WO2015032200A1 - All-solid-state electrochromic composite device and manufacturing method therefor - Google Patents

All-solid-state electrochromic composite device and manufacturing method therefor Download PDF

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Publication number
WO2015032200A1
WO2015032200A1 PCT/CN2014/074989 CN2014074989W WO2015032200A1 WO 2015032200 A1 WO2015032200 A1 WO 2015032200A1 CN 2014074989 W CN2014074989 W CN 2014074989W WO 2015032200 A1 WO2015032200 A1 WO 2015032200A1
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layer
color
solid
transparent
electrochromic
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PCT/CN2014/074989
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French (fr)
Chinese (zh)
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蔡明�
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华为技术有限公司
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Publication of WO2015032200A1 publication Critical patent/WO2015032200A1/en

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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
    • G02F1/1506—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 caused by electrodeposition, e.g. electrolytic deposition of an inorganic material on or close to an electrode
    • G02F1/1508—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 caused by electrodeposition, e.g. electrolytic deposition of an inorganic material on or close to an electrode using a solid electrolyte
    • 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
    • G02F1/1533—Constructional details structural features not otherwise provided for
    • 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
    • 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
    • G02F1/1533—Constructional details structural features not otherwise provided for
    • G02F2001/1536—Constructional details structural features not otherwise provided for additional, e.g. protective, layer inside the cell

Definitions

  • the invention relates to an all-solid-state electrochromic composite device and the application number thereof is submitted to the Chinese Patent Office on September 5, 2013, and the application number is 201310400363.X.
  • the priority of the Chinese Patent Application the entire disclosure of which is incorporated herein by reference.
  • the present invention relates to the field of electrochromic devices, and more particularly to an all-solid electrochromic composite device and a method of fabricating the same. Background technique
  • Electrochromism refers to the phenomenon that the optical properties (reflectance, transmittance, absorptivity, etc.) of a material undergo a stable and reversible color change under the action of an applied electric field, and the appearance is a reversible change in color and transparency.
  • a material having electrochromic properties is called an electrochromic material, and a device made of an electrochromic material is called an electrochromic device.
  • the electrochromic device is divided into two types: all solid state and non-all solid state.
  • the all solid state electrochromic device is composed of pure inorganic materials, and there is no problem of high sealing property and leakage of the device, and the life is long, so Widely used;
  • the existing inorganic all-solid electrochromic device is a five-layer film structure, a transparent conductive layer-electrochromic layer-ion conductive layer-ion storage layer-transparent conductive layer, existing mature inorganic electrochromic layer
  • the material is tungsten trioxide. At present, only such materials are relatively mature in transition between blue and colorless, while other colors such as red, yellow, and green are difficult to achieve applicable inorganic all-solid electrochromic.
  • the first aspect of the embodiments of the present invention provides an all-solid-state electrochromic composite device, which is used to solve the problem that the all-solid-state electrochromic device in the prior art has few variable colors, and can only realize colorless to blue.
  • the color of mature industrial applications is discolored, and it is not possible to achieve multiple color conversions, as well as the problem of discoloration from mature industrial applications from color to color.
  • an embodiment of the present invention provides an all-solid-state electrochromic composite device comprising a substrate, an electrochromic unit and an intrinsic color unit, wherein the electrochromic unit comprises a first transparent conductive layer laminated in sequence, and an electro-induced a color changing layer, an ion conductive layer, an ion storage layer, and a second transparent conductive layer, the intrinsic color unit comprising a PVD decorative plating color layer and a metal layer sequentially stacked, the PVD decorative plating color layer and the second transparent conductive layer Laminated together;
  • the first transparent conductive layer is disposed on the substrate; or the metal layer is disposed on the substrate.
  • the PVD decorative plating color layer is a gradient film layer, and the PVD decorative plating color layer contains a metal element.
  • the metal layer comprises any one or any combination of the following:
  • One or more layers of metal elemental film are One or more layers of metal elemental film
  • a mixed film of a metal and a metal compound formed of a metal and a gas is a mixed film of a metal and a metal compound formed of a metal and a gas.
  • the metal layer has a thickness of 50 to 1000 nm.
  • the all solid state electrochromic composite device further comprises a transparent insulating film disposed between the second transparent conductive layer and the PVD decorative plating color layer.
  • the all-solid-state electrochromic composite device further comprises a transparent UV paint layer, a transparent organic color film layer or a transparent inorganic color film layer disposed between the second transparent conductive layer and the PVD decorative plating color layer.
  • the transparent organic color film layer and the transparent inorganic color film layer are doped with a pigment or Color ions.
  • the substrate is a transparent or opaque substrate
  • the transparent substrate is a transparent glass, an organic transparent material or an inorganic transparent material
  • the opaque substrate is an opaque glass, a plastic product, a ceramic, a sapphire or a metal alloy.
  • PVD decorative plating color layer is used as the ground color, that is, when the electrochromic layer is not applied with voltage to be transparent and colorless, the device presents a pre-designed color of the PVD decorative plating color layer.
  • the transmittance can be adjusted by adjusting the voltage value, so that the PVD decorative plating layer is combined with the electrochromic layer to form different colors, thereby realizing various kinds.
  • Color conversion is even a conversion between color and color; in addition, by designing the PVD decorative color layer to a different color, a variety of color change requirements can be achieved.
  • the all-solid-state electrochromic composite device provided by the first aspect of the present invention includes an all-solid-state electrochromic unit and an intrinsic color unit of the existing five-layer film structure, and the intrinsic color unit includes a PVD decorative plating color layer and a metal layer.
  • the color conversion of a plurality of colors is realized even in a mature industrial application from color to color.
  • the all-solid-state electrochromic composite device provided by the first aspect of the present invention can be applied to, but not limited to, a logo applied to an electronic product such as a mobile phone or a tablet computer. Parts, rear shells and other related parts.
  • an embodiment of the present invention provides a method for preparing an all-solid-state electrochromic composite device, including the following steps:
  • the manner of depositing the PVD comprises evaporation plating, magnetron sputtering or ion plating.
  • the PVD decorative plating color layer contains a metal element and is a gradient film layer
  • the specific preparation method is as follows: a metal element or a metal alloy is used as a target, and one of argon gas, nitrogen gas, oxygen gas, decane and acetylene is introduced. One or more gases, adjusting the flow of the incoming gas during the preparation, or simultaneously adjusting one or more of the power, current, negative bias, and positive bias to form a series of gradients containing metal and gas elements Membrane layer.
  • the preparation method of the all-solid-state electrochromic composite device provided by the second aspect of the present invention is an effective combination of the existing mature inorganic electrochromic technology and the PVD decorative plating technology, and the process is simple and easy to realize industrial production, and Compared with the existing conventional electrochromic devices, the preparation cost is not increased much, and it is easy to commercialize.
  • FIG. 1 is a schematic structural view of an all solid state electrochromic composite device prepared according to Embodiment 1 of the present invention. detailed description
  • the first aspect of the embodiments of the present invention provides an all-solid-state electrochromic composite device, which is used to solve the problem that the all-solid-state electrochromic device in the prior art has few variable color types, and can only realize the maturity from colorless to blue. Industrial applications are discolored, and it is not possible to achieve multiple color conversions, as well as the problem of discoloration from mature industrial applications from color to color.
  • an embodiment of the present invention provides an all-solid-state electrochromic composite device comprising a substrate, an electrochromic unit and an intrinsic color unit, wherein the electrochromic unit comprises a first transparent conductive layer laminated in sequence, and an electro-induced a color changing layer, an ion conductive layer, an ion storage layer, and a second transparent conductive layer, the intrinsic color unit comprising a PVD decorative plating color layer and a metal layer sequentially stacked, the PVD decorative plating color layer and the second transparent conductive layer Laminated together;
  • the first transparent conductive layer is disposed on the substrate; or the metal layer is disposed on the substrate.
  • the all-solid electrochromic composite device of the present invention comprises an all-solid electrochromic unit and an intrinsic color unit of the existing five-layer film structure, and the intrinsic color unit comprises a PVD decorative plating layer and a metal layer which are sequentially laminated. Floor.
  • the color change principle of the device is: PVD decorative plating color layer as the ground color, that is, when the electrochromic layer is not applied with voltage, the device presents a pre-designed color of the PVD decorative plating color layer; and when the electrochromic layer is applied with voltage (voltage)
  • the transmittance can be adjusted by adjusting the voltage value, so that the PVD decorative plating color layer is combined with the electrochromic layer to form different colors, thereby realizing
  • the conversion of multiple colors is even a conversion between color and color; in addition, by designing the PVD decorative color layer to different colors, a variety of color change requirements can be realized.
  • the invention effectively combines the existing inorganic electrochromic technology with the PVD decorative plating technology, and realizes the discoloration of the full-solid electrochromic device from color to color in mature industrial applications.
  • the PVD decorative plating color layer is a gradient film layer, and the PVD decorative plating color layer contains a metal element.
  • Gradient film layer means that the PVD decorative plating color layer is not uniform composition, but has a gradient distribution. This arrangement is beneficial to light absorption and light reflection, and has good luminescence effect. At the same time, it can reduce film stress and prevent film cracking during use. .
  • the material and thickness of the PVD decorative plating color layer are not particularly limited, and may be modulated according to a specific color effect. In order to satisfy a good lighting effect, different color thickness settings are different.
  • PVD decorative plating color layer has a good metal texture.
  • PVD decorative plating technology has high yields such as black, gray, silver, blue, yellow, etc., and colors with lower yield due to factors such as equipment and the like. Purple, rose red, green and other colors.
  • the PVD decorative plating color layer contains a metal element, and the metal element includes zirconium (Zr), titanium (Ti), chromium (Cr), etc., and the material of the PVD decorative plating color layer is usually an oxide, a nitride, and a nitrogen of the above metal element. Oxide, carbon oxide or carbide.
  • the metal layer comprises any one or any combination of the following:
  • One or more layers of metal elemental film are One or more layers of metal elemental film
  • a mixed film of a metal and a metal compound formed of a metal and a gas is a mixed film of a metal and a metal compound formed of a metal and a gas.
  • the metal layer is mainly used for the purpose of enhancing the color effect.
  • the metal layer has a thickness of 50 to 1000 nm.
  • the all solid state electrochromic composite device further comprises a transparent insulating film disposed between the second transparent conductive layer and the PVD decorative plating color layer.
  • the transparent insulating film is made of an existing insulating material such as silicon oxide.
  • the all-solid-state electrochromic composite device further includes a plurality of layers of a transparent conductive film and a transparent insulating film which are alternately stacked in this order on the transparent insulating film.
  • the transparent insulating film is used to isolate the electrochromic unit and the intrinsic color unit, and when the electrochromic unit is applied with a voltage, the current is shunted to the intrinsic color unit.
  • the current shunt will reduce the degree of color discoloration, and the electrochromic layer actually withstands the voltage instability and affects the discoloration stability effect.
  • the all-solid-state electrochromic composite device is disposed in a structure, including the first transparent conductive layer, the electrochromic layer, the ion conductive layer, and the separation layer sequentially disposed on the substrate.
  • the all-solid-state electrochromic composite device is inverted, including a metal layer sequentially disposed on the substrate.
  • the PVD decorative plating color layer, the second transparent conductive layer, the ion storage layer, the ion conductive layer, the electrochromic layer and the first transparent conductive layer in practical applications, a specific setting manner can be selected according to requirements.
  • the all-solid-state electrochromic composite device further comprises a transparent UV paint layer, a transparent organic color film layer or a transparent inorganic color film layer disposed between the second transparent conductive layer and the PVD decorative plating color layer.
  • the transparent organic color film layer and the transparent inorganic color film layer are doped with a pigment or a colored ion.
  • the colored ions are common colored ions such as Cu 2+ , Fe 3+ , and the like.
  • the transparent UV paint layer or the transparent organic color film layer or the transparent inorganic color film layer can be arranged to enable the all-solid-state electrochromic composite device to realize the double color layer of the intrinsic color unit to obtain a richer color change effect.
  • the substrate is a transparent or opaque substrate
  • the transparent substrate is a transparent glass, an organic transparent material or an inorganic transparent material
  • the opaque substrate is an opaque glass, a plastic product, a ceramic, a sapphire or a metal alloy.
  • Metal alloys include stainless steel and the like.
  • the invention does not limit the material and thickness of each film layer of the electrochromic unit, and the existing materials are all suitable for the invention, and the thickness can be adjusted according to specific needs.
  • the material of the transparent conductive layer may be indium tin oxide (ITO), aluminum oxide ( ⁇ ) or graphene film, the thickness is 20 ⁇ 500 nm, the electrochromic layer material may be W0 3 , the thickness is 50 ⁇ 500 nm,
  • the ion conductive layer may be made of LiTa0 3 or LiNb0 3 and has a thickness of 20 to 500 nm.
  • the ion storage layer may be an oxide of nickel or an oxide of vanadium, having a thickness of 50 to 500 nm, and the transparent conductive layer may be indium tin.
  • the all-solid-state electrochromic composite device provided by the first aspect of the present invention includes an all-solid-state electrochromic unit and an intrinsic color unit of the existing five-layer film structure, and the intrinsic color unit includes a PVD decorative plating color layer and a metal layer. Achieve multi-color conversion and even discoloration from mature industrial applications from color to color;
  • the all-solid-state electrochromic composite device provided by the first aspect of the present invention can be applied to, but not limited to, a logo portion, a rear shell, and the like on an electronic product such as a mobile phone or a tablet computer.
  • an embodiment of the present invention provides a method for preparing an all-solid-state electrochromic composite device, including the following steps:
  • the manner in which the PVD is deposited includes evaporation plating, magnetron sputtering, or ion plating.
  • the entire seven-layer membrane structure of the all-solid electrochromic composite device can be plated in the same furnace, such as all in an evaporation furnace, or all in a magnetron sputtering furnace, or in a composite furnace of both; Or in a separate furnace, in order to improve efficiency and save cost, the seven-layer membrane structure is plated in the same furnace as much as possible, that is, direct evaporation of seven layers, or direct magnetron sputtering continuous furnace plating of seven-layer membrane structure. In the same furnace, efficiency can be improved, cost can be saved, and the cost can be improved less than the ordinary five-layer electrochromic structure.
  • the PVD deposition equipment used, with a film thickness test system and a transmittance test system is better for real-time control of film and transmittance during deposition.
  • the PVD decorative plating color layer contains a metal element and is a gradient film layer
  • the specific preparation method is as follows: a metal element or a metal alloy is used as a target, and one of argon gas, nitrogen gas, oxygen gas, decane and acetylene is introduced. One or more gases, adjusting the flow of the incoming gas during the preparation process, or simultaneously adjusting one or more of the power, current, negative bias, and positive bias to form a series of metal-containing and gaseous elements Gradient film layer.
  • the metal layer comprises any one or any combination of the following:
  • One or more layers of metal elemental film are One or more layers of metal elemental film
  • a mixed film of a metal and a metal compound formed of a metal and a gas is a mixed film of a metal and a metal compound formed of a metal and a gas.
  • the metal layer has a thickness of 50 to 1000 nm.
  • the method for preparing the all-solid-state electrochromic composite device further comprises the steps of: preparing a transparent insulating film between the second transparent conductive layer and the PVD decorative plating color layer.
  • the transparent insulating film is made of a conventional insulating material such as silicon oxide.
  • the method of producing the all-solid-state electrochromic composite device further comprises preparing a plurality of transparent conductive films and transparent insulating films which are alternately stacked in this order on the transparent insulating film.
  • the method for preparing the all-solid-state electrochromic composite device further comprises preparing a transparent UV paint layer, a transparent organic color film layer or a transparent inorganic color between the second transparent conductive layer and the PVD decorative plating color layer.
  • the film layer, the transparent organic color film layer and the transparent inorganic color film layer are doped with a pigment or a colored ion.
  • the substrate is subjected to surface pretreatment by vapor deposition coating, electrochemical coating, electroless plating, anodizing, micro-arc oxidation, thermal spraying, painting or forming an organic film.
  • surface pretreatment by vapor deposition coating, electrochemical coating, electroless plating, anodizing, micro-arc oxidation, thermal spraying, painting or forming an organic film. After pretreatment, it facilitates the preparation of subsequent layers to make the binding more compact.
  • the specific parameter setting of the PVD deposition process is set according to the material and thickness of the film layer, and is not particularly limited in the present invention.
  • the preparation method of the all-solid-state electrochromic composite device provided by the second aspect of the present invention is an effective combination of the existing mature inorganic electrochromic technology and the PVD decorative plating technology, and the process is simple and easy to realize industrial production, and Compared with the existing conventional electrochromic devices, the preparation cost is not increased much, and is easy to implement. commercialize.
  • the all-solid-state electrochromic composite device provided by the first aspect of the present invention effectively combines the existing inorganic electrochromic technology with the PVD decorative plating technology, and can realize conversion of multiple colors or even mature from color to color.
  • the all-solid-state electrochromic composite device provided by the first aspect of the present invention can be applied to, but is not limited to, a logo portion, a rear shell, and the like on an electronic product such as a mobile phone or a tablet computer.
  • the preparation method of the all-solid electrochromic composite device provided by the second aspect of the present invention is an effective combination of the existing mature inorganic electrochromic technology and the PVD decorative plating technology, the process is simple, the industrial production is easy, and the present invention is relatively The manufacturing cost of a conventional electrochromic device is not increased much, and it is easy to commercialize.
  • a method for preparing an all-solid-state electrochromic composite device comprising the steps of:
  • the layer (NiO x ) and the second transparent conductive layer (ITO) are specifically operated as follows: the glass substrate is placed in an evaporation plating apparatus, and the steamed material powder, the W0 3 steam powder, and the LiNb0 3 steam powder, NiO x steam powder, ITO steam powder, start electron beam evaporation, and sequentially prepare each film layer of the electrochromic unit;
  • the first transparent conductive layer ITO is 80 nm
  • the electrochromic layer W0 3 is 200 nm
  • the ion conductive layer LiNb0 3 is 180 nm
  • the ion storage layer NiO is 200 nm
  • the second transparent conductive layer ITO is 80 nm.
  • PVD decorative plating color layer and metal layer preparation equipment is medium frequency magnetron sputtering equipment, equipment diameter 1200mm, height 800mm, target is pure Ti target, the inlet gas is argon, oxygen, nitrogen, the process parameter is argon 150sccm 50% duty cycle, 50 volts negative bias, target power 8KW, the above parameters remain unchanged; oxygen starting flow rate 20sccm remains unchanged, nitrogen starts flow rate 60sccm for 3000 seconds and then becomes 40sccm to 3600 seconds, get light green The gradient film layer was then turned off by oxygen and nitrogen to prepare a metal Ti layer for 600 seconds, and the metal Ti layer was 400 nm thick.
  • FIG. 1 is a schematic structural view of an all-solid electrochromic composite device prepared in the first embodiment.
  • 10 is a transparent substrate
  • 20 is an electrochromic unit
  • 30 is an intrinsic color unit
  • the electrochromic unit 20 includes a first transparent conductive layer 201, an electrochromic layer 202, an ion conductive layer 203, and an ion storage layer which are sequentially stacked.
  • the intrinsic color unit 30 includes a PVD decorative plating color layer 301 and a metal layer 302.
  • the PVD decorative plating color layer is light green
  • the electrochromic layer is blue material.
  • a method for preparing an all-solid-state electrochromic composite device comprising the steps of:
  • the first transparent conductive layer (AZO) and the electrochromic layer are sequentially prepared on the glass substrate.
  • W0 3 ), ion Conductive layer (LiTa0 3 ), ion storage layer (VO x ) and second transparent conductive layer (AZO) the specific operation is: placing the glass substrate in PVD (RF magnetron sputtering + medium frequency magnetron sputtering) continuous furnace equipment (in-line line), put different target Zn-Al target (A1 accounted for 2% by weight), pure W target, pure V target, LiNb0 3 target into the furnace cavity, start the device, and then Preparing each film layer of the electrochromic unit, wherein the Zn-Al target, the pure W target and the pure V target are sputtered by medium frequency magnetron, and the LiNb0 3 target is irradiated by radio frequency magnetron;
  • the PVD decorative plating color layer and metal layer are specifically prepared as follows: the target is a pure Zr target, 50% duty cycle, 100 volts negative bias, target power 8 KW, gas into acetylene, argon gas, process parameters are: First, argon gas 150sccm, acetylene 200sccm, 100 seconds later gradually reduce the gas flow rate in 5sccm grade, each time to maintain 100s; to 100sccm after 20sccm grade to reduce the gas flow, each reduction for 80s; until the acetylene is turned off, Only a argon gas was used to prepare a pure Zr layer, which was maintained for 600 seconds to obtain a black film layer.
  • the PVD decorative plating color layer is black
  • the electrochromic layer is blue material.
  • the electrochromic layer is not applied with voltage, that is, when the reverse voltage is turned on, the device appears black; and when the electrochromic layer is added
  • the voltage that is, when the forward voltage is turned on, the device exhibits an ink blue effect; and by adjusting the voltage value to adjust the blue light transmittance, a composite color effect of black and light blue can be obtained.
  • a method for preparing an all-solid-state electrochromic composite device comprising the steps of:
  • PVD RF magnetron sputtering + medium frequency magnetron sputtering
  • first transparent conductive layer AZO
  • electrochromic layer W0 3
  • ion conductive layer LiTa0 3
  • VO x ion storage layer
  • second transparent conductive layer AZO
  • the glass substrate is placed in PVD (RF magnetron sputtering + medium frequency magnetron sputtering equipment, different targets Zn-Al target (A1 accounts for 1% by weight), pure W target, pure V target, LiNb0 3
  • the target is placed in the furnace chamber, the equipment is started, and the layers of the electrochromic unit are sequentially prepared, wherein the Zn-Al target, the pure W target and the pure V target are subjected to medium frequency magnetron sputtering, and the LiNb0 3 target is used.
  • RF magnetron sputtering RF magnetron sputtering
  • the first transparent conductive layer AZO is 65 nm
  • the electrochromic layer W0 3 is 170 nm
  • the ion conductive layer LiTa0 3 is 75 nm
  • the second transparent conductive layer AZO is 65 nm).
  • the PVD decorative plating color layer and metal layer are specifically prepared as follows:
  • the target is a pure Ti target, and the gas is nitrogen and argon.
  • the process parameters are: negative bias 50 volts, 20% duty cycle, target power 8 KW, gas
  • the flow rate of nitrogen is initially 220sccm, argon is 150sccm, and it is maintained for 200 seconds. After that, the nitrogen flow rate is reduced by 10sccm for 100 seconds. At 80sccm, the nitrogen flow rate is reduced by 20sccm for 100s until the nitrogen is 0.
  • Pure pure metal is prepared by pure argon.
  • the Ti layer was maintained for 600 seconds to obtain a yellow film layer having a thickness of 500 nm.
  • the PVD decorative plating color layer is yellow
  • the electrochromic layer is blue material.
  • the electrochromic layer is not applied with voltage, that is, when the reverse voltage is turned on, the device appears yellow; and when the electrochromic layer is added
  • the voltage that is, when the forward voltage is turned on, the device has a blue effect; and by adjusting the voltage value to adjust the blue light transmittance, a composite color effect of yellow and light blue can be obtained.
  • a method for preparing an all-solid-state electrochromic composite device comprising the steps of:
  • the specific preparation of the metal layer and the PVD decorative plating layer is as follows:
  • the target is a pure Ti target, and the gas is nitrogen and argon.
  • the process parameters are: firstly, the negative bias is raised to 800 volts, 50% duty cycle, Argon gas to 150sccm for ion cleaning to activate the ceramic surface, during which the metal target can be opened or the metal target can be opened for 300 seconds; then the negative bias voltage is reduced to 100 volts, 20% duty cycle, and the nitrogen flow rate is gradually increased to 20sccm. Each time, each time for 150 seconds, to 160 sccm, the nitrogen flow rate was increased every time by 10 sccm, and each time was maintained for 100 seconds to 220 sccm to obtain a yellow film layer.
  • the first transparent conductive layer AZO is 70 nm
  • the electrochromic layer W0 3 is 160 nm
  • the ion conductive layer LiTa0 3 is 80 nm
  • the ion storage layer 160 nm
  • the second transparent conductive layer AZO is 70 nm
  • the PVD decorative plating color layer is yellow
  • the electrochromic layer is blue material.
  • the electrochromic layer is not applied with voltage, that is, when the reverse voltage is turned on, the device appears yellow; and when the electrochromic layer is added
  • the voltage that is, when the forward voltage is turned on, the device has a blue effect; and by adjusting the voltage value to adjust the blue light transmittance, a composite color effect of yellow and light blue can be obtained.
  • a method for preparing an all-solid-state electrochromic composite device comprising the steps of: (1) providing a glass substrate having a transmittance of 92%;
  • the second transparent conductive layer (ITO) is specifically operated by: placing the glass substrate in an evaporation plating apparatus, and separately adding the steaming powder, the W0 3 steam powder, the LiNb0 3 steam powder, and the different materials in the evaporation plating. NiO x steam powder, ITO steam powder, start evaporation coating equipment, and sequentially prepare each film layer of the electrochromic unit;
  • the first transparent conductive layer ITO is 80 nm
  • the electrochromic layer W0 3 is 200 nm
  • the ion conductive layer LiNb0 3 is 180 nm
  • the ion storage layer NiO is 200 nm
  • the second transparent conductive layer ITO is 80 nm.
  • PVD decorative plating color layer and metal layer preparation equipment is medium frequency magnetron sputtering equipment, equipment diameter 1200mm, height 800mm, target is pure Ti-Al target, the inlet gas is argon, oxygen, nitrogen, the process parameter is argon Gas 150sccm, 50% duty cycle, 50 volts negative bias, target power 8KW, the above parameters remain unchanged; oxygen starting flow rate 20sccm remains unchanged, nitrogen starts flow rate 60sccm for 3000 seconds and then becomes 40sccm to 3600 seconds, get A light green gradient film layer, then oxygen and nitrogen were turned off to prepare a metal Ti-Al layer for 600 seconds, and the metal Ti-Al layer thickness was 450 nm.
  • the PVD decorative plating color layer is light green
  • the electrochromic layer is blue material.
  • the light green to blue color can be realized.
  • the transformation between colors, and due to the change in blue transmittance, the combination of light green and light blue forms a special color.
  • These can also be adjusted by adjusting the thickness of the PVD decorative plating layer and the electrochromic layer. Line color adjustment.
  • the storage medium may be a magnetic disk, an optical disk, a read-only memory (ROM), or a random access memory (RAM).

Abstract

The present invention provides an all-solid-state electrochromic composite device. The all-solid-state electrochromic composite device comprises a substrate, an electrochromic unit, and an inherent color unit. The electrochromic unit comprises a first transparent conducting layer, an electrochromic layer, an ion conducting layer, an ion storage layer, and a second transparent conducting layer all sequentially stacked. The inherent color unit comprises a PVD decorative color plating layer and a metal layer sequentially stacked. The PVD decorative color plating layer and the second transparent conducting layer are combined together in a stacked manner. The first transparent conducting layer is disposed on the substrate, or the metal layer is disposed on the substrate. The all-solid-state electrochromic composite device can implement conversion between multiple colors, and can implement mature industrial application color change from multiple colors to multiple colors. An embodiment of the present invention also provides a method for manufacturing the all-solid-state electrochromic composite device.

Description

一种全固态电致变色复合器件及其制备方法 本申请要求于 2013年 9月 5日提交中国专利局的申请号为 201310400363.X, 其发明名称为 "一种全固态电致变色复合器件及其制备方法" 的中国专利申请 的优先权， 其全部内容通过引用结合在本申请中。  The invention relates to an all-solid-state electrochromic composite device and the application number thereof is submitted to the Chinese Patent Office on September 5, 2013, and the application number is 201310400363.X. The priority of the Chinese Patent Application, the entire disclosure of which is incorporated herein by reference.
技术领域 Technical field
本发明涉及电致变色器件领域， 特别是涉及一种全固态电致变色复合器件 及其制备方法。 背景技术  The present invention relates to the field of electrochromic devices, and more particularly to an all-solid electrochromic composite device and a method of fabricating the same. Background technique
电致变色是指材料的光学属性（反射率、 透过率、 吸收率等）在外加电场的 作用下发生稳定、 可逆的颜色变化的现象， 在外观上表现为颜色和透明度的可 逆变化。 具有电致变色性能的材料称为电致变色材料， 用电致变色材料做成的 器件称为电致变色器件。  Electrochromism refers to the phenomenon that the optical properties (reflectance, transmittance, absorptivity, etc.) of a material undergo a stable and reversible color change under the action of an applied electric field, and the appearance is a reversible change in color and transparency. A material having electrochromic properties is called an electrochromic material, and a device made of an electrochromic material is called an electrochromic device.
电致变色器件分为全固态和非全固态两种，其中，全固态电致变色器件为纯 无机物组成的， 不存在对器件密封性要求高和泄露方面问题， 且寿命较长， 因 而被广泛应用； 现有的无机全固态电致变色器件为五层膜结构， 透明导电层-电 致变色层-离子导电层-离子存储层-透明导电层， 现有成熟的无机电致变色层的 材料为三氧化钨， 目前只有此种材料实现蓝色和无色之间的转变比较成熟， 而 其它颜色如红， 黄， 绿等彩色很难实现可应用的无机全固态电致变色。 发明内容 有鉴于此， 本发明实施例第一方面提供了一种全固态电致变色复合器件， 用以解决现有技术中全固态电致变色器件可变颜色种类少， 只能实现从无色到 蓝色的成熟工业应用变色， 而不能实现多种颜色的转换， 以及从彩色到彩色的 成熟工业应用变色的问题。 The electrochromic device is divided into two types: all solid state and non-all solid state. Among them, the all solid state electrochromic device is composed of pure inorganic materials, and there is no problem of high sealing property and leakage of the device, and the life is long, so Widely used; the existing inorganic all-solid electrochromic device is a five-layer film structure, a transparent conductive layer-electrochromic layer-ion conductive layer-ion storage layer-transparent conductive layer, existing mature inorganic electrochromic layer The material is tungsten trioxide. At present, only such materials are relatively mature in transition between blue and colorless, while other colors such as red, yellow, and green are difficult to achieve applicable inorganic all-solid electrochromic. Summary of the invention In view of this, the first aspect of the embodiments of the present invention provides an all-solid-state electrochromic composite device, which is used to solve the problem that the all-solid-state electrochromic device in the prior art has few variable colors, and can only realize colorless to blue. The color of mature industrial applications is discolored, and it is not possible to achieve multiple color conversions, as well as the problem of discoloration from mature industrial applications from color to color.
第一方面， 本发明实施例提供了一种全固态电致变色复合器件， 包括基底， 电致变色单元和固有颜色单元， 所述电致变色单元包括依次层叠的第一透明导 电层、 电致变色层、 离子导电层、 离子存储层和第二透明导电层， 所述固有颜 色单元包括依次层叠的 PVD装饰镀颜色层和金属层， 所述 PVD装饰镀颜色层 与所述第二透明导电层层叠结合在一起；  In a first aspect, an embodiment of the present invention provides an all-solid-state electrochromic composite device comprising a substrate, an electrochromic unit and an intrinsic color unit, wherein the electrochromic unit comprises a first transparent conductive layer laminated in sequence, and an electro-induced a color changing layer, an ion conductive layer, an ion storage layer, and a second transparent conductive layer, the intrinsic color unit comprising a PVD decorative plating color layer and a metal layer sequentially stacked, the PVD decorative plating color layer and the second transparent conductive layer Laminated together;
所述第一透明导电层设置在所述基底上； 或者所述金属层设置在所述基底 上。  The first transparent conductive layer is disposed on the substrate; or the metal layer is disposed on the substrate.
优选地， 所述 PVD装饰镀颜色层为梯度膜层， 所述 PVD装饰镀颜色层含 有金属元素。  Preferably, the PVD decorative plating color layer is a gradient film layer, and the PVD decorative plating color layer contains a metal element.
优选地， 所述金属层包括下述中的任意一种或任意组合：  Preferably, the metal layer comprises any one or any combination of the following:
一层或多层的金属单质膜层；  One or more layers of metal elemental film;
两种或两种以上的金属形成的合金膜层；  An alloy film layer formed of two or more metals;
金属和气体形成的金属与金属化合物的混合膜层。  A mixed film of a metal and a metal compound formed of a metal and a gas.
优选地， 所述金属层的厚度为 50 ~ 1000nm。  Preferably, the metal layer has a thickness of 50 to 1000 nm.
优选地， 所述全固态电致变色复合器件进一步包括设置在所述第二透明导 电层与所述 PVD装饰镀颜色层之间的透明绝缘膜。  Preferably, the all solid state electrochromic composite device further comprises a transparent insulating film disposed between the second transparent conductive layer and the PVD decorative plating color layer.
优选地， 所述全固态电致变色复合器件进一步包括设置在所述第二透明导 电层与所述 PVD装饰镀颜色层之间的透明 UV漆层、 透明有机颜色膜层或透明 无机颜色膜层， 所述透明有机颜色膜层和透明无机颜色膜层中掺杂有色素或有 色离子。 Preferably, the all-solid-state electrochromic composite device further comprises a transparent UV paint layer, a transparent organic color film layer or a transparent inorganic color film layer disposed between the second transparent conductive layer and the PVD decorative plating color layer. The transparent organic color film layer and the transparent inorganic color film layer are doped with a pigment or Color ions.
优选地， 所述基底为透明或不透明基底， 所述透明基底为透明玻璃、 有机 透明材料或无机透明材料， 所述不透明基底为不透明玻璃、 塑料制品、 陶瓷、 蓝宝石或金属合金。  Preferably, the substrate is a transparent or opaque substrate, and the transparent substrate is a transparent glass, an organic transparent material or an inorganic transparent material, and the opaque substrate is an opaque glass, a plastic product, a ceramic, a sapphire or a metal alloy.
本发明全固态电致变色复合器件的变色原理为： PVD装饰镀颜色层作为底 色， 即当电致变色层未加电压表现为透明无色时， 器件呈现 PVD装饰镀颜色层 预先设计的颜色； 而当电致变色层加上电压表现为有颜色时， 便可通过调整电 压值来调节透过率， 这样， PVD装饰镀颜色层便与电致变色层复合形成不同颜 色，从而实现多种颜色的转换甚至是彩色与彩色之间的转换； 另外，通过将 PVD 装饰镀颜色层设计成不同颜色， 便可实现多种颜色变化需求。  The principle of discoloration of the all-solid electrochromic composite device of the present invention is as follows: PVD decorative plating color layer is used as the ground color, that is, when the electrochromic layer is not applied with voltage to be transparent and colorless, the device presents a pre-designed color of the PVD decorative plating color layer. When the electrochromic layer is applied with a voltage and the color is expressed, the transmittance can be adjusted by adjusting the voltage value, so that the PVD decorative plating layer is combined with the electrochromic layer to form different colors, thereby realizing various kinds. Color conversion is even a conversion between color and color; in addition, by designing the PVD decorative color layer to a different color, a variety of color change requirements can be achieved.
本发明实施例第一方面提供的全固态电致变色复合器件， 包括现有五层膜 结构的全固态电致变色单元和固有颜色单元， 固有颜色单元包括 PVD装饰镀颜 色层和金属层， 可实现多种颜色的转换甚至从彩色到彩色的成熟工业应用变色； 本发明实施例第一方面提供的全固态电致变色复合器件可应用但不限定应用于 手机、 平板电脑等电子产品上的 logo部位， 后壳等相关部位。  The all-solid-state electrochromic composite device provided by the first aspect of the present invention includes an all-solid-state electrochromic unit and an intrinsic color unit of the existing five-layer film structure, and the intrinsic color unit includes a PVD decorative plating color layer and a metal layer. The color conversion of a plurality of colors is realized even in a mature industrial application from color to color. The all-solid-state electrochromic composite device provided by the first aspect of the present invention can be applied to, but not limited to, a logo applied to an electronic product such as a mobile phone or a tablet computer. Parts, rear shells and other related parts.
第二方面， 本发明实施例提供了一种全固态电致变色复合器件的制备方法， 包括以下步骤：  In a second aspect, an embodiment of the present invention provides a method for preparing an all-solid-state electrochromic composite device, including the following steps:
提供一基底；  Providing a substrate;
釆用 PVD沉积的方式， 先在所述基底上依次制备第一透明导电层、 电致变 色层、 离子导电层、 离子存储层和第二透明导电层； 再在所述第二透明导电层 上依次制备 PVD装饰镀颜色层和金属层， 得到全固态电致变色复合器件；  Preparing a first transparent conductive layer, an electrochromic layer, an ion conductive layer, an ion storage layer and a second transparent conductive layer on the substrate in a manner of PVD deposition; and then on the second transparent conductive layer Preparing a PVD decorative plating color layer and a metal layer in sequence to obtain an all-solid electrochromic composite device;
或釆用 PVD沉积的方式， 先在所述基底上依次制备金属层和 PVD装饰镀 颜色层，再在所述 PVD装饰镀颜色层上依次制备第二透明导电层、 离子存储层、 离子导电层、 电致变色层和第一透明导电层， 得到全固态电致变色复合器件。 优选地， 所述 PVD沉积的方式包括蒸发镀、 磁控溅射或离子镀。 Or sequentially using a PVD deposition method to sequentially prepare a metal layer and a PVD decorative plating color layer on the substrate, and then sequentially preparing a second transparent conductive layer and an ion storage layer on the PVD decorative plating color layer. The ion conductive layer, the electrochromic layer and the first transparent conductive layer obtain an all solid state electrochromic composite device. Preferably, the manner of depositing the PVD comprises evaporation plating, magnetron sputtering or ion plating.
优选地， 所述 PVD装饰镀颜色层含有金属元素， 为梯度膜层， 具体制备方 式为： 以金属单质或金属合金为靶材， 通入氩气、 氮气、 氧气、 曱烷和乙炔中 的一种或多种气体， 制备过程中调节通入的气体流量， 或同时调整功率、 电流、 负偏压和正偏压中的一种或多种参数， 最终形成一系列含金属元素和气体元素 的梯度膜层。  Preferably, the PVD decorative plating color layer contains a metal element and is a gradient film layer, and the specific preparation method is as follows: a metal element or a metal alloy is used as a target, and one of argon gas, nitrogen gas, oxygen gas, decane and acetylene is introduced. One or more gases, adjusting the flow of the incoming gas during the preparation, or simultaneously adjusting one or more of the power, current, negative bias, and positive bias to form a series of gradients containing metal and gas elements Membrane layer.
本发明实施例第二方面提供的一种全固态电致变色复合器件的制备方法，为 现有成熟工艺无机电致变色技术与 PVD装饰镀技术的有效结合， 工艺简单， 易 实现工业化生产， 且相对现有普通电致变色器件的制备成本增加不多， 易实现 商业化。  The preparation method of the all-solid-state electrochromic composite device provided by the second aspect of the present invention is an effective combination of the existing mature inorganic electrochromic technology and the PVD decorative plating technology, and the process is simple and easy to realize industrial production, and Compared with the existing conventional electrochromic devices, the preparation cost is not increased much, and it is easy to commercialize.
本发明实施例的优点将会在下面的说明书中部分阐明，一部分根据说明书是 显而易见的， 或者可以通过本发明实施例的实施而获知。 附图说明  The advantages of the embodiments of the present invention will be set forth in part in the description which follows. DRAWINGS
图 1是本发明实施例一制备的全固态电致变色复合器件结构示意图。 具体实施方式  1 is a schematic structural view of an all solid state electrochromic composite device prepared according to Embodiment 1 of the present invention. detailed description
以下所述是本发明实施例的优选实施方式， 应当指出， 对于本技术领域的 普通技术人员来说， 在不脱离本发明实施例原理的前提下， 还可以做出若干改 进和润饰， 这些改进和润饰也视为本发明实施例的保护范围。  The following are the preferred embodiments of the embodiments of the present invention, and it should be noted that those skilled in the art can make some improvements and refinements without departing from the principles of the embodiments of the present invention. And retouching is also considered to be the scope of protection of the embodiments of the present invention.
本发明实施例第一方面提供了一种全固态电致变色复合器件， 用以解决现 有技术中全固态电致变色器件可变颜色种类少， 只能实现从无色到蓝色的成熟 工业应用变色， 而不能实现多种颜色的转换， 以及从彩色到彩色的成熟工业应 用变色的问题。 The first aspect of the embodiments of the present invention provides an all-solid-state electrochromic composite device, which is used to solve the problem that the all-solid-state electrochromic device in the prior art has few variable color types, and can only realize the maturity from colorless to blue. Industrial applications are discolored, and it is not possible to achieve multiple color conversions, as well as the problem of discoloration from mature industrial applications from color to color.
第一方面， 本发明实施例提供了一种全固态电致变色复合器件， 包括基底， 电致变色单元和固有颜色单元， 所述电致变色单元包括依次层叠的第一透明导 电层、 电致变色层、 离子导电层、 离子存储层和第二透明导电层， 所述固有颜 色单元包括依次层叠的 PVD装饰镀颜色层和金属层， 所述 PVD装饰镀颜色层 与所述第二透明导电层层叠结合在一起；  In a first aspect, an embodiment of the present invention provides an all-solid-state electrochromic composite device comprising a substrate, an electrochromic unit and an intrinsic color unit, wherein the electrochromic unit comprises a first transparent conductive layer laminated in sequence, and an electro-induced a color changing layer, an ion conductive layer, an ion storage layer, and a second transparent conductive layer, the intrinsic color unit comprising a PVD decorative plating color layer and a metal layer sequentially stacked, the PVD decorative plating color layer and the second transparent conductive layer Laminated together;
所述第一透明导电层设置在所述基底上； 或者所述金属层设置在所述基底 上。  The first transparent conductive layer is disposed on the substrate; or the metal layer is disposed on the substrate.
与现有技术相比， 本发明全固态电致变色复合器件包括现有五层膜结构的 全固态电致变色单元和固有颜色单元， 其固有颜色单元包括依次层叠的 PVD装 饰镀颜色层和金属层。 该器件的变色原理为： PVD装饰镀颜色层作为底色， 即 当电致变色层未加电压时， 器件呈现 PVD装饰镀颜色层预先设计的颜色； 而当 电致变色层加上电压（电压必须加在第一透明导电层和第二透明导电层上）时， 便可通过调整电压值来调节透过率， 这样， PVD装饰镀颜色层便与电致变色层 复合形成不同颜色， 从而实现多种颜色的转换甚至是彩色与彩色之间的转换； 另夕卜，通过将 PVD装饰镀颜色层设计成不同颜色，便可实现多种颜色变化需求。 本发明将现有无机电致变色技术与 PVD装饰镀技术有效结合， 实现了全固态电 致变色器件从彩色到彩色的成熟工业应用变色。  Compared with the prior art, the all-solid electrochromic composite device of the present invention comprises an all-solid electrochromic unit and an intrinsic color unit of the existing five-layer film structure, and the intrinsic color unit comprises a PVD decorative plating layer and a metal layer which are sequentially laminated. Floor. The color change principle of the device is: PVD decorative plating color layer as the ground color, that is, when the electrochromic layer is not applied with voltage, the device presents a pre-designed color of the PVD decorative plating color layer; and when the electrochromic layer is applied with voltage (voltage) When it is necessary to add to the first transparent conductive layer and the second transparent conductive layer), the transmittance can be adjusted by adjusting the voltage value, so that the PVD decorative plating color layer is combined with the electrochromic layer to form different colors, thereby realizing The conversion of multiple colors is even a conversion between color and color; in addition, by designing the PVD decorative color layer to different colors, a variety of color change requirements can be realized. The invention effectively combines the existing inorganic electrochromic technology with the PVD decorative plating technology, and realizes the discoloration of the full-solid electrochromic device from color to color in mature industrial applications.
优选地， 所述 PVD装饰镀颜色层为梯度膜层， 所述 PVD装饰镀颜色层含 有金属元素。 梯度膜层是指 PVD装饰镀颜色层并非均一组成成分， 而是呈梯度 分布， 这样设置有利于光吸收和光反射， 得到良好的发光效果， 同时能降低膜 层应力， 防止使用过程中膜层开裂。 所述 PVD装饰镀颜色层的材质和厚度不作特殊限定， 可根据具体的颜色效 果进行调制， 为了满足良好的发光效果， 不同的颜色厚度设置不一样。 Preferably, the PVD decorative plating color layer is a gradient film layer, and the PVD decorative plating color layer contains a metal element. Gradient film layer means that the PVD decorative plating color layer is not uniform composition, but has a gradient distribution. This arrangement is beneficial to light absorption and light reflection, and has good luminescence effect. At the same time, it can reduce film stress and prevent film cracking during use. . The material and thickness of the PVD decorative plating color layer are not particularly limited, and may be modulated according to a specific color effect. In order to satisfy a good lighting effect, different color thickness settings are different.
PVD装饰镀颜色层具有良好的金属质感， 目前 PVD装饰镀技术良率较高的 有黑色、 灰色、 银白、 蓝色、 黄色等颜色， 还有由于设备等因素限制而良率较 低的颜色如紫色、玫瑰红、绿色等颜色。 所述 PVD装饰镀颜色层含有金属元素， 金属元素包括锆（Zr )、 钛（Ti )、 铬（Cr )等， PVD 装饰镀颜色层的材质通常 为上述金属元素的氧化物、 氮化物、 氮氧化物， 碳氧化物或碳化物等。  PVD decorative plating color layer has a good metal texture. At present, PVD decorative plating technology has high yields such as black, gray, silver, blue, yellow, etc., and colors with lower yield due to factors such as equipment and the like. Purple, rose red, green and other colors. The PVD decorative plating color layer contains a metal element, and the metal element includes zirconium (Zr), titanium (Ti), chromium (Cr), etc., and the material of the PVD decorative plating color layer is usually an oxide, a nitride, and a nitrogen of the above metal element. Oxide, carbon oxide or carbide.
优选地， 所述金属层包括下述中的任意一种或任意组合：  Preferably, the metal layer comprises any one or any combination of the following:
一层或多层的金属单质膜层；  One or more layers of metal elemental film;
两种或两种以上的金属形成的合金膜层；  An alloy film layer formed of two or more metals;
金属和气体形成的金属与金属化合物的混合膜层。  A mixed film of a metal and a metal compound formed of a metal and a gas.
金属层主要起增强颜色效果目的。  The metal layer is mainly used for the purpose of enhancing the color effect.
优选地， 所述金属层的厚度为 50 ~ 1000nm。  Preferably, the metal layer has a thickness of 50 to 1000 nm.
优选地， 所述全固态电致变色复合器件进一步包括设置在所述第二透明导 电层与所述 PVD装饰镀颜色层之间的透明绝缘膜。 所述透明绝缘膜的材质为现 有绝缘材料， 如氧化硅。  Preferably, the all solid state electrochromic composite device further comprises a transparent insulating film disposed between the second transparent conductive layer and the PVD decorative plating color layer. The transparent insulating film is made of an existing insulating material such as silicon oxide.
更优选地， 所述全固态电致变色复合器件进一步包括设置在所述透明绝缘 膜上的多层依次交替叠加的透明导电膜和透明绝缘膜。  More preferably, the all-solid-state electrochromic composite device further includes a plurality of layers of a transparent conductive film and a transparent insulating film which are alternately stacked in this order on the transparent insulating film.
所述透明绝缘膜用于隔离电致变色单元和固有颜色单元， 避免电致变色单 元加上电压时， 电流分流至固有颜色单元。 电流分流会使颜色变色时程度降低， 电致变色层实际承受电压不稳定影响变色稳定效果。  The transparent insulating film is used to isolate the electrochromic unit and the intrinsic color unit, and when the electrochromic unit is applied with a voltage, the current is shunted to the intrinsic color unit. The current shunt will reduce the degree of color discoloration, and the electrochromic layer actually withstands the voltage instability and affects the discoloration stability effect.
当第一透明导电层设置在基底上， 此时， 全固态电致变色复合器件顺置结 构， 包括依次设置在基底上的第一透明导电层、 电致变色层、 离子导电层、 离 子存储层、 第二透明导电层、 PVD装饰镀颜色层和金属层； 而当金属层设置在 基底上， 此时， 全固态电致变色复合器件倒置结构， 包括依次设置在基底上的 金属层、 PVD装饰镀颜色层、 第二透明导电层、 离子存储层、 离子导电层、 电 致变色层和第一透明导电层； 实际应用中， 可根据需要选择具体设置方式。 When the first transparent conductive layer is disposed on the substrate, at this time, the all-solid-state electrochromic composite device is disposed in a structure, including the first transparent conductive layer, the electrochromic layer, the ion conductive layer, and the separation layer sequentially disposed on the substrate. a sub-storage layer, a second transparent conductive layer, a PVD decorative plating color layer, and a metal layer; and when the metal layer is disposed on the substrate, at this time, the all-solid-state electrochromic composite device is inverted, including a metal layer sequentially disposed on the substrate The PVD decorative plating color layer, the second transparent conductive layer, the ion storage layer, the ion conductive layer, the electrochromic layer and the first transparent conductive layer; in practical applications, a specific setting manner can be selected according to requirements.
优选地，所述全固态电致变色复合器件进一步包括设置在所述第二透明导电 层与所述 PVD装饰镀颜色层之间的透明 UV漆层、 透明有机颜色膜层或透明无 机颜色膜层， 所述透明有机颜色膜层和透明无机颜色膜层中掺杂有色素或有色 离子。 所述有色离子为常见的有颜色离子， 如 Cu2+、 Fe3+等。 透明 UV漆层或透 明有机颜色膜层或透明无机颜色膜层的设置， 可以使全固态电致变色复合器件 实现固有颜色单元的双重颜色层调色， 从而获得更丰富的变色效果。 Preferably, the all-solid-state electrochromic composite device further comprises a transparent UV paint layer, a transparent organic color film layer or a transparent inorganic color film layer disposed between the second transparent conductive layer and the PVD decorative plating color layer. The transparent organic color film layer and the transparent inorganic color film layer are doped with a pigment or a colored ion. The colored ions are common colored ions such as Cu 2+ , Fe 3+ , and the like. The transparent UV paint layer or the transparent organic color film layer or the transparent inorganic color film layer can be arranged to enable the all-solid-state electrochromic composite device to realize the double color layer of the intrinsic color unit to obtain a richer color change effect.
优选地， 所述基底为透明或不透明基底， 所述透明基底为透明玻璃、 有机 透明材料或无机透明材料， 所述不透明基底为不透明玻璃、 塑料制品、 陶瓷、 蓝宝石或金属合金。 金属合金包括不锈钢等。  Preferably, the substrate is a transparent or opaque substrate, and the transparent substrate is a transparent glass, an organic transparent material or an inorganic transparent material, and the opaque substrate is an opaque glass, a plastic product, a ceramic, a sapphire or a metal alloy. Metal alloys include stainless steel and the like.
本发明对电致变色单元的各膜层材质和厚度不做限制， 现有材质均适用于 本发明， 厚度可以根据具体需要进行调整。 透明导电层材质可以为铟锡氧化物 ( ITO )、 辞铝氧化物 （ΑΖΟ )或石墨烯薄膜， 厚度为 20 ~ 500纳米， 电致变色 层材质可以为 W03， 厚度为 50 ~ 500纳米， 离子导电层材质可以为 LiTa03或 LiNb03， 厚度为 20 ~ 500纳米， 离子存储层材质可以为镍的氧化物或钒的氧化 物， 厚度为 50 ~ 500纳米， 透明导电层材质可以为铟锡氧化物 （ITO )、 辞铝氧 化物 （ΑΖΟ )或石墨烯薄膜， 厚度为 20 ~ 500纳米。 The invention does not limit the material and thickness of each film layer of the electrochromic unit, and the existing materials are all suitable for the invention, and the thickness can be adjusted according to specific needs. The material of the transparent conductive layer may be indium tin oxide (ITO), aluminum oxide (ΑΖΟ) or graphene film, the thickness is 20 ~ 500 nm, the electrochromic layer material may be W0 3 , the thickness is 50 ~ 500 nm, The ion conductive layer may be made of LiTa0 3 or LiNb0 3 and has a thickness of 20 to 500 nm. The ion storage layer may be an oxide of nickel or an oxide of vanadium, having a thickness of 50 to 500 nm, and the transparent conductive layer may be indium tin. An oxide (ITO), an aluminum oxide (ΑΖΟ) or a graphene film having a thickness of 20 to 500 nm.
本发明实施例第一方面提供的全固态电致变色复合器件， 包括现有五层膜 结构的全固态电致变色单元和固有颜色单元， 固有颜色单元包括 PVD装饰镀颜 色层和金属层， 可实现多种颜色的转换甚至从彩色到彩色的成熟工业应用变色； 本发明实施例第一方面提供的全固态电致变色复合器件可应用但不限定应用于 手机、 平板电脑等电子产品上的 logo部位， 后壳等相关部位。 The all-solid-state electrochromic composite device provided by the first aspect of the present invention includes an all-solid-state electrochromic unit and an intrinsic color unit of the existing five-layer film structure, and the intrinsic color unit includes a PVD decorative plating color layer and a metal layer. Achieve multi-color conversion and even discoloration from mature industrial applications from color to color; The all-solid-state electrochromic composite device provided by the first aspect of the present invention can be applied to, but not limited to, a logo portion, a rear shell, and the like on an electronic product such as a mobile phone or a tablet computer.
第二方面， 本发明实施例提供了一种全固态电致变色复合器件的制备方法， 包括以下步骤：  In a second aspect, an embodiment of the present invention provides a method for preparing an all-solid-state electrochromic composite device, including the following steps:
提供一基底；  Providing a substrate;
釆用 PVD沉积的方式， 先在所述基底上依次制备第一透明导电层、 电致变 色层、 离子导电层、 离子存储层和第二透明导电层； 再在所述第二透明导电层 上依次制备 PVD装饰镀颜色层和金属层， 得到全固态电致变色复合器件；  Preparing a first transparent conductive layer, an electrochromic layer, an ion conductive layer, an ion storage layer and a second transparent conductive layer on the substrate in a manner of PVD deposition; and then on the second transparent conductive layer Preparing a PVD decorative plating color layer and a metal layer in sequence to obtain an all-solid electrochromic composite device;
或釆用 PVD沉积的方式， 先在所述基底上依次制备金属层和 PVD装饰镀 颜色层，再在所述 PVD装饰镀颜色层上依次制备第二透明导电层、 离子存储层、 离子导电层、 电致变色层和第一透明导电层， 得到全固态电致变色复合器件。  Or, by means of PVD deposition, firstly preparing a metal layer and a PVD decorative plating color layer on the substrate, and then sequentially preparing a second transparent conductive layer, an ion storage layer, an ion conductive layer on the PVD decorative plating color layer. The electrochromic layer and the first transparent conductive layer obtain an all-solid electrochromic composite device.
所述 PVD沉积的方式包括蒸发镀、 磁控溅射或离子镀。  The manner in which the PVD is deposited includes evaporation plating, magnetron sputtering, or ion plating.
全固态电致变色复合器件的整个七层膜结构可以在同一炉中镀制， 如全部 在蒸发炉中制备， 或全部在磁控溅射炉中制备， 或在两者的复合炉中制备； 或 者在分开的炉中制备， 为提高效率， 节省成本， 七层膜结构尽量在同一炉中镀 制， 即直接蒸发镀七层， 或者直接磁控溅射连续炉镀七层膜结构。 在同一炉中 可以提高效率， 节省成本， 使成本比普通的五层电致变色结构提高不多。 所用 PVD沉积设备， 有膜厚测试***以及透过率测试***更佳， 这样可以更好地对 膜层和透过率在沉积时进行实时控制。  The entire seven-layer membrane structure of the all-solid electrochromic composite device can be plated in the same furnace, such as all in an evaporation furnace, or all in a magnetron sputtering furnace, or in a composite furnace of both; Or in a separate furnace, in order to improve efficiency and save cost, the seven-layer membrane structure is plated in the same furnace as much as possible, that is, direct evaporation of seven layers, or direct magnetron sputtering continuous furnace plating of seven-layer membrane structure. In the same furnace, efficiency can be improved, cost can be saved, and the cost can be improved less than the ordinary five-layer electrochromic structure. The PVD deposition equipment used, with a film thickness test system and a transmittance test system, is better for real-time control of film and transmittance during deposition.
优选地， 所述 PVD装饰镀颜色层含有金属元素， 为梯度膜层， 具体制备方 式为： 以金属单质或金属合金为靶材， 通入氩气、 氮气、 氧气、 曱烷和乙炔中 的一种或多种气体， 制备过程中调节通入的气体流量， 或同时调整功率、 电流、 负偏压和正偏压中的一种或多种参数， 最终形成一系列含金属元素和气体元素 的梯度膜层。 Preferably, the PVD decorative plating color layer contains a metal element and is a gradient film layer, and the specific preparation method is as follows: a metal element or a metal alloy is used as a target, and one of argon gas, nitrogen gas, oxygen gas, decane and acetylene is introduced. One or more gases, adjusting the flow of the incoming gas during the preparation process, or simultaneously adjusting one or more of the power, current, negative bias, and positive bias to form a series of metal-containing and gaseous elements Gradient film layer.
优选地， 所述金属层包括下述中的任意一种或任意组合：  Preferably, the metal layer comprises any one or any combination of the following:
一层或多层的金属单质膜层；  One or more layers of metal elemental film;
两种或两种以上的金属形成的合金膜层；  An alloy film layer formed of two or more metals;
金属和气体形成的金属与金属化合物的混合膜层。  A mixed film of a metal and a metal compound formed of a metal and a gas.
优选地， 金属层的厚度为 50 ~ 1000nm。  Preferably, the metal layer has a thickness of 50 to 1000 nm.
优选地， 所述全固态电致变色复合器件的制备方法进一步包括如下步骤： 在所述第二透明导电层与所述 PVD装饰镀颜色层之间制备透明绝缘膜。 所述透 明绝缘膜的材质为现有绝缘材料， 如氧化硅。  Preferably, the method for preparing the all-solid-state electrochromic composite device further comprises the steps of: preparing a transparent insulating film between the second transparent conductive layer and the PVD decorative plating color layer. The transparent insulating film is made of a conventional insulating material such as silicon oxide.
更优选地， 所述全固态电致变色复合器件的制备方法进一步包括在所述透 明绝缘膜上制备多层依次交替叠加的透明导电膜和透明绝缘膜。  More preferably, the method of producing the all-solid-state electrochromic composite device further comprises preparing a plurality of transparent conductive films and transparent insulating films which are alternately stacked in this order on the transparent insulating film.
优选地， 所述全固态电致变色复合器件的制备方法进一步包括在所述第二 透明导电层与所述 PVD装饰镀颜色层之间制备透明 UV漆层、 透明有机颜色膜 层或透明无机颜色膜层， 所述透明有机颜色膜层和透明无机颜色膜层中掺杂有 色素或有色离子。  Preferably, the method for preparing the all-solid-state electrochromic composite device further comprises preparing a transparent UV paint layer, a transparent organic color film layer or a transparent inorganic color between the second transparent conductive layer and the PVD decorative plating color layer. The film layer, the transparent organic color film layer and the transparent inorganic color film layer are doped with a pigment or a colored ion.
优选地， 将基底釆用气相沉积镀膜、 电化学镀膜、 化学镀膜、 阳极氧化、 微弧氧化、 热喷涂、 喷漆或形成有机物膜的方法进行表面预处理。 预处理后有 利于后续膜层的制备， 使结合更紧密。  Preferably, the substrate is subjected to surface pretreatment by vapor deposition coating, electrochemical coating, electroless plating, anodizing, micro-arc oxidation, thermal spraying, painting or forming an organic film. After pretreatment, it facilitates the preparation of subsequent layers to make the binding more compact.
其中， PVD沉积过程的具体参数设置根据膜层材质、 厚度等进行设定， 本 发明不作特殊限定。  The specific parameter setting of the PVD deposition process is set according to the material and thickness of the film layer, and is not particularly limited in the present invention.
本发明实施例第二方面提供的一种全固态电致变色复合器件的制备方法，为 现有成熟工艺无机电致变色技术与 PVD装饰镀技术的有效结合， 工艺简单， 易 实现工业化生产， 且相对现有普通电致变色器件的制备成本增加不多， 易实现 商业化。 The preparation method of the all-solid-state electrochromic composite device provided by the second aspect of the present invention is an effective combination of the existing mature inorganic electrochromic technology and the PVD decorative plating technology, and the process is simple and easy to realize industrial production, and Compared with the existing conventional electrochromic devices, the preparation cost is not increased much, and is easy to implement. commercialize.
综上，本发明实施例第一方面提供的全固态电致变色复合器件，将现有无机 电致变色技术与 PVD装饰镀技术有效结合， 可实现多种颜色的转换甚至从彩色 到彩色的成熟工业应用变色； 本发明实施例第一方面提供的全固态电致变色复 合器件可应用但不限定应用于手机、 平板电脑等电子产品上的 logo部位， 后壳 等相关部位。 本发明实施例第二方面提供的全固态电致变色复合器件的制备方 法， 为现有成熟工艺无机电致变色技术与 PVD装饰镀技术的有效结合， 工艺简 单， 易实现工业化生产， 且相对现有普通电致变色器件的制备成本增加不多， 易实现商业化。  In summary, the all-solid-state electrochromic composite device provided by the first aspect of the present invention effectively combines the existing inorganic electrochromic technology with the PVD decorative plating technology, and can realize conversion of multiple colors or even mature from color to color. Industrial Applicable Discoloration; The all-solid-state electrochromic composite device provided by the first aspect of the present invention can be applied to, but is not limited to, a logo portion, a rear shell, and the like on an electronic product such as a mobile phone or a tablet computer. The preparation method of the all-solid electrochromic composite device provided by the second aspect of the present invention is an effective combination of the existing mature inorganic electrochromic technology and the PVD decorative plating technology, the process is simple, the industrial production is easy, and the present invention is relatively The manufacturing cost of a conventional electrochromic device is not increased much, and it is easy to commercialize.
下面分多个实施例对本发明实施例进行进一步的说明。 本发明实施例不限 定于以下的具体实施例。 在不变主权利的范围内， 可以适当的进行变更实施。  The embodiments of the present invention are further described below in various embodiments. The embodiments of the present invention are not limited to the specific embodiments below. Changes can be implemented as appropriate within the scope of the invariable principal rights.
实施例一  Embodiment 1
一种全固态电致变色复合器件的制备方法， 包括以下步骤：  A method for preparing an all-solid-state electrochromic composite device, comprising the steps of:
( 1 )提供一玻璃基底， 透过率为 92%;  (1) providing a glass substrate with a transmittance of 92%;
( 2 )釆用蒸发镀的方式， 先对玻璃基底进行表面离子活化， 然后依次制备 第一透明导电层（ITO )、 电致变色层 （W03 )、 离子导电层（LiNb03 )、 离子存 储层 （NiOx )和第二透明导电层 （ITO )， 具体操作为： 将玻璃基底置于蒸发镀 设备中，在蒸发镀的不同坩埚中分别放入 ΙΤΟ蒸料粉末、 W03蒸料粉末、 LiNb03 蒸料粉末、 NiOx蒸料粉末、 ITO 蒸料粉末， 启动电子束蒸发， 依次制备电致变 色单元的各膜层； (2) using the method of evaporation plating, first performing surface ion activation on the glass substrate, and then sequentially preparing a first transparent conductive layer (ITO), an electrochromic layer (W0 3 ), an ion conductive layer (LiNb0 3 ), and an ion storage. The layer (NiO x ) and the second transparent conductive layer (ITO) are specifically operated as follows: the glass substrate is placed in an evaporation plating apparatus, and the steamed material powder, the W0 3 steam powder, and the LiNb0 3 steam powder, NiO x steam powder, ITO steam powder, start electron beam evaporation, and sequentially prepare each film layer of the electrochromic unit;
其中， 第一透明导电层 ITO为 80nm、 电致变色层 W03为 200nm、 离子导 电层 LiNb03为 180nm、离子存储层 NiO为 200nm，第二透明导电层 ITO为 80nm。 The first transparent conductive layer ITO is 80 nm, the electrochromic layer W0 3 is 200 nm, the ion conductive layer LiNb0 3 is 180 nm, the ion storage layer NiO is 200 nm, and the second transparent conductive layer ITO is 80 nm.
( 3 )再釆用磁控溅射的方式在第二透明导电层上依次制备 PVD装饰镀颜 色层和金属层， 得到全固态电致变色复合器件； (3) sequentially preparing PVD decorative coating on the second transparent conductive layer by magnetron sputtering a color layer and a metal layer to obtain an all-solid electrochromic composite device;
PVD 装饰镀颜色层和金属层的制备设备为中频磁控溅射设备， 设备直径 1200mm, 高 800mm， 靶材为纯 Ti靶， 通入气体为氩气、 氧气、 氮气， 工艺参 数为氩气 150sccm， 50%占空比、 50伏的负偏压， 靶功率 8KW， 上述参数保持 不变； 氧气开始流量 20sccm保持不变， 氮气开始流量 60sccm保持 3000秒后变 为 40sccm到 3600秒， 得到浅绿色的梯度膜层， 然后关掉氧气和氮气制备金属 Ti层 600秒， 金属 Ti层厚度为 400nm。  PVD decorative plating color layer and metal layer preparation equipment is medium frequency magnetron sputtering equipment, equipment diameter 1200mm, height 800mm, target is pure Ti target, the inlet gas is argon, oxygen, nitrogen, the process parameter is argon 150sccm 50% duty cycle, 50 volts negative bias, target power 8KW, the above parameters remain unchanged; oxygen starting flow rate 20sccm remains unchanged, nitrogen starts flow rate 60sccm for 3000 seconds and then becomes 40sccm to 3600 seconds, get light green The gradient film layer was then turned off by oxygen and nitrogen to prepare a metal Ti layer for 600 seconds, and the metal Ti layer was 400 nm thick.
图 1为实施例一制备的全固态电致变色复合器件结构示意图。 其中 10为透 明基底、 20为电致变色单元、 30为固有颜色单元， 电致变色单元 20包括依次 层叠设置的第一透明导电层 201、 电致变色层 202、 离子导电层 203、 离子存储 层 204和第二透明导电层 205，固有颜色单元 30包括 PVD装饰镀颜色层 301和 金属层 302。  1 is a schematic structural view of an all-solid electrochromic composite device prepared in the first embodiment. Wherein 10 is a transparent substrate, 20 is an electrochromic unit, 30 is an intrinsic color unit, and the electrochromic unit 20 includes a first transparent conductive layer 201, an electrochromic layer 202, an ion conductive layer 203, and an ion storage layer which are sequentially stacked. 204 and a second transparent conductive layer 205, the intrinsic color unit 30 includes a PVD decorative plating color layer 301 and a metal layer 302.
本实施例中， PVD 装饰镀颜色层为浅绿色， 电致变色层为蓝色材料， 通过 在两层透明导电层之间加上正负电压， 并调节电压值， 可以实现从浅绿色到蓝 色之间的变换， 并且由于蓝色透过率的变化， 浅绿色与浅蓝色的复合形成比较 特殊的颜色。 这些也可以通过调节 PVD装饰镀颜色层和电致变色层的厚度来进 行颜色的调整。 实施例二  In this embodiment, the PVD decorative plating color layer is light green, and the electrochromic layer is blue material. By adding positive and negative voltages between the two transparent conductive layers and adjusting the voltage value, the light green to blue color can be realized. The transformation between colors, and due to the change in blue transmittance, the combination of light green and light blue forms a special color. These can also be adjusted by adjusting the thickness of the PVD decorative plating layer and the electrochromic layer. Embodiment 2
一种全固态电致变色复合器件的制备方法， 包括以下步骤：  A method for preparing an all-solid-state electrochromic composite device, comprising the steps of:
( 1 )提供一玻璃基底， 透过率为 92%;  (1) providing a glass substrate with a transmittance of 92%;
( 2 )在 PVD (射频磁控溅射 +中频磁控溅射 )连续炉设备 ( in-line线） 中， 先在玻璃基底上依次制备第一透明导电层 （AZO )、 电致变色层 （W03 )、 离子 导电层（LiTa03 )、 离子存储层（VOx )和第二透明导电层（AZO )， 具体操作为： 将玻璃基底置于 PVD (射频磁控溅射 +中频磁控溅射）连续炉设备（in-line线） 中， 将不同靶材 Zn-Al靶材（ A1占 2%重量百分比）、 纯 W靶材、 纯 V靶材、 LiNb03靶材放入炉腔中，启动设备，依次制备电致变色单元的各膜层，其中 Zn-Al 靶材、 纯 W靶材和纯 V靶材用中频磁控溅射， LiNb03靶材用射频磁控溅射； 其中， 第一透明导电层 AZO为 60nm、 电致变色层 W03为 160nm、 离子导 电层 LiTa03为 70nm、离子存储层 ( 为 160nm，第二透明导电层 AZO为 60nm。 (2) In the PVD (RF magnetron sputtering + medium frequency magnetron sputtering) continuous furnace equipment (in-line line), the first transparent conductive layer (AZO) and the electrochromic layer are sequentially prepared on the glass substrate. W0 3 ), ion Conductive layer (LiTa0 3 ), ion storage layer (VO x ) and second transparent conductive layer (AZO), the specific operation is: placing the glass substrate in PVD (RF magnetron sputtering + medium frequency magnetron sputtering) continuous furnace equipment (in-line line), put different target Zn-Al target (A1 accounted for 2% by weight), pure W target, pure V target, LiNb0 3 target into the furnace cavity, start the device, and then Preparing each film layer of the electrochromic unit, wherein the Zn-Al target, the pure W target and the pure V target are sputtered by medium frequency magnetron, and the LiNb0 3 target is irradiated by radio frequency magnetron; wherein, the first transparent conductive The layer AZO was 60 nm, the electrochromic layer W0 3 was 160 nm, the ion conductive layer LiTa0 3 was 70 nm, the ion storage layer (160 nm, and the second transparent conductive layer AZO was 60 nm).
( 3 )再在步骤（2 ) 的设备中在第二透明导电层上依次制备 PVD装饰镀颜 色层和金属层， 得到全固态电致变色复合器件；  (3) sequentially preparing a PVD decorative plating color layer and a metal layer on the second transparent conductive layer in the apparatus of the step (2) to obtain an all-solid electrochromic composite device;
PVD装饰镀颜色层和金属层的具体制备为： 靶材为纯 Zr靶， 50%占空比、 100伏的负偏压， 靶功率 8KW， 通入气体为乙炔、 氩气， 工艺参数为： 先通入 氩气 150sccm,乙炔 200sccm， 100秒后逐渐以 5sccm的档次减少气体流量， 每次 减少维持 100s; 至 lOOsccm后以 20sccm档次减少气体流量， 每次减少量维持 80s; 直至关掉乙炔， 只有氩气来制备纯 Zr层， 维持 600秒， 得到黑色的膜层。  The PVD decorative plating color layer and metal layer are specifically prepared as follows: the target is a pure Zr target, 50% duty cycle, 100 volts negative bias, target power 8 KW, gas into acetylene, argon gas, process parameters are: First, argon gas 150sccm, acetylene 200sccm, 100 seconds later gradually reduce the gas flow rate in 5sccm grade, each time to maintain 100s; to 100sccm after 20sccm grade to reduce the gas flow, each reduction for 80s; until the acetylene is turned off, Only a argon gas was used to prepare a pure Zr layer, which was maintained for 600 seconds to obtain a black film layer.
本实施例中， PVD 装饰镀颜色层为黑色， 电致变色层为蓝色材料， 当电致 变色层未加电压， 即开反向电压时， 器件呈现黑色； 而当电致变色层加上电压， 即开正向电压时， 器件呈现墨蓝色效果； 而通过调整电压值来调节蓝色光透过 率， 便可得到黑色与浅蓝色形成的复合颜色效果。 实施例三  In this embodiment, the PVD decorative plating color layer is black, and the electrochromic layer is blue material. When the electrochromic layer is not applied with voltage, that is, when the reverse voltage is turned on, the device appears black; and when the electrochromic layer is added The voltage, that is, when the forward voltage is turned on, the device exhibits an ink blue effect; and by adjusting the voltage value to adjust the blue light transmittance, a composite color effect of black and light blue can be obtained. Embodiment 3
一种全固态电致变色复合器件的制备方法， 包括以下步骤：  A method for preparing an all-solid-state electrochromic composite device, comprising the steps of:
( 1 )提供一玻璃基底， 透过率为 92%;  (1) providing a glass substrate with a transmittance of 92%;
( 2 )在 PVD (射频磁控溅射 +中频磁控溅射）设备中， 先在玻璃基底上依 次制备第一透明导电层（AZO )、 电致变色层（W03 )、 离子导电层 （LiTa03 )、 离子存储层 （VOx )和第二透明导电层 （AZO )， 具体操作为： 将玻璃基底置于 PVD (射频磁控溅射 +中频磁控溅射设备中， 将不同靶材 Zn-Al靶材（ A1占 1% 重量百分比）、 纯 W靶材、 纯 V靶材、 LiNb03靶材放入炉腔中， 启动设备， 依 次制备电致变色单元的各膜层， 其中 Zn-Al靶材、 纯 W靶材和纯 V靶材用中频 磁控溅射， LiNb03靶材用射频磁控溅射； (2) In PVD (RF magnetron sputtering + medium frequency magnetron sputtering) equipment, first on the glass substrate Preparing a first transparent conductive layer (AZO), an electrochromic layer (W0 3 ), an ion conductive layer (LiTa0 3 ), an ion storage layer (VO x ), and a second transparent conductive layer (AZO ), respectively, as follows: The glass substrate is placed in PVD (RF magnetron sputtering + medium frequency magnetron sputtering equipment, different targets Zn-Al target (A1 accounts for 1% by weight), pure W target, pure V target, LiNb0 3 The target is placed in the furnace chamber, the equipment is started, and the layers of the electrochromic unit are sequentially prepared, wherein the Zn-Al target, the pure W target and the pure V target are subjected to medium frequency magnetron sputtering, and the LiNb0 3 target is used. RF magnetron sputtering;
其中， 第一透明导电层 AZO为 65nm、 电致变色层 W03为 170nm、 离子导 电层 LiTa03为 75nm、离子存储层 ( 为 170nm，第二透明导电层 AZO为 65nm。 The first transparent conductive layer AZO is 65 nm, the electrochromic layer W0 3 is 170 nm, the ion conductive layer LiTa0 3 is 75 nm, the ion storage layer (170 nm, and the second transparent conductive layer AZO is 65 nm).
( 3 )再在步骤（2 ) 的设备中在第二透明导电层上依次制备 PVD装饰镀颜 色层和金属层， 得到全固态电致变色复合器件；  (3) sequentially preparing a PVD decorative plating color layer and a metal layer on the second transparent conductive layer in the apparatus of the step (2) to obtain an all-solid electrochromic composite device;
PVD装饰镀颜色层和金属层的具体制备为： 靶材为纯 Ti靶， 通入气体为氮 气、 氩气， 工艺参数为： 负偏压 50伏， 20%占空比， 靶功率 8KW， 气体流量氮 气最开始为 220sccm，氩气为 150sccm,维持 200秒；后每次减少氮气流量 lOsccm 维持 100秒， 至 80sccm时每次减少氮气流量 20sccm维持 100s， 直至氮气为 0， 以纯氩气制备纯金属 Ti层维持 600秒，得到黄色的膜层，金属 Ti层厚度为 500nm。  The PVD decorative plating color layer and metal layer are specifically prepared as follows: The target is a pure Ti target, and the gas is nitrogen and argon. The process parameters are: negative bias 50 volts, 20% duty cycle, target power 8 KW, gas The flow rate of nitrogen is initially 220sccm, argon is 150sccm, and it is maintained for 200 seconds. After that, the nitrogen flow rate is reduced by 10sccm for 100 seconds. At 80sccm, the nitrogen flow rate is reduced by 20sccm for 100s until the nitrogen is 0. Pure pure metal is prepared by pure argon. The Ti layer was maintained for 600 seconds to obtain a yellow film layer having a thickness of 500 nm.
本实施例中， PVD 装饰镀颜色层为黄色， 电致变色层为蓝色材料， 当电致 变色层未加电压， 即开反向电压时， 器件呈现黄色； 而当电致变色层加上电压， 即开正向电压时， 器件呈现蓝色效果； 而通过调整电压值来调节蓝色光透过率， 便可得到黄色与浅蓝色形成的复合颜色效果。 实施例四  In this embodiment, the PVD decorative plating color layer is yellow, and the electrochromic layer is blue material. When the electrochromic layer is not applied with voltage, that is, when the reverse voltage is turned on, the device appears yellow; and when the electrochromic layer is added The voltage, that is, when the forward voltage is turned on, the device has a blue effect; and by adjusting the voltage value to adjust the blue light transmittance, a composite color effect of yellow and light blue can be obtained. Embodiment 4
一种全固态电致变色复合器件的制备方法， 包括以下步骤:  A method for preparing an all-solid-state electrochromic composite device, comprising the steps of:
( 1 )提供一氧化锆陶瓷基底； ( 2 )在 PVD (射频磁控溅射 +中频磁控溅射）设备中， 在陶瓷基底上依次 制备金属层和 PVD装饰镀颜色层； (1) providing a zirconia ceramic substrate; (2) in a PVD (RF magnetron sputtering + medium frequency magnetron sputtering) device, sequentially preparing a metal layer and a PVD decorative plating color layer on a ceramic substrate;
金属层和 PVD装饰镀颜色层的具体制备为： 靶材为纯 Ti靶，通入气体为氮 气、氩气，工艺参数为：首先将负偏压升至 800伏， 50%占空比，开氩气至 150sccm 进行离子清洗活化陶瓷表面， 期间可以开金属靶或者不开金属靶， 时间为 300 秒； 后将负偏压降至 100伏， 20%占空比， 逐渐加大氮气流量以 20sccm每次， 每次维持 150秒， 至 160sccm时以 lOsccm每次加大氮气流量， 每次维持 100秒 至 220sccm， 得到黄色膜层。  The specific preparation of the metal layer and the PVD decorative plating layer is as follows: The target is a pure Ti target, and the gas is nitrogen and argon. The process parameters are: firstly, the negative bias is raised to 800 volts, 50% duty cycle, Argon gas to 150sccm for ion cleaning to activate the ceramic surface, during which the metal target can be opened or the metal target can be opened for 300 seconds; then the negative bias voltage is reduced to 100 volts, 20% duty cycle, and the nitrogen flow rate is gradually increased to 20sccm. Each time, each time for 150 seconds, to 160 sccm, the nitrogen flow rate was increased every time by 10 sccm, and each time was maintained for 100 seconds to 220 sccm to obtain a yellow film layer.
( 2 )再在步骤（2 ) 的设备中在 PVD装饰镀颜色层上依次制备第二透明导 电层（AZO )、 离子存储层（VOx )、 离子导电层（LiTa03 )、 电致变色层（W03 ) 和第一透明导电层（AZO )， 得到全固态电致变色复合器件； 具体操作为： 将不 同靶材 Zn-Al靶材（ A1占 2%重量百分比）、 纯 W靶材、 纯 V靶材、 LiNb03靶 材放入炉腔中， 启动设备， 依次制备电致变色单元的各膜层， 其中 Zn-Al靶材、 纯 W靶材和纯 V靶材用中频磁控溅射， LiNb03靶材用射频磁控溅射； (2) sequentially preparing a second transparent conductive layer (AZO), an ion storage layer (VO x ), an ion conductive layer (LiTa0 3 ), an electrochromic layer on the PVD decorative plating color layer in the apparatus of the step (2). (W0 3 ) and the first transparent conductive layer (AZO), to obtain an all-solid electrochromic composite device; the specific operation is: different target Zn-Al target (A1 accounts for 2% by weight), pure W target, The pure V target and LiNb0 3 target are placed in the furnace chamber, the equipment is started, and the layers of the electrochromic unit are sequentially prepared, wherein the Zn-Al target, the pure W target and the pure V target are splattered by the intermediate frequency magnetron. Shot, LiNb0 3 target with RF magnetron sputtering;
其中， 第一透明导电层 AZO为 70nm、 电致变色层 W03为 160nm、 离子导 电层 LiTa03为 80nm、离子存储层 ( 为 160nm，第二透明导电层 AZO为 70nm。 The first transparent conductive layer AZO is 70 nm, the electrochromic layer W0 3 is 160 nm, the ion conductive layer LiTa0 3 is 80 nm, the ion storage layer (160 nm, and the second transparent conductive layer AZO is 70 nm).
本实施例中， PVD 装饰镀颜色层为黄色， 电致变色层为蓝色材料， 当电致 变色层未加电压， 即开反向电压时， 器件呈现黄色； 而当电致变色层加上电压， 即开正向电压时， 器件呈现蓝色效果； 而通过调整电压值来调节蓝色光透过率， 便可得到黄色与浅蓝色形成的复合颜色效果。 实施例五  In this embodiment, the PVD decorative plating color layer is yellow, and the electrochromic layer is blue material. When the electrochromic layer is not applied with voltage, that is, when the reverse voltage is turned on, the device appears yellow; and when the electrochromic layer is added The voltage, that is, when the forward voltage is turned on, the device has a blue effect; and by adjusting the voltage value to adjust the blue light transmittance, a composite color effect of yellow and light blue can be obtained. Embodiment 5
一种全固态电致变色复合器件的制备方法， 包括以下步骤: ( 1 )提供一玻璃基底， 透过率为 92%;； A method for preparing an all-solid-state electrochromic composite device, comprising the steps of: (1) providing a glass substrate having a transmittance of 92%;
( 2 )釆用蒸发镀的方式， 在玻璃基底上依次制备第一透明导电层 （ITO )、 电致变色层 （W03 )、 离子导电层 （LiNb03 )、 离子存储层 （NiOx )和第二透明 导电层 （ITO )， 具体操作为： 将玻璃基底置于蒸发镀设备中， 在蒸发镀的不同 坩埚中分别放入 ΙΤΟ蒸料粉末、 W03蒸料粉末、 LiNb03蒸料粉末、 NiOx蒸料粉 末、 ITO蒸料粉末， 启动蒸发镀设备， 依次制备电致变色单元的各膜层； (2) preparing a first transparent conductive layer (ITO), an electrochromic layer (W0 3 ), an ion conductive layer (LiNb0 3 ), an ion storage layer (NiO x ), and the like on the glass substrate by evaporation plating. The second transparent conductive layer (ITO) is specifically operated by: placing the glass substrate in an evaporation plating apparatus, and separately adding the steaming powder, the W0 3 steam powder, the LiNb0 3 steam powder, and the different materials in the evaporation plating. NiO x steam powder, ITO steam powder, start evaporation coating equipment, and sequentially prepare each film layer of the electrochromic unit;
其中， 第一透明导电层 ITO为 80nm、 电致变色层 W03为 200nm、 离子导 电层 LiNb03为 180nm、离子存储层 NiO为 200nm，第二透明导电层 ITO为 80nm。 The first transparent conductive layer ITO is 80 nm, the electrochromic layer W0 3 is 200 nm, the ion conductive layer LiNb0 3 is 180 nm, the ion storage layer NiO is 200 nm, and the second transparent conductive layer ITO is 80 nm.
( 3 )在第二透明导电层上釆用蒸发镀制备一层透明氧化硅绝缘层为 50nm， 再在氧化硅层上再制备一层氧化辞铝透明导电层 50nm， 再在氧化辞铝透明导电 层上再制备第二层透明氧化硅绝缘层 50nm;  (3) preparing a transparent silicon oxide insulating layer on the second transparent conductive layer by evaporation plating to 50 nm, and then preparing a transparent aluminum oxide transparent conductive layer 50 nm on the silicon oxide layer, and then transparently conducting the aluminum oxide in the aluminum oxide layer. Preparing a second transparent silicon oxide insulating layer 50 nm on the layer;
( 4 )再釆用磁控溅射的方式在第二透明氧化硅绝缘层上依次制备 PVD装 饰镀颜色层和金属层， 得到全固态电致变色复合器件；  (4) sequentially preparing a PVD decorative plating color layer and a metal layer on the second transparent silicon oxide insulating layer by magnetron sputtering to obtain an all-solid electrochromic composite device;
PVD 装饰镀颜色层和金属层的制备设备为中频磁控溅射设备， 设备直径 1200mm, 高 800mm， 靶材为纯 Ti-Al靶， 通入气体为氩气、 氧气、 氮气， 工艺 参数为氩气 150sccm， 50%占空比、 50伏的负偏压， 靶功率 8KW， 上述参数保 持不变； 氧气开始流量 20sccm保持不变， 氮气开始流量 60sccm保持 3000秒后 变为 40sccm到 3600秒， 得到浅绿色的梯度膜层， 然后关掉氧气和氮气制备金 属 Ti-Al层 600秒， 金属 Ti-Al层厚度为 450nm。  PVD decorative plating color layer and metal layer preparation equipment is medium frequency magnetron sputtering equipment, equipment diameter 1200mm, height 800mm, target is pure Ti-Al target, the inlet gas is argon, oxygen, nitrogen, the process parameter is argon Gas 150sccm, 50% duty cycle, 50 volts negative bias, target power 8KW, the above parameters remain unchanged; oxygen starting flow rate 20sccm remains unchanged, nitrogen starts flow rate 60sccm for 3000 seconds and then becomes 40sccm to 3600 seconds, get A light green gradient film layer, then oxygen and nitrogen were turned off to prepare a metal Ti-Al layer for 600 seconds, and the metal Ti-Al layer thickness was 450 nm.
本实施例中， PVD 装饰镀颜色层为淡绿色， 电致变色层为蓝色材料， 通过 在两层透明导电层之间加上正负电压， 并调节电压值， 可以实现从浅绿色到蓝 色之间的变换， 并且由于蓝色透过率的变化， 淡绿色与浅蓝色的复合形成比较 特殊的颜色。 这些也可以通过调节 PVD装饰镀颜色层和电致变色层的厚度来进 行颜色的调整。 In this embodiment, the PVD decorative plating color layer is light green, and the electrochromic layer is blue material. By adding positive and negative voltages between the two transparent conductive layers and adjusting the voltage value, the light green to blue color can be realized. The transformation between colors, and due to the change in blue transmittance, the combination of light green and light blue forms a special color. These can also be adjusted by adjusting the thickness of the PVD decorative plating layer and the electrochromic layer. Line color adjustment.
本领域普通技术人员可以理解实现上述实施例方法中的全部或部分流程，是 可以通过计算机程序来指令相关的硬件来完成， 所述的程序可存储于一计算机 可读取存储介质中， 该程序在执行时， 可包括如上述各方法的实施例的流程。 其中， 所述的存储介质可为磁碟、 光盘、 只读存储记忆体（ Read-Only Memory， ROM )或随机存储记忆体 ( Random Access Memory, RAM )等。  A person skilled in the art can understand that all or part of the process of implementing the above embodiment method can be completed by a computer program to instruct related hardware, and the program can be stored in a computer readable storage medium, the program In execution, the flow of an embodiment of the methods as described above may be included. The storage medium may be a magnetic disk, an optical disk, a read-only memory (ROM), or a random access memory (RAM).

Claims

权 利 要 求 Rights request
1、 一种全固态电致变色复合器件， 其特征在于， 包括基底， 电致变色单元 和固有颜色单元， 所述电致变色单元包括依次层叠的第一透明导电层、 电致变 色层、 离子导电层、 离子存储层和第二透明导电层， 所述固有颜色单元包括依 次层叠的 PVD装饰镀颜色层和金属层， 所述 PVD装饰镀颜色层与所述第二透 明导电层层叠结合在一起； 1. An all-solid-state electrochromic composite device, characterized in that it includes a substrate, an electrochromic unit and an inherent color unit, and the electrochromic unit includes a first transparent conductive layer, an electrochromic layer, and an ion layer laminated in sequence. A conductive layer, an ion storage layer and a second transparent conductive layer. The inherent color unit includes a PVD decorative color plating layer and a metal layer stacked in sequence. The PVD decorative color plating layer and the second transparent conductive layer are stacked together. ;
所述第一透明导电层设置在所述基底上； 或者所述金属层设置在所述基底 上。 The first transparent conductive layer is provided on the substrate; or the metal layer is provided on the substrate.
2、 如权利要求 1所述的全固态电致变色复合器件， 其特征在于， 所述 PVD 装饰镀颜色层为梯度膜层， 所述 PVD装饰镀颜色层含有金属元素。 2. The all-solid-state electrochromic composite device according to claim 1, wherein the PVD decorative color plating layer is a gradient film layer, and the PVD decorative color plating layer contains metal elements.
3、 如权利要求 1所述的全固态电致变色复合器件， 其特征在于， 所述金属 层包括下述中的任意一种或任意组合： 3. The all-solid-state electrochromic composite device according to claim 1, wherein the metal layer includes any one or any combination of the following:
一层或多层的金属单质膜层； One or more layers of metal elemental films;
两种或两种以上的金属形成的合金膜层； An alloy film formed of two or more metals;
金属和气体形成的金属与金属化合物的混合膜层。 A mixed film of metal and metal compounds formed by metal and gas.
4、 如权利要求 1所述的全固态电致变色复合器件， 其特征在于， 所述金属 层的厚度为 50 ~ 1000nm。 4. The all-solid-state electrochromic composite device according to claim 1, wherein the thickness of the metal layer is 50 to 1000 nm.
5、 如权利要求 1所述的全固态电致变色复合器件， 其特征在于， 进一步包 括设置在所述第二透明导电层与所述 PVD装饰镀颜色层之间的透明绝缘膜。 5. The all-solid-state electrochromic composite device according to claim 1, further comprising a transparent insulating film disposed between the second transparent conductive layer and the PVD decorative color plating layer.
6、 如权利要求 1所述的全固态电致变色复合器件， 其特征在于， 进一步包 括设置在所述第二透明导电层与所述 PVD装饰镀颜色层之间的透明 UV漆层、 透明有机颜色膜层或透明无机颜色膜层， 所述透明有机颜色膜层和所述透明无 机颜色膜层中掺杂有色素或有色离子。 6. The all-solid-state electrochromic composite device according to claim 1, further comprising a transparent UV paint layer disposed between the second transparent conductive layer and the PVD decorative color plating layer, A transparent organic color film layer or a transparent inorganic color film layer, the transparent organic color film layer and the transparent inorganic color film layer are doped with pigments or colored ions.
7、 如权利要求 1所述的全固态电致变色复合器件， 其特征在于， 所述基底 为透明或不透明基底， 所述透明基底为透明玻璃、 有机透明材料或无机透明材 料， 所述不透明基底为不透明玻璃、 塑料制品、 陶瓷、 蓝宝石或金属合金。 7. The all-solid-state electrochromic composite device according to claim 1, wherein the substrate is a transparent or opaque substrate, the transparent substrate is transparent glass, an organic transparent material or an inorganic transparent material, and the opaque substrate Available in opaque glass, plastic, ceramic, sapphire or metal alloys.
8、一种全固态电致变色复合器件的制备方法， 其特征在于， 包括以下步骤： 提供一基底； 8. A method for preparing an all-solid-state electrochromic composite device, which is characterized in that it includes the following steps: providing a substrate;
釆用 PVD沉积的方式， 先在所述基底上依次制备第一透明导电层、 电致变 色层、 离子导电层、 离子存储层和第二透明导电层； 再在所述第二透明导电层 上依次制备 PVD装饰镀颜色层和金属层， 得到全固态电致变色复合器件； Using PVD deposition, firstly prepare a first transparent conductive layer, an electrochromic layer, an ion conductive layer, an ion storage layer and a second transparent conductive layer on the substrate in sequence; and then on the second transparent conductive layer Prepare the PVD decorative color coating layer and the metal layer in sequence to obtain an all-solid-state electrochromic composite device;
或釆用 PVD沉积的方式， 先在所述基底上依次制备金属层和 PVD装饰镀 颜色层，再在所述 PVD装饰镀颜色层上依次制备第二透明导电层、 离子存储层、 离子导电层、 电致变色层和第一透明导电层， 得到全固态电致变色复合器件。 Or adopt the PVD deposition method, first prepare a metal layer and a PVD decorative color plating layer on the substrate in sequence, and then sequentially prepare a second transparent conductive layer, an ion storage layer, and an ion conductive layer on the PVD decorative plating color layer. , electrochromic layer and first transparent conductive layer to obtain an all-solid electrochromic composite device.
9、如权利要求 8所述的全固态电致变色复合器件的制备方法，其特征在于， 所述 PVD沉积的方式包括蒸发镀、 磁控溅射或离子镀。 9. The method for preparing an all-solid-state electrochromic composite device according to claim 8, wherein the PVD deposition method includes evaporation plating, magnetron sputtering or ion plating.
10、 如权利要求 8 所述的全固态电致变色复合器件的制备方法， 其特征在 于， 所述 PVD装饰镀颜色层含有金属元素， 为梯度膜层， 具体制备方式为： 以 金属单质或金属合金为靶材， 通入氩气、 氮气、 氧气、 曱烷和乙炔中的一种或 多种气体， 制备过程中调节通入的气体流量， 或同时调整功率、 电流、 负偏压 和正偏压中的一种或多种参数， 最终形成一系列含金属元素和气体元素的梯度 膜层。 10. The preparation method of an all-solid-state electrochromic composite device as claimed in claim 8, characterized in that the PVD decorative color plating layer contains metal elements and is a gradient film layer. The specific preparation method is: using metal element or metal The alloy is used as the target material, and one or more gases from argon, nitrogen, oxygen, methane and acetylene are introduced. During the preparation process, the gas flow rate is adjusted, or the power, current, negative bias voltage and positive bias voltage are adjusted simultaneously. One or more parameters in the film ultimately form a series of gradient film layers containing metal elements and gas elements.
PCT/CN2014/074989 2013-09-05 2014-04-09 All-solid-state electrochromic composite device and manufacturing method therefor WO2015032200A1 (en)

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