Articles having holes with morphological properties and methods of making same

Abstract

An article including a glass-based substrate having a hole, a semiconductor package including an article having a hole, and a method of making a hole in a substrate are disclosed. In one embodiment, an article includes a glass-based substrate having a first surface, a second surface, and at least one aperture extending from the first surface. The at least one hole has an inner wall having a surface roughness Ra less than or equal to 1 m. The at least one aperture has a first opening present in the first surface having a first diameter. A first plane is defined by a first surface of the glass-based substrate based on an average thickness of the glass-based substrate. The ratio of the depth of the recess to the first diameter of the at least one aperture is less than or equal to 0.007.

Description

[0001] This application is a divisional application of Corning Incorporated's patent application No. 201780055422.0 entitled "Article with Morphologically Attributed Holes and Method of Manufacturing Thereof" (hereinafter referred to as the "parent application"). The parent application is the Chinese national phase of PCT application PCT / US2017 / 050503, which claims priority to U.S. patent application 62 / 384,923, with a priority date of September 8, 2016.

[0002] Cross-reference of related applications

[0003] This application claims priority to U.S. Provisional Application No. 62 / 384923, filed on 09 / 08 / 2016, pursuant to 35 USC § 119, the contents of which are incorporated herein by reference in their entirety. background Technical Field

[0004] This disclosure generally relates to articles having etched holes. In particular, this disclosure relates to articles having holes with desired morphology, and to laser and etching methods for manufacturing said articles. Background Technology

[0005] Substrates (such as silicon) have been used as interposers between various electrical components (such as printed circuit boards, integrated circuits, etc.). Metallized vias through the substrate provide a path through the interposer to allow electrical signals to pass between opposite sides of the interposer. Glass is a substrate material that is highly advantageous for electrical signal transmission because of its good dimensional stability, tunable coefficient of thermal expansion (“CTE”), excellent low electrical losses at high frequencies, high thermal stability, and the ability to be formed in a certain thickness and large panel size. However, in the development of the glass interposer market, the formation and metallization of vias through glass (“TGV”) present two major challenges.

[0006] The morphological properties of pores play a role in the proper metallization of pores in glass substrates. Pores with excessively rough inner walls can prevent conductive materials from adhering to the surface and can also result in high resistance, especially at high operating frequencies. Furthermore, laser-drilled and etched pores through the glass substrate may have depressions, protrusions, and other anomalies around the pore opening. These anomalies cause problems for downstream processes, such as depositing a redistribution layer on the substrate surface.

[0007] Therefore, there is a need for alternative articles with improved pore morphological properties, as well as methods for obtaining such improved morphological properties. Summary of the Invention

[0008] In a first aspect, an article of article includes a glass substrate having a first surface, a second surface, and at least one hole extending from the first surface. The at least one hole has an inner wall with a surface roughness R. a Less than or equal to 1 µm. The at least one hole has a first opening at a first surface having a first diameter. A first plane is defined by the first surface of the glass substrate based on the average thickness of the glass substrate. The ratio of the recess depth to the first diameter of the at least one hole is less than or equal to 0.007. The recess depth is measured from the first plane to the first surface at the first opening of the at least one hole.

[0009] According to the second aspect of the first aspect, wherein the at least one hole is a perforation extending from a first surface to a second surface, such that a second opening with a second diameter exists on the second surface, a second plane is defined by the second surface of the glass substrate based on the average thickness of the glass substrate, and the ratio of the second recess depth to the second diameter of the at least one hole is less than or equal to 0.007. The second recess depth is measured from the second plane to the second surface at the second opening of the at least one hole.

[0010] According to the third aspect described in the second aspect, the difference between the first diameter and the second diameter is less than or equal to 2 µm.

[0011] According to the fourth aspect of the second aspect, wherein the at least one hole includes a waist having a waist diameter, and the waist diameter is greater than or equal to 80% of the larger of the first diameter and the second diameter.

[0012] According to the fifth aspect of the second aspect, wherein the at least one hole includes a waist having a waist diameter, and the waist diameter is in the range of 20% to 100% of the largest of the first diameter and the second diameter.

[0013] According to the sixth aspect described in any of the preceding aspects, the ratio of the recess depth to the first diameter is less than or equal to 0.005.

[0014] According to the seventh aspect described in any of the preceding aspects, the ratio of the recess depth to the first diameter is less than or equal to 0.003.

[0015] According to the eighth aspect described in any of the foregoing aspects, the surface roughness R of the inner wall a Within the range of 0.1 µm to 1 µm.

[0016] According to the ninth aspect of any of the foregoing aspects, the first diameter of the at least one hole is in the range of 5 µm to 250 µm.

[0017] The tenth aspect according to any one of the first to seventh aspects, wherein the first diameter of the at least one hole is in the range of 5 µm to 100 µm.

[0018] According to the eleventh aspect of any of the preceding aspects, the glass substrate is transparent to at least one wavelength in the range of 390 nm to 1100 nm.

[0019] According to the 12th aspect described in any of the preceding aspects, the at least one hole is a plurality of holes.

[0020] The 13th aspect is as described in any one of aspects 1 and 6 to 12, wherein the at least one hole is a blind hole.

[0021] According to the 14th aspect of any of the preceding aspects, the roundness of the at least one hole is less than or equal to 5 µm.

[0022] According to the 15th aspect of any of the preceding aspects, the aspect ratio of the average thickness of the glass substrate to the first diameter of the at least one hole is in the range of 1:1 to 15:1.

[0023] According to the 16th aspect of the first aspect, wherein the at least one hole is a perforation such that a second opening having a second diameter exists on the second surface, the difference between the first diameter and the second diameter is less than or equal to 2 µm, the roundness of the at least one hole is less than or equal to 5 µm, the first diameter and the second diameter are each in the range of 5 µm to 250 µm, and the average thickness of the glass substrate is in the range of 1:1 to 15:1 in aspect ratio to at least one of the first diameter and the second diameter.

[0024] According to the 17th aspect of the 16th aspect, the at least one hole includes a waist having a waist diameter, and the waist diameter of the at least one hole is greater than or equal to 80% of the larger of the first diameter and the second diameter.

[0025] According to the 18th aspect of the 16th aspect, wherein the at least one hole includes a waist having a waist diameter, and the waist diameter is in the range of 20% to 100% of the largest of the first diameter and the second diameter.

[0026] In a 19th aspect, a semiconductor package includes a glass substrate, the glass substrate including a first surface, a second surface, and at least one aperture extending from the first surface. The at least one aperture includes an inner wall with a surface roughness R. aThe depth is less than or equal to 1 µm. The at least one hole includes a first opening having a first diameter on a first surface and a second opening having a second opening on a second surface. A first plane is defined by a first surface of the glass substrate based on the average thickness of the glass substrate. The ratio of the recess depth to the first diameter of the at least one hole is less than or equal to 0.007. The recess depth is measured from the first plane to the first surface at the first opening of the at least one hole. A conductive material is disposed in the at least one hole. The semiconductor package also includes a semiconductor device electrically coupled to the conductive material disposed in the at least one hole.

[0027] According to the 20th aspect of the 19th aspect, the ratio of the second recess depth to the second diameter of the at least one hole is less than or equal to 0.007, wherein the second recess depth is measured from the second plane to the second surface at the second opening of the at least one hole, and the second plane is defined by the first surface of the glass substrate based on the average thickness of the glass substrate.

[0028] According to the 21st aspect of the 20th aspect, the difference between the first diameter and the second diameter is less than or equal to 2 µm.

[0029] According to the 22nd aspect of the 21st aspect, the at least one hole includes a waist having a waist diameter, and the waist diameter is greater than or equal to 80% of the larger of the first diameter and the second diameter.

[0030] According to the 23rd aspect of the 21st aspect, wherein the at least one hole includes a waist having a waist diameter, and the waist diameter is in the range of 20% to 100% of the largest of the first diameter and the second diameter.

[0031] According to the 24th aspect of any one of aspects 19 to 23, the semiconductor package further includes a conductive layer disposed on a first surface of a glass substrate, wherein the conductive layer is electrically coupled to a conductive material disposed in the at least one hole.

[0032] The 25th aspect according to any one of aspects 19 to 24, wherein the ratio of the recess depth to the first diameter of the at least one hole is less than or equal to 0.005.

[0033] The 26th aspect according to any one of aspects 19 to 25, wherein the ratio of the recess depth to the first diameter of the at least one hole is less than or equal to 0.003.

[0034] The 27th aspect according to any one of aspects 19 to 26, wherein the surface roughness R of the inner wall of the at least one hole is... aWithin the range of 0.1 µm to 1 µm.

[0035] The 28th aspect is as described in any one of aspects 19 to 27, wherein the first diameter is in the range of 5 µm to 250 µm.

[0036] The 29th aspect is as described in any one of aspects 19 to 28, wherein the at least one hole is a plurality of holes.

[0037] The 30th aspect according to any one of aspects 19 to 29, wherein the roundness of the at least one hole is less than or equal to 5 µm.

[0038] According to the 31st aspect as described in any one of aspects 19 to 30, the average thickness of the glass substrate is in the range of 1:1 to 15:1 in aspect ratio to the first diameter.

[0039] According to the 32nd aspect of the 19th aspect, the difference between the first diameter and the second diameter is less than or equal to 2 µm, the roundness of the at least one hole is less than or equal to 5 µm, the first diameter and the second diameter are each in the range of 5 µm to 250 µm, and the average thickness of the glass substrate is in the range of 1:1 to 15:1 in aspect ratio to at least one of the first diameter and the second diameter.

[0040] According to the 33rd aspect of the 32nd aspect, the at least one hole includes a waist having a waist diameter, and the waist diameter of the at least one hole is greater than or equal to 80% of the larger of the first diameter and the second diameter.

[0041] According to the 34th aspect of the 32nd aspect, wherein the at least one hole includes a waist having a waist diameter, and the waist diameter is in the range of 20% to 100% of the largest of the first diameter and the second diameter.

[0042] According to the 35th aspect of the 32nd aspect, wherein the semiconductor package is a radio frequency antenna chip.

[0043] In a 36th aspect, an article of article includes a glass substrate, the glass substrate including a first surface, a second surface, and at least one aperture extending from at least one of the first surface and the second surface, wherein the at least one aperture includes a surface roughness R. a The inner wall is less than or equal to 1 µm, and the at least one hole includes a first opening having a first diameter at a first surface, and the first diameter is in the range of 5 µm to 250 µm.

[0044] According to aspect 37 of aspect 36, wherein the surface roughness R of the inner wall a Less than or equal to 0.3 µm.

[0045] According to aspect 38 as described in aspect 36 or aspect 37, wherein the surface roughness R of the inner wall is... a Less than or equal to 0.2 µm.

[0046] The 39th aspect according to any one of aspects 36 to 38, wherein the first diameter of the at least one hole is in the range of 5 µm to 100 µm.

[0047] In a 40th aspect, a method of forming a hole in a substrate includes: applying a pulsed laser beam to the substrate to form at least one laser-damaged region in the substrate, and etching the substrate in a liquid etching solution to expand the at least one laser-damaged region, thereby forming at least one hole in the substrate, such that the at least one hole includes a surface roughness R. a The inner wall is less than or equal to 1 µm; the at least one hole includes a first opening having a first diameter on a first surface of the substrate, and the ratio of the recess depth to the first diameter of the at least one hole is less than or equal to 0.007, wherein the recess depth is measured from a first plane to the first surface at the first opening of the at least one hole, the first plane being defined by the first surface of the substrate based on the average thickness of the substrate.

[0048] According to the 41st aspect of the 40th aspect, the etching rate of the etching solution is in the range of 1 µm / min to 10 µm / min.

[0049] According to the 42nd aspect of the 41st aspect, the etching rate of the etching solution is in the range of 3 µm / min to 4 µm / min.

[0050] According to aspect 43 of any one of aspects 40 to 42, wherein the pH of the etching solution is in the range of 1.0 to 2.0.

[0051] The 44th aspect according to any one of aspects 40 to 42, wherein the pH of the etching solution is in the range of 1.0 to 2.0, and the etching solution provides an etching rate of less than about 4 µm / min.

[0052] According to the 45th aspect of any one of aspects 40 to 44, etching the substrate further includes applying ultrasonic stirring to the etching solution, said ultrasonic stirring having a frequency in the range of 40 kHz to 192 kHz.

[0053] According to the 46th aspect of the 40th aspect, the etching solution contains 1.5M HF and 1.6M HNO3.

[0054] According to the 47th aspect of the 40th aspect, the etching solution contains 1.5M HF and 1.6M HNO3, the temperature of the etching solution is in the range of 10°C to 30°C, and ultrasonic stirring is applied to the etching solution at a frequency in the range of 40 kHz to 192 kHz.

[0055] According to the 48th aspect of any one of aspects 40 to 47, applying a pulsed laser beam to the substrate further includes: attaching a sacrificial cover layer to the surface of the substrate, positioning the laser beam at a predetermined position relative to the substrate and such position corresponds to a desired position of the at least one hole, forming the at least one laser-damaged region in the sacrificial cover layer by repeatedly pulsed laser beam at the predetermined position, and pulse the laser beam into a perforation formed in the sacrificial cover layer at the predetermined position, thereby forming the at least one damaged region in the substrate.

[0056] According to the 49th aspect of the 48th aspect, the numerical aperture of the laser beam is between about 0.02 and about 0.4, and the focusing position of the laser beam is within about 100 μm of the surface of the sacrificial coating.

[0057] According to the 50th aspect as described in aspect 48 or aspect 49, the wavelength of the laser beam is about 355 nm, the pulse width of the laser beam is between about 5 ns and about 75 ns, the laser beam pulses at a repetition frequency of about 1 kHz to about 30 kHz, and the pulse energy of the laser beam is between about 25 μJ and about 175 μJ.

[0058] According to the 51st aspect of any one of aspects 40 to 47, applying a pulsed laser beam to the substrate further includes: forming a destruction trace that defines the at least one laser destruction region in the substrate by focusing the pulsed laser beam into a laser beam focal line oriented along the beam propagation direction and guiding the laser beam focal line into the substrate.

[0059] According to aspect 52 of aspect 51, wherein the focal line of the laser beam extends through the entire body of the substrate.

[0060] According to the 53rd aspect as described in aspect 51 or aspect 52, the wavelength of the pulsed laser beam is approximately 532 nm.

[0061] According to aspect 54 as described in any one of aspects 51 to 53, wherein the pulsed laser beam comprises a series of pulse trains, and each laser beam comprises a series of pulses.

[0062] According to the 55th aspect of the 54th aspect, the number of pulses in each pulse train is in the range of 10 to 20, and the average energy of each pulse train is in the range of 100 µJ to 200 µJ.

[0063] According to aspect 56, which is described in any one of aspects 40 to 55, the surface roughness R of the inner wall a Within the range of 0.1 µm to 1 µm.

[0064] The 57th aspect is as described in any one of aspects 40 to 56, wherein the first diameter of the at least one hole is in the range of 5 µm to 250 µm.

[0065] According to the 58th aspect described in the 57th aspect, the first diameter is in the range of 5 µm to 100 µm.

[0066] The 59th aspect according to any one of aspects 40 to 58, wherein the substrate is transparent to at least one wavelength in the range of 390 nm to 1100 nm.

[0067] The 60th aspect is as described in any one of aspects 40 to 59, wherein the substrate is a glass-based substrate.

[0068] The 61st aspect is as described in any one of aspects 40 to 60, wherein the at least one hole is a plurality of holes.

[0069] The 62nd aspect is as described in any one of aspects 40 to 61, wherein the at least one hole is a blind hole.

[0070] The 63rd aspect according to any one of aspects 40 to 61, wherein the at least one hole is a perforation such that a first opening having a second diameter is present on a first surface and a second opening is present on a second surface, the second plane is defined by the second surface of the substrate based on the average thickness of the substrate, and the ratio of the second recess depth to the second diameter of the at least one hole is less than or equal to 0.007, wherein the second recess depth is measured from the second plane to the second surface at the second opening of the at least one hole.

[0071] According to the 64th aspect of the 63rd aspect, the first opening has a first diameter, the second opening has a second diameter, and the difference between the first diameter and the second diameter is less than or equal to 2 µm.

[0072] According to the 65th aspect of the 64th aspect, the at least one hole includes a waist having a waist diameter, and the waist diameter is greater than or equal to 80% of the largest of the first diameter of the first opening and the second diameter of the second opening.

[0073] According to the 66th aspect of the 64th aspect, wherein the at least one hole includes a waist having a waist diameter, and the waist diameter is in the range of 20% to 100% of the largest of the first diameter and the second diameter.

[0074] The 67th aspect according to any one of aspects 40 to 66, wherein the roundness of the at least one hole is less than or equal to 5 µm.

[0075] The 68th aspect according to any one of aspects 40 to 66, wherein the aspect ratio of the average thickness of the substrate to the first diameter of the at least one hole is in the range of 1:1 to 15:1.

[0076] According to the 69th aspect of the 40th aspect, wherein the substrate is a glass-based substrate, the at least one hole is a perforation such that a second opening having a second diameter exists on a second surface, a first opening has a first diameter, a second opening has a second diameter, the difference between the first diameter and the second diameter is less than or equal to 2 µm, the roundness of the at least one hole is less than or equal to 5 µm, the first diameter and the second diameter are each in the range of 5 µm to 250 µm, and the average thickness of the substrate is in the range of 1:1 to 15:1 in aspect ratio to at least one of the first diameter and the second diameter.

[0077] According to the 70th aspect of the 69th aspect, the at least one hole includes a waist having a waist diameter, and the waist diameter of the at least one hole is greater than or equal to 80% of the largest of the first diameter of the first opening and the second diameter of the second opening.

[0078] According to the 71st aspect of the 69th aspect, the at least one hole includes a waist having a waist diameter, and the waist diameter is in the range of 20% to 100% of the largest of the first diameter of the first opening and the second diameter of the second opening.

[0079] The 72nd aspect includes articles manufactured in accordance with any one of aspects 40 to 71.

[0080] Other features and advantages of this disclosure are set forth in the following detailed description, some of which will be readily understood by those skilled in the art from the description made, or will be recognized by practicing the embodiments described herein, including the following detailed description, the claims and the drawings.

[0081] It should be understood that the foregoing general description and the following detailed description both depict various embodiments and are intended to provide an overall assessment or framework for understanding the nature and characteristics of the claimed subject matter. The included drawings provide a further understanding of the various embodiments and are incorporated in and form a part of this specification. The drawings illustrate the various embodiments described herein and, together with the description, serve to explain the principles and operation of the claimed subject matter. Attached Figure Description

[0082] The embodiments illustrated in the accompanying drawings are merely illustrative and exemplary, and are not intended to limit the subject matter defined by the claims. A detailed description of the illustrative embodiments can be understood by reading the following drawings, in conjunction with which the same structures are indicated by the same reference numerals, wherein: Figure 1 An exemplary article of a wafer configured to have holes is schematically depicted according to one or more embodiments described and illustrated herein; Figure 2A A top view of an exemplary article having a hole is schematically depicted according to one or more embodiments described and illustrated herein; Figure 2B According to one or more embodiments described and illustrated herein, a top view of an exemplary article having holes is schematically depicted, the figure being used to determine the average thickness of the article; Figure 3A A cylindrical hole is schematically depicted according to one or more embodiments described and illustrated herein; Figure 3B An hourglass-shaped aperture is schematically depicted according to one or more embodiments described and illustrated herein; Figure 4 The calculation of the roundness of holes in an article is illustrated according to one or more embodiments described and shown herein; Figure 5 Exemplary edge detection in an image of a hole is illustrated according to one or more embodiments described and shown herein; Figure 6 According to one or more embodiments described and illustrated herein, an exemplary computer-implemented method for calculating the roughness of the inner wall of a hole is schematically depicted. Figure 7 According to one or more embodiments described and illustrated herein, the roughness R of the inner surface of an exemplary hole is illustrated. a ; Figure 8AAccording to one or more embodiments described and illustrated herein, an exemplary hole having a recessed area around the opening of the hole is schematically depicted; Figure 8B An exemplary article having an array of holes is schematically depicted according to one or more embodiments described and illustrated herein; Figure 9 According to one or more embodiments described and illustrated herein, an exemplary semiconductor package comprising the article described herein as an interposer is schematically depicted; Figure 10 According to one or more embodiments described and illustrated herein, an exemplary etching method for opening a laser-drilled laser-damaged area or via is schematically depicted. Figure 11 An exemplary laser system for forming laser-damaged regions or vias in an article of manufacture is schematically depicted according to one or more embodiments described and illustrated herein. Figures 12A-12C This is an exemplary graph of laser emission changing over time for a picosecond laser, based on one or more embodiments described and illustrated herein. Figure 13A This is an example of using Figure 11 The illustrated exemplary laser system, for different pulse train energies and the number of subpulses in each pulse train, and the morphological images of the holes in the glass; Figure 13B This is a top-view image showing holes on a glass substrate after laser exposure and etching at different laser pulse energies; Figure 13C This is an image showing a side view of a hole in a glass substrate after laser exposure and etching at different pulse energies; Figure 14 The figure illustrates the experimental measurements of the relationship between the peak-axis intensity of a Gaussian-Bessel beam and the distance along the beam propagation (optical) axis. Figure 15 According to one or more embodiments described and illustrated herein, an exemplary impact laser drilling system for forming a laser-damaged region or guide hole through an article is schematically illustrated; Figure 16 According to one or more embodiments described and illustrated herein, exemplary etching apparatuses for opening laser-damaged areas or vias in a work-in-progress are schematically illustrated. Figure 17 The figure illustrates the effect of ultrasonic stirring during the etching process on the surface roughness of glass products. Figures 18A-18F This is an image of a hole illustrating the effect of the pH of the etching solution on the depth of the indentation surrounding the opening of the hole; Figure 19 The figure illustrates the effect of the etching solution pH on the indentation depth surrounding the opening of the hole; and Figure 20 The figure illustrates the effect of reducing the etching rate and increasing the pH of the etching solution on the depth of the indentation around the opening of the hole. Detailed Implementation

[0083] Generally, with reference to the accompanying drawings, embodiments of this disclosure generally relate to articles of manufacture that can be used as interposers in semiconductor packages, the articles of manufacture having holes (e.g., vias) and surface properties that facilitate successful downstream processing, including but not limited to metallization of vias and application of redistribution layers (RDLs) for use in semiconductor devices, radio frequency (RF) devices (e.g., antennas, switches, etc.), interposer devices, microelectronic devices, optoelectronic devices, microelectromechanical systems (MEMS) devices, and other applications that can utilize vias.

[0084] More specifically, the embodiments described herein relate to articles having holes formed by laser destruction and etching methods, and the holes having desired morphological properties, particularly including low surface roughness (R0). a The inner wall (less than 1 µm) and the depth D of the recess surrounding the opening of the hole. 凹陷 This makes the depth of the depression D 凹陷 The ratio of the aperture diameter to the surface diameter is less than 0.007. Finally, the aperture can be coated or filled with a conductive material. A aperture with low inner wall surface roughness allows for increased adhesion between the conductive material and the inner wall, as well as reduced resistance. The small recess depth D around the aperture opening... 凹陷 This improves the reliability of downstream processes.

[0085] Embodiments of this disclosure also relate to methods of laser drilling and etching, which result in an article having a hole with a desired morphology. Articles with desired hole morphology described herein (e.g., glass articles) can be used, for example, as interposers in semiconductor devices (e.g., RF antennas).

[0086] The following describes in detail various embodiments of articles, semiconductor packages, and methods for forming holes in substrates.

[0087] Figure 1 A perspective view of an exemplary article 100 having a plurality of holes 120 is schematically illustrated. Figure 2 schematically illustrates... Figure 1 A top view of the exemplary article 100 shown. Although Figure 1Figures 1 and 2 depict an article 100 configured as a wafer, but it should be understood that the article can take any shape, such as, but not limited to, a panel. The article described herein is made of a light-transmitting substrate capable of allowing radiation having wavelengths within the visible spectrum to pass through. For example, the substrate can transmit at least 70%, at least 75%, at least 80%, at least 85%, or at least 90% of at least one wavelength in the range of 390 nm to 700 nm. The substrate can be a glass-based substrate. As used herein, a glass-based substrate material means glass (including fused silica) and glass ceramics. In some embodiments, the substrate can be glass, and the glass may include fused silica, alkali metal-containing glass, alkali metal-free glass (e.g., alkali metal-free alkaline aluminoborosilicate glass), or laminated glass comprising layers of different glass compositions. In some embodiments, the substrate may have a low coefficient of thermal expansion (e.g., less than or equal to 4 ppm / °C), and in other embodiments, the substrate may have a high coefficient of thermal expansion (e.g., greater than 4 ppm / °C).

[0088] As described above, article 100 can serve as an interposer in an electronic device to allow electrical signals to pass between one or more electronic components connected to a first surface 110 of article 100 and one or more electronic components connected to a second surface 112 of article 100. Holes 120 of article 100 are filled with a conductive material to provide conductive vias through which electrical signals can pass. Holes 120 can be, for example, through-holes or blind vias. As used herein, through-holes extend from the first surface 110 to the second surface 112, extending through the thickness of the substrate. As used herein, blind vias originate from one of the first surface 110 or the second surface 112 but do not extend to the other, thus only partially extending through the thickness of the substrate. Other features can be formed in the first surface 110 or the second surface 112 of article 100, such as, but not limited to, channels that can be metallized to provide patterns of one or more electrical traces. Other features may also be provided.

[0089] Depending on the end use, article 100 can be of any size and shape. By way of example and not limitation, the thickness T of article 100 can range from 25 µm to 3,000 µm. The opening diameter D of the hole 120 of article 100 is relatively small, for example, but not limited to, less than or equal to 250 µm, less than or equal to 200 µm, less than or equal to 150 µm, less than or equal to 100 µm, less than or equal to 100 µm, less than or equal to 50 µm, less than or equal to 20 µm, or less than or equal to 10 µm. As used herein, the opening diameter D is the diameter of the opening of the hole at the first or second surface of the substrate. Brief Reference Figure 8AThe opening of hole 120 is at position 131, which marks the transition between the curved slope of recessed region 123 and the vertical wall 124 of hole 120. The starting point of vertical wall 124—and therefore the starting point of the opening of hole 120—is at position 131, where the angle α between the tangent TL of the hole entrance and the first plane 126 defined by the average thickness T of article 100 is greater than or equal to 75 degrees. The opening diameter D of hole 120 is calculated by finding the diameter of the least-squares best-fit circle of the entrance edge of hole 120 as imaged by an optical microscope. The pitch p of the hole 120 is the center-to-center distance between adjacent holes 120. Depending on the application, it can be any size, such as, but not limited to, 10 µm, 50 µm, 100 µm, 250 µm, 1000 µm, or any range of pitches, such as 10 µm to 100 µm, 25 µm to 500 µm, 10 µm to 1000 µm, or 250 µm to 2000 µm.

[0090] As defined herein, the average thickness T of article 100 is determined by calculating the average of three thickness measurements, which is performed outside of any recessed area 123 on the first surface 110 or the second surface 112 due to the formation of hole 120 (see [link to article 100]). Figure 8A and 8B As defined herein, thickness measurements are performed using an interferometer. As described in more detail below, laser destruction and etching methods can create recessed regions 123 around holes formed in article 100. Therefore, the average thickness T is determined by measuring the thickness of article 100 at three locations outside the recessed regions. As used herein, the phrase "outside the recessed regions" means measurements taken at distances from the nearest hole 120 ranging from 500 µm to 2,000 µm. Furthermore, to obtain an accurate representation of the average thickness of the article, the measurement points should be at least 100 µm apart from each other. In other words, there should be no other measurement point within 100 µm of a measurement point.

[0091] Now for reference Figure 2B The figure schematically depicts a non-limiting example of determining the average thickness T of article 100. It should be understood that the implementation is not limited to this. Figure 2B The structure of hole 120 and the locations of measuring points M1, M2, and M3 are shown. Figure 2B For illustrative purposes only. Figure 2BThe exemplary article 100 shown has multiple holes, three of which are numbered 120A, 120B, and 120C. Three thickness measurements are performed at measurement points M1, M2, and M3 using an interferometer. As mentioned above, the thickness measurements should be performed outside any recessed areas of the article 100 (e.g., recessed areas created by manufacturing holes). With respect to measurement point M1, the nearest hole is hole 120A. The distance MD1 from measurement point M1 to hole 120A is in the range of 500 µm to 2,000 µm. Similarly, the distance MD2 from measurement point M2 to hole 120B and the distance MD3 from measurement point M3 to hole 120C are in the range of 500 µm to 2,000 µm. It should be noted that although... Figure 2B The example illustrates that the nearest holes 120A-120C are different for measurement points M1, M2, and M3, but the implementation is not limited to this. As a non-limiting example, a single hole can be used as a reference point to determine the distance to the nearest hole (e.g., hole 120A).

[0092] After three thickness measurements were performed at measurement points M1, M2 and M3 using an interferometer, the average of the three thickness measurements was calculated to determine the average thickness T.

[0093] As described above, any known technique can be used to fill the holes 120 (and other features in some embodiments) with a conductive material, including but not limited to sputtering, electroless plating and / or electrolytic plating, chemical vapor deposition, etc. The conductive material can be, for example, copper, silver, aluminum, titanium, gold, platinum, nickel, tungsten, magnesium, or any other suitable material. When the holes 120 are filled, they can electrically couple the traces of electronic components disposed on the first surface 110 and the second surface 112 of the article 100.

[0094] The morphology of the hole 120 plays a role in the final filling quality of the hole 120. The internal shape (i.e., profile) and roughness of the hole are crucial to the success of the metallization process. For example, holes with excessively rough textures can lead to poor metallization and insufficient electrical properties after metallization. Furthermore, adjusting the size of the waist (narrowest point) in the hole can be advantageous depending on the metallization process used—paste filling, vacuum sputtering, electroplating, etc. In some cases, it is advantageous to have as many cylindrical holes as possible (large waist percentage) (e.g., >50%, >60%, or >75% or >80%), while in others, holes with specific waist openings are desired (e.g., waist percentages of 20-80%, 20-60%, 30-50%, 40-50%, or 35-45%). Metallization processes, such as vacuum deposition coating, often have visibility problems, meaning that the applied coating cannot reach the innermost regions of a rough texture. Alternatively, in a single-sided sputtering process, the lower region of an hourglass-shaped aperture may be difficult to coat because some points on the surface "obscure" other points, preventing the coating process from proceeding. However, for some metallization processes, an hourglass-shaped aperture may be desirable because it allows for easier surface coating compared to a cylindrical aperture. Any suboptimal shape or rough texture can also lead to reliability issues after metallization, such as cracking and other failures when the part is subjected to environmental stresses (e.g., thermal cycling). Additionally, recesses or protrusions near the inlet and / or outlet of aperture 120 along the top and bottom surfaces of the article can also cause plating, coating, and bonding problems when a re-layering process is applied. Therefore, the morphology of the aperture should be strictly controlled to manufacture a technically feasible product. Embodiments of this disclosure provide articles with desired morphological properties and tolerances, and exemplary manufacturing methods for obtaining articles with said morphological properties and tolerances.

[0095] Figure 3A and 3B Two holes 120 and 12 in article 100 are illustrated independently and schematically. . Figure 3A The hole 120 shown is substantially cylindrical, such that a first diameter D1 (e.g., the diameter of a first opening at a first surface) is substantially equal to a second diameter D2 (e.g., the diameter of a second opening at a second surface), and the diameter along the entire length of the hole 120 is substantially equal to both the first diameter D1 and the second diameter D2. However, Figure 3B Hole 12 shown The hole has an "hourglass" shape, resulting in a waist diameter W that is smaller than the first diameter D1 and the second diameter D2. As used herein, the waist diameter W refers to the narrowest portion of the hole located between the first and second surfaces. It should be noted that the waist does not need to be at the midpoint of the hole's depth, but can appear at any point between the two surfaces. As mentioned above, an "hourglass" shaped hole may be undesirable for metallization processes because the narrow waist may prevent the conductive material from being fully deposited within the hole.

[0096] In some embodiments, the waist diameter W may be greater than or equal to 80% of the largest of the first diameter D1 and the second diameter D2. In other embodiments where an hourglass shape may be desired, the waist diameter W ranges from 20% to 100% of the largest of the first diameter D1 and the second diameter D2. In other embodiments, the waist diameter W may be 85% of the largest of the first diameter D1 and the second diameter D2, 90% of the largest of the first diameter D1 and the second diameter D2, 30% to 100% of the largest of the first diameter D1 and the second diameter D2, 40% to 100% of the largest of the first diameter D1 and the second diameter D2, 50% to 100% of the largest of the first diameter D1 and the second diameter D2, 60% to 100% of the largest of the first diameter D1 and the second diameter D2, 70% to 100% of the largest of the first diameter D1 and the second diameter D2, 80% to 100% of the largest of the first diameter D1 and the second diameter D2, or 90% to 100% of the largest of the first diameter D1 and the second diameter D2.

[0097] In some implementations, the first diameter D1 is substantially equal to the second diameter D2. By way of example and not limitation, the difference between the first diameter D1 and the second diameter D2 is less than or equal to 2 µm, less than or equal to 1.50 µm, less than or equal to 1 µm, less than or equal to 0.75 µm, less than or equal to 0.5 µm, less than or equal to 0.25 µm, less than or equal to 0.1 µm, or less than or equal to 0 µm.

[0098] The aspect ratio of the thickness T of article 100 to the hole diameter D1 or D2 is not limited by this disclosure. In some embodiments, the aspect ratio is in the range of 1:1 to 15:1. This aspect ratio may be specified by the final product specifications. The diameter of the hole (including D1, D2, and W) can be determined, for example, by imaging the hole with an optical microscope and calculating the least-squares best-fit circle of the edge of the hole 120.

[0099] By utilizing the manufacturing method described below, uniformity of hole diameter and waist diameter is maintained throughout the article 100. In some embodiments, for holes 120 having desired equal diameters in the article 100, the hole diameter uniformity of the article 100, configured as a wafer with a maximum diameter of 300 mm, is ±3%. In some embodiments, for holes 120 having desired equal diameters in the article 100, the waist diameter uniformity of the article 100, configured as a wafer with a maximum diameter of 300 mm, is ±5%. As used herein, hole diameter uniformity is expressed by the expression... Confirmed, among which D 最小 It is the smallest hole diameter on the surface (either the top surface or the bottom surface of the article 100) among all holes 120 having the required equal diameter. D 最大 In each of the holes 120 having the required equal diameter, in conjunction with D 最小 The maximum hole diameter on the same surface, and D 平均 It is the average diameter among the holes 120 on the surface that have the required equal diameter.

[0100] As used in this article, the uniformity of the waist diameter is expressed by the expression It is confirmed that, among them, W 最小 It is the smallest waist diameter among the holes 120 with the required equal diameter. W 最大 It is the largest waist diameter among the holes 120 with the required equal diameter, and W 平均 It is the average waist diameter among the holes 120 with the required equal diameter.

[0101] Precisely arranging the holes 120 in the article 100 is also important in the final product. As a non-limiting example, for the article 100 constructed as a wafer with a diameter up to 300 mm, the hole-to-hole arrangement accuracy can be less than ±5 µm, less than ±4 µm, less than ±3 µm, less than ±2 µm, or less than ±1 µm. As another non-limiting example, for the article 100 constructed as a panel with a maximum size of 600 mm × 600 mm, the hole-to-hole arrangement accuracy can be less than ±10%, less than ±9 µm, less than ±8 µm, less than ±7 µm, less than ±6 µm, less than ±5 µm, less than ±4 µm, less than ±3 µm, less than ±2 µm, or less than ±1 µm. Although various alignment techniques exist, in this disclosure, an alignment scheme of "best fit" is employed. To determine the hole arrangement accuracy, once all holes in the article have been measured, a hole arrangement accuracy is achieved. m The point set {C1, C2, …, C} of the product with holes m The point set {N1, N2, ..., N} can be transformed by rotation and translation (but not by scaling) to match the point set {N1, N2, ..., N}. m}, point set {N1, N2, … , N m} represents the nominal location of the hole on the product, thus... Minimize the quantity.

[0102] Another morphological property that can affect the metallization process is the roundness of the hole 120. The roundness of the hole 120 can also affect the performance of the article 100 as an interposer. For example, a non-circular hole may not be able to fully connect to the conductive traces on the surface of the article 100. In addition, after the hole is filled with a conductive material, a non-circular hole may cause it to not align with the redistribution layer deposited on the surface. Furthermore, the resistivity of the metallized hole 120 can be adversely affected by a non-circular hole, especially when high-frequency signals propagate through the article 100.

[0103] Figure 4 The roundness of the sample well is schematically depicted. As used herein, roundness is determined by fitting circles onto a microscopic image of well 120. Let H = { h 1 , h 2 , … , h n ) as a point identified along the edge of aperture 120 when viewed from above (e.g., from a microscopic image of aperture 120). h i = ( x i , y iThe set of points. The resolution of the points can be, but is not limited to, about 1 µm / pixel. A least-squares fitted circle can be accurately evaluated. The center point of the circle. C = ( x c, y c ) and its radius R make Minimize the quantity.

[0104] Given distance (diameter) d i = dist ( h i , C The minimum value can be obtained from the set of ). d 最小 and maximum value d 最大 . d 最大 - d 最小 The difference is referred to as roundness in this paper. Therefore, the total distance d i Theoretically, all perfect circles should have equal numbers of digits. d 最大 and d 最小 The roundness value is set to zero. A larger roundness value indicates a less round hole. The roundness of the articles described herein is less than or equal to 5 µm, less than or equal to 4 µm, less than or equal to 3 µm, less than or equal to 2 µm, less than or equal to 1 µm, or equal to 0 µm.

[0105] As described above, the surface roughness of the inner wall of the hole 120 adversely affects the metallization process, causing insufficient electrical performance at high frequencies and reliability issues (such as cracking or other failures). The process described below enables the production of an article 100 having a hole 120 with a smooth inner surface, which promotes adhesion of the conductive material to the inner surface. As used herein, "smooth inner surface" refers to the surface roughness R of the inner surface of the hole. a The inner surface is as follows, and the surface roughness R is... a For less than or equal to 1 µm, less than or equal to 0.9 µm, less than or equal to 0.8 µm, less than or equal to 0.7 µm, or less than or equal to 0.6 µm, less than or equal to 0.5 µm, less than or equal to 0.4 µm, less than or equal to 0.3 µm, less than or equal to 0.2 µm, less than or equal to 0.1 µm, in the range of 0.1 µm to 1 µm, in the range of 0.1 µm to 0.5 µm, or in the range of 0.1 µm to 0.3 µm.

[0106] Figure 5-7 The figure illustrates a determination of the surface roughness R of the inner surface of hole 120. a The method involves determining the surface roughness R of a curved surface, where the inner surface may be curved. Therefore, embodiments of this disclosure provide a method for determining the surface roughness R of a curved surface. a A computer-implemented method is described. According to the method, a side profile image of a hole is captured, for example, by means of an optical microscope. An edge detection algorithm is applied to the image of the hole to determine the edges of the hole and the body of the substrate. As a non-limiting example, the "minimum method" in ImageJ is employed, where a macro written in ImageJ converts an 8-bit image of the side profile of the hole into a binary number. Subsequently, an edge detection algorithm is employed, in which each row in the image is scanned until a transition from 0 to 255 (corresponding to the edge of the hole) is detected in the intensity scale.

[0107] Figure 5 The illustration shows the outline of a hole detected by an edge detection algorithm. (Reference) Figure 6 In box 302, the position of the hole's edge is shown relative to its position within the depth of the substrate (i.e., the hole's edge now appears rotated or horizontal). Although box 302 only shows half of the hole's outline, it should be understood that both sides of the hole can be analyzed and evaluated. In box 304, the detected edges 305 are fitted to a polynomial curve 307 using a least-squares minimization fitting procedure, which is typically a quadratic polynomial of the following type: y=ax 2 +bx+c ,in y It is the distance from the horizontal axis to the detection edge. x It is the position on the horizontal axis corresponding to the depth in the substrate. a , b and c These are constants calculated during the fitting process. Next, in box 306, the inherent curvature is removed by subtracting the fitted polynomial curve 307 from the detected edge data 305, and the residual is calculated to obtain the straightened roughness distribution 309. In box 308, various statistical roughness parameters, such as, but not limited to, Ra, Rq, Rz, peak, valley, top diameter, bottom diameter, and waist percentage, can be obtained from the straightened roughness distribution 309.

[0108] The statistical parameters described above are calculated using data from the edges of the hole, which extend for at least 50%, 80%, 90%, or 95% of the entire depth of the hole. That is, the roughness data should not represent only the roughness of a small patch (e.g., a 50 µm × 50 µm area) on the side of the hole. Instead, the internal surface of the hole should be captured as much as possible through its depth to capture any bulges, protrusions, or other undesirable features in the surface analysis. Any of these features will ultimately affect the ability of the conductive material deposited by vacuum deposition or liquid phase plating methods to uniformly and thoroughly coat and fill the hole. Therefore, ignoring certain areas when analyzing the internal roughness of the hole is useless, as any defective areas will hinder the success of subsequent metallization steps.

[0109] Surface roughness R a It is a good indicator of hole quality. Figure 7 The surface roughness R in Figure 311 is illustrated. a The determination of the bisector ML is based on the average depth of the straightened roughness distribution 309, which is defined by Z(x). a Defined as the arithmetic mean of the absolute values ​​of the deviations Z(x) of the distribution relative to the bisector ML:

[0110] As described above, by employing the hole manufacturing method described below, the hole 120 of the article 100 has a surface roughness R. a Low inner surface roughness R a Less than 1 µm.

[0111] Another morphological property is the surface shape of the article 100 near the opening defined by the hole 120. When subsequent processes are performed (such as a re-layering process), depressions, protrusions, or other anomalies near the hole can cause plating, coating, and bonding problems.

[0112] Figure 8A Two holes 120 in an exemplary article 100 are schematically illustrated. Each hole 120 has a first opening 121 at a first surface 110 and a second opening 125 at a second surface 112. Figure 8AAs shown, a first recessed region 123 surrounds a first opening 121, and a second recessed region 127 surrounds a second opening 125. These recessed regions are an effect of the etching process. Removing material surrounding a hole during the etching process can cause recesses or protrusions around the periphery of the hole. For example, laser-damaged glass can be etched at a faster rate than undamaged glass, thus forming recessed regions. Protrusions can form when the glass substrate is etched without stirring. For example, when the glass substrate is etched without stirring, glass substrate material removed from the inside of the hole can accumulate at the inlet and / or outlet of the hole.

[0113] Make the depression depth D of these depression areas 凹陷 The article 100, for example, is improved by minimizing its use as an interlayer device. When a depression exists, a cavity can form between the glass substrate and the subsequently deposited metal layer. The depression depth D is minimized when a redistribution layer of the interlayer device is applied to one or both surfaces of the article 100. 凹陷 It can reduce plating, coating and bonding problems.

[0114] In some embodiments, the recess depth D of the recessed region surrounding the opening 凹陷 Less than or equal to the desired depth, for example, the desired depth is less than or equal to about 0.2 µm, less than or equal to about 0.15 µm, less than or equal to about 0.1 µm, or less than or equal to about 0.05 µm, in the range of about 0.01 µm to about 0.2 µm, in the range of about 0.01 µm to about 0.15 µm, in the range of about 0.05 µm to about 0.2 µm, in the range of about 0.05 µm to about 0.15 µm, in the range of about 0.1 µm to about 0.2 µm, or in the range of about 0.1 µm to about 0.15 µm.

[0115] Figure 8A An example is given for determining the depression depth D of a depression region. 凹陷 The method. Based on the average thickness T of the article 100, the first plane 126 is defined by the first surface 110 of the article 100. Similarly, based on the average thickness T of the article 100, the second plane 128 is defined by the second surface 112 of the article 100. As mentioned above regarding Figure 2B The average thickness T of the article is determined by averaging three thickness measurements performed by an interferometer, which are performed outside of any recessed region 123 (i.e., at a distance of 500 µm to 2,000 µm from the recessed region 123).

[0116] The recess depth D of the hole 120 at the first surface 11- 凹陷Measured from the first surface 110 at the opening of the hole 120, the opening of the hole 120 is the starting position 131 of the vertical wall 124 of the hole 120 (i.e., the position where the recessed region 123 transitions to the vertical wall 124 of the hole 120). The starting position 131 of the vertical wall 124 is determined by measuring the angle α between the tangent TL of the curved surface of the recessed regions 123, 127 and the first plane 126 or the second plane 128. The starting position 131 of the vertical wall 124, and thus the opening position of the hole 120, is a position where the angle α is greater than 75 degrees. In other words, the recessed regions 123, 127 are regions where all angles α are less than 75 degrees. As a non-limiting example, the depth D of the first recessed region 123 and the second recessed region 127... 凹陷 It can be measured using an optical surface profilometer, such as the NewView 7300 purchased from Zygo Corporation.

[0117] It should be noted that the larger the diameter of the hole, the greater the depth D of the recess near the hole opening. 凹陷 The larger the diameter, the greater the etching time required, thus removing more material from the glass substrate during the etching process. As described in more detail below, in some embodiments, the parameter of the hole-making method is the depth D of the recessed area within the trimmed region of radius R. 凹陷 The ratio to the average hole diameter is less than or equal to 0.007, less than or equal to 0.006, less than or equal to 0.006, less than or equal to 0.005, less than or equal to 0.004, less than or equal to 0.003, less than or equal to 0.002, or less than or equal to 0.0015.

[0118] In some cases, an array of holes with a small center-to-center spacing (i.e., pitch) can cause the entire glass surface at the hole array to be recessed compared to the glass surface outside the hole array. This recessed area can occur when the spacing between the holes is smaller than the radius of the recessed area surrounding the holes due to the etching process. By way of example, and not limitation, a pitch p between holes less than about 300 µm, less than about 200 µm, less than about 150 µm, less than about µm, or less than about 50 µm can cause the surface of the article to be recessed at the hole array.

[0119] Figure 8B An exemplary glass article 10 depicts an array 129 having holes 120. The center-to-center spacing causes the first surface 110 and the second surface 112 to become recessed at the array 129 of holes 120. Specifically, at the array 129 of holes 120, the first surface 110 and the second surface 112 are recessed from the first plane 126 and the second plane 128, respectively, with a recess depth D. 凹陷As described above, the first plane 126 and the second plane 128 can be determined by the average thickness T. It should be understood that the recess depth D at the first surface 110... 凹陷 The depth D of the recess at the second surface 112 can be compared with 凹陷 They are not the same. In the embodiments described herein, the laser process parameters and etching process parameters are controlled to achieve a recess depth D at either the first surface 110 or the second surface 112. 凹陷 The ratio of the average thickness T of the product to the average thickness T of the product is less than 0.007.

[0120] Now for reference Figure 9 The figure schematically illustrates an exemplary semiconductor package 190. The semiconductor package 190 includes an article 100 located between a first semiconductor device 185 and a second semiconductor device 186 and a substrate 187, the article 100 serving as an interposer. A first metallization layer 181 (e.g., a first redistribution layer) is disposed on a first surface 110 of the interposer 100, and a second metallization layer 182 (e.g., a second redistribution layer) is disposed on a second surface 112 of the interposer 100. In the illustrated embodiment, the first semiconductor device 185 is electrically coupled to the first metallization layer 181 and the interposer 100 via a first ball grid array 183, and the second semiconductor device 186 is electrically coupled to the first metallization layer 181 and the interposer 100 via a second ball grid array 184. The second metallization layer 182 and the interposer 100 are electrically coupled to the substrate 187 via a third ball grid array 188. It should be understood that embodiments of this disclosure are not limited to ball grid array interconnects, and any other interconnects may be used. Hole 120 is a through hole that is metallized with a conductive material (e.g., copper) to allow electrical signals to pass through the interposer 100.

[0121] The functionality of the semiconductor package is not limited to this disclosure. As a non-limiting example, the semiconductor package can be a high-frequency radio frequency (“RF”) device (e.g., with a frequency between about 100 kHz and about 100 GHz) for use in wireless communication devices. The smooth inner walls of the etched vias provide low high-frequency resistance, which is desirable in such high-frequency RF devices.

[0122] Embodiments of this disclosure also include a method for manufacturing a hole 120 having the above-described morphological properties in an article 100. Generally, the hole 120 is manufactured by a laser destruction and etching process, wherein a laser destruction region or via is formed by applying a laser beam, and then the laser destruction region or via is further opened by an etching solution, thereby obtaining a hole 120 having the desired diameter and morphology.

[0123] Now for reference Figure 10The figure schematically illustrates an exemplary article 100 performing a hole-making method. Generally, a laser-damaged region 140 or a via is first formed through the body of the article 100. The laser-damaged region 140 forms a damaged area in the article 100, which is etched at a faster rate than undamaged areas when an etching solution 130 is applied. The etching solution 130 removes material (e.g., glass material) from the article 100 through the laser-damaged region 140 and the first surface 110 and the second surface 112. As schematically shown by dashed lines, the etching solution 130 removes material at a certain rate, and the rate at the region near the laser-damaged region 140 is faster than the rate at the first surface 110 and the second surface 112. The etching solution 130 can be applied to the article 100 until a desired first diameter D1 is obtained at the first surface 110 and / or a desired second diameter D2 is obtained at the second surface 112. Various laser and etching methods are described in detail below.

[0124] It should be noted that not all laser methods can be used to create high-quality holes in glass materials in work-in-progress 100. For example, excessive deposition of thermal energy into the glass can create microcracks, glass sheets may eject from the laser inlet or outlet holes in the glass, and ablation methods often create very rough surfaces. All of these characteristics result in non-ideal shapes that subsequent chemical etching cannot remove or smooth.

[0125] Figure 11 This paper illustrates a first-of-its-kind laser method for forming laser-damaged regions or vias, which rapidly and efficiently produces high-quality results (e.g., smooth inner walls, minimal indentation depth, etc., as described above). The method uses short-pulse lasers combined with line-focusing optics to drill vias or laser-damaged regions, with each laser pulse penetrating completely through the body of the glass slide. Figure 11 An optical device 150 for producing such an extended focus is illustrated. Further details regarding an exemplary line focusing process are provided in U.S. Patent No. 2015 / 0166395, which is incorporated herein by reference in its entirety.

[0126] The optical components may include an axial prism 154 that receives the pulsed laser beam 152 and generates a line focal point 155 along the optical axis of the axial prism 154. A telescopic lens assembly then receives the laser beam 152, the telescopic lens assembly including a first lens 156 and a second lens 158, the first lens 156 calibrating the laser beam 152 received from the axial prism 154, and the second lens 158 focusing the laser beam into a line focal point 159 that at least partially passes through the body of the article 100. Figure 11 In the example shown, the line focus 159 extends through the first surface 110 and the second surface 112 of the article.

[0127] One advantage of this method is that each laser pulse (or Figures 12A-12C The pulse train sufficiently forms the via or laser-damaged region 140. Therefore, the time to create the via or laser-damaged region 140 is extremely short (e.g., about 10 picoseconds with a single pulse, or even about several hundred nanoseconds with a complete pulse train).

[0128] Another advantage of the described line-focusing method is that it breaks down the bulk of the glass, resulting in a hole 120 with nearly equal top and bottom diameters (i.e., D1 and D2) after etching. This contrasts sharply with many other laser-based hole-forming methods, where a constant angle (e.g., 10 degrees) is often seen in the hole walls, or the top and bottom of the via can have completely different dimensions, for example, a diameter difference of about 10 µm.

[0129] In the case of in-line focusing, the internal roughness of the hole can be controlled by changing the parameters of the hole formation process. Specifically, these parameters can be divided into two categories: laser parameters and etching parameters. The laser parameters for the in-line process are described below, and the etching parameters will be described in detail later.

[0130] It has been observed that the quality of the aperture is highly dependent on the laser conditions used. The material should be transparent to the wavelength of the pulsed laser beam. By way of example and not limitation, the wavelength can be in the range of 355 nm to 1100 nm. Commonly used high-energy pulsed laser wavelengths include 1064 nm and its harmonics (532 nm, 355 nm), or 1030 nm and its harmonics (515 nm, 343 nm). In particular, it has been observed that laser beams with a wavelength of approximately 532 nm produce high-quality apertures 120 with lower internal surface roughness compared to using longer wavelengths (e.g., 1064 nm).

[0131] The pulse duration and intensity should be short enough to achieve the multiphoton absorption effect. Ultrashort pulsers, such as picosecond or femtosecond laser sources, can be used. In some embodiments, pulsed lasers of approximately 10 picoseconds can be used. Operating such a picosecond laser as described herein can generate a “pulse train” 160, which contains subpulses 160A. Figure 12ATwo consecutive pulse trains 160 are shown, each containing three subpulses 160A. Pulse train generation is a type of laser operation where the emission of pulses is not in the form of a uniform and stable stream but rather as a dense cluster of subpulses. Each pulse train 160 contains multiple individual subpulses 160A of very short duration (e.g., at least 2 subpulses, at least 3 subpulses, at least 4 subpulses, at least 5 subpulses, at least 10 subpulses, at least 15 subpulses, at least 20 subpulses, or more). That is, the pulse train 160 is a “reservoir” of subpulses 160A, and each pulse train 160 is separated from each other by a duration longer than the separation between adjacent pulses within each pulse train. Reference Figure 12B The diagram depicts... Figure 12A A graph of single subpulse 160A laser emission versus time, with the pulse duration T of the subpulse. d The maximum value can be up to 100 picoseconds (e.g., 0.1 picosecond, 5 picosecond, 10 picosecond, 15 picosecond, 18 picosecond, 20 picosecond, 22 picosecond, 25 picosecond, 30 picosecond, 50 picosecond, 75 picosecond, or values ​​between these). These individual subpulses 160A within a single pulse train 160A are referred to herein as subpulses to indicate their presence within the single pulse train. The energy or intensity of each individual subpulse 160A within the pulse train 160 may not be equal to that of the other subpulses in the pulse train, and the intensity distribution of multiple subpulses within the pulse train typically follows an exponential decay over time, determined by the laser design.

[0132] refer to Figure 12C Preferably, in the exemplary embodiment described herein, each subpulse 160A in the pulse train 160 is time-intervaled with subsequent subpulses in the pulse train by a duration T. p This time interval is from 1 nanosecond to 50 nanoseconds (e.g., 10⁻⁵⁰ nanoseconds or 10⁻³⁰ nanoseconds, where the time is often determined by the laser cavity design). For a given laser, the time interval T between each subpulse 160A in the pulse train 160 is... p The intervals between subpulses are relatively uniform (±10%). For example, in some embodiments, each subpulse 160A in the pulse train 160 may be time-intervald with subsequent subpulses by approximately 20 nanoseconds (50 MHz). For example, for the generated subpulse interval T... p A laser pulse of approximately 20 nanoseconds, with the interval T between subpulses in the pulse train. p The time difference should be maintained within approximately ±10%, or within approximately ±2 nanoseconds. The time between each pulse train 160 of the subpulse 160A (i.e., the time interval T between pulse trains) should be... b The duration will be significantly longer (e.g., 0.25 microseconds ≤ T). b≤ 1000 microseconds, for example 1-10 microseconds or 3-8 microseconds). In the exemplary embodiments of the laser described herein, for a laser with a pulse train repetition rate or repetition frequency of about 200 kHz, the time interval T is... b It takes about 5 microseconds.

[0133] The laser pulse train repetition rate (also referred to herein as the pulse train repetition frequency) is defined as the time between the first pulse 160A in pulse train 160 and the first pulse 160A in subsequent pulse trains 160. In some embodiments, the pulse train repetition frequency can be in the range of about 1 kHz to about 4 MHz. More preferably, the laser pulse train repetition rate can be in the range of, for example, about 10 kHz to 650 kHz. The time T between the first pulse in each pulse train and the first pulse in subsequent pulse trains is defined as follows. b The duration can range from 0.25 microseconds (4 MHz pulse train repetition rate) to 1000 microseconds (1 kHz pulse train repetition rate), for example, 0.5 microseconds (2 MHz pulse train repetition rate) to 40 microseconds (25 kHz pulse train repetition rate) or 2 microseconds (500 kHz pulse train repetition rate) to 20 microseconds (50 kHz pulse train repetition rate). The precise timing, pulse duration, and pulse train repetition rate can vary depending on the laser design, but high-intensity, short subpulses (T0) are generally preferred. d <20 picoseconds, preferably T d 15 picoseconds showed particular effectiveness. Generally, for a fixed energy per pulse train, increasing the number of pulses alters the peak intensity experienced by the material, as well as the temporal distribution of the energy. Generally, a larger number of subpulses results in better aperture quality and a larger process window (e.g., greater than 10 subpulses / pulse train).

[0134] The amount of pulse train energy used to modify materials will depend on the material composition of the substrate and the length of the line focal point used to interact with the substrate. The longer the interaction area, the more energy is dispersed, and therefore a higher pulse train energy will be required. Precise timing, subpulse duration, and pulse train repetition rate can vary depending on the laser design, but short subpulses with high intensity (<15 picoseconds or ≤10 picoseconds) have shown particular effectiveness for this technique.

[0135] The energy of each pulse train 160 and the number of subpulses 160A within each pulse train affect the characteristics of the resulting aperture 120. If the pulse train energy is below a certain threshold (which depends on the substrate composition and thickness), transverse cracks formed during laser processing after etching can lead to uncontrolled profile formation. On the other hand, when the pulse train energy is too high, the wall exhibits higher roughness values ​​and the inlet and outlet have elliptical shapes.

[0136] Figure 13A -C illustrates the effect of the energy of each pulse train and the number of subpulses in each pulse train on the aperture characteristics for a fixed laser wavelength (532 nm). Figure 13A The morphology of holes in 400 µm thick Eagle XG® glass is illustrated using 532 nm and subsequently the etching method described below, for different pulse train energies and the number of subpulses in each pulse train. The etching method opens the vias, or laser-damped areas, to a diameter of approximately 80 µm. For Figures 13A-13C The etching method used an etching solution containing 1.5 M HF and 1.6 M HNO3 at room temperature, along with three-dimensional ultrasonic stirring at 80 kHz. The ultrasonic stirring was performed using a TRU-SWEEP ultrasonic sensor, model 4HI10146ST, sold by Crest Ultrasonics in Trenton, New Jersey. TM supply.

[0137] Figure 13B This is a top view of a hole in a 400 µm thick Eagle XG® glass substrate after laser exposure and etching. Figure 13B As shown, when the pulse train energy is too high, the hole becomes elliptical because the transverse cracks create a preferred orientation for the etchant (Image 170). The glass substrate shown in Image 170 was drilled using a laser pulse train energy of 180 µJ. When the pulse train energy is too low, the hole closes, even after etching (Image 174). Image 174 depicts the glass substrate after exposure to a laser with a pulse train energy of 180 µJ. Image 172 shows a hole with good roundness, both before and after etching. The pulse train energy that produced the hole shown in Image 172 was 90 µJ. Figure 13C The side profiles (cross-sectional views) of holes in a 400 μm thick EXG glass are described under the conditions of excessively high, excessively low, and ideal pulse train energies. The image with excessively high pulse train energy is shown in image 171 (180 µJ pulse train energy), the image with excessively low pulse train energy is shown in image 175 (40 µJ pulse train energy), and the image with ideal pulse train energy is shown in image 173 (90 µJ pulse train energy).

[0138] Furthermore, a uniform distribution of optical energy across the entire thickness of the material can produce smoother pores. If the optical energy is too high in one part of the material, it can create microcracks rather than simply modifying the material. These microcracks create preferred etching paths and result in bulges in the sidewalls of the pore, leading to elliptical pores. However, if the energy is too low in one part of the material, a preferred path is not created, resulting in the inability to form a pore after etching, or the inability to control the direction of the etchant path, which can lead to large "bulges" in the sidewalls of the pore. The solution is to extend the length of the focal line to keep the power variation across the entire glass thickness low. In fact, it is advantageous to keep the energy density variation across the entire glass thickness less than 10%. This can be achieved by increasing the energy density of the etchant. Figure 11 The diameter of the laser beam 152 of the illustrative axial prism 154 is used to achieve this, which flattens the energy distribution along the optical axis. Figure 14 Experimental measurements of the peak intensity of a Gaussian-Bessel beam are shown. This represents the peak intensity in each radial beam distribution, varying with distance along the optical axis. Figure 14 The laser beam shown uses Figure 11 The axial prism and bilens telescope shown are used to form a line focal point of approximately 2 mm in length.

[0139] Increasing the length of the focal line with a flat-top distribution offers the advantage of confining the optical energy in the laser beam to a region within or near the material, thereby making the optical system more efficient and thus enabling the use of lower-energy lasers.

[0140] Figure 15 A second exemplary laser method is illustrated schematically. Figure 15 The second exemplified laser method is the shock laser drilling method, which uses ultraviolet (“UV”) (e.g., 355 nm) under a pulsed laser of about 30 ns and one or more sacrificial capping layers. An exemplary shock laser drilling method is described in U.S. Publication No. 2014 / 0147623, which is incorporated herein by reference in its entirety.

[0141] Figure 15 Components for an exemplary laser drilling method 250 are illustrated. The components of the laser drilling method 250 generally include an article 100, a sacrificial capping layer 300, and a laser beam 252. As described above, the article 100 can be a glass article. The sacrificial capping layer 300 can be made of any material, such as, but not limited to, glass, polymers, inks, waxes, etc. Figure 15 In the illustrated embodiment, the sacrificial cover layer 300 and the article 100 can be removably attached. The article 100 can be detachably attached to the sacrificial cover layer 300 through direct physical contact or through indirect attachment.

[0142] A gap 301 may exist between the bottom surface 312 of the sacrificial cover layer 300 and the article 100. The gap 301 may be a thin gap, for example, less than 200 mm. m, less than 100 m or less than 50 m. Gap 301 may be an air gap formed when the article 100 is attached to the sacrificial cover layer 300 through direct physical contact. Alternatively, gap 301 may be filled with oil or other chemical substances that provide adhesion when the glass article 200 is attached to the sacrificial cover layer 300 by chemical adhesion.

[0143] The desired location and pattern of the holes to be formed in the work-in-process 100 can be determined before forming the holes 120, based on the intended use of the work-in-process 100. (Reference) Figure 15 The laser beam 252 can be positioned so that, after being focused by the lens 253, it is incident on the top surface 310 of the sacrificial cover layer 300. The laser beam 252 can be positioned at a certain location on the top surface 310 of the sacrificial cover layer 300, which corresponds to a predetermined location of a hole in the article 100.

[0144] The laser beam 252 can be any optically capable laser beam capable of drilling through the sacrificial capping layer 300 and the article 100. In one embodiment, the laser beam 252 can be an ultraviolet (UV) laser beam, specifically a third-harmonic neodymium-doped yttrium orthovanadate (Nd:YVO4) laser emitting a wavelength of approximately 355 nm. The laser beam 252 can interact with the material of the sacrificial capping layer 300, causing the material to evaporate, and in the case of a glass sacrificial capping layer, generating plasma that ejects the material from the glass, thereby forming a hole. While an Nd:YVO4 laser has been described above, it should be understood that any laser capable of forming a perforation in the sacrificial capping layer 300 can be used. The numerical aperture of the laser beam 252 incident on the sacrificial capping layer 300 can be between 0.01 and 0.5, for example between 0.02 and 0.4, between 0.05 and 0.3, between 0.06 and 0.2, preferably 0.07. The focal point of the laser beam 252 relative to the top surface 310 of the sacrificial cladding layer 300 can be placed at approximately 200 degrees of the top surface 310. Within m, for example, about 100 on the top surface 310. Within m, or about 50 on the top surface 310. Within m.

[0145] refer to Figure 15A laser beam 252 can be pulsed at a predetermined location to form a perforation 320 in the sacrificial capping layer 300. The pulse duration can be about 20 nanoseconds to about 40 nanoseconds, or about 25 nanoseconds to about 35 nanoseconds, or about 30 nanoseconds. The pulse repetition rate can be between 1 kHz and 150 kHz, for example, between 1 kHz and 75 kHz, or between 1 kHz and 15 kHz. For example, the energy of each pulse can be 75-150 µJ. The number of pulses required to form a perforation in the sacrificial capping layer 300 will vary depending on the material and thickness of the sacrificial capping layer 300.

[0146] Generally, each laser pulse passing through the sacrificial cladding layer 300 forms approximately 0.75. The hole depth is m. Therefore, at 300 Creating a perforation in a m-thick glass can require approximately 400 pulses. Creating a perforation in a 700-meter-thick glass may require approximately 675 pulses, while in a 700-meter-thick glass... Creating a perforation in a m-thick glass layer requires approximately 950 pulses. A laser beam of any number of pulses can be used to form a perforation in the sacrificial capping layer 300.

[0147] A laser beam 252 can be pulsed into a perforation 320 in the sacrificial capping layer 300, thereby exposing the article 100 to the laser beam 252 at a predetermined location, said predetermined location being the position where the perforation 320 is formed in the sacrificial capping layer 300. The laser beam 252 can be pulsed into the perforation 320 any number of times to form a hole 120 in the article 100. Although Figure 15 The depiction is of a blind hole 120, but it should be understood that the depth of the hole 120 in the article 100 depends on the number of pulses applied to the article 100 and is not limited by this disclosure. For example, the hole 120 in the article 100 may be a through hole or a blind hole with any desired depth.

[0148] When using the aforementioned impact laser drilling technique, the resulting laser-drilled holes are often very smooth, exhibiting a "flame-polished" texture, and the measured surface roughness of the inner wall is approximately 0.2 µm R. a To approximately 0.8 µm R a Between. In order to obtain these low R values. aThe numerical aperture of the laser beam should be optimally controlled to focus the laser beam onto the material surface. A sacrificial capping layer suppresses damage at the laser entry aperture. Furthermore, a narrow pulse energy range (e.g., 75–150 µJ) limits the formation of microcracks due to overheating of the material. If these process parameters are followed, holes with smooth interiors and very round top / bottom holes (<5 µm roundness) can be fabricated. This low roughness is retained even after acid etching, which is described in more detail below.

[0149] The following describes an etching method that will be used in conjunction with one of the laser methods described above to obtain the desired morphology of the hole.

[0150] Now for reference Figure 16 The figure schematically illustrates an exemplary etching apparatus 400 used to open a laser-drilled pilot hole or laser-damaged area. The exemplary etching apparatus 400 generally includes a container 402 holding an etching solution 404, a holder 407 holding one or more articles 100, and one or more ultrasonic transducers 403 that are controllable to generate ultrasonic agitation 406 in the etching solution 404. In some embodiments, the etching solution 404 may be held in an inner container located in water or another liquid held by an outer container, as described in U.S. Application No. 15 / 177,431, which is incorporated herein by reference in its entirety. In such an embodiment, the ultrasonic transducer 403 is positioned in the outer container, and the water is ultrasonically agitated, which is then transferred to the etching solution in the inner container.

[0151] Although article 100 is shown as being held in a vertical position, the implementation is not limited to this. For example, article 100 may be held in a horizontal position or any other position.

[0152] As mentioned above, another factor controlling the surface roughness of the inner wall of the hole 120 in article 100 is the etching conditions. When the laser beam breaks the material, transverse cracks are generated. If the etching rate is too low, the acid has enough time to diffuse into these transverse cracks, causing them to propagate and create protrusions along the glass thickness. Conversely, if the etching rate is too high, the acid cannot diffuse into the laser-broken lines or vias, and the hole will open in an hourglass shape (see [link to article]). Figure 3B The etching process should be fast enough to etch the transverse cracks before they reach too far from the center of the hole, but slow enough to ensure that the etching along the glass thickness is uniform and achieves the desired hole aspect ratio.

[0153] For articles made of alkali metal borosilicate glass [such as Eagle XG® sold by Corning Incorporated, Corning, New York], when opening a laser-damaged area or via created by one of the two laser methods described above, an etching rate of approximately 1 µm / min to 10 µm / min provides a hole with a smooth inner wall (R). a < 1 µm (measured by the method described above). As another example, the etching rate can be in the range of 1 µm / min to 4 µm / min, or in the range of 3 µm / min to 4 µm / min. As a non-limiting example of an etching solution and method for obtaining an etching rate of about 1 µm / min for Eagle XG® glass, an etching solution comprising 1.5 M HF and 1.6 M HNO3, ultrasonic stirring in a frequency range of about 40 kHz to about 192 kHz, and an etching solution temperature of 20°C provides the aperture with a smooth inner wall as described herein. As another non-limiting example, an etching solution comprising 3 M HF and 2.4 M HNO3 etches Eagle XG® glass at a rate of about 2 µm / min in a frequency range of about 40 kHz to about 192 kHz and at 20°C. In some embodiments, the frequency of ultrasonic stirring can be varied between a minimum frequency and a maximum frequency.

[0154] The pH of the ultrasonic stirring and etching solution affects the surface roughness of the workpiece (including the top and bottom surfaces). Reference Figure 17 Three different etching solutions were used to represent different pH levels. HF and HNO3 provided pH values ​​less than or equal to zero. Figure 17 (The square in the middle), HF provides a pH range of 1 to 2 ( Figure 17 (The rhombus shape in the image). HF and NH4F provide higher pH values ​​in the range of 2 to 3 ( Figure 17 (The triangle in the image). The deepened shape indicates the application of ultrasonic stirring. The ultrasonic stirring was performed at 40 kHz using a TRU-SWEEP ultrasonic stirrer, model 4HI10146ST. TM Provided. The 400 µm Eagle XG® samples were etched using the etching solution mentioned above, both with and without ultrasonic stirring. As... Figure 17 As illustrated, the glass becomes rougher when etched in a low-pH etching solution. When etching glass in low-pH etchants (HF, HF-HNO3), ultrasonic agitation makes the etched surface rougher, but this is not the case in high-pH etchants (HF-NH4F).

[0155] In a non-limiting example, eight laser-drilled holes were formed in a 300 µm thick EagleXG® glass substrate using the line-focused drilling method described above. The sample holes were fabricated using an optics device that generated a focal length of approximately 1.3 mm full width at half maximum (FWHM), a wavelength of 532 nm, and a laser pulse train energy of 180 µJ, with 15 subpulses / pulse trains. The glass substrate was then etched at room temperature using an etching solution containing 1.5 M HF and 1.6 M HNO3, along with three-dimensional ultrasonic stirring at 80 kHz. The ultrasonic stirring was performed using a TRU-SWEEP (model 4HI10146ST). TM Provided. Referring to Table 1 below, after etching, the average surface roughness of the inner wall of the sample hole is less than 0.2 µm Ra, which was obtained using the calculation method described above.

[0156] Table 1. Surface roughness (Ra) of holes formed in 300 µm Eagle XG® glass

[0157] It is also possible to control the parameters of the etching process to make Figure 8A The recess depth D around hole 120 is shown. 凹陷 Minimize. As mentioned above, during the etching process, recesses may appear around the top and / or bottom openings of the hole 120, as well as plateau regions between the holes. Low surface roughness should be maintained in these plateau regions to allow for the bonding of additional material to the part surface during downstream processing. Two methods have been found to suppress the recess depth D around the hole 120. 凹陷 (1) Reduce the etching rate during hole opening and (2) Increase the pH of the etching solution.

[0158] Figures 18A-18F The effect of increased pH is illustrated when creating 20 µm, 50 µm, and 90 µm diameter holes in 200 µm EagleXG® glass sold by Corning Incorporated, Inc., Corning, New York. The guide hole pattern is formed via a UV laser shock drilling process. In this process, a 355 nm, approximately 30 nanosecond pulsed laser is focused onto the glass substrate surface using Gaussian optics at a depth of approximately 6 µm 1 / e. 2A laser spot of diameter. Prior to etching, individual laser pulses, with a repetition rate of 5 kHz and a pulse strength of 60-90 µJ, are used to drill through "guide" holes in the glass substrate. During this impact drilling process, each laser pulse removes a small depth of glass at a rate of approximately 1 µm / pulse, and the total hole depth is controlled by the number of pulses used at specific hole locations. This results in slightly tapered guide holes with a diameter of approximately 5-15 µm, which are subsequently enlarged by a liquid etching process. While this specific laser process is used to form... Figures 18A-18F The etching results are shown in detail, but it should be understood that these results are also applicable to etching of guide holes formed by other laser methods, such as the Bessel beam-based drilling described above.

[0159] and Figures 18A-18C The corresponding high-pH etching solution was prepared as 3M HF and 1M NH4F, with a pH of approximately 1.6. Figure 18D-18F The corresponding low-pH etching solution was prepared as 3M HF and 2.4M HNO3, with a pH of approximately 0.4. Ultrasonic energy of 40 kHz was applied during etching to agitate the glass and the etching solution. Figures 18A-18F The image was captured by an optical interferometer sold by Zyco Corporation in Middletown, Connecticut. Figures 18A-18F The shading variations in the image represent the surface waviness and the degree of indentation around the hole. Figure 19 The illustration shows the recess depth D of glass articles with holes of 20 µm, 50 µm, and 90 µm diameter obtained using the two different etching solutions. 凹陷 . Figures 18A-18F Examples 19 and 19 demonstrate that surface depressions around holes were significantly suppressed by etching laser-drilled glass in an etching solution with a high pH.

[0160] Table 2 below provides additional non-limiting exemplary etching solutions and the corresponding observed etching rates and estimated pH values ​​when ultrasonically stirred.

[0161] Table 2. Exemplary etching solutions and corresponding etching rates and pH values

[0162] Figure 20 The illustration shows the effects of decreasing etching rate (curve 500) and increasing pH on glass articles containing 400 µm thick Eagle XG® glass with holes of diameters of 20 µm, 50 µm, and 90 µm. Figure 20 As shown, decreasing the etching rate and increasing the pH reduced the recess depth D around the opening of the hole. 凹陷 .

[0163] As mentioned above, the laser and etching process parameters affect the recess depth D. 凹陷 The ratio of the orifice diameter D to the opening diameter D is less than or equal to 0.007, 0.0040, 0.005, 0.003, 0.002, or 0.0015. Table 3 illustrates this. Figure 20 The ratio of the recess depth to the opening diameter (D) in the non-limiting example shown 凹陷 / D).

[0164] Table 3. Exemplary indentation depth to opening diameter (D) 凹陷 / D)

[0165] As shown in Table 3 above, both decreasing the etching rate provided by the etching solution and increasing the pH of the etching solution reduced the ratio of the pit depth to the opening diameter (D). 凹陷 / D).

[0166] Brief Reference Figure 8A The etching process rounds the entrance 122 of the hole 120. In contrast, the side profile of a hole drilled by laser or mechanical means typically has a sharp angular transition (e.g., 90 degrees) between the top or bottom surface of the hole and the vertical wall of the hole. The removal of glass material during the etching process provides a curved hole entrance 122 (i.e., a transition from the surfaces 110, 112 of the glass substrate 100 to the inner wall 124 of the hole).

[0167] During the etching process, the physical properties of the glass substrate change. As a non-limiting example, for fused-drawn glass substrates, the etching solution described herein increases the surface roughness of the glass substrate (e.g., from about 0.2 nm – about 0.4 nm (Ra) before etching to about 0.6 nm (Ra) after etching). The surface roughness of the glass substrate can be measured by any known or yet-to-be-developed measurement technique. Additionally, fluorides may be present on the surface of glass substrates that have been etched but not acid-cleaned (e.g., cleaned with acids such as HCl, H₂SO₄, etc.). Fluorides can be detected by any suitable method, such as, but not limited to, time-of-flight secondary ion mass spectrometry. Thus, the presence of fluorides can indicate that the glass substrate has been etched.

[0168] In addition, acid etching also creates a surface leaching layer on the surface of the glass substrate. When a glass composition containing modifiers [such as alkali metals and alkaline earth metals (such as K, Na, Ca, Mg, etc.)] is etched, these modifiers are removed and reacted with protons (H). +The surface leaching layer extends into the glass substrate to a depth that is replaced by the surface of the glass substrate. This region extending from the surface of the glass substrate to a certain depth is called the surface leaching layer. By way of example and not limitation, the thickness of the surface leaching layer can be less than 100 nm, for example, between 10 nm and 20 nm, between 10 nm and 30 nm, between 10 nm and 40 nm, between 10 nm and 50 nm, between 10 nm and 60 nm, between 10 nm and 70 nm, between 10 nm and 80 nm, between 10 nm and 90 nm, and between 10 nm and 100 nm. The surface leaching layer can be present at every surface exposed to the etching solution, such as on the top surface, bottom surface, and sidewalls of the holes in the glass substrate. The surface leaching layer, and therefore the absence of the modifier, can be detected by secondary ion mass spectrometry. It should be noted that the surface leaching layer is not present in the etched glass substrate made of fused silica.

[0169] Modifiers (such as K, Na, Ca, and Mg) in the glass substrate can be depleted at the laser-damaged locations formed by the aforementioned laser beam. For example, if the hole is formed by a laser process, there will be less modifier near the laser-drilled hole compared to other areas of the glass substrate. However, during the etching process, the modifier is not removed from the surface of the glass substrate that has never been laser-damaged.

[0170] It should be understood that the embodiments described herein relate to articles having holes that possess desired morphological properties, particularly including low roughness (R). a The inner wall is less than 1 µm and the depth of the recess around the opening of the hole is less than 200 nm. 凹陷 The low surface roughness of the orifice allows for increased adhesion between the conductive material and the inner wall. This provides high thermal stability and excellent electrical loss at high frequencies. The small recess depth D around the orifice opening... 凹陷 The reliability of downstream processes (such as re-layering processes) is increased by minimizing plating, coating, and bonding issues that exist when the surface is wavy.

[0171] Embodiments of this disclosure also relate to methods of laser drilling and etching, which produce articles with holes of desired morphology. In particular, embodiments relate to laser line focusing methods and impact laser drilling methods, the laser line focusing method being able to rapidly form a laser-damaged region or guide hole through the article, and the impact laser drilling method being able to produce laser-drilled holes with minimal lateral microcracks. Etching solutions with etching rates of approximately 1 µm / min to approximately 10 µm / min and high pH values ​​between 1.0 and 2.0 open laser-drilled holes manufactured by one of the above two methods, resulting in holes with inner walls of low surface roughness and a small recess depth D around the hole opening.凹陷 Articles having the desired aperture morphology described herein (e.g., glass articles) can be used, for example, as interposers in semiconductor devices (e.g., RF antennas).

[0172] It will be apparent to those skilled in the art that various modifications and variations can be made to the embodiments described herein without departing from the spirit and scope of the claimed subject matter. Therefore, this specification is intended to cover modifications and variations of the various embodiments described herein, provided that such modifications and variations fall within the scope of the appended claims and their equivalents.

Claims

1. An article comprising: A glass-based substrate includes a first surface, a second surface, and at least one hole extending from the first surface, wherein: The at least one hole includes an inner wall, the surface roughness R of which is... a Less than or equal to 1 µm; The at least one hole has a first opening having a first diameter at the first surface; Based on the average thickness of the glass substrate, the first plane is defined by the first surface of the glass substrate; and The ratio of the recess depth to the first diameter of the at least one hole is less than or equal to 0.007, wherein the recess depth is measured from the first plane to the first surface at the first opening of the at least one hole.

2. The article of claim 1, wherein: The at least one hole is a perforation extending from the first surface to the second surface, such that a second opening having a second diameter exists on the second surface; Based on the average thickness of the glass substrate, the second plane is defined by the second surface of the glass substrate; and The ratio of the second recess depth to the second diameter of the at least one hole is less than or equal to 0.007, wherein the second recess depth is measured from the second plane to the second surface at the second opening of the at least one hole.

3. The article of manufacture as claimed in any of the preceding claims, wherein, The ratio of the recess depth to the first diameter of the at least one hole is less than or equal to 0.

005.

4. The article of manufacture as described in any of the preceding claims, wherein, Surface roughness R of the inner wall a Within the range of 0.1 µm to 1 µm.

5. The article of manufacture as claimed in any of the preceding claims, wherein, The roundness of the at least one hole is less than or equal to 5 µm.

6. The article of manufacture as claimed in any of the preceding claims, wherein: The at least one hole is a perforation, such that the at least one hole has a second opening with a second diameter on the second surface; The difference between the first diameter and the second diameter is less than or equal to 2 µm; The roundness of the at least one hole is less than or equal to 5 µm; The first and second diameters are each in the range of 5 µm to 250 µm; and The average thickness of the glass substrate is in the range of 1:1 to 15:1 in aspect ratio to at least one of the first diameter and the second diameter.

7. The article of claim 6, wherein: The at least one hole includes a waist with a waist diameter; and The waist diameter of the at least one hole is greater than or equal to 80% of the larger of the first diameter and the second diameter.

8. The article of claim 6, wherein: The at least one hole includes a waist with a waist diameter; and The waist diameter is within 20% to 100% of the larger of the first and second diameters.

9. An article comprising: A glass-based substrate includes a first surface, a second surface, and at least one aperture extending from at least one of the first surface and the second surface, wherein: The at least one hole includes an inner wall, the surface roughness R of which is... a Less than or equal to 1 µm; The at least one hole includes a first opening having a first diameter at a first surface; and The first diameter is in the range of 5 µm to 250 µm.

10. The article of manufacture as claimed in claim 9, wherein, Surface roughness R of the inner wall a Less than or equal to 0.3 µm.

11. The article of manufacture as claimed in claim 9 or 10, wherein, The first diameter of the at least one hole is in the range of 5 µm to 100 µm.

12. A semiconductor package comprising: The article as described in any of the preceding claims, wherein the article is provided with a conductive material in the at least one hole; and A semiconductor device electrically coupled to a conductive material disposed in the at least one hole.

13. A method for forming a hole in a substrate, the method comprising: A pulsed laser beam is applied to a substrate to form at least one laser-damaged region in the substrate; as well as The substrate is etched in a liquid etching solution to expand the at least one laser-damaged area, thereby forming at least one hole in the substrate, such that: The at least one hole includes an inner wall, the surface roughness R of which is... a Less than or equal to 1 µm; The at least one hole includes a first opening having a first diameter, which exists on a first surface of the substrate; and The ratio of the recess depth to the first diameter of the at least one hole is less than or equal to 0.007, wherein the recess depth is measured from the first plane to the first surface at the first opening of the at least one hole, and the first plane is defined by the first surface of the substrate based on the average thickness of the substrate.

14. The method of claim 13, wherein, The liquid etching solution has a pH range of 1.0 to 2.0 and provides an etching rate of less than about 4 µm / min.

15. The method of claim 13 or 14, wherein, Etching the substrate also includes applying ultrasonic stirring to the liquid etching solution, the frequency of which is in the range of 40 kHz to 192 kHz.

16. The method according to any one of claims 13-15, wherein: The liquid etching solution contains 1.5M HF and 1.6M HNO3; The temperature of the liquid etching solution is in the range of 10°C to 30°C; and An ultrasonic stirring is applied to the liquid etching solution, the frequency of which is in the range of 40 kHz to 192 kHz.

17. The method according to any one of claims 13-16, wherein, Applying a pulsed laser beam to a substrate also includes: The sacrificial cover layer is fixed to the surface of the substrate; The laser beam is positioned relative to the substrate at a predetermined location, and this location corresponds to the desired location of the at least one hole; At least one laser-damaged region is formed in the sacrificial cover layer by repeatedly pulsed laser beams at predetermined locations; and A laser beam is pulsed into a perforation formed in a sacrificial capping layer at a predetermined location, thereby forming the at least one damaged region in the substrate.

18. The method of claim 17, wherein, The numerical aperture of the laser beam is between approximately 0.02 and approximately 0.4, and the laser beam is focused within approximately 100 μm of the surface of the sacrificial capping layer.

19. The method of claim 18, wherein, The laser beam has a wavelength of approximately 355 nm, a pulse width between approximately 5 ns and approximately 75 ns, pulses at a repetition rate of approximately 1 kHz to approximately 30 kHz, and a pulse energy between approximately 25 μJ and approximately 175 μJ.

20. The method according to any one of claims 13-19, wherein, Applying a pulsed laser beam to a substrate further includes forming a destruction trace by focusing the pulsed laser beam into a focal line oriented along the beam propagation direction and guiding the focal line into the substrate, the destruction trace defining the at least one laser destruction region within the substrate.

21. The method of claim 20, wherein, The laser beam focal line extends through the entire body of the substrate.

22. The method of claim 20 or 21, wherein, A pulsed laser beam consists of a series of pulses, with each laser beam containing a series of pulses.

23. The method of claim 22, wherein: The number of pulses in each pulse train is in the range of 10 to 20; and The average energy of each pulse train is in the range of 100 µJ to 200 µJ.

24. The method according to any one of claims 13-23, wherein, Surface roughness R of the inner wall a Within the range of 0.1 µm to 1 µm.

25. The method according to any one of claims 13-24, wherein, The substrate is a glass-based substrate.

26. The method according to any one of claims 13-25, wherein: The at least one hole is a perforation, such that a second opening with a second diameter exists on the second surface; Based on the average thickness of the substrate, the second plane is defined by the second surface of the substrate; and The ratio of the second recess depth to the second diameter of the at least one hole is less than or equal to 0.007, wherein the second recess depth is measured from the second plane to the second surface at the second opening of the at least one hole.

27. The method according to any one of claims 13-26, wherein: The substrate is a glass-based substrate; The at least one hole is a perforation, such that a second opening with a second diameter exists on the second surface of the glass substrate. The difference between the first diameter and the second diameter is less than or equal to 2 µm; The roundness of the at least one hole is less than or equal to 5 µm; The first and second diameters are each in the range of 5 µm to 250 µm; and The average thickness of the substrate is in the range of 1:1 to 15:1 in aspect ratio to at least one of the first diameter and the second diameter.

28. The method of claim 27, wherein: The at least one hole includes a waist with a waist diameter; and The waist diameter of the at least one hole is greater than or equal to 80% of the largest of the first diameter of the first opening and the second diameter of the second opening.

29. The method of claim 27, wherein: The at least one hole includes a waist with a waist diameter; and The waist diameter is in the range of 20% to 100% of the larger of the first diameter of the first opening and the second diameter of the second opening.

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