CN105722923A - Anti-reflection article and methods thereof - Google Patents
Anti-reflection article and methods thereof Download PDFInfo
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- CN105722923A CN105722923A CN201480059097.1A CN201480059097A CN105722923A CN 105722923 A CN105722923 A CN 105722923A CN 201480059097 A CN201480059097 A CN 201480059097A CN 105722923 A CN105722923 A CN 105722923A
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
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Abstract
An antireflection article including: a transparent substrate having a refractive index of from 1.48 to 1.53; a binder layer associated with the substrate, the binder having a refractive index of from 1.55 to 1.75; and a nanoparticulate monolayer or near monolayer associated with the binder layer, the nanoparticulate layer having an effective refractive index less than the refractive index of binder. Methods of making and using the article are also disclosed.
Description
This application claims the priority of the U. S. application number 61/872037 submitted on 08 30th, 2013, it is incorporated herein by reference in full.
CROSS-REFERENCE TO RELATED APPLICATIONS
The present invention relates to the USSN13/440183 owning together and transferring the possession of, it was submitted on 04 05th, 2012 and is published as US2012-0281292；USSN61/557490, it was submitted on November 05th, 2012, and was USSN13/668537 now；USPSN61/731924, it was submitted on November 30th, 2012；USSN13/090561, it was submitted on 04 20th, 2011；USSN13/662789, it was submitted on October 29th, 2012；USSN13/900659, it was submitted on 05 23rd, 2013；And USSN61/872043, it was submitted on 08 30th, 2013, and the full content of above each literary composition is totally incorporated herein by reference, but does not require their priority.
Background
This patent disclosure relates generally to antireflective (AR) surface, its goods and preparation and application.
General introduction
In some embodiments, the present invention provides antireflective (AR) coating with at least one layer, and this at least one layer comprises nano-particle monolayer or nano-particle approximate monolayer (near-monolayer).
In some embodiments, the present invention provides the goods in conjunction with AR coating.
In some embodiments, the present invention provides a kind of method preparing goods, and described method is included in deposited on substrates binding agent；Deposit nano-particle monolayer or nano-particle approximate monolayer on the adhesive.
In some embodiments, the present invention provides the method using goods, for instance, for display device, described method comprises goods in conjunction with the present invention in a display device.
Accompanying drawing is sketched
In embodiments of the present invention:
Fig. 1 shows the AR goods with multilamellar AR surface, and it has the nano-particle monolayer being in closs packing setting.
Fig. 2 A and 2B shows view (the 2A side view of exemplary AR goods；2B top view), it has multilamellar AR coating, and this multilamellar AR coating comprises nano-particle monolayer, and this nano-particle monolayer has the nano-particle being in not closed packing hexagonal array.
Fig. 3 shows when high index of refraction numerical value is 1.6, for the schematic diagram of coating performance of various pitch/diameter ratios or numerical value and the high index of refraction layer thickness relative to size grade scale.
The example of the reflectance collection of illustrative plates that Fig. 4 A and 4B display obtains from the preferred design space of Fig. 3.
The picture that Fig. 5 shows provides the 100nm granule being deposited directly on base material (without the second layer；500) and the refractive index (n of this granulep) it is such as 1.51, and (from the topology example that preferably designs of Fig. 4 there is 100nm granule and there is the second intermediary adhesive layer；510) comparison between.
The picture of Fig. 6 A and 6B display provides the spectral width of two embodiments shown in Fig. 5 and the comparison of angle of incidence (AOI).
Fig. 7 A to 7E provides for some highs index of refraction (ng) exemplary spectrum of number of plies value, its refractive index is 1.55 (Fig. 7 A) to 1.75 (Fig. 7 E).
Fig. 8 provides the schematic diagram of another kind of goods (800), and it includes glass baseplate (810) and nano-particle monolayer (830), and this nano-particle single-layer portions ground caves in or is submerged into high refractive index layer (820).
Fig. 9 A and 9B display is for designing the exemplary spectrum of structure, and wherein the nanosphere of nano-particle monolayer is partly submerged into high refractive index layer.
Detailed description
The various embodiments of the (if there is) detailed description present invention below with reference to the accompanying drawings.The reference of various embodiments is not limited the scope of the invention, the restriction of the scope that the scope of the invention is limited only by the following claims.Additionally, any embodiment listed in this manual is not restrictive, and only list some embodiments in the many possible embodiment of the claimed present invention.
Definition
" antireflective " refers to always reflect the reduction of (direct reflection and diffuse-reflectance) with similar term, and it can be produced by coating or surface treatment.
" binding agent ", " adhesive phase, " etc. refer to can be used to combine or the material of connection between strengthening surface, the such as connection between granule or between granule and glass surface.
" nano-particle monolayer " and similar terms refer to simple layer granule, it generally contacts a certain surface or base material, the wherein average-size of granule or average diameter generally less than or equal to approximately 500nm, and the change in size of most of granule is less than approximately plus or minus (+/-) 100%.Interval between granule is preferably substantially uniform.
" approximate monolayer " refers to such as nano-particle monolayer as defined above with similar term, and it can have some defect areas such as incomplete surface and cover, or the granule of double stacked, or irregular interval between granule.Generally, the ratio of the gross area that these defect areas account for monolayer is not more than 50%.
" with ... combine " and similar terms refer to that adhesive phase is relative to relation relative to base material of the relation of base material and/or nano-particle, it can comprise such as physical contact, Physical interaction (such as mechanical interlocked), chemical bonding interacts, with similar interaction, or its combination.
" effective refractive index " and similar terms refer to the mean refractive index of nano structural material or the coating measured, it can use known optical means such as ellipsometry or prism-coupled to measure, the effective refractive index wherein measured is some superpositions of the refractive index of independent material (such as glass and air), and this independent material forms the independent nano-structures territory of nanostructured.Because nano structural material has the feature less than visible wavelength, it is believed that the refractive index measured is effective refractive index.
" reflectance " and similar terms refer to such as the single surface of goods or side, on the spectral width of at least 100nm, these goods have the average reflectance less than 0.1 to 0.2%, and the spectral width of this at least 100nm covers visible wavelength collection of illustrative plates at least some of of 400-700nm.
" the second binding agent between nano-particle monolayer and binding agent " and similar terms or phrase refer to such as between nano-particle, between nano-particle and adhesive phase, between nano-particle and coating, between granule and base material, or the combination of above-mentioned situation builds the material of connection, such as adhesive, chemistry connect and interact or similar connection interacts.
" include ", " comprising " and similar terms mean and include but not limited to, namely include and nonexclusive.
The change of " about " exponential quantity being used for describing in the modification such as compositions of embodiment of the present invention the numerical value such as the amount of composition, concentration, volume, process temperature, process time, yield, flow velocity, pressure and their scope, can occur such as: the typical case preparing material, compositions, complex, concentrate or application preparation measures and processes in step；Error unintentionally in these steps；Manufacture, source or be used for implementing the difference of the purity aspect of the raw material of described method or composition；And in similar Consideration.Term " about " also includes owing to having the compositions of specific initial concentration or mixture or the amount of the aging and different of preparation, and owing to mixing or processing the compositions or preparation and different amounts with specific initial concentration or mixture.
" being mainly made up of following " in embodiment can refer to, for instance:
There are the goods of deflection surfaces, as defined herein；
Preparation or the method using antireflective goods, as defined herein；Or
In conjunction with the display system of goods, as defined herein.
The goods of the present invention, display system, preparation and the method for use goods, compositions, preparation or any equipment can include component listed in claims or step, add the fundamental property of the preparation and application to compositions, goods, equipment or the present invention and novel character does not have component or the step of materially affect, such as specific reactant, specific additive or composition, specific reagent, specific surface modifier or condition, or similar structure, material, or selected state-variable.The fundamental property being likely to the assembly to the present invention or step causes substantial effect, or it is likely to bring the project of unfavorable characteristic to include the surface such as with disagreeable high reflectance character to the present invention, its beyond as defined herein with described numerical value, comprise intermediate value and scope.
Unless otherwise indicated, otherwise, indefinite article used herein " " or " one " and corresponding definite article " being somebody's turn to do " thereof represent at least one (pcs/species), or a (pcs/species) or many (pcs/species).
Abbreviation well known within the skill of those ordinarily skilled (such as, " h " or " hr " represented hour, represent " mL " of milliliter, represent " rt " of room temperature, " nm " and the similar abbreviation represented nanometer) can be adopted.
The disclosed concrete and preferred value of component, composition, additive and similar aspect and scope thereof are merely to illustrate, and they are not excluded for other numerical value in other definition numerical value or the range of definition.The composition of the present invention, equipment and method can include any numerical value as herein described or any combination of numerical value, concrete numerical value, more specifically numerical value and preferred value.
Antireflective (AR) coating is used for decades.Nearest work focuses on and manufactures the antireflection coatings being made up of the nano-particle monolayer on base material.These nano-particle monolayers can have the unique combination of following characteristics, for instance: low reflection；The durability higher than the nanoporous coating with identical effective refractive index；Ion exchange strengthening has easily been carried out with the glass baseplate of nano-particle single layer coating；Compared to many floor heights-low-refraction AR coating, there is less effective fingerprint visibility；Width reflection belt width, and low reflection angle sensitivity.In the relevant application owned together and transfer the possession of as above, describe these AR coatings entered most and the example of relevant preparation method.
For the nanoparticle size in given monolayer and interval, it is usually preferable to reduce minimal reflection by certain methods and/or widen the low reflection wavelength band for AR coating.
In some embodiments, the present invention provides antireflective goods, and it comprises:
Transparent base material, its refractive index (ns) for 1.48-1.53；
The adhesive phase (that is, coating composition) of the combination with base material, this binding agent has the high index (n of about 1.55-about 1.75g), this adhesive phase refractive index (ng) more than the refractive index (n of transparent base materials) (that is, ng>ns)；With
The nano-particle monolayer being combined with this adhesive phase or nano-particle approximate monolayer, the effective refractive index (n of this nano-particle layerP is effective) less than refractive index (that is, the n of adhesive phaseg>nP is effective), such as nP is effectiveLess than 1.55.
In some embodiments, the effective refractive index (n of nano-particle monolayerP is effective) can be such as 1.1-1.5,1.15-1.3, and similar numerical value, comprise intermediate value and scope.
In some embodiments, on the spectral width of at least 100nm, the antireflective reflectance of described goods can have such as average reflectance less than 0.2%, and the spectral width of this at least 100nm covers at least some of of the visible wavelength collection of illustrative plates of 400-700nm.
In some embodiments, nano-particle monolayer can comprise the nano-particle for instance in not closed packing hexagon geometrical morphology, its pitch (p) is (namely, separating distance between the center of adjacent nanoparticles) and nano-particle diameter (D) ratio (p/D) be 1.05-1.35, with preferably 1.15-1.25, comprise intermediate value and scope.
In some embodiments, the thickness of binding agent can be such as 1xD to 2xD, and is preferably 1.3xD-1.8xD, comprises intermediate value and scope, and wherein D is nano-particle average diameter (D).
In some embodiments, transparent base material can be such as glass, polymer, glass-ceramic, crystalline oxide, quasiconductor and similar material, or its combination.
In some embodiments, antireflective goods also can comprise such as the second binding agent between nano-particle monolayer and binding agent.
In some embodiments, the nano grain surface coverage rate of nano-particle monolayer can be the surface coverage of such as 85-100%, 90-93% etc., comprise intermediate value and scope, and nano-particle approximate monolayer can comprise such as the nano-particle of substantially monolayer, its nano grain surface coverage rate is the surface coverage of 50-90%, 65-90% etc., comprises intermediate value and scope.This surface area coverage is to use the standard microscope including ultramicroscope to measure, or by (such as, by calculating the percentage ratio (think cover area) of wherein granule visible microscopy surface image relative to the visible percentage ratio of wherein base material (thinking unlapped region)) that will the visible outline projection of nano-particle to substrate surface be measured.
In some embodiments, nano-particle layer can comprise the nano-particle of example at least one material described as follows: silicon oxide, aluminium oxide, zirconium oxide, polystyrene, latex, and similar material, or its combination.
In some embodiments, nano-particle monolayer can comprise the nano-particle that such as average diameter (D) is 50-300nm, and the geometrical morphology of this nano-particle is selected from following at least one: spheroid, hemisphere, ellipsoid, disk like, pyramid, cylinder, pillars and analogous shape and geometrical morphology, or its combination.
In some embodiments, the nano-particle monolayer being combined with binding agent can comprise such as, the nano-particle on adhesive surface；It is partially embedded into or is partly submerged into the nano-particle of binding agent；The nano-particle that is completely covered by binding agent or be totally submerged the nano-particle into binding agent, or its combination.
In some embodiments, the nano-particle monolayer being combined with binding agent can such as be partially embedded into the distance of binding agent 0.1xD to 0.5xD, and wherein D is nano-particle average diameter (D).
In some embodiments, the thickness of the adhesive phase on base material can be such as 60-300nm, comprises intermediate value and scope.
In some embodiments, binding agent can comprise such as polymer, the material that nano-particle is filled, such as with the polymer of the silicon oxide nano-particle filling that diameter is 10nm or sol-gel substrate, inorganic oxide material, inorganic nitride material, quasiconductor, transparent conductor, and similar material, or its combination.
In some embodiments, binding agent also can comprise granule or the salt of following at least one material: the compound of silver, copper, silver or copper, or its combination, and wherein specific granule or salt can provide such as antimicrobial benefit.
In some embodiments, the present invention provides a kind of method preparing antireflective goods as above, and described method comprises:
Base material at least some of on deposit adherent oxidant layer；With
Deposition nano-particle monolayer or nano-particle approximate monolayer over the binder layer.
In some embodiments, preparation method also can comprise such as, by such as solidifying, crosslinking, fusion, sintering and similar fixing means, or its combination, nano-particle monolayer is fixed on adhesive phase or within.
In some embodiments, preparation method also can comprise such as deposition nano-particle before, in process, afterwards or its combination, solidify adhesive phase.
In some embodiments, fixing on the adhesive or fusion nano-particle monolayer can comprise such as: thermal sintering；Deposit binder between the nano-particle monolayer of binding agent and deposition；The second binding agent is deposited on the first binding agent of combination and the nano-particle monolayer of deposition；Or its combination.
In some embodiments, method also can comprise such as by following at least one object carries out next these goods chemical enhanced of ion exchange: the base material before deposit binder；Binding agent on base material；Fix the base material before nano-particle monolayer on the adhesive；Base material after deposition or fixing nano-particle monolayer；Or its combination.
In some embodiments, the present invention provides the goods with multilamellar AR coating, and wherein one layer is made up of monolayer or the approximate monolayer of nano-particle.The size of the nano-particle constituting monolayer or approximate monolayer can be such as 50-300nm, comprises intermediate value and scope.The monolayer of nano-particle or approximate monolayer can comprise such as nanosphere, nano-hemisphere and similar three-dimensional geometry pattern.
In some embodiments, can arranging at least one adhesive phase with high index layer below nano-particle monolayer, its effective refractive index is higher than the effective refractive index of nano-particle monolayer.Adhesive phase below nano-particle can be used for reducing reflection or widening the low zone of reflections formed by AR nano-particulates coating.
In some embodiments, the present invention provides optical modeling result, its preferred thickness range and ranges of indices of refraction of can be used for such as limiting the adhesive phase from the combination of different nano-particle monolayer constructions will, and discloses manufacture method.Adhesive phase can be optionally used for other function, for instance self-cleaning function, for instance uses TiO2Material, hydrophobicity or oleophobic property function, or provide gluing, bonding, or it is prone to the surface of sintering and nano-particle may be connected to this surface.Exemplarily, when the compound by silver, copper, silver or copper, or when its mixture is combined into adhesive phase, antimicrobial benefit can be obtained.
In some embodiments, with only containing compared with nano-particle monolayer from the teeth outwards, the AR nanoparticle coating of the present invention may be provided in the less reflection of certain wave strong point or the wavelength band of broader low reflection.
In some embodiments, the present invention provides antireflective goods, and it comprises:
Transparent base material, it has first refractive index (ns)；
The adhesive phase being combined with base material, the second refractive index (n of this binding agentg) more than base material refractive index (ns)；With
The nano-particle monolayer being combined with adhesive phase or nano-particle approximate monolayer, the effective refractive index (n of described nano-particle monolayer or nano-particle approximate monolayerP is effective) less than base material refractive index (ns)。
In some embodiments, on the spectral width of at least 100nm, the reflectance of described goods has the average reflectance less than 0.2%, and the spectral width of this at least 100nm covers visible wavelength collection of illustrative plates at least some of of 400-700nm.
In some embodiments, base material refractive index nsIt is about 1.4-1.55, adhesive phase refractive index ngIt is about 1.55-1.75, nano-particle monolayer or nano-particle approximate monolayer effective refractive index (nP is effective) it is about 1.15-1.4.
With reference to figure, Fig. 1 shows the illustrative embodiments of the AR goods (100) with multilamellar AR coating, nano-particle monolayer (130) is combined into base material (110) by it, and this base material is coated with the adhesive phase (120) with high index.
In some embodiments, the nano-particle of monolayer can be such as be deposited on the monox nanometer ball on high refractive index adhesives layer coating.The refractive index of single nanosphere can such as close to 1.45, but the air of the signal portion within nano-particle monolayer or between single nanoparticle or free space form the effective refractive index (n of nano-particle monolayerP is effective), it can be such as 1.15-1.30.In some embodiments, high index adhesive phase coating can comprise at least some of of transparent base (such as glass) top surface.Nano-particulates can be such as monox nanometer ball, its diameter with 50-300nm or size, has some pitch interval between the center of granule.Pitch interval has minimum value D (1x nano-particle diameter), and is not particularly limited greatest measure.Pitch interval preferred numerical value relative to diameter is discussed further below.Interval between nano granule ball needs not be rule, but opposite pitch could dictate that as at (10 λo)2Region on the equispaced of nanosphere, wherein λoIt it is the central wavelength of required AR performance.Pitch variation in same area should be less than about 5%.
Refractive index (the n of the high index of refraction could generally have 1.55-1.75 of the adhesive phase of contact nanometer-granular cell layerg), and the thickness of high refractive index layer can be such as 60-300nm, thus providing good AR performance in visible wavelength.The more detailed description of preferable range to high refractive index adhesives layer thickness is provided below.
Transparent base material can be such as glass or other transparent base material such as plastics any.When external environment condition medium is air, and as the refractive index (n of transparent base materials) when being about 1.48-1.53, the ranges of indices of refraction of the preferred structure of calculating is usually effective.But, when the refractive index of base material is outside this scope, preferred structure can be changed and to work well with base material.
Use effective media theory, the multilamellar geometrical morphology of inventive article is modeled.This model has shown that the reflection of the measurement of the nanoparticle coating with dip-coating has the concordance of excellence.Assume base material refractive index (ns) it is 1.51 and granule refractive index (np) it is 1.46, simulation is for various high refractive index adhesives layer thicknesses (0-100xD), refractive index (1.55-1.75), and the reflectance of pitch numerical value (1-1.3xD).Then, use the tolerance of spectral width, flatness and mass reflex rate level, at each thickness-refractive index-pitch numerical value evaluation and test reflectance collection of illustrative plates.
Fig. 2 A and 2B shows view (the 2A side view of exemplary AR goods；2B top view), it has multilamellar AR coating, and this multilamellar AR coating comprises nano-particle monolayer, and this nano-particle monolayer has the nano-particle being in not closed packing hexagonal array.
Fig. 3 shows when binding agent high index of refraction numerical value is 1.6, for the schematic diagram of coating performance of various pitch/diameter numerical value and the high refractive index adhesives layer thickness relative to size grade scale.Shadow outline region shows the average reflectance of this part collection of illustrative plates, and wherein reflectance is lower than 0.5%；The deepest shade shows less numerical value.The contour line of black corresponds to the reflectance figure spectral width lower than 0.5%；This spectral width is relative to size grade scale.Show preferred design space or region with the region of oval marks, wherein can obtain on about 2.5xD less than 0.5% reflectance and on this band, obtain the average reflectance less than 0.2%.Show reflectance scale on the right.
Fig. 3 is adhesive phase refractive index when being 1.6, the example of the schematic diagram that reflectance changes with pitch (p) and adhesive phase thickness (g).What can determine that the present invention from this schematic diagram is preferred embodiment such as, and pitch/D is about 1.15-about 1.25, and layer thickness (g) is 1xD-2xD or 1.3xD-1.8xD.
The example of the reflectance collection of illustrative plates that Fig. 4 A and 4B display obtains from the preferred design space of Fig. 3.Fig. 4 A shows average nanoparticle pitch (p) sphere diameter (D) (it is 1.2 nanometers) equal to 1.2 times and high index of refraction layer thickness is D the time collection of illustrative plates of 1.6 times.Fig. 4 B is identical solution, but display 100nm diameter nano-particle, wherein D is equal to 100 nanometers, and this builds antiradar reflectivity band at the visible light part of collection of illustrative plates.
Pitch/the D of Fig. 4 A reflectance collection of illustrative plates is equal to 1.2, refractive index (ng) equal to 1.6, and thickness/D is equal to 1.6.It is generally desirable to AR coating and there is superperformance at visible wavelengths, thus such as can to the selected D of this identical design structure equal to 100nm, ngEqual to 1.6, thickness is equal to 160nm, and pitch/D is equal to 1.2, this obtain 450nm to 650nm 0.14% average reflectance.Table 1 lists the width of this collection of illustrative plates, and it drops on given reflectance and blocks (cutoff) below.
Table 1. composing in discrete maximum reflection rate score below figure for following geometrical morphology: D=100nm, layer refractive index=1.6, layer thickness=160nm, and pitch=120nm.
For the intermediary adhesive layer of the high index of refraction with 1.55-1.75, the mean pitch (p) in monox nanometer ball monolayer can be such as 1xD-1.3xD, and preferably 1.15xD-1.25xD.The thickness (t) of high refractive index layer can be such as 1xD-2xD, and more preferably 1.3-1.8xD.Use thicker intermediary adhesive layer can obtain antiradar reflectivity performance, but the spectrum of this thicker bed methods tends to more uneven.But, smooth spectral response is usually more preferably.The diameter (D) that can select spherical nanoparticle or nanosphere obtains low reflection in required wave-length coverage.For the exemplary preferred parameter of some high refractive index adhesives layer refractive indexs referring to table 2.
Table 2. is for the example of the preferred numerical value of high refractive index adhesives layer.
The picture that Fig. 5 shows compares the reflectance spectrum of the modeling on the surface of two kinds of granule coatings.A kind of surface (500) includes 100nm nano-particle (such as, silicon oxide particle), and this granule is deposited directly on base material, and without adhesive phase.The base material refractive index on the surface that the granule without adhesive phase is coated with is equal to 1.51.Such as, the surface (510) of another kind of granule coating includes 100nm nano-particle (identical with surface (500) silicon oxide particle) and adhesive phase (that is, has the intermediary adhesive layer of high index of refraction, such as SiO2-TiO2Sol-gel blend), it originates from the preferred example designing structure of Fig. 4.At refractive index (ng) on high refractive index adhesives layer equal to 1.6 deposition nano-particle spheroid widen collection of illustrative plates low-reflectance part, and reduce mass reflex rate.
The picture of Fig. 6 A and 6B display provides the spectral width of two embodiments shown in Fig. 5 and the comparison of angle of incidence (AOI).The picture of Fig. 6 A is shown in 0.5% reflectance below figure spectral width (unit is nm), and wherein curve (610) comprises adhesive phase, and curve (600) does not comprise adhesive phase.The picture of Fig. 6 B shows that wherein curve (630) comprises adhesive phase, and curve (620) does not comprise adhesive phase for the identical result that 1% wide reflection rate is blocked.These results show that the goods by the present invention and method can obtain the angular properties of improvement.
Fig. 7 A to 7E provides the exemplary % reflectance spectrum for some the intermediary adhesive layer numerical value shown in table 3, and this intermediary adhesive layer has the refractive index increasing to 1.75 (Fig. 7 E) from 1.55 (Fig. 7 A).
For the numerical value of selected intermediary adhesive layer in table 3. Fig. 7.
Fig. 8 provides the schematic diagram of another kind of exemplary article (800), it includes glass baseplate (810), with nano-particle monolayer (830), this nano-particle single-layer portions ground caves in or is submerged into high index adhesive phase (820).In order to improve the hardness of AR coating, it may be desired to nanosphere is partly recessed into adhesive phase, as shown in Figure 8.Such as this can be realized by following: adds adhesive phase after depositing spheroid from the teeth outwards, or in such as heat treatment step process, spheroid can be recessed into layer.By being recessed into adhesive phase with making nano particle portion, broadband, antiradar reflectivity performance can be obtained.
Fig. 9 A and 9B shows the exemplary spectrum of antiradar reflectivity structure, and wherein nanosphere is partly submerged into adhesive phase.Can passing through the part of depression diameter as given by legend (the right), cave in spheroid.The chart of Fig. 9 A shows that depressed particle causes that low reflectivity regions moves to shorter wavelength, and also reduces relative to the bandwidth of nano-particle spheroid diameter (D) standardized reflectance.The chart of Fig. 9 B shows identical one group spectrum, maps as nano-particle spheroid diameter (D) of target to using the antiradar reflectivity in visible ray collection of illustrative plates now.Because more depression needs bigger diameter, the actual bandwidth degree of low reflectivity regions slightly increases along with nano-particle depression.Diameter (unit is nm) used is provided together with the depression mark in legend (the right).The intermediary adhesive layer that in Fig. 9 A and 9B, all simulations of display all use refractive index to be 1.6.For other parameters of these spectrum referring to table 4.
Table 4. is for the parameter of Fig. 9 B spectrum
Another preferred design space that concrete parameter caves in from various level particles: wherein t/D is the ratio of adhesive phase thickness (t) and particle diameter (D)；G/D is the mark that the amount that nano-particle (such as spheroid) caves in accounts for sphere diameter, and wherein g is the distance that granule is recessed into adhesive phase, and D is the nominal diameter of nano-particle；P is pitch；" 0.5% width " is figure spectral width, and wherein reflectance is lower than 0.5%；" average reflectance (AveRefl) " refers to the average reflectance of the collection of illustrative plates lower than 0.5% reflectance.
As shown in by the spectrum in Fig. 9, when nanosphere caves in 0-0.33xD and during even up to 0.5xD, required AR performance can be obtained.Granule being recessed into high refractive index adhesives layer and really slightly changes required design space, for instance for given particle diameter, when the mark that caves in increases, low reflectivity regions moves to shorter wavelength.Refer again to Fig. 9 A, when the mark that caves in increases, it is necessary to increase nanosphere diameter, thus by antiradar reflectivity property retention at identical wavelength band.In this case, although somewhat tending to bigger bandwidth for bigger depression mark, but most of spectral band width remain without change.
The preparation method being not particularly limited the present invention.In some embodiments, can by any one in the known various thin film coated methods of following the art in transparent deposited on substrates adhesive phase coating: comprise such as thermal evaporation, electron beam evaporation, DC sputtering, reactive AC sputtering, CVD, liquid-based sol-gel or polymer-coated, spin coating, dip-coating, spraying, slit/crack coating, roller coat and similar painting method, or it combines.Material for adhesive phase and adhesive phase coating can comprise such as polymer (material that such as acrylate polymer, polyester, polyimides, nano-particulates are filled) and inorganic matter (such as SiO2-TiO2Blend, SiOx-SiNy blend (referring to such as, " nanoscale research bulletin (NanoscaleResearchLetters) ", February 2012,7:124), Al2O3, nitride and oxynitride such as AlOxNy, SiAlxOyNz, Si3N4, TiN, TiNwOv (referring to such as, U.S. Patent Application Publication No. 20110020638)), and similar material, or its combination.
In some embodiments, can by such as SiO2-TiO2Sol-gel blend formed adhesive phase, its be adjusted to refractive index be 1.60 and thickness (t) be 100-150nm.This sol-gel binder layer or coating can be prepared by such as dip-coating, spin coating, spraying or the like, and solidify at 150-550 DEG C subsequently.Then, can at SiO2-TiO2Deposition nano-particle monolayer on layer.Can use such as, dip-coating, spin coating, spraying, and similar approach, or its combination, aqueous or solvent-based suspension deposit nano-particle monolayer.Optionally by such as thermal sintering, nano-particle monolayer is fused to the surface of high refractive index adhesives layer.Optionally by the following surface that nano-particle monolayer is fused to high refractive index adhesives layer: such as very thin layer is added in the interface on such as particle surface or between adhesive phase and nano-particle.By another kind of material (such as silane, polymer, copolymer, adhesive, siloxanes, sol-gel SiO that such as dip-coating or spraying apply2Material or similar material) very thin layer thickness be such as 1-20nm, and can be used as extra or the second adhesive material.
In some embodiments, can use such as, dip-coating, spin coating, spraying, and similar approach, or its combination, on alkaline silicate glass baseplate, first form nano-particle monolayer.Optionally by thermal sintering, nano-particle monolayer is fused to the surface of alkaline silicate glass.Then can by following come optionally this alkaline silicate glass chemical enhanced: such as make less ion in glass and bigger natural ion carry out ion exchange, for instance with the natural sodium ion that potassium ion carries out ion exchange.Finally, can passing through to carry out ion exchange in the bath comprising metal ion (such as silver ion) and raise the refractive index of the glass surface below nano-particle monolayer, the metal ion comprised in this bath has high relative dielectric constant.Have shown that the refractive index of alkaline silicate is increased to 1.61 (referring to such as R. A Luojiao (R.Araujo) from such as 1.51 by this ion-exchange reactions, " comprise the flint glass of the silver of ion exchange " " Application Optics device (AppliedOptics) ", reel number: 31,25, the page number: 5221-5224).In order to use ion exchange process to build thin layer high-index material, can wish at low temperatures ion exchange to be carried out the shorter time, such as less than 450 DEG C, or it is even less than 350 DEG C, such as 250-400 DEG C, temperature under carry out less than 1 hour, less than 20 minutes or be even less than 5 minutes, the time period of such as 1-60 minute, comprise intermediate value and scope.The ion exchange of the electrostatic drive that can be preferably employed under low temperature in some cases forms sharp-pointed diffusion profile.
In some embodiments, glass baseplate or glass can comprise following, be mainly made up of following, or be made up of following: in soda lime glass, alkaline earth metal aluminosilicate glass, alkali alumino-silicates glass, alkaline borosilicate glass and their combination.In some embodiments, glass can be such as alkali alumino-silicates glass, and it has following composition: 60-72 mole of %SiO2；9-16 mole of %Al2O3；5-12 mole of %B2O3；8-16 mole of %Na2O；With 0-4 mole of %K2O, wherein meets ratio
Wherein alkali metals modified agent is alkali metal oxide.In some embodiments, alkali alumino-silicates glass baseplate can be such as: 61-75 mole of %SiO2；7-15 mole of %Al2O3；0-12 mole of %B2O3；9-21 mole of %Na2O；0-4 mole of %K2O；0-7 mole of %MgO；With 0-3 mole of %CaO.In some embodiments, alkali alumino-silicates glass baseplate can be such as: 60-70 mole of %SiO2；6-14 mole of %Al2O3；0-15 mole of %B2O3；0-15 mole of %Li2O；0-20 mole of %Na2O；0-10 mole of %K2O；0-8 mole of %MgO；0-10 mole of %CaO；0-5 mole of %ZrO2；0-1 mole of %SnO2；0-1 mole of %CeO2；Less than 50ppmAs2O3；With less than 50ppmSb2O3；Wherein 12 moles of %≤Li2O+Na2O+K2O≤20 mole % and 0 mole of %≤MgO+CaO≤10 mole %.In some embodiments, alkali alumino-silicates glass baseplate can be such as: 64-68 mole of %SiO2；12-16 mole of %Na2O；8-12 mole of %Al2O3；0-3 mole of %B2O3；2-5 mole of %K2O；4-6 mole of %MgO；With 0-5 mole of %CaO, wherein: 66 moles of %≤SiO2+B2O3+ CaO≤69 mole %；Na2O+K2O+B2O3+ MgO+CaO+SrO > 10 mole of %；5 moles of %≤MgO+CaO+SrO≤8 mole %；(Na2O+B2O3)-Al2O3≤ 2 moles of %；2 moles of %≤Na2O-Al2O3≤ 6 moles of %；With 4 moles of %≤(Na2O+K2O)-Al2O3≤ 10 moles of %.In some embodiments, alkali alumino-silicates glass can be such as: 50-80 weight %SiO2；2-20 weight %Al2O3；0-15 weight %B2O3；1-20 weight %Na2O；0-10 weight %Li2O；0-10 weight %K2O；With 0-5 weight % (MgO+CaO+SrO+BaO)；0-3 weight % (SrO+BaO)；With 0-5 weight % (ZrO2+TiO2), wherein 0≤(Li2O+K2O)/Na2O≤0.5.In some embodiments, alkali alumino-silicates glass can such as be substantially free of lithium.In some embodiments, alkali alumino-silicates glass such as, can be substantially free of at least one in arsenic, antimony, barium or its combination.In some embodiments, glass can optionally by least one clarifier dispensing of 0 mole of %-2 mole of %, and described clarifier is such as Na2SO4、NaCl、NaF、NaBr、K2SO4、KCl、KF、KBr、SnO2And the like or its combination.
In some embodiments, selected glass can such as carry out drop-down, can by known in the art as slot draw or fusion drawing shape.In these cases, the liquidus viscosity of described glass can be at least 130,000 pools.The example of alkali aluminosilicate glass has description in following patent application: Larry Ellison (Ellison) etc. on July 31st, 2007 submit to be entitled as " the down-drawable chemically reinforced glass for cover plate " (Down-Drawable, ChemicallyStrengthenedGlassforCoverPlate) the U.S. Patent application the 11/888th owned together and transfer the possession of, No. 213, it requires the priority of the U.S. Provisional Application the 60/930th, 808 submitted on May 22nd, 2007；The U.S. Patent application the 12/277th being entitled as " there is the toughness of improvement and the glass of Scratch Resistance " (GlassesHavingImprovedToughnessandScratchResistance) that De Jineika (Dejneka) etc. submitted on November 25th, 2008, No. 573, it requires the priority of the U.S. Provisional Application the 61/004th, 677 submitted on November 29th, 2007；The U.S. Patent application the 12/392nd being entitled as " clarifier for silicate glass " (FiningAgentsforSilicateGlasses) that De Jineika (Dejneka) etc. submitted on February 25th, 2009, No. 577, it requires the priority of the U.S. Provisional Application the 61/067th, 130 submitted on February 26th, 2008；De Jineika (Dejneka) etc. on February 26th, 2009 submit to be entitled as " through ion exchange quick cooled glass " (Ion-Exchanged, FastCooledGlasses) U.S. Patent application the 12/393rd, No. 241, it requires the priority of the U.S. Provisional Application the 61/067th, 732 submitted on February 29th, 2008；The U.S. Patent application the 12/537th being entitled as " strengthening glass and preparation method thereof " (StrengthenedGlassArticlesandMethodsofMaking) that Bel's volt (Barefoot) etc. were submitted on August 7th, 2009, No. 393, it requires the priority of the U.S. Provisional Application the 61/087th, 324 being entitled as " chemical tempering cover plate " (ChemicallyTemperedCoverGlass) submitted on August 8th, 2008；The U.S. Provisional Patent Application the 61/235,767th being entitled as " cracking resistance and anti-scratch glass and case prepared therefrom " (CrackandScratchResistantGlassandEnclosuresMadeTherefrom) that Bel's volt (Barefoot) etc. were submitted on August 21st, 2009；And the U.S. Provisional Patent Application the 61/235,762nd being entitled as " the zircon compatible glass for glass tube down-drawing " (ZirconCompatibleGlassesforDownDraw) that De Jineika (Dejneka) etc. submitted on August 21st, 2009.
Glass surface described in following example can use the glass baseplate of any suitable carried out granule coating or similar base material with sheet glass, it may include such as glass composition 1-11 listed by table 5 or its combination.
Table 5. representative transparent glass baseplate forms
Embodiment
Following example are for being described more fully below using the mode of the invention described above and being listed as the preferred forms implementing each side of the present invention and consider further.Should be appreciated that the scope of the present invention is not construed as limiting by these embodiments, and merely for the sake of the purpose illustrated.Working Examples further describes the goods how preparing the present invention.
The preparation on the surface of granule coating
Embodiment 1 (predictability)
Prepare high refractive index adhesives layer.The TEOS (tetraethyl orthosilicate or tetraethoxysilane, Ao get Ritchie company (Aldrich)) and 25mL0.01MHCl of the methanol of 200mL with 25mL are mixed by water, it is provided that pH is about the solution of 3.Under the reflux of about 65 DEG C, this mixture is stirred 2 hours, form solution " A ".Independently, under agitation according to following order by the cellosolvo of 126.5mL respectively with 2.86mL deionized water, 0.64mL69%HNO3, and 18.18mL isopropyl titanate (IV) mixing, and at ambient conditions entire mixture is stirred 1 hour, form solution " B ".It follows that 1.6mL solution " B " is mixed with 1.8mL solution " A " and 2.0mL2-propanol, to form coating solution " C ".Spin coating 60 seconds under about 575rpm, are spun on glass baseplate by coating solution " C " (such as healthy and free from worry GorillaTMOr healthy and free from worry EagleXGTMGlass), then solidify 1 hour at 410 DEG C and solidify 15 minutes in atmosphere, being consequently formed adhesive phase coating, it has the high index (n of about 1.67g) and the thickness (t) of about 75nm.Can again repeat this adhesive application procedures, to form the coating layer thickness of about 150nm.Concentration and coated conditions can be carried out less change, prepare other adhesive phase coating layer thickness.
Embodiment 2 (predictability)
Prepare nanoparticle coating.In 2-propanol, dispersion diameter is about the monox nanometer ball of 100nm, to form the suspension of about 1.5% solids content.By adding HCl, by the pH regulator of suspension to about 3.5.If it is desired, can carry out ultrasonic to solution, thus promote good Granular composite.Using the pull rate of 30-35 mm/min, dip-coating glass specimen sample in nano granule suspension, thus forming 100nmSiO on the glass surface2The substantially monolayer of nano-particle.If needed, this process can be changed by adjustment pH, solids content, temperature, humidity and dip-coating speed, to form similar coating on the first adhesive phase as above, and by heat treatment at 400-600 DEG C more than or equal to 1 hour, granule can be sintered or be partly sintered to high index adhesive phase.
Embodiment 3 (predictability)
Preparation has the granulating surface of substantially uniform intervals or separating distance, the evenly spaced and not closed packing hexagon geometrical morphology of such as adjacent particle between adjacent particle.
Have been developed for several method recently on various base materials, manufacture the nano-particle monolayer of the not closed packing between particles with controlled interval, comprise and show anti-reflective effect.These methods include the transmission on Lithographic pattern and assemble (referring to root of Rhizoma Nelumbinis ripple nurse (Hoogenboom) etc., " in solvent evaporates the growth of the colloidal crystal that the closelypacked and not close of template-mediated is piled up ", " nanometer news flash ", 4,2, the page number: 205,2004.)；The dip-coating of hydrogel spheroid, it or can shrink (referring to opening (Zhang) etc. drying after deposition in heating process, " the bidimensional not close derived from the self assembly of biomineralization hydrogel spheroid piles up array and the application of their patterning ", Chem.Mater.17, the page number: 5268,2005, and Fig. 3 and relevant text)；SiO2The spin coating of nanosphere and shearing alignment, optionally add this template to (referring to Wen Katesi (Venkatesh) etc., " the general manufacture of the non-stacking colloidal crystal of bidimensional " by other material, Langmuir, 23, the page number: 8231,2007, and Fig. 5 and relevant text)；And transfer to the self assembly at air-water interface or the Electrostatic Control at alkane water termination place of base material, optionally use the adhesive layer of very thin (about 17nm) (referring to Gordon Ray (Ray) etc., " use the sub-micron surface patterning of interface gel particles self assemble ", Langmuir, 25, the page number: 7265,2009, and Fig. 8 and relevant text；Ba Waka (Bhawalkar) etc., " developing the colloid lithographic process for the patterning in non-planar surface ", Langmuir, 26, the page number: 16662,2010).But, these existing work do not illustrate example and are recessed into base material or adhesive phase and the relation between high refractive index adhesives layer at particle size, granule interval, granule as required.The present invention specifically illustrates this relation, and obtains the excellent low reflecting properties for visible ray, and because of optional granule depression or the durability sintering the raising brought.
Claims (20)
1. antireflective goods, comprising:
Transparent base material, its refractive index (ns) for 1.48-1.53；
With the adhesive phase that described base material is combined, the refractive index (n of this binding agentg) it is 1.55-1.75；With
The nano-particle monolayer being combined with described adhesive phase or nano-particle approximate monolayer, the effective refractive index (n of described nano-particle monolayer or nano-particle approximate monolayerP is effective) less than the refractive index of described adhesive phase.
2. antireflective goods as claimed in claim 1, it is characterised in that the effective refractive index (n of described nano-particle monolayerP is effective) it is 1.15-1.3.
3. the antireflective goods as according to any one of claim 1-2, it is characterized in that, on the spectral width of at least 100nm, the reflectance of described goods has the average reflectance less than 0.2%, and the spectral width of this at least 100nm covers visible wavelength collection of illustrative plates at least some of of 400-700nm.
4. the antireflective goods as according to any one of claim 1-3, it is characterized in that, described nano-particle monolayer comprises the nano-particle being in not closed packing hexagon geometrical morphology, and its pitch (p) and nano-particle diameter (D) ratio (p/D) are 1.15-1.25.
5. the antireflective goods as according to any one of claim 1-4, it is characterised in that the thickness (g) of described binding agent is 1xD to 2xD, wherein D is nano-particle average diameter (D).
6. the antireflective goods as according to any one of claim 1-5, it is characterised in that described transparent base material is glass, polymer, glass-ceramic, crystalline oxide, quasiconductor, or its combination.
7. the antireflective goods as according to any one of claim 1-6, it is characterized in that, the nano grain surface coverage rate of described nano-particle monolayer is 90%-93%, and described nano-particle approximate monolayer basically comprises the nano-particle monolayer that nano grain surface coverage rate is 65%-90%.
8. the antireflective goods as according to any one of claim 1-7, it is characterised in that described nano-particle comprises following at least one nano-particle: silicon oxide, aluminium oxide, zirconium oxide, polystyrene, latex, or its combination.
9. the antireflective goods as according to any one of claim 1-8, it is characterized in that, described nano-particle monolayer comprises nano-particle, the average diameter (D) of this nano-particle is 50nm-300nm, and the geometrical morphology of this nano-particle is selected from following at least one: spheroid, hemisphere, ellipsoid, disk like, pyramid, cylinder, pillars or its combination.
10. antireflective goods as claimed in any one of claims 1-9 wherein, it is characterised in that the nano-particle monolayer being combined with described binding agent is included in the nano-particle on described adhesive surface；It is partially embedded into the nano-particle of described binding agent；The nano-particle being completely covered by described binding agent；Or its combination.
11. the antireflective goods as according to any one of claim 1-10, it is characterised in that embed to the nano-particle single-layer portions being combined with described binding agent the distance of described binding agent 0.1xD to 0.5xD, wherein D is nano-particle average diameter (D).
12. the antireflective goods as according to any one of claim 1-11, it is characterised in that the thickness of described binding agent on the substrate is 60nm-300nm.
13. the antireflective goods as according to any one of claim 1-12, it is characterized in that, described binding agent comprises following at least one: material, inorganic oxide material, inorganic nitride material, quasiconductor, transparent conductor or its combination that polymer, nano-particulates are filled.
14. the antireflective goods as according to any one of claim 1-13, it is characterised in that described binding agent also includes following at least one granule or salt: silver, copper or its combination.
15. the method preparing antireflective goods as according to any one of claim 1-14, described method comprises:
Deposit described binding agent on the substrate；
Described binding agent deposits nano-particle, to form described nano-particle monolayer or nano-particle approximate monolayer；With
The nano-particle of described nano-particle monolayer or nano-particle approximate monolayer is fixed on described adhesive phase.
16. method as claimed in claim 15, it is characterised in that described nano-particle monolayer is fixed on described adhesive phase and comprises: thermal sintering；The second binding agent is deposited between the nano-particle monolayer of described binding agent and deposition；The second binding agent is deposited on the described binding agent of combination and the nano-particle monolayer of deposition；The second binding agent is deposited between the adjacent nanoparticles of the nano-particle monolayer of deposition；Or its combination.
17. the method as according to any one of claim 15-16, it is characterised in that also include by carrying out the next chemical enhanced described goods of ion exchange in following at least one position: deposit the described base material before described binding agent；Described binding agent on described base material；Described base material before nano-particle monolayer is fixed on described binding agent；Described base material after deposition or fixing nano-particle monolayer；Or its combination.
18. antireflective goods, comprising:
Transparent base material, it has first refractive index (ns)；
The adhesive phase being combined with base material, the second refractive index (n of this binding agentg) more than base material refractive index (ns)；With
The nano-particle monolayer being combined with adhesive phase or nano-particle approximate monolayer, the effective refractive index (n of described nano-particle monolayer or nano-particle approximate monolayerP is effective) less than base material refractive index (ns)。
19. antireflective goods as claimed in claim 18, it is characterized in that, on the spectral width of at least 100nm, the reflectance of described goods has the average reflectance less than 0.2%, and the spectral width of this at least 100nm covers visible wavelength collection of illustrative plates at least some of of 400-700nm.
20. the antireflective goods as according to any one of claim 18-19, it is characterised in that described base material refractive index nsIt is about 1.4-1.55, described adhesive phase refractive index ngIt is about 1.55-1.75, and the effective refractive index (n of described nano-particle monolayer or nano-particle approximate monolayerP is effective) it is about 1.15-1.4.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
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| US201361872037P | 2013-08-30 | 2013-08-30 | |
| US61/872,037 | 2013-08-30 | ||
| PCT/US2014/053140 WO2015031603A1 (en) | 2013-08-30 | 2014-08-28 | Anti-reflection article and methods thereof |
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| CN105722923A true CN105722923A (en) | 2016-06-29 |
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| CN (1) | CN105722923A (en) |
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| KR20170014755A (en) * | 2015-07-31 | 2017-02-08 | 삼성전자주식회사 | Display panel and display apparutus having the same |
| CN108699357A (en) * | 2015-12-28 | 2018-10-23 | 汉高股份有限及两合公司 | Nano-complex anti-fingerprint coating |
| CN115584145A (en) * | 2022-11-02 | 2023-01-10 | 合肥昊泰新材料科技有限责任公司 | Preparation method of low-emissivity colored composite pigment |
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| WO2012151097A1 (en) * | 2011-05-02 | 2012-11-08 | Corning Incorporated | Glass article having antireflective layer and method of making |
| US20130163087A1 (en) * | 2010-09-01 | 2013-06-27 | Agc Glass Europe | Glass substrate coated with an anti-reflective layer |
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2014
- 2014-08-28 WO PCT/US2014/053140 patent/WO2015031603A1/en active Application Filing
- 2014-08-28 CN CN201480059097.1A patent/CN105722923A/en active Pending
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| CN101257980A (en) * | 2002-09-19 | 2008-09-03 | 力特光电科技股份有限公司 | Antiglare and antireflection coatings of surface active nanoparticles |
| WO2004066001A1 (en) * | 2003-01-22 | 2004-08-05 | Fuji Photo Film Co., Ltd. | Antireflection film, polarizing plate and display device |
| CN101770041A (en) * | 2008-12-22 | 2010-07-07 | 日油株式会社 | Antireflection film |
| US20110164322A1 (en) * | 2009-12-08 | 2011-07-07 | Sony Corporation | Antireflective film, method of production thereof, and uv-curable resin material composition coating liquid |
| US20130163087A1 (en) * | 2010-09-01 | 2013-06-27 | Agc Glass Europe | Glass substrate coated with an anti-reflective layer |
| CN102736138A (en) * | 2011-03-30 | 2012-10-17 | 株式会社腾龙 | Antireflection film and optical device |
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| WO2015031603A1 (en) | 2015-03-05 |
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