CN115195226A - Transparent electric heating composite film and preparation method thereof - Google Patents

Transparent electric heating composite film and preparation method thereof Download PDF

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Publication number
CN115195226A
CN115195226A CN202210597030.XA CN202210597030A CN115195226A CN 115195226 A CN115195226 A CN 115195226A CN 202210597030 A CN202210597030 A CN 202210597030A CN 115195226 A CN115195226 A CN 115195226A
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layer
film
semiconductor layer
dielectric layer
metal grid
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吕建国
陆杨丹
赵振云
叶志镇
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Zhejiang Zinc Core Optoelectronics Technology Co ltd
Wenzhou Research Institute Of Zhejiang University
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Zhejiang Zinc Core Optoelectronics Technology Co ltd
Wenzhou Research Institute Of Zhejiang University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B32B27/365—Layered products comprising a layer of synthetic resin comprising polyesters comprising polycarbonates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B32B5/028—Net structure, e.g. spaced apart filaments bonded at the crossing points
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • B32B9/005—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising one layer of ceramic material, e.g. porcelain, ceramic tile
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • B32B9/04—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • B32B9/04—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B9/045—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • B32B9/04—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B9/047—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material made of fibres or filaments
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B3/00—Ohmic-resistance heating
    • H05B3/20—Heating elements having extended surface area substantially in a two-dimensional plane, e.g. plate-heater
    • H05B3/34—Heating elements having extended surface area substantially in a two-dimensional plane, e.g. plate-heater flexible, e.g. heating nets or webs
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B3/00—Ohmic-resistance heating
    • H05B3/84—Heating arrangements specially adapted for transparent or reflecting areas, e.g. for demisting or de-icing windows, mirrors or vehicle windshields
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/10—Inorganic fibres
    • B32B2262/103—Metal fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B32B2307/204—Di-electric
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/412—Transparent
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
    • Y02B30/00—Energy efficient heating, ventilation or air conditioning [HVAC]

Abstract

The invention discloses a transparent electric heating composite film, which comprises a back dielectric layer, a substrate layer, a bottom dielectric layer, a first semiconductor layer, a middle metal grid layer, a second semiconductor layer and a top dielectric layer from bottom to top; each layer is transparent in a visible light region;the first semiconductor layer, the middle metal grid layer and the second semiconductor layer are active thin film layers; the middle metal grid layer is formed by connecting metal wires in a criss-cross manner. The back dielectric layer is Si 3 N 4 A film, wherein the bottom dielectric layer is an oxide taking Si as a main body; the first semiconductor layer is a doped ZnSiO film; the middle metal grid layer is an alloy film containing Zn; the second semiconductor layer is a doped ZnO film, and the top dielectric layer is an aluminum oxide film. The flexible transparent electric heating composite film provided by the invention can simultaneously meet the comprehensive performance requirements of transparency, conductivity, flexibility, controllable heating and the like, realizes quick and stable electric heating response, has good photoelectric performance and stable environment, and has wide application prospect in the field of transparent electronics.

Description

Transparent electric heating composite film and preparation method thereof
Technical Field
The invention relates to an electric heating film, in particular to a transparent flexible electric heating composite film and a preparation method thereof.
Background
The transparent conductive film can generate heat after being electrified due to high conductivity, can be applied to windshields of vehicles such as automobiles, trains, airplanes and the like, antifogging camera lenses, glasses with special purposes and glass covers of instrument windows, can play a role in heat insulation and protection, and can remove frost after the film is electrified and heated. The transparent conductive film based on the semiconductor material can generate a heat effect after being electrified, and can be widely used as a transparent heating element to prevent the formation of mist; in addition, the material can also be used as a defrosting and antifogging material for a refrigerator window and door; the application prospect on the automobile windshield is particularly wide. Generally, under the same heating voltage, the lower the film resistance, the higher the heating power, and the better the defogging and defrosting effects.
At present, people develop various electric heating films which respectively have different characteristics of high heating temperature, transparency, electric conduction or flexibility and the like. Among them, the flexible transparent electric heating film has a large application market such as: the adhesive film can be used for various scenes such as door and window glass, vehicle windshields, instrument windows, aerospace vehicles and the like; and can also be used in the fields of various portable and wearable products and the like. However, the flexible transparent electric heating film needs to have the following characteristics at the same time: first, the transparent, visible light region transmittance is above 85%; secondly, the conductive film is conductive, and the square resistivity is lower than 10 ohm/sq; thirdly, the flexible and transparent conductive film can be deposited on a common flexible organic polymer substrate, and the deposited film has high quality and good bending or bending stability; fourthly, the electric heating temperature is controllable, and the stable and controllable electric heating temperature is related to the resistivity of the electric heating film and the composite structure of the film. In the current products, the four requirements cannot be met at the same time.
For flexible transparent electrically heated films, the main difficulties are: (1) If the composite film has high transmittance, the thickness is required to be very thin and no metal layer is provided, but if the requirements are met, the resistivity is very high, and the transparency and the conductivity are contradictory, so that the coordination and consideration are very difficult; (2) The flexible electric heating film usually takes an organic polymer as a substrate, and most organic polymers (such as PET, PC and the like) are resistant to the temperature generally lower than 150 ℃, so that the electric heating film is required to grow at a low temperature, even at room temperature, but the film grown at the low temperature is usually not high in quality, particularly the adhesion with the substrate is not good, and the bending or bending stability is not high; (3) Since the coordination of transparency and conductivity is difficult, a high-quality thin film is difficult to grow on an organic polymer substrate at room temperature, and thus a flexible transparent electric heating film is difficult to realize stable and controllable electric heating performance.
Aiming at the problems, the invention designs a flexible transparent electric heating composite film, which adopts the layout of a metal grid middle layer and a multilayer composite film structure, simultaneously realizes the performances of transparency, electric conduction, flexibility, controllable electric heating and the like, and provides a preparation scheme of the product.
Disclosure of Invention
A transparent electric heating composite film is sequentially provided with a back dielectric layer, a substrate layer, a bottom dielectric layer, a first semiconductor layer, a middle metal grid layer, a second semiconductor layer and a top dielectric layer from bottom to top; the first semiconductor layer, the middle metal grid layer and the second semiconductor layer are active thin film layers.
Each layer is made of a material transparent in a visible light region, wherein the substrateThe layer is a flexible organic polymer, preferably PC, PEN, PI or PET; the back dielectric layer is Si 3 N 4 A film; the bottom dielectric layer is a chemically stable Si-based oxide, preferably N-lightly doped SiO 2 (ii) a The first semiconductor layer is a ZnSiO film doped with M element, wherein the atomic percentage Si (Zn + Si) is 7 to 10 at.%, and the atomic percentage M (Zn + Si + M) is 1 to 5 at.%; the middle metal grid layer is an alloy film containing Zn, and comprises a Zn-Ag alloy, a Zn-Cu alloy and a Zn-Al alloy, wherein the Zn content is not less than 2 at%; the second semiconductor layer is a ZnO film doped with M element, wherein the atomic percentage M (Zn + M) is 1 to 5 at.%; the top dielectric layer is an Al-based oxide with certain hardness, preferably N-micro-doped Al 2 O 3 . Wherein, M element is B, al, ga, in, preferably Al; and the M elements adopted by the first semiconductor layer and the second semiconductor layer are the same.
The intermediate metallic mesh layer is preferably a Zn-Al alloy with a Zn content not less than 2 at.% and not more than 98 at.%.
The middle metal grid layer is an interconnected metal network which is fully distributed on the whole first semiconductor layer plane, the metal network is formed by connecting metal wires in a criss-cross mode, the metal network is interconnected and communicated with each other, the wire breakage phenomenon does not exist, and the metal network patterns are distributed on the whole first semiconductor layer plane in a balanced mode; the line width of the metal grid is 1-20 mu m, and the area of the metal grid is 5-10% of the area of the substrate layer; the metal network can be any interconnected pattern combination, preferably regular polygons including squares, regular triangles and regular hexagons, and more preferably regular hexagons.
The thickness of each layer of material is as follows: the thickness of the substrate layer is determined according to actual requirements; 30 to 40nm of a back dielectric layer; the bottom dielectric layer is 20-30 nm; the first semiconductor layer is 30-60 nm; the middle metal grid layer is 30-100 nm; the second semiconductor layer is 30-60 nm; the top dielectric layer is 20-30 nm.
The preparation method of the flexible transparent heating film comprises the following steps: except the substrate layer, all the layers of films are prepared by a magnetron sputtering method, and in the growth process of the films, the growth atmosphere is plasma atmosphere containing argon (Ar); during the growth process, theIn the ultraviolet enhancement mode, the substrate is irradiated by 254 nm ultraviolet light, and the power of an ultraviolet light source is 120W. Firstly, carrying out double-sided bombardment on a substrate layer by adopting Ar plasma so as to form surfaces with certain roughness on both sides of the substrate layer; si is used for growing the back dielectric layer 3 N 4 Ceramic target material, ar plasma atmosphere; when the bottom dielectric layer film grows, siO is adopted 2 Ceramic target material, ar-NH 3 A plasma atmosphere; when the first semiconductor layer film grows, znSiO ceramic target material containing M element, ar-O 2 A plasma atmosphere; when the intermediate metal grid layer film grows, a metal target material and Ar plasma atmosphere are adopted; when the second semiconductor layer film grows, znO ceramic target material containing M element, ar-O 2 A plasma atmosphere; when growing the top dielectric layer film, al is adopted 2 O 3 Ceramic target material, ar-N 2 O plasma atmosphere. After all the layers of films grow, carrying out infrared radiation annealing treatment, irradiating the sample by adopting medium wave infrared rays with wave bands of 2 to 15 mu m, wherein the power density of infrared heating is 1 to 5W/cm 2 The irradiation time is 10 to 60min.
The grid structure of the intermediate metal grid layer is formed by a photoetching method or a mask plate method.
The flexible transparent heating film formed by the method has the following properties: the average transmittance in a visible light region is more than 85 percent, the square resistance is less than 10 ohm/sq, and the transparent and conductive properties are achieved; the temperature can be controllably raised to 50-150 ℃ within 40-80 s under the voltage of 2-5V, and is stabilized at the temperature, and the electric heating is controllable; 3000 circles of cycle test is carried out, the change rate of the electric heating performance is not more than 1 percent, and the stability is high; when the curvature radius is 1 cm, the change rate of the electric heating performance is not more than 3 percent, the bending is carried out for 1000 times according to the curvature radius, the change rate of the electric heating performance is not more than 5 percent, and the electric heating device has good flexibility and good bending stability; two similar samples are stacked together face to face, after the samples are rubbed back and forth for 1000 times under the pressure of 10N, the change rate of the electric heating performance is not more than 0.5 percent, and the composite film has high quality, good adhesive force and wear resistance.
The flexible transparent electric heating composite film provided by the invention adopts a metal grid structure, the transmittance can be regulated and controlled through the transverse line width, and the conductivity (resistivity) can be regulated and controlled through the longitudinal thickness, so that the independent regulation of the transmittance and the conductivity is realized, and the excellent comprehensive performance is achieved. Furthermore, a first semiconductor layer and a second semiconductor layer are added, and the first semiconductor layer, the middle metal grid layer and the second semiconductor layer are jointly used as an active thin film layer of the electric heating composite film, so that more coordinated optimization and regulation and control can be performed on the photoelectric characteristics of the flexible transparent electric heating composite film; more importantly, the middle metal grid layer in the active thin film layer is of an interconnected and communicated bent network structure, has good tensile and compressive properties, can effectively ensure that the metal networks are still communicated with each other and cannot be disconnected when being bent or bent, and can ensure that the electric heating composite film still maintains basically unchanged electric conduction properties under the deformation condition by the aid of the coordination effect of the first semiconductor layer and the second semiconductor layer. In addition, the second semiconductor layer and the top dielectric layer play double roles, and one function is used as a double-layer antireflection film, so that the antireflection effect is more easily realized, and the visible light transmittance is increased; and secondly, the second semiconductor layer can internally protect the middle metal grid layer from being influenced by oxidation, the top dielectric layer can play a role in passivation protection, and the top dielectric layer has certain hardness and therefore has a wear-resisting characteristic. In practical application, the back dielectric layer and the bottom dielectric layer play an important role, and the back dielectric layer and the bottom dielectric layer are compact amorphous films, so that moisture and gas molecules in the environment can be effectively isolated from entering an active thin film layer of the electric heating composite film through an organic polymer, and a good protection effect is achieved. The substrate is bombarded by Ar plasma on two sides, the surfaces with certain roughness are formed on two sides of the substrate, the adhesion between the back dielectric layer and the substrate layer and the adhesion between the bottom dielectric layer and the substrate layer can be effectively and obviously improved, and the flexible transparent electric heating composite film still has firm binding force with the substrate under the working condition of bending or bending. The measures play a role together, and the flexible transparent electric heating composite film provided by the invention has good electric heating characteristics, performance stability and environmental weather resistance.
In the flexible transparent electric heating composite film, the middle metal grid layer is preferably Zn-Al alloy, the first semiconductor layer is a ZnSiO film, the second semiconductor layer is a ZnO film, and the Zn element, the ZnSiO film and the ZnO film all contain Zn elements, so that the combination and interface matching among the three layers of films are facilitated, and the stability of the active thin film layer can be improved. Furthermore, each layer of film is selected from the same elements as possible and gradually transited, for example, the preferable material system is: si 3 N 4 Back dielectric layer, substrate layer, siO 2 An N bottom dielectric layer, a ZnSiO Al first semiconductor layer, a Zn-Al intermediate metal grid layer, a ZnO Al second semiconductor layer, and Al 2 O 3 The gradual transition between each element of the N top dielectric layer is beneficial to the combination and matching at the interface, thereby improving the overall performance.
In the invention, the metal alloy containing Zn is adopted, the content of Zn in the metal layer can be utilized to more effectively regulate and control the conductivity (resistivity) of the active thin film layer, the bonding force and cohesion of the active thin film layer are increased, and the saturation temperature of the electric heating composite film is further influenced.
The parameters of each layer of film and material of the flexible transparent electric heating composite film disclosed by the invention are carefully designed and optimized, and the film and the material are an organic whole and cannot be split; the corresponding preparation method and process parameters are also carefully designed and optimized, and an organic integral process is also adopted, and the cracking cannot be realized. The structure and the preparation method of the product correspond to each other and are mutually adaptive, and the product is also an organic whole and cannot be seen as a crack.
The above summary is the core summary of the present invention, but the present invention is not limited to the above summary, and any result obtained by using similar ideas and schemes of the present invention is within the protection scope of the present invention.
The invention has the advantages that:
(1) Except the middle metal grid layer, all the other layers on the front surface of the substrate layer are made of oxide-based thin film materials, are easy to grow at room temperature, are compatible with an organic polymer substrate, are favorable for interface matching and physicochemical property matching of the thin films of all the layers, are favorable for matching the thin film layer and the substrate, and enhance the adhesive force.
(2) The ultraviolet enhancement mode is adopted in the growth process, so that the activity of deposited atoms can be improved under the condition of not causing obvious temperature rise, the migration and the diffusion of the deposited atoms to lattice positions can be promoted, the defect state is reduced, and the quality of a deposited film is improved.
(3) Adopt infrared heating mode to carry out accurate rapid thermal treatment, be favorable to carrying out thermal treatment to the product on the whole, through control infrared heating parameter, make its temperature rise effectively control, can alleviate the stress in each layer film again simultaneously, reinforcing interface matching characteristic promotes the wholeness ability of electrical heating membrane.
(4) The preparation scheme provided by the invention can be completed at room temperature, meets the low-temperature processing requirements of flexible transparent electronic products, is suitable for organic polymer substrates, can be suitable for various hard substrates, is compatible with semiconductor processes, flexible device processes and the like, and can greatly expand the application range of the flexible transparent electronic products.
(5) The flexible transparent electric heating composite film provided by the invention can simultaneously meet the comprehensive performance requirements of transparency, conductivity, flexibility, controllable heating and the like, realizes quick, uniform and stable electric heating response, has good photoelectric performance and stable environment, and has wide application prospect in the field of transparent electronics.
(6) The product provided by the invention has the comprehensive effects of transparency, conductivity, heating and the like, is friction-resistant, heat-resistant and oxidation-resistant, can be wound, is light in weight, small in size, not easy to break, low in cost and convenient to transport, and has universality in practical application scenes.
(7) The preparation method provided by the invention has the advantages of simple process, high equipment industrialization degree, easy operation and large-area production, high preparation speed and efficiency, growth at room temperature, process time saving and preparation energy consumption saving, and large-scale application and industrialization realization.
Drawings
Fig. 1 is a schematic structural diagram of a transparent electrically heated composite film according to embodiments of the present invention.
Wherein 1 is a back dielectric layer, 2 is a substrate layer, 3 is a bottom dielectric layer, 4 is a first semiconductor layer, 5 is an intermediate metal grid layer, 6 is a second semiconductor layer, and 7 is a top dielectric layer.
Fig. 2 is a schematic diagram of an irregular intermediate metal mesh layer for interconnection.
Fig. 3 is a schematic diagram of a regular triangle, a regular quadrangle and a regular hexagon of the metal mesh.
Fig. 4 is a schematic perspective view of a structure of the transparent electrically heated composite film of example 1.
Fig. 5 is an optical photograph of the flexible transparent electrically heated composite film obtained in example 1.
FIG. 6 is an optical transmission spectrum of the flexible transparent electrically heated composite film prepared in example 1.
Fig. 7 is an electrical heating graph of the flexible transparent electrical heating composite film prepared in example 1.
Detailed Description
The invention will be further explained and explained with reference to the drawings and the embodiments.
Fig. 1 is a schematic structural diagram of a transparent electrical heating composite film manufactured according to embodiments of the present invention, which includes, from bottom to top, a back dielectric layer, a substrate layer, a bottom dielectric layer, a first semiconductor layer, an intermediate metal grid layer, a second semiconductor layer, and a top dielectric layer. The middle metal grid layer is an interconnected metal network which is fully distributed on the whole plane of the first semiconductor layer, the metal network is formed by connecting metal wires in a criss-cross manner, the metal networks are interconnected and intercommunicated, the phenomenon of wire breakage does not exist, the metal network can be any pattern combination of interconnection and intercommunication, and fig. 2 is a schematic diagram of an irregular middle metal grid layer, which is one of metal grid patterns; fig. 3 is a schematic diagram of regular triangular, regular quadrilateral and regular hexagonal metal meshes, which are examples of regular intermediate metal mesh layers.
Example 1
Fig. 4 is a schematic perspective view of the structure of the transparent composite electrical heating film according to the embodiment, wherein the middle metal mesh layer is a regular hexagon. The transparent electric heating composite film comprises the following materials in parts by weight: the substrate layer is PET; the back dielectric layer is Si 3 N 4 A thin film with the thickness of 30nm; the bottom dielectric layer is N micro-doped SiO 2 A thin film with the thickness of 20 nm; the first semiconductor layer is a ZnSiO film doped with Al, wherein the atomic percentage of Si (Zn + Si) is 7 at.%, the atomic percentage of Al (Zn + Si + Al) is 1 at.%, and the thickness of the film is 30nm; the middle metal grid layer is Zn-Al alloy, the Zn content is 2 at.%, the regular hexagon pattern network has the line width of 1 μm, the metal grid area is 5% of the base layer area, the thickness of the grid layer is 30nm, and the network structure is formed by a photoetching method; the second semiconductor layer is a ZnO film doped with Al, wherein the atomic percentage of Al (Zn + Al) is 1 at.%, and the thickness of the film is 30nm; the top dielectric layer is N micro-doped Al 2 O 3 Thin film, thickness 20 nm.
The preparation method of the flexible transparent heating film comprises the following steps: except the substrate layer, all the layers of films are prepared by a magnetron sputtering method, and in the growth process of the films, the growth atmosphere is plasma atmosphere containing argon (Ar); in the growth process, an ultraviolet enhancement mode is adopted, the substrate is irradiated by ultraviolet light with 254 nm, and the power of an ultraviolet light source is 120W. Firstly, bombarding a substrate layer by Ar plasma to form a substrate with certain roughness; si is used for growing the back dielectric layer 3 N 4 Ceramic target material, ar plasma atmosphere; when the bottom dielectric layer film grows, siO is adopted 2 Ceramic target material, ar-NH 3 A plasma atmosphere; when the first semiconductor layer film grows, znSiO ceramic target material containing Al element, ar-O 2 A plasma atmosphere; when the intermediate metal grid layer film grows, a metal target material and Ar plasma atmosphere are adopted; when the second semiconductor layer film grows, znO ceramic target material containing Al element, ar-O is adopted 2 A plasma atmosphere; when the top dielectric layer film grows, al is adopted 2 O 3 Ceramic target material, ar-N 2 And (4) O plasma atmosphere. After all the layers of films are grown, infrared radiation is carried outPerforming injection annealing treatment, irradiating the sample by adopting medium wave infrared rays with wave bands of 2 to 15 mu m, wherein the power density of infrared heating is 1W/cm 2 Irradiation time 10min.
Example 2
The transparent electric heating composite film comprises the following materials in parts by weight: the substrate layer is PI; the back dielectric layer is Si 3 N 4 A film with the thickness of 40nm; the bottom dielectric layer is N micro-doped SiO 2 A thin film with the thickness of 30nm; the first semiconductor layer is a ZnSiO film doped with Al, wherein the atomic percentage of Si (Zn + Si) is 10 at.%, the atomic percentage of Al (Zn + Si + Al) is 5 at.%, and the thickness of the film is 60nm; the middle metal grid layer is Zn-Al alloy, the Zn content is 98 at.%, the regular hexagon pattern network has the line width of 20 μm, the metal grid area is 10% of the base layer area, the thickness of the grid layer is 100nm, and the network structure is formed by a mask method; the second semiconductor layer is a ZnO film doped with Al, wherein the atomic percentage of Al (Zn + Al) is 5 at.%, and the thickness of the film is 60nm; the top dielectric layer is N micro-doped Al 2 O 3 Film thickness of 30nm.
The preparation method of the flexible transparent heating film comprises the following steps: except the substrate layer, all the layers of films are prepared by a magnetron sputtering method, and in the growth process of the films, the growth atmosphere is plasma atmosphere containing argon (Ar); in the growth process, an ultraviolet enhancement mode is adopted, 254 nm ultraviolet light is used for irradiating the substrate, and the power of an ultraviolet light source is 120W. Firstly, bombarding a substrate layer by Ar plasma to form a substrate with certain roughness; si is used for growing the back dielectric layer 3 N 4 Ceramic target material, ar plasma atmosphere; when the bottom dielectric layer film grows, siO is adopted 2 Ceramic target material, ar-NH 3 A plasma atmosphere; when the first semiconductor layer film grows, znSiO ceramic target material containing Al element, ar-O 2 A plasma atmosphere; when the intermediate metal grid layer film grows, a metal target material and Ar plasma atmosphere are adopted; when the second semiconductor layer film grows, znO ceramic target material containing Al element, ar-O is adopted 2 A plasma atmosphere; when the top dielectric layer film grows, al is adopted 2 O 3 Ceramic target material, ar-N 2 And (4) O plasma atmosphere. All layersAfter the films are grown, carrying out infrared radiation annealing treatment, irradiating the sample by adopting medium-wave infrared rays with wave bands of 2-15 mu m, wherein the power density of infrared heating is 5W/cm 2 Irradiation time 60min.
Example 3
The transparent electric heating composite film comprises the following materials in parts by weight: the substrate layer is PEN; the back dielectric layer is Si 3 N 4 A film with the thickness of 40nm; the bottom dielectric layer is N micro-doped SiO 2 A thin film with a thickness of 25 nm; the first semiconductor layer is a ZnSiO film doped with B element, wherein the atomic percentage of Si (Zn + Si) is 8 at.%, and B (Zn + Si + B) is 2 at.%, and the film thickness is 40nm; the middle metal grid layer is Zn-Ag alloy, the Zn content is 10 at.%, and the middle metal grid layer is an interconnected irregular pattern network with the line width of 10 mu m, the area of the metal grid is 10 percent of the area of the substrate layer, and the thickness of the grid layer is 40nm; the second semiconductor layer is a ZnO film doped with B element, wherein the atomic percentage B (Zn + B) is 2 at.%, and the thickness of the film is 40nm; the top dielectric layer is N micro-doped Al 2 O 3 Thin film, thickness 25 nm.
The preparation method of the flexible transparent heating film comprises the following steps: except the substrate layer, all the layers of films are prepared by a magnetron sputtering method, and in the growth process of the films, the growth atmosphere is plasma atmosphere containing argon (Ar); in the growth process, an ultraviolet enhancement mode is adopted, 254 nm ultraviolet light is used for irradiating the substrate, and the power of an ultraviolet light source is 120W. Firstly, bombarding a substrate layer by Ar plasma to form a substrate with certain roughness; si is used for growing the back dielectric layer 3 N 4 Ceramic target material, ar plasma atmosphere; when growing the bottom dielectric layer film, siO is adopted 2 Ceramic target material, ar-NH 3 A plasma atmosphere; when the first semiconductor layer film grows, znSiO ceramic target material containing B element, ar-O 2 A plasma atmosphere; when the intermediate metal grid layer film grows, a metal target material and Ar plasma atmosphere are adopted; when the second semiconductor layer film grows, znO ceramic target material containing B element, ar-O is adopted 2 A plasma atmosphere; when the top dielectric layer film grows, al is adopted 2 O 3 Ceramic target material, ar-N 2 And (4) O plasma atmosphere. What is neededAfter the growth of each layer of film is finished, carrying out infrared radiation annealing treatment, irradiating the sample by adopting medium-wave infrared rays with wave bands of 2-15 mu m, wherein the power density of infrared heating is 2W/cm 2 Irradiation time 20 min.
Example 4
The transparent electric heating composite film comprises the following materials in parts by weight: the basal layer is PC; the back dielectric layer is Si 3 N 4 A film with the thickness of 40nm; the bottom dielectric layer is N micro-doped SiO 2 A thin film with a thickness of 25 nm; the first semiconductor layer is a ZnSiO film doped with Ga element, wherein the atomic percentage Si (Zn + Si) is 9 at.%, the atomic percentage Ga (Zn + Si + Ga) is 3 at.%, and the film thickness is 40nm; the middle metal grid layer is Zn-Cu alloy, the Zn content is 5 at.%, the grid is a regular triangle pattern network, the line width is 10 μm, the area of the metal grid is 10% of the area of the substrate layer, and the thickness of the grid layer is 70 nm; the second semiconductor layer is a ZnO film doped with Ga, wherein the atomic percentage Ga (Zn + Ga) is 3 at.%, and the thickness of the film is 40nm; the top dielectric layer is N micro-doped Al 2 O 3 Thin film, thickness 25 nm.
The preparation method of the flexible transparent heating film comprises the following steps: except the substrate layer, all the layers of films are prepared by a magnetron sputtering method, and in the growth process of the films, the growth atmosphere is plasma atmosphere containing argon (Ar); in the growth process, an ultraviolet enhancement mode is adopted, 254 nm ultraviolet light is used for irradiating the substrate, and the power of an ultraviolet light source is 120W. Firstly, bombarding a substrate layer by Ar plasma to form a substrate with certain roughness; si is used in the growth of the back dielectric layer 3 N 4 Ceramic target material, ar plasma atmosphere; when growing the bottom dielectric layer film, siO is adopted 2 Ceramic target material, ar-NH 3 A plasma atmosphere; when the first semiconductor layer film grows, znSiO ceramic target material containing Ga element, ar-O 2 A plasma atmosphere; when the intermediate metal grid layer film grows, a metal target material and Ar plasma atmosphere are adopted; when the second semiconductor layer film grows, znO ceramic target material containing Ga element, ar-O is adopted 2 A plasma atmosphere; when the top dielectric layer film grows, al is adopted 2 O 3 Ceramic target material, ar-N 2 O plasma atmosphere. After all the layers of films are grown, carrying out infrared radiation annealing treatment, irradiating the sample by adopting medium-wave infrared rays with wave bands of 2-15 mu m, wherein the power density of infrared heating is 4W/cm 2 Irradiation time 45 min.
Example 5
The transparent electric heating composite film comprises the following materials in parts by weight: the basal layer is PC; the back dielectric layer is Si 3 N 4 A film with the thickness of 40nm; the bottom dielectric layer is N micro-doped SiO 2 A thin film with a thickness of 25 nm; the first semiconductor layer is a ZnSiO film doped with In, wherein the atomic percentage of Si (Zn + Si) is 9 at.%, the atomic percentage of In (Zn + Si + In) is 3 at.%, and the film thickness is 40nm; the middle metal grid layer is Zn-Cu alloy, the Zn content is 95 at.%, the middle metal grid layer is a regular triangular pattern network, the line width is 10 mu m, the area of the metal grid is 10 percent of the area of the substrate layer, and the thickness of the grid layer is 50 nm; the second semiconductor layer is a ZnO film doped with In element, wherein the atomic percentage In (Zn + In) is 3 at.%, and the thickness of the film is 40nm; the top dielectric layer is N micro-doped Al 2 O 3 Thin film, thickness 25 nm.
The preparation method of the flexible transparent heating film comprises the following steps: except the substrate layer, all the layers of films are prepared by a magnetron sputtering method, and in the growth process of the films, the growth atmosphere is plasma atmosphere containing argon (Ar); in the growth process, an ultraviolet enhancement mode is adopted, 254 nm ultraviolet light is used for irradiating the substrate, and the power of an ultraviolet light source is 120W. Firstly, bombarding a substrate layer by Ar plasma to form a substrate with certain roughness; si is used in the growth of the back dielectric layer 3 N 4 Ceramic target material, ar plasma atmosphere; when the bottom dielectric layer film grows, siO is adopted 2 Ceramic target material, ar-NH 3 A plasma atmosphere; when the first semiconductor layer film grows, znSiO ceramic target material containing Ga element, ar-O 2 A plasma atmosphere; when the intermediate metal grid layer film grows, a metal target material and Ar plasma atmosphere are adopted; when the second semiconductor layer film grows, znO ceramic target material containing Ga element, ar-O is adopted 2 A plasma atmosphere; when the top dielectric layer film grows, al is adopted 2 O 3 Ceramic target material, ar-N 2 O plasmaAn atmosphere. After all the layers of films are grown, carrying out infrared radiation annealing treatment, irradiating the sample by adopting medium-wave infrared rays with wave bands of 2-15 mu m, wherein the power density of infrared heating is 4W/cm 2 Irradiation time 45 min.
The above examples were tested. Fig. 5 is a photograph of a real object of example 1, and it can be seen that the sample is very transparent and has excellent flexibility. FIG. 6 is an optical transmission spectrum of a sample obtained in example 1, and the average transmittance in the visible light region is about 90.4%. The electrical properties were measured using a four-probe tester, which showed a square resistance of 9.7 ohm/sq. FIG. 7 is a graph of the electrical heating profile of example 1, with 80 s heating up to 50 ℃ and stabilizing at this temperature at 2V; heating to 150 ℃ in 40 s under the voltage of 5V, and stabilizing at the temperature; the flexible transparent electric heating composite film quickly reaches a stable temperature after being electrified, and has a high response speed. Further tests showed that: in repeated electric heating tests, 3000 circles of tests are carried out in a circulating way, and the change rate of the electric heating performance is not more than 1%; when the curvature radius is 1 cm, the change rate of the electric heating performance is not more than 3 percent, the bending is carried out for 1000 times according to the curvature radius, the change rate of the electric heating performance is not more than 5 percent, and the electric heating device has good flexibility and good bending stability; two similar samples are stacked together face to face, after the samples are rubbed back and forth for 1000 times under the pressure of 10N, the change rate of the electric heating performance is not more than 0.5 percent, and the composite film has high quality, good adhesive force and wear resistance.
The above tests were performed on each example, and substantially similar results were obtained. Table 1 shows the main technical indexes obtained by the tests of the examples.
TABLE 1 test data for the examples
Index (I) Transmittance of visible light Square resistance (ohm/sq) 2V temperature stabilization by heating (. Degree. C.)
Example 1 90.4 9.7 50
Example 2 85.6 3.4 150
Example 3 87.1 7.2 123
Example 4 88.7 8.5 70
Example 5 89.5 6.1 106
To further illustrate the technical effects of the present invention, comparative example tests were conducted.
Comparative example 1:
using the same transparent organic polymer substrate as in example 1, a metallic layer Zn-Al alloy, which is a thin film with a uniform thickness of 30nm, was grown only on the substrate layer, which was the same thickness as the intermediate metal mesh layer in example 1. The other films do not grow. Comparative example 1 gives a Zn-Al alloy thin film without a lattice structure, and the test shows that: the average transmittance in the visible light region was only about 7.1%, and the film had almost no transparency.
Comparative example 2:
using the same transparent organic polymer substrate as in example 1, only growing the intermediate metal grid layer Zn-Al alloy on the substrate layer, the film parameters of the Zn-Al alloy layer are: zn content 2 at.%, regular hexagonal pattern network, line width 1 μm, metal mesh area 5% of the substrate layer area, mesh layer thickness 30nm, network structure formed by photolithography, consistent with example 1. Other films do not grow. The pure Cu metal mesh electric heating film obtained in the comparative example 2 is tested to show that the pure Cu mesh is easily oxidized in an air environment, the maximum temperature which can be reached by the Cu mesh electric heating film under the voltage of 5V is only 30 ℃, the maximum temperature is far lower than that which can be reached in the example 1, the maximum temperature which can be reached in subsequent cycles is gradually reduced, and the electric heating composite film of the example 1 has no failure degradation phenomenon.
Comparative example 3:
a ZnO film doped with an Al element, in which the atomic percentage of Al (Zn + Al) was 1 at.%, and the film thickness was 30nm, was grown only on the substrate layer using the same transparent organic polymer substrate as in example 1, in accordance with example 1. Other films do not grow. The film obtained in comparative example 3 is a pure AZO electric heating film, and tests show that the temperature is only raised to 21 ℃ at 5V, and the highest temperature which can be reached under the same voltage is far lower than that of example 1 due to larger sheet resistance.
Comparative example 4:
the same technical scheme as that of the embodiment 2 is adopted, the only difference is that the middle metal grid layer adopts pure Zn metal, and the parameters of the Zn metal layer film are as follows: the line width of the regular hexagonal pattern network is 1 mu m, the area of the metal grid is 5 percent of the area of the substrate layer, the thickness of the grid layer is 30nm, and the network structure is formed by a photoetching method. The other films were the same as in example 2. The visible light transmittance of the flexible transparent electric heating composite film obtained in the comparative example 4 is 83.7%, the square resistance is 29.6 ohm/sq, and the performance index is obviously lower than that of the above examples.
Comparative example 5:
the same technical scheme as that of the embodiment 4 is adopted, the only difference is that the middle metal grid layer adopts pure Cu metal, and the parameters of the Cu metal layer film are as follows: the line width of the regular triangular pattern network is 10 mu m, the area of the metal grid is 10 percent of the area of the substrate layer, and the thickness of the grid layer is 30nm. The other films were all in accordance with example 4. The visible light transmittance of the flexible transparent electric heating composite film obtained in the comparative example 5 is 81.5%, the square resistance is 93.2 ohm/sq, and the performance index is obviously lower than that of the flexible transparent electric heating composite film obtained in the above examples.
Therefore, under the same external environment, the flexible transparent electric heating composite film provided by the invention has excellent characteristics and stability, and has longer service life in actual service; on the premise of ensuring transparency and flexibility, the response speed and the highest (saturation) temperature which can be reached are more excellent, and the temperature of 150 ℃ can be quickly reached under the safety voltage of 5V.

Claims (10)

1. A transparent electrical heating complex film which characterized in that: the transparent electric heating composite film is sequentially arranged into a back dielectric layer, a substrate layer, a bottom dielectric layer, a first semiconductor layer, a middle metal grid layer, a second semiconductor layer and a top dielectric layer from bottom to top; each layer is transparent in a visible light region;
the first semiconductor layer, the middle metal grid layer and the second semiconductor layer are active thin film layers;
the middle metal grid layer is an interconnected metal network which is distributed on the whole first semiconductor layer plane, the metal network is formed by connecting metal wires in a criss-cross mode and is interconnected, and the metal network patterns are distributed on the whole first semiconductor layer plane in a balanced mode.
2. A transparent electrically heatable composite film according to claim 1 wherein: the line width of the metal grid is 1 to 20 mu m, and the area of the metal grid is 5 to 10 percent of the area of the base layer.
3. A transparent composite electrical heating film according to claim 1, wherein: 30 to 40nm of a back dielectric layer; the bottom dielectric layer is 20-30 nm; the first semiconductor layer is 30-60 nm; the middle metal grid layer is 30-100 nm; the second semiconductor layer is 30-60 nm; the top dielectric layer is 20-30 nm.
4. A transparent composite electrical heating film according to claim 1, wherein:
the back dielectric layer is Si 3 N 4 A film;
the bottom dielectric layer is an oxide taking Si as a main body;
the first semiconductor layer is a ZnSiO film doped with an M element, wherein the atomic percentage of Si (Zn + Si) is 7 to 10 at.%, and the atomic percentage of M (Zn + Si + M) is 1 to 5 at.%;
the middle metal grid layer is an alloy film containing Zn, the alloy film is selected from Zn-Ag alloy, zn-Cu alloy and Zn-Al alloy, and the Zn content is not lower than 2 at.% and not higher than 98 at.%;
the second semiconductor layer is a ZnO film doped with M element, wherein the atomic percentage of M (Zn + M) is 1 to 5 at.%;
the top dielectric layer is an oxide taking Al as a main body;
wherein, M element is selected from B, al, ga or In; and the M elements adopted by the first semiconductor layer and the second semiconductor layer are the same.
5. A transparent electrically heatable composite film according to claim 4 wherein: the bottom dielectric layer is N micro-doped SiO 2 (ii) a The middle metal grid layer is Zn-Al alloy; the top dielectric layer is N-doped Al 2 O 3 。
6. A transparent electrically heatable composite film according to claim 5 wherein: the first semiconductor layer is an Al-doped ZnSiO film, and the second semiconductor layer is an Al-doped ZnO film.
7. A transparent electrically heatable composite film according to claim 1 wherein: the substrate layer is a flexible organic polymer selected from PC, PEN, PI or PET.
8. A transparent electrically heatable composite film according to claim 1 wherein: and two sides of the substrate layer are subjected to rough treatment.
9. A method for preparing a transparent electrically heatable composite film according to any one of claims 1 to 8, characterized in that: the back dielectric layer, the bottom dielectric layer, the first semiconductor layer, the middle metal grid layer, the second semiconductor layer and the top dielectric layer are all prepared by a magnetron sputtering method; in the process of growing the film by the magnetron sputtering method, the growing atmosphere is the plasma atmosphere containing argon; in the process of growing the film, an ultraviolet enhancement mode is adopted, 254 nm ultraviolet light is used for irradiating the substrate, and the power of an ultraviolet light source is 120W.
10. A method for preparing a transparent composite electrical heating film according to claim 9, wherein the method comprises the steps of:
1) Performing double-sided bombardment on the substrate layer by adopting Ar plasma to form rough surfaces on two sides of the substrate layer;
2) Growing a back dielectric layer on one side of the substrate layer, using Si 3 N 4 Ceramic target material, ar plasma atmosphere;
3) Growing a bottom dielectric layer on the other surface of the substrate layer by using SiO 2 Ceramic target material, ar-NH 3 A plasma atmosphere;
4) Growing a first semiconductor layer on the bottom dielectric layer by using ZnSiO ceramic target material containing M element, ar-O 2 A plasma atmosphere;
5) Growing an intermediate metal grid layer on the first semiconductor layer, and adopting a metal target material and Ar plasma atmosphere; forming a grid structure of the intermediate metal grid layer by a photoetching method or a mask method; the metal target is selected from Zn-Ag alloy, zn-Cu alloy or Zn-Al alloy, and the Zn content is not lower than 2 at.% and not higher than 98 at.%;
6) Growing a second semiconductor layer on the intermediate metal grid layer by using ZnO ceramic target material containing M element, ar-O 2 A plasma atmosphere;
7) Growing a top dielectric layer on the second semiconductor layer by using Al 2 O 3 Ceramic target material, ar-N 2 An O plasma atmosphere;
8) Carrying out infrared radiation annealing treatment, irradiating the sample by adopting medium wave infrared rays with wave bands of 2-15 mu m, wherein the power density of infrared heating is 1-5W/cm 2 The irradiation time is 10 to 60min;
the M element is B, al, ga or In, and the M elements adopted In the step 4) and the step 6) are the same.
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