Barrier layers for silver reflective coatings and HPC workflows for rapid screening of materials for such barrier layers

• US 9,206,078 B2
• Filed: 03/13/2013
• Issued: 12/08/2015
• Est. Priority Date: 03/13/2013
• Status: Active Grant

• Current Assignee: Guardian Glass LLC (KOCH Industries Incorporated)
• Original Assignee: Intermolecular Incorporated
• Inventors: Zhang, Guizhen, Cheng, Jeremy, Ding, Guowen, Le, Minh Huu, Schweigert, Daniel, Wang, Yu
• Primary Examiner(s): Sample, David
• Assistant Examiner(s): COLGAN, LAUREN ROBINSON
• Application Number:
  US13/801,635
• Publication Number:
  US 20140272454A1
• Time in Patent Office: 1,000 Days
• Field of Search: 428/426, 428/428, 428/432, 428/433, 428/434, 428/688, 428/689, 428/697, 428/699, 428/701, 428/702
• US Class Current: 1/1
• CPC Class Codes: C03C 17/36 at least one coating being a metal
• CPC Class Codes: C03C 17/3605 Coatings of the type glass/metal/inorganic compound
• CPC Class Codes: C03C 17/3618 Coatings of type glass/inorganic compound/other inorganic layers, at least one layer being metallic
• CPC Class Codes: C03C 17/3644 the metal being silver
• CPC Class Codes: C03C 17/3652 the coating stack containing at least one sacrificial layer to protect the metal from oxidation
• CPC Class Codes: C03C 17/366 Low-emissivity or solar control coatings
• CPC Class Codes: C03C 17/3681 the multilayer coating being used in glazing, e.g. windows or windscreens
• CPC Class Codes: C23C 14/0036 Reactive sputtering
• CPC Class Codes: C23C 14/042 using masks
• CPC Class Codes: C23C 14/14 Metallic material, boron or silicon
• CPC Class Codes: C23C 14/22 characterised by the process of coating
• CPC Class Codes: C23C 14/34 Sputtering
• CPC Class Codes: G02B 1/12 by surface treatment, e.g. by irradiation
• CPC Class Codes: G02B 1/14 Protective coatings, e.g. hard coatings
• CPC Class Codes: Y10T 428/12542 More than one such component
• CPC Class Codes: Y10T 428/12549 Adjacent to each other
• CPC Class Codes: Y10T 428/12611 Oxide-containing component
• CPC Class Codes: Y10T 428/12778 Alternative base metals from diverse categories
• CPC Class Codes: Y10T 428/31678 Of metal

Abstract

Provided is High Productivity Combinatorial (HPC) testing methodology of semiconductor substrates, each including multiple site isolated regions. The site isolated regions are used for testing different compositions and/or structures of barrier layers disposed over silver reflectors. The tested barrier layers may include all or at least two of nickel, chromium, titanium, and aluminum. In some embodiments, the barrier layers include oxygen. This combination allows using relative thin barrier layers (e.g., 5-30 Angstroms thick) that have high transparency yet provide sufficient protection to the silver reflector. The amount of nickel in a barrier layer may be 5-10% by weight, chromium—25-30%, titanium and aluminum—30%-35% each. The barrier layer may be co-sputtered in a reactive or inert-environment using one or more targets that include all four metals. An article may include multiple silver reflectors, each having its own barrier layer.

Claims

1. An article comprising:

a substrate;

a reflective layer formed above the substrate,

the reflective layer comprising silver; and

a barrier layer formed above the reflective layer,

the barrier layer comprising nickel, chromium, titanium, and aluminum, wherein a concentration of nickel in the barrier layer is between 5% by weight and 10% by weight, wherein a concentration of chromium in the barrier layer is between 25% by weight and 30% by weight, wherein a concentration of titanium in the barrier layer is between 30% by weight and 35% by weight, and wherein a concentration of aluminum in the barrier layer is between 30% by weight and 35% by weight,

the barrier layer being configured to protect metallic silver in the reflective layer from oxidation during processing and operation of the article.

2. The article of claim 1, wherein the barrier layer further comprises oxygen.

3. The article of claim 1, wherein a weight ratio of titanium to aluminum is between 0.5 and 2.

4. The article of claim 1, wherein a weight ratio of titanium to aluminum is about 1.

5. The article of claim 1, wherein nickel, chromium, titanium, and aluminum are uniformly distributed throughout the barrier layer.

6. The article of claim 1, wherein the barrier layer consists essentially of nickel, chromium, titanium, and aluminum.

7. The article of claim 1, wherein the barrier layer has a thickness of between 1 Angstroms and 100 Angstroms.

8. The article of claim 1, wherein the barrier layer has a thickness of between 5 Angstroms and 30 Angstroms.

9. The article of claim 1, wherein the barrier layer has a thickness of between 10 Angstroms and 20 Angstroms.

10. The article of claim 1, wherein the barrier layer is deposited using physical vapor deposition.

11. The article of claim 1, wherein the barrier layer is formed using co-sputtering of nickel, chromium, titanium, and aluminum.

12. The article of claim 1, further comprising a seed layer formed between the substrate and the reflective layer, the seed layer directly contacting the reflective layer and comprising one of ZnO, SnO₂, Sc₂O₃, Y₂O₃, TiO₂, ZrO₂, HfO₂, V₂O₅, Nb₂O₅, Ta₂O₅, CrO₃, WO₃, or MoO₃ in a crystalline phase.

13. The article of claim 12, further comprising a dielectric layer formed between the seed layer and the substrate or formed over the barrier layer, the dielectric layer comprising one of TiO₂, SnO₂, or ZnSn.

14. The article of claim 13, wherein the dielectric layer comprises a dopant, the dopant comprising one of Al, Ga, In, Mg, Ca, Sr, Sb, Bi, Ti, V, Y, Zr, Nb, Hf, or Ta.

15. The article of claim 1, further comprising:

an additional reflective layer formed above the barrier layer,

the additional reflective layer comprising silver; and

an additional barrier layer formed above the additional reflective layer,

the additional barrier layer comprising nickel, chromium, titanium, and aluminum.

16. An article comprising:

a substrate;

a bottom diffusion layer formed above the substrate, the bottom diffusion layer comprising silicon nitride;

a bottom dielectric layer formed above the bottom diffusion layer, the bottom dielectric layer comprising one of TiO₂, SnO₂, or ZnSn and having a thickness of between 100 Angstroms and 300 Angstroms;

a seed layer formed above the bottom dielectric layer, the seed layer comprising one of ZnO, SnO₂, Sc₂O₃, Y₂O₃, TiO₂, ZrO₂, HfO₂, V₂O₅, Nb₂O₅, Ta₂O₅, CrO₃, WO₃, or MoO₃ in a crystalline phase and having a thickness of between 50 Angstroms and 200 Angstroms;

a reflective layer formed above and directly contacting the seed layer, the reflective layer comprising silver and having a thickness of between 50 Angstroms and 200 Angstroms;

a barrier layer formed above and directly contacting the reflective layer, the barrier layer comprising nickel, chromium, titanium, and aluminum, wherein a concentration of nickel in the barrier layer is between 5% by weight and 10% by weight, wherein a concentration of chromium in the barrier layer is between 25% by weight and 30% by weight, wherein a concentration of titanium in the barrier layer is between 30% by weight and 35% by weight, and wherein a concentration of aluminum in the barrier layer is between 30% by weight and 35% by weight, the barrier layer being configured to protect metallic silver of the reflective layer from oxidation during processing and operation of the article;

a top dielectric layer formed above the barrier layer, the top dielectric layer comprising one of TiO₂, SnO₂, or ZnSn and having a thickness of between 100 Angstroms and 300 Angstroms; and

a top diffusion layer formed above the top dielectric layer, the top diffusion layer comprising silicon nitride.

17. A method of forming an article, the method comprising:

providing a substrate;

forming a reflective layer over the substrate,

wherein forming the reflective layer comprises sputtering silver in a non-reactive environment; and

forming a barrier layer over the reflective layer, wherein the barrier layer comprises nickel, chromium, titanium and aluminum, a concentration of nickel in the barrier layer is between 5% by weight and 10% by weight, wherein a concentration of chromium in the barrier layer is between 25% by weight and 30% by weight, wherein a concentration of titanium in the barrier layer is between 30% by weight and 35% by weight, and wherein a concentration of aluminum in the barrier layer is between 30% by weight and 35% by weight,

wherein forming the barrier layer comprises co-sputtering nickel, chromium, titanium, and aluminum in a non-reactive environment; and

forming a dielectric layer over the barrier layer,

wherein forming the dielectric layer comprises sputtering titanium or tin in an oxygen containing environment, and wherein the barrier layer prevents oxygen in the oxygen containing environment from reaching and reacting with silver in the reflective layer.