Methods for etching vias in glass-based articles employing positive charge organic molecules

Abstract

Methods of forming vias in a glass-based article by laser-damage-and-etch processes including etching solutions having positive charge organic molecules are disclosed. In some embodiments, a method of forming a via in a glass-based article includes forming a damage track through a bulk of the glass-based article extending from a first surface of the glass-based article to a second surface of the glass-based article, and applying an etching solution to the glass-based article to form the via. The etching solution includes at least one acid and a positive charge organic molecule. An etch rate at the first surface and the second surface is lower than an etch rate at the damage track.

Claims

1. A method of forming a via in a glass-based article, the method comprising: applying an etching solution to at least a first surface of the glass-based article, the etching solution comprising a positive charge organic molecule and at least one acid, wherein: prior to the application of the etching solution, the glass-based article has a damage track formed through a bulk of the glass-based article in a damaged region of the glass-based article the damage track extending from the first surface of the glass-based article to a second surface of the glass-based article, and a pH value of the etching solution is greater than an isoelectric point of the glass-based article; forming an etching inhibitor layer with the positive charge organic molecule on an undamaged region of the glass-based article such that the etching inhibitor layer retards etching of the glass-based article from the at least one acid such that an etch rate of the undamaged region E.sub.2 is lower than an etch rate of the damaged region E.sub.1, a ratio of E.sub.1/E.sub.2 being greater than 1 and less than 20; and etching the damage track in the damaged region with the at least one acid to form the via.

2. The method of claim 1, wherein the positive charge organic molecule comprises: a hydrophilic portion comprising a positive charge; and a hydrophobic portion.

3. The method of claim 1, wherein the positive charge organic molecule comprises one or more of at least one surfactant and at least one polyelectrolyte.

4. The method of claim 1, wherein the positive charge organic molecule comprises cetrimonium bromide.

5. The method of claim 1, wherein the positive charge organic molecule comprises poly(diallyldimethylammonium chloride).

6. The method of claim 5, wherein a concentration of the positive charge organic molecule is with a range of 0.0035 wt % to 10 wt % including endpoints.

7. The method of claim 1, wherein the at least one acid comprises hydrofluoric acid.

8. The method of claim 7, wherein a concentration of the hydrofluoric acid is within a range of 1 wt % to 20 wt % including endpoints.

9. The method of claim 7, wherein the at least one acid further comprises a mineral acid.

10. The method of claim 9, wherein a concentration of the mineral acid is less than or equal to 40 wt %.

11. The method of claim 9, wherein the mineral acid is one or more of hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, acetic acid, and tartaric acid.

12. The method of claim 11, wherein the etching solution further comprises a fluoride-containing compound.

13. The method of claim 12, wherein the fluoride-containing compound comprises one or more of ammonium fluoride, potassium fluoride, sodium fluoride, ammonium bifluoride, potassium bifluoride, and sodium bifluoride.

14. The method of claim 1, wherein the glass-based article comprises aluminosilicate glass, borosilicate glass, fused silica, soda lime glass, or glass-ceramic.

15. The method of claim 1, wherein: the glass-based article has a thickness within a range of 200 m to 700 m after etching, including endpoints, and the via has a waist diameter D.sub.w that is less than a first diameter D.sub.1 at the first surface and is less than a second diameter D.sub.2 at the second surface.

16. The method of claim 15, wherein the via has a delta via diameter that is less than or equal to 50 m.

17. The method of claim 1, wherein the etching inhibitor layer further comprises a layer of glass by-products.

18. The method of claim 1, wherein the etching inhibitor layer comprises a polyelectrolyte.

19. A method of forming a via in a glass-based article, the method comprising: applying a pulsed laser beam having a line focus through a bulk of the glass-based article to form a damage track in a damaged region of the glass-based article, the damage track extending through the bulk of the glass-based article from a first surface of the glass-based article to a second surface of the glass-based article; applying an etching solution to at least first surface of the glass-based article, the etching solution comprising PDADMAC and hydrofluoric acid, and a pH value of the etching solution being greater than an isoelectric point of the glass-based article; and forming an etching inhibitor layer with the PDADMAC on an undamaged region of the glass-based article such that the etching inhibitor layer retards etching of the glass-based article from the hydrofluoric acid such that an etch rate of the undamaged region E.sub.2 is lower than an etch rate of the damaged region E.sub.1, a ratio of E.sub.1/E.sub.2 being greater than 1 and less than 20.

20. The method of claim 19, wherein the etching solution comprises 4-6 wt % hydrofluoric acid and between 0.0035 wt % and 0.05 wt % PDADMAC.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) The foregoing will be apparent from the following more particular description of the example embodiments, as illustrated in the accompanying drawings in which like reference characters refer to the same parts throughout the different views. The drawings are not necessarily to scale, emphasis instead being placed upon illustrating the representative embodiments.

(2) FIG. 1 schematically depicts a partial side view of a glass-based article having vias according to one or more embodiments described and illustrated herein;

(3) FIG. 2A schematically depicts a partial side view of a glass-based article having a damage track formed therethrough according to one or more embodiments described and illustrated herein;

(4) FIG. 2B schematically depicts a partial side view of the glass-based article of FIG. 2A being etched by an etching process according to one or more embodiments described and illustrated herein;

(5) FIG. 3A schematically depicts a partial side view of the glass-based article of FIG. 2A after etching wherein E.sub.1/E.sub.2=1, where E.sub.1 is a via etch rate and E.sub.2 is a bulk etch rate;

(6) FIG. 3B schematically depicts a partial side view of the glass-based article of FIG. 2A after etching wherein 1<E.sub.1/E.sub.2<20;

(7) FIG. 3C schematically depicts a partial side view of the glass-based article of FIG. 2A after etching wherein E.sub.1/E.sub.220;

(8) FIG. 4 schematically depicts a glass-based article having negatively charged surfaces subjected to three different etching scenarios including, positive charge surfactant, no positive charge organic molecules, and positive charge polyelectrolyte according to one or more embodiments described and illustrated herein;

(9) FIG. 5 schematically depicts a glass-based article and multiple layers of positive charge polyelectrolytes and a layer of glass by-products according to one or more embodiments described and illustrated herein;

(10) FIG. 6 schematically depicts a via being etched in a glass-based article by an etching solution including hydrogen fluoride and positive charge polyelectrolyte according to one or more embodiments described and illustrated herein;

(11) FIG. 7 schematically depicts a via being etched in a glass-based article by an etching solution arranged in multiple layers of positive charge polyelectrolyte, hydrogen fluoride and glass by-products according to one or more embodiments described and illustrated herein;

(12) FIG. 8A is an image of a first surface of a glass coupon having vias etched by hydrofluoric acid without positive charge organic molecules with a focus of the image on the first surface to illustrate a first diameter of the vias;

(13) FIG. 8B is an image of the first surface of the glass coupon shown in FIG. 8A with a focus of the image within a bulk of the glass coupon to illustrate the waist diameter of the vias;

(14) FIG. 8C is a side image of the glass coupon shown in FIGS. 8A and 8B;

(15) FIG. 9A is an image of a first surface of a glass coupon having vias etched by an etching solution including hydrofluoric acid and CTAB with a focus of the image on the first surface to illustrate a first diameter of the vias according to one or more embodiments described and illustrated herein;

(16) FIG. 9B is an image of the first surface of the glass coupon shown in FIG. 9A with a focus of the image within a bulk of the glass coupon to illustrate the waist diameter of the vias according to one or more embodiments described and illustrated herein;

(17) FIG. 9C is a side image of the glass coupon shown in FIGS. 9A and 9B according to one or more embodiments described and illustrated herein;

(18) FIG. 10A is an image of a first surface of a glass coupon having vias etched by an etching solution including hydrofluoric acid and PDADMAC with a focus of the image on the first surface to illustrate a first diameter of the vias according to one or more embodiments described and illustrated herein;

(19) FIG. 10B is an image of the first surface of the glass coupon shown in FIG. 10A with a focus of the image within a bulk of the glass coupon to illustrate the waist diameter of the vias according to one or more embodiments described and illustrated herein;

(20) FIG. 10C is a side image of the glass coupon shown in FIGS. 10A and 10B according to one or more embodiments described and illustrated herein;

(21) FIG. 11 graphically depicts the delta via diameter for glass coupons etched by a plurality of etching solution compositions according to one or more embodiments described and illustrated herein;

(22) FIG. 12 graphically depicts the delta via diameter and etch rate for glass coupons etched by a plurality of etching solution compositions having varying concentrations of PDADMAC according to one or more embodiments described and illustrated herein;

(23) FIGS. 13A-13D are images of the first surface of glass coupons etched by the etching solution compositions of FIG. 12 according to one or more embodiments described and illustrated herein;

(24) FIG. 14 graphically depicts the delta via diameter and etch rate for glass coupons etched by a plurality of etching solution compositions having varying concentrations of PDADMAC and with and without HNO.sub.3, according to one or more embodiments described and illustrated herein;

(25) FIG. 15 schematically depicts a glass-based article in an etching solution including a positive charge polyelectrolyte and a negative charge organic molecule according to one or more embodiments described and illustrated herein;

(26) FIG. 16 graphically depicts the delta via diameter and etch rate for glass coupons etched by a plurality of etching solution compositions having varying concentrations of PDADMAC and SDS according to one or more embodiments described and illustrated herein;

(27) FIG. 17A is an image of a top surface of a glass coupon etched by hydrofluoric acid without positive charge organic molecules with a focus of the image within a bulk of the glass coupon to illustrate the waist diameter of the vias;

(28) FIG. 17B is an image of a top surface of a glass coupon etched by an etching solution including hydrofluoric acid and PDADMAC with a focus of the image within a bulk of the glass coupon to illustrate the waist diameter of the vias according to one or more embodiments described and illustrated herein;

(29) FIG. 17C is an image of a top surface of a glass coupon etched by an etching solution including hydrofluoric acid, PDADMAC and SDS with a focus of the image within a bulk of the glass coupon to illustrate the waist diameter of the vias according to one or more embodiments described and illustrated herein; and

(30) FIG. 17D is an image of a top surface of a glass coupon etched by an etching solution including hydrofluoric acid and SDS with a focus of the image within a bulk of the glass coupon to illustrate the waist diameter of the vias according to one or more embodiments described and illustrated herein.

DETAILED DESCRIPTION

(31) The embodiments disclosed herein relate to methods for etching vias in glass-based articles using an etching solution including positive charge organic molecules (e.g., surfactants and polyelectrolytes) that retard the bulk etch rate of the surface of the glass-based article and do not retard, or retard to a lesser extent, a via etch rate. Thus, vias etched in glass-based articles according to the methods described herein have a larger waist diameter, and therefore less of an hourglass shape, than vias etched by an etching solution not including positive charge organic molecules. Embodiments described herein improve via shape without changing glass composition or glass properties.

(32) The larger waist diameter of the vias may lead to improvement in downstream processes, such as metallization of the vias. Non-limiting example metallization methods include bottom-up plating and paste filling. The glass-based articles described herein may include metalized vias and may be provided as components in electronic devices, such as a redistribution layer (e.g., in a wireless communications device) or as an interposer.

(33) Various embodiments of methods for forming vias in glass-based articles are described in detail below.

(34) Referring now to FIG. 1, a glass-based article 100 having a plurality of vias 110 (vias) disposed therethrough is schematically illustrated. The glass-based article 100 may be used as a product in an electronic device, for example. Non-limiting products include a redistribution layer and an interposer. It should be understood that the glass-based article 100 may be utilized as other products performing other functions.

(35) The glass-based article 100 has a first surface 102 and a second surface 104. The vias 110 extend through a bulk of the glass-based article 100 from the first surface 102 to the second surface 104. Although the vias 110 depicted in FIG. 1 are through-hole vias, embodiments are not limited thereto. Vias of the present disclosure may be blind vias that do not extend fully through the glass-based article. The thickness of the glass-based articles described herein is not limited by this disclosure. As an example and not a limitation, the glass-based articles 100 described herein may have a thickness after etching within a range of 200 m to 700 m, or within a range of 200 m, to 500 m, including endpoints. It should be understood that the glass-based articles 100 may have other thicknesses depending on the end application.

(36) The glass-based article 100 may be fabricated from any glass-based material capable of being etched by a chemical etching process. Non-limiting example glass-based materials include aluminosilicate glass, borosilicate glass, fused silica, soda lime glass, and glass-ceramic materials. The glass-based materials described herein have transparency for at least one laser operating wavelength that is sufficient to allow the creation of damage tracks. Non-limiting examples of suitable laser operating wavelengths include 532 nm and 1064 nm. Any suitable glass-based material may be used.

(37) Each via 110 has a first opening 112 at the first surface, a second opening 114 at the second surface, and a waist W. The waist W of the vias 110 is located between the first opening 112 and the second opening 114. As described in more detail below, the diameter of the waist W of the via 110 may be less than a diameter of the first opening 112 and/or the second opening 114. In some embodiments, the diameter of the waist W is substantially equal to the diameter of the first opening 112 and/or the second opening 114.

(38) Depending on the application of the glass-based article 100, the vias 110 may be filled with an electrically conductive material by way of a metallization process. The type of metallization process used to fill the vias 110 is not limited by this disclosure. Generally, it may be desirable in metallization processes to have a waist W with a diameter close to the diameter of the first opening 112 and/or the second opening 114. Vias with a high waist diameter D.sub.W to first diameter D.sub.1 (or second diameter D.sub.2) may result in more reliable metallization of the vias 110. Thus, it may be desirable to increase the diameter of the waist W of the vias.

(39) The vias 110 of the glass-based articles 100 described herein are formed by a laser-damage-and-etch process wherein a damage track through a bulk of the glass-based article 100 is formed by a laser beam. Referring to FIG. 2A, a glass-based article 100 having a damage track 120 formed from the first surface 102 to the second surface 104 is schematically illustrated. The damage track 120 is a damaged region within the glass-based article 100 formed by application of a laser beam. The damage track 120 has a higher etch rate than the regions of the glass-based article outside of the damage track 120. The laser methods of forming the damage track 120 are not limited by this disclosure. Methods of forming a damage track through a glass substrate in a laser-damage-and-etch process by use of a laser beam focused into a line focus are described in U.S. Pat. Publ. No 2015/0166396, which is hereby incorporated by reference in its entirety. As an example and not a limitation, a picosecond laser may be focused into a line focus that passes through the thickness of the glass-based article 100 to damage the glass material and create a damage track 120. To form a through-hole via, the damage track 120 extends from the first surface 102 to the second surface 104. To form a blind via, the damage track 120 may start at the first surface 102 or the second surface 104, but not extend fully to the opposite surface.

(40) Referring now to FIG. 2B, a glass-based article 100 having one or more damage tracks therethrough is then etched in an etching solution. As non-limiting examples, the etching solution includes hydrofluoric acid in a concentration of 0.5 to 10 wt %, including endpoints, or 2.5 wt to 10 wt %, including endpoints. The etching solutions described herein may or may not include one or more mineral acids and/or strong acids. Example mineral acids and strong acids include, but are not limited to, hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, acetic acid, and tartaric acid. In embodiments, the etching solution may include 0 to 40 wt % mineral acid, including endpoints. The etching solutions described herein may also include one or more fluoride-containing compounds, such as, without limitation, ammonium fluoride, potassium fluoride, sodium fluoride, ammonium bifluoride, potassium bifluoride, and sodium bifluoride. As an example, and not a limitation, the concentration of other fluoride compounds may be 0 to 10 wt %.

(41) The etching solution etches the first surface 102 and the second surface 104 of the glass-based article 100, as well as through the damage track 120. The glass-based article 100 may be statically etched or with applied agitation, such as ultrasonic agitation. During the etching process, the etch rate of the damaged region of the damage track 120 is defined as E.sub.1 and the etch rate of the bulk region (undamaged region) is defined as E.sub.2 in FIG. 2B. The ratio of E.sub.1/E.sub.2 is defined as R herein.

(42) As shown in FIG. 3A, when R is equal to 1, the glass-based article 100 becomes thinner but a via is not formed because E.sub.1 is equal to E.sub.2. However, when R is greater than 1 but less than 20, a via 110 is formed such that the first diameter D.sub.1 of the first opening 112 and the second diameter D.sub.2 of the second opening 114 are significantly larger than the waist diameter D.sub.W of the waist W. When the ratio R is greater than 20, the via 110 is formed such that the waist diameter D.sub.W is close to the first diameter D.sub.1 and/or the second diameter D.sub.2, thereby forming a substantially cylindrical through via.

(43) As stated above, it may be desirable to increase the ratio D.sub.W/D.sub.1 to improve the metallization process that fills the vias 110 with electrically conductive material (e.g., copper). It is noted that the first diameter D.sub.1 and the second diameter D.sub.2 may be used interchangeably herein because the first diameter D.sub.1 and the second diameter D.sub.2 may be close in value. Thus, the ratio D.sub.W/D.sub.1 also refers to the ratio D.sub.W/D.sub.2 herein.

(44) Embodiments of the present disclosure increase the waist diameter D.sub.W without requiring a change in glass composition or a change in the laser damage process, as well as without significantly changing the initial glass thickness. Particularly, the laser-damage-and-etch processes described herein increase the waist diameter, and thus improve the ratio D.sub.W/D.sub.1 by introducing positive charge organic molecules into the etching solution.

(45) The positive charge organic molecules self-assemble and form an etching inhibitor layer on the first surface 102 and the second surface 104 of the glass-based article 100 that slows the rate at which the acid (e.g., hydrofluoric acid) of the etching solution reaches these surfaces. This effect reduces the bulk etch rate E.sub.2. When the access of the hydrofluoric acid to the glass surface is regulated (i.e., slowed down), the bulk etching rate E.sub.2 may be reduced in a controllable manner. As non-limiting examples, the concentration of positive charge organic molecules may be within a range of 0.0035 wt % to 10 wt %, or 0.0035 wt % to 1 wt %, 0.0035 wt % to 0.1 wt %, or 0.0035 wt % to 0.05 wt %, including endpoints.

(46) As shown in FIG. 4, the first surface 102 and the second surface 104 of the glass-based article 100 is negatively charged. Particularly, the first surface 102 and the second surface 104 are negatively charged within the etching solution when the pH of the etching solution is above the isoelectric point of the material of the glass-based article 100. Thus, the etching solutions described herein have a pH value that is greater than the isoelectric point of the glass-based article 100 being etched to cause the surfaces to be negatively charged. The isoelectric point of the glass-based article 100 may depend on the composition of the glass-based article 100. The isoelectric point of the glass-based articles described herein is measured by the Zetasizer Nano ZS90 sold by Malvern Instruments Ltd of the United Kingdom. First, the glass-based article is powderized to 100 m in average diameter particles. The particles are suspended in aqueous solutions at different pH values. The particle concentration is less than 1% by volume. Ultrasonic agitation is applied until the particles are uniformly distributed. The solution is then provided in a testing vial for zeta-potential measurement in the Zetasizer Nano ZS90. The zeta-potential of the sample is measured using the Zetasizer Nano ZS90 standard operating procedure. The zeta potential may be neutral, positive or negative. The isoelectric point is the pH value where the zeta potential is neutral.

(47) The etching chemistry of the embodiments described herein include positive charge organic molecules to self-assemble on the negatively-charged glass surface and therefore retard glass surface etching and improve etching selectivity between laser damaged and non-damaged areas.

(48) The positive charge molecules described herein may be any molecule that has a positive charge that is attracted to the negatively charged first surface 102 and second surface 104 of the glass-based article 100 and provides an etching inhibitor layer for hydrofluoric acid molecules that retards the etching effect of the hydrofluoric acid on the first surface 102 and the second surface 104. As a non-limiting example, the positive charge organic molecules may have a positive charged hydrophilic head (i.e., a hydrophilic portion) and a hydrophobic tail (i.e., a hydrophobic portion). The positive charged head is balanced with a negative charge ion, and is covalently bonded to the hydrophobic tail. Non-limiting examples of positive charge organic molecules include positive charge surfactants and positive charge polyelectrolytes. A non-limiting example of a positive charge surfactant includes cetrimonium bromide ([C.sub.16H.sub.33)N(CH.sub.3).sub.3]Br) hereinafter CTAB). A non-limiting example of a positive charge polyelectrolyte is poly(dailydimethylammonium chloride) (hereinafter PDADMAC). It should be understood that the etching solutions described herein may comprise a combination of one or more positive charge surfactants and one or more positive charge polyelectrolytes. Other non-limiting examples of positive charge polyelectrolytes is amine-containing polymers having a positive charge in the etching solution, such as, without limitation, polyamine, polyethylene amine, and the like.

(49) FIG. 4 illustrates three different etching scenarios in a first region 130A, a second region 130B and a third region 130C. In all scenarios, the etching solution includes hydrogen fluoride molecules 132 that remove glass material of the glass-based article 100 when in contact with the first surface 102 and the second surface 104. It is noted that the etching solution is shown as only contacting the first surface 102 in FIGS. 4-7 and 15 for ease of illustration. It should be understood that the etching solution may contact all surfaces of the glass-based article 100. In the scenario illustrated by the second region 130B, the etching solution does not include positive charge organic molecules and thus the hydrofluoric acid molecules have access to the first surface 102 with no etching inhibitor layer. In such a case, the bulk etch rate E.sub.2 is not retarded. However, in the scenario illustrated by the first region 130A, the negative charge of the first surface 102 attracts positive charge surfactant molecules 134. Therefore, the positive surfactant molecules form an etching inhibitor layer that inhibits access of the hydrogen fluoride molecules 132 to the first surface 102 (and the second surface 104) of the glass-based article 100. The hydrogen fluoride molecules 132 need to pass through the surfactant layer formed by the positive charge surfactant molecules 134. The positive charge surfactant molecules 134 reduce the ability for the hydrogen fluoride molecules 132 to contact and etch the surfaces of the glass-based article 100. Accordingly the bulk etch rate E.sub.2 of the scenario illustrated by the first region 130A is slower than that of the scenario illustrated by the second region 130B.

(50) The third region 130C illustrates positive charge polyelectrolyte molecules 136 attracted to the negatively charged first surface 102, thereby forming an etching inhibitor layer in a manner similar to the positive charge surfactant molecules 134 within the first region 130A. The positive charge polyelectrolyte molecules 136 reduce the ability for the hydrogen fluoride molecules 132 to contact and etch the first surface 102. The hydrogen fluoride molecules 132 still access the surfaces of the class-based article but at a much slower rate than when no positive charge polyelectrolyte molecules 136 are present. It is noted that, compared to the layer formed by the positive charge surfactant molecules 134, the layer formed by the positive charge polyelectrolyte molecules 136 may be more rigid and more effective in regulating the hydrogen fluoride molecules than the positive charge surfactant molecules 134. Because the positive charge polyelectrolyte molecules 136 contain more than one charge per molecule, it may be more difficult to detach from the glass surface than the positive charge surfactant molecules 134. Generally, it has been shown that the etch rate from high to low ranks as: the second region 130B>the first region 130A>the third region 130C. Thus, if the glass-based article 100 is etched using the same etching solution and at the same etch condition, adding positive charge organic molecules can modulate glass etch rate.

(51) FIG. 5 schematically illustrates a scenario similar to that of the third region 130C illustrated by FIG. 4 but with the addition of a graphical representation of glass by-products (e.g., CaAlF.sub.5, CaSiF.sub.6, MgSiF.sub.6, MgAlF.sub.5 depending on the composition) 138 etched by the hydrofluoric acid. In some cases, the glass by-products 138 may form an additional layer that inhibits the hydrogen fluoride molecules 132 from reaching the surfaces of the glass-based article 100. Thus, several layers formed by positive charge organic molecules and glass by-products may be formed. FIG. 5 schematically illustrates two layers of positive charge polyelectrolyte molecules 136A, 136B and one layer of glass by-products 138. It should be understood that FIG. 5 is merely a simplified illustration of the various layers that may be formed during the etching process, and that embodiments are not limited thereto.

(52) Modulation of the bulk etch rate E.sub.2 using positive charge organic molecules may be used to increase the waist diameter D.sub.W of vias 110 formed in glass-based articles 100. Additionally, positive charge organic molecules may be used to form cylindrically shaped blind vias that are less tapered in shape. FIG. 6 schematically illustrates etching of a via 110 within a glass-based article 100 using a hydrofluoric acid etching solution including positive charge organic molecules (positive charge polyelectrolyte molecules 136 in this example). During etching, a via can be classified into two areas: an opened area on the first surface 102 (and second surface 104) proximate and within the first opening 112 (and second opening 114) and a restricted area 117 within a waist W. In the opened area, positive charge polyelectrolyte molecules 136 can effectively align and slow down etching process by inhibiting the hydrogen fluoride molecules 132. Positive charge surfactant molecules 134 perform a similar function. Both the bulk etch rate E.sub.2 and a via widening rate within the first opening 112 is slowed down as compared to when no positive charge polyelectrolyte molecules 136 are provided in the etching solution. However, access of the positive charge polyelectrolyte molecules 136 into the restricted area 117 is restricted and thus the positive charge polyelectrolyte molecules 136 cannot as effectively inhibit etching as compared to the opened area. Accordingly, the via etch rate E.sub.1 is not as significantly influenced by the positive charge polyelectrolyte molecules 136 as compared to the surface etch rate E.sub.2. Positive charge surfactant molecules 134 perform in a similar manner.

(53) FIG. 7 is similar to the etching process depicted by FIG. 6 but further includes the depiction of glass by-products 138 that, along with the positive charge polyelectrolyte molecules 136, further inhibit the hydrogen fluoride molecules 132 from contacting the opened area of the first surface 102. However, the positive charge polyelectrolyte molecules 136 and the glass by-products 138 do not easily enter the restricted area 117, allowing the hydrogen fluoride molecules 132 to enter the restricted area 117 and widen the waist W of the via 110, as described above with respect to FIG. 6.

EXAMPLE 1

(54) To illustrate the effects of positive charge surfactant molecules and positive charge polyelectrolyte molecules within an etching solution in widening the waist of vias, glass coupons were subjected to a laser-and-damage-and-etch process. The 50 mm50 mm glass coupons were fabricated from alkaline earth boro-aluminosilicate under the trade name Eagle XG sold by Corning, Inc. of Corning, New York and had a thickness of 0.4 mm. One glass coupon was fabricated per etching condition. 10,000 damage tracks 120 were formed in each of the glass coupons using a 50 ps pulsed laser having 532 nm wavelength, a 3 mm beam diameter that entered the first surface 102, a 30 mm working distance objective, and a 0.7 mm focus line length was present through the glass coupons. Each damage track was created using one laser burst with a burst number of 15 pulses and a burst energy of about 800.

(55) Following the laser damage process, the glass coupons were statically etched at room temperature (20 C.) in an etching solution comprising a solution of 2.5 wt % HF and 3.5 wt % HNO.sub.3 with and without positive charge organic molecules. The final thickness of the glass coupons, the waist diameter, and the first diameter of the first opening (i.e., the openings at the surface into which the laser beam enters the glass coupons) were measured using an optical microscope. The etch time was also recorded. The average top diameter D.sub.1, waist diameter D.sub.W, final glass coupon thickness, initial glass coupon thickness, etch time, via shape, etch rate E.sub.1, etch rate E.sub.2, etch ratio, and through time were recorded. It is noted that the via shape is quantified by a thickness of the etched glass coupon divided by two times the difference between the top diameter D.sub.1 and the waist diameter D.sub.W. Through time is the time that the etching takes to connect the vias from the first surface to the second surface (etch timeD.sub.W/(2*E.sub.2). The results are shown in Table 1 below.

(56) TABLE-US-00001 TABLE 1 Delta (Top via Diameter final initial etch shape E1 E2 etch through Top D Waist D Waist thickness thickness time (T/2)/ (Via), (bulk), ratio time etching solution (m) (m) Diameter) (m) (m) (min) (Dt Dw) m/min m/min (E1/E2) (min) 2.5 wt % HF + 3.5 wt % HNO3 82.5 27.6 54.8 305 405 168.3 2.8 1.66 0.297 5.60 121.8 2.5 wt % HF + 3.5 wt % HNO3 + 81.0 46.5 34.5 303 404 335 4.4 1.12 0.151 7.41 180.8 0.35 wt % PDAD MAC(<100 K) 2.5 wt % HF + 3.5 wt % HNO3 + 87.1 42.0 45.1 302 402 325 3.3 1.07 0.154 6.93 188.5 0.2 wt % PDAD MAC(100-200 K) 2.5 wt % HF + 3.5 wt % HNO3 + 85.6 46.9 38.6 301 402 326.5 3.9 1.15 0.155 7.44 174.8 0.4 wt % PDAD MAC(100-200 K) 2.5 wt % HF + 3.5 wt % HNO3 + 91.0 47.5 43.6 300 400 340 3.4 1.12 0.147 7.61 178.6 0.2 wt % PDAD MAC(>400 K) 2.5 wt % HF + 3.5 wt % HNO3 + 81.3 33.0 48.4 304 403 261 3.1 1.16 0.190 6.10 174.1 1 wt % CTAB

(57) FIGS. 8A-8C depict images of vias of etched glass coupons that were etched by 2.5 wt % HF and 3.5 wt % HNO.sub.3 (1.45M HF and 0.8M HNO.sub.3). Thus, the etched glass coupons shown in FIGS. 8A-8C are representative of control group glass coupons because no positive charge organic molecules were included in the etching solution. The focus of the image of FIG. 8A is on the top surface of the glass coupon to depict the top diameter D.sub.1 of the openings (e.g., the first openings 112 shown in FIG. 1), which is represented by the diameter of the dark circles. The focus of the image of FIG. 8B is within the bulk of the glass coupon to depict the waist diameter D.sub.W of the vias, which is represented by the center white circles. FIG. 8C is a side view of the vias of the control glass coupons depicted in FIGS. 8A and 8B.

(58) Referring to Table 1 above, the average top diameter D.sub.1 and the average waist diameter D.sub.W of the control glass coupons were 82.5 m and 27.6 m, respectively. This resulted in vias with a narrow waist and having an hourglass shape as shown in FIG. 8C.

(59) FIGS. 9A-9C depict images of vias of etched glass coupons that were etched by 2.5 wt % HF and 3.5 wt % HNO.sub.3 and 1 wt % CTAB (1.45M HF and 0.8M HNO.sub.3 and 1 wt % CTAB). Similar to FIG. 8A, the focus of the image of FIG. 9A is on the top surface of the glass coupon to depict the top diameter D.sub.1 of the openings (e.g., the first openings 112 shown in FIG. 1), which is represented by the diameter of the dark circles. The focus of the image of FIG. 9B is within the bulk of the glass coupon to depict the waist diameter D.sub.W of the vias, which is represented by the center white circles. FIG. 9C is a side view of the vias of the glass coupons depicted in FIGS. 9A and 9B.

(60) Referring to Table 1 above, the average top diameter D.sub.1 and the average waist diameter D.sub.W for these glass coupons were 81.3 m and 33.0 m, respectively. Thus, the CTAB increased the average waist diameter from 27.6 m to 33.0 m as compared to the vias of the control glass coupons. The resulting vias as shown in FIG. 9C have less of an hourglass shape than those depicted in FIG. 8C.

(61) FIGS. 10A-10C depict images of vias of etched glass coupons that were etched by 2.5 wt % HF and 3.5 wt % HNO.sub.3 and 0.35 wt % PDADMAC as a positive charge polyelectrolyte (1.45M HF and 0.8M HNO3 and 0.35 wt % PDADMAC at 100K of molecular weight). Similar to FIGS. 8A and 9A, the focus of the image of FIG. 10A is on the top surface of the glass coupon to depict the top diameter D.sub.1 of the openings (e.g., the first openings 112 shown in FIG. 1), which is represented by the diameter of the dark circles. The focus of the image of FIG. 10B is within the bulk of the glass coupon to depict the waist diameter D.sub.W of the vias, which is represented by the center white circles. FIG. 10C is a side view of the vias of the glass coupons depicted in FIGS. 10A and 10B.

(62) Referring to Table 1 above, the average top diameter D.sub.1 and the average waist diameter D.sub.W for these glass coupons were 81.0 m and 46.5 m, respectively. Thus, the PDADMAC increased the average waist diameter from 27.6 m to 46.5 m as compared to the vias of the control glass coupons. The vias of FIG. 10C have less of an hourglass shape than those depicted in FIGS. 8C and 9C.

(63) Referring to Table 1, the glass coupons etched by an etching solution including positive charge organic molecules had a waist diameter D.sub.W of greater than 30 m.

(64) FIG. 11 graphically depicts a chart illustrating a delta via diameter between the top diameter D.sub.1 and the waist diameter D.sub.W (D.sub.1-D.sub.W) using the data from Table 1. The etching solutions illustrated by FIG. 11 are as follows from left to right in the chart: 1) 2.5 wt % HF+3.5 wt % HNO.sub.3+1 wt % CTAB, 2) 2.5 wt % HF+3.5 wt % HNO.sub.3+0.2 wt % PDADMAC (100-200K), 3) 2.5 wt % HF+3.5 wt % HNO.sub.3+0.4 wt % PDADMAC (100-200K), 4) 2.5 wt % HF+3.5 wt % HNO.sub.3+0.2 wt % PDADMAC (>400K), 5) 2.5 wt % HF+3.5 wt % HNO.sub.3, and 6) 2.5 wt % HF+3.5 wt % HNO.sub.3+0.35 wt % PDADMAC (<100K).

(65) Referring to Table 1 and the graph of FIG. 1, glass coupons etched by etching solutions including positive charge organic molecules had a delta via diameter of less than 50 m. In some embodiments, the glass-based articles may have a delta via diameter of less than or equal to 50 m for glass-based article thicknesses between 200 m and 700 m, including endpoints. The control glass coupons had vias with the highest delta via diameter (about 54.8 m), while the glass coupons etched by 2.5 wt % HF and 3.5 wt % HNO.sub.3 and 0.35 wt % PDADMAC at 100K molecular weight had the smallest delta via diameter (about 34.5 m). Table 1 shows that the presence of positive charge organic molecules decreases the delta via diameter. The delta via diameter reflects the shape of the etch via and implicates the capability of etching solutions to generate wide opening via waist. The lower delta via diameter suggests better via waist opening, which may provide vias with a more desirable shape for metallization.

(66) Generally, the example shows that positive charge PDADMAC reduced the delta via diameter more effectively than positive charge CTAB. Without being bound by theory, this may be for at least two reasons: (1) the positive charge polyelectrolyte molecule can stay on glass surface much longer (retention time) due to the stronger electrostatic interaction of multiple positive charges per molecule while the positive charge surfactant molecule contains only one positive charge per molecule and has greater potential to depart the glass surface quicker, and (2) the etching inhibitor layer of positive charge polyelectrolyte molecule may make it more difficult for the hydrogen fluoride molecules to penetrate through to reach the surfaces of the glass-based article. For at least these reasons, the positive charge polyelectrolyte molecule reduced the bulk etch rate E.sub.2 from 0.3 um/min to 0.15 um/min in this example. The positive charge surfactant molecule reduced the bulk etch rate E.sub.2 to 0.2 um/min. In one non-limiting embodiment, the etching solution comprises 4 wt % to 6 wt % HF and 0.0035 wt % to 0.05 wt % PDADMAC, including endpoints.

(67) The size (i.e., the molecular weight) of the positive charge polyelectrolyte molecule may also play a role in restricting via opening at the surfaces, and thus etching vias with a smaller delta via diameter. Polyelectrolytes of smaller molecular weight (100K or less) may be able to access to the via area earlier than polyelectrolytes having a larger size (e.g., molecular weights of 100K-200K, and 400K or larger). Positive charge polyelectrolytes having a smaller size may reduce the via widening rate earlier, and reduce the delta via diameter more effectively.

(68) Accordingly, the above-example shows that positive charge surfactants and positive charge polyelectrolytes, when included in a hydrofluoric acid etching solution, are capable of increasing the waist diameter D.sub.W and therefore decreasing the delta via diameter between the top diameter and the waist diameter (D.sub.1-D.sub.W).

EXAMPLE 2

(69) To illustrate the impact of the concentration of positive charge polyelectrolyte in the etching solution on delta via diameter and etching rate, damage tracks were formed in glass coupons as described above with respect to Example 1. The composition and thickness of the glass coupons were the same as the glass coupons of Example 1.

(70) Four sets of glass coupons were etched using an etching solution comprising hydrofluoric acid without mineral acids. A first set included control glass coupons that were etched using 3M HF (5 wt %) without positive charge organic molecules. An image of the waists of sample vias of the control glass coupons is illustrated in FIG. 13A. FIG. 12 is a bar graph showing delta diameter versus etchant for the glass coupons shown in FIGS. 13A-13D. For FIGS. 13A-13D, the focus of the images is on the waist of the vias to illustrate waist diameter D.sub.W. A second set of glass coupons was etched using 3M HF (5 wt %) with 0.35 wt % PDADMAC having a molecular weight of 100K. FIG. 13B shows the resulting vias. A third set of glass coupons was etched using 3M HF (5 wt %) with 0.035 wt % PDADMAC having a molecular weight of 100K. FIG. 13C shows the resulting vias. A fourth set of glass coupons was etched using 3M HF (5 wt %) with 0.0035 wt % PDADMAC having a molecular weight of 100K. FIG. 13D shows the resulting vias.

(71) Referring to FIG. 12, low concentration of PDADMAC (0.0035 wt %) provided the smallest delta via diameter and therefore the most ideal via shapes. Thus, only a small amount of positive charge polyelectrolyte may be needed to have a large impact on via shape. Additionally, use of a lower concentration of positive charge polyelectrolytes may also reduce the etch time as compared with higher concentrations of positive charge polyelectrolytes.

(72) To illustrate the effect of the concentration of positive charge polyelectrolyte in etching solutions with and without a mineral acid on delta via diameter and etching rate, damage tracks were formed in glass coupons as described above with respect to Example 1. The composition and thickness of the glass coupons were the same as the glass coupons of Example 1.

(73) Nine sets of glass coupons having damage tracks were etched according to the compositions shown in the graph of FIG. 14. As shown in FIG. 14, when the etching solution includes HNO.sub.3 (etching solution formulation 2.5 wt % HF-3.5 wt % HNO.sub.3) in the example) a higher concentration (0.35 wt %) of PDADMAC yields a smaller delta via diameter than a lower concentration (0.035 wt %) of PDADMAC. When the etching solution included 2.5 wt % HF without a mineral acid, the delta via diameter and the etch time were nearly the same whether the etching solution included 0.35 wt % or 0.035 wt % PDADMAC. However, as also shown in FIG. 13, a lowest evaluated concentration PDADMAC (0.0035 wt %) provides the smallest delta via diameter and etch time.

(74) It is noted that the presence of residue positive charge organic molecules in the etching solution tank may undesirably affect the etching results of subsequent etching processes. Thus, the etching solution tank should be cleaned to remove the positive charge organic molecules if the effects of the positive charge organic molecules are not desired. According to some embodiments, the etching solution tank may be neutralized of the positive charge organic molecules by adding negative charge organic molecules that are attracted to the positive charge organic molecules and remove the positive charge organic molecules from the surfaces of the glass-based article. Example negative charge organic molecules include, but are not limited to, anionic surfactants. Example anionic surfactants include, but are not limited to, sodium dodecyl sulfate (NaC.sub.12H.sub.25SO.sub.4) (SDS) and fatty acid salts, such as sodium stearate.

(75) FIG. 15 schematically depicts an etching solution including negative charge SDS molecules 140, positive charge polyelectrolyte molecules 136, and hydrogen fluoride molecules 132. The negative charge SDS molecules 140 are attracted to the positive charge polyelectrolyte molecules 136 and remove the positive charge polyelectrolyte molecules 136 from the first surface 102 (and second surface 104) of the glass-based article 100. This allows access for the hydrogen fluoride molecules 132 to contact the first surface 102 (and second surface 104) of the glass-based article 100. Thus, the negative charge SDS molecules 140 counteract the positive charge polyelectrolyte molecules 136 resulting in a fast bulk etch rate E.sub.2.

EXAMPLE 3

(76) To illustrate the effect of negative SDS molecules on the delta via diameter and etch time, two additional sets of glass coupons were etched by a laser-damage-and-etch process using a first etching solution comprising 5 wt % HF+0.0035 wt % PDADMAC (100K)+0.1 wt % SDS and a second etching solution comprising 5 wt % HF+0.1 wt % SDS. The composition and thickness of the glass coupons were the same as the glass coupons of Example 1. The damage tracks were formed as described above with respect to Example 1.

(77) FIG. 16 is a chart that compares the etching solutions shown in FIG. 12 with the two etching solutions including SDS as described above. As shown in FIG. 16, the presence of SDS increases the delta via diameter (i.e., decreases the waist diameter D.sub.W of the vias) and decreases the etch time. This may be due to a lack of positive charge PDADMAC molecules that reduces access of the hydrogen fluoride molecules to the surfaces of the glass coupons.

(78) FIGS. 17A-17D illustrate the evolution of the change in waist diameter size as positive charge PDADMAC molecules are added to the etching solution and then negative charge SDS molecules are added to the etching solution. Particularly, FIG. 17A depicts a glass coupon with vias etched by 5 wt % HF, FIG. 17B depicts a glass coupon etched by 5 wt % HF+0.035 wt % PDADMAC (100K), FIG. 17C depicts a glass coupon etched by 5 wt % HF+0.035 wt % PDADMAC (100K)+0.1 wt % SDS, and FIG. 17D depicts a glass coupon etched by 5 wt % HF+0.1 wt % SDS. As shown in FIGS. 17A-17D, the vias have a narrow waist when no PDADMAC is present (FIG. 17A), and comparatively widened vias when PDADMAC is present. FIGS. 17C and 17D illustrate that the vias are once again narrow when SDS is present. Thus, negative SDS molecules may be provided to the etching solution tank to remove residue positive charge organic molecules.

(79) It should now be understood that embodiments of the present disclosure are directed to methods of etching vias in glass-based articles that increase the waist diameter of vias by slowing down the bulk etch rate of the open areas of the surfaces of the glass-based article while permitting etching of the waist of the via. Therefore, embodiments may result in vias having a more cylindrical and less hourglass-shaped profile which may be beneficial for downstream metallization processes. Particularly, positive charge organic molecules are added to the etching solution to provide an etching inhibitor layer at the surfaces of the glass-based article. However, hydrogen fluoride molecules are able to enter the waist such that etching of the waist of the vias is not substantially impeded. Because the bulk etch rate is reduced, less glass is etched away and less etching solution may be used, which reduces material costs.

(80) While the embodiments herein are described with respect to hourglass and cylindrical shaped vias, the embodiments are equally applicable to any other via shape where it is desired to slow the bulk etch rate of the surfaces of the glass-based article relative to the etch rate of via surfaces.

(81) It is noted that, in some cases, a surface haze is present in the etched glass-based articles. The surface haze may be reduced by including nitric acid in the etching solution, increasing the concentration of hydrogen fluoride, or increasing the concentration of positive charge polyelectrolyte molecules.

(82) While exemplary embodiments have been described herein, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the scope encompassed by the appended claims.