Glass device intermediates

Abstract

To enable the provision of glass devices with thin glass substrates of 300 μm or less glass thickness more easily.SOLUTION: In the glass device manufacturing method, one or more through holes 40 are formed in the glass substrate 10, and the first wiring 14 on the first side of the glass substrate and the second wiring 15 on the second side are conducted through the through holes 40. After forming the first wiring 14, the through holes 40 are formed by etching and the glass substrate 10 is thinned, and then the wiring into the through-holes 40 and the second wiring 15 are formed, and the thickness of the glass substrate 10 after thinning is between 50 μm and 300 μm, and the through-holes 40 are conical in shape.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present invention relates to a method for manufacturing a glass device having a glass substrate with through holes, and to a glass device. [Background technology]

[0002] Conventionally, for example, as a mounting technology for LSI (Large-Scale Integration), a mounting technology using through silicon vias (TSV: Through Silicon Via) is known. Silicon substrates having through electrodes are widely used, for example, as interposers. An interposer is a substrate that relays substrates having different inter-terminal distances, such as ICs (Integrated Circuits) and printed circuit boards, each of which has different wiring design rules.

[0003] As described in Non-Patent Document 1, when forming TSVs on a silicon substrate, a method is known in which the TSVs are formed before, after, or during a process of forming elements such as transistors and circuits such as electrodes. Here, silicon substrates are expensive, and silicon is a semiconductor. For this reason, in TSV technology, insulation processing is required after forming through holes in the silicon substrate, which increases the cost of the substrate. Therefore, for example, in order to reduce the cost of the interposer, a glass substrate with through electrodes, which has through holes (TGV: Through Glass Via) formed in an inexpensive, large-area glass substrate, is attracting attention.

[0004] When a glass substrate with a through electrode is used, it is necessary to form a through hole in the glass substrate in the TGV technology. As a technology for forming a through hole in a glass substrate, for example, a technology for forming a through hole by irradiating a pulsed YAG laser as described in Patent Document 1 is known. Patent Document 2 also describes a method for forming fine holes in a photosensitive glass substrate. In the method described in Patent Document 2, a photomask is placed at a predetermined position on the photosensitive glass substrate, and ultraviolet light is irradiated to form a latent image. Next, the photosensitive glass substrate is heat-treated to crystallize the latent image. After that, a processing hole smaller than the latent image is formed in the center of the part where the latent image is formed by laser light. Next, etching is performed using hydrogen fluoride, and the crystallized part is selectively etched to form a hole. Furthermore, Patent Document 3 describes a method of forming holes in a glass plate by using a pair of upper and lower core drills on the same axis facing each other from both sides of the glass plate. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] JP 2000-61667 A [Patent Document 2] JP 2001-105398 A [Patent Document 3] Japanese Patent Application Publication No. 54-126215 [Non-patent literature]

[0006] [Non-Patent Document 1] Takashi Yoshinaga and Nene Nomura, "Trends in Research and Development of TSV Technology for 3D LSI Packaging," Science and Technology Trends, National Institute of Science and Technology Policy, April 2010, No. 10 Summary of the Invention [Problem to be solved by the invention]

[0007] Forming through holes in a glass substrate can reduce the mechanical strength of the glass substrate. In particular, when using glass with a thickness of 300 μm or less, the reduced mechanical strength can cause glass cracks during the transfer process when forming conductive parts such as circuits, making the glass substrate difficult to handle. In addition, in TSV technology, methods such as the Bosch process, which uses dry etching, have been established as a method for forming through-holes in silicon substrates. However, forming through-holes in glass substrates using dry etching takes a long time and is difficult to say is practical. In particular, forming through-holes in glass substrates with a thickness of 300 μm or less, and applying it to electronic device substrates such as interposers, are technically very difficult and difficult to say are practical.

[0008] The present invention has been made in view of the above problems, and has an object to more easily provide a glass device having a glass substrate with a glass thickness of 300 μm or less. [Means for solving the problem]

[0009] In order to solve the problem, one embodiment of the present invention relates to a method for manufacturing a glass device, in which one or more through holes are formed in a glass substrate, and a first wiring on a first surface side of the glass substrate and a second wiring on a second surface side, which is the surface opposite to the first surface, are electrically connected through the through holes, the through holes are formed by etching after the first wiring is formed, and the glass substrate is thinned, and then wiring in the through holes and the second wiring are formed to connect the first wiring and the second wiring via the wiring to the through holes, and the thickness of the glass substrate after the thinning is 50 μm or more and 300 μm or less, the shape of the through holes is a truncated cone shape with the opening on the second surface side as a bottom surface, and the relationship between the first surface side opening diameter and the second surface side opening diameter of the through holes (second surface side opening diameter / first surface side opening diameter) is 1.8 or more and 2.2 or less.

[0010] A method for manufacturing a glass device according to another aspect of the present invention includes a step of forming a first wiring on a first surface of a glass substrate, a step of supporting the first wiring side of the glass substrate on which the first wiring is formed with a support, and a step of forming a laser modified portion that serves as a starting point for forming a through hole extending from the first surface toward the surface opposite to the first surface, using a laser irradiated from the surface opposite to the first surface. A step subsequent to the step of supporting with the support and the step of forming the laser modified portion, in which etching is performed using a hydrogen fluoride etching solution from the surface opposite to the first surface of the glass substrate to form a through hole while thinning the glass substrate, and a step of forming a through hole after the step of forming the through hole, forming a through electrode inside the through hole and forming a second wiring on the surface opposite to the first surface of the glass substrate, and connecting the first wiring and the second wiring via the through electrode. The step of removing the support from the glass substrate after forming the second wiring. Effect of the Invention

[0011] According to an embodiment of the present invention, after wiring on one side, the glass substrate is thinned while forming through holes, and the processing is performed by etching, making it possible to more easily manufacture a glass device having a glass substrate with a glass thickness of 300 μm or less. In this case, if the glass substrate is supported by a support such as a glass carrier and the glass is thinned by etching while through-holes are formed, the glass substrate can be easily handled when forming conductive parts such as circuits, and it is possible to stably form glass devices with through-electrodes and a glass substrate thickness of 300 μm or less. [Brief description of the drawings]

[0012] [Figure 1] 1A to 1C are cross-sectional views showing steps of a method for manufacturing a glass device according to a first embodiment of the present invention. [Diagram 2] 5A to 5C are cross-sectional views showing steps of a method for manufacturing a glass device according to a second embodiment of the present invention. [Diagram 3] FIG. 2 is a diagram showing the relationship between the thickness T1 of a glass substrate before being thinned (reduced in thickness) and a laser modified portion M1. [Figure 4] 1 is a diagram showing the relationship between a diameter D1 of a through hole and a thickness T2 of a glass substrate after a hydrofluoric acid treatment. [Diagram 5] 1 is an example of a glass device for RF applications using the present invention. [Figure 6] 1 is a glass interposer as an example of a glass device using the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0013] Hereinafter, an embodiment of the present invention will be described with reference to the drawings. It should be noted that the following description is merely an example of the present invention, and the present invention is not limited thereto.

[0014] First Embodiment A method for manufacturing a glass device according to a first embodiment will be described with reference to FIG. (Process 1) 1(a), a laser is irradiated onto the glass substrate 10 from the first surface 10a side to form a laser-modified portion 20 that serves as the starting point of the through-hole 40. The laser-modified portion 20 is formed so as to extend downward, for example vertically, from the first surface 10a and so that its lower end remains on the glass substrate 10.

[0015] (Process 2) 1(b), a hydrofluoric acid resistant metal film 11 is formed on the first surface 10a of the glass substrate 10 to a thickness of 10 nm or more and 500 nm or less. Then, a copper layer 111 is formed on the hydrofluoric acid resistant metal film 11 to a thickness of 100 nm or more and 500 nm or less. By this step 2, a seed layer 112 is formed on the first surface 10a of the glass substrate 10. The material of the hydrofluoric acid resistant metal film 11 is appropriately selected from, for example, chromium, nickel, and nickel chromium.

[0016] (Step 3) Next, as shown in FIG. 1(c), a photoresist with a desired pattern is formed. Generally, a dry photoresist is used, but here, a direct-drawing type photosensitive film such as RD-1225 manufactured by Hitachi Chemical Co., Ltd. is used to laminate the first surface 10a side, and then a set pattern is drawn and developed to expose the seed layer 112 formed in step 2. Electricity is supplied to this exposed seed layer, and electrolytic copper plating is performed to a thickness of 2 μm to 10 μm. After plating, the unnecessary dry film resist is dissolved and peeled off, and the seed layer is etched to form wiring.

[0017] (Step 4) Next, as shown in (d) of FIG. 1, the insulating resin 12 is laminated, and a blind via is formed in the insulating resin 12 by a laser. Next, a dry film resist is laminated on top of that, and a preset pattern is drawn and developed. Thereafter, the dry film resist that is no longer needed is dissolved and peeled off, and wiring is formed. After the wiring is formed, a solder resist layer 13 is formed, and a first surface wiring layer 14, which is the wiring on the first surface 10a side, is formed.

[0018] (Step 5) Next, as shown in FIG. 1(e), a glass carrier 30 constituting a support is attached to the first-side wiring layer 14 via a temporary adhesive 35. The thickness of the glass carrier 30 is preferably in the range of 0.7 mm to 1.5 mm in consideration of transportability after thinning. The thickness of the glass carrier 30 may be appropriately set depending on the thickness of the glass substrate. Although the glass carrier 30 is exemplified as the support, the support does not have to be made of glass, and may be made of metal or resin.

[0019] (Step 6) Next, as shown in FIG. 1(f), the wiring board formed by bonding the glass carrier 30 to the glass substrate 10 via the adhesive 35 is etched with a hydrogen fluoride solution from the surface of the glass substrate 10 opposite to the first surface 10a (the surface on the lower side in the figure). The glass in the portion where the laser modified portion 20 is not formed is etched with the hydrogen fluoride solution, and is thinned parallel to the first surface 10a of the glass substrate 10. When the hydrogen fluoride solution comes into contact with the laser modified portion 20, the laser modified portion 20 is preferentially dissolved, and the through hole 40 is formed. As a result, the glass substrate 10 is thinned while the through hole 40 is formed. That is, the thinning and the formation of the through hole 40 are performed in a single etching process. The lower surface of the thinned glass substrate 10 becomes the second surface 10b on which the second surface wiring layer 15 is formed. The amount of etching with the hydrogen fluoride solution may be appropriately set depending on the thickness of the glass device. For example, when the thickness T1 of the glass substrate 10 used in step 1 is 400 μm, the amount of etching is preferably in the range of 100 μm to 350 μm. The thickness T2 of the glass substrate 10 after being thinned is preferably 50 μm or more and 300 μm or less.

[0020] (Step 7) Next, as shown in (g) of FIG. 1, the same processes as in steps 1 and 2 are performed. That is, a seed layer for power supply is formed on the second surface on which the through hole 40 is formed, and a pattern is formed with a dry film resist. Next, power is supplied to the seed layer, and electrolytic plating is performed to a thickness of 2 μm to 10 μm, and then the unnecessary dry film resist is dissolved and peeled off to form a through electrode. Thereafter, the unnecessary seed layer is removed, and an outer protective film such as an insulating resin or a solder resist is coated. The seed layer for power supply on the second surface can be made of a material different from the hydrofluoric acid-resistant metal, since no etching treatment with a hydrogen hydrofluoric acid solution is performed in the subsequent process. In this case, a metal layer made of a material different from the hydrofluoric acid-resistant metal is formed on the side of the through hole 40. Examples of materials different from the hydrofluoric acid-resistant metal include Ti, Cu, and electroless Ni, and at least one metal layer made of such a material is formed at least on the side of the through hole 40. The materials, number of layers, and the like are not limited to those described herein, and may be appropriately set as necessary. The first wiring and the second wiring are each formed by laminating at least one layer, and the number of layers may be set as required. Also, openings may be provided if external connection terminals are required. A second surface wiring layer 15, which is wiring on the second surface 10b side, is formed by coating with an outer protective film such as insulating resin or solder resist.

[0021] (Step 8) Next, as shown in FIG. 1(h), the glass carrier 30 that was temporarily attached in step 5 is removed, and the glass device is completed.

[0022] <Second embodiment> A method for manufacturing a glass device according to the second embodiment will be described with reference to FIG. (Process 1) 2(a), a hydrofluoric acid resistant metal film 11 is formed on a first surface 10a of a glass substrate 10 to a thickness of 10 nm or more and 500 nm or less, and a copper layer 111 is formed on the hydrofluoric acid resistant metal film 11 to a thickness of 100 nm or more and 500 nm or less to form a seed layer 112. The material of the hydrofluoric acid resistant metal film 11 is appropriately selected from, for example, chromium, nickel, and nickel chromium.

[0023] (Process 2) Next, as shown in FIG. 2(b), a photoresist having a preset pattern is formed on the first surface 10a of the glass substrate 10. Generally, a dry film resist is used, but here, a photosensitive film such as RD-1225 manufactured by Hitachi Chemical Co., Ltd., which is a direct drawing type, is laminated on the first surface 10a of the glass substrate 10. Next, a preset pattern is drawn and then developed to expose the seed layer 112 formed in step 1. After supplying power to this exposed seed layer to perform electrolytic copper plating to a thickness of 2 μm to 10 μm, the unnecessary dry film resist is dissolved and peeled off, the seed layer is removed, and wiring is formed.

[0024] (Step 3) Next, as shown in FIG. 2(c), the first surface 10a side is laminated with insulating resin 12, and blind vias are formed in the insulating resin 12 by a laser. Next, dry film resist is laminated, and a preset pattern is drawn and developed. Thereafter, the unnecessary dry film resist is dissolved and peeled off, and wiring is formed. After the wiring is formed, a solder resist layer 13 is formed, and a first surface wiring layer 14, which is the wiring on the first surface 10a side, is formed.

[0025] (Step 4) 2(d), the glass carrier 30 is attached to the first-side wiring layer 14 via a temporary adhesive 35. The thickness of the glass carrier 30 is preferably in the range of 0.7 mm to 1.5 mm in consideration of transportability after thinning. The thickness of the glass carrier 30 may be appropriately set depending on the thickness of the glass substrate 10.

[0026] (Step 5) 2(e), a laser is irradiated from the surface of the glass substrate 10 opposite to the first surface 10a (the lower surface in the figure) to form a laser modified portion 20 on the glass substrate 10. The laser modified portion 20 is formed perpendicular to the hydrofluoric acid resistant metal film 11 formed in step 1, and is formed so that the lower end remains inside the glass substrate 10.

[0027] (Step 6) Next, as shown in FIG. 2(f), the glass substrate on which the laser modified portion 20 was formed in step 5 is etched with a hydrogen fluoride solution from the surface opposite to the first surface 10a (the surface on the lower side in the figure). The glass in the portion on which the laser modified portion 20 is not formed is etched with the hydrogen fluoride solution, and the glass substrate 10 is thinned parallel to the first-surface wiring layer 14. When the hydrogen fluoride solution comes into contact with the laser modified portion 20, the laser modified portion 20 is preferentially dissolved, and a through hole 40 is formed. As a result, the glass substrate 10 is thinned and the through hole 40 is formed. The lower surface of the thinned glass substrate 10 becomes the second surface 10b on which the second-surface wiring layer 15 is formed. The amount of etching with the hydrogen fluoride solution may be appropriately set depending on the thickness of the glass device. For example, when the thickness T1 of the glass substrate used in step 1 is 400 μm, the amount of etching is preferably in the range of 100 μm to 350 μm. The thickness T2 of the glass substrate 10 after being thinned is preferably 50 μm or more and 300 μm or less.

[0028] (Step 7) Next, as shown in FIG. 2(g), an electroless nickel plating layer or an electroless copper plating layer is formed on the second surface 10b on which the through hole 40 is formed, as a seed layer for power supply, a pattern is formed with a dry film resist, power is supplied to the seed layer, and electrolytic plating with a thickness of 2 μm to 10 μm is formed. Then, the unnecessary dry film resist is dissolved and peeled off to form a through electrode. Then, the unnecessary seed layer is removed, and an outer protective film such as an insulating resin or a solder resist layer is coated. If an external connection terminal or the like is required, an opening may be provided. By coating an outer protective film such as an insulating resin or a solder resist layer, a second wiring layer, which is the wiring on the second surface 10b side, is formed. Here, the first-side wiring layer 14 and the second-side wiring layer 15 are each electrically connected to the through electrodes formed in the through holes 40 via the hydrofluoric acid resistant metal film 11 .

[0029] (Step 8) Next, as shown in FIG. 2(h), the glass carrier 30 that was temporarily attached in step 5 is removed, and the glass device is completed.

[0030] (Regarding the formation of laser modified parts) The laser modified portion 20 is a linear or rod-shaped area extending downward from the first surface 10a of the glass substrate 10, for example, in a direction perpendicular to the first surface 10a. The length of the laser modified portion 20 is set to be shorter than the thickness T1 of the glass substrate 10 in step 1 before being thinned; specifically, the length of the laser modified portion 20 corresponds to the thickness of the glass substrate 10 in the final glass device. The wavelength λ of the laser used to form the laser modified portion 20 inside the glass as shown in (a) of Figure 1 and (e) of Figure 2 is 535 nm or less. The wavelength λ is preferably in the range of 355 nm or more and 535 nm or less. If the wavelength λ is less than 355 nm, it may be difficult to obtain laser output, and it may be difficult to stably form the laser modified portion 20. On the other hand, if the wavelength λ is greater than 535 nm, the irradiation spot becomes larger, making it difficult to form the laser modified portion 20. In addition, due to the influence of heat, it becomes an ablation process rather than a modification process, and microcracks occur, making it easier to break.

[0031] Also, it is desirable for the laser pulse width to be in the range of picoseconds to femtoseconds. If it is longer than nanoseconds, it becomes difficult to control the amount of energy per pulse, and microcracks are likely to occur, making the material more susceptible to breakage. The energy of the laser pulse is selected to a preferred value depending on the material of the glass substrate 10 and the type of laser modified portion 20 to be formed. In one example, it is in the range of 5 μJ to 150 μJ. By increasing the energy of the laser pulse, it is possible to increase the length of the laser modified portion 20 in proportion thereto.

[0032] (Etching with hydrogen fluoride solution) The etching solution using a hydrogen fluoride solution shown in FIG. 1(f) and FIG. 2(f) contains, as the hydrogen fluoride solution, one or more inorganic acids selected from the group consisting of nitric acid, hydrochloric acid, and sulfuric acid. The concentration of hydrofluoric acid is, for example, 1.0 wt % or more and 6.0 wt % or less, and preferably 2.0 wt % or more and 5.0 wt % or less. The inorganic acid concentration is in the range of 1.0 wt% to 20.0 wt%, preferably 3.0 wt% to 16.0 wt%. The hydrogen fluoride solution set in the above range and the etching rate of 1.0 μm / min or less are preferable. The temperature of the etching solution during etching is preferably 10°C to 40°C.

[0033] Etching with the hydrogen fluoride solution is performed uniformly over the entire surface from the surface opposite to first surface 10a. At this time, etching is performed parallel to first surface 10a toward first surface 10a until it reaches laser-modified portion 20, thinning the glass. When the hydrogen fluoride solution reaches the end of laser-modified portion 20, etching of laser-modified portion 20 is performed preferentially, and through-hole 40 is formed along the position of laser-modified portion 20. At this time, etching is performed from the bottom toward the first surface 10a, so that the formed through hole 40 is processed into a truncated cone shape with a smaller diameter from the second surface 10b toward the first surface 10a, and with the opening on the second surface side having a larger diameter (bottom surface). The relationship between the first surface side opening diameter and the second surface side opening diameter (bottom surface side opening diameter) of the through hole 40 is processed so that (second surface side opening diameter / first surface side opening diameter) is 1.8 to 2.2, for example.

[0034] Here, as shown in FIG. 3 and FIG. 4, the length M1 of the laser modified portion 20 can be calculated from the glass thickness T2 after etching with the hydrogen fluoride solution and the diameter D1 of the second surface side of the through hole, and has a relationship of "M1 = (D1 / 2) + T2" or approximately "M1 = (D1 / 2) + T2". Approximately "M1 = (D1 / 2) + T2" means that "M1" and "(D1 / 2) + T2" are substantially equal, for example, |M1| / |(D1 / 2) + T2)| is 0.95 or more and 1.05 or less. Therefore, the length M1 of the laser modified portion 20 may be appropriately set based on the desired diameter D1 of the through hole and the glass thickness T2 after etching. In addition, the amount of etching with the hydrogen fluoride solution can be calculated from "T1-T2", which is the thickness to be thinned. According to the manufacturing method of the glass device of this embodiment, after wiring is provided on the first surface 10a side, the glass substrate is thinned by etching together with the through holes, making it possible to more easily manufacture a glass device having a glass substrate with a glass thickness of 300 μm or less.

[0035] In this case, while the glass substrate 10 is supported by the glass carrier 30, the glass is thinned by etching and through-holes are formed at the same time, which ensures ease of handling of the glass substrate when forming conductive parts such as circuits, and makes it possible to stably form glass devices with through-electrodes and a glass substrate thickness of 300 μm or less. The etching process for thinning the glass and forming the through holes does not necessarily have to be performed all at once, and may be performed in a number of steps. What is important is that the etching process is performed to thin the glass and form the through holes at the same time. The glass device described above can be used for glass devices such as an RF device shown in Fig. 5 and a glass interposer shown in Fig. 6. Moreover, this embodiment can be used for glass devices equipped with through electrodes by easily adjusting the plate thickness of the glass device and forming through electrodes in the through holes.

[0036] The scope of the present invention is not limited to the exemplary embodiments shown and described, but includes all embodiments that achieve equivalent effects to the object of the present invention. Moreover, the scope of the present invention is not limited to the combination of inventive features defined by the claims, but may be defined by any desired combination of specific features among all the respective disclosed features. In addition, the entire contents of Japanese Patent Application No. 2018-110668 (filed June 8, 2018), from which this application claims priority, are incorporated by reference into this disclosure. [Explanation of symbols]

[0037] 10: Glass substrate 11: Hydrofluoric acid resistant metal film 12: Insulating resin 13: Solder resist layer 14: First surface wiring layer (first wiring) 15: Second surface wiring layer (second wiring) 20: Laser modification section 30: Glass carrier (support) 35: Glue 40:Through hole T1: Glass substrate thickness T2: Glass substrate thickness after etching M1: Length of the laser modified part D1: Diameter of the second side of the through hole RF: RF device G-IP: Glass Interposer

Claims

1. a first wiring formed on a first surface of a glass substrate; an insulating resin layer laminated on the first surface and the first wiring so as to cover the first wiring and expose an outermost surface of the first wiring; the first wiring is made of a laminated structure in which layers made of different materials are laminated, a layer of the laminated structure in contact with the first surface is made of a hydrofluoric acid resistant metal layer containing at least a metal selected from chromium and a nickel-chromium alloy; The glass substrate has a laser modified portion extending in a thickness direction of the glass substrate inside, A support is provided above the first wiring and the insulating resin layer via an adhesive layer. Glass device intermediate.

2. a first wiring formed on a first surface of a glass substrate; an insulating resin layer laminated on the first surface and the first wiring so as to cover the first wiring and expose an outermost surface of the first wiring; the first wiring is made of a laminated structure in which layers made of different materials are laminated, a layer of the laminated structure in contact with the first surface is made of a hydrofluoric acid resistant metal layer containing at least a metal selected from chromium and a nickel-chromium alloy; The glass substrate has a laser modified portion extending in a thickness direction of the glass substrate inside, The laser modified portion has one end directly below the hydrofluoric acid resistant metal layer and the other end fixed inside the glass substrate. Glass device intermediate.

3. The thickness of the glass substrate is greater than 300 μm. The glass device intermediate according to claim 1 or 2.

4. a first wiring formed on a first surface of a glass substrate; an insulating resin layer laminated on the first surface and the first wiring so as to cover the first wiring and expose an outermost surface of the first wiring; the first wiring is made of a laminated structure in which layers made of different materials are laminated, a layer of the laminated structure in contact with the first surface is made of a hydrofluoric acid resistant metal layer containing at least a metal selected from chromium, nickel, and a nickel-chromium alloy; The glass substrate has a laser modified portion extending in a thickness direction of the glass substrate inside, A support is provided above the first wiring and the insulating resin layer via an adhesive layer. Glass device intermediate.

5. a first wiring formed on a first surface of a glass substrate; an insulating resin layer laminated on the first surface and the first wiring so as to cover the first wiring and expose an outermost surface of the first wiring; the first wiring is made of a laminated structure in which layers made of different materials are laminated, a layer of the laminated structure in contact with the first surface is made of a hydrofluoric acid resistant metal layer containing at least a metal selected from chromium, nickel, and a nickel-chromium alloy; The glass substrate has a laser modified portion extending in a thickness direction of the glass substrate inside, The laser modified portion has one end directly below the hydrofluoric acid resistant metal layer and the other end fixed inside the glass substrate. Glass device intermediate.

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