CN106872052B - Absorption film system structure of wide-spectrum pyroelectric detector and preparation method thereof - Google Patents

Absorption film system structure of wide-spectrum pyroelectric detector and preparation method thereof Download PDF

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CN106872052B
CN106872052B CN201710087387.2A CN201710087387A CN106872052B CN 106872052 B CN106872052 B CN 106872052B CN 201710087387 A CN201710087387 A CN 201710087387A CN 106872052 B CN106872052 B CN 106872052B
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metal film
film
porosity
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layer metal
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CN106872052A (en
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于贺
太惠玲
黎威志
杜晓松
刘子骥
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University of Electronic Science and Technology of China
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    • GPHYSICS
    • G01MEASURING; TESTING
    • G01JMEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRARED, VISIBLE OR ULTRAVIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY
    • G01J5/00Radiation pyrometry, e.g. infrared or optical thermometry
    • G01J5/10Radiation pyrometry, e.g. infrared or optical thermometry using electric radiation detectors
    • G01J5/34Radiation pyrometry, e.g. infrared or optical thermometry using electric radiation detectors using capacitors, e.g. pyroelectric capacitors
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14Metallic material, boron or silicon
    • C23C14/18Metallic material, boron or silicon on other inorganic substrates
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14Metallic material, boron or silicon
    • C23C14/18Metallic material, boron or silicon on other inorganic substrates
    • C23C14/185Metallic material, boron or silicon on other inorganic substrates by cathodic sputtering
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/24Vacuum evaporation
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34Sputtering
    • C23C14/35Sputtering by application of a magnetic field, e.g. magnetron sputtering

Abstract

The invention discloses an absorption film system structure of a wide-spectrum pyroelectric detector and a preparation method thereof, belongs to the field of infrared absorption layers of pyroelectric detectors, and solves the problems that in the prior art, a porous material and a substrate have poor adhesion and can only be used as an absorption layer independently. The film system structure is prepared on the top layer of the pyroelectric detector sensitive unit and comprises three layers of metal films, wherein the bottom metal film has low porosity and high density and can keep good adhesiveness with a substrate, the middle metal film is used as a transition layer, the porosity is improved, the density is reduced, and the top metal film is a loose layer and can effectively enhance the infrared absorption rate. The prepared metal absorption layer can be used as an absorption layer and an upper electrode of a detector at the same time, so that the preparation process is greatly simplified, the cost is saved, the process compatibility is improved, and powerful support is provided for the development of a high-performance pyroelectric detector.

Description

Absorption film system structure of wide-spectrum pyroelectric detector and preparation method thereof
Technical Field
the invention relates to the technical field of infrared absorption layers of pyroelectric detectors, in particular to an absorption film system structure of a wide-spectrum pyroelectric detector and a preparation method thereof.
background
The pyroelectric detector is a detection device of infrared radiation and is prepared by utilizing the characteristic that spontaneous polarization of a pyroelectric body changes along with temperature. Compared with other detectors, the thermal detector not only keeps the advantages of the thermal detector working in the room temperature wave band, but also can bear large radiation power, has higher detection rate in a wide temperature and frequency range, has smaller time constant and the like. The pyroelectric detector is widely applied to the fields of national defense, industry, medicine, scientific research and the like, such as intrusion alarm, safety monitoring, fire alarm, industrial production monitoring, auxiliary driving of aircraft and vehicles, medical diagnosis and the like.
The detection rate is a main index for measuring the performance of the pyroelectric detector, and the increase of the absorption coefficient is a direct way for improving the detection rate of the detector. Researches find that the pyroelectric material has high reflectivity in a far infrared band. In particular, the reflectance is as high as 85% in the 11-20 μm band (V.Norkus, etc. "A256 pixel piezoelectric array with new coating", Proc.of SPI E, vol.8012, pp.80123V, 2011). Increasing the thickness of the sensing element can reduce the reflectivity to some extent, but can affect the material pyroelectric coefficient. In order to effectively absorb the heat radiation and further improve the response rate of the device, an absorption layer or an antireflection layer is required to cover the surface of the sensitive element. The infrared absorbing layer is required to have a low reflectance and good adhesion to the underlying material.
Currently, commonly used infrared radiation absorbing layer materials mainly include: ultrathin metal films, organic black bodies, porous black metals, and the like. Of these materials, ultra-thin metal films also have low reflectivity and high thermal conductivity, but low theoretical limits for absorption. The black resin has high infrared absorption rate, but poor compatibility with device processes, and high thermal resistance, and may block heat from propagating to the sensitive film. The porous black gold has low reflectivity and high wide-spectrum absorption characteristic, but the porous black gold has weak adhesion and is easy to break. In addition, some documents report that a reflection reducing layer (a. finn, etc., "microstuturedsurccess LiTaO 3-basedpyroelectroconduction front detectors", ieee sensssors journal, vol.11, pp.2204,2011) with a graded refractive index is etched on the surface of the lithium tantalate (LiTaO3) as a sensitive material, and based on the structure of the reflection reducing layer, the absorption rate is obviously improved, but the method changes the surface morphology of the sensitive material, and the response characteristics of the device are influenced to a certain extent.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: how to provide a membrane system structure that realizes wide spectrum infrared absorption, this structure can effectively strengthen the infrared radiation absorptivity, provides powerful support for the development of high performance pyroelectric detector.
the technical scheme of the invention is as follows: the absorption film system structure of the wide-spectrum pyroelectric detector is positioned on the top layer of a sensitive unit of the pyroelectric detector and comprises a bottom layer metal film, a middle layer metal film and a top layer metal film, wherein the porosity of the bottom layer metal film, the porosity of the middle layer metal film and the porosity of the top layer metal film are sequentially increased.
further, the material of the bottom layer metal film, the middle layer metal film and the top layer metal film is black gold, bismuth, aluminum, titanium, nickel, chromium or an alloy of the above metals.
Furthermore, the infrared absorption rate of the film system structure in the wave band of 1-20 μm is better than 60%.
Furthermore, the porosity of the bottom metal film is 15-20%, the porosity of the middle metal film is 30-35%, and the porosity of the top metal film is 45-50%.
Furthermore, the thickness of the bottom layer metal film is 8nm-12nm, the thickness of the middle layer metal film is 10nm-15nm, and the thickness of the top layer metal film is 10nm-15 nm.
A preparation method of an absorption film system structure of a wide-spectrum pyroelectric detector comprises the following steps:
(1) preparing a densified bottom metal film on the top layer of the pyroelectric sensitive unit by adopting a magnetron sputtering method;
(2) Preparing a loose middle layer metal film on the densified bottom layer metal film obtained in the step (1) by adopting a magnetron sputtering method;
(3) And (3) preparing a loose top metal film on the intermediate metal film obtained in the step (2) by adopting an evaporation method or a magnetron sputtering method.
Further, the specific steps of the step (1) are as follows: the bottom layer metal film is prepared by adopting a magnetron sputtering method, bismuth, aluminum, titanium, nickel, chromium or alloys of the bismuth, the aluminum, the titanium, the nickel and the chromium are used as materials, the working air pressure is controlled to be 4Pa-6Pa, the sputtering current is controlled to be 0.4A-0.6A, meanwhile, the porosity of the film is controlled to be 15-20%, and the thickness of the film is controlled to be 8nm-12 nm.
Further, the specific steps of the step (2) are as follows: the intermediate layer metal film is prepared by adopting a magnetron sputtering method, bismuth, aluminum, titanium, nickel, chromium or alloys of the bismuth, the aluminum, the titanium, the nickel and the chromium are used as materials, the working air pressure is controlled to be 8Pa-10Pa, the sputtering current range is 0.2A-0.3A, meanwhile, the porosity range of the film is controlled to be 30-35%, and the thickness range of the film is 10nm-15 nm.
further, the specific steps of step (3) are: the top metal film is prepared by adopting a magnetron sputtering method, bismuth, aluminum, titanium, nickel, chromium or alloys of the bismuth, the aluminum, the titanium, the nickel and the chromium are used as materials, the process air pressure is 12Pa-14Pa, the sputtering current is 0.1A, meanwhile, the porosity of the film is controlled within the range of 45-50%, and the thickness of the film is controlled within the range of 10nm-15 nm.
Further, the specific steps of step (3) are: preparing a top metal film by an evaporation method, taking black gold, bismuth, aluminum, titanium, nickel, chromium or alloy thereof as a material, and adjusting N2The air pressure is 20Pa, the film thickness is controlled to be less than 20nm, and loose porous metal layers are formed.
Compared with the prior art, the invention has the following beneficial effects:
The bottom layer metal film of the prepared film system structure has high density, keeps good adhesiveness with the sensitive layer, and the top layer metal film is loose and porous, so that the infrared absorption rate is effectively enhanced. The prepared metal absorption layer can be used as an absorption layer and an upper electrode of a detector at the same time, so that the preparation process is greatly simplified, the cost is saved, the process compatibility is improved, and powerful support is provided for the development of a high-performance pyroelectric detector.
Drawings
FIG. 1 is a schematic diagram of a simple process for preparing a membrane system structure according to the present invention;
FIG. 2 is a schematic structural diagram of a membrane system structure prepared according to the present invention;
The reference numbers in the figure are 1, a pyroelectric sensitive unit, 2, a bottom metal film, 3, a middle metal film, 4, a top metal film, 5 and a lower electrode.
Detailed Description
The absorption film system structure of the wide-spectrum pyroelectric detector is positioned on the top layer of a sensitive unit of the pyroelectric detector and comprises a bottom layer metal film, a middle layer metal film and a top layer metal film, wherein the porosity of the bottom layer metal film, the porosity of the middle layer metal film and the porosity of the top layer metal film are gradually increased. The preparation process is shown in figure 1.
The bottom layer metal film prepared on the substrate is required to be very high in density and very low in porosity, and good adhesion between the absorption layer and the substrate is achieved. The metal material can be bismuth, aluminum, titanium, nickel, chromium or alloy films thereof prepared by adopting magnetron sputtering equipment. The density of the material is adjusted through the air pressure and the sputtering current, the atomic scattering effect is weakened and the kinetic energy of the sputtered atoms is improved through the reduction of the air pressure and the improvement of the current, and the densification of the microstructure of the film is facilitated. Therefore, when the metal film of the bottom layer is prepared, the working pressure needs to be controlled to be 4Pa-6Pa, and the sputtering current needs to be 0.4A-0.6A. The porosity range is controlled to be 15-20%, the film thickness range is controlled to be 8-12 nm, and the influence on the heat capacity of the detector is reduced.
The intermediate layer metal film is a transition layer, and the porosity and the looseness can be properly improved. The metal material of the layer can be bismuth, aluminum, titanium, nickel, chromium or alloy films thereof prepared by adopting magnetron sputtering equipment. By properly increasing the air pressure and reducing the sputtering current, the densification of the film structure is reduced, and the porosity is controlled within the range of 30-35%. The working pressure needs to be controlled within 8Pa-10Pa, and the sputtering current range is 0.2A-0.3A. Meanwhile, the film thickness range is controlled to be 10nm-15nm, and the influence on the heat capacity of the detector is reduced.
The top metal film is required to be loose and porous, so that the infrared absorption rate is effectively enhanced. The metal material can be bismuth, aluminum, titanium, nickel, chromium or alloy films thereof prepared by adopting magnetron sputtering equipment. By adopting Ar plasma sputtering in a high-pressure environment and using low sputtering current, the atomic scattering effect is effectively enhanced and the atomic kinetic energy is reduced, a loose porous metal layer structure similar to black gold is formed, and the wide-spectrum absorption of infrared radiation is realized. The porosity range is controlled to be 45-50%, the film thickness range is controlled to be 10-15 nm, and the influence on the heat capacity of the detector is reduced. The top layer metal absorption layer can also beBlack gold, bismuth, aluminum, titanium, or alloy films, such as NiCr, are prepared by evaporation. By N at high gas pressure2The metal film prepared in the environment is looser than the metal film prepared by the sputtering method, and the infrared absorption rate can be further improved.
The invention is further illustrated by the following examples:
Example 1
As shown in FIG. 2, an absorption film structure of a wide-spectrum pyroelectric detector comprises three metal films with gradually increasing porosity, and the structure is formed by LiTaO3The crystal sheet is spread out as the top layer of the pyroelectric sensitive unit 1.
LiTaO3the early preparation process of the crystal slice comprises the following steps: in LiTaO3Preparing a lower electrode 5 on the wafer; by grinding and polishing LiTaO3The wafer is thinned to form the pyroelectric sensitive unit 1.
Cleaning LiTaO3And a crystal sheet is patterned on the upper surface by photoetching. A bottom nickel-chromium alloy film is prepared by adopting a magnetron sputtering technology to serve as a bottom metal film 2, the process air pressure is adjusted to be 4Pa, the sputtering current is adjusted to be 0.6A, a compact nickel-chromium metal layer is obtained, the porosity range is controlled to be 15%, and the thickness range is controlled to be 10 nm.
The intermediate layer metal film 3 is prepared by adopting a magnetron sputtering technology, is a nickel-chromium alloy film, the process air pressure is adjusted to be 8Pa, the sputtering current is 0.4A, the porosity range is controlled to be 30 percent, and the thickness range is controlled to be 15 nm.
the top metal film 4 is prepared by adopting a magnetron sputtering technology, is a nickel-chromium alloy film, the process air pressure is adjusted to be 12Pa, the sputtering current is adjusted to be 0.3A, the porosity range is controlled to be 50 percent, the thickness range is controlled to be 15nm, a very loose porous metal layer is obtained, and then floating and cleaning are carried out.
And obtaining the infrared absorption layer for the wide-spectrum pyroelectric detector, and sequentially forming a loose porous nickel-chromium metal layer, a nickel-chromium metal transition layer and a compact nickel-chromium metal layer from top to bottom according to the incident radiation sequence.
example 2
As shown in figure 2, a wide spectrum pyroelectric detector absorption film systemA structure comprising three metal films with gradually increasing porosity, the structure being formed by LiTaO3The crystal sheet is spread out as the top layer of the pyroelectric sensitive unit 1.
LiTaO3The early preparation process of the crystal slice comprises the following steps: preparing a lower electrode 5 on the lithium tantalate wafer; and thinning the lithium tantalate wafer by grinding and polishing to form the pyroelectric sensitive unit 1.
Cleaning LiTaO3And a crystal sheet is patterned on the upper surface by photoetching. The bottom layer metal film 2 is prepared by adopting a magnetron sputtering technology, is a bismuth metal film, the process air pressure is adjusted to be 5Pa, the sputtering current is adjusted to be 0.7A, and the compact bismuth metal layer is obtained, the porosity range is controlled to be 20%, and the thickness range is controlled to be 10 nm.
The intermediate layer metal film 3 is prepared by adopting a magnetron sputtering technology, is a bismuth metal film, and has the process air pressure of 7Pa, the sputtering current of 0.5A, the porosity range of 30 percent and the thickness range of 15 nm.
Preparing a top metal film 4 which is a bismuth metal film by an evaporation method, and adjusting N2The air pressure is 20Pa, the porosity range is controlled at 45%, the film thickness is controlled to be lower than 20nm, a loose porous bismuth metal layer is formed, and then floating glue is cleaned.
the infrared absorption layer for the wide-spectrum pyroelectric detector is obtained, and the top loose porous bismuth metal film, the middle layer bismuth metal film and the bottom compact bismuth metal film are sequentially arranged from top to bottom according to the incident radiation sequence.

Claims (2)

1. An absorption film system structure of a wide-spectrum pyroelectric detector is positioned on the top layer of a sensitive unit of the pyroelectric detector and is characterized by comprising a bottom layer metal film, a middle layer metal film and a top layer metal film, wherein the porosity of the bottom layer metal film, the porosity of the middle layer metal film and the porosity of the top layer metal film are sequentially increased;
The preparation method comprises the following steps:
(1) The top layer of the pyroelectric sensitive unit is provided with a densified bottom metal film by adopting a magnetron sputtering method, and the method specifically comprises the following steps: preparing a bottom layer metal film by adopting a magnetron sputtering method, taking bismuth, aluminum, titanium, nickel, chromium or alloys thereof as materials, controlling the working air pressure to be 4Pa-6Pa, the sputtering current to be 0.4A-0.6A, and simultaneously controlling the porosity of the film to be 15-20% and the thickness of the film to be 8nm-12 nm;
(2) Preparing a loose middle layer metal film on the densified bottom layer metal film obtained in the step (1) by adopting a magnetron sputtering method, which specifically comprises the following steps: preparing an intermediate layer metal film by adopting a magnetron sputtering method, taking bismuth, aluminum, titanium, nickel, chromium or alloys thereof as materials, controlling the working air pressure to be 8Pa-10Pa, controlling the sputtering current range to be 0.2A-0.3A, and simultaneously controlling the porosity range of the film to be 30-35% and the thickness range of the film to be 10nm-15 nm;
(3) Preparing a loose top metal film on the intermediate metal film obtained in the step (2) by adopting an evaporation method or a magnetron sputtering method, and specifically: preparing a top metal film by adopting a magnetron sputtering method, taking bismuth, aluminum, titanium, nickel, chromium or alloys thereof as materials, controlling the process air pressure to be 12Pa-14Pa, the sputtering current to be 0.1A, and simultaneously controlling the porosity of the film to be 45-50% and the thickness of the film to be 10nm-15 nm; or preparing the top metal film by an evaporation method, taking black gold, bismuth, aluminum, titanium, nickel, chromium or alloy thereof as a material, and adjusting N2the air pressure is 20Pa, the film thickness is controlled to be lower than 20nm, a loose porous metal layer is formed, and the porosity is 45-50%.
2. The absorption film structure of the wide-spectrum pyroelectric detector as claimed in claim 1, wherein the absorption rate of the film structure in the infrared band of 1 μm-20 μm is better than 60%.
CN201710087387.2A 2017-02-17 2017-02-17 Absorption film system structure of wide-spectrum pyroelectric detector and preparation method thereof Active CN106872052B (en)

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CN101043065A (en) * 2006-03-21 2007-09-26 同济大学 Pyroelectric infrared detector and used detecting member
CN102529211A (en) * 2011-12-22 2012-07-04 电子科技大学 Film system structure for enhancing Terahertz radiation absorption rate and preparation method thereof
CN103035981A (en) * 2012-12-11 2013-04-10 电子科技大学 Ultrathin metal membrane terahertz absorbed layer and preparation method thereof
JP5760297B2 (en) * 2009-03-06 2015-08-05 日本電気株式会社 Thermal infrared sensor and method for manufacturing thermal infrared sensor

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Publication number Priority date Publication date Assignee Title
CN101043065A (en) * 2006-03-21 2007-09-26 同济大学 Pyroelectric infrared detector and used detecting member
JP5760297B2 (en) * 2009-03-06 2015-08-05 日本電気株式会社 Thermal infrared sensor and method for manufacturing thermal infrared sensor
CN102529211A (en) * 2011-12-22 2012-07-04 电子科技大学 Film system structure for enhancing Terahertz radiation absorption rate and preparation method thereof
CN103035981A (en) * 2012-12-11 2013-04-10 电子科技大学 Ultrathin metal membrane terahertz absorbed layer and preparation method thereof

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