CN105758800A - Flexible film based optical hydrogen detector and preparation method thereof - Google Patents
Flexible film based optical hydrogen detector and preparation method thereof Download PDFInfo
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- CN105758800A CN105758800A CN201610128635.9A CN201610128635A CN105758800A CN 105758800 A CN105758800 A CN 105758800A CN 201610128635 A CN201610128635 A CN 201610128635A CN 105758800 A CN105758800 A CN 105758800A
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- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
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- G—PHYSICS
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- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
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Abstract
The invention belongs to the technical field of micronano devices and particularly relates to a flexible film based optical hydrogen detector and a preparation method thereof.The preparation method includes: performing pattern photoetching on a clean substrate; depositing to obtain a metal film with an internal stress and a metal film with a hydrogen volume expansion effect; selectively corroding a sacrificial layer between each metal film and the substrate to obtain flexible films.The optical hydrogen detector realizes a hydrogen detection function by taking the advantage that the films are increased in curvature radius or changed into a flat status from a curled status to result in macroscopic color variation after feeding of hydrogen.Since electric current transmission is avoided in a detection process, safety is achieved, and real-time monitoring of hydrogen and direct display of results without additional energy sources and devices can be realized.In addition, the preparation method is simple and applicable to industrial production and has practical application significance.
Description
Technical field
The invention belongs to micro-nano device technical field, be specifically related to a kind of optics hydrogen detector being made up of curling film
And preparation method thereof.
Background technology
Along with the development of society, the deposit of the traditional fossil energy such as coal, oil is the most exhausted, and thus causes
Environmental pollution the most become current world have to pay attention to a problem.Find the cleaning that exploitation is new in this context
The energy is extremely the most urgent.In numerous new forms of energy, Hydrogen Energy has huge development potentiality, receives extensive concern.?
There is substantial amounts of research to pay close attention to the preparation of hydrogen, store, transport, post that hope works out new forms of energy transporting equipment with this, industry sets
Standby etc..But hydrogen has the features such as molecular weight little, inflammable and explosive (in the range of 4%-75%), colorless and odorless.It is difficult to after leakage
Discover, the most easily cause serious security incident.Therefore need reliable detector that the hydrogen in environment is monitored in real time.
Following several mechanism have mainly been used in the at present research of hydrogen context of detection: (1) electrical signal detection: many metals,
Oxide material can produce impedance variations with hydrogen after contacting, based on this detector prepared by measuring electric current, voltage, resistance
The change of antinoise signal detects the hydrogen in environment；(2) optical signal detecting: the method is that measurement based on fiber-optic signal realizes
, optical fiber is modified the material with hydrogen sensitive characteristic, the optical transmission signal in optical fiber can be caused after contacting with hydrogen
Change thus detect hydrogen；(3) mechanical signal detection: the method is set up at noble metals such as Pt, Pd after contacting with hydrogen
Volumetric expansion can be produced, thus produce mechanical change or mechanical deformation.Compared with electricity and optical detection, the method is more
Safety, it is not necessary to extra signal input.But general this mechanical deformation is the faintest, measures this in low-concentration hydrogen environment
The device that signal demand such as micro-cantilever etc. are complicated, greatly limit its development.
Summary of the invention
It is an object of the invention to provide and a kind of use safely, be easy to the optics hydrogen detector and the preparation thereof that detect in real time
Method.
The optics hydrogen detector that the present invention provides, is curled into by multiple layer metal thin film system；Utilize the gold of innermost layer
Belong to layer in atmosphere of hydrogen, produce the change of the film wrapped configuration that Volumetric expansion causes, produce macroscopical visible optics and become
Change, be achieved in detecting without the independent hydrogen of other optional equipments.
The preparation method of above-mentioned based on curling film the optics hydrogen detector that the present invention proposes, specifically comprises the following steps that
(1) substrate is cleaned；
(2) litho pattern on substrate；
(3) membrane deposition method is used to have the metallic film of internal stress at deposition on substrate；
(4) membrane deposition method is used to have the metallic film of hydrogen volume bulking effect at deposition on substrate；
(5) selective corrosion photoresist obtains crimping film.
In the present invention, step (1) described substrate is the one of which of silicon chip, sheet glass or quartz plate.
In the present invention, there is described in step (3) one-component that metal is titanium, chromium, iron, cobalt, nickel, copper, aluminium of internal stress,
Or the multiple layer metal film of several compositions in these metals.
In the present invention, there is described in step (4) one-component that metal is platinum, palladium of hydrogen volume bulking effect, or
Alloy containing these metal components.
In the present invention, step (3)-(4) described membrane deposition method refers to thermal evaporation deposition, electron-beam evaporation, swashs
Light pulse deposition, magnetron sputtering etc..
In the present invention, step (3)-(4) described thickness of metal film is 5-200 nanometer.
The optics hydrogen detector based on curling film that the present invention provides, specific works principle is as follows:
After described curling film is passed through hydrogen, the diameter of micron tube increases or is changed into flattened state (Fig. 2) by wrapped configuration, by
This causes macroscopic color to change, it is achieved the detection function to hydrogen.
Beneficial effect: optics hydrogen detector based on curling film that the present invention provides and preparation method thereof, it is achieved that
Hydrogen is monitored in real time without additional source of energy and equipment and visual result is reflected.With traditional electricity hydrogen detection
Device is compared, and the hydrogen detector of the present invention does not has electric current to transmit, thus the safest.Provided by the present invention
Preparation method is relatively simple, is applicable in industrial production, therefore has actual application value.
The originality of the present invention is to utilize the method for selective corrosion sacrifice layer can prepare large-scale curling
Membrane array, by having the noble metal film that hydrogen produces Volumetric expansion in internal layer deposition, makes curling film at hydrogen
The environment that gas exists changes wrapped configuration, produces macroscopic change, it is achieved the real-time detection to hydrogen.
Accompanying drawing explanation
Fig. 1 is the flow chart that the present invention prepares curling film.Wherein, (a) is clean substrate；B () is at substrate glazing
Needle drawing shape；C () is for carrying out the deposition with internal stress metallic film；D () is for carrying out the metal with hydrogen volume bulking effect
The deposition of film；E () is that selective corrosion photoresist obtains crimping film.
Fig. 2 is the fundamental diagram of curling film hydrogen response.Wherein, before (a) is for being passed through hydrogen, (b) is for being passed through hydrogen
After.
Label in figure: 1-substrate；2-photoresist；3-has the metallic film of internal stress；4-has hydrogen volume and expands effect
The metallic film answered；5-evaporation source.
Detailed description of the invention
Below with reference to accompanying drawing, as a example by the curling film that titanium, chromium double-layer metal film-palladium metal film form specifically
Bright its preparation method and effect.Following example are used for illustrating the present invention, but not as the restriction to present invention.
Embodiment 1
(1) take the sheet glass of 1 cm × 1 cm as substrate, carry out ultrasonic cleaning very successively by acetone, ethanol, deionized water
Clock, is dried (Fig. 1 (a)) in nitrogen stream.
(2) the KW-4A type sol evenning machine using Xin Youyan company of China revolves figure one layer photoetching glue at substrate surface.Photoresist
Model is the AR-P3510T positive photoresist of Allresist company of Germany.The slow-speed of revolution is 600 rpm, and rotational time is 6 s；High
Rotating speed is 3000 rpm, and rotational time is 30 s.It is subsequently placed on electric hot plate front baking 60 s at 100 DEG C.Use Germany SUSS
The MA6 ultraviolet photolithographic machine photoetching of company is circular.Substrate after photoetching is immersed in Suzhou Ruihong Electronic Chemical Product Co., Ltd.
RZX-3038 type developer for positive photoresist cleans by deionized water after 22 s, after nitrogen fluidized drying, obtains the photolithograhic substrates of circle
(Fig. 1 (b)).
(3) use TianXing, Shenzhen to reach company's T SV700 type electron beam evaporation deposition machine and carry out the electron beam steaming of metallic film
Send out deposition.Tilt to be fixed on specimen holder by substrate so that evaporation material inclined deposition is on substrate, and angle of inclination is 60 °, as
Shown in Fig. 1 (c) (d).Initially evaporate the metallic film with internal stress: deposit 10 nm titaniums with the speed of 1/s, then with 1
The speed of/s deposits 10 nm chromium metals.Then evaporation has the metallic film of hydrogen volume bulking effect: with the speed of 1/s
Deposit 80 nm palladium metal.
(4) the Autosamdri-815B Series Type B supercritical drying instrument of Tousimis company of the U.S. is used to carry out
The selective corrosion of sacrifice layer.Sample is positioned in the cavity of supercritical drying instrument, in cavity, then pours proper amount of acetone into
Supercritical drying is carried out after dissolving photoresist.Take out sample after EP (end of program) to be dried, obtain by titanium, chromium, palladium metal film
The curling film (Fig. 1 (e)) of system composition.
(5) response test of hydrogen detector: be placed in transparent airtight container by sample, is passed through certain body in container
The hydrogen nitrogen mixed gas of fraction, is changed into flattened state by light microscope record curling film by rolled state (Fig. 2 (a))
Time needed for (Fig. 2 (b)) is as the response time.Remove hydrogen afterwards, sample is opened in air, measure curling film by putting down
Exhibition state becomes rolled state required time as recovery time.
(6) response time recorded under 5% concentration hydrogen is 10 s, and recovery time is 60 s.Survey under 4% concentration hydrogen
The response time obtained is 32 s, and recovery time is 60 s.The response time recorded under 2% concentration hydrogen is 65 s, recovery time
It is 60 s.
Embodiment 2
Same as in Example 1, simply the thickness of palladium metal changes 120 nm into.This hydrogen detector records under 5% concentration hydrogen
Response time is 20 s, and recovery time is 60 s.The response time recorded under 4% concentration hydrogen is 50 s, and recovery time is 70
s.The response time recorded under 2% concentration hydrogen is 90 s, and recovery time is 65 s.
Claims (7)
1. the preparation method of an optics hydrogen detector based on curling film, it is characterised in that specifically comprise the following steps that
(1) substrate is cleaned；
(2) litho pattern on substrate；
(3) membrane deposition method is used to have the metallic film of internal stress at deposition on substrate；
(4) membrane deposition method is used to have the metallic film of hydrogen volume bulking effect at deposition on substrate；
(5) selective corrosion photoresist obtains crimping film.
Preparation method the most according to claim 1, it is characterised in that substrate used in step (1) is silicon chip, sheet glass
Or the one of which of quartz plate.
Preparation method the most according to claim 1 and 2, it is characterised in that the gold with internal stress used in step (3)
Belong to the multiple layer metal film for several compositions in titanium, chromium, iron, cobalt, nickel, copper, the one-component of aluminium, or these metals.
Preparation method the most according to claim 3, it is characterised in that the hydrogen volume that has used in step (4) expands
The metal of effect is the one-component of platinum, palladium, or the alloy containing these metal components.
5. according to the preparation method described in claim 1 or 3, it is characterised in that thin film deposition side used in step (3)-(4)
Method refers to thermal evaporation deposition, electron-beam evaporation, pulsed laser deposition or magnetron sputtering.
6. according to the preparation method described in claim 1 or 3, it is characterised in that in step (3)-(4), the thickness of metallic film is
5-200 nanometer.
7. the optics hydrogen detector based on curling film obtained by the preparation method one of claim 1-6 Suo Shu.
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| CN201610128635.9A CN105758800B (en) | 2016-03-07 | 2016-03-07 | A kind of optics hydrogen detector and preparation method thereof based on curling film |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106959272A (en) * | 2017-03-02 | 2017-07-18 | 复旦大学 | A kind of hydrogen gas detector and method based on curling film |
| CN108051422A (en) * | 2017-11-21 | 2018-05-18 | 复旦大学 | A kind of trace explosive and drug detector and its application method |
| CN110455751A (en) * | 2019-08-22 | 2019-11-15 | 复旦大学 | A kind of hydrogen trace detection method based on curling film |
| CN113497323A (en) * | 2021-07-27 | 2021-10-12 | 合肥工业大学 | Circular waveguide based on film self-curling technology |
| CN115287589A (en) * | 2022-01-12 | 2022-11-04 | 青岛大学 | Preparation method and application of gas sensor based on coiled silicon nano-film |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106959272A (en) * | 2017-03-02 | 2017-07-18 | 复旦大学 | A kind of hydrogen gas detector and method based on curling film |
| CN108051422A (en) * | 2017-11-21 | 2018-05-18 | 复旦大学 | A kind of trace explosive and drug detector and its application method |
| CN108051422B (en) * | 2017-11-21 | 2020-09-29 | 复旦大学 | Trace explosive and drug detector and using method thereof |
| CN110455751A (en) * | 2019-08-22 | 2019-11-15 | 复旦大学 | A kind of hydrogen trace detection method based on curling film |
| CN113497323A (en) * | 2021-07-27 | 2021-10-12 | 合肥工业大学 | Circular waveguide based on film self-curling technology |
| CN113497323B (en) * | 2021-07-27 | 2022-03-18 | 合肥工业大学 | Circular waveguide based on film self-curling technology |
| CN115287589A (en) * | 2022-01-12 | 2022-11-04 | 青岛大学 | Preparation method and application of gas sensor based on coiled silicon nano-film |
| CN115287589B (en) * | 2022-01-12 | 2024-01-30 | 青岛大学 | Preparation method and application of gas sensor based on curled silicon nano film |
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