CN108801966B - Multi-element pyroelectric sensitive element for multi-type gas sensing - Google Patents
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- G01N21/35—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light
- G01N21/3504—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light for analysing gases, e.g. multi-gas analysis
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Abstract
The invention belongs to the technical field of infrared gas sensing, and particularly relates to a multi-element pyroelectric sensing element for multi-type gas sensing. According to the invention, by designing a single infrared sensitive unit, the bottom metal layer of the M-I-M metamaterial structure of the second structural layer is simultaneously used as the upper electrode of the first structural layer. By carrying out partition graphical processing on the top metal graphic layer of the second structural layer, multi-sensitive element integration, multi-infrared-band absorption and multi-gas-type response on a single pyroelectric material are realized. The invention combines the pyroelectric sensitive material with the metamaterial perfect wave-absorbing structure, is applied to gas sensing, directly realizes high infrared selectivity of sensitive elements, omits an optical filter part in the existing infrared gas sensor, reduces the volume of a device, improves the integration level of the device and is beneficial to batch manufacturing.
Description
Technical Field
The invention belongs to the technical field of infrared gas sensing, relates to an infrared sensing element, and particularly relates to a multi-element pyroelectric sensing element for multi-type gas sensing.
Background
In an infrared gas detection element, a detection unit is generally composed of a sensitive element (pyroelectric material) and its upper and lower electrodes, an infrared absorption layer, and an optical filter. Infrared light penetrates through the optical filter and is absorbed by the infrared absorption layer, so that the pyroelectric material generates temperature rise, an electric signal changes and is led out by the upper electrode and the lower electrode, and infrared detection is realized. The wavelength of infrared light cannot be selected by a common infrared absorption layer, and the infrared absorption layer can respond in a wide wavelength range, but only infrared light of a certain waveband is needed in application. Therefore, when the device is manufactured, the infrared ray is subjected to light splitting treatment to filter useless wave bands, only required wave bands are left, interference is eliminated, and therefore the infrared detection device has high selectivity and anti-interference performance.
The method commonly used today is to add a filter between the sensing element and the light source, the filter is usually a high-transmittance wafer with a multi-layer thin-film structure, and the function of the filter is to select a desired infrared band before infrared light reaches the sensing element, which is also the biggest characteristic of an infrared detection device of NDIR (non-dispersive infrared) type. When gas detection is realized, a plurality of sensitive elements are required to form a signal channel and a reference channel so as to improve the accuracy of signals. If multiple gas detection is desired, the number of channels needs to be increased, which means that more different filters are required and the final structure and the manufacturing process thereof become more complicated. Therefore, in the process of current NDIR device miniaturization and high integration research, the development of the device is greatly limited by the characteristics of the indispensable and structural properties of the optical filter. Thus, it becomes necessary to find new ways or structures to replace the filters.
Meta-materials refer to artificial composites or composite structures with extraordinary physical properties not possessed by natural materials. Experiments show that the metamaterial with a certain special structure can realize ultrahigh selectivity and absorptivity to infrared rays with different wave bands, and the metamaterial with the structure is also called as a metamaterial perfect wave absorbing structure (MPA). The metamaterial is small in size, is in a nanometer level, is mainly prepared on a substrate in a patterned thin film mode, and can select the central position of an absorption waveband through designing certain sizes of the metamaterial.
Disclosure of Invention
Aiming at the problems or the defects, the problems that the device is miniaturized, the high integration process is complex and the mass preparation is not facilitated due to the optical filter in the existing infrared gas detection sensitive device are solved; the invention provides a multi-element pyroelectric sensitive element for multi-type gas sensing.
A multi-element pyroelectric sensitive element for multi-type gas sensing comprises n infrared sensitive units, wherein n is more than or equal to 1.
Each infrared sensitive unit has the same structure and comprises two structural layers: the first structural layer comprises a pyroelectric material, an upper electrode and a lower electrode, and forms a traditional infrared sensitive element; the second structure layer is an M-I-M metamaterial structure, namely three films of a bottom metal layer, a medium layer and a top metal pattern layer form a metamaterial infrared perfect wave absorbing structure (MPA). And the bottom metal layer of the second structural layer is simultaneously used as the upper electrode of the first structural layer. And optimizing the utilization rate of the structure. When the upper electrode layer is prepared on the pyroelectric material layer, a small area is reserved to be not covered with a subsequent metamaterial infrared absorption structure, so that the upper electrode of the pyroelectric material is exposed and used for leading out an electric signal.
Furthermore, the top metal pattern layer of the metamaterial infrared perfect wave-absorbing structure is subjected to partition graphical processing, metal nanometer pattern structures with different design sizes are prepared in different areas, and the metal nanometer pattern structures aim at infrared absorption peak wavelengths of different gases. Different areas after the partition graphical processing are cut, each area serves as an infrared sensitive unit, cutting channels among the units are used for thermal isolation and signal isolation, and therefore multi-sensitive element integration, multi-infrared band absorption and multi-gas type response on a single pyroelectric material are achieved.
In conclusion, the pyroelectric sensitive material and the metamaterial perfect wave-absorbing structure are combined, the material is applied to gas sensing, and metamaterials with different shapes and sizes are designed according to absorption peak positions of different gases; the high infrared selectivity of the sensitive element is directly realized, an optical filter part in the infrared gas sensor is omitted, the size of the device is greatly reduced, and the integration level of the device is improved. And a plurality of infrared sensitive elements aiming at different gas absorption wave bands can be simultaneously prepared on one pyroelectric material unit, so that multi-gas detection is realized, the integration level of the device is greatly improved, and the size of the device is reduced. Has application prospect in the infrared gas detection field.
Drawings
FIG. 1 is a schematic side cross-sectional view of an embodiment;
FIG. 2 is a schematic 3D structure diagram of a single infrared-sensitive unit of an embodiment;
FIG. 3 is a cross-sectional view of a dual-band sensor of a single pyroelectric material unit according to an embodiment.
Fig. 4 is a schematic top view of a single pyroelectric material unit multi-element graphic design of an embodiment.
FIG. 5 is a schematic view of the laser cutting process of the exemplary embodiment;
reference numerals: 101 lower electrode, 102 pyroelectric material, 103 upper electrode, 104 dielectric layer, 105 top metal pattern layer, 106 top metal pattern layer, A, B, C, D top metal pattern layer with different pattern size, and E upper electrode.
Detailed Description
In order to make the objects, aspects and advantages of the present invention more apparent, the present invention will be described in detail with reference to the accompanying drawings and specific embodiments.
Fig. 1 shows a side cross-sectional view of a single sensor of a multi-type gas sensing multi-pyroelectric sensor, which comprises a lower electrode 101, a pyroelectric material 102, an upper electrode 103, a dielectric layer 104 and a metal pattern layer 105 on the top.
101, the lower electrode is used for leading out the change of the electric signal of the pyroelectric unit; the gold electrode prepared by electron beam evaporation completely covers the whole range of the pyroelectric material. The gold electrode metal film has poor adhesiveness, and a chromium metal film is plated as an adhesion layer before preparation to improve the gold adhesion, so that the layer 101 of the embodiment is composed of two metal films.
102 is a pyroelectric material, adopts LTO (lithium tantalate) thin film, is a standard 4-inch wafer, and is cut by laser to form small pieces for preparing a detection unit in the device.
The 103 layer is an upper electrode, the preparation method and the material are the same as those of the 101 layer, and meanwhile, the 103 layer is also used as a bottom metal layer required in the metamaterial infrared absorption structure.
104 layer is SiO2The dielectric layer is prepared by a PECVD method.
105 layers are metal pattern layers of the gold top layer, are patterned films with the size between nanometer and micron, and are prepared through electron beam exposure and electron beam evaporation; according to the principle of a metamaterial infrared absorption structure, metal film nano structures with different shapes and sizes are prepared, and the central absorption waveband of the infrared absorption structure can be selected by changing the thickness of a dielectric layer; the infrared sensitive element sensitive to different wave bands is realized by designing the shape and the size of the 105 layers and the thickness of the 104 layers differently.
In the whole structure, 101, 102 and 103 form a standard infrared sensitive element, which comprises a pyroelectric sensitive material and upper and lower electrodes for leading out electric signal change. 103, 104 and 105 form a metamaterial infrared absorption structure which respectively corresponds to the bottom metal layer, the dielectric layer and the top metal pattern layer. Wherein, the 103 layers are used as an upper electrode of the infrared sensitive element and a bottom metal layer of the metamaterial infrared absorption structure at the same time and are shared by the two parts.
Fig. 4 is a top plan view thereof, including a top metal pattern layer of the metamaterial infrared absorbing structure in the region A, B, C, D, and an electrode in the region E. A. B, C, D, i.e., 105 in fig. 1, covers almost the entire pyroelectric material upper electrode area for selective absorption of infrared light in a certain wavelength band. There are no 104, 105 layers above the E region, which is an exposed upper electrode 103 layer for leading out the pyroelectric material signal.
Fig. 2 is a 3D structure diagram, in which 101, 102, 103, 104, and 105 correspond to the respective layers in fig. 1. In the figure, when the layers 104 and 105 cover the layer 103, a corner is lacked, so that the layer 103 is exposed on the corner, and a circuit can be connected to the exposed layer 103 by Wire Bonding or the like, so as to lead out a pyroelectric material signal.
When the element is prepared, graphical design is carried out on a large piece of pyroelectric material, each layer structure is prepared by graphical preparation of the large-area pyroelectric material in different areas, then each area is cut by laser cutting, and each area is an infrared sensitive unit element. As shown in the dual cross-section of fig. 3, different top metal pattern layers 105 and 106 are fabricated on one pyroelectric unit. The two materials are respectively cut by laser aiming at different wave bands, and originally connected 102, 103 and 104 and contacted 105 and 106 are cut to form two sensitive elements, so that a dual-element structure on a single pyroelectric material is realized. Based on the design, when a top metal pattern layer is designed in a graphical mode, multiple regions are divided aiming at a single pyroelectric material, and metamaterial infrared absorption structures with different central wave bands are prepared in different regions, as shown in A, B, C, D in a multi-element top view of fig. 4, A, B, C, D four regions are metamaterial infrared absorption structures designed for different top metal pattern layers and aim at different infrared absorption wave bands. The region E is the layer 103 in FIG. 1, which is the upper electrode of the sensing element for signal extraction. Under the design, the multiband response of a single pyroelectric unit is realized, a multi-sensitive element structure is formed, and the multi-sensitive element structure can be used for multi-gas infrared detection with high integration level.
The invention can be prepared by the following technical processes:
1. ti films with the thickness of 10nm are respectively plated on the upper and lower parts of a 4-inch wafer pyroelectric single crystal LTO by a standard electron beam evaporation plating process to be used as an adhesion layer of an Au film, and then the Au film with the thickness of 100nm is also plated on the Ti film by electron beam evaporation to form upper and lower electrodes of the pyroelectric material, namely layers 101 and 103 in figure 1.
2. And coating photoresist on the 103 layer, carrying out patterned exposure, curing certain areas in the 103 layer, then washing away the photoresist, and leaving small square areas of the photoresist to be used as exposed areas of the upper electrode of the sensitive element, namely areas E shown in FIG. 4.
3. A full coverage SiO2 film was prepared by a standard PECVD process on layer 103 to a thickness of 70nm, layer 104 in fig. 1.
4. And coating photoresist on the layer 104, and developing and curing the patterned nano structure required by the metamaterial perfect absorbing structure by an electron beam exposure technology. According to the design of different sizes of nanopattern structures in different regions of the wafer, such as A, B, C, D region shown in fig. 4, the absorption peak wavelengths of different gases, such as CO2, CH4, SO2, NH3, etc., are respectively aimed at. Then, exposure and washing were carried out to prepare a Ti film having a thickness of 5nm by electron beam evaporation, followed by preparing an Au film having a thickness of 31 nm.
5. The photoresist remaining in region E of fig. 4 in step 2 is washed away. Finally, the regions with different absorption bands are separated by laser cutting, as shown in fig. 5.
In summary, the invention realizes a multi-element pyroelectric sensing element for multi-type gas sensing, can realize multi-band response, is used for multi-gas infrared detection, can reduce the volume of the whole sensor device and improve the integration level, and is beneficial to batch preparation.
Claims (2)
1. A multi-element pyroelectric sensitive element for multi-type gas sensing comprises n infrared sensitive units, wherein n is more than or equal to 1, and the multi-element pyroelectric sensitive element is characterized in that:
each infrared sensitive unit has the same structure and comprises two structural layers: the first structural layer comprises a pyroelectric material, an upper electrode and a lower electrode, and forms a traditional infrared sensitive element; the second structure layer is an M-I-M metamaterial structure, namely a three-layer film consisting of a bottom metal layer, a medium layer and a top metal pattern layer, so that the metamaterial infrared perfect wave-absorbing structure MPA is formed; the bottom metal layer of the second structural layer is simultaneously used as the upper electrode of the first structural layer;
the top metal pattern layer of the metamaterial infrared perfect wave-absorbing structure is subjected to partition graphical processing, metal nanometer pattern structures with different design sizes are prepared in different areas, and the infrared absorption peak wavelengths of different gases are aimed at; and cutting different areas subjected to partition imaging processing, wherein each area is used as an infrared sensitive unit, and cutting channels among the units are used for thermal isolation and signal isolation.
2. The multi-type pyroelectric sensor element for gas sensing of claim 1, wherein: a small area is reserved in the upper electrode and does not cover a subsequent metamaterial infrared absorption structure, so that the upper electrode of the pyroelectric material is exposed and used for leading out an electric signal.
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| CN110687067B (en) * | 2019-09-17 | 2021-08-17 | 中国科学院上海微系统与信息技术研究所 | Infrared gas sensor |
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