A silicon-based CMOS fluorescence oxygen sensor and its detection method
Through silicon-based microstructure processing based on integrated circuit technology, the light source, light guide system and silicon-based photodiode units necessary for optical signal acquisition are designed and integrated, solving the challenges of optical MEMS sensors in device miniaturization and scale integration, and achieving high-integration and low-power optical oxygen sensors.
Patent Information
- Application Number
- CN202111385737.6
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2021-11-22
- Publication Date
- 2025-04-29
- Estimated Expiration
- 2041-11-22
AI Technical Summary
Existing optical MEMS sensors have challenges in device miniaturization and scale integration, especially in miniaturization design of light sources and optical signal acquisition systems, as well as machining and packaging and testing processes for integrated silicon-based microstructures.
Through silicon-based microstructure processing based on integrated circuit technology, the light source, light guide system and silicon-based photodiode units required for optical signal acquisition are designed and integrated, and the photoelectric signal conversion and modulation and mediation are used to realize photoelectric signal conversion and modulation and mediation, and an optical oxygen sensor based on the principle of fluorescence quenching is designed and manufactured.
It realizes the miniaturization and scale integration of devices, improves the integration and production efficiency of silicon-based CMOS optical sensors, and reduces production costs, and is suitable for low-power and high-integration application scenarios.
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Figure CN114113014B_ABST
Abstract
Description
Technical Field
[0001] The invention relates to the technical field of silicon-based sensor micro-electromechanical system integration, and in particular to a silicon-based CMOS micro-electromechanical fluorescence oxygen sensor and a detection method thereof. Background Art
[0002] Traditional optical sensors are limited by the structural size of light sources (such as light-emitting diodes (LEDs), laser diodes, and laser light sources of various wavelengths), as well as the volume of electronic components and integrated circuit boards used in control circuits, making device miniaturization and large-scale integration difficult to achieve.
[0003] The micro-electromechanical system (MEMS) based on different application scenarios is a 3D microstructure sensing unit with a size ranging from millimeters to micrometers or even smaller. With the development of MEMS technology, a single MEMS chip can integrate more sensing units to achieve higher integration through optimized design and improved packaging and testing processes, while adopting batch production to reduce the production cost of MEMS sensing systems. Compared with traditional sensors, MEMS sensors manufactured using silicon-based processes have the advantages of miniaturization and high integration, and have very broad application prospects in current and future IoT data acquisition intelligent systems.
[0004] However, at present, the key problems that optical MEMS sensors need to solve are based on two aspects: one is the miniaturization design of light sources and optical signal acquisition systems; the other is the processing and packaging and testing technology of integrated silicon-based microstructures.
[0005] Therefore, it is urgent to develop a fluorescent oxygen sensor that can achieve device miniaturization and large-scale integration. Summary of the invention
[0006] In order to solve such problems, the present invention designs and integrates the light source, light guide system and silicon-based photodiode unit necessary for optical signal acquisition through silicon-based microstructure processing based on integrated circuit technology, realizes photoelectric signal conversion and modulation through silicon-based photoelectric conversion array, and designs and manufactures a MEMS gas optical sensor, especially an optical oxygen sensor based on the principle of fluorescence quenching. The optical system design, data detection and packaging and testing process of the silicon-based CMOS microstructure sensing unit developed by the present invention can provide principle guidance for the development of other low-power, high-integration silicon-based CMOS optical sensing units.
[0007] The present invention provides a silicon-based CMOS fluorescence oxygen sensor, comprising a light source, a silicon-based CMOS driver, a microcontroller module and a communication module;
[0008] The silicon-based CMOS driver is arranged on the back side of the integrated circuit board PCB;
[0009] The silicon-based CMOS driver is provided with metal anodes and detection elements arranged in an array, and the array of the metal anodes and the array of the detection elements are arranged in an alternating manner;
[0010] The light source is constructed as an OLED thin film layer with autonomous light-emitting performance, and the OLED thin film layer is deposited on the metal anode; a common transparent cathode is deposited on the OLED thin film layer; the transparent cathode is encapsulated with a transparent glass plate, and the transparent glass plate is coated with a fluorescent sensor film layer on the outside;
[0011] The detection element is configured as a silicon-based photodiode.
[0012] As a further improvement of the implementation mode of the present invention, the primary colors of the OLED thin film layer are three light sources: red light, green light and blue light; the red light is used as a reference light source, and the green light and blue light are used as excitation light sources; the red light, green light and blue light are all constructed as a top-emitting microstructure.
[0013] As a further improvement to the implementation manner of the present invention, the metal anode deposited with the OLED thin film layer and the silicon-based photodiode are constructed in a combined array mode N-in-1 structure, wherein N is the number of light sources, 1 is the number of drivers, N includes a combination of one or more red, green and blue light sources, and N is N=3, 6, 9, ... N, and the value of N is determined according to application requirements.
[0014] As a further improvement of the implementation mode of the present invention, the metal anode deposited with the OLED thin film layer and the silicon-based photodiode adopt a (3X+2Y)XM array, wherein M is the number of rows and (3X+2Y) represents the number of columns; each row includes at least one group of red, green and blue three-color units and two silicon-based photodiodes, 3X is also the number of light sources, and Y is the number of silicon-based photodiodes.
[0015] As a further improvement of the implementation manner of the present invention, the silicon-based CMOS driver is connected to a microcontroller module, and the communication module is connected to the microcontroller module.
[0016] As a further improvement of the embodiment of the present invention, the metal anode is configured in an array arrangement on the silicon-based CMOS driver by using a standard CMOS process through mask transfer and evaporation processes;
[0017] The OLED thin film layer is deposited on the metal anode by plasma cleaning and vacuum evaporation;
[0018] The silicon-based photodiode is fabricated on the CMOS driver by wafer bonding technology.
[0019] As a further improvement of the embodiment of the present invention, a filter film is deposited on the front end of the silicon-based photodiode by vacuum evaporation, so as to selectively receive light of a preset wavelength band;
[0020] The reference red light and the fluorescence after stimulated radiation enter the silicon-based photodiode after reflection. The silicon-based photodiode receives the red light entering the silicon-based photodiode after being filtered by the filter film and converts the optical signal into an electrical signal.
[0021] As a further improvement of the embodiment of the present invention, the fluorescent sensing film layer at least includes a black protective coating, a fluorescent reflection coating and a fluorescent dye molecule coating. The reference red light and the fluorescence after stimulated radiation are reflected by the fluorescent reflection coating and enter the silicon-based photodiode.
[0022] As a further improvement of the embodiment of the present invention, the fluorescent reflective coating is made of one or more nanoparticle mixtures of SiO2, hexagonal boron nitride, ZrO2, MgF2, TiO2, Al2O3, MgO, and ZnO, and the particle size of the nanoparticles is in the range of 1nm-500nm.
[0023] As a further improvement of the embodiment of the present invention, the fluorescent dye molecular coating adopts a porphine series fluorescent dye molecule as shown in Formula I:
[0024]
[0025] The fluorescent dye molecule includes a metal ion M and a conjugated side chain group R, the metal ion M is one of Zn, Cu, Cd, Fe, Pt, Pd, and Ru, and the concentration of the dye molecule is controlled at 0.1 μg-10 g / L.
[0026] As a further improvement of the embodiment of the present invention, the side chain group R also includes the same or different R1, R2, R3, R4, and an extended π-conjugated system is obtained by adjusting the conjugated side chain group R to obtain a stable fluorescence signal with an emission wavelength of 570-780 nm.
[0027] As a further improvement of an embodiment of the present invention, the black protective coating is made of one or more black particles, and the concentration of the black particles is controlled at 1-100 g / L; the black particles are selected from one or more of black graphite, carbon powder, and black metal nanoparticles, and the solid content of the black protective coating is 86 g / L.
[0028] As a further improvement of the embodiment of the present invention, the green light film in the OLED thin film layer is a doped composite film of one or both of the organic small molecule coumarin C545T and the metal chelate Alq3; the vacuum degree of the evaporation equipment used is controlled at 2.5×10-4 Pa below, the evaporation rate is controlled based on different luminous intensity requirements. It should be pointed out that the evaporation parameters of different evaporation equipment need to be optimized according to actual needs to process the film thickness.
[0029] The molecular structure of Alq3 is shown in the formula:
[0030]
[0031] The molecular structure of C545T is as follows:
[0032]
[0033] As a further improvement of the embodiment of the present invention, the blue light film in the OLED thin film layer uses small molecule organic matter such as tetra-tert-butylperylene (TPBe), and the vacuum degree of the evaporation equipment used is controlled at 2.5×10 -4 Pa below, the evaporation rate is controlled based on different luminous intensity requirements.
[0034] The molecular structure of TPBe is shown in the formula:
[0035]
[0036] As a further improvement of the present invention, the red light film in the OLED thin film layer is used as a reference light source, and the organic small molecule DCM derivative series JCDTB is used, or it is doped with Alq3 molecules for evaporation, and the proportion of JCTDB is controlled to be 0.1-5%. The preferred JCDTB proportion is 2.0% by mass.
[0037] As a further improvement of the implementation manner of the present invention, the transparent cover plate is encapsulated by a glass material, and the glass material is an acrylic or sapphire glass plate.
[0038] As a further improvement of the embodiment of the present invention, a layer of calcium oxide or aluminum oxide coating is vacuum deposited on the surface of the transparent cathode, and the calcium oxide or aluminum oxide coating is formed by deposition after plasma and UV / O3 cleaning and activation; then a transparent organic coating polyimide or polyacrylate film is deposited on the calcium oxide or aluminum oxide coating. The above inorganic-organic deposition is repeated 1-5 times, and the thickness of the dielectric film is controlled to be 20-100nm. The UV glue side sealing is completed by an automatic glue dispenser, and a transparent glass cover is added.
[0039] On the other hand, the present invention also provides a detection method of a silicon-based CMOS fluorescence oxygen sensor, comprising the following steps:
[0040] The red light, green light and blue light in the OLED light source react with the fluorescent sensing film layer after being emitted. The fluorescent dye molecular coating in the fluorescent sensing film layer is excited and emits a preset spectrum after being irradiated by the green light and the blue light.
[0041] The CMOS integrated circuit system collects reference red light and emits fluorescence signals by frequency modulation control of silicon-based photodiodes, converting optical signals into electrical signals;
[0042] The silicon-based CMOS driving circuit performs algorithmic processing on the electrical quantity difference corresponding to the above red light, and can obtain the optical phase difference under different oxygen molecule concentrations.
[0043] The present invention designs and integrates the light source, light guide system and silicon-based photodiode unit necessary for optical signal acquisition through silicon-based microstructure processing based on integrated circuit technology, realizes photoelectric signal conversion and modulation through silicon-based photoelectric conversion array, and designs and manufactures MEMS gas optical sensors, especially an optical oxygen sensor based on the principle of fluorescence quenching. The optical system design, data detection and packaging and testing process of the silicon-based CMOS microstructure sensing unit developed by the present invention can provide principle guidance for the development of other low-power, high-integration silicon-based CMOS optical sensing units. BRIEF DESCRIPTION OF THE DRAWINGS
[0044] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.
[0045] Figure 1 This is a schematic diagram of the structure of a silicon-based CMOS fluorescence oxygen sensor according to the present invention;
[0046] Figure 2 A top view of a silicon-based CMOS driver according to the present invention;
[0047] Figure 3 A three-dimensional diagram of a silicon-based CMOS driver according to the present invention;
[0048] Figure 4 It is a schematic diagram of a fluorescent sensing film functional layer including a three-layer structure according to the present invention;
[0049] Figure 5 The fluorescent molecules involved in the present invention are excited and emitted by OLED light sources 470nm blue light and 508-540nm green light;
[0050] Figure 6Design of silicon-based CMOS driving circuit and optical signal acquisition circuit involved in the present invention;
[0051] Figure 7 The gain multiple and output fluorescence intensity variation curve of the silicon-based CMOS optical system of the present invention in air at different driving voltages;
[0052] Figure 8 A graph showing the fluorescence intensity and oxygen concentration (or partial pressure) collected by a fluorescence oxygen sensor in the prior art;
[0053] Fig. 9 A graph showing the fluorescence intensity and oxygen concentration (or partial pressure) collected by the silicon-based CMOS fluorescence oxygen sensor of the present invention;
[0054] The corresponding parts represented by the numbers in the figure are as follows:
[0055] 1- back of integrated circuit board; 2- silicon-based CMOS driver; 3- metal anode; 4- OLED thin film layer; 5- silicon-based photodiode; 6- filter film; 7- common transparent cathode; 8- transparent glass plate; 9- fluorescent sensing film layer; 10- black protective coating; 11- fluorescent reflective coating; 12- fluorescent dye molecular coating. DETAILED DESCRIPTION
[0056] In order to facilitate the understanding of the present invention, the present invention will be described in more comprehensive and detailed manner in conjunction with the accompanying drawings and preferred embodiments below, but the protection scope of the present invention is not limited to the following specific embodiments. It should be noted that the embodiments and features in the embodiments of the present invention can be combined with each other without conflict.
[0057] Example 1
[0058] The embodiment of the present invention provides a silicon-based CMOS fluorescence oxygen sensor, including a light source, a silicon-based CMOS driver 2, a microcontroller module and a communication module;
[0059] Among them, Figure 1 As shown, the silicon-based CMOS driver 2 is arranged on the back side 1 of the integrated circuit board PCB; the silicon-based CMOS driver 2 is provided with metal anodes 3 and detection elements arranged in an array, and the array of metal anodes 3 and the array of detection elements are arranged in an alternating manner;
[0060] The light source is constructed as an OLED thin film layer 4 with autonomous luminous properties, and the OLED thin film layer 4 is deposited on a metal anode 3; a common transparent cathode 7 is deposited on the OLED thin film layer 4; the transparent cathode 7 is encapsulated with a transparent glass plate 8, and the transparent glass plate 8 is coated with a fluorescent sensing film layer 9 on the outside; in an embodiment of the present invention, the detection element is constructed as a silicon-based photodiode 5.
[0061] In the embodiment of the present invention, Figure 2 and Figure 3 As shown, the primary colors of the OLED thin film layer are red light, green light, and blue light; among them, red light is used as a reference light source, and green light and blue light are used as excitation light sources; red light, green light, and blue light are all constructed as top-emitting microstructures.
[0062] Preferably, the metal anode 3 deposited with the OLED thin film layer 4 and the silicon-based photodiode 5 are constructed in a combined array mode N-in-1 structure, wherein N=3, 6, 9, ... N, and the value of N is determined according to application requirements.
[0063] The metal anode 3 and the silicon-based photodiode 5 on which the OLED thin film layer 4 is deposited are constructed in a combined array mode N-in-1 structure, wherein N is the number of light sources (the number of metal anodes 3), 1 is the number of drivers, and N includes a combination of one or more red, green, and blue light sources, and N is N=3, 6, 9, ... N, and the value of N is determined according to application requirements; in other optional embodiments, in theory, each group of light sources can select at least two types of red and blue or red and green.
[0064] Furthermore, the metal anode 3 deposited with the OLED thin film layer 4 and the silicon-based photodiode 5 adopt a (3X+2Y)XM array, where M is the number of rows and (3X+2Y) represents the number of columns; each row includes at least one group of red, green and blue three-color units and two silicon-based photodiodes, 3X is also the number of light sources, and Y is the number of silicon-based photodiodes.
[0065] Specifically, the OLED light source and silicon-based photodiode array adopt scalable structures such as 5X1, 5X2, and preferably, a 5X3 array is adopted, in which 5 represents the number of columns and 1 represents the number of rows. Each row has at least red, green and blue color units and 2 PDs, so the number is 5.
[0066] In the embodiment of the present invention, the silicon-based CMOS driver 2 is connected to a microcontroller module, and the communication module is connected to the microcontroller module.
[0067] Preferably, the metal anode 3 is constructed in an array arrangement on the silicon-based CMOS driver 2 by mask transfer and evaporation process using standard CMOS technology; the OLED thin film layer 4 is deposited on the metal anode 3 by plasma cleaning and vacuum evaporation; and the silicon-based photodiode 5 is prepared on the CMOS driver by wafer bonding technology.
[0068] Furthermore, a filter film is deposited on the front end of the silicon-based photodiode 5 by vacuum evaporation, which is used to selectively receive light of a preset wavelength band;
[0069] The reference red light and the fluorescence after stimulated radiation enter the silicon-based photodiode 5 after reflection. The silicon-based photodiode 5 receives the red light after being filtered by the filter film and enters the silicon-based photodiode 5, and converts the optical signal into an electrical signal.
[0070] Specifically, Figure 4 As shown, the fluorescent sensing film layer 9 at least includes a black protective coating 10, a fluorescent reflective coating 11 and a fluorescent dye molecule coating 12. The reference red light and the fluorescence after stimulated radiation are reflected by the fluorescent reflective coating 11 and enter the silicon-based photodiode 5.
[0071] The fluorescent reflective coating 11 is made of one or more nanoparticle mixtures of SiO2, hexagonal boron nitride, ZrO2, MgF2, TiO2, Al2O3, MgO, and ZnO, and the particle size of the nanoparticles is in the range of 1nm-500nm.
[0072] Preferably, the fluorescent dye molecule coating 12 uses a porphine series fluorescent dye molecule as shown in Formula I:
[0073]
[0074] The fluorescent dye molecule includes a metal ion M and a conjugated side chain group R, wherein the metal ion M is one of Zn, Cu, Cd, Fe, Pt, Pd, and Ru, and the concentration of the dye molecule is controlled at 0.1 μg-10 g / L.
[0075] The side chain group R also includes the same or different R1, R2, R3, and R4. By adjusting the conjugated side chain group R, an extended π-conjugated system is obtained to obtain a stable fluorescence signal with an emission wavelength of 570-780 nm.
[0076] Preferably, the black protective coating 10 is made of one or more black particles, and the concentration of the black particles is controlled at 1-100 g / L; the black particles are selected from one or more of black graphite, carbon powder, and black metal nanoparticles.
[0077] Preferably, the solid content of the black protective coating is 86 g / L.
[0078] Furthermore, the green light film in the OLED thin film layer 4 is a doped composite film of one or both of the organic small molecule coumarin C545T and the metal chelate Alq3; the vacuum degree of the evaporation equipment used is controlled at 2.5×10 -4 Pa below, the evaporation rate is controlled based on different luminous intensity requirements. It should be pointed out that the evaporation parameters of different evaporation equipment need to be optimized according to actual needs to process the film thickness. The process parameters of different equipment are different. The pressure, surface treatment and evaporation rate required to prepare the above-mentioned film with optimal luminescent performance may be different).
[0079] The molecular structure of Alq3 is shown in the formula:
[0080]
[0081] The molecular structure of C545T is as follows:
[0082]
[0083] Preferably, the blue light film in the OLED thin film layer 4 uses small molecule organic matter such as tetra-tert-butylperylene (TPBe), and the vacuum degree of the evaporation equipment used is controlled at 2.5×10 -4 Pa below, the evaporation rate is controlled based on different luminous intensity requirements.
[0084] The molecular structure of TPBe is shown in the formula:
[0085]
[0086] Preferably, the red light film in the OLED thin film layer 4 is used as a reference light source, and the organic small molecule DCM derivative series JCDTB is used, or it is doped with Alq3 molecules for evaporation, and the proportion of JCTDB is controlled at 0.1-5%. The preferred JCDTB proportion is 2.0% by mass.
[0087] In the embodiment of the present invention, the transparent cover plate 8 is encapsulated by glass material, and the glass material is preferably acrylic or sapphire glass plate.
[0088] A layer of calcium oxide or aluminum oxide coating is vacuum deposited on the surface of the common transparent cathode 9, and the calcium oxide or aluminum oxide coating is formed by deposition after being cleaned and activated by plasma and UV / O3; then a layer of transparent organic coating polyimide or polyacrylate film is deposited on the calcium oxide or aluminum oxide coating. The above inorganic-organic deposition is repeated 1-5 times, and the thickness of the dielectric film is controlled to be 20-100nm. The UV glue side sealing is completed by an automatic glue dispenser, and a transparent glass cover is added.
[0089] Example 2
[0090] The present invention also provides a detection method for a silicon-based CMOS fluorescence oxygen sensor, comprising the following steps:
[0091] The red light, green light and blue light in the OLED light source react with the fluorescent sensing film layer after being emitted. The fluorescent dye molecular coating in the fluorescent sensing film layer is excited and emits a preset spectrum after being irradiated by the green light and the blue light.
[0092] The CMOS integrated circuit system collects reference red light and emits fluorescence signals by frequency modulation control of silicon-based photodiodes, converting optical signals into electrical signals;
[0093] The silicon-based CMOS driving circuit performs algorithmic processing on the electrical quantity difference corresponding to the above red light, and can obtain the optical phase difference under different oxygen molecule concentrations.
[0094] Specific as Figure 5 As shown: After the fluorescent molecules are irradiated by OLED light sources 470nm blue light and 508-540nm green light ( Figure 5 Solid line excitation spectrum curve-Excitation), the emission fluorescence (red light) wavelength is located at 648nm and 710nm ( Figure 5 The dotted line shows the emission spectrum curve -Emission). After the photodiode (PD) converts the reference red light and fluorescence (red light) emitted by the collected OLED into electrical signals, the silicon-based CMOS driving circuit performs algorithm processing on the electrical quantity difference corresponding to the above red light to obtain the optical phase difference under different oxygen molecule concentrations.
[0095] In the embodiment of the present invention, the silicon-based CMOS driving circuit design and the optical signal acquisition circuit are as follows Figure 6 shown.
[0096] The gain multiple and output fluorescence intensity of the silicon-based CMOS optical system in air at different driving voltages are shown in the figure below. Figure 7 Preferably, the gain multiple is selected to be 40-60, and the corresponding driving voltage required for the OLED light source is 5-8V.
[0097] To achieve the above purpose, the sensor system developed by the present invention is further configured to: by controlling different ratios of nitrogen and oxygen, the real-time data of fluorescence intensity and oxygen concentration (or partial pressure) collected by the sensor system are as follows: Figure 8 As shown. Fig. 9 It can be seen from the oxygen partial pressure and fluorescence intensity curve that when the oxygen concentration is 100% pure oxygen, the fluorescence generated by stimulated radiation is quenched to the greatest extent, and the detectable fluorescence intensity is the minimum. Conversely, when the oxygen concentration is 0% (under 99.99% pure N2 conditions), the fluorescence intensity is the maximum.
[0098] The present invention designs and integrates the light source, light guide system and silicon-based photodiode unit necessary for optical signal acquisition through silicon-based microstructure processing based on integrated circuit technology, realizes photoelectric signal conversion and modulation through silicon-based photoelectric conversion array, and designs and manufactures MEMS gas optical sensors, especially an optical oxygen sensor based on the principle of fluorescence quenching. The optical system design, data detection and packaging and testing process of the silicon-based CMOS microstructure sensing unit developed by the present invention can provide principle guidance for the development of other low-power, high-integration silicon-based CMOS optical sensing units.
Claims
1. A silicon-based CMOS fluorescence oxygen sensor, characterized in that: It includes a light source, a silicon-based CMOS driver, a microcontroller module and a communication module; The silicon-based CMOS driver is arranged on the back side of the integrated circuit board PCB; The silicon-based CMOS driver is provided with metal anodes and detection elements arranged in an array, and the array of the metal anodes and the array of the detection elements are arranged in an alternating manner; The light source is constructed as an OLED thin film layer with autonomous light-emitting performance, and the OLED thin film layer is deposited on the metal anode; a common transparent cathode is deposited on the OLED thin film layer; the transparent cathode is encapsulated with a transparent glass plate, and the transparent glass plate is coated with a fluorescent sensor film layer on the outside; The detection element is constructed as a silicon-based photodiode; The silicon-based CMOS driver is connected to a microcontroller module, and the communication module is connected to the microcontroller module.
2. The silicon-based CMOS fluorescence oxygen sensor according to claim 1, characterized in that: The primary colors of the OLED film layer are three light sources: red light, green light, and blue light; the red light is used as a reference light source, and the green light and blue light are used as excitation light sources; the red light, green light, and blue light are all constructed as a top-emitting microstructure.
3. The silicon-based CMOS fluorescence oxygen sensor according to claim 2, characterized in that: The metal anode deposited with the OLED thin film layer and the silicon-based photodiode are constructed in a combined array mode N in 1 structure, where N is the number of light sources, 1 is the number of drivers, N includes a combination of one or more red, green and blue light sources, and N is N=3, 6, 9, ... N, and the value of N is determined according to application requirements.
4. The silicon-based CMOS fluorescence oxygen sensor according to claim 3, characterized in that: The metal anode deposited with the OLED thin film layer and the silicon-based photodiode adopt a (3X+2Y)XM array, where M is the number of rows and (3X+2Y) represents the number of columns; each row includes at least one group of red, green and blue three-color units and two silicon-based photodiodes, 3X is also the number of light sources, and Y is the number of silicon-based photodiodes.
5. The silicon-based CMOS fluorescence oxygen sensor according to claim 1, characterized in that: A filter film is deposited on the front end of the silicon-based photodiode by vacuum evaporation to selectively receive light of a preset wavelength band; The reference red light and the fluorescence after stimulated radiation enter the silicon-based photodiode after reflection. The silicon-based photodiode receives the red light entering the silicon-based photodiode after being filtered by the filter film and converts the optical signal into an electrical signal.
6. The silicon-based CMOS fluorescence oxygen sensor according to claim 1, characterized in that: The fluorescent sensing film layer at least includes a black protective coating, a fluorescent reflection coating and a fluorescent dye molecule coating; the reference red light and the fluorescence after stimulated radiation are reflected by the fluorescent reflection coating and then enter the silicon-based photodiode.
7. The silicon-based CMOS fluorescence oxygen sensor according to claim 6, characterized in that: The fluorescent reflective coating is made of one or more nanoparticle mixtures of SiO2, hexagonal boron nitride, ZrO2, MgF2, TiO2, Al2O3, MgO, and ZnO, and the particle size of the nanoparticles is in the range of 1nm-500nm.
8. The silicon-based CMOS fluorescence oxygen sensor according to claim 7, characterized in that: The fluorescent dye molecular coating adopts the fluorescent dye molecules of the porphine series as shown in Formula I; The fluorescent dye molecule includes a metal ion M and a conjugated side chain group R, wherein the metal ion M is one of Zn, Cu, Cd, Fe, Pt, Pd, and Ru, and the concentration of the dye molecule is controlled at 0.1µg-10g / L; 。 9. The silicon-based CMOS fluorescence oxygen sensor according to claim 8, characterized in that: The side chain group R also includes the same or different R1, R2, R3, and R4. An extended π-conjugated system is obtained by adjusting the conjugated side chain group R to obtain a stable fluorescence signal with an emission wavelength of 570-780nm.
10. The silicon-based CMOS fluorescence oxygen sensor according to claim 6, characterized in that: The black protective coating is made of one or more black particles, and the concentration of the black particles is controlled at 1-100g / L; the black particles are selected from one or more of black graphite, carbon powder, and black metal nanoparticles, and the solid content of the black protective coating is 86g / L.
11. The silicon-based CMOS fluorescence oxygen sensor according to claim 1, characterized in that: The green light film in the OLED thin film layer is a doped composite film of one or both of the organic small molecule coumarin C545T and the metal chelate Alq3; the vacuum degree of the evaporation equipment used is controlled at 2.5×10 -4 Below Pa, the evaporation rate is controlled at 0.1-2.5Å / s based on different luminescence intensity requirements.
12. The silicon-based CMOS fluorescence oxygen sensor according to claim 1, characterized in that: The blue light film in the OLED thin film layer uses small molecule organic matter such as tetra-tert-butylperylene (TPBe), and the vacuum degree of the evaporation equipment used is controlled at 2.5×10 - 4 Below Pa, the evaporation rate is controlled at 0.1-2.5Å / s based on different luminescence intensity requirements.
13. The silicon-based CMOS fluorescence oxygen sensor according to claim 1, characterized in that: The red light film in the OLED thin film layer is used as a reference light source, and the organic small molecule DCM derivative series JCDTB is used, or it is doped with Alq3 molecules and evaporated, and the proportion of JCTDB is controlled to be 0.1-5%.
14. The silicon-based CMOS fluorescence oxygen sensor according to claim 1, characterized in that: A layer of calcium oxide or aluminum oxide coating is vacuum deposited on the surface of the transparent cathode, and the calcium oxide or aluminum oxide coating is deposited after being activated by plasma and UV / O3 cleaning; then a transparent organic coating polyimide or polyacrylate film is deposited on the calcium oxide or aluminum oxide coating.
15. The silicon-based CMOS fluorescence oxygen sensor according to claim 1, characterized in that: The metal anode is configured in an array arrangement on the silicon-based CMOS driver by using a standard CMOS process through mask transfer and evaporation processes; The OLED thin film layer is deposited on the metal anode by plasma cleaning and vacuum evaporation; The silicon-based photodiode is fabricated on the CMOS driver by wafer bonding technology.
16. A detection method for a silicon-based CMOS fluorescence oxygen sensor as claimed in claim 1, characterized in that: The following steps are involved: The red light, green light and blue light in the OLED light source react with the fluorescent sensing film layer after being emitted. The fluorescent dye molecular coating in the fluorescent sensing film layer is excited and emits a preset spectrum after being irradiated by the green light and the blue light. The CMOS integrated circuit system collects reference red light and emits fluorescence signals by frequency modulation control of silicon-based photodiodes, converting optical signals into electrical signals; The silicon-based CMOS driving circuit performs algorithmic processing on the electrical quantity difference corresponding to the above red light, and can obtain the optical phase difference under different oxygen molecule concentrations.
Citation Information
Patent Citations
Integrated light emitting display and sensors for detecting biologic characteristics
CN109475328A
OLED light source-based optical dissolved oxygen sensor probe and manufacturing method thereof
CN109490273A
Composite sensing film for detecting oxygen based on fluorescence method and use method thereof
CN111548788A