CN104597082B - Preparation method of hybridized hierarchical structure sensitive thin-film sensing device based on two-dimensional material - Google Patents
Preparation method of hybridized hierarchical structure sensitive thin-film sensing device based on two-dimensional material Download PDFInfo
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Abstract
The invention discloses a preparation method of a hybridized hierarchical structure sensitive thin-film sensing device based on a two-dimensional material. The sensing device comprises a single crystal semiconductor substrate, an insulation layer, an interdigital electrode layer, a first PDDA film layer, a reduction-oxidation graphene film layer, a second PDDA film layer and a hierarchical structure ZnO-PSS thin film which are sequentially overlapped according to a preparation order. The preparation method mainly comprises the following steps: preparing an interdigital electrode device; preparing a film layer material required by the sensing device, and preparing the hybridized hierarchical structure sensitive sensing device by adopting a layer-by-layer self-assembling method. The preparation method has the advantages of fully utilizing characteristics of large specific area, low electronic noise, good semiconductor property and negative electricity of reduced-oxidized graphene and combining the structure characteristic of a hierarchical structure zinc oxide to prepare a hybridized hierarchical structure sensitive thin film; the process is simple, the repeatability is good, and the prepared sensing device can be used in the field of gas detection.
Description
Technical field
The invention belongs to gas sensor and sensing electronics field are and in particular to a kind of be based on two-dimensional material reduction-oxidation
Gas sensing device of hydridization hierarchy sensitive thin film of Graphene and zinc oxide and preparation method thereof.
Background technology
In recent years, the New Two Dimensional stratified nano materials based on Graphene are because of its unique construction features, electricity, heat,
The aspects such as light, power show the property of many uniquenesses, cause rapidly extensive concern in the world.Two-dimensional material has
The features such as bigger serface, good characteristic of semiconductor and low electronic noise, is so as to very sensitive to surrounding, for gas
The development of sensor brings new opportunity.
Stripping method or chemical vapor deposition (Chemical can be passed through in the Graphene of gas sensor domain application
Vapor Deposition, CVD) growth is prepared from, but the Graphene Product size that mechanical stripping method obtains is not easily controlled,
Yield is relatively low；CVD method can obtain the graphene film of large area, homoepitaxial, but as during gas sensitive material due to
Graphene heat energy itself is not enough to overcome energy needed for desorbing gas and restorative poor.Redox graphene removes to be had and stone
Outside black alkene identical property, also there is hydrophilic, be suitable to solution film forming mode, preparation process is simple, meanwhile, the scattered oxygen of solution
Graphite alkene can also form composite system with polymer or metal/metal oxide.Therefore, redox graphene exists
Gas sensitization field is also widely adopted.
Simultaneously as single Graphene also lacks specificity as sensitive material, various gas molecules are likely to draw
Rise its electric property change, therefore, by Graphene is carried out functionalization be combined can be with this problem of effectively solving and right
Air-sensitive performance also has a certain degree of potentiation.Especially metal oxide nano-material, can enter after being combined with Graphene
One step increases specific surface area, accelerates gas transmission process, additionally, the depleted of electrons layer of metal oxide surface is for gas molecule
Adsorption process also there is facilitation.In metal oxide nano-material, zinc oxide is because having good semiconductive, electricity
Chemical stability and to being also widely used in gas sensitization field the features such as gas sensitization.
At present, redox graphene and the preparation method of the composite sensitive material thin film of zinc oxide mainly adopt hydro-thermal method
In conjunction with drop coating or spin-coating film technique, gas blowout film-forming process prepare layered film and and electrochemical method deposition process etc., pass through
The gas sensitization device of these methods preparation shows certain sensitive property to acetone, carbon dioxide and hydrogen peroxide, but
Detectable gas concentration is all higher than 5ppm, and air-sensitive performance needs to be improved further, and some gas sensitization devices also need hot operation
Condition.If Xinjiang University Jianjiang He et al. is in paper " Reduced graphene oxide anchored with
zinc oxide nanoparticles with enhanced photocatalytic activity and gas
Sensing properties " (The Royal Society of Chemistry Advances, 2014,4,60253
60259) adopt graphene oxide and zinc acetate as presoma in, be prepared for reduction-oxidation by two step hydro-thermal catalysis process
Graphene Zinc oxide nanoparticle composite, is scattered in ethanol solution and then drop coating is in the platinum of aluminium sesquioxide substrate
On electrode, prepared device shows certain response to the acetone of 5 1000ppm concentration under 260 DEG C of temperature conditionss
Can, but the high temperature operating conditions that this device needs are it is impossible to realize under room temperature condition, the low concentration of acetone gas being detected.
Content of the invention
The purpose of the present invention is the weak point for overcoming prior art, there is provided a kind of divided based on the hydridization of two-dimensional material
Level structure sensitive film sensor part preparation method；The method is using the preparation of LBL self-assembly method based on reduction-oxidation graphite
The hydridization hierarchy gas sensitization device of alkene/zinc oxide, using the big feature of two-dimensional material specific surface area, by tying with classification
The raising being compounded with beneficial to air-sensitive performance of structure zinc oxide, and preparation process is simple, low cost.
It is characterized in that：(1) described sensitive thin film adopts graphene oxide as sensitive prime material；(2) described sensitivity
Thin film is combined to the graphene oxide of reduction using the zinc oxide with hierarchy；(3) described sensitive thin film adopts layer
Layer self-assembling method preparation；(4) described sensitive thin film has hydridization hierarchy；(5) described Sensitive Apparatuses can achieve to low dense
The effective detection of degree toxic and harmful.
The above-mentioned hydridization based on two-dimensional material redox graphene and zinc oxide based on the preparation of LBL self-assembly method
The gas sensing device of hierarchy sensitive thin film has following feature：
(1) sensitive thin film of method preparation adopt LBL self-assembly method, combining using electrostatic force, has good equal
Even property；Can control the thickness of self-assembled film by control settlement/pull rate and soak time；The method preparation technology letter
Single, reproducible；
(2) graphene oxide has the advantages that bigger serface, low electronic noise and good semiconductor property, additionally, filling
Divide and utilize the electronegative characteristic of graphene oxide, two-dimensional material self-assembled film can be obtained, its method is simple, uniformity is good；
(3) there is the zinc oxide of hierarchy and compared to common zinc oxide material, there is bigger specific surface area and more
Gas absorption position is it is adaptable to gas sensor domain；
(4) hydridization is carried out to the graphene oxide film of reduction using the zinc oxide of hierarchy, the hydridization being formed is divided
Level structure sensitive thin film has more preferable air-sensitive performance compared to single oxidation graphene film or zinc-oxide film；This
Outward, the hetero-junctions that zinc oxide and redox graphene are formed, also has a certain degree of facilitation for air-sensitive performance；
(5) adopt interdigital electrode device architecture, preparation method is simple, can achieve and simultaneously and concurrently detects.
The ultimate principle of the hydridization hierarchy sensitive film sensor part based on two-dimensional material proposed by the present invention is：Two
Dimension material oxidation Graphene has the characteristics that bigger serface, good electrical characteristic and low electronic noise, the oxidation of hierarchy
Zinc has bigger serface and good gas-sensitive property, in conjunction with the feature of the two, prepares oxygen reduction fossil using electrostatic force
Black alkene/zinc oxide hybridization hierarchy sensitive thin film, prepared sensitive thin film has good gas absorption condition, works as gas
When molecule is contacted with this hydridization hierarchy sensitive thin film, gas molecule occurs anti-first with the oxygen of hierarchy zinc oxide surface
Electronic transfer process and should be there is, gas molecule contributes electronics or hole thus causing it to lead to redox graphene simultaneously
Electrically change, so that the electric conductivity of hydridization sensitive thin film changes.Meanwhile, Graphene and zinc oxide contact interface will
Form heterojunction structure, this is conducive to accelerating the transmission process of gas.Additionally, using in deionized water in membrane-film preparation process
Soak to obtain the ultrathin membrane of excellent homogeneity, be conducive to making senser element that gas molecule is made with quick response and recovery spy
Property.
In sum, the hydridization classification based on redox graphene/zinc oxide using the preparation of LBL self-assembly method
Formation gases Sensitive Apparatuses, using the big feature of two-dimensional material specific surface area, by compound favourable with hierarchy zinc oxide
In the raising of air-sensitive performance, and preparation process is simple, low cost.
Brief description
Fig. 1 is the hydridization hierarchy sensitive thin film based on two-dimensional material redox graphene and zinc oxide of the present invention
Gas sensing device structural representation.
Specific embodiment
Below in conjunction with the accompanying drawings and embodiment is described in detail to the present invention.
Hydridization hierarchy sensitive film sensor part based on two-dimensional material proposed by the present invention, as shown in figure 1, this biography
Inductor component includes：The single crystal semiconductor substrate 1 being stacked gradually according to preparation order, insulating barrier 2, interdigital electrode layer 3, first poly- two
Allyl ammonium chloride (PDDA) thin layer 4, oxidation graphene film layer 5, the 2nd PDDA thin layer 6, hierarchy aoxidizes
Zinc (ZnO)-poly- (sodium p styrene sulfonate) (PSS) thin film 7.
Proposed by the invention prepares the above-mentioned preparation of the hydridization hierarchy sensitive film sensor part based on two-dimensional material
Method, technological process comprises the following steps：
1) interdigital electrode device preparation：
1.1) clean single crystal semiconductor substrate 1：Single crystal semiconductor substrate is put into volume ratio 1:4 hydrogen peroxide and concentrated sulphuric acid
Boil 10～15min in mixed liquor at a temperature of 80～85 DEG C, remove surface blot, deionized water rinses 10～15min, dry
Standby；Wherein, single crystal semiconductor substrate is that N-type phosphorus doping list throws silicon substrate, (100) crystal orientation, resistivity 1～10 Ω cm；
1.2) grow insulating barrier 2：Silicon dioxide (SiO is grown using thermal oxidation process2), thickness is 100～300nm, oxygen
After the completion of change, by SiO2Layer front is protected with photoresist, puts into volume ratio 6:Super in 1 deionized water and hydrofluoric acid solution
Sound 2～3min removes the SiO at the back side2Layer, with acetone-ethanol-deionized water rinsing until photoresist removes totally；
1.3) photoetching：Aligning the silicon chip of long good insulating layer of silicon oxide of looking unfamiliar, photolithographic exposure develops interdigital electrode figure；Just
Face spin coating photoresist, 3000～5000rpm, 30～60s；100～120 DEG C of front baking, 1～3min；Exposure 3～5s；Development；After bake
100～120 DEG C, 10～15min, standby；Exposed portion is Ti/Au interdigital electrode；
1.4) prepare electrode 3：Titanium (Ti)/gold (Au) electricity is deposited with insulating layer of silicon oxide successively using e-beam evaporation
Pole, titanium film, the thickness of golden film are respectively 10～30/80～120nm；
1.5) peel off：Print obtained above is put in acetone soln, ultrasonic stripping removes photoresist；With ethanol, go
Ionized water cleans successively, and nitrogen dries up and obtains interdigital electrode device；
2) prepare film material needed for senser element
2.1) preparation has the zinc oxide of hierarchy：By 0.5～0.8g commercialization Zinc oxide powder and 1～3g sodium hydroxide
Add 50～100mL deionized water, under the conditions of 80～100 DEG C, stir 2h, separate out precipitate and dry 12h under the conditions of 105 DEG C；
2.2) prepare PDDA aqueous solution, this aqueous solution mass percent concentration is 0.1～0.5wt%：
2.3) prepare two-dimensional material graphene oxide water solution, this concentration of aqueous solution is 0.2～2mg/mL；
2.4) prepare PSS aqueous solution, this aqueous solution mass percent concentration is 0.1～0.5wt%；
2.5) prepare ZnO-PSS aqueous solution：Hierarchy zinc oxide is scattered in PSS aqueous solution, this aqueous solution dense
Spend for 0.2～2mg/mL；
3) LBL self-assembly method is adopted to prepare hydridization hierarchy senser element：
3.1) prepare a PDDA thin layer 4：By step 1) be obtained interdigital electrode device with 8.56～85.6mm/min
Sedimentation velocity immersion PDDA aqueous solution in, soak time is 5～20min, is then lifted with same speed and takes out, nitrogen blows
Dry；
3.2) by step 3.1) the interdigital electrode device that is obtained with the immersion of the sedimentation velocity of 8.56～85.6mm/min go from
In sub- water, soak time is 1～10min, is then lifted with same speed and takes out, and nitrogen dries up；
3.3) prepare oxidation graphene film layer 5：
3.31) by step 3.2) the interdigital electrode device that is obtained is with the immersion oxidation of the sedimentation velocity of 8.56～85.6mm/min
In graphene aqueous solution, soak time is 5～20min, is then lifted with same speed and takes out, and nitrogen dries up；
3.32) by step 3.31) the interdigital electrode device that is obtained goes with the immersion of the sedimentation velocity of 8.56～85.6mm/min
In ionized water, soak time is 1～10min, is then lifted with same speed and takes out, and nitrogen dries up；
3.33) by step 3.32) the interdigital electrode device that is obtained anneal at a temperature of 150～400 DEG C 10～60min, makes
Obtain oxidation graphene film layer 5；
3.4) prepare the 2nd PDDA thin layer 6：By step 3.3) be obtained interdigital electrode device with 8.56～85.6mm/
In the sedimentation velocity immersion PDDA aqueous solution of min, soak time is 5～20min, is then lifted with same speed and takes out, nitrogen
Air-blowing is done；
3.5) by step 3.4) the interdigital electrode device that is obtained with the immersion of the sedimentation velocity of 8.56～85.6mm/min go from
In sub- water, soak time is 1～10min, is then lifted with same speed and takes out, and nitrogen dries up；
3.6) prepare ZnO-PSS thin layer 7：By step 3.5) be obtained interdigital electrode device with 8.56～85.6mm/min
Sedimentation velocity immerse in ZnO-PSS aqueous solution and carry out the hybridisation process of hierarchical Z nO and redox graphene, during immersion
Between be 5～20min, then lifted with same speed and take out, nitrogen dries up；
3.7) by step 3.6) the interdigital electrode device that is obtained with the immersion of the sedimentation velocity of 8.56～85.6mm/min go from
In sub- aqueous solution, soak time is 1～10min, is then lifted with same speed and takes out, and nitrogen dries up, prepared hydridization classification
Structure sensitive film-sensing device.
Embodiment 1：
Embodiment 1 is the representative instance of present invention.
The hydridization hierarchy sensitive film sensor part based on two-dimensional material of the present embodiment, as shown in figure 1, include single
Brilliant Semiconductor substrate 1, insulating barrier 2, interdigital electrode 3, a PDDA thin layer 4, oxidation graphene film layer 5, second
PDDA thin layer 6, ZnO-PSS thin film 7.Wherein, the single crystal semiconductor substrate 1 of employing throws Si, (100) crystal orientation, resistance for N-type list
Rate 3～6 Ω cm, thickness 470um；Insulating barrier 2 is the SiO of thermal oxide growth2Layer, thickness is 1000nm；Electrode 3 is Ti/Au
Lamination interdigital structure, thickness is followed successively by 10/80nm；Thin layer 4 is the PDDA thin film using self-assembling method deposition；Thin layer 5
It is the graphene oxide film layer using self-assembling method deposition, and obtain oxidation graphene film through high annealing
Layer, the graphene oxide water solution of use is Nanjing Xian Feng Nono-material Science ＆ Technology Ltd.；Thin layer 6 is using self assembly side
The PDDA thin film of method deposition；Thin layer 7 is the ZnO-PSS thin layer using self-assembling method deposition.
The technological process of the present embodiment is：
1) interdigital electrode device preparation：
1.1) clean single crystal semiconductor substrate 1：Place the substrate into volume ratio 1:In 4 hydrogen peroxide and concentrated sulphuric acid mixed liquor
Boil 10min at a temperature of 85 DEG C, remove surface blot, deionized water rinses 10～15min, dry for standby；
1.2) grow insulating barrier 2：SiO is grown using thermal oxidation process2, thickness is 300nm, after the completion of oxidation, by front
SiO2(AZ601) is protected layer with photoresist, puts into volume ratio 6:Ultrasonic 3min in 1 deionized water and hydrofluoric acid solution
Remove the SiO at the back side2Layer, with acetone-ethanol-deionized water rinsing until photoresist removes totally；
1.3) photoetching：Aligning the silicon chip of long good insulating layer of silicon oxide of looking unfamiliar, photolithographic exposure develops interdigital electrode figure；Just
Face spin coating photoresist AZ601,3000rpm, 60s；100 DEG C of front baking, 1min；Exposure 5s；Development；100 DEG C of after bake, 10min；Exposure
Part is Ti/Au interdigital electrode；
1.4) prepare electrode 3：Using e-beam evaporation in SiO2Ti/Au electrode is deposited with insulating barrier, thickness divides successively
Wei not 10/80nm；
1.5) peel off：Print obtained above is put in acetone soln, ultrasonic stripping removes photoresist；With ethanol and going
Ionized water cleans successively, and nitrogen dries up and obtains interdigital electrode device.
2) prepare film material needed for senser element
2.1) preparation has the zinc oxide of hierarchy：0.5g commercialization Zinc oxide powder and 1g sodium hydroxide are added 50mL
Deionized water, stirs 2h under the conditions of 80 DEG C, separates out precipitate and dries 12h under the conditions of 105 DEG C；
2.2) prepare polydiene propyl ammonium chloride (PDDA) aqueous solution, the mass percent concentration of this aqueous solution is
0.1wt%：
2.3) prepare two-dimensional material graphene oxide water solution, the concentration of this aqueous solution is 0.2mg/mL；
2.4) prepare poly- (sodium p styrene sulfonate) (PSS) aqueous solution, the mass percent concentration of this aqueous solution is
0.1wt%；
2.5) prepare ZnO-PSS aqueous solution：Hierarchy zinc oxide is scattered in PSS aqueous solution, this aqueous solution dense
Spend for 0.2mg/mL；
3) LBL self-assembly method is adopted to prepare hydridization hierarchy senser element：
3.1) prepare a PDDA thin layer 4：By step 1) be obtained interdigital electrode device with the sedimentation of 8.56mm/min
In speed immersion PDDA aqueous solution, soak time is 5min, is then lifted with same speed and takes out, and nitrogen dries up；
3.2) by step 3.1) the interdigital electrode device that is obtained with the sedimentation velocity of 8.56mm/min immersion deionized water,
Soak time is 1min, is then lifted with same speed and takes out, and nitrogen dries up；
3.3) prepare oxidation graphene film layer 5：
3.31) by step 3.2) the interdigital electrode device that is obtained immerses graphene oxide with the sedimentation velocity of 8.56mm/min
In aqueous solution, soak time is 5min, is then lifted with same speed and takes out, and nitrogen dries up；
3.32) by step 3.31) the interdigital electrode device that is obtained immerses deionized water with the sedimentation velocity of 8.56mm/min
In, soak time is 1min, is then lifted with same speed and takes out, and nitrogen dries up；
3.33) by step 3.32) the interdigital electrode device that is obtained anneals 10min at a temperature of 150 DEG C, prepared reduction-oxidation
Graphene film layer 5：；
3.4) prepare the 2nd PDDA thin layer 6：By step 3.3) the interdigital electrode device that is obtained is heavy with 8.56mm/min
In reduction of speed degree immersion PDDA aqueous solution, soak time is 5min, is then lifted with same speed and takes out, and nitrogen dries up；
3.5) by step 3.4) the interdigital electrode device that is obtained with the sedimentation velocity of 8.56mm/min immersion deionized water,
Soak time is 1min, is then lifted with same speed and takes out, and nitrogen dries up；
3.6) prepare ZnO-PSS thin layer 7：By step 3.5) be obtained interdigital electrode device with the sedimentation of 8.56mm/min
Speed immerses the hybridisation process carrying out hierarchical Z nO and redox graphene in ZnO-PSS aqueous solution, and soak time is
5min, is then lifted with same speed and takes out, and nitrogen dries up；
3.7) by step 3.6) the interdigital electrode device that is obtained is water-soluble with the sedimentation velocity of 8.56mm/min immersion deionization
In liquid, soak time is 1min, is then lifted with same speed and takes out, and nitrogen dries up, and prepared hydridization hierarchy sensitivity is thin
Film sensors part.
Embodiment 2：
Embodiment 2 is the representative instance of this content of the invention.
The present embodiment single crystal semiconductor is included based on the hydridization hierarchy sensitive film sensor part structure of Graphene
Substrate 1, insulating barrier 2, interdigital electrode layer 3, a PDDA thin layer 4, oxidation graphene film layer 5, the 2nd PDDA thin film
Layer 6, ZnO-PSS thin film 7.Wherein, the single crystal semiconductor substrate 1 of employing throws Si, (100) crystal orientation, resistivity 3～6 for N-type list
Ω cm, thickness 470um；Insulating barrier 2 is the SiO of thermal oxide growth2Layer, thickness is 300nm；Electrode layer 3 is pitched for Ti/Au lamination
Refer to structure, thickness is followed successively by 30/120nm；Thin layer 4 is the PDDA thin film using self-assembling method deposition；Thin layer 5 is employing
The graphene oxide film layer of self-assembling method deposition, and obtain oxidation graphene film layer through high annealing, use
Graphene oxide water solution be Nanjing Xian Feng Nono-material Science ＆ Technology Ltd.；Thin layer 6 is using self-assembling method deposition
PDDA thin film；Thin layer 7 is the ZnO-PSS thin layer using self-assembling method deposition.
The technological process of the present embodiment is：
1.1) clean single crystal semiconductor substrate 1：Place the substrate into volume ratio 1:In 4 hydrogen peroxide and concentrated sulphuric acid mixed liquor
Boil 15min at a temperature of 80 DEG C, remove surface blot, deionized water rinses 15min, dry for standby；
1.2) grow insulating barrier 2：SiO is grown using thermal oxidation process2, thickness is 300nm, after the completion of oxidation, by SiO2Layer
Front is protected with photoresist, puts into volume ratio 6:In 1 deionized water and hydrofluoric acid solution, ultrasonic 2～3min removes the back side
SiO2Layer, with acetone-ethanol-deionized water rinsing until photoresist removes totally；
1.3) photoetching：Aligning the silicon chip of long good insulating layer of silicon oxide of looking unfamiliar, photolithographic exposure develops interdigital electrode figure；Just
Face spin coating photoresist, 5000rpm, 30s；120 DEG C of front baking, 3min；Exposure 3s；Development；120 DEG C of after bake, 10min, standby；Exposure
Part is Ti/Au interdigital electrode；
1.4) prepare electrode 3：Titanium (Ti)/gold (Au) electricity is deposited with insulating layer of silicon oxide successively using e-beam evaporation
Pole, titanium film, the thickness of golden film are respectively 30/120nm；
1.5) peel off：Print obtained above is put in acetone soln, ultrasonic stripping removes photoresist；With ethanol, go
Ionized water cleans successively, and nitrogen dries up and obtains interdigital electrode device；
2) prepare film material needed for senser element：
2.1) preparation has the zinc oxide of hierarchy：0.8g commercialization Zinc oxide powder and 3g sodium hydroxide are added
100mL deionized water, stirs 2h under the conditions of 100 DEG C, separates out precipitate and dries 12h under the conditions of 105 DEG C；
2.2) prepare polydiene propyl ammonium chloride (PDDA) aqueous solution, the mass percent concentration of this aqueous solution is
0.5wt%：
2.3) prepare two-dimensional material graphene oxide water solution, the concentration of this aqueous solution is 2mg/mL；
2.4) prepare poly- (sodium p styrene sulfonate) (PSS) aqueous solution, the mass percent concentration of this aqueous solution is
0.5wt%；
2.5) prepare ZnO-PSS aqueous solution：Hierarchy zinc oxide is scattered in PSS aqueous solution, this aqueous solution dense
Spend for 2mg/mL；
3) LBL self-assembly method is adopted to prepare hydridization hierarchy senser element：
3.1) prepare a PDDA thin layer 4：By step 1) be obtained interdigital electrode device with the sedimentation of 85.6mm/min
In speed immersion PDDA aqueous solution, soak time is 20min, is then lifted with same speed and takes out, and nitrogen dries up；
3.2) by step 3.1) the interdigital electrode device that is obtained with the sedimentation velocity of 85.6mm/min immersion deionized water,
Soak time is 10min, is then lifted with same speed and takes out, and nitrogen dries up；
3.3) prepare oxidation graphene film layer 5：
3.31) by step 3.2) the interdigital electrode device that is obtained immerses graphene oxide with the sedimentation velocity of 85.6mm/min
In aqueous solution, soak time is 20min, is then lifted with same speed and takes out, and nitrogen dries up；
3.32) by step 3.31) the interdigital electrode device that is obtained immerses deionized water with the sedimentation velocity of 85.6mm/min
In, soak time is 10min, is then lifted with same speed and takes out, and nitrogen dries up；
3.33) by step 3.32) the interdigital electrode device that is obtained anneals 10min at a temperature of 400 DEG C, prepared reduction-oxidation
Graphene film layer 5：；
3.4) prepare the 2nd PDDA thin layer 6：By step 3.3) the interdigital electrode device that is obtained is heavy with 85.6mm/min
In reduction of speed degree immersion PDDA aqueous solution, soak time is 20min, is then lifted with same speed and takes out, and nitrogen dries up；
3.5) by step 3.4) the interdigital electrode device that is obtained with the sedimentation velocity of 85.6mm/min immersion deionized water,
Soak time is 10min, is then lifted with same speed and takes out, and nitrogen dries up；
3.6) prepare ZnO-PSS thin layer 7：By step 3.5) the interdigital electrode device that is obtained is heavy with 885.6mm/min
Reduction of speed degree immerses the hybridisation process carrying out hierarchical Z nO and redox graphene in ZnO-PSS aqueous solution, and soak time is
20min, is then lifted with same speed and takes out, and nitrogen dries up；
3.7) by step 3.6) the interdigital electrode device that is obtained is water-soluble with the sedimentation velocity of 85.6mm/min immersion deionization
In liquid, soak time is 10min, is then lifted with same speed and takes out, and nitrogen dries up, and prepared hydridization hierarchy sensitivity is thin
Film sensors part.
Embodiment 3：
The present embodiment is similar to embodiment 1 technical process, and difference is：Step 3.32) complete after repeat step
3.1) -3.32) prepare double-deck self assembly graphene oxide film.The graphene oxide film of double-deck self assembly has compared to monolayer
There are more gas absorption positions, be favorably improved the sensitivity characteristic of senser element.
Embodiment 4：
The present embodiment is similar to embodiment 2 technical process, and difference is：Step 3.32) complete after repeat step
3.1) -3.32) prepare double-deck self assembly graphene oxide film.The graphene oxide film of double-deck self assembly has compared to monolayer
There are more gas absorption positions, be favorably improved the sensitivity characteristic of senser element.
Embodiment 5：
The present embodiment is similar to embodiment 1 technical process, and difference is：Step 3.7) complete after repeat step
3.4) -3.7) prepare double-deck self-assembly zinc oxide thin film.The zinc-oxide film of double-deck self assembly has more compared to monolayer
Gas absorption position, is favorably improved the sensitivity characteristic of senser element.
Embodiment 6：
The present embodiment is similar to embodiment 2 technical process, and difference is：Step 3.7) complete after repeat step
3.4) -3.7) prepare double-deck self-assembly zinc oxide thin film.The zinc-oxide film of double-deck self assembly has more compared to monolayer
Gas absorption position, is favorably improved the sensitivity characteristic of senser element.
Claims (1)
1. a kind of hydridization hierarchy sensitive film sensor part preparation method based on two-dimensional material is it is characterised in that this biography
Inductor component includes：The single crystal semiconductor substrate being stacked gradually according to preparation order, insulating layer of silicon oxide, interdigital electrode, first gathers
Diallyl ammonium chloride thin layer, oxidation graphene film layer, the second polydiene propyl ammonium chloride thin layer, hierarchy
Zinc oxide-poly (sodium 4-styrenesulfonate) thin film；
The method comprises the following steps：
1) interdigital electrode device preparation：
1.1) clean single crystal semiconductor substrate：Single crystal semiconductor substrate is put into volume ratio 1:4 hydrogen peroxide and concentrated sulphuric acid mixing
Boil 10～15min in liquid at a temperature of 80～85 DEG C, remove surface blot, deionized water rinses 10～15min, dry standby
With；
1.2) grow insulating barrier：Using thermal oxidation process in substrate growth silicon dioxide insulating layer, thickness is 100～300nm, oxygen
After the completion of change, the silicon dioxide layer of substrate face is protected with photoresist, put into volume ratio 6:1 deionized water and hydrogen fluorine
In acid solution, ultrasonic 2～3min removes the silicon dioxide layer of substrate back, rinsed successively with acetone-ethanol-deionized water until
Photoresist removes clean；
1.3) photoetching：Aligning the silicon chip of long good silicon dioxide insulating layer of looking unfamiliar, photolithographic exposure develops interdigital electrode figure；Front
Spin coating photoresist, 3000～5000rpm, 30～60s；100～120 DEG C of front baking, 1～3min；Exposure 3～5s；Development；After bake
100～120 DEG C, 10～15min, standby；Exposed portion is Ti/Au interdigital electrode figure；
1.4) prepare electrode：Titanium/gold electrode, titanium film, gold are deposited with silicon dioxide insulating layer successively using e-beam evaporation
The thickness of film is respectively 10～30/80～120nm；
1.5) peel off：By step 1.4) print that obtains puts in acetone soln, and ultrasonic stripping removes photoresist；With ethanol, go
Ionized water cleans successively, and nitrogen dries up and obtains interdigital electrode device；
2) prepare film material needed for senser element：
2.1) preparation has the zinc oxide of hierarchy：0.5～0.8g commercialization Zinc oxide powder and 1～3g sodium hydroxide are added
50～100mL deionized water, stirs 2h under the conditions of 80～100 DEG C, separates out precipitate and dries 12h under the conditions of 105 DEG C；
2.2) prepare polydiene propyl ammonium chloride aqueous solution, the mass percent concentration of this aqueous solution is 0.1～0.5wt%：
2.3) prepare two-dimensional material graphene oxide water solution, the concentration of this aqueous solution is 0.2～2mg/mL；
2.4) prepare poly (sodium 4-styrenesulfonate) aqueous solution, the mass percent concentration of this aqueous solution is 0.1～0.5wt%；
2.5) prepare zinc oxide-poly (sodium 4-styrenesulfonate) aqueous solution：Hierarchy zinc oxide is scattered in and gathers to styrene sulphur
In acid sodium aqueous solution, the concentration of this zinc oxide-poly (sodium 4-styrenesulfonate) aqueous solution is 0.2～2mg/mL；
3) LBL self-assembly method is adopted to prepare hydridization hierarchy senser element：
3.1) prepare the first polydiene propyl ammonium chloride thin layer：By step 1) the interdigital electrode device that is obtained with 8.56～
In the sedimentation velocity immersion polydiene propyl ammonium chloride aqueous solution of 85.6mm/min, soak time is 5～20min, then with phase
Same speed lifting is taken out, and nitrogen dries up；
3.2) by step 3.1) the interdigital electrode device that is obtained immerses deionized water with the sedimentation velocity of 8.56～85.6mm/min
In, soak time is 1～10min, is then lifted with same speed and takes out, and nitrogen dries up；
3.3) prepare oxidation graphene film layer：
3.31) by step 3.2) the interdigital electrode device that is obtained immerses graphite oxide with the sedimentation velocity of 8.56～85.6mm/min
In aqueous solution, soak time is 5～20min, is then lifted with same speed and takes out, and nitrogen dries up；
3.32) by step 3.31) the interdigital electrode device that is obtained immerses deionization with the sedimentation velocity of 8.56～85.6mm/min
In water, soak time is 1～10min, is then lifted with same speed and takes out, and nitrogen dries up；
3.33) by step 3.32) the interdigital electrode device that is obtained anneal 10～60min at a temperature of 150～400 DEG C, be obtained and also
Former graphene oxide film layer；
3.4) prepare the second polydiene propyl ammonium chloride thin layer：By step 3.3) the interdigital electrode device that is obtained with 8.56～
In the sedimentation velocity immersion polydiene propyl ammonium chloride aqueous solution of 85.6mm/min, soak time is 5～20min, then with phase
Same speed lifting is taken out, and nitrogen dries up；
3.5) by step 3.4) the interdigital electrode device that is obtained immerses deionized water with the sedimentation velocity of 8.56～85.6mm/min
In, soak time is 1～10min, is then lifted with same speed and takes out, and nitrogen dries up；
3.6) prepare zinc oxide-poly (sodium 4-styrenesulfonate) thin layer：By step 3.5) the interdigital electrode device that is obtained is with 8.56
～85.6mm/min sedimentation velocity immersion zinc oxide-poly (sodium 4-styrenesulfonate) aqueous solution in carry out hierarchy zinc oxide with
The hybridisation process of redox graphene, soak time is 5～20min, is then lifted with same speed and takes out, and nitrogen blows
Dry；
3.7) by step 3.6) the interdigital electrode device that is obtained immerses deionized water with the sedimentation velocity of 8.56～85.6mm/min
In solution, soak time is 1～10min, is then lifted with same speed and takes out, and nitrogen dries up, prepared hydridization hierarchy
Sensitive film sensor part.
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