CN105699445A - Environment monitoring device with input and output humidity data - Google Patents
Environment monitoring device with input and output humidity data Download PDFInfo
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- CN105699445A CN105699445A CN201610065995.9A CN201610065995A CN105699445A CN 105699445 A CN105699445 A CN 105699445A CN 201610065995 A CN201610065995 A CN 201610065995A CN 105699445 A CN105699445 A CN 105699445A
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Abstract
The invention discloses an environment monitoring device with input and output humidity data. A ZnO-based humidity-sensitive sensor module is mounted at the outer part of the environment monitoring device; a humidity-sensitive sensitive element part of the ZnO-based humidity-sensitive sensor module is prepared by taking a silicon nano-pore column material as a base, and taking a zinc oxide nano wire combined graphene material as a sensitive material; the structure of the device is an interdigital electrode type; the structure has an extremely large specific surface area and a good gas diffusion channel; and furthermore, the surface layer of the environment monitoring device is provided with a dehumidified polyvinyl alcohol-ethylene diamine tetramethylene phosphonic acid-polysulfone-based film hollow fiber composite film assembly, so that humidity induction, moisture absorption and corrosion prevention functions of the device are greatly improved.
Description
Technical field
The present invention relates to environmental area, be specifically related to a kind of environment monitoring device with input and output humidity data。
Background technology
Environment monitoring device is generally made up of multiple detector nodes and monitoring terminal, and wherein, probe node can to the collection of environmental information, process and data transmit-receives etc. such as temperature, illumination, humidity in environment
But, the humidity probe node in existing correlation technique yet suffers from the shortcomings such as not high, the response time length of sensitivity。
Summary of the invention
It is an object of the invention to avoid above-mentioned weak point of the prior art to provide a kind of environment monitoring device with input and output humidity data。
The purpose of the present invention is achieved through the following technical solutions:
The invention provides a kind of environment monitoring device with input and output humidity data, it is characterised in that: the outside of described environment monitoring device (1) is provided with zno-based moisture sensor module (2)；Described zno-based moisture sensor module (2) is mainly made up of wet sensitive sensing element and data read element, described wet sensitive sensing element is interdigital electrode type, including silicon chip substrate (10), Si NPA (20), zinc oxide nanowire (30) and graphene layer (40)；The output electric wire sidewall of described environment monitoring device (1) is provided with a polyvinyl alcohol ethylenediamine tetraacetic methene phosphoric acid polysulfones basement membrane hollow fiber composite membrane assembly for dehumidification, polyvinyl alcohol ethylenediamine tetraacetic methene phosphoric acid polysulfones basement membrane hollow fiber composite membrane is fixed in glass electrode by this membrane module, and glass electrode is connected with moisture sensor；Described zinc oxide nanowire (30) length about 6 μm。
Preferably, the preparation method of described wet sensitive sensing element is as follows:
Step one, prepares Si-NPA substrate: the silicon chip substrate (10) of 3cm × 3cm is included clean dirt, hydro-thermal method corrosion preparation Si-NPA substrate；1. taking the silicon chip of 3cm × 3cm, be placed in by silicon chip in the mixed solution of sulphuric acid and hydrogen peroxide volume ratio 4:1, supersound process 20min, taking-up deionized water cleans, to remove the organic impurities of silicon chip surface；It is H that silicon chip is positioned over volume ratio2O:H2O2: NH4In the mixed solution of OH=5:2:1, ultrasonic cleaning 20min, the deionized water of taking-up subsequently cleans, to remove Organic substance and the metal complex of silicon chip surface；2. hydro-thermal method corrosion is utilized to prepare Si-NPA: to weigh the Fe (NO of 1.0g3)·9H2O pours in politef, is added thereto to the HF solution of 20ml deionized water and 30ml40% subsequently；Putting in solution by the silicon chip that upper step is cleaned, add a cover and put in water heating kettle, put in drying baker by water heating kettle subsequently, 180 DEG C of constant temperature keep 30min, after natural cooling, take out Wafer Cleaning and namely obtain Si-NPA substrate；
Step 2, growth of zinc oxide nano line: adopt magnetron sputtering to prepare zinc oxide nanowire in conjunction with thermal oxidation method；Silicon nano hole column substrate is put in magnetic control sputtering device, when sputtering voltage 220V, sputtering current 0.8A, magnetron sputtering Zn film, thickness is 50nm, puts it into subsequently in batch-type furnace, and at 400 DEG C, thermal oxidation method processes 4h, obtaining length about 6 μm, diameter is about the zinc oxide nanowire of 30nm；
Step 3, grows graphene layer: adopt process for preparing graphenes by chemical vapour deposition；First magnetron sputtering layer of metal Ni film on the substrate that upper step obtains, thickness is about 5nm；Secondly, putting in tube furnace by this substrate, be warming up to 900 DEG C, pass into hydrogen as protection reducing gas by given pace, stablize 30min, then, pass into methane 2h according to a certain percentage simultaneously, stopping starts Temperature fall after passing into methane；Under Ni catalyst action, methane molecule at high temperature can be cracked into carbon atom and hydrogen atom, and at temperature-fall period and under the protection of hydrogen, carbon atom can formation of deposits one layer graphene thin film；
Step 4, is deposited with interdigital electrode: after obtaining growing the silicon nano hole column substrate having zinc oxide nanowire and Graphene, covers interdigital electrode mask at substrate surface, utilizes magnetron sputtering method to be deposited with Au thin film thick for one layer of 500nm on its surface as electrode；
Step 5, assembles sensing element and reads data element: the both positive and negative polarity wire reading data element is connected in interdigital electrode, two parts composition Zinc oxide-base moisture sensor device；
The preparation method of described polyvinyl alcohol-ethylenediamine tetraacetic methene phosphoric acid-polysulfones basement membrane hollow fiber composite membrane assembly is as follows:
Step one, polysulfone hollow fibre basement membrane pretreatment: polysulfone hollow fibre basement membrane to carry out pretreatment before coating, after soaking 12h with deionized water, with the soak with hydrochloric acid 60min of 1.0mol/l, remove glycerin layer and other organic solvents on film surface；Then use in the sodium hydroxide solution of 1.0mol/l and excessive hydrochloric acid, finally repeatedly rinse with deionized water, make film surface in neutrality, dry in the shade standby；
Step 2, prepare polyvinyl alcohol-ethylenediamine tetraacetic methene phosphoric acid-polysulfone hollow fibre composite membrane: add in deionized water by the polyvinyl alcohol that the average degree of polymerization of certain mass is 1750 ± 50, it is about 3h 50 DEG C of stirred in water bath to be completely dissolved to polyvinyl alcohol, obtains 5wt% polyvinyl alcohol homogeneous phase aqueous solution；Adding a certain amount of ethylenediamine tetraacetic methene phosphoric acid after solution is cooled to room temperature, and at room temperature stir 1.5h, namely standing and defoaming obtains casting solution；Polysulfones basement membrane (molecular cut off 30000) through pretreatment is taken out after casting solution soaks 20min, is vertically fixed on the guide frame that dries in the air and dries in the shade；After the film of primary coating soaks 20min again in casting solution, will reversely be fixed on and dry in the air on guide frame, dry at room temperature over night, prepare required PVA-EDTMPA/PS hollow fiber composite membrane。
Step 3, fixing: polyvinyl alcohol-ethylenediamine tetraacetic methene phosphoric acid-polysulfone hollow fibre composite membrane is fixed in glass electrode。
There is advantages that
1. configuration aspects, the present invention adopts Si-NPA (silicon nano hole column) material to be substrate, ZnONWs (zinc oxide nanowire) is sensitive material in conjunction with Graphene, this structure has great specific surface area and good gas diffusion paths, substantially increases the sensitivity of sensitive material in this environment monitoring device；
2. adopting grapheme material can increase the conductivity of material greatly, hydrone primary attachment is on the surface of nano wire Yu Graphene simultaneously, it is easy to desorption, and the repeatability that humidity is responded by this environment monitoring device is good；
3. preparation process material consumption is few, and the controllable degree of technique is high, device small volume and less weight, it is easy to batch production。
Accompanying drawing explanation
Utilize accompanying drawing that invention is described further, but the embodiment in accompanying drawing does not constitute any limitation of the invention, for those of ordinary skill in the art, under the premise not paying creative work, it is also possible to obtain other accompanying drawing according to the following drawings。
Fig. 1 is the schematic diagram of environment monitoring device of the present invention。
Fig. 2 is sensor sensing componentry schematic diagram。
Detailed description of the invention
Sensor technology is able to obtain main path and the means of various information in nature, production field。It is the cutting edge technology of a kind of modern science and technology, and it is one of three big pillars of modern information technologies, is the important benchmark weighing a national science and technology level of development。According to definition, sensor is: " can experience the measured of regulation and convert device or the device of usable output signal according to certain rule to, being generally made up of sensing element, conversion element and measuring circuit。" to be able to direct feeling measured and be converted into and the measured element of physical quantity having the electricity determining relation or easily becoming electricity for sensing element。Conversion element is able to the measured element being converted directly into the electricity determining relation experienced by sensing element。Measuring circuit is that the signal of telecommunication that conversion element exports is converted to the circuit of easy-to-handle capable telecommunications number。
Humidity refers to the content of water vapor in air。Along with the development of modern science and technology, the Detection & Controling of humidity in productive life being had very important meaning, the application of moisture sensor is also more and more extensive, and such as moisture sensor has a wide range of applications in the such as field such as household electrical appliance, automobile, industrial or agricultural。
Dew cell refers to that ambient humidity has response maybe can be converted to the element that can measure signal accordingly by ambient humidity, and it has a wide range of applications in fields such as industrial and agricultural production, environment measuring and Engineering Control。The core of humidity sensor is humidity-sensitive material, and it is the hydrone utilizing adsorption effect directly to adsorb in air, makes the electrology characteristic etc. of material change, thus detecting the change of humidity。Zinc oxide is a kind of semiconductor material with wide forbidden band, and it is all widely used in fields such as sensor, solaode, lithium battery, catalysis。And zinc oxide material to have preparation cost low, chemical stability, Heat stability is good, prepare the advantages such as controlled and pattern is abundant, be a kind of desirably humidity sensor material。The advantage of the aspects such as the pattern that has additionally, due to nano material itself, structure, nano zinc oxide material is very sensitive to humidity of external environment condition etc., has obvious Unordered system。
Humidity sensor refers to after utilizing humidity-sensitive material adsorbed water molecule, and the principle that measured amount changes is made。Generally accepted theory be the Water Molecular Adsorption in air when sensitive material surface and grain boundaries, reduce surface and the grain boundary resistance of material。
The problem such as not high, response recovery time length for existing moisture sensor sensitivity, this programme, based on nano zinc oxide material, is prepared for the zinc oxide nanowire with large specific surface area, and in conjunction with the high grapheme material of conductivity, makes moisture sensor。
Moisture sensor of the present invention is made up of wet sensitive sensing element part and data read element part。Wherein, wet sensitive sensing element is based on zinc oxide nanowire, make in conjunction with grapheme material, device architecture is interdigital electrode type, when moisture sensor periphery humidity changes, Water Molecular Adsorption can change in the speed of sensitive material surface and crystal boundary, causes the conductivity of sensitive material to change, and then reflects its capacitance variations from read element part；Digital independent element is with microprocessor, and it is the voltage applying characteristic frequency to sensing element, reads different numerical value according to the change of sensing element electric capacity at this voltage and carrys out the change of display environment humidity。
Illustrate that the present invention is further described below in conjunction with accompanying drawing。
Fig. 1 is the schematic diagram of environment monitoring device of the present invention。
Fig. 2 is sensor sensing componentry schematic diagram。Wherein: 10-silicon chip substrate, 20-Si-NPA, 30-zinc oxide nanowire, 40-graphene layer。
The invention will be further described with the following Examples。
Embodiment 1:
A kind of environment monitoring device with input and output humidity data as shown in Figure 1, the outside of described environment monitoring device 1 is provided with zno-based moisture sensor module 2；Described zno-based moisture sensor module 2 is mainly made up of wet sensitive sensing element and data read element。As in figure 2 it is shown, described wet sensitive sensing element is interdigital electrode type, it includes silicon chip substrate 10, Si-NPA20, zinc oxide nanowire 30 and graphene layer 40；The output electric wire sidewall of described environment monitoring device is provided with a polyvinyl alcohol for dehumidification-ethylenediamine tetraacetic methene phosphoric acid-polysulfones basement membrane hollow fiber composite membrane assembly, polyvinyl alcohol-ethylenediamine tetraacetic methene phosphoric acid-polysulfones basement membrane hollow fiber composite membrane is fixed in glass electrode by this membrane module, and glass electrode is connected with moisture sensor；Described zinc oxide nanowire 30 length about 6 μm。
Preferably, the preparation method of described wet sensitive sensing element is as follows:
Step one, prepares Si-NPA substrate: the silicon chip substrate of 3cm × 3cm is included clean dirt, hydro-thermal method corrosion preparation Si-NPA substrate；1. taking the silicon chip of 3cm × 3cm, be placed in by silicon chip in the mixed solution of sulphuric acid and hydrogen peroxide volume ratio 4:1, supersound process 20min, taking-up deionized water cleans, to remove the organic impurities of silicon chip surface；It is H that silicon chip is positioned over volume ratio2O:H2O2: NH4In the mixed solution of OH=5:2:1, ultrasonic cleaning 20min, the deionized water of taking-up subsequently cleans, to remove Organic substance and the metal complex of silicon chip surface；2. hydro-thermal method corrosion is utilized to prepare Si-NPA: to weigh the Fe (NO of 1.0g3)·9H2O pours in politef, is added thereto to the HF solution of 20ml deionized water and 30ml40% subsequently；Putting in solution by the silicon chip that upper step is cleaned, add a cover and put in water heating kettle, put in drying baker by water heating kettle subsequently, 180 DEG C of constant temperature keep 30min, after natural cooling, take out Wafer Cleaning and namely obtain Si-NPA substrate；
Step 2, growth of zinc oxide nano line: adopt magnetron sputtering to prepare zinc oxide nanowire in conjunction with thermal oxidation method；Silicon nano hole column substrate is put in magnetic control sputtering device, when sputtering voltage 220V, sputtering current 0.8A, magnetron sputtering Zn film, thickness is 50nm, puts it into subsequently in batch-type furnace, and at 400 DEG C, thermal oxidation method processes 4h, obtaining length about 6 μm, diameter is about the zinc oxide nanowire of 30nm；
Step 3, grows graphene layer: adopt process for preparing graphenes by chemical vapour deposition；First magnetron sputtering layer of metal Ni film on the substrate that upper step obtains, thickness is about 5nm；Secondly, putting in tube furnace by this substrate, be warming up to 900 DEG C, pass into hydrogen as protection reducing gas by given pace, stablize 30min, then, pass into methane 2h according to a certain percentage simultaneously, stopping starts Temperature fall after passing into methane；Under Ni catalyst action, methane molecule at high temperature can be cracked into carbon atom and hydrogen atom, and at temperature-fall period and under the protection of hydrogen, carbon atom can formation of deposits one layer graphene thin film；
Step 4, is deposited with interdigital electrode: after obtaining growing the silicon nano hole column substrate having zinc oxide nanowire and Graphene, covers interdigital electrode mask at substrate surface, utilizes magnetron sputtering method to be deposited with Au thin film thick for one layer of 500nm on its surface as electrode；
Step 5, assembles sensing element and reads data element: the both positive and negative polarity wire reading data element is connected in interdigital electrode, two parts composition Zinc oxide-base moisture sensor device；
Wherein, the preparation method of described polyvinyl alcohol-ethylenediamine tetraacetic methene phosphoric acid-polysulfones basement membrane hollow fiber composite membrane assembly is as follows:
Step one, polysulfone hollow fibre basement membrane pretreatment: polysulfone hollow fibre basement membrane to carry out pretreatment before coating, after soaking 12h with deionized water, with the soak with hydrochloric acid 60min of 1.0mol/l, remove glycerin layer and other organic solvents on film surface；Then use in the sodium hydroxide solution of 1.0mol/l and excessive hydrochloric acid, finally repeatedly rinse with deionized water, make film surface in neutrality, dry in the shade standby；
Step 2, prepare polyvinyl alcohol-ethylenediamine tetraacetic methene phosphoric acid-polysulfone hollow fibre composite membrane: add in deionized water by the polyvinyl alcohol that the average degree of polymerization of certain mass is 1750 ± 50, it is about 3h 50 DEG C of stirred in water bath to be completely dissolved to polyvinyl alcohol, obtains 5wt% polyvinyl alcohol homogeneous phase aqueous solution；Adding a certain amount of ethylenediamine tetraacetic methene phosphoric acid after solution is cooled to room temperature, and at room temperature stir 1.5h, namely standing and defoaming obtains casting solution；Polysulfones basement membrane (molecular cut off 30000) through pretreatment is taken out after casting solution soaks 20min, is vertically fixed on the guide frame that dries in the air and dries in the shade；After the film of primary coating soaks 20min again in casting solution, will reversely be fixed on and dry in the air on guide frame, dry at room temperature over night, prepare required PVA-EDTMPA/PS hollow fiber composite membrane。
Step 3, fixing: polyvinyl alcohol-ethylenediamine tetraacetic methene phosphoric acid-polysulfone hollow fibre composite membrane is fixed in glass electrode。
Wet sensitive is tested:
Zinc oxide-base moisture sensor is put in control appliance of temperature and humidity。Test temperature is set as 20 DEG C, then controls relative humidity variations and ranges for 10%～95%, reads the electric capacity of sensing element with humidity situation of change；
The sensitivity definition of dew cell is: CRH-C11/ C11× 100%, wherein CRHFor the component capacitance value obtained under test environment humidity, C11Capacitance for 11% time element of relative humidity。Are defined as the response of dew cell or recovery time testing capacitor value and reach the time used by total variation 80% at the variable quantity of 11%RH to 75%RH；
When testing frequency and being 100Hz, under the relative humidity of 15%, 35%, 55%, 75%, 95%, the sensitivity of sensing element respectively 4,39,174,997 and 2371, response and respectively 8s and 11s recovery time, test result shows that this environment monitoring device has good wet sensitive performance, it is possible to realize the humidity data output of environment monitoring device。
Embodiment 2
A kind of environment monitoring device with input and output humidity data as shown in Figure 1, the outside of described environment monitoring device 1 is provided with zno-based moisture sensor module 2；Described zno-based moisture sensor module 2 is mainly made up of wet sensitive sensing element and data read element。As in figure 2 it is shown, described wet sensitive sensing element is interdigital electrode type, it includes silicon chip substrate 10, Si-NPA20, zinc oxide nanowire 30 and graphene layer 40；The output electric wire sidewall of described environment monitoring device is provided with a polyvinyl alcohol for dehumidification-ethylenediamine tetraacetic methene phosphoric acid-polysulfones basement membrane hollow fiber composite membrane assembly, polyvinyl alcohol-ethylenediamine tetraacetic methene phosphoric acid-polysulfones basement membrane hollow fiber composite membrane is fixed in glass electrode by this membrane module, and glass electrode is connected with moisture sensor；Described zinc oxide nanowire 30 length about 7 μm。
Preferably, the preparation method of described wet sensitive sensing element is as follows:
Step one, prepares Si-NPA substrate: the silicon chip substrate of 3cm × 3cm is included clean dirt, hydro-thermal method corrosion preparation Si-NPA substrate；1. taking the silicon chip of 3cm × 3cm, be placed in by silicon chip in the mixed solution of sulphuric acid and hydrogen peroxide volume ratio 4:1, supersound process 20min, taking-up deionized water cleans, to remove the organic impurities of silicon chip surface；It is H that silicon chip is positioned over volume ratio2O:H2O2: NH4In the mixed solution of OH=5:2:1, ultrasonic cleaning 20min, the deionized water of taking-up subsequently cleans, to remove Organic substance and the metal complex of silicon chip surface；2. hydro-thermal method corrosion is utilized to prepare Si-NPA: to weigh the Fe (NO of 1.0g3)·9H2O pours in politef, is added thereto to the HF solution of 20ml deionized water and 30ml50% subsequently；Putting in solution by the silicon chip that upper step is cleaned, add a cover and put in water heating kettle, put in drying baker by water heating kettle subsequently, 180 DEG C of constant temperature keep 30min, after natural cooling, take out Wafer Cleaning and namely obtain Si-NPA substrate；
Step 2, growth of zinc oxide nano line: adopt magnetron sputtering to prepare zinc oxide nanowire in conjunction with thermal oxidation method；Silicon nano hole column substrate is put in magnetic control sputtering device, when sputtering voltage 210V, sputtering current 0.8A, magnetron sputtering Zn film, thickness is 26nm, puts it into subsequently in batch-type furnace, and at 400 DEG C, thermal oxidation method processes 4h, obtaining length about 7 μm, diameter is about the zinc oxide nanowire of 30nm；
Step 3, grows graphene layer: adopt process for preparing graphenes by chemical vapour deposition；First magnetron sputtering layer of metal Ni film on the substrate that upper step obtains, thickness is about 5nm；Secondly, putting in tube furnace by this substrate, be warming up to 900 DEG C, pass into hydrogen as protection reducing gas by given pace, stablize 30min, then, pass into methane 2h according to a certain percentage simultaneously, stopping starts Temperature fall after passing into methane；Under Ni catalyst action, methane molecule at high temperature can be cracked into carbon atom and hydrogen atom, and at temperature-fall period and under the protection of hydrogen, carbon atom can formation of deposits one layer graphene thin film；
Step 4, is deposited with interdigital electrode: after obtaining growing the silicon nano hole column substrate having zinc oxide nanowire and Graphene, covers interdigital electrode mask at substrate surface, utilizes magnetron sputtering method to be deposited with Au thin film thick for one layer of 500nm on its surface as electrode；
Step 5, assembles sensing element and reads data element: the both positive and negative polarity wire reading data element is connected in interdigital electrode, two parts composition Zinc oxide-base moisture sensor device；
Wherein, the preparation method of described polyvinyl alcohol-ethylenediamine tetraacetic methene phosphoric acid-polysulfones basement membrane hollow fiber composite membrane assembly is as follows:
Step one, polysulfone hollow fibre basement membrane pretreatment: polysulfone hollow fibre basement membrane to carry out pretreatment before coating, after soaking 12h with deionized water, with the soak with hydrochloric acid 60min of 1.0mol/l, remove glycerin layer and other organic solvents on film surface；Then use in the sodium hydroxide solution of 1.0mol/l and excessive hydrochloric acid, finally repeatedly rinse with deionized water, make film surface in neutrality, dry in the shade standby；
Step 2, prepare polyvinyl alcohol-ethylenediamine tetraacetic methene phosphoric acid-polysulfone hollow fibre composite membrane: add in deionized water by the polyvinyl alcohol that the average degree of polymerization of certain mass is 1750 ± 50, it is about 3h 50 DEG C of stirred in water bath to be completely dissolved to polyvinyl alcohol, obtains 5wt% polyvinyl alcohol homogeneous phase aqueous solution；Adding a certain amount of ethylenediamine tetraacetic methene phosphoric acid after solution is cooled to room temperature, and at room temperature stir 1.5h, namely standing and defoaming obtains casting solution；Polysulfones basement membrane (molecular cut off 30000) through pretreatment is taken out after casting solution soaks 20min, is vertically fixed on the guide frame that dries in the air and dries in the shade；After the film of primary coating soaks 20min again in casting solution, will reversely be fixed on and dry in the air on guide frame, dry at room temperature over night, prepare required PVA-EDTMPA/PS hollow fiber composite membrane。
Step 3, fixing: polyvinyl alcohol-ethylenediamine tetraacetic methene phosphoric acid-polysulfone hollow fibre composite membrane is fixed in glass electrode。
Wet sensitive is tested:
Zinc oxide-base moisture sensor is put in control appliance of temperature and humidity。Test temperature is set as 20 DEG C, then controls relative humidity variations and ranges for 10%～95%, reads the electric capacity of sensing element with humidity situation of change；
The sensitivity definition of dew cell is: CRH-C11/ C11× 100%, wherein CRHFor the component capacitance value obtained under test environment humidity, C11Capacitance for 11% time element of relative humidity。Are defined as the response of dew cell or recovery time testing capacitor value and reach the time used by total variation 80% at the variable quantity of 11%RH to 75%RH；
When testing frequency and being 100Hz, under the relative humidity of 15%, 35%, 55%, 75%, 95%, the sensitivity of sensing element respectively 4,38,148,953 and 2171, response and respectively 11s and 12s recovery time, test result shows that this environment monitoring device has good wet sensitive performance, it is possible to realize the humidity data output of environment monitoring device。
Embodiment 3:
A kind of environment monitoring device with input and output humidity data as shown in Figure 1, the outside of described environment monitoring device 1 is provided with zno-based moisture sensor module 2；Described zno-based moisture sensor module 2 is mainly made up of wet sensitive sensing element and data read element。As in figure 2 it is shown, described wet sensitive sensing element is interdigital electrode type, it includes silicon chip substrate 10, Si-NPA20, zinc oxide nanowire 30 and graphene layer 40；The output electric wire sidewall of described environment monitoring device is provided with a polyvinyl alcohol for dehumidification-ethylenediamine tetraacetic methene phosphoric acid-polysulfones basement membrane hollow fiber composite membrane assembly, polyvinyl alcohol-ethylenediamine tetraacetic methene phosphoric acid-polysulfones basement membrane hollow fiber composite membrane is fixed in glass electrode by this membrane module, and glass electrode is connected with moisture sensor；Described zinc oxide nanowire 30 length about 9 μm。
Preferably, the preparation method of described wet sensitive sensing element is as follows:
Step one, prepares Si-NPA substrate: the silicon chip substrate of 3cm × 3cm is included clean dirt, hydro-thermal method corrosion preparation Si-NPA substrate；1. taking the silicon chip of 3cm × 3cm, be placed in by silicon chip in the mixed solution of sulphuric acid and hydrogen peroxide volume ratio 4:3, supersound process 20min, taking-up deionized water cleans, to remove the organic impurities of silicon chip surface；It is H that silicon chip is positioned over volume ratio2O:H2O2: NH4In the mixed solution of OH=5:2:1, ultrasonic cleaning 20min, the deionized water of taking-up subsequently cleans, to remove Organic substance and the metal complex of silicon chip surface；2. hydro-thermal method corrosion is utilized to prepare Si-NPA: to weigh the Fe (NO of 1.0g3)·9H2O pours in politef, is added thereto to the HF solution of 20ml deionized water and 60ml40% subsequently；Putting in solution by the silicon chip that upper step is cleaned, add a cover and put in water heating kettle, put in drying baker by water heating kettle subsequently, 180 DEG C of constant temperature keep 30min, after natural cooling, take out Wafer Cleaning and namely obtain Si-NPA substrate；
Step 2, growth of zinc oxide nano line: adopt magnetron sputtering to prepare zinc oxide nanowire in conjunction with thermal oxidation method；Silicon nano hole column substrate is put in magnetic control sputtering device, when sputtering voltage 190V, sputtering current 0.8A, magnetron sputtering Zn film, thickness is 50nm, puts it into subsequently in batch-type furnace, and at 400 DEG C, thermal oxidation method processes 2h, obtaining length about 9 μm, diameter is about the zinc oxide nanowire of 60nm；
Step 3, grows graphene layer: adopt process for preparing graphenes by chemical vapour deposition；First magnetron sputtering layer of metal Ni film on the substrate that upper step obtains, thickness is about 5nm；Secondly, putting in tube furnace by this substrate, be warming up to 900 DEG C, pass into hydrogen as protection reducing gas by given pace, stablize 30min, then, pass into methane 2h according to a certain percentage simultaneously, stopping starts Temperature fall after passing into methane；Under Ni catalyst action, methane molecule at high temperature can be cracked into carbon atom and hydrogen atom, and at temperature-fall period and under the protection of hydrogen, carbon atom can formation of deposits one layer graphene thin film；
Step 4, is deposited with interdigital electrode: after obtaining growing the silicon nano hole column substrate having zinc oxide nanowire and Graphene, covers interdigital electrode mask at substrate surface, utilizes magnetron sputtering method to be deposited with Au thin film thick for one layer of 500nm on its surface as electrode；
Step 5, assembles sensing element and reads data element: the both positive and negative polarity wire reading data element is connected in interdigital electrode, two parts composition Zinc oxide-base moisture sensor device；
Wherein, the preparation method of described polyvinyl alcohol-ethylenediamine tetraacetic methene phosphoric acid-polysulfones basement membrane hollow fiber composite membrane assembly is as follows:
Step one, polysulfone hollow fibre basement membrane pretreatment: polysulfone hollow fibre basement membrane to carry out pretreatment before coating, after soaking 12h with deionized water, with the soak with hydrochloric acid 60min of 1.0mol/l, remove glycerin layer and other organic solvents on film surface；Then use in the sodium hydroxide solution of 1.0mol/l and excessive hydrochloric acid, finally repeatedly rinse with deionized water, make film surface in neutrality, dry in the shade standby；
Step 2, prepare polyvinyl alcohol-ethylenediamine tetraacetic methene phosphoric acid-polysulfone hollow fibre composite membrane: add in deionized water by the polyvinyl alcohol that the average degree of polymerization of certain mass is 1750 ± 50, it is about 3h 40 DEG C of stirred in water bath to be completely dissolved to polyvinyl alcohol, obtains 5wt% polyvinyl alcohol homogeneous phase aqueous solution；Adding a certain amount of ethylenediamine tetraacetic methene phosphoric acid after solution is cooled to room temperature, and at room temperature stir 1.5h, namely standing and defoaming obtains casting solution；Polysulfones basement membrane (molecular cut off 30000) through pretreatment is taken out after casting solution soaks 20min, is vertically fixed on the guide frame that dries in the air and dries in the shade；After the film of primary coating soaks 20min again in casting solution, will reversely be fixed on and dry in the air on guide frame, dry at room temperature over night, prepare required PVA-EDTMPA/PS hollow fiber composite membrane。
Step 3, fixing: polyvinyl alcohol-ethylenediamine tetraacetic methene phosphoric acid-polysulfone hollow fibre composite membrane is fixed in glass electrode。
Wet sensitive is tested:
Zinc oxide-base moisture sensor is put in control appliance of temperature and humidity。Test temperature is set as 20 DEG C, then controls relative humidity variations and ranges for 10%～95%, reads the electric capacity of sensing element with humidity situation of change；
The sensitivity definition of dew cell is: CRH-C11/ C11× 100%, wherein CRHFor the component capacitance value obtained under test environment humidity, C11Capacitance for 11% time element of relative humidity。Are defined as the response of dew cell or recovery time testing capacitor value and reach the time used by total variation 80% at the variable quantity of 11%RH to 75%RH；
When testing frequency and being 100Hz, under the relative humidity of 15%, 35%, 55%, 75%, 95%, the sensitivity of sensing element respectively 4,31,138,953 and 1922, response and respectively 11s and 10s recovery time, test result shows that this environment monitoring device has good wet sensitive performance, it is possible to realize the humidity data output of environment monitoring device。
Embodiment 4
A kind of environment monitoring device with input and output humidity data as shown in Figure 1, the outside of described environment monitoring device 1 is provided with zno-based moisture sensor module 2；Described zno-based moisture sensor module 2 is mainly made up of wet sensitive sensing element and data read element。As in figure 2 it is shown, described wet sensitive sensing element is interdigital electrode type, it includes silicon chip substrate 10, Si-NPA20, zinc oxide nanowire 30 and graphene layer 40；The output electric wire sidewall of described environment monitoring device is provided with a polyvinyl alcohol for dehumidification-ethylenediamine tetraacetic methene phosphoric acid-polysulfones basement membrane hollow fiber composite membrane assembly, polyvinyl alcohol-ethylenediamine tetraacetic methene phosphoric acid-polysulfones basement membrane hollow fiber composite membrane is fixed in glass electrode by this membrane module, and glass electrode is connected with moisture sensor；Described zinc oxide nanowire 30 length about 13 μm。
Preferably, the preparation method of described wet sensitive sensing element is as follows:
Step one, prepares Si-NPA substrate: the silicon chip substrate of 3cm × 3cm is included clean dirt, hydro-thermal method corrosion preparation Si-NPA substrate；1. taking the silicon chip of 3cm × 3cm, be placed in by silicon chip in the mixed solution of sulphuric acid and hydrogen peroxide volume ratio 4:1, supersound process 20min, taking-up deionized water cleans, to remove the organic impurities of silicon chip surface；It is H that silicon chip is positioned over volume ratio2O:H2O2: NH4In the mixed solution of OH=5:2:1, ultrasonic cleaning 20min, the deionized water of taking-up subsequently cleans, to remove Organic substance and the metal complex of silicon chip surface；2. hydro-thermal method corrosion is utilized to prepare Si-NPA: to weigh the Fe (NO of 1.0g3)·9H2O pours in politef, is added thereto to the HF solution of 20ml deionized water and 30ml40% subsequently；Putting in solution by the silicon chip that upper step is cleaned, add a cover and put in water heating kettle, put in drying baker by water heating kettle subsequently, 180 DEG C of constant temperature keep 30min, after natural cooling, take out Wafer Cleaning and namely obtain Si-NPA substrate；
Step 2, growth of zinc oxide nano line: adopt magnetron sputtering to prepare zinc oxide nanowire in conjunction with thermal oxidation method；Silicon nano hole column substrate is put in magnetic control sputtering device, when sputtering voltage 220V, sputtering current 0.9A, magnetron sputtering Zn film, thickness is 50nm, puts it into subsequently in batch-type furnace, and at 450 DEG C, thermal oxidation method processes 4h, obtaining length about 13 μm, diameter is about the zinc oxide nanowire of 30nm；
Step 3, grows graphene layer: adopt process for preparing graphenes by chemical vapour deposition；First magnetron sputtering layer of metal Ni film on the substrate that upper step obtains, thickness is about 15nm；Secondly, putting in tube furnace by this substrate, be warming up to 900 DEG C, pass into hydrogen as protection reducing gas by given pace, stablize 30min, then, pass into methane 2h according to a certain percentage simultaneously, stopping starts Temperature fall after passing into methane；Under Ni catalyst action, methane molecule at high temperature can be cracked into carbon atom and hydrogen atom, and at temperature-fall period and under the protection of hydrogen, carbon atom can formation of deposits one layer graphene thin film；
Step 4, is deposited with interdigital electrode: after obtaining growing the silicon nano hole column substrate having zinc oxide nanowire and Graphene, covers interdigital electrode mask at substrate surface, utilizes magnetron sputtering method to be deposited with Au thin film thick for one layer of 500nm on its surface as electrode；
Step 5, assembles sensing element and reads data element: the both positive and negative polarity wire reading data element is connected in interdigital electrode, two parts composition Zinc oxide-base moisture sensor device；
Wherein, the preparation method of described polyvinyl alcohol-ethylenediamine tetraacetic methene phosphoric acid-polysulfones basement membrane hollow fiber composite membrane assembly is as follows:
Step one, polysulfone hollow fibre basement membrane pretreatment: polysulfone hollow fibre basement membrane to carry out pretreatment before coating, after soaking 12h with deionized water, with the soak with hydrochloric acid 60min of 2.0mol/l, remove glycerin layer and other organic solvents on film surface；Then use in the sodium hydroxide solution of 1.0mol/l and excessive hydrochloric acid, finally repeatedly rinse with deionized water, make film surface in neutrality, dry in the shade standby；
Step 2, prepare polyvinyl alcohol-ethylenediamine tetraacetic methene phosphoric acid-polysulfone hollow fibre composite membrane: add in deionized water by the polyvinyl alcohol that the average degree of polymerization of certain mass is 1750 ± 50, it is about 3h 50 DEG C of stirred in water bath to be completely dissolved to polyvinyl alcohol, obtains 5wt% polyvinyl alcohol homogeneous phase aqueous solution；Adding a certain amount of ethylenediamine tetraacetic methene phosphoric acid after solution is cooled to room temperature, and at room temperature stir 1.5h, namely standing and defoaming obtains casting solution；Polysulfones basement membrane (molecular cut off 30000) through pretreatment is taken out after casting solution soaks 20min, is vertically fixed on the guide frame that dries in the air and dries in the shade；After the film of primary coating soaks 20min again in casting solution, will reversely be fixed on and dry in the air on guide frame, dry at room temperature over night, prepare required PVA-EDTMPA/PS hollow fiber composite membrane。
Step 3, fixing: polyvinyl alcohol-ethylenediamine tetraacetic methene phosphoric acid-polysulfone hollow fibre composite membrane is fixed in glass electrode。
Wet sensitive is tested:
Zinc oxide-base moisture sensor is put in control appliance of temperature and humidity。Test temperature is set as 20 DEG C, then controls relative humidity variations and ranges for 10%～95%, reads the electric capacity of sensing element with humidity situation of change；
The sensitivity definition of dew cell is: CRh-C11/ C11× 100%, wherein CRHFor the component capacitance value obtained under test environment humidity, C11Capacitance for 11% time element of relative humidity。Are defined as the response of dew cell or recovery time testing capacitor value and reach the time used by total variation 80% at the variable quantity of 11%RH to 75%RH；
When testing frequency and being 100Hz, under the relative humidity of 15%, 35%, 55%, 75%, 95%, the sensitivity of sensing element respectively 3,47,110,788 and 1746, response and respectively 15s and 13s recovery time, test result shows that this environment monitoring device has good wet sensitive performance, it is possible to realize the humidity data output of environment monitoring device。
Embodiment 5
A kind of environment monitoring device with input and output humidity data as shown in Figure 1, the outside of described environment monitoring device 1 is provided with zno-based moisture sensor module 2；Described zno-based moisture sensor module 2 is mainly made up of wet sensitive sensing element and data read element。As in figure 2 it is shown, described wet sensitive sensing element is interdigital electrode type, it includes silicon chip substrate 10, Si-NPA20, zinc oxide nanowire 30 and graphene layer 40；The output electric wire sidewall of described environment monitoring device is provided with a polyvinyl alcohol for dehumidification-ethylenediamine tetraacetic methene phosphoric acid-polysulfones basement membrane hollow fiber composite membrane assembly, polyvinyl alcohol-ethylenediamine tetraacetic methene phosphoric acid-polysulfones basement membrane hollow fiber composite membrane is fixed in glass electrode by this membrane module, and glass electrode is connected with moisture sensor；Described zinc oxide nanowire 30 length about 25 μm。
Preferably, the preparation method of described wet sensitive sensing element is as follows:
Step one, prepares Si-NPA substrate: the silicon chip substrate of 3cm × 3cm is included clean dirt, hydro-thermal method corrosion preparation Si-NPA substrate；1. taking the silicon chip of 3cm × 3cm, be placed in by silicon chip in the mixed solution of sulphuric acid and hydrogen peroxide volume ratio 4:1, supersound process 20min, taking-up deionized water cleans, to remove the organic impurities of silicon chip surface；It is H that silicon chip is positioned over volume ratio2O:H2O2: NH4In the mixed solution of OH=5:2:1, ultrasonic cleaning 20min, the deionized water of taking-up subsequently cleans, to remove Organic substance and the metal complex of silicon chip surface；2. hydro-thermal method corrosion is utilized to prepare Si-NPA: to weigh the Fe (NO of 1.0g3)·9H2O pours in politef, is added thereto to the HF solution of 20ml deionized water and 30ml60% subsequently；Putting in solution by the silicon chip that upper step is cleaned, add a cover and put in water heating kettle, put in drying baker by water heating kettle subsequently, 180 DEG C of constant temperature keep 30min, after natural cooling, take out Wafer Cleaning and namely obtain Si-NPA substrate；
Step 2, growth of zinc oxide nano line: adopt magnetron sputtering to prepare zinc oxide nanowire in conjunction with thermal oxidation method；Silicon nano hole column substrate is put in magnetic control sputtering device, when sputtering voltage 220V, sputtering current 0.8A, magnetron sputtering Zn film, thickness is 50nm, puts it into subsequently in batch-type furnace, and at 400 DEG C, thermal oxidation method processes 4h, obtaining length about 25 μm, diameter is about the zinc oxide nanowire of 30nm；
Step 3, grows graphene layer: adopt process for preparing graphenes by chemical vapour deposition；First magnetron sputtering layer of metal Ni film on the substrate that upper step obtains, thickness is about 15nm；Secondly, putting in tube furnace by this substrate, be warming up to 700 DEG C, pass into hydrogen as protection reducing gas by given pace, stablize 36min, then, pass into methane 2h according to a certain percentage simultaneously, stopping starts Temperature fall after passing into methane；Under Ni catalyst action, methane molecule at high temperature can be cracked into carbon atom and hydrogen atom, and at temperature-fall period and under the protection of hydrogen, carbon atom can formation of deposits one layer graphene thin film；
Step 4, is deposited with interdigital electrode: after obtaining growing the silicon nano hole column substrate having zinc oxide nanowire and Graphene, covers interdigital electrode mask at substrate surface, utilizes magnetron sputtering method to be deposited with Au thin film thick for one layer of 500nm on its surface as electrode；
Step 5, assembles sensing element and reads data element: the both positive and negative polarity wire reading data element is connected in interdigital electrode, two parts composition Zinc oxide-base moisture sensor device；
Wherein, the preparation method of described polyvinyl alcohol-ethylenediamine tetraacetic methene phosphoric acid-polysulfones basement membrane hollow fiber composite membrane assembly is as follows:
Step one, polysulfone hollow fibre basement membrane pretreatment: polysulfone hollow fibre basement membrane to carry out pretreatment before coating, after soaking 12h with deionized water, with the soak with hydrochloric acid 60min of 1.3mol/l, remove glycerin layer and other organic solvents on film surface；Then use in the sodium hydroxide solution of 1.0mol/l and excessive hydrochloric acid, finally repeatedly rinse with deionized water, make film surface in neutrality, dry in the shade standby；
Step 2, prepare polyvinyl alcohol-ethylenediamine tetraacetic methene phosphoric acid-polysulfone hollow fibre composite membrane: add in deionized water by the polyvinyl alcohol that the average degree of polymerization of certain mass is 1750 ± 50, it is about 3h 50 DEG C of stirred in water bath to be completely dissolved to polyvinyl alcohol, obtains 5wt% polyvinyl alcohol homogeneous phase aqueous solution；Adding a certain amount of ethylenediamine tetraacetic methene phosphoric acid after solution is cooled to room temperature, and at room temperature stir 1.5h, namely standing and defoaming obtains casting solution；Polysulfones basement membrane (molecular cut off 30000) through pretreatment is taken out after casting solution soaks 20min, is vertically fixed on the guide frame that dries in the air and dries in the shade；After the film of primary coating soaks 20min again in casting solution, will reversely be fixed on and dry in the air on guide frame, dry at room temperature over night, prepare required PVA-EDTMPA/PS hollow fiber composite membrane。
Step 3, fixing: polyvinyl alcohol-ethylenediamine tetraacetic methene phosphoric acid-polysulfone hollow fibre composite membrane is fixed in glass electrode。
Wet sensitive is tested:
Zinc oxide-base moisture sensor is put in control appliance of temperature and humidity。Test temperature is set as 20 DEG C, then controls relative humidity variations and ranges for 10%～95%, reads the electric capacity of sensing element with humidity situation of change；
The sensitivity definition of dew cell is: CRH-C11/ C11× 100%, wherein CRHFor the component capacitance value obtained under test environment humidity, C11Capacitance for 11% time element of relative humidity。Are defined as the response of dew cell or recovery time testing capacitor value and reach the time used by total variation 80% at the variable quantity of 11%RH to 75%RH；
When testing frequency and being 100Hz, under the relative humidity of 15%, 35%, 55%, 75%, 95%, the sensitivity of sensing element respectively 4,21,143,78 and 2132, response and respectively 15s and 17s recovery time, test result shows that this environment monitoring device has good wet sensitive performance, it is possible to realize the humidity data output of environment monitoring device。
Finally should be noted that; above example is only in order to illustrate technical scheme; but not limiting the scope of the invention; although having made to explain to the present invention with reference to preferred embodiment; it will be understood by those within the art that; technical scheme can be modified or equivalent replacement, without deviating from the spirit and scope of technical solution of the present invention。
Claims (2)
1. an environment monitoring device with input and output humidity data, it is characterised in that: the outside of described environment monitoring device (1) is provided with zno-based moisture sensor module (2)；Described zno-based moisture sensor module (2) is mainly made up of wet sensitive sensing element and data read element, described wet sensitive sensing element is interdigital electrode type, including silicon chip substrate (10), Si NPA (20), zinc oxide nanowire (30) and graphene layer (40)；The output electric wire sidewall of described environment monitoring device (1) is provided with a polyvinyl alcohol ethylenediamine tetraacetic methene phosphoric acid polysulfones basement membrane hollow fiber composite membrane assembly for dehumidification, polyvinyl alcohol ethylenediamine tetraacetic methene phosphoric acid polysulfones basement membrane hollow fiber composite membrane is fixed in glass electrode by this membrane module, and glass electrode is connected with moisture sensor；Described zinc oxide nanowire (30) length about 6 μm。
2. environment monitoring device according to claim 1, it is characterised in that the preparation method of described wet sensitive sensing element is as follows:
Step one, prepares Si NPA substrate: the silicon chip substrate (10) of 3cm × 3cm is included clean dirt, hydro-thermal method corrosion preparation Si NPA substrate；1. taking the silicon chip of 3cm × 3cm, be placed in by silicon chip in the mixed solution of sulphuric acid and hydrogen peroxide volume ratio 4:1, supersound process 20min, taking-up deionized water cleans, to remove the organic impurities of silicon chip surface；It is H that silicon chip is positioned over volume ratio2O:H2O2: NH4In the mixed solution of OH=5:2:1, ultrasonic cleaning 20min, the deionized water of taking-up subsequently cleans, to remove Organic substance and the metal complex of silicon chip surface；2. hydro-thermal method corrosion is utilized to prepare Si NPA: to weigh the Fe (NO of 1.0g3)·9H2O pours in politef, is added thereto to the HF solution of 20ml deionized water and 30ml40% subsequently；Putting in solution by the silicon chip that upper step is cleaned, add a cover and put in water heating kettle, put in drying baker by water heating kettle subsequently, 180 DEG C of constant temperature keep 30min, after natural cooling, take out Wafer Cleaning and namely obtain Si NPA substrate；
Step 2, growth of zinc oxide nano line: adopt magnetron sputtering to prepare zinc oxide nanowire in conjunction with thermal oxidation method；Silicon nano hole column substrate is put in magnetic control sputtering device, when sputtering voltage 220V, sputtering current 0.8A, magnetron sputtering Zn film, thickness is 50nm, puts it into subsequently in batch-type furnace, and at 400 DEG C, thermal oxidation method processes 4h, obtaining length about 6 μm, diameter is about the zinc oxide nanowire of 30nm；
Step 3, grows graphene layer: adopt process for preparing graphenes by chemical vapour deposition；First magnetron sputtering layer of metal Ni film on the substrate that upper step obtains, thickness is about 5nm；Secondly, putting in tube furnace by this substrate, be warming up to 900 DEG C, pass into hydrogen as protection reducing gas by given pace, stablize 30min, then, pass into methane 2h according to a certain percentage simultaneously, stopping starts Temperature fall after passing into methane；Under Ni catalyst action, methane molecule at high temperature can be cracked into carbon atom and hydrogen atom, and at temperature-fall period and under the protection of hydrogen, carbon atom can formation of deposits one layer graphene thin film；
Step 4, is deposited with interdigital electrode: after obtaining growing the silicon nano hole column substrate having zinc oxide nanowire and Graphene, covers interdigital electrode mask at substrate surface, utilizes magnetron sputtering method to be deposited with Au thin film thick for one layer of 500nm on its surface as electrode；
Step 5, assembles sensing element and reads data element: the both positive and negative polarity wire reading data element is connected in interdigital electrode, two parts composition Zinc oxide-base moisture sensor device；
The preparation method of described polyvinyl alcohol-ethylenediamine tetraacetic methene phosphoric acid-polysulfones basement membrane hollow fiber composite membrane assembly is as follows:
Step one, polysulfone hollow fibre basement membrane pretreatment: polysulfone hollow fibre basement membrane to carry out pretreatment before coating, after soaking 12h with deionized water, with the soak with hydrochloric acid 60min of 1.0mol/l, remove glycerin layer and other organic solvents on film surface；Then use in the sodium hydroxide solution of 1.0mol/l and excessive hydrochloric acid, finally repeatedly rinse with deionized water, make film surface in neutrality, dry in the shade standby；
Step 2, prepare polyvinyl alcohol-ethylenediamine tetraacetic methene phosphoric acid-polysulfone hollow fibre composite membrane: add in deionized water by the polyvinyl alcohol that the average degree of polymerization of certain mass is 1750 ± 50, it is about 3h 50 DEG C of stirred in water bath to be completely dissolved to polyvinyl alcohol, obtains 5wt% polyvinyl alcohol homogeneous phase aqueous solution；Adding a certain amount of ethylenediamine tetraacetic methene phosphoric acid after solution is cooled to room temperature, and at room temperature stir 1.5h, namely standing and defoaming obtains casting solution；Polysulfones basement membrane (molecular cut off 30000) through pretreatment is taken out after casting solution soaks 20min, is vertically fixed on the guide frame that dries in the air and dries in the shade；After the film of primary coating soaks 20min again in casting solution, will reversely be fixed on and dry in the air on guide frame, dry at room temperature over night, prepare required PVA-EDTMPA/PS hollow fiber composite membrane。
Step 3, fixing: polyvinyl alcohol-ethylenediamine tetraacetic methene phosphoric acid-polysulfone hollow fibre composite membrane is fixed in glass electrode。
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| CN101259381A (en) * | 2007-12-19 | 2008-09-10 | 天津大学 | Hollow fiber compound film, preparation and application |
| WO2015085537A1 (en) * | 2013-12-12 | 2015-06-18 | 中国科学院微电子研究所 | Sensor module based on flexible substrate |
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|---|---|---|---|---|
| CN101259381A (en) * | 2007-12-19 | 2008-09-10 | 天津大学 | Hollow fiber compound film, preparation and application |
| WO2015085537A1 (en) * | 2013-12-12 | 2015-06-18 | 中国科学院微电子研究所 | Sensor module based on flexible substrate |
| CN204789450U (en) * | 2015-07-16 | 2015-11-18 | 吕银兰 | Humidity detection alarm device based on zigbee |
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