Metallized glass substrate structure with low stress and high bonding strength and preparation method thereof

Abstract

The invention relates to the technical field of semiconductors, and discloses a low-stress high-bonding-strength metalized glass substrate structure and a preparation method thereof. The metalized glass substrate structure with low stress and high bonding strength comprises a glass plate subjected to roughening and chemical modification treatment and a metalized circuit structure, and the glass plate is connected with the metalized circuit structure through an adhesive layer. According to the invention, the adhesive layer is used as an intermediate layer of the glass plate and the metalized circuit structure and can absorb and reduce the stress of the glass plate and reduce the probability of fragmentation of the glass plate, and after the glass plate is subjected to coarsening and chemical modification treatment, the bonding strength between the metalized circuit structure and the glass plate can be improved.

Description

Technical Field

[0001] The present invention relates to the field of semiconductor technology, and in particular to a metallized glass substrate structure with low stress and high bonding strength and a preparation method thereof. Background Art

[0002] In integrated circuit packaging technology, in order to improve the bonding strength between the substrate and the metallized circuit structure, it is usually necessary to roughen the surface of the substrate. The conventional practice is to use a roughening liquid to etch and roughen the surface of the substrate to form a roughened structure. For a glass substrate, the roughening time takes 30 minutes, so that the circuit and the substrate can have sufficient bonding strength when the circuit is subsequently made. The disadvantages of this roughening process are: the roughening time is long; due to the high brittleness of glass, the high roughness will cause the glass plate to break easily. Summary of the invention

[0003] The object of the present invention is to provide a metallized glass substrate structure with low stress and high bonding strength and a preparation method thereof. The preparation method and the metallized glass substrate structure prepared by the method can reduce the surface stress of the glass plate, improve the bonding strength between the metallized circuit structure and the glass plate, and the glass plate is not easy to break.

[0004] To achieve the above object, the present invention provides the following technical solutions:

[0005] On the one hand, the present invention provides a metallized glass substrate structure with low stress and high bonding strength, comprising a roughened and chemically modified glass plate and a metallized circuit structure, wherein the glass plate is connected to the metallized circuit structure via an adhesive layer.

[0006] In the present invention, the adhesive layer serves as an intermediate layer between the glass plate and the metallized circuit structure, which can absorb and reduce the stress of the glass plate, thereby reducing the probability of the glass plate breaking. After the glass plate is roughened and chemically modified, the bonding strength between the metallized circuit structure and the glass plate can be improved.

[0007] On the other hand, the present invention provides a method for preparing a metallized glass substrate structure with low stress and high bonding strength, which is used to prepare the metallized glass substrate structure with low stress and high bonding strength, comprising the following steps:

[0008] S10, providing a glass plate, and sequentially performing a roughening treatment and a chemical modification treatment on the glass plate;

[0009] S20, attaching an adhesive layer to the surface of the modified glass plate;

[0010] S30, manufacturing a metallized circuit structure on the surface of the adhesive layer to obtain a metallized glass substrate structure with low stress and high bonding strength.

[0011] Beneficial effects of the present invention: In the present invention, the adhesive layer is used as an intermediate layer between the glass plate and the metallized circuit structure, which can absorb and reduce the stress of the glass plate, thereby reducing the probability of the glass plate breaking. After the glass plate is roughened and chemically modified, the bonding strength between the metallized circuit structure and the glass plate can be improved. BRIEF DESCRIPTION OF THE DRAWINGS

[0012] In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the following briefly introduces the drawings required for use in the embodiments of the present invention. Obviously, the drawings described below are only some embodiments of the present invention, and for ordinary technicians in this field, other drawings can be obtained based on these drawings without creative work.

[0013] Figure 1 It is a schematic diagram of the metallized glass substrate structure described in Example 1 of the present invention.

[0014] In the figure:

[0015] 1. Glass plate; 1a. Roughened interface; 2. Bonding layer; 3. Glue layer; 4. Metallized circuit structure; 41. Seed layer; 42. Rewiring layer. DETAILED DESCRIPTION

[0016] The technical solution of the present invention is further described below with reference to the accompanying drawings and through specific implementation methods.

[0017] Among them, the drawings are only used for illustrative explanations, and they only represent schematic diagrams rather than actual pictures, and should not be understood as limitations on this patent; in order to better illustrate the embodiments of the present invention, some parts of the drawings may be omitted, enlarged or reduced, and do not represent the size of the actual product; for those skilled in the art, it is understandable that some well-known structures and their descriptions in the drawings may be omitted.

[0018] The same or similar numbers in the drawings of the embodiments of the present invention correspond to the same or similar parts; in the description of the present invention, it should be understood that if the terms "upper", "lower", "left", "right", "inner", "outer", etc. appear, the orientation or position relationship indicated is based on the orientation or position relationship shown in the drawings, which is only for the convenience of describing the present invention and simplifying the description, rather than indicating or implying that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation. Therefore, the terms describing the position relationship in the drawings are only used for illustrative purposes and cannot be understood as a limitation on this patent. For ordinary technicians in this field, the specific meanings of the above terms can be understood according to specific circumstances.

[0019] In the description of the present invention, unless otherwise clearly specified and limited, if the term "connection" or the like appears to indicate the connection relationship between components, the term should be understood in a broad sense, for example, it can be a fixed connection, a detachable connection, or an integral connection; it can be a mechanical connection or an electrical connection; it can be a direct connection or an indirect connection through an intermediate medium, it can be the internal connection of two components or the interaction relationship between two components. For ordinary technicians in this field, the specific meanings of the above terms in the present invention can be understood according to specific circumstances.

[0020] An embodiment of the present invention provides a metallized glass substrate structure with low stress and high bonding strength, comprising a roughened and chemically modified glass plate and a metallized circuit structure, wherein the glass plate is connected to the metallized circuit structure via an adhesive layer.

[0021] In a preferred embodiment, the glass plate has a plurality of through holes along its thickness direction, the surface of the glass plate along its thickness direction and the hole walls of the through holes are roughened and chemically modified, and the adhesive layer extends from both sides of the glass plate along its thickness direction to cover the hole walls of the through holes.

[0022] In a preferred embodiment, the material of the adhesive layer is selected from any one of BCB (benzocyclobutene) resin, PI (polyimide) resin, ABF resin, epoxy resin, phenolic resin, polytetrafluoroethylene resin, acrylic resin and their derivatives, or a composite of at least two thereof.

[0023] In a preferred embodiment, the thickness of the adhesive layer is 0.01 μm-0.25 mm.

[0024] In a preferred embodiment, after the glass plate is roughened, a roughened interface is formed on the surface of the glass plate, a bonding layer obtained by chemical modification is attached to the roughened interface, and the bonding layer is located between the roughened interface and the adhesive layer.

[0025] In a preferred embodiment, the roughness of the roughened interface is Ra=1 nm-10 μm.

[0026] On the other hand, a metallized glass substrate structure with low stress and high bonding strength is provided, and the method for preparing the metallized glass substrate structure with low stress and high bonding strength comprises the following steps:

[0027] S10, providing a glass plate, and sequentially performing a roughening treatment and a chemical modification treatment on the glass plate;

[0028] S20, attaching an adhesive layer to the surface of the modified glass plate;

[0029] S30, manufacturing a metallized circuit structure on the surface of the adhesive layer to obtain a metallized glass substrate structure with low stress and high bonding strength.

[0030] In a preferred embodiment, step S10 specifically includes:

[0031] S10a, providing a glass plate, and performing a hole-opening process on the glass plate to form a through hole;

[0032] S10b, structurally treating the surface of the glass plate and the wall of the through hole by a roughening process to form a roughened interface;

[0033] S10c, performing chemical modification treatment on the roughened interface to form a bonding layer attached to the roughened interface;

[0034] Step S20 specifically refers to attaching an adhesive layer on the surface of the bonding layer.

[0035] The roughening process is to roughen the surface of the glass plate (structural treatment) by using a roughening liquid to form a roughened interface on the surface of the glass plate, thereby increasing the surface area of ​​the glass plate and improving the bonding strength between the glass plate and the subsequently manufactured metallized circuit structure. The composition of the roughening liquid and the roughening process are conventional technologies in the art and will not be described in detail.

[0036] In a preferred embodiment, after step S10a and before step S10b, the process further includes: performing surface hardening treatment on the glass plate with the roughened interface, so that the surface of the glass plate can be more firmly and stably bonded with the bonding layer and the adhesive layer after hardening.

[0037] In a preferred embodiment, the surface hardening treatment refers to tempering the glass plate or performing an alkali metal infiltration strengthening treatment, wherein the alkali metal infiltration strengthening treatment refers to immersing the glass plate in an alkali metal solution to allow the alkali metal to penetrate into the crystal structure of the surface of the glass plate to change the crystal structure of the surface of the glass plate and make the lattice on the surface of the glass plate denser.

[0038] Among them, tempering is a conventional processing technology for glass plates, and the details will not be repeated here.

[0039] The alkali metal strengthening treatment is selected from any one of K strengthening treatment, Na strengthening treatment and Li strengthening treatment.

[0040] In a preferred embodiment, the temperature of the alkali metal solution is 400° C.-800° C., preferably 450° C.-750° C., and the soaking time is 10 min-6 h, preferably 30 min-5 h.

[0041] In a preferred embodiment, the concentration of the alkali metal solution is 10 wt.%-55 wt.%.

[0042] In a preferred embodiment, the alkali metal solution is selected from any one of chlorides, sulfates or nitrates of Na, K or Li, for example, the alkali metal solution is selected from any one of NaCl solution, KCl solution, LiCl solution, Na2SO4 solution, K2SO4 solution, Li2SO4 solution, NaNO3 solution, KNO3 solution and LiNO3 solution. In other embodiments, a combination of at least two alkali metal solutions may also be selected, which will not be described in detail.

[0043] In a preferred embodiment, in step S10, the time for the structuring treatment does not exceed 20 minutes, which is much shorter than the conventional roughening time, and can make the metallized circuit structure have good bonding strength.

[0044] In a preferred embodiment, the roughness of the roughened interface formed after the structural treatment of the glass plate is Ra=1nm-10μm, preferably Ra=10nm-100nm, more preferably 20nm-60nm, and even more preferably 25nm-50nm.

[0045] In a preferred embodiment, in step S20, the bonding layer is made of nitrogen-containing silane coupling agent, water glass or sintered glass powder, which can improve the bonding strength between the metallized circuit structure and the glass plate.

[0046] In a preferred embodiment, in step S30, the material of the adhesive layer is PI resin, ABF resin, epoxy resin or phenolic resin.

[0047] In a preferred embodiment, in step S30, the thickness of the adhesive layer is 0.01 μm-0.25 mm, preferably 0.05 μm-0.2 mm.

[0048] The material of the bonding layer is formed by the hydrolysis product of the silane coupling agent attached to the surface of the glass plate, which can reduce the surface stress of the glass plate, and at the same time, combined with the roughened interface, the bonding strength between the metallized circuit structure and the glass plate can be maximized. Among them, the silane coupling agent can be a nitrogen-containing silane coupling agent. Specifically, the glass plate that has been structured is dipped in the hydrolysis product of the nitrogen-containing silane coupling agent for 5s-10min, preferably 1min-8min, to form a bonding layer on the surface of the glass plate. Among them, the hydrolysis process of the nitrogen-containing silane coupling agent belongs to the prior art and will not be described in detail.

[0049] In a preferred embodiment, the metallized circuit structure includes a conductive column in a through hole and a circuit layer attached to the adhesive layer on both sides of the glass plate, the circuit layers on both sides are connected through the conductive column, the hole wall of the through hole is a roughened interface, and a bonding layer and an adhesive layer are attached to the hole wall, the conductive column includes a seed layer attached to the adhesive layer and a columnar conductive structure attached to the seed layer, and the circuit layer includes a seed layer and a redistribution layer located on the seed layer.

[0050] The technical solution of the present invention is further illustrated below with specific embodiments.

[0051] Example 1

[0052] The steps of the method for preparing the metallized glass substrate structure of this embodiment are as follows:

[0053] (1) providing a glass plate 1, and performing a roughening treatment on the glass plate 1 using a roughening liquid (i.e., performing a structural treatment using a roughening process) for 3 minutes to form a roughened interface 1a. After measurement, the roughness Ra of the roughened interface 1a is 35 nm;

[0054] (2) placing the glass plate 1 in a 20 wt.% NaCl solution at 500° C. for 4 h to allow Na ions to penetrate into the surface of the glass plate 1;

[0055] (3) forming a bonding layer 2 on the roughened interface 1a of the glass plate 1, wherein the bonding layer 2 is formed by providing a nitrogen-containing silane coupling agent, hydrolyzing the nitrogen-containing silane coupling agent to obtain a hydrolyzate (refer to the method for forming a coating in patent CN112951800A), and then dip-coating the hydrolyzate on the surface of the glass plate 1 having the roughened interface 1a, wherein the dip-coating is equivalent to soaking, and the dip-coating time is 3 minutes;

[0056] (4) PI resin (i.e., adhesive layer 3) is attached to bonding layer 2, and the thickness of PI resin (the maximum distance between the outer surface of PI resin and the glass plate) is 6 μm;

[0057] (5) forming a seed layer 41 on the surface of the PI resin by vacuum sputtering;

[0058] (6) Pressing a photosensitive film on the seed layer 41, and exposing and developing the photosensitive film to form a patterned window;

[0059] (7) forming a redistribution layer 42 in the patterned window by electroplating;

[0060] (8) Removing the remaining photosensitive film and etching the seed layer 41 exposed to the redistribution layer 42 to obtain Figure 1 The metallized glass substrate structure shown.

[0061] like Figure 1As shown, the metallized glass substrate structure prepared by the above method includes:

[0062] A glass plate 1, wherein the surface of the glass plate 1 has a roughened interface 1a, the roughness of the roughened interface 1a is Ra=35nm, and the roughness extreme difference value Rz is less than 1μm; metal Na is infiltrated into the roughened interface 1a;

[0063] A bonding layer 2, attached to the surface of the glass plate 1 having a roughened interface 1a;

[0064] PI resin layer (glue layer 3), with a thickness of 6 μm, attached to the bonding layer 2;

[0065] refer to Figure 1 The metallized circuit structure 4 includes a seed layer 41 attached to the PI resin layer and a redistribution layer 42 located on the seed layer 41 .

[0066] Example 2

[0067] For reference Figure 1 The steps of the preparation method of the metallized glass substrate structure of this embodiment are as follows:

[0068] (1) providing a glass plate 1, and performing a roughening treatment on the glass plate 1 using a roughening liquid (i.e., performing a structural treatment using a roughening process) for 2 minutes to form a roughened interface 1a. After measurement, the roughness Ra of the roughened interface 1a is 25 nm;

[0069] (2) placing the glass plate 1 in a KNO3 solution with a concentration of 50 wt.% and immersing it at 700°C for 1 hour to allow the metal K to penetrate into the lattice on the surface of the glass plate 1;

[0070] (3) forming a bonding layer 2 on the roughened interface 1a of the glass plate 1, wherein the bonding layer 2 is formed by providing a nitrogen-containing silane coupling agent, hydrolyzing the nitrogen-containing silane coupling agent to obtain a hydrolyzate (refer to the coating formation method in patent CN112951800A), and dip-coating the hydrolyzate on the surface of the glass plate 1 having the roughened interface 1a, wherein the dip-coating is equivalent to soaking, and the dip-coating time is 5 minutes;

[0071] (4) coating the bonding layer 2 with epoxy resin (i.e., the adhesive layer 3), wherein the thickness of the epoxy resin (the maximum distance between the outer surface of the epoxy resin and the glass plate) is 0.1 mm;

[0072] (5) forming a seed layer 41 on the epoxy resin surface by vacuum sputtering;

[0073] (6) Pressing a photosensitive film on the seed layer 41, and exposing and developing the photosensitive film to form a patterned window;

[0074] (7) forming a redistribution layer 42 in the patterned window by electroplating;

[0075] (8) Removing the remaining photosensitive film and etching the seed layer 41 exposed to the redistribution layer 42 to obtain Figure 1 The metallized glass substrate structure shown.

[0076] The structure of the metallized glass substrate of this embodiment is basically the same as that of the above-mentioned embodiment 1, except that:

[0077] The roughness of the roughened interface 1a of the glass plate 1 is Ra=25 nm; the roughened interface 1a is infiltrated with metal K;

[0078] The thickness of the epoxy resin (glue layer 3) is 0.1 mm.

[0079] Example 3

[0080] Reference Figure 1 The steps of the preparation method of the metallized glass substrate structure of this embodiment are as follows:

[0081] (1) providing a glass plate 1, and performing a roughening treatment on the glass plate 1 using a roughening liquid (i.e., performing a structural treatment using a roughening process) for 4 minutes to form a roughened interface. After measurement, the roughness of the roughened interface is Ra=45 nm;

[0082] (2) placing the glass plate 1 in a Li2SO4 solution with a concentration of 20 wt.% and immersing it at 550°C for 2.5 h to allow the metal Li to penetrate into the lattice on the surface of the glass plate 1;

[0083] (9) forming a bonding layer 2 on the roughened interface 1a of the glass plate 1, wherein the bonding layer 2 is formed by providing a nitrogen-containing silane coupling agent, hydrolyzing the nitrogen-containing silane coupling agent to obtain a hydrolyzate (refer to the coating formation method in patent CN112951800A), and dip-coating the hydrolyzate on the surface of the glass plate 1 having the roughened interface 1a, wherein the dip-coating is equivalent to soaking, and the dip-coating time is 6 minutes;

[0084] (3) ABF resin (i.e., adhesive layer 3) is laminated to the surface of bonding layer 2 by vacuum pressing, and the thickness of the ABF resin layer (the maximum distance between the outer surface of the ABF resin and the glass plate) is 0.4 mm;

[0085] (4) forming a seed layer 41 on the surface of the ABF resin layer by vacuum sputtering;

[0086] (5) Pressing a photosensitive film on the seed layer 41, and exposing and developing the photosensitive film to form a patterned window;

[0087] (6) forming a redistribution layer 42 in the patterned window by electroplating;

[0088] (7) The remaining photosensitive film is removed, and the seed layer 41 exposed on the redistribution layer 42 is etched.

[0089] The structure of the metallized glass substrate of this embodiment is basically the same as that of the above-mentioned embodiment 1, except that:

[0090] The roughness of the roughened interface 1a of the glass plate 1 is Ra=45 nm; the roughened interface 1a is infiltrated with metal Li;

[0091] The thickness of the ABF resin layer (glue layer 3) is 0.4 mm.

[0092] Example 4

[0093] This embodiment is basically the same as the above-mentioned embodiment 1, except for step (2): performing surface tempering treatment on the glass plate 1 having the roughened interface 1a.

[0094] Example 5

[0095] This embodiment is basically the same as the above-mentioned embodiment 1, except that step (2) is not included.

[0096] Comparative Example 1

[0097] The steps of the preparation method of the metallized glass substrate structure of this comparative example are as follows:

[0098] (1) providing a glass plate, and attaching a PI resin layer on the surface of the glass plate, wherein the thickness of the PI resin layer (the maximum distance between the outer surface of the PI resin and the glass plate) is 6 μm;

[0099] (2) preparing a seed layer on the surface of the PI resin layer by vacuum sputtering;

[0100] (3) Pressing a photosensitive film on the seed layer, and exposing and developing the photosensitive film to form a patterned window;

[0101] (4) making a redistribution layer in the patterned window by electroplating;

[0102] (5) Removing the remaining photosensitive film and etching the seed layer exposed on the redistribution layer.

[0103] The metallized glass substrate structure prepared by the above method includes:

[0104] A glass plate and a PI resin layer (glue layer), wherein the PI resin layer (glue layer) has a thickness of 6 μm and is attached to the surface of the glass plate;

[0105] The metallized circuit structure comprises a seed layer attached to a PI resin layer and a redistribution layer located on the seed layer.

[0106] Comparative Example 2

[0107] This comparative example is basically the same as the above-mentioned Example 1, except that step (2) and step (3) are not included.

[0108] Comparative Example 3

[0109] This comparative example is substantially the same as the above-mentioned Example 1, except that step (3) is not included.

[0110] In the above embodiments, the roughening liquid used is commonly used in the art and will not be described in detail.

[0111] The metallized glass substrate structure samples prepared in Examples 1-5 and Comparative Examples 1-3 were tested for peel strength between the metallized circuit structure and the glass plate according to the test standard "IPC-TM-6502.4.8C:1994", that is, the bonding strength between the metallized circuit structure of the metallized glass substrate structure and the glass plate. The results are shown in Table 1.

[0112] Table 1. Bonding strength between metallized circuit structure and glass plate

[0113]

[0114]

[0115] It can be seen from Table 1 that the method of the present invention can effectively improve the bonding strength between the metallized circuit structure and the glass plate.

[0116] It should be noted that the above specific implementations are only preferred embodiments of the present invention and the technical principles used. Those skilled in the art should understand that various modifications, equivalent substitutions, changes, etc. can be made to the present invention. However, as long as these changes do not deviate from the spirit of the present invention, they should be within the scope of protection of the present invention. In addition, some terms used in the specification and claims of this application are not restrictive, but are only for the convenience of description.

Claims

1. A metallized glass substrate structure with low stress and high bonding strength, characterized in that: The invention comprises a roughened and chemically modified glass plate and a metallized circuit structure, wherein the glass plate is connected to the metallized circuit structure through an adhesive layer.

2. The low stress and high bonding strength metallized glass substrate structure according to claim 1, characterized in that: The glass plate has a plurality of through holes along its thickness direction, the surface of the glass plate along its thickness direction and the hole walls of the through holes are roughened and chemically modified, and the adhesive layer extends from both sides of the glass plate along its thickness direction to cover the hole walls of the through holes.

3. The low stress and high bonding strength metallized glass substrate structure according to claim 1, characterized in that: The material of the adhesive layer is selected from any one of BCB resin, PI resin, ABF resin, epoxy resin, phenolic resin, polytetrafluoroethylene resin, acrylic resin and derivatives thereof, or a composite of at least two of them.

4. The low stress and high bonding strength metallized glass substrate structure according to claim 1, characterized in that: The thickness of the adhesive layer is 0.01 μm-0.25 mm.

5. The low stress and high bonding strength metallized glass substrate structure according to claim 1, characterized in that: After the glass plate is roughened, a roughened interface is formed on the surface of the glass plate, a bonding layer obtained by chemical modification is attached to the roughened interface, and the bonding layer is located between the roughened interface and the adhesive layer.

6. The low-stress and high-bonding-strength metallized glass substrate structure according to claim 5, characterized in that: The roughness of the roughened interface is Ra=1nm-10μm.

7. A method for preparing a metallized glass substrate structure with low stress and high bonding strength, for preparing the metallized glass substrate structure with low stress and high bonding strength as claimed in any one of claims 1 to 6, characterized in that: The following steps are involved: S10, providing a glass plate, and sequentially performing a roughening treatment and a chemical modification treatment on the glass plate; S20, attaching an adhesive layer to the surface of the modified glass plate; S30, manufacturing a metallized circuit structure on the surface of the adhesive layer to obtain a metallized glass substrate structure with low stress and high bonding strength.

8. The method for preparing a metallized glass substrate structure with low stress and high bonding strength according to claim 7, characterized in that: Step S10 specifically includes: S10a, providing a glass plate, and performing a hole-opening process on the glass plate to form a through hole; S10b, structurally treating the surface of the glass plate and the wall of the through hole by a roughening process to form a roughened interface; S10c, performing chemical modification treatment on the roughened interface to form a bonding layer attached to the roughened interface; Step S20 specifically refers to attaching an adhesive layer on the surface of the bonding layer.

9. The method for preparing a metallized glass substrate structure with low stress and high bonding strength according to claim 8, characterized in that: After step S10a and before step S10b, the method further includes: performing surface hardening treatment on the glass plate having the roughened interface.

10. The method for preparing a metallized glass substrate structure with low stress and high bonding strength according to claim 8, characterized in that: The surface hardening treatment refers to tempering the glass plate or performing an alkali metal infiltration strengthening treatment, wherein the alkali metal infiltration strengthening treatment refers to immersing the glass plate in an alkali metal solution to allow the alkali metal to infiltrate the glass plate.

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