CN104374819B - A kind of multilayer film Schottky diode hydrogen gas sensor core body and preparation method thereof - Google Patents
A kind of multilayer film Schottky diode hydrogen gas sensor core body and preparation method thereof Download PDFInfo
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- CN104374819B CN104374819B CN201410611746.6A CN201410611746A CN104374819B CN 104374819 B CN104374819 B CN 104374819B CN 201410611746 A CN201410611746 A CN 201410611746A CN 104374819 B CN104374819 B CN 104374819B
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Abstract
The present invention relates to hydrogen gas sensor field, more particularly to a kind of multilayer film Schottky diode hydrogen gas sensor core body and preparation method thereof.The multilayer film Schottky diode hydrogen gas sensor core body, includes substrate, first medium layer and hydrogen sensitive layer successively, and it is second dielectric layer to increase polyschiff's base thin film between first medium layer and hydrogen sensitive layer.Above-mentioned core body is made hydrogen gas sensor, under the density of hydrogen of 2000 ppm, the sensitivity of the multilayer film Schottky diode hydrogen gas sensor core body is more than 56 mV, can detect density of hydrogen lower limit be 5 ppm, these characteristics show the present invention there is potential using value in hydrogen sensory field.
Description
Technical field
A kind of the present invention relates to hydrogen gas sensor field, more particularly to multilayer film Schottky diode hydrogen gas sensor core body
And preparation method thereof.
Background technology
Hydrogen as a kind of clean energy resource of high burning efficiency, in the boosting system of Aero-Space, vehicle and ship etc.
It is widely applied in system；Meanwhile, hydrogen as a kind of important reducibility gas and carrier gas, in chemical industry, electronics, medical treatment etc.
Field also plays extremely important effect.But, hydrogen is a kind of inflammable and explosive hazardous gas, aerial content position
When between 4-75%, run into naked light and explode.Hydrogen molecule diameter is very little and colourless, tasteless, in production, storage, transport
With easily leak during use and be difficult to discover, so as to bring very big potential safety hazard, threaten personal safety as well as the property safety.Cause
This, develops for detecting the highly sensitive hydrogen gas sensor of density of hydrogen and hydrogen gas leakage in environment, has become people
The problem of growing interest, the development of high performance hydrogen gas sensor also become one of the emphasis in sensor research field at present.
Current hydrogen gas sensor be mainly resistor-type hydrogen gas sensor based on palladium or palldium alloy material and with
Semi-conductor type hydrogen gas sensor based on Schottky diode, mos capacitance and MOS transistor etc..Pass compared to resistor-type hydrogen
Sensor, semi-conductor type hydrogen gas sensor generally has fast response time, detection density of hydrogen lower limit is low and sensitivity is big.
The sensitive core body of hydrogen gas sensor is the core component of hydrogen gas sensor, is mainly used to detect density of hydrogen.Hydrogen
The core body of sensor generally includes three layers：Substrate, dielectric layer, hydrogen sensitive layer.Using the electricity between hydrogen sensitive layer and substrate
The change of potential difference is detecting hydrogen.Substrate uses semi-conducting material, and silicon chip is usually used, and hydrogen sensitive layer is usually used Metal Palladium
And its alloy.At present, the research of dielectric layer is concentrated mainly in the oxide materials such as silicon dioxide, and this kind of material is used as dielectric layer
Have that hydrogen gas sensor sensitivity is low, detect the problem of the lower limit for height of density of hydrogen.
Content of the invention
The object of the invention is to provide a kind of multilayer film Schottky diode hydrogen gas sensor core body and preparation method thereof, with
Solve hydrogen gas sensor sensitivity in prior art low, detect the problem of the lower limit for height of density of hydrogen.
One of technical scheme is to provide the multilayer film Schottky diode hydrogen gas sensor core body, successively
Including substrate, first medium layer and hydrogen sensitive layer, increase polyschiff's base thin film between first medium layer and hydrogen sensitive layer
For second dielectric layer.
Further, the poly-Schiff-Base film thickness is 3～15 nm.
Further, the first medium thickness degree is 2～10 nm.
Further, the substrate is N-type silicon chip.
Further, the resistivity of the N-type silicon chip is 0.1～20 Ω cm.
Further, the first medium layer is titanium oxide, aluminium oxide or silicon oxide film.
Further, the hydrogen sensitive layer is palladium or palldium alloy.
Further, the preferred palladium evanohm of the palldium alloy.
The two of technical scheme are to provide the preparation of the multilayer film Schottky diode hydrogen gas sensor core body
Method, is comprised the following steps successively：
A. first clean substrate surfaces, then the oxide layer for removing substrate surface；
B. first medium layer is prepared in substrate surface again；
C. polyschiff's base is dissolved, polyschiff's base thin film is prepared on the first medium layer for second dielectric layer；
D. hydrogen sensitive layer is prepared in second dielectric layer.
Further, the method for preparing polyschiff's base thin film in step c is that drop coating, spraying or spin coating are a kind of or several
Kind.
The method for preparing titanium deoxid film on substrate includes magnetron sputtering, ion beam sputtering, pulsed laser deposition, leads to
Power when control is sputtered and time is spent, by the THICKNESS CONTROL of titanium deoxid film between 2～10 nm.Prepare polyschiff's base
Thin film using the method that solution is processed is：Polyschiff's base is dissolved in solvent, then with one or more in drop coating, spraying, spin coating
Mode, by controlling concentration, coating speed and the coating number of times of poly-Schiff-Base solution, the THICKNESS CONTROL of poly-Schiff-Base thin film is existed
Between 3～15 nm.
The method for preparing palladium evanohm hydrogen sensitive layer film on polyschiff's base thin film includes that magnetron sputtering, ion beam splash
Penetrate, pulsed laser deposition, thermal evaporation and electron beam evaporation, the power and time when being sputtered or evaporated by control, by palladium chromium
The THICKNESS CONTROL of alloy firm is between 15～100 nm.Palladium evanohm hydrogen sensitive layer is using photoetching or hard mask plate
Method obtains different shapes.
The operation principle of this Schottky diode hydrogen gas sensor is：Hydrogen adsorption behind the surface of hydrogen sensitive layer,
Under its catalytic action, hydrogen molecule decomposes generation hydrogen atom, and hydrogen atom diffuses through metal film, reaches hydrogen sensitive layer-medium
At bed boundary.Under the attraction of interface charge, hydrogen atom is attracted to the interface of metal-dielertric, is formed with dipole layer, should
Dipole layer will change the work function of hydrogen sensitive layer, cause the potential barrier of Schottky diode to reduce, and the I-V of Schottky diode is special
Property send drift.Therefore, test at constant current, the drift of output voltage is response signal of the sensor to hydrogen, and
With the increasing of density of hydrogen, the drift value of output voltage is also responsive to increase.
Generally from the metal containing palladium, simple metal palladium can become fragile during absorbing hydrogen or even break above-mentioned hydrogen sensitive layer
Split, typically from palldium alloy as hydrogen sensitive layer.
Beneficial effects of the present invention：The present invention increases poly-Schiff-Base thin film as second dielectric layer, in the hydrogen of 2000 ppm
Under gas concentration, the sensitivity of the multilayer film Schottky diode hydrogen gas sensor core body more than 56 mV, can detect hydrogen is dense
Degree lower limit be 5 ppm, these characteristics show the present invention there is potential using value in hydrogen sensory field.
Description of the drawings
The profile of the multilayer film Schottky diode hydrogen gas sensor core body that Fig. 1 present invention is provided.
Specific embodiment
As shown in figure 1, a kind of described multilayer film Schottky diode hydrogen gas sensor core body includes substrate 1, first is situated between
Matter layer 2, second dielectric layer 3, hydrogen sensitive layer 4.Wherein, N-type silicon chip selected by substrate 1, and it is thin that N-type silicon chip surface arranges Titanium Dioxide
The first medium layer 2 that film is made, 2 surface of first medium layer arrange the second dielectric layer 3 that poly-Schiff-Base thin film is made, second medium
3 surface of layer arrange palladium evanohm thin film and make hydrogen sensitive layer 4.
The preparation method of above-mentioned core body in turn includes the following steps：Successively with the acetone of purity assay, dehydrated alcohol ultrasound
Cleaning resistivity is 5 min of phosphorus doping N-type silicon chip of 0.1～20 Ω cm；HF again with 10 % of mass percent concentration is molten
Corrosion falls the natural oxidizing layer on N-type silicon chip surface, and deionized water rinses N-type silicon substrate surface, then with nitrogen gun silicon
Piece is dried up；The method of ion beam sputtering is recycled to prepare the titanium deoxid film of 3 nm thickness in N-type silicon chip as first Jie
Matter layer 2；Poly-Schiff-Base is dissolved in N again, N- dimethyl acetylamide is made into the solution of mass percent concentration 2%；Then exist
Then 2 surface of first medium layer is dried in 100 DEG C of vacuum drying oven with 10 s of rotating speed spin coating of 800 rpm, obtains poly- west
Buddhist alkali thin film, gained film thickness are about 7 nm, form second dielectric layer 3；Ion beam sputtering is recycled in poly-Schiff-Base thin film
Surface prepares the palladium evanohm of 60 nm thickness（Wherein, the chromium of 17.5 wt%, the palladium of 82.5 wt%）As hydrogen sensitive layer 4.
The hydrogen gas sensor core body of above-mentioned preparation is made hydrogen gas sensor to be tested, and sensitivity is obtained for 56.4 mV,
Detect density of hydrogen lower limit be 5 ppm.
Claims (10)
1. a kind of multilayer film Schottky diode hydrogen gas sensor core body, includes substrate successively（1）, first medium layer（2）And hydrogen
Gas sensitive layer（4）, it is characterised in that：In first medium layer（2）With hydrogen sensitive layer（4）Between increase polyschiff's base thin film conduct
Second dielectric layer（3）.
2. core body as claimed in claim 1, it is characterised in that：The polyschiff's base film thickness is 3～15 nm.
3. core body as claimed in claim 1, it is characterised in that：The first medium layer（2）Thickness is 2～10 nm.
4. core body as claimed in claim 1, it is characterised in that：The substrate（1）For N-type silicon chip.
5. core body as claimed in claim 4, it is characterised in that：The resistivity of the N-type silicon chip is 0.1～20 Ω cm.
6. core body as claimed in claim 1, it is characterised in that：The first medium layer（2）For titanium oxide, aluminium oxide or oxidation
Silicon thin film.
7. core body as claimed in claim 1, it is characterised in that：The hydrogen sensitive layer（4）For palladium or palldium alloy.
8. core body as claimed in claim 7, it is characterised in that：The preferred palladium evanohm of the palldium alloy.
9. a kind of preparation method of core body as described in claim 1-8, comprises the following steps：
A. first clean substrate surfaces, then the oxide layer for removing substrate surface；
B. first medium layer is prepared in substrate surface again；
C. polyschiff's base is dissolved, polyschiff's base thin film is prepared on the first medium layer as second dielectric layer；
D. hydrogen sensitive layer is prepared in second dielectric layer.
10. preparation method as claimed in claim 9, it is characterised in that：The method for preparing polyschiff's base thin film in step c
For one or more in drop coating, spraying, spin coating.
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