Methods for etching vias in glass-based articles employing positive charge organic molecules
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.
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 2 is lower than an etch rate of the damaged region E 1 , a ratio of E 1 /E 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 μm to 700 μm after etching, including endpoints, and
the via has a waist diameter D w that is less than a first diameter D 1 at the first surface and is less than a second diameter D 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 μm.
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 2 is lower than an etch rate of the damaged region E 1 , a ratio of E 1 /E 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.