CN104966551A - ITO conductive film with copper-plated surface - Google Patents
ITO conductive film with copper-plated surface Download PDFInfo
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- CN104966551A CN104966551A CN201510293080.9A CN201510293080A CN104966551A CN 104966551 A CN104966551 A CN 104966551A CN 201510293080 A CN201510293080 A CN 201510293080A CN 104966551 A CN104966551 A CN 104966551A
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Abstract
The invention provides an ITO conductive film with a copper-plated surface. The ITO conductive film comprises an optical adjusting layer, an ITO layer and a copper lead layer which are sequentially arranged on one side of a substrate in a laminated way. The copper lead layer is formed on the ITO layer. An optically-adjusting hardening coating layer is arranged between the substrate and the optical adjusting layer. The thickness of the copper lead layer ranges from 50 nm to 800 nm. The refractive index of the optically-adjusting hardening coating layer ranges from 1.6 to 1.7. The thickness of the ITO layer ranges from 15 nm to 35 nm. The surface resistance of the ITO layer is no more than 400 omega/square. The copper lead layer is arranged on the ITO. In this way, no adhesive agents are required. Required conductive effects can be achieved by a thickness of only hundreds of nanometers. Meanwhile, the bending problem is solved.
Description
Technical field
The present invention relates to a kind of nesa coating, particularly relate to a kind of ITO conducting film of copper coating.
Background technology
Touch-screen general at present comprises the resistive touch screen and projected capacitive touch screen that are applicable to mobile device and consumption electronic product, along with the release of Apple IPhone mobile phone, caused the upsurge of capacitive touch screen, capacitive touch screen permeates to various electronics field.Along with the progress of technology, the various structures of capacitive touch screen continue to bring out, the wherein the most frequently used two-sided ITO structure having apple classics, one side TP bridge construction, film-glass structure, film-film-glass structures etc., wherein for the capacitive screen structure of film-film structure, contact conductor adopts silk-screen silver slurry mostly.After being generally ITO conducting film making induction pattern, above avris, make wire, so that signal is connected to drive IC.When printing conductive silver paste at present above ITO, adhesive agent need be added in silver slurry, if adhesive agent is too high, electrical conductivity can be caused poor; The adherence of adhesive agent too low then silver slurry is strong, then having the silver of making to conduct electricity, thickness is thicker and live width is wider, and flexing effect is also poor, easily causes the problem of broken string.
Summary of the invention
The present invention be directed to the deficiencies in the prior art, provide a kind of ITO conducting film of copper coating, electrode sticking is good, avoids using adhesive agent, and effectively solves the problem that flexing effect is poor, easily cause broken string.
The technical solution used in the present invention is as follows: a kind of ITO conducting film of copper coating, comprise the optical adjustment layer be cascading in base material side, ITO layer and copper conductor layer, described copper conductor layer passes through sputter, evaporation process makes on the ito layer, light modulation hardening coat is provided with between base material and optical adjustment layer, described copper conductor layer thickness is 50nm ~ 800nm, described light modulation hardening coat refractive index is between 1.6 ~ 1.7, described light modulation hardening coat thickness is between 300nm ~ 2um, described ITO layer thickness is at 15nm ~ 35nm, the Biao Mian electricity Zu≤400 Ω/ of described ITO layer.
Further, the opposite side of described base material is provided with light modulation hardening coat.
Further, the opposite side of described base material is relatively provided with light modulation hardening coat, optical adjustment layer, ITO layer and copper conductor layer.
Further, described copper conductor layer thickness is preferably 100nm ~ 300nm.
Further, described ITO layer thickness is preferably 20nm ~ 30nm.
Further, described copper conductor layer material adopts fine copper or copper alloy.
Further, described light modulation hardening coat wet is formed in substrate surface.
Further, described light modulation hardening coat Thickness is at 300nm to 1 μm.
Further, the ITO conducting film of described copper coating is after etching away copper conductor layer, and its colour is between 0 ~ 2.0.
Further, the refractive index of described optical adjustment layer is 1.4 ~ 1.5, and thickness is 10 ~ 40nm.
Compared with prior art, the present invention above ITO conducting film, by copper conductor layer in making ITO above, do not need to add adhesive agent, and only need the thickness of hundreds of how rice can reach the conductive effect of demand, simultaneously because of the interpolation without adhesive agent, thus while also solve the problem of flexing.
Accompanying drawing explanation
Fig. 1 is the Rotating fields schematic diagram of the first better embodiment of the ITO conducting film of copper coating of the present invention;
Fig. 2 is the Rotating fields schematic diagram of the second better embodiment of the present invention;
Fig. 3 is the Rotating fields schematic diagram of the 3rd better embodiment of the present invention.
Embodiment
Below in conjunction with the accompanying drawing in the embodiment of the present invention, technical scheme in the embodiment of the present invention is clearly and completely described, obviously, described embodiment is only the present invention's part embodiment, instead of whole embodiments, when not conflicting, the embodiment in the application and the feature in embodiment can combine mutually, below with reference to the accompanying drawings and describe the present invention in detail in conjunction with the embodiments.
As shown in Figure 1, a kind of ITO conducting film of copper coating, its first better embodiment comprises base material 1 and stacked optical adjustment layer 2, ITO layer 3 and the copper conductor layer 4 being arranged on base material 1 upper surface.Described base material 1 is light-permeable material, surface uniform and smooth, its material can be in PET, PEN, COC (Cyclic Olefin Copolymer), COP (Cyclic Olefin Polymers) any one.Make the light modulation hardening coat 5 having light modulation and anti scuffing effect concurrently between base material 1 and optical adjustment layer 2, ITO layer 3 is arranged in optical adjustment layer 2, and copper conductor layer 4 passes through the fabrication techniques such as sputter, evaporation in ITO layer 3.
Second better embodiment of the present invention, a kind of ITO conducting film of copper coating, on the basis of the first better embodiment, as shown in Figure 2, the lower surface of described base material 1 is provided with another light modulation hardening coat 5 further.
3rd better embodiment of the present invention, a kind of ITO conducting film of copper coating, on the basis of the first better embodiment, as shown in Figure 3, described base material 1 lower surface has been cascading light modulation hardening coat 5, optical adjustment layer 2, ITO layer 3 and copper conductor layer 4 further, symmetrical with each layer of base material 1 upper surface.
In the various embodiments described above mode, described light modulation hardening coat 5 refractive index is 1.6 ~ 1.7, and thickness is in 300nm ~ 2 μm.
Described optical adjustment layer 2 is for adjusting the refractive index of incident light, and refractive index is 1.4 ~ 1.5, and its thickness is 10 ~ 40nm.
Described ITO layer 3 is indium tin oxide conductive layer, and tin oxide (SnO
2) ratio between 1 ~ 10%, be formed at optical adjustment layer 2 on the surface in the mode of thin film deposition.ITO layer 3 under 150 DEG C of conditions after the heat treatment of 60 minutes, its sheet resistance rate of change through soaking Hou 1N hydrochloric acid 3 minutes≤20%.Described ITO layer 3 thickness is chosen as 15nm ~ 35nm, the sheet resistance You Xuan Wei≤400 Ω/ of ITO layer 3.
Ω/ is the unit of film resistor, i.e. ohm-sq.Film resistor has measuring of uniform thickness film resistor.Be often used as the result of assessment semiconductor doping.The example of this technique has: the doping field (such as silicon or polysilicon) of semiconductor, and is screen printed to the suprabasil resistance of thin film hybrids.The use of this concept of film resistor, relative with resistance or resistivity, be that it is directly measured with four terminal induction mensurations (also referred to as four-point probe mensuration).Film resistor ohm-sq is measured, and can be applied to two-dimentional system film being thought of as a 2d solid.The concept equity of resistivity used under it and three dimension system.In time using film resistor one word, electric current must flow along thin film planar, but not perpendicular.For conventional three-dimensional conductor, resistance can be written as
wherein ρ represents resistivity, and A represents area of section and L represents length.Area of section can be broken down into width W and film thickness t.When resistivity and thickness are put together, resistance can be designated as
be film resistor.Because it take advantage of by the characteristic, so unit is still ohm.And this unit of ohm-sq is because which give the resistance flowing to relative square area from a square area in units of ohm by use, regardless of the size of square area.For square situation, L=W.Therefore, to any squared magnitude, R=R is had
s.Four-point probe is the problem made for reducing contact resistance, and it is often used for the sheet resistance values confirming material.Measurement of inductance is also have to be used.The method measures the shield effectiveness produced by eddy current.The wherein one of this technology is that tested conducting strip is placed between two coils.In addition, the method for measurement of this contactless sheet resistance values also can measure film in encapsulation or the large film of surface roughness.
Described copper conductor layer 4 is not limited to fine copper, also can be the copper alloy of conduction, and its thickness is between 50nm ~ 800nm, wherein, is preferably 100nm ~ 500nm.According to the thickness of the different copper conductor layer 4 used, the resistance that ITO and copper sheet resistance (i.e. ITO layer 3 and copper conductor layer 4) produce and copper conductor layer 4 drive situation and copper surface pinholes situation all can difference to some extent to IC after normal temperature adherence, copper make circuit, below will illustrate further according to embodiment.
Comparative example 1: first substrate 1 is done electricity slurry cleaning pre-treatment, then optical adjustment layer 2, ITO layer 3 is sequentially plated by the mode of sputter or evaporation in its surface, wherein ITO sheet resistance is 150 Ω/, the normal temperature density of substrate 1 is 5B, adopt hundred lattice methods of testing, test article is utilized cross-cut tester and 3M-600 type adhesive tape, observe its density, density has 0B ~ 5B totally six grades, and 5B is best.
Embodiment 1: the present embodiment 1 is when making, first substrate 1 is done electricity slurry cleaning pre-treatment, then on its surface to be measured, sequentially plate light modulation hardening coat 5, optical adjustment layer 2, ITO layer 3 and copper conductor layer 4 by the mode of sputter or evaporation, wherein copper conductor layer 4 thickness is 50nm.
Embodiment 2: the preparation flow of embodiment 2 is identical with embodiment 1 with structure, does not exist together and is only: copper conductor layer 4 thickness is 100nm.
Embodiment 3: the preparation flow of embodiment 3 is identical with embodiment 1 with structure, does not exist together and is only: copper conductor layer 4 thickness is 200nm.
Embodiment 4: the preparation flow of embodiment 4 is identical with embodiment 1 with structure, does not exist together and is only: copper conductor layer 4 thickness is 300nm.
Embodiment 5: the preparation flow of embodiment 5 is identical with embodiment 1 with structure, does not exist together and is only: copper conductor layer 4 thickness is 500nm.
Embodiment 6: the preparation flow of embodiment 6 is identical with embodiment 1 with structure, does not exist together and is only: copper conductor layer 4 thickness is 800nm.
Embodiment 1 to 6 and comparative example 1 are carried out respectively resistance that ITO+ copper surface produces, the checking of the effect such as IC driver circuit situation that the normal temperature density between copper and ITO, copper conductor layer make and copper surface pinholes situation, and by result taxonomic revision as shown in following table one.
Table one: copper conductor layer thickness efficacy outcomes:
Can see from table one, along with the increase of copper conductor layer 4 thickness, the resistance that produces of ITO+ copper surface progressively diminishes, when copper conductor layer 4 thickness is too thin be 50mm time, ITO+ copper sheet resistance is too high, and copper conductor layer being made into wire cannot drive IC; When copper conductor layer thickness is too thick reach 800mm time, the adherence between copper and ITO is poor, also can produce surface pinholes, cause mass defect.As can be seen here, the scope of application of the thickness of copper conductor layer 4, at 50mm to 800mm, after tested, time between 100 ~ 500nm, has best use effect.
Owing to needing to use etching solution to etch in manufacturing process, if ITO layer 3 sheet resistance is excessive, then cannot bear the erosion of etching solution, ITO layer 3 is caused to be damaged, therefore, the size of ITO layer 3 sheet resistance there is is important impact to interpolation copper conductor layer 4, will illustrate further according to embodiment below:
Comparative example 2: first substrate 1 is done electricity slurry cleaning pre-treatment, then optical adjustment layer 2, ITO layer 3 and copper conductor layer 4 on sputter or evaporation in its surface, wherein copper conductor layer 4 thickness is 200nm, ITO layer 3 selects sheet resistance to be 600 Ω/ after the heat treatment of 60 minutes under 150 DEG C of conditions, obtained ITO conducting film is invaded 1N hydrochloric acid within 3 minutes, etch, then measure the sheet resistance of ITO layer 3 after resistance change rate and etch copper conductor layer.
Embodiment 7: first substrate 1 is done electricity slurry cleaning pre-treatment, then optical adjustment layer 2, ITO layer 3 and copper conductor layer 4 is sequentially plated by the mode of sputter or evaporation on substrate 1, wherein copper conductor layer 4 thickness is 200nm, ITO layer 3 selects sheet resistance to be 400 Ω/ after the heat treatment of 60 minutes under 150 DEG C of conditions, obtained ITO conducting film is invaded 1N hydrochloric acid within 3 minutes, etch, then measure the sheet resistance of ITO layer 3 after resistance change rate and etch copper conductor layer.
Embodiment 8: the preparation flow of embodiment 8 is identical with embodiment 7 with structure, does not exist together and is only: ITO layer 3 selects sheet resistance to be 250 Ω/.
Embodiment 9: the preparation flow of embodiment 9 is identical with embodiment 7 with structure, does not exist together and is only: ITO layer 3 selects sheet resistance to be 150 Ω/.
Embodiment 10: the preparation flow of embodiment 10 is identical with embodiment 7 with structure, does not exist together and is only: ITO layer 3 selects sheet resistance to be 100 Ω/.
Embodiment 11: the preparation flow of embodiment 11 is identical with embodiment 7 with structure, does not exist together and is only: ITO layer 3 selects sheet resistance to be 80 Ω/.
Embodiment 12: the preparation flow of embodiment 12 is identical with embodiment 7 with structure, does not exist together and is only: ITO layer 3 selects sheet resistance to be 50 Ω/.
Embodiment 7 to 12 and comparative example 2 are carried out respectively the checking of the effects such as ITO sheet resistance after resistance change rate, etch copper conductor layer, and by result taxonomic revision as shown in following table two.
Table two: ITO sheet resistance rate of change result:
Can see from table two, along with the reduction of ITO layer sheet resistance, after adopting the carrying out of 1N hydrochloric acid to etch, resistance change rate progressively diminishes, during ITO Biao Mian electricity Zu≤400 Ω/, immersion 1N hydrochloric acid resistance Bianization Shuai≤20% after 3 minutes, and during ITO Biao Mian electricity Zu≤150 Ω/, resistance change rate is all less than or equal to 5%.And during ITO Biao Mian electricity Zu≤80 Ω/, immersion 1N hydrochloric acid resistance Bianization Shuai≤2% after 3 minutes, though crystallinity is better, ITO thickness is blocked up, and after causing ITO to be made into circuit, the etching area with or without ITO is obvious, cannot meet the requirement without etched mark.During ITO sheet resistance >400 Ω/, after etch copper conductor layer, ITO surface electrical resistive is large, and ITO crystallinity is poor, cannot be acidproof, can etch away ITO layer in the lump during etch copper conductor layer.
As can be seen here, when the sheet resistance of ITO layer 3 is between 80 ~ 400 Ω/, has and use effect preferably, preferably, the sheet resistance of ITO layer 3 is between 80 ~ 150 Ω/.And described ITO layer 3 thickness is between 15nm ~ 35nm.
Because only copper conductor layer 4 is as avris conducting wire; therefore after center etches away copper conductor layer 4; again ITO layer 3 can be etched (as etching induction line); the etching area at center can, because causing the equation of light in reflection different with or without ITO, so, need to be provided with optical adjustment layer 2 and light modulation hardening coat 5 with non-etching area; just can reach best effect; if improve without optical adjustment layer 2, then etching mark can clearly, cause light efficiency poor.
To illustrate further according to embodiment below:
Comparative example 3: sequentially make general hardening coat, ITO layer 3 and copper conductor layer 4 on base material 1, its thickness is 1000nm, refractive index is 1.54, copper conductor layer 4 thickness is 200nm, ITO layer 3 thickness is 20nm, obtained ITO conducting film is invaded 1N hydrochloric acid within 3 minutes, etch, then measure the sheet resistance of ITO layer 3 after resistance change rate and etch copper conductor layer.
Embodiment 13-25: sequentially make light modulation hardening coat 5, ITO layer 3, copper conductor layer 4 on base material 1, and light modulation hardening coat 5, hardening coat 5, the thickness of optical adjustment layer 2, refractive index, and copper conductor layer 4, ITO layer 3 thickness are respectively shown in embodiment, obtained ITO conducting film is invaded 1N hydrochloric acid within 3 minutes, etch, then the sheet resistance of ITO layer 3 after resistance change rate and etch copper conductor layer is measured, wherein, described light modulation hardening coat 5 adopts wet to be formed in base material 1 surface.
Table three, has each embodiment parameter of light modulation hardening coat:
According to the parameter of above comparative example, each embodiment, measure and etch away correlation properties after copper conductor layer 4, measurement result as shown in Table 4:
Table four,
Comparative example 3, embodiment 13 can be found out: the hardening coat of comparative example 3 is adopted as general hard conating structure, and the aberration not for ITO layer 3 etching front and back carries out optical design, causes colourity b value higher (being 2.5), cause etching aberration existing defects.The light modulation hardening coat of the application and the different of general hardening coat, described light modulation hardening coat 5 is for having the slip hard conating of anti scuffing effect or the anti-hyun smooth hard conating containing outstanding particle, and its thickness is 300nm ~ 2um, and etching look desirable.
Further, can find out from embodiment 13-17: when the thickness of light modulation hardening coat 5 is lower than 300nm, case hardness Hui≤HB, HB is pencil hardness unit, easily causes face scratch; When the thickness of light modulation hardening coat 5 reaches 2000nm, though case hardness reaches 3H, product reelability is deteriorated, after carrying out 180 degree of flexings with coil diameter 10mm pole, cause light modulation hard conating to occur slight crack, therefore the thickness of light modulation hard coat layer thickness 5 need between more than 300nm and within 2 microns.
From embodiment 18,19,20 can find out: the refractive index of light modulation hardening coat 5 is 1.8 Shi ， Although light transmittances, b value, etch aberration all OK with or without during ITO, but in NG in appearance, occur the interference of rainbow line.
Can find out from embodiment 13-20: the refractive index of light modulation hardening coat 5 for good, comprehensive light transmittance, b value, reaches the optimum condition of a balance between 1.6 ~ 1.7 with or without etching aberration during ITO, outward appearance.
From embodiment 13,21,22,23 can find out: the thickness of optical adjustment layer 2 is between 10 ~ 40nm, and refractive index is for good between 1.4 ~ 1.5.From embodiment 13,24,25 can find out: when ITO layer 3 thickness reaches 40nm, even if there is optical adjustment layer still cannot the blocked up color distortion caused of modifying factor ITO, and cause aberration obvious, therefore ITO layer 3 thickness be good with below 40nm.
In sum, the present invention is by setting up copper conductor layer 4, and light modulation hardening coat is set to refractive index between 1.6 ~ 1.7 and thickness is greater than the pH effect hard conating of 300nm, and, copper conductor layer 4 thickness increased is at 100 ~ 500nm, and during ITO layer 3 Biao Mian electricity Zu≤400 Ω/, there is good resistance change rate, obtain good result of use.
The present invention above ITO conducting film by copper conductor layer in making ITO on, because conductive layer is metal, do not need to add adhesive agent, therefore only need the thickness of hundreds of how rice can reach the conductive effect of demand, simultaneously because of the interpolation without adhesive agent, so also solve the problem of flexing simultaneously.By technique scheme, the present invention only needs to use existing printing or yellow photolithographic techniques, printed wire on copper conductor layer, can etch the wire of demand.
The foregoing is only embodiments of the invention; not thereby the scope of the claims of the present invention is limited; every utilize description of the present invention to do equivalent structure or equivalent flow process conversion; or be directly or indirectly used in other relevant technical fields, be all in like manner included in scope of patent protection of the present invention.
Claims (10)
1. the ITO conducting film of a copper coating, comprise the optical adjustment layer (2) be cascading in base material (1) side, ITO layer (3) and copper conductor layer (4), it is characterized in that: between base material (1) and optical adjustment layer (2), be provided with light modulation hardening coat (5), described copper conductor layer (4) thickness is 50nm ~ 800nm, described light modulation hardening coat (5) refractive index is between 1.6 ~ 1.7, described light modulation hardening coat (5) thickness is between 300nm ~ 2um, described ITO layer (3) thickness is at 15nm ~ 35nm, the Biao Mian electricity Zu≤400 Ω/ of described ITO layer (3).
2. the ITO conducting film of copper coating according to claim 1, is characterized in that: the opposite side of described base material (1) is provided with light modulation hardening coat (5).
3. the ITO conducting film of copper coating according to claim 1, is characterized in that: the opposite side of described base material (1) is relatively provided with light modulation hardening coat (5), optical adjustment layer (2), ITO layer (3) and copper conductor layer (4).
4. the ITO conducting film of the copper coating according to any one of claims 1 to 3, is characterized in that: described copper conductor layer (4) thickness is preferably 100nm ~ 500nm.
5. the ITO conducting film of the copper coating according to any one of claims 1 to 3, is characterized in that: described ITO layer (3) thickness is preferably 20nm ~ 30nm.
6. the ITO conducting film of the copper coating according to any one of claims 1 to 3, is characterized in that: described copper conductor layer (4) material adopts fine copper or copper alloy.
7. the ITO conducting film of the copper coating according to any one of claims 1 to 3, is characterized in that: described light modulation hardening coat (5) wet is formed in base material (1) surface.
8. the ITO conducting film of the copper coating according to any one of claims 1 to 3, is characterized in that: described light modulation hardening coat (5) Thickness is at 300nm to 1 μm.
9. the ITO conducting film of copper coating according to claim 1, is characterized in that: after etching away copper conductor layer (4), its colour is between 0 ~ 2.0.
10. the ITO conducting film of the copper coating according to any one of claims 1 to 3, is characterized in that: the refractive index of described optical adjustment layer (2) is 1.4 ~ 1.5, and thickness is 10 ~ 40nm.
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