Omnidirectional structural color made from metal and dielectric layers
10690823 ยท 2020-06-23
Assignee
- TOYOTA MOTOR CORPORATION (Toyota, Aichi, JP)
- Toyota Motor Engineering & Manufacturing North America, Inc. (Plano, TX, US)
Inventors
Cpc classification
G02B5/286
PHYSICS
G02B5/0825
PHYSICS
International classification
Abstract
A high-chroma omnidirectional structural color multilayer structure is provided. The structure includes a multilayer stack that has a core layer, a dielectric layer extending across the core layer, and an absorber layer extending across the dielectric layer. An interface is present between the dielectric layer and the absorber layer and a near-zero electric field for a first incident electromagnetic wavelength is present at this interface. In addition, a large electric field at a second incident electromagnetic wavelength is present at the interface. As such, the interface allows for high transmission of the first incident electromagnetic wavelength and high absorption of the second incident electromagnetic wavelength such that a narrow band of reflected light is produced by the multilayer stack.
Claims
1. A high-chroma omnidirectional structural color multilayer structure comprising: a multilayer stack having: a core layer; a dielectric layer extending across said core layer; and an absorber layer extending across said dielectric layer with an interface therebetween; said interface between said dielectric layer and said absorber layer having a near-zero electric field at a first incident electromagnetic wavelength and a large electric field at a second incident electromagnetic wavelength, said second incident electromagnetic wavelength not equal to said first incident electromagnetic wavelength, said multilayer stack having a single narrow reflection band with a full width half maximum (FWHM) width of less than 200 nanometers in the visible spectrum and a minimum color change with a hue shift of less than 30 degrees when viewed from angles between 0 and 45 degrees that provides a high-chroma omnidirectional structural color; said dielectric layer having a thickness of less than or equal to 2 quarter wave (QW) of a center wavelength of said narrow reflection band.
2. The high-chroma omnidirectional structural color multilayer structure of claim 1, wherein said core layer has a complex refractive index represented by the expression RI.sub.1=n.sub.1+ik.sub.1 with n.sub.1<<k.sub.1, where RI.sub.1 is said complex refractive index, n.sub.1 is a refractive index of said core layer, k.sub.1 is an extinction coefficient of the said core layer and i is 1.
3. The high-chroma omnidirectional structural color multilayer structure of claim 2, wherein said core layer is made from a material selected from the group consisting of silver, copper, chromium aluminum, gold and alloys thereof.
4. The high-chroma omnidirectional structural color multilayer structure of claim 3, wherein said core layer is made from a material selected from the group consisting of said aluminum and said alloys thereof.
5. The high-chroma omnidirectional structural color multilayer structure of claim 4, wherein said core layer has a thickness between 50 and 200 nm.
6. The high-chroma omnidirectional structural color multilayer structure of claim 1, wherein said dielectric layer contains at least one of TiO.sub.2, MgF.sub.2, ZnS, HfO.sub.2, Nb.sub.2O.sub.5, Ta.sub.2O.sub.5, SiO.sub.2 and combinations thereof.
7. The high-chroma omnidirectional structural color multilayer structure of claim 6, wherein said dielectric layer is ZnS.
8. The high-chroma omnidirectional structural color multilayer structure of claim 7, wherein said absorber layer has a complex refractive index represented by the expression RI.sub.2=n.sub.2+ik.sub.2 with n.sub.2k.sub.2, where RI.sub.2 is said complex refractive index, n.sub.2 is a refractive index of said dielectric layer, k.sub.2 is an extinction coefficient of the said absorber layer.
9. The high-chroma omnidirectional structural color multilayer structure of claim 8, wherein said absorber layer is made from a material selected from at least one of chromium, tantalum, tungsten, molybdenum, titanium, titanium nitride, niobium, cobalt, silicon, germanium, nickel, palladium, vanadium, ferric oxide and alloys thereof.
10. The high-chroma omnidirectional structural color multilayer structure of claim 9, wherein said absorber layer is made from at least one of said chromium and said alloys thereof.
11. The high-chroma omnidirectional structural color multilayer structure of claim 10, wherein said absorber layer has a thickness between 5 and 20 nm.
12. The high-chroma omnidirectional structural color multilayer structure of claim 11, further comprising another dielectric layer extending across an outer surface of said absorber layer.
13. The high-chroma omnidirectional structural color multilayer structure of claim 12, further comprising another absorber layer between said core layer and said dielectric layer.
14. The high-chroma omnidirectional structural color multilayer structure of claim 11, further comprising another absorber layer between said core layer and said dielectric layer.
15. A high-chroma omnidirectional structural color multilayer structure comprising: a multilayer stack having: a core layer having a first outer surface and an oppositely disposed spaced apart second outer surface; a first dielectric layer extending across said first outer surface and a second dielectric layer extending across said second outer surface of said core layer; and a first absorber layer extending across said first dielectric layer and a second absorber layer extending across said second dielectric layer; said multilayer stack having a near-zero electric field at a first interface between said first absorber layer and said first dielectric layer and at a second interface between said second absorber layer and said second dielectric layer; said multilayer stack having a single narrow reflection band with a full width half maximum (FWHM) width of less than 200 nanometers in the visible spectrum and a minimum color change with a hue shift of less than 30 degrees when viewed from angles between 0 and 45 degrees that provides a high-chroma omnidirectional structural color; said dielectric layer having a thickness of less than or equal to 2 quarter wave (QW) of a center wavelength of said narrow reflection band.
16. The high-chroma omnidirectional structural color multilayer structure of claim 15, wherein said core layer is made from a material selected from the group consisting of aluminum and alloys thereof.
17. The high-chroma omnidirectional structural color multilayer structure of claim 16, wherein said core layer has a thickness between 50 and 200 nm.
18. The high-chroma omnidirectional structural color multilayer structure of claim 15, wherein said dielectric layer contains at least one of TiO.sub.2, MgF.sub.2, ZnS, HfO.sub.2, Nb.sub.2O.sub.5, Ta.sub.2O.sub.5, SiO.sub.2 and combinations thereof.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
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DETAILED DESCRIPTION OF THE INVENTION
(13) A high-chroma omnidirectional structural color multilayer structure is provided. As such, the multilayer structure has use as a paint pigment, a thin film that provides a desired color, and the like.
(14) The high-chroma omnidirectional structural color multilayer structure includes a core layer and a dielectric layer extending across the core layer. In addition, an absorber layer extends across the dielectric layer with an interface therebetween. The thickness of the absorber layer and/or dielectric layer is designed and/or fabricated such that the interface between the two layers exhibits a near-zero electric field at a first incident electromagnetic wavelength and a large electric field at a second incident electromagnetic wavelengththe second incident electromagnetic wavelength not being equal to the first incident electromagnetic wavelength.
(15) It should be appreciated that the near-zero electric field at the interface affords for a high percentage of the first incident electromagnetic wavelength to be transmitted therethrough, whereas the large electric field affords for a high percentage of the second incident electromagnetic wavelength to be absorbed by the interface. In this manner, the multilayer structure reflects a narrow band of electromagnetic radiation, e.g. a narrow reflection band of less than 400 nanometers, less than 300 nanometers, or less than 200 nanometers. In addition, the narrow reflection band has a very low shift of its center wavelength when viewed from different angles, e.g. angles between 0 and 45 degrees, 0 and 60 degrees and/or 0 and 90 degrees.
(16) The core layer is made from a material such that its complex refractive index has a refractive index that is much less than an extinction coefficient for the material where the complex refractive index is represented by the expression RI.sub.1=n.sub.1+ik.sub.1, and n.sub.1 is the refractive index of the core layer material, k.sub.1 is the extinction coefficient of the core layer material and i is the square root of 1. Materials that fall within this criterion include silver, aluminum, gold, and alloys thereof. In addition, the thickness of the core layer can be between 10 and 500 nanometers in some instances, between 25 and 300 nanometers in other instances, and between 50 and 200 nanometers in yet other instances.
(17) The dielectric layer has a thickness of less than or equal to twice the quarter wave (2 QW) of a center wavelength of the narrow reflection band. In addition, the dielectric layer can be made from a titanium oxide (e.g., TiO.sub.2), magnesium fluoride (e.g., MgF.sub.2), zinc sulfide (e.g., ZnS), hafnium oxide (e.g., HfO.sub.2), niobium oxide (e.g., Nb.sub.2O.sub.5), tantalum oxide (e.g., Ta.sub.2O.sub.5), silicon oxide (e.g., SiO.sub.2), and combinations thereof.
(18) Regarding the absorber layer, a material having a refractive index generally equal to an extinction coefficient for the material is used. Materials that meet this criteria include chromium, tantalum, tungsten, molybdenum, titanium, titanium nitride, niobium, cobalt, silicon, germanium, nickel, palladium, vanadium, ferric oxide, and/or alloys or combinations thereof. In some instances, the thickness of the absorber layer is between 5 and 50 nanometers, while in other instances the thickness is between 5 and 20 nanometers.
(19) Regarding the electric field across a thin film structure and a desired thickness of a dielectric layer, and not being bound by theory,
(20) For a single dielectric layer, .sub.s=.sub.F and the electric filed (E) can be expressed as E(z) when z=d. From Maxwell's equations, the electric field can be expressed for s polarization as:
E(d)={u(z),0,0}exp(iky)|.sub.z=d(1)
and for p polarization as:
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where
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and is a desired wavelength to be reflected. Also, =n.sub.s sin .sub.s where s corresponds to the substrate in
|E(d)|.sup.2=|u(z)|.sup.2exp(2iky)|.sub.z=d(3)
for s polarization and
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for p polarization.
(24) It is appreciated that variation of the electric field along the Z direction of the dielectric layer 4 can be estimated by calculation of the unknown parameters u(z) and v(z) where it can be shown that:
(25)
Using the boundary conditions u|.sub.z=0=1, v|.sub.z=0=q.sub.s, and the following relations:
q.sub.s=n.sub.s cos .sub.s for s-polarization(6)
q.sub.s=n.sub.s/cos .sub.s for p-polarization(7)
q=n cos .sub.F for s-polarization(8)
q=n/cos .sub.F for p-polarization(9)
=k.Math.n.Math.d cos(.sub.F)(10)
u(z) and v(z) can be expressed as:
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Therefore:
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for s polarization with =k.Math.n.Math.d cos(.sub.F), and:
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for p polarization where:
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Thus for a simple situation where .sub.F=0 or normal incidence, =k.Math.n.Math.d, and =0:
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which allows for the thickness d to be solved for when the electric field is zero.
(31) The inventive multilayer structures can include a five layer structure with a central core layer with a pair of dielectric layers on opposite sides of the core layer and a pair of absorber layers extending across an outer surface of the dielectric layers. A seven layer multilayer structure is included in which another pair of dielectric layers extend across outer surfaces of the two absorber layers. A different seven layer structure is included in which the initial five layer structure described above includes a pair of absorber layers that extend between opposite surfaces of the core layer and the dielectric layer. In addition, a nine layer multilayer structure is included in which yet another pair of absorber layers extend between the opposite surfaces of the core layer and the dielectric layer for the seven layer structure described above.
(32) Turning now to
(33) With reference to
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(35) It is appreciated from the graphical representations shown in
(36) Regarding omnidirectional behavior of the multilayer structure 10, the thickness of the dielectric layer 110 is designed or set such that only the first harmonics of reflected light is provided. In particular, and referring to
(37) Turning now to
(38) The color map shown in
(39) Referring to
(40) With respect to the hue and chroma of the multilayer structure,
(41) Turning now to
(42) Referring to
(43) Referring now to
(44) Referring to the graphical plot shown in
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(46) A comparison of current state of the art layered structures, two five layer structures that have a dielectric layer with an optical thickness of greater than 3 QW (hereafter referred to as 5 layer>3 QW) and a seven layer structure having at least one dielectric layer with an optical thickness of less than 2 QW (hereafter referred to as 7 layer<2 QW structure) and produced or simulated according to an embodiment of the present invention is shown on an a*b* color map in
(47) Table 1 below shows numerical data for the 5 layer>3 QW and 7 layer<2 QW structures. It is appreciated that those skilled in the art recognize that a 1 or 2 point increase in chroma (C*) is a significant increase with a 2 point increase being visually recognizable to the human eye. As such, the 6.02 point increase (16.1% increase) exhibited by the 7 layer<2 QW structure is exceptional. In addition, the hue shift for the 7 layer<2 QW structure (15) is approximately half the hue shift of the 5 layer>3 QW structure (29). Thus given the approximately equal lightness (L*) between the two structures, the 7 layer<2 QW structure provides a significant and unexpected increase in color properties compared to prior art structures.
(48) TABLE-US-00001 TABLE 1 Property 5 layer (>3 QW) 7 Layer (<2 QW) L* 36.03 36.85 C* 37.42 43.44 Hue 279 281 Color Shift 29 15
(49) Another embodiment of a high chroma omnidirectional structural color multilayer structure is shown generally at reference numeral 14 in
(50) Pigments from such multilayer structures can be manufactured as a coating on a web with a sacrificial layer having subsequent layers of materials deposited thereon using any kind of deposition method or process known to those skilled in the art including electron-beam deposition, sputtering, chemical vapor deposition, sol-gel processing, layer-by-layer processing, and the like. Once the multilayer structure has been deposited onto the sacrificial layer, freestanding flakes having a surface dimension on the order of 20 microns and a thickness dimension on the order of 0.3-1.5 microns can be obtained by removing the sacrificial layer and grinding the remaining multilayer structure into flakes. Once the flakes have been obtained, they are mixed with polymeric materials such as binders, additives, and base coat resins to prepare omnidirectional structural color paint.
(51) The omnidirectional structural color paint has a minimum color change with a hue shift of less than 30 degrees. Such a minimum hue shift should be appreciated to appear to be omnidirectional to a human eye. The definition of hue as tan.sup.1(b*/a*) where a* and b* are color coordinates in the lab color system.
(52) In summary, the omnidirectional structural color pigment has a reflector or core layer, one or two dielectric layers, and one or two absorber layers with at least one of the dielectric layers having a typical width greater than 0.1 QW but less than or equal to 2 QW where the control wavelength is determined by the target wavelength at the peak reflectance in the visible spectrum. In addition, the peak reflectance is for the first harmonic reflectance peak and provides a single reflected band in the visible spectrum. In some instances, the width of the one or more dielectric layers is greater than 0.5 QW and less than 2 QW. In other instances, the width of one or more dielectric layers is greater than 0.5 QW and less than 1.8 QW.
(53) The above examples and embodiments are for illustrative purposes only and changes, modifications, and the like will be apparent to those skilled in the art and yet still fall within the scope of the invention. As such, the scope of the invention is defined by the claims.