Anti-reflective lenses and methods for manufacturing the same

• US 9,042,019 B2
• Filed: 10/10/2012
• Issued: 05/26/2015
• Est. Priority Date: 04/15/2011
• Status: Expired due to Fees

• Current Assignee: QSpex Technologies, Inc.
• Original Assignee: QSpex Technologies, Inc.
• Inventors: Su, Kai C., Stebbins, Leslie F., Mantch, Bill, Letter, Eugene C.
• Primary Examiner(s): Allen, Stephone B
• Assistant Examiner(s): Kakalec, Kimberly N
• Application Number:
  US13/648,642
• Publication Number:
  US 20130033753A1
• Time in Patent Office: 958 Days
• Field of Search: 249117-174, 2491871-204, 264 11- 27, 351/159.01, 351/159.49, 351/159.55, 351/159.57, 351/159.6, 351/159.62, 351/159.63, 351/159.64, 351/159.65, 351/159.73, 359577-590, 359/642, 359/722, 359/723, 359/738
• US Class Current: 359/581
• CPC Class Codes: B05D 1/18 performed by dipping
• CPC Class Codes: B05D 1/60 Deposition of organic layers from vapour phase vapour phase deposition in general C23C14/00, C23C16/00
• CPC Class Codes: B82Y 30/00 Nanotechnology for materials or surface science, e.g. nanocomposites
• CPC Class Codes: B82Y 40/00 Manufacture or treatment of nanostructures
• CPC Class Codes: C23C 16/486 using ion beam radiation
• CPC Class Codes: G02B 1/041 Lenses
• CPC Class Codes: G02B 1/11 Anti-reflection coatings
• CPC Class Codes: G02B 1/115 Multilayers
• CPC Class Codes: G02B 1/14 Protective coatings, e.g. hard coatings

Abstract

The present invention relates to a method of applying an anti-reflective coating to an optical surface of a mold. In one embodiment, the method includes the steps of: providing a lens mold having an optical surface; forming a layer of a super hydrophobic material with a thickness of about 30 to 40 nm over the optical surface, wherein the super hydrophobic material contains dipodal silane; forming an anti-reflective coating layered structure over the layer of the super hydrophobic material; and forming a layer of a cyclic azasilane coupling agent that is deposited with a monolayer thickness to the anti-reflective coating layered structure using vapor deposition or by dip coating using a solution of cyclic azasilane coupling agent in an aprotic solvent.

Claims

1. A mold with an optical surface having an anti-reflective coating that is transferable to an optical surface of a lens, comprising:

(a) a deposition layer of a fluoride or oxide material deposited to the optical surface;

(b) a layer of a hydrophobic material over the deposition layer wherein the hydrophobic material consists essentially of a super hydrophobic material and a dipodal silane;

(c) a first layer of SiO₂ that is deposited without using ion assist and with a thickness of about 5 to 40 nm deposited to the layer of hydrophobic material;

(d) an anti-reflective coating layered structure deposited to the first layer of SiO₂;

(e) a layer of a silane coupling agent that is deposited using vapor deposition and with a monolayer thickness deposited over the anti-reflective coating layered structure or by dip coating using a solution of silane coupling agent in an aprotic solvent, and

(f) a scratch resistant hard coating,

wherein the dipodal silane is different from the super hydrophobic material, and an amount of the dipodal silane is effective to prevent the anti-reflective coating layered structure from crazing.

2. The mold of claim 1, wherein the deposition layer is adapted to provide temporary adhesion between the mold surface and the hydrophobic layer such that all subsequent layers remain adherent to one another.

3. The mold of claim 1 wherein the deposition layer is formed of LiF, MgF₂, CaF₂, SrF₂, BaF₂, LaF₃, CeF₃, HfF₄, NdF₄, SiO₂, ZrO₂, Al₂O₃, Cr₂O₃, HfO₂, In₂O3, Ta₂O₅, TiO₂, Y₂O₃, or a combination of them.

4. The mold of claim 2 wherein the first deposition layer is formed of MgF₂ using ion assist and has a thickness of about 45 nm.

5. The mold of claim 1, wherein a thickness of the hydrophobic layer is about 30 to 40 nm and the amount of dipodal silane is 1.7-8.3% of said super hydrophobic material.

6. The mold of claim 1, wherein the anti-reflective coating layered structure comprises:

(a) a second layer of SiO₂ that is deposited using ion assist and with a thickness of about 5 to 100 nm to the first layer of SiO₂;

(b) a first layer of ZrO₂ with a thickness of about 40 to 50 nm deposited to the second layer of SiO₂;

(c) a third layer of SiO₂ that is deposited using ion assist and with a thickness of about 10 to 20 nm to the first layer of ZrO₂;

(d) a second layer of ZrO₂ with a thickness of about 50 to 70 nm deposited to the third layer of SiO₂;

(e) a fourth layer of SiO₂ that is deposited using ion assist and with a thickness of about 25 to 40 nm to the second layer of ZrO₂;

(f) a third layer of ZrO₂ with a thickness of about 10 to 25 nm deposited to the fourth layer of SiO₂; and

(g) a fifth layer of SiO₂ that is deposited using ion assist and with a thickness of about 5 to 15 nm to the third layer of ZrO₂.

7. The mold of claim 1, wherein the dipodal silane comprises bis(trimethoxysilylpropyl)amine, and the hydrophobic layer has a thickness of about 30 to 40 nm.

8. The mold of claim 1, wherein the layer of the silane coupling agent is a cyclic azasilane.

9. The mold of claim 8, wherein the layer of the silane coupling agent is formed of N-n-butyl-aza-2,2-dimethoxy-silacyclopentane.

10. The mold of claim 1, wherein the anti-reflective coating layered structure comprises:

(a) a first layer of a first material with a first index of refraction, which is deposited using ion assist and with a thickness of about 5 to 100 nm, deposited to the first layer of SiO₂;

(b) a second layer of a second material with a second index of refraction, with a thickness of about 40 to 50 nm, deposited to the first layer of the first material;

(c) a third layer of the first material with the first index of refraction, which is deposited using ion assist and with a thickness of about 10 to 20 nm, deposited to the second layer of the second material;

(d) a fourth layer of the second material with the second index of refraction, with a thickness of about 50 to 70 nm, deposited to the third layer;

(e) a fifth layer of the first material with the first index of refraction, which is deposited using ion assist and with a thickness of about 25 to 40 nm, deposited to the fourth layer;

(f) a sixth layer of the second material with the second index of refraction, with a thickness of about 10 to 25 nm, deposited to the fifth layer; and

(g) a seventh layer of the first material with the first index of refraction, which is deposited using ion assist and with a thickness of about 5 to 15 nm, deposited to the sixth layer.

11. The mold of claim 10, wherein the first index of refraction L and the second index of refraction H satisfy a ratio of H/L>

1.

12. The mold of claim 11, wherein the first material with the first index of refraction comprises SiO₂, and the second material with the second index of refraction comprises ZrO₂.

13. A mold with an optical surface having an anti-reflective coating that is transferable to an optical surface of a lens, comprising:

(a) a layer of a hydrophobic material deposited over an optical surface of the mold, wherein the hydrophobic material consists essentially of a super hydrophobic material and a dipodal silane;

(b) an anti-reflective coating layered structure deposited over the layer of the hydrophobic material;

(c) a layer of a coupling agent that is deposited with a monolayer thickness over the anti-reflective coating layered structure using vapor deposition or by dip coating using a solution consisting of a coupling agent in an aprotic solvent, and

(d) a scratch resistant hard coating, wherein the dipodal silane is different from the super hydrophobic material, and an amount of the dipodal silane is effective to prevent the anti-reflective coating layered structure from crazing.

14. The mold of claim 13, wherein the amount of the dipodal silane is about 1.7-8.3% of said super hydrophobic material by weight.

15. The mold of claim 13, wherein the anti-reflective coating layered structure comprises:

(a) a first layer of a first material with a first index of refraction and a thickness of about 5 to 100 nm deposited over the layer of the hydrophobic material;

(b) a second layer of a second material with a second index of refraction and a thickness of about 40 to 50 nm, deposited to the first layer;

(c) a third layer of the first material with the first index of refraction and a thickness of about 10 to 20 nm, deposited to the second layer;

(d) a fourth layer of the second material with the second index of refraction and a thickness of about 50 to 70 nm, deposited to the third layer;

(e) a fifth layer of the first material with the first index of refraction and a thickness of about 25 to 40 nm, deposited to the fourth layer;

(f) a sixth layer of the second material with the second index of refraction and a thickness of about 10 to 25 nm, deposited to the fifth layer; and

(g) a seventh layer of the first material with the first index of refraction and a thickness of about 5 to 15 nm, deposited to the sixth layer.

16. The mold of claim 15, wherein the first index of refraction L and the second index of refraction H satisfy a ratio of H/L>

1.

17. The mold of claim 16, wherein the first material with the first index of refraction is SiO₂, and the second material with the second index of refraction is ZrO₂.

18. The mold of claim 14, further comprising a deposition layer of a fluoride or oxide material formed between the layer of the hydrophobic material and the optical surface.

19. The mold of claim 18, wherein the deposition layer is formed of LiF, MgF₂, CaF₂, SrF₂, BaF₂, LaF₃, CeF₃, HfF₄, NdF₄, SiO₂, ZrO₂, Al₂O₃, Cr₂O₃, HfO₂, In₂O3, Ta₂O₅, TiO₂, Y₂O₃, or a combination of them.

20. The mold of claim 15, further comprising a layer of SiO₂ that is deposited without ion assist and with a thickness of 5 to 40 nm and over the layer of the hydrophobic material such that the layer of SiO₂ is formed between the layer of the hydrophobic material and the first layer of the first material.

21. The mold of claim 17, wherein each layer of SiO₂ is deposited using ion assist or without using ion assist.

22. The mold of claim 13, wherein the dipodal silane comprises bis(trimethoxysilylpropyl)amine, and the hydrophobic layer has a thickness of about 30 to 40 nm.

23. The mold of claim 13, wherein the layer of the coupling agent is a cyclic azasilane.

24. The mold of claim 23, wherein the layer of the coupling agent is formed of N-n-butyl-aza-2,2-dimethoxy-silacyclopentane.