CN109164050B - Optical fiber Fabry-Perot hypersensitive gas sensor based on tungsten selenide film channel structure - Google Patents
Optical fiber Fabry-Perot hypersensitive gas sensor based on tungsten selenide film channel structure Download PDFInfo
- Publication number
- CN109164050B CN109164050B CN201811131211.3A CN201811131211A CN109164050B CN 109164050 B CN109164050 B CN 109164050B CN 201811131211 A CN201811131211 A CN 201811131211A CN 109164050 B CN109164050 B CN 109164050B
- Authority
- CN
- China
- Prior art keywords
- tungsten selenide
- single mode
- perot
- optical fiber
- gas sensor
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/41—Refractivity; Phase-affecting properties, e.g. optical path length
- G01N21/45—Refractivity; Phase-affecting properties, e.g. optical path length using interferometric methods; using Schlieren methods
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/41—Refractivity; Phase-affecting properties, e.g. optical path length
- G01N21/45—Refractivity; Phase-affecting properties, e.g. optical path length using interferometric methods; using Schlieren methods
- G01N2021/458—Refractivity; Phase-affecting properties, e.g. optical path length using interferometric methods; using Schlieren methods using interferential sensor, e.g. sensor fibre, possibly on optical waveguide
Landscapes
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Investigating Or Analysing Materials By Optical Means (AREA)
Abstract
The invention belongs to the field of sensing, and particularly relates to an optical fiber Fabry-Perot hypersensitive gas sensor based on a tungsten selenide film channel structure. The invention adopts a mature and stable sensing principle, combines optics, metamaterial disciplines and advanced technologies of micro-nano processing, integrates a tungsten selenide-gold conductive structure on the end surface of a single-mode optical fiber, depends on the physical adsorption and electric adjustable characteristics of tungsten selenide, and realizes the adsorption and release of gas molecules by modulating the voltage applied by the tungsten selenide. The response speed and the sensitivity of the sensor are considered, and meanwhile, the device is small in size, good in thermal stability and small in sensing power consumption: the response time of the sensor is only one thousandth of that of an electrochemical gas sensor, the sensitivity of the sensor can reach over 1000 times of that of a traditional optical gas sensor, and the sensing power consumption is as low as 100 nanowatts. The sensor can be directly integrated in an all-optical system, and high-speed information sensing of an all-optical network is realized.
Description
Technical Field
The invention belongs to the field of sensing, and particularly relates to an optical fiber Fabry-Perot hypersensitive gas sensor based on a tungsten selenide film channel structure, which can detect the concentration of gas by detecting the drift amount of a transmission spectrum.
Background
With the continuous improvement of living standard and the increasing attention on environmental protection, higher requirements are put forward on gas sensors for the detection of various toxic and harmful gases, the monitoring of atmospheric pollution and industrial waste gas, the detection of food and living environment quality and the like. The successful application of the development technology of new materials such as nano and thin film technologies provides good precondition for the integration and intellectualization of the gas sensor. The high-performance gas sensor can greatly improve the information acquisition, processing and deep processing levels, improve the accuracy of real-time accident prediction, continuously eliminate accident potential and greatly reduce accidents, particularly major accidents. The system can effectively realize electronization of safety supervision and safety production supervision management, changes passive disaster relief into active disaster prevention, and advances safety production to scientific management.
At present, the gas sensor mainly comprises an electrochemical gas sensor and an optical gas sensor. The traditional electrochemical gas sensor generally realizes sensing of biochemical molecules by using electrolytic current intensity through a chemical electrolysis method, and although the gas sensing method is mature and reliable, the defects of the gas sensing method are obvious: the sensor depends on chemical reaction, and has the advantages of high energy consumption, large volume, complex system, weak anti-electromagnetic interference capability, strong gas selectivity and low sensing sensitivity. However, a batch of electrical sensors developed in recent years based on the MEMOS technology have made great breakthrough in the aspects of volume, energy consumption, sensitivity and the like, but still have not solved the problems of slow response speed, complex system, weak anti-electromagnetic interference capability and the like.
The optical gas sensor based on the optical fiber sensing technology can basically solve the defects of the electrical gas sensor, and compared with the traditional electrochemical gas sensor, the optical gas sensor has the advantages of simple structure, small size, high response speed, electromagnetic interference resistance and the like. Optical sensors are used as an important means for information acquisition, are used for converting various information into optical signals which can be widely transmitted, quickly analyzed and processed in a large scale, play an important role in modern information systems which take optical fibers as media for transmission, and are used for various industries such as safety monitoring, environmental science, precision processing, aerospace, life science and the like according to a large number of different principles. However, most of the current optical sensors, especially those used for gas analysis, are complex in structure and expensive, and are difficult to be applied to large-scale markets.
Disclosure of Invention
Aiming at the problems or the defects, the invention provides the optical fiber Fabry-Perot hypersensitive gas sensor based on the tungsten selenide film channel structure, which aims to solve the problems that the existing gas sensor has low cost, simple structure, small size, good controllability, high sensitivity and low power consumption and can not be obtained at the same time.
Tungsten selenide is a two-dimensional material similar to graphene, has excellent surface activity and rapid information transfer capability, and is mainly composed of an upper layer of selenium atoms and a lower layer of selenium atoms which are connected with a middle layer of tungsten atoms 1. Chemical bonds among atoms of the tungsten selenide and electronic states outside the core are extremely sensitive to the surrounding environment, and the dielectric constant of the tungsten selenide can be effectively influenced by the adsorption of trace gas molecules, so that the effective refractive index is adjusted, and the optical gas sensing of single molecular level is realized. Meanwhile, the molecular adsorption has very quick influence on the conductivity of the tungsten selenide, the quick response of an optical signal can be realized, and the response speed is greatly improved.
The invention adopts the following technical scheme:
the optical fiber Fabry-Perot hypersensitive gas sensor based on the tungsten selenide thin film comprises a coated single-mode optical fiber, a tungsten selenide-single-mode optical fiber and a quartz capillary tube.
The two coated single-mode optical fibers are single-mode optical fibers with one ends coated with dielectric films and reflectivity of more than 95% at 1550 nm waveband; the dielectric film is formed by sequentially superposing and depositing silicon dioxide films and zirconium dioxide films.
The tungsten selenide-single mode fiber is a single mode fiber with one end plated with a gold film, the gold film on the core part of the single mode fiber is removed in a through mode with the channel width of more than or equal to 10 microns, the gold film is divided into two sections and then inserted into the tungsten selenide thin film, and finally the tungsten selenide thin film is attached to the end face of the single mode fiber and forms a tungsten selenide-gold conductive structure together with the two sections of the gold film.
The tungsten selenide-single mode fiber is placed in the middle, the coated single mode fiber is positioned at two ends, and the coated end faces are placed in the middle, and the coated single mode fiber is inserted into a quartz capillary tube which is used as a Fabry-Perot cavity collimation and encapsulation structure and also used as a gas microflow channel. The coating end of the tungsten selenide-single mode fiber is not in contact with the corresponding medium film-single mode fiber coating end to form an air gap of 1-3 mm, the quartz capillary tube of the air gap part is provided with an air hole, the air gap structure is used as a microflow channel of gas molecules, and the two coated single mode fibers form a Fabry-Perot microcavity. And the light path between the tungsten selenide-single mode fiber and the two dielectric thin film-single mode fibers is aligned.
Furthermore, the number of the air holes is two, and the two air holes are symmetrically arranged on the corresponding quartz capillary tube.
The working process of the invention is as follows: the method comprises the steps that a scanning laser signal with a scanning range of 1550-1560 nm is injected into a Fabry-Perot microcavity through a common single-mode optical fiber, interference is formed in an interference area of a Fabry-Perot resonant cavity, the external bias voltage is set to be 0 volt, when external gas molecules flow into the Fabry-Perot cavity through a microfluidic channel, and trace gas molecules are attached to a tungsten selenide film, extra-nuclear electrons of tungsten selenide are combined with the gas molecules to form a new 'covalent bond', the electron energy distribution (carrier concentration) on the surface of the tungsten selenide is changed in the process, the conductivity of the tungsten selenide is further changed, and the optical refractive index of a tungsten selenide material is finally influenced. And then through the interference of this Fabry-Perot chamber, the relevant interference frequency shift of test gas concentration realizes the sensing of gas concentration, and its sensitivity reaches 0.1 ppb. Then, the external bias voltage is modulated to be 5 volts, and due to the heat effect, the gas molecules adsorbed on the surface of the tungsten selenide are released, so that the gas sensor shows good recoverability.
The invention adopts a mature and stable sensing principle, combines optics, metamaterial disciplines and micro-nano processing advanced technologies, integrates a tungsten selenide-gold conductive structure on the end face of a single-mode optical fiber with the diameter of only 125 microns, relies on the physical adsorption and electric adjustable characteristics of tungsten selenide, and realizes the adsorption and release of gas molecules by modulating the voltage applied by the tungsten selenide. The response speed and the sensitivity of the sensor are considered, and meanwhile, the device is small in size, good in thermal stability and small in sensing power consumption: the response time of the sensor is only one thousandth of that of an electrochemical gas sensor, the sensitivity of the sensor can reach over 1000 times of that of a traditional optical gas sensor, and the sensing power consumption is as low as 100 nanowatts. The sensor can be directly integrated in an all-optical system, and high-speed information sensing of an all-optical network is realized.
Drawings
FIG. 1 is a schematic three-dimensional structure of the present invention;
fig. 2 is a schematic diagram of the three-dimensional structure of the tungsten selenide-gold conductive structure of the invention;
FIG. 3 is a diagram of an embodiment test apparatus;
FIG. 4 is a schematic diagram of the interference frequency shift of a sensor according to an embodiment for different ammonia concentrations;
fig. 5 is a schematic view showing the sensing recoverability of the sensor of the embodiment at an ammonia gas concentration of 1 ppb.
Reference numerals: the optical fiber comprises a single-mode optical fiber-1, a tungsten selenide-gold conductive structure-2, a fiber core-3, an air gap-4, a dielectric film-5, a gold film-6, a tungsten selenide film-7, a scanning laser-8, a Fabry-Perot microcavity sensor-10, a power supply-9 and a spectrometer-11.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings and examples.
An optical fiber Fabry-Perot hypersensitivity gas sensor based on a tungsten selenide thin film channel structure is shown in figure 1. The method adopts a mature and stable Fabry-Perot interference sensing principle, the single-mode optical fiber is 6 mm, the Fabry-Perot cavity is 1 cm long, and the Fabry-Perot cavity is integrated in a quartz capillary tube with the inner diameter of 125 microns, so that the interference sensing of the polar gas molecule concentration is realized.
Referring to fig. 1 and 2, after an end face of a common single-mode optical fiber is cut, polished and polished to have surface smoothness of a mirror level, a vacuum evaporation method is adopted for the end face to evaporate 16 layers of silicon dioxide and zirconium dioxide dielectric films (5) so that the reflectivity of the dielectric films can reach 97.188% at a 1550 nm waveband, and the single-mode optical fiber (1) with the high-reflectivity dielectric film is formed.
A single-mode optical fiber with the length of 6 mm and two cut-off ends is adopted to sputter a gold film (6) with the thickness of 30 nanometers by using an ion sputtering instrument, the gold film with the channel width of 10 micrometers is removed from a fiber core part (3), then the gold film is inserted into a tungsten selenide film with the thickness of 30 nanometers, which is prepared by a liquid phase deposition method, and the tungsten selenide film (7) is attached to the end face of the optical fiber due to Van der Waals force to form a conductive structure (2) together with an upper section of gold electrode and a lower section of gold electrode. A tungsten selenide-gold conductive structure with the length of 6 mm and a single-mode optical fiber with two ends plated with high-reflectivity dielectric films are respectively inserted into a quartz capillary with the inner diameter of 125 microns, an air gap (4) with the length of 1 mm is reserved between the tungsten selenide-gold conductive structure and the high-reflectivity dielectric film on one side of the quartz capillary, and two air holes are symmetrically arranged on the quartz capillary at the air gap. And the collimation and the encapsulation of a light path are completed, and the assembly of the optical fiber Fabry-Perot hypersensitivity gas sensor based on the tungsten selenide film channel structure is realized.
As shown in fig. 3, a scanning laser signal output by a scanning laser (8) with a scanning range of 1550 nm to 1560 nm is injected into the fabry-perot microcavity sensor (10), interference is formed in an interference region of the fabry-perot resonant cavity, an external bias voltage is set to 0 volt by using a power supply (9), when external gas molecules flow into the fabry-perot cavity through a microfluidic channel and trace gas molecules are attached to a tungsten selenide film, extra-nuclear electrons of the tungsten selenide are combined with the gas molecules to form a new covalent bond, and the electron energy distribution (carrier concentration) on the surface of the tungsten selenide is changed in the process, so that the conductivity of the tungsten selenide is changed, and the optical refractive index of the tungsten selenide material is finally influenced. Further, the interference of the Fabry-Perot cavity is utilized to test the interference frequency shift related to the gas concentration by a spectrometer (11), so that the gas concentration is sensed, and the sensitivity of the sensor reaches 0.1 ppb. And then, the external bias voltage is modulated to be 5 volts, due to the heat effect, the gas molecules adsorbed on the surface of the tungsten selenide are released, the gas sensor shows good recoverability, and the single sensing recoverability reaches 99%. Fig. 4 reflects the interference frequency shift variation characteristics of the sensor of the present embodiment under different ammonia gas concentrations. Fig. 5 reflects that the sensor recoverability of the sensor of this example was as high as 99% at an ammonia gas concentration of 1 ppb.
In conclusion, the invention gives consideration to the response speed and the sensitivity of the sensor, and meanwhile, the sensor has the advantages of small size, good thermal stability and small sensing power consumption: the response time of the sensor is only one thousandth of that of an electrochemical gas sensor, the sensitivity of the sensor can reach more than 1000 times of that of a traditional optical gas sensor, and the sensing power consumption is as low as 100 nanowatts; and the system can be directly integrated in an all-optical system to realize high-speed information sensing of an all-optical network.
Claims (3)
1. The optical fiber Fabry-Perot hypersensitive gas sensor based on the tungsten selenide film channel structure comprises a coated single-mode optical fiber, a tungsten selenide-single-mode optical fiber and a quartz capillary tube, and is characterized in that:
the two coated single-mode optical fibers are single-mode optical fibers with one ends coated with dielectric films and reflectivity of more than 95% at 1550 nm waveband;
the tungsten selenide-single mode fiber is a single mode fiber with one end plated with a gold film, the gold film at the core part of the single mode fiber is removed in a through mode with the channel width of more than or equal to 10 microns, the gold film is divided into two sections and then inserted into the tungsten selenide thin film, and finally the tungsten selenide thin film is attached to the end face of the single mode fiber and forms a tungsten selenide-gold conductive structure together with the two sections of the gold film;
the tungsten selenide-single mode fiber is placed in the middle, the coated single mode fiber is positioned at two ends, and the coated end faces are placed in the middle, and the coated single mode fiber is inserted into a quartz capillary tube which is used as a Fabry-Perot cavity collimation and encapsulation structure and also used as a gas micro-flow channel; the coating end of the tungsten selenide-single mode fiber is not in contact with the corresponding medium film-single mode fiber coating end to form an air gap of 1-3 mm, a quartz capillary tube at the air gap part is provided with an air hole, the air gap structure is used as a microflow channel of gas molecules, and the two coated single mode fibers form a Fabry-Perot microcavity; and the light path between the tungsten selenide-single mode fiber and the two dielectric thin film-single mode fibers is aligned.
2. The optical fiber Fabry-Perot hypersensitivity gas sensor based on the tungsten selenide thin film channel structure as claimed in claim 1, wherein: the number of the air holes is two, and the two air holes are symmetrically arranged on the quartz capillary tube of the air gap part.
3. The optical fiber Fabry-Perot hypersensitivity gas sensor based on the tungsten selenide thin film channel structure as claimed in claim 1, wherein: the dielectric film is formed by sequentially superposing and depositing silicon dioxide films and zirconium dioxide films.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811131211.3A CN109164050B (en) | 2018-09-27 | 2018-09-27 | Optical fiber Fabry-Perot hypersensitive gas sensor based on tungsten selenide film channel structure |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811131211.3A CN109164050B (en) | 2018-09-27 | 2018-09-27 | Optical fiber Fabry-Perot hypersensitive gas sensor based on tungsten selenide film channel structure |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109164050A CN109164050A (en) | 2019-01-08 |
| CN109164050B true CN109164050B (en) | 2021-02-09 |
Family
ID=64892591
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811131211.3A Active CN109164050B (en) | 2018-09-27 | 2018-09-27 | Optical fiber Fabry-Perot hypersensitive gas sensor based on tungsten selenide film channel structure |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109164050B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109738112B (en) * | 2019-01-30 | 2021-04-16 | 中山大学 | Pressure intensity detection device based on nano sensor |
| CN109900667B (en) * | 2019-03-15 | 2021-08-06 | 电子科技大学 | All-fiber laser type selective hypersensitivity biochemical sensor |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101387608B (en) * | 2008-05-27 | 2010-09-15 | 重庆大学 | Ultralong Fabry-Parot interferent gas sensor and gas tester based on the sensor |
| CN105186271A (en) * | 2015-10-16 | 2015-12-23 | 深圳大学 | Transition metal sulfide saturable absorption mirror and mode locking fiber laser |
| CN205941335U (en) * | 2016-08-24 | 2017-02-08 | 马鞍山市安工大工业技术研究院有限公司 | High sensitivity's optic fibre EFPI sensor |
| CN106248602B (en) * | 2016-09-19 | 2019-09-03 | 电子科技大学 | Hydrogen sulfide gas sensing device based on fiber F-P interferometer |
| CN106908389B (en) * | 2017-03-17 | 2018-02-16 | 哈尔滨翰奥科技有限公司 | Gas sensor and the method for detecting hydrogen fluoride gas change in concentration |
| CN207051192U (en) * | 2017-04-21 | 2018-02-27 | 中国计量大学 | A kind of self-calibration device based on the double F P verniers amplification hydrogen gas sensors of optical fiber microcavity |
| CN206710289U (en) * | 2017-05-24 | 2017-12-05 | 中国计量大学 | A kind of hydrogen gas sensor based on F P interferometers non-sensitive to temperature |
-
2018
- 2018-09-27 CN CN201811131211.3A patent/CN109164050B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN109164050A (en) | 2019-01-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109358038B (en) | Microstructure optical fiber surface plasma resonance multifunctional sensor and preparation method thereof | |
| Yang et al. | Hydrogen sensing performance comparison of Pd layer and Pd/WO3 composite thin film coated on side-polished single-and multimode fibers | |
| Lokman et al. | Optical fiber relative humidity sensor based on inline Mach–Zehnder interferometer with ZnO nanowires coating | |
| FI85768B (en) | FOERFARANDE FOER UTFOERNING AV YTPLASMONRESONANSMAETNING SAMT I FOERFARANDET ANVAENDBAR GIVARE. | |
| CN109164050B (en) | Optical fiber Fabry-Perot hypersensitive gas sensor based on tungsten selenide film channel structure | |
| Tong et al. | Relative humidity sensor based on small up-tapered photonic crystal fiber Mach–Zehnder interferometer | |
| Zhao et al. | Reflective highly sensitive Fabry–Pérot magnetic field sensor based on magneto-volume effect of magnetic fluid | |
| CN109164051B (en) | Graphene embedded echo wall microsphere cavity monomolecular gas sensor | |
| CN104483498A (en) | Sensing chip and preparation method thereof | |
| CN102062729A (en) | Integrated structure of micro-ring cavity structure-based two-channel sensors and microfluidic channels and manufacture method of integrated structure | |
| CN108414474A (en) | A kind of SPR fibre optical sensors and preparation method thereof based on temperature self-compensation | |
| Zhao et al. | Preparation and structure dependence of H2 sensing properties of palladium-coated tungsten oxide films | |
| CN110186875A (en) | Surface plasmon resonance optical-fiber type pH value measurement method and sensor | |
| CN106093150A (en) | A kind of self assembly graphene field effect cast biochemical sensor manufacture method | |
| Chen et al. | Formic acid gas sensor based on coreless optical fiber coated by molybdenum disulfide nanosheet | |
| CN109253986B (en) | Double-ring optical sensor of cascade Fourier transform spectrometer | |
| CN107966422B (en) | Hydrogen sensing microstructure based on surface plasmon resonance effect | |
| Yang et al. | Hydrogen leakage detectors based on a polymer microfiber decorated with Pd nanoparticles | |
| Zhao et al. | Tunability of Pd-nanogapped H2 sensors made on SiO2-coated Si micropillar arrays | |
| CN208043656U (en) | A kind of SPR fibre optical sensors based on temperature self-compensation | |
| Li et al. | An ultraviolet sensor based on surface plasmon resonance in no-core optical fiber deposited by Ag and ZnO film | |
| JP6401667B2 (en) | Optical sensor element | |
| CN107290422B (en) | A kind of biochemical detection system and method based on electrochemistry enhancing reflectance spectrum signal | |
| Jakšic et al. | Performance limits to the operation of nanoplasmonic chemical sensors: noise-equivalent refractive index and detectivity | |
| Iwami et al. | Plasmon-resonance dew condensation sensor made of gold-ceramic nanocomposite and its application in condensation prevention |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CB03 | Change of inventor or designer information |
Inventor after: Yao Baicheng Inventor after: Yuan Zhongye Inventor after: Cao Zhongxu Inventor after: Wu Yu Inventor after: Rao Yunjiang Inventor before: Cao Zhongxu Inventor before: Yuan Zhongye Inventor before: Yao Baicheng Inventor before: Wu Yu Inventor before: Rao Yunjiang |
|
| CB03 | Change of inventor or designer information |