CN104730737A - Red omnidirectional structural color made from metal and dielectric layers - Google Patents

Abstract

A multilayer stack displaying a red omnidirectional structural color. The multilayer stack includes a reflector layer, a dielectric layer extending across the reflector layer, and an absorbing layer extending across the dielectric layer. The dielectric layer reflects more than 70% of incident white light that has a wavelength greater than 580 nanometers (nm). In addition, the absorbing layer absorbs more than 70% of the incident white light with a wavelength less than 580 nm. In combination, the reflector layer, dielectric layer, and absorbing layer form an omnidirectional reflector that reflects a narrow band of electromagnetic radiation with a center wavelength between 580-680 nm, has a width of less than 200 nm wide and a color shift of less than 100 nm when the reflector is viewed from angles between 0 and 45 degrees.

Description

The omnirange schemochrome of the redness be made up of metal and dielectric layer

The cross reference of related application

The application is the U.S. Patent Application Serial Number 13/913 submitted on June 8th, 2013, the part of 402 continues (CIP), application 13/913, 402 is then the U.S. Patent Application Serial Number 13/760 submitted on February 6th, 2013, the CIP of 699, application 13/760, 699 is then submit on August 10th, 2012 13/572, the CIP of 071, application 13/572, 071 is then the U.S. Patent Application Serial Number 13/021 submitted on February 5th, 2011, the CIP of 730, application 13/021, 730 is then the application 12/793 submitted on June 4th, 2010, the CIP of 772, application 12/793, 772 is then the U.S. Patent Application Serial Number 12/388 submitted on February 18th, 2009, the CIP of 395, application 12/388, 395 is then the U.S. Patent Application Serial Number 11/837 submitted on August 12nd, 2007, 529 (United States Patent (USP)s 7, 903, 339) CIP.The U.S. Patent Application Serial Number 13/021,730 submitted on February 5th, 2011 is also the CIP of 11/837,529 (United States Patent (USP) 7,903,339) that on August 12nd, 2007 submits to.The U.S. Patent Application Serial Number 13/760,699 submitted on February 6th, 2013 is also the CIP of submit on May 18th, 2009 12/467,656, and the entire contents of above-mentioned all applications is incorporated in this by reference.

Technical field

The present invention relates to omnirange schemochrome (omnidirectional structural color), and the omnirange schemochrome of the redness provided by multilayer laminated (the multilayer stack) with absorber layers and dielectric layer is provided.

Background technology

The colorant (pigment) made with sandwich construction is known.In addition, present or provide the colorant of the omnirange schemochrome of high chroma to be also known.But the colorant of this prior art needs to reach 39 thin layers to obtain the color characteristics of wishing.

Understand, the cost relevant with the production of thin-film multilayer colorant and the required number of plies proportional.Therefore, relevant with the production of the multilayer laminated high chroma omnirange schemochrome of carrying out using dielectric substance cost may be too high.So the high chroma omnirange schemochrome needing the thin layer of minimum number is desirable.

Summary of the invention

Red the multilayer laminated of omnirange schemochrome can be provided to be provided.Multilayer laminated comprise reflector layer, throughout (across) reflector layer extend dielectric layer and throughout dielectric layer extend absorber layers.Dielectric layer is greater than the incident white light of the wavelength of 550 nanometers (nm) in conjunction with reflector layer reflection having more than 70%.In addition, absorber layers absorbs the incident white light that having more than 70% is generally less than the wavelength of 550nm.Combine, reflector layer, dielectric layer and absorption layer form such omnirange reflecting body: (1) its reflection has centre wavelength between 550nm to 700nm and is less than the arrowband (reflection peak or band) of both visible electromagnetic radiation of the wide width of 200nm; (2) when this omnirange reflecting body is watched from the angle between 0 degree and 45 degree, it has the gamut (color shift) being less than 100nm.In some instances, be less than 175nm by the width of the arrowband of both visible electromagnetic radiation reflected, be preferably less than 150nm, be more preferably and be less than 125nm, and be more preferably again and be less than 100nm.

Reflector layer has the thickness between 50nm to 200nm and is made up of metals such as such as aluminium, silver, platinum, tin and their alloys.

In some instances, dielectric layer have 0.1 to 2.0 wish by the optical thickness of the quarter-wave (QW, quarter wave) of centre wavelength reflected.In other instances, dielectric layer have be greater than 2.0 wish by the optical thickness of the QW of centre wavelength reflected.Dielectric layer also have be greater than 1.6 refractive index and comprise such as zinc sulphide (ZnS), titania (TiO ₂), hafnia (HfO ₂), niobium oxide (Nb ₂o ₅), tantalum oxide (Ta ₂o ₅), their dielectric substance such as combination.Dielectric layer also can comprise such as iron oxide (Fe ₂o ₃), cuprous oxide (Cu ₂o) dielectric substance that, their combination etc. is colored.

Absorption layer, is also referred to as absorber layers at this, can be or can not be colored or optionally absorption layer.Such as, achromatic or nonselective absorber layers can comprise the layer be made up of chromium, silver, platinum etc.In replacement scheme, absorption layer can be the colour be made up of copper, gold, such as bronze and the alloy etc. of brass or optionally absorber layers.In another replacement scheme, colored or optionally absorber layers comprise such as Fe ₂o ₃, Cu ₂the dielectric substance that O, their combination etc. are colored.

Understand, selective absorbing body layer is selected to absorb the wavelength of scope desired in white-light spectrum and is reflected the white-light spectrum of the scope that another is wished.Such as, selective absorbing body layer can be designed and manufactured to its is absorbed have with bluish violet, blueness, green, yellow corresponding wavelength (such as, 400nm to 550nm) electromagnetic radiation and the reflection electromagnetic radiation corresponding with redness (that is, 580 to the scope of infrared (IR)).

In some instances, comprise the second dielectric layer outside the multilayer laminated dielectric layer (that is, the first dielectric layer) except mentioning before, the second dielectric layer extends throughout absorption layer and relatively arranges about absorption layer with the first dielectric layer.In addition, other embodiments comprising the second absorption layer, the 3rd dielectric layer etc. are provided.But multilayer laminated gross thickness disclosed herein is less than 2 microns (μm), is less than 1.5 μm in some instances, is less than 1.0 μm in other instances, and is less than 0.75 μm in other examples.

Accompanying drawing explanation

Figure 1A is the schematic diagram of zero or nearly 1 electric field point in the ZnS dielectric layer being exposed to the electromagnetic radiation (EMR) with 500nm wavelength;

Figure 1B be the absolute value of the electric field when being exposed to the EMR of the wavelength with 300nm, 400nm, 500nm, 600nm and 700nm square (| E| ²) diagram to the thickness of the ZnS dielectric layer shown in Figure 1A;

Fig. 2 extends and is exposed to the schematic diagram of the dielectric layer of electromagnetic radiation relative to the angled θ of the normal direction of the outside surface of dielectric layer on substrate or reflector layer;

Fig. 3 is the schematic diagram of the ZnS dielectric layer with Cr absorber layers, wherein said Cr absorber layers be positioned at ZnS dielectric layer for zero or nearly zero electric field point place of incident EMR with 434nm wavelength;

Fig. 4 is for being exposed to not having Cr absorber layers multilayer laminated (such as, Figure 1A) and having the reflectivity percentages of multilayer laminated (such as, Fig. 3 A) of Cr absorber layers to represent by the figure of EMR wavelength reflected of white light;

Fig. 5 A is the diagram of first harmonic and the second harmonic presented by the ZnS dielectric layer (such as, Figure 1A) extended in Al absorber layers;

Fig. 5 B makes the absorbed multilayer laminated reflectivity percentages of the second harmonic shown in Fig. 5 A to by the diagram of EMR wavelength of reflecting for having the Cr absorber layers of the ZnS dielectric layer additional ZnS of being positioned at dielectric layer extended throughout Al reflector layer;

Fig. 5 C makes the absorbed multilayer laminated reflectivity percentages of the first harmonic shown in Fig. 5 A to the diagram of the EMR wavelength of reflection for the Cr absorber layers with the ZnS dielectric layer additional ZnS of the being positioned at dielectric layer extended throughout Al reflector layer;

Fig. 6 A shows for the diagram of the electric field being exposed to the electric field angle correlativity of the Cr absorber layers of incident light with 0 and 45 degree square to dielectric layer thickness;

Fig. 6 B is that the absorptivity number percent of the Cr absorber layers when the normal relative to outside surface becomes 0 and 45 degree (0 ° is perpendicular to surface) to be exposed to white light is to by the diagram of EMR wavelength of reflecting;

Fig. 7 A is the schematic diagram multilayer laminated according to the omnirange schemochrome of the redness of the embodiment of the present invention;

Fig. 7 B is exposed to white light for the multilayer laminated incident angle with 0 and 45 ° shown in Fig. 7 A, and the absorptivity number percent of the Cu absorber layers shown in Fig. 7 A is to by the diagram of EMR wavelength of reflecting;

Fig. 8 is for the multilayer laminated card example (proof) of the concept being exposed to white light with the incident angle of 0 ° red omnirange schemochrome, for reflectivity percentages to by the graphics Web publishing between the calculation/simulation data of EMR wavelength that reflect and experimental data;

Fig. 9 is the schematic diagram multilayer laminated according to the omnirange schemochrome of the embodiment of the present invention;

Figure 10 is the schematic diagram multilayer laminated according to the omnirange schemochrome of the embodiment of the present invention;

Figure 11 is the schematic diagram multilayer laminated according to the omnirange schemochrome of the embodiment of the present invention; And

Figure 12 is the schematic diagram multilayer laminated according to the omnirange schemochrome of the embodiment of the present invention;

Figure 13 is the thin slice (flake) of the multi-layer laminate structure had according to the embodiment of the present invention or scanning electron microscope (SEM) image of colorant;

Figure 14 is the SEM image of the xsect of the single sheet shown in Figure 13;

Figure 15 A uses according to embodiment of the present invention Design and manufacture and the orange colorant that the tone (hue) had in the color diagram (color map) shown in Figure 15 D is 36 ° is coated with the schematic diagram of the plate painted;

Figure 15 B uses according to embodiment of the present invention Design and manufacture and the wine-colored colorant that the tone had in the color diagram shown in Figure 15 D is 26 ° is coated with the schematic diagram of the plate painted;

Figure 15 C uses according to embodiment of the present invention Design and manufacture and the colorant that the tone had in the color diagram shown in Figure 15 D is the bright pink colour of 354 ° is coated with the schematic diagram of the plate painted;

Figure 15 D is the a*b* color diagram using CIELAB color space;

Figure 15 E is the schematic diagram designed for the eleventh floor of the colorant in the pigment of model shown in Figure 15 A to 15C;

Figure 16 A is the schematic diagram of seven layer laminate according to the embodiment of the present invention;

Figure 16 B is the schematic diagram of seven layer laminate according to the embodiment of the present invention;

Figure 16 C is the schematic diagram of seven layer laminate according to the embodiment of the present invention;

Figure 16 D is the schematic diagram of seven layer laminate according to the embodiment of the present invention;

Figure 17 uses the figure of a part of a*b* color diagram of CIELAB color space to represent, wherein traditional pigment and for be coated with the plate shown in drawing 15B pigment between compare colourity (chroma) and hue shift;

Figure 18 is the diagram of the reflectivity vs. wavelength for seven layers of design according to the embodiment of the present invention; And

Figure 19 is the diagram of the reflectivity vs. wavelength for seven layers of design according to the embodiment of the present invention.

Embodiment

Multilayer laminated being provided of omnirange schemochrome (such as red omnirange look) can be provided.Therefore, described multilayer laminatedly have as purposes such as pigment colorant (paint pigment), the films providing the color of hope.

The multilayer laminated dielectric layer comprising reflector layer and extend throughout reflector layer of omnirange schemochrome can be provided.Reflector layer and dielectric layer reflection having more than 70% are greater than the incident white light of the wavelength of 550nm.What understand is that the thickness of dielectric layer can be defined as in advance and makes to be greater than 550nm, 560nm, 580nm, 600nm, 620nm, 640nm, 660nm, 680nm or the wavelength between them at the incident white light more than 70% by the wavelength reflecting part.In other words, the thickness of dielectric layer can be selected and be produced as making on Lab color system figure tool tone likely, the particular color of colourity and/or brightness reflected and arrived by eye-observation.

In some instances, the multilayer laminated tone had in lab color space between 315 ° and 45 °.In addition, multilayer laminated have the colourity being greater than 50 and the hue shift being less than 30 °.In other instances, colourity is greater than 55, is preferably greater than 60, and is more preferably and is greater than 65, and/or hue shift is less than 25 °, is preferably less than 20 °, is more preferably to be less than 15 ° and to be more preferably to be less than 10 °.

Absorption layer extends throughout dielectric layer, and for all wavelengths that general more corresponding than the reflection wavelength of the hope with dielectric layer wavelength is little, described absorption layer absorbs the incident white light more than 70%.Such as, make having more than 70% be greater than the incident white light of the wavelength of 600nm by the thickness reflected if dielectric layer has, then the absorption layer extended throughout dielectric layer absorbs the incident white light that having more than 70% is generally less than the wavelength of 600nm.By this way, the sharp-pointed reflection peak of the wavelength had in red color space is provided.In some instances, reflector layer and dielectric layer reflection having more than 80% are greater than the incident white light of the wavelength of 550nm, and in other instances for more than 90%.In addition, in some instances, absorber layers absorb the little wavelength of the general wavelength more corresponding than the reflection wavelength of the hope with dielectric layer more than 80%, and in other instances for more than 90%.

What understand is that term " generally " in this context is just referring to and/or negative 20nm in some instances, be just and/or negative 30nm in other instances, in some other example be just and/or negative 40nm and in other examples for just and/or negative 50nm.

Reflector layer, dielectric layer and absorption layer form omnirange reflecting body, and described omnirange reflecting body reflects the arrowband (hereinafter referred to as reflection peak or the zone of reflections) of such electromagnetic radiation: the zone of reflections that it has centre wavelength between visible-infrared edge of 550nm and EMR spectrum, width is less than 200nm and be less than the gamut of 100nm when omnirange reflecting body is exposed to white light and is watched by the angle between from 0 and 45 degree.Described gamut can be the form of the skew of the centre wavelength of the zone of reflections, or in replacement scheme, is the form of the skew of the UV lateral edges (UV-sided edge) of the zone of reflections.For the purposes of the present invention, the width of the zone of reflections of electromagnetic radiation is restricted to the width of the zone of reflections at the half reflection height place of maximum reflection wavelength in visible spectrum.In addition, by the arrowband of electromagnetic radiation reflected, i.e. " color " of omnirange reflecting body, has the hue shift being less than 25 degree.In some instances, reflector layer has thickness between 50nm to 200nm and is made by such as aluminium, silver, platinum, tin, their metal such as alloy or comprised described metal.

About the dielectric layer extended throughout reflector layer, dielectric layer has the optical thickness between 0.1 QW and 2.0 QW.In some instances, dielectric layer has the optical thickness between 0.1 QW and 1.9 QW, and in other instances, dielectric layer has the thickness between 0.1 QW and 1.8 QW.In other examples, dielectric layer has the optical thickness being less than 1.9 QW, such as, be less than 1.8 QW, be less than 1.7 QW, be less than 1.6 QW, be less than 1.5 QW, be less than 1.4 QW, be less than 1.3 QW, be less than 1.2 QW or be less than 1.1 QW.In replacement scheme, dielectric layer can have the optical thickness being greater than 2.0 QW.

Dielectric layer has the refractive index being greater than 1.60,1.62,1.65 or 1.70, and can by such as ZnS, TiO ₂, HfO ₂, Nb ₂o ₅, Ta ₂o ₅, their dielectric substance such as combination makes.In some instances, dielectric layer is by such as Fe ₂o ₃, Cu ₂the colour that the colored dielectric substance such as O is made or optionally dielectric layer.For the purposes of the present invention, term " colored dielectric substance " or " colored dielectric layer " refer to dielectric substance or the dielectric layer of another part of transmitting white light while a part for reflection incident white light.Such as, colored dielectric layer transmissive has the electromagnetic radiation of the wavelength between 400nm and 600nm and reflects the wavelength being greater than 600nm.Therefore, colored dielectric substance or the dielectric layer of colour have visual appearance that is orange, red and/or reddish orange.

Except dielectric layer, omnirange reflecting body can comprise the selective absorbing body layer of the thickness had between 5nm to 200nm.In some instances, colored absorber layers replaces or replaces absorber layers recited above.Be similar to description above, selective absorbing body layer Absorbable rod has the light of the wavelength relevant to bluish violet, blueness, yellow, green etc., and the wavelength that reflection and orange, red, reddish orange etc. are corresponding.In some instances, colored absorber layers comprises the chromatic metallic such as its alloy of such as copper, gold and such as bronze and brass, or is made up of described chromatic metallic.In other instances, colored absorber layers can comprise such as Fe ₂o ₃, Cu ₂the dielectric substance that O etc. are colored, or be made up of the dielectric substance of described colour.

The position of absorber layers for make zero or nearly zero energy interface appear between absorber layers and dielectric layer.In other words, dielectric layer have make zero or nearly zero energy field be positioned at the thickness of dielectric layer-absorber layers interface.Understand be zero or nearly zero energy field occur that the thickness of the dielectric layer of part is the function of incident EMR wavelength.In addition, also will understand, the wavelength corresponding with zero or nearly zero electric field will be transmitted through dielectric layer-absorber layers interface, but not corresponding with zero or nearly zero electric field at interface place wavelength will not be transmitted through described interface.Therefore, the thickness of dielectric layer is designed and manufactured to and makes the wavelength transmission of desired incident white light by dielectric layer-absorber layers interface, reflects away, be then back transmitted through dielectric layer-absorption layer interface from reflector layer.Similarly, the thickness of dielectric layer is manufactured so that the wavelength of undesirable incident white light is not transmitted through dielectric layer-absorber layers interface.

Described in above, not corresponding with zero or nearly zero electric field interface of hope wavelength is absorbed by absorber layers and is not therefore reflected.By this way, the color of desired " distinctness " is provided, also referred to as schemochrome.In addition, the thickness of dielectric layer is for making the reflection producing first harmonic and/or the second harmonic of wishing to provide the surface with red color, and it also has omnidirectional outward appearance.

Can comprise the second dielectric layer except the multilayer laminated dielectric layer (also referred to as the first dielectric layer) except mentioning before, described second dielectric layer extends throughout absorber layers.In addition, the second dielectric layer is relatively arranged about absorber layers with the first dielectric layer mentioned.

Thickness and zero or nearly 1 electric field point, Figure 1A about dielectric layer mentioned above is the schematic diagram of the ZnS dielectric layer extended throughout Al reflector layer.ZnS dielectric layer has the gross thickness of 143nm, and for having the incidence electromagnetic radiation of 500nm wavelength, zero or nearly zero energy point appear at 77nm place.In other words, ZnS dielectric layer, for the incident EMR with 500nm wavelength, presents zero or nearly zero electric field in the distance at a distance of Al reflector layer 77nm.In addition, Figure 1B provides the diagram of the energy field across ZnS dielectric layer for many different incident EMR wavelength.As described in Figure, dielectric layer has zero electric field for 500nm wavelength at 77nm thickness place, but has non-zero electric field for the EMR wavelength of 300,400,600 and 700nm at 77nm place.

Not bound by theory, discuss below for zero of dielectric layer (all dielectric layers as shown in Figure 1A) or the calculating of nearly zero energy dot thickness.

With reference to Fig. 2, show and there is refractive index n _ssubstrate or core layer 2 on the dielectric layer 4 with gross thickness ' D ', incremental thickness ' d ' and refractive index ' n '.Incident light to be mapped on the outside surface 5 of dielectric layer 4 relative to the angled θ of straight line 6 and to reflect from outside surface 5 with identical angle, and described straight line 6 is perpendicular to outside surface 5.Incident light is transmitted through outside surface 5 and relative to the angled θ of straight line 6 _fenter dielectric layer 4 and with angle θ _sbe mapped on the surface 3 of substrate layer 2.

For single dielectric layer, θ _s=θ _fand energy field/electric field (E) can be expressed as E (z) as z=d.According to Maxwell equation, for s polarization, electric field can be expressed as:

And can be expressed as p polarization:

Wherein and λ is the wavelength to be reflected of wishing.In addition, α=n _ssin θ _s, wherein ' s ' is corresponding with the substrate in Fig. 1, and function as z is the specific inductive capacity of layer.Therefore, for s polarization:

|E(d)| ²＝|u(z)| ²exp(2ikαy)| _z＝d(3)

For p polarization:

${\left|E\left(d\right)\right|}^2=[{\left|u\left(z\right)\right|}^2+{\left|\frac{\mathrm{\α}}{\sqrt{n}}v\left(z\right)\right|}^2]\exp \left(2\mathrm{ik\αy}\right){|}_{z=d}---\left(4\right)$

Understand be along the Z-direction of dielectric layer 4 electric field change can by calculate unknown parameter u (z) and v (z) estimate, wherein said calculating can show for:

Certainly, ' i ' is the square root of-1.Use boundary condition u| _z=0=1, v| _z=0=q _s, then there is following relationship:

For s polarization: q _s=n _scos θ _s(6)

For p polarization: q _s=n _s/ cos θ _s(7)

For s polarization: q=n cos θ _f(8)

For p polarization: q=n/cos θ _f(9)

U (z) and v (z) can be expressed as:

And

So, when, for s polarization:

Further, for p polarization:

Wherein:

α＝n _ssinθ _s＝n sinθ _F(15)

$q_s=\frac{n_s}{\cos {\mathrm{\θ}}_s}---\left(16\right)$

And

$q_s=\frac{n}{\cos {\mathrm{\θ}}_F}---\left(17\right)$

Therefore for θ _f=0 or the simple case of vertical incidence, and α=0:

It take into account the thickness ' d ' that will solve, and namely dielectric layer internal electric field is position or the location at zero place.

Referring now to Fig. 3, it is at 70nm place the 77nm of 500nm wavelength (instead of for) that equation 19 is used to zero or the nearly 1 electric field point calculated in ZnS dielectric layer when being exposed to the EMR of the wavelength with 434nm shown in Figure 1A.In addition, the Cr absorber layers that 15nm the is thick thickness be inserted at a distance of Al reflector layer 70nm is sentenced and is provided zero or nearly zero electric field ZnS-Cr interface.This creationary structure allows to have the light of 434nm wavelength through Cr-ZnS interface, but absorbs the light without 434nm wavelength.In other words, Cr-ZnS interface has zero or nearly zero electric field about the light with 434nm wavelength, and therefore the light of 434nm is through this interface.But Cr-ZnS interface does not then have zero or nearly zero electric field for the light without 434nm wavelength, therefore such light is absorbed by Cr absorber layers and/or Cr-ZnS interface and is not reflected by Al reflector layer.

Understand, a certain proportion of light within the +/-10nm of desired 434nm will through Cr-ZnS interface.But, also to understand, the arrowband of this reflected light, such as 434+/-10nm, still provide distinct schemochrome to human eye.

In the diagram exemplified with the result of the multilayer laminated Cr absorber layers in Fig. 3, illustrated therein is reflectivity percentages to by the EMR wavelength reflected.Shown in dotted line, described dotted line is corresponding with the ZnS dielectric layer when not having Cr absorber layers shown in Fig. 3, and a narrow reflection peak appears at about 400nm place, but one much wide that peak appears at about 550+nm place.In addition, a considerable number of light is still had to be reflected in 500nm wavelength region may.Therefore, occurred that obstruction is multilayer laminated have or present the bimodal of schemochrome.

On the contrary, the solid line in Fig. 4 is corresponding with the structure shown in Fig. 3 when Cr absorber layers exists.As shown in FIG., there is sharp-pointed peak at about 434nm place and provided the sharply decline of the reflectivity for the wavelength being greater than 434nm by Cr absorber layers.Understand, the sharp-pointed peak showed by solid line is visually revealed as strikingly color/schemochrome.In addition, Fig. 4, exemplified with the place of width measuring reflection peak or band, namely determines bandwidth at 50% place of the reflectivity of maximum reflection wavelength, also referred to as halfwidth degree (FWHM).

Omnirange about the sandwich construction shown in Fig. 3 shows, and the thickness of ZnS dielectric layer can be designed or be arranged so that the first harmonic only having reflected light is provided.Understand, this is enough for " indigo plant " look, but the generation of " red " look needs extra consideration.Such as, for the control difficulty of the angle independence of redness, this is because need thicker dielectric layer, this so that result in higher hamonic wave design, namely the appearance of second harmonic and possible third harmonic is inevitable.In addition, wine-colored tone space is very narrow.Therefore, the multilayer laminated of redness has higher angular variance (angular variance).

In order to overcome the higher angular variance for redness, this application discloses uniqueness, the novel design/configuration that angle independently red color can be provided.Such as, Fig. 5 A exemplified with when dielectric layer outside surface by from present during 0 and 45 degree of viewing for incident white light once with the dielectric layer of second harmonic.As shown in this figure represents, provide low angle-dependence (little Δ λ by the thickness of dielectric layer _c), but therefore this multilayer laminated combination with blueness (first harmonic) and red (second harmonic) is also not suitable for desired " Shan Hong " look.So, have developed and used absorber layers to absorb the concept/structure of undesired harmonic series.Fig. 5 A is also exemplified with the zone of reflections centre wavelength (λ for given reflection peak _c) position and when sample is by from the residual quantity of centre wavelength during 0 and 45 degree of viewing or skew (Δ λ _c) example.

Turn to now Fig. 5 B, absorb the second harmonic shown in Fig. 5 A by the Cr absorber layers being positioned at suitable dielectric layer thickness (such as, 72nm) place and provide distinct blueness.The more important thing is for the present invention, Fig. 5 C provides red exemplified with by absorbing first harmonic by the Cr absorber layers being positioned at different dielectric layer thickness (such as, 125nm) place.But Fig. 5 C also still causes exemplified with the use by multilayer laminated Cr absorber layers the angle-dependence exceeding hope, be namely greater than the Δ λ of hope _c.

Understand, for the λ of redness compared with blueness _cin relatively large skew be because peony tone space is very narrow and Cr absorber layers absorbs the fact of the wavelength (that is, when electric field be zero or nearly zero do not absorb light) relevant to non-zero electric field.Therefore, Fig. 6 A exemplified with the optical wavelength for different incidence angles, zero or non-zero points be different.This factor result in the absorptivity that the angle shown in Fig. 6 B is correlated with, i.e. the difference of 0 ° and 45 ° absorbance curves.Therefore in order to improve multilayer laminated design and angle independence performance further, employ no matter whether electric field is zero absorber layers all absorbing such as blue light.

Particularly, Fig. 7 A shows and has throughout the Cu absorber layers of dielectric ZnS layer extension but not the multilayer laminated of Cr absorber layers.Show the result using this " colored " or " optionally " absorber layers in Fig. 7 B, which show for 0 ° and the 45 ° multilayer laminated absorbance curves shown in Fig. 7 A " compact " more than gather.Therefore, the comparison between Fig. 6 B and Fig. 7 B is exemplified with the remarkable improvement when using selective absorbing body layer instead of use neutral absorber layer in absorptivity angle independence.

Described in above, the card example of Design and manufacture concept multi-layer laminate structure.In addition, the calculation/simulation result of the card example about concept sample and the experimental data of reality are compared.Particularly, and as shown in the chart in Fig. 8, create distinct redness (wavelength being greater than 700nm typically can not be seen by human eye) and obtain unanimously extraordinary between calculation/simulation light data and the experiment light data obtained according to actual sample.In other words, calculation/simulation can and/or be used to emulate the multilayer laminated design of one or more embodiment according to the present invention and/or the multilayer laminated result of prior art.

The list of provide in table 1 below emulation and/or actual fabrication multilayer laminated sample.As shown in Table, Creative Design disclosed herein comprises at least 5 different layer structures.In addition, according to many different materials, sample is simulated and/or make.Provide the sample presenting high chroma, low key tone skew and outstanding reflectivity.In addition, three layers and five layers of sample have the gross thickness between 120nm to 200nm; Seven layers of sample has the gross thickness between 350nm to 600nm; Nine layers of sample has the gross thickness between 440nm to 500nm; And eleventh floor sample has the gross thickness between 600nm to 660nm.

Table 1

About the layer order of reality, Fig. 9 is with the half of Reference numeral 10 exemplified with five layers of design.Omnirange reflecting body 10 has reflector layer 100, extends the dielectric layer 110 of 100 and extend the absorber layers 120 of 110 throughout dielectric layer throughout reflector layer.Understand, another dielectric layer and another absorber layers relatively can arrange to provide five layers of design about reflector layer 100.

Reference numeral 20 in Figure 10 is exemplified with the half of seven layers of design, and wherein another dielectric layer 130 makes dielectric layer 130 and dielectric layer 110 relatively be arranged about absorber layers 120 throughout absorber layers extension 120.

Figure 11 is exemplified with the half of nine layers of design, and wherein the second absorber layers 105 is between reflector layer 100 and dielectric layer 110.Finally, the half that Figure 12 designs exemplified with eleventh floor, wherein another absorber layers 140 extends and another dielectric layer 150 extends on absorber layers 140 on dielectric layer 130.

Figure 13 illustrates scanning electron microscope (SEM) image of multiple colorants of the sandwich construction had according to the embodiment of the present invention.Figure 14 is the SEM image of under the more high-amplification-factor of display sandwich construction in colorant.This colorant is used to the different red pigment of making three kinds, and then described red pigment is applied on three blocks of plates for test.Figure 15 A to 15C is the schematic diagram of the actual plate of having tinted, because the practical photograph of plate looks like grey/black when printing by black and white mode and copy.Figure 15 A represents the orange of the 36 ° of tones had on the color table shown in Figure 15 D, and Figure 15 B representative has the peony of 26 ° of tones and Figure 15 C represents the bright pink colour with 354 ° of tones.In addition, the dark red colour table represented in Figure 15 B has the chrominance C * of the brightness L* and 67 of 44.

Figure 15 E is that representative is for being coated with the schematic diagram of the eleventh floor design of the colorant of the plate shown in drawing 15A to 15C.About the exemplary thickness of various layer, table 2 provides the actual (real) thickness of each in multilayer laminated/colorant accordingly.As shown in the one-tenth-value thickness 1/10 in table 2, the gross thickness of eleventh floor design is less than 2 microns and can be less than 1 micron.

Table 2

Color=>	Orange	Peony	Bright pink colour
				Layer ↓ ↓	Layer thickness (nm)	Layer thickness (nm)	Layer thickness (nm)
ZnS	28	31	23
				Cu	25	28	28
ZnS	141	159	40
				Cu	32	36	72
ZnS	55	63	41
				Al	80	80	80
ZnS	55	63	41
				Cu	32	36	72
ZnS	141	159	40
				Cu	25	28	28
ZnS	28	31	23

Understand, seven layers of design and seven layer multi-layer laminations can be used to make this colorant.The example of 4 kind of seven layer multi-layer lamination has been shown in Figure 16 A to 16D.Figure 16 A is exemplified with seven layer laminate, and it has: (1) reflector layer 100; (2) a pair dielectric layer 110, it extends 100 throughout reflector layer and relatively arranges about reflector layer 100; (3) a pair selective absorbing body layer 120a, its outside surface throughout described a pair dielectric layer 110 extends; And (4) a pair dielectric layers 130, its outside surface throughout described a pair selective absorbing body layer 120a extends.

Naturally, the thickness of dielectric layer 110 and selective absorbing body layer 120a is for making the interface between selective absorbing body layer 120a and dielectric layer 110 and the interface between selective absorbing body layer 120a and dielectric layer 130 relative to optical wavelength (315 ° of < tones <45 ° and/or the 550nm< λ of the hope in the pink colour-red-orange region of the color diagram shown in Figure 15 D _c<700nm) zero or nearly zero electric field is presented.By this way, the red light across-layer 130-120a-110 wished, reflects away from layer 100, and passes back through a layer 110-120a-130.On the contrary, non-red light is absorbed by selectivity absorber layers 120a.In addition, as discussed above and shown in Fig. 7 A to 7B, selective absorbing body layer 120a has angle independently absorptivity for non-red light.

Understand, the thickness of dielectric layer 100 and/or 130 is that it is omnidirectional for making by the reflection of multilayer laminated red light of carrying out.By the little Δ λ of reflected light _cmeasure or determine that omnirange reflects.Such as, in some instances, Δ λ _cbe less than 120nm.In other instances, Δ λ _cbe less than 100nm.In other other examples, Δ λ _cbe less than 80nm, be preferably less than 60nm, be more preferably and be less than 50nm, and be more preferably again and be less than 40nm.

Omnirange reflection also can be offset by low key tone measures.Such as, it is 30 ° or less with the hue shift of the colorant of the multilayer laminated manufacture according to the embodiment of the present invention, as shown in Figure 17 (see Δ θ ₁), and hue shift is in some instances 25 ° or less, is preferably less than 20 °, is more preferably to be less than 15 ° and to be more preferably to be less than 10 °.On the contrary, traditional colorant presents 45 ° or larger hue shift (see Δ θ ₂).

Figure 16 B is exemplified with seven layer laminate, and it has: (1) selective reflecting body layer 100a; (2) a pair dielectric layer 110, it extends 100a throughout reflector layer and relatively arranges about reflector layer 100a; (3) a pair selective absorbing body layer 120a, its outside surface throughout described a pair dielectric layer 110 extends; And (4) a pair dielectric layers 130, its outside surface throughout described a pair selective absorbing body layer 120a extends.

Figure 16 C is exemplified with seven layer laminate, and it has: (1) selective reflecting body layer 100a; (2) a pair dielectric layer 110, it extends 100a throughout reflector layer and relatively arranges about reflector layer 100a; (3) a pair neutral absorber layer 120, its outside surface throughout described a pair dielectric layer 110 extends; And (4) a pair dielectric layers 130, its outside surface throughout described a pair absorber layers 120 extends.

Figure 16 D is exemplified with seven layer laminate, and it has: (1) reflector layer 100; (2) a pair dielectric layer 110, it extends 100 throughout reflector layer and relatively arranges about reflector layer 100; (3) a pair absorber layers 120, its outside surface throughout described a pair dielectric layer 110 extends; And (4) a pair dielectric layers 130, its outside surface throughout described a pair selective absorbing body layer 120 extends.

Turn to Figure 18 now, for seven layers of design omnirange reflecting bodys display reflectivity percentages when the angle of the surface one-tenth 0 and 45 ° relative to reflecting body is exposed to white light to the curve map of the EMR wavelength of reflection.As shown in this graph, 0 ° and 45 ° of curves all exemplified with by the low-down reflectivity provided for the omnirange reflecting body being less than 550nm wavelength, such as, are less than 10%.But as shown in the graph, the wavelength place of reflecting body between 560 to 570nm provides increase sharply and reaches the maximal value of about 90% at 700nm place.Understand, the IR part of the zone of reflections that the part of the figure of the right-hand side (IR side) of curve or Regional Representative are provided by reflecting body.

The feature sharply increased of the reflectivity provided by omnirange reflecting body is that the antiradar reflectivity part from below 550nm wavelength of each curve extends until the UV lateral edges of high reflectance part (such as >70%).The linear segment 200 of UV lateral edges tilts with the angle (β) being greater than 60 ° relative to X-axis, reflectivity axle has the length L of about 40 and has the slope of 1.4.In some instances, linear segment is with the angular slope being greater than 70 ° relative to X-axis, and β is greater than 75 ° in other instances.In addition, the zone of reflections has the visible FWHM being less than 200nm, and has the visible FWHM being less than 150nm in some instances, and has the visible FWHM being less than 100nm in other instances.In addition, for the central wavelength lambda of visible reflectance band as shown in Figure 18 _cbe restricted to such wavelength: it is equal with the distance between the IR edge of the IR spectrum at visible FWHM place with the UV lateral edges of the zone of reflections.

Understand, term " visible FWHM " refers to the width of the zone of reflections between the UV lateral edges of curve and the edge of IR spectral range, and the reflectivity that exceeding " visible FWHM " is then provided by omnirange reflecting body is sightless concerning human eye.By this way, the sightless IR part of Creative Design disclosed herein and multilayer laminated use electromagnetic radiation spectrum provides strikingly color or schemochrome.In other words, omnirange reflecting body disclosed herein utilizes the sightless IR part of electromagnetic radiation spectrum to provide by the arrowband of the visible ray reflected, although in fact reflecting body can reflect much wide band of the electromagnetic radiation extending into IR region.

Referring now to Figure 19, show the figure of reflectivity percentages to wavelength for the another kind seven layers design omnirange reflecting body when the angle of the surface one-tenth 0 and 45 ° relative to reflecting body is exposed to white light.In addition, definition or the sign of the omnirange characteristic provided by omnirange reflecting body disclosed herein are provided.Particularly, and when the zone of reflections that be provided by creationary reflecting body has maximal value (that is, peak), as shown in FIG., each curve has central wavelength lambda _c, described central wavelength lambda _cbe restricted to the wavelength presenting or experience maximum reflectivity.The maximum reflection wavelength of term also can be used for λ _c.

As shown in Figure 19, when the outside surface of omnirange reflecting body is by from 45° angle (λ _c(45 °)) when observing (such as outside surface tilts 45 ° relative to the human eye on this surface of viewing), compared to this surface by from the angle (λ of 0 ° _c(0 °)) namely perpendicular to this surface observation time, there is λ _cskew or displacement.This λ _cskew (Δ λ _c) provide measuring of the omnirange characteristic of omnirange reflecting body.Certainly, zero offset, does not namely offset at all, is ideally omnidirectional reflecting body.But omnirange reflecting body disclosed herein can provide the Δ λ being less than 100nm _c, it does not change color for seeming the surface of this reflecting body human eye, therefore from this reflecting body practical term be omnidirectional.In some instances, omnirange reflecting body disclosed herein can provide the Δ λ being less than 75nm _c, the Δ λ being less than 50nm can be provided in other instances _c, and the Δ λ being less than 25nm can be provided in other examples _c, and the Δ λ being less than 15nm is provided in other example _c.By the actual reflectance for reflecting body to the figure of wavelength, and/or in replacement scheme, if material and layer thickness are the known modeling by reflecting body, this Δ λ can be determined _cskew.

The another kind definition of the omnirange characteristic of reflecting body or characterize and can be determined by the skew of the lateral edges for one group of given angle reflection band.Such as, with the reflectivity (S for the omnirange reflecting body observed from 45 ° _l(45 °)) UV lateral edges compare, for the reflectivity (S that carries out of same reflection body observed from 0 ° _l(0 °)) the skew of UV lateral edges or displacement provide measuring of the omnirange characteristic of this omnirange reflecting body.In addition, such as, for the reflecting body providing the zone of reflections similar with the zone of reflections shown in Figure 18 and namely have the zone of reflections (see Figure 18) at the peak corresponding with the maximum reflection wavelength not in visible range, use Δ S _lcan be better than using Δ λ as measuring of isotropic directivity _c.Understand, skew (the Δ S of UV lateral edges _l) measure in visible FWHM, and/or can measure in visible FWHM.

Certainly, zero offset, does not namely offset (Δ S at all _l=0nm), ideally omnidirectional reflecting body will be characterized.But omnirange reflecting body disclosed herein can provide the Δ S being less than 100nm _l, it does not change color for seeming the surface of this reflecting body human eye, therefore from this reflecting body of practical term be omnidirectional.In some instances, omnirange reflecting body disclosed herein can provide the Δ S being less than 75nm _l, the Δ S being less than 50nm can be provided in other embodiments _l, and the Δ S being less than 25nm can be provided in other examples _l, and the Δ S being less than 15nm is provided in other example _l.By the actual reflectance for reflecting body to the figure of wavelength, and/or in replacement scheme, if material and layer thickness are the known modeling by reflecting body, this Δ S can be determined _lskew.

Can be any method well known by persons skilled in the art or technique for the production of multilayer laminated method disclosed herein, or the method that those skilled in the art not yet know.Typical known method comprises such as collosol and gel process (sol gel processing), successively processes the wet method such as (layer-by-layer processing), rotary coating.Other known dry methods comprise the physical vapour deposition (PVD) process such as chemical vapor deposition process and such as sputtering, electron beam deposition.

Disclosed hereinly multilayer laminatedly can be used for the application of almost any color, such as pigment colorant, be applied to the film etc. on surface.

Example above and embodiment just in order to illustrative object, and change, amendment etc. will be to those skilled in the art clearly and fall into scope of the present invention.Therefore, scope of the present invention is limited by claim and all equivalents thereof.

Claims (31)

1. one kind shows the multilayer laminated of red omnirange schemochrome, comprising:

Reflector layer;

Dielectric layer, it extends throughout described reflector layer, and described reflector layer and described dielectric layer reflection having more than 70% are greater than the incident white light of the wavelength of 550nm; And

Selectively absorbing layers, it extends throughout described dielectric layer, and described selectively absorbing layers absorbs the described incident white light that having more than 70% is less than the wavelength of 550nm;

Described reflector layer, dielectric layer and selectively absorbing layers form omnirange reflecting body, and described omnirange reflecting body reflects the arrowband of such both visible electromagnetic radiation: it has centre wavelength between 550nm to 700nm, be less than the wide width of 200nm and be less than the gamut of 100nm when described omnirange reflecting body is watched by the angle between from 0 and 45 degree.

2. multilayer laminated as claimed in claim 1, wherein said reflector layer has the thickness between 50nm to 200nm.

3. multilayer laminated as claimed in claim 2, wherein said dielectric layer has the thickness between 30nm to 300nm.

4. multilayer laminated as claimed in claim 3, wherein said selectively absorbing layers has the thickness between 20nm to 80nm.

5. multilayer laminated as claimed in claim 4, wherein said omnirange reflecting body has the gross thickness being less than 2 microns.

6. multilayer laminated as claimed in claim 4, wherein said gross thickness is less than 1 micron.

7. multilayer laminated as claimed in claim 2, wherein said reflector layer comprises the metal selected the group formed from Al, Ag, Pt, Cr, Cu, Zn, Au, Sn and their alloy.

8. multilayer laminated as claimed in claim 1, wherein said centre wavelength has the hue shift being less than 30 degree.

9. multilayer laminated as claimed in claim 1, wherein said dielectric layer has and is greater than 0.1 QW and the optical thickness being less than 3.0 QW.

10. multilayer laminated as claimed in claim 9, wherein said optical thickness is less than 2.0 QW.

11. is multilayer laminated as claimed in claim 1, wherein said dielectric layer have be greater than 1.6 refractive index and comprise the dielectric substance selected from the group of ZnS, TiO2, HfO2, Nb2O5, Ta2O5 and combination composition thereof.

12. is multilayer laminated as claimed in claim 1, and wherein said dielectric layer comprises the colored dielectric material selected the group formed from Fe2O3, Cu2O and combination thereof.

13. is multilayer laminated as claimed in claim 1, and wherein said selectively absorbing layers comprises the chromatic metallic selected the group formed from Cu, Au, Zn, Sn and their alloy.

14. is multilayer laminated as claimed in claim 1, and the absorption layer of wherein said colour comprises the colored dielectric material selected the group formed from Fe2O3, Cu2O and combination thereof.

15. is multilayer laminated as claimed in claim 1, except described dielectric layer noted earlier, also comprise the second dielectric layer, described second dielectric layer extends throughout described selectively absorbing layers and relatively arranges about described selectively absorbing layers with described dielectric layer;

Described reflector layer, dielectric layer, selectively absorbing layers and the second dielectric layer form described omnirange reflecting body.

16. is multilayer laminated as claimed in claim 1, and wherein said second dielectric layer has the thickness between 30nm to 300nm.

17. is multilayer laminated as claimed in claim 16, except described selectively absorbing layers noted earlier, also comprise the second selectively absorbing layers, described second selectively absorbing layers extends throughout described second dielectric layer and relatively arranges about described second dielectric layer with described selective absorbing body;

Described reflector layer, dielectric layer, selectively absorbing layers, the second dielectric layer and the second selectively absorbing layers form described omnirange reflecting body.

18. is multilayer laminated as claimed in claim 17, and wherein said second selectively absorbing layers has the thickness between 10nm to 80nm.

19. is multilayer laminated as claimed in claim 18, also comprises the 3rd dielectric layer, and described 3rd dielectric layer extends throughout described second absorption layer and relatively arranges about described second selectively absorbing layers with described second dielectric layer;

Described reflector layer, dielectric layer, selectively absorbing layers, the second dielectric layer, the second selectively absorbing layers and the 3rd dielectric layer form described omnirange reflecting body.

20. multilayer laminated as claimed in claim 19, wherein said 3rd dielectric layer has the thickness between 10nm to 300nm.

21. is multilayer laminated as claimed in claim 1, except the described selectively absorbing layers mentioned before, also comprise the second selectively absorbing layers, and described second selectively absorbing layers extends between described reflector layer and described dielectric layer;

Described reflector layer, dielectric layer, selectively absorbing layers and the second selectively absorbing layers form described omnirange reflecting body.

22. is multilayer laminated as claimed in claim 21, except the described dielectric layer mentioned before, also comprise the second dielectric layer, described second dielectric layer extends throughout described selectively absorbing layers and relatively arranges about described selectively absorbing layers with described dielectric layer;

Described reflector layer, dielectric layer, selectively absorbing layers, the second selectively absorbing layers and the second dielectric layer form described omnirange reflecting body.

23. is multilayer laminated as claimed in claim 22, also comprises the 3rd selectively absorbing layers, and described 3rd selectively absorbing layers extends throughout described second dielectric layer and relatively arranges about described second dielectric layer with described selectively absorbing layers;

Described reflector layer, dielectric layer, selectively absorbing layers, the second selectively absorbing layers, the second dielectric layer and the 3rd selectively absorbing layers form described omnirange reflecting body.

24. is multilayer laminated as claimed in claim 23, also comprises the 3rd dielectric layer, and described 3rd dielectric layer extends throughout described 3rd selectively absorbing layers and relatively arranges about described 3rd selectively absorbing layers with described second dielectric layer;

Described reflector layer, dielectric layer, selectively absorbing layers, the second selectively absorbing layers, the second dielectric layer, the 3rd selectively absorbing layers and the 3rd dielectric layer form described omnirange reflecting body.

25. is multilayer laminated as claimed in claim 24, and wherein said omnirange reflecting body has the gross thickness being less than 2 microns.

26. is multilayer laminated as claimed in claim 25, and wherein said gross thickness is less than 1 micron.

27. is multilayer laminated as claimed in claim 1, and the arrowband of wherein said both visible electromagnetic radiation is the zone of reflections with UV lateral edges, when described omnirange reflecting body is less than 100nm by described UV lateral edges skew during angle viewing between from 0 and 45 degree.

28. is multilayer laminated as claimed in claim 27, wherein when described omnirange reflecting body is less than 75nm by the described UV lateral edges skew of described zone of reflections during angle viewing between from 0 and 45 degree.

29. is multilayer laminated as claimed in claim 28, wherein when described omnirange reflecting body is less than 50nm by the described UV lateral edges skew of described zone of reflections during angle viewing between from 0 and 45 degree.

The pigment colorant of 30. 1 kinds of multilayer laminated forms, described pigment colorant comprises:

Reflector layer;

Dielectric layer, it extends throughout described reflector layer, and described reflector layer and described dielectric layer reflection having more than 70% are greater than the incident white light of the wavelength of 550nm; And

Selectively absorbing layers, it extends throughout described dielectric layer, and described selectively absorbing layers absorbs the described incident white light that having more than 70% is less than the wavelength of 550nm;

Described absorption layer, dielectric layer and selectively absorbing layers form omnirange reflecting body, and described omnirange reflecting body reflects the arrowband of such both visible electromagnetic radiation: it has centre wavelength between 550nm to 700nm, be less than the wide width of 100nm and be less than the gamut of 100nm when described omnirange reflecting body is watched by the angle between from 0 and 45 degree.

The pigment colorant of 31. 1 kinds of multilayer laminated forms, described pigment colorant comprises:

Reflector layer;

Dielectric layer, it extends throughout described reflector layer, and described reflector layer and described dielectric layer reflection having more than 70% are greater than the incident white light of the wavelength of 550nm; And

Selectively absorbing layers, it extends throughout described dielectric layer, and described selectively absorbing layers absorbs the described incident white light that having more than 70% is less than the wavelength of 550nm;

Described reflector layer, dielectric layer and selectively absorbing layers form omnirange reflecting body, the reflection of described omnirange reflecting body has the arrowband of the both visible electromagnetic radiation of UV lateral edges and IR spectral edges, and the arrowband of described both visible electromagnetic radiation has the skew being less than the wide width of 200nm and being less than the described UV lateral edges of 100nm when described omnirange reflecting body is watched by the angle between from 0 and 45 degree.