CN1389346A - Antireflective optical multilayer film - Google Patents
Antireflective optical multilayer film Download PDFInfo
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- CN1389346A CN1389346A CN01118612A CN01118612A CN1389346A CN 1389346 A CN1389346 A CN 1389346A CN 01118612 A CN01118612 A CN 01118612A CN 01118612 A CN01118612 A CN 01118612A CN 1389346 A CN1389346 A CN 1389346A
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Abstract
The anti-reflection optical multilayer film possesses five-layer structure, the layer farthest from base plate is used as first layer, and the next can be second layer, third layer, fourth layer and fifth layer. Said multilayer film comprises ITO as first layer, SiO2 as second layer, NbO as third layer, SiO2 as fourth layer and NbO as fifth layer. Said film possesses good electric conductivity, can shield EMI, can be used as touch sensing panel material with high transparency, low reflection, low cost and high scrath resistance.
Description
The present invention relates to a kind of plastics or optical multilayer film of glass substrate of being used for, particularly relating to a kind of outermost layer is the high antireflective optical multilayer film of high refractive index transparent conducting film.
U.S. Pat 4,921,790 disclose a kind of multi-layer anti-reflective film, have at CeO
2Reach excellent adhesion is arranged between the synthetic resin.This assembly of thin films turnkey contains CeO
2, Al
2O
3, ZrO
2, SiO
2, TiO
2And Ta
2O
5All films in this multilayer film system are all oxide material, and this multilayer film system has 3 to 5 layer films.According to its cited example, its multilayer film system has 5 layers of structure, and gross thickness is 3580 dusts.The superficial layer of this membrane system is SiO
2, in optical design a kind of low-index material, its refractive index is 1.46 at wavelength during for 550nm.
U.S. Pat 5,105,310 disclose a kind of multi-layer anti-reflective film, can produce in continuous vacuum coating machinery by the reaction sputtering method.This assembly of thin films turnkey contains TiO
2, SiO
2, ZnO, ZrO
2And Ta
2O
5All films in this multilayer film system are all oxide material, and this multilayer film system has 4 to 6 layer films.According to its cited example, its multilayer film system has 6 layers of structure, and gross thickness is 4700 dusts.The superficial layer of this membrane system is SiO
2, in optical design a kind of low-index material, its refractive index is 1.46 at wavelength during for 550nm.
U.S. Pat 5,091,244 and US 5,407,733 disclose a kind of novel conduction, optical attenuation and antireflection multilayer films.Its main claim is for providing a kind of conduction, optical attenuation and antireflective optical multi-layer film material and structure.Its assembly of thin films turnkey contains TiN, NbN, SnO
2, SiO
2, Al
2O
3, and Nb
2O
5All films of this multilayer film system are all oxide or nitride material, and this multilayer film system has 3 to 4 layer films.According to its cited example, its multilayer film system has 4 layers of structure, and gross thickness is 1610 dusts, and is lower than 50% for the transmittance of visible light.The superficial layer of this membrane system is SiO
2, in optical design a kind of low-index material, its refractive index is 1.46 at wavelength during for 550nm.
U.S. Pat 5,147,125 disclose a kind of multi-layer anti-reflective film, have the uvioresistant effect of zinc paste so that wavelength to be provided less than 380nm.This assembly of thin films turnkey contains TiO
2, SiO
2, ZnO and MgF
2All films of this multilayer film system are all oxide or fluoride materials, and this multilayer film system has 4 to 6 layer films.According to its cited example, its multilayer film system has 5 layers of structure, and gross thickness is 7350 dusts.The superficial layer of this membrane system is MgF
2, in optical design a kind of low-index material, its refractive index is 1.38 at wavelength during for 550nm.
U.S. Pat 5,170, a kind of four-level membrane of 291 announcements system has optical effect and high anti-reflection effect is arranged.This multilayer film system can use pyrolysismethod, electricity slurry assistant chemical vapor deposition process, method for sputtering or chemical deposition forms.This assembly of thin films turnkey contains TiO
2, SiO
2, Al
2O
3, ZnS, MgO, and Bi
2O
3According to its cited example, its multilayer film system has 4 layers of structure, and gross thickness is 2480 dusts.The superficial layer of this membrane system is SiO
2, in optical design a kind of low-index material, refractive index is 1.46 at wavelength during for 550nm.
U.S. Pat 5,216,542 disclose a kind of five layer film systems, have high anti-reflection effect.It comprises a thickness and is about 1nm, and material is Ni, Cr or the adhesion layer of NiCr, and other four layer materials can comprise SnO
2, ZnO, Ta
2O
5, NiO, CrO
2, TiO
2, Sb
2O
3, In
2O
3, Al
2O
3, SiO
2, TiN and ZrN.According to its cited example, its membrane system has 5 layers of structure, and gross thickness is 2327 dusts, and is lower than 30% for the transmittance of visible light.The superficial layer of this membrane system is SiO
2, in optical design a kind of low-index material, its refractive index is 1.46 at wavelength during for 55Onm.
U.S. Pat 5,541,770 disclose a kind of four or five layer film systems, be optical attenuation and antireflection multilayer film, and one deck conductive layer is arranged.This membrane system comprises an extinction high index of refraction metal level, Cr for example, and Mo and W, this extinction high index of refraction metal level is as the optical effect film in this membrane system.Other three or four layers of this membrane system is TiO
2, ITO, Al
2O
3, SiO
2And TiN.All films of this multilayer film system mostly are oxide or nitride material greatly.According to its cited example, its membrane system has 5 layers of structure, and gross thickness is 1495 dusts, and is lower than 60% for the transmittance of visible light.The superficial layer of this membrane system is SiO
2, in optical design a kind of low-refraction material section, its refractive index is 1.46 at wavelength during for 550nm.
U.S. Pat 5,362,552 disclose a kind of six layer film systems, be an antireflection multilayer film, and three-layer metal oxide conducting layer is arranged.This membrane system comprises SiO
2, ITO, Nb
2O
5And Ta
2O
5The metal oxide optical thickness that can comprise at most in this membrane system is about a visible wavelength.Two the thickest SiO that film is 854 dusts of these six layers of structures
2And the ITO of 1975 dusts.The superficial layer of this membrane system is SiO
2, in optical design a kind of low-index material, its refractive index is 1.46 at wavelength during for 550nm.
U.S. Pat 5,579,162 disclose a kind of four layers of antireflection multilayer film, and are used for the thermal sensitivity substrate as plastics and so on.One deck in this membrane system is a DC reaction jet-plating metallization oxide skin(coating), and this DC reaction jet-plating metallization oxide skin(coating) can fast deposition and can not brought substrate too much heat.Two the thickest SiO that film is 940 dusts of this four-layer structure
2And the SnO of 763 dusts
2The superficial layer of this membrane system is SiO
2, in optical design a kind of low-index material, its refractive index is 1.46 at wavelength during for 550nm.
U.S. Pat 5,728,456 and US 5,783,049 disclose a kind of modification method on plastics, to deposit antireflection multilayer film.This multilayer book film system uses scroll bar formula vacuum coating system (Roller Coater) to cooperate sputtering process.This membrane system comprises ITO, SiO
2And a book lubricating layer, this thin lubricating layer is the fluoride of solubility.According to its cited example, its membrane system has 6 layers of structure, and gross thickness is 2630 dusts.The superficial layer of this membrane system is SiO
2, in optical design a kind of low-index material, its refractive index is 1.46 at wavelength during for 550nm.
Among above-mentioned each known patent, the surface film of optical system is SiO
2Or MgF
2, in optical design a kind of low-index material, its refractive index is 1.46 or 1.38 at wavelength during for 550nm.
The process of traditional a large amount of manufacturing sulls has high reliability, and is widely used in semiconductor, CD reading head, LCD, CRT, building glass, contact type panel, screen eye-protection screen and coating film on glass, and oneself has the history of many decades.
The structure of traditional antireflective optical multilayer film has a general rule.The cardinal rule superficial layer of antireflective optical multilayer film for this reason is the material with low-refraction, and for example surface film is SiO
2Or MgF
2, and its refractive index is respectively 1.46 or 1.38.Yet this antireflective optical multilayer film is being applied to display industry, for example when fluoroscopic eye-protection screen of computing machine or the low-reflection glass of plane CRT, because traditional antireflective optical multi-layer film surface layer is SiO
2Or MgF
2, therefore when a large amount of production, can run into obstacle.
In the general design concept of traditional antireflective optical multilayer film, the film that is plating at the substrate surface ground floor is the membraneous material (calling H in the following text) with high index of refraction, and the ensuing second layer is the membraneous material (calling L in the following text) with low-refraction.Therefore, the structure of traditional antireflective optical multilayer film is HLHL or HLHLHL.Lifting a comparatively simple example, is SiO if the material H of high index of refraction is the material L of ITO, low-refraction
2, then this four-layer structure is glass/ITO/SiO
2/ ITO/SiO
2Because ITO has electric conductivity, therefore, the resistance coefficient of this multilayer system can be lower than 1000 Ω/.When this conductive layer ground connection, this conductive layer can be used as the EMI screen layer or static is got rid of layer.Yet traditional antireflective optical multilayer film superficial layer is SiO
2, and its thickness is 1000 dusts.SiO
2Properties of materials is high density, chemical inertness and electrical insulating property, therefore, and when this antireflective optical multilayer film is used for display, because the ITO layer is by SiO
2Layer envelopes, and therefore is difficult to form contact electrode with the conducting of ITO layer.This antireflective optical multilayer film need use ultrasonic welding process to destroy this SiO
2Layer makes scolding tin good electric the contact be arranged with the ITO layer.When using multilayer optical film shield as EMI, Flat-Panel CRT or other display desire often meet with this difficulty, the obstacle of Here it is this antireflective optical multilayer film of extensive application.
On the other hand, liquid tin in this supersonic welding termination process and the ultrasonic energy sparklet that can cause scolding tin pollutes.And this supersonic welding termination process can't guarantee to destroy SiO equably
2Layer makes metallic tin and ITO layer form uniform contact.
Above-mentioned shortcoming can reduce the yield rate that traditional antireflective optical multilayer film is used in display industry, therefore, if the ITO layer can then can overcome the problems referred to above as the superficial layer of antireflective optical multilayer film.Yet this has violated the principle of design of general HLHL.
In view of the above-mentioned shortcoming of prior art, the object of the present invention is to provide and a kind ofly when commercial Application, can simplify ground connection technology, and can be applied to the display of glass or plastic base or the antireflection conductive multilayer film of touch screen.
For achieving the above object, have the five-layer structure that is formed on the substrate according to antireflective optical multilayer film of the present invention, this five-layer structure comprises by the ground floor of counting away from orientation substrate, the second layer, the 3rd layer, the 4th layer and layer 5 sandwich construction; Ground floor is the oxide with high index of refraction, and its solid thickness is 10-60nm; The second layer is the oxide with low-refraction, and its solid thickness is 10-70nm; The 3rd layer of oxide for having high index of refraction, its solid thickness is 30-100nm; The 4th layer is the oxide with low-refraction, and its solid thickness is 10-70nm; Layer 5 is the oxide with high index of refraction, and its solid thickness is 10-60nm.
Ground floor according to antireflective optical multilayer film of the present invention, be that superficial layer is an including transparent conducting oxide layer, this including transparent conducting oxide layer is preferably the ITO layer, it omits the tool absorbability under visible light, under wavelength 550nm, its refractive index is 1.9-2.1, and its solid thickness is 10nm-40nm under this wavelength.
The second layer is an oxide material, is preferably SiO
2, it does not absorb visible light, and under wavelength 550nm, refractive index is 1.45-1.50, and its solid thickness is 30nm-50nm under this wavelength.
The 3rd layer is oxide material also, is preferably NbO, and it does not absorb visible light, and under wavelength 550nm, refractive index is 2.0-2.3, and its solid thickness is 30nm-80nm under this wavelength.
The 4th layer is oxide material, is preferably SiO
2, it does not absorb visible light, and under wavelength 550nm, refractive index is 1.45-1.50, and its solid thickness is 20nm-30nm under this wavelength.
Layer 5 (innermost layer) is an oxide material also, is preferably NbO, and it does not absorb visible light, and under wavelength 550nm, refractive index is 2.0-2.3, and its solid thickness is 10nm-30nm under this wavelength.
According to antireflective optical multilayer film of the present invention, it is that ITO and thickness are that the ground floor of 25nm, a material are SiO that its five-layer structure comprises a material
2Thickness be the second layer of 40nm, material for NbO thickness be that the 3rd layer, one material of 60nm is SiO
2Thickness is that the 4th layer of 26nm and a material are the layer 5 of 18nm for NbO thickness.
According to the present invention, the ITO layer can make the low 100 Ω/-1000 Ω/ that reaches of the superficial layer resistance value of this antireflective optical multilayer film.Moreover this antireflective optical multilayer film can be used for glass or plastic base, and wavelength coverage is 400-700nm.It is one simple and easy, reliable and meet the antireflective optical multilayer film of economic benefit that the present invention can provide.This antireflective optical multilayer film has surface of good electric conductivity.The particularly important is the present invention and can use the continous way sputter system capable to come this multilayer optical book film of deposit, reach and reduce cost and mass-produced purpose.
On the other hand, have the good electrical conductivity that can shield EMI, the high grade of transparency that can be used as touch sensing panel material, the antiradar reflectivity that meets visual effect, anti scuffing characteristic and low cost according to antireflective optical multilayer film of the present invention.This antireflective optical multilayer film can realize meeting the anti scuffing characteristic of MIL-C-48497 standard.
In the present invention, can use DC or AC magnetron sputter reactor to make first tunic by the ITO target, production environment atmosphere is Ar gas and a spot of O
2, pressure is the 2m torr.Can use the AC magnetron sputter reactor to make second and the 4th layer SiO by silicon target
2Layer, production environment atmosphere is Ar and O
2Mixed gas, pressure are the 2m torr.Can use DC or AC magnetron sputter reactor to be made the 3rd and the NbO layer of layer 5 by the Nb target, production environment atmosphere is Ar and O
2Mixed gas, pressure are the 2.5m torr.
Because the present invention is provided with the ITO conductive layer on antireflection multilayer optical thin film surface, thus in the prior art ITO conductive layer by SiO
2The problem that layer buries can be resolved.The invention provides the antireflective optical multilayer film of one five layer system, superficial layer is the ITO conductive layer, and refractive index is up to 1.9-2.1.
Because the superficial layer of this antireflective optical coating layer is a conductive layer, electrode can be formed on this antireflective optical multilayer film at an easy rate, and the present invention is particularly advantageous in the application of tactile sensor.
When antireflective optical multilayer film being applied to plane CRT or screen light filter, existing ultrasound wave earthing mode can cause sparklet to pollute.Can head it off according to the antireflection multilayer film with electrically conducting transparent superficial layer of the present invention, make the ITO layer no longer include inhomogeneous electric contact, the rate of pass is increased.
On the other hand, antireflective optical multilayer film of the present invention system can be as the basic multilayer film of tactile sensor.
Therefore, simple and easy and economic effect is arranged according to five layer systems with electrically conducting transparent superficial layer of the present invention, can be as the antireflective optical multilayer film of plastics or glass substrate.
Brief Description Of Drawings:
Fig. 1 is the film layer structure figure according to the antireflective optical multilayer film of the preferred embodiments of the present invention;
Fig. 2 is the wavelength response curve according to the reflectivity of antireflective optical multilayer film of the present invention.
Preferred embodiment describes in detail
The invention provides a kind ofly based on oxide and have the antireflective optical multilayer film of five-layer structure, the sandwich construction of this antireflective optical multilayer film is by the outermost layer open numbering.The thickness of each layer can represent with solid thickness or optical thickness, and wherein optical thickness is that the thickness of this layer multiply by the refractive index of this layer, and can calculate with wavelength, and in the present invention, wavelength set is 550nm.
As shown in Figure 1, the substrate 7 of antireflective optical multilayer film of the present invention can be glass, plastic foil or other transparent material, and this substrate 7 has a front surface 6 (observing along arrow 8 indicated directions).Rete 5 touches the front surface 6 of substrate 7, is the layer 55 of antireflective optical multilayer film of the present invention; Along the direction to the observer then is the 4th layer 4, and this 4th layer 4 is positioned on the 55; Along the direction to the observer then is the 3rd layer 3, and this 3rd layer 3 is positioned on the 4th layer 4; Then be the second layer 2 along the direction to the observer, this second layer 2 is positioned on the 3rd layer 3; Then be ground floor 1.These five retes 1,2,3,4,5 constitute five layer systems of antireflective optical multilayer film of the present invention.
Fig. 2 is the wavelength response curve according to the reflectivity of antireflective optical multilayer film of the present invention.System is by surface measuring before the glass, and visible wavelength is by 400nm to 700nm.By curve as can be seen, this five-layer structure is at core wavelength (460nm to 600nm), and reflection coefficient is low to 0.3%.This result and similar by the multilayer system of traditional HLHL processing procedure manufacturing.
Table one is the detailed reflection coefficient of wavelength by 400nm to 700nm.In the present invention, oxide layer 2,3,4,5 tie up to the AC method for sputtering and use a magnetron electrode, and processing environment atmosphere is Ar and O
2Mixed gas.On the other hand, for the ITO of ground floor 1, be to use AC, DC or DC pulse wave mode, and containing Ar and minority O
2Form in the processing environment atmosphere of reaction mixture gas body.For rete 5,4,3,2,1 target material is respectively Nb, Si, Nb, Si, ITO.Target to the distance of substrate is 15 centimeters.And use this sputter system capable of a heater heats, make substrate temperature remain on 100-300 ℃.
Table one
In the present invention, the processing procedure pressure condition is as follows: for the sputter of layer 5: 2.5m Torr is for the 4th layer sputter: 2m Torr is for the 3rd layer sputter: 2.5m Torr is for the sputter of the second layer: 2m Torr is for the sputter of ground floor: 3m Torr
Wavelength (nm) | Reflection coefficient (%) |
????400 | ????7.40 |
????420 | ????1.96 |
????440 | ????0.27 |
????460 | ????0.18 |
????480 | ????0.16 |
????500 | ????0.15 |
????520 | ????0.14 |
????540 | ????0.10 |
????560 | ????0.11 |
????580 | ????0.41 |
????600 | ????0.90 |
????620 | ????0.60 |
????640 | ????2.50 |
????660 | ????3.54 |
????680 | ????4.68 |
????700 | ????5.90 |
In sum, according to antireflective optical multilayer book film of the present invention have good electric conductivity with shielding EMI, the high grade of transparency with material that touch sensing panel is provided, antiradar reflectivity to meet visual effect, anti scuffing characteristic and low cost.
Claims (11)
- One kind to have nesa coating be outermost antireflective optical multilayer film, this antireflective optical multilayer film has five-layer structure and forms on a substrate, and these 5 layers of structures comprise by the ground floor of counting away from orientation substrate, the second layer, the 3rd layer, the 4th layer and layer 5 sandwich construction; It is characterized in thatThis ground floor is positioned on this second layer, and for having the oxide of high index of refraction, its solid thickness is 10-60nm;This second layer is positioned on the 3rd layer, and for having the oxide of low-refraction, its solid thickness is 10-70nm;The 3rd layer is positioned on the 4th layer, and for having the oxide of high index of refraction, its solid thickness is 30-100nm;The 4th layer is positioned on this layer 5, and for having the oxide of low-refraction, its solid thickness is 10-70nm;This layer 5 is positioned on this substrate, and for having the oxide of high index of refraction, its solid thickness is 10-60nm.
- 2. according to the antireflective optical multilayer film of claim 1 record, it is characterized in that described substrate is a plastic plate, its material is PC, PMMA, PET, ARTON etc.
- 3. according to the antireflective optical multilayer film of claim 1 record, it is characterized in that described substrate is a glass.
- 4. according to the antireflective optical multilayer film of claim 1 record, it is characterized in that described ground floor material is ITO; The second and the 4th layer material is SiO 2The 3rd and the layer 5 material be NbO.
- 5. according to the antireflective optical multilayer film of claim 1 record, it is characterized in that described ground floor material can be ITO, SnO 2, ZnO, In 2O 3, SnO 2: F, SnO 2: Sb, ZnO: Al, In 2O 3: ZnO, SnO 2: ZnO and In 2O 3: MgO.
- 6. according to the antireflective optical multilayer film of claim 1 record, it is characterized in that the described second and the 4th layer material can be SiO 2And SiAlO 2
- 7. according to the antireflective optical multilayer film of claim 1 record, it is characterized in that the described the 3rd and the layer 5 material can be ITO, Ta 2O 5, NbO, TiO, Al 2O 3, SiN, SiNO, AlN, AlNO, and composition thereof.
- 8. according to the antireflective optical multilayer film of claim 1 record, it is characterized in that described layer 5 material can be TaO, NbO, TiO, Al 2O 3, SiN, SiNO, AlN, AlNO, and composition thereof.
- 9. according to the antireflective optical multilayer film of claim 1 record, it is characterized in that described ground floor is an oxide skin(coating), refractive index is 1.9-2.1; Second and the 4th layer is oxide skin(coating), and refractive index is 1.46-1.5; The 3rd and layer 5 be oxide skin(coating), refractive index is 2.1-2.3.
- 10. according to the antireflective optical multilayer film of claim 1 record, it is characterized in that described multilayer made by the evaporation or the sputter system capable of batch or continous way production.
- 11. the antireflective optical multilayer film according to claim 1 record is characterized in that can be applicable to display relevant industries such as LCD, CRT and contact type panel.
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