IP Library Granted Patent US 12,384,715
Granted Patent B2
US 12,384,715 · App. 16/632,636 · Granted Aug 12, 2025

Photodeposition of metal oxides for electrochromic devices

Inventors: Curtis Berlinguette (Vancouver, CA); Wei Cheng (Vancouver, CA)
Assignee: Miru Smart Technologies Corp.
C03C17/25B05D3/065B05D5/12C03C17/256C23C14/088C23C14/5853C23C16/40G02F1/1524G02F1/1525C03C2217/212C03C2217/217C03C2217/218C03C2217/219C03C2218/116C03C2218/32
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Quick Facts
Patent No.
US 12,384,715
App. No.
16/632,636
Granted
Aug 12, 2025
Kind
B2
Abstract

The present invention provides scalable, solution based processes for manufacturing electrochromic materials comprising metal oxide films for use in electrochromic devices. The electrochromic material comprises a transparent conductive substrate coated with an electrochromic metal oxide film, wherein the metal oxide film is formed by a process comprising the steps of: a) providing the conductive substrate; b) coating the substrate with a solution of one or more metal precursors; and c) exposing the coated substrate to near-infrared radiation, UV radiation and/or ozone in an aerobic atmosphere. The present invention also provides electrochromic devices incorporating these electrochromic materials.

Claims (27)

1. A process for forming an electrochromic material suitable for use in an electrochromic device, the process comprising:

providing a transparent conductive substrate;

coating the transparent conductive substrate with a solution of one or more metal precursors, wherein a metal precursor comprises a ligand selected from chloride, bromide and nitrate and is converted to a metal oxide upon exposure to UV radiation and/or ozone; and

exposing the coated transparent conductive substrate to UV radiation and/or ozone in an aerobic atmosphere at ambient temperature and ambient pressure to effect conversion of the one or more metal precursors to a metal oxide film on the transparent conductive substrate without application of a heat treatment with an external heat source, thereby forming the electrochromic material,

wherein the electrochromic device comprises:

a first electrode comprising the electrochromic material,

a counter electrode, and

an ion-conductor layer for conducting ions between the first electrode and the counter electrode.

2. The process according to claim 1 , further comprising annealing the metal oxide film, wherein annealing is carried out at a temperature of about 50° C. to about 750° C.

3. The process according to claim 1 , further comprising annealing the metal oxide film, wherein the annealing is carried out at about 100° C., 200° C. or 600° C. for 1 hour.

4. The process according to claim 1 , wherein the metal oxide film comprises a metal oxide selected from the group consisting of NiO x , WO x , NbO x , MoO x , MnO x , CoO x , VO x , TaO x , TiO x , FeO x , IrO x , and combinations thereof, a mixed metal oxide selected from LiNiO x , TiWO x , and FeNiO x , or a doped metal oxide selected from Nb doped WO 3 and Ti doped WO 3 .

5. The process according to claim 4 , wherein the metal oxide film comprises WO3.

6. The process according to claim 1 , wherein the transparent conductive substrate is formed of a conductive material.

7. The process according to claim 1 , wherein the transparent conductive substrate is formed of a transparent material coated with a conductive film.

8. The process according to claim 7 , wherein the transparent conductive substrate is a substrate coated with fluorine tin oxide (FTO), indium tin oxide (ITO), or aluminum zinc oxide (AZO).

9. The process according to claim 1 , wherein coating and exposing are repeated until a desired thickness of the metal oxide film is achieved.

10. The process according to claim 1 , wherein the metal oxide film is an amorphous metal oxide film.

11. The process according to claim 1 , wherein the metal oxide film is a crystalline metal oxide film.

12. The process according to claim 1 , wherein the first electrode comprises FTO glass coated with an amorphous WO 3 film.

13. The process according to claim 1 , wherein the counter electrode comprises bare FTO glass.

14. The process according to claim 1 , wherein the metal oxide film is a first metal oxide film and the counter electrode comprises FTO glass coated with a second metal oxide film prepared using the process as defined in claim 1 .

15. The process according to claim 14 , wherein the counter electrode comprises FTO glass coated with NiO x or TiO x .

16. The process according to claim 1 , wherein the ion-conductor layer is an electrolytic solution.

17. The process according to claim 16 , wherein the electrolytic solution is a LiClO 4 -propylene carbonate electrolyte solution.

18. The process according to claim 1 , wherein the electrochromic device is a solid-state device and the ion-conductor layer is an electrolytic gel.

19. The process according to claim 18 , wherein the ion-conductor layer is LiClO 4 -propylene carbonate-poly (methyl methacrylate) gel electrolyte.

20. The process according to claim 7 , wherein the transparent conductive substrate is indium tin oxide (ITO) coated polyethylene terephthalate (PET).

Assignments (2)
CHANGE OF NAME Recorded May 3, 2024
From: CLICK MATERIALS CORP.
To: MIRU SMART TECHNOLOGIES CORP.
Reel/Frame 067303/0830 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Feb 10, 2020
From: BERLINGUETTE, CURTIS; CHENG, WEI
To: CLICK MATERIALS CORP.
Reel/Frame 051766/0333 →
Continuity (2)
Provisional Application 62534785 · Jul 20, 2017
Related Publication 20200165161A1 · May 28, 2020
References Cited (112)
US 3669724A · Warren · 1972 [cited by applicant]
US 4996083A · Moser · 1991 [cited by examiner]
US 5034246A · Mance et al. · 1991 [cited by applicant]
US 5384157A · Tambo · 1995 [cited by applicant]
US 5384653A · Benson · 1995 [cited by examiner]
US 5470673A · Tseung et al. · 1995 [cited by applicant]
US 5661092A · Koberstein · 1997 [cited by examiner]
US 5772978A · Bailey et al. · 1998 [cited by applicant]
US 5825526A · Bommarito · 1998 [cited by examiner]
US 5834157A · Scheler · 1998 [cited by applicant]
US 5871853A · Azuma · 1999 [cited by examiner]
US 6074471A · Foot · 2000 [cited by examiner]
US 6582972B1 · Joshi · 2003 [cited by examiner]
US 6859297B2 · Lee et al. · 2005 [cited by applicant]
US 7564611B2 · Jang et al. · 2009 [cited by applicant]
US 8432603B2 · Wang et al. · 2013 [cited by applicant]
US 8687261B2 · Gillaspie et al. · 2014 [cited by applicant]
US 8894827B2 · Jiang et al. · 2014 [cited by applicant]
US 9905414B2 · Gordon · 2018 [cited by examiner]
US 10804098B2 · Raisanen · 2020 [cited by examiner]
US 20020047148A1 · Won · 2002 [cited by examiner]
US 20040266211A1 · Tao · 2004 [cited by examiner]
US 20100071810A1 · Nadaud · 2010 [cited by examiner]
US 20100245973A1 · Wang · 2010 [cited by examiner]
US 20110260124A1 · Gillaspie · 2011 [cited by examiner]
US 20120090679A1 · Chittibabu · 2012 [cited by examiner]
US 20120212794A1 · Giron et al. · 2012 [cited by applicant]
US 20130101867A1 · Yukinobu et al. · 2013 [cited by applicant]
US 20130286459A1 · Burdis et al. · 2013 [cited by applicant]
US 20140043666A1 · Weir · 2014 [cited by examiner]
US 20140220362A1 · Milliron et al. · 2014 [cited by applicant]
US 20150225845A1 · Park · 2015 [cited by examiner]
US 20160005879A1 · Takata · 2016 [cited by examiner]
US 20170075182A1 · Nguyen · 2017 [cited by examiner]
US 20170239931A1 · Wolk · 2017 [cited by examiner]
US 20170316847A1 · Hitosugi · 2017 [cited by applicant]
US 20190023981A1 · Van Der Boom · 2019 [cited by examiner]
CA 2991892 · 2017 [cited by applicant]
CN 1560185 · 2006 [cited by applicant]
CN 103814107 · 2014 [cited by applicant]
EP 0493043A2 · 1992 [cited by applicant]
JP S58110444A · 1987 [cited by applicant]
JP H04300212A · 1992 [cited by applicant]
JP H05306144A · 1993 [cited by applicant]
JP 5306144 · 2013 [cited by applicant]
JP 2016509689 · 2016 [cited by applicant]
KR 1020110057257 · 2011 [cited by applicant]
KR 1020120085242 · 2012 [cited by applicant]
KR 20170040615 · 2017 [cited by applicant]
KR 1020170063749 · 2017 [cited by applicant]
WO 2010047177 · 2010 [cited by applicant]
WO 2011155635 · 2011 [cited by applicant]
WO 2013013135 · 2013 [cited by applicant]
WO 2013141375A1 · 2013 [cited by applicant]
WO 2014025876A2 · 2014 [cited by applicant]
WO 2014113796 · 2014 [cited by applicant]
WO 2016101067A1 · 2016 [cited by applicant]
WO WO2016088882A1 · 2016 [cited by examiner]
Azens et al., “Ozone coloration of Ni and Cr oxide films,” Solar Energy Materials & Solar Cells, 2003, pp. 147-153, vol. 76. [cited by applicant]
Azens et al., “Sputter-deposited nickel oxide for electrochromic applications,” Solid State lonics, 1998, pp. 449-456, vol. 113-115. [cited by applicant]
Brezesinski et al., “Highly Crystalline WO3, Thin Films with Ordered 3D Mesoporosity and Improved Electrochromic Performance,” Small, 2006, pp. 1203-1211, vol. 2, No. 10. [cited by applicant]
Cai et al., “Inkjet-printed all solid-state electrochromic devices based on NiO/WO3 nanoparticle complementary electrodes,” Nanoscale, 2016, pp. 348-357, vol. 8. [cited by applicant]
Cheng et al., “Synthesis and electrochromic properties of mesoporous tungsten oxide,” J. Mater. Chem., 2001, pp. 92-97, vol. 11. [cited by applicant]
Chiang et al., “Fuel-Assisted Solution Route to Nanostructured Nickel Oxide Films for Electrochromic Device Application,” ACS Appl. Mater. Interfaces, 2013, pp. 6502-6507, vol. 5. [cited by applicant]
Dalavi et al., “Electrochromic performance of sol-gel deposited NiO thin film,” Materials Letters, 2013, pp. 60-63, vol. 90. [cited by applicant]
Decker et al., “The Electrochromic Process in Non-Stoichiometric Nickel Oxide Thin Film Electrodes,” Electrochimica Acta, 1992, pp. 1033-1038, vol. 37, No. 6. [cited by applicant]
Estrada et al., “Electrochromic nickel-oxide-based coatings made by reactive dc magnetron sputtering: Preparation and optical properties,” J. Appl. Phys., Oct. 1, 1988, pp. 3678-3683. [cited by applicant]
Gillaspie et al., “Metal oxide films for electrochromic applications: present technology and future directions,” J. Mater. Chem, 2010, pp. 9585-9592, vol. 20. [cited by applicant]
Hsu et al., “Electrochromic properties of nanocrystalline MoO3 thin films,” Thin Solid Films, 2008, pp. 4839-4844, vol. 516. [cited by applicant]
Korošec et al., “The role of thermal analysis in optimization of the electrochromic effect of nickel oxide thin films, prepared by the sol-gel method: Part II,” Thermochimica Acta, 2004, pp. 65-71, vol. 410. [cited by applicant]
Liang et al., “High-performance flexible electrochromic device based on facile semiconductor-to-metal transition realized by WO3 2H2O ultrathin nanosheets,” Scientific Reports, 2013, 8 pages, vol. 3, Article No. 1936. [cited by applicant]
Liao et al., “WO3-x nanowires based electrochromic devices,” Solar Energy Materials & Solar Cells, 2006, pp. 1147-1155, vol. 90. [cited by applicant]
Liu et al., “Ultrthin W18O49 Nanowire Assemblies for Electrochromic Devices,” Nano Lett., 2013, pp. 3589-3593, vol. 13. [cited by applicant]
Liu et al., “Electrolytes-relevant cyclic durability of nickel oxide thin films as an ion-storage layer in an all-solid-state complementary electrochromic device,” Solar Energy Materials & Solar Cells, 2016, pp. 844-852… [cited by applicant]
Livage et al., “Sol-gel electrochromic coatings and devices: A review,” Solar Energy Materials & Solar Cells, 2001, pp. 365-381, vol. 68. [cited by applicant]
Llordés et al., “Linear topology in amorphous metal oxide electrochromic networks obtained via low-temperature solution processing,” Nature Materials, Dec. 2016, pp. 1267-1273, vol. 15. [cited by applicant]
Mahmoud et al., “Electrochromic characterisation of electrochemically deposited nickel oxide films,” Physica B, 2000, pp. 125-131, vol. 293. [cited by applicant]
Maruyama et al., “Electrochromic Properties of Molybdenum Trioxide Thin Films Prepared by Chemical Vapor Deposition,” J. Electrochem. Soc., May 1995, pp. 1644-1647, vol. 142, No. 5. [cited by applicant]
Mortimer, Roger J., “Electrochromic Materials,” Annu. Rev. Mater. Res., 2011, pp. 241-268, vol. 41. [cited by applicant]
Nakaoka et al., “Semiconductor and electrochromic properties of electrochemically deposited nickel oxide films,” Journal of Electroanalytical Chemistry, 2004, pp., 93-99, vol. 571. [cited by applicant]
Niklasson et al., “Electrochromics for smart windows: thin films of tungsten oxide and nickel oxide, and devices based on these,” J. Mater. Chem., 2007, pp. 127-156, vol. 17. [cited by applicant]
Passerini et al., “An Electrochromic Window Based on LixWO3/(PEO)8LiClO4/NiO,” J. Electrochem. Soc., Nov. 1989, pp. 3394-3395, vol. 136, No. 11. [cited by applicant]
Passerini et al., “The Intercalation of Lithium in Nickel Oxide and Its Electrochromic Properties,” J. Electrochem. Soc., Oct. 1990, pp. 3297-3300, vol. 137, No. 10. [cited by applicant]
Runnerstrom et al., “Nanostructured electrochromic smart windows: traditional materials and NIR-selective plasmonic nanocrystals,” Chem. Commun., 2014, pp. 10555-10572, vol. 50. [cited by applicant]
Salvatore et al., “Near-infrared-driven decomposition of metal precursors yields amorphous electrocatalytic films,” Sci. Adv., Mar. 2015, 6 pages. [cited by applicant]
Scherer et al., “Enhanced Electrochromism in Gyroid-Structured Vanadium Pentoxide,” Adv. Mater., 2012, pp. 1217-1221, vol. 24. [cited by applicant]
Smith et al., “Photochemical Route for Accessing Amorphous Metal Oxide Materials for Water Oxidation Catalysis,” Science, Apr. 5, 2013, pp. 60-63, vol. 340. [cited by applicant]
Srivastava et al., “Microstructural and electrochromic characteristics of electrodeposited and annealed WO3 films,” Solid State Ionics, 2005, pp. 1161-1168, vol. 176. [cited by applicant]
Svensson et al., “Electrochromic hydrated nickel oxide coatings for energy efficient windows: Optical properties and coloration mechanism,” Appl. Phys. Lett., Dec. 8, 1986, pp. 1566-1568, vol. 49, No. 23. [cited by applicant]
Tong et al., “Novel morphology changes from 3D ordered macroporous structure to V2O5 nanofiber grassland and its application in electrochromism,” Scientific Reports, 2015, 11 pages. [cited by applicant]
Wen et al., “Anodic Electrochromism for Energy-Efficient Windows: Cation/Anion-Based Surface Processes and Effects of Crystal Facets in Nickel Oxide Thin Films,” Adv. Funct. Mater., 2015, pp. 3359-3370, vol. 25. [cited by applicant]
Wen et al., “Electrochromic nickel oxide films and their compatibility with potassium hydroxide and lithium perchlorate in propylene carbonate: Optical, electrochemical and stress-related properties,” Thin Solid Films, … [cited by applicant]
Wen et al., “Electrochromic performance of Ni oxide thin films intercalated with Li+ ions,” INERA Workshop of SCMP2014, Journal of Physics: Conference Series, 2014, 6 pages, vol. 559. [cited by applicant]
Wu et al., “Resistive Switching Behavior and Multiple Transmittance States in Solution-Processed Tungsten Oxide,” ACS Appl. Mater. Interfaces, 2011, pp. 2616-2621, vol. 3. [cited by applicant]
Zhang et al., “An all-solid-state electrochromic device based on NiOWO3 complementary structure and solid hybrid polyelectrolyte,” Solar Energy Materials & Solar Cells, 2009, pp. 1840-1845, vol. 93. [cited by applicant]
Zhang et al., “Hydrothermally synthesized WO3 nanowire arrays with highly improved electrochromic performance,” J. Mater. Chem., 2011, pp. 5492-5498, vol. 21. [cited by applicant]
Gesheva et al., “Optical Coatings of CVD-Transition Metal Oxides as Functional Layers in “Smart Windows” and X-ray Mirrors,” Journal of Optoelectronics and Advanced Materials, 2005, pp. 1243-1252, vol. 7, No. 3. [cited by applicant]
Jeon et al., “Amorphous Tungstate Precursor Route to Nanonstructure Tungsten Oxide Film with Electrochromic Property,” Nanotechnology, 2011, pp. 6518-6522, vol. 11, No. 7 (Abstract Only). [cited by applicant]
European Patent Office, Extended European Search Report mailed on May 25, 2021, issued in connection with European Patent Application No. 18834936.9, 6 pages. [cited by applicant]
Japanese Patent Office, Office Action issued on Aug. 30, 2022 in connection with Japanese Patent Application No. JP2020-524658, 7 pages. [cited by applicant]
Japanese Office Action dated Apr. 25, 2023 issued in Japanese Patent Application No. 2020-524658. [cited by applicant]
Canadian Intellectual Property Office, Exam Report issued on Apr. 2, 2024 in connection with Canadian Patent application No. 3,070,511, 3 pages. [cited by applicant]
China National Intellectual Property Administration, Exam Report issued on Mar. 1, 2023 in connection with Chinese Patent application No. 201880048500.9 and English translation, 15 pages. [cited by applicant]
China National Intellectual Property Administration, Exam Report issued on Mar. 20, 2024 in connection with Chinese Patent application No. 201880048500.9 and English translation, 13 pages. [cited by applicant]
China National Intellectual Property Administration, Exam Report issued on Oct. 19, 2023 in connection with Chinese Patent application No. 201880048500.9 and English translation, 11 pages. [cited by applicant]
Japanese Patent Office, Office Action issued on Apr. 25, 2023 in connection with Japanese Patent application No. 2020-524658 and English translation, 11 pages. [cited by applicant]
Japanese Patent Office, Office Action issued on Aug. 30, 2022 in connection with Japanese Patent application No. 2020-524658 and English translation, 14 pages. [cited by applicant]
Japanese Patent Office, Office Action issued on Jan. 16, 2024 in connection with Japanese Patent application No. 2020-524658 and English translation, 11 pages. [cited by applicant]
Japanese Patent Office, Search Report issued on Jul. 12, 2022 in connection with Japanese Patent Application No. 2020-524658 and English translation, 61 pages. [cited by applicant]
Jeon et al., “Amorphous Tungstate Precursor Route to Nanonstructure Tungsten Oxide Film with Electrochromic Property,” Journal of Nanoscience and Nanotechnology, 2011, pp. 6518-6522, vol. 11, No. 7. [cited by applicant]
Korean Intellectual Property Office, Notice of Reasons for Rejection issued on Apr. 17, 2023 in connection with Korean Patent application No. 10-2020-7004856, and English translation, 12 pages. [cited by applicant]
Korean Intellectual Property Office, Notice of Reasons for Rejection issued on Feb. 29, 2024 in connection with Korean Patent application No. 10-2020-7004856, and English translation, 6 pages. [cited by applicant]