WO2024219376A1 - Glass sheet production method - Google Patents

Abstract

Provided is a glass sheet production method comprising: a modification step S1 for modifying a part 3, in which a through hole 10 is to be formed, by irradiating with laser beam L; and an etching step S2 for, after the modification step S1, immersing the glass sheet 2 in an etching solution 6 containing HF and thus forming the through hole 10 in the part 3 for the formation. The etching step S2 includes: a first etching step S2a for forming an initial through hole 9 in the part 3 for the formation; and a second etching step S2b for enlarging the initial through hole 9 to form the through hole 10. In the first etching step S2a, when the temperature of the etching solution 6 is x [°C] and the HF concentration of the etching solution 6 is y [mol/L], a relational expression of -0.04x+2.4≤y≤-0.04x+3.2 is established.

Description

Glass plate manufacturing method

The present invention relates to a method for manufacturing a glass plate having a through hole.

For example, glass plates with minute through-holes for wiring (through electrodes, etc.) are used as substrates for tiling displays (micro LEDs, etc.), bezel-less displays, glass interposers, etc.

A method for manufacturing a glass plate having this type of through hole includes, for example, a modification step in which the portion of the glass plate where the through hole is to be formed is modified by irradiating the portion with laser light, and an etching step in which a through hole is formed in the portion by etching after the modification step (see, for example, Patent Document 1).

The modified portion modified in the modification process has a higher etching speed (etching rate) than the unmodified portion not modified in the modification process. Therefore, the modified portion is preferentially removed in the etching process. Therefore, if a modified portion is formed in the portion where a through hole is to be formed, a through hole can be formed in the portion by etching.

JP 2020-196665 A

When forming through holes as described above, the closer to the main surface of the glass plate, the more easily it is etched due to the longer contact with the etching solution, and the diameter of the through hole closer to the main surface is larger than that of the central portion in the plate thickness direction, and the inner wall surface of the through hole becomes tapered. If the taper angle of the through hole becomes small, the hole diameter of the main surface of the glass plate becomes too large, which may result in problems such as the inability to form high density through holes and the inability to form a high-definition pattern on the main surface of the glass plate. Here, the taper angle of the through hole is the angle between the direction perpendicular to the plate thickness direction and the inner wall surface of the through hole (see θ2 in Figure 6 described below).

The objective of the present invention is to increase the taper angle of through holes formed in glass plates.

The inventor has made the following findings as a result of intensive research. That is, by reducing the etching rate in the etching process, it is possible to increase the selectivity ratio (etching rate of modified part/etching rate of non-modified part) of the etching rate of the modified part in the diffusion rate-limited state to the etching rate of the non-modified part in the reaction rate-limited state. When the selectivity ratio is increased, the preferential removal of the modified part is promoted, and the taper angle of the through hole can be increased. However, the selectivity ratio does not always increase monotonically with a decrease in the etching reaction rate. In other words, if the etching reaction rate is reduced too much, at a certain point the modified part also becomes the etching reaction rate-limited, and the selectivity ratio changes from an increasing trend to a decreasing trend. In addition, since the diffusion rate and the reaction rate have different temperature dependencies, the concentration of the etching solution at which the diffusion rate-limited state transitions to the reaction rate-limited state also differs depending on the temperature of the etching solution. Therefore, it is necessary to select the optimum concentration of the etching solution according to the temperature of the etching solution.

(1) Based on the above findings, the present invention has been invented to solve the above problems. It is a method for manufacturing a glass plate having a first main surface, a second main surface, and a through hole penetrating between the first and second main surfaces, and includes a modification step of modifying a portion where a through hole is to be formed by irradiating the portion with laser light, and an etching step of forming a through hole in the portion where the through hole is to be formed by immersing the glass plate in an etching solution containing HF after the modification step. The etching step includes a first etching step of forming an initial through hole in the portion where the through hole is to be formed, and a second etching step of enlarging the initial through hole to form a through hole, and is characterized in that in the first etching step, the relational expression -0.04x+2.4≦y≦-0.04x+3.2 holds when the temperature of the etching solution is x [°C] and the HF concentration of the etching solution is y [mol/L].

In this way, by performing etching in the first etching step so that the above relationship holds, it is possible to select the optimal HF concentration of the etching solution to match the temperature of the etching solution. As a result, it is possible to form an initial through hole with a large taper angle, and it is also possible to form a through hole with an even larger taper angle.

(2) In the configuration of (1) above, the relationship -0.04x+2.4≦y≦-0.04x+3.2 holds true in both the first etching process and the second etching process.

In this way, there is no need to change the temperature of the etching solution or the HF concentration of the etching solution between the first and second etching steps. Therefore, the etching steps can be performed with a simple device configuration and control method.

(3) In the above configuration (1) or (2), the temperature of the etching solution is preferably 5°C or higher and 30°C or lower.

If the temperature of the etching solution is too low, it may freeze, making it impossible to carry out the etching process. On the other hand, if the temperature of the etching solution is too high, it may vaporize, making it difficult to maintain a constant concentration of the etching solution. By contrast, if the temperature of the etching solution is kept within the above numerical range, the occurrence of these problems can be suppressed. In other words, the concentration of the etching solution can be stabilized while preventing the etching solution from freezing.

(4) In any of the above configurations (1) to (3), it is preferable that the etching solution further contains HCl.

When etching is performed using an etching solution containing HF, fluorides containing glass components are generated as insoluble by-products. Fluorides can be a factor in reducing productivity, such as slowing down the etching rate and causing defects. However, if a mixed acid of HF and HCl is used as the etching solution as described above, the fluorides can be replaced with soluble chlorides and efficiently removed, preventing a decrease in productivity.

(5) In any of the configurations (1) to (4) above, in the first etching step, when the etching speed in the plate thickness direction of the modified portion modified in the modification step is V1 [μm/min] and the etching speed in the plate thickness direction of the unmodified portion not modified in the modification step is V2 [μm/min], it is preferable that the selectivity ratio (V1/V2) between V1 and V2 is 3.0 or more.

This promotes preferential removal of the modified area, resulting in the formation of a through hole with a good taper angle.

(6) In any of the above configurations (1) to (5), the glass plate is preferably non-alkali glass.

In this way, it is possible to produce glass plates with through holes that are ideal for display applications.

(7) The present invention, which has been invented to solve the above problems, is a method for manufacturing a glass plate having a first main surface, a second main surface, and a through hole penetrating between the first main surface and the second main surface, comprising a modification step of modifying a portion where a through hole is to be formed by irradiating the portion with laser light, and an etching step of immersing the glass plate in an etching solution containing HF after the modification step to form a through hole in the portion where the through hole is to be formed, characterized in that the etching step satisfies the relational expression -0.04x + 2.4≦y≦-0.04x + 3.2, where x [°C] is the temperature of the etching solution and y [mol/L] is the HF concentration of the etching solution.

In this way, the same effect as the configuration (1) above can be achieved.

(8) A glass plate manufactured by the method for manufacturing a glass plate having any of the configurations (1) to (6) above, characterized in that the plate thickness is 25 μm or more and 2500 μm or less, the diameter of the through hole in the first main surface or the second main surface is 3 μm or more and 500 μm or less, and the angle between the direction perpendicular to the plate thickness direction and the inner wall surface of the through hole is 75° or more.

With such a glass plate, the large taper angle makes it possible to form a high density of through holes.

(9) The present invention, which was invented to solve the above problems, is a glass plate having a first main surface, a second main surface, and a through hole penetrating between the first main surface and the second main surface, the plate thickness being 25 μm or more and 2500 μm or less, the diameter of the through hole in the first main surface or the second main surface being 3 μm or more and 500 μm or less, and the angle between the direction perpendicular to the plate thickness direction and the inner wall surface of the through hole being 75° or more.

With such a glass plate, the large taper angle makes it possible to form a high density of through holes.

According to the present invention, it is possible to increase the taper angle of the through hole formed in the glass plate.

FIG. 2 is a flow diagram showing a method for producing a glass plate according to an embodiment of the present invention. FIG. 10A to 10C are cross-sectional views showing an etching step. 4 is a cross-sectional view of the glass plate in a first etching step, illustrating a state before a portion to be formed in the glass plate is penetrated. FIG. FIG. 4 is a cross-sectional view of the glass plate in a first etching step, showing a state when a portion to be formed in the glass plate has penetrated therethrough to form an initial through hole. FIG. 4 is a cross-sectional view of the glass plate in a second etching step, showing a state in which an initial through hole has been enlarged to form a glass plate having a through hole. 1 is a graph showing the relationship between the HF concentration of an etching solution and a selectivity ratio. 1 is a graph showing the relationship between the HF concentration of an etching solution and the taper angle of a through hole. 1 is a graph showing the relationship between the temperature of an etching solution and the optimum HF concentration of the etching solution.

Below, the form for implementing the present invention will be explained with reference to the drawings.

As shown in FIG. 1, the method for manufacturing a glass plate according to this embodiment includes a modification process S1 and an etching process S2.

(Modification process)
As shown in FIG. 2, the modification step S1 is a step of modifying a through-hole formation planned portion 3 in the glass plate 2 by a laser light L irradiated from a laser device 1. The formation planned portion 3 includes a modified portion 4 that has been modified by the modification step S1. The modified portion 4 extends along the plate thickness direction and has a property of being more easily etched than the unmodified non-modified portion 5 that has not been modified. The modified portion 4 is a portion that differs from the unmodified portion 5 in density, refractive index, stress, etc. The diameter of the modified portion 4 is, for example, 2 μm or more and 10 μm or less. The modified portion 4 may also include a non-through hole or a minute crack. The modified portion 4 is preferably formed continuously along the plate thickness direction, but may be formed intermittently along the plate thickness direction. When a plurality of through holes 10 (see FIG. 6 described later) are formed in the glass plate 2, a plurality of formation planned portions 3 including the modified portion 4 are also formed.

The type and irradiation conditions of the laser light L are not particularly limited as long as it is capable of forming the modified portion 4 in the portion to be formed 3. In this embodiment, the laser light L is a short-pulse laser light (picosecond laser light, nanosecond laser light, femtosecond laser light). The diameter W of the modified portion 4 can be adjusted by the spot diameter of the laser light L, for example. The spot diameter of the laser light L is, for example, 2 μm or more and 10 μm or less. The output of the laser light L is, for example, 1 W or more and 20 W or less. The focus of the laser light L is set, for example, at the middle part in the thickness direction of the glass plate 2, but is not limited to this position.

The glass plate 2 may be, for example, a glass plate made of alkali-free glass, and the glass composition preferably contains, in mass %, 58-68% SiO _{2 ,} 15-23% Al ₂ O ₃ (particularly 17-21%), 3-9% B ₂ O ₃ (particularly 5-7%), 0-1% or less of Li ₂ O + Na ₂ O + K ₂ O (particularly 0-0.5%), 1-6% MgO (particularly 1-4%), 3-13% CaO (particularly 5-10%), 0-10% SrO (particularly 0.1-3%), and 0-10% BaO (particularly 2-7%). In this way, the glass plate can be suitably used as a glass substrate for a display.

The lower limit of the thickness of the glass plate 2 before the etching process is preferably 30 μm or more, more preferably 200 μm or more, and even more preferably 400 μm or more. The upper limit of the thickness of the glass plate 2 before the etching process is preferably 3000 μm or less, more preferably 2400 μm or less, and even more preferably 1200 μm or less.

(Etching process)
The etching step S2 is a step of forming a through hole 10 penetrating in the plate thickness direction between the first main surface 2a and the second main surface 2b of the glass plate 2 in the formation-intended portion 3 including the modified portion 4. As shown in Fig. 1, the etching step S2 includes a first etching step S2a of forming an initial through hole 9 in the formation-intended portion 3, and a second etching step S2b of enlarging the initial through hole 9 to form the through hole 10.

As shown in FIG. 3, in the etching step S2, the glass plate 2 is immersed in an etching solution 6 containing HF. The etching solution 6 is stored in an etching tank 7. In this embodiment, etching proceeds simultaneously from both the first main surface 2a and the second main surface 2b of the glass plate 2.

The etching solution 6 containing HF may be, for example, an aqueous solution containing only HF as an acid, or an aqueous solution containing HF and at least one acid selected from HCl, _HNO3 , and _{H2SO4 .} By using a mixed acid of HCl or the like and HF as the etching solution 6 in this way, the poorly soluble fluorides generated as by-products during etching can be replaced with soluble chlorides and efficiently removed, thereby suppressing a decrease in productivity. In particular, it is preferable to use a mixed acid of HCl and HF as the etching solution 6.

When the etching process S2 is performed after the modification process S1, the modified area 4 is preferentially removed because the etching rate of the modified area 4 is faster than that of the non-modified area 5. As a result, as shown in Figures 4 to 6, the area to be formed 3, including the modified area 4, is gradually removed by etching. Note that in Figures 4 to 6, the symbols 2ao and 2b indicate the positions of the main surfaces 2a and 2b before etching.

In detail, as shown in FIG. 4, in the early stage of the first etching step S2a, the portion 3 to be formed does not penetrate in the plate thickness direction, and a bottomed recess 8 having a tapered inner wall surface 8a whose opening area becomes smaller toward the center in the plate thickness direction is formed on each of the first main surface 2a side and the second main surface 2b side of the portion to be formed 3.

After the bottomed recess 8 is formed, as shown in FIG. 5, in the first etching step S2a, the portion to be formed 3 is penetrated in the plate thickness direction to form an initial through hole 9. The initial through hole 9 has a tapered first inner wall surface 9a whose opening area decreases from the first main surface 2a side toward the center in the plate thickness direction, and a tapered second inner wall surface 9b whose opening area decreases from the second main surface 2b side toward the center in the plate thickness direction, and both inner wall surfaces 9a, 9b are connected to each other at the center in the plate thickness direction.

After the initial through hole 9 is formed, in the second etching process S2b, the diameter of the initial through hole 9 is enlarged, and finally, a through hole 10 having a tapered first inner wall surface 10a and a tapered second inner wall surface 10b as shown in FIG. 6 is formed.

In the first etching step S2a, when the temperature of the etching solution 6 is x [°C] and the HF concentration of the etching solution 6 is y [mol/L], the following relational expression is established: -0.04x + 2.4 ≦ y ≦ -0.04x + 3.2. In this way, the optimal HF concentration of the etching solution 6 can be selected according to the temperature of the etching solution 6. Therefore, the selection ratio (V1/V2) between the etching speed V1 [μm/min] in the thickness direction of the modified portion 4 and the etching speed V2 [μm/min] in the thickness direction of the non-modified portion 5 can be increased. As a result, the taper angle θ1 of the initial through hole 9 when the portion to be formed 3 penetrates becomes large. The taper angle θ2 of the through hole 10 that is finally formed is largely dependent on the taper angle θ1 of the initial through hole 9, so if the taper angle θ1 of the initial through hole 9 becomes large, the taper angle θ2 of the through hole 10 will inevitably become large. In this embodiment, the relationship -0.04x+2.4≦y≦-0.04x+3.2 is established in both the first etching step S2a and the second etching step S2b, but this relationship may be established only in the first etching step S2a.

In this embodiment, the first etching step S2a is performed, and then the second etching step S2b is performed consecutively. That is, after the first etching step S2a is performed, the second etching step S2b is performed in the same etching tank 7 without changing the etching conditions. This allows the etching step S2 to be performed with a simple device configuration and control method, and allows the etching step S2 to be performed without the time required to transfer the glass plate 2 to another etching tank 7 or to change the etching conditions.

The taper angle θ1 of the initial through hole 9 is preferably 75° or more, more preferably 80° or more, and even more preferably 84° or more. The taper angle θ1 of the initial through hole 9 is ideally 90°, but when the productivity of the glass plate 2 is taken into consideration, it can be, for example, 85° or less.

The temperature of the etching solution 6 is preferably 5°C or higher. The temperature of the etching solution 6 is preferably 30°C or lower, more preferably 20°C or lower, and even more preferably 15°C or lower. In this way, it is possible to prevent problems such as the etching solution 6 freezing due to the etching solution 6 becoming too cold, or the etching solution 6 becoming too hot, causing a large change in the HF concentration. Note that changes in the HF concentration can occur due to evaporation of the HF and moisture contained in the etching solution 6.

In the first etching step S2a, the selection ratio (V1/V2) is preferably 3.0 or more, more preferably 6.0 or more, and even more preferably 10.0 or more. In this way, preferential removal of the modified portion 4 is promoted, and an initial through hole 9 having a good taper angle θ1 can be formed. As a result, it becomes easier to form a through hole 10 having a large taper angle θ2. On the other hand, the upper limit of the selection ratio can be set to, for example, 12 or less. Here, the selection ratio (V1/V2) can be obtained, for example, as shown in FIG. 5, by the ratio (E1/E2) of the etching amount E1 in the plate thickness direction of the modified portion 4 when the initial through hole 9 is formed and the planned formation portion 3 is penetrated to the etching amount E2 in the plate thickness direction of the non-modified portion 5 when the initial through hole 9 is formed and the planned formation portion 3 is penetrated. The etching amounts E1 and E2 are obtained based on the position 2a0 of the main surface 2a and/or the position 2b of the main surface 2b of the glass plate 2 before etching. Specifically, for example, the etching amount E1 of the modified portion 4 can be calculated by (thickness of the glass plate 2 before etching)/2, and the etching amount E2 of the non-modified portion 5 can be calculated by [(thickness of the glass plate 2 before etching)-(thickness of the glass plate 2 when the portion to be formed 3 penetrates)]/2. When calculating the selectivity (V1/V2), the etching amounts E1 and E2 may be calculated from one glass plate 2, or, if the processing conditions are the same, the etching amounts E1 and E2 may be calculated from two glass plates 2, respectively. In this embodiment, the second etching process S2b also maintains substantially the same selectivity as the first etching process S2a.

The lower limit of the thickness of the glass plate 2 after the etching process is preferably 25 μm or more, more preferably 150 μm or more, and even more preferably 300 μm or more. The upper limit of the thickness of the glass plate 2 after the etching process is preferably 2500 μm or less, more preferably 2000 μm or less, and even more preferably 1000 μm or less.

The glass plate 2 can be used as a substrate for a tiling display (micro LED, etc.), a bezel-less display, a glass interposer, etc., or as a core substrate for a semiconductor package.

The lower limit of the diameter of the through hole 10 is preferably 3 μm or more, more preferably 20 μm or more, and even more preferably 40 μm or more on the first main surface 2a and the second main surface 2b. The upper limit of the diameter of the through hole 10 is preferably 500 μm or less, more preferably 400 μm or less, and even more preferably 200 μm or less on the first main surface 2a and the second main surface 2b. If the through hole 10 is in such a range, it can be suitably used as a substrate for a tiling display (micro LED, etc.), a bezel-less display, a glass interposer, or a core substrate for a semiconductor package.

The present invention is not limited to the configuration of the above embodiment, nor is it limited to the above-mentioned effects. Various modifications of the present invention are possible without departing from the gist of the present invention.

In the above embodiment, the etching process S2 may include a measurement process for measuring the temperature of the etching solution 6 and the HF concentration of the etching solution 6, and an adjustment process for adjusting at least one of the temperature and the HF concentration of the etching solution 6 based on the results of the measurement process. In this way, it is possible to reliably maintain the optimal HF concentration of the etching solution 6 in accordance with the temperature of the etching solution 6.

In the above embodiment, the etching step S2 may include a cleaning step in which the glass plate 2 is removed from the etching solution 6 and cleaned. In this way, impurities such as fluoride formed in the etching step S2 can be efficiently removed.

In the above embodiment, when multiple through holes 10 are formed, the multiple through holes 10 may be formed regularly and at high density.

In the above embodiment, the etching solution 6 may be stirred while the etching step S2 is being performed. Methods of stirring the etching solution 6 include vibrating the etching solution 6 with ultrasonic waves, and stirring the etching solution 6 by rotating or vibrating a stirring member. In addition, the output of ultrasonic waves or the rotation speed or vibration frequency of the stirring member may be changed while the etching step S2 is being performed.

In the above embodiment, the first etching step S2a is followed by the second etching step S2b, but this is not limited to the above. The etching conditions may be changed between the first etching step S2a and the second etching step S2b. For example, in the first etching step S2a, the initial through hole 9 is not formed, so the etching liquid in the recess 8 cannot move in the plate thickness direction. Therefore, even if the stirring speed of the etching liquid 6 is increased in the first etching step S2a, the exchange efficiency of the etching liquid 6 in the recess 8 is difficult to improve. On the other hand, in the second etching step S2b, the initial through hole 9 is formed, so the etching liquid 6 in the initial through hole 9 can move in the plate thickness direction. Therefore, in the second etching step S2b, the stirring speed of the etching liquid 6 can be increased to improve the exchange efficiency of the etching liquid in the initial through hole 9. In addition, after the first etching step S2a is performed, the glass plate 2 may be transferred to another etching tank 7, and the second etching step S2b may be performed. This allows the change in etching conditions to be completed quickly when changing the etching conditions between the first etching process S2a and the second etching process S2b.

The present invention will be described in detail below based on examples, but the present invention is not limited to these examples.

A glass plate made of alkali-free glass (OA-11 manufactured by Nippon Electric Glass Co., Ltd.) with a thickness of 500 μm before etching was prepared. Next, a modified portion was formed by irradiating the intended formation portion of the prepared glass plate with short-pulse laser light using an LPKF Vitrion 5510 device. After that, the glass plate with the modified portion formed was immersed in an etching solution containing HF and etched to form a through hole in the intended formation portion.

In the first evaluation test, when forming through holes as described above, the temperature of the etching solution was 5°C, 10°C, 20°C, and 30°C, and the HF concentration of the etching solution was changed to evaluate how the selectivity ratio (etching speed V1 in the thickness direction of the modified area/etching speed V2 in the thickness direction of the unmodified area) changed. The results of the first evaluation test are shown in Figure 7.

In addition, as a second evaluation test, when forming the through holes as described above, the temperature of the etching solution was 5°C, 10°C, 20°C, and 30°C, and an evaluation was performed to see how the taper angle of the initial through holes changed when the HF concentration of the etching solution was changed. The results of the second evaluation test are shown in Figure 8.

The results in Figure 7 also confirm that, regardless of whether the temperature of the etching solution is 5°C, 10°C, 20°C, or 30°C, there is a peak at which the selectivity is maximum as the HF concentration of the etching solution decreases. This is because, as the HF concentration of the etching solution decreases, the etching reaction in the modified area transitions from diffusion-limited to reaction-limited. In other words, the selectivity peaks at a maximum at the HF concentration at which the etching reaction in the modified area transitions from diffusion-limited to reaction-limited.

The results in Figure 8 also confirm that, regardless of whether the etching solution temperature is 5°C, 10°C, 20°C, or 30°C, the taper angle reaches a maximum peak as the HF concentration of the etching solution decreases. In addition, the change in taper angle in Figure 8 corresponds to the change in selectivity in Figure 7. In other words, regardless of whether the etching solution temperature is 5°C, 10°C, 20°C, or 30°C, it can be confirmed that the taper angle increases as the selectivity increases.

Then, in the results of Figure 8, the data for etching solution temperatures of 5°C, 10°C, 20°C, and 30°C were fitted with a quadratic function to determine the HF concentration of the etching solution (optimum HF concentration) at which the taper angle was maximum for each temperature. Figure 9 shows the relationship between the temperature of the etching solution (liquid temperature) and the optimal HF concentration of the etching solution.

When the temperature of the etching solution is x [° C.] and the optimum HF concentration of the etching solution is y [mol/L], the relationship between the optimum HF concentration of the etching solution and the temperature of the etching solution shown in FIG. 9 can be approximated by the following formula (1).
y=-0.04x+2.8 (1)

8, if the optimum HF concentration of the etching solution is within ±0.4 [mol/L] of the optimum HF concentration of the etching solution, the decrease in the taper angle of the initial through hole is 0.1° or less. Therefore, it can be seen that if the relationship between the optimum HF concentration of the etching solution and the temperature of the etching solution satisfies the following formula (2), the taper angle of the initial through hole can be maintained large.
-0.04x+2.4≦y≦-0.04x+3.2 (2)

In FIG. 8, when the temperature of the etching solution is 5° C., the four data points from the left are comparative examples that do not satisfy formula (2), and the two data points from the right are working examples that satisfy formula (2). When the temperature of the etching solution is 10° C., the three data points from the left and the one data point from the right are comparative examples that do not satisfy formula (2), and the two data points between them are working examples that satisfy formula (2). When the temperature of the etching solution is 20° C., the three data points from the left and the two data points from the right are comparative examples that do not satisfy formula (2), and the one data point between them is working examples that satisfy formula (2). When the temperature of the etching solution is 30° C., the two data points from the left and the two data points from the right are comparative examples that do not satisfy formula (2), and the two data points between them are working examples that satisfy formula (2).

Reference Signs List 1 Laser device 2 Glass plate 3 Formation target portion 4 Modified portion 5 Non-modified portion 6 Etching solution 7 Etching bath 8 Recess 9 Initial through hole 10 Through hole L Laser light S1 Modification step S2 Etching step S2a First etching step S2b Second etching step θ1 Taper angle of initial through hole θ2 Taper angle of through hole

Claims (9)

A method for producing a glass plate having a first main surface, a second main surface, and a through hole penetrating between the first main surface and the second main surface, comprising:
a modification step of modifying a portion where the through hole is to be formed by irradiating the portion with laser light; and an etching step of immersing the glass plate in an etching solution containing HF after the modification step to form the through hole in the portion where the through hole is to be formed,
the etching step includes a first etching step of forming an initial through hole in the intended formation portion, and a second etching step of enlarging the initial through hole to form the through hole,
In the first etching step, when the temperature of the etching solution is x [°C] and the HF concentration of the etching solution is y [mol / L], a relational formula of -0.04x + 2.4 ≦ y ≦ -0.04x + 3.2 is satisfied. A method for producing a glass plate, characterized in that The method for manufacturing a glass plate according to claim 1, wherein the relationship -0.04x+2.4≦y≦-0.04x+3.2 is satisfied in both the first etching step and the second etching step. The method for manufacturing a glass plate according to claim 1 or 2, wherein the temperature of the etching solution is 5°C or higher and 30°C or lower. The method for manufacturing a glass plate according to claim 1 or 2, wherein the etching solution further contains HCl. The method for manufacturing a glass plate according to claim 1 or 2, wherein in the first etching step, when the etching speed in the plate thickness direction of the modified portion modified in the modification step is V1 [μm/min] and the etching speed in the plate thickness direction of the non-modified portion not modified in the modification step is V2 [μm/min], the selectivity ratio (V1/V2) between V1 and V2 is 3.0 or more. The method for manufacturing a glass plate according to claim 1 or 2, wherein the glass plate is non-alkali glass. A method for producing a glass plate having a first main surface, a second main surface, and a through hole penetrating between the first main surface and the second main surface, comprising:
a modification step of modifying a portion where the through hole is to be formed by irradiating the portion with laser light; and an etching step of immersing the glass plate in an etching solution containing HF after the modification step to form the through hole in the portion where the through hole is to be formed,
In the etching step, when the temperature of the etching solution is x [°C] and the HF concentration of the etching solution is y [mol / L], a relational expression of -0.04x + 2.4 ≦ y ≦ -0.04x + 3.2 is satisfied. A method for manufacturing a glass plate, characterized in that A glass plate manufactured by the manufacturing method according to claim 1 or 2,
The plate thickness is 25 μm or more and 2500 μm or less,
The diameter of the through hole in the first main surface or the second main surface is 3 μm or more and 500 μm or less,
A glass plate, wherein an angle between a direction perpendicular to a plate thickness direction and an inner wall surface of the through hole is 75° or more. A glass plate having a first main surface, a second main surface, and a through hole penetrating between the first main surface and the second main surface,
The plate thickness is 25 μm or more and 2500 μm or less,
The diameter of the through hole in the first main surface or the second main surface is 3 μm or more and 500 μm or less,
A glass plate, wherein an angle between a direction perpendicular to a plate thickness direction and an inner wall surface of the through hole is 75° or more.

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