Hermetic fully-filled metallized through-hole via

Abstract

To provide alternative methods for metallizing through-glass vias that are hermetically sealed.SOLUTION: An article comprises: a glass or glass-ceramic substrate having a first major surface and a second major surface opposite the first major surface; and a via extending axially through the substrate from the first major surface to the second major surface over an axial length L, and defining an interior surface, and a first axial portion, a third axial portion, and a second axial portion disposed between the first axial portion and the third axial portion. The article further comprises: a helium-tight adhesive layer disposed on the interior surface within at least the first axial portion and / or the third axial portion; and a metal connector disposed in the via, and attached to the helium-tight adhesive layer. The metal connector completely fills the via over the axial length L of the via, the via has a maximum diameter, Φmax, of 30 μm or less and the axis length L and the maximum diameter Φmax satisfy a predetermined equation.SELECTED DRAWING: Figure 2

Description

Related Applications

[0001] This application claims the benefit of priority from U.S. Provisional Patent Application No. 62 / 801418, filed February 5, 2019, the contents of which are incorporated herein by reference in their entirety. This application is also a divisional application of International Patent Application No. 2021-545682, filed January 22, 2020. [Technical field]

[0002] FIELD OF THE DISCLOSURE This disclosure relates generally to vias in glass and glass-ceramic substrates, and more particularly to hermetically sealed, completely filled, metallized vias in glass and glass-ceramic substrates. [Background technology]

[0003] Glass and glass-ceramic substrates with vias are desirable for many applications, including use as interposers used as electrical interfaces, RF filters and RF switches. Glass substrates have become an attractive alternative to silicon and fiber-reinforced polymers for such applications.

[0004] It is desirable to fill such vias with a conductor. Copper is currently the most desirable material for such a conductor. However, copper does not adhere well to glass. In particular, a hermetic seal between copper and glass is desirable for some applications. Such a seal is difficult to obtain because copper does not adhere well to glass and because of the large mismatch in thermal expansion coefficients between many conductor materials, such as copper, and many desirable glass and glass-ceramic substrate compositions. In addition, when copper is bonded to glass, the large mismatch in thermal expansion coefficients between copper and glass can lead to the formation of radial and / or circumferential cracks in the glass when the glass article is subjected to high temperature processing. Radial cracks form during heating due to the constraint of free expansion of copper by the matrix glass. The constraint of free expansion leads to high stress buildup that leads to the formation of radial cracks. Circumferential cracks, on the other hand, form during cooling. The free contraction of copper is restricted by the glass matrix, resulting in stress buildup and circumferential crack formation.

[0005] Conformal coatings having cavities in the conductor material can reduce stress build-up and circumferential crack formation, but such cavities can become contaminated with corrosive materials during post-processing or use, resulting in degradation of the conductor material. Summary of the Invention [Problem to be solved by the invention]

[0006] Therefore, there is a need for an alternative method for metallizing hermetically sealed through-glass vias. [Means for solving the problem]

[0007] The article according to embodiment 1 comprises a glass or glass-ceramic substrate having a first major surface and a second major surface opposite the first major surface, and a via extending axially through the substrate from the first major surface toward the second major surface over an axial length L and defining an inner surface and a first axial portion, a third axial portion, and a second axial portion disposed along the axial direction between the first axial portion and the third axial portion. The article further comprises a helium-tight adhesive layer disposed on the inner surface at least in the first axial portion and / or the third axial portion, and a metallic connector disposed within the via and bonded to the helium-tight adhesive layer. The metallic connector completely fills the via over the axial length L of the via, and the via has a maximum diameter Φ of 30 μm or less. max having an axial length L and a maximum diameter Φ max is the formula, i.e.

[0008]

number

[0009] Meet the following.

[0010] The article according to embodiment 2 includes the article of embodiment 1, wherein the helium hermetic adhesion layer comprises Ti, TiN, Ta, TaN, Cr, Ni, and a metal oxide.

[0011] The article according to embodiment 3 includes the article of embodiment 1 or 2, wherein the metallic connector consists essentially of copper.

[0012] The article according to Example 4 includes the article of any one of Examples 1 to 3, wherein the metallic connector hermetically seals the via.

[0013] The article according to example 5 includes the article of any one of examples 1 to 4, wherein the via has a first diameter at the first major surface, a second diameter at the second major surface, and a third diameter at the second axial portion, the third diameter being smaller than the first and second diameters.

[0014] An article according to embodiment 6 includes the article of embodiment 5, wherein a helium hermetic adhesive layer is disposed on the inner surface at the first axial portion, the second axial portion, and the third axial portion.

[0015] The article according to embodiment 7 has a maximum diameter Φ max is 27 μm or less.

[0016] The article according to embodiment 8 includes the article of embodiment 5, wherein the helium gas-tight adhesive layer is disposed on the inner surface at the first axial portion and / or the third axial portion, but not on the inner surface at the second axial portion.

[0017] The article according to embodiment 9 has a maximum diameter Φ max is 25 μm or less.

[0018] The article according to example 10 includes the article of any one of examples 1 to 4, wherein the via has a first diameter at the first major surface, a second diameter at the second major surface, and a third diameter at the second axial portion, the first diameter being larger than the second and third diameters, and the third diameter being larger than the second diameter.

[0019] An article according to an embodiment 11 includes the article of embodiment 10, wherein a helium hermetic adhesive layer is disposed on the inner surface at the first axial portion, the second axial portion, and the third axial portion.

[0020] The article according to embodiment 12 has a maximum diameter Φ max is 19 μm or less.

[0021] An article according to embodiment 13 includes the article of embodiment 10, wherein a helium gas-tight adhesive layer is disposed on the inner surface at the first axial portion and / or the third axial portion, but not on the inner surface at the second axial portion.

[0022] The article according to embodiment 14 has a maximum diameter Φ maxis 17 μm or less.

[0023] The article according to example 15 includes the article of any one of examples 1 to 4, wherein the via has a first diameter at the first major surface, a second diameter at the second major surface, and a third diameter at the second axial portion, the first diameter being equal to the second diameter and the third diameter.

[0024] An article according to embodiment 16 includes the article of embodiment 15, wherein a helium hermetic adhesive layer is disposed on the inner surface at the first axial portion, the second axial portion, and the third axial portion.

[0025] An article according to embodiment 17 includes the article of embodiment 15, wherein a helium gas-tight adhesive layer is disposed on the inner surface at the first axial portion and / or the third axial portion, but not on the inner surface at the second axial portion.

[0026] The article according to embodiment 18 has a maximum diameter Φ max is 25 μm or less.

[0027] The article according to Example 19 includes the article of any one of Examples 1 to 18, wherein the axial length L of the via is 150 μm or more and 500 μm or less.

[0028] The article according to embodiment 20 has an axial length L and a maximum diameter Φ max But the formula, i.e.

[0029]

number

[0030] 20. The article of any one of claims 1 to 19,

[0031] The article according to embodiment 21 has no cracks and the article has a crack-free surface area of ​​10 mm or less before and after the article is heated to a temperature of 450° C. and cooled to a temperature of 23° C. -5 ATM* cc / s (approx. 9.87×10 -5 Pa·m 3 21. The article of any one of embodiments 1 to 20, having a helium permeability of less than 1 / s.

[0032] The article according to embodiment 22 comprises the article of any one of embodiments 1 to 21, wherein the substrate comprises at least 90% by weight of silica.

[0033] A method of manufacturing a glass article according to embodiment 23 includes depositing a helium-tight adhesive layer on an inner surface portion of a via extending axially through a glass or glass-ceramic substrate having a first major surface and a second major surface opposite the first major surface from the first major surface toward the second major surface, the helium-tight adhesive layer including a first axial portion, a third axial portion, and a second axial portion disposed between the first axial portion and the third axial portion, the helium-tight adhesive layer being deposited on the inner surface of the via at least in the first axial portion and / or the third axial portion, and depositing a metallic connector on the first axial portion, the second axial portion, and the third axial portion of the via to completely fill the via. The metallic connector completely fills the via in an axial direction over the axial length L of the via, and the via has a maximum diameter Φ of less than 30 μm. max having an axial length L and a maximum diameter Φ max is the formula, i.e.

[0034]

number

[0035] Meet the following.

[0036] The method according to embodiment 24 includes the method of embodiment 23, wherein the helium-tight adhesion layer comprises one or more of Ti, TiN, Ta, TaN, Cr, Ni, and a metal oxide.

[0037] The method according to embodiment 25 includes the method of embodiment 23 or 24, wherein the metallic connector consists essentially of copper.

[0038] The method according to aspect 26 includes any one of embodiments 23 to 25, wherein the metal connector hermetically seals the via.

[0039] The method according to embodiment 27 includes the method of any one of embodiments 23 to 26, wherein depositing the metallic connector includes depositing the metallic connector using electroplating.

[0040] The method according to aspect 28 includes any one of the methods of aspects 23 to 27, wherein the step of depositing a helium hermetic adhesion layer includes depositing a helium hermetic adhesion layer on an inner surface of the via in the first axial portion, the second axial portion, and the third axial portion.

[0041] The method according to aspect 29 includes any one of the methods of aspects 23 to 27, wherein the step of depositing a helium hermetic adhesion layer includes a step of depositing a helium hermetic adhesion layer on the inner surface of the via in the first axial portion and the third axial portion, but not on the inner surface in the second axial portion.

[0042] The method according to embodiment 30 includes the method of any one of embodiments 23 to 29, wherein the substrate comprises at least 90% by weight of silica. [Brief description of the drawings]

[0043] [Figure 1] 1 shows a perspective view of a substrate having vias. [Diagram 2] 2 shows a cross-section of a partially bonded via having a pinch configuration taken along line 2-2' of FIG. 1. [Diagram 3] FIG. 2 shows a cross section of a fully bonded via having a pinch configuration taken along line 2-2' of FIG. [Figure 4] 2 shows a cross-section of a partially bonded via having a tapered configuration taken along line 2-2' of FIG. 1. [Diagram 5]FIG. 2 shows a cross-section of a fully bonded via having a tapered configuration taken along line 2-2' of FIG. [Figure 6] 2 shows a cross-section of a partially bonded via having a cylindrical configuration taken along line 2-2' of FIG. 1. [Figure 7] 2 shows a cross-section of a fully bonded via having a cylindrical configuration taken along line 2-2' of FIG. 1. [Figure 8] FIG. 1 shows a flow chart for a method of manufacturing a via. [Figure 9] FIG. 1 shows the configuration of vias with conformal copper coverage used for modeling. [Figure 10A] FIG. 2 shows a plot of the stress-strain relationship for an elastically perfectly plastic material used in the modeling described herein. [Figure 10B] FIG. 2 is a plot of temperature dependent yield stress of copper used in the modeling described herein. [Figure 11] FIG. 1 is a plot of modeled first maximum principal stress and modeled maximum radial stress (y-axis) for various copper cladding thicknesses (x-axis). [Figure 12] FIG. 13 is a plot of modeled first maximum principal stress (y-axis) for various via diameters (x-axis) for fully filled and partially bonded vias. [Figure 13] FIG. 13 is a plot of modeled first maximum principal stress (y-axis) for various via diameters (x-axis) for a fully filled and fully bonded via. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0044] Unless otherwise stated, it is never intended that any method described herein be interpreted as requiring that its steps be performed in a particular order, or as requiring a particular orientation of any device. Thus, if a method claim does not actually recite the order in which its steps are to be followed, or if any device claim does not actually recite an order or orientation for individual components, or if the claim or description does not specifically state in any way that the steps are to be limited to a particular order or that a particular order or orientation for the device components is not recited, then no order or orientation is ever intended to be inferred in any respect. This applies to any possible implicit basis for interpretation, including matters of logic regarding the arrangement of steps, operational flow, component order or component orientation, plain meaning derived from grammatical organization or punctuation, and the number or type of embodiments described herein.

[0045] As used herein, the singular forms "a," "an," and "the" include plural referents unless specifically noted otherwise. Thus, for example, reference to an element preceded by "a" includes aspects having two or more such elements unless specifically noted otherwise. Also, the word "or" should be interpreted as inclusive (e.g., "x or y" means either x or y, or both) when used without the preceding "either" (or other similar words indicating that "or" is exclusive - e.g., means only one of x or y, etc.).

[0046] The term "and / or" should also be construed as inclusive (e.g., "x and / or y" means either x or y or both). When "and / or" or "or" is used as a conjunction for a group of three or more items, the group should be construed as including only one item, all items together, or any combination or number of those items. Furthermore, as used in the specification and claims, terms such as have, having, include, and including should be construed as synonymous with the terms comprise and comprising.

[0047] As used herein, the term "about" means that amounts, sizes, formulations, parameters and other quantities and characteristics are not and need not be exact, but may be approximate and / or larger or smaller as necessary, reflecting tolerances, conversion factors, rounding, measurement errors, and the like, and other factors known to those skilled in the art. When the term "about" is used to describe a value or an end point of a range, the disclosure should be understood to include the specific value or end point mentioned. Whether or not a numerical value or an end point of a range in this specification is recited with "about", the numerical value or end point of the range is intended to include two embodiments, one embodiment modified by "about" and the other embodiment not modified by "about". It is further understood that both end points of the range are clear, both in relation to the other end point and independently of the other end point.

[0048] All disclosed ranges should be understood to include and provide support for claims that recite any and all subranges or any and all individual values ​​subsumed within each range. For example, a stated range of 1 to 10 should be considered to include and provide support for claims that recite any and all subranges or individual values ​​between and / or including a minimum value of 1 and a maximum value of 10. That is, all subranges beginning with a minimum value of 1 or more and ending with a maximum value of 10 or less (e.g., 5.5 to 10, 2.34 to 3.56, etc.), or any value between 1 and 10 (e.g., 3, 5.8, 9.9994, etc.).

[0049] Glass and glass-ceramic substrates with vias Glass and glass-ceramic substrates with vias are desirable for many applications. For example, 3D interposers with through package via (TPV) interconnects connecting logic devices on one side of the interposer and memory on the other side of the interposer are desirable for high bandwidth devices. Current substrates are formed from either organic materials or silicon. However, organic interposers suffer from poor dimensional stability, while silicon wafers are expensive and suffer from high dielectric loss. Glass and glass-ceramics can be excellent substrate materials due to their relatively low dielectric constant, thermal stability and relatively low cost. There are applications for glass or glass-ceramic substrates with through glass vias (TGVs). These vias typically need to be filled completely or conformally with a conductive metal, e.g., copper, to form an electrical path. Copper is a particularly desirable conductive metal, but it does not adhere well to glass, and there is a large mismatch in the thermal expansion coefficient between copper and many substrate compositions. The large mismatch in the thermal expansion coefficients of copper and glass can result in the formation of radial and / or circumferential cracks in the glass when the glass article is subjected to high temperature processing. Thus, various embodiments described herein have vias that are limited in diameter to less than a critical threshold to allow the vias to be completely filled with copper without cracking the substrate when subjected to high temperature processing.

[0050] FIG. 1 shows an article comprising a substrate 100, shown diagrammatically in a partial perspective view. Substrate 100 comprises a first major surface 102 and a second major surface 104 opposite first major surface 102. A plurality of vias 110 extend through the bulk of substrate 100 from first major surface 102 to second major surface 104. Metallic connectors 150 fill vias 110. It should be understood that any number of vias 110 may extend through substrate 100 in any arrangement. Coordinate markers 101 indicate the direction of axial dimension z perpendicular to the plane of first major surface 102 and second major surface 104. Unless otherwise noted, the "length" of a via or metallic connector is axial dimension z. The thickness t of substrate 100, sometimes referred to herein as axial length L, which is an axial dimension, may be any suitable thickness depending on the application.

[0051] In various embodiments, the substrate 100 can comprise any suitable glass or glass-ceramic substrate. In some particular embodiments, a high silica glass or glass-ceramic substrate is desirable for certain applications due to its dielectric properties. For example, glass or glass-ceramic materials having a silica content of 50 mol%, 55 mol%, 60 mol%, 65 mol%, 70 mol%, 75 mol%, 80 mol%, 85 mol%, 90 mol%, 95 mol%, or 100 mol%, or any range having any two of these values ​​as endpoints (inclusive), can be used. Glass or glass-ceramic materials having a silica content of 50 mol% to 100 mol%, or 75 mol% to 100 mol%, can be used. In certain embodiments, the substrate comprises at least 90% silica by weight.

[0052] For substrates having the dimensions described herein, it is particularly difficult to achieve hermetically sealed vias with copper metal connectors in high silica glass for at least two reasons. First, copper does not adhere well to glass. Second, the CTE mismatch between copper and high silica glass is particularly large, which may lead to crack formation in the substrate when the substrate is subjected to thermal cycling. The articles and methods described herein achieve hermetic sealing despite these reasons by providing an excellent stress relief mechanism.

[0053] 2-7 show an article comprising a substrate 100, which is shown as a cross-section of FIG. 1 along line 2-2'. 2-7 show the substrate 100, the coordinate marker 101, the first major surface 102, the second major surface 104, the via 110 and the metal connector 150 of FIG. 1. The inner surface 114 of the via 110 is divided into a first axial portion 116, a second axial portion 118 and a third axial portion 120. A helium-tight adhesive layer 122 is disposed on the inner surface 114 of the via 110 at the first axial portion 116 and the third axial portion 120. In an embodiment, the helium-tight adhesive layer 122 is disposed on the inner surface 114 of the via 110 along the entire circumference of at least one of the first axial portion 116 and / or the third axial portion 120. Thus, although in Figures 2-7 the helium gas-tight adhesive layer 122 is shown as being located at least on the first axial portion 116 and the third axial portion 120, it is contemplated that in other embodiments the helium gas-tight adhesive layer 122 may be located on the first axial portion 116 but not on the third axial portion 120, or on the third axial portion 120 but not on the first axial portion 116. In some embodiments, such as those shown in Figures 2, 4 and 6, the helium gas-tight adhesive layer 122 is not present on the second axial portion 118. Such embodiments are referred to as "partially bonded". However, in other embodiments, such as those shown in Figures 3, 5 and 7, the helium gas-tight adhesive layer 122 is also present on the second axial portion 118 and extends along the entire axial length from the first major surface 102 to the second major surface 104. Such an embodiment is referred to as “fully bonded.” In a partially bonded embodiment, the helium-tight adhesive layer 122 is absent from the second axial portion 118, and thus the metal connector 150 is not as strongly bonded to the inner surface 114 along the second axial portion 118.

[0054] As used herein, the expression "helium-tight adhesive layer" refers to a layer that adheres a metal connector 150 to the inner surface 114 of a via 110 and that has a helium leak resistance of 100% or more, as measured using a vacuum-based helium leak test system. -5 ATM* cc / s (approx. 9.87×10 -5 Pa·m 3 In some embodiments, the adhesive layer provides helium tightness with a permeability of less than 10 -8 ATM * cc / s (approx. 9.87×10 -8 Pa·m 3 The helium-tight adhesive layer provides helium tightness with a permeability of less than 1000 nm / s. Suitable helium-tight adhesive layer materials include metals such as titanium (Ti), chromium (Cr), tantalum (Ta), vanadium (V), nickel (Ni), tungsten (W), or metal oxides such as zinc oxide, tungsten oxide, and manganese oxide, or nitrides such as titanium nitride (TiN) and tantalum nitride (TaN). In various embodiments, the helium-tight adhesive layer includes one or more of Ti, TiN, Ta, TaN, Cr, Ni, and metal oxides. The helium-tight adhesive layer has a thickness of 1 nm or more and 500 nm or less. For example, in some specific embodiments, the helium-tight adhesive layer has a thickness of about 100 nm.

[0055] In some embodiments, e.g., partially bonded embodiments, the axial length of the first axial portion 116 or the third axial portion 120 can be referred to as the "bond length" since it is the length within the via 110 along which the metal connector 150 is strongly bonded to the substrate 100. In some such embodiments, the bond length is 5 μm to 148 μm. The bond length can be 10 μm to 135 μm, 10 μm to 130 μm, 10 μm to 125 μm, 10 μm to 120 μm, 10 μm to 115 μm, 15 μm to 140 μm, 15 μm to 135 μm, 15 μm to 130 μm, 15 μm to 125 μm, 15 μm to 120 μm, 20 μm to 30 μm, 30 μm to 40 μm, 40 μm to 50 μm, 50 μm to 60 μm, 60 μm to 80 μm, 80 μm to 90 μm, 90 μm to 100 μm, 100 μm to 115 μm, 100 μm to 120 μm, 100 μm to 135 μm, 100 μm to 130 μm, 100 μm to 12 ... In some embodiments, the bond length is 40 μm to 140 μm, 40 μm to 130 μm, 40 μm to 120 μm, 40 μm to 110 μm, 40 μm to 90 μm, 40 μm to 80 μm, 40 μm to 70 μm, or 40 μm to 60 μm. For example, the bond length can be about 40 μm, 50 μm, 60 μm, or 70 μm. In various embodiments, it is contemplated that other bond lengths can be utilized.

[0056] The via 110 has an axial via length 130, sometimes referred to herein as the axial length L of the via 110. In a fully bonded embodiment, the bond length may be equal to the via length 130. The via 110 has a first diameter 132a at the first major surface 102, a second diameter 132b at the second major surface 104, and a third diameter 132c at the second axial portion 118.

[0057] As shown in FIGS. 2-7, the metal connector 150 completely fills the via 110 from the first major surface 102 to the second major surface 104 over the axial length L of the via 110, thereby eliminating the possibility of contamination within the cavity in the metal connector 150. The metal connector can be formed from any suitable metal. In some embodiments, copper can be a desirable metal due to its particularly high electrical conductivity. Gold, silver and other conductive metals and alloys of conductive metals may also be used. In embodiments, the metal connector includes copper. In some particular embodiments, the metal connector consists essentially of copper. Glued into the via 110, the metal connector 150 hermetically seals the via 110.

[0058] Via Shape In the embodiments described herein, the via 110 can have any one of a variety of shapes. In the embodiment shown in Figures 2 and 3, the via 110 has a tapered inner surface 114 that tapers or narrows from a first diameter 132a at the first major surface 102 and a second diameter 132b at the second major surface 104 to a waist 125 having a waist diameter equal to a third diameter 132c. Such a configuration is referred to herein as a fully filled pinched via or FPV. As used herein, the "waist" of a via refers to the portion of the variable diameter via that has a minimum diameter. In these embodiments, the diameter of the via 110 can vary as a function of axial position. All "diameters" of the via 110 are confined to a maximum diameter Φ max Unless otherwise specified, "via diameter" refers to the largest diameter. If via 110 is not circular, the "diameter" of via 110 is the diameter of a circle that has the same cross-sectional area as via 110 in a plane perpendicular to the axial direction.

[0059] The via waist 125 has a smallest diameter along the axial length of the via. The diameter of the beer waist as a percentage of the first diameter can be 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80% or any range having any two of these values ​​as the endpoints (inclusive). The diameter of the beer waist as a percentage of the second diameter can be 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80% or any range having any two of these values ​​as the endpoints (inclusive). The diameter of the beer waist can be 75% or less of the first diameter and the diameter of the beer waist can be 75% or less of the second diameter. The diameter of the via waist can be 20% to 50% of the first diameter, and the diameter of the via waist can be 20% to 50% of the second diameter. In various embodiments, the third diameter 132c or the beer waist is 10 μm to 30 μm. The third diameter 132c can be 20 μm to 30 μm or 22 μm to 27 μm. For example, the third diameter 132c can be 10 μm, 15 μm, 20 μm, 22 μm, 25 μm, 27 μm, or 30 μm. In various embodiments, the ratio of the third diameter 132c to the first diameter 132a is 1:6 or less, 1:5 or less, 1:4 or less, 1:3 or less, or 1:2 or less, and / or the ratio of the third diameter 132c to the second diameter 132b is 1:6 or less, 1:5 or less, 1:4 or less, 1:3 or less, or 1:2 or less.

[0060] The via 110 optionally has rounded fillets 124 on its inner edges, including at the via waist 125, to reduce stress concentrations. As used herein, "fillet" refers to a rounded corner along the inner corner of the via 110. Such rounded fillets can be used on any edge in the via's geometry. The rounded fillets 124 can have any suitable diameter, for example, 3 mm, 4 mm, 5 mm, 6 mm, 7 mm, 8 mm, or any range having any two of these values ​​as endpoints (inclusive). Other diameters may be used.

[0061] The via 110 has an inner surface 114 with two distinct slopes that change slope at a fillet 124. The via 110 can have a single slope from each of the first and second major surfaces 102, 104 to the waist 125, two slopes as illustrated in Figure 2, or a more complex shape. One or more of the slopes can be perpendicular to the first and second major surfaces 102, 104, as shown in Figure 2.

[0062] In the embodiment shown in Figures 4 and 5, the via 110 has a tapered inner surface 114 that tapers or narrows from a first diameter 132a at the first major surface 102 to a second diameter 132b at the second major surface 104. The via 110 also includes a third diameter 132c located within a second axial portion that is smaller than the first diameter 132a and larger than the second diameter 132b. Thus, the first diameter 132a is larger than the second diameter 132b and the third diameter 132c, which is larger than the second diameter 132b. Such a configuration is referred to herein as a fully filled tapered via or FTV. In such an embodiment, the first diameter 132a is smaller than the maximum via diameter Φ max It is.

[0063] In the embodiment shown in Figures 6 and 7, the via 110 has an inner surface 114 perpendicular to the first major surface 102 and the second major surface 104. The via has a first diameter 132a at the first major surface 102, a second diameter 132b at the second major surface 104, and a third diameter 132c at a second axial portion that is equal to the first diameter 132a and the second diameter 132b. Such a configuration is referred to herein as a fully filled cylindrical via or FCV. In such an embodiment, the diameter of the via 110 is constant with axial position.

[0064] The via 110 can have any suitable via length 130 or axial length L. As non-limiting examples, the thickness of the substrate 100 (and via length 130) can be 150 μm, 180 μm, 240 μm, 300 μm, 360 μm, 420 μm, 480 μm, 500 μm, or any range having any two of these values ​​as the endpoints (inclusive). In some embodiments, the thickness t and via length are between 150 μm and 500 μm or between 200 μm and 360 μm.

[0065] The via 110 can have any suitable first diameter 132a, second diameter 132b, and third diameter 132c. By way of non-limiting example, these diameters can be 5 μm, 10 μm, 13 μm, 15 μm, 17 μm, 19 μm, 20 μm, 21 μm, 22 μm, 24 μm, 25 μm, 27 μm, 30 μm, or any range having any two of these values ​​as endpoints (inclusive). In some embodiments, the via diameter can be 1 μm to 30 μm, 1 μm to 25 μm, 1 μm to 19 μm, or 1 μm to 17 μm. As will be described in more detail below, in various embodiments, the maximum diameter Φ of the via 110 can be 1 μm to 30 μm, 1 μm to 25 μm, 1 μm to 19 μm, or 1 μm to 17 μm. maxmay be 30 μm or less, 27 μm or less, 25 μm or less, 24 μm or less, 22 μm or less, 21 μm or less, 19 μm or less, even less than 17 μm, 15 μm or less, or even less than 13 μm to reduce stress and prevent cracking of the board, depending on the geometry of the via and whether the metal connector is partially or fully bonded.

[0066] In some embodiments, the vias 110 have a maximum diameter Φ of 30 μm or less, 27 μm or less, or 24 μm or less. max In other embodiments, the via 110 has a maximum diameter Φ of 25 μm or less, 22 μm or less, or 19 μm or less. max In yet other embodiments, the via 110 is a fully filled and partially bonded cylindrical via having a maximum diameter Φ of 19 μm or less, 17 μm or less, or 15 μm or less. max In other embodiments, the via 110 has a maximum diameter Φ of 17 μm or less, 15 μm or less, or 13 μm or less. max In other embodiments, the via 110 has a maximum diameter Φ of 27 μm or less, 24 μm or less, or 21 μm or less. max In yet other embodiments, the via 110 is a fully filled and fully bonded pinched via having a maximum diameter Φ of 25 μm or less, 22 μm or less, or 19 μm or less. max A fully filled and partially bonded pinched via having

[0067] The axial lengths of the first, second and third axial portions can be any suitable length. In various embodiments, lengths are selected that achieve a combination of low maximum principal stress and helium tightness. In some embodiments, the first axial portion and the third axial portion have lengths independently selected from 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 15%, 20%, 25%, 30%, 35% and 40% of the length of the via or any range having any two of these values ​​as the endpoints (inclusive). The second axial portion has a length of 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97% or 98% of the length of the via, or any range having any two of these values ​​as the endpoints (inclusive). The first axial portion and the third axial portion can have a length between 2% and 40% of the length of the via, while the second axial portion has a length between 20% and 96% of the length of the via.

[0068] In various embodiments, the vias are high aspect ratio vias having a via length of 150 μm to 500 μm and a via diameter of 1 μm to 30 μm. As used herein, "aspect ratio" refers to the ratio of the average thickness of the glass substrate to the average diameter of the via. "High aspect ratio" refers to an aspect ratio of greater than 3.

[0069] In various embodiments described herein, the via 110 has the following formula:

[0070]

number

[0071] The axial length L and maximum diameter Φ satisfy max has.

[0072] In some embodiments, the via 110 has a capacitance of:

[0073]

number

[0074] The axial length L and maximum diameter Φ satisfy max has.

[0075] Conventionally, the aspect ratio (L / Φ max ) is used as an important parameter, but the ratio L / (Φ max ) 1 / 2 It has been found that this may be related to the difficulties associated with both electroless and electrolytic plating of through-vias. For example, two through-glass via geometries with the same aspect ratio may have different L / (Φ max ) 1 / 2 It may have a higher L / (Φ max ) 1 / 2 It can be shown that metallization is more difficult when the via has a value of Φ. Without being bound by theory, it is believed that the difficulty arises from the fact that the rate of diffusion of copper ions into the via center must be sufficiently fast compared to their consumption by reaction at the sidewalls, either for autocatalytic reasons (in the case of electroless plating) or charge transfer reactions (in the case of electroplating). From the theoretical analysis of the diffusion-reaction equation for the system, it can be seen that the diffusion / reaction ratio is L / (Φ max ) 1 / 2 In particular, it can be shown that L / (Φ max ) 1 / 2 The higher the value of , the more difficult it is to achieve metallization without forming defects inside the via due to copper depletion.

[0076] Manufacturing method A through glass via with a tapered shape can be manufactured by any suitable method. One method is to form a damage track in the substrate 100 with a laser, followed by etching. Exemplary methods are described in U.S. Pat. No. 9,656,909 and U.S. Patent Application No. 62 / 588,615, the contents of which are incorporated herein by reference in their entirety. Another method is to modify a photosensitive glass with a laser, followed by etching.

[0077] 8 shows a flow chart illustrating a method for metallizing a through-glass via. In step 810, a helium-tight adhesive layer is deposited on an inner surface of the via in at least a first axial portion and a third axial portion. Then, in step 820, a metal connector is deposited in the via such that the metal connector adheres to the helium-tight adhesive layer in at least the first axial portion and the third axial portion.

[0078] The helium-tight adhesive layer can be deposited on the inner surface of the first and third axial portions and optionally the second axial portion by any suitable method. For example, the length of the first and third axial portions in the z dimension can be easily controlled by using line-of-sight deposition methods, such as sputtering, and adjusting the deposition angle. The substrate may be rotated during deposition to ensure that the adhesive length is constant all around the inner surface of the via.

[0079] A helium-tight adhesion layer in the form of a thin film formed from a metal, metal oxide or metal nitride can be applied to the glass surface using many different methods, such as sputtering, E-beam deposition, ion beam deposition, atomic layer deposition, chemical vapor deposition and solution coating.

[0080] Metal connectors can be deposited by any suitable means. One suitable method for depositing copper (and other metals) is to deposit a catalyst, such as Pd, onto a helium hermetic adhesion layer, followed by electroless deposition of copper, followed by electroplating of copper. In various embodiments, the electroplating process involves the use of an electroplating bath containing metal salts, supporting electrolyte and additives, and a current of 1.5 mA / cm. 2 More than 5mA / cm 2 Less than or equal to 1.5mA / cm 2 More than 2.5mA / cm 2 This involves application of an electric current at the following current density: The metal salt can be a salt of a metal that forms a metal connector, for example CuSO4.

[0081] Another suitable method includes depositing a metal connector at the "bottom" of the via and continuing to deposit metal so that the metal material continues to grow and fill the via until it reaches the "top" of the via. Such a process is sometimes referred to as "bottom-up electrolytic plating."

[0082] Other suitable methods for depositing metal connectors include filling the vias with a metal paste and sintering or chemical vapor deposition (CVD). Suitable methods for depositing copper are further described in U.S. Patent Application Publication No. 2017-0287728 (see, e.g., paragraphs

[0004] -

[0005] ), the entire contents of which are incorporated by reference.

[0083] Thermal Cycle Glass and glass-ceramic substrates with filled vias are often subjected to thermal cycling, which may occur during device operation or during manufacturing steps subsequent to via filling, in some embodiments, for example, glass substrates may be subjected to thermal cycling for annealing.

[0084] As mentioned above, there is a large mismatch between the coefficient of thermal expansion (CTE) of copper and other metals and the CTE of many glass and glass-ceramic materials. Due to the CTE mismatch, upon heating, the metal connector expands more quickly than the surrounding glass or glass-ceramic substrate. Similarly, upon cooling, the metal connector contracts more quickly than the surrounding substrate. This difference in expansion and contraction creates stresses that can lead to a number of failure mechanisms, such as delamination or cracking. These failure mechanisms can cause loss of hermeticity and other problems.

[0085] Delamination is one failure mechanism. Delamination occurs when the conductive metal, e.g., copper, peels off from the inside of a via. If there is a weak bond between the conductor and the board, the stresses caused by thermal cycling can lead to delamination. Delamination can lead to loss of hermeticity because gases and liquids can enter the board along the interface between the delaminated metal connector and the inner surface of the via.

[0086] Delamination can be reduced or eliminated by forming a sufficiently strong bond between the substrate and the metal connector. Such a bond can be formed using a helium-tight adhesive layer disposed on the inner surface of the via between the substrate and the metal connector. As used herein, "adhesive layer" refers to any layer or surface treatment that results in a bond between the metal connector and the substrate that is strong enough to withstand thermal cycling from 23°C to 450°C.

[0087] Delamination can be prevented by forming a strong bond between the metal connector and the substrate, but this stronger bond prevents the metal connector from moving relative to the substrate during thermal cycling, which can result in stresses in the substrate that lead to cracks and loss of hermeticity.

[0088] A 2D plane-strain solution to the classical Lame problem in elasticity to predict the stress field at the center of the glass is given by

[0089]

number

[0090] As stated above.

[0091] In the formula, σ r and σ θ are the radial and circumferential stresses, respectively, and ε T =(α f -α m ) ΔT is the mismatch strain due to thermal loading ΔT. The material properties α, E, and ν are the CTE, Young's modulus, and Poisson's ratio, with subscripts f and m for the via (fiber) and glass (matrix), respectively.

[0092] Failure may occur during both the heating and cooling parts of the thermal cycle. During heating, the expansion mismatch is greatest at the highest temperature. Most of the stress in the substrate is compressive at higher temperatures because the metal connectors expand more than the substrate. During heating, the circumferential tensile stress in the glass prevails, which may result in radial cracks around the metal connectors. This tensile stress may propagate to the next via. During cooling, the contraction mismatch is greatest at the lowest temperature. Most of the stress in the substrate is tensile at lower temperatures because the metal connectors contract more than the substrate. During cooling, the radial stress prevails, which may result in cracks. The radial stress is tensile in the glass near the surface, which may cause circumferential cracks (C-cracks) in the glass. For both heating and cooling, the presence of shear stresses along the interface may induce interfacial failure through delamination.

[0093] Towards the end of the cooling portion of the thermal cycle, the metal connector 150 has contracted more than the substrate 100 due to the difference in CTE. Because the metal connector 150 is bonded to the substrate 100, the contraction of the metal connector 150 pulls the substrate 100, placing the substrate 100 under tensile stress. Without sufficient freedom for stress relaxation, this tensile stress would cause microcracks in the substrate 100, which in turn may result in loss of hermeticity.

[0094] Various embodiments described herein can exhibit helium tightness and no cracks after being subjected to thermal cycling. In particular, in various embodiments, the articles are crack-free and exhibit a helium tightness of 10% or more before and after the articles are heated to a temperature of 450° C. and cooled to a temperature of 23° C. -5 ATM * cc / s (approx. 9.87×10 -5 Pa·m 3 / s), and even less than 10 -8 ATM * cc / s (approx. 9.87×10 -8 Pa·m 3 / s). In various embodiments described herein, the maximum diameter Φ of the via 110 max Maintaining a thickness of 30 μm or less provides helium tightness while allowing the substrate and metal connectors to shrink at different rates without creating a sufficient amount of tensile stress to cause microcracks.

[0095] modeling For modeling, the geometry of FIG. 9 was used. In this case, the inner surface of the via is conformally clad with copper for all but 37.5 μm on either side of the waist where the via is completely filled, and 75 μm of axial length. The via length was 300 μm. The first and second diameters were each 50 μm. The 50 μm diameter is maintained for a distance of 50 μm along the axial length from both sides. Starting 50 μm from the surface, the via tapers inwardly to a 20 μm diameter at waist 125, midway along the axial length. Both the first and second major surfaces have a 20 μm thick cladding of copper. It is expected that the modeling results will extend to other via and metal connector shapes that have a cavity in the metal connector and a second axial portion without a strong bond between the metal connector and the substrate.

[0096] In one process flow for fabricating an actual device, the geometry of Figure 9, including the adhered copper cladding, is provided where the most severe thermal cycling occurs, after which the cladding may be removed and further processing performed, although the geometry of Figure 9 is relevant to the thermal cycling modeled herein.

[0097] The modeling is based on theory drawn from Ryu SK, Lu KH, Zhang X, Im JH, Ho PS, Huang R. Impact of near-surface thermal stresses on interfacial reliability of through-silicon vias for 3-D interconnects. IEEE Transactions on Device and Materials Reliability. 2011 Mar;11(1):35 (hereafter referred to as "Ryu"). According to Ryu, analytical solutions exist to predict the surface stresses of vias and wafers when the vias are placed in the wafer. However, there is no closed form to predict the stress from thickness. Hence, modeling is necessary. For modeling, one single hole in a finite plate was modeled. Two-dimensional axisymmetricity is assumed and a sufficiently small mesh size of about 0.5 μm is used. The modeling was performed using ANSYS v.19 structural modeling software.

[0098] For modeling purposes, glass was assumed to be elastic and have the properties of fused silica: E (Young's modulus) = 73 GPa, ν (Poisson's ratio) = 0.17, and α (coefficient of thermal expansion) = 0.55 ppm / °C. Copper was assumed to have elastically perfectly plastic properties and have a temperature dependent yield stress. FIG. 10A shows a graph 1000 illustrating the stress-strain relationship for an elastically perfectly plastic material. FIG. 10B shows a graph 1010 illustrating the temperature dependent copper yield stress. The elastic properties of copper used in modeling were E (Young's modulus) = 121 GPa, ν (Poisson's ratio) = 0.35, and α (coefficient of thermal expansion) = 17 ppm / °C. It was also assumed that the system including the copper vias and fused silica was in a stress-free state at 25°C. The modeling calculated the stress after thermal cycling from 25°C to 400°C and back to 25°C.

[0099] If the glass were to crack, it would first crack where the first principal stress is highest, i.e., the "first maximum principal stress." Referring to FIG. 9, modeling shows that the first principal stress is highest at two points. First, there was a high maximum principal stress at the surface of the substrate 100 along line 190, a short distance from the interface between the helium-tight adhesive layer 122 and the substrate 100. This first point of high stress corresponds to the failure mechanism observed in the sample, surface microcracking.

[0100] Second, there was a maximum principal stress at point 192, which is the dominant stress component in inducing crack initiation and propagation. Figure 11 shows a plot of the modeled first maximum principal stress and maximum radial stress along line 190 for various copper wall thicknesses. As shown in Figure 11, the maximum values ​​of both the radial stress and the first maximum principal stress grow exponentially with temperature. For coating thicknesses of 12 μm and above, both the first maximum principal stress and the maximum radial stress meet or exceed the threshold values ​​(140 MPa for the first maximum principal stress and 80 MPa for the maximum radial stress for the configuration shown in Figure 9).

[0101] In additional experiments, the percentage of vias with cracks was examined for various copper cladding thicknesses after the wafers were annealed at a maximum temperature of 400°C. The cladding thickness was measured on either the first or second major surface, and groups were formed based on integers of cladding thickness measurements. That is, group "8 μm" included cladding thicknesses between 8.00 μm and 8.99 μm, group "9 μm" included cladding thicknesses between 9.00 μm and 9.99 μm, etc. Based on experimental data, vias do not crack until cladding thicknesses reach 12 μm or greater. Based on modeling and experimental data, the threshold stresses for crack formation were determined to correspond to 140 MPa for the first maximum principal stress and 80 MPa for the radial stress. Therefore, for values ​​below this stress threshold, cracks are not expected to occur.

[0102] Using a critical threshold of 140 MPa for the maximum principal stress, modeling was used to determine the crack-free via diameter required in a fully filled configuration, such as the configurations shown in Figures 2-7. The same material inputs for the metallized conformal copper configuration shown in Figure 9 were used in modeling the fully filled via configuration. For the tapered configuration, a taper ratio of 5:3 (maximum diameter: minimum diameter) was used.

[0103] A margin of error of ±10% was applied to account for variability in the stress calculations related to the mesh size used in the model. Therefore, a lower limit of 126 MPa was used to determine the critical via diameter required for crack removal in a fully filled via.

[0104] Figure 12 is a plot showing the predicted glass surface stress around the via for partially bonded and fully filled vias. For the configurations shown in Figures 2 and 6 (FPV and FCV, respectively), the lower limit of the critical stress threshold is reached at a diameter of 25 μm or less. Meanwhile, the configuration shown in Figure 4 (FTV) reaches the critical stress threshold at a diameter of 17 μm or less. Thus, the FCV and FPV via geometry configurations allow the largest via diameter tolerance to provide partially bonded, crack-free, hermetic, fully filled vias.

[0105] Figure 13 is a plot showing the predicted glass surface stress around a fully bonded and fully filled via. Based on modeling, the configuration shown in Figure 3 (FPV) reaches a critical stress threshold at a diameter of 27 μm or less, the configuration shown in Figure 7 (FCV) reaches a critical stress threshold at a diameter of 30 μm or less, and the configuration shown in Figure 5 reaches a critical stress threshold at a diameter of 19 μm or less. The modeling results for various via configurations and bonding parameters are summarized in Table 1.

[0106] [Table 1]

[0107] As can be seen from the data presented in Table 1, the fully bonded via configuration can support a larger diameter than the partially bonded via configuration. Without being bound by theory, it is believed that in the fully bonded configuration, there is a greater distribution of stress throughout the thickness of the glass as opposed to the partially bonded configuration where the stress may be concentrated in the center and near the surface of the substrate. Additionally, experiments performed have shown that the fully bonded configuration exhibits a greater protrusion of the metal connector from the surface of the via compared to the partially bonded configuration.

[0108] summary As used herein, certain transitional phrases such as "consisting essentially of" limit the scope of a claim to the particular materials or steps of the claimed invention "and to materials or steps that do not materially affect the basic and novel characteristics."

[0109] Those skilled in the art will recognize and appreciate that many modifications can be made to the various embodiments described herein while still obtaining beneficial results. It will also be apparent that some of the desired benefits of the present embodiment can be obtained by selecting some features without utilizing other features. Thus, those skilled in the art will recognize that many modifications and adaptations are possible and may even be desirable in certain circumstances and are part of this disclosure. Thus, it is to be understood that the present disclosure is not limited to the specific compositions, articles, devices and methods disclosed, unless otherwise specified. 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. The features shown in the drawings are illustrative of selected embodiments of the present description and are not necessarily drawn to scale. The features of these drawings are illustrative and are not intended to be limiting.

[0110] Unless otherwise specified, it is in no way intended that any method described herein be construed as requiring that its steps be performed in a particular order, and thus, unless a method claim actually lists the order in which its steps should be followed or unless the claims or description are somehow specifically stated to limit the steps to a particular order, no particular order is intended to be inferred.

[0111] Preferred embodiments of the present invention will be described below in detail.

[0112] EMBODIMENT 1 An article, a glass or glass ceramic substrate having a first main surface and a second main surface opposite the first main surface; a via extending axially through the substrate from the first major surface toward the second major surface over an axial length L and defining an inner surface and a first axial portion, a third axial portion, and a second axial portion disposed along the axial direction between the first axial portion and the third axial portion; a helium-tight adhesive layer disposed on the inner surface at least in the first axial portion and / or the third axial portion; a metallic connector disposed within the via and bonded to the helium hermetic adhesive layer; Equipped with the metallic connector completely fills the via over the axial length L of the via; The vias have a maximum diameter Φ of 30 μm or less. max having The axial length L and the maximum diameter Φ max is the formula, i.e.

[0113]

number

[0114] An item that satisfies.

[0115] EMBODIMENT 2 2. The article of embodiment 1, wherein the helium hermetic adhesion layer comprises one or more of Ti, TiN, Ta, TaN, Cr, Ni, and a metal oxide.

[0116] EMBODIMENT 3 3. The article of claim 1 or 2, wherein the metallic connector consists essentially of copper.

[0117] EMBODIMENT 4 The article of any one of claims 1 to 3, wherein the metallic connector hermetically seals the via.

[0118] EMBODIMENT 5 5. The article of any one of claims 1 to 4, wherein the via has a first diameter at the first major surface, a second diameter at the second major surface, and a third diameter at the second axial portion, the third diameter being smaller than the first diameter and the second diameter.

[0119] EMBODIMENT 6 6. The article of claim 5, wherein the helium hermetic adhesive layer is disposed on the inner surface of the first axial portion, the second axial portion, and the third axial portion.

[0120] EMBODIMENT 7 The maximum diameter Φ max 7. The article of embodiment 6, wherein the thickness is 27 μm or less.

[0121] EMBODIMENT 8 6. The article of claim 5, wherein the helium gas tight adhesive layer is disposed on the inner surface at the first axial portion and / or the third axial portion, and is not disposed on the inner surface at the second axial portion.

[0122] EMBODIMENT 9 The maximum diameter Φ max 9. The article of embodiment 8, wherein the thickness is 25 μm or less.

[0123] EMBODIMENT 10 5. The article of any one of claims 1 to 4, wherein the via has a first diameter at the first major surface, a second diameter at the second major surface, and a third diameter at the second axial portion, the first diameter being larger than the second diameter and the third diameter, and the third diameter being larger than the second diameter.

[0124] EMBODIMENT 11 11. The article of claim 10, wherein the helium hermetic adhesive layer is disposed on the interior surface of the first axial portion, the second axial portion, and the third axial portion.

[0125] EMBODIMENT 12 The maximum diameter Φ max 12. The article of embodiment 11, wherein the thickness is 19 μm or less.

[0126] EMBODIMENT 13 An article as described in embodiment 10, wherein the helium gas tight adhesive layer is disposed on the inner surface at the first axial portion and / or the third axial portion, and is not disposed on the inner surface at the second axial portion.

[0127] EMBODIMENT 14 The maximum diameter Φ max 14. The article of embodiment 13, wherein the thickness is 17 μm or less.

[0128] EMBODIMENT 15 5. The article of any one of claims 1 to 4, wherein the via has a first diameter at the first major surface, a second diameter at the second major surface, and a third diameter at the second axial portion, the first diameter being equal to the second diameter and the third diameter.

[0129] EMBODIMENT 16 16. The article of claim 15, wherein the helium hermetic adhesive layer is disposed on the inner surface of the first axial portion, the second axial portion, and the third axial portion.

[0130] EMBODIMENT 17 16. The article of claim 15, wherein the helium gastight adhesive layer is disposed on the inner surface at the first axial portion and / or the third axial portion, and the helium gastight adhesive layer is not disposed on the inner surface at the second axial portion.

[0131] EMBODIMENT 18 The maximum diameter Φ max 18. The article of embodiment 17, wherein the thickness is 25 μm or less.

[0132] EMBODIMENT 19 19. The article of any one of claims 1 to 18, wherein the axial length L of the via is 150 μm or more and 500 μm or less.

[0133] EMBODIMENT 20 The axial length L and the maximum diameter Φ max But the formula, i.e.

[0134]

number

[0135] 20. The article of any one of claims 1 to 19,

[0136] EMBODIMENT 21 The article is free of cracks and has a crack-resistant tensile strength of 100% before and after the article is heated to a temperature of 450° C. and cooled to a temperature of 23° C. -5 ATM * cc / s (approx. 9.87×10 -5 Pa·m 3 21. The article of any one of the preceding claims, having a helium permeability of less than 1 / s.

[0137] EMBODIMENT 22 22. The article of any one of the preceding claims, wherein the substrate comprises at least 90% by weight silica.

[0138] EMBODIMENT 23 1. A method of manufacturing a glass article, the method comprising: depositing a helium-tight adhesive layer on an inner surface portion of a via extending axially from a first major surface to a second major surface opposite the first major surface through a glass or glass ceramic substrate, the via extending axially from the first major surface to the second major surface, the helium-tight adhesive layer including a first axial portion, a third axial portion, and a second axial portion disposed between the first axial portion and the third axial portion, the helium-tight adhesive layer being deposited on the inner surface of the via at least in the first axial portion and / or the third axial portion; depositing a metallic connector onto the first axial portion, the second axial portion, and the third axial portion of the via to completely fill the via; Including, the metallic connector completely fills the via in the axial direction over the axial length L of the via; The vias have a maximum diameter Φ of less than 30 μm. max having The axial length L and the maximum diameter Φ max is the formula, i.e.

[0139]

number

[0140] A way to satisfy.

[0141] EMBODIMENT 24 24. The method of embodiment 23, wherein the helium-tight adhesion layer comprises one or more of Ti, TiN, Ta, TaN, Cr, Ni, and a metal oxide.

[0142] EMBODIMENT 25 25. The method of embodiment 23 or 24, wherein the metallic connector consists essentially of copper.

[0143] EMBODIMENT 26 26. The method of any one of embodiments 23 to 25, wherein the metal connector hermetically seals the via.

[0144] EMBODIMENT 27 27. The method of any one of embodiments 23 to 26, wherein the step of depositing the metallic connector comprises depositing the metallic connector using electroplating.

[0145] EMBODIMENT 28 28. The method of any one of embodiments 23 to 27, wherein the step of depositing the helium hermetic adhesion layer includes a step of depositing the helium hermetic adhesion layer on the inner surface of the via in the first axial portion, the second axial portion and the third axial portion.

[0146] EMBODIMENT 29 28. The method of any one of embodiments 23 to 27, wherein the step of depositing the helium hermetic adhesion layer includes depositing the helium hermetic adhesion layer on the inner surface of the via in the first axial portion and the third axial portion, but not on the inner surface in the second axial portion.

[0147] EMBODIMENT 30 30. The method of any one of embodiments 23 to 29, wherein the substrate comprises at least 90% by weight silica.

Claims

1. An article, a glass or glass-ceramic substrate (100) having a first major surface (102) and a second major surface (104) opposite the first major surface (102), the glass or glass-ceramic substrate (100) comprising at least 50 mol % silica, the glass or glass-ceramic substrate (100) extending axially from the first major surface (102) to the second major surface (104) over an axial length L; The inner surface (114) and a glass or glass ceramic substrate (100) having a via (110) defining a first axial portion (116), a third axial portion (120), and a second axial portion (118) disposed along the axis between the first axial portion (116) and the third axial portion (120); a helium-tight adhesive layer (122) comprising titanium, chromium, tantalum, vanadium, nickel, tungsten, zinc oxide, tungsten oxide, titanium nitride, or tantalum nitride, the adhesive layer having a thickness of 1 nm to 500 nm, the adhesive layer being disposed on the inner surface (114) of at least the first axial portion (116) and / or the third axial portion (120); a metal connector (150) comprising copper, gold, silver, or an alloy of copper, gold, and silver, disposed within the via (110) and bonded to the helium-tight adhesive layer (122); Equipped with The metal connector (150) completely fills the via (110) over the axial length L of the via (110); The via (110) has a maximum diameter Φ of 30 μm or less. ｍａｘ and the axial length L and the maximum diameter Φ ｍａｘ is the formula, i.e. [Equation 1] Satisfying, goods.

2. 2. The article of claim 1, wherein the via has a first diameter at the first major surface, a second diameter at the second major surface, and a third diameter at the second axial portion, the third diameter being smaller than the first diameter and the second diameter.

3. The helium-tight adhesive layer is disposed on the inner surface of the first axial portion, the second axial portion, and the third axial portion, and the maximum diameter Φ ｍａｘ 3. The article of claim 1, wherein the thickness is 27 μm or less.

4. the helium gas-tight adhesive layer is disposed on the inner surface of the first axial portion and / or the third axial portion, and is not disposed on the inner surface of the second axial portion; and the maximum diameter Φ ｍａｘ 3. The article of claim 1, wherein the thickness is 25 μm or less.

5. 2. The article of claim 1, wherein the via has a first diameter at the first major surface, a second diameter at the second major surface, and a third diameter at the second axial portion, the first diameter being larger than the second diameter and the third diameter, and the third diameter being larger than the second diameter.

6. The helium-tight adhesive layer is disposed on the inner surface of the first axial portion, the second axial portion, and the third axial portion, and the maximum diameter Φ ｍａｘ 6. The article of claim 5, wherein the thickness is 19 μm or less.

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