CN112114391B - Plasmon absorber and preparation method thereof - Google Patents
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Abstract
The invention discloses a plasmon absorber which comprises a periodic unit, wherein the periodic unit sequentially comprises a substrate layer, a metal film layer and a metal nano ring from bottom to top, the axial direction of the metal nano ring is vertical to the surface of the metal film layer, the periphery of the metal nano ring in the circumferential direction is wrapped by a dielectric layer, the inner area of the metal nano ring is filled by the dielectric layer, and the tops of the metal nano ring and the dielectric layer are covered with a protective layer. The plasmon absorber disclosed by the invention wraps and fills the metal nano ring by using the dielectric layer, the metal nano ring can be effectively protected, the stability of the metal nano ring is improved, the dielectric layer has good thermal stability, the metal nano ring is prevented from being permanently deformed in a high-temperature environment, the stable light absorption performance of the plasmon absorber is ensured, the working temperature of the plasmon absorber can be improved, and the application range is wider.
Description
Technical Field
The invention relates to the technical field of photoelectronic devices, in particular to a plasmon absorber and a preparation method thereof.
Background
The light absorption is a research hotspot in the field of optics, particularly, the research on the wide-band light absorption draws more attention, and the nanoscale plasmon absorber has the characteristics of small volume, high sensitivity, easiness in large-scale production and the like, and has wide market application prospect. By reasonably designing the plasmon absorber, light can be limited in the device, and the ideal broadband plasmon absorber requires wide-angle incidence, polarization insensitivity, high absorption efficiency and the like. The working temperature of the existing plasmon absorber is mostly lower than 1000K, but in the application of solar thermophotovoltaic, the working temperature is higher than 1300K, the traditional plasmon absorber usually generates permanent deformation after being exposed to high temperature for a long time, which greatly influences the light absorption performance of the plasmon absorber.
Disclosure of Invention
The invention aims to solve the technical problems and provide a plasmon absorber which is an improvement on the prior art and solves the problems that the plasmon absorber is difficult to apply in a high-temperature environment, and has poor chemical property stability and poor optical absorption property in the prior art.
In order to solve the technical problems, the technical scheme of the invention is as follows:
a plasmon absorber comprises a periodic unit, wherein the periodic unit is sequentially provided with a substrate layer, a metal film layer and a metal nano ring from bottom to top, the axial direction of the metal nano ring is perpendicular to the surface of the metal film layer, the circumferential periphery of the metal nano ring is wrapped by a dielectric layer, the inner area of the metal nano ring is filled by the dielectric layer, and the tops of the metal nano ring and the dielectric layer are covered by a protective layer. The plasmon absorber of the invention utilizes the dielectric layer to wrap and fill the metal nano-ring, the dielectric layer plays a role in supporting and reinforcing the metal nano-ring, the structural stability of the metal nano-ring is improved, in a high-temperature environment, the dielectric layer has good thermal stability, so that the metal nano ring can be effectively prevented from being deformed, the stable light absorption performance of the plasmon absorber is ensured, the working temperature of the plasmon absorber can be improved, the application range is wider, the dielectric layer is utilized to reinforce and stabilize the metal nano ring, so that the metal nano-ring still can adopt noble metal with good chemical property stability and good optical absorption property, for example, gold, silver and the like, metal materials with high melting point, poor chemical stability and poor spectral absorption selectivity are not required, so that the stable working performance of the excimer absorber can be guaranteed.
Furthermore, a plurality of metal nano rings are distributed on the metal film layer at intervals, so that the absorption efficiency can be improved.
Furthermore, at least one of the inner diameters of the metal nano rings is the same as the rest of the metal nano rings or different from the rest of the metal nano rings, so that the spectrum absorption in a broadband range can be realized, and the absorption efficiency is high.
Further, the axial heights of the metal nanorings are the same.
Furthermore, five metal nanorings are arranged, wherein one metal nanoring is arranged in the central area of the metal thin film layer, and the other four metal nanorings are circumferentially distributed on the metal thin film layer.
Furthermore, the dielectric layer and the protective layer are respectively made of at least one of aluminum oxide and hafnium oxide, the dielectric layer and the protective layer are made of the same or different materials, the thermal stability of the aluminum oxide and the hafnium oxide is good, the size stability of the metal nano ring can be guaranteed under a high-temperature environment, the metal nano ring is prevented from being permanently deformed, and the stable working performance of the excimer absorber is guaranteed.
Furthermore, the metal nanoring and the metal thin film layer are respectively made of one of gold, silver and aluminum, the materials of the metal nanoring and the metal thin film layer are the same or different, and the absorption wavelength range and the absorption efficiency can be adjusted by adopting different materials.
Further, the substrate layer and the metal thin film layer are square and overlapped together, the substrate layer and the metal thin film layer are the same in size, the side length of the substrate layer and the metal thin film layer is 900nm, the thickness of the metal thin film layer is larger than or equal to 100nm, the axial height of the metal nano ring is larger than or equal to 6 microns, the inner diameter of the metal nano ring is 200-400 nm, the wall thickness of the metal nano ring is 20nm, and the thickness of the protective layer is smaller than 100 nm.
The preparation method of the plasmon absorber comprises the following steps:
A. growing a metal film layer on the substrate layer;
B. depositing a silicon layer on the metal thin film layer, etching the silicon layer to the surface of the metal thin film layer, and etching a silicon column matched with the inner diameter of a preset metal nano ring;
C. growing a metal nano ring with a preset thickness on the circumferential surface of the silicon column;
D. depositing a dielectric layer on the periphery of the metal nanoring;
E. etching to remove the silicon column, and depositing a dielectric layer in the inner area of the metal nanoring;
F. depositing a protective layer on the tops of the metal nanoring and the dielectric layer in a covering manner;
G. and packaging to obtain a finished product of the plasmon absorber.
According to the preparation method of the plasmon absorber, the etched silicon column is used as a basis for forming the metal nano ring, the forming quality of the metal nano ring is improved, and the shape and the size of the metal nano ring meet preset requirements, so that the metal nano ring plasmon absorber is guaranteed to have good optical absorption performance, and the range of absorption wavelength is accurately controlled within the preset requirements.
Further, in the step C, a silicon dioxide layer is firstly deposited on the surface of the silicon column, and the thickness of the silicon dioxide layer is the same as the preset thickness of the metal nanoring; then spin-coating a polymer layer on the metal thin film layer, wherein the polymer layer wraps the circumferential direction of the silicon dioxide layer; then etching to remove the silicon dioxide layer, and forming an annular gap between the polymer layer and the silicon column; growing a metal nano ring in the annular gap; the polymer layer was removed using dichloromethane. The wall thickness and the shape of the metal nano ring are accurate and controllable, the forming quality of the metal nano ring is effectively improved, and the good working performance of the plasmon absorber is further guaranteed.
Compared with the prior art, the invention has the advantages that:
the plasmon absorber disclosed by the invention wraps and fills the metal nano ring by using the dielectric layer, the metal nano ring can be effectively protected, the stability of the metal nano ring is improved, the dielectric layer has good thermal stability, the metal nano ring is prevented from being permanently deformed in a high-temperature environment, the stable light absorption performance of the plasmon absorber is ensured, the working temperature of the plasmon absorber can be improved, and the application range is wider;
the plasmon absorber can provide a nano-sized platform for photo-thermal conversion;
the plasmon absorber can change the wave band of the absorption peak by changing the material, size, distribution condition and number of the metal nano rings, thereby realizing the adjustability of one periodic unit;
the plasmon absorber can be applied to liquid for a long time, the metal nano ring is protected by the dielectric layer and cannot be contacted with the outside, the use stability is high, and the condition that materials on the carbon-based absorber are easy to fall off is avoided.
Drawings
FIG. 1 is a schematic diagram of a side view vertical profile structure of a plasmonic absorber;
FIG. 2 is a schematic cross-sectional structure of a plasmonic absorber at a metal nanoring;
fig. 3(a) - (k) are schematic views of the preparation process of the plasmon absorber.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The plasmon absorber disclosed by the embodiment of the invention is good in thermal stability, can be applied to a high-temperature environment, has stable and good optical absorption performance and chemical stability, can realize spectral absorption in a broadband range, and is high in absorption efficiency.
Example one
As shown in fig. 1 and 2, a plasmon absorber includes a periodic unit, the periodic unit is sequentially a substrate layer 1, a metal thin film layer 2 and a metal nanoring 3 from bottom to top, an axial direction of the metal nanoring 3 is perpendicular to a surface of the metal thin film layer 2, a circumferential periphery of the metal nanoring 3 is wrapped by a dielectric layer 4, an inner region of the metal nanoring 3 is filled by the dielectric layer 4, and a protective layer 5 covers tops of the metal nanoring 3 and the dielectric layer 4.
The metal nano rings 3 are spaced apart from each other, the inner diameters of the five metal nano rings 3 are the same, the inner diameter of the metal nano ring 3 positioned at the central area of the metal thin film layer 2 is the smallest, and the metal nano rings 3 distributed at the four corners are sequentially increased along the circumferential direction; and the axial heights of all the metal nanorings 3 are the same, and the axial heights of the dielectric layer 4 and the metal nanorings 3 are also completely the same, so that the protective layer 5 covering the metal nanorings 3 and the dielectric layer 4 is a planar layer.
Specifically, the side length of the substrate layer 1 and the metal thin film layer 2 is 900nm, the thickness of the metal thin film layer 2 is 200nm, and as shown in fig. 2, the inner diameter of the five metal nanorings 3 may be d specifically1＝400nm，d2＝360nm，d3＝280nm，d4＝200nm，d5120nm and the wall thickness of the metal nanoring 3 is 20nm, goldThe axial height of the metal nano-ring 3 is 6 mu m, and the thickness of the protective layer 5 is 40 nm; the substrate layer is made of aluminum oxide, the metal nano-ring 3 and the metal film layer 2 are made of gold, and the dielectric layer 4 is made of aluminum oxide;
the plasmon absorber can realize the absorption wavelength range of 300nm to 1400nm, and the average absorption efficiency can reach 96%.
Example two
The difference from the first embodiment is that two metal nanorings 3 of the plasmon absorber are provided at intervals on the metal thin film layer 2, one metal nanoring 3 is provided at each corner on the diagonal of the metal thin film layer 2, and the inner diameters of the two metal nanorings 3 are 400nm and 320nm, respectively.
The wall thickness of the metal nano ring 3 is 20nm, the axial height of the metal nano ring 3 is 6 microns, the side length of the substrate layer 1 and the metal thin film layer 2 is 900nm, the thickness of the metal thin film layer 2 is 200nm, and the thickness of the protective layer 5 is 40 nm; the substrate layer 1 is made of alumina, the metal nano-ring 3 and the metal thin film layer 2 are made of gold, and the dielectric layer 4 is made of alumina;
the plasmon absorber can realize the absorption wavelength range of 300nm to 1500nm, and the average absorption efficiency can reach 94%.
EXAMPLE III
The difference from the first embodiment is that the base layer is made of hafnium oxide, and the dielectric layer 4 is made of hafnium oxide.
Five metal nanorings 3 are arranged, the distribution condition is the same as that of the first embodiment, and the inner diameter of the five metal nanorings 3 can be specifically d1＝400nm，d2＝360nm，d3＝280nm，d4＝200nm，d5120nm, the wall thickness of the metal nanoring 3 is 20nm, the axial height of the metal nanoring 3 is 6 μm, the side length of the substrate layer 1 and the metal thin film layer 2 is 900nm, the thickness of the metal thin film layer 2 is 200nm, and the thickness of the protective layer 5 is 40 nm; the metal sodiumThe rice ring 3 and the metal film layer 2 are made of gold;
the plasmon absorber can achieve absorption wavelength range of 300nm to 1600nm, and the average absorption efficiency can reach 94%.
Example four
The difference from the first embodiment is that the metal nanoring 3 and the metal thin film layer 2 are made of silver.
Five metal nanorings 3 are arranged, the distribution condition is the same as that of the first embodiment, and the inner diameter of the five metal nanorings 3 can be specifically d1＝400nm，d2＝360nm，d3＝280nm，d4＝200nm，d5120nm, the wall thickness of the metal nanoring 3 is 20nm, the axial height of the metal nanoring 3 is 6 μm, the side length of the substrate layer 1 and the metal thin film layer 2 is 900nm, the thickness of the metal thin film layer 2 is 200nm, and the thickness of the protective layer 5 is 40 nm; the substrate layer 1 is made of alumina, and the dielectric layer 4 is made of alumina;
the plasmon absorber can realize the absorption wavelength range of 300nm to 1300nm, and the average absorption efficiency can reach 97%.
EXAMPLE five
The difference from the first embodiment is that the metal nanoring 3 and the metal thin film layer 2 are made of aluminum;
five metal nanorings 3 are arranged, the distribution condition is the same as that of the first embodiment, and the inner diameter of the five metal nanorings 3 can be specifically d1＝400nm，d2＝360nm，d3＝280nm，d4＝200nm，d5120nm, the wall thickness of the metal nanoring 3 is 20nm, the axial height of the metal nanoring 3 is 6 μm, the side length of the substrate layer 1 and the metal thin film layer 2 is 900nm, the thickness of the metal thin film layer 2 is 200nm, and the thickness of the protective layer 5 is 40 nm; the substrate layer 1 is made of alumina, and the dielectric layer 4 is made of alumina;
the plasmon absorber can realize the absorption wavelength range of 300nm to 1300nm, and the average absorption efficiency can reach 92%.
The preparation method of the plasmon absorber mainly comprises the following steps:
A. as shown in fig. 3(a), high temperature resistant metal or dielectric such as aluminum oxide, hafnium oxide or tungsten is selected as a substrate layer 1, and a metal thin film layer 2 is grown on the substrate layer 1, which may be formed by electron beam evaporation or magnetron sputtering;
B. depositing a silicon layer with the thickness of 6 microns on the metal thin film layer 2, forming the silicon layer by adopting an electron beam evaporation or magnetron sputtering method, spin-coating a layer of photoresist on the upper surface of the silicon layer, obtaining a circular photoresist pattern by adopting electron beam lithography and exposure processes, then etching the silicon layer by adopting a metal auxiliary chemical method controlled in the vertical direction until the etching depth reaches the surface of the metal thin film layer 2, and etching a silicon column 6 matched with the inner diameter of a preset metal nano ring 3, as shown in fig. 3 (b);
C. growing a metal nano ring 3 with a preset thickness on the circumferential surface of the silicon column 6;
specifically, as shown in fig. 3(c), a silicon dioxide layer 7 is deposited on the surface of the silicon pillar 6, the thickness of the silicon dioxide layer 7 is the same as the preset thickness of the metal nanoring 3, and the thickness of the silicon dioxide layer 7 is 20 nm;
as shown in fig. 3(d), a polymer layer 8 is then spin-coated on the metal thin film layer 2, wherein the polymer layer 8 wraps the silica layer 7 in the circumferential direction;
as shown in fig. 3(e), the silicon dioxide layer 7 is then removed by etching using a dry etching process or a wet etching process, the specific etching methods of silicon dioxide and silicon are different, so that only the silicon dioxide layer 7 is removed and the silicon pillars 6 are not removed, and an annular gap is formed between the polymer layer 8 and the silicon pillars 6;
as shown in fig. 3(f), a metal nanoring 3 is formed in the annular gap by electrochemical growth;
as shown in fig. 3(g), the polymer layer 8 was removed using dichloromethane;
D. as shown in fig. 3(h), a dielectric layer 4 is deposited on the periphery of the metal nanoring 3, and is formed by electron beam evaporation or magnetron sputtering;
E. as shown in fig. 3(i) and 3(j), the silicon pillar 6 is removed by etching using a dry etching process or a wet etching process, and the dielectric layer 4 is deposited in the inner region of the metal nanoring 3 by using an electron beam evaporation or magnetron sputtering method;
F. as shown in fig. 3(k), a protective layer 5 is deposited on the top of the metal nanoring 3 and the dielectric layer 4, and is formed by electron beam evaporation, magnetron sputtering or atomic layer deposition;
G. and packaging to obtain a finished product of the plasmon absorber.
The above is only a preferred embodiment of the present invention, and it should be noted that the above preferred embodiment should not be considered as limiting the present invention, and the protection scope of the present invention should be subject to the scope defined by the claims. It will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the spirit and scope of the invention, and these modifications and adaptations should be considered within the scope of the invention.
Claims (9)
1. The utility model provides a plasmon absorber, characterized in that, includes periodic unit, periodic unit is stratum basale (1), metal thin film layer (2) and metal nanoring (3) from bottom to top in proper order, the axial of metal nanoring (3) perpendicular to metal thin film layer (2) surface, and the circumference periphery of metal nanoring (3) wrap up by dielectric layer (4), and the inner region of metal nanoring (3) fill by dielectric layer (4), it has protective layer (5) to cover at the top of metal nanoring (3) and dielectric layer (4), metal nanoring (3) be provided with five, one of them sets up in the central zone department of metal thin film layer (2), and other four are in its circumference encirclement distribution.
2. The plasmon absorber of claim 1, wherein a plurality of metal nanorings (3) are spaced on the metal thin film layer (2).
3. The plasmonic absorber of claim 2, wherein at least one of the inner diameters of the number of metal nanorings (3) is the same as the others or different from each other.
4. The plasmonic absorber of claim 2, wherein the axial heights of the number of metal nanorings (3) are the same.
5. The plasmon absorber of any of claims 1 to 4, wherein the dielectric layer (4) and the protective layer (5) are respectively made of at least one of aluminum oxide and hafnium oxide, and the materials of the dielectric layer (4) and the protective layer (5) are the same or different.
6. The plasmon absorber of any of claims 1 to 4, wherein the metal nanoring (3) and the metal thin film layer (2) are respectively made of one of gold, silver and aluminum, and the metal nanoring (3) and the metal thin film layer (2) are made of the same or different materials.
7. The plasmon absorber of any of claims 1 to 4, wherein the substrate layer (1) and the metal thin film layer (2) are square and laminated together, the substrate layer (1) and the metal thin film layer (2) have the same size, the side length of the substrate layer (1) and the metal thin film layer (2) is 900nm, the thickness of the metal thin film layer (2) is greater than or equal to 100nm, the axial height of the metal nanoring (3) is greater than or equal to 6 μm, the inner diameter of the metal nanoring (3) is 200-400 nm, the wall thickness of the metal nanoring (3) is 20nm, and the thickness of the protective layer (5) is less than 100 nm.
8. A method of making a plasmonic absorber according to any of claims 1 to 7, comprising the steps of:
A. growing a metal film layer (2) on the substrate layer (1);
B. depositing a silicon layer on the metal film layer (2), etching the silicon layer to the depth of the surface of the metal film layer (2), and etching a silicon column (6) matched with the inner diameter of the preset metal nanoring (3);
C. growing a metal nano ring (3) with a preset thickness on the circumferential surface of the silicon column (6);
D. depositing a dielectric layer (4) at the periphery of the metal nanoring (3);
E. etching to remove the silicon column (6), and depositing a dielectric layer (4) in the inner area of the metal nano ring (3);
F. covering and depositing a protective layer (5) on the tops of the metal nanoring (3) and the dielectric layer (4);
G. and packaging to obtain a finished product of the plasmon absorber.
9. The preparation method according to claim 8, wherein in the step C, a silicon dioxide layer (7) is deposited on the surface of the silicon pillar (6), and the thickness of the silicon dioxide layer (7) is the same as the preset thickness of the metal nanoring (3); then, a polymer layer (8) is coated on the metal film layer (2) in a spinning mode, and the polymer layer (8) wraps the circumferential direction of the silicon dioxide layer (7); then etching to remove the silicon dioxide layer (7), and forming an annular gap between the polymer layer (8) and the silicon column (6); growing and forming a metal nano ring (3) in the annular gap; the polymer layer (8) was removed using dichloromethane.
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