CN104730737B - The red omnidirection schemochrome made of metal and dielectric layer - Google Patents
The red omnidirection schemochrome made of metal and dielectric layer Download PDFInfo
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- CN104730737B CN104730737B CN201410693385.4A CN201410693385A CN104730737B CN 104730737 B CN104730737 B CN 104730737B CN 201410693385 A CN201410693385 A CN 201410693385A CN 104730737 B CN104730737 B CN 104730737B
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- layer
- reflector
- dielectric layer
- omnidirection
- multilayer laminated
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 7
- 239000002184 metal Substances 0.000 title claims abstract description 7
- 230000005670 electromagnetic radiation Effects 0.000 claims abstract description 21
- 239000006096 absorbing agent Substances 0.000 claims description 57
- 239000003086 colorant Substances 0.000 claims description 21
- 230000005611 electricity Effects 0.000 claims description 11
- 239000000049 pigment Substances 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 11
- 238000010521 absorption reaction Methods 0.000 claims description 10
- 230000003287 optical effect Effects 0.000 claims description 10
- 239000003989 dielectric material Substances 0.000 claims description 7
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910045601 alloy Inorganic materials 0.000 claims description 4
- 239000000956 alloy Substances 0.000 claims description 4
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims description 4
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052737 gold Inorganic materials 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 229910052718 tin Inorganic materials 0.000 claims description 4
- 101000863856 Homo sapiens Shiftless antiviral inhibitor of ribosomal frameshifting protein Proteins 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- CJNBYAVZURUTKZ-UHFFFAOYSA-N hafnium(IV) oxide Inorganic materials O=[Hf]=O CJNBYAVZURUTKZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000002329 infrared spectrum Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims 5
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Chemical compound O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims 2
- 229910052725 zinc Inorganic materials 0.000 claims 2
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 claims 1
- 239000010410 layer Substances 0.000 description 278
- 238000010586 diagram Methods 0.000 description 35
- 239000005083 Zinc sulfide Substances 0.000 description 26
- 230000005684 electric field Effects 0.000 description 22
- 239000011651 chromium Substances 0.000 description 21
- 238000002310 reflectometry Methods 0.000 description 20
- 238000013461 design Methods 0.000 description 18
- 238000000034 method Methods 0.000 description 10
- 239000010949 copper Substances 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 8
- 239000003973 paint Substances 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- 238000004364 calculation method Methods 0.000 description 4
- 239000010408 film Substances 0.000 description 4
- 238000003475 lamination Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 238000004088 simulation Methods 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 229910001369 Brass Inorganic materials 0.000 description 2
- 229910000906 Bronze Inorganic materials 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 241000736199 Paeonia Species 0.000 description 2
- 235000006484 Paeonia officinalis Nutrition 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000010951 brass Substances 0.000 description 2
- 239000010974 bronze Substances 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 2
- 230000000149 penetrating effect Effects 0.000 description 2
- 238000005240 physical vapour deposition Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000001054 red pigment Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000011135 tin Substances 0.000 description 2
- 229910000967 As alloy Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 241001062009 Indigofera Species 0.000 description 1
- 230000002902 bimodal effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000012792 core layer Substances 0.000 description 1
- 229940112669 cuprous oxide Drugs 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000000313 electron-beam-induced deposition Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910000449 hafnium oxide Inorganic materials 0.000 description 1
- 229910000484 niobium oxide Inorganic materials 0.000 description 1
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 1
- 239000001061 orange colorant Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 229910001936 tantalum oxide Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000001429 visible spectrum Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/0015—Pigments exhibiting interference colours, e.g. transparent platelets of appropriate thinness or flaky substrates, e.g. mica, bearing appropriate thin transparent coatings
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/0102—Constructional details, not otherwise provided for in this subclass
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
- C01P2006/65—Chroma (C*)
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
- C01P2006/66—Hue (H*)
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C2200/00—Compositional and structural details of pigments exhibiting interference colours
- C09C2200/10—Interference pigments characterized by the core material
- C09C2200/1054—Interference pigments characterized by the core material the core consisting of a metal
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C2200/00—Compositional and structural details of pigments exhibiting interference colours
- C09C2200/24—Interference pigments comprising a metallic reflector or absorber layer, which is not adjacent to the core
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C2200/00—Compositional and structural details of pigments exhibiting interference colours
- C09C2200/30—Interference pigments characterised by the thickness of the core or layers thereon or by the total thickness of the final pigment particle
- C09C2200/301—Thickness of the core
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C2200/00—Compositional and structural details of pigments exhibiting interference colours
- C09C2200/30—Interference pigments characterised by the thickness of the core or layers thereon or by the total thickness of the final pigment particle
- C09C2200/308—Total thickness of the pigment particle
Landscapes
- Physics & Mathematics (AREA)
- Nonlinear Science (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Laminated Bodies (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
Abstract
Disclose red omnidirection schemochrome made of metal and dielectric layer.A kind of omnidirection schemochrome being displayed in red it is multilayer laminated.This is multilayer laminated including reflector layer, the dielectric layer throughout reflector layer extension and the absorbed layer throughout dielectric layer extension.Dielectric layer reflection is more than 70% incident white light having greater than 580 nanometers of (nm) wavelength.In addition, it is more than 70% with the incident white light less than 580nm wavelength that absorbed layer, which absorbs,.If combining, reflector layer, dielectric layer and absorbed layer form omnidirection reflector, which reflects the narrowband of such electromagnetic radiation: it is with 580nm to the central wavelength between 680nm, the gamut with the width for being less than 200nm wide and when the reflector is watched from the angle between 0 and 45 degree less than 100nm.
Description
Cross reference to related applications
The application is that the part for the U.S. Patent Application Serial Number 13/913,402 submitted on June 8th, 2013 is continued
(CIP), the U.S. Patent Application Serial Number 13/760,699 that application 13/913,402 was submitted for 2 months on the 6th followed by 2013
CIP, 13/572,071 CIP that application 13/760,699 was submitted on the 10th followed by August in 2012, application 13/572,071 connect
Be the U.S. Patent Application Serial Number 13/021,730 submitted for 5th for 2 months in 2011 CIP, application 13/021,730 followed by
The CIP for the application 12/793,772 that on June 4th, 2010 submits, application 12/793,772 were submitted followed by 2 18th, 2009
U.S. Patent Application Serial Number 12/388,395 CIP, application 12/388,395 submitted followed by August 12nd, 2007
The CIP of U.S. Patent Application Serial Number 11/837,529 (United States Patent (USP) 7,903,339).The U.S. submitted is special on 2 5th, 2011
Sharp patent application serial numbers 13/021,730 are also 11/837,529 (United States Patent (USP) 7,903,339) that August in 2007 is submitted on the 12nd
CIP.2 months 2013 U.S. Patent Application Serial Numbers 13/760,699 submitted for 6th are also to submit on May 18th, 2009
The entire contents of 12/467,656 CIP, above-mentioned all applications are incorporated in this by reference.
Technical field
The present invention relates to omnidirection schemochrome (omnidirectional structural color), and more specifically
The red omnidirection knot provided by multilayer laminated (multilayer stack) with absorber layers and dielectric layer is provided
Structure color.
Background technique
The colorant made of multilayered structure (pigment) is known.In addition, being presented or providing the omnidirection knot of high chroma
The colorant of structure color is also known.However, colorant needs up to 39 film layers of this prior art are desired to obtain
Color characteristics.
It is to be appreciated that and thin-film multilayer colorant the relevant cost of production it is proportional to the required number of plies.Therefore, and make
It may be excessively high with the relevant cost of the multilayer laminated production come the high chroma omnidirection schemochrome carried out of dielectric substance.Institute
With it is desirable for needing the high chroma omnidirection schemochrome of the film layer of minimum number.
Summary of the invention
It can provide red the multilayer laminated of omnidirection schemochrome to be provided.It is multilayer laminated include reflector layer, spread
(across) dielectric layer and the absorber layers extended throughout dielectric layer that reflector layer extends.Dielectric layer combines reflection
The reflection of body layer is more than 70% incident white light with the wavelength greater than 550 nanometers (nm).In addition, absorber layers absorption is more than
70% incident white light with the wavelength for being generally less than 550nm.If combining, reflector layer, dielectric layer and absorption
Layer forms such omnidirection reflector: (1) its reflection has 550nm to the central wavelength between 700nm and is less than 200nm
The narrowband (reflection peak or band) of the both visible electromagnetic radiation of wide width；(2) when the omnidirection reflector is by between 0 degree and 45 degree
Angle viewing when its have less than 100nm gamut (color shift).In some instances, the visible electromagnetic reflected
The width of the narrowband of radiation is less than 175nm, preferably less than 150nm, more preferably less than 125nm, and still more preferably from small
In 100nm.
Reflector layer has 50nm to the thickness between 200nm and by such as aluminium, silver, platinum, tin and their alloy
Equal metals are made.
In some instances, dielectric layer there is 0.1 to 2.0 desired by the quarter-wave of central wavelength that is reflected
The optical thickness of (QW, quarter wave).In other instances, dielectric layer have be greater than 2.0 desired by reflected
The optical thickness of the QW of central wavelength.Dielectric layer also has the refractive index greater than 1.6 and includes such as zinc sulphide (ZnS), two
Titanium oxide (TiO2), hafnium oxide (HfO2), niobium oxide (Nb2O5), tantalum oxide (Ta2O5), the dielectric substances such as their combination.Electricity
Dielectric layer also may include such as iron oxide (Fe2O3), cuprous oxide (Cu2O), the dielectric substance of the colour such as their combination.
Absorbed layer, also referred to as absorber layers, may or may not be colored or selective absorbed layer herein.
For example, achromatic or non-selective absorber layers may include the layer made of chromium, silver, platinum etc..In alternative solution, absorb
Layer can be colored or selective absorber layers made of alloy of copper, gold, bronze and brass etc..It is replaced another
For in scheme, colored or selective absorber layers include such as Fe2O3、Cu2O, the dielectric material of the colour such as their combination
Material.
It is to be appreciated that selective absorbing body layer is chosen so as to absorb in white-light spectrum the wavelength of desired range and anti-
Penetrate the white-light spectrum of another desired range.For example, selective absorbing body layer can be designed and manufactured to so that its absorption has
Corresponding with bluish violet, blue, green, yellow wavelength (for example, the electromagnetic radiation of 400nm to 550nm) and also reflection with
It is red (that is, 580 to infrared (IR) range) corresponding electromagnetic radiation.
In some instances, multilayer laminated includes the other than the dielectric layer (that is, first dielectric layer) mentioned before
Two dielectric layers, the second dielectric layer extend throughout absorbed layer and are oppositely disposed with the first dielectric layer about absorbed layer.Separately
Outside, the other embodiments comprising the second absorbed layer, third dielectric layer etc. are provided.However, disclosed herein multilayer laminated
Overall thickness is less than 2 microns (μm), in some instances less than 1.5 μm, in other instances less than 1.0 μm, and at other
Less than 0.75 μm in example.
Detailed description of the invention
Figure 1A is zero or nearly zero in the ZnS dielectric layer for being exposed to the electromagnetic radiation with 500nm wavelength (EMR)
The schematic diagram of electric field point；
Figure 1B is the electric field when being exposed to the EMR of the wavelength with 300nm, 400nm, 500nm, 600nm and 700nm
Absolute value square (| E |2) diagram to the thickness of ZnS dielectric layer shown in Figure 1A；
Fig. 2 is that the normal direction of extension and the outer surface relative to dielectric layer is at an angle of θ on substrate or reflector layer
It is exposed to the schematic diagram of the dielectric layer of electromagnetic radiation；
Fig. 3 is the schematic diagram with the ZnS dielectric layer of Cr absorber layers, wherein the Cr absorber layers are located at ZnS electricity
The zero or nearly zero electric site for the incident EMR with 434nm wavelength in dielectric layer；
Fig. 4 be for be exposed to white light without Cr absorber layers multilayer laminated (for example, Figure 1A) and have Cr absorber
Graphical representation of the reflectivity percentages of multilayer laminated (for example, the Fig. 3) of layer to the EMR wavelength reflected；
Fig. 5 A is the first harmonic and two presented by the ZnS dielectric layer (for example, Figure 1A) extended in Al absorber layers
The diagram of subharmonic；
Fig. 5 B is for additional in ZnS dielectric layer throughout the ZnS dielectric layer that Al reflector layer extends
Cr absorber layers make the absorbed multilayer laminated reflectivity percentages of second harmonic shown in Fig. 5 A to the EMR reflected
The diagram of wavelength；
Fig. 5 C is for additional in ZnS dielectric layer throughout the ZnS dielectric layer that Al reflector layer extends
Cr absorber layers make the absorbed multilayer laminated reflectivity percentages of first harmonic shown in Fig. 5 A to the EMR wave of reflection
Long diagram；
Fig. 6 A is to show the electricity of the electric field angle correlation for the Cr absorber layers for being exposed to incident light with 0 and 45 degree
Diagram of the field square to dielectric layer thickness；
Fig. 6 B is that Cr inhales when the normal relative to outer surface is exposed to white light at 0 and 45 degree (0 ° is perpendicular to surface)
Diagram of the absorptivity percentage of acceptor layer to the EMR wavelength reflected；
Fig. 7 A is the multilayer laminated schematic diagram of the omnidirection schemochrome of red according to an embodiment of the present invention；
Fig. 7 B is that white light is exposed to for the multilayer laminated incidence angle with 0 and 45 ° shown in Fig. 7 A, shown in Fig. 7 A
Diagram of the absorptivity percentage of Cu absorber layers to the EMR wavelength reflected；
Fig. 8 is the card example multilayer laminated for the concept red omnidirection schemochrome for being exposed to white light with 0 ° of incidence angle
(proof), for reflectivity percentages to the figure between the calculation/simulation data and experimental data of the EMR wavelength reflected
Compare；
Fig. 9 is the multilayer laminated schematic diagram of omnidirection schemochrome according to an embodiment of the present invention；
Figure 10 is the multilayer laminated schematic diagram of omnidirection schemochrome according to an embodiment of the present invention；
Figure 11 is the multilayer laminated schematic diagram of omnidirection schemochrome according to an embodiment of the present invention；And
Figure 12 is the multilayer laminated schematic diagram of omnidirection schemochrome according to an embodiment of the present invention；
Figure 13 is the scanning electricity with the thin slice (flake) or colorant of multi-layer laminate structure according to an embodiment of the present invention
Sub- microscope (SEM) image；
Figure 14 is the SEM image of the cross section of single sheet shown in Figure 13；
Figure 15 A is to be designed and manufactured and using according to embodiments of the present invention with color diagram (color shown in Figure 15 D
Map the orange colorant that the tone (hue) on) is 36 ° carrys out the schematic diagram of the plate of paint；
Figure 15 B is using designing and manufacturing according to embodiments of the present invention and with the color in color diagram shown in Figure 15 D
It is adjusted to the schematic diagram that 26 ° of wine-colored colorant carrys out the plate of paint；
Figure 15 C is using designing and manufacturing according to embodiments of the present invention and with the color in color diagram shown in Figure 15 D
Be adjusted to 354 ° of bright pink colour colorant come paint plate schematic diagram；
Figure 15 D is the a*b* color diagram using CIELAB color space；
Figure 15 E is the schematic diagram of the eleventh floor design of the colorant in the pigment for model shown in Figure 15 A to 15C；
Figure 16 A is the schematic diagram of seven layer laminate according to an embodiment of the present invention；
Figure 16 B is the schematic diagram of seven layer laminate according to an embodiment of the present invention；
Figure 16 C is the schematic diagram of seven layer laminate according to an embodiment of the present invention；
Figure 16 D is the schematic diagram of seven layer laminate according to an embodiment of the present invention；
Figure 17 is using the graphical representation of a part of a*b* color diagram of CIELAB color space, wherein in traditional pigment
Compare coloration (chroma) and hue shift between the pigment for plate shown in paint Figure 15 B；
Figure 18 is the diagram for the reflectivity vs. wavelength of seven layers according to an embodiment of the present invention design；And
Figure 19 is the diagram for the reflectivity vs. wavelength of seven layers according to an embodiment of the present invention design.
Specific embodiment
It can provide multilayer laminated being provided of omnidirection schemochrome (such as red omnidirection color).Therefore, the multilayer
Lamination has as purposes such as pigment colorant (paint pigment), the films for providing desired color.
It can provide the multilayer laminated including reflector layer and the dielectric layer extended throughout reflector layer of omnidirection schemochrome.
Reflector layer and dielectric layer reflection are more than 70% incident white light with the wavelength greater than 550nm.It is to be appreciated that electricity is situated between
The thickness of matter layer can be previously defined as so that wavelength in place of the incident white light for being more than 70% is reflected be greater than 550nm,
560nm, 580nm, 600nm, 620nm, 640nm, 660nm, 680nm or the wavelength between them.In other words, dielectric layer
Thickness can be selected and be produced as so that with the specific of desired tone, coloration and/or brightness on Lab color system figure
Color is reflected and is arrived by eye-observation.
In some instances, multilayer laminated that there is the tone between 315 ° and 45 ° in lab color space.In addition, multilayer
Lamination has the coloration greater than 50 and the hue shift less than 30 °.In other instances, coloration is greater than 55, preferably greater than 60,
And more preferably higher than 65 and/or hue shift less than 25 °, preferably less than 20 °, more preferably less than 15 ° and again more
Preferably less than 10 °.
Absorbed layer extends throughout dielectric layer, for general than wave corresponding with the desired reflection wavelength of dielectric layer
Long small all wavelengths, the absorbed layer absorption are more than 70% incident white light.For example, if dielectric layer has so that being more than
70% thickness that there is the incident white light of the wavelength greater than 600nm to be reflected then is inhaled throughout the absorbed layer that dielectric layer extends
Receipts are more than 70% incident white light with the wavelength for being generally less than 600nm.In this way, it provides with red color
The sharp reflection peak of wavelength in space.In some instances, reflector layer and dielectric layer reflection are more than 80% to have
The incident white light of wavelength greater than 550nm, and in other instances for more than 90%.In addition, in some instances, absorber
It is more than 80% that layer, which absorbs the general wavelength smaller than wavelength corresponding with the desired reflection wavelength of dielectric layer, and at it
For more than 90% in his example.
It is to be appreciated that the term " general " in this context refers to just and/or negative 20nm in some instances, at it
It is positive and/or negative 30nm, is positive in some other example and/or negative 40nm and is positive in his example in other examples
And/or negative 50nm.
Reflector layer, dielectric layer and absorbed layer form omnidirection reflector, as the omnidirection reflector reflection
The narrowband (hereinafter referred to as reflection peak or reflection band) of electromagnetic radiation: it is with the visible-infrared of 550nm and EMR spectrum
The reflection band of central wavelength, width between edge less than 200nm and when omnidirection reflector is exposed to white light and by from 0
And gamut less than 100nm when angle viewing between 45 degree.The gamut can be the offset of the central wavelength of reflection band
Form, or be the form for reflecting the offset of UV side edge (UV-sided edge) of band in alternative solution.For this hair
The width of bright purpose, the reflection band of electromagnetic radiation is defined as the half reflection height of the maximum reflection wavelength in visible spectrum
The width of the reflection band at place.In addition, the narrowband for the electromagnetic radiation reflected, i.e. " color " of omnidirection reflector, have and are less than
25 degree of hue shift.In some instances, reflector layer have 50nm to the thickness between 200nm and by such as aluminium, silver,
Platinum, tin, their metals such as alloy are made or comprising the metal.
About the dielectric layer extended throughout reflector layer, dielectric layer has between 0.1 QW and 2.0 QW
Optical thickness.In some instances, dielectric layer has the optical thickness between 0.1 QW and 1.9 QW, and at it
In his example, dielectric layer has the thickness between 0.1 QW and 1.8 QW.In other examples, dielectric layer tool
Have the optical thickness less than 1.9 QW, be, for example, less than 1.8 QW, less than 1.7 QW, less than 1.6 QW, less than 1.5 QW,
Less than 1.4 QW, less than 1.3 QW, less than 1.2 QW or less than 1.1 QW.In alternative solution, dielectric layer can have
Greater than the optical thickness of 2.0 QW.
Dielectric layer has the refractive index greater than 1.60,1.62,1.65 or 1.70, and can be by such as ZnS, TiO2、
HfO2、Nb2O5、Ta2O5, the dielectric substances such as their combination are made.In some instances, dielectric layer is by such as Fe2O3、
Cu2Colored or selective dielectric layer made of the dielectric substance of the colour such as O.For the purposes of the present invention, term is " color
The dielectric substance of color " or " colored dielectric layer " refer to transmitting white light while reflecting a part of incident white light
The dielectric substance or dielectric layer of another part.For example, colored dielectric layer transmissive has between 400nm and 600nm
Wavelength electromagnetic radiation and reflect greater than the wavelength of 600nm.Therefore, the dielectric layer of colored dielectric substance or colour tool
There is orange, red and/or reddish orange visual appearance.
Other than dielectric layer, omnidirection reflector may include that selectivity 5nm to the thickness between 200nm is inhaled
Acceptor layer.In some instances, colored absorber layers replace or replace absorber layers recited above.It is retouched similar to above
It states, the absorbable light with wavelength relevant to bluish violet, blue, yellow, green etc. of selective absorbing body layer, and also reflects
Wavelength corresponding with orange, red, reddish orange etc..In some instances, colored absorber layers include such as copper, gold and
The chromatic metallics such as its alloy of bronze and brass, or be made of the chromatic metallic.In other instances, colored absorption
Body layer may include such as Fe2O3、Cu2The dielectric substance of the colour such as O, or be made of the dielectric substance of the colour.
The position of absorber layers be so that zero or nearly zero energy interface appear between absorber layers and dielectric layer.It changes
Sentence is talked about, dielectric layer have so that zero or nearly zero energy field be located at dielectric layer-absorber layers interface thickness.Understand
Be zero or nearly zero energy field dielectric layer that place occur thickness be incident EMR wavelength function.In addition, it will again be appreciated that
Be that wavelength corresponding with zero or nearly zero electric field will be transmitted through dielectric layer-absorber layers interface, however not with interface
The corresponding wavelength of zero or nearly zero electric field at place will be not transmitted through the interface.Therefore, the thickness of dielectric layer is designed
Pass through dielectric layer-absorber layers interface with the wavelength transmission for being manufactured so that desired incident white light, from reflector layer
It reflects away, it is then past to be transmitted back through dielectric layer-absorbed layer interface.Similarly, the thickness of dielectric layer is manufactured to
So that the wavelength of undesirable incident white light is not transmitted through dielectric layer-absorber layers interface.
In view of described above, wavelength not corresponding with desired zero or nearly zero electric field interface is absorbed body layer and absorbs simultaneously
Therefore it is not reflected.In this way, the color of desired " distinctness ", also referred to as schemochrome are provided.In addition, dielectric layer
With a thickness of the reflection for generate desired first harmonic and/or second harmonic in order to provide the surface for having red color,
Also there is omnidirectional appearance.
Multilayer laminated may include the second electricity other than the dielectric layer (also referred to as the first dielectric layer) mentioned before
Dielectric layer, second dielectric layer extend throughout absorber layers.In addition, the second dielectric layer and the first dielectric layer mentioned
It is oppositely disposed about absorber layers.
About the thickness of dielectric layer mentioned above and zero or nearly zero electric field point, Figure 1A is prolonged throughout Al reflector layer
The schematic diagram for the ZnS dielectric layer stretched.ZnS dielectric layer has the overall thickness of 143nm, and is directed to 500nm wavelength
Incidence electromagnetic radiation, zero or nearly zero energy point present in 77nm.In other words, ZnS dielectric layer, which is directed to, has 500nm wave
Zero or nearly zero electric field is presented in long incident EMR at the distance at a distance of Al reflector layer 77nm.It is directed in addition, Figure 1B is provided
The diagram of the energy field across ZnS dielectric layer of many different incident EMR wavelength.As described in Figure, dielectric layer is directed to
500nm wavelength has zero electric field at 77nm thickness, but for the EMR wavelength of 300,400,600 and 700nm at 77nm
With non-zero electric field.
It is without being bound by theory, zero or close for dielectric layer (dielectric layer shown in such as Figure 1A) is discussed below
The calculating of zero energy dot thickness.
Referring to Fig. 2, show with refractive index nsSubstrate or core layer 2 on have overall thickness ' D ', incremental thickness
The dielectric layer 4 of ' d ' and refractive index ' n '.Incident light is at an angle of θ relative to straight line 6 and is mapped on the outer surface 5 of dielectric layer 4 simultaneously
It is reflected from outer surface 5 with identical angle, the straight line 6 is perpendicular to outer surface 5.Incident light is transmitted through outer surface 5 and phase
θ is at an angle of for straight line 6FInto dielectric layer 4 and with angle, θsIt is mapped on the surface 3 of substrate layer 2.
For single dielectric layer, θs=θFAnd energy field/electric field (E) is represented by E (z) as z=d.According to
Maxwell equation, polarizes s, and electric field may be expressed as:
And p-polarization may be expressed as:
WhereinAnd the wavelength to be reflected that λ is desirable to.In addition, α=ns sinθs, wherein in ' s ' and Fig. 1
Substrate is corresponding, andFunction as z is the dielectric constant of layer.Therefore, s is polarized:
|E(d)|2=| u (z) |2exp(2ikαy)|Z=d (3)
For p-polarization:
It is to be appreciated that can be by calculating unknown parameter u (z) and v along the electric field change of the Z-direction of dielectric layer 4
(z) it estimates, wherein the calculating can be shown as:
Certainly, ' i ' is -1 square root.Use boundary condition u |Z=0=1, v |Z=0=qs, then there is following relationship:
S is polarized: qs=ns cosθs (6)
For p-polarization: qs=ns/cosθs (7)
S is polarized: q=n cos θF (8)
For p-polarization: q=n/cos θF (9)
U (z) and v (z) may be expressed as:
And
SoIn the case where, s is polarized:
Also, for p-polarization:
Wherein:
α=nssinθs=n sin θF (15)
And
Therefore for θF=0 or vertical incidence simple case,And α=0:
It is considered the thickness to be solved ' d ', i.e., dielectric layer internal electric field is the position at zero or positioning.
Referring now to Fig. 3, equation 19 is used to calculate when being exposed to the EMR of the wavelength with 434nm shown in Figure 1A
ZnS dielectric layer in zero or nearly zero electric field point be at 70nm the 77nm of 500nm wavelength (rather than be directed to).In addition,
The Cr absorber layers of 15nm thickness are inserted at the thickness of Al reflector layer 70nm to provide zero or nearly zero electric field ZnS-Cr
Interface.The structure of this creativeness allows the light with 434nm wavelength to pass through Cr-ZnS interface, but absorbs and do not have
The light of 434nm wavelength.In other words, Cr-ZnS interface has zero or nearly zero electric field about the light with 434nm wavelength, because
The light of this 434nm passes through the interface.However, Cr-ZnS interface for do not have 434nm wavelength light do not have then zero or
Nearly zero electric field, therefore such light is by Cr absorber layers and/or the absorption of Cr-ZnS interface and anti-not by Al reflector layer
It penetrates.
It is to be appreciated that a certain proportion of light within the +/- 10nm of desired 434nm passes through the boundary Cr-ZnS
Face.However, it will again be appreciated that, the narrowband of this reflected light, such as 434+/- 10nm, distinct knot is still provided to human eye
Structure color.
Be illustrated in FIG. 4 the multilayer laminated Cr absorber layers in Fig. 3 as a result, reflectivity percentages are shown
To the EMR wavelength reflected.Shown in dotted line, the dotted line and ZnS electricity shown in Fig. 3 in the case where no Cr absorber layers
Dielectric layer is corresponding, and a narrow reflection peak is present in about 400nm, but a much broader peak appears in about 550+ nm
Place.In addition, still thering is a considerable number of light to be reflected in 500nm wavelength region.Therefore, occur obstruction it is multilayer laminated have or
The bimodal of schemochrome is presented.
On the contrary, the solid line in Fig. 4 is corresponding with structure shown in Fig. 3 in the presence of Cr absorber layers.Such as figure
Shown in, occur sharp peak at about 434nm and is provided by Cr absorber layers for the wavelength greater than 434nm
The sharply decline of reflectivity.It is to be appreciated that being visually revealed as strikingly color/structure by the sharp peak that solid line shows
Color.In addition, Fig. 4 instantiates the place of the width of measurement reflection peak or band, i.e., at the 50% of the reflectivity of maximum reflection wavelength
Determine bandwidth, also referred to as halfwidth degree (FWHM).
The omnidirection of the multilayered structure shown in Fig. 3 shows, and the thickness of ZnS dielectric layer can be designed or be set as
So that the first harmonic of only reflected light is provided.It is to be appreciated that this is enough, the still production of " red " color for " indigo plant " color
It is raw to need additional consideration.For example, the control for red angle independence is difficult, this is because needing thicker dielectric
Layer, this results in higher hamonic wave in turn and designs, i.e. second harmonic and possible triple-frequency harmonics is inevitable.This
Outside, wine-colored tone space is very narrow.Therefore, red multilayer laminated to there is higher angular variance (angular
variance)。
It is directed to red higher angular variance in order to overcome, this application discloses the uniquenesses that can provide the independent red color of angle
, novel design/configuration.It is directed to for example, Fig. 5 A instantiates to present when the outer surface of dielectric layer is by from 0 and 45 degree of viewing
The dielectric layer of the primary and secondary harmonic wave of incident white light.As shown in the graphical representation, provided by the thickness of dielectric layer low
Angle-dependence (small Δ λc), however, this multilayer laminated group with blue (first harmonic) and red (second harmonic)
Merge and is therefore not suitable for desired " Shan Hong " color.So having been developed for absorbing using absorber layers undesired humorous
Concept/structure of wave system.Fig. 5 A also illustrates the reflection band central wavelength (λ for given reflection peakc) position and work as sample
By the residual quantity or offset (Δ λ from central wavelength when 0 and 45 degree of viewingc) example.
Turning now to Fig. 5 B, absorbed with the Cr absorber layers being located at suitable dielectric layer thickness (for example, 72nm)
Second harmonic shown in Fig. 5 A simultaneously provides distinct blue.It is more importantly for this invention that Fig. 5 C is instantiated and is passed through use
Cr absorber layers at different dielectric layer thickness (for example, 125nm) absorb first harmonic to provide red.However, figure
5C, which is also illustrated, to be still resulted in by the use of multilayer laminated Cr absorber layers more than desired angle-dependence, that is, is greater than and is wished
Δ λc。
It is to be appreciated that for red λ compared with bluecIn relatively large offset be since peony tone is empty
Between very narrow and Cr absorber layers absorb wavelength (that is, not absorbing light when electric field is zero or nearly zero) relevant to non-zero electric field
The fact.Therefore, Fig. 6 A instantiates the optical wavelength for different incidence angles, and zero or non-zero points are different.This factor causes
Angle relevant absorptivity shown in Fig. 6 B, i.e., the difference of 0 ° and 45 ° absorbance curves.Therefore more in order to further improve
Layer stack design and angle independence performance have been used regardless of whether electric field is zero absorber layers for all absorbing such as blue light.
Specifically, Fig. 7 A show with the Cu absorber layers extended throughout dielectric ZnS layer rather than Cr absorber layers
It is multilayer laminated.It is shown in Fig. 7 B using this " colored " or " selective " absorber layers as a result, which show be directed to
The gathering much of " compact " of 0 ° and 45 ° multilayer laminated absorbance curves shown in Fig. 7 A.Therefore, between Fig. 6 B and Fig. 7 B
Comparison instantiate when using selective absorbing body layer rather than while using neutral absorber layer, is independent in absorptivity angle
Significantly improving in terms of property.
Based on described above, the card example of concept multi-layer laminate structure has been designed and manufactured.In addition, to about concept sample
The calculation/simulation result and actual experimental data for demonstrate,proving example are compared.Specifically, it and as shown in the chart in Fig. 8, generates
Distinct red (wavelength greater than 700nm cannot be typically seen by human eye) and calculation/simulation light data and according to
It is obtained between the experiment light data that actual sample obtains extraordinary consistent.In other words, calculation/simulation can with and/or by
For the multilayer laminated knot to multilayer laminated design and/or the prior art according to one or more embodiments of the present invention
Fruit is emulated.
The list of emulation and/or actual fabrication multilayer laminated sample is provided in following table 1.Such as institute in table
Show, Creative Design disclosed herein includes the different layer structure of at least five.In addition, according to many different materials, sample
It is simulated and/or is made.Provide the sample that high chroma, low key tone offset and outstanding reflectivity is presented.In addition, three layers and five
Layer sample has 120nm to the overall thickness between 200nm；Seven layers of sample have 350nm to the overall thickness between 600nm；Nine layers
Sample has 440nm to the overall thickness between 500nm；And eleventh floor sample has 600nm to the overall thickness between 660nm.
Table 1
About actual layer sequence, Fig. 9 instantiates the half of five layers of design with appended drawing reference 10.Omnidirection reflector 10 has
There is reflector layer 100, extend 100 dielectric layer 110 throughout reflector layer and extends 110 absorber layers throughout dielectric layer
120.It is to be appreciated that another dielectric layer and another absorber layers can be oppositely disposed about reflector layer 100 with
Five layers of design are provided.
Appended drawing reference 20 in Figure 10 instantiates the half of seven layers of design, and another one dielectric layer 130 is throughout absorption
Body layer extends 120 and dielectric layer 130 is oppositely disposed with dielectric layer 110 about absorber layers 120.
Figure 11 instantiates the half of nine layers of design, wherein the second absorber layers 105 are located at reflector layer 100 and dielectric layer
Between 110.Finally, Figure 12 instantiates the half of eleventh floor design, another one absorber layers 140 are on dielectric layer 130
Face extends and another dielectric layer 150 extends on absorber layers 140.
The scanning electron microscopy of multiple colorants with multilayered structure according to an embodiment of the present invention is shown in FIG. 13
Mirror (SEM) image.Figure 14 is one SEM image under the more high-amplification-factor of display multilayered structure in colorant.This color
Material is used to three kinds of different red pigments of production, and the red pigment is applied on three blocks of plates for testing.Figure 15 A
It is the schematic diagram of the actual plate tinted to 15C, because the practical photograph of plate has been seen when being printed and being replicated by black and white mode
Being gray/black.Figure 15 A, which is represented, has the orange of 36 ° of tones on color table shown in Figure 15 D, and Figure 15 B represents tool
There is 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
Chrominance C * with 44 brightness L* and 67.
Figure 15 E is the schematic diagram for representing the eleventh floor design for the colorant of plate shown in paint Figure 15 A to 15C.It closes
In the exemplary thickness of various layers, table 2 provides the actual (real) thickness of each of corresponding multilayer laminated/colorant.In table 2
Thickness value shown in, the overall thickness of eleventh floor design is less than 2 microns and can be less than 1 micron.
Table 2
| Color=> | It is orange | Peony | Bright pink colour |
| Layer ↓ ↓ | Thickness degree (nm) | Thickness degree (nm) | Thickness degree (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 |
It is to be appreciated that seven layers of design and seven layer multi-layer laminations can be used to make this colorant.Show in Figure 16 A into 16D
The example of 4 kind of seven layer multi-layer lamination is gone out.Figure 16 A instantiates seven layer laminates, includes (1) reflector layer 100；(2) a pair of of electricity
Dielectric layer 110 extends 100 throughout reflector layer and is oppositely disposed about reflector layer 100；(3) a pair of of selective absorbing
Body layer 120a extends throughout the outer surface of the pair of dielectric layer 110；And (4) a pair of of dielectric layer 130, it spreads
The outer surface of the pair of selective absorbing body layer 120a extends.
Naturally, dielectric layer 110 and selective absorbing body layer 120a with a thickness of making selective absorbing body layer 120a
The interface between interface and selective absorbing body layer 120a and dielectric layer 130 between dielectric layer 110 is opposite
In the pink colour of the color diagram shown in Figure 15 D-red-orange region desired optical wavelength (315 ° < tone < 45 ° and/or
550nm<λc< 700nm) zero or nearly zero electric field is presented.In this way, it is desirable to red light pass through layer 130-120a-110, from
Layer 100 reflects away, and passes back through a layer 110-120a-130.On the contrary, non-red light is absorbed by selective absorber layers 120a.
In addition, selective absorbing body layer 120a has angle for non-red light as discussed above and shown in Fig. 7 A to 7B
Independent absorptivity.
It is to be appreciated that dielectric layer 100 and/or 130 with a thickness of making by the anti-of the red light of multilayer laminated progress
It is omnidirectional for penetrating.By the small Δ λ of reflected lightcTo measure or determine that omnidirection reflects.For example, in some instances, Δ λcIt is small
In 120nm.In other instances, Δ λcLess than 100nm.In yet other example, Δ λcLess than 80nm, preferably less than
60nm, more preferably less than 50nm, and still more preferably from less than 40nm.
Omnidirection reflection can also be measured by low key tone offset.For example, with multi-laminate according to an embodiment of the present invention
The hue shift of the colorant of layer manufacture is 30 ° or smaller, as shown in Figure 17 (see Δ θ1), and tone is inclined in some instances
It moves for 25 ° or smaller, preferably less than 20 °, more preferably less than 15 ° and still more preferably from less than 10 °.On the contrary, traditional
45 ° or bigger of hue shift is presented (see Δ θ in colorant2)。
Figure 16 B instantiates seven layer laminates, includes (1) selective reflecting body layer 100a；(2) a pair of of dielectric layer 110,
It extends 100a throughout reflector layer and is oppositely disposed about reflector layer 100a；(3) a pair of of selective absorbing body layer
120a extends throughout the outer surface of the pair of dielectric layer 110；And (4) a pair of of dielectric layer 130, throughout described
The outer surface of a pair of of selective absorbing body layer 120a extends.
Figure 16 C instantiates seven layer laminates, includes (1) selective reflecting body layer 100a；(2) a pair of of dielectric layer 110,
It extends 100a throughout reflector layer and is oppositely disposed about reflector layer 100a；(3) a pair of of neutral absorber layer
120, extend throughout the outer surface of the pair of dielectric layer 110；And (4) a pair of of dielectric layer 130, spread described one
The outer surface of absorber layers 120 is extended.
Figure 16 D instantiates seven layer laminates, includes (1) reflector layer 100；(2) a pair of of dielectric layer 110, throughout anti-
Beam layer extends 100 and is oppositely disposed about reflector layer 100；(3) a pair of of absorber layers 120, spread the pair of electricity
The outer surface of dielectric layer 110 extends；And (4) a pair of of dielectric layer 130, spread the pair of selective absorbing body layer 120
Outer surface extend.
Turning now to Figure 18, for seven layers when the surface relative to reflector is exposed to white light at 0 and 45 ° of angle
Designing omnidirection reflector shows reflectivity percentages to the curve graph of the EMR wavelength of reflection.As shown in this graph, 0 ° and
45 ° of curves all instantiate the low-down reflectivity by providing for the omnidirection reflector less than 550nm wavelength, are, for example, less than
10%.However, as shown in the graph, reflector provides increase sharply at 560 to the wavelength between 570nm and in 700nm
Place reaches about 90% maximum value.It is to be appreciated that the part of the figure of the right-hand side (side IR) of curve or Regional Representative are by anti-
The part IR for the reflection band that beam provides.
The reflectivity provided by omnidirection reflector sharply increases slave 550nm or less the wave for being characterized in that each curve
The antiradar reflectivity part of strong point extends up to the UV side edge of high reflectance part (such as > 70%).The linear portion of UV side edge
Points 200 are tilted with the angle (β) relative to X-axis greater than 60 °, on reflectivity axis with about 40 length L and with 1.4
Slope.In some instances, linear segment is with the angle tilt relative to X-axis greater than 70 °, and β is greater than in other instances
75°.In addition, reflection band has the visible FWHM less than 200nm, and have in some instances visible less than 150nm
FWHM, and there is the visible FWHM less than 100nm in other instances.In addition, being directed to the visible reflectance band as shown in Figure 18
Central wavelength lambdacIt is defined as such wavelength: itself and the UV side edge of reflection band and the IR of the IR spectrum at visible FWHM
The distance between edge is equal.
It is to be appreciated that term " visible FWHM " refers between the UV side edge of curve and the edge of IR spectral region
Reflection band width, the reflectivity then provided by omnidirection reflector beyond " visible FWHM " is invisible for human eye
's.In this way, Creative Design disclosed herein and the multilayer laminated sightless part IR using electromagnetic radiation spectrum
To provide strikingly color or schemochrome.In other words, omnidirection reflector disclosed herein utilizes electromagnetic radiation spectrum not
Visible IR is partially in order to provide the narrowband of the visible light reflected, despite the fact that reflector, which can reflect, extends into the area IR
The much broader band of the electromagnetic radiation in domain.
Referring now to fig. 19, for another when the surface relative to reflector is exposed to white light at 0 and 45 ° of angle
Seven layers of design omnidirection reflector of kind show reflectivity percentages to the figure of wavelength.In addition it is shown that by disclosed herein complete
The definition or characterization for the omnidirection characteristic that direction reflector provides.Specifically, and it is anti-when being provided by creative reflector
When penetrating band has maximum value (that is, peak), as shown in the figure, each curve has central wavelength lambdac, the central wavelength lambdacIt is defined
For the wavelength for being presented or undergoing maximum reflectivity.The maximum reflection wavelength of term can also be used for λc。
As shown in Figure 19, when the outer surface of omnidirection reflector is by from 45° angle (λc(45 °)) observation (such as outer surface
45 ° are tilted relative to the human eye for watching the surface) when, compared to the surface by the angle (λ from 0 °c(0 °)) i.e. perpendicular to the table
When face is observed, there are λcOffset or displacement.This λcOffset (Δ λc) provide the omnidirection spy of omnidirection reflector
The measurement of property.Certainly, zero offset does not deviate at all, be ideally omnidirectional reflector.However, disclosed herein complete
Direction reflector can provide the Δ λ less than 100nmc, the surface of the reflector can be seemed for human eye
Do not change color, therefore the reflector is omnidirectional for practical term.In some instances, full side disclosed herein
It can provide the Δ λ less than 75nm to reflectorc, can provide the Δ λ less than 50nm in other instancesc, and in other examples
In can provide Δ λ less than 25nmc, and the Δ λ for being less than 15nm is provided in other examplec.It can be by for reflector
Actual reflectance is to the figure of wavelength, and/or in alternative solution, if material and layer are with a thickness of passing through reflector if known
Modeling, to determine this Δ λcOffset.
Another definition of the omnidirection characteristic of reflector or characterization can be by being directed to one group of given angle reflection band
The offset of side edge determines.For example, with the reflectivity (S for the omnidirection reflector from 45 °L(45 °)) the side UV
Edge is compared, the reflectivity (S carried out for the same reflection body from 0 °L(0 °)) UV side edge offset or displacement mention
The measurement of the omnidirection characteristic of the omnidirection reflector is supplied.In addition, for example for providing and reflect band shown in Figure 18
The i.e. reflection band (see Figure 18) with peak corresponding with the maximum reflection wavelength not in visible range of similar reflection band
Reflector uses Δ SLMeasurement as isotropic directivity can be better than using Δ λc.It is to be appreciated that offset (the Δ of UV side edge
SL) measured in visible FWHM, and/or can be measured in visible FWHM.
Certainly, zero offset, i.e., it is basic without offset (Δ SL=0nm), ideally omnidirectional reflector will be characterized.So
And omnidirection reflector disclosed herein can provide the Δ S less than 100nmL, seem this for human eye
The surface of reflector does not change color, therefore the reflector is omnidirectional from the point of view of practical term.In some instances, exist
The omnidirection reflector of the displosure can provide the Δ S less than 75nmL, can provide the Δ S less than 50nm in other embodimentsL, and
And it can provide Δ S less than 25nm in other examplesL, and the Δ S for being less than 15nm is provided in other exampleL.It can lead to
The actual reflectance for reflector is crossed to the figure of wavelength, and/or in alternative solution, if material and layer are with a thickness of known
The modeling by reflector is talked about, to determine this Δ SLOffset.
For produce multilayer laminated method disclosed herein can be known to the skilled in the art any method or
Technique or the not known method of those skilled in the art.Typical known method includes that such as collosol and gel handles (sol
Gel processing), successively processing (layer-by-layer processing), the wet methods such as rotary coating.Other
Known dry method includes the physical vapour deposition (PVD) process such as chemical vapor deposition process and sputtering, electron beam deposition.
It is disclosed herein it is multilayer laminated can be used for virtually any of color application, such as the colorant of pigment, be applied to
The film etc. on surface.
Above example and embodiment simply to illustrate that property purpose, and change, modify etc. for art technology
It will be apparent for personnel and fall into the scope of the present invention.Therefore, the scope of the present invention is by claim and its all equivalent
Object limits.
Claims (29)
1. a kind of omnidirection schemochrome being displayed in red is multilayer laminated, comprising:
Reflector layer；
Dielectric layer, spreads reflector layer extension, and the reflector layer and dielectric layer reflection are more than 70% tool
There is the incident white light of the wavelength greater than 550nm；And
Selective absorbing body layer extends throughout the dielectric layer, is watched when multilayer laminated from the angle between 0 and 45 degree
When, the selective absorbing body layer absorption is more than 70% incident white light with the wavelength less than 550nm；
The reflector layer, dielectric layer and selective absorbing body layer form omnidirection reflector, when the omnidirection reflector
When being watched from the angle between 0 and 45 degree, the omnidirection reflector reflects the narrowband of such both visible electromagnetic radiation: described
There is 550nm to the central wavelength between 700nm, the width less than 200nm wide and to be less than for the narrowband of both visible electromagnetic radiation
The gamut of 60nm, the omnidirection schemochrome that omnidirection reflector is displayed in red,
Wherein, the selective absorbing body layer includes chromatic metallic or colored dielectric material.
2. it is as described in claim 1 multilayer laminated, wherein the reflector layer has 50nm to the thickness between 200nm.
3. it is as claimed in claim 2 multilayer laminated, wherein the dielectric layer has 30nm to the thickness between 300nm.
4. it is as claimed in claim 3 multilayer laminated, wherein the selective absorbing body layer has 20nm to the thickness between 80nm
Degree.
5. it is as claimed in claim 4 multilayer laminated, wherein the omnidirection reflector has the overall thickness less than 2 microns.
6. it is as claimed in claim 5 multilayer laminated, wherein the overall thickness is less than 1 micron.
7. it is as claimed in claim 2 multilayer laminated, wherein the reflector layer includes from Al, Ag, Pt, Cr, Cu, Zn, Au, Sn
And the metal selected in the group of their composition of alloy.
8. it is as described in claim 1 multilayer laminated, wherein the central wavelength has the hue shift less than 30 degree.
9. it is as described in claim 1 multilayer laminated, wherein the dielectric layer, which has, is greater than 0.1 QW and less than 3.0 QW
Optical thickness.
10. it is as claimed in claim 9 multilayer laminated, wherein less than 2.0 QW of the optical thickness.
11. as described in claim 1 multilayer laminated, wherein the dielectric layer have the refractive index greater than 1.6 and include from
ZnS、TiO2、HfO2、Nb2O5、Ta2O5And combinations thereof the dielectric substance that selects in the group of composition.
12. it is as described in claim 1 multilayer laminated, wherein the dielectric layer includes from Fe2O3、Cu2O and combinations thereof composition
Group in the colored dielectric material that selects.
13. it is as described in claim 1 multilayer laminated, wherein the case where the selective absorbing body layer includes chromatic metallic
Under, from selecting chromatic metallic in the group of Cu, Au, Zn, Sn and their composition of alloy.
14. it is as described in claim 1 multilayer laminated, wherein including colored dielectric material in the selective absorbing body layer
In the case of, from Fe2O3、Cu2Colored dielectric material is selected in the group of O and combinations thereof composition.
15. it is as described in claim 1 multilayer laminated, it further include that the second electricity is situated between other than the dielectric layer noted earlier
Matter layer, second dielectric layer extend throughout the selective absorbing body layer and with the dielectric layer about the selectivity
Absorber layers are oppositely disposed；
The reflector layer, dielectric layer, selective absorbing body layer and the second dielectric layer form the omnidirection reflector.
16. it is as claimed in claim 15 multilayer laminated, wherein second dielectric layer has 30nm to the thickness between 300nm
Degree.
17. it is as claimed in claim 16 multilayer laminated, further include other than the selective absorbing body layer noted earlier
Second selective absorbing body layer, the second selective absorbing body layer throughout second dielectric layer extend and with the selection
Property absorber layers are oppositely disposed about second dielectric layer；
The reflector layer, dielectric layer, selective absorbing body layer, the second dielectric layer and the second selective absorbing body layer are formed
The omnidirection reflector.
18. as claimed in claim 17 multilayer laminated, wherein the second selective absorbing body layer have 10nm to 80nm it
Between thickness.
19. it is as claimed in claim 18 multilayer laminated, it further include third dielectric layer, the third dielectric layer is throughout described
Second selective absorbing body layer extends and relatively sets with second dielectric layer about the second selective absorbing body layer
It sets；
The reflector layer, dielectric layer, selective absorbing body layer, the second dielectric layer, the second selective absorbing body layer and
Three dielectric layers form the omnidirection reflector.
20. it is as claimed in claim 19 multilayer laminated, wherein the third dielectric layer has 10nm to the thickness between 300nm
Degree.
21. it is as described in claim 1 multilayer laminated, it further include second other than the selective absorbing body layer mentioned before
Selective absorbing body layer, the second selective absorbing body layer extend between the reflector layer and the dielectric layer；
It is anti-that the reflector layer, dielectric layer, selective absorbing body layer and the second selective absorbing body layer form the omnidirection
Beam.
22. it is as claimed in claim 21 multilayer laminated, it further include that the second electricity is situated between other than the dielectric layer mentioned before
Matter layer, second dielectric layer extend throughout the selective absorbing body layer and with the dielectric layer about the selectivity
Absorber layers are oppositely disposed；
The reflector layer, dielectric layer, selective absorbing body layer, the second selective absorbing body layer and the second dielectric layer are formed
The omnidirection reflector.
23. it is as claimed in claim 22 multilayer laminated, wherein the omnidirection reflector has the overall thickness less than 2 microns.
24. it is as claimed in claim 23 multilayer laminated, wherein the overall thickness is less than 1 micron.
25. as described in claim 1 multilayer laminated, wherein the narrowband of the both visible electromagnetic radiation is have UV side edge anti-
Band is penetrated, the UV side edge offset is less than 75nm when the omnidirection reflector is watched from the angle between 0 and 45 degree.
26. as claimed in claim 25 multilayer laminated, wherein when the omnidirection reflector is by from the angle between 0 and 45 degree
The UV side edge offset of the reflection band is less than 50nm when viewing.
27. as claimed in claim 26 multilayer laminated, wherein when the omnidirection reflector is by from the angle between 0 and 45 degree
The UV side edge offset of the reflection band is less than 25nm when viewing.
28. a kind of pigment colorant of multilayer laminated form, the pigment colorant include:
Reflector layer；
Dielectric layer, spreads reflector layer extension, and the reflector layer and dielectric layer reflection are more than 70% tool
There is the incident white light of the wavelength greater than 550nm；And
Selective absorbing body layer, throughout the dielectric layer extend, when it is multilayer laminated by between 0 and 45 degree angle viewing when
The selective absorbing body layer absorption is more than 70% incident white light with the wavelength less than 550nm；
The reflector layer, dielectric layer and selective absorbing body layer form omnidirection reflector, when the omnidirection reflector
When being watched from the angle between 0 and 45 degree, the omnidirection reflector reflects the narrowband of such both visible electromagnetic radiation: described
There is 550nm to the central wavelength between 700nm, the width less than 100nm wide and to be less than for the narrowband of both visible electromagnetic radiation
The gamut of 60nm, the omnidirection schemochrome that omnidirection reflector is displayed in red,
Wherein, the selective absorbing body layer includes chromatic metallic or colored dielectric material.
29. a kind of pigment colorant of multilayer laminated form, the pigment colorant include:
Reflector layer；
Dielectric layer, spreads reflector layer extension, and the reflector layer and dielectric layer reflection are more than 70% tool
There is the incident white light of the wavelength greater than 550nm；And
Selective absorbing body layer, throughout the dielectric layer extend, when it is multilayer laminated by between 0 and 45 degree angle viewing when
The selective absorbing body layer absorption is more than 70% incident white light with the wavelength less than 550nm；
The reflector layer, dielectric layer and selective absorbing body layer form omnidirection reflector, when the omnidirection reflector
When being watched from the angle between 0 and 45 degree, the omnidirection reflector reflection has the edge IR of UV side edge and IR spectrum
Both visible electromagnetic radiation narrowband, the narrowband of the both visible electromagnetic radiation has width less than 200nm wide and less than 75nm's
The offset of the UV side edge, the omnidirection schemochrome that omnidirection reflector is displayed in red,
Wherein, the selective absorbing body layer includes chromatic metallic or colored dielectric material.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US14/138,499 | 2013-12-23 | ||
| US14/138,499 US9739917B2 (en) | 2007-08-12 | 2013-12-23 | Red omnidirectional structural color made from metal and dielectric layers |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104730737A CN104730737A (en) | 2015-06-24 |
| CN104730737B true CN104730737B (en) | 2019-10-25 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410693385.4A Expired - Fee Related CN104730737B (en) | 2013-12-23 | 2014-11-26 | The red omnidirection schemochrome made of metal and dielectric layer |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP6437817B2 (en) |
| CN (1) | CN104730737B (en) |
| DE (1) | DE102014119261B4 (en) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10870740B2 (en) | 2007-08-12 | 2020-12-22 | Toyota Jidosha Kabushiki Kaisha | Non-color shifting multilayer structures and protective coatings thereon |
| US10788608B2 (en) | 2007-08-12 | 2020-09-29 | Toyota Jidosha Kabushiki Kaisha | Non-color shifting multilayer structures |
| US10690823B2 (en) | 2007-08-12 | 2020-06-23 | Toyota Motor Corporation | Omnidirectional structural color made from metal and dielectric layers |
| WO2015153043A1 (en) | 2014-04-01 | 2015-10-08 | Toyota Motor Engineering & Manufacturing North America, Inc. | Non-color shifting multilayer structures |
| DE102016110095A1 (en) * | 2015-07-07 | 2017-01-12 | Toyota Motor Engineering & Manufacturing North America, Inc. | OMNIDIRECTIONAL RED STRUCTURAL COLOR HIGH CHROMA WITH COMBINATION OF METAL ABSORBER AND DIELECTRIC ABSORBENT LAYERS |
| DE102016110314A1 (en) * | 2015-07-07 | 2017-01-12 | Toyota Motor Engineering & Manufacturing North America, Inc. | OMNIDIRECTIONAL RED STRUCTURAL COLOR HIGH CHROMA WITH COMBINATION OF SEMICONDUCTOR ABSORBER AND DIELECTRIC ABSORBENT LAYERS |
| DE102016110192A1 (en) * | 2015-07-07 | 2017-01-12 | Toyota Motor Engineering & Manufacturing North America, Inc. | High chroma omnidirectional red structural color with semiconductor absorber layer |
| DE102017107230A1 (en) * | 2016-05-02 | 2017-11-02 | Toyota Motor Engineering & Manufacturing North America Inc. | Omnidirectional red structural color of high chroma |
| TWI766106B (en) * | 2017-09-29 | 2022-06-01 | 荷蘭商耐克創新有限合夥公司 | Articles having structural color |
| US11118062B2 (en) | 2017-12-06 | 2021-09-14 | Toyota Motor Engineering & Manufacturing North America, Inc. | LiDAR reflecting dark colored pigments and vehicles comprising the same |
| CN110093583B (en) * | 2018-01-29 | 2024-01-30 | 蓝思科技（长沙）有限公司 | Photochromic decorative film and manufacturing method thereof |
| CN108957604A (en) * | 2018-09-27 | 2018-12-07 | 中国计量大学 | A kind of multilayered structure absorbed with selection |
| CN110568534A (en) * | 2019-09-10 | 2019-12-13 | 中国科学院上海技术物理研究所 | structural color nano film with good angle robustness and preparation method thereof |
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- 2014-11-26 CN CN201410693385.4A patent/CN104730737B/en not_active Expired - Fee Related
- 2014-12-19 DE DE102014119261.3A patent/DE102014119261B4/en not_active Expired - Fee Related
- 2014-12-24 JP JP2014261063A patent/JP6437817B2/en active Active
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| US5214530A (en) * | 1990-08-16 | 1993-05-25 | Flex Products, Inc. | Optically variable interference device with peak suppression and method |
| CN1313953A (en) * | 1998-11-24 | 2001-09-19 | 福来克斯产品公司 | Color shifting thin film pigments |
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Also Published As
| Publication number | Publication date |
|---|---|
| JP2015120350A (en) | 2015-07-02 |
| CN104730737A (en) | 2015-06-24 |
| JP6437817B2 (en) | 2018-12-12 |
| DE102014119261B4 (en) | 2021-04-22 |
| DE102014119261A1 (en) | 2015-06-25 |
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