CN108723618B - Laser scanning removal method for improving edge quality and performance of metal grid - Google Patents

Laser scanning removal method for improving edge quality and performance of metal grid Download PDF

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CN108723618B
CN108723618B CN201810547781.4A CN201810547781A CN108723618B CN 108723618 B CN108723618 B CN 108723618B CN 201810547781 A CN201810547781 A CN 201810547781A CN 108723618 B CN108723618 B CN 108723618B
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scanning
square array
laser
grid
outer frame
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CN108723618A (en
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李保家
李皇
黄立静
任乃飞
王轶伦
王永瑛
王天宇
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Jiangsu University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K26/00—Working by laser beam, e.g. welding, cutting or boring
    • B23K26/60—Preliminary treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K26/00—Working by laser beam, e.g. welding, cutting or boring
    • B23K26/36—Removing material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K26/00—Working by laser beam, e.g. welding, cutting or boring
    • B23K26/70—Auxiliary operations or equipment
    • B23K26/702—Auxiliary equipment

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  • Optics & Photonics (AREA)
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  • Mechanical Engineering (AREA)
  • Surface Treatment Of Glass (AREA)
  • Laser Beam Processing (AREA)

Abstract

The invention provides a laser scanning removal method for improving the edge quality and performance of a metal grid, which comprises the following steps of firstly drawing a frame series square array or an outer frame inner line type composite square array, wherein a square in the frame series square array is formed by nesting a plurality of squares or rectangles with different sizes; the outer frame inner line type composite square array consists of a plurality of parallel linear lines and a square or rectangle surrounding the plurality of linear lines; for the frame type series square array, firstly removing the outline outer frame of the edge of the removal area to a preset depth, and then sequentially reducing the outer frame to gradually remove the inner part; for the linear composite square array in the outer frame, a linear cyclic scanning removal method is firstly utilized to form a preliminary grid shape, and then the uneven part of the edge of the grid is removed through outer frame scanning. The invention can relieve the heat influence of the edge of the removed area, improve the dimensional accuracy and the resolution of the metal grid, improve the quality of the edge of the removed area and improve the light transmittance of the metal grid type transparent electrode.

Description

Laser scanning removal method for improving edge quality and performance of metal grid
Technical Field
The invention relates to the field of laser processing technology and photoelectric functional materials, in particular to a laser scanning removal method for improving the edge quality and performance of a metal grid.
Background
With the gradual depletion of primary energy sources such as coal and petroleum and the influence of combustion on the deterioration of the environment, an environmentally friendly renewable energy source is urgently needed by human beings. Solar energy has attracted attention as a clean, safe and renewable energy source. The transparent electrode is an indispensable component of the solar cell, and the performance of the transparent electrode directly affects the performance of the solar cell. Therefore, research and development of high-performance transparent electrodes are of great significance for improving the performance of the solar cell. The currently common transparent electrode materials mainly include graphene, Carbon Nanotubes (CNTs), Transparent Conductive Oxides (TCOs), conductive polymers, metal nanowires, metal grids, and the like. Compared with other transparent electrode materials, the metal grid has attracted attention due to its advantages of low resistance, high light transmittance, good flexibility, etc.
The invention patent application CN201711275941.6 discloses a method for preparing a metal grid type transparent electrode by utilizing a laser localization removal technology, which comprises the steps of firstly sputtering a metal layer with a certain thickness on the surface of a substrate by a magnetron sputtering coating instrument, then scanning and removing the metal layer by utilizing a focused laser beam according to a square array drawn in advance by EZCAD software, and finally obtaining a metal grid with controllable width. The method is simple to operate and good in controllability, but in the method, laser beams are subjected to line-by-line cyclic scanning (namely line cyclic scanning) in a single line mode to realize localized removal of the metal layer, the edges of metal grid lines obtained by the scanning method are usually uneven, partial metal residues can be generated, the metal residues can reduce the light transmittance of the metal grid type transparent electrode, and the comprehensive photoelectric performance of the metal grid type transparent electrode is finally influenced.
Disclosure of Invention
The invention aims to overcome the defects that the edge of a metal grid line is not flat and the light transmittance is reduced due to partial metal residue in the prior art, and provides a laser scanning removal method capable of improving the edge quality of a metal grid.
The technical scheme adopted by the invention is as follows:
the laser scanning removal method for improving the edge quality and the performance of the metal grid comprises the following steps:
firstly, cleaning a substrate, and sputtering a layer of metal with a certain thickness on the surface of the substrate by using a magnetron sputtering coating instrument; then placing the obtained metal/substrate on a sample table of a laser, adjusting the position of the sample table and related laser parameters, drawing a square array by utilizing EZCAD software, wherein the areas among squares in the square array form the shape of a grid; scanning and removing the metal/substrate by the focused laser beam according to the drawn square array to obtain a metal grid type transparent electrode; it is characterized in that the preparation method is characterized in that,
the square array is a frame series square array or an outer frame inner line type composite square array, and the square in the frame series square array is formed by nesting a plurality of squares or rectangles with different sizes; the outer frame inner line type composite square array consists of a plurality of parallel linear lines and a square or rectangle surrounding the plurality of linear lines;
the laser beam scanning method comprises the following steps:
for the frame type series square array, firstly removing the outline outer frame of the edge of the removal area to a preset depth, and then sequentially reducing the outer frame to gradually remove the inner part;
for the linear composite square array in the outer frame, a linear cyclic scanning removal method is firstly utilized to form a preliminary grid shape, and then the uneven part of the edge of the grid is removed through outer frame scanning.
Further, the substrate is glass, PET (polyethylene terephthalate), TCO/glass or TCO/PET, wherein the TCO material comprises zinc oxide (ZnO), indium oxide (In)2O3) Tin oxide (SnO)2) And doped systems thereof, such as aluminum-doped zinc oxide (AZO), tin-doped indium oxide (ITO), fluorine-doped tin oxide (FTO).
Further, the specific cleaning process of the substrate is as follows: the substrate is sequentially placed into deionized water, acetone and absolute ethyl alcohol for ultrasonic cleaning for 10min (25 ℃, 60W), and then the substrate is placed in nitrogen flow for drying, wherein the acetone and the ethyl alcohol are analytically pure, and the deionized water is self-made by a laboratory (the resistivity is more than 16 omega. m).
Further, the operation process of sputtering coating comprises the following steps: the method comprises the steps of placing a substrate on a sample table of a magnetron sputtering coating instrument, sputtering a metal layer with the thickness of 50-400 nm, wherein the sputtering power is 30-60W, the sputtering pressure is 4-15 Pa, and the working gas is argon.
Further, the sputtered metal layer material is one of Ag, Cu, Au, Pt, Ni and Al.
Furthermore, an ultrashort pulse laser is selected, the pulse width is required to be less than 20ns, the wavelength is 355-1064 nm, and the focus of the laser beam after being focused by the lens is 0.5-1% above the surface layer of the sampleAt 0mm, the laser energy density is 0.4-0.8J/cm2The scanning speed is 15-25 mm/s, and the scanning area of the laser beam is 15mm multiplied by 15 mm.
Furthermore, when the laser scans in each square block, the line overlapping rate is 56% -65%, and the localized removal of the metal layer in each square block can be realized.
Furthermore, the side length of each square in the square array is controlled to be 0.8-1.3 mm, so that the preparation of the metal grid type transparent electrode with the grid spacing of 800-1300 mu m can be realized.
Furthermore, the preparation of the metal grid type transparent electrode with the grid width of 15-80 mu m can be realized by controlling the interval between adjacent squares in the square array to be 0.015-0.080 mm.
The principle of laser localized removal is as follows: under the action of laser, the metal in the square array area is quickly heated to be vaporized and volatilized, so that the localized removal of the metal layer in the area is realized. The principle of changing the laser scanning removal method to improve the edge quality and the performance of the metal grid is as follows: the pulse laser realizes the localized removal of the whole line on the surface of the material in a mode of overlapping pulses one by one, so that two ends of a scanning line are generally in a semicircular shape, the middle part of the scanning line is a flat and smooth straight line, the laser action time in the area where the laser scanning starts and ends is longer than that in other areas, and the adjacent grid lines are influenced by heat to a certain extent. Based on this, in the prior art, the edges of the metal grid lines obtained by the conventional linear cyclic scanning removal method usually form grid lines with edges recessed inwards and relatively rough due to the influence of laser thermal influence and pulse distribution, and part of metal even breaks off the connection with the grid lines to form metal residues affecting the light transmittance of the metal grid type transparent electrode. According to the invention, a frame-type series scanning removal method is adopted, on one hand, the laser action time at the edge is reduced by removing the outline outer frame along the edge of the removed area, the heat influence at the edge of the removed area can be relieved, and the size precision and the resolution of the prepared metal grid are improved, on the other hand, the middle part of the outer frame with relatively flat scanning lines is used for removing, the edge quality of the removed area can be improved, the obtained grid lines are relatively flat and have no metal residue, and therefore, the light transmittance of the metal grid type transparent electrode can be effectively improved. Similarly, the outer frame inner line type composite scanning removal method firstly utilizes the conventional line type circular scanning removal method to preliminarily form grid lines with uneven edges, and then removes the parts with uneven edges and metal residues along the edge outline outer frame of the removal area to obtain the grid lines which are smooth and clean and have higher dimensional accuracy and resolution, and can also improve the edge quality and performance of the metal grid.
Compared with the prior art, the invention has the advantages that:
1) and the EZCAD software can be used for flexibly drawing square arrays corresponding to different laser scanning removal methods, and the operation is simple.
2) The preparation of the metal grid type transparent electrode with smooth edge and no metal residue can be realized by simply changing the laser scanning method during the localized removal of the metal layer, so that the performance of the transparent electrode is further optimized, and the repeatability is good.
3) The laser removal method of frame type series scanning and outer frame inner line type composite scanning can relieve the heat influence of the edge of a removal area, so that the size deviation of the obtained metal grid is smaller and the resolution is higher.
Drawings
FIG. 1 shows the block arrays drawn by EZCAD software corresponding to different laser scanning removal methods, (a) is the linear cyclic block array used in the prior art, and (b) and (c) are the frame series block array and the in-frame linear composite block array proposed by the present invention, respectively.
FIG. 2 is an optical microscopic image comparison of Ag mesh/glass transparent electrodes obtained under the linear cyclic scan (a) and frame series scan (b) removal method in example 1.
FIG. 3 is an optical microscopic image comparison of Ag mesh/glass transparent electrodes obtained under the linear cyclic scan (a) and frame series scan (b) removal method in example 2.
Fig. 4 is an optical microscopic image comparison of Ag mesh/glass transparent electrode obtained under the linear cyclic scanning (a) and outline frame linear compound scanning (b) removal method in example 3.
FIG. 5 is a comparison of transmission spectra of Cu grid/FTO glass transparent electrodes under different laser scanning removal methods in example 4.
Detailed Description
The invention will be further described with reference to the following figures and specific examples, but the scope of the invention is not limited thereto.
The invention relates to a laser scanning removal method for improving the edge quality and the performance of a metal grid, which comprises the following steps:
firstly, cleaning a substrate, and sputtering a layer of metal with a certain thickness on the surface of the substrate by using a magnetron sputtering coating instrument; then placing the obtained metal/substrate on a sample table of a laser, adjusting the position of the sample table and related laser parameters, drawing a square array by utilizing EZCAD software, wherein the areas among squares in the square array form the shape of a grid; and scanning and removing the metal/substrate by the focused laser beam according to the drawn square array to obtain the metal grid type transparent electrode.
The square array is a frame series square array or an outer frame inner line type composite square array, and the square in the frame series square array is formed by nesting a plurality of squares or rectangles with different sizes, as shown in a figure 1 (b); the outline border-in line type composite square array is composed of a plurality of parallel linear lines and a square or rectangle surrounding the plurality of linear lines, as shown in fig. 1 (c).
The conventional linear cyclic block array used in the prior art, as shown in fig. 1(a), performs linear cyclic scanning of the laser beam under the array in a single line according to the drawn block array to realize localized removal of the metal layer.
The method for scanning the laser beam comprises the following steps:
for the frame type series square array, firstly removing the outline outer frame of the edge of the removal area to a preset depth, and then sequentially reducing the outer frame to gradually remove the inner part;
for the linear composite square array in the outer frame, a linear cyclic scanning removal method is firstly utilized to form a preliminary grid shape, and then the uneven part of the edge of the grid is removed through outer frame scanning.
According to the invention, a frame-type series scanning removal method is adopted, on one hand, the laser action time at the edge is reduced by removing the outline outer frame along the edge of the removal area, the heat influence at the edge of the removal area can be relieved, and the size precision and the resolution of the prepared metal grid are improved, on the other hand, the middle part of the outer frame with relatively flat scanning lines is used for removing, the edge quality of the removal area can be improved, the obtained grid lines are relatively flat and have no metal residue, and therefore, the light transmittance of the metal grid type transparent electrode can be effectively improved. Similarly, the outer frame inner line type composite scanning removal method firstly utilizes the conventional line type circular scanning removal method to preliminarily form grid lines with uneven edges, and then removes the parts with uneven edges and metal residues along the edge outline outer frame of the removal area to obtain the grid lines which are smooth and clean and have higher dimensional accuracy and resolution, and can also improve the edge quality and performance of the metal grid.
Example 1:
selecting quartz glass as a substrate, firstly cleaning the quartz glass substrate, sequentially putting the substrate into deionized water, acetone and absolute ethyl alcohol for ultrasonic cleaning for 10min, and then blowing the substrate in nitrogen flow for drying. Then, the cleaned quartz glass substrate was placed on a sample stage of a magnetron sputtering coating apparatus, and 100nm of Ag was sputtered on the quartz glass surface under a sputtering power of 30W, a sputtering pressure of 4Pa, and an argon atmosphere (the purity of the Ag target was 99.99%). Then placing the Ag/glass on a sample stage of a laser, adjusting the position of the sample stage, enabling the focus of a laser beam emitted by the laser after being focused by a lens to be 1.0mm above the surface of the Ag/glass, scanning and removing the laser beam on the surface of the Ag/glass at a line overlapping rate of 56% according to a line circulation square array and a frame series square array drawn by EZCAD software respectively, wherein the scanning and removing method comprises the following steps:
for the linear circulation block array shown in fig. 1(a), linear circulation scanning removal is adopted;
for the frame-type series square array shown in fig. 1(b), the outline outer frame of the edge of the removed area is removed to a predetermined depth, and then the inner part of the outer frame pair is gradually removed by sequentially shrinking.
The number of scanning removal times is 1, the side length (namely the grid interval) of each square in the array under the two scanning removal methods is 0.8mm, and the interval between every two adjacent squares is 0.015 mm. Under the action of laser, Ag in the square array area is quickly heated, vaporized and removed, and the Ag layer which is not removed forms an Ag grid. The pulse width of the laser beam is 1ns, the wavelength is 532nm, the repetition frequency is 1kHz, and the laser energy density is 0.8J/cm2The scanning speed was 15mm/s and the scanning area was 15mm × 15 mm. And finally, taking out the electrode, and blowing off splashes on the surface layer by using an ear washing ball to obtain the Ag grid/glass transparent electrode.
Fig. 2 is an optical microscopic image comparison of Ag mesh/glass transparent electrodes obtained under different scanning removal methods. FIG. 2(a) is an optical microscope image of the Ag mesh/glass transparent electrode obtained by the in-line cyclic scanning removal method, and it can be seen from FIG. 2(a) that Ag meshes with a mesh pitch of 800 μm exist on the glass surface. The inset in fig. 2(a) is a partial enlarged view of the Ag grid lines, and it can be seen from the inset in fig. 2(a) that the Ag grid lines have rough edges and have partial metal residue, so that the grid width has a large deviation from the pre-designed 15 μm. FIG. 2(b) is an optical microscope photograph of the Ag mesh/glass transparent electrode obtained under the frame-type series scanning removal method, and as in FIG. 2(a), the glass surface also formed Ag meshes with a mesh pitch of 800 μm. As can be seen from the partially enlarged view of Ag grid lines in fig. 2(b), the edges of the grid lines are relatively flat, no metal residue occurs under the similar line type cyclic scanning removal method, and the grid width is consistent with the pre-designed 15 μm. Through detection, the average light transmittance (T) of the Ag grid/glass transparent electrode with the grid spacing of 800 mu m in the 400-800 nm wave band is removed according to linear cyclic scanningav) 86.69% square resistance (R)sh) Is 15.1 omega/sq; removing the average light transmittance (T) of the Ag grid/glass transparent electrode with the grid spacing of 800 mu m in the wave band of 400-800 nm according to frame type series scanningav) 87.56% square resistance (R)sh) It was 14.6. omega./sq. Quality factor (F)TC＝Tav 10/Rsh) The calculation result shows that the frameThe comprehensive photoelectric property (quality factor of 1.81 multiplied by 10) of the prepared Ag grid/glass transparent electrode is removed by series scanning-2Ω-1) The prepared Ag grid/glass transparent electrode (quality factor of 1.58 multiplied by 10) is removed by the linear cyclic scanning-2Ω-1) Good results are obtained.
Example 2:
quartz glass is selected as a substrate. Firstly, a quartz glass substrate is cleaned, then the cleaned quartz glass substrate is placed on a sample stage of a magnetron sputtering coating instrument, and 100nm of Ag (the purity of an Ag target is 99.99%) is sputtered on the surface of the quartz glass under the sputtering power of 30W, the sputtering pressure of 4Pa and the argon atmosphere. Then placing the Ag/glass on a sample stage of a laser, adjusting the position of the sample stage, enabling the focus of a laser beam emitted by the laser after being focused by a lens to be 1.0mm above the surface of the Ag/glass, drawing a linear circulation square array and a frame series square array by the laser beam according to EZCAD software respectively, and scanning and removing the Ag/glass surface at a line overlapping rate of 56%, wherein the scanning and removing method comprises the following steps:
for the linear circulation block array shown in fig. 1(a), linear circulation scanning removal is adopted;
for the frame-type series square array shown in fig. 1(b), the outline outer frame of the edge of the removed area is removed to a predetermined depth, and then the inner part of the outer frame pair is gradually removed by sequentially shrinking.
The number of scanning removal times is 1, the side length (namely the grid distance) of each square in the array under the two scanning removal methods is 0.8mm, and the interval between every two adjacent squares is 0.04 mm. Under the action of laser, Ag in the square array area is quickly heated, vaporized and removed, and the Ag layer which is not removed forms an Ag grid. The pulse width of the laser beam is 1ns, the wavelength is 532nm, the repetition frequency is 1kHz, and the laser energy density is 0.8J/cm2The scanning speed was 15mm/s and the scanning area was 15mm × 15 mm. And finally, taking out the electrode, and blowing off splashes on the surface layer by using an ear washing ball to obtain the Ag grid/glass transparent electrode.
Fig. 3 is an optical microscopic image comparison of Ag mesh/glass transparent electrodes obtained under different scanning removal methods. FIG. 3(a) is obtained under the in-line cyclic scanning removal methodAn optical microscope photograph of the Ag mesh/glass transparent electrode shows that there are Ag meshes with a mesh pitch of 800 μm on the glass surface, as shown in FIG. 3 (a). The inset of fig. 3(a) is a partial enlarged view of the Ag grid lines, and it can be seen from the inset of fig. 3(a) that the Ag grid lines have rough edges and have partial metal residue, so that the grid width has a larger deviation than the pre-designed 40 μm. FIG. 3(b) is an optical microscope photograph of the Ag mesh/glass transparent electrode obtained under the frame-type series scanning removal method, and as in FIG. 3(a), the glass surface also formed Ag meshes with a mesh pitch of 800 μm. As can be seen from the partially enlarged view of Ag grid lines in fig. 3(b), the edges of the grid lines are relatively flat, no metal residue occurs in the line-like cyclic scanning method, and the grid width is consistent with the pre-designed 40 μm. Through detection, the average light transmittance (T) of the Ag grid/glass transparent electrode with the grid spacing of 800 mu m in the 400-800 nm wave band is removed according to linear cyclic scanningav) 84.50% square resistance (R)sh) Is 9.7 omega/sq; removing the average light transmittance (T) of the Ag grid/glass transparent electrode with the grid spacing of 800 mu m in the wave band of 400-800 nm according to frame type series scanningav) 85.35% square resistance (R)sh) And 9.4 omega/sq. Quality factor (F)TC＝Tav 10/Rsh) The calculation result shows that the frame type series scanning removes the comprehensive photoelectric property (the quality factor is 2.18 multiplied by 10) of the prepared Ag grid/glass transparent electrode-2Ω-1) The prepared Ag grid/glass transparent electrode (quality factor of 1.91X 10) is removed by linear scanning-2Ω-1) Good results are obtained.
Example 3:
quartz glass is selected as a substrate, the quartz glass substrate is firstly cleaned, then the quartz glass substrate is placed on a sample stage of a magnetron sputtering coating instrument, and 400nm of Ag (the purity of an Ag target is 99.99%) is sputtered on the surface of the quartz glass under the sputtering power of 30W, the sputtering pressure of 4Pa and the argon atmosphere. Then placing the Ag/glass on a sample stage of a laser, adjusting the position of the sample stage, enabling the focus of a laser beam emitted by the laser after being focused by a lens to be 1.0mm above the surface of the Ag/glass, drawing a linear circulation square array and an outer frame linear composite square array by the laser beam according to EZCAD software respectively, and scanning and removing the Ag/glass surface at a line overlapping rate of 56%, wherein the scanning and removing method comprises the following steps:
for the linear circulation block array shown in fig. 1(a), linear circulation scanning removal is adopted;
for the outline border inner line type composite square array shown in fig. 1(c), a preliminary grid shape is formed by a line type cyclic scanning removal method, and then uneven portions of the grid edge are removed by outline border scanning.
The number of scanning removal times is 4, the side length (namely the grid interval) of each square in the array under the two scanning removal methods is 1.0mm, and the interval of the outer frame between the adjacent squares is 0.06 mm. Under the action of laser, Ag in the square array area is quickly heated, vaporized and removed, and the Ag layer which is not removed forms an Ag grid. The pulse width of the laser beam is 5-8 ns, the wavelength is 1064nm, the repetition frequency is 10Hz, and the laser energy density is 0.8J/cm2The scanning speed was 15mm/s and the scanning area was 15mm × 15 mm. And finally, taking out the electrode, and blowing off splashes on the surface layer by using an ear washing ball to obtain the Ag grid/glass transparent electrode.
Fig. 4 is an optical microscopic image comparison of Ag mesh/glass transparent electrodes obtained under different scanning removal methods. Fig. 4(a) is an optical microscope image of the Ag grid/glass transparent electrode obtained by the in-line cyclic scanning removal method, and it can be seen from fig. 4(a) that the Ag grid is evident on the glass surface and the Ag grid spacing is 1000 μm. The inset in fig. 4(a) is a partial enlarged view of the Ag grid lines, and it can be seen from the inset in fig. 4(a) that the edges of the grid lines are rough and there is metal residue, so that the grid width has a large deviation from the pre-designed 60 μm. FIG. 4(b) is an optical microscope photograph of the Ag mesh/glass transparent electrode obtained by the outer frame in-line composite scanning removal method, and as in FIG. 4(a), the glass surface has Ag meshes with a mesh pitch of 1000 μm. As can be seen from the partially enlarged view of Ag grid lines in fig. 4(b), the edges of the grid lines are relatively flat, no metal residue occurs under the similar line type cyclic scanning removal method, and the grid width is consistent with the predesigned 60 μm. The distance between the grids is 1000 μm after detection and removal by linear cyclic scanningThe average light transmittance (T) of the Ag grid/glass transparent electrode in a wave band of 400-800 nmav) 82.03% square resistance (R)sh) Is 4.2 omega/sq; the average light transmittance (T) of the Ag grid/glass transparent electrode with the grid spacing of 1000 mu m in the wave band of 400-800 nm is removed by the inner linear compound scanning of the outer frameav) 83.59% square resistance (R)sh) And 3.5 omega/sq. Quality factor (F)TC＝Tav 10/Rsh) The calculation result shows that the comprehensive photoelectric property (quality factor of 4.75 multiplied by 10) of the Ag grid/glass transparent electrode prepared by the inner line type compound scanning removal of the outer frame-2Ω-1) The prepared Ag grid/glass transparent electrode (quality factor of 3.28 multiplied by 10) is removed by the linear cyclic scanning-2Ω-1) Good results are obtained.
Example 4:
selecting FTO glass as a substrate, firstly cleaning the FTO glass, then placing the FTO glass on a sample table of a magnetron sputtering coating instrument, and sputtering 50nm of high-purity copper Cu (the purity of a Cu target is 99.9995%) on the surface of the FTO glass under the sputtering power of 60W, the sputtering pressure of 15Pa and the argon atmosphere. Then placing the Cu/FTO glass on a sample stage of a laser, adjusting the position of the sample stage, enabling the focus of a laser beam emitted by the laser after being focused by a lens to be 0.5mm above the surface of the Cu/FTO glass, drawing a linear circulation square array, a frame series square array and an outer frame inner linear composite square array by the laser beam according to EZCAD software, and scanning and removing the Ag/glass surface at a linear overlapping rate of 65 percent, wherein the scanning and removing method respectively comprises the following steps:
for the linear circulation block array shown in fig. 1(a), linear circulation scanning removal is adopted;
for the frame-type series square array shown in fig. 1(b), the outline outer frame of the edge of the removed area is removed to a predetermined depth, and then the inner part of the outer frame pair is sequentially reduced to be removed step by step;
for the outline border inner line type composite square array shown in fig. 1(c), a preliminary grid shape is formed by a line type cyclic scanning removal method, and then uneven portions of the grid edge are removed by outline border scanning.
The number of scanning removal times is 1, and three kinds of scanningIn the removal method, the side length (namely the grid distance) of each square in the array is 1.3mm, and the interval between every two adjacent squares is 0.08 mm. Under the action of laser, Cu in the square array area is rapidly heated, vaporized and removed, and the unremoved Cu layer forms a Cu grid. The pulse width of the laser beam is 5-8 ns, the wavelength is 355nm, the repetition frequency is 10Hz, and the laser energy density is 0.4J/cm2The scanning speed was 25mm/s and the scanning area was 15mm × 15 mm. And finally, taking out the electrode, and blowing off splashes on the surface layer by using an ear washing ball to obtain the Cu grid/FTO glass transparent electrode with the grid spacing of 1300 mu m and the grid width of 80 mu m.
FIG. 5 is a comparison of the transmission spectra of the Cu grid/FTO glass transparent electrode obtained by different scanning removal methods, and it can be seen from the comparison that the light transmittance of the Cu grid/FTO glass transparent electrode obtained by the three scanning methods is slightly reduced compared with the original FTO glass substrate, and the average light transmittance (T) of the original FTO glass substrate is obtained by calculationav) 75.19 percent, and the average light transmittance of the Cu grid/FTO glass transparent electrode prepared by adopting linear cyclic scanning removal, frame type series scanning removal and outer frame linear composite scanning removal at the wave band of 400-800 nm is 72.04 percent, 72.81 percent and 73.59 percent respectively. Through detection, the square resistances of the Cu grid/FTO glass transparent electrode prepared by adopting linear cyclic scanning removal, frame type series scanning removal and outer frame linear composite scanning removal are respectively 6.1 omega/sq, 6.4 omega/sq and 6.2 omega/sq, and compared with the original FTO glass substrate (the square resistance is 9.6 omega/sq), the conductivity is obviously improved. Finally passing the quality factor (F)TC＝Tav 10/Rsh) Comparing the comprehensive performance of the transparent electrode, and determining the quality factor of the Cu grid/FTO glass transparent electrode under the linear cyclic scanning removal method to be 6.2 multiplied by 10-3Ω-1And the quality factor of the Cu grid/FTO glass transparent electrode under the frame type series scanning removal method is 6.5 multiplied by 10-3Ω-1And the quality factor of the Cu grid/FTO glass transparent electrode under the outer frame inner line type composite scanning removal method is 7.5 multiplied by 10-3Ω-1And the original FTO glass substrate (quality factor of 6.0 x 10)-3Ω-1) Compared with the prior art, the lifting is improved to a certain degree, so that the lifting is visibleThe two laser scanning removal methods provided by the invention can effectively optimize the performance of the metal grid type transparent electrode.
The present invention is not limited to the above-described embodiments, and any obvious improvements, substitutions or modifications can be made by those skilled in the art without departing from the spirit of the present invention.

Claims (9)

1. The laser scanning removal method for improving the edge quality and the performance of the metal grid comprises the following steps:
firstly, cleaning a substrate, and sputtering a layer of metal with a certain thickness on the surface of the substrate by using a magnetron sputtering coating instrument; then placing the obtained metal/substrate on a sample table of a laser, adjusting the position of the sample table and related laser parameters, drawing a square array by utilizing EZCAD software, wherein the areas among squares in the square array form the shape of a grid; scanning and removing the metal/substrate by the focused laser beam according to the drawn square array to obtain a metal grid type transparent electrode; it is characterized in that the preparation method is characterized in that,
the square array is a frame series square array or an outer frame inner line type composite square array, and the square in the frame series square array is formed by nesting a plurality of squares or rectangles with different sizes; the outer frame inner line type composite square array consists of a plurality of parallel linear lines and a square or rectangle surrounding the plurality of linear lines;
the laser beam scanning method comprises the following steps:
for the frame type series square array, firstly removing the outline outer frame of the edge of the removal area to a preset depth, and then sequentially reducing the outer frame to gradually remove the inner part;
for the linear composite square array in the outer frame, a linear cyclic scanning removal method is firstly utilized to form a preliminary grid shape, and then the uneven part of the edge of the grid is removed through outer frame scanning.
2. The improvement of metal grid edge quality as set forth in claim 1The laser scanning removal method of the performance is characterized In that the substrate is glass, PET (polyethylene terephthalate), TCO/glass or TCO/PET, wherein TCO material comprises zinc oxide (ZnO) and indium oxide (In)2O3) Tin oxide (SnO)2) And doped systems thereof.
3. The laser scanning removal method for improving the quality and performance of the edge of the metal grid according to claim 1, wherein the specific cleaning process of the substrate is as follows: and sequentially putting the substrate into deionized water, acetone and absolute ethyl alcohol, ultrasonically cleaning for 10min, and then blowing in nitrogen flow for drying.
4. The laser scanning removal method for improving the quality and performance of the edge of the metal grid according to claim 1, wherein the operation process of sputtering coating is as follows: the method comprises the steps of placing a substrate on a sample table of a magnetron sputtering coating instrument, sputtering a metal layer with the thickness of 50-400 nm, wherein the sputtering power is 30-60W, the sputtering pressure is 4-15 Pa, and the working gas is argon.
5. The laser scanning removal method for improving the edge quality and performance of a metal grid according to claim 1, wherein the sputtered metal layer material is one of Ag, Cu, Au, Pt, Ni and Al.
6. The laser scanning removal method for improving the edge quality and performance of a metal grid according to claim 1, wherein an ultrashort pulse laser is selected, the pulse width of the ultrashort pulse laser is less than 20ns, the wavelength of the ultrashort pulse laser is 355-1064 nm, the focal point of the laser beam after being focused by the lens is located 0.5-1.0 mm above the surface layer of the sample, and the laser energy density is 0.4-0.8J/cm2The scanning speed is 15-25 mm/s, and the scanning area of the laser beam is 15mm multiplied by 15 mm.
7. The laser scanning removal method for improving the edge quality and performance of a metal grid according to claim 1, wherein the line overlapping rate is 56% to 65% when the laser scans in each block.
8. The laser scanning removal method for improving the edge quality and performance of the metal grid according to claim 1, wherein the side length of each square in the square array is 0.8-1.3 mm.
9. The laser scanning removal method for improving the edge quality and performance of the metal grid according to claim 1, wherein the interval between adjacent squares in the square array is 0.015-0.080 mm.
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