COUNTER ELECTRODE FOR ELECTROCHROMIC DEVICES

• US 20170003564A1
• Filed: 07/07/2016
• Published: 01/05/2017
• Est. Priority Date: 03/31/2009
• Status: Active Grant

• Current Assignee: View Incorporated
• Original Assignee: View Incorporated
• Inventors: Gillaspie, Dane, Kailasam, Sridhar K., Rozbicki, Robert T.
• Granted Patent: US 10,591,795 B2
• Time in Patent Office: Days
• US Class Current: 1/1
• CPC Class Codes: B23K 20/10 making use of vibrations, e.g. ultrasonic welding
• CPC Class Codes: C03C 17/3417 all coatings being oxide coatings
• CPC Class Codes: C03C 2217/94 Transparent conductive oxide layers [TCO] being part of a multilayer coating
• CPC Class Codes: C23C 10/28 using solids, e.g. powders, pastes
• CPC Class Codes: C23C 14/083 of refractory metals or yttrium
• CPC Class Codes: C23C 14/085 of iron group metals
• CPC Class Codes: C23C 14/185 by cathodic sputtering
• CPC Class Codes: C23C 14/3407 Cathode assembly for sputtering apparatus, e.g. Target
• CPC Class Codes: C23C 14/568 Transferring the substrates through a series of coating stations C23C14/562 takes precedence
• CPC Class Codes: C23C 14/5806 Thermal treatment
• CPC Class Codes: C23C 14/5853 Oxidation
• CPC Class Codes: G02F 1/1524 Transition metal compounds

Abstract

The embodiments herein relate to electrochromic stacks, electrochromic devices, and methods and apparatus for making such stacks and devices. In various embodiments, an anodically coloring layer in an electrochromic stack or device is fabricated to include a heterogeneous structure, for example a heterogeneous composition and/or morphology. Such heterogeneous anodically coloring layers can be used to better tune the properties of a device.

Claims

1. An electrochromic device comprising:

a substrate;

an electrochromic layer disposed on or over the substrate, said electrochromic layer comprising a cathodically tinting electrochromic material; and

a counter electrode layer also disposed on or over the substrate, said counter electrode layer comprising (a) a first sublayer comprising a first anodically tinting material, and (b) a second sublayer comprising a second anodically tinting material, wherein the first and second anodically tinting materials have different compositions but each comprise an oxide of at least one transition metal, and wherein the first sublayer is disposed between the electrochromic layer and the second sublayer.

2. The electrochromic device of claim 1, wherein each of the first and second anodically tinting materials comprises the at least one transition metal and another non-alkali metal.

3. The electrochromic device of claim 2, wherein the first and second anodically tinting materials each comprise nickel and tungsten.

4. The electrochromic device of claim 3, wherein the second anodically tinting material further comprises tantalum.

5. The electrochromic device of claim 3, wherein the second anodically tinting material further comprises niobium.

6. The electrochromic device of claim 3, wherein the second anodically tinting material further comprises tin.

7. The electrochromic device of claim 2, wherein the second anodically tinting material comprises the at least one transition metal, the other non-alkali metal, and a second non-alkali metal, and wherein the first anodically tinting material contains the at least one transition metal and the other non-alkali metal as its only metals.

8. The electrochromic device of claim 2, wherein the first and second anodically tinting materials each comprise the at least one transition metal, the other non-alkali metal, and a second non-alkali metal, and wherein the second anodically tinting material has a higher atomic concentration of the second non-alkali metal in comparison to the first anodically tinting material.

9. The electrochromic device of claim 2, wherein one of the at least one transition metal is selected from the group consisting of tungsten (W), tantalum (Ta), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), rhodium (Rh), ruthenium (Ru), vanadium (V), iridium (Ir), and combinations thereof.

10. The electrochromic device of claim 9, wherein the other non-alkali metal is selected from the group consisting of silver (Ag), aluminum (Al), arsenic (As), gold (Ag), boron (B), barium (Ba), beryllium (Be), bismuth (Bi), calcium (Ca), cadmium (Cd), cerium (Ce), cobalt (Co), chromium (Cr), copper (Cu), europium (Eu), iron (Fe), gallium (Ga), gadolinium (Gd), germanium (Ge), hafnium (Hf), mercury (Hg), indium (In), iridium (Ir), lanthanum (La), magnesium (Mg), manganese (Mn), molybdenum (Mo), niobium (Nb), neodymium (Nd), osmium (Os), protactinium (Pa), lead (Pb), palladium (Pd), praseodymium (Pr), promethium (Pm), polonium (Po), platinum (Pt), radium (Ra), rhenium (Re), rhodium (Rh), ruthenium (Ru), antimony (Sb), scandium (Sc), selenium (Se), silicon (Si), samarium (Sm), tin (Sn), strontium (Sr), tantalum (Ta), terbium (Tb), technetium (Tc), tellurium (Te), thorium (Th), titanium (Ti), thallium (Tl), uranium (U), vanadium (V), tungsten (W), yttrium (Y), zinc (Zn), zirconium (Zr), and combinations thereof.

11. The electrochromic device of claim 10, wherein the other non-alkali metal is selected from the group consisting of silver (Ag), arsenic (As), gold (Au), boron (B), cadmium (Cd), copper (Cu), europium (Eu), gallium (Ga), gadolinium (Gd), germanium (Ge), mercury (Hg), osmium (Os), lead (Pb), palladium (Pd), promethium (Pm), polonium (Po), platinum (Pt), radium (Ra), terbium (Tb), technetium (Tc), thorium (Th), thallium (Tl), and combinations thereof.

12. The electrochromic device of claim 10, wherein the other non-alkali metal is selected from the group consisting of tantalum (Ta), tin (Sn), and niobium (Nb).

13. The electrochromic device of claim 12, wherein the other non-alkali metal is tantalum (Ta).

14. The electrochromic device of claim 12, wherein the other non-alkali metal is tin (Sn).

15. The electrochromic device of claim 12, wherein the other non-alkali metal is niobium (Nb).

16. The electrochromic device of claim 1, wherein the first and second anodically tinting materials each comprise a first transition metal, a second transition metal, and oxygen, and wherein the ratio of the first transition metal to the second transition metal is different in the first and second anodically tinting materials.

17. The electrochromic device of claim 1, wherein the counter electrode layer further comprises a third sublayer comprising a third anodically tinting electrochromic material, wherein the first, second, and third anodically tinting materials have different compositions but each comprise the at least one transition metal, and wherein the second sublayer is disposed between the first sublayer and the third sublayer.

18. The electrochromic device of claim 17, wherein the first anodically tinting material comprises the at least one transition metal, a second transition metal, but no other transition metals, and oxygen;

the second anodically tinting material comprises the at least one transition metal, the second transition metal, a third transition metal, and oxygen; and

the third anodically tinting material comprises the at least one transition metal, the second metal, the third transition metal, and oxygen, and wherein the second and third anodically tinting materials have different concentrations of the third transition metal.

19. The electrochromic device of claim 1, wherein the first and second sublayers of the counter electrode layer are in physical contact with one another.

20. The electrochromic device of claim 1, wherein the first and second sublayers of the counter electrode layer are separated from one another by a defect-mitigating-insulating layer, the defect-mitigating-insulating layer having an electronic resistivity of between about 1 and 5×

10¹⁰ Ohm-cm.

21. The electrochromic device of claim 1, wherein the first anodically coloring material has a first affinity for lithium and the second anodically coloring material has a second affinity for lithium, wherein the first affinity for lithium and the second affinity for lithium are different.

22. The electrochromic device of claim 1, wherein a transmitted b* value of the electrochromic device is about 14 or lower when the electrochromic device is in its clearest state.

23. The electrochromic device of claim 1, wherein a transmitted b* value of the electrochromic device is about 10 or lower when the electrochromic device is in its clearest state.

24. The electrochromic device of claim 1, wherein the visible transmittance of the electrochromic device is at least about 55% when the electrochromic device is in its clearest state.

25. The electrochromic device of claim 1, wherein the counter electrode layer has an overall thickness between about 50 nm and about 650 nm.

26. The electrochromic device of claim 1, wherein the counter electrode layer has an overall thickness between about 100 nm and about 400 nm.

27. The electrochromic device of claim 1, wherein the counter electrode layer has an overall thickness between about 150 nm and about 300 nm.

28. The electrochromic device of claim 1, wherein the first and second sublayers of the counter electrode layer each have a morphology that is a mixture of amorphous and nanocrystalline phases with nanocrystallites having a diameter of less than about 50 nm.

29. The electrochromic device of claim 1, wherein the second sublayer is a defect-mitigating insulating layer having an electronic resistivity between about 1 and 5×

10¹⁰ Ohm-cm.

30. The electrochromic device of claim 1, further comprising a transparent conductive layer disposed on or over the electrochromic layer and the counter electrode layer.

31. The electrochromic device of claim 30, wherein the transparent conductive layer comprises a doped indium oxide.

32. The electrochromic device of claim 1, wherein at least one of the first and second anodically tinting materials comprises nickel, aluminum, and oxygen.

33. The electrochromic device of claim 32, wherein the first anodically tinting material comprises nickel, tungsten, and oxygen, and wherein the second anodically tinting material comprises nickel, aluminum, and oxygen.

34. The electrochromic device of claim 1, wherein at least one of the first and second anodically tinting materials comprises nickel, silicon, and oxygen.

35. The electrochromic device of claim 34, wherein the first anodically tinting material comprises nickel, tungsten, and oxygen, and wherein the second anodically tinting material comprises nickel, silicon, and oxygen.

36-89. -89. (canceled)

90. A method of fabricating an electrochromic device, the method comprising:

depositing an electrochromic layer comprising a cathodically coloring electrochromic material;

depositing a counter electrode layer by;

depositing a first anodically tinting sublayer,

lithiating the first anodically tinting sublayer, and

after lithiating the first anodically tinting sublayer, depositing a second anodically tinting sublayer, wherein the first anodically tinting sublayer is positioned between the electrochromic layer and the second anodically tinting sublayer, and wherein the first and second anodically tinting sublayers have different compositions and each comprise an oxide of at least one transition metal.

95. The method of claim 90, wherein depositing the counter electrode layer further comprises depositing a third anodically tinting sublayer comprising an oxide of at least one transition metal, wherein the second anodically tinting sublayer is positioned between the first and third anodically tinting sublayers, wherein the first anodically tinting sublayer substantially consists of nickel tungsten oxide, wherein the second and third anodically tinting sublayers substantially consist of nickel tungsten tantalum oxide, and wherein a concentration of tantalum is higher in the third anodically tinting sublayer than in the second anodically tinting sublayer.

96. The method of claim 90, wherein the first anodically tinting sublayer is deposited at a higher rate of deposition than the second anodically tinting sublayer.

97. The method of claim 90, wherein the first anodically tinting sublayer is deposited at a lower sputter power than is used to deposit the second anodically tinting sublayer.

98. The method of claim 97, wherein the first anodically tinting sublayer is deposited at a sputter power between about 5-20 kW/m², and wherein the second sublayer is deposited at a sputter power between about 20-45 kW/m².

99. The method of claim 90, wherein a temperature of the partially fabricated electrochromic device is lower during deposition of the first anodically tinting sublayer than during deposition of the second anodically tinting sublayer.

100. The method of claim 90, further comprising:

depositing lithium on the second anodically tinting sublayer, and then

depositing a third anodically tinting sublayer on the second anodically tinting sublayer.

101. The method of claim 90, further comprising:

depositing a third anodically tinting sublayer on the second anodically tinting sublayer, and then

depositing lithium on the third anodically tinting sublayer.

91-94. -94. (canceled)