram illustrating a work window for fixing a trace by a laser pulse according to an embodiment of the present invention. The data points in the figure show the number of pulses applied to a given point on the substrate 22 on the abscissa axis, and the energy fluence per pulse on the ordinate axis. The lower curve 60 represents the minimum fluence required to fix the pattern in the matrix, for a given number of pulses. In other words, the matrix will not be removed from the point after the fixing step as long as the pulses at a given point have this minimum fluence for the specified number of pulses. The upper curve 62 represents, for a given number of pulses, the maximum fluence that can be used without damaging the trace. Above this fluence level, rapid heating of the matrix causes removal and/or delamination to occur.

Thus, curves 60 and 62 define the working window for the pulsed fixation of the matrix. As shown in Figure 5, a larger number of low-fluence pulses provides a wider window and thus allows for a larger range of process error. Within these bounds, the pulse fluence and number of pulses applied to each position are chosen to provide the required robust fixation while maximizing process throughput.

The optimal choice also depends on the laser wavelength and spot size, as well as other process parameters such as the thickness and composition of the matrix 28 . Curves 60 and 62 were generated using a diode laser operating at 980 nm on a 460 nm thick matrix film. Alternatively, ultraviolet, visible, or other partial pulse lasers in the infrared range may be used. The number of pulses (reflected by curve 60) required to fix the pattern tends to vary in magnitude exponentially with respect to film thickness.

pulsed laser sintering

6A is a schematic plan view of a substrate in which dots 74 and 78 are written to an array of points by a pulsed beam with variable pulse parameters, in accordance with an embodiment of the present invention. In this embodiment, the substrate was coated with a matrix comprising nanoparticulate material. A pulsed laser beam is directed to impinge on each point of the substrate in the array with sufficient fluence to fix the material to the substrate and sinter the material at the point. The laser beam in this case is a diode laser operating at 980 nm in pulsed mode. The peak power of the laser pulse applied to create points 74 and 78 increased from the bottom to the top of the array shown in Figure 6A, the pulse duration increased from left to right, and the maximum pulse time was set to be about 20 ns. lost. Similar results are obtained for other waveforms.

Two different pulse profiles were used to sinter the points shown in FIG. 6A: a rectangular pulse profile 70 was used at the sintering point 74, and a ramp pulse profile 72 at the sintering point 78. was used Profile 72 is "ramped" in that the instantaneous power of the pulse increases progressively over the duration of the pulse, with the greatest power occurring near the trailing edge of the pulse. The ramped transient profile and the fluence of the ramped pulses are selected to allow evaporation of organic compounds from the matrix prior to sintering the nanoparticulate material, and no removal or exfoliation of material due to explosive evaporation of organic compounds. This beneficial effect of the ramped profile can be seen over a wide range of peak power and pulse duration, as shown by point 78 . In contrast, dots 74 created using profile 70 represent areas 76 of damage due to removal and exfoliation of the nanoparticulate material.

Ramped profile 72 is particularly useful for creating single sintered dots on a substrate. These points will have a larger diameter than the laser beam due to the transverse thermal spread of the beam energy in the proximal region of the matrix. (The ramped beam profile is less important in line scanning, as each point in the line, not the first point, is preheated as the previous point is sintered.) Single points of these same points create a pattern on the coated substrate. It can be used to create a pattern on a substrate by directing a laser pulse to impinge on a sequence of points it creates. Since each point has a larger area than the laser beam used to anchor and sinter it, these sequence points may not overlap each other. That is, the beam regions of the laser pulses used to generate the neighboring points do not need to overlap. After creating the pattern in this way, the matrix remaining on the substrate outside the position of the pattern is removed in the previous embodiment.

6B is a schematic plan view of a pattern 80 formed on a substrate by applying a pulsed beam in a sequence of points 82, in accordance with an embodiment of the present invention. In this embodiment, pattern 80 includes lines formed by the overlap of points 78, although points 82 themselves do not overlap. A pattern of the desired shape can be efficiently generated in this way.

The above-described embodiments have been described as examples, and the present invention is not limited to these examples. The protection scope of the present invention includes combinations and sub-combinations of various features described above, and includes various features and modifications and variations that can be known to those skilled in the art with reference to the above description and are not described in the prior art.

Claims (38)

A manufacturing method comprising:
coating the substrate with a matrix comprising a material to be patterned on the substrate;
By directing a pulsed energy beam to impinge on a locus of the pattern such that adhesion of the material occurs along the pattern to the substrate without sintering the material completely into the pattern. fixing the pattern in the matrix;
removing the matrix remaining on the substrate outside the fixed pattern; and
after removing the matrix, sintering the material in the pattern;
including,
wherein the material to be patterned comprises nanoparticles, the material in the nanoparticles is electrically conductive, and the pulsed energy beam is such that the trace resistance after fixing the pattern is sufficient for complete sintering of the material in the pattern after removing the matrix. a radiation pulse having an energy fluence and a repetition rate selected to remain at least ten times greater than the final resistance to be achieved by manufacturing method. The method of claim 1 , wherein directing the pulsed energy beam comprises directing a pulse sequence of energy beams to impinge on respective locations within a trajectory on the substrate. The method of claim 1 , wherein the pulse repetition rate is at least 10 MHz or higher. The method of claim 1 , wherein the matrix further comprises an organic compound in the material to be patterned, and directing the pulsed energy beam evaporates the organic compound from the matrix without completely sintering the material into the pattern. directing a pulse sequence of an energy beam having a per-pulse fluence selected to generate 5. The method of claim 4, wherein the fluence per pulse applied to fix the pattern is such that the organic compound can evaporate through holes in the material without removal or delamination of the material due to evaporation of the organic compound. wherein the material is selected to remain sufficiently porous. 6 . The method of claim 1 , wherein sintering the material comprises applying a bulk sintering treatment to the pattern fixed on the substrate. 6. The method of any preceding claim, wherein sintering the material comprises directing additional pulses of the pulsed energy beam to sinter the pattern fixed on the substrate. , manufacturing method. 6 . The method of claim 1 , wherein coating the substrate comprises drying the matrix on the substrate prior to irradiating the coated substrate. 6 . The fabrication of claim 1 , wherein removing the matrix comprises applying a solvent to remove the matrix remaining on the substrate out of the fixed pattern. Way. A manufacturing system comprising:
a coating machine configured to coat the substrate with a matrix comprising a material to be patterned on the substrate;
immobilizing the pattern in the matrix by directing a pulsed energy beam to impinge on the trajectory of the pattern such that adhesion of the material occurs along the pattern to the substrate without sintering the material completely into the pattern; a recording machine configured to
a matrix removal machine configured to remove the matrix remaining on the substrate out of the fixed pattern; and
a sintering machine configured to sinter the material in the pattern after removal of the matrix;
wherein the material to be patterned comprises nanoparticles, the material in the nanoparticles is electrically conductive, and the pulsed energy beam is such that the trace resistance after fixing the pattern is sufficient for complete sintering of the material in the pattern after removing the matrix. and a radiation pulse having an energy fluence and repetition rate selected to remain at least 10 times greater than a final resistance to be achieved by the method, wherein the pulsed energy beam has a pulse repetition rate of at least 1 MHz or greater. The manufacturing system of claim 10 , wherein the writing machine is further configured to direct a pulse sequence of an energy beam to impinge on each location in the trajectory on the substrate. 11. The manufacturing system of claim 10, wherein the pulse repetition rate is at least 10 MHz or greater. 11. The method of claim 10, wherein the matrix further comprises an organic compound in the material to be patterned, and wherein the recording machine is further configured to cause evaporation of the organic compound from the matrix without sintering the material completely within the pattern. and direct a pulse sequence of an energy beam having a per-pulse fluence selected to 14. The method of claim 13, wherein the fluence per pulse applied to fix the pattern is such that the organic compound can evaporate through holes in the material without removal or delamination of the material due to evaporation of the organic compound. wherein the material is selected to remain sufficiently porous. 15. The manufacturing system according to any one of claims 10 to 14, wherein the sintering machine is further configured to apply a bulk sintering treatment to the pattern fixed on the substrate. 15 . The manufacturing system according to claim 10 , wherein the sintering machine is further configured to apply additional pulses of the pulsed energy beam to sinter the pattern fixed on the substrate. . 15. A manufacturing system according to any one of claims 10 to 14, further comprising a drying machine configured to dry the matrix on the substrate prior to irradiating the coated substrate. 15. The manufacturing system of any of claims 10-14, wherein the matrix removal machine is further configured to apply a solvent to remove the matrix remaining on the substrate out of the fixed pattern. delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete

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