CN102063951B - Transparent conductive film and manufacturing method thereof - Google Patents
Transparent conductive film and manufacturing method thereof Download PDFInfo
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- CN102063951B CN102063951B CN 201010533228 CN201010533228A CN102063951B CN 102063951 B CN102063951 B CN 102063951B CN 201010533228 CN201010533228 CN 201010533228 CN 201010533228 A CN201010533228 A CN 201010533228A CN 102063951 B CN102063951 B CN 102063951B
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
- H05K3/12—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using thick film techniques, e.g. printing techniques to apply the conductive material or similar techniques for applying conductive paste or ink patterns
- H05K3/1208—Pretreatment of the circuit board, e.g. modifying wetting properties; Patterning by using affinity patterns
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
- H05K3/12—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using thick film techniques, e.g. printing techniques to apply the conductive material or similar techniques for applying conductive paste or ink patterns
- H05K3/1258—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using thick film techniques, e.g. printing techniques to apply the conductive material or similar techniques for applying conductive paste or ink patterns by using a substrate provided with a shape pattern, e.g. grooves, banks, resist pattern
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
- H05K3/12—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using thick film techniques, e.g. printing techniques to apply the conductive material or similar techniques for applying conductive paste or ink patterns
- H05K3/1283—After-treatment of the printed patterns, e.g. sintering or curing methods
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/01—Tools for processing; Objects used during processing
- H05K2203/0104—Tools for processing; Objects used during processing for patterning or coating
- H05K2203/0108—Male die used for patterning, punching or transferring
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/11—Treatments characterised by their effect, e.g. heating, cooling, roughening
- H05K2203/1131—Sintering, i.e. fusing of metal particles to achieve or improve electrical conductivity
Abstract
The invention provides a transparent conductive film. The transparent conductive film comprises a transparent substrate and a conductive metal, wherein grooves for embedding conductive metal particles and grids for transmitting light are pressed on the transparent substrate by nanoimprint lithography technology; and by designing the line width and the depth of the grooves and the specific gravity of the grooves to the whole transparent conductive film, the transparent conductive film with high transparency and conductivity is manufactured. Meanwhile, the conductive metal part is embedded inside the transparent substrate and is difficult to separate and oxidize, and the transparent substrate can be made of a flexible material, so the transparent conductive film which can be applied in various situations can be developed. Furthermore, the invention also provides a manufacturing method of the transparent conductive film.
Description
Technical field
The present invention relates to a kind of nesa coating and preparation method thereof, especially a kind of Embedded nesa coating and preparation method thereof.
Background technology
Nesa coating is widely used in fields such as touch control liquid crystal panel, organic diode of giving out light (OLED) and electromagnetic shielding.At present, more common nesa coating has two kinds of ITO film and metal films, the former is on transparent glass or plastic base surface, method by evaporation or sputter forms the transparent conductivity material of one deck indium-tin-oxide film (ITO) etc., the latter is on transparent glass or plastic base surface, by the method for metal-plated or evaporation, forms metallic film on whole surface, by photoetching it is processed then, metal level is etched into fine metal grill.
But though ITO film light transmission excellence, its electric conductivity is general, is not suitable for the field that electric, aviation etc. is had relatively high expectations.Though and metal film has preferable conductivity, in the processing metal film, need remove most metallic film, so exist the shortcoming that waste is many, production cost is high.
In recent years, some scientists have proposed direct method at the latticed plain conductor of transparent substrates surface one-shot forming.Wherein a kind of is with raw material fusion and emulsifications such as silver-colored nanoparticle, organic solvent, interface activating agent and aqueous solvents, when this ink is coated on the transparency carrier surface, because the difference of polarity of solvent, surface energy and volatility, be able to form automatically at substrate surface the silver-colored reticulated structure of arbitrary shape, after oversintering, just become nesa coating.About 4～270 Ω of present its sheet resistance value of the nesa coating of delivering of this technology/sq, visible light transmittance rate about 75～86%.
But the net metal that is obtained by this method silver line, its shape size and position distribution rely on the characteristic of solvent itself fully, the non-constant of controllability, cause some zone excessively intensive easily, some place is then very sparse, makes the printing opacity uniformity of nesa coating and the conduction uniformity all be affected.All are produced on nesa coating on the film surface with conductive metal wire in addition, and its metal level is oxidation and dropping easily all, has influenced the useful life of nesa coating greatly.
Summary of the invention
At above problem, the present invention proposes a kind of nesa coating and preparation method thereof.This nesa coating utilizes the method for nano impression, submicron figure in surperficial formation rule, conducting metal filled out to be located in these submicron figures form conductive metal wire, thereby reach allocation position and the size of strict control metal wire, make this electrically conducting transparent film conductivity and light transmission when significantly improving, can also carry out controlled design according to the difference of application occasion.In addition, because plain conductor is embedded in film inside, its stability and oxidation resistant ability also are improved.
A kind of nesa coating according to purpose of the present invention proposes comprises transparent substrates and conducting metal, and this transparent substrates comprises conduction region and transparent area, and this conduction region is the netting twine shape groove that is interconnected, the grid that this transparent area surrounds for this netting twine shape groove; This conducting metal is filled in the netting twine shape groove of this conduction region, and wherein the area of this groove and the ratio of the area of this grid are less than 5%.
According to a kind of nesa coating that purpose of the present invention proposes, the grid of wherein said transparent area is the regular polygon grid, and its length of side yardstick is less than 200um.
According to a kind of nesa coating that purpose of the present invention proposes, wherein said transparent substrates is flexible clear materials, and its light transmittance is greater than 85%.
According to a kind of nesa coating that purpose of the present invention proposes, the groove depth-to-width ratio of wherein said conduction region was greater than 1: 1.
The manufacture method of a kind of nesa coating that proposes according to purpose of the present invention comprises the steps:
Imprint process: use metal die to impress out lattice in a transparent substrates, wherein the sideline of this grid is groove, and the ratio of the area of this groove and the area of this grid is less than 5%;
Metallization process: this transparent substrates is metallized, make to be full of conducting metal in the groove;
Glossing: remove the unnecessary conducting metal in transparent substrates surface, only keep the conducting metal in the groove, thereby form nesa coating.
The manufacture method of a kind of nesa coating that proposes according to purpose of the present invention, wherein said metallization process is wet coating technology, comprising:
Adopt the continous way coating process, be mixed with the nanometer silver paste of hydrophobic solvent in the coating of transparent substrates surface;
According to the silver slurry is deposited in the groove;
Heated baking condenses the silver slurry, forms wire grating in groove.
The manufacture method of a kind of nesa coating that proposes according to purpose of the present invention wherein at transparent substrates coating one deck hydrophobic layer, is assembled in groove to accelerate nanometer silver paste.
The manufacture method of a kind of nesa coating that proposes according to purpose of the present invention, wherein said metallization process is electroforming process or sputtering technology, by electroforming or sputter, grows conducting metal in the groove of transparent substrates.
The manufacture method of a kind of nesa coating that proposes according to purpose of the present invention wherein also comprises the preparation technology of the protruding film of metal, and this preparation technology comprises:
Photoetching process: adopt scanning photoetching or tiling photoetching, go out lattice in the photoresist surface etch, the sideline of this grid is groove, and the depth-to-width ratio of this groove was greater than 1: 1;
Plated electrode: by the method for vacuum sputtering or chemical plating, the photoresist with groove pattern is metallized, make whole photoresist surface, comprise groove part, form electrode layer;
The electroforming motherboard: the photoresist dry plate that has conductive layer is inserted in the electrotyping bath, carries out the electro-deposition of metal ion, and progressively deposition forms the certain thickness sheet metal on electrode layer;
Come unstuck: sheet metal is separated from the photoresist dry plate, and remove photoresist, form the grid pattern structure of convex at metallic plate.
The manufacture method of a kind of nesa coating that proposes according to purpose of the present invention, wherein said imprint process is volume to volume roller impression.
The manufacture method of a kind of nesa coating that proposes according to purpose of the present invention, wherein said glossing are a kind of in mechanical polishing, chemical electrolysis or the chemical corrosion.
Above-mentioned nesa coating and preparation method thereof, utilize nanometer embossing to make the groove of burying underground for conducting metal in the transparent substrates surface pressure, by live width and the degree of depth of design groove and the proportion that accounts for whole nesa coating, obtained the nesa coating of a kind of light transmittance height and good conductivity.Simultaneously, because conducting metal partly is embedded in transparent substrates inside, difficult drop-off and oxidation, and can adopt flexible material as transparent substrates, develop the nesa coating that can under more occasions, use.
The present invention is elaborated with specific embodiment below in conjunction with accompanying drawing.
Description of drawings
Fig. 1 is nesa coating schematic diagram of the present invention;
Fig. 2 is the schematic diagram of transparent substrates among Fig. 1;
Fig. 3 is the cutaway view on the A-A direction among Fig. 1;
Fig. 4 is protruding film preparation flow chart of the present invention;
Fig. 5 is the making flow chart of nesa coating of the present invention.
Embodiment
Please in the lump referring to Fig. 1, Fig. 2, Fig. 1 is nesa coating schematic diagram of the present invention, and Fig. 2 is the schematic diagram of transparent substrates among Fig. 1.As shown in the figure, this nesa coating 100 comprises transparent substrates 110 and conducting metal 120.Transparent substrates 110 comprises conduction region 111 and transparent area 112, the meshed grooves of conduction region 111 for being interconnected, and conducting metal 120 is filled out and is located in the conduction region 111, the grid that transparent area 112 surrounds for meshed grooves.This conducting metal 120 can be the silver particles line that is formed by silver slurry sintering, also can be other conductor wires that are deposited on formation in this conduction region 111 such as metals such as copper, nickel, aluminium by the method for electroforming or sputter.To do analysis to light transmission and the conductivity of nesa coating 100 respectively below.
For light transmission: generally, this conduction region 111 fills out that to establish conducting metal 120 backs light tight, so the actual light transmittance of this nesa coating 100 is by the light transmittance decision of the area size of conduction region 111 and transparent substrates 110 self.It is more little to be that the area of conduction region 111 accounts for the ratio of transparent area area, and the light transmittance of nesa coating 100 is more high.Usually, conduction region 111 is 5% with the area ratio of transparent area 112, and transparent substrates 110 light transmittances own are 90% o'clock, and the light transmittance of nesa coating 100 can reach more than 85%.In order to obtain higher light transmittance, we select the ratio of area and the area of whole grid of groove of conduction region 111 less than 5%, and the light transmittance of transparent substrates 110 is greater than 90%.Especially, when the grid of transparent area 112 was regular polygon, the ratio of the area of conduction region 111 and transparent area 112 can be calculated by following formula:
P＝1-a
2/(a+L*tan180/n)
2 (1)
In the formula (1): a is the length of side of regular polygon, and L is the width of conduction region 111, the limit number of n for just being out of shape.
Be example with the regular hexagon grid, when the grid length of side is 35um, light transmittance is 90% o'clock, and the live width of metal conductive wire is about 3um.
For conductivity: the conductivity of this nesa coating mainly relies on electrical characteristics and the cross section of conducting metal 120, sees also Fig. 3, and Fig. 3 is the cutaway view on the A-A direction among Fig. 1.As shown in the figure, the cross section of conducting metal 120 is determined by width and the degree of depth of conduction region 111.Because width is subjected to the influence of light transmittance, that can not do is very wide, therefore, need be with the depth design of conduction region 111 deep, to improve the cross section of conducting metal 120.Preferably, we are designed to depth-to-width ratio greater than 1: 1, are example with the argent, and when width was 3um, the surface impedance of this nesa coating 100 can reach the scope greater than 3.5 Ω/sq.
In the practical application, we can be according to the conductivity of nesa coating and the balance needs on the light transmission, and the limit of employed occasion causes the width of design flexible netting twine and the degree of depth.In addition, for some applications that transparent light guide film surface monolithic conductive is had relatively high expectations, such as in the built-in tactile empty screen in contact, during perhaps some electromagnetic shieldings are used, need the highdensity conduction netting twine of design, therefore with the size design of grid below 200um.
To specifically introduce the manufacture method of nesa coating of the present invention below.
The present invention selects to form with the method for nano impression the meshed grooves on this nesa coating surface when making above-mentioned nesa coating.Especially, when transparent substrates is flexible material, method this nesa coating of production at a high speed that can impress by the roller of volume to volume.Thereby before film processed, at first need to carry out the preparation of protruding film.
See also Fig. 4, Fig. 4 is protruding film preparation flow chart of the present invention.As shown in the figure, the preparation of this protruding film comprises: adopt scanning photoetching or tiling photoetching, go out lattice in the photoresist surface etch, the sideline of this grid is groove, and the depth-to-width ratio of this groove was greater than 1: 1;
By the method for vacuum sputtering or chemical plating, the photoresist with groove pattern is metallized, make whole photoresist surface, comprise groove part, form electrode layer;
The photoresist dry plate that has conductive layer is inserted in the electrotyping bath, carries out the electro-deposition of metal ion, and progressively deposition forms the certain thickness sheet metal on conductive layer;
Sheet metal is separated from the photoresist dry plate, and remove photoresist, form the grid pattern structure of convex at metallic plate.
Wherein, when grid is square, adopt the method for scanning photoetching, select the dressing luminous point of 0.5um that the double exposure of vertical and horizontal is carried out on the photoresist surface, this kind lithographic method advantage is that etching speed is fast, and etches dark line pattern easily.
When grid is other polygons, adopt the method for tiling projection exposure, set in advance exposure figure on the diaphragm now, with this figure exposed in the photoresist surface then, directly form the grid with regular polygon pattern, and by mechanical assistance, the graphic joining one-tenth of single exposure is whole, the etching of realization grid.The advantage of this kind lithographic method is that exposure figure is controlled, but mechanical precision is had relatively high expectations.
Please again referring to Fig. 5, Fig. 5 is the making flow chart of nesa coating of the present invention.As shown in the figure, this method mainly comprises three big technologies: at first be imprint process, the metal die that grid pattern is arranged by a surface, exerted pressure in the transparent substrates surface, when exerting pressure, can adopt heating or means such as ultra-violet curing, on transparent substrates, be the lattice of groove to form netting twine with the design transfer of convex mould surface.Wherein the sideline of this lattice is groove, and the ratio of the area of this groove and the area of this grid is less than 5%.
Next is metallization process, and the purpose of this technology is to fill out to establish conducting metal in the groove of conduction region, it is full of or overflows groove.Particularly, this metallization process can be undertaken by following several method:
First method can be wet coating technology.This method comprises:
Adopt the continous way coating process, be coated with the nanometer silver paste that is mixed with hydrophobic solvent on the transparent substrates surface, the silver particles diameter in this nanometer silver paste is about 50nm-70nm, and its hydrophobic solvent proportion is between the 10%-20%;
According to from the levelling effect, the silver slurry can be deposited in the groove automatically, perhaps can increase the hydrophobic layer that is coated with one deck 10% on the transparent substrates surface, the THICKNESS CONTROL of this hydrophobic layer is in 200nm, make it much smaller than the degree of depth of groove, then cooperate the water-repelling agent composition that itself contains in the silver slurry, can accelerate silver particles and assemble toward groove, after the continous way coating, guarantee that silver particles riddles in the groove;
Heated baking condenses the silver slurry, finally forms wire grating in groove.
The advantage of this method is that technology is simple, and is easy to operate, can cooperate the continous way coating process of volume to volume (Roll to Roll), and high speed is large-sized to be produced.But the adhesive force that shortcoming is silver starches is not good, comes off easily, and the uniformity poor effect of coating, makes the many of some local silver slurry gatherings easily, and some places are then more sparse.
Second method is electroforming process or sputtering technology.On transparent substrates, by electroforming process or vacuum sputtering process deposits metal conducting layer, because the inside both side surface of groove deposits simultaneously, therefore, the metal filled speed in groove is than the fast twice of speed of the metal deposition of patterned surface.For example, be 2um for the groove live width, then groove is filled when finishing, and surface metal thickness is about 1um.
The advantage of this method is that technology is ripe relatively, and the metal deposition evenly can select multiple metal such as copper, nickel, aluminium etc. to deposit as conducting metal, and the strong adhesion difficult drop-off.Shortcoming is that the surface has metal all, causes waste easily, and the inapplicable large-sized making of length consuming time.
Be glossing at last, this step mainly in order to remove the metal level unnecessary on the surface, keeps the conducting metal in the conduction region groove, to improve the light transmission of transparent light guide film integral body.This glossing can adopt a kind of in mechanical polishing, chemical electrolysis or the chemical corrosion.
In sum, the invention provides a kind of nesa coating, this nesa coating utilizes nanometer embossing to make the groove of burying underground for conducting metal in the transparent substrates surface pressure, by live width and the degree of depth of design groove and the proportion that accounts for whole nesa coating, obtained the nesa coating of a kind of light transmittance height and good conductivity.Simultaneously, because conducting metal partly is embedded in transparent substrates inside, difficult drop-off and oxidation, and can adopt flexible material as transparent substrates, develop the nesa coating that can under more occasions, use.
By the above detailed description of preferred embodiments, hope can be known description feature of the present invention and spirit more, and is not to come claim scope of the present invention is limited with above-mentioned disclosed preferred embodiment.On the contrary, its objective is that hope can contain in the scope of claim of being arranged in of various changes and tool equality institute of the present invention desire application.
Claims (2)
1. nesa coating, comprise transparent substrates and conducting metal, it is characterized in that: described transparent substrates comprises conduction region and transparent area, and this conduction region is netting twine shape groove, this groove is suppressed the surface in described transparent substrates, the grid that this transparent area surrounds for this netting twine shape groove; Described conducting metal is filled in the netting twine shape groove of this conduction region, wherein the area of this groove and the ratio of the area of this grid are less than 5%, the grid of described transparent area is regular polygon, its length of side yardstick is less than 200um, described transparent substrates is flexible clear materials, its light transmittance is greater than 90%, the groove depth-to-width ratio of described conduction region was greater than 1: 1, described groove forms by nano-imprint process, this nano-imprint process is volume to volume roller impression, use punch to impress out lattice in a transparent substrates, wherein the sideline of this grid is groove, and the preparation technology of described punch comprises:
Adopt scanning photoetching or tiling photoetching, go out lattice in the photoresist surface etch, the sideline of this grid is groove, and the depth-to-width ratio of this groove was greater than 1: 1;
By the method for vacuum sputtering or chemical plating, the photoresist with groove pattern is metallized, make whole photoresist surface, comprise groove part, form electrode layer;
The photoresist dry plate that has conductive layer is inserted in the electrotyping bath, carries out the electro-deposition of metal ion, and progressively deposition forms the certain thickness sheet metal on conductive layer;
Sheet metal is separated from the photoresist dry plate, and remove photoresist, form the grid pattern structure of convex at metallic plate.
2. the manufacture method of a nesa coating is characterized in that, comprises the steps:
Imprint process: described imprint process is nanometer embossing, described imprint process is volume to volume roller impression, use punch to impress out lattice in a transparent substrates, wherein the sideline of this grid is groove, and the ratio of the area of this groove and the area of this grid is less than 5%, the grid of described transparent area is regular polygon, and its length of side yardstick is less than 200um;
Metallization process: described metallization process is a kind of in wet coating technology, electroforming process or the sputtering technology, this transparent substrates is metallized, make and be full of conducting metal in the groove, wherein when this metallization process is wet coating technology, comprise step: adopt the continous way coating process, be mixed with the nanometer silver paste of hydrophobic solvent in the coating of transparent substrates surface; Be deposited in the groove according to silver is starched, and at transparent substrates coating one deck hydrophobic layer, assemble in groove to accelerate nanometer silver paste; Heated baking condenses the silver slurry, forms wire grating in groove;
Glossing: remove the unnecessary conducting metal in transparent substrates surface, only keep the conducting metal in the groove, thereby form nesa coating;
Wherein, the preparation technology of described punch comprises:
Adopt scanning photoetching or tiling photoetching, go out lattice in the photoresist surface etch, the sideline of this grid is groove, and the depth-to-width ratio of this groove was greater than 1: 1;
By the method for vacuum sputtering or chemical plating, the photoresist with groove pattern is metallized, make whole photoresist surface, comprise groove part, form electrode layer;
The photoresist dry plate that has conductive layer is inserted in the electrotyping bath, carries out the electro-deposition of metal ion, and progressively deposition forms the certain thickness sheet metal on conductive layer;
Sheet metal is separated from the photoresist dry plate, and remove photoresist, form the grid pattern structure of convex at metallic plate.
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