CN113188669A - Infrared absorption composite membrane structure and carbon dioxide pyroelectric infrared detector - Google Patents
Infrared absorption composite membrane structure and carbon dioxide pyroelectric infrared detector Download PDFInfo
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- 238000010521 absorption reaction Methods 0.000 title claims abstract description 77
- 239000002131 composite material Substances 0.000 title claims abstract description 39
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims description 50
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims description 38
- 239000001569 carbon dioxide Substances 0.000 title claims description 25
- 239000012528 membrane Substances 0.000 title description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 22
- 238000002310 reflectometry Methods 0.000 claims abstract description 21
- 229910052581 Si3N4 Inorganic materials 0.000 claims abstract description 18
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 17
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000010408 film Substances 0.000 claims description 52
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 16
- 238000007747 plating Methods 0.000 claims description 15
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 13
- 229910052737 gold Inorganic materials 0.000 claims description 13
- 239000010931 gold Substances 0.000 claims description 13
- 239000013078 crystal Substances 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- 239000010409 thin film Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 19
- 230000008569 process Effects 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 239000000853 adhesive Substances 0.000 abstract description 4
- 230000001070 adhesive effect Effects 0.000 abstract description 4
- 229910052814 silicon oxide Inorganic materials 0.000 abstract description 3
- RJCRUVXAWQRZKQ-UHFFFAOYSA-N oxosilicon;silicon Chemical compound [Si].[Si]=O RJCRUVXAWQRZKQ-UHFFFAOYSA-N 0.000 abstract description 2
- 239000007789 gas Substances 0.000 description 16
- 230000004044 response Effects 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 5
- 238000001514 detection method Methods 0.000 description 4
- WSMQKESQZFQMFW-UHFFFAOYSA-N 5-methyl-pyrazole-3-carboxylic acid Chemical compound CC1=CC(C(O)=O)=NN1 WSMQKESQZFQMFW-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 229910052681 coesite Inorganic materials 0.000 description 3
- 229910052906 cristobalite Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000012544 monitoring process Methods 0.000 description 3
- 229910052682 stishovite Inorganic materials 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 229910052905 tridymite Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005566 electron beam evaporation Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000002440 industrial waste Substances 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910000623 nickel–chromium alloy Inorganic materials 0.000 description 2
- 238000001020 plasma etching Methods 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 238000000985 reflectance spectrum Methods 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 244000144972 livestock Species 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01J—MEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRARED, VISIBLE OR ULTRAVIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY
- G01J5/00—Radiation pyrometry, e.g. infrared or optical thermometry
- G01J5/02—Constructional details
- G01J5/08—Optical arrangements
- G01J5/0803—Arrangements for time-dependent attenuation of radiation signals
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Abstract
The invention relates to a method for CO2Pyroelectric infrared detector's infrared absorption complex film structure includes from last to down in proper order: the infrared absorption film comprises a first silicon dioxide layer, a silicon nitride layer and a second silicon dioxide layer, wherein the silicon nitride layer is used for infrared absorption. The invention also provides corresponding CO2Pyroelectric infrared detector. The infrared absorption composite film structure adopts the silicon oxide-silicon nitride-silicon oxide multilayer dielectric film as the infrared absorption layer, mainly aiming at CO2The high-efficiency infrared absorption of gas is designed, the thickness is controlled within 2um, the reflectivity of less than 5 percent can be obtained, the highest absorptivity can reach 99.94 percent, the absorption efficiency is high, the manufacturing process is simple, the process compatibility is good, the adhesive force is good, the manufacturing cost is low, and the mass production is easy.
Description
Technical Field
The invention relates to the field of pyroelectric infrared detectors, in particular to an infrared absorption composite film structure for a carbon dioxide pyroelectric infrared detector and the carbon dioxide pyroelectric infrared detector.
Background
Along with the improvement of living standard of people and the continuous development of industrial technologyExhibition of carbon dioxide (CO) in the environment2) Monitoring of gas concentrations is becoming increasingly important because of CO2Gases are closely related to the health and quality of life of people. In recent years, with the continuous emergence of technologies and instruments for measuring gas concentration, CO2The application fields of the gas sensor are also wider and wider, such as industrial waste gas control, monitoring the concentration of carbon dioxide in a chimney when industrial waste gas is discharged, strictly controlling the content of the concentration of the carbon dioxide in the waste gas and reducing the greenhouse effect caused by the increase of carbon emission; monitoring greenhouse cultivation, detecting and controlling the concentration of carbon dioxide, so that crops can have high quality and high yield, and a good cultivation environment is provided for the growth and development of livestock; indoor air detects, and harmful gas's sensor in the detection air can know indoor air quality in real time, builds good living environment.
CO based on pyroelectric infrared absorption2The gas detection is designed by utilizing the characteristic that spontaneous polarization in the pyroelectric body changes along with temperature, and has the advantages of quick response time, good gas selectivity, stable and reliable device and the like. The sensor has high sensitivity, small generated interference signal, high signal-to-noise ratio and compact structure. The performance of the pyroelectric infrared detector is mainly characterized by response speed and sensitivity, and the detector is required to be in CO to obtain good sensitivity2The absorption rate of the absorption band is high (i.e. the reflectivity is low), and the response speed is fast, so that the heat capacity of the absorption layer is required to be small, and the interference is avoided.
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. Therefore, the design of the absorption layer of the pyroelectric infrared detector is receiving more and more attention. The current common infrared radiation absorbing layer materials include gold black, organic black bodies, ultrathin metal films and the like. The materials respectively have the problems of poor device process compatibility, poor adhesive force, low absorption efficiency and the like, and CO is generated2The gas only absorbs infrared light of a specific wavelength, which requires it to be in CO2The absorption band has higher absorptivity, and the above materials can not meet the requirement of CO2Gas detection performance.
Chinese patent CN 105789428B, 1The pyroelectric infrared detector with the composite absorption layer adopts the parallel plane cavity to enable light rays to oscillate back and forth in the periodic lens waveguide without overflowing out of the waveguide, so that the frequency of the incident light passing through the absorption layer is increased, the absorption coefficient of the absorption layer is indirectly improved, and the stable lens waveguide is formed. The infrared absorption layer is of a composite structure and sequentially comprises a titanium metal layer, a dielectric layer, a nickel-chromium alloy layer, a lithium tantalate crystal layer and a reflection layer from the top layer to the bottom layer, wherein the dielectric layer is made of silicon nitride, the absorption efficiency is improved mainly through multiple resonant reflections of the titanium metal layer and the reflection layer, the dielectric layer is not mentioned as a main infrared absorption effect, and more of the dielectric layer between the titanium metal layer and the nickel-chromium alloy layer plays the roles of insulation and light transmission. In the pyroelectric detector, the composite absorption layer is compared with a single metal absorption layer film as a heat sensitive layer, so that the pyroelectric detector has better surface compactness, high absorption coefficient and smaller heat loss, can obtain high-performance thermal response, and is favorable for preparing a high-precision infrared detector based on pyroelectric crystals. However, the multiple resonance absorption is mainly performed for infrared light of a specific wavelength band, and for CO2The superiority of the infrared absorption is not clearly indicated.
Study of absorption layer of Yangjianming, Wuxiaqing, Yaozhi pyroelectric Infrared Detector [ J]Infrared technology, 2002, Vol24 (4): 53-54, 58, in this prior art, studies were made mainly on the preparation of gold black absorber layers in nitrogen (N)2) Gold with a purity of 99.99% is evaporated in an atmosphere to form a porous structure consisting of fine crystal particles. This technique is accompanied by N2The air pressure is increased, the infrared reflectivity of the prepared gold black layer is reduced, the absorptivity is increased, and the best N is beneficial to the response of the detector to infrared rays2The air pressure is between 100 and 200 Pa. However, this technique is to control N2The gold-black absorbing layer with the reflectivity less than 5% can be obtained only when the pressure reaches 150Pa, the gold-black layer is not uniform on the surface of the sample due to overhigh air pressure, and the gold-black plating layer is generally poor in adhesive force and poor in process compatibility.
Disclosure of Invention
The main purpose of the present invention is to solve the above problems, and to provide a method forCO2Infrared absorption composite film structure of pyroelectric infrared detector and CO2Pyroelectric infrared detector.
The invention provides a method for preparing CO2Pyroelectric infrared detector's infrared absorption complex film structure, infrared absorption complex film structure from last to including down in proper order: the composite film comprises a first silicon dioxide layer, a silicon nitride layer and a second silicon dioxide layer, wherein the silicon nitride layer is used for infrared absorption, and the composite film is designed for an antireflection film layer.
Preferably, the thickness of the first silicon dioxide layer is 20-80 nm, the thickness of the silicon nitride layer is 1020-1200 nm, the thickness of the second silicon dioxide layer is 600-640 nm, and the reflectivity of the anti-reflection film layer is less than 5%.
Preferably, the thickness of the first silicon dioxide layer is 50nm, the thickness of the silicon nitride layer is 1110nm, and the thickness of the second silicon dioxide layer is 620nm, and the first silicon dioxide layer is an anti-reflection film layer with the lowest reflectivity.
The invention also provides CO2The pyroelectric infrared detector comprises the infrared absorption composite film structure, an upper electrode, a pyroelectric thin film crystal layer and a lower electrode in sequence from top to bottom, wherein the infrared absorption composite film structure comprises one of claims 1 to 3.
Preferably, the upper electrode comprises an upper electrode gold-plating layer and an upper electrode nickel-plating bonding layer from top to bottom; the lower electrode comprises a lower electrode nickel plating bonding layer and a lower electrode gold plating layer from top to bottom.
The infrared absorption composite film structure adopts the silicon oxide-silicon nitride-silicon oxide multilayer dielectric film as the infrared absorption layer, mainly aiming at CO2The high-efficiency infrared absorption of gas is designed, the thickness is controlled within 2um, the reflectivity of less than 5 percent can be obtained, the highest absorptivity can reach 99.94 percent, the absorption efficiency is high, the manufacturing process is simple, the process compatibility is good, the adhesive force is good, the manufacturing cost is low, and the mass production is easy.
Drawings
FIG. 1 is a CO of the present invention2The structure of the pyroelectric infrared detector is schematic.
FIG. 2 is a reflectance spectrum of the infrared absorbing composite film structure of example 1.
FIG. 3 is a reflectance spectrum of an infrared absorbing composite film structure of example 2.
FIGS. 4-5 are reflection spectra of the infrared absorbing composite film structure of example 3.
FIG. 6 shows CO2An infrared spectrum.
Detailed Description
The scheme of the invention will be explained with reference to the examples. It will be appreciated by those skilled in the art that the following examples are illustrative of the invention only and should not be taken as limiting the scope of the invention.
As shown in FIG. 1, the CO provided by the present invention2The pyroelectric infrared detector comprises an infrared absorption composite film structure, an upper electrode, a pyroelectric film crystal layer 6 and a lower electrode from top to bottom in sequence.
The infrared absorption composite film structure of the invention comprises from top to bottom: the composite film comprises a first silicon dioxide layer 1, a silicon nitride layer 2 and a second silicon dioxide layer 3, wherein the silicon nitride layer is used for infrared absorption, and meanwhile, the composite film is designed as an anti-reflection film layer. The infrared absorption composite film is prepared from SiO2-Si3N4-SiO2Multilayer dielectric film system structure for CO2High absorption rate at characteristic wavelength of CO2The absorption peak has very low reflectivity, and CO of the pyroelectric device is realized2And (5) infrared detection.
The upper electrode comprises an upper electrode gold-plating layer 4 and an upper electrode nickel-plating bonding layer 5 from top to bottom; the lower electrode comprises a lower electrode nickel plating bonding layer 7 and a lower electrode gold plating layer 8 from top to bottom.
The infrared absorption composite film structure can be prepared by adopting a Plasma Enhanced Chemical Vapor Deposition (PECVD) method, the PECVD is common equipment for semiconductors, the processes for growing silicon nitride and silicon oxide are mature at present, and the thickness, the uniformity and the growth rate are easy to regulate and control.
The invention provides the following specific processing steps of the pyroelectric detector:
the upper electrode can be deposited on the first surface of the grinding surface lithium tantalate crystal layer by any suitable method, and the nickel film and the gold film are respectively evaporated by a vacuum electron beam evaporation method, wherein the thickness of the nickel is 10-30 nm, and the thickness of the gold is 50-100 nm. The nickel plated film acts primarily as an adhesion layer for gold plating.
The lower electrode may be deposited on the second surface of the polished surface lithium tantalate crystal layer by any suitable method, and the vacuum electron beam evaporation method is used in the present invention. The thickness of the nickel and gold film is the same as that of the upper electrode.
The IR absorbing layer may be deposited on the top layer of the top electrode by any suitable method, and the present invention uses a Plasma Enhanced Chemical Vapor Deposition (PECVD) method to deposit SiO from the bottom up2 620nm，Si3N4 1110nm，SiO250 nm. The absorption rate of the composite absorption film layer can reach 99.94%.
Patterning the infrared absorption layer by photolithography, and performing Reactive Ion Etching (RIE) to form windows with size of 80x80um on the surface of the absorption layer2-120x120um2So as to expose the lead area of the gold plating layer and connect with the external output circuit.
In the embodiment provided by the invention, the reflectivity at 4260nm is adjusted by adjusting the thickness of the three-layer structure, specifically, the thickness of the first silicon dioxide layer is 20-80 nm, the thickness of the silicon nitride layer is 1020-1200 nm, and the thickness of the second silicon dioxide layer is 600-640 nm. Wherein, the silicon nitride layer both can reduce the residual thermal stress problem of absorbed layer film as main infrared absorption rete, can design out high absorption rate rete structure simultaneously, and three layer construction reaches and subtracts the reflection mesh, and the reflectivity in wavelength 4.26um department is less than 5%, and the absorptivity is higher than 95% promptly, and the process error tolerance is strong, is fit for batch production.
The absorption coefficient of infrared light by gas is a constant within a certain gas concentration range. The higher the gas concentration is, the more infrared light is absorbed, and the relation between the intensity of the absorbed infrared light and the gas concentration satisfies the lambert-beer law. According to CO, as shown in FIG. 62Infrared spectrum, and a higher absorption peak appears at the wavelength of 4260 nm. As the middle infrared spectral region is the fundamental frequency absorption, the absorption amplitude is much larger, therefore, the infrared absorption of the invention is complexFilm-laminated structure, CO2The absorption peak wavelength has a very low reflectance at 4.26 um.
The following specific examples are provided for the infrared absorbing composite film structure of the present invention.
Example 1
The three-layer structure thickness of the infrared absorption composite film structure is respectively 80nm, 1200nm and 640nm from top to bottom.
As shown in FIG. 2, the infrared absorbing composite film structure has a reflectivity of 5.16% at a wavelength of 4.26 um.
Example 2
The thickness of the three-layer structure of the infrared absorption composite film structure is respectively 20nm, 1020nm and 600nm from top to bottom.
As shown in fig. 3, the infrared absorbing composite film structure has a reflectivity of 5.07% at a wavelength of 4.26 um.
Example 3
The thickness of the three-layer structure of the infrared absorption composite film structure is respectively 50nm, 1110nm and 620nm from top to bottom, and the total thickness is 1.78 um.
As shown in FIGS. 4-5, the infrared absorption composite film structure has a lowest reflectivity of 0.06% at a wavelength of 4.26um, and an absorption rate of 99.94%.
Comparative example 1
The thickness of the three-layer structure of the infrared absorption composite film structure is designed into SiO from top to bottom2 150nm，Si3N4 950nm，SiO2300nm and a reflectivity of 12.93 percent at an infrared wavelength of 4260 nm.
The above embodiments show that the carbon dioxide reflectivity of the infrared absorption composite film structure of the present invention can be less than 5%, even less than 1%, and the purpose of reducing the reflectivity is achieved mainly by improving the absorption of carbon dioxide. The composite film structure of the invention is superior to the product of the CN108196332A patent, and as can be known by combining with the attached figure 9 of the CN108196332A patent, the composite film structure can filter other wave bands while achieving the aim of reducing reflection of carbon dioxide, namely, the other wave bands need to reach high reflectivity, and the reflectivity of carbon dioxide is less than 15 percent and is incompatible with a detector process. The composite absorption film structure provided by the invention reduces the reflectivity of carbon dioxide, does not make requirements on the reflectivity of other wave bands, and is mainly used for improving the absorption of carbon dioxide.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (5)
1. The utility model provides an infrared absorption complex film structure for carbon dioxide pyroelectric infrared detector, its characterized in that, infrared absorption complex film structure from last to including down in proper order: the infrared absorption film comprises a first silicon dioxide layer, a silicon nitride layer and a second silicon dioxide layer, wherein the silicon nitride layer is used for infrared absorption.
2. The infrared absorption composite film structure of claim 1, wherein the first silica layer has a thickness of 20 to 80nm, the silicon nitride layer has a thickness of 1020 to 1200nm, the second silica layer has a thickness of 600 to 640nm, and the composite film has a reflectivity of less than 5%.
3. The infrared absorption composite film structure of claim 1, wherein the first silicon dioxide layer has a thickness of 50nm, the silicon nitride layer has a thickness of 1110nm, and the second silicon dioxide layer has a thickness of 620 nm.
4. A carbon dioxide pyroelectric infrared detector, characterized by comprising the infrared absorption composite film structure of any one of claims 1 to 3, an upper electrode, a pyroelectric thin film crystal layer, and a lower electrode in this order from top to bottom.
5. The carbon dioxide pyroelectric infrared detector as claimed in claim 4, wherein the upper electrode comprises an upper electrode gold plating layer and an upper electrode nickel plating bonding layer from top to bottom; the lower electrode comprises a lower electrode nickel plating bonding layer and a lower electrode gold plating layer from top to bottom.
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