IP Library Granted Patent US 9,785,031
Granted Patent B2
US 9,785,031 · App. 14/671,061 · Granted Oct 10, 2017

Conductive transition metal oxide nanostructured electrochromic material and optical switching devices constructed thereof

Inventors: Tracy M. Mattox (Pleasanton, CA); Bonil Koo (Walnut Creek, CA); Guillermo Garcia (Oakland, CA); Delia J. Milliron (Oakland, CA); Luca De Trizio (Bergamo, IT); Clayton Dahlman (Berkeley, CA)
Assignees: HELIOTROPE TECHNOLOGIES, INC.; THE REGENTS OF THE UNIVERSITY OF CALIFORNIA
G02F1/1523G02F2202/06G02F2202/36G02F2203/10
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Quick Facts
Patent No.
US 9,785,031
App. No.
14/671,061
Granted
Oct 10, 2017
Kind
B2
Abstract

An electrochromic device includes a nanostructured transition metal oxide bronze layer that includes one or more transition metal oxide and one or more dopant, a solid state electrolyte, and a counter electrode. The nanostructured transition metal oxide bronze selectively modulates transmittance of near-infrared (NIR) spectrum and visible spectrum radiation as a function of an applied voltage to the device.

Claims (38)

1. An electrochromic device comprising:

at least one transparent conductor layer;

a nanostructured transition metal oxide bronze layer comprising:

one or more transition metal oxide;

a dopant species that causes a surface plasmon resonance effect on the one or more transition metal oxide by creating delocalized electron carriers that selectively modulate transmittance in response to a first applied voltage to the device; and

an intercalation species that causes a change in the oxidation state of transition metal ions in the transition metal oxide due to intercalation into and deintercalation from the metal oxide, which selectively modulates transmittance in response to a second applied voltage to the device, the second applied voltage having a larger absolute value than the first applied voltage;

a solid state electrolyte; and

a counter electrode;

wherein the nanostructured transition metal oxide bronze independently, selectively modulates transmittance of near-infrared (NIR) spectrum radiation and visible spectrum radiation as a function of the first and the second applied voltage to the device.

2. The electrochromic device of claim 1 , wherein the dopant species that cause the surface plasmon resonance effect on the one or more transition metal oxide by creating delocalized electron carriers selectively modulate the transmittance of the NIR spectrum radiation in response to the first applied voltage to the device.

3. The electrochromic device of claim 2 , wherein the intercalation species causes the change in the oxidation state of transition metal ions in the transition metal oxide due to intercalation into and deintercalation from the metal oxide which selectively modulates the transmittance of the visible spectrum radiation in response to the second applied voltage to the device.

4. The electrochromic device of claim 1 , wherein the dopant species that causes the surface plasmon resonance effect comprises at least one of cesium, cerium, lanthanum, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, and rubidium ions.

5. The electrochromic device of claim 1 , wherein:

the intercalation species migrates between the solid state electrolyte and the nanostructured transition metal oxide bronze layer; and

the intercalation species comprises at least one of:

lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, or barium ions;

cerium, lanthanum, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, or lutetium ions; and

a charged proton species.

6. The electrochromic device of claim 1 , wherein:

the nanostructured transition metal oxide bronze layer comprises a plurality of nanoparticles; and

the solid state electrolyte is a material comprising at least a polymer, a lithium salt, and a plasticizer, wherein the solid state electrolyte material permeates into crevices between the nanoparticles of the nanostructured transition metal oxide bronze layer.

7. The electrochromic device of claim 6 , wherein the solid state electrolyte material comprises 40-60 wt % of the plasticizer, wherein the polymer comprises polyvinylbutyral (PVB), and wherein the lithium salt comprises lithium bis(trifluoromethane).

8. The electrochromic device of claim 1 , wherein the solid state electrolyte comprises lithium phosphorus oxynitride (UPON) or Ta 2 O 5 .

9. The electrochromic device of claim 1 , wherein the one or more transition metal oxide comprises at least one of niobium, tungsten, molybdenum, vanadium, and titanium oxide.

10. The electrochromic device of claim 9 , wherein the counter electrode comprises a passive electrode material selected from CeO 2 , CeVO 2 , TiO 2 , indium tin oxide, indium oxide, tin oxide, manganese or antimony doped tin oxide, aluminum doped zinc oxide, zinc oxide, gallium zinc oxide, indium gallium zinc oxide, molybdenum doped indium oxide, Fe 2 O 3 , and V 2 O 5 , or a complementary electrode material selected from Cr 2 O3, MnO 2 , FeO 2 , CoO 2 , NiO 2 , RhO 2 , and IrO 2 .

11. The electrochromic device of claim 9 , wherein the intercalation species is selected from a group comprising at least one of:

lithium, sodium, potassium, rubidium, cesium, calcium, beryllium, magnesium, calcium, strontium, or barium ions;

cerium, lanthanum, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, or lutetium, ions; and

a charged proton species.

12. The electrochromic device of claim 11 , wherein at least one of the one or more transition metal oxide comprises tungsten oxide (WO 3-x ), where 0≦x≦0.1, and wherein at least one of the one or more dopant species comprises cesium ions.

13. The electrochromic device of claim 11 , wherein the nanostructured transition metal oxide bronze layer comprises Nb:TiO 2 .

14. The electrochromic device of claim 1 , wherein the nanostructured transition metal oxide bronze layer comprises nanoparticles having a plurality of facets.

15. The electrochromic device of claim 14 , wherein the nanoparticles comprise isohedrons having at least 20 facets.

16. The electrochromic device of claim 1 , wherein the first and the second applied voltage is between −5V and 5V.

17. The electrochromic device of claim 16 , wherein the first and the second applied voltage is between −2V and 2V.

18. The electrochromic device of claim 16 , wherein the first applied voltage comprises a negative bias, and wherein the nanostructured transition metal oxide bronze layer absorbs NIR spectrum radiation and is transparent to visible spectrum radiation.

19. The electrochromic device of claim 18 , wherein increasing the applied negative bias voltage causes the nanostructured transition metal oxide bronze layer to absorb visible spectrum radiation and NIR spectrum radiation.

20. The electrochromic device of claim 16 , wherein the second applied voltage comprises a positive bias, and wherein the nanostructured transition metal oxide bronze layer is transparent to NIR spectrum radiation and visible spectrum radiation.

Assignments (6)
CHANGE OF NAME Recorded Apr 25, 2023
From: HELIOTROPE EUROPE S.L.
To: HIVISQ TECHNOLOGIES, SOCIEDAD LIMITADA
Reel/Frame 063441/0258 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Aug 5, 2022
From: HELIOTROPE TECHNOLOGIES, INC.,
To: HELIOTROPE EUROPE S.L.
Reel/Frame 061087/0606 →
CONFIRMATORY LICENSE Recorded Oct 22, 2021
From: UNIVERSITY OF CALIF-LAWRENC BERKELEY LAB
To: UNITED STATES DEPARTMENT OF ENERGY
Reel/Frame 057878/0516 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Aug 31, 2016
From: KOO, BONIL; GARCIA, GUILLERMO
To: HELIOTROPE TECHNOLOGIES, INC.
Reel/Frame 039607/0355 →
CONFIRMATORY LICENSE Recorded Jun 29, 2015
From: REGENTS OF THE UNIVERSITY OF CALIFORNIA, THE
To: ENERGY, UNITED STATES DEPARTMENT OF
Reel/Frame 036035/0824 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jun 10, 2015
From: MATTOX, TRACY M.; MILLIRON, DELIA J.; DE TRIZIO, LUCA; DAHLMAN, CLAYTON
To: THE REGENTS OF THE UNIVERSITY OF CALIFORNIA
Reel/Frame 035886/0236 →
Continuity (2)
Provisional Application 61973331 · Apr 1, 2014
Related Publication 20150277202A1 · Oct 1, 2015