Silicate glass compositions useful for efficient production of through-glass vias - Patent Application 20070122999

Abstract

Disclosed herein are glass compositions that exhibit several advantages over glasses and other materials currently used in redistribution layers for RF, interposer, and similar applications. The glasses disclosed herein are low-cost flat glasses that have high productivity for the laser damage and etching processes used to create through glass vias (TGVs). TGVs fabricated using the silicate glasses and processes described herein have large waist diameters (D w ), which is a desirable feature for manufacturing glass articles such as interposers.

Description

Priority

[0001] This application claims the benefit of priority to U.S. Provisional Patent Application No. 62 / 846,059, filed May 10, 2019, the contents of which are relied upon and incorporated herein by reference in their entirety. [Technical Field]

[0002] The present disclosure relates to silicate glass compositions useful for the efficient manufacture of through glass vias. [Background technology]

[0003] Today, there is strong interest in thin glass with precisely formed holes for electronics applications. The holes are filled with conductive materials and used to conduct electrical signals from one component to another, providing precision connections for central processing units, memory chips, graphic processing units, or other electronic components. For such applications, substrates with metallized holes therein are commonly referred to as "interposers." Compared to currently used interposer materials, such as fiber-reinforced polymers or silicon, glass has many advantageous properties. Glass can be formed thin and smooth in large sheets without the need for polishing; it has higher stiffness and excellent dimensional stability than organic alternatives; it is a much better electrical insulator than silicon; it has better dimensional (thermal and stiffness) stability than organic options; and it can be tailored to different thermal expansion coefficients to control stack flex in integrated circuits. Because glass is an insulator, electrical losses associated with the glass element are low, while resistivity is high.

[0004] Although the diameter of the holes at the surface of the glass (also called "through glass vias" or TGVs when the etching process is complete) is wide, the diameter at the center or narrowest part of the glass (the "waist") is often much smaller. Improved TGV metallization, and therefore improved electrical performance, will result from TGVs with wider waist diameters. In particular, a wider waist diameter will help reduce the dissipation of electromagnetic energy as heat (e.g., dielectric loss, Joule heating); this can be achieved if the interposer material has a low loss angle or loss tangent. Summary of the Invention [Problem to be solved by the invention]

[0005] What is needed are new glass compositions that enable highly productive glass manufacturing and allow for the production of through-glass vias with large waist diameters. Ideally, the glass compositions would also have desirable electrical properties for use in laminated integrated circuits and other electronics technologies. The subject matter of the present disclosure addresses these needs. [Means for solving the problem]

[0006] Disclosed herein are glass compositions that exhibit several advantages over glasses and other materials currently used in redistribution layers for RF, interposer, and similar applications. The glasses disclosed herein are low-cost flat glasses that have high productivity for the laser damage and etching processes used to create through-glass vias (TGVs). TGVs made using the silicate glasses and processes described herein have large waist diameters, a desirable feature for manufacturing glass articles such as interposers.

[0007] In a first embodiment, a silicate glass article comprises one or more through-glass vias; (a) The through glass via has a first surface diameter (D S1 ), second surface diameter (D S2), and waist diameter (D w ) and D S1 / D w The ratio of is 1:1 to 2:1, and D S2 / D w The ratio is 1:1 to 2:1, (b) the silicate glass comprises (1) B2O3 in an amount of at least 5 mol%, or (2) Al2O3 in an amount of less than 10 mol% and a total amount of RO less than 10 mol%, where R is Mg, Ca, Ba, Sr, or any combination thereof.

[0008] In a second embodiment, the silicate glass article of the first embodiment has B2O3 in an amount of at least 10 mol %.

[0009] In a third embodiment, the silicate glass article of the first embodiment has B2O3 in an amount from 5 mol% to 30 mol%.

[0010] In a fourth embodiment, the silicate glass article of the first embodiment has B2O3 in an amount of 5 mol% to 20 mol%.

[0011] In a fifth embodiment, the silicate glass article of the first embodiment has Al2O3 in an amount less than 7.5 mol%.

[0012] In a sixth aspect, the silicate glass article of the first aspect has Al2O3 in an amount less than 5 mol%.

[0013] In a seventh aspect, the silicate glass article of the first aspect has Al2O3 in an amount from 1 mol% to 5 mol%.

[0014] In an eighth embodiment, the silicate glass article of the first embodiment has an amount of RO less than 7.5 mol %.

[0015] In a ninth embodiment, the silicate glass article of the first embodiment has an amount of RO less than 5 mol %.

[0016] In a tenth aspect, the silicate glass article of the first aspect has RO in an amount from 1 mol % to 5 mol %.

[0017] In an eleventh embodiment, the silicate glass article of the first embodiment has Al2O3 in an amount from 1 mol% to 5 mol% and RO in an amount from 1 mol% to 5 mol%.

[0018] In a twelfth embodiment, the silicate glass article of the first embodiment comprises B2O3 in an amount of at least 5 mol%, SiO2 in an amount from 50 mol% to 75 mol%, Al2O3 in an amount from 4 mol% to 20 mol%, MgO in an amount from 0 mol% to 20 mol%, CaO in an amount from 0 mol% to 20 mol%, SrO in an amount from 0 mol% to 15 mol%, BaO in an amount from 0 mol% to 15 mol%, and PO5 in an amount from 0 mol% to 10 mol%.

[0019] In a thirteenth embodiment, the silicate glass article of the first embodiment further comprises P2O5, wherein the silicate glass article comprises Al2O3 in an amount less than 10 mol%, SiO2 in an amount between 50 mol% and 75 mol%, MgO in an amount between 0 mol% and 10 mol%, CaO in an amount between 0 mol% and 10 mol%, SrO in an amount between 0 mol% and 10 mol%, BaO in an amount between 0 mol% and 10 mol%, and P2O5 in an amount between 0 mol% and 10 mol%, with the total of RO being less than 10 mol%.

[0020] In a fourteenth embodiment, the silicate glass article of the first embodiment has a surface diameter of from 10 μm to 100 μm.

[0021] In a fifteenth embodiment, the silicate glass article of the first embodiment has a waist diameter of from 5 μm to 90 μm.

[0022] In a sixteenth embodiment, the silicate glass article of the first embodiment has a thickness of from 50 μm to 500 μm.

[0023] In a seventeenth embodiment, there is provided a method of making a through glass via in a silicate glass article, comprising: (1) irradiating the silicate glass article with a non-diffracting laser beam to form a laser beam focal line in which induced absorption occurs to form a damage track, the glass article comprising: (1) B2O3 in an amount of at least 5 mol %; or (2) Al2O3 in an amount of less than 10 mol % and RO in an amount of less than 10 mol %, where R is Mg, Ca, Ba, Sr, or any combination thereof; and (2) etching the silicate glass article with an acid-containing etchant to produce a through-glass via; The method comprising:

[0024] In an eighteenth embodiment, the laser beam of the seventeenth embodiment is formed by a picosecond laser.

[0025] In a nineteenth embodiment, the laser beam of the seventeenth embodiment has a wavelength greater than 500 nm.

[0026] In a twentieth embodiment, the laser beam of the seventeenth embodiment has a wavelength greater than 535 nm.

[0027] In a twenty-first embodiment, the laser beam of the seventeenth embodiment has a wavelength of greater than 500 nm to 1,100 nm and an output power of 40 μJ to 120 μJ.

[0028] In a twenty-second embodiment, the laser beam of the seventeenth embodiment is a laser burst.

[0029] In a twenty-third embodiment, the etching solution of the seventeenth embodiment comprises hydrofluoric acid.

[0030] In a twenty-fourth embodiment, the hydrofluoric acid of the twenty-third embodiment is an aqueous hydrofluoric acid solution having a hydrofluoric acid concentration of 1% to 50% by mass.

[0031] In a twenty-fifth embodiment, the etching solution of the twenty-third embodiment comprises hydrofluoric acid in combination with hydrochloric acid, sulfuric acid, nitric acid, acetic acid, or any combination thereof.

[0032] In a twenty-sixth embodiment, the silicate glass article of the seventeenth embodiment is etched at a temperature of from 0°C to 50°C.

[0033] In a twenty-seventh embodiment, the non-diffracting laser beam of the seventeenth embodiment is a Bessel beam or a Gaussian-Bessel beam.

[0034] In a twenty-eighth embodiment, the irradiating step of the twenty-seventh embodiment includes forming a laser beam focal line with a Bessel beam or a Gaussian-Bessel beam within the silicate glass article.

[0035] In a twenty-ninth embodiment, the etching step of the seventeenth embodiment produces etching by-products, the etching by-products having a solubility of the etching by-products in the etching solution of 0.5 g / L or more.

[0036] In a 30th embodiment, the solubility of the glass of the 29th embodiment is determined at 20° C. using an etching solution comprising 1.45 M HF and 0.8 M HNO 3 .

[0037] In a thirty-first aspect, in the method of any one of the seventeenth to thirtieth aspects, the etching rate of the damage track (E1) is greater than the etching rate of the silicate glass article undamaged by the laser (E2).

[0038] In a thirty-second embodiment, the ratio of E1 / E2 of the thirty-first embodiment is from 1 to 50.

[0039] In a thirty-third embodiment, the acid is hydrofluoric acid, and the etching rate E2 of the thirty-first embodiment is from 0.25 μm / min to 0.9 μm / min.

[0040] In a thirty-fourth aspect, a glass article is produced by the method of any one of the seventeenth to thirty-third aspects.

[0041] In a thirty-fifth embodiment, the silicate glass comprises (1) B2O3 in an amount of at least 5 mol%, or (2) Al2O3 in an amount less than 10 mol% and a total amount of RO less than 10 mol%, where R is Mg, Ca, Ba, Sr, or any combination thereof.

[0042] In a thirty-sixth embodiment, the silicate glass of the thirty-fifth embodiment comprises B2O3 in an amount of at least 5 mol%, SiO2 in an amount from 50 mol% to 75 mol%, Al2O3 in an amount from 4 mol% to 20 mol%, MgO in an amount from 0 mol% to 20 mol%, CaO in an amount from 0 mol% to 20 mol%, SrO in an amount from 0 mol% to 15 mol%, BaO in an amount from 0 mol% to 15 mol%, and P2O5 in an amount from 0 mol% to 10 mol%.

[0043] In a thirty-seventh embodiment, the silicate glass of the thirty-fifth embodiment further comprises P2O5, wherein the silicate glass comprises Al2O3 in an amount less than 10 mol%, SiO2 in an amount from 50 mol% to 75 mol%, MgO in an amount from 0 mol% to 10 mol%, CaO in an amount from 0 mol% to 10 mol%, SrO in an amount from 0 mol% to 10 mol%, BaO in an amount from 0 mol% to 10 mol%, and P2O5 in an amount from 0 mol% to 10 mol%, with the total of RO being less than 10 mol%.

[0044] The advantages of the materials, methods, and devices described herein will be set forth in part in the description that follows or may be learned by practice of the embodiments described below. The advantages described below will be realized and attained by means of the elements and combinations particularly pointed out in the appended claims. It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive. [Brief explanation of the drawings]

[0045] The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate several aspects described below. [Figure 1] Illustrative process for fabricating through-glass vias using a laser damage and etching strategy. [Figure 2] 2A-2E show a comparison of the waist diameters of two glass compositions produced by the methods described herein. [Figure 3] 3A-3C show that the solubility of glass by-products in the etching solution affects the etch rate ratio (E1 / E2) for etching through-glass vias. [Figure 4] Contour plot of via waist diameter (Dw) when top via diameter (D1) is approximately 90 μm and final glass thickness is approximately 300 μm [Figure 5] FIG. 1 shows that the solubility of glass by-products in the etching solution can be increased by decreasing the mole percent of aluminum oxide and total alkaline earth metals in the glass composition. [Figure 6] Graph showing the correlation of electronic properties (loss tangent) with B2O3 concentration for alkali-metal-free borosilicate glass DETAILED DESCRIPTION OF THE INVENTION

[0046] Before the present materials, articles, and / or methods are disclosed and described, it is to be understood that the embodiments described below are not limited to particular compounds, synthetic methods, or uses, as these may, of course, vary. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only, and is not intended to be limiting.

[0047] In this specification and in the claims that follow, reference will be made to a number of terms that shall be defined to have the following meanings.

[0048] It should be noted that, as used in this specification and the appended claims, nouns include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to an "alkaline earth metal oxide" in a glass composition includes a mixture of two or more alkaline earth metal oxides, etc.

[0049] "Optional" or "optionally" means that the subsequently described event or circumstance may or may not occur, and that the description includes instances in which the event or circumstance occurs and instances in which it does not occur. For example, the glass compositions described herein may optionally contain an alkaline earth metal oxide, where the alkaline earth metal oxide may or may not be present.

[0050] As used herein, the term "about" is used to provide flexibility to the endpoints of a range of numerical values ​​by acknowledging that a given numerical value may be "slightly more" or "slightly less" than the endpoint without affecting the desired result. For purposes of this disclosure, "about" refers to a range extending from 10% below that numerical value to 10% above that numerical value. For example, if the numerical value is 10, then "about 10" means between 9 and 11, inclusive of the endpoints of 9 and 11.

[0051] Throughout this specification, unless the context requires otherwise, the word "comprise" or variations such as "comprising" will be understood to include the inclusion of a stated element, integer, step, or group of elements, integers, or steps, and not the exclusion of any other element, integer, step, or group of elements, integers, or steps.

[0052] As used herein, a "through glass via (TGV)" is a microscopic hole through a glass article. In one embodiment, a TGV is filled or metallized with a conductive material such as copper. A TGV refers to a single through glass via.

[0053] The TGV has a surface opening and extends across the glass article. As used herein, "surface diameter" refers to the diameter (usually measured in μm) of the TGV at either surface of the glass, and here refers to the first surface diameter (D S1 ) and the second surface diameter (D S2) TGVs also have a "waist." As used herein, a "waist diameter" refers to the diameter of the TGV at its waist (also typically measured in μm), the waist being the narrowest point of the TGV and located within the glass between the first and second faces. Unless otherwise specified, the length of a TGV refers to the linear dimension of the TGV in the thickness direction of the glass article, and the diameter of a TGV refers to the linear dimension of the TGV in the direction transverse to the thickness dimension of the glass article. The term "diameter" is used with respect to TGVs even when the cross-sectional shape of the TGV deviates from a purely circular shape. In such cases, the diameter refers to the longest linear dimension of the cross-sectional shape of the TGV (e.g., the major axis if the TGV has an elliptical cross-sectional shape). As used herein, the thickness direction of a glass article is the smallest of the length, height, and width dimensions of the glass article. When TGVs are formed by a process that includes creating damage tracks with a laser (see below), the thickness direction of the glass article corresponds to the direction of propagation of the laser beam.

[0054] The term "RO" refers individually or collectively to alkaline earth metal oxides and includes any one or combination of two or more of MgO, CaO, SrO, and BaO. The "amount" of RO present in a composition refers to the sum of the mole percent of MgO, CaO, SrO, and BaO present in that composition.

[0055] References in the specification and claims to the atomic percent of a particular element in a composition or article refer to the molar relationship between that element or component and any other element or component in the composition or article for which the atomic percent is expressed. Thus, in a composition containing 2 atomic percent of component X and 5 atomic percent of component Y, X and Y are present in a molar ratio of 2:5, and are present in such ratio regardless of whether additional components are used in the composition.

[0056] As used herein, a plurality of items, structural elements, compositional elements, and / or materials may be presented in common lists for convenience. However, these lists should be construed as though each member of the list were individually identified as a separate and unique member. Therefore, no individual member of any such list should be construed as a de facto equivalent of any other member of the same list based solely on presentation in a common group, unless indicated to the contrary.

[0057] Concentrations, amounts, and other numerical data may be expressed or presented herein in range format. It should be understood that such range format is used merely for convenience and brevity and, therefore, should be interpreted flexibly to include not only the numerical values ​​expressly recited as the limits of the range, but also all individual numerical values ​​or subranges subsumed within that range, as if each numerical value and subrange were expressly recited. As an example, a numerical range of "about 1" to "about 5" should be interpreted not only to include the explicitly recited value of about 1 to about 5, but also to include each individual value and subrange within that recited range. Thus, this numerical range includes individual values ​​such as 2, 3, and 4, subranges such as 1 to 3, 2 to 4, 3 to 5, about 1 to about 3, and about 1 to 3, as well as 1, 2, 3, 4, and 5 individually. The same principle applies to ranges reciting only one numerical value as the minimum or maximum value. Furthermore, such interpretation should apply regardless of the literal width or range described.

[0058] Disclosed are materials and components that can be used in, can be used with, can be used in preparation for, or are products of the disclosed compositions and methods. These and other materials are disclosed herein, and where combinations, subsets, interactions, groups, etc. of these materials are disclosed, it should be understood that each is specifically contemplated and described herein, even if specific reference to each of the various individual combinations and permutations of these compounds is not expressly disclosed. For example, where alkali metal oxide additives are disclosed and contemplated, and multiple different alkaline earth metal oxide additives are contemplated, each and every possible combination of alkali metal oxide additives and alkaline earth metal oxide additives is specifically contemplated unless specifically stated otherwise. For example, if groups A, B, and C of alkali metal oxide additives and groups D, E, and F of alkaline earth metal oxide additives are disclosed, and an exemplary combination of A+D is disclosed, then each is individually and collectively contemplated, even if each is not individually listed. Thus, in this example, each of the combinations A+E, A+F, B+D, B+E, B+F, C+D, C+E, and C+F is specifically contemplated and should be construed from the disclosure of the exemplary combinations of A, B, and C; D, E, and F; and A+D. Likewise, any subset or combination of these is also specifically contemplated and disclosed. Thus, for example, the subgroups A+E, B+F, and C+E are specifically contemplated and should be construed from the disclosure of the exemplary combinations A, B, and C; D, E, and F; and A+D. This concept applies to all aspects of the present disclosure, including, but not limited to, steps in methods of making and using the disclosed compositions. Thus, where there are various additional steps that can be performed in any particular embodiment or combination of embodiments of the disclosed methods, each such composition should be construed as specifically contemplated and disclosed.

[0059] I. Glass Composition Disclosed herein are silicate glass compositions that can be processed by the laser damage and etching processes described herein to produce glass articles having one, several, or multiple TGVs. The glass compositions are formulated so that the formed TGVs have waist diameters that approach the respective surface diameters of the glass. Without intending to be bound by theory, the glass composition can be formulated with specific ingredients and amounts selected to increase the solubility of by-products formed during the etching process, thereby reducing the likelihood of the by-products accumulating as insoluble solids in the TGVs. The accumulation of by-products in the TGVs is undesirable because it results in a decrease in the waist diameter. By designing the glass composition to produce by-products with increased solubility during etching, the accumulation of insoluble solids in the TGVs is reduced, resulting in a larger waist diameter. This is discussed in more detail below.

[0060] The glasses disclosed herein are silicate glasses. As used herein, a silicate glass is a glass that includes SiO in an amount of 50 mol% or greater. In one embodiment, the glass composition includes SiO in an amount from about 50 mol% to about 75 mol%. In another embodiment, SiO is present at about 50, 55, 60, 65, 70, or 75 mol%, where any value can be a lower or upper endpoint (e.g., 55 to 70 mol%).

[0061] In one embodiment, the glass compositions disclosed herein include B2O3. In another embodiment, the glass compositions include B2O3 in an amount of at least 5 mol%, or at least 10 mol%. In another embodiment, the glass compositions include B2O3 in an amount from about 5 mol% to about 30 mol%. In further embodiments, B2O3 is present at about 5, 10, 15, 20, 25, or about 30 mol%, where any value can be a lower or upper endpoint (e.g., 5 to 20 mol%).

[0062] In another embodiment, the glass composition may include a small amount of Al2O3. In one embodiment, the glass composition includes Al2O3 in an amount less than 10 mol%, less than 7.5 mol%, or less than 5 mol%. In another embodiment, the glass composition includes Al2O3 in an amount from about 5 mol% to about 30 mol%, or from about 10 mol% to about 20 mol%. In another embodiment, the amount of Al2O3 in the silicate glass is at least 1 mol%, or at least 5 mol%, or at least 10 mol%. In a further embodiment, Al2O3 is present at about 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, or about 10 mol%, where any value can be a lower or upper endpoint (e.g., 1 to 5 mol%). In another embodiment, the glass does not include Al2O3.

[0063] In another embodiment, the glass composition comprises one or more alkaline earth metal oxides (RO), where the amount of RO (the sum of MgO, BaO, CaO, and SrO) is about 10 mol% or less, about 7.5 mol% or less, or about 5 mol% or less. In another embodiment, the alkaline earth metal oxides (RO) are present at about 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 mol%, where any value can be the lower and upper endpoints (e.g., 1 to 5 mol%).

[0064] In one embodiment, the glass composition comprises 0 to 10 mol% MgO, or about 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 mol% MgO, where any value can be the lower and upper endpoints (e.g., 1 to 5 mol%). In another embodiment, the glass composition comprises 0 to 10 mol% CaO, or about 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 mol% CaO, where any value can be the lower and upper endpoints (e.g., 1 to 5 mol%). In yet another embodiment, the glass composition comprises 0 to 10 mol% SrO, or about 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 mol% SrO, where any value can be the lower and upper endpoints (e.g., 1 to 5 mol%). In another embodiment, the glass composition comprises 0 to 10 mol% BaO, or about 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 mol% BaO, where any value can be a lower or upper endpoint (e.g., 1 to 5 mol%).

[0065] In another embodiment, the glass composition comprises MgO, CaO, BaO, SrO, or any combination thereof, where the sum of MgO, CaO, BaO, and SrO is 0 to 10 mol%, or about 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 mol%, where any value can be a lower or upper endpoint (e.g., 1 to 5 mol%).

[0066] In another embodiment, the glass composition includes small amounts of Al2O3 and RO. In one embodiment, the glass composition includes (1) Al2O3 in an amount less than 10 mol%, less than 7.5 mol%, or less than 5 mol%, and (2) RO in an amount less than 10 mol%, less than 7.5 mol%, or less than 5 mol%. In another embodiment, the glass composition includes no Al2O3 and RO in an amount of 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 mol%, where any value can be a lower and upper endpoint (e.g., 5 to 10 mol%).

[0067] In yet another embodiment, the glass composition contains 0 to 10 mol% P2O5, or 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 mol% P2O5, where any value can be a lower or upper endpoint (e.g., 1 to 5 mol%).

[0068] In another embodiment, the glass composition comprises B2O3 in an amount of at least 5 mol%, SiO2 in an amount from 50 mol% to 75 mol%, Al2O3 in an amount from 4 mol% to 20 mol%, MgO in an amount from 0 mol% to 20 mol%, CaO in an amount from 0 mol% to 20 mol%, SrO in an amount from 0 mol% to 15 mol%, BaO in an amount from 0 mol% to 15 mol%, and P2O5 in an amount from 0 mol% to 10 mol%.

[0069] In another aspect, the glass composition comprises Al2O3 in an amount less than 10 mol%, SiO2 in an amount between 50 mol% and 75 mol%, MgO in an amount between 0 mol% and 10 mol%, CaO in an amount between 0 mol% and 10 mol%, SrO in an amount between 0 mol% and 10 mol%, BaO in an amount between 0 mol% and 10 mol%, and PO5 in an amount between 0 mol% and 10 mol%, and RO is less than 10 mol%.

[0070] In one embodiment, the glass composition can be manufactured into glass sheets and / or other glass articles using high productivity processes, hi a further embodiment, the glass composition can be processed by a fusion draw, float, or rolling process.

[0071] The "fusion draw" process is a method for forming high-performance flat glass. In the fusion draw process, raw materials are introduced into a melting tank at temperatures greater than 1,000°C. The molten glass is thoroughly mixed and then projected in a uniform stream into the air, where it is lengthened and begins to cool as it is fed into a drawing machine. In one embodiment, glass formed by this process does not require surface polishing. In another embodiment, glass formed by this process has a uniform thickness and can withstand large amounts of heat. In one embodiment, the glasses disclosed herein can be formed into sheets using the fusion draw process.

[0072] The "float" process of forming glass is another method for forming flat glass. After the raw materials are melted and mixed, the molten glass flows onto a bath of hot tin. Float-formed glass may require surface polishing and / or other post-fabrication processing. In one embodiment, the glasses disclosed herein can be formed into sheets using the float process.

[0073] As used herein, the "rolling" process of forming glass is similar to the drawing process, but is performed horizontally on rollers. Glass sheets produced using the rolling process require grinding and polishing. In one embodiment, the glasses disclosed herein can be formed into sheets using the rolling process.

[0074] II. Process for Manufacturing Through Glass Vias The process for producing through-glass vias in silicate glass articles comprises the steps of (1) irradiating a silicate glass article with a laser beam to produce a damage track, and (2) etching the glass article with an acid to produce the through-glass vias, each of which is described in detail below.

[0075] a. Formation of scars The first step of the process described herein involves creating one or more damage tracks in a silicate glass article. As used herein, a "damage track" is an area of ​​glass that has been structurally altered by irradiation with a laser. The damage track is shown in FIG. 1 as a dotted line through the laser-damaged glass. In some embodiments, the damage track has a lower refractive index than the surrounding undamaged glass. In one embodiment, the lower refractive index may be due to volumetric expansion of the glass in the laser-irradiated area. In further embodiments, the glass at the damage track has a lower density than the surrounding undamaged glass. In one embodiment, the damage track is a small depression on the surface of the glass. In another embodiment, the damage track is cylindrical or columnar in shape and extends partially or completely through the glass. In some embodiments, the damage track comprises a bubble, void, or gap. The damage track may also be referred to as a "pilot hole."

[0076] The damage track can be created using several different techniques. In one embodiment, a pulsed laser beam is focused into a laser beam focal line oriented along the beam propagation direction and directed toward a glass article, where the laser beam focal line causes induced absorption in the glass. This induced absorption creates a damage track along the laser beam focal line in the glass. As used herein, "induced absorption" refers to multiphoton or nonlinear absorption of the laser beam. In another embodiment, the glass article is transparent to the wavelength of the laser beam. As used herein, transparency refers to a linear absorption by the glass article of less than 10% of the laser wavelength per mm of thickness. As used herein, a laser beam focal line corresponds to a substantially cylindrical irradiated area in the glass article with a central axis extending in the direction of the damage track and a length greater than 0.1 mm. The intensity of the laser light is substantially uniform throughout the laser beam focal line and is sufficiently high throughout the laser beam focal line to cause induced absorption.

[0077] In another embodiment, by successfully utilizing a dedicated optical delivery system and a picosecond pulsed laser, damage tracks can be formed in a glass article with as few as a single laser pulse (or a single pulse burst) required to form each damage track. In a further embodiment, this process allows for damage track formation rates that are 100 times or more faster than could be achieved with an ablative nanosecond laser process.

[0078] In one embodiment, the laser beam focal line can be created by using a Bessel beam, a Gaussian-Bessel beam, or other non-diffracting beam. As used herein, a non-diffracting laser beam is a laser beam that has a Rayleigh range that is at least two times larger than the Rayleigh range of a Gaussian beam at the same wavelength and with the same pulse duration. Further information regarding Bessel beams, Gaussian-Bessel beams, beam divergence, and Rayleigh range can be found in previous papers: "High Aspect Ratio Nanochannel Machining Using Single Shot Femtosecond Bessel Beams," M.K.Bhuyan et al., Appl. Phys. Lett., 97, 081102 (2010); 2 "Factor of Bessel-Gauss Beams", R. Borghi and M. Santasiero, Opt. Lett., 22, 262 (1997); and "Application of Femtosecond Bessel-Gauss Beam in Microstructuring of Transparent Materials", A. Marcinkevicius et al., in Optical Pulse and Beam Propagation III, YBBand, ed., Proc. SPIE Volume 4271, 150-15 (2001).

[0079] Furthermore, in one embodiment, the laser beam focal line can be generated using an axicon or an optical element with spherical aberration. In some embodiments, the laser beam focal line can have a length in the range of between about 0.1 mm and about 10 mm, or a length in the range of between about 0.1 mm and about 1 mm, such as about 1 mm, about 2 mm, about 3 mm, about 4 mm, about 5 mm, about 6 mm, about 7 mm, about 8 mm, or about 9 mm, and an average diameter in the range of between about 0.1 μm and about 5 μm.

[0080] In some embodiments, the pulse duration can be in the range between greater than about 1 picosecond and less than about 100 picoseconds, such as greater than about 5 picoseconds and less than about 20 picoseconds, and the repetition rate can be in the range between about 1 kHz and 4 MHz, such as in the range between about 10 kHz and 650 kHz.

[0081] In addition to single pulses at the repetition rates described above, in one embodiment, the pulses can occur in bursts of two or more pulses (e.g., three, four, five, or more) separated by periods ranging from about 1 nanosecond to about 50 nanoseconds, e.g., 10 nanoseconds to 30 nanoseconds, such as about 20 nanoseconds ± 2 nanoseconds, with an energy of at least 40 μJ per burst, and the burst repetition frequency can be in the range of about 1 kHz to about 200 kHz. In another embodiment, the energy of each individual pulse within the burst can be smaller, with the exact individual laser pulse energy depending on the number of pulses in the burst and the decay rate (e.g., exponential decay rate) of the laser pulses over time. For example, for a constant energy per burst, if a burst contains 10 individual laser pulses, then each individual laser pulse will contain less energy than if the same burst had only two individual laser pulses.

[0082] In one aspect, the damage marks are formed in the glass when a single burst of pulses collides with substantially the same position on the glass article. That is, a number of laser pulses within a single burst correspond to a single damage mark in the glass. Further, in this aspect, the glass is translated (e.g., by a stage moving at a constant speed) or the beam is moved relative to the glass, so that the individual pulses within the burst cannot be at exactly the same spatial position on the glass. However, they are close enough to each other within 1 μm to collide with the glass at substantially the same position. For example, those pulses may collide with the glass at an interval (sp) of 0 < sp ≦ 500 nm from each other. For example, when a burst of 20 pulses is applied to a position on the glass, the individual pulses within that burst collide with the glass within 250 nm of each other. Therefore, in some aspects, the interval sp is in the range from about 1 nm to about 250 nm or from about 1 nm to about 100 nm.

[0083] The damage marks created by the laser generally take the form of a structurally altered region having internal dimensions (e.g., the longest dimension (such as diameter) transverse to the propagation direction of the laser beam) in the range from about 0.1 μm to 2 μm, for example, 0.1 - 1. = 1.5 μm (according to which it contains debris resulting from damage to the glass within the laser beam focus). In a further aspect, the damage marks formed by the laser are small in size (less than one digit μm). In some embodiments, the damage marks have a diameter from 0.2 μm to 0.7 μm. In some aspects, the damage marks are not continuous holes or passages. Further, in these aspects, the diameter of the damage marks can be 5 μm or less, 4 μm or less, 3 μm or less, 2 μm or less, or 1 μm or less, where the diameter refers to the linear dimension transverse to the propagation direction of the laser beam. In some aspects, the diameter of the damage marks can be in the range greater than 100 nm to less than 2 μm, or greater than 100 nm to less than = 0.5 μm. In a further aspect, at this stage, these damage marks are not etched (i.e., they have not yet been widened by etching).

[0084] In one embodiment, the damage scar may perforate the entire thickness of the glass article, and may or may not form a continuous opening or passageway throughout the depth of the glass. In alternative embodiments, the damage scar does not extend through the entire thickness of the glass. In either of these embodiments, there will often be areas of glass debris blocking or occupying the damage scar, but they are generally small in size, e.g., on the order of microns.

[0085] In another embodiment, the glass has a plurality of damage tracks, each of which has a diameter of less than 5 μm, a spacing between adjacent damage tracks of at least 20 μm, and an aspect ratio of 20:1 or greater. The diameter of the damage tracks can be less than 1 μm.

[0086] In yet another embodiment, the glass article includes a stack of glass substrates having a plurality of damage tracks formed through the stack, the damage tracks extending through each of the glass substrates, the damage tracks being between about 1 μm and about 100 μm in diameter and having a spacing between adjacent damage tracks of about 25 μm to about 1000 μm. In one embodiment, the glass article can include at least two glass substrates separated by an air (or gas) gap of more than 10 μm. Furthermore, in this embodiment, the focal line length must be longer than the height of the stack. In another embodiment, the stack of substrates can contain substrates of different glass compositions throughout the stack.

[0087] In another aspect, in addition to translating the glass article under the laser beam, other methods for rapidly moving the laser across the surface of the glass article to form multiple damage tracks can also be used, including, but not limited to, moving an optical head that delivers the laser beam, using galvanometers and f-theta lenses, acousto-optic deflectors, spatial light modulators, etc.

[0088] In some embodiments, depending on the desired pattern of damage marks, the marks can be made at a rate of greater than about 50 damage marks / second, greater than about 100 damage marks / second, greater than about 500 damage marks / second, greater than about 1,000 damage marks / second, greater than about 2,000 damage marks / second, greater than about 3,000 damage marks / second, greater than about 4,000 damage marks / second, greater than about 5,000 damage marks / second, greater than about 6,000 damage marks / second, greater than about 7,000 damage marks / second, greater than about 8,000 damage marks / second, greater than about 9,000 damage marks / second, greater than about 10,000 damage marks / second, greater than about 25,000 damage marks / second, greater than about 50,000 damage marks / second, greater than about 75,000 damage marks / second, or greater than about 100,000 damage marks / second.

[0089] In one embodiment, the glass article is irradiated with a picosecond (ps) laser. In another embodiment, the wavelength of the irradiation is 500 nm or greater, or 535 nm or greater, or between 500 nm and 1100 nm, or 500 nm, 535 nm, 550 nm, 600 nm, 650 nm, 700 nm, 750 nm, 800 nm, 850 nm, 900 nm, 950 nm, 1000 nm, 1050 nm, or 1100 nm, where any value is the lower or upper endpoint of a range.

[0090] In a further embodiment, a single laser burst is used to irradiate the glass article. In one embodiment, the irradiation uses a power per burst of 40 μJ to 120 μJ, or 40 μJ, 50 μJ, 60 μJ, 70 μJ, 80 μJ, 90 μJ, 100 μJ, 110 μJ, or 120 μJ, where any value is the lower or upper endpoint of a range. In another embodiment, the single laser burst has a burst count of about 20, or between 10 and 30. In one embodiment, the glass article can be irradiated with a wavelength of 500 nm to 1100 nm at a power of 40 μJ to 120 μJ. In one embodiment, the glass article can be irradiated with a wavelength of 500 nm to 550 nm at a power of 40 μJ to 120 μJ.

[0091] Exemplary settings and parameters for producing damage tracks in the glass compositions described herein are provided in the Examples.

[0092] b. Etching After forming a damage track in the glass article, the glass article is etched with acid to create a through-glass via from the damage track. Acid etching can create through-glass vias with dimensions that are useful for metallization or other chemical coatings. Here, all damage tracks are expanded parallel to the target diameter in a parallel process, which is much faster than using repeated laser pulses to expand the damage track and form a via with a large diameter. In a further aspect, acid etching creates a stronger part compared to using a laser alone to form the TGV by avoiding the formation of microcracks or other damage typically caused by a laser in the sidewalls of the TGV.

[0093] The products of the reaction of the acid with the glass article are referred to herein as "etching by-products." The etching by-products may include soluble and / or insoluble compounds. As used herein, glass solubility refers to the solubility of the etching by-products in the etching solution. In one embodiment, "glass solubility in the etching solution" is the amount of glass dissolved in 1 L of etching solution.

[0094] In one embodiment, a glass article having a damage track is etched with hydrofluoric acid (HF). In another embodiment, the HF is an aqueous HF solution, the HF having a concentration of 1% to 50% by weight in water, or about 1%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, or 50% by weight in water, where any value can be the lower and upper endpoints of a range (e.g., 5% to 20% by weight). In another embodiment, the etching solution comprises an aqueous HF solution having a concentration of 1.0 M, 1.1 M, 1.2 M, 1.3 M, 1.4 M, 1.5 M, 1.6 M, 1.7 M, 1.8 M, 1.9 M, or 2 M, where any value can be the lower and upper endpoints of a range (e.g., 1.3 M to 1.5 M), and where "M" refers to concentration in units of molarity (moles / liter).

[0095] In another embodiment, the glass article is etched with HF in combination with one or more additional acids, including, but not limited to, hydrochloric acid, sulfuric acid, nitric acid, acetic acid, or any combination or aqueous variation thereof. In another embodiment, the etching solution comprises an aqueous HF solution having a concentration of 1.0M, 1.1M, 1.2M, 1.3M, 1.4M, 1.5M, 1.6M, 1.7M, 1.8M, 1.9M, or 2M (where any value can be the lower and upper endpoints of a range, e.g., 1.3M to 1.5M) combined with HNO3 having a concentration of 0.2M, 0.4M, 0.6M, 0.8M, 1.0M, 1.2M, 1.4M, 1.6M, 1.8M, or 2.0M (where any value can be the lower and upper endpoints of a range, e.g., 0.6M to 1.0M). In another embodiment, the etching solution comprises an aqueous solution of HF having a concentration of about 1.45 M and HNO 3 having a concentration of about 0.8 M.

[0096] In further embodiments, the glass article can be etched at a temperature of 0° C. to 50° C., or can be etched at 0° C., 5° C., 10° C., 15° C., 20° C., 25° C., 30° C., 35° C., 40° C., 45° C., or 50° C., where any value can be the lower or upper endpoint of a range (e.g., 10° C. to 30° C.). In another embodiment, the glass article can be etched at room temperature.

[0097] In another embodiment, the acid used is 10% HF / 15% HNO by volume. In yet another embodiment, the glass article can be etched at about 25° C. for a time sufficient to remove about 100 μm of material from the thickness of the glass article. In further embodiments, the glass article is etched for 30 minutes to 2 hours, or 40 minutes to 1.5 hours, or 50 minutes to 1 hour.

[0098] In one embodiment, the glass article to be etched can be added to a bath of acid and physically agitated. In further embodiments, the agitation can take the form of mechanical agitation, ultrasonic agitation, bubbling in the bath, etc. In one embodiment, the glass article can be immersed in an acid bath, and ultrasonic agitation at a combination of 40 kHz and 80 kHz frequencies can be used to promote fluid (e.g., etchant) penetration and fluid exchange in the damage track. Additionally, manual agitation (e.g., mechanical agitation) of the glass article within the ultrasonic field can be performed to prevent standing wave patterns from the ultrasonic field from creating "hot spots" or cavitation-related damage on the glass article and to provide macroscopic fluid flow across the glass article.

[0099] The use of the glass compositions and other process conditions described herein allows for minimizing the accumulation of etching by-products that collect within through-glass vias in glass articles. The accumulation of etching by-products that collect within through-glass vias can reduce the surface diameter D of the through-glass vias. s (As shown in Figure 1, 3, D s1 or D s2(the smaller of the two) w As used here, the waist diameter D w is the upper diameter D s1 and bottom diameter D s2 The waist diameter D is the narrowest part of the via, located between the w decreases, which is undesirable.

[0100] Accumulation of etching by-products occurs when the etching by-products contain insoluble compounds (i.e., portions of the etching by-products that are insoluble in the etching solution). These insoluble compounds become trapped in the TGV and increase the waist diameter D of the TGV. w The etching by-products typically include salts of metals present in the glass composition and the counterion (acid) of the etching solution. For example, when the etching solution is HF, fluoride salts of metals present in the glass composition are formed as etching by-products. Fluoride salts formed as etching by-products of common glass compositions include alkali metal fluorides, alkaline earth metal fluorides, aluminum fluoride, metal fluorosilicates, metal fluoroaluminates, and metal fluoroborates.

[0101] The present disclosure recognizes that the glass solubilities in etchant solutions of different possible fluoride compounds that may be present in the etchant by-products vary, and the proportion of insoluble fluoride compounds present in the etchant by-products can be controlled by selecting the glass composition. Specifically, the proportion of insoluble compounds can be reduced by minimizing the concentrations of components in the glass composition that form fluoride compounds with low solubility. For example, alkaline earth metal fluorides and fluoroaluminate compounds are known to have low solubility in acid etchants. In one embodiment, the glass compositions described herein contain low concentrations of alkaline earth metals (or alkaline earth metal oxides R0) and / or low concentrations of aluminum (or Al2O3). Preferred amounts of alkaline earth metal oxides and aluminum oxides are described in the glass compositions previously disclosed. Fluorosilicate compounds, in contrast, have relatively high solubility, and in one embodiment, the glass compositions disclosed herein have high silica (SiO2) concentrations (e.g., greater than 50 mol%).

[0102] In some embodiments, etching by-products are produced by the processes and methods described herein. In some embodiments, the etching by-products are soluble or slightly soluble in the etching solution, and the etching by-products do not precipitate in the etching solution until a predetermined concentration of etching by-products is produced by the processes and methods described herein. In some embodiments, the etching by-products have an etching by-product solubility of 0.5 g / L or greater in the etching solution. In some embodiments, the etching by-products have an etching by-product solubility of 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, or 5 g / L of the etching solution, where any value can be the lower and upper endpoints of a range (e.g., 1 to 5 g / L, 2 to 4 g / L).

[0103] In some embodiments, the etching solution used to determine the solubility of etching by-products comprises water, HF, and HNO. In some embodiments, the etching solution used to determine the solubility of etching by-products consists of water, HF at a concentration of 0.1 M to 3 M, 0.5 M to 1.8 M, 1 M to 1.6 M, or 1.3 M to 1.5 M, and HNO at a concentration of 0.1 M to 3 M, 0.2 M to 1.5 M, 0.5 M to 1 M, or 0.6 M to 0.9 M. In some embodiments, the etching solution used to determine the solubility of the etching by-products consists of water, HF at a concentration of 0.1 M to 2 M, 0.5 M to 1.8 M, 1 M to 1.6 M, or 1.3 M to 1.5 M, and HNO at a concentration of 0.1 M to 2 M, 0.2 M to 1.5 M, 0.5 M to 1 M, or 0.6 M to 0.9 M, and the solubility of the etching by-products is determined at 20° C. In some embodiments, the etching solution used to determine the solubility of the etching by-products consists of water, HF at a concentration of 1.45 M, and HNO at a concentration of 0.8 M, and the solubility of the etching by-products is determined at 20° C. Unless otherwise specified, the solubility of the etching by-products is determined for a particular process using the lowest temperature at which etching occurs during that process.

[0104] In one embodiment, the etch rate of the glass article can affect the waist diameter of a through-glass via. Referring to FIG. 1, a glass article includes a damage scar (shown by a dotted line, corresponding to the portion of glass that has been laser-treated) surrounded by undamaged glass (the portion of glass that has not been laser-treated). As shown in FIG. 1, 2, the damage scar has an etch rate E1, and the undamaged glass has an etch rate E2. The etch rates E1 and E2 are different due to differences in the physical or chemical state of the damage scar relative to the undamaged glass (e.g., see FIG. 1, 3). Typically, E1 > E2 because the damage scar contains a high concentration of structural defects that increase the reactivity of etchants (e.g., acid solutions). As etching byproducts accumulate within the damage scar, the etch rate E1 decreases. By varying the etch rate E1 relative to the etch rate E2, the waist diameter D of the via can be adjusted. w can be adjusted (i.e., increased or decreased).

[0105] In one embodiment, the etch rate ratio E1:E2 is used to determine the waist diameter D of the TGV. w can be adjusted. In one embodiment, the etch rate ratio E1:E2 is from 1 to 50, or about 10, 20, 30, 40, or 50, where any value can be the lower and upper endpoints of the range (e.g., 5 to 50, 10 to 40, or 15 to 30). In another embodiment, the etch rate ratio E1:E2 is greater than 10, greater than 20, greater than 30, or greater than 40.

[0106] In another embodiment, for example, an etching rate E2 of less than about 2 μm / min allows the etching solution (e.g., acid solution) to sufficiently penetrate the damage scar, especially when combined with agitation to replace fresh etching solution and remove dissolved material (e.g., soluble compounds that are etching by-products) from the damage scar, which is typically very narrow when first formed by the laser. In this embodiment, the damage scar propagates during etching at approximately the same rate across the thickness of the glass article (i.e., across the depth or length of the damage scar). In some embodiments, the etching rate E2 can be less than about 10 μm / min, such as less than about 5 μm / min, or less than about 2 μm / min.

[0107] In one embodiment, the etching rates E1 and E2 can be controlled by adjusting the acid concentration in the etching solution. In other embodiments, the orientation of the glass article in the etching bath, mechanical agitation, and / or the addition of surfactants to the etching solution can be modified to adjust the etching rates E1 and E2 and the attributes of the TGVs formed by expanding the damage scar. In some embodiments, the etching solution is ultrasonically agitated, and the glass article is oriented and positioned in the etching bath so that the top and bottom openings of the damage scar are substantially uniformly exposed to ultrasonic waves to promote uniform etching of the damage scar. For example, if an ultrasonic transducer is located at the bottom of the etching bath, the glass article can be oriented in the etching bath so that the surface of the glass article bearing the damage scar is perpendicular to the bottom of the etching bath rather than parallel to the bottom of the etching bath. In some embodiments, the etching bath can be mechanically agitated in the x, y, and z directions to improve the uniformity of etching of the damage scar. In some embodiments, the mechanical agitation in the x, y, and z directions can be continuous.

[0108] Using the glass compositions and processing conditions described herein, the waist diameter D w is the surface diameter D s As shown in Figure 1, s Ds1 and D s2 In one embodiment, a TGV can be produced in the glass article, which corresponds to the smaller of D s1 and D s2 In another embodiment, the ratio of the surface diameter (D s ) and waist diameter (D w ) is 1:1 to 2:1, or 1:1, 1.1:1, 1.2:1, 1.3:1, 1.4:1, 1.5:1, 1.6:1, 1.7:1, 1.8:1, 1.9:1, or 2:1, where any value can be the lower and upper endpoints of a range (e.g., 1.2:1 to 1.8:1).

[0109] In another embodiment, the waist diameter D w is the surface diameter of the via, D s about 50% or more, about 55% or more, about 60% or more, about 65% or more, about 70% or more, about 75% or more, about 80% or more, about 85% or more, about 90% or more, about 95% or more, or about 100% of s is D s1 and D s2 In another embodiment, the diameter of the waist of the hole D w is the surface diameter of the via, D s50% to 100%, 50% to 95%, 50% to 90%, 50% to 85%, 50% to 80%, 50% to 75%, 50% to 70%, 55% to 100%, 55% to 95%, 55% to 90%, 55% to 85%, 55% to 80%, 55% to 75%, 55% to 70%, 60% to 100%, 60% to 95%, 60% to 60%, 60% to 85%, 60% to 80%, 60% to 75%, 60% to 70%, 65% to 100%, 65% to 95%, 65% to 90%, 65% to 85%, 65% to 80%, 65% to 75%, 65% to 70%, 70% to 100%, 70% to 95%, 70% to 90%, 70% to 85%, 70% to 80%, 70% to 75%, 75% to 100%, 75% to 95%, 75% to 90%, 75% to 85%, 75% to 80%, 80% to 100%, 80% to 95%, 80% to 90%, 80% to 85%, 85% to 100%, 85% to 95%, 85% to 90%, 90% to 100%, 90% to 95%, or 95% to 100%, where any value may be the lower or upper endpoint of a range; s D s1 and D s2 corresponds to the smaller of

[0110] In some embodiments, a surfactant can be added to the etching solution to enhance wettability of the damage track. Without intending to be bound by theory, enhancing wettability with a surfactant reduces the diffusion time of the etching solution into the damage track, reducing the surface diameter D of the TGV. s TGV waist diameter D w The ratio of surfactant to etchant can be increased. In some embodiments, the surfactant can be any suitable surfactant that dissolves in the etchant and does not react with the acid in the etchant. In some embodiments, the surfactant is Capstone® FS-50 or "Capstone" FS-54. In some embodiments, the concentration of surfactant in mL of surfactant / L of etchant is about 1, about 1.1, about 1.2, about 1.3, about 1.4, about 1.5, about 1.6, about 1.7, about 1.8, about 1.9, about 2, or more.

[0111] Each surface diameter D of the through glass via s (i.e., D s1 and D s2 ) may vary depending on the processing conditions. In one embodiment, each surface diameter D s In another embodiment, each surface diameter D of the TGV s is 10 μm, 15 μm, 20 μm, 25 μm, 30 μm, 35 μm, 40 μm, 45 μm, 50 μm, 55 μm, 60 μm, 65 μm, 70 μm, 75 μm, 80 μm, 85 μm, 90 μm, 95 μm, or 100 μm, where any value can be a lower or upper endpoint (e.g., 20 μm to 80 μm). s In another embodiment, the waist diameter D of the TGV is 10 μm to 100 μm. w is 5 μm, 10 μm, 15 μm, 20 μm, 25 μm, 30 μm, 35 μm, 40 μm, 45 μm, 50 μm, 55 μm, 60 μm, 65 μm, 70 μm, 75 μm, 80 μm, 85 μm, or 90 μm, where any value can be a lower or upper endpoint (e.g., 10 μm to 90 μm, or 20 to 80 μm, or 3 μm to 70 μm).

[0112] The glass article may have a plurality of through-glass vias, hi one embodiment, the spacing (center-to-center) between adjacent vias is about 10 μm or more, or about 20 μm or more, or about 30 μm or more, or about 40 μm or more, or about 50 μm or more, or in the range of 10 μm to 100 μm, or in the range of 20 μm to 90 μm.

[0113] In still further embodiments, the glass article is a single glass sheet comprised of the glass composition disclosed herein. In one embodiment, the glass sheet has a thickness of 50 μm to 500 μm, or about 50, 100, 150, 200, 250, 300, 350, 400, 450, or 500 μm, where any value can be a lower or upper endpoint (e.g., 100 μm to 300 μm). In other embodiments, the glass article can be comprised of two or more glass sheets, one or more of which comprises the glass composition disclosed herein and having a thickness disclosed herein.

[0114] In one embodiment, the through glass via has an aspect ratio (ratio of length to diameter) of about 1:1 or greater, about 2:1 or greater, about 3:1 or greater, about 4:1 or greater, about 5:1 or greater, about 6:1 or greater, about 7:1 or greater, about 8:1 or greater, about 9:1 or greater, about 10:1 or greater, about 11:1 or greater, about 12:1 or greater, about 13:1 or greater, about 14:1 or greater, about 15:1 or greater, about 16:1 or greater, about 17:1 or greater, about 18:1 or greater, about 19:1 or greater, about 20:1 or greater, about 25:1 or greater, about 30:1 or greater, or about 35:1 or greater. In another embodiment, the aspect ratio of the through glass via can range from about 5:1 to about 10:1, from about 5:1 to about 20:1, from about 5:1 to about 30:1, or from about 10:1 to 20:1, or from about 10:1 to 30:1.

[0115] The damage trace is enlarged to show a diameter of D w and D sAcid etching of a glass article to form TGVs having a structure as described above can have a number of benefits: 1) the acid etching transforms the TGVs from a size too small to be practically metallized and used in an interposer (e.g., about 1 μm for the initial damage scar) to a more convenient size (e.g., 5 μm or larger); 2) the etching can take the form of what may begin as a discrete damage scar through the glass and etch it to form a continuous through-glass via; 3) the etching is a highly parallel process in which all of the damage scars in the part are expanded simultaneously to form TGVs, which is much faster than it would be if the laser had to revisit the damage scar multiple times to successively remove more material and expand the damage scar; and 4) the etching helps round off any edges or small cracks in the glass article, especially in the sidewalls of the TGVs that may occur with repeated or long-term laser application, increasing the overall strength and reliability of the material.

[0116] III. Use of glass articles with TGV In one embodiment, once formed, the glass article having TGVs may then be coated and / or filled with a conductive material, for example, by metallization, to create an interposer fabricated from the glass article. As used herein, "metallization" refers to the technique of coating a metal or other conductive material on the surface of an object or filling a TGV with a metal or conductive material. Metallization and subsequent conductivity through the TGVs is determined by the ratio of the surface diameter to the waist diameter (D s :D w ) approaches 1, the shape of the TGV becomes more cylindrical, and the cross-sectional area of ​​the metal or conductive material within the TGV becomes uniform.

[0117] In one embodiment, examples of metals or conductive materials include copper, aluminum, gold, silver, lead, tin, indium tin oxide, or combinations or alloys thereof. In another embodiment, the process used to metallize the interior of the TGV includes, for example, electroplating, electroless plating, physical vapor deposition, chemical vapor deposition, or evaporative coating. In an alternative embodiment, the TGV may be coated or lined with a catalytic material such as platinum, palladium, titanium dioxide, or other material that promotes chemical reactions within the TGV to facilitate metallization. In yet another embodiment, the TGV may be coated or lined with chemical functionalization to alter surface wetting properties or to enable attachment of biomolecules and use in biochemical analysis. Furthermore, in this embodiment, such chemical functionalization may be silanization of the glass surface of the TGV and / or the additional attachment of specific proteins, antibodies, or other biologically specific molecules designed to promote attachment of biomolecules to the surface of the TGV for the desired application.

[0118] In another embodiment, the glass composition can be modified to reduce the loss tangent. A low loss tangent means that the circuit element (e.g., an interposer) exhibits a small amount of induced absorption. In one embodiment, increasing the amount of B2O3 in the glass composition reduces the loss tangent of the glass. This embodiment is further described in the Examples. [Example]

[0119] The following examples are set forth so as to provide those of ordinary skill in the art with a complete disclosure and description of how the compounds, compositions, and methods described and claimed herein are made and evaluated, and are intended to be purely illustrative and are not intended to limit the scope of the presently disclosed discoveries. Efforts have been made to ensure accuracy with respect to numbers (e.g., amounts, temperatures, etc.), but some error and deviation should be accounted for. Unless otherwise specified, parts are parts by weight, temperatures are in °C or are ambient, and pressures are at or near atmospheric. Numerous variations and combinations of reaction conditions (e.g., concentrations of components, desired solvents, solvent mixtures, temperatures, pressures, and other reaction ranges and conditions) can be used to maximize the purity and yield of the products obtained from the described processes. No more than reasonable routine experimentation will be required to optimize such process conditions.

[0120] Example 1: Glass composition The silicate glasses having Al2O3 and RO (total of BaO, CaO, MgO, SrO) evaluated herein are given in Tables 1 and 2. Two glass samples not listed in Table 1 were also evaluated. Samples 4 and 5 were samples of Eagle XG® glass and IRIS™ glass, respectively (both available from Corning Incorporated, Corning, NY).

[0121] [Table 1]

[0122] [Table 2]

[0123] Example 2: Laser damage testing Before etching, the silicate glasses in Tables 1 and 2 were subjected to a laser treatment process to form damage tracks. The laser treatment parameters are given in Table 3. Different burst energies affect the D of different TGVs. wvalues ​​were obtained (see Examples 3 and 4 below). Glass samples were laser treated to form damage tracks using a system equipped with a Coherent Hyper-Rapid-50 picosecond laser operating at a wavelength of 532 nm. The beam delivery optics were configured to create a Gaussian-Bessel laser beam focal line. The optical intensity distribution along the beam propagation axis was 0.74 mm full width at half maximum, and the spot size was 1.2 μm in diameter, as measured by the diameter of the first null or minimum intensity in the cross-sectional profile of the Gaussian-Bessel laser beam. Each damage track was formed by exposing the substrate to a single laser burst containing 20 laser pulses (burst number = 20), where each burst had a duration of 7.2 picoseconds and the time interval between pulses within each burst was 20 nanoseconds. Laser bursts with various burst energies ranging from 16 μJ to 108 μJ were used for each experiment. The burst energies used for this test are shown in Table 3. The spacing between each damage track was 150 μm.

[0124] [Table 3]

[0125] Example 3: Glass Etching Properties After laser treatment, the glass samples were etched as follows: A 400 μm thick specimen of each glass sample was statically etched at room temperature in 1.45 M HF and 0.8 M HNO3 until the thickness was reduced to 300 μm using the procedure of Example 5. The procedure of Example 5 was also used to measure glass solubility. The etching time was recorded. In most cases, the final top diameter (D1) was close to 80 μm. The waist diameter and final thickness were measured using an optical microscope.

[0126] The following procedure was used to calculate the sludge / glass conversion ratio. The term "sludge" refers to the insoluble portion of the etching by-product. Sludge concentrations (grams / L of etching solution) were measured at different input glass concentrations (grams / L). The sludge / glass conversion ratio was determined by adding glass to the etching solution in an amount corresponding to the solubility limit to form a saturated solution of glass in the etching solution. An additional mass of glass was then added to the saturated etching solution, and the mass of sludge formed was determined. The sludge / glass conversion ratio is the ratio of the mass of sludge formed to the mass of additional glass added under these conditions. For example, if 1 gram / L of sludge is generated after 4 grams / L of glass is added to the saturated etching solution, the sludge / glass conversion ratio is 0.25. At least two to three data points were obtained, varying the sludge concentration and input glass concentration. The sludge concentration (Y-axis) was plotted against the input glass concentration (X-axis). The slope of the plot is the sludge / glass conversion rate and the intercept on the x-axis is the glass solubility in the etchant.

[0127] [Table 4]

[0128] Example 4: Comparison of different glass compositions under different laser damage conditions Glass compositions 4 and 8 were laser treated using bursts of different energies and etched as described in Examples 2 and 5. After laser treatment and etching at burst energies of 68 μJ and 79 μJ, the D w The solubility of the etched glass of glass compositions 4 and 8 was determined to be 3.4 g / L and greater than 13 g / L, respectively, as determined using the procedure of Example 5. Each glass sample had a thickness of 400 μm before etching. The etching process removed approximately 100 μm from the sample. The final top diameter D of the TGV was s1was approximately 80 μm for both glass compositions. Glass composition 8 (squares shown in FIG. 2A) exhibited a consistently higher D over a range of laser damage conditions compared to glass composition 4 (diamonds shown in FIG. 2A). w values ​​are shown. Side profiles of glass composition 4 damaged by laser bursts with energies of 68 μJ and 79 μJ, respectively, can be seen in FIGS. 2B and 2C, while side profiles of glass composition 8 damaged by laser bursts of 68 μJ and 79 μJ, respectively, can be seen in FIGS. 2D and 2E. In FIGS. 2B-2E, the bright areas correspond to undamaged glass, and the vias correspond to the dark areas between the bright areas. In the perspective views of FIGS. 2B-2E, the glass specimens are oriented so that the thickness of the glass specimen corresponds to the horizontal length of the bright spots. The approximately hourglass shape of the TGV is evident, as is the top diameter D of the TGV. s1 (left side of TGV) and bottom diameter D s2 (right side of TGV) are roughly equal.

[0129] Example 5: Determination of glass solubility in etching solutions Glass solubility in the etchant (1.45 M HF and 0.8 M HNO3) was evaluated. The etchant influences the etch rate ratio E1 / E2 for etching the damage track to form the TGV. When the etch rate E2 is relatively slow, the etchant can diffuse deep into the damage track, causing the damage track (or the TGV formed therefrom) to expand more uniformly radially along the depth of the TGV (i.e., perpendicular to the TGV depth direction). When the etch rate E2 is fast, a proportionally larger fraction of the etchant penetrates the TGV inlet (top diameter D s1 or bottom diameter D s2 The etching solution that penetrates the depth direction of the TGV is reduced, and the surface diameter D s D w becomes smaller.

[0130] Desired D w values ​​and / or higher D w / D sSolubility studies were conducted on various glass compositions to determine which were most likely to exhibit the formation of TGVs with a ratio of 0.1 g / L to 0.4 g / L. Glass solubility in a particular etchant (e.g., in 1.45 M HF and 0.8 M HNO) is defined as the maximum amount of glass that can be added to 1 liter of etchant at a specified temperature (room temperature, approximately 20°C) without exhibiting a solid precipitate (solid precipitate is less than 0.1 g / L). The unit of glass solubility used herein is grams of glass per liter of etchant, i.e., g / L.

[0131] To measure glass solubility in the etchant, the following procedure was used.

[0132] Glass powder (100 mesh) / etchant mixtures were prepared at concentrations of 4 g / L, 7 g / L, 10 g / L, and (if necessary) 13 g / L. Additional HF was added to compensate for the loss of HF during glass dissolution. Generally, 0.8 to 1 mole of additional HF is added for every 10 grams of glass powder melted. For example, 1 mole of additional HF was added to a 10 g / L glass / etchant mixture to compensate for the loss of HF during glass dissolution.

[0133] The mixture was stirred for 5 days to ensure complete reaction between the glass powder and the etching solution. The precipitate (i.e., insoluble etching by-products) was allowed to layer at the bottom of the container by settling for 1 day. The insoluble etching by-products were separated by centrifugation, air-dried, and weighed. A plot of glass / etchant concentration (X-axis) versus mass of insoluble etching by-products (Y-axis) was created. The intercept of the X-axis is the maximum amount of glass (g / L) that can be added to the etching solution without exhibiting a precipitate. This value is the reported glass solubility in the etching solution. The solubility study results and additional experimental parameters for different glass samples are given in Tables 4 and 5, respectively.

[0134] [Table 5]

[0135] Figures 3A and 3B show the side profiles (oriented vertically) of the TGVs formed at different etching rates, where the etching rate is determined by measuring the change in the thickness of the glass before and after etching. Figure 3A (glass composition 4 in Table 1) shows the side profile of the glass via when the etching rate is less than 0.9 μm / min. When the etching rate E2 is relatively slow, the etchant diffuses deep into the via as described above, and the waist diameter D w of the TGV (or damage mark) can be enlarged. Figure 3B (glass composition 2 in Table 1) shows the side profile of the glass via when the etching rate is faster than 0.9 μm / min. When the etching rate E2 is fast, the etchant is significantly consumed at the part of the TGV (or damage mark) adjacent to the point where the etchant enters the TGV. The efficient etching in the radial direction near the upper and lower surfaces consumes the etching rate and inhibits the penetration of the etchant in the depth (length) direction of the via. As a result, the waist diameter D w of the via is reduced compared to the surface diameter D s . This effect is clear when the waist diameter D w of the glass in Figure 3B is compared with the waist diameter D w of the glass in Figure 3A.

[0136] Figure 3C is a graph of the correlation between the glass solubility in the etchant (1.45 M HF and 0.8 M HNO3) and the etching rate ratio. The etching rate ratio can be significantly improved by decreasing the etching rate E2 (comparing the symbols of squares (E2 < 0.25 μm / min), diamonds (0.25 μm / min < E2 < 0.9 μm / min), and triangles (E2 > 0.9 μm / min)). When the etching rate E2 is too fast (triangles), the change in glass solubility does not significantly affect the etching rate ratio. When the etching rate E2 is between 0.25 μm / min and 0.29 μm / min, as the glass solubility increases, the etching rate ratio also increases.

[0137] Furthermore, the etching rate E2 and TGV (surface diameter D s D, which is related to the glass solubility in the etching solution (glass sheet samples with thicknesses of 90 μm and 300 μm), w As can be seen from Figure 4, which is a contour plot of the waist diameter D w can be increased more effectively by decreasing the etching rate E2 or by increasing the glass solubility in the etching solution (1.45 M HF and 0.8 M HNO3). The waist diameter D, expressed in μm, w Isosurfaces are shown using contour lines numbered 25.0, 30.0, 35.0, 40.0, and 45.0, corresponding to the values ​​of 25.0, 30.0, 35.0, 40.0, and 45.0. The black dots represent the measured values.

[0138] Example 6: Effect of Glass Composition on Glass Solubility in Etching Solutions Glass composition can also affect glass solubility in the etching solution. Figure 5 shows the effect of Al2O3 mole percent (left axis) and alkaline earth metal oxide (RO) mole percent (horizontal axis) on glass solubility in 1.45 M HF and 0.8 M HNO3 at room temperature, with the leftmost contour (contour label 12) indicating the optimal glass solubility in the etching solution. Black dots represent measured glass solubility in 1.45 M HF and 0.8 M HNO3 etching solutions expressed in units of g / L. Contour labels also correspond to glass solubility in the same etching solution expressed in a single unit of g / L. Compositions with decreasing Al2O3 and RO mole percents exhibited the highest glass solubility in the etching solution.

[0139] Example 7: Correlation of Electronic Properties with B2O3 Concentration for Alkali-Metal-Free Borosilicate Glasses Compositions with reduced mole percentages of Al2O3 and RO are favorable for TGVs, with a large ratio D w :D sHowever, reducing or eliminating RO may adversely affect the electronic properties of the glass composition. For example, when alkaline earth metal oxides are removed from the glass composition, the loss tangent is adversely affected. During the course of this disclosure, it was discovered that the loss tangent of alkali-metal-free glass compositions can be reduced by increasing the borate (BO) concentration. Figure 6 shows a plot of loss tangent versus BO in mole percent. Generally, low loss tangent performance can be achieved by increasing the borate concentration. In one embodiment, the borate concentration is greater than 5 mole percent or greater than 10 mole percent.

[0140] Throughout this publication, various publications are cited, the disclosures of which in their entireties are hereby incorporated by reference into the present application to more fully describe the methods, compositions, and compounds herein.

[0141] Various modifications and variations can be made to the materials, methods, and articles described herein. Other aspects of the materials, methods, and articles described herein will be apparent from consideration of the specification and practice of the materials, methods, and articles disclosed herein. It is intended that the specification and examples be considered as exemplary.

[0142] Preferred embodiments of the present invention will be described below in detail.

[0143] Embodiment 1 1. A silicate glass article comprising one or more through-glass vias, (a) the through glass via has a first surface diameter (D S1 ), second surface diameter (D S2 ), and waist diameter (D w ) and D S1 / D w The ratio of is 1:1 to 2:1, and D S2 / D w The ratio is 1:1 to 2:1, (b) the silicate glass comprises (1) B2O3 in an amount of at least 5 mol%, or (2) Al2O3 in an amount of less than 10 mol% and RO in an amount of less than 10 mol%, where R is Mg, Ca, Ba, Sr, or any combination thereof; (c) the silicate glass contains SiO2 in an amount of 50 mol% or more; Silicate glass articles.

[0144] Embodiment 2 2. The article of claim 1, wherein the amount of B2O3 in the silicate glass is at least 10 mol%.

[0145] Embodiment 3 2. The article of claim 1, wherein the amount of B2O3 in the silicate glass is from 5 mol% to 30 mol%.

[0146] Embodiment 4 2. The article of claim 1, wherein the amount of B2O3 in the silicate glass is from 5 mol% to 20 mol%.

[0147] Embodiment 5 5. The article of any one of claims 1 to 4, wherein the amount of Al2O3 in the silicate glass is less than 7.5 mol%.

[0148] Embodiment 6 5. The article of any one of claims 1 to 4, wherein the amount of Al2O3 in the silicate glass is less than 5 mol%.

[0149] Embodiment 7 5. The article of any one of claims 1 to 4, wherein the amount of Al2O3 in the silicate glass is from 1 mol% to 5 mol%.

[0150] Embodiment 8 8. The article of any one of claims 1 to 7, wherein the amount of RO in the silicate glass is less than 7.5 mol%.

[0151] Embodiment 9 8. The article of any one of claims 1 to 7, wherein the amount of RO in the silicate glass is less than 5 mol%.

[0152] Embodiment 10 8. The article of any one of claims 1 to 7, wherein the amount of RO in the silicate glass is 1 mol% to 5 mol%.

[0153] Embodiment 11 2. The article of claim 1, wherein the amount of Al2O3 in the silicate glass is from 1 mol% to 5 mol% and the amount of RO in the silicate glass is from 1 mol% to 5 mol%.

[0154] Embodiment 12 2. The article of claim 1, wherein the silicate glass comprises B2O3 in an amount of at least 5 mol%, SiO2 in an amount from 50 mol% to 75 mol%, Al2O3 in an amount from 4 mol% to 20 mol%, MgO in an amount from 0 mol% to 20 mol%, CaO in an amount from 0 mol% to 20 mol%, SrO in an amount from 0 mol% to 15 mol%, BaO in an amount from 0 mol% to 15 mol%, and P2O5 in an amount from 0 mol% to 10 mol%.

[0155] Embodiment 13 2. The article of claim 1, wherein the silicate glass further comprises P2O5, and the silicate glass article comprises Al2O3 in an amount less than 10 mol%, SiO2 in an amount between 50 mol% and 75 mol%, MgO in an amount between 0 mol% and 10 mol%, CaO in an amount between 0 mol% and 10 mol%, SrO in an amount between 0 mol% and 10 mol%, BaO in an amount between 0 mol% and 10 mol%, and P2O5 in an amount between 0 mol% and 10 mol%.

[0156] Embodiment 14 14. The article of any one of the preceding claims, wherein each of the first surface diameter and the second surface diameter is from 10 μm to 100 μm.

[0157] Embodiment 15 15. The article of any one of the preceding claims, wherein the waist diameter is from 5 μm to 90 μm.

[0158] Embodiment 16 16. The article of any one of claims 1 to 15, wherein the article has a thickness of 50 μm to 500 μm.

[0159] Embodiment 17 1. A method for producing a through glass via in a silicate glass article, comprising: (1) irradiating the silicate glass article with a non-diffracting laser beam to form a laser beam focal line in which induced absorption occurs to form a damage track, the glass article comprising (1) B2O3 in an amount of at least 5 mol%, or (2) Al2O3 in an amount of less than 10 mol% and RO in an amount of less than 10 mol%, where R is Mg, Ca, Ba, Sr, or any combination thereof; and (2) etching the silicate glass article with an acid-containing etching solution to produce the through glass via; The method comprising:

[0160] Embodiment 18 18. The method of embodiment 17, wherein the laser beam is formed by a picosecond laser.

[0161] Embodiment 19 19. The method of claim 17 or 18, wherein the laser beam has a wavelength greater than 500 nm.

[0162] Embodiment 20 19. The method of claim 17 or 18, wherein the laser beam has a wavelength greater than 535 nm.

[0163] Embodiment 21 19. The method of claim 17 or 18, wherein the laser beam has a wavelength of 500 nm to 1,100 nm and an output of 40 μJ to 120 μJ.

[0164] Embodiment 22 22. The method of any one of claims 17 to 21, wherein the laser beam consists of a laser burst.

[0165] Embodiment 23 23. The method of any one of embodiments 17 to 22, wherein the etching solution comprises hydrofluoric acid.

[0166] Embodiment 24 24. The method of embodiment 23, wherein the hydrofluoric acid is an aqueous hydrofluoric acid solution having a hydrofluoric acid concentration of 1% to 50% by weight.

[0167] Embodiment 25 25. The method of claim 23 or 24, wherein the etchant comprises hydrofluoric acid in combination with hydrochloric acid, sulfuric acid, nitric acid, acetic acid, or any combination thereof.

[0168] Embodiment 26 26. The method of any one of claims 17 to 25, wherein the silicate glass article is etched at a temperature of from 0°C to 50°C.

[0169] Embodiment 27 27. The method of any one of embodiments 17 to 26, wherein the non-diffracting laser beam is a Bessel beam or a Gaussian-Bessel beam.

[0170] Embodiment 28 28. The method of claim 27, wherein the irradiating step comprises forming a laser beam focal line with the Bessel beam or Gaussian-Bessel beam within the silicate glass article.

[0171] Embodiment 29 29. The method of any one of embodiments 17 to 28, wherein the etching step produces etching by-products, the etching by-products having a solubility of etching by-products in the etching solution of 0.5 g / L or more.

[0172] Embodiment 30 30. The method of embodiment 29, wherein the solubility of the glass is determined using an etching solution comprising 1.45 M HF and 0.8 M HNO at 20°C.

[0173] Embodiment 31 31. The method of any one of claims 17 to 30, wherein the etching rate of the damage scar (E1) is greater than the etching rate of a silicate glass article not damaged by the laser (E2).

[0174] Embodiment 32 32. The method of embodiment 31, wherein the ratio of E1 / E2 is 1 to 50.

[0175] Embodiment 33 32. The method of embodiment 31, wherein the acid is hydrofluoric acid and the etching rate E2 is 0.25 μm / min to 0.9 μm / min.

[0176] Embodiment 34 34. A glass article produced by the method of any one of claims 17 to 33.

[0177] Embodiment 35 In silicate glasses, (1) B2O3 in an amount of at least 5 mol%, or (2) Al2O3 in an amount of less than 10 mol% and RO in an amount of less than 10 mol%, where R is Mg, Ca, Ba, Sr, or any combination thereof; and (2) SiO2 in an amount of 50 mol% or more; A silicate glass comprising:

[0178] Embodiment 36 36. The silicate glass of embodiment 35, comprising B2O3 in an amount of at least 5 mol%, SiO2 in an amount from 50 mol% to 75 mol%, Al2O3 in an amount from 4 mol% to 20 mol%, MgO in an amount from 0 mol% to 20 mol%, CaO in an amount from 0 mol% to 20 mol%, SrO in an amount from 0 mol% to 15 mol%, BaO in an amount from 0 mol% to 15 mol%, and P2O5 in an amount from 0 mol% to 10 mol%.

[0179] Embodiment 37 36. The silicate glass of embodiment 35, further comprising P2O5, and comprising Al2O3 in an amount less than 10 mol%, SiO2 in an amount between 50 mol% and 75 mol%, MgO in an amount between 0 mol% and 10 mol%, CaO in an amount between 0 mol% and 10 mol%, SrO in an amount between 0 mol% and 10 mol%, BaO in an amount between 0 mol% and 10 mol%, and P2O5 in an amount between 0 mol% and 10 mol%.

Claims

1. 1. A silicate glass article comprising one or more through-glass vias, (a) the through glass via has a first surface diameter (D Ｓ１ ), second surface diameter (D Ｓ２ ), and waist diameter (D ｗ ) and D Ｓ１ / D ｗ The ratio of D is 1:1 to 2:

1. Ｓ２ / D ｗ is in the ratio of 1:1 to 2:1, (b) the silicate glass contains SiO 2 in an amount of 50 mol % to 75 mol %, Al in an amount of 6 mol % or more but less than 10 mol %; ２ O ３ , B 2 O 3 in an amount of 5 mol % to 15 mol %, and RO in a total amount of less than 10 mol %, where R is Mg, Ca, Ba, Sr, or any combination thereof; P in an amount of 0 mol % to 10 mol %. ２ O ５ and further comprising TiO ２ Does not include Silicate glass articles.

2. The silicate glass contains B in an amount of 15 moles. ２ O ３ The article of claim 1 , comprising:

3. The article of claim 1 , wherein the silicate glass comprises a total amount of RO from 1 mol % to 5 mol %.

4. The silicate glass is SiO in an amount of 50 mol % to 75 mol % ２ , Al in an amount of 6 mol % or more and less than 10 mol % ２ O ３ , MgO in an amount from 0 mol % to 20 mol %, CaO in an amount from 0 mol % to 20 mol %, SrO in an amount from 0 mol % to 15 mol %, BaO in an amount from 0 mol% to 15 mol%, and P in an amount of 0 mol % to 10 mol % ２ O ５ The article of claim 2 comprising:

5. The first surface diameter (D ｓ１ ) is 10 μm to 100 μm, and the second surface diameter (D ｓ２ 5. The article of claim 1, wherein the thickness of the first and second electrodes is from 10 μm to 100 μm.

6. 1. A method for producing a through glass via in a silicate glass article, comprising: (1) irradiating the silicate glass article with a non-diffracting laser beam to form a laser beam focal line, and induced absorption occurs within the laser beam focal line to form a damage track, wherein the glass article is made of SiO 2 in an amount of 50 mol % to 75 mol %, Al in an amount of 6 mol % or more but less than 10 mol %. ２ O ３ , B 2 O 3 in an amount of 5 mol % to 15 mol %, and RO in a total amount of less than 10 mol %, where R is Mg, Ca, Ba, Sr, or any combination thereof; P in an amount of 0 mol % to 10 mol %. ２ O ５ and further comprising TiO ２ and (2) etching the silicate glass article with an etching solution containing an acid to produce the through glass via; The method comprising:

7. The method of claim 6 , wherein the etchant comprises hydrofluoric acid in combination with hydrochloric acid, sulfuric acid, nitric acid, acetic acid, or any combination thereof.

8. 8. The method of claim 6, wherein the non-diffracting laser beam is a Bessel beam or a Gauss-Bessel beam.

9. 9. The method of claim 6, wherein the etching step produces etching by-products, the etching by-products having an etching by-product solubility in the etching solution of 0.5 g / L or greater.

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