CN107645988A - Titanium ickel-niobium alloy barrier layer for low-emissivity coating - Google Patents

Abstract

A kind of method for preparing Low emissivity panel, including：The composition on the barrier layer that control is formed on thin conductive silver layer.The barrier structure containing nickel, titanium, niobium ternary alloy three-partalloy, it shows and had improved properties on the whole compared with binary barrier layer.The percentage of nickel can be 5 15wt%, and the percentage of titanium can be 30 50wt%, and the percentage of niobium can be 40 60wt%.

Description

Titanium ickel-niobium alloy barrier layer for low-emissivity coating

The interaction reference of related application

The application is that the part for the U.S. Patent application No.13/797,504 applications submitted on March 12nd, 2013 continues.Its It is included into and is herein incorporated by reference.

Technical field

It is particularly a kind of to configure on the transparent substrate the present invention relates to a kind of film for providing high-transmission rate and low-E Film.

Background technology

Solar-control glazing is generally used for following application, such as building glass window and vehicle window, the commonly provided higher visible Light transmission and low-E.Higher transmission of visible light can make more sunlight pass through windowpane, therefore by more preferably Applied in many windows.Low-E can prevent infrared (IR) radiation from reducing undesirable indoor heating.

In low-E glass, infra-red radiation is mainly shown as with minimal absorption rate and radiation, low so as to reduce The heat transfer of emissivity surfaces.Low-E or Low emissivity panel are typically that reflecting layer (such as silver) is deposited on substrate by shape Into such as glass.The total quality in the reflecting layer, it is particularly significant for the performance needed for realizing such as texture and crystal orientation, it is such as higher Transmission of visible light and low-E (that is, higher heat reflection).In order to provide bonding force and protection, generally in reflecting layer Above and below forms some other layers.These layers generally include dielectric layer, such as silicon nitride, tin oxide, and zinc oxide, in storehouse Stop is provided between substrate and environment, and it is special to improve the optics of panel as optics filler and as ARC Property.

The known method for realizing low-E is to form the silver layer of relative thick.However, with the increase of silver thickness, instead The transmission of visible light for penetrating layer is reduced, and manufacture handling capacity also declines, and overall manufacturing cost is increased.Therefore, desirable form It is to make silver layer as thin as possible, while the radiance for being suitable for Low emissivity application is provided.

The content of the invention

In certain embodiments, there is provided a kind of barrier structure, and the method for forming the barrier structure, for will be The infrared reflecting layer used in low-emissivity coating.The barrier layer may include the ternary alloy three-partalloy of titanium, nickel and niobium.The percentage of titanium can For 5-15wt%.The percentage of nickel can be 30-50wt%, and the percentage of niobium can be 40-60wt%.

In some implementations, there is provided a kind of barrier structure, and the method for forming the barrier structure, for will be low The infrared reflecting layer used in emissivity coatings.The barrier layer may include the ternary alloy three-partalloy of nickel, titanium and niobium.The percentage of nickel can be 5-15wt%.The percentage of titanium can be 30-50wt%, and the percentage of niobium can be 40-60wt%.

In certain embodiments, infrared reflecting layer may be formed on bottom, such as anti-reflecting layer or Seed Layer.Bottom can wrap Include metal oxide materials, such as zinc oxide, the zinc oxide of doping, tin oxide, the tin oxide of doping, or the oxide of zinc and tin Alloy.

In certain embodiments, the optically and mechanically performance of barrier structure can be optimised, including low visible light absorbs Rate, higher transmission of visible light, higher infrared reflectivity, higher mechanical endurance and adhesive property.For example, high content Nickel and niobium can improve the durability of coating, such as pass through the interface strengthened with silver layer.With binary nickel alloy and other combine The ternary nickel alloy of thing scope is compared, and ternary alloy three-partalloy can show more preferable overall performance.

Brief description of the drawings

In order to make it easy to understand, it is used to represent identical part using identical reference marks in the conceived case.It is attached Figure does not have a ratio, and the relative size of each part is schematically shown and Non-scale in figure.

It is described in detail referring to the drawings, so as to which the technology of the present invention can be best understood from, wherein：

Figure 1A shows the exemplary film coating according to some embodiments.

Figure 1B shows the low-E transparent panel 105 according to some embodiments.

Fig. 2A -2B show physical vapour deposition (PVD) (PVD) system according to some embodiments.

Fig. 3 shows the exemplary online depositing system according to some embodiments.

Fig. 4 shows to be responded according to the sheet resistance of the Low emissivity storehouse with different blocking material of some embodiments.

Fig. 5 shows the flow chart of the splash coating according to some embodiments.

Fig. 6 shows the flow chart of the splash coating according to some embodiments.

Fig. 7 shows the performance data table of the various materials as barrier layer.

Fig. 8 shows the flow chart of the splash coating according to some embodiments.

Embodiment

One or more embodiments are described in detail referring to the drawings.Detailed description be for these embodiments and There is provided, but be not limited to any particular example.Scope is only limitted to claim, and includes various replacements, modification and equivalent. Many details are suggested to provide thorough explanation in the following description.These details are carried as the purpose of example For, and the technology illustrated can be carried out according to claim, without some or all of details.For the sake of clarity, Known technology material in the technical field related to embodiment is not described in detail to avoid making explanation smudgy.

In certain embodiments, a kind of method and apparatus for manufacturing coating panel is disclosed.The coating panel can include The coating being formed thereon, such as the thin infrared reflecting layer with such as low-resistivity of silver etc conductive material.This is infrared anti- Conductive material can be included by penetrating layer, and its reflectivity is proportional to electrical conductivity.Thus, for example the metal level of silver, can be in Low emissivity It is used as infrared reflecting layer in rate coating.In order to keep the conductance of infrared reflecting layer, such as silver layer, the oxygen of subsequent deposited layers is prevented Change or follow-up high annealing, barrier layer can be formed on silver layer.

In certain embodiments, the method and apparatus for manufacturing low-emissivity coating panel, it is included under this condition Barrier layer is deposited on the conductive layer of similar silver, it is optimal to make the resistivity of silver and the radiance of coating panel.For example, pass through Contain the barrier layer protected of titanium, niobium and nickel, it is possible to achieve low resistance silver layer or low-E panel.

Titanium can be as the barrier layer of low-emissivity coating, and this is due to its high oxygen affinity, such as attracts oxygen to prevent Silver layer aoxidizes.Using the low-emissivity coating of titanium barrier layer can show outstanding transmission of visible light and minimum it is infrared Reflectivity.However, due to poor with the bonding force of silver layer, poor machinery is shown using the low-emissivity coating of titanium barrier layer Durability.

Nickel can be added into titanium barrier layer to change barrier properties.In general, Ti-Ni alloy can improve antiacid Corrosion in property or alkaline solution, provides protection in high-temperature oxidation process.Nickel-containing alloys be described with enough with it is infrared The bonding force in reflecting layer, so as to improve overall chemistry and mechanical endurance.

In certain embodiments, various nickel alloys are evaluated, including binary nickel alloy (such as nickel chromium triangle and NiTi) With ternary nickel alloy (such as nickel titanium niobium).Generally, different binary nickel alloys shows difference under different requirements Performance.For example, NiTi can provide slight improvement in terms of translucency, almost do not improve in terms of mechanical endurance. Nickel content is higher in Ti-Ni alloy, and silver-colored bonding force is stronger.For example, compared with there is 50wt% nickel in Ti-Ni alloy, titanium nickel More preferable bonding force can be shown when there is 80wt% nickel in alloy.In contrast, nickel chromium triangle can be in mechanical endurance side Face provides significant improvement, but poor in terms of optical property.

In certain embodiments, the ternary alloy three-partalloy of nickel, titanium and niobium can show more preferable overall performance, for example, with titanium phase Than there is more preferable mechanical endurance, improve the bonding force with silver layer.Nickel, titanium and niobium ternary alloy three-partalloy are in optical property Have similar or slightly improve, such as reduce radiance and absorptivity, while improve light transmittance.For example, resistance measurement as shown by data, Compared with titanium and bianry alloy, such as NiTi or NiCr, ternary alloy three-partalloy, which provides, preferably stops protection.

Document shows that the niobium in titanium alloy can isolate with interface, so as to be favorably improved the bonding force of silver.However, simultaneously Not all titanium, nickel, niobium ternary alloy three-partalloy all have good optics, electricity and mechanical property.

In certain embodiments, the ternary alloy three-partalloy of the titanium with different range composition, nickel and niobium is disclosed, alloy tool There are outstanding combination property, including good optical property and good mechanical performance.For example, the percentage of niobium is higher, such as 40-60wt%, it can be used for improving mechanical endurance and not influence optics or electric property.Equally, of a relatively high percentage Nickel, such as higher than titanium but it is less than niobium, such as 30-50wt%, do not influence available for raising mechanical endurance and optics or electrical property Matter.The percentage of titanium can be relatively low, such as 5-15wt%, to provide required optical property.As an example, with titanium and Ti-Ni alloy Compare, the ternary alloy three-partalloy of the nickel of niobium, 40wt% with 50wt% and 10wt% titanium can show more preferable overall performance.

In certain embodiments, the ternary alloy three-partalloy of the titanium with different range composition, nickel and niobium is disclosed, the alloy can Preferably (i.e. relatively low) absorptivity, resistance and radiance are provided.The alloy can include the niobium of high percentage, such as 40-60wt%, optics or electric property are not influenceed available for improvement mechanical endurance and.The titanium of of a relatively high percentage, such as Higher than nickel but it is less than niobium, such as 30-50wt% can be used.The percentage of nickel can be with relatively low, such as 5-15wt%.As showing Example, ternary alloy three-partalloy can include 50wt% niobium, 40wt% titanium, and 10wt% nickel.

In certain embodiments, barrier layer can include the ternary oxide alloy of titanium, nickel and niobium.Oxide alloy stops Layer can be the oxide of stoichiometry, such as aoxidize ternary alloy three-partalloy containing enough oxygen.Oxide alloy barrier layer can To be protoxide alloy, for example, the amount of the oxygen atom in oxide alloy is less than stoichiometric proportion.

Barrier layer can improve low-emissivity coating panel, such as reduce the absorptivity in visible-range, such as allow Higher transmission of visible light, is reduced or eliminated and silver reaction to greatest extent, can be prevented the color degradation of coat system, be caused Muted color panel, improve the bonding force between silver and top barrier.

In certain embodiments, for manufacturing low-E panel method and apparatus, it includes low-resistance thin infrared anti- Layer is penetrated, the infrared reflecting layer includes conductive material, such as disclosed silver, gold or copper.Thin silver layer is smaller than 15nm, for example, 7 or 8nm.Silver layer can have relatively low roughness, and preferential deposition is in the same Seed Layer having compared with low roughness.For conduction Property, physical aspects and thickness, low-E panel can have the infrared reflecting layer that total quality is enhanced.For example, the party Method improves the electric conductivity in reflecting layer, can reduce so as to the thickness in reflecting layer but still provide preferable low-E.

Generally, reflecting layer preferably has relatively low sheet resistance, and this is due to that relatively low sheet resistance is relevant with low-E. In addition, reflecting layer is preferably the relatively thin transmission of visible light higher with offer.Therefore, in certain embodiments, disclose and be used for Deposit relatively thin and high conductivity reflecting layer method and apparatus, there is provided there is the painting of high visible light transmissivity and low-infrared radiation rate Layer.These methods can also improve the volumetric production of the manufacturing process for forming low-E panel to greatest extent, handle up Amount and efficiency.

In certain embodiments, the coating transparent panel being enhanced, such as coated glass are disclosed, have it is acceptable can See light transmission and infrared external reflection.Also disclose improved, coating, transparent panel the method for manufacture, the transparent panel bag Include the certain layer applied in layer stack.

The transparent panel of coating can include glass substrate or any other transparency carrier, such as be made up of organic polymer Substrate.The transparent panel of coating can be applied in window and used, such as vehicle and building window, skylight or glass door, monolithic Glass assembles or divided glass assembling, can with or can also not have plastic sandwich or be filled with the seal clearance of gas.

Figure 1A shows the exemplary film coating according to some embodiments.Barrier layer 115 is configured on infrared reflecting layer 113, Such as silver layer, silver layer configuration are saturating to form the coating with high visible light transmissivity and low-infrared radiation rate on substrate 110 Bright panel 100.

Layer 115 can be sputtered by using different engineering and equipment, for example, object can be in direct current (DC), arteries and veins Rush direct current, alternating current (AC), radio frequency (RF) or any other it is suitable under the conditions of be sputtered.In certain embodiments, disclose For the physical gas-phase deposite method of sedimentary 115, has minimum influence for infrared reflecting layer 113.

Infrared reflecting layer can include conductive material, have the reflectivity directly proportional to conductance.Metal is often used as Infrared reflecting layer, silver provides 95-99% reflectivity in region of ultra-red and gold provides 98-99% reflectivity.Therefore, similar silver Metal level, can be as the infrared reflecting layer in low-emissivity coating.The deposition of silver layer can be optimized to obtain higher lead Electrically, such as by reducing the impurity in silver layer.

Silver layer is as pure as possible, and the layer (for example, barrier layer) on silver layer is for preventing the oxidation of silver very It is important, for example, the oxygen reactive sputtering process in succeeding layer deposition.In addition, the barrier layer can prevent silver during glass tempering Layer and oxygen diffusion reaction, or sheet glass is exposed to environment or got wet in long-term use.

In order to keep the electric conductivity of infrared reflecting layer, such as silver layer, prevent when succeeding layer deposition or subsequent high temperature from annealing Oxidation, barrier layer can be formed on silver layer.Barrier layer can be oxygen diffusion impervious layer, and to protect silver layer, anti-block diffusion is worn Barrier layer is crossed to react with silver layer.

In addition to oxygen diffusion impervious layer feature, barrier layer also has other preferable features.For example, because barrier layer is straight Configuration is connect on silver layer, therefore low in silver of barrier material or can ideally make barrier layer and silver on interface without dissolubility Between reaction minimize.This is due to that reaction between barrier layer and silver can add impurities to silver layer so as to reduce electric conductivity.

In addition, in the manufacture of low-emissivity coating panel, pyroprocess, such as annealing deposited film or tempering can be used Glass substrate.Pyroprocess can have a negative impact to low-emissivity coating, such as change the structure or optical property of film, such as Refractive index n or absorption coefficient k.Therefore, for optical property, heat endurance is more satisfactory, for example, barrier material can have it is low Extinction coefficient, such as relatively low visible-light absorptivity, metallic forms and oxide form.

In certain embodiments, barrier layer structure and the method for forming it are disclosed, for will be in low-emissivity coating The infrared reflecting layer used.Barrier layer structure can be formed on infrared reflecting layer, to prevent infrared external reflection in manufacturing process Layer is influenceed by impurity diffusion, while has good bonding force and good optical property.

The barrier layer structure can include titanium, nickel, the ternary alloy three-partalloy of niobium.The nickel of the niobium of high percentage and low percentage, example As nickel is less than niobium, available for improving mechanical endurance energy and not influenceing optical property.The nickel of low percentage, for example, nickel is less than niobium And titanium, it can be used for providing oxygen diffusion impervious layer for silver-colored bottom.

In certain embodiments, the method for disclosing the forming layer 115 on high-transmission rate, low-emissivity coating product, institute Stating coated article has substrate and including the smooth metal reflectance coating of one in silver, gold, copper.In certain embodiments, may be used also With including other layers, such as oxide layer, Seed Layer, conductive layer, anti-reflecting layer or protective layer.

In certain embodiments, disclose for difference in functionality purpose containing multiple layers of painting layer stack.For example, coating heap Stack can include：Seed Layer, promote the deposition in reflecting layer；The oxygen diffusion layer on reflecting layer is configured, to prevent the oxygen in reflecting layer Change；The protective layer on substrate is configured, to prevent from physically or chemically wearing；Or anti-reflecting layer, to reduce visible reflectance.Coating Storehouse can include multilayer reflective layers to improve infrared emittance.

Figure 1B shows the low-E transparent panel 105 according to some embodiments.Low-E transparent panel can include Glass substrate 120 and low-E (low-e) storehouse 190, are formed on glass substrate 120.Glass in certain embodiments Substrate 120 is made up of the glass of similar Pyrex, and has 1-10 millimeters (mm) thickness.Substrate 120 can be square or Rectangle, about cross 0.5-2 meter (m).In certain embodiments, substrate 120 can be made up of plastics or makrolon.

Low emissivity storehouse 190 includes lower protective layer 130, bottom oxide layer 140, Seed Layer 150, reflecting layer 154, stops Layer 156, top oxide layer 160, optics packing layer 170 and upper protective layer 180.Some layers can be selective, and can To add other layers, such as boundary layer or adhesive linkage.Exemplary illustration about each layer 130-180 functions of being provided is following It is provided.

By using physical vapour deposition (PVD) (PVD) and/or reaction (or plasma enhancing) sputter process instrument, Low emissivity Each layer in storehouse 190 can be formed on glass substrate 120 (i.e. from bottom to top) in order.In certain embodiments, Low emissivity storehouse 190 is formed on whole glass substrate 120.However, in further embodiments, Low emissivity storehouse 190 can It is made only in the isolated part of glass substrate 120.

Lower protective layer 130 is formed on the upper surface of glass substrate 120.Lower protective layer 130 can include silicon nitride, Silicon oxynitride or other nitride materials, such as SiZrN, for example, prevent other layers in storehouse 190 spread from substrate 120 or Improve haze reducing property.In certain embodiments, lower protective layer 130 is made up of silicon nitride, and its thickness is about 10-50nm, Such as 25nm.

Bottom oxide layer 140 is formed on lower protective layer 130 and on glass substrate 120.Bottom oxide layer Preferably metal or metal alloy oxide skin(coating), and anti-reflecting layer can be used as.Lower metal oxide skin(coating) 140 can be strengthened instead The crystallinity of layer 154 is penetrated, such as by strengthening the crystallinity of the Seed Layer for reflecting layer, it will carried out in more detail below Explanation.

Layer 150 can be used to the Seed Layer of infrared reflection film, for example, the depositing zinc oxide before argentum reflecting layer is deposited During layer, it is possible to provide have the silver layer of low resistivity, it can improve reflection characteristic.Seed Layer can include metal, as titanium, zirconium and/ Or hafnium, or metal alloy, such as zinc oxide, nickel oxide, nickel chromium triangle oxide, nickel alloy oxide, chromated oxide or evanohm oxygen Compound.

In certain embodiments, Seed Layer 150 can be made of metal, such as titanium, zirconium, and/or hafnium, and with for exampleOr less thickness.Generally, Seed Layer is formed in the material layer of the relative thin on surface (for example, substrate), to promote Form the special characteristics of the succeeding layer of (such as in Seed Layer) on the surface.For example, Seed Layer can be used for influenceing succeeding layer Crystal structure (or crystal orientation), sometimes referred to as " templating ", the phase of particularly follow-up layer material and Seed Layer crystal structure Interaction, the crystal structure of succeeding layer is set to be formed in a certain direction.

For example, metal seed layer is used to promote reflecting layer to grow with particular crystal orientation.In certain embodiments, the gold Category Seed Layer is that have the material of hexagonal crystal structure and be formed with (002) crystal orientation to promote reflecting layer with (111) side To growth, when reflecting layer has cubic crystal structure (such as the silver) of the center of area, preferably Low emissivity panel application.

In certain embodiments, crystal orientation can be characterized by X-ray diffraction (XRD) technology, and it is based on observation The scattering strength of the X-ray beam of shock layer, silver layer and Seed Layer, it is used as the characteristic function of X ray, such as incidence wave and scattering Angle.For example, zinc oxide seed layer can show obvious (002) peak value and high-order θ -2 θ diffraction patterns.This shows zinc oxide crystalline substance Each plane of grain is parallel with substrate surface.

In certain embodiments, the zinc oxide of " silver layer with (111) crystal orientation " or " with (002) crystal orientation " Seed Layer term is respectively comprising " being used for (111) crystal orientation of silver layer or (002) crystal orientation for zinc oxide seed layer Implication.For example, crystal orientation can be determined by observing obvious crystal peak value in XRD signs.

In certain embodiments, Seed Layer 150 can be by continuous and cover whole substrate.In addition, Seed Layer 150 can not be with complete The mode of Total continuity is formed.Seed Layer can be distributed in substrate surface, so as to Seed Layer region each with through substrate Other Seed Layer regions on surface are spaced laterally apart, and endless all standing substrate surface.For example, the thickness of Seed Layer 150 can To be individual layer or thinner, such asAnd the separation between interval may result in and form the thin Seed Layer and (that is, should Thin layer does not form pantostrat).

Reflecting layer 154 is formed in Seed Layer 150.Infrared reflecting layer can be metallic reflective coating, such as silver, gold or copper. Generally, infrared reflection film includes good electric conductor, stops the passage of heat energy.In certain embodiments, reflecting layer 154 is by silver It is made, has for exampleThickness.Because reflecting layer 154 is formed in Seed Layer 150, for example, due to Seed Layer 150 (002) crystal orientation, (111) crystalline orientation argentum reflecting layer 154 growth is promoted, so as to provide relatively low sheet resistance, Relatively low panel radiance.

Due to Seed Layer 150, (111) textured orientation in reflecting layer 154 is promoted, thus the electrical conductivity in reflecting layer 154 and Radiance is enhanced.As a result, thinner reflecting layer 154 can be formed and enough reflection characteristics and visible transmission still can be provided Rate.In addition, the reduction of the thickness of reflecting layer 154 makes each panel, using less material, be gulped down when being produced so as to improve production The amount of telling and efficiency, add the service life of the target (such as silver) for forming reflecting layer 154, and reduce overall be manufactured into This.

In addition, Seed Layer 150 can provide stop between metal oxide layer 140 and reflecting layer 154, to reduce reflection Any reaction that oxygen in material and the lower metal oxide skin(coating) 140 of layer 154 may occur, particularly subsequent heated Cheng Zhong.As a result, the resistivity in reflecting layer 154 can be reduced, so as to improve the performance in reflecting layer 154 by reducing radiance.

The barrier layer 156 formed on reflecting layer 154 can prevent reflecting layer 154 to be oxidized.For example, barrier layer can be Diffusion impervious layer, oxygen is prevented to be diffused into from upper oxide 160 in silver layer.Barrier layer 156 can include titanium, nickel and niobium. In some embodiments, barrier layer 156 can include titanium, nickel, niobium and oxygen.

The upper oxide formed on barrier layer 156 can be used as anti-reflective film storehouse, including single or multiple lift with For different functional purposes.Anti-reflecting layer 160 is used to reduce the reflection of visible ray, based on transmissivity, refractive index, cementability, Chemical durability and heat endurance are chosen.In certain embodiments, anti-reflecting layer 160 includes tin oxide, has high heat steady It is qualitative.Anti-reflecting layer 160 may also include titanium dioxide, silicon nitride, silica, silicon oxynitride, niobium oxide, SiZrN, oxidation Tin, zinc oxide, or any other suitable dielectric material.

Optics packing layer 170 can be used for providing appropriate thickness for Low emissivity storehouse, such as, there is provided antireflective property. Optics packing layer preferably has high visible light transmissivity.In certain embodiments, optics packing layer 170 is made up of tin oxide, With for exampleThickness.Optics packing layer can be used for the optical property of adjustment Low emissivity panel 105.For example, optics filler The thickness and refractive index of layer can be used to make thickness degree increase to lambda1-wavelength several times, be effectively reduced light reflectivity, from And improve light transmission.

Upper protective layer 180 can be used to protect whole film stack, for example, protecting the panel from physically or chemically wearing.On Portion's protective layer 180 can be exterior cover sheets, such as silicon nitride, silicon oxynitride, titanium oxide, tin oxide, zinc oxide, niobium oxide, or SiZrN。

In certain embodiments, adhesive linkage can be used for providing bonding force in interlayer.Adhesive linkage can be by similar NiTi Metal alloy is made, and has thickness, such as

According to used material, some layers 190 of Low emissivity storehouse can have some common elements.The stack layer Example can use the material based on zinc in oxide dielectric layer 140 and 160.Therefore, the different targets of relatively small amount can be used To form Low emissivity storehouse 190.

In certain embodiments, coating can include bilayer or three layer stacks with multiple infrared reflecting layers.At some In embodiment, these layers can be formed by plasma enhancing or reactive sputtering, and wherein vector gas (such as argon) are used for Ion is sprayed from target, then passes through vector gas and the mixture of reacting gas (such as oxygen) or plasma before deposition.

In certain embodiments, the shadow of the layer deposition process that is deposited on silver conductive layer for silver conductive layer quality is disclosed Ring.Because silver conductive layer is relatively thin, for example, being less than 20nm, there is provided high visible light transmissivity, therefore the quality of silver conductive layer may be by Deposition to the layer of subsequent deposition influences, such as barrier layer and reflecting layer.

In certain embodiments, the sputtering sedimentation engineering that can be applied to deposit barrier layer on the electrically conductive is disclosed.Example Such as, barrier layer can prevent infrared reflecting layer to be oxidized.Oxide skin(coating) can play a part of anti-reflecting layer.The material on barrier layer The oxidation reaction of conductive substrate can be reduced, prevent resistivity and radiance degeneration etc..

In certain embodiments, deposition engineering and the coated article prepared through the engineering are disclosed, in the sputtering sedimentation phase Between using tool higher oxygen affinity material and the alloy compared with low oxygen affinity material, for example, realizing the coating and coating of high quality Panel.

In certain embodiments, the alloy barrier layer can be sputtered from alloys target or is total to from different element targets Sputtering is on the same substrate.The engineering can be with fine silver (barrier layer of its depositing pure gold category) or can include oxygen makes film light Low-level oxidation.

Fig. 2A -2B show physical vapour deposition (PVD) (PVD) system according to some embodiments.In fig. 2, PVD system is also logical Being commonly referred to as sputtering system or sputtering depositing system 200 includes shell, and it defines or surrounded process chamber 240, substrate 230, target group Part 210 and the reactive species delivered from external source 220.In deposition process, target is impacted through argon ion, and it is to substrate 230 Discharge sputtering particle.Sputtering system 200 can perform covering deposition on substrate 230, form sedimentary to cover whole substrate, For example, the sputter particles generated in target assembly 210 can reach substrate regions.

The material used in target 210, it may for example comprise tin, zinc, magnesium, aluminium, lanthanum, yttrium, titanium, antimony, strontium, bismuth, niobium, silicon, silver, nickel, Chromium, copper, gold or its any combinations (i.e. single target can be made up of the alloy of several metals).In addition, the material used in target Oxygen, nitrogen or oxygen can be included and nitrogen is combined to form the nitrogen oxides of oxide, nitride and above-mentioned metal.In addition, Although only showing a target assembly 210, additional target assembly can also be used.Therefore, it is possible to use different target combinations comes Form dielectric layer as described above.For example, in certain embodiments, barrier material is titanium nickel niobium, the titanium, nickel, and niobium can be by Independent titanium, nickel, niobium target are provided, and can also be provided by single titanium ickel-niobium alloy target.For example, target assembly 210 can wrap Include silver-colored target, and together with argon ion by layer sputtering sedimentation on substrate 230.Target assembly 210 can include metal or metal closes Gold target, such as tin, zinc or red brass, and the sputtering sedimentation metal or metal alloy oxide skin(coating) together with active oxygen species.

Sputtering depositing system 200 can include miscellaneous part, and the substrate for being such as used for supporting substrate supports.Substrate support includes Vacuum cup, electrostatic chuck or other known mechanism.Substrate support can surround its axis rotation perpendicular to substrate surface.This Outside, substrate support can move in vertical direction or in-plane.It should be understood that the rotation and movement of vertical direction or in-plane Can be implemented by known driving mechanism, including magnetic driven device, Linear actuator, worm screw, leading screw, differential pump feed turntable Deng

In certain embodiments, substrate support includes the electrode being connected with power supply, for example, it is inclined to provide RF or DC to substrate Pressure, or provide plasma environment in process chamber 240.Target assembly 210 can include the electrode being connected with power supply, so as to locate Reason produces plasma in room.Target assembly 210 is preferably towards substrate 230.

Sputtering depositing system 200 can include power supply, be coupled with target electrode.The power supply provides power supply to electrode, makes material At least it is sputtered in certain embodiments from target.In sputter procedure, inert gas, may be by entering such as argon gas or Krypton Gas port 220 enters process chamber 240.In embodiment, when using reactive sputtering, reacting gas may also be introduced into, such as oxygen Or nitrogen, it forms oxide, nitride, and/or nitrogen oxides with the Interaction between particles sprayed in target on substrate.

Sputtering depositing system 200 also includes control system (not shown), for example, processor and memory, its by operation with Miscellaneous part communicates and is used to control its running to perform method described herein.

In certain embodiments, the method and apparatus for preparing layer on thin lower resistance silver layer, the party are disclosed Method includes the ion energy in control base board, is performed so as to deposit with low ion energy, so as to reduce the damage for silver layer Wound.

Fig. 2 B show the sputtering system with cosputtering target according to some embodiments.Sputtering settling chamber 205 may include two Individual target 212 and 214, is configured in plasma environment 245, wherein including the reactive species from external source 225.Target 212 With 214 the first elements that can include alloy barrier layer, for example, Ta, Nb, Zr, Hf, Mn, Y, Si and Ti, and alloy barrier layer Second element, for example, Pd, Ru, Ni, Co, Mo and W, together with the reactive oxygen species of selectivity, the 230 deposition resistance on substrate Barrier alloy.The configuration is merely illustrative, can also be configured using other sputtering systems, such as the single target with alloy material.

In certain embodiments, the method and apparatus for preparing low-E panel are disclosed, this method, which is included in, to be contained Have and form infrared reflecting layer under or over the barrier structure of titanium, nickel and niobium ternary alloy three-partalloy.For example, because barrier layer protection is infrared Reflecting layer and will not make the low-emissivity coating characteristic reduction, therefore can show optimal infrared external reflection, heat endurance and Durability.

In certain embodiments, the method for preparing Low emissivity panel in Large area coatings machine is disclosed.It can provide Transport mechanism moves the substrate under one or more sputtering targets, in deposition barrier layer, anti-reflecting layer and similar surfaces protection The conductive layer of bottom is deposited before other layers of layer.

In certain embodiments, online depositing system, including transport mechanism are disclosed, for moving the base between deposition table Plate.

Fig. 3 shows the exemplary online depositing system according to some embodiments.Transport mechanism 370, for example, conveyer belt or Multiple rollers, can between different sputtering sedimentation platforms transmission base plate 330.For example, substrate can be placed in target assembly 310A platform #1, the platform #2 with target assembly 310B is then transmitted to, is then transmitted to the platform #3 with target assembly 310C. Platform #1 with target assembly 310A can be deposition of silver platform, and sputtering has pale rose colour outer reflective layer.Platform #2 with target 310B can be with It is barrier layer deposition station, sputtering has titanium, nickel, the metal alloy of niobium material.As illustrated, platform #2 includes single target 310B. However, it is possible to use other configurations, such as the cosputtering system using two kinds of different targets.Platform #3 with target 310C can be used to sink Other layers of product, such as anti-reflecting layer or protective layer.

In certain embodiments, there is provided the particular composition percentage of titanium, nickel and niobium, included optically and mechanically with realizing The excellent properties in all properties including performance.The niobium of high percentage can be used for improving mechanical performance, including bonding force, heat are surely Qualitative and panel durability.For example, the niobium higher than 40wt% can be used for obtaining required mechanical endurance, for example, being comparable to Nichrome barrier layer and more preferable than titanium barrier layer.Optical property can not be reduced less than 60wt% niobiums, for example, keeping similar Or more preferable transmission of visible light, and antiradar reflectivity, or absorptivity.The titanium of low percentage can be used, such as oxygen is provided and expanded Dissipate barrier properties.For example, the titanium higher than 5wt% can be used for providing good oxygen barrier layers.Titanium less than 15wt% can quilt It is good barrier layer protected for providing.The nickel of moderate proportions, such as less than niobium, higher than titanium, it can be used for further improving machine Tool performance and maintenance oxygen barrier layers performance.For example, 30-50wt% nickel can strengthen the performance of titanium and niobium, and without any degraded. In certain embodiments, barrier layer thickness can be 0.3-8nm, such as 0.5-5nm.

In certain embodiments, there is provided specific nickel, titanium, the composition ratio of niobium, at least for absorptivity, resistivity and Radiance (i.e. relatively low), to realize excellent performance.For example, the niobium higher than 40wt% can be used for obtaining required machinery Durability, for example, being comparable to nichrome barrier layer and more preferable than titanium barrier layer.Niobium less than 60wt% can not reduce Optical property, for example, similar or more preferable transmission of visible light is kept, and antiradar reflectivity, or absorptivity.Low hundred can be used The nickel (for example, 5wt%-15wt%) of point ratio, and moderate proportions titanium (for example, being less than niobium, higher than nickel, such as 30wt%- 50wt%).In certain embodiments, barrier layer thickness can be 0.3-8nm, such as 0.5-5nm.

Fig. 4 shows to be responded according to the sheet resistance of the Low emissivity storehouse with different barrier materials of some embodiments. Sheet resistance can provide optical characteristics assessment, and for same silver thickness, sheet resistance values are lower, then transmissivity is higher and reflectivity It is lower.The Low emissivity storehouse used in sheet resistance measurement includes the stop on the silver layer of the 8nm in 10nm ZnO Seed Layers Layer.The barrier material includes the Ti-Ni alloy of the nickel of titanium, the titanium with 20wt% and 80wt%, and has 10wt%'s The titanium ickel-niobium alloy of nickel, 40wt% titanium and 50wt% niobium.The thickness range on barrier layer is 0.3-7nm, such as 1.5- 4.5nm。

As illustrated, titanium, nickel, the alloy of niobium have relatively low sheet resistance, for example, with titanium and titanium nickel bianry alloy phase Than there is more preferable optical property, available for all thickness.In the specific example, optimal barrier performance is reducible For 2nm, for example, 1.5-2.7nm.

Fig. 5 shows the flow chart of the splash coating according to some embodiments.Formed on substrate after conductive layer, such as silver Layer, can sputter barrier layer on the electrically conductive.Barrier layer can include the ternary alloy three-partalloy of titanium, nickel and niobium；Ternary metal alloy, example Such as it is made up of the metal ingredient of titanium, nickel and niobium；And ternary oxide alloy, such as titanium, nickel, niobium and oxygen.

In operation 500, there is provided substrate.The substrate can be transparency carrier, such as glass substrate or polymeric substrates. Other substrates can also be used.In operation 510, first layer is formed on substrate.First layer may be used as infrared reflecting layer.The One layer can include conductive material or metal material, such as silver.The thickness of first layer can be approximately less than or equal to 20nm, or can be with It is approximately less than or equal to 10nm.

In operation 520, the second layer is sputtered deposition on the first layer.The second layer may be used as barrier layer.The second layer can To include the alloy of titanium, nickel and niobium.The percentage of titanium can be 5-15wt%, the percentage of nickel can be 30-50wt% (or 35-45wt%), and the percentage of niobium can be (or between 45 and 45wt%) between 40-60wt%.

In certain embodiments, the second layer can include the alloy of nickel, titanium and niobium.The percentage of nickel can be 5- 15wt%, the percentage of titanium can be 30-50wt% (or 35-45wt%), and the percentage of niobium can be 40-60wt% (or 45- 45wt%).

In certain embodiments, the second layer can also include oxygen, form oxide alloy.The second layer can be closed with ternary Gold or ternary oxide alloy are deposited.Ternary metal alloy can be oxidized, such as the deposition by succeeding layer, turn into ternary oxygen Compound layer.Ternary oxide alloy can also be further oxidized.After whole storehouse deposits and/or is heat-treated, the second layer Ternary metal alloy can be kept, or ternary oxide or ternary protoxide can be turned into, to obtain more preferable radiativity Energy.

In certain embodiments, bottom can be formed under first layer, such as the zinc oxide seed layer for silver layer.Seed Layer can improve the crystal orientation of silver, so as to have more preferable electric conductivity.In certain embodiments, it can be formed on the second layer His layer.

Fig. 6 shows the flow chart of the splash coating according to some embodiments.Formed on substrate after conductive layer, such as silver Layer, can sputtering sedimentation barrier layer on the electrically conductive.Barrier layer can include the ternary alloy three-partalloy of titanium, nickel and niobium.

In operation 600, there is provided substrate.Substrate can be transparency carrier, such as glass substrate or polymeric substrates.Also can make With other substrates.In operation 610, metal oxide layer is formed on substrate.Metal oxide layer may be used as succeeding layer Seed Layer.For example, metal oxide layer can have crystal orientation to promote the crystal orientation of deposited first layer.

In certain embodiments, the metal oxide layer can include the Seed Layer of tool crystal orientation, and it promotes silver layer (111) crystal orientation.For example, metal oxide layer can include the zinc oxide of tool (002) crystal orientation, it can be used as growth (111) template of silver layer.The thickness of metal oxide layer can be approximately less than or equal to 20nm, or can be approximately less than or be equal to 10nm。

In operation 620, first layer is formed on metal oxide layer.First layer may be used as infrared reflecting layer.The One layer can include conductive material or metal material, such as silver.The thickness of first layer can be approximately less than or equal to 20nm, or can be about Less than or equal to 10nm.

In operation 630, the second layer is sputtered deposition on the first layer.The second layer may be used as barrier layer.The second layer can To include the alloy of titanium, nickel and niobium.The percentage of titanium can be 5-15wt%, the percentage of nickel can be 30-50wt% (or 35-45wt%), and the percentage of niobium can be 40-60wt% (or 45-45wt%).

In certain embodiments, the second layer can include the alloy of nickel, titanium and niobium.The percentage of nickel can be 5- 15wt%, the percentage of titanium can be 30-50wt% (or 35-45 (wt%), the percentage of niobium can be 40-60wt% (or 45-45wt%).

In certain embodiments, the second layer can also include oxygen, to form oxide alloy.The second layer can be with ternary Alloy or ternary oxide alloy are deposited.Ternary metal alloy can be oxidized, for example, by the deposition of succeeding layer, turn into three First oxide skin(coating).Ternary oxide alloy can also be further oxidized.After whole storehouse deposits and/or is heat-treated, the Two layers can keep ternary metal alloy, or can turn into ternary oxide or ternary protoxide, to obtain more preferable spoke Penetrate performance.In certain embodiments, other layers can also be included.

In certain embodiments, barrier layer (for example, barrier layer 156 in barrier layer 115 and/or Figure 1B in Figure 1A) bag Ternary alloy three-partalloy (such as being made up of ternary alloy three-partalloy) is included, compared to titanium and niobium, comprising less nickel (for example, 5-15wt% nickel, 30- 50wt% titanium, and 40-60wt% niobium).Resulting barrier performance may be based on compared with nickel and/or titanium Niobium quantity and it is different (at least a portion).

Fig. 7 shows the data of the various material properties used in barrier layer.Material includes nichrome (i.e. 80wt% nickel With 20wt% chromium), NiTi, and various NiTi niobium alloys (i.e. 15:60:25,10:40:50, and 5:20:75).Shown in Fig. 7 Compared with other materials, particularly compared with other NiTi niobium materials, 10:40:The performance of 50 titanium nickel niobiums is more preferable.

For example, when using niobium (for example, 15% nickel, 60wt% titanium, and 25wt% niobium) of relatively low quantities, should Layer can show relatively poor absorptivity (that is, Avis, Abs% 400nm, 550nm, 1000nm), but show preferably Resistivity (i.e. Rs) and radiance (i.e. ε), at least compared with nickel chromium triangle and NiTi.On the other hand, when the higher relative amounts of niobium of use When (for example, 5wt% nickel, 20wt% titanium, and 75wt% niobium), absorptivity is more satisfactory, but resistivity and radiance compare Difference.As illustrated, by (at least relatively) using 50wt% niobium (for example, 10wt% nickel, 40wt% titanium, and 50wt% niobium) performance is optimised, and absorptivity, resistivity and radiance are all desirable (i.e. relatively low).

Fig. 8 shows the flow chart of the splash coating according to some embodiments.Formed on substrate after conductive layer, such as silver Layer, can sputter barrier layer on the electrically conductive.Barrier layer can include nickel, titanium, and the ternary alloy three-partalloy of niobium；Ternary metal alloy, Such as it is made up of the metal ingredient of nickel, titanium, and niobium；And ternary oxide alloy, such as contain nickel, titanium, niobium and oxygen.

In operation 800, there is provided substrate.Substrate can be transparency carrier, such as glass substrate or polymeric substrates.Also can make With other substrates.In operation 810, first layer is formed on substrate.First layer may be used as infrared reflecting layer.First layer can With including conductive material or metal material, such as silver.The thickness of first layer can be approximately less than or equal to 20nm, or can be approximately less than Or equal to 10nm.

In operation 820, the second layer is sputtered deposition on the first layer.The second layer may be used as barrier layer.The second layer can To include the alloy of nickel, titanium and niobium.The percentage of nickel can be 5-15wt% (for example, 10wt%, or about 10wt%), the hundred of titanium Point ratio can be 30-50wt% (for example, 40wt%, or about 40wt%), and the percentage of niobium can be 40-60wt% (examples Such as, 50wt%, or about 50wt%).

In certain embodiments, the second layer can also include oxygen, to form oxide alloy.The second layer can be with ternary Alloy or ternary oxide alloy are deposited.Ternary metal alloy can be oxidized.For example, by the deposition of succeeding layer, turn into three First oxide skin(coating).Ternary oxide alloy can also be further oxidized.After whole storehouse deposits and/or is heat-treated, the Two layers can keep ternary metal alloy, or can turn into ternary oxide or ternary protoxide, to obtain more preferable spoke Penetrate performance.

In certain embodiments, above with reference to other at least some layers can also be formed described in Figure 1B, on substrate, so as to Form Low emissivity transparent panel.For example, in certain embodiments, bottom can be formed under first layer, such as silver layer Zinc oxide seed layer.Seed Layer can improve the crystal orientation of silver, so as to have more preferable electric conductivity.In certain embodiments, may be used To form other layers on the second layer.

In order to make it easy to understand, although above-mentioned example is explained in detail in some details, the present invention is not limited to The detailed description provided.The present invention can be performed by many other methods.Disclosed example is only illustrative, It is and without limitation.

Claims (20)

1. a kind of method for forming Low emissivity panel, methods described include：

Transparency carrier is provided；

First layer is formed on the transparency carrier, wherein, the first layer contains silver；

The second layer is formed on the first layer, wherein the second layer contains the alloy of nickel, titanium, niobium,

Wherein, the percentage of nickel is about 10wt% in the alloy, and the percentage of titanium is about 40wt% in the alloy, the conjunction The percentage of niobium is about 50wt% in gold.

2. according to the method for claim 1, wherein, the thickness of the second layer is 0.3-7nm.

3. according to the method for claim 1, wherein, the second layer further comprises oxygen.

4. according to the method for claim 1, wherein, the thickness of the first layer is less than 15nm.

5. according to the method for claim 1, further comprise：Third layer is formed on the transparency carrier, wherein described Third layer contains metal oxide and the first layer is formed in the third layer.

6. according to the method for claim 5, wherein, the first layer is formed directly into the third layer.

7. according to the method for claim 6, wherein, the third layer contain zinc oxide, doping zinc oxide, tin oxide, Or the tin oxide of doping.

8. according to the method for claim 7, wherein, the second layer is formed directly on the first layer.

9. a kind of method for forming Low emissivity panel, methods described include：

Transparency carrier is provided；

First layer is formed on the transparency carrier, wherein, the first layer includes metal oxide；

The second layer is formed on the first layer, wherein, the second layer contains silver；

Third layer is formed on the second layer, wherein, the third layer contains nickel, titanium, the alloy of niobium,

Wherein, the percentage of nickel is about 10wt% in the alloy, and the percentage of titanium is about 40wt% in the alloy, the conjunction The percentage of niobium is about 50wt% in gold.

10. according to the method for claim 9, wherein, the second layer further comprises oxygen.

11. according to the method for claim 9, wherein, the second layer is formed directly on the first layer.

12. according to the method for claim 11, wherein, the third layer is formed directly on the second layer.

13. according to the method for claim 12, further comprise：The 4th layer is directly formed in the third layer, wherein, Described 4th layer comprising in titanium dioxide, silicon nitride, silica, silicon oxynitride, niobium oxide, SiZrN, tin oxide, zinc oxide It is at least one, or its combination.

14. according to the method for claim 13, wherein, the first layer and described 4th layer contain zinc oxide respectively.

15. according to the method for claim 14, further comprise：Layer 5 is formed on described 4th layer, wherein, it is described Layer 5 can be used as optics packing layer；And

Layer 6 is formed on the layer 5, the layer 6 contains silicon nitride, silicon oxynitride, titanium oxide, tin oxide, oxidation It is at least one in zinc, niobium oxide, SiZrN, or its combination.

16. a kind of method for forming Low emissivity panel, this method include：

Transparency carrier is provided；

Lower protective layer is formed on the transparency carrier, wherein the lower protective layer contains nitride；

Seed Layer is formed on the lower protective layer, wherein the lower protective layer contains zinc oxide；

Reflecting layer is formed in the Seed Layer, wherein the reflecting layer contains silver and with the thickness less than 15nm；

Barrier layer is formed on the reflecting layer, wherein, nickel, titanium are contained in the barrier layer, the alloy of niobium, wherein, the alloy The percentage of middle nickel is about 10wt%, and the percentage of titanium is about 40% in the alloy, and the percentage of niobium is about in the alloy 50wt%；And

Metal oxide layer is formed on the barrier layer, wherein the metal oxide layer contains zinc oxide.

17. according to the method for claim 16, wherein, the reflecting layer is formed directly into the Seed Layer.

18. according to the method for claim 17, wherein, the barrier layer is formed directly on the reflecting layer.

19. according to the method for claim 18, wherein, the thickness on the barrier layer is 0.3-7nm.

20. according to the method for claim 16, wherein, the barrier layer is made up of the alloy.