CN106773436A - A kind of full-solid electrochromic glass devices and preparation method thereof - Google Patents
A kind of full-solid electrochromic glass devices and preparation method thereof Download PDFInfo
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- CN106773436A CN106773436A CN201611230324.XA CN201611230324A CN106773436A CN 106773436 A CN106773436 A CN 106773436A CN 201611230324 A CN201611230324 A CN 201611230324A CN 106773436 A CN106773436 A CN 106773436A
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect
- G02F1/1514—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material
- G02F1/1523—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material comprising inorganic material
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect
- G02F1/1514—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material
- G02F1/1523—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material comprising inorganic material
- G02F1/1525—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material comprising inorganic material characterised by a particular ion transporting layer, e.g. electrolyte
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect
- G02F1/153—Constructional details
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- Electrochromic Elements, Electrophoresis, Or Variable Reflection Or Absorption Elements (AREA)
Abstract
The invention discloses a kind of full-solid electrochromic glass devices and preparation method thereof, including transparent substrates, also include growth on a transparent substrate, and bottom conductive layer, electrochromic layer I, electrochromic layer II, ion storage, the top layer conductive layer for setting gradually;Electrochromic layer I is lower than the oxygen content of electrochromic layer II.The beneficial effects of the invention are as follows:Two-layer or multilayer electrochromic layer are used by preparing, prepare staged crystal structure and various sizes of ion channel, reach enhancing ionic conductance, improve the corresponding time, increase electrochromism efficiency, device overall structure matching is difficult mismatch well during long-time use simultaneously, ion implanting abjection passage is hardly damaged, greatly strengthen service life cycle, two-layer or multilayer electrochromism Rotating fields are more fine and close simultaneously, the function of electronic isolation is played enough can also omit preparing ion conducting layer.
Description
Technical field
The invention belongs to electrochomeric glass field, especially a kind of full-solid electrochromic glass devices and its preparation side
Method.
Background technology
Since being come out for electrochromism technology from nineteen fifty, electrochromism technology is with the correlation such as material, vacuum, electronics section
Development is healthy and strong, and people are devoted to preparing discoloration, becomes the remarkable electrochromism of colour efficiency, Life Cycle number of times
Device, be desirable to extensively should in directions such as building curtain wall, interior decoration, function machine, communications and transportation, reach intelligence it is comfortable,
The purpose of energy-conserving and environment-protective.Electrochomeric glass refers to the various electrochromism correlation function material films in deposition on glass,
It is general to be made up of bottom conductive layer, electrochromic layer, ion conducting layer, ion storage and top layer conductive layer.
Electrochromic device is divided into organic electrochromic glass, inorganic electrochromic glass due to the difference of its material;By
It is divided into full-solid electrochromic glass, liquid electrochomeric glass in its structure difference.Due to inorganic material, material is special in itself
Property, all solid state inorganic electrochromic glass is using anti-solar irradiation under electric field circulation, and the life-span is more long with respect to organic material, Quan Gu
The advantages of state structure is safe and reliable.But all solid state inorganic electrochromic glass also has shortcoming simultaneously, due to all solid state knot of membrane system
Structure, ion during movement causes discoloration from ion storage to electrochromic layer, can be subject to electroluminescent change under electric field action
The influence of chromatograph crystal structure and ion solid solubility, strong influence color changeable effect and electrochromism efficiency, and routine is electroluminescent
Lattice mismatch after discoloration film layer structure, ion implanting and abjection circulation repeatedly between film layer is serious, can cause a series of film layers
Quality problems, trigger electrochromism defunctionalization.With electrochomeric glass application on building materials, the electroluminescent change of large area
The demand of color glass increasingly highlights that electrochromism efficiency is low and problem of service life cycle.
The content of the invention
For the technical problem that prior art is present, the present invention is proposed a kind of with least two layer crystals by many experiments
The full-solid electrochromic glass devices of body structure and the different electrochromic layer of consistency, what is be connected with transparency conducting layer is electroluminescent
Photochromic layer I structures are dense, it is ensured that film layer and transparency conducting layer binding ability, the structure of electrochromic layer II is with respect to electrochromism
I is loose for layer, it is ensured that possess " electrochromism passage " that ion can be passed through, reaches enhancing ionic conductance, recycles the longevity
The purpose of life, enhancing memory time and change colour efficiency, to solve the difficulty of prior art.
The technical solution adopted for the present invention to solve the technical problems is:A kind of full-solid electrochromic glass devices knot
Structure, is divided by function successively, successively growth bottom conductive layer, at least two-layer electrochromic layer I and electroluminescent on a transparent substrate
Photochromic layer II, ion storage, top layer conductive layer, preferably, the present invention includes electrochromic layer I and electrochromic layer II.
Wherein ion storage can also be simultaneously with electrochromic layer I, electrochromic layer II each other the electrochromic layer of anode and cathode and
The mixed layer of ion, after being processed through Overheating Treatment or light, integral device is five-layer structure, improves response speed and uses the longevity
Life.Preferably, bottom transparent substrates are probably soda-lime glass, and Pyrex, ultra-clear glasses, quartz glass, resin film etc..
Preferably, bottom conductive layer, top layer conductive layer can be tin indium oxide, zinc oxide aluminum, fluorine doped tin oxide, nanometer
One kind of silver-colored net, Graphene etc., more preferably tin indium oxide;The thickness of conductive layer be 100~1000nm, sheet resistance be 3~
30Ω/□;Preparation technology is probably vapour deposition process (including physical vapor deposition (PVD) and chemical vapor infiltration
(CVD), method common in physical vapor deposition has magnetron sputtering etc., thermal evaporation etc.), sol-gal process.
Preferably, the material of electrochromic layer I, electrochromic layer II can be titanium oxide, vanadium oxide, zirconium oxide, oxygen
Change niobium, molybdenum oxide, tantalum oxide, one kind of tungsten oxide, or it is several;The thickness of electrochromic layer I is 300~1000nm, electroluminescent
The thickness of photochromic layer II is 150~500nm;Preparation technology is probably vapour deposition process, including chemical vapour deposition technique (CVD),
Thermal evaporation and physical vapor deposition (PVD) (such as common are magnetron sputtering etc.);Preferably, physical vapor can be used
Sedimentation growth electrochromic layer I, electrochromic layer II, as further preferred, can grow electroluminescent change using magnetron sputtering method
Chromatograph I, electrochromic layer II.
Preferably, when the metal material of electrochromic layer I, electrochromic layer II use is consistent, preparation technology parameter can
Difference can be had, element ratio in material may be adjusted, technological temperature, operating air pressure one or more.Such as:As excellent
Choosing, in electrochromic layer I, electrochromic layer II, oxygen element ratio is different in may adjusting material, oxygen unit in electrochromic layer I
Element is than content in electrochromic layer II few 1%~20%, more preferably 1%~5%.Preferably, electrochromic layer I,
Electrochromic layer II, technological temperature difference, temperature in the preparation process of electrochromic layer I than electrochromic layer II low 50~
200℃.Preferably, electrochromic layer I, electrochromic layer II, operating air pressure difference, the preparation process of electrochromic layer I
In operating air pressure than the low 0.1~0.3Pa of electrochromic layer II.
Preferably, in the electrochromic layer I, metallic atom is 1 with the mol ratio of oxygen atom:(2~3);The electricity
In mutagens chromatograph II, metallic atom is 1 with the mol ratio of oxygen atom:(2.5~3.5).As further preferred, the electroluminescent change
Chromatograph I, the selective oxidation tungsten of electrochromic layer II:WOx, in the electrochromic layer I, x=2.5~2.95;The electrochromism
In layer II, x=2.98~3.0.Calculated in weight percent, the content of oxygen element is 17~21% in the electrochromic layer I;
The content of oxygen element is 20~21% in the electrochromic layer II.
Preferably, ion storage can be nickel oxide, cobalt oxide, iron oxide, manganese oxide, chromium oxide, rhodium oxide, oxygen
Change iridium, nickel-tungsten oxide, nickel oxide vanadium, nickel manganese oxide, one or more in nickel oxide aluminium, ion can be hydrogen ion, lithium from
One or more in son, sodium ion, potassium ion, magnesium ion;These ions can from its corresponding simple substance, oxide,
One or more of peroxide.As further preferred, the ion storage layer material selective oxidation nickel tungsten;Ion gun is lithium
Ion;Ion gun can be when preparing ion storage doping or ion storage prepare after by sputtering, thermal evaporation,
Sol-gal process injects;Ion storage is a tunic on the whole, i.e. the oxide skin(coating) comprising ion;The thickness of ion storage
It is 100~350nm to spend;Ions dosage is being 0.1%~10%.
Preferably, electrochromic layer I, electrochromic layer II are used as cathodic electrochromic layer, ion storage is used as sun
Pole electrochromic layer.
Preferably, bottom conductive layer, electrochromic layer I, electrochromic layer II, ion storage, top layer conductive layer
The thickness evenness of each film layer is less than equal to 5%, and the thickness evenness after all thin film depositions is less than and is equal to
5%;
Present invention also offers a kind of preparation method of full-solid electrochromic glass devices, including:Successively in transparent base
Bottom growth bottom conductive layer, at least two-layer electrochromic layer I and electrochromic layer II, ion storage, top layer conductive layer.
Preferably, the electrochromic layer I, electrochromic layer II are completed in magnetic control sputtering system, electrochromic layer I
Temperature in preparation process is than II low 50~200 DEG C of electrochromic layer.
Preferably, operating air pressure in the preparation process of the electrochromic layer I than electrochromic layer II low 0.1~
0.3Pa。
Used as carrying out Post isothermal treatment after preferred all film preparations, heat treatment is probably vacuum annealing, ambient anneal, big
One or more of gas annealing, 200~450 DEG C of annealing temperature, 15~200min of annealing time, vacuum is during vacuum annealing
10-2~10-4Pa, vacuum is 10 during ambient anneal-1Pa, in nitrogen atmosphere.
The beneficial effects of the invention are as follows:Two-layer or multilayer electrochromic layer are used by preparing, by controlling to every layer of life
Process conditions long and oxygen content, prepare staged crystal structure and various sizes of ion channel, reach enhancing ionic conductance,
Shorten the corresponding time, increase electrochromism efficiency, ion implanting abjection passage is hardly damaged, and greatly enhancing recycles the longevity
Life, while two-layer or multilayer electrochromism Rotating fields, more fine and close after heat treatment, can play the function of electronic isolation, omit system
Standby ion conducting layer.
Brief description of the drawings
Fig. 1 is structural representation of the invention;
In figure:1st, transparent substrates, 2, bottom conductive layer, 3, electrochromic layer I, 4, electrochromic layer II, 5, ion storage
Layer, 6, ion gun, 7, top layer conductive layer.
Specific embodiment
Below by specific embodiment, and with reference to accompanying drawing, technical scheme is described in further detail.
A kind of preparation method of full-solid electrochromic device (referring to accompanying drawing 1), passes through physical vapor in transparent substrates 1
Deposition process growth bottom conductive layer 2, the deposition growing electrochromic layer I 3 on bottom transparency conducting layer, electrochromic layer II 4,
Redeposited ion storage 5, depositing ions source 6, ion gun is one or more in lithium or lithia or lithium peroxide,
Redeposited growth top layer conductive layer 7, device is completed after top layer transparency conducting layer deposition growing by heat treatment after ion source deposit
Preparation.
Bottom transparency conducting layer and top layer transparency conducting layer can be tin indium oxide, zinc oxide aluminum, fluorine doped tin oxide, nanometer
One or more of silver-colored net, Graphene etc., the thickness of conductive layer is 100~1000nm, and sheet resistance is 3~30 Ω/;Preparation technology
It is probably vapour deposition process (CVD), sputtering, thermal evaporation, sol-gal process;Bottom transparency conducting layer and top layer transparency conducting layer
Sheet resistance it is substantially uniform consistent, sheet resistance difference is within 5 Ω/.
Electrochromic layer I, the material of electrochromic layer II can be titanium oxide, vanadium oxide, zirconium oxide, niobium oxide, oxidation
Molybdenum, tantalum oxide, one kind of tungsten oxide, or it is several;The thickness of electrochromic layer I is 300~1000nm, electrochromic layer II
Thickness is 150~500nm;Preparation technology is probably vapour deposition process (CVD), sputtering, one kind of thermal evaporation.
The material of main part of ion storage can be nickel oxide, cobalt oxide, iron oxide, manganese oxide, chromium oxide, rhodium oxide,
One or more of yttrium oxide, nickel-tungsten oxide, nickel oxide vanadium, nickel manganese oxide, nickel oxide aluminium, ion gun can be hydrogen ion, lithium
One or more of ion, sodium ion, potassium ion, magnesium ion;Ion gun can be when preparing ion storage doping or from
Sub- accumulation layer is injected after preparing by sputtering, thermal evaporation, sol-gal process;Ion storage is a tunic on the whole,
Include the oxide skin(coating) of ion;The thickness of ion storage is 100~350nm.Middle depositing ions source in ion storage, from
The deposition of component is with the thickness of ion storage about, it is necessary to ensure that ion is entirely capable of being diffused into the ion storage up to this thickness
In layer, complete ionisation ion accumulation layer and a tunic is formed with ion storage, ion can not independently form a tunic.
Post isothermal treatment is carried out after film preparation, heat treatment is probably vacuum annealing, ambient anneal, one kind of air annealing
Or several, 200-450 DEG C of annealing temperature, annealing time 15-200min, vacuum is 10 during vacuum annealing-2~10-4Pa, atmosphere
Vacuum is 10 during annealing-1Pa, in nitrogen atmosphere.
Embodiment 1:
All plated films are completed in magnetic control sputtering system, and bottom transparency conducting layer is using tin indium oxide (ITO), thickness
150nm, electrochromic layer I is tungsten oxide (WO2.8), thickness is 500nm, and electrochromic layer II is tungsten oxide (WO3), thickness is
150nm, electrochromic layer I is lower than the oxygen content of electrochromic layer II, and structure is relatively compact, and ion storage is nickel-tungsten oxide,
Thickness is 250nm, its ion storage is ionized as ion gun using lithium, 5%, it should be noted that lithium ion
When content is few, product is partially yellow, and when lithium ion content is more, product is partially blue;Deposited oxide on nickel-tungsten oxide after ionizing completely
Indium tin (ITO) is top layer transparency conducting layer, and thickness is 200nm, by 450 DEG C of vacuum annealing 10min, vacuum after the completion of plated film
It is 10-6Torr, air annealing is carried out at 300 DEG C, and anneal 1h.The electrochomeric glass of obtained 620nm × 840nm can be
Change colour completely in 4min, the transmitance after discoloration in visible region 550nm is less than 5%, and the transmitance after fading about exists
65%.
Embodiment 2:
All plated films are completed in magnetic control sputtering system, and bottom transparency conducting layer is using tin indium oxide (ITO), thickness
150nm, electrochromic layer I is tungsten oxide (WO2.7), thickness is 300nm, and electrochromic layer II is tungsten oxide (WO2.9), thickness is
200nm, electrochromic layer I is lower than the oxygen content of electrochromic layer II, and structure is relatively compact, and ion storage is nickel-tungsten oxide,
Thickness is 250nm, and its ion storage is ionized as ion gun using lithium, ions dosage 8%, it is necessary to note
It is that when lithium ion content is few, product is partially yellow, and when lithium ion content is more, product is partially blue;On nickel-tungsten oxide after ionizing completely
Depositing indium tin oxide (ITO) is top layer transparency conducting layer, and thickness is 400nm, by 450 DEG C of vacuum annealings after the completion of plated film
10min, vacuum is 10-6Torr, air annealing is carried out at 300 DEG C, and anneal 1h.The electrochromism of obtained 370nm × 470nm
Glass can completely change colour in 3min, after discoloration visible region 550nm transmitance be less than 5%, and fade after transmission
Rate is about 65%.
Embodiment described above is several preferred versions of the invention, and any formal limit is not made to the present invention
System, also has other variants and remodeling on the premise of without departing from the technical scheme described in claim.
Claims (10)
1. a kind of full-solid electrochromic glass devices, including transparent substrates, it is characterised in that also including being grown in transparent substrates
On, and the bottom conductive layer, at least two-layer electrochromic layer I and electrochromic layer II, ion storage, the top layer that set gradually lead
Electric layer;Electrochromic layer I is lower than the oxygen content of electrochromic layer II.
2. full-solid electrochromic glass devices according to claim 1, it is characterised in that in percentage by weight
Calculate, the content of oxygen element is than content in electrochromic layer II few 1%~20% in the electrochromic layer I.
3. full-solid electrochromic glass devices according to claim 1, it is characterised in that the ion storage be with
The mixed layer of electrochromic layer I, electrochromic layer II electrochromic layer of anode and cathode and ion each other.
4. full-solid electrochromic glass devices according to claim 3, it is characterised in that the ion storage body
Material is selected from nickel oxide, cobalt oxide, iron oxide, manganese oxide, chromium oxide, rhodium oxide, yttrium oxide, nickel-tungsten oxide, nickel oxide vanadium, oxygen
Change one or more in nickel manganese, nickel oxide aluminium, ion gun is selected from hydrogen ion, lithium ion, sodium ion, potassium ion, magnesium ion
One or more, ions dosage is 0.1~10%;The thickness of ion storage is 100~350nm.
5. full-solid electrochromic glass devices according to claim 1, it is characterised in that the electrochromic layer I, electricity
The material of mutagens chromatograph II is selected from the one kind in titanium oxide, vanadium oxide, zirconium oxide, niobium oxide, molybdenum oxide, tantalum oxide, tungsten oxide
Or it is several;The thickness of electrochromic layer I is 300~1000nm, and the thickness of electrochromic layer II is 150~500nm.
6. full-solid electrochromic glass devices according to claim 1, it is characterised in that in the electrochromic layer I,
Metallic atom is 1 with the mol ratio of oxygen atom:(2~3);In the electrochromic layer II, metallic atom and oxygen atom mole
Than being 1:(2.5~3.5).
7. the preparation method of the full-solid electrochromic glass devices described in a kind of claim 1, it is characterised in that including:According to
It is secondary to grow bottom conductive layer, at least two-layer electrochromic layer I and electrochromic layer II, ion storage, top layer in transparent substrates
Conductive layer.
8. the preparation method of full-solid electrochromic glass devices according to claim 7, it is characterised in that described electroluminescent
Photochromic layer I, electrochromic layer II are completed in magnetic control sputtering system, and the temperature in the preparation process of electrochromic layer I is than electroluminescent change
II low 50~200 DEG C of chromatograph.
9. the preparation method of the full-solid electrochromic glass devices according to claim 7 or 8, it is characterised in that described
Operating air pressure in the preparation process of electrochromic layer I is than the low 0.1~0.3Pa of electrochromic layer II.
10. the preparation method of full-solid electrochromic glass devices according to claim 7, it is characterised in that all layers
It is heat-treated after preparation, heat treatment includes one or more of vacuum annealing, ambient anneal, air annealing, annealing temperature
200-450 DEG C, annealing time 15-200min, vacuum is 1*10 during vacuum annealing-2~10-4Pa, vacuum during ambient anneal
It is 10-1Pa, selects nitrogen atmosphere.
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US11898233B2 (en) | 2009-03-31 | 2024-02-13 | View, Inc. | Electrochromic devices |
US11947232B2 (en) | 2009-03-31 | 2024-04-02 | View, Inc. | Fabrication of low defectivity electrochromic devices |
US11960188B2 (en) | 2014-11-26 | 2024-04-16 | View, Inc. | Counter electrode for electrochromic devices |
US11966140B2 (en) | 2009-03-31 | 2024-04-23 | View, Inc. | Counter electrode for electrochromic devices |
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