CN113188669B - Infrared absorption composite film structure and carbon dioxide pyroelectric infrared detector - Google Patents
Infrared absorption composite film structure and carbon dioxide pyroelectric infrared detector Download PDFInfo
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- 238000010521 absorption reaction Methods 0.000 title claims abstract description 72
- 239000002131 composite material Substances 0.000 title claims abstract description 41
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims description 34
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims description 17
- 239000001569 carbon dioxide Substances 0.000 title claims description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910052581 Si3N4 Inorganic materials 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 17
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 16
- 239000000377 silicon dioxide Substances 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
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 15
- 239000010931 gold Substances 0.000 claims description 15
- 229910052737 gold Inorganic materials 0.000 claims description 15
- 238000007747 plating Methods 0.000 claims description 15
- 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 3
- 239000010410 layer Substances 0.000 claims 11
- 239000012790 adhesive layer Substances 0.000 claims 1
- 238000002310 reflectometry Methods 0.000 abstract description 19
- 238000000034 method Methods 0.000 abstract description 18
- 230000008569 process Effects 0.000 abstract description 7
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- 239000000853 adhesive Substances 0.000 abstract description 4
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- 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
- 229910004298 SiO 2 Inorganic materials 0.000 description 5
- 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
- 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
- 238000001514 detection method Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000012544 monitoring process Methods 0.000 description 3
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- 229910052719 titanium Inorganic materials 0.000 description 3
- 239000006096 absorbing agent Substances 0.000 description 2
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- 238000000985 reflectance spectrum Methods 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
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- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 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 CO 2 The infrared absorption composite film structure of the pyroelectric infrared detector sequentially comprises the following components from top to bottom: the first silicon dioxide layer, the silicon nitride layer and the second silicon dioxide layer, wherein the silicon nitride layer is used for infrared absorption. The invention also provides corresponding CO 2 Pyroelectric infrared detector. The infrared absorption composite film structure adopts a silicon oxide-silicon nitride-silicon oxide multilayer dielectric film as an infrared absorption layer, and mainly aims at CO 2 The high-efficiency infrared absorption of the gas is designed, the thickness is controlled within 2um, the reflectivity of less than 5 percent can be obtained, the absorption rate can be up to 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
With the improvement of living standard of people and the continuous development of industrial technology, people are about carbon dioxide (CO 2 ) Monitoring of gas concentration is becoming more and more important because of CO 2 Gases are closely related to the health and quality of life of people. In recent years, with the continuous emergence of gas concentration measuring technology and instruments, CO 2 The application field of the gas sensor is also wider and wider, such as industrial waste gas control, monitoring the carbon dioxide concentration in a chimney when the industrial waste gas is discharged, strictly controlling the content of the carbon dioxide concentration in the waste gas, and reducing the greenhouse effect caused by the increase of the carbon emission; monitoring the greenhouse cultivation, detecting and controlling the concentration of carbon dioxide, and enabling crops to have high quality and high yieldProviding a good breeding environment for the growth and development of livestock; the sensor for detecting harmful gas in the air can know indoor air quality in real time and create a good living environment.
CO based on pyroelectric infrared absorption 2 The 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 interference signal, high signal-to-noise ratio and compact structure. The performance of pyroelectric infrared detector is mainly characterized by response speed and sensitivity, and the detector is required to be in CO to obtain good sensitivity 2 The absorption rate of the absorption band is high (i.e., the reflectivity is low), and the response speed is high, so that the heat capacity of the absorption layer is required to be small, and interference is avoided.
In order to effectively absorb heat radiation and further improve the response rate of the device, an absorption layer or an anti-reflection layer needs to be covered on 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 materials of the infrared radiation absorbing layer commonly used at present are gold black, organic black bodies, ultrathin metal films and the like. The materials have the problems of poor device process compatibility, poor adhesive force, low absorption efficiency and the like, and CO 2 The gas absorbs only infrared light of a specific wavelength, which requires it to be CO 2 The absorption wave band has higher absorptivity, and the materials can not well meet the requirement of CO 2 Gas detection performance.
Chinese patent CN 105789428B discloses a composite absorption layer pyroelectric infrared detector, which adopts parallel plane cavities to enable light to oscillate back and forth in a periodic lens waveguide without overflowing outside the waveguide, and increases the times of incident light passing through the absorption layer, thereby indirectly improving the absorption coefficient of the absorption layer and forming a stable lens waveguide. The infrared absorption layer is a composite structure and sequentially comprises a titanium metal layer, a dielectric layer, a nichrome layer, a lithium tantalate crystal layer and a reflecting layer from top to bottom, wherein the dielectric layer is made of silicon nitride, the absorption efficiency is mainly improved through multiple resonance reflection of the titanium metal layer and the reflecting layer, and the dielectric layer is not mentioned as a main infrared absorptionWith dielectric layers between the titanium metal layer and nichrome, more of them serve as insulation and light transmission. In the pyroelectric detector, compared with a single metal absorption layer film serving as a heat sensitive layer, the composite absorption layer has better surface compactness, high absorption coefficient and smaller heat loss, can obtain high-performance thermal response, and is beneficial to preparing the high-precision infrared detector based on the pyroelectric crystal. However, the infrared light mainly in a specific wavelength band is subjected to resonance absorption for a plurality of times, and CO 2 The superiority of the infrared absorption of (C) is not clearly pointed out.
Yang Jianming, wu Xiaoqing, yao Xi absorption layer study of pyroelectric Infrared detector [ J]Infrared technology, 2002, vol24 (4): 53-54, 58, in this prior art, the preparation of a gold black absorber layer was studied mainly, the absorber layer being under nitrogen (N 2 ) Gold with the purity of 99.99% is evaporated in the atmosphere to form a porous structure composed of fine crystal particles. The technique is carried out along with N 2 The infrared reflectivity of the prepared gold black layer is reduced, the absorption rate is increased, and the optimal N response of the detector to infrared rays is facilitated 2 The air pressure is between 100 Pa and 200 Pa. However, this technique is achieved by controlling N 2 The gold black absorption layer with the reflectivity less than 5% can be obtained under the pressure of 150Pa, the gold black layer is uneven on the surface of a sample due to the fact that the air pressure is too high, and the gold black coating is poor in adhesive force and poor in process compatibility.
Disclosure of Invention
The main object of the present invention is to provide a method for CO in view of the above problems 2 Infrared absorption composite film structure of pyroelectric infrared detector and CO 2 Pyroelectric infrared detector.
The invention provides a method for CO 2 The infrared absorption composite film structure of the pyroelectric infrared detector comprises the following components in sequence from top to bottom: 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 antireflection 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, which is the anti-reflection film layer with the lowest reflectivity.
The invention also provides a CO 2 The pyroelectric infrared detector comprises the infrared absorption composite film structure, an upper electrode, a pyroelectric thin film crystal layer and a lower electrode as claimed in any one of claims 1 to 3 from top to bottom.
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 a silicon oxide-silicon nitride-silicon oxide multilayer dielectric film as an infrared absorption layer, and mainly aims at CO 2 The high-efficiency infrared absorption of the gas is designed, the thickness is controlled within 2um, the reflectivity of less than 5 percent can be obtained, the absorption rate can be up to 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 invention 2 The structure of the pyroelectric infrared detector is schematically shown.
Fig. 2 is a reflectance spectrum of the infrared absorbing composite film structure of example 1.
Fig. 3 is a reflectance spectrum of the infrared absorbing composite film structure of example 2.
Fig. 4 to 5 are reflection maps of the infrared absorbing composite film structure of example 3.
FIG. 6 is CO 2 And (5) infrared spectrogram.
Detailed Description
The scheme of the present invention will be explained below with reference to examples. It will be appreciated by those skilled in the art that the following examples are illustrative of the present invention and should not be construed as limiting the scope of the invention.
As shown in FIG. 1, the CO provided by the invention 2 The pyroelectric infrared detector comprises an infrared absorption composite film structure, an upper electrode, a pyroelectric thin film crystal layer 6 and a lower electrode from top to bottom.
The infrared absorption composite film structure of the invention comprises the following components in sequence from top to bottom: the first silicon dioxide layer 1, the silicon nitride layer 2 and the second silicon dioxide layer 3, wherein the silicon nitride layer is used for infrared absorption, and meanwhile, the composite film is generally designed as an anti-reflection film layer. The infrared absorption composite film uses SiO 2 -Si 3 N 4 -SiO 2 Multilayer dielectric film system structure for CO 2 High absorption rate at characteristic wavelength, in CO 2 The absorption peak has very low reflectivity, and realizes CO of the pyroelectric device 2 And (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, and the process for growing silicon nitride and silicon oxide is mature at present, and the thickness, uniformity and growth rate are easy to regulate and control.
The invention provides the processing steps of a pyroelectric detector, which comprise the following steps:
the upper electrode can be deposited on the first surface of the grinding surface lithium tantalate crystal layer by any suitable method, and the invention adopts a vacuum electron beam evaporation method to respectively evaporate nickel films and gold films, wherein the nickel thickness is 10-30 nm, and the gold thickness is 50-100 nm. The nickel plating film acts mainly as a bonding 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 present invention employs a vacuum electron beam evaporation process. The thickness of nickel and gold film vapor plating is the same as that of the upper electrode.
The infrared absorbing layer can be deposited on the top layer of the upper electrode by any suitable method, and the invention adopts a Plasma Enhanced Chemical Vapor Deposition (PECVD) method from bottom to topDeposition of SiO 2 620nm，Si 3 N 4 1110nm，SiO 2 50nm. The absorption rate of the composite absorption film layer can reach 99.94 percent.
Patterning the infrared absorption layer by photoetching, and opening a window on the surface of the absorption layer by Reactive Ion Etching (RIE), wherein the window size is 80x80um 2 -120x120um 2 To expose the gold-plated lead area for connection with an 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. The silicon nitride layer is used as a main infrared absorption film layer, so that the problem of residual thermal stress of an absorption layer film can be reduced, meanwhile, a high-absorptivity film layer structure can be designed, the three-layer structure achieves the purpose of antireflection, the reflectivity at the position of 4.26um is less than 5%, namely, the absorptivity is higher than 95%, the process error tolerance is high, and the silicon nitride film is suitable for batch production.
The absorption coefficient of the gas to infrared light is a constant in a certain gas concentration range. The higher the gas concentration, the more infrared light is absorbed, and the relationship between the intensity of the absorbed infrared light and the gas concentration satisfies the lambert-beer law. As shown in FIG. 6, according to CO 2 Infrared spectrum, higher absorption peak appears at the wavelength of 4260 nm. Because the mid-infrared spectrum region is the absorption of fundamental frequency and the absorption amplitude is much larger, the infrared absorption composite film structure of the invention, CO 2 The absorption peak wavelength has a very low reflectivity at 4.26 um.
For the infrared absorbing composite film structure of the present invention, the following specific examples are provided.
Example 1
The thickness of the three-layer structure of the infrared absorption composite film structure is 80nm,1200nm and 640nm respectively 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 20nm, 10200 nm and 600nm respectively 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 1.78um.
As shown in fig. 4-5, the infrared absorbing composite film structure has a minimum reflectance of 0.06% at a wavelength of 4.26um, and an absorptivity of 99.94%.
Comparative example 1
The thickness of the three-layer structure of the infrared absorption composite film structure is designed to be SiO from top to bottom 2 150nm，Si 3 N 4 950nm，SiO 2 300nm, and a reflectance of 12.93% at an infrared wavelength of 4260 nm.
It can be seen from the above examples that the carbon dioxide reflectivity of the infrared absorption composite film structure of the present invention can be made to 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 the composite film structure is combined with the attached figure 9 of the CN108196332A patent, so that the carbon dioxide antireflection purpose is achieved, other wave bands are filtered, namely, the other wave bands reach high reflectivity, the reflectivity of the carbon dioxide is less than 15%, and the composite film structure is incompatible with the detector technology. The composite absorption film structure of the invention is mainly used for improving the absorption of carbon dioxide when reducing the reflectivity of carbon dioxide and the reflectivity of other wave bands is not required, and the detector related TO the invention can filter other wave bands by matching with TO packaging.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (4)
1. An infrared absorption composite film structure for a carbon dioxide pyroelectric infrared detector is characterized by comprising the following components in sequence from top to bottom: the infrared absorption silicon nitride 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 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.
2. The infrared absorbing composite film structure of claim 1, wherein the composite film has a reflectance of <5%.
3. A carbon dioxide pyroelectric infrared detector, which is characterized by comprising the infrared absorption composite film structure, an upper electrode, a pyroelectric thin film crystal layer and a lower electrode according to claim 1 or 2 from top to bottom.
4. A carbon dioxide pyroelectric infrared detector as recited in claim 3 wherein said upper electrode comprises, from top to bottom, an upper electrode gold plating layer and an upper electrode nickel plating adhesive layer; 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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| CN105258806A (en) * | 2015-11-02 | 2016-01-20 | 电子科技大学 | Pyroelectric infrared detection unit and manufacture method thereof, and pyroelectric infrared detector |
| CN106092334A (en) * | 2016-07-19 | 2016-11-09 | 中国科学院重庆绿色智能技术研究院 | A kind of Infrared Detectors based on carbon nanometer infrared absorption layer |
| CN205898309U (en) * | 2016-07-19 | 2017-01-18 | 中国科学院重庆绿色智能技术研究院 | Infrared detector based on carbon nanometer infrared absorption layer |
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