Method for producing metal wiring, device for producing metal wiring, laser beam irradiation control device and laser beam irradiation control program

Abstract

To provide a method for producing a metal wiring capable of producing the metal wiring with excellent appearance and high reliability, a device for producing the metal wiring, a laser beam irradiation control device and a laser beam irradiation control program.SOLUTION: A method for producing a metal wiring that includes a wiring formation step of forming the metal wiring by irradiating a laser beam to a pre-set irradiation area of a film containing metal and / or metal oxide. In the step of forming the metal wiring, a laser beam irradiation target position is scanned in a first direction while being moved in a second direction that is different from the first direction, thereby scanning the irradiation target position over a scanning area that includes the irradiation area. The time T from when the laser beam is radiated on a point X on a first scanning line S1 until when it is radiated on a point Y, which is on a second scanning line S2 that is different from the first scanning line S1 and is within a distance from the point X that is less than or equal to twice a beam diameter of the laser beam is set to be 1 ms or more, and the energy density of the laser beam radiated to the irradiation area is set to be 1 W / mm2 or more and 5000 W / mm2 or less.SELECTED DRAWING: Figure 1A

Description

[Technical field]

[0001] The present invention relates to a method for manufacturing metal wiring, a metal wiring manufacturing apparatus, a laser light irradiation control device, and a laser light irradiation control program. [Background technology]

[0002] A circuit board has a structure in which conductive wiring is applied on a substrate. The manufacturing method of a circuit board is generally as follows. First, a photoresist is applied onto a substrate to which a metal foil is attached. Next, the photoresist is exposed and developed to obtain a negative shape of a desired circuit pattern. Next, the metal foil not covered with the photoresist is removed by chemical etching to form a pattern. This makes it possible to manufacture a high-performance conductive substrate. However, the conventional method has disadvantages such as a large number of steps, cumbersomeness, and the need for a photoresist material. In contrast, a direct wiring printing technique that directly prints desired metal wiring on a substrate using a dispersion in which particles selected from the group consisting of metal particles and metal oxide particles are dispersed has attracted attention. This technique has a small number of steps, does not require the use of a photoresist material, and is therefore extremely productive.

[0003] As an example of a direct printed wiring technique, a method is known in which a coating film is formed by printing a dispersion on a substrate by screen printing, inkjet printing, or the like, and then the coating film is thermally sintered by scanning irradiation with laser light, or the like, to obtain low-resistance metal wiring. By irradiating laser light only to the portion requiring thermal sintering, the desired metal wiring can be easily formed even if the heat resistance of the substrate is relatively low. For example, a method has been proposed in which a coating film formed by applying a dispersion containing fine particles of a metal or metal oxide to a substrate is scanned with laser light.

[0004] Patent Document 1 describes a method for manufacturing metal wiring, which includes a step of repeatedly scanning a light beam over a surface containing metal particles to sinter the metal particles and form a metal wiring, and is characterized in that the speed at which the light beam is scanned is varied depending on the length of the scanning line that constitutes the metal wiring. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] JP 2019-140284 A Summary of the Invention [Problem to be solved by the invention]

[0006] In circuit boards, in addition to low resistance of metal wiring, it is required that the variation in resistance from one part to another (i.e., high reliability) is small. A laser beam is repeatedly scanned on the coating film. This is advantageous from the viewpoint of improving the sintering property of the metal particles contained in the coating film. However, this method has a problem in that the heat generated by the laser light when forming the wiring causes the pattern (especially the pattern end) to burn, resulting in defects such as ablation. Such defects are disadvantageous in terms of the appearance and reliability of the metal wiring.

[0007] The present invention aims to solve the above problems and provide a metal wiring manufacturing method, a metal wiring manufacturing apparatus, a laser light irradiation control device, and a laser light irradiation control program that are capable of manufacturing metal wiring with a good appearance and high reliability. [Means for solving the problem]

[0008] This disclosure encompasses the following items. [Item 1] A method for manufacturing a metal wiring, comprising: a wiring formation step of forming a metal wiring by irradiating a laser beam to a predetermined irradiation area of ​​a film containing a metal and / or a metal oxide, In the wiring forming step, a scanning region including the irradiation region is scanned by moving an irradiation target position of the laser light in a second direction different from the first direction while scanning the irradiation target position in a first direction; a time T from when the laser light is irradiated onto a point X on a first scanning line S1 until when the laser light is irradiated onto a point Y which is on a second scanning line S2 different from the first scanning line S1 and is located at a distance from the point X not more than twice the beam diameter of the laser light is 1 ms or more; The energy density of the laser light irradiated to the irradiation area is 1 W / mm 2 More than 5000W / mm 2 The method is as follows. [Item 2] The wiring forming step includes: A scan area pattern generating step of generating a scan area pattern including an illumination area pattern; assigning scanning parameters to the scan area pattern; and an irradiating step of irradiating the irradiation area with laser light by scanning the irradiation target position according to the scanning area pattern and the scanning parameters; Including, 2. The method according to claim 1, wherein the scanning parameters include a beam diameter of the laser light, an output intensity of the laser light, and a scanning speed of the irradiation target position. [Item 3] The scanning area pattern is composed of the irradiation area pattern and a non-irradiation area pattern, the non-irradiation area patterns are arranged to sandwich the irradiation area pattern in the first direction, The scanning parameters further include irradiation and non-irradiation of laser light; 3. The method according to item 2, wherein in the parameter assignment step, irradiation of laser light is assigned to the irradiation area pattern and non-irradiation of laser light is assigned to the non-irradiation area pattern. [Item 4] 4. The method according to claim 3, wherein in the first direction, a total length of the non-irradiated area pattern is 0.1% or more relative to 100% of a length of the irradiated area pattern. [Item 5] 5. The method according to any one of items 1 to 4, wherein the film has an absorptivity of 50% or more for a laser beam having a central wavelength of 355 nm. [Item 6] A metal wiring manufacturing apparatus for forming a metal wiring by irradiating a laser beam to a preset irradiation area of ​​a film containing a metal and / or a metal oxide, comprising: The metal wiring manufacturing apparatus comprises: A membrane holder that holds the membrane; A laser oscillator that generates laser light; A laser beam scanning device that scans the laser beam emitted from the laser oscillation device; and a processing device for controlling the laser oscillation device and the laser beam scanning device; Equipped with The processing device comprises: A scan field pattern including an illumination field pattern; and scanning parameters assigned to said scan area pattern; to the laser oscillation device and the laser light scanning device, thereby operating the laser oscillation device and the laser light scanning device so as to scan the irradiation target position of the laser light in a first direction while moving the irradiation target position in a second direction different from the first direction in accordance with the scanning control signal, thereby scanning the irradiation target position over a scanning region including the irradiation region; A time T from when the laser light is irradiated onto a point X on a first scanning line S1 until when the laser light is irradiated onto a point Y which is on a second scanning line S2 different from the first scanning line S1 and is located at a distance from the point X not more than twice the beam diameter of the laser light is 1 ms or more, and an energy density of the laser light irradiated onto the irradiation region is 1 W / mm 2 More than 5000W / mm 2 is as follows: The metal wiring manufacturing apparatus, wherein the scanning parameters include a beam diameter of a laser light, an output intensity of the laser light, and a scanning speed of an irradiation target position. [Item 7] The scanning area pattern is composed of the irradiation area pattern and a non-irradiation area pattern, the non-irradiation area patterns are arranged to sandwich the irradiation area pattern in the first direction, The scanning parameters further include irradiation and non-irradiation of laser light; 7. The metal wiring manufacturing apparatus according to item 6, wherein the irradiation area pattern is assigned to be irradiated with laser light and the non-irradiation area pattern is assigned to be non-irradiated with laser light. [Item 8] A laser light irradiation control device that controls a laser oscillation device and a laser light scanning device of a metal wiring manufacturing apparatus to irradiate a laser light to a preset irradiation area of ​​a film containing a metal and / or metal oxide, a coordinate data generating unit that generates coordinate data of a scanning area pattern including an irradiation area pattern; a scanning control signal generating unit that assigns preset scanning parameters to the coordinate data and generates a scanning control signal according to the coordinate data and the scanning parameters; an output unit that outputs the scanning control signal to a laser oscillator and a laser beam scanning device; The scanning parameters include a beam diameter of the laser light, an output intensity of the laser light, and a scanning speed of the irradiation target position; According to the scanning control signal, the irradiation target position of the laser light is moved in a second direction different from the first direction while scanning in a first direction, so that the irradiation target position is scanned over a scanning region including the irradiation region, a time T from when the laser light is irradiated to a point X on a first scanning line S1 to when the laser light is irradiated to a point Y which is on a second scanning line S2 different from the first scanning line S1 and is located at a distance from the point X not more than twice the beam diameter of the laser light is 1 ms or more, and an energy density of the laser light irradiated to the irradiation region is 1 W / mm 2 More than 5000W / mm 2 Below is the Laser light irradiation control device. [Item 9] The scanning area pattern is composed of the irradiation area pattern and a non-irradiation area pattern, the non-irradiation area patterns are arranged to sandwich the irradiation area pattern in the first direction, The scanning parameters further include irradiation and non-irradiation of laser light; 9. The laser light irradiation control device according to item 8, wherein the irradiation area pattern is assigned with irradiation of a laser light and the non-irradiation area pattern is assigned with non-irradiation of a laser light. [Item 10] A laser light irradiation control program for controlling a laser oscillator and a laser light scanner of a metal wiring manufacturing apparatus in order to irradiate a laser light to a preset irradiation area of ​​a film containing a metal and / or metal oxide, comprising: Generate coordinate data of the input scanning area pattern including the irradiation area pattern; Assigning preset scanning parameters to the coordinate data; generating a scan control signal according to the coordinate data and the scan parameters; outputting the scanning control signal; and making the laser light irradiation control device execute the above steps, The scanning parameters include a beam diameter of the laser light, an output intensity of the laser light, and a scanning speed of the irradiation target position; According to the scanning control signal, the irradiation target position of the laser light is moved in a second direction different from the first direction while scanning in a first direction, so that the irradiation target position is scanned over a scanning region including the irradiation region, a time T from when the laser light is irradiated to a point X on a first scanning line S1 to when the laser light is irradiated to a point Y which is on a second scanning line S2 different from the first scanning line S1 and is located at a distance from the point X not more than twice the beam diameter of the laser light is 1 ms or more, and an energy density of the laser light irradiated to the irradiation region is 1 W / mm 2 More than 5000W / mm 2 Below is the Laser light irradiation control program. [Item 11] The scanning area pattern is composed of the irradiation area pattern and a non-irradiation area pattern, the non-irradiation area patterns are arranged to sandwich the irradiation area pattern in the first direction, The scanning parameters further include irradiation and non-irradiation of laser light; Item 11. The laser light irradiation control program according to item 10, wherein the irradiation area pattern is assigned with laser light irradiation and the non-irradiation area pattern is assigned with laser light non-irradiation. [Item 12] Item 12. A computer-readable recording medium or recording device storing the program according to item 10 or 11. Effect of the Invention

[0009] According to one aspect of the present invention, it is possible to provide a metal wiring manufacturing method, a metal wiring manufacturing apparatus, a laser light irradiation control device, and a laser light irradiation control program that are capable of manufacturing metal wiring with a good appearance and high reliability. [Brief description of the drawings]

[0010] [Figure 1A] 4A to 4C are diagrams illustrating examples of scanning area patterns in the present embodiment. [Figure 1B] 4A to 4C are diagrams illustrating examples of scanning area patterns in the present embodiment. [Figure 1C] 4A to 4C are diagrams illustrating examples of scanning area patterns in the present embodiment. [Figure 1D] 4A to 4C are diagrams illustrating examples of scanning area patterns in the present embodiment. [Figure 1E] 4A to 4C are diagrams illustrating examples of scanning area patterns in the present embodiment. [Figure 1F] 4A to 4C are diagrams illustrating examples of scanning area patterns in the present embodiment. [Figure 1G] 4A to 4C are diagrams illustrating examples of scanning area patterns in the present embodiment. [Diagram 2] 1 is a schematic diagram showing a configuration example of a metal wiring manufacturing apparatus according to an embodiment of the present invention; [Diagram 3] 1 is a block diagram showing an example of the configuration of a metal wiring manufacturing apparatus according to an embodiment of the present invention; [Figure 4] 5 is a flowchart illustrating a process executed by a laser light irradiation control program according to the present embodiment. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011] Hereinafter, one embodiment of the present invention (hereinafter, abbreviated as "this embodiment") will be described in detail.

[0012] <Metal Wiring Manufacturing Method> One aspect of the present invention provides a method for manufacturing metal wiring, including a wiring forming step of forming metal wiring by irradiating a preset irradiation area of ​​a film containing a metal and / or metal oxide with a laser beam. In the wiring forming step according to one aspect, the irradiation target position of the laser beam is scanned in a first direction while being moved in a second direction different from the first direction, thereby scanning the irradiation target position over a scanning area including the irradiation area. In the wiring forming step according to one aspect, the time from when the laser beam is irradiated to a point X on a first scanning line S1 to when the laser beam is irradiated to a point Y on a second scanning line S2 different from the first scanning line S1 and the point Y is located at a distance from the point X not more than twice the beam diameter of the laser beam is 1 ms or more. In the wiring forming step according to one aspect, the energy density of the laser beam irradiated to the irradiation area is 1 W / mm 2 More than 5000W / mm 2 The following is the result.

[0013] <Wiring formation process> In this process, a metal wiring is formed by irradiating a laser beam to a preset irradiation area of ​​a film containing a metal and / or metal oxide. In one embodiment, the film is repeatedly irradiated with a laser beam to sinter the metal and / or metal oxide to produce a metal wiring. The obtained metal wiring may or may not be conductive. The type of laser light source that can be used includes YAG (yttrium aluminum garnet), YVO4 (yttrium vanadate), Yb (ytterbium), semiconductors (GaAs, GaAlAs, GaInAs), carbon dioxide gas, fiber laser, etc. The laser beam may be not only a fundamental wave but also a harmonic wave extracted as necessary.

[0014] In one embodiment, the irradiation target position is scanned over a scanning area including the irradiation area by scanning the irradiation target position of the laser light in a first direction while moving it in a second direction different from the first direction, for example, a direction perpendicular to the first direction. The scanning in the first direction may be a one-way scan or a reciprocating scan. In a reciprocating scan, two scanning lines are generated in one round trip. By moving the irradiation target position in the second direction for each scanning line, adjacent scanning lines may not overlap or may overlap by a part of the beam diameter (i.e., scanning line width). In this way, the irradiation target position may be scanned so as to fill the entire scanning area without gaps.

[0015] The time T from irradiation of the point X on the first scanning line S1 to irradiation of the point Y on the second scanning line S2 different from the first scanning line S1, which is located at a distance from the point X not more than twice the beam diameter, is 1 ms or more in one embodiment, preferably 5 ms or more, and more preferably 10 ms or more, from the viewpoint of suppressing scorching and ablation of the wiring. Also, from the viewpoint of industrial productivity, the time T is preferably 1000 ms or less, more preferably 500 ms or less, and more preferably 100 ms or less. In one embodiment, the time T is in the above range throughout the entire laser light irradiation, that is, when the point X is at all positions within the irradiation area. By controlling the time T to a predetermined value or more, the amount of heat given to the film by the laser light can be suppressed to a predetermined value or less. In this way, scorching and ablation of the wiring are suppressed, and thus wiring with good appearance and uniformity (hence reliability) can be formed. The means for adjusting the time T include the beam diameter of the laser light, the scanning length of the irradiation target position, the scanning speed of the irradiation target position, and switching between irradiation and non-irradiation of the laser light during scanning of the irradiation target position. In one embodiment, the scanning length of the irradiation target position can be controlled by designing the shape and size of the scanning region pattern of the present disclosure. The beam diameter of the laser light, the scanning speed of the irradiation target position, and irradiation and non-irradiation of the laser light can be controlled as the scanning parameters of the present disclosure.

[0016] In one embodiment, the energy density of the laser light irradiated to the irradiation area is 1 W / mm 2 More than 5000W / mm 2 The energy density is equal to or less than 100 W / mm 2 . By adjusting the energy density to an appropriate range, the amount of energy absorbed by the film can be controlled. The energy density of the laser light is determined by the output intensity of the laser light and the beam diameter of the laser light when it is irradiated to the film. In the present disclosure, the output intensity means the average output intensity of the pulse wave in the case of a pulse wave. The beam diameter of the laser light may differ between when it is emitted and when it is irradiated to the film due to a focusing lens, a spot adjustment mechanism, etc. Therefore, the energy density is equal to the output density of the laser light (i.e., the output intensity per beam cross-sectional area of ​​the emitted light) in one embodiment, but is a value obtained by multiplying the output density of the laser light by the ratio of [beam cross-sectional area at the time of emission] / [beam cross-sectional area at the time of irradiation to the film] in another embodiment. The preferred range of the energy density differs for each substrate. Resin substrates generally have low thermal conductivity and heat resistance, and from the viewpoint of easily forming metal wiring excellent in appearance and reliability by suppressing scorching and ablation of the film, in one embodiment, the energy density is 3000 W / mm 2 . 2 or less than 2000W / mm 2 or less than 1000W / mm 2 On the other hand, from the viewpoint of smoothly progressing the formation of a conductor inside the film by sintering, contact between particles, etc., it is preferable that the conductor density is 1 W / mm 2 or more than 5W / mm 2 or more than 10W / mm 2 Inorganic substrates generally have high thermal conductivity and heat resistance, and from the viewpoint of smoothly advancing the formation of conductors inside the film through sintering and contact between particles, etc., it is desirable to have a thermal conductivity of 100 W / mm 2 or more than 500W / mm 2 or more than 1000W / mm 2 On the other hand, from the viewpoint of easily forming metal wiring excellent in appearance and reliability by suppressing the burning and ablation of the film, in one embodiment, the electric field strength is preferably 5000 W / mm 2 or less than 4000W / mm 2 or less than 3000W / mm 2 The following is the result.

[0017] In one embodiment, the wiring formation step includes: A scan area pattern generating step of generating a scan area pattern including an illumination area pattern; A parameter assignment step of assigning scanning parameters to the scan area pattern; and an irradiating step of irradiating an irradiation area with laser light by scanning an irradiation target position according to a scanning area pattern and scanning parameters; In one aspect, the scanning parameters include a beam diameter of the laser light, a power intensity of the laser light, and a scanning speed of the irradiation target position.

[0018] In one embodiment, the scanning area pattern is composed of an irradiation area pattern and a non-irradiation area pattern. The non-irradiation area is an area where the irradiation target position is scanned but not irradiated with laser light. In this case, the scanning parameters further include irradiation and non-irradiation of laser light, and in the parameter allocation step, the irradiation of the laser light is assigned to the irradiation area pattern and the non-irradiation of the laser light is assigned to the non-irradiation area pattern. The non-irradiation area pattern may be arranged so as to sandwich the irradiation area pattern in the first direction. By providing the non-irradiation area pattern, the time T can be extended, and in particular, the time until the irradiation target position on the second scanning line S2 approaches the end of the irradiation area pattern on the first scanning line S1 again after the irradiation target position passes the end can be extended. It is advantageous in terms of simplicity that a predetermined time T or more can be realized by a simple operation of switching between laser light irradiation / non-irradiation. An exemplary embodiment of each step will now be described.

[0019] [Scanning area pattern generation step] In this step, generate a scanning area pattern including an irradiation area pattern. The shapes of each of the irradiation area pattern and the scanning area pattern are not particularly limited, and may be various shapes such as irregular shapes (L-shape, H-shape, etc.), polygons (triangles, squares, etc.), circles, ellipses, etc. In one aspect, the scanning area pattern is composed of an irradiation area pattern and a non-irradiation area pattern.

[0020] 1A to 1G are diagrams for explaining examples of scanning area patterns in this embodiment. Scanning of the irradiation target position may start from starting points P, P1, and P2, and may be reciprocating scanning as shown in FIGS. 1A, 1C to 1G, or unidirectional scanning as shown in FIG. 1B. Referring to FIGS. 1A to 1G, the scanning length L1, L1a, and L1b (unit: mm) (hereinafter, scanning length L1) of the irradiation target position, which is the length of the scanning area patterns R, Ra, and Rb, is the sum of the scanning length L2, L2a, and L2b (unit: mm) (hereinafter, scanning length L2) of the laser light irradiation part, which is the length of the irradiation area patterns R1, R1a, and R1b, and the scanning length L3, L3a, and L3b (unit: mm) (hereinafter, scanning length L3) and L4, L4a, and L4b (unit: mm) (hereinafter, scanning length L4) of the laser light non-irradiation part, which is the length of the non-irradiation area patterns R2, R2a, and R2b. In one embodiment, the scan length L1 is always longer than the scan length L2 throughout the entire scanning area pattern. This makes it easy to set conditions such that the time T is equal to or longer than a predetermined value in any part of the irradiation area pattern. In one embodiment, the relationship between the scan lengths L1 to L4 is expressed by the following formula. L1=L2+L3+L4, L3>0 and L4>0 In one embodiment, the scanning length L2 and the scanning lengths L3 and L4 can be easily set by switching between irradiation and non-irradiation of the laser light.

[0021] In one embodiment, in one-way scanning, it is easier to set a time interval for irradiating a point on the film with laser light than in reciprocating scanning. That is, in one embodiment of one-way scanning, a non-irradiated area pattern may not be provided. When a non-irradiated area pattern is not provided, the irradiation area pattern and the scanning area pattern are the same. That is, the relationship between the scanning lengths L1 to L4 is expressed by the following formula. L1=L2+L3+L4, L3=0, and L4=0

[0022] In the reciprocating scan, at the end of the scanning area pattern R, Ra, Rb in the first direction, the irradiation target position is turned back to transition from the first scanning line to the second scanning line, so that when the end is irradiated with laser light, the amount of laser light irradiation tends to be larger at the end than at other parts. When the non-irradiated area pattern R2, R2a, R2b exists, the irradiation target position can be turned back within the non-irradiated area pattern, so that excessively long irradiation time and / or excessively short irradiation interval (hence excessive laser light irradiation amount) can be avoided, especially at the end of the irradiation area pattern R1, R1a, R1b. This makes it possible to form a metal wiring in which film scorching and / or ablation due to the latent heat of the laser light is suppressed.

[0023] Across the entire scanning area pattern, when the scanning length L2 is 100%, each of the scanning lengths L3 and L4 is preferably 0.05% or more, or 0.25% or more, or 0.5% or more from the viewpoint of suppressing film scorching and / or ablation due to the latent heat of the laser light, and is preferably 15% or less, or 10% or less, or 5% or less from the viewpoint of industrial productivity.

[0024] Across the entire scanning area pattern, the sum of scanning lengths L3 and L4 when scanning length L2 is 100% is preferably 0.1% or more, or 0.5% or more, or 1% or more from the viewpoint of suppressing film scorching and / or ablation due to the latent heat of the laser light, and is preferably 30% or less, or 20% or less, or 10% or less from the viewpoint of industrial productivity.

[0025] The first direction D1 and the second direction D2 may be set to any direction with respect to the scanning region pattern. For example, with respect to the scanning region pattern R having the shape shown in Figures 1C to 1E, the first and second directions may be set to the directions shown in each of Figures 1C to 1E, or any other direction. In one embodiment, it may be advantageous in terms of process efficiency to set the first and second directions so as to minimize the number of scanning lines required to cover the entire scanning region pattern (i.e., to fill the entire scanning region pattern).

[0026] In each of the scanning region pattern, the irradiation region pattern, and the non-irradiation region pattern, the scanning length may be the same over the entire pattern, or may be different depending on the part. For example, the scanning length of the irradiation target position set for one scanning region pattern R may be the same over the entire pattern as the scanning length L1 shown in Figures 1A to 1C and E, or may be different depending on the part as the scanning lengths L1a and L1b shown in Figure 1D.

[0027] The relationship between the number of scanning area patterns and the number of irradiation area patterns and / or non-irradiation area patterns is not particularly limited and may be set arbitrarily as desired. For example, as shown in Fig. 1F, one scanning area pattern R may include multiple irradiation area patterns R1a, R1b, and as shown in Fig. 1G, multiple scanning area patterns Ra, Rb may include irradiation area patterns R1a, R1b and non-irradiation area patterns R2a, R2b, respectively.

[0028] In one embodiment, the scanning area of ​​the laser light on the film surface may be an area in which the shape of a two-dimensional scanning area pattern (in one embodiment, a combination of an irradiated area pattern and a non-irradiated area pattern) is projected onto a three-dimensional shape pattern of the film surface previously acquired. The three-dimensional shape pattern of the film surface can be acquired by a conventionally known means, for example, the shape of the film surface may be read and acquired by an image recognition device such as an image sensor. The two-dimensional scanning area pattern may be projected onto the acquired three-dimensional shape pattern. The alignment of the two-dimensional scanning area pattern and the three-dimensional shape pattern of the film surface may be performed by software known to those skilled in the art, or manually. In one embodiment, an XYZ coordinate system and its reference point (origin) are specified, and a three-dimensional shape pattern of the film surface is positioned within the XYZ coordinate system so that the height in the Z-axis direction is minimum, and a two-dimensional scanning area pattern is positioned on the XY plane above the three-dimensional shape pattern in the Z-axis direction (i.e., in the + direction).If desired, the two-dimensional scanning area pattern and the three-dimensional shape pattern of the film surface are aligned using a top view image, etc., and then the shape of the two-dimensional scanning area pattern is projected in the Z direction onto the three-dimensional shape pattern to generate a three-dimensional scanning area pattern.

[0029] In one aspect, the scanning area pattern may be a two-dimensional projection pattern of a three-dimensional pattern generated on a three-dimensional shape pattern of a film surface previously acquired. In one aspect, the scanning area pattern may be generated by generating a three-dimensional pattern for determining a scanning area on a three-dimensional shape pattern of a film surface previously acquired, and then projecting the three-dimensional pattern for determining a scanning area in two dimensions. When using the three-dimensional pattern for determining a scanning area generated in this manner, it is possible to set the scanning area more precisely taking into account the three-dimensional shape of the film surface, which is particularly advantageous in improving the appearance and reliability of the metal wiring. In one aspect, the scanning area may be formed by further back projecting the two-dimensional scanning area pattern onto the three-dimensional shape pattern.

[0030] In one aspect, the scan area pattern is: A two-dimensional base pattern previously generated on an XY plane is projected onto a previously acquired XYZ three-dimensional shape pattern of the film surface to generate a three-dimensional pattern for determining a scanning region; Measuring a dimension B1 of a span B in the Y-axis direction on the two-dimensional base pattern; Measuring a dimension B2 of a projection of the span B on a three-dimensional pattern for determining a scanning area; multiplying a dimension B1 of the two-dimensional base pattern by B1 / B2 to generate a reduced correction pattern; The reduced correction pattern may be generated by the above method. In one embodiment, the dimension B1 in the Y-axis direction is measured over the entire X-axis region of a two-dimensional base pattern having an X-axis dimension A1 and a Y-axis dimension B1, and the dimension B2 of a portion corresponding to each dimension B1 is measured, and for each pair of dimensions B1 and B2, B1 / B2 is calculated and the dimension B1 is reduced and corrected. When the scanning region pattern generated in this manner is used, it is possible to set the scanning region more precisely taking into account the three-dimensional shape of the film surface, which is particularly advantageous in improving the appearance and reliability of the metal wiring. In one embodiment, the scanning region may be formed by further back projecting the two-dimensional scanning region pattern onto the three-dimensional shape pattern.

[0031] [Parameter assignment step] In this step, preset scanning parameters are assigned to the above-mentioned scanning area pattern. This allows a scanning control signal to be generated that includes position information of the irradiation area pattern and the scanning area pattern including the irradiation area pattern, and the associated scanning parameters. Since the scanning length related to the laser light irradiation and the scanning length of the irradiation target position are determined by defining the irradiation area pattern and the scanning area pattern, the time T and the energy density of this embodiment can be controlled within a desired range by assigning the scanning parameters to the scanning area pattern. The laser oscillation device and the laser light scanning device of the metal wiring manufacturing device, as well as mechanisms such as an output adjustment mechanism and a spot adjustment mechanism, can receive the scanning control signal and perform laser light irradiation under desired conditions. When there are two or more patterns in the irradiation area pattern or the scanning area pattern, the scanning parameters may be the same or different between the patterns, and are preferably the same between the patterns.

[0032] In one aspect, the scanning parameters include a beam diameter of the laser light, an output intensity of the laser light, and a scanning speed of the irradiation target position. In one aspect, the scanning parameters include laser light irradiation to the irradiation area pattern and non-irradiation of the non-irradiation area pattern. In one aspect, the irradiation target position is scanned over the entire scanning area pattern, but laser light is irradiated only to the irradiation area pattern. In one aspect, the scanning parameters assigned to the non-irradiation area pattern differ from the scanning parameters assigned to the irradiation area pattern only in that the laser light is not irradiated. In this case, the irradiation target position can be scanned over both the irradiation area pattern and the non-irradiation area pattern simply by switching between irradiation and non-irradiation of the laser light, which is advantageous in terms of ease of process control. Examples of scanning parameters are given below, but the scanning parameters are not limited to these.

[0033] (Laser beam diameter) The beam diameter of the laser light irradiated to the film may be set to a desired value. The beam diameter can be adjusted by the spot diameter and the amount of deviation from the focus of the laser light. The amount of deviation from the focus can be adjusted, for example, by changing the defocus value. In one embodiment, the beam diameter is 1 μm or more, or 5 μm or more, and in one embodiment, is 200 μm or less, or 100 μm or less.

[0034] (laser light output intensity) The output intensity of the laser light may be set to a desired value in combination with the beam diameter of the laser light so that the energy density of the laser light irradiated to the irradiation area is in a desired range. In one embodiment, the output intensity is 1 mW or more, or 10 mW or more, and in another embodiment, 10 W or less, or 5 W or less.

[0035] (Scanning speed of irradiation target position) The scanning speed of the irradiation target position may be set to a desired value in combination with the scanning length so that the time T is in a desired range. In one embodiment, the scanning speed is 1 mm / sec or more, or 5 mm / sec or more, and in one embodiment, 3000 mm / sec or less, or 1000 mm / sec or less. In one embodiment, the scanning speed is a value obtained by multiplying the scanning period by the scanning length.

[0036] (Center wavelength of laser light, pulse frequency) In one embodiment, the central wavelength of the laser light is 350 nm or more and 600 nm or less, preferably 355 nm or 532 nm. The laser light may be a CW wave (continuous wave), but may be a pulse wave from the viewpoint of preventing diffusion of heat and proceeding with baking instantaneously by irradiating a light beam with a high peak value. The width of one pulse of the pulse wave is preferably 1 to 100 nanoseconds, 2 to 50 nanoseconds, or 3 to 30 nanoseconds from the viewpoint of suppressing ablation of the film during light irradiation.

[0037] (overlap rate, scanning line spacing) When the laser beam is repeatedly scanned on the film while overlapping in the scanning line width direction, the overlap rate (i.e., the ratio in the scanning line width direction of the portion irradiated the second time among the portion irradiated the first time) is preferably 10% to 99%, or 20% to 95%, or 30% to 90%, or 40% to 85%. When the overlap rate is 10% or more, the formation of a conductor by sintering of metal and / or metal oxide, contact between particles, etc., proceeds well, and when it is 99% or less, wiring can be manufactured at an industrially practical production speed. The traveling direction of the irradiation target position of the second irradiation is the same direction as the first irradiation in the case of unidirectional scanning, and is the opposite direction to the first irradiation in the case of reciprocating scanning. The scanning line interval of the laser beam may be set based on the desired beam diameter and overlap rate.

[0038] (Defocus value) The defocus value may be appropriately specified to adjust the beam diameter within a desired range. In one embodiment, the defocus value may be set in the range of −10.0 mm to 10.0 mm when the focusing position is set to 0 in the height in the irradiation direction of the laser light.

[0039] (Laser light irradiation control (irradiation / non-irradiation)) The means for switching between irradiation and non-irradiation of the laser light is not particularly limited, and examples thereof include on-off control of a light source, an optical shutter, or a solenoid valve using an AW element.

[0040] (Angle of incidence of laser light to the film) The incident angle of the laser light to the film is preferably 0 to 50 degrees, or 0 to 48 degrees, or 0 to 45 degrees. When the incident angle is 50 degrees or less, sintering of the film caused by the laser light being reflected on the surface of the film or the amount of light rays penetrating into the film being small, and insufficient formation of a conductor caused by contact between particles, etc. can be prevented, and the resistance value of the metal wiring can be made low and uniform.

[0041] (Scanning direction of irradiation target position) The scanning direction of the irradiation target position may be specified according to the purpose, for example, the direction in which the minimum value of the scanning length in the irradiation region is maximized, the direction in which the number of scans is minimized, etc.

[0042] (Irradiation atmosphere) The laser beam irradiation to the target may be performed in the air or in an inert gas atmosphere such as Ar or N2. The inert gas atmosphere is preferable because it allows easy formation of low resistance wiring.

[0043] In one aspect, a combination of numerical values ​​of a plurality of parameter elements (e.g., beam diameter of laser light, output intensity of laser light, and scanning speed of the irradiation target position) may be one template. A plurality of such templates may be prepared, and one template selected from the plurality of templates may be assigned to a scanning area pattern. In a typical aspect, the same scanning parameters are applied within each irradiation area pattern, but different scanning parameters according to the site may be assigned within one irradiation area pattern.

[0044] The scanning parameters may be set in advance based on the results of a study of the relationship between the film properties and the laser light irradiation conditions suitable for the properties. In this embodiment, the film is irradiated with laser light to form a metal wiring, which is a fired product of the film. The film in this embodiment is a thin film containing metal and / or metal oxide, and in one aspect further contains an organic substance such as a dispersant. In such a film, the fired state differs depending on the laser light irradiation requirements. For example, when the scanning speed is slowed without changing the output intensity of the laser light, the film tends to be heated more significantly, but the degree of heating of the film differs depending on the film properties (chemical composition, thickness, laser light penetration length, form (presence of holes, etc.)). Therefore, it is desirable to select the scanning parameters appropriately according to the film properties. In one aspect, a plurality of data sets including film property data and scanning parameter data (for example, the above-mentioned template) associated with the film property data are generated and stored, and when assigning scanning parameters, the data set is read, and scanning parameters associated with film property data that is the same as or similar to the properties of the film actually used are selected and assigned to the scanning area pattern. Alternatively, the scanning parameters may be generated based on direct input of numerical values ​​from a user.

[0045] The scanning control signal may include information regarding the designation of the irradiation area pattern to be first irradiated with the laser light when there are multiple irradiation area patterns, the designation of the scanning start position of the irradiation target position in the scanning area pattern, and the like.

[0046] [Irradiation step] In this step, the irradiation target position is scanned according to the scanning area pattern and the scanning parameters assigned thereto, so that the irradiation area is irradiated with the laser light. According to the method of the present embodiment, the scorching and ablation of the film can be suppressed regardless of the shape of the irradiation area, so that the metal wiring having a good appearance and high reliability can be formed in any desired shape.

[0047] The irradiation area may be set as a two-dimensional or three-dimensional area. A three-dimensional irradiation area may be specified on a three-dimensional shape pattern on the film surface.

[0048] <Substrate and film containing metal and / or metal oxide> In one embodiment, the film containing metal and / or metal oxide to be subjected to the wiring formation step may be formed by coating, lamination, deposition, or the like. For example, a coating film containing metal and / or metal oxide may be formed on the surface constituting the substrate. In one embodiment, the film may be a coating film formed by applying a paste material containing metal and / or metal oxide. Before application, the surface of the substrate may be washed in advance. The paste material contains metal and / or metal oxide, and may optionally contain an organic substance, and may further contain a solvent. In one embodiment, the solvent is capable of dissolving or dispersing, preferably dissolving, the organic substance, and dispersing metal and / or metal oxide (for example, particles thereof). The method of applying the paste material is not particularly limited, and application methods such as die coating, spin coating, slit coating, bar coating, knife coating, spray coating, and dip coating can be used. After the above application, the solvent remaining in the coating film may be removed as necessary. In this manner, a structure containing a substrate and a film containing metal and / or metal oxide arranged on the substrate is obtained. Examples of a substrate and a film containing a metal and / or a metal oxide suitable for producing the metal wiring of this embodiment include the following.

[0049] [Base material] The shape of the substrate is not particularly limited as long as it constitutes a surface on which a film containing a metal and / or metal oxide is disposed. The substrate is preferably made of an insulating material to ensure electrical insulation from the metal wiring described below. However, it is not essential that the entire substrate is made of an insulating material. It is sufficient that only the portion constituting the surface on which the film containing a metal and / or metal oxide is disposed is made of an insulating material.

[0050] The surface of the substrate on which the film containing a metal and / or metal oxide is disposed may be a flat or curved surface, or may be a surface including steps. More specifically, the substrate may be a substrate (e.g., a plate, a film, or a sheet) or a three-dimensional object (e.g., a housing, etc.). The plate is, for example, a support used in a circuit board such as a printed circuit board. The film or sheet is, for example, a base film that is a thin-film insulator used in a flexible printed circuit board.

[0051] Examples of the three-dimensional object include the housings of electrical devices such as mobile phone terminals, smartphones, smart glasses, televisions, personal computers, etc. Other examples of the three-dimensional object include dashboards, instrument panels, steering wheels, chassis, etc. in the automotive field.

[0052] Specific examples of the substrate include a substrate made of an inorganic material (hereinafter referred to as an "inorganic substrate") and a substrate made of a resin (hereinafter referred to as a "resin substrate").

[0053] The inorganic substrate is, for example, composed of glass, silicon, mica, sapphire, quartz, clay film, ceramic material, etc. As the resin substrate, polyimide (PI), polyethylene terephthalate (PET), and polyethylene naphthalate (PEN) are preferable because they have excellent adhesion to metal wiring, are easily distributed in the market, and are available at low cost, and therefore are advantageous from a business perspective, and at least one selected from the group consisting of polypropylene (PP), polyamide (PA), acrylonitrile-butadiene-styrene (ABS), polyethylene (PE), polycarbonate (PC), polyacetal (POM), polybutylene terephthalate (PBT), modified polyphenylene ether (m-PPE), and polyphenylene sulfide (PPS) is preferable, particularly in the case of a housing, because it has excellent adhesion to metal wiring, is excellent in moldability and mechanical strength after molding, and has heat resistance sufficient to withstand laser irradiation when forming metal wiring.

[0054] The thickness of the substrate, when it is, for example, a plate, film or sheet, can be from 1 μm to 10 mm, and preferably from 25 μm to 250 μm. When the thickness of the substrate is 250 μm or less, the electronic device to be produced can be made lighter, more space-saving and more flexible, which is preferable.

[0055] When the substrate is a three-dimensional object, its maximum dimension (i.e., the maximum length of one side) can be, for example, 1 μm or more and 10 mm or less, and preferably 200 μm or more and 5 mm or less. A substrate having a thickness in the above range has good mechanical strength and / or heat resistance after molding.

[0056] [Metals and / or metal oxides] The metal contained in the film containing a metal and / or metal oxide is, for example, silver, copper, silicon, aluminum, zirconium, titanium, hafnium, tantalum, tin, chromium, cobalt, magnesium, manganese, molybdenum, nickel, tungsten, zinc, indium, tin, etc., and may be an alloy or mixture containing two or more of these, with copper being particularly preferred. Examples of the metal oxide include the oxides of the metals exemplified above, with copper oxide (CuO and Cu2O) being particularly preferred.

[0057] The metal and / or metal oxide may be a particle, and the particle may have a core / shell structure. For example, the core and / or shell may be a metal and / or metal oxide, and the core and shell may contain different metals and / or metal oxides. The metal and / or metal oxide may form a complex.

[0058] (Paste material containing metal and / or metal oxide) A paste material (dispersion) containing a metal and / or a metal oxide, which can be used to form a film, may contain metal particles and / or metal oxide particles. The metal particles are typically made of metal, but may contain other components as long as the effect of the present invention is not impaired. Similarly, the metal oxide particles are typically made of metal oxide, but may contain other components as long as the effect of the present invention is not impaired. Examples of metals and metal oxides are as described above. The dispersion may further contain a dispersion medium, a dispersant, and / or a reducing agent.

[0059] Copper oxide, which is a suitable example of a metal oxide, includes cuprous oxide (CuO) and cupric oxide (CuO), with cuprous oxide being preferred. Cuprous oxide is advantageous in that it is inexpensive compared to precious metals such as silver, and migration is unlikely to occur, since it is copper. Cuprous oxide is also advantageous in that it has high absorbance to laser light, can be sintered at a low temperature, and can form a sintered product with low resistance. As the copper oxide, a commercially available product or a synthetic product may be used.

[0060] In one embodiment, the average particle diameter of the metal particles and / or metal oxide particles (when both metal particles and metal oxide particles are present, the average particle diameter of the whole of them) is preferably 1 nm or more, or 3 nm or more, or 5 nm or more, and preferably 100 nm or less, or 50 nm or less, or 40 nm or less. Here, the average particle diameter is the particle diameter when dispersed in the dispersion, and is a value measured by the cumulant method (for example, using FPAR-1000 manufactured by Otsuka Electronics). That is, the average particle diameter is not limited to the primary particle diameter, and may be the secondary particle diameter. When the average particle diameter is 100 nm or less, it is preferable in that a pattern can be formed at a low temperature, the versatility of the substrate is expanded, and there is a tendency that a fine pattern is easily formed on the substrate. In addition, when the average particle diameter is 1 nm or more, it is preferable in that the dispersion stability of the metal particles and metal oxide particles in the dispersion is good, the long-term storage stability of the dispersion is good, and a uniform thin film can be produced. In one embodiment, the particles in the dispersion are substantially only metal particles and / or metal oxide particles. In this case, the average particle size measured for the dispersion can be regarded as the average particle size of the metal particles and metal oxide particles.

[0061] In one embodiment, the metal particles and / or metal oxide particles contain hydrazine. The hydrazine may form a hydrate (i.e., the concept of hydrazine in the present disclosure also includes hydrazine hydrate). The hydrazine may be, for example, a residue of hydrazine used as a reducing agent for metal oxide (copper oxide in one embodiment) during the production of metal oxide (copper oxide in one embodiment) particles or metal (copper) particles, or may be added separately during the production of the particles.

[0062] The metal content in the metal particles and the metal oxide content in the metal oxide particles are preferably 10 mass% or more, or 30 mass% or more, or 50 mass% or more, or 70 mass% or more, and preferably 100 mass% or less, or 99 mass% or less, or 98 mass% or less.

[0063] The hydrazine content of the metal particles and metal oxide particles is preferably 0.000000001% by mass or more, or 0.0000001% by mass or more, or 0.0000005% by mass or more, and is preferably 10% by mass or less, or 5% by mass or less, or 1% by mass or less.

[0064] The mass ratio of hydrazine to the metal in the metal particles or to the metal oxide in the metal oxide particles is preferably 0.00001 or more, or 0.0001 or more, or 0.0002 or more, and preferably 1 or less, or 0.1 or less, or 0.01 or less.

[0065] The mass ratio of the metal, the mass ratio of the metal oxide, or the total mass ratio of the metal and metal oxide in 100 mass% of the dispersion is preferably 5 mass% or more, or 10 mass% or more, or 15 mass% or more, and preferably 60 mass% or less, or 55 mass% or less, or 50 mass% or less.

[0066] (dispersion medium) The dispersion medium is capable of dispersing metal particles and / or metal oxide particles. In one embodiment, the dispersion medium is capable of dissolving a dispersant. From the viewpoint of forming metal wiring using a dispersion, the volatility of the dispersion medium affects the workability. Therefore, it is preferable that the dispersion medium is suitable for the method of forming metal wiring, for example, a coating method (particularly printing). In other words, it is preferable to select the dispersion medium according to the dispersibility and the workability of printing.

[0067] As the dispersion medium, alcohols (monohydric alcohols and polyhydric alcohols (eg, glycols)), ethers of alcohols (eg, glycols), esters of alcohols (eg, glycols), and the like can be used. Specific examples of the dispersion medium include propylene glycol monomethyl ether acetate, 3-methoxy-3-methyl-butyl acetate, ethoxyethyl propionate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol tertiary butyl ether, dipropylene glycol monomethyl ether, ethylene glycol butyl ether, ethylene glycol ethyl ether, ethylene glycol methyl ether, ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, 2-pentanediol, 2-methylpentane-2,4-diol, 2,5-hexanediol, 2,4-heptanediol, 2-ethylhexane-1,3-diol, diethylene glycol, hexanediol, octanediol, triethylene glycol, tri-1,2-propylene glycol, glycerol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene ...ethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl Examples of the alcohol include ethylhexyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, ethylene glycol monobutyl acetate, diethylene glycol monoethyl ether acetate, methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, 2-butanol, t-butanol, n-pentanol, i-pentanol, 2-methylbutanol, 2-pentanol, t-pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, 2-hexanol, 2-ethylbutanol, 1-heptanol, 2-heptanol, 3-heptanol, n-octanol, 2-ethylhexanol, 2-octanol, n-nonyl alcohol, 2,6-dimethyl-4-heptanol, n-decanol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, and diacetone alcohol.These may be used alone or in combination, and are selected in consideration of the volatility, the equipment used for coating, the solvent resistance of the substrate (i.e., the substrate to be coated), etc., depending on the coating method. It is particularly preferable that the dispersion contains one or more dispersion media selected from the group consisting of 1-hexanol, 1-heptanol, and 1-octanol, in that drying is slow and aggregation of the dispersion is unlikely to occur when continuous printing is used, and that intermittent stability is good and abnormal flight is few when inkjet printing is used.

[0068] The boiling point of the dispersion medium is preferably high from the viewpoint of improving printing continuity, and is, for example, preferably 50° C. or higher, more preferably 100° C. or higher, and even more preferably 150° C. or higher. On the other hand, from the viewpoint of obtaining a good function as a dispersion medium, the boiling point is preferably 400° C. or lower, more preferably 300° C. or lower, and even more preferably 250° C. or lower.

[0069] The content of the dispersion medium in the entire dispersion is preferably 30% by mass or more, or 40% by mass or more, or 50% by mass or more, and preferably 95% by mass or less, or 90% by mass or less.

[0070] (Dispersant) As the dispersant, a compound capable of dispersing metal particles and / or metal oxide particles in a dispersion medium can be used. The number average molecular weight of the dispersant is preferably 300 or more, or 350 or more, or 400 or more, and preferably 300,000 or less, or 200,000 or less, or 150,000 or less. The number average molecular weight of the present disclosure is a value obtained by using gel permeation chromatography in standard polystyrene conversion. When the number average molecular weight is 300 or more, there is a tendency that the insulating property is excellent and the contribution to the dispersion stability of the dispersion is large, and when it is 300,000 or less, it is preferable in terms of handleability. The dispersant preferably has a group having affinity for metal particles and / or metal oxide particles, particularly copper oxide particles. Examples of such groups include a phosphate group, a hydroxyl group, an amino group, and a carboxy group. From this viewpoint, the dispersant preferably contains or is a phosphorus-containing organic compound, contains or is a phosphate ester, or contains or is a polymeric phosphate ester. As the polymeric phosphate ester, for example, a compound represented by the following formula (1):

[0071] [ka]

[0072] (In the formula, l is an integer of 1 to 10,000, m is an integer of 1 to 10,000, and n is an integer of 1 to 10,000.) The structure represented by the formula (I) is preferred because it has excellent adsorptivity to metal oxides, particularly copper oxide, and particularly cuprous oxide, and excellent adhesion to substrates. In the chemical formula (1), 1 is more preferably 1 to 5,000, and further preferably 1 to 3,000. In the chemical formula (1), m is more preferably 1 to 5,000, and further preferably 1 to 3,000. In the chemical formula (1), n ​​is more preferably 1 to 5,000, and further preferably 1 to 3,000.

[0073] In one embodiment, the decomposition temperature of the phosphorus-containing organic compound is preferably 600°C or less, more preferably 400°C or less, and even more preferably 200°C or less. The decomposition temperature may be 50°C or more, or 80°C or more, or 100°C or more, from the viewpoint of facilitating the selection of a dispersant having an excellent effect of improving the dispersion stability of the dispersion. In one embodiment, the boiling point of the phosphorus-containing organic compound is preferably 300°C or less, more preferably 200°C or less, and even more preferably 150°C or less. The boiling point may be 30°C or more, or 50°C or more, or 80°C or more. In the present disclosure, the decomposition temperature is a value measured by thermogravimetry differential thermal analysis.

[0074] In one embodiment, the phosphorus-containing organic compound is preferable in that peeling of the coating film and the plating layer is unlikely to occur during plating.

[0075] As the dispersant, a known one may be used. For example, a polymer having a basic group, such as a salt of a long-chain polyaminoamide and a polar acid ester, an unsaturated polycarboxylic acid polyaminoamide, a polycarboxylate of a polyaminoamide, or a salt of a long-chain polyaminoamide and an acid polymer, may be used. In addition, an alkyl ammonium salt, an amine salt, or an amidoamine salt of a polymer such as an acrylic (co)polymer, a modified polyester acid, a polyether ester acid, a polyether carboxylic acid, or a polycarboxylic acid may be used.

[0076] The dispersant of the present disclosure may be a commercially available one. Commercially available dispersants include, for example, DISPERBYK (registered trademark)-101, DISPERBYK-102, DISPERBYK-110, DISPERBYK-111, DISPERBYK-112, DISPERBYK-118, DISPERBYK-130, DISPERBYK-140, DISPERBYK-142, DISPERBYK-145, DISPERBYK-160, DISPERBYK-161, DISPERBYK-162, DISPERBYK-163, DISPERBYK-2155, DISPERBYK-2163, DISPERBYK-2164, DISPERBYK-180, DISPERBYK-2000, DISPERBYK-2025, DISPERBYK-2 163, DISPERBYK-2164, BYK-9076, BYK-9077, TERRA-204, and TERRA-U (all manufactured by BYK-Chemie), FLOWRENE DOPA-15B, FLOWRENE DOPA-15BHFS, FLOWRENE DOPA-22, FLOWRENE DOPA-33, FLOWRENE DOPA-44, FLOWRENE DOPA-17HF, FLOWRENE TG-662C, and FLOWRENE KTG-2400 (all manufactured by Kyoeisha Chemical Co., Ltd.), ED-117, ED-118, ED-212, ED-213, ED-214, ED-216, ED-350, and ED-360 (all manufactured by Kusumoto Chemical Co., Ltd.), Plysurf M208F, and Plysurf DBS (all manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), etc. These may be used alone or in combination.

[0077] The acid value (mgKOH / g) of the dispersant is preferably 20 or more, or 30 or more, and preferably 130 or less, or 100 or less. When the acid value is in the above range, the dispersion has good dispersion stability, which is preferable. In particular, when the average particle size of the metal compound-containing particles and / or the metal-containing particles is small, an acid value in the above range is effective. Specifically, BYK-Chemie's "DISPERBYK-102" (acid value 101), "DISPERBYK-140" (acid value 73), "DISPERBYK-142" (acid value 46), "DISPERBYK-145" (acid value 76), "DISPERBYK-118" (acid value 36), "DISPERBYK-180" (acid value 94), etc. are preferably mentioned.

[0078] The difference between the amine value (mgKOH / g) and the acid value of the dispersant ([amine value]-[acid value]) is preferably -50 or more and 0 or less. The amine value indicates the total amount of free bases and free base-derived sites, and the acid value indicates the total amount of free fatty acids and free fatty acid-derived sites. The amine value and acid value are measured by a method conforming to JIS K 7700 or ASTM D2074, respectively. When the value of [amine value]-[acid value] is -50 or more and 0 or less, the dispersion has good dispersion stability, which is preferable. The value of [amine value]-[acid value] is more preferably -40 or more and 0 or less, and even more preferably -20 or more and 0 or less.

[0079] The content of the dispersant is preferably adjusted in proportion to the amount of metal and metal oxide, taking into consideration the required dispersion stability. The mass ratio of the dispersant to the metal and metal oxide in the dispersion (dispersant mass / total mass of metal and metal oxide) is preferably 0.0050 or more, or 0.050 or more, or 0.10 or more, and preferably 0.30 or less, or 0.25 or less, or 0.23 or less. The amount of the dispersant affects the dispersion stability of the dispersion, and if the amount is small, the metal particles and / or metal oxide particles tend to aggregate, and if the amount is large, the dispersion stability of the dispersion tends to improve. However, if the content of the dispersant in the dispersion is 35% by mass or less, the influence of the residue derived from the dispersant can be suppressed in the metal (e.g., copper)-containing film, particularly in the metal (e.g., copper)-containing film obtained after the plating process when a plating process is performed, and the conductivity can be improved. In one embodiment, the amount of dispersant in 100% by weight of the dispersion is preferably 0.5% by weight or more, or 0.8% by weight or more, or 1.0% by weight or more, and preferably 35% by weight or less, or 30% by weight or less, or 25% by weight or less.

[0080] (reducing agent) When the dispersion contains metal oxide (e.g., copper oxide) particles, the dispersion may contain a reducing agent. Examples of the reducing agent include hydrazine, sodium, sodium borohydride, potassium iodide, sulfite, sodium thiosulfate, formic acid, oxalic acid, ascorbic acid, iron (II) sulfide, tin (II) chloride, diisobutylaluminum hydride, carbon, and the like, and preferably hydrazine. The hydrazine may be in the form of hydrazine hydrate (i.e., the hydrazine of the present disclosure is a concept that also includes hydrazine hydrate). By containing hydrazine in the dispersion, for example, in the plating process, the hydrazine contributes to the reduction of metal oxide, particularly copper oxide, particularly cuprous oxide, and a reduced metal layer (as a metal-containing film), particularly a reduced copper layer (as a copper-containing film) with lower resistance can be formed. In addition, hydrazine is advantageous in maintaining the dispersion stability of the dispersion, and is also preferable from the viewpoint of improving productivity during plating. The hydrazine in the dispersion may be present as a component in the metal oxide particles and / or separate from the metal oxide particles.

[0081] The content of the reducing agent in the dispersion (in the case of a hydrate, the amount excluding water of hydration) is preferably adjusted in proportion to the amount of metal oxide, taking into consideration the required reducing property. In one embodiment, the mass ratio of the reducing agent to the metal oxide in the dispersion (reducing agent mass / metal oxide mass) is preferably 0.0001 or more, and preferably 0.1 or less, or 0.05 or less, or 0.03 or less. When the mass ratio of the reducing agent is 0.0001 or more, it is preferable in that the dispersion has good dispersion stability and the resistance of the reduced metal layer (reduced copper layer in one embodiment) is low, and when it is 0.1 or less, the long-term stability of the dispersion is good.

[0082] Two or more kinds of reducing agents may be used in combination. For example, when hydrazine and a reducing agent other than hydrazine are used in combination, the total content of hydrazine and the reducing agent other than hydrazine in the dispersion is preferably adjusted in proportion to the amount of metal oxide, taking into consideration the required reducing property. In one embodiment, the total mass ratio of hydrazine and the reducing agent other than hydrazine to the metal oxide in the dispersion (total mass of reducing agent / mass of metal oxide) is preferably 0.0001 or more, and preferably 0.1 or less, or 0.05 or less, or 0.03 or less. When the total mass ratio of the reducing agent is 0.0001 or more, it is preferable in that the dispersion has good dispersion stability and the resistance of the reduced metal layer (reduced copper layer in one embodiment) is low, and when it is 0.1 or less, the long-term stability of the dispersion is good.

[0083] The dispersion can be produced by mixing the ingredients and dispersing them using a mixer, ultrasonic method, three-roll method, two-roll method, attritor, homogenizer, Banbury mixer, paint shaker, kneader, ball mill, sand mill, planetary mixer, or the like. The viscosity of the dispersion can be designed according to the intended application method. For example, the viscosity of the dispersion for inkjet printing is preferably 4 mPa·s or more, more preferably 6 mPa·s or more, and even more preferably 8 mPa·s or more, and preferably 15 mPa·s or less, more preferably 13 mPa·s or less, and even more preferably 11 mPa·s or less. For example, the viscosity of the dispersion for screen printing is preferably 50 mPa·s or more, more preferably 100 mPa·s or more, and even more preferably 200 mPa·s or more, and preferably 50000 mPa·s or less, more preferably 10000 mPa·s or less, and even more preferably 5000 mPa·s or less. The viscosity of the dispersion is a value measured at 23°C using a cone-plate type rotational viscometer.

[0084] [Laser light absorptivity of film] From the viewpoint of efficiently converting the laser light into thermal energy and improving the sinterability, the absorptivity at the desired laser wavelength in the entire thickness of the film containing the metal and / or metal oxide is preferably 50% or more, or 60% or more, or 70% or more. In addition, from the viewpoint of suppressing scorching or ablation due to excessive heat generation, the absorptivity at the desired laser wavelength in the entire film containing the metal and / or metal oxide is preferably 99% or less, or 95% or less, or 90% or less. In one aspect, the absorptivity at the central wavelength of 355 nm of the laser light is preferably in the above range. The absorptivity is a value measured by an ultraviolet-visible spectrophotometer. The absorptivity increases or decreases depending on the film thickness, the properties of the material constituting the film, and the like. In one aspect, setting the thickness of the film to be irradiated with the laser light to the same range as the thickness of the metal wiring described later can contribute to the adjustment of the absorptivity. In one embodiment, the thickness of the film may be 0.1 μm or more, or 0.5 μm or more, or 1 μm or more, and in one embodiment, it may be 20 μm or less, or 10 μm or less, or 8 μm or less. In addition, the absorptivity can be adjusted by the content of the metal and / or metal oxide contained in the film containing the metal and / or metal oxide, the particle size when the metal and / or metal oxide is a particle, the amount of other components (organic substances, etc.), etc. For example, reducing the content of the metal and / or metal oxide tends to reduce the absorptivity, and conversely, increasing the content tends to increase the absorptivity. In addition, the presence of a light-absorbing organic material (e.g., a phosphorus-containing organic compound) tends to increase the absorptivity.

[0085] <Metal wiring manufacturing device, laser light irradiation control device, laser light irradiation control program> One aspect of the present invention provides a metal wiring manufacturing apparatus for forming metal wiring by irradiating a preset irradiation region of a film containing a metal and / or metal oxide with a laser beam. In one aspect, the metal wiring manufacturing apparatus includes a film holding unit, a laser oscillation device, a laser beam scanning device, and a processing device. Another aspect of the present invention provides a laser beam irradiation control device and a laser beam irradiation control program that control the laser oscillation device and the laser beam scanning device of the metal wiring manufacturing apparatus, and optionally mechanisms such as an output adjustment mechanism and a spot adjustment mechanism, in order to irradiate a preset irradiation region of a film containing a metal and / or metal oxide with a laser beam.

[0086] FIG. 2 is a schematic diagram showing a configuration example of the metal wiring manufacturing apparatus of this embodiment, and FIG. 3 is a block diagram showing a configuration example of the metal wiring manufacturing apparatus of this embodiment. Referring to FIGS. 2 and 3, in one embodiment, the metal wiring manufacturing apparatus 100 includes a film holding unit 101 that holds a film containing a metal and / or metal oxide, a laser oscillator 102 that generates a laser beam, a laser beam scanning device 103 that scans the laser beam emitted from the laser oscillator, and a processing device 104 that controls the laser oscillator 102 and the laser beam scanning device 103, and typically further includes a storage device 105, a display device 106, an input device 107, and an interface device 108, which is also one embodiment of the output unit of the present disclosure. The metal wiring manufacturing apparatus 100 may further include mechanisms such as an output adjustment mechanism (not shown) and a spot adjustment mechanism (not shown). The form of the apparatus constituting the metal wiring manufacturing apparatus 100 is not limited, and each apparatus may constitute a separate device, or two or more apparatuses may constitute one device.

[0087] The processing device 104, together with the storage device 105, the display device 106, the input device 107, and the interface device 108, constitutes a laser light irradiation control device 400. The laser light irradiation control device 400 may be configured as dedicated hardware, or a program may be installed in a general-purpose computer to function as the laser light irradiation control device 400. The processing device 104 outputs a scanning control signal via the interface device 108 to the laser oscillation device 102 and the laser light scanning device 103, and optionally to mechanisms such as an output adjustment mechanism and a spot adjustment mechanism, to control the operations of these devices.

[0088] <Membrane holding part 101> The film holding part 101 holds the film 11b, and in one embodiment, holds the structure 11 including the base material 11a and the film 11b. In one embodiment, the film holding part 101 is a sample chamber. The sample chamber may have a window. The window has light transparency that allows the laser light La to reach the film 11b through the window. In one embodiment, the light transmittance of the window at a wavelength of 355 nm may be 80% or more, or 85% or more, or 90% or more. The light transmittance is ideally 100%, but may be, for example, 98% or less, or 95% or less from the viewpoint of ease of forming the window. The light transmittance is a value measured by an ultraviolet-visible spectrophotometer. The sample chamber may have an inert gas inlet, and may be configured such that, for example, an inert gas generated by an inert gas generator (not shown) is introduced into the sample chamber through the inert gas inlet. The membrane holding unit 101 may include a drive mechanism (eg, a motor or the like) that moves or tilts the membrane in three dimensional directions, XYZ.

[0089] <Laser Oscillation Device 102> The laser oscillator 102 is configured to emit a laser beam of a desired wavelength. The laser oscillator 102 is, for example, a laser oscillator. The type of laser light source that can be used includes YAG (yttrium aluminum garnet), YVO4 (yttrium vanadate), Yb (ytterbium), semiconductors (GaAs, GaAlAs, GaInAs), carbon dioxide gas, and the like. As the laser beam, not only the fundamental wave but also higher harmonics may be extracted and used as necessary.

[0090] The laser oscillator may include a cooling device or the like. In one aspect, the laser oscillator may be configured to emit pulsed light. In this case, the laser oscillator may include a pulse suppression mechanism that suppresses the initial pulse of the pulsed light. The pulse suppression mechanism prevents ablation or scorching by preventing excessive pulsed light at the start of emission from being irradiated onto the film. The pulse suppression mechanism may have, for example, a first pulse suppression function (FPS function), that is, a function of predicting excess output of the initial pulse in advance and reducing the excess output.

[0091] <Laser light scanning device 103> The laser beam scanning device 103 scans the laser beam La emitted from the laser oscillation device 102. In one embodiment, the laser beam scanning device is a galvanometer scanner including a galvanometer motor and a galvanometer mirror, and FIG. 2 illustrates the galvanometer scanner. The galvanometer scanner is preferable in that it can easily scan the laser beam regardless of the shape of the substrate, but is not particularly limited. The galvanometer scanner as the laser beam scanning device 103 has an X-axis galvanometer mirror 103a, an X-axis galvanometer motor 103b, a Y-axis galvanometer mirror 103c, and a Y-axis galvanometer motor 103d. The galvanometer scanner may have an fθ lens (not shown), a Z-axis adjustment drive lens (not shown), and the like. The X-axis galvanometer motor 103b and the Y-axis galvanometer motor 103d are electrically connected to the processing device 104.

[0092] The galvano scanner is configured to be capable of controlling the rotation angle and rotation speed of the X-axis galvano motor 103b and the Y-axis galvano motor 103d in accordance with a scanning control signal from the processing device 104. The laser light La is scanned by the laser light scanning device 103 and irradiated onto the surface of the film 11b.

[0093] In the above, a galvano scanner is exemplified as the laser beam scanning device 103, but a laser beam scanning device other than a galvano scanner can also be used. For example, the laser beam scanning device 103 may use an XY stage, which can move the film 11b in both the X-axis direction and the Y-axis direction, as a mounting table instead of the galvano scanner, and move the film 11b instead of moving the irradiation point p of the laser beam La.

[0094] The galvanometer scanner as the laser light scanning device 103 shown in FIG. 2 uses an X-axis galvanometer mirror 103a and a Y-axis galvanometer mirror 103c for movement in the X-axis and Y-axis directions, respectively. However, it is also possible to use a galvanometer mirror for either the X-axis or the Y-axis, for example, to use a galvanometer mirror for movement only in the X-axis direction and a motor of a mounting table (not shown) on which the film 11b is placed, for movement in the Y-axis direction.

[0095] <Output adjustment mechanism> The metal wiring manufacturing apparatus may have an output adjustment mechanism (not shown) for adjusting the output of the laser light. Adjusting the output can suppress ablation or scorching during laser light irradiation. One example of the output adjustment mechanism is an attenuator disposed on the path of the laser light. The attenuator is electrically connected to the processing device 104, and can change the output value to an arbitrary value in response to a control signal from the processing device 104. Alternatively, the output adjustment mechanism may be configured so that the output value can be changed by manual operation.

[0096] <Spot adjustment mechanism> The metal wiring manufacturing apparatus may have a spot adjustment mechanism (not shown) for adjusting the spot diameter at the focal position of the laser light. The spot adjustment mechanism prevents ablation or scorching by controlling the concentration density of the laser light to adjust the spot diameter. An example of the spot adjustment mechanism is a device for expanding or contracting the diameter of the light beam incident on the galvano scanner, and for example, a beam expander can be used. By changing the diameter of the laser light, the spot diameter at the focal point where the light is concentrated by the focusing lens can be changed. By expanding the diameter of the laser light, the spot diameter becomes smaller, and by contracting the diameter of the laser light, the spot diameter becomes larger. In one aspect, the beam expander may be controlled according to the laser light irradiation position in the Z-axis direction.

[0097] <Processing device 104> The processing device 104 is, for example, a central processing unit (CPU). The processing device 104 may be, for example, a digital signal processor (DSP), a large scale integration (LSI), an application specific integrated circuit (ASIC), a field programmable gate array (FPGA), or the like.

[0098] The processing device 104 controls the laser oscillation device 102 and the laser light scanning device 103, and further controls the power adjustment mechanism and / or the spot adjustment mechanism, if present. The processing device 104: A scan field pattern including an illumination field pattern; and Scanning parameters assigned to the scan area pattern; In one embodiment, the processing device 104 outputs a scanning control signal according to the above to the laser oscillation device 102 and the laser light scanning device 103, and optionally mechanisms such as a power adjustment mechanism and a spot adjustment mechanism, via an interface device 108 as an output unit. This causes the laser oscillation device 102 and the laser light scanning device 103, and optionally mechanisms such as a power adjustment mechanism and a spot adjustment mechanism, to operate so as to move the irradiation target position p of the laser light La in a second direction (for example, the Y-axis direction in FIG. 2) different from the first direction while scanning in a first direction (for example, the X-axis direction in FIG. 2) in accordance with the scanning control signal. At this time, the processing device 104 scans the irradiation target position p over a scanning region including the irradiation region, and determines whether the time from when the laser light is irradiated to point X on the first scanning line S1 until when the laser light is irradiated to point Y which is on a second scanning line S2 different from the first scanning line S1 and is located at a distance from point X not more than twice the beam diameter of the laser light is 1 ms or more, and the energy density of the laser light irradiated to the irradiation region is 1 W / mm 2 More than 5000W / mm 2 The laser oscillation device and the laser beam scanning device, and optionally mechanisms such as a power adjustment mechanism and a spot adjustment mechanism, are operated as follows. In one aspect, the scanning parameters include the beam diameter of the laser beam, the energy density of the laser beam, and the scanning speed of the irradiation target position. The details of the scanning parameters may be the same as those described above in the section "Method of manufacturing metal wiring".

[0099] In one embodiment, the processing device 104 functions as a coordinate data generating unit 410 and a scan control signal generating unit 420 by reading each program stored in the storage device 105 and operating in accordance with the read programs.

[0100] The coordinate data generating unit 410 generates coordinate data of a scanning area pattern consisting of the irradiation area pattern and the non-irradiation area pattern after specifying a non-irradiation area pattern for the input irradiation area pattern. Alternatively, in a mode in which a non-irradiation area pattern is not provided, the coordinate data generating unit 410 generates coordinate data of a scanning area pattern consisting of the irradiation area pattern based on the input irradiation area pattern.

[0101] In one embodiment, the coordinate data generating unit 410 includes a pattern generating unit 411 , a graphic designating unit 412 , and a data converting unit 413 .

[0102] The scan control signal generating unit 420 assigns preset scan parameters to the coordinate data generated by the coordinate data generating unit 410, and generates a scan control signal in accordance with the coordinate data and the scan parameters.

[0103] The interface device 108 as an output unit outputs the scan control signal generated by the scan control signal generating unit 420 to the laser oscillation device 102 and the laser light scanning device 103, and optionally to mechanisms such as an output adjustment mechanism and a spot adjustment mechanism.

[0104] <Storage device 105> The storage device 105 includes a memory device such as a RAM (Random Access Memory) or a ROM (Read Only Memory), a fixed disk device such as a hard disk, or a portable storage device such as a flexible disk or an optical disk. The storage device 105 also stores computer programs, databases, tables, and the like used for various processes of the metal wiring manufacturing apparatus 100 or the laser light irradiation control device 400. The computer programs may be installed in the storage device 105 from a computer-readable portable recording medium using a known setup program or the like. The portable recording medium is, for example, a CD-ROM (compact disc read only memory), a DVD-ROM (digital versatile disc read only memory), or the like.

[0105] The storage device 105 stores a laser light irradiation control program consisting of a coordinate data generation program, a scan control signal generation program, and a scan control signal output program. Each of these programs is a functional module implemented by software running on a processor. The program stored in the storage device 105 causes the laser light irradiation control device to execute the following: specify a non-irradiation area pattern for the input irradiation area pattern, generate coordinate data of a scanning area pattern consisting of the irradiation area pattern and the non-irradiation area pattern (or generate coordinate data of a scanning area pattern consisting of the input irradiation area pattern in an embodiment in which a non-irradiation area pattern is not provided), assign preset scanning parameters to the coordinate data, generate a scanning control signal according to the coordinate data and the scanning parameters, and output a scanning control signal.

[0106] <Display device 106, input device 107, interface device 108> The display device 106 may be a display (such as an organic EL display) or the like, and displays information input to the input device 107, the state of the processing device 104, and the like. The input device 107 may be an input device such as a keyboard or a mouse, and accepts input from a user. The interface device 108 may be a hardware interface such as a USB, a network interface such as a wired LAN (Local Area Network) or a wireless LAN, etc., and enables communication between the laser oscillation device 102 and the laser light scanning device 103 as well as any other mechanisms and the processing device 104.

[0107] <Laser light irradiation control process> Fig. 4 is a flowchart for explaining the processing executed by the laser light irradiation control program of this embodiment. An example of the operation of the metal wiring manufacturing apparatus 100 and the laser light irradiation control device 400 will be explained below with reference to the flowchart shown in Fig. 4. The flow of the operation explained below is executed mainly by the processing device 104 in cooperation with each element of the metal wiring manufacturing apparatus 100 based on a program stored in advance in the storage device 105.

[0108] First, the pattern generating means 411 generates an irradiation area pattern (step S101). The irradiation area pattern is generated by inputting from an external device in which irradiation area pattern information is stored in advance, inputting by drawing or the like from a user, reading out irradiation area pattern information stored in the storage device 105 in advance, or the like.

[0109] Following step S101, the graphic designation means 412 designates a non-irradiation area pattern that is in contact with the irradiation area pattern (step S102).

[0110] In step S102, the non-irradiation area pattern may be specified by the user. In step S102 according to one embodiment, the figure specification means 412 outputs shape data of the irradiation area pattern and obtains shape data of the non-irradiation area pattern. In an embodiment in which the non-irradiation area pattern is not provided, step S102 may not be performed.

[0111] The pattern generating means 411 generates a scanning area pattern based on the irradiation area pattern generated in step S101 and the non-irradiation area pattern designated in step S102 (step S103). In a mode in which step S102 is not performed, the pattern generating means 411 generates a scanning area pattern based on the irradiation area pattern generated in step S101 and configured with the irradiation area pattern.

[0112] After step S103, the data conversion means 413 acquires the data of the scanning area pattern generated in step S103 and converts it into coordinate data, thereby generating coordinate data indicating the scanning area pattern (step S104).

[0113] Next, the scanning control signal generating unit 420 generates scanning parameters that define the laser light irradiation conditions by input from an external device in which scanning parameter information is stored in advance, input from a user, reading out scanning parameter information stored in advance in the storage device 105, etc. (Step S105). In one aspect, the scanning parameters include the beam diameter of the laser light, the output intensity of the laser light, and the scanning speed of the irradiation target position. In one aspect, the scanning parameters include on / off switching of the laser oscillation device for controlling laser light irradiation and non-laser light irradiation.

[0114] The scanning control signal generating unit 420 generates a scanning control signal by assigning the scanning parameters generated in step S105 to the coordinate data generated in step S104 (step S106). In one embodiment, the scanning parameters assigned to the non-irradiation area pattern are different from the scanning parameters assigned to the irradiation area pattern only in that the laser light is not irradiated. That is, in one embodiment, the scanning control signal generating unit 420 assigns the same scanning parameters to the irradiation area pattern and the non-irradiation area except for the on / off switching of the laser oscillation device.

[0115] The interface device 108, acting as an output section, outputs the scanning control signal generated in step S106 to the laser oscillator 102 and laser light scanning device 103 of the metal wiring manufacturing apparatus 100, and optionally to mechanisms such as an output adjustment mechanism and a spot adjustment mechanism (step S107), thereby completing the series of steps.

[0116] In the metal wiring manufacturing apparatus, laser light irradiation control device, and laser light irradiation control program disclosed herein, specific examples of various aspects other than those described above (e.g., generation of scanning area pattern, details of scanning parameters, etc.) may be similar to those described above in the <Wiring formation process> of the <Metal wiring manufacturing method>, and the description will not be repeated here.

[0117] <Recording media or recording devices> One aspect of the present invention also provides a computer-readable recording medium or recording device that stores the laser light irradiation control program of the present disclosure. The computer may have a general hardware configuration including a CPU, a main memory, a storage, an input / output device, a hardware interface, and the like. The recording medium may be a memory device such as a RAM or a ROM, or a portable storage device such as a CD-ROM, a DVD-ROM, or an optical disk. The above program includes those that are stored in the recording medium and distributed, as well as those that are distributed by downloading through a network line such as the Internet. The recording device may be a general-purpose or dedicated device in which the above program is implemented in an executable state in the form of software, firmware, or the like. Each process and function included in the program may be executed by a program software that can be executed by a computer, or the process of each part may be realized by a predetermined hardware, or a form in which the program software and a partial hardware module that realizes some elements of the hardware are mixed. EXAMPLES

[0118] The following examples further illustrate exemplary embodiments of the present invention, but the present invention is not limited to these examples.

[0119] [Example 1] (Preparation of paste material) 80 g of copper(II) acetate monohydrate (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) was dissolved in a mixed solvent consisting of 800 g of water and 400 g of 1,2-propylene glycol (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.), 20 g of hydrazine hydrate (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) was added, and the mixture was stirred. Then, the supernatant and precipitate were separated using centrifugation.

[0120] 0.4 g of DISPERBYK-145 (trade name, manufactured by BYK-Chemie) (BYK-145) as a phosphorus-containing organic compound and 6.6 g of ethanol (manufactured by Fujifilm Wako Pure Chemical Industries) as a dispersion medium were added to 2.8 g of the obtained precipitate, and dispersed using a homogenizer. Dilution and concentration with ethanol were further repeated, thereby obtaining a paste material containing cuprous oxide fine particles including cuprous oxide (copper (I) oxide). The final composition was 2.8 g of precipitate, 0.4 g of BYK-145, 6.6 g of ethanol, and 0.01 g of hydrazine hydrate.

[0121] (Membrane formation) A polycarbonate substrate was prepared as the base material, and the surface was subjected to UV ozone treatment. The paste material was then spin-coated (500 rpm x 30 seconds), dried at 25°C for 10 minutes, and then dried at 60°C for 1 hour, obtaining a structure in which a 3.0 μm-thick film was formed on the base material.

[0122] (Preparation of metal wiring manufacturing equipment) The metal wiring manufacturing equipment was prepared with a Spectra-Physics Explorer One HP 355 laser oscillator, a Raylase AXIALSCAN-20 DIGITAL II TY200 galvanometer scanner, a compressed air inlet nozzle and exhaust port in the workspace, and a Contec VPC-3100 control computer. The compressed air volume was measured with a KOFLOC flow meter and found to be 10 L / min.

[0123] The metal wiring manufacturing apparatus was equipped with an attenuator that could be controlled by a computer to adjust the output of the laser light, and a galvano controller was used to issue a laser command to control the on / off state of the laser light. Other scanning parameters were a central wavelength of 355 nm, a frequency of 300 kHz, a pulse width of 20 ns, and an output of 110 mW. The height of the sample chamber was adjusted so that the beam diameter of the laser light irradiated on the film was 50 μm. Therefore, the energy density of the laser light irradiated on the film was 0.1 mW / μm. 2 was set to.

[0124] (Scan length setting) The scanning area pattern was set as shown in Figure 1A. In the first direction, the scanning area pattern length (i.e., the scanning length L2 irradiated with laser light) was set to 10 mm, and the scanning area pattern length (i.e., the scanning length L1 of the irradiation target position) was set to 12 mm. The non-irradiation area pattern lengths (i.e., the scanning lengths L3 and L4 of the non-irradiated laser light) were both set to 1 mm.

[0125] (Laser light irradiation) The above structure was placed on the work table with the coating film facing up. The target position for laser light irradiation was scanned back and forth as follows. First, starting from point P in FIG. 1A, 1 mm of scanning was performed in the first direction D1 without laser light irradiation at a maximum speed of 30 mm / sec. Then, 10 mm of scanning was performed with laser light irradiation without changing the scanning speed and scanning direction. Further, 1 mm of scanning was performed without laser light irradiation. The structure was moved 30 μm in the second direction D2 perpendicular to the first direction D1, and 1 mm of scanning was performed in the direction D1 without laser light irradiation at a maximum speed of 30 mm / sec. Then, 10 mm of scanning was performed with laser light irradiation without changing the scanning speed and scanning direction. Further, 1 mm of scanning was performed without laser light irradiation. By repeating this, the desired wiring pattern was drawn. The time T from when the laser light was irradiated to point X on the first scanning line S1 until when the laser light was irradiated to point Y which was on a second scanning line S2 different from the first scanning line S1 and whose distance from point X was less than twice the beam diameter of the laser light was 65 ms at the pattern end where the time T was the shortest.

[0126] (Measurement of film absorptivity) The absorbance at a wavelength of 355 nm was measured using an ultraviolet-visible spectrophotometer (Shimadzu Corporation, UV-3600) and was found to be 86%.

[0127] (Calculation of overlap rate) The beam diameter of the laser light used in Example 1 when irradiating the film was measured using an Ophir Beam Profiler SP928 and was found to be 50 μm in diameter. The overlap rate of the scanning lines in Example 1 was calculated to be 40%.

[0128] (Evaluation of wiring appearance) When the wiring surface was observed at 200x magnification using an optical microscope (Nikon ECLIPSE LV100), no noticeable scorching or ablation was observed at the ends of the wiring.

[0129] (Wiring reliability evaluation) When a peeling test was performed using tape (Nichiban No. 405 tape was used), the wiring remained without peeling.

[0130] [Example 2] The maximum speed of the laser light is 10 mm / sec. The energy density of the laser light irradiated on the film is 0.01 mW / μm. 2 Except for this, the wiring pattern was written in the same manner as in Example 1. The time T was 193 ms at the pattern end where the time T was the shortest. (Evaluation of wiring appearance) When the wiring surface was observed at 200x magnification using an optical microscope (Nikon ECLIPSE LV100), no noticeable scorching or ablation was observed at the ends of the wiring. (Wiring reliability evaluation) When a peeling test was performed using tape (Nichiban No. 405 tape was used), the wiring remained without peeling.

[0131] [Example 3] The maximum speed of the laser light was set to 100 mm / sec, the length of the non-irradiated area pattern (i.e., the scanning lengths L3 and L4 of the non-irradiated laser light) was set to 0.1 mm, and the energy density of the laser light irradiated to the film was set to 0.14 mW / μm 2 Except for this, the wiring pattern was written in the same manner as in Example 1. At this time, the calculated time T was 2 ms at the pattern end. (Evaluation of wiring appearance) When the wiring surface was observed at 200x magnification using an optical microscope (Nikon ECLIPSE LV100), no noticeable scorching or ablation was observed at the ends of the wiring. (Wiring reliability evaluation) When a peeling test was performed using tape (Nichiban No. 405 tape was used), the wiring remained without peeling.

[0132] [Example 4] An aluminum oxide substrate (N-99 manufactured by Nishimura Ceramics Co., Ltd.) was used as the base material, and the laser light was irradiated in a nitrogen inert atmosphere. The energy density of the laser light irradiated to the film was 4.6 mW / μm 2 A wiring pattern was drawn in the same manner as in Example 1, except for the above. (Evaluation of wiring appearance) When the wiring surface was observed at 200x magnification using an optical microscope (Nikon ECLIPSE LV100), no noticeable scorching or ablation was observed at the ends of the wiring. (Wiring reliability evaluation) When a peeling test was performed using tape (Nichiban No. 405 tape was used), the wiring remained without peeling.

[0133] [Comparative Example 1] 1A, the same procedure as in Example 1 was carried out except that the scanning length L1 of the irradiation target position was set to 10 mm, and L3 and L4 were both set to 0 mm. The time T from when the laser light was irradiated to point X on the first scanning line S1 until when the laser light was irradiated to point Y which was on a second scanning line S2 different from the first scanning line S1 and whose distance from point X was less than twice the beam diameter of the laser light was 0 ms at the pattern end where the time T was the shortest.

[0134] (Evaluation of wiring appearance) When the wiring surface was observed at 200x magnification using an optical microscope (Nikon ECLIPSE LV100), a 100 μm wide burnt mark was found on the end of the wiring.

[0135] (Wiring reliability evaluation) When evaluated in the same manner as in Example 1, a part of the wiring was peeled off. [Industrial Applicability]

[0136] The metal wiring obtained according to one embodiment of the present invention can be suitably used for producing wiring materials for electronic circuit boards and the like, antennas, heaters, mesh electrodes, electromagnetic shielding materials, and heat dissipation materials. [Explanation of symbols]

[0137] P, P1, P2: starting point L1, L1a, L1b: Scan length of irradiation target position L2, L2a, L2b: Scanning length of laser light irradiation area L3, L3a, L3b, L4, L4a, L4b: scanning length of non-irradiated part of laser light D1: First direction D2: Second direction 11 Structure 11a Base material 11b Membrane 100 Metal wiring manufacturing equipment 101 Membrane holding part 102 Laser Oscillation Device 103 Laser beam scanning device 103a X-axis galvanometer mirror 103b X-axis galvanometer motor 103c Y-axis galvanometer mirror 103d Y-axis galvanometer motor 104 Processing equipment 400 Laser light irradiation control device

Claims

1. A method for manufacturing a metal wiring, comprising: a wiring formation step of forming a metal wiring by irradiating a laser beam to a predetermined irradiation area of ​​a film containing a metal and / or a metal oxide, In the wiring forming step, a scanning region including the irradiation region is scanned by moving an irradiation target position of the laser light in a second direction different from the first direction while scanning the irradiation target position in a first direction; a time T from when the laser light is irradiated onto a point X on a first scanning line S1 until when the laser light is irradiated onto a point Y which is on a second scanning line S2 different from the first scanning line S1 and is located at a distance from the point X not more than twice the beam diameter of the laser light is 1 ms or more; The energy density of the laser light irradiated to the irradiation area is 1 W / mm 2 More than 5000W / mm 2 The method is as follows.

2. The wiring forming step includes: A scan area pattern generating step of generating a scan area pattern including an illumination area pattern; assigning scanning parameters to the scan area pattern; and an irradiating step of irradiating the irradiation area with laser light by scanning the irradiation target position according to the scanning area pattern and the scanning parameters; Including, The method of claim 1 , wherein the scanning parameters include a beam diameter of the laser light, a power intensity of the laser light, and a scanning speed of the illuminated target location.

3. The scanning area pattern is composed of the irradiation area pattern and a non-irradiation area pattern, the non-irradiation area patterns are arranged to sandwich the irradiation area pattern in the first direction, The scanning parameters further include irradiation and non-irradiation of laser light; The method according to claim 2 , wherein in the parameter assignment step, irradiation of the laser light is assigned to the irradiation region pattern and non-irradiation of the laser light is assigned to the non-irradiation region pattern.

4. The method according to claim 3 , wherein a total length of the non-irradiated area pattern relative to 100% of a length of the irradiated area pattern in the first direction is 0.1% or more.

5. The method according to claim 1 , wherein the film has an absorptivity of 50% or more for laser light having a central wavelength of 355 nm.

6. A metal wiring manufacturing apparatus for forming a metal wiring by irradiating a laser beam to a preset irradiation area of ​​a film containing a metal and / or a metal oxide, comprising: The metal wiring manufacturing apparatus comprises: a membrane holder for holding the membrane; A laser oscillator that generates laser light; A laser beam scanning device that scans the laser beam emitted from the laser oscillation device; and a processing device for controlling the laser oscillation device and the laser beam scanning device; Equipped with The processing device comprising: A scan area pattern including an illumination area pattern; and scanning parameters assigned to said scan area pattern; to the laser oscillation device and the laser light scanning device, thereby operating the laser oscillation device and the laser light scanning device so as to scan an irradiation target position of the laser light in a first direction while moving the irradiation target position in a second direction different from the first direction in accordance with the scanning control signal, thereby scanning the irradiation target position over a scanning region including the irradiation region; A time T from when the laser light is irradiated to a point X on a first scanning line S1 until when the laser light is irradiated to a point Y which is on a second scanning line S2 different from the first scanning line S1 and is located at a distance from the point X not more than twice the beam diameter of the laser light is 1 ms or more, and an energy density of the laser light irradiated to the irradiation region is 1 W / mm 2 More than 5000W / mm 2 is as follows: The metal wiring manufacturing apparatus, wherein the scanning parameters include a beam diameter of a laser light, an output intensity of the laser light, and a scanning speed of an irradiation target position.

7. The scanning area pattern is composed of the irradiation area pattern and a non-irradiation area pattern, the non-irradiation area patterns are arranged to sandwich the irradiation area pattern in the first direction, The scanning parameters further include irradiation and non-irradiation of laser light; 7. The metal wiring manufacturing apparatus according to claim 6, wherein the irradiation area pattern is assigned to be irradiated with laser light, and the non-irradiation area pattern is assigned to be non-irradiated with laser light.

8. A laser light irradiation control device that controls a laser oscillation device and a laser light scanning device of a metal wiring manufacturing apparatus to irradiate a laser light to a preset irradiation area of ​​a film containing a metal and / or metal oxide, a coordinate data generating unit that generates coordinate data of a scanning area pattern including an irradiation area pattern; a scanning control signal generating unit that assigns preset scanning parameters to the coordinate data and generates a scanning control signal according to the coordinate data and the scanning parameters; an output unit that outputs the scanning control signal to a laser oscillator and a laser beam scanning device; The scanning parameters include a beam diameter of the laser light, an output intensity of the laser light, and a scanning speed of the irradiation target position; According to the scanning control signal, an irradiation target position of the laser light is moved in a second direction different from the first direction while scanning in a first direction, so that the irradiation target position is scanned over a scanning region including the irradiation region, a time T from when the laser light is irradiated to a point X on a first scanning line S1 to when the laser light is irradiated to a point Y which is on a second scanning line S2 different from the first scanning line S1 and is located at a distance from the point X not more than twice the beam diameter of the laser light is 1 ms or more, and an energy density of the laser light irradiated to the irradiation region is 1 W / mm 2 More than 5000W / mm 2 Below is the Laser light irradiation control device.

9. The scanning area pattern is composed of the irradiation area pattern and a non-irradiation area pattern, the non-irradiation area patterns are arranged to sandwich the irradiation area pattern in the first direction, The scanning parameters further include irradiation and non-irradiation of laser light; The laser light irradiation control device according to claim 8 , wherein the irradiation area pattern is assigned with irradiation of a laser light, and the non-irradiation area pattern is assigned with non-irradiation of a laser light.

10. A laser light irradiation control program for controlling a laser oscillator and a laser light scanner of a metal wiring manufacturing apparatus in order to irradiate a laser light onto a preset irradiation region of a film containing a metal and / or metal oxide, comprising: Generate coordinate data of the input scanning area pattern including the irradiation area pattern; Assigning preset scanning parameters to the coordinate data; generating a scan control signal according to the coordinate data and the scan parameters; outputting the scanning control signal; and making the laser light irradiation control device execute the above steps, The scanning parameters include a beam diameter of the laser light, an output intensity of the laser light, and a scanning speed of the irradiation target position; According to the scanning control signal, an irradiation target position of the laser light is moved in a second direction different from the first direction while scanning in a first direction, so that the irradiation target position is scanned over a scanning region including the irradiation region, a time T from when the laser light is irradiated to a point X on a first scanning line S1 to when the laser light is irradiated to a point Y which is on a second scanning line S2 different from the first scanning line S1 and is located at a distance from the point X not more than twice the beam diameter of the laser light is 1 ms or more, and an energy density of the laser light irradiated to the irradiation region is 1 W / mm 2 More than 5000W / mm 2 Below is the Laser light irradiation control program.

11. The scanning area pattern is composed of the irradiation area pattern and a non-irradiation area pattern, the non-irradiation area patterns are arranged to sandwich the irradiation area pattern in the first direction, The scanning parameters further include irradiation and non-irradiation of laser light; 11. The laser light irradiation control program according to claim 10, wherein irradiation of the laser light is assigned to the irradiation area pattern and non-irradiation of the laser light is assigned to the non-irradiation area pattern.

12. A computer-readable recording medium or recording device storing the program according to claim 10 or 11.

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