Anti-crosstalk fluorescent array multi-component gas sensing chip as well as preparation method and application thereof
By designing an anti-crosstalk fluorescent array multi-component gas sensing chip in a fluorescent gas sensor, the combination of optical filtered metasurface and microchannel arrays is used to solve the interference of excitation light sources on the photodetector and the different fluorescent signals. Crosstalk problem realizes high-precision detection of multi-component gases.
Patent Information
- Application Number
- CN202411631210.0
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-11-15
- Publication Date
- 2025-02-21
AI Technical Summary
In a highly integrated micro multicomponent environment, existing fluorescent gas sensors have severe crosstalk between the non-target light signal of the excitation light source and the fluorescent signals of different fluorescent dyes, resulting in a reduced detection accuracy.
An anti-crosstalk fluorescent array multi-component gas sensing chip is designed, using a silicon-based photodetector array and a silicon-based OLED, and an optical filtered metasurface and microchannel array are integrated on the photodetector array, and optical filtering is passed through optical filtering. The metasurface filters non-target optical signals, and the microchannel array is filled with a variety of fluorescent dyes to reduce crosstalk.
It effectively prevents the photodetector from receiving non-target optical signals, reduces crosstalk between different fluorescence signals, and realizes high-precision detection of multi-component gases.
Smart Images
Figure CN119492718A_ABST
Abstract
Description
Technical Field
[0001] The present invention belongs to the technical field related to gas sensors, and more specifically, relates to an anti-crosstalk fluorescent array multi-component gas sensor chip and a preparation method and application thereof. Background Art
[0002] Gas sensors are widely used in many fields such as environmental monitoring, industrial safety, and medical health. Optical gas sensors have become an important part of the high-end sensor market due to their long life, easy maintenance, and good selectivity. Among them, fluorescent gas sensors achieve accurate detection of gas concentration by detecting changes in fluorescent signals before and after the fluorescent dye adsorbs gas. This detection principle allows the main components, light excitation unit, fluorescence detection unit, and fluorescent gas-sensitive dye, to be closely arranged. However, fluorescent gas sensors currently still use discrete light sources and spectrometers for light excitation and detection, and the integrated integration of light sources, detectors, and fluorescent dyes has not yet been fully broken through. In particular, for highly integrated miniature multi-component fluorescent gas sensors, there is serious crosstalk between the non-target light signals of the excitation light source and the fluorescent signals of different fluorescent dyes, which has become the main challenge in the development of fluorescent array multi-component gas sensor chips. Summary of the invention
[0003] In view of the above defects or improvement needs of the prior art, the present invention provides an anti-crosstalk fluorescent array multi-component gas sensor chip and its preparation method and application, which aims to solve the interference of the excitation light source on the light detector and the crosstalk problem between different fluorescent signals.
[0004] To achieve the above-mentioned purpose, according to one aspect of the present invention, there is provided an anti-crosstalk fluorescent array multi-component gas sensor chip, the sensor chip comprising a silicon substrate, a silicon-based photodetector array and a silicon-based OLED arranged side by side in a groove of the silicon substrate, an insulating layer, an optical filtering supersurface and a microchannel array arranged in sequence on the silicon-based photodetector array, and a packaged optical reflector arranged on the silicon substrate, the insulating layer, the optical filtering supersurface and the microchannel array are accommodated in the packaged optical reflector; the microchannel array is filled with a variety of fluorescent dyes.
[0005] Furthermore, the packaged optical reflector is formed with a receiving groove, and the receiving groove is used to receive the insulating layer, the optical filtering metasurface and the microchannel array; the receiving groove is arranged opposite to the groove and is in communication with each other.
[0006] Furthermore, the packaged optical reflector is provided with a plurality of ventilation holes.
[0007] Furthermore, an insulating layer is also provided between the microchannel array and the optical filtering metasurface.
[0008] Furthermore, the material of the insulating layer is SiO 2 、Si 3 N 4 Or Al 2 O 3 , with a thickness of 100 nanometers to 1 micron.
[0009] Furthermore, the nanostructure of the optical filtering metasurface is a striped grating, wherein the grating spacing is 200 nanometers to 450 nanometers, the grating height is 50 nanometers to 500 nanometers, and the grating material is Ag, Al, Au, Si, Si 3 N 4 or TiO 2 .
[0010] Furthermore, the material of the microchannel is SiO 2 Or Si 3 N 4 The depth of the microchannel is 1 micron-30 microns, and the arrangement of the microchannel is a square arrangement or a ring arrangement.
[0011] Furthermore, the material of the silicon-based packaged optical reflector is Si, and it is provided with 2 to 10 air holes.
[0012] The present invention also provides a method for preparing an anti-crosstalk fluorescence array multi-component gas sensor chip, wherein the method is used to prepare the anti-crosstalk fluorescence array multi-component gas sensor chip as described above.
[0013] The present invention also provides a gas detection method, which uses the above-mentioned anti-crosstalk fluorescent array multi-component gas sensor chip to perform gas detection.
[0014] In general, compared with the prior art, the anti-crosstalk fluorescent array multi-component gas sensor chip and its preparation method and application provided by the present invention mainly have the following beneficial effects:
[0015] 1. The optical filtering metasurface is set on the silicon-based photodetector array, which effectively prevents the silicon-based photodetector from receiving non-target light signals from the silicon-based OLED, thereby filtering out the interference signals of the emission source.
[0016] 2. The microchannel array is filled with a variety of fluorescent dyes. The multi-component fluorescent dyes in this structure can selectively respond to different gases, generate corresponding fluorescent signals, and support the simultaneous detection of multiple gases. At the same time, the microchannel array structure can make the fluorescent signal only transmit along the axial direction, inhibit lateral transmission, avoid crosstalk between different fluorescent signals, and thus achieve high-precision detection of multi-component gases.
[0017] 3. The silicon-based photodetector array is arranged adjacent to the silicon-based OLED in parallel, forming an ultra-planar integrated structure of light excitation and light detection, which helps to achieve a high degree of integration of the gas sensor chip. BRIEF DESCRIPTION OF THE DRAWINGS
[0018] Figure 1 This is a structural cross-sectional view of an anti-crosstalk fluorescent array multi-component gas sensor chip provided by the present invention;
[0019] Figure 2 yes Figure 1 Flow chart of the method for preparing the anti-crosstalk fluorescent array multi-component gas sensor chip.
[0020] In all the drawings, the same figure numbers are used to represent the same elements or structures, where: 1-silicon substrate, 2-silicon-based OLED, 3-encapsulated optical reflector, 4-air permeable hole, 5-fluorescent dye, 6-microchannel array, 7-optical filtering metasurface, 8-insulating layer, 9-silicon-based photodetector array. DETAILED DESCRIPTION
[0021] In order to make the purpose, technical solutions and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not intended to limit the present invention. In addition, the technical features involved in the various embodiments of the present invention described below can be combined with each other as long as they do not conflict with each other.
[0022] See also Figure 1 The present invention provides an anti-crosstalk fluorescent array multi-component gas sensor chip, the sensor chip comprises a silicon substrate 1, a silicon-based photodetector array 9 and a silicon-based OLED 2 arranged side by side in a groove of the silicon substrate 1, an insulating layer 8, an optical filtering metasurface 7 and a microchannel array 6 arranged on the silicon-based photodetector array 9 in sequence, and a packaged optical reflector 3 covered on the insulating layer 8, the optical filtering metasurface 7 and the microchannel array 6, the packaged optical reflector 3 is a concave structure, and its open end is arranged on the silicon substrate 1. The microchannel array 6 is filled with a variety of fluorescent dyes 5.
[0023] The packaged optical reflector 3 is formed with a receiving groove, and the receiving groove is used to receive the insulating layer 8, the optical filtering metasurface 7 and the microchannel array 6. The shape and size of the receiving groove respectively correspond to the shape and size of the groove of the silicon substrate.
[0024] The packaged optical reflector 3 is provided with a plurality of air holes 4. An insulating layer is also provided between the microchannel array 6 and the optical filtering metasurface 7.
[0025] See also Figure 2 The present invention also provides a method for preparing an anti-crosstalk fluorescent array multi-component gas sensor chip, the preparation method mainly comprising the following steps:
[0026] Step 1: prepare a plurality of silicon-based photodetectors arranged at intervals on a silicon substrate to form a silicon-based photodetector array 9 for detecting fluorescence signals emitted by a plurality of gas-sensitive fluorescent dyes 5 .
[0027] Step 2: In-situ integrate the optical filtering metasurface on the surface of the silicon-based photodetector array 9 to prevent the silicon-based photodetector from receiving non-target light signals emitted by the silicon-based OLED 2.
[0028] An insulating layer is deposited between the silicon-based photodetector array 9 and the optical filtering supersurface, and between the optical filtering supersurface and the microchannel array, wherein the material of the insulating layer can be SiO 2 、Si 3 N 4 Or Al 2 O 3 , with a thickness of 100 nanometers to 1 micron.
[0029] The optical filtering metasurface is prepared by standard semiconductor processes such as photolithography, etching and vapor deposition. The nanostructure of the optical filtering metasurface is a striped grating, wherein the grating spacing is 200 nanometers to 450 nanometers, the grating height is 50 nanometers to 500 nanometers, and the grating material can be Ag, Al, Au, Si, Si 3 N 4 or TiO 2 , suitable for optical filtering in the range of 200 nm - 450 nm.
[0030] Step three, arrange multiple spaced microchannels on the optical filtering metasurface to form a microchannel array, which is used to control the fluorescence signal to propagate only along the axial direction, inhibit lateral propagation, and prevent optical crosstalk between different fluorescence signals.
[0031] The microchannel array is prepared by using standard semiconductor processes such as photolithography, etching and vapor deposition. The material of the microchannel can be SiO 2 Or Si 3 N 4 The geometric shape of the microchannel can be circular, triangular, square, or hexagonal, the depth of the microchannel is 1 micron-30 microns, the characteristic size of the microchannel is 1 micron-50 microns, the number of microchannels is 1-100, and the arrangement of the microchannel is a square arrangement or a ring arrangement.
[0032] Step 4: Fill a plurality of specific gas-sensitive fluorescent dyes 5 in the microchannels respectively to form a multi-component gas-sensitive fluorescent dye microchannel array for selectively exciting different gases to generate corresponding fluorescent signals.
[0033] A variety of specific gas-sensitive fluorescent dyes are suitable for CH 4 , H 2 , CO 2 , CO, DMC, EMC and other gases can be detected simultaneously. The fluorescent dye can be injected into the microchannel by drop coating, inkjet printing and electrofluidic printing.
[0034] Step five, arrange silicon-based OLEDs in parallel at adjacent positions of the silicon-based photodetector array 9 as excitation light sources for fluorescent dyes to form an ultra-planar integrated light-excitation luminescence detection structure.
[0035] Step six, integrate and package an optical reflector above the ultra-planar integrated light-excitation luminescence detection structure to reflect the excitation light of the silicon-based OLED to the top of the microchannel array, thereby effectively exciting the fluorescent dye to emit a fluorescent signal and improving the utilization efficiency of the excitation light.
[0036] The silicon-based packaged optical reflector may be in the shape of a square cap or a hemispherical shape, made of Si, and provided with 2-10 air holes 4. The reflector is connected to the underlying super-plane structure through a silicon-silicon bond.
[0037] The silicon-based OLED has a light emission band of 275 nanometers to 450 nanometers and a light power of 10 microwatts to 10 milliwatts, and is arranged in parallel next to a silicon-based photodetector.
[0038] The present invention also provides a gas detection method, which uses the above-mentioned anti-crosstalk fluorescent array multi-component gas sensor chip to perform gas detection.
[0039] Example 1
[0040] The method for preparing a crosstalk-resistant fluorescent array multi-component gas sensor chip provided in Example 1 of the present invention mainly comprises the following steps:
[0041] (1) Select a silicon wafer of appropriate size and prepare a silicon-based photodetector array using existing processes.
[0042] (2) A 200-nanometer-thick SiO2 layer was deposited on the surface of the silicon-based photodetector array by chemical vapor deposition. 2 Insulation layer.
[0043] (3) Using a spin coater, polymethyl methacrylate photoresist is spin-coated on the surface of the insulating layer, and using electron beam lithography and evaporation coating technology, a silver grating pattern with a height of 150 nanometers and a pitch of 250 nanometers is deposited on the insulating layer to form an optical filtering metasurface.
[0044] (4) Depositing Si with a thickness of 10 μm on the optical filtering metasurface by chemical vapor deposition 3 N 4 ; Spin coating on Si 3 N 4 The surface was spin-coated with polymethyl methacrylate photoresist, and a planar pattern of a microchannel array was prepared on the photoresist using electron beam lithography. The obtained sample was placed in a hydrofluoric acid solution for etching to remove part of the Si 3 N 4 , a microchannel array structure is obtained, and then the remaining photoresist is removed with acetone.
[0045] (5) 5 nanometers of triphenylethane, 10 nanometers of triphenylborane, 15 nanometers of carbazole benzophenone, 30 nanometers of organic light-emitting material, and 20 nanometers of aluminum oxide are sequentially evaporated at adjacent positions of the silicon-based photodetector as a hole injection layer, a hole transport layer, an electron transport layer, a light-emitting layer, and a blocking layer, respectively, to obtain a silicon-based OLED.
[0046] (6) A variety of fluorescent dyes are injected into the microchannel array by inkjet printing, and then dried and cured to obtain a semi-finished gas sensor chip.
[0047] (7) spin coating polymethyl methacrylate photoresist on the surface of another silicon wafer, using electron beam lithography technology to prepare the plane shape of the air holes, mounting grooves, etc. of the packaged optical reflector, and placing the obtained sample in a hydrofluoric acid solution for etching to remove part of the silicon, thereby obtaining an optical reflector;
[0048] (8) Align the optical reflector above the semi-finished gas sensor chip, and use a hot press bonding machine to complete the packaging bonding of the two silicon wafers at 350° C. and 150 g force, thereby obtaining a miniature integrated anti-crosstalk fluorescent array multi-component gas sensor chip.
[0049] Example 2
[0050] The method for preparing a crosstalk-resistant fluorescent array multi-component gas sensor chip provided in Example 2 of the present invention mainly comprises the following steps:
[0051] (1) Select a silicon wafer of appropriate size and prepare a silicon-based photodetector array using existing processes.
[0052] (2) A 200-nanometer-thick Al layer was deposited on the surface of the silicon-based photodetector array by atomic layer deposition. 2 O 3Insulation layer.
[0053] (3) A 300-nanometer-thick gold film was deposited on the surface of the insulating layer using evaporation coating technology, polymethyl methacrylate photoresist was spin-coated on the surface of the gold film using a spin coater, and a grating pattern was prepared on the surface of the gold film using electron beam lithography technology. The obtained sample was placed in a hydrofluoric acid solution for etching to remove part of the gold, and the remaining photoresist was removed with acetone to obtain an optical filtering metasurface with a grating spacing of 350 nanometers.
[0054] (4) SiO with a thickness of 5 μm is deposited on the optical filtering metasurface by chemical vapor deposition. 2 ; Spin coating on SiO 2 The surface was spin-coated with polymethyl methacrylate photoresist, and a planar pattern of a microchannel array was prepared on the photoresist using electron beam lithography. The obtained sample was placed in a hydrofluoric acid solution for etching to remove part of the SiO 2 , and then use acetone to remove the remaining photoresist to obtain a microchannel array structure.
[0055] (5) 30 nanometers of poly (3,4-ethylenedioxythiophene), 10 nanometers of triphenylborane, 30 nanometers of organic light-emitting material, 15 nanometers of benzimidazolylpyridine, and 20 nanometers of aluminum oxide are sequentially evaporated at adjacent positions of the silicon-based photodetector as a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, and a blocking layer, respectively, to obtain a silicon-based OLED.
[0056] (6) A variety of fluorescent dyes are injected into the microchannel array by electrofluidic printing, and then dried and cured to obtain a semi-finished gas sensor chip.
[0057] (7) Spin-coating polymethyl methacrylate photoresist on the surface of another silicon wafer, using electron beam lithography technology to prepare the planar shapes of the air holes, mounting grooves, etc. of the packaged optical reflector, and placing the obtained sample in a hydrofluoric acid solution for etching to remove part of the silicon, thereby obtaining an optical reflector.
[0058] (8) Align the optical reflector above the semi-finished gas sensor chip, and use a hot press bonding machine to complete the packaging bonding of the two silicon wafers at 350° C. and 150 g force, thereby obtaining a miniature integrated anti-crosstalk fluorescent array multi-component gas sensor chip.
[0059] It will be easily understood by those skilled in the art that the above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should be included in the protection scope of the present invention.
Claims
1. An anti-crosstalk fluorescent array multi-component gas sensor chip, characterized in that: The sensor chip includes a silicon substrate, a silicon-based photodetector array and a silicon-based OLED arranged side by side in a groove of the silicon substrate, an insulating layer, an optical filtering supersurface and a microchannel array arranged in sequence on the silicon-based photodetector array, and a packaged optical reflector arranged on the silicon substrate, wherein the insulating layer, the optical filtering supersurface and the microchannel array are accommodated in the packaged optical reflector; and the microchannel array is filled with a variety of fluorescent dyes.
2. The anti-crosstalk fluorescent array multi-component gas sensor chip according to claim 1, characterized in that: The packaged optical reflector is formed with a receiving groove, and the receiving groove is used to receive the insulating layer, the optical filtering metasurface and the microchannel array; the receiving groove is arranged opposite to the groove and is in communication with each other.
3. The anti-crosstalk fluorescent array multi-component gas sensor chip according to claim 1, characterized in that: The packaged optical reflector is provided with a plurality of ventilation holes.
4. The anti-crosstalk fluorescent array multi-component gas sensor chip according to claim 1, characterized in that: An insulating layer is also arranged between the microchannel array and the optical filtering metasurface.
5. The anti-crosstalk fluorescent array multi-component gas sensor chip according to any one of claims 1 to 4, characterized in that: The insulating layer is made of SiO2, Si3N4 or Al2O3, and has a thickness of 100 nanometers to 1 micrometer.
6. The anti-crosstalk fluorescent array multi-component gas sensor chip according to any one of claims 1 to 4, characterized in that: The nanostructure of the optical filtering metasurface is a striped grating, wherein the grating spacing is 200 nanometers to 450 nanometers, the grating height is 50 nanometers to 500 nanometers, and the grating material is Ag, Al, Au, Si, Si3N4 or TiO2.
7. The anti-crosstalk fluorescent array multi-component gas sensor chip according to any one of claims 1 to 4, characterized in that: The material of the microchannel is SiO2 or Si3N4, the depth of the microchannel is 1 micron-30 microns, and the arrangement of the microchannel is a square arrangement or a ring arrangement.
8. The anti-crosstalk fluorescent array multi-component gas sensor chip according to any one of claims 1 to 4, characterized in that: The material of the silicon-based packaged optical reflector is Si, and it is provided with 2 to 10 air holes.
9. A method for preparing an anti-crosstalk fluorescent array multi-component gas sensor chip, characterized in that: The preparation method is used to prepare the anti-crosstalk fluorescent array multi-component gas sensor chip according to any one of claims 1 to 8.
10. A gas detection method, characterized in that: The gas detection method uses the anti-crosstalk fluorescent array multi-component gas sensor chip described in any one of claims 1 to 8 to perform gas detection.