CN117250672A - Multiband compatible programmable heat radiator based on indium-antimony-tellurium and application method - Google Patents
Multiband compatible programmable heat radiator based on indium-antimony-tellurium and application method Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 27
- 230000033228 biological regulation Effects 0.000 claims abstract description 71
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- 230000005855 radiation Effects 0.000 claims abstract description 42
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- 229910052984 zinc sulfide Inorganic materials 0.000 claims abstract description 26
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000005083 Zinc sulfide Substances 0.000 claims abstract description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052714 tellurium Inorganic materials 0.000 claims abstract description 10
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 claims abstract description 9
- JBRZTFJDHDCESZ-UHFFFAOYSA-N AsGa Chemical compound [As]#[Ga] JBRZTFJDHDCESZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910001218 Gallium arsenide Inorganic materials 0.000 claims abstract description 7
- 229910052732 germanium Inorganic materials 0.000 claims abstract description 7
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims abstract description 7
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 7
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 7
- 239000000758 substrate Substances 0.000 claims abstract description 7
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 4
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052738 indium Inorganic materials 0.000 claims abstract description 4
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims abstract description 4
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims abstract description 4
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- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
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- G—PHYSICS
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- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
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Abstract
A multiband compatible programmable heat radiator based on indium, antimony and tellurium and an application method belong to the technical field of micro-nano photon devices. The invention aims at the problems of small regulation amplitude and narrow regulation wavelength range of the heat radiation characteristics of the existing heat radiator. The regulator consists of a plurality of square regulating monomers which are periodically arranged on the silicon dioxide substrate; each square regulation monomer is of a four-layer planar laminated structure and comprises a silver metal layer, an intermediate medium layer, an amorphous phase-change material layer and a medium antireflection layer from bottom to top in sequence; the medium anti-reflection layer comprises four sub-layers, and each sub-layer is made of one of gallium arsenide, germanium and zinc sulfide; the material and thickness of the intermediate medium layer and each sub-layer and the thickness of the amorphous phase-change material layer are determined through optimization so as to reflect a specific target color; and determining the area ratio of the crystalline phase transition interval of the grating structure in the periodic structure according to the infrared dual-band emissivity target value. The invention can be used for visible-infrared multi-band compatible thermal camouflage of target environment.
Description
Technical Field
The invention relates to a visible-infrared multiband compatible indium-antimony-tellurium-based multiband compatible programmable heat radiator and an application method thereof, belonging to the technical field of micro-nano photon devices.
Background
The active control device can actively control the color characteristic like animals in nature and has the infrared heat emission characteristic, and has important significance for military and industrial fields. For a long time, materials and devices for realizing compatible regulation and control of spectrum radiation characteristics of visible wave bands and infrared wave bands are one of important research fields of people, and particularly have important roles in the national defense field.
In recent years, volatile phase change materials such as VO 2 Liquid crystal and WO 3 The electrochemical materials have been used for active regulation of radiation characteristics. However, current spectrum regulation materials or devices usually regulate and control only for a single wave band, and it is difficult to realize characteristic regulation and control of visible-infrared multiband compatibility. Therefore, the development of programmable optical materials and devices compatible with visible-infrared multiband having a simple driving mechanism, ultra-wide regulation spectral range and a large-scale thermal radiation characteristic variation capability is a necessary condition for realizing the wide application of active regulation devices.
Disclosure of Invention
Aiming at the problems of small heat radiation characteristic regulation amplitude and narrow regulation wavelength range of the traditional heat radiation characteristic adjustable device, the invention provides an indium-antimony-tellurium-based multiband compatible programmable heat radiator and an application method thereof.
The multiband compatible programmable heat radiator based on indium, antimony and tellurium consists of a plurality of square regulating monomers which are periodically arranged on a silicon dioxide substrate, wherein the square regulating monomers are arranged to form a rectangular array;
each square regulating monomer is of a four-layer planar laminated structure and comprises a silver metal layer, a metal layer and a metal layer, wherein the silver metal layer and the metal layer are sequentially arranged from bottom to top,Intermediate dielectric layer, amorphous phase In 3 SbTe 2 A phase change material layer and a dielectric anti-reflection layer; the medium anti-reflection layer comprises four sub-layers, and each sub-layer is made of one of gallium arsenide, germanium and zinc sulfide;
optimizing each square regulation monomer with the aim of representing target color In visible wave band and having maximum spectral emissivity regulation range In infrared wave band of 3-5 microns and 8-14 microns, and determining material and thickness of intermediate medium layer and each sub-layer and amorphous phase In 3 SbTe 2 The thickness of the phase change material layer;
the amorphous phase In 3 SbTe 2 The phase change material layer extends In the middle section by adopting a laser direct writing excitation source heating mode to form a grating structure crystalline phase In 3 SbTe 2 A phase change section; grating structure crystalline phase In 3 SbTe 2 The phase transition zone is heated to the melting temperature by high-energy instantaneous laser and then cooled to be amorphous In 3 SbTe 2 A phase change material layer;
for each square regulation monomer, determining the crystal phase In of the grating structure according to the target value of the spectral emissivity 3 SbTe 2 Phase transition region relative to amorphous phase In 3 SbTe 2 The area ratio of the phase change material layer.
The thickness of the silver metal layer is at least 100 nanometers.
According to the indium-antimony-tellurium-based multiband compatible programmable heat radiator, the square regulation monomer has the transmittance of 0 in the infrared band of 3-5 microns and 8-14 microns, the sum of the spectral absorptivity and the reflectance is 1, and the spectral absorptivity and the spectral emissivity are the same.
According to the indium-antimony-tellurium-based multiband compatible programmable heat radiator, the period of the square regulation monomer is 2 microns; the material of the intermediate dielectric layer is one of gallium arsenide, germanium or zinc sulfide.
According to the indium-antimony-tellurium-based multiband compatible programmable heat radiator, a silver metal layer, an intermediate dielectric layer, an amorphous phase In3SbTe2 phase change material layer and a dielectric anti-reflection layer are sequentially prepared and formed on a silicon dioxide substrate by adopting a magnetron sputtering method.
According to the indium-antimony-tellurium-based multiband compatible programmable heat radiator, the spectral emissivity of each square regulation monomer In the infrared band of 3-5 microns and 8-14 microns can be continuously regulated and controlled between 0 and 1 by regulating the area ratio of the phase change interval of the crystalline phase In3SbTe2 of the grating structure.
According to the indium-antimony-tellurium-based multiband compatible programmable heat radiator, the incident light wavelength range of the square regulating and controlling monomer is 360-830 nanometers in a visible band, and 3-5 microns and 8-14 microns in an infrared band.
The invention relates to an application method of an indium-antimony-tellurium-based multiband compatible programmable heat radiator, which is realized based on the indium-antimony-tellurium-based multiband compatible programmable heat radiator and comprises the following steps of,
step one, a plurality of programmable heat emission controllers are combined to form a multi-band heat camouflage device; setting the material and thickness of an intermediate medium layer and each sub-layer and the thickness of an amorphous In3SbTe2 phase change material layer of each programmable heat emission controller according to the target color of the thermal camouflage and the regulation range of the maximum spectral emissivity In the infrared wave bands of 3-5 microns and 8-14 microns;
and step two, adjusting the area ratio of the phase change interval of the grating structure crystalline phase In3SbTe2 In each programmable heat emission controller according to the spectral emissivity target value, so that the spectral emissivity of each programmable heat emission controller In the infrared bands of 3-5 microns and 8-14 microns is close to the spectral emissivity target value, and the camouflage of the multiband thermal camouflage device is realized.
According to the application method of the indium-antimony-tellurium-based multiband compatible programmable heat radiator, in the first step, the thermal camouflage target color is represented by coordinates in a CIE1931xy chromaticity system:
wherein x is the abscissa of the thermal camouflage target color in the CIE1931xy chromaticity system and y is the ordinate of the thermal camouflage target color in the CIE1931xy chromaticity system; x is the stimulus value of red in the three primary colors, Y is the stimulus value of green in the three primary colors, and Z is the stimulus value of blue in the three primary colors;
wherein lambda is the wavelength of incident light of the square regulation monomer, S (lambda) is the standard spectral radiant energy distribution of the D65 light source, and R (lambda) is the spectral reflectivity of the thermal camouflage environmental background or the thermal camouflage object in the visible wave band;is->Respectively, the standard matching functions of the tristimulus values.
According to the application method of the indium-antimony-tellurium-based multiband compatible programmable heat radiator, a target value of the spectral emissivity is obtained through inversion of normalized radiation intensity; the calculation method of the normalized radiation intensity comprises the following steps:
in which I norm Normalized radiation intensity, I for each programmable thermal emission modulator min Minimum radiation intensity for all programmable heat emission modulators in the multi-band thermal camouflage device; i max Maximum radiation intensity for all programmable heat emission modulators in the multi-band thermal camouflage device; i is the radiation intensity of each programmable heat emission controller:
wherein ε (λ) is a programmable thermal emission controllerSpectral emissivity, T is the temperature of the programmable thermal emission regulator, lambda min Lambda is the initial wavelength of the incident light max C is the cut-off wavelength of the incident light 1 For the first radiation constant, the value 3.7419 ×10 -16 W·m 2 ；c 2 For the second radiation constant, the value 1.4388 ×10 -2 m·K。
The invention has the beneficial effects that: the invention realizes compatibility of the thermal camouflage device in visible color characteristics and infrared multiband internal heat emission regulation and control based on the optical multi-mode coupling effect, and can be used for thermal camouflage of a target environment. The thermal emission regulator not only can show most of color characteristics, but also ensures extremely high regulation amplitude in an infrared detection wave band; the color characteristics and the infrared thermal emission characteristics of the visible wave band can be independently regulated and controlled.
According to the regulator, through optimally designing the material composition sequence and thickness of the top four-layer laminated antireflection layer, almost all visible wave band color characteristics can be realized on the basis of ensuring that the infrared regulation and control capability is not influenced according to the optical multi-mode coupling theory. The ultra-large-amplitude active regulation and control of the emissivity in the multiband ultra-wide spectrum range is realized by changing the duty ratio f of the phase change region of the device, and the device has the advantages of large regulation and control amplitude, wide regulation and control wavelength range and good regulation and control stability, and endows the multiband emissivity regulation and control device with extremely large initiative.
The controller provided by the invention has a simple structure, is easy to prepare, can complete the preparation of devices and the regulation of emission characteristics by utilizing magnetron sputtering equipment and laser or electric excitation, provides a very promising method and platform for regulating the emission characteristics of visible-infrared multi-band compatible thermal emitters, and provides references for the design and application of subsequent visible-infrared multi-band compatible programmable optical modulation devices.
Drawings
FIG. 1 is a schematic diagram of the stacked structure of square tuning monomers of an InSb Te based multiband compatible programmable heat radiator according to the present invention;
FIG. 2 is an amorphous phase In 3 SbTe 2 The middle section of the phase change material layer forms a grating structure crystalline phase In 3 SbTe 2 Schematic diagram of phase transition section;
FIG. 3 is a graph of simulation results of spectral emissivity of a programmable thermal emission regulator when the four sub-layers of the dielectric anti-reflection layer and the middle dielectric layer are both made of zinc sulfide; optimizing the design of each layer thickness by adopting a genetic optimization method, ensuring the maximum regulating amplitude of infrared 3-5 microns and 8-14 microns dual-band emissivity, and determining the ZnS total thickness of the medium anti-reflection layer to be 1.336 microns and the amorphous phase In 3 SbTe 2 The thickness of the phase change material layer is 11 nanometers, the thickness of the intermediate dielectric layer is 1.493 micrometers, and the thickness of the silver metal layer is 0.2 micrometers;represents the average emissivity change in the infrared 3-5 micron band,/for the wavelength range>Representing the average emissivity variation of the infrared 8-14 micron wave band;
fig. 4 shows the optimized indium-antimony-tellurium-based multiband compatible programmable heat radiator of fig. 3 In a grating structure crystalline phase In 3 SbTe 2 When the area occupation ratio f of the phase change region is changed, the polarization average spectral emissivity cloud picture in the wave band of 3-5 microns and 8-14 microns is corresponding; the white dotted line in the figure is the position with a wavelength of 5 microns and 8 microns;
FIG. 5 is an average emissivity of polarization averages over 3-5 microns and 8-14 microns for different crystalline phase IST phase change material layer duty cycles f for the optimized InSb Te based multi-band compatible programmable heat radiator of FIG. 3Schematic of (2); in the figure->Represents the average emissivity of the infrared 3-5 micron band,/for>Representing average emission in the infrared 8-14 micron bandA rate;
FIG. 6 is the optimized programmable thermal emission controller of FIG. 3 In amorphous phase In 3 SbTe 2 When the phase change material layer is not phase-changed, the incident light phase change result in the cavity formed by the top air/zinc sulfide/aIST; in the figure @ represents the wavelength position of the corresponding point;
FIG. 7 is the optimized programmable thermal emission controller of FIG. 3 In amorphous phase In 3 SbTe 2 When the phase change material layer is not phase-changed, the incident light phase change result in the cavity formed by the bottom layer aIST/zinc sulfide/silver;
FIG. 8 is an amorphous phase In of the optimized programmable thermal emission controller of FIG. 3 3 SbTe 2 After the phase change material layer is subjected to phase change, the incident light phase change result in a cavity formed by the top layer air/zinc sulfide/cIST; air in the figure, cavity represents the Cavity;
FIG. 9 is the optimized programmable thermal emission controller of FIG. 3 In amorphous phase In 3 SbTe 2 After the phase change material layer is subjected to phase change, the incident light phase change result in the cavity formed by the bottom layer cIST/zinc sulfide/silver;
FIG. 10 shows that the device obtained by adopting the genetic optimization method can realize the color range of the visible light wave band under the condition of IST phase change without changing the thickness of each layer and the material composition of each dielectric layer on the basis of ensuring that the wave bands of 3 micrometers to 5 micrometers and 8 micrometers to 14 micrometers have higher average emissivity regulation capability; red star symbols in the figures represent labeled example samples e.g.1 through e.g.6 drawn therefrom; coordinates x represents the x-Coordinate and Coordinates y represents the y-Coordinate in the figure;
FIG. 11 is a visible band color range of the modulator of the structure of FIG. 10 after a complete phase transition of the IST layer; wherein the red star symbol represents the phase-changed color results corresponding to labeled example samples e.g.1 through e.g.6 in fig. 10;
FIG. 12 is an illustration of the programmable thermal emission controller of the present invention In amorphous phase In shown In FIG. 10 and FIG. 11 labeled example 1 (E.g.1) 3 SbTe 2 When the phase change material layer is all amorphous (aIST) and crystalline (cIST), the visible light spectral reflectance under normal incidence unpolarized light is calculatedA figure; the figure is illustrated as amorphous In 3 SbTe 2 The CIE1931 chromaticity diagram coordinate values when the phase change material layer is in an amorphous phase (aIST) and is in a crystalline phase (cIST);
FIG. 13 is an illustration of the programmable thermal emission controller of the present invention In amorphous phase In shown In FIG. 10 and FIG. 11 labeled example 2 (E.g.2) 3 SbTe 2 When the phase change material layer is all amorphous phase (aIST) and all crystalline phase (cIST), the visible light spectral reflectance under normal incidence unpolarized light is calculated;
FIG. 14 is an illustration of the programmable thermal emission controller of the present invention In amorphous phase In shown In FIG. 10 and FIG. 11 labeled example 3 (E.g.3) 3 SbTe 2 When the phase change material layer is all amorphous phase (aIST) and all crystalline phase (cIST), the visible light spectral reflectance under normal incidence unpolarized light is calculated;
FIG. 15 is an illustration of the programmable thermal emission controller of the present invention In amorphous phase In shown In FIG. 10 and FIG. 11 labeled example 4 (E.g.4) 3 SbTe 2 When the phase change material layer is all amorphous phase (aIST) and all crystalline phase (cIST), the visible light spectral reflectance under normal incidence unpolarized light is calculated;
FIG. 16 is an illustration of the programmable thermal emission controller of the present invention In amorphous phase In shown In FIG. 10 and FIG. 11 labeled example 5 (E.g.5) 3 SbTe 2 When the phase change material layer is all amorphous phase (aIST) and all crystalline phase (cIST), the visible light spectral reflectance under normal incidence unpolarized light is calculated;
FIG. 17 is an illustration of the programmable thermal emission controller of the present invention In amorphous phase In shown In FIG. 10 and FIG. 11 labeled example 6 (E.g.6) 3 SbTe 2 When the phase change material layer is all amorphous phase (aIST) and all crystalline phase (cIST), the visible light spectral reflectance under normal incidence unpolarized light is calculated;
FIG. 18 is an illustration of the programmable thermal emission controller of the present invention In amorphous phase In shown In FIG. 10 and FIG. 11 labeled example 1 (E.g.1) 3 SbTe 2 When the phase change material layer is all amorphous phase (aIST) and all crystalline phase (cIST), calculating an infrared spectrum emissivity in an ultra-wide band of 3-14 microns under normal incidence of unpolarized light;
FIG. 19 is an illustration of the programmable thermal emission controller of the present invention In amorphous phase In shown In FIG. 10 and FIG. 11 labeled example 2 (E.g.2) 3 SbTe 2 When the phase change material layer is all amorphous phase (aIST) and all crystalline phase (cIST), calculating an infrared spectrum emissivity in an ultra-wide band of 3-14 microns under normal incidence of unpolarized light;
FIG. 20 is an illustration of the programmable thermal emission controller of the present invention In amorphous phase In shown In FIG. 10 and FIG. 11 labeled example 3 (E.g.3) 3 SbTe 2 When the phase change material layer is all amorphous phase (aIST) and all crystalline phase (cIST), calculating an infrared spectrum emissivity in an ultra-wide band of 3-14 microns under normal incidence of unpolarized light;
FIG. 21 is an illustration of the programmable thermal emission controller of the present invention In amorphous phase In shown In FIG. 10 and FIG. 11 labeled example 4 (E.g.4) 3 SbTe 2 When the phase change material layer is all amorphous phase (aIST) and all crystalline phase (cIST), calculating an infrared spectrum emissivity in an ultra-wide band of 3-14 microns under normal incidence of unpolarized light;
FIG. 22 is an illustration of the programmable thermal emission controller of the present invention In amorphous phase In shown In FIG. 10 and FIG. 11 labeled example 5 (E.g.5) 3 SbTe 2 When the phase change material layer is all amorphous phase (aIST) and all crystalline phase (cIST), calculating an infrared spectrum emissivity in an ultra-wide band of 3-14 microns under normal incidence of unpolarized light;
FIG. 23 shows the programmable thermal emission controller of the present invention shown In reference example 6 (E.g.6) In FIGS. 10 and 11 In an amorphous phase In 3 SbTe 2 When the phase change material layer is all amorphous phase (aIST) and all crystalline phase (cIST), calculating an infrared spectrum emissivity in an ultra-wide band of 3-14 microns under normal incidence of unpolarized light;
FIG. 24 is a schematic diagram showing the programmable thermal emission modulator of the present invention shown In reference example 1 (E.g.1) In FIGS. 10 and 11 In modulating the crystalline phase In of the grating structure 3 SbTe 2 When the area of the phase change region is f, a polarization average spectrum emissivity epsilon (lambda) cloud picture in the wave bands of 3-5 microns and 8-14 microns; the white dotted line in the figure is the position with a wavelength of 5 microns and 8 microns;
FIG. 25 is the view of FIG. 10The programmable thermal emission modulator of the present invention shown In fig. 11 labeled example 1 (e.g.1) modulates the grating structure crystalline phase In 3 SbTe 2 Average emissivity of polarization average in 3-5 micron and 8-14 micron bands at area ratio f of phase transition regionSchematic of (2);
FIG. 26 is a schematic diagram showing the programmable thermal emission modulator of the present invention shown In reference example 1 (E.g.1) In FIGS. 10 and 11 In modulating the crystalline phase In of the grating structure 3 SbTe 2 The area of the phase change section is the spectral reflectivity in the visible wave band when the area of the phase change section is occupied by f, and the right side is the visible color characteristic corresponding to the different phase change area occupied by f, which indicates that the color characteristic of the visible wave band is not affected by infrared regulation;
FIG. 27 is a schematic illustration of the programmable arrangement of label example 1-label example 6 of FIGS. 10 and 11 to form a visible band color camouflage;
FIG. 28 is a schematic diagram of a programmable camouflage pattern in which the phase change region area ratio f in each color block in FIG. 27 is modulated to achieve the desired customization of the heat radiation characteristics between different color blocks, thereby achieving an infrared 3-5 micron band;
FIG. 29 is a schematic diagram of a programmable camouflage pattern in the infrared 8-14 micron band by modulating the phase change region area duty ratio f in each color block of FIG. 27 to achieve the desired customization of the heat radiation characteristics between the different color blocks.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
It should be noted that, without conflict, the embodiments of the present invention and features of the embodiments may be combined with each other.
The invention is further described below with reference to the drawings and specific examples, which are not intended to be limiting.
The invention provides an indium-antimony-tellurium-based multiband compatible programmable heat radiator, which is composed of a plurality of square regulation monomers periodically arranged on a silicon dioxide substrate, wherein the square regulation monomers are arranged to form a rectangular array;
each square regulating monomer is of a four-layer planar laminated structure and comprises a silver metal layer 1, an intermediate medium layer 2 and an amorphous phase In from bottom to top In sequence 3 SbTe 2 A phase change material layer 3 and a dielectric antireflection layer 5; the medium anti-reflection layer 5 comprises four sub-layers, and each sub-layer is made of one of gallium arsenide, germanium and zinc sulfide;
optimizing each square regulation monomer with the aim of representing target color In visible wave band and having maximum spectral emissivity regulation range In infrared wave band of 3-5 microns and 8-14 microns, and determining material and thickness of intermediate medium layer 2 and each sub-layer and amorphous phase In 3 SbTe 2 The thickness of the phase change material layer 3; the optimization method can adopt a common intelligent optimization method, such as a genetic optimization method, a particle swarm optimization method and the like;
the amorphous phase In 3 SbTe 2 The phase change material layer 3 extends In the middle section by adopting a laser direct writing excitation source heating mode to form a grating structure crystalline phase In 3 SbTe 2 A phase transition section 4; grating structure crystalline phase In 3 SbTe 2 The phase transition zone 4 is heated to the melting temperature by high-energy instantaneous laser and then cooled to be amorphous phase In 3 SbTe 2 A phase change material layer 3;
for each square regulation monomer, according to the spectral emissivity target value of the corresponding position, the crystal phase In of the grating structure can be determined through inversion by methods such as genetic optimization 3 SbTe 2 Phase transition region 4 is relative to amorphous phase In 3 SbTe 2 The area ratio of the phase change material layer 3.
Grating structure crystalline phase In 3 SbTe 2 Phase transition region 4 is relative to amorphous phase In 3 SbTe 2 The area ratio of the phase change material layer 3 is denoted as f:
f＝L cIST /Λ，
in which L cIST Represents the grating structure crystalline phase In 3 SbTe 2 The width of the phase change interval, Λ, represents the period of the square regulation monomer.
The optimal design method for the programmable heat emission controller is to realize two targets of maximum emissivity regulation and control capacity of a square regulation and control monomer according to a corresponding CIE1931 chromaticity xy coordinate target value and middle infrared 3-5 microns and far infrared 8-14 microns, reversely optimize and design the thickness of each layer and the selection of the constituent materials of each medium layer through a genetic optimization algorithm, so that the device can show expected color characteristics on the basis of realizing the maximum heat emission regulation and control range of infrared 3-5 microns and 8-14 microns, and reverse design the optimized fitness function value F 1 F (F) 2 The method comprises the following steps:
in the middle ofIs->To be the average emissivity difference, x, before and after the phase change of the device in the wave bands of 3-5 microns, 5-8 microns and 8-14 microns aim ，y aim Is the coordinate value of the target color in CIE1931 chromaticity coordinates.
The infrared detection band (3-5 microns and 8-14 microns) is one of the most important atmospheric windows for infrared detection, optical camouflage and thermal control. The non-volatile phase change material shows stable performance and huge optical contrast between amorphous state and crystalline state, and shows great potential of being integrated into an infrared optical modulation platform.In 3 SbTe 2 The (IST) is used as a non-volatile phase change material, can show the metalloid characteristic of huge negative dielectric constant in the full infrared region in a crystalline phase (cIST), is used as a lossless dielectric medium in the infrared region in an amorphous phase (aIST), can realize non-volatile local phase change through laser or electric excitation, and lays a foundation for developing a medium infrared emissivity regulating device with continuous regulation, programmability and large conversion degree.
Further, the silver metal layer 1 has a thickness of at least 100 nm.
As an example, the thickness of the silver metal layer 1 is selected to be 200 nm.
In this embodiment, the thickness of the silver metal layer 1 is far greater than the skin depth of the silver metal layer in the mid-infrared band, so that the square regulation and control monomer can be guaranteed to have a transmittance of 0 in the infrared band of 3-5 microns and 8-14 microns, the sum of the spectral absorptivity and the reflectance is 1, and the spectral absorptivity and the spectral emissivity are the same.
As an example structure of infrared detection wave band regulation capability and regulation principle, the period of the square regulation monomer is 2 micrometers; the material of the intermediate dielectric layer 2 is one of gallium arsenide, germanium or zinc sulfide.
The materials of each layer In the middle dielectric layer 2 and the top four-layer laminated dielectric antireflection layer 5 can be zinc sulfide, the thickness of the middle dielectric layer 2 is 1336 nanometers, the total thickness of the dielectric antireflection layer 5 is 1493 nanometers, and the amorphous phase In 3 SbTe 2 The thickness of the phase change material layer 3 is 11 nm.
The silver metal layer 1, the intermediate dielectric layer 2, the amorphous phase In3SbTe2 phase change material layer 3 and the dielectric antireflection layer 5 are sequentially prepared and formed on a silicon dioxide substrate by adopting a magnetron sputtering method.
Experiments prove that by adjusting the area ratio f of the phase change section 4 of the crystal phase In3SbTe2 of the grating structure, the spectral emissivity of each square regulation monomer In the double infrared wave bands of 3-5 microns and 8-14 microns can be continuously regulated and controlled between approximately 0 and approximately 1, and the large enough spectral emissivity amplitude regulation capacity is realized. The average emissivity regulation and control amplitude of the middle infrared detection wave band 3-5 microns obtained in the embodiment is 0.843, the average emissivity regulation and control amplitude of the far infrared detection wave band 8-14 microns obtained is 0.921, and huge middle infrared emissivity switching is realized as shown in fig. 3.
In this embodiment, the incident light wavelength range of the square regulating monomer is 360-830 nm in the visible band, 3-5 microns and 8-14 microns in the infrared band.
As shown In fig. 4 and 5, in the present embodiment, the amorphous phase In is applied by laser or electric excitation 3 SbTe 2 The phase change material layer 3 can be In an amorphous phase In 3 SbTe 2 The phase change material layer 3 generates a grating-shaped crystalline phase In 3 SbTe 2 The average emissivity of the mid-infrared 3-5 micron wave band of the regulator can be realized from 0.031 (In) by controlling the duty ratio f of the phase change region In the phase change region 4 3 SbTe 2 The layer is all amorphous phase) is continuously regulated to 0.874 (In) 3 SbTe 2 The layers are all crystalline phases), and the average emissivity of the far infrared 8-14 micron wave band In the regulation period can be realized from 0.039 (In 3 SbTe 2 The layer is all amorphous phase) is continuously regulated to 0.96 (In) 3 SbTe 2 The layers are all crystalline). At the same time, high-power laser or electric excitation is adopted to lead the crystal phase In 3 SbTe 2 After heating to a molten state, the material is cooled rapidly to form a crystalline phase In 3 SbTe 2 Transition back to amorphous phase In 3 SbTe 2 Realizing reversible regulation and control.
In this embodiment, when the modulator is used for infrared thermal radiation programmable camouflage, each thermal radiation modulator calculates the phase change duty ratio f of the square modulating monomer in the thermal radiation modulator according to the spectral emissivity of the camouflage target at the corresponding position, thereby realizing programmable thermal camouflage in a complex camouflage environment. By utilizing laser and electric excitation, unit structures with different phase change ranges can be prepared in different areas in a large area range, and the programmable customized regulation and control of the middle infrared emissivity in different area ranges according to the actual environment requirements can be realized.
The working process and principle of the invention in the regulation of infrared heat radiation characteristics are described with reference to fig. 6 to 9: the multilayer laminated structure enables two nano cavities of air/zinc sulfide/IST and IST/ZnS/Ag to be formed, and the air/zinc sulfide/IST/ZnS/Ag nano cavities can be excited to generate F-P resonance when the net phase shift of incident light in the cavity is an integral multiple of 2 pi, so that the absorption in the cavity is increased. Before phase transition, the phase shift in the Air/ZnS/aIST and aIST/ZnS/Ag nano cavities is an integral multiple of 2 pi at the wavelengths of 3.69 mu m, 5.17 mu m and 8.48 mu m, which is extremely similar to the calculated peak emissivity wavelengths 3.697 mu m, 5.184 mu m and 8.447 mu m of the device before phase transition, so that F-P resonance can be considered to occur in the two cavities, but the aIST and ZnS are almost transparent mediums in the infrared band, only Ag is weakly absorbed, and the device as a whole presents extremely weak infrared spectrum emission characteristics. After phase transition, the phase shift results show that the net phase shift after 8 μm in the Air/ZnS/cIST nano cavity of the top layer is close to 0, which means that ZnS of the top layer in the band plays a role of an antireflection layer and promotes the generation of high emission characteristic of heat radiation in the 8-14 μm band. Meanwhile, in the Air/ZnS/cIST nano cavity and the cIST/ZnS/Ag nano cavity on the top layer, the calculated phase shift shows that the phase shift is generated at 4.607 mu m by an integral multiple of 2 pi, and is similar to the calculated peak wavelength 4.609 mu m of the emissivity of the spectrum in the 3-5 mu m wave band, which means that the high emissivity generated at 4.609 mu m is generated by F-P resonance generated by the Air/ZnS/cIST cavity on the top layer, and the high emissivity at 3.715 mu m is generated by F-P resonance mode coupling obtained at 3.664 mu m and 3.601 mu m of the upper nano cavity and the lower nano cavity, so that the optical mode coupling based on the upper nano cavity and the lower nano cavity can be determined to generate higher spectrum heat emission characteristics in the 3-5 mu m wave band after the device is subjected to phase transition. Because the optical modal coupling effect is not dependent on specific structure and material arrangement, various material selection and arrangement structures exist, extremely high regulation and control amplitude can be realized in infrared 3-5 microns and 8-14 microns, and a foundation is provided for subsequent visible color characteristic regulation and control.
In this embodiment, the modulator is used for the visible color programmable camouflage, and on the basis of ensuring that each thermal radiation modulator has higher average emissivity regulation capability of 3 micrometers to 5 micrometers and 8 micrometers to 14 micrometers, the thickness of each layer and the material composition of each dielectric layer are changed through optimal design, so that the obtained device can realize the required visible light wave band color characteristic under the condition of IST (integrated circuit) phase transition.
Combined drawing10-23 illustrate the thermal radiation characteristic tuning capability of the present invention in visible-infrared multiband compatible: FIGS. 10 and 11 show the In 3 SbTe 2 The method can realize almost all color characteristics on the basis of combining different dielectric layer materials before and after layer phase transition and guaranteeing larger regulation and control amplitude of an infrared detection wave band. Due to In 3 SbTe 2 The optical characteristics in the visible wavelength band are less changed and the thickness is thinner, so that the visible color characteristics before and after the phase change are not changed. Fig. 12-17 show the visible band spectral reflectivities R (λ) and the coordinates and color characteristics in the CIE1931 coordinate diagram for 6 exemplary devices having different visible color characteristics. Fig. 18 to 23 are calculation results of infrared spectrum thermal emission characteristics of the devices illustrated in fig. 12 to 17, which all show extremely high control potential in an infrared detection band, and the visible-infrared multiband compatible indium-antimony-tellurium programmable thermal emission controller based on optical multi-mode coupling can realize the visible-infrared multiband compatible characteristic.
In this embodiment, referring to fig. 24 and 25, the example device 1 is shown applied to an amorphous phase In by laser or electric excitation 3 SbTe 2 The phase change material layer 3 can be In an amorphous phase In 3 SbTe 2 The phase change material layer 3 generates a grating-shaped crystalline phase In 3 SbTe 2 The average emissivity of the mid-infrared 3-5 micron wave band of the regulator can be realized from 0.03 (In) by controlling the duty ratio f of the phase change region In the phase change region 4 3 SbTe 2 The layer is all amorphous phase) is continuously regulated to 0.88 (In 3 SbTe 2 The layers are all crystalline phases), and the average emissivity of the far infrared 8-14 micron wave band In the regulation period can be realized from 0.034 (In 3 SbTe 2 The layer is all amorphous phase) is continuously regulated to 0.955 (In) 3 SbTe 2 The layers are all crystalline). At the same time, high-power laser or electric excitation is adopted to lead the crystal phase In 3 SbTe 2 After heating to a molten state, the material is cooled rapidly to form a crystalline phase In 3 SbTe 2 Transition back to amorphous phase In 3 SbTe 2 Realizing reversible regulation and control.
In summary, the optical multi-mode coupling effect of the programmable thermal emission modulator according to the present embodiment is not dependent on a specific optical structure, and the same optical characteristics can be achieved by adopting different structures; in theory, similar infrared spectrum characteristics can be realized by optimally designing the material composition arrangement and the thickness of each layer of the top four-layer medium anti-reflection layer 5. The top four-layer medium anti-reflection layer 5 with different material composition arrangement and thickness can show different color characteristics in the visible light range, so that different colors can be shown under the condition of ensuring the unchanged infrared characteristics. The dielectric function of indium, antimony and tellurium is not changed much before and after the phase change of the visible wave band, and the reflection characteristic of the visible wave band is changed little before and after the phase change under the condition of thinner thickness, so that the color characteristic of a device of the visible wave band is unchanged when the infrared heat emission characteristic is regulated and controlled by changing the phase change duty ratio, and the characteristic that the regulation and control of the visible-infrared multiband spectral characteristic are not mutually influenced and compatible is realized.
The invention provides a method for applying an indium-antimony-tellurium-based multiband compatible programmable heat radiator, which can realize visible-infrared multiband compatible thermal camouflage based on optical multimode coupling, and is realized based on the indium-antimony-tellurium-based multiband compatible programmable heat radiator in the embodiment, and comprises the following steps of,
step one, a plurality of programmable heat emission controllers are combined to form a multi-band heat camouflage device; setting the material and thickness of the intermediate medium layer 2 and each sub-layer and the thickness of the amorphous In3SbTe2 phase change material layer 3 according to the thermal camouflage target color and the regulation range of the maximum spectral emissivity In the infrared wave bands of 3-5 microns and 8-14 microns;
and step two, adjusting the area ratio of the phase change section 4 of the grating structure crystalline phase In3SbTe2 In each programmable heat emission controller according to the spectral emissivity target value, so that the spectral emissivity of each programmable heat emission controller In the infrared wave bands of 3-5 microns and 8-14 microns is close to the spectral emissivity target value, and the camouflage of the multiband thermal camouflage device is realized.
In the first step, the thickness and material selection of each medium layer of the heat emission controller in each color block are determined according to the optimal design, so that devices in different color blocks can show different color characteristics in a visible wave band as required on the basis of ensuring that the infrared detection wave band has larger adjustable capacity in the wave bands of 3-5 microns and 8-14 microns, and therefore the programmable color camouflage in the visible wave band is realized.
In the second step, the imaging of the infrared detector performs maximum and minimum normalization on the received thermal radiation density, so that the amorphous phase In at the corresponding position is obtained by adjusting the area ratio f of the phase change section 4 of the grating structure crystalline phase In3SbTe2 3 SbTe 2 The phase change material layer 3 is heated and converted into a grating structure crystal phase In 3 SbTe 2 Phase transition section 4 or phase In of grating structure 3 SbTe 2 The phase change region 4 is reheated and then cooled, so that the normalized heat emission characteristics of different color blocks can be controlled as required, and the camouflage with the programmable infrared heat emission characteristics can be realized.
Further, in step one, the thermal camouflage target color is represented by coordinates in the CIE1931xy chromaticity system:
wherein x is the abscissa of the thermal camouflage target color in the CIE1931xy chromaticity system and y is the ordinate of the thermal camouflage target color in the CIE1931xy chromaticity system; x is the stimulus value of red in the three primary colors, Y is the stimulus value of green in the three primary colors, and Z is the stimulus value of blue in the three primary colors;
wherein lambda is the wavelength of incident light of the square regulation monomer, S (lambda) is the standard spectral radiant energy distribution of the D65 light source, and R (lambda) is the spectral reflectivity of the thermal camouflage environmental background or the thermal camouflage object in the visible wave band;is->Respectively, the standard matching functions of the tristimulus values.
The target value of the spectral emissivity is obtained through inversion of normalized radiation intensity; the calculation method of the normalized radiation intensity comprises the following steps:
in which I norm Normalized radiation intensity, I for each programmable thermal emission modulator min Minimum radiation intensity for all programmable heat emission modulators in the multi-band thermal camouflage device; i max Maximum radiation intensity for all programmable heat emission modulators in the multi-band thermal camouflage device; i is the radiation intensity of each programmable heat emission controller:
wherein ε (λ) is the spectral emissivity of the programmable thermal emission controller, T is the temperature of the programmable thermal emission controller, λ min Lambda is the initial wavelength of the incident light max C is the cut-off wavelength of the incident light 1 For the first radiation constant, the value 3.7419 ×10 -16 W·m 2 ；c 2 For the second radiation constant, the value 1.4388 ×10 -2 m·K。
Specific examples:
firstly, the thickness of each layer and the material selection of a medium layer of a plurality of InSb Te programmable visible-infrared multi-band compatible thermal emission regulators based on optical multi-mode coupling are optimally designed, on the basis of ensuring that the infrared detection wave band has larger adjustable capacity in the wave bands of 3-5 microns and 8-14 microns, a plurality of devices show different color characteristics in the visible wave band as required, and then the obtained devices are used as color blocks of the thermal camouflage equipment to be arranged and combined into a camouflage device with visible color camouflage characteristics. Taking the structures of examples 1 to 6 in fig. 10 and 11 as an example, HIT patterns as shown in fig. 27 may be formed by arrangement as needed, or more confusing patterns may be arranged as needed.
By crystalline In for each color patch In fig. 27 3 SbTe 2 The phase change area duty ratio f is regulated and controlled, so that different color blocks can show different heat radiation characteristics. By design, when the phase change region duty ratio f of examples 1 to 6 is 0.5, 0.1, 0.75, 0.85, 0.2, respectively, the normalized heat radiation density images of the thermal camouflage device shown in fig. 27 in the 3-5 micron and 8-14 micron detectors are as shown in fig. 28 and 29, and the more confusing infrared images can be realized by changing the phase change region duty ratio f of different color blocks.
Referring to fig. 26, the color of the square regulation monomer obtained by the corresponding phase change region area ratio f in the graph at different values shows that the color characteristics of the square regulation monomer can be kept unchanged when the phase change region area ratio f is changed.
Although the invention herein has been described with reference to particular embodiments, it is to be understood that these embodiments are merely illustrative of the principles and applications of the present invention. It is therefore to be understood that numerous modifications may be made to the illustrative embodiments and that other arrangements may be devised without departing from the spirit and scope of the present invention as defined by the appended claims. It should be understood that the different dependent claims and the features described herein may be combined in ways other than as described in the original claims. It is also to be understood that features described in connection with separate embodiments may be used in other described embodiments.
Claims (10)
1. The multiband compatible programmable heat radiator based on indium, antimony and tellurium is characterized by comprising a plurality of square regulation and control monomers which are periodically arranged on a silicon dioxide substrate, wherein the square regulation and control monomers are arranged to form a rectangular array;
each square regulating monomer is of a four-layer planar laminated structure and comprises a silver metal layer (1), an intermediate medium layer (2) and an amorphous phase In from bottom to top In sequence 3 SbTe 2 A phase change material layer (3) and a dielectric antireflection layer (5); the medium anti-reflection layer (5) comprises four sub-layers, and each sub-layer is made of one of gallium arsenide, germanium and zinc sulfide;
optimizing each square regulation monomer with the aim of representing target color In visible wave band and having maximum spectral emissivity regulation range In infrared wave band of 3-5 microns and 8-14 microns, and determining material and thickness of intermediate medium layer (2) and each sub-layer and amorphous phase In 3 SbTe 2 The thickness of the phase change material layer (3);
the amorphous phase In 3 SbTe 2 The phase change material layer (3) adopts a laser direct writing excitation source heating mode to extend In the middle section to form a grating structure crystalline phase In 3 SbTe 2 A phase transition section (4); grating structure crystalline phase In 3 SbTe 2 The phase transition section (4) adopts high-energy instantaneous laser to heat to a melting temperature and then is cooled into amorphous phase In 3 SbTe 2 A phase change material layer (3);
for each square regulation monomer, determining the crystal phase In of the grating structure according to the target value of the spectral emissivity 3 SbTe 2 Phase transition section (4) is relative to amorphous phase In 3 SbTe 2 The area ratio of the phase change material layer (3).
2. An indium antimony tellurium based multiband compatible programmable heat radiator according to claim 1, wherein,
the silver metal layer (1) has a thickness of at least 100 nm.
3. The indium-antimony-tellurium-based multiband compatible programmable heat radiator according to claim 1, wherein the square regulating monomer has a transmittance of 0 in the infrared band of 3-5 microns and 8-14 microns, the sum of the spectral absorptance and the reflectance is 1, and the spectral absorptance is the same as the spectral emittance.
4. An indium antimony tellurium based multiband compatible programmable heat radiator according to claim 1, wherein,
the period of the square regulating monomer is 2 micrometers; the material of the middle dielectric layer (2) is one of gallium arsenide, germanium or zinc sulfide.
5. An indium antimony tellurium based multiband compatible programmable heat radiator according to claim 1, wherein,
the silver metal layer (1), the intermediate dielectric layer (2), the amorphous phase In3SbTe2 phase change material layer (3) and the dielectric anti-reflection layer (5) are sequentially prepared and formed on the silicon dioxide substrate by adopting a magnetron sputtering method.
6. An indium antimony tellurium based multiband compatible programmable heat radiator according to claim 1, wherein,
the area ratio of the phase change interval (4) of the crystal phase In3SbTe2 of the grating structure is adjusted, so that the spectral emissivity of each square regulation monomer In the infrared band of 3-5 microns and 8-14 microns can be continuously regulated and controlled between 0 and 1.
7. An indium antimony tellurium based multiband compatible programmable heat radiator according to claim 1, wherein,
the incident light wavelength range of the square regulating monomer is 360-830 nanometers in the visible wave band, 3-5 microns and 8-14 microns in the infrared wave band.
8. A method of applying an indium-antimony-tellurium based multiband compatible programmable heat radiator, characterized in that an indium-antimony-tellurium based multiband compatible programmable heat radiator is realized on the basis of any one of claims 1 to 7, characterized in that it comprises,
step one, a plurality of programmable heat emission controllers are combined to form a multi-band heat camouflage device; setting the material and thickness of an intermediate medium layer (2) and each sub-layer and the thickness of an amorphous In3SbTe2 phase change material layer (3) of each programmable heat emission controller according to the target color of the thermal camouflage and the regulation range of the maximum spectral emissivity In the infrared wave bands of 3-5 microns and 8-14 microns;
and step two, adjusting the area ratio of the phase change interval (4) of the grating structure crystalline phase In3SbTe2 In each programmable heat emission controller according to the spectral emissivity target value, so that the spectral emissivity of each programmable heat emission controller In the infrared bands of 3-5 microns and 8-14 microns is close to the spectral emissivity target value, and the camouflage of the multiband heat camouflage device is realized.
9. The method of using an indium antimony tellurium based multiband compatible programmable heat radiator according to claim 8,
in step one, the thermal camouflage target color is represented by coordinates in the CIE1931xy chromaticity system:
wherein x is the abscissa of the thermal camouflage target color in the CIE1931xy chromaticity system and y is the ordinate of the thermal camouflage target color in the CIE1931xy chromaticity system; x is the stimulus value of red in the three primary colors, Y is the stimulus value of green in the three primary colors, and Z is the stimulus value of blue in the three primary colors;
wherein lambda is the wavelength of incident light of the square regulation monomer, S (lambda) is the standard spectral radiant energy distribution of the D65 light source, and R (lambda) is the spectral reflectivity of the thermal camouflage environmental background or the thermal camouflage object in the visible wave band;is->Standard matching functions with three primary stimulus values respectivelyA number.
10. The method of applying an indium-antimony-tellurium based multiband compatible programmable heat radiator according to claim 9, wherein the spectral emissivity target value in step two is obtained by normalized radiation intensity inversion; the calculation method of the normalized radiation intensity comprises the following steps:
in which I norm Normalized radiation intensity, I for each programmable thermal emission modulator min Minimum radiation intensity for all programmable heat emission modulators in the multi-band thermal camouflage device; i max Maximum radiation intensity for all programmable heat emission modulators in the multi-band thermal camouflage device; i is the radiation intensity of each programmable heat emission controller:
wherein ε (λ) is the spectral emissivity of the programmable thermal emission controller, T is the temperature of the programmable thermal emission controller, λ min Lambda is the initial wavelength of the incident light max C is the cut-off wavelength of the incident light 1 For the first radiation constant, the value 3.7419 ×10 -16 W·m 2 ；c 2 For the second radiation constant, the value 1.4388 ×10 -2 m·K。
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