CN104614410B - A kind of flexible pH sensor based on nano-gap electrode and manufacture method - Google Patents
A kind of flexible pH sensor based on nano-gap electrode and manufacture method Download PDFInfo
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Abstract
A kind of flexible pH sensor based on nano-gap electrode and manufacture method, flexible pH sensor includes flexible substrate, spin-on epoxy layer on flexible substrates, more than one pair of 50～500 nanometers of nano-gap electrode is prepared on epoxy resin layer, carboxyl-functional SWCN is assembled between every a pair of nano-gap electrode, manufacture method is first to make carboxyl-functional SWCN suspension, then prepare nano-gap electrode, dielectrophoresis assembling carboxyl-functional SWCN again, finally carry out flexible pH sensor pretreatment, remove and be connected weaker carboxyl-functional SWCN with nano-gap electrode and retain the carboxyl-functional SWCN pretended with nano-gap electrode.Present invention flexibility pH sensor construction is simple, and applied widely, sensitivity is high, fast response time, test voltage are relatively low and can be compatible with integrated circuit, has vast development prospect.
Description
Technical field
The present invention relates to nano-gap electrode technical field of sensor manufacture is and in particular to a kind of be based on nano-gap electrode
Flexible pH sensor and manufacture method.
Background technology
PH value is one of most important monitoring index in various physical and chemical process.With scientific development, this index is got over
To have influence on all experiments related to solution or technological process manyly.For example, various industry, agricultural, medical and health, ring
Protection used solution in border is it is necessary to detect H+Concentration, because this parameter may directly or indirectly affect reaction yield, product
The important indicators such as thing activity, product structure.The application that pH measures this measuring technology becomes more and more extensive.
As the representative of pH sensor, ISFET (ion-sensitive field effect transistor) is developed rapidly, progressively
Replace traditional ISE (ion selective electrode), be applied in every field such as biomedicine, biochemical engineering, environment measurings.
ISFET is the combination product of MOSFET and ISE.As the extension of MOSFET, ISFET is with ion sensitive membrane/electrolyte/reference
Electrode structure instead of the metal gates of metal-oxide-semiconductor.If the pH value of detected solution changes, it will lead to interface charge to change, thus
Make transmembrane potential change, then read the signal of telecommunication by rearmounted amplifying circuit to be measured.Compared with traditional ISE, ISFET is not only
There is small-sized, easy of integration, low-power consumption, low output impedance, can also be using standard CMOS process processing, manufacturing cost
Low.But, ISFET yet suffers from following both sides problem：
(1) rigid substrate, sensor can not conformal adhere to, and is of limited application it is impossible to meet integrated on flexible substrates
The demand of environment sensitive type sensor；
(2) electrode gap is excessive, generally in micron or some tens of pm magnitude.This sensitivity that will result in sensor and response
Time can not meet the demand of high-precision sensor, and operating voltage is higher.
Content of the invention
In order to overcome the shortcoming of above-mentioned prior art, it is an object of the invention to provide a kind of based on nano-gap electrode
Flexible pH sensor and manufacture method, this sensor construction is simple, it is flexible and applied widely to have, detection volume is few,
Sensitivity height, fast response time, test voltage are relatively low and can be compatible with integrated circuit.
To achieve these goals, the present invention adopts following technical solution：
A kind of flexible pH sensor based on nano-gap electrode, including flexible substrate 1, spin coating ring in flexible substrate 1
Oxygen tree lipid layer 2, prepares more than one pair of 50～500 nanometers of nano-gap electrode 3 on epoxy resin layer 2, receives at every a pair
Carboxyl-functional SWCN 4 is assembled between rice clearance electrode 3.
A kind of manufacture method of described flexible pH sensor based on nano-gap electrode, comprises the steps：
The first step, the surface modification of SWNTs：Weigh 5mg SWNTs and 100ml 67%HNO first3Ultrasonic mixing, subsequently
Above-mentioned solution is stirred, 110 DEG C of condensing refluxes process 12h so that SWNTs surface and end introduce carboxyl simultaneously, then adopt
, by above-mentioned solution with 12000r/min, 30min centrifugal treating 5～6 times is until solution partial neutral, finally ultrasonic place for deionized water
Reason is to obtain scattered carboxyl-functional SWCN suspension；
Second step, prepares nano-gap electrode 3：Spin-on epoxy layer 2 first in flexible substrate 1, treats that it is completely solid
Spin coating photoresist after change, carries out positive and negative exposure respectively after drying, then carry out development treatment and turn nano-gap electrode figure
Move on on epoxy resin layer 2, peeled off after sputtering electrode metal level 5, finally using alcohol-pickled swelling go out gap be 50～
500 nanometers of nano-gap electrode 3；
3rd step, dielectrophoresis assembles carboxyl-functional SWCN 4：Deca carboxyl between nano-gap electrode 3
Functionalization SWCN suspension, carboxyl-functional SWCN 4 will be along electric field line in the presence of dielectric power
Direction mobile and rotate, be eventually deposited between nano-gap electrode 3 and connect both sides nano-gap electrode 3, simultaneously model moral
Magnificent power can strengthen the bonding strength between carboxyl-functional SWCN 4 and nano-gap electrode 3, the parameter of self assembly
For 100～500KHz, 2.5～3.0Vpp, the concentration of carboxyl-functional SWCN suspension is 0.05～0.15mg/ml,
Dripping quantity is 20～50 μ l, is controlled by the concentration adjusting voltage and frequency and carboxyl-functional SWCN suspension
The quantity of the carboxyl-functional SWCN 4 of system assembling, thus improve the performance of device；
4th step, flexible pH sensor pretreatment：Before carrying out pH test, first flexible pH sensor is carried out,
It is connected weaker carboxyl-functional SWCN 4 with nano-gap electrode 3 and retains and nano-gap electrode the last 3 to remove
The carboxyl-functional SWCN 4 of effect.
The present invention solves that traditional pH sensor manufacturing cost is high, volume is big, not portable, ask more than detectable consumption etc.
Topic.Meanwhile, this flexible pH sensor construction is simple, have that flexible and applied widely, sensitivity is high, fast response time, test
Voltage is relatively low and can be compatible with integrated circuit, has vast development prospect.
Brief description
Fig. 1 is the schematic diagram of present invention flexibility pH sensor.
Fig. 2-1 is the top view of the flexible pH sensor after stripping photoresist；Fig. 2-2 is the section in the A-A direction of Fig. 2-1
Figure.
Fig. 3-1 flexible pH sensor top view after swelling for ethanol；Fig. 3-2 is the profile in the B-B direction of Fig. 3-1；
Fig. 3-3 is the partial enlarged drawing of part A in Fig. 3-1.
Specific embodiment
Describe the present invention below in conjunction with accompanying drawing.
With reference to Fig. 1, a kind of flexible pH sensor based on nano-gap electrode, including flexible substrate 1, in flexible substrate 1
Upper spin-on epoxy layer 2, prepares more than one pair of 50～500 nanometers of nano-gap electrode 3 on epoxy resin layer 2,
Carboxyl-functional SWCN 4 is assembled, by carboxyl-functional SWCN between every a pair of nano-gap electrode 3
The change of 4 resistances is detecting the pH value of solution.
A kind of manufacture method of described flexible pH sensor based on nano-gap electrode, comprises the steps：
The first step, the surface modification of SWNTs：Weigh 5mg SWNTs and 100ml 67%HNO first3In beaker with
100W supersound process 30min makes both be sufficiently mixed；Subsequently above-mentioned solution is placed in round-bottomed flask and is stirred with 200r/min
Mix, 110 DEG C of condensing refluxes process 12h so that SWNTs surface and end introduce carboxyl simultaneously；Then will be above-mentioned using deionized water
With 12000r/min, 30min centrifugal treating 5～6 times is until solution partial neutral for solution；Finally by above-mentioned solution supersound process
To obtain scattered carboxyl-functional SWCN suspension, the carboxyl in modification can make SWNTs produce proton to 30min
Change and deprotonation process, detect the pH value of solution by the change of carboxyl-functional SWCN 4 resistance；
Second step, " swelling method " prepares nano-gap electrode 3：With one-level rotating speed 1000r/ first in flexible substrate 1
Min, 18s and Second-Stage Rotating Speed 2000r/min, 30s spin-on epoxy layer 2, with 95 DEG C of baking the affected part after applying some drugs 6h, treat that epoxy resin layer 2 is complete
With 500r/min after solidification, 18s spin coating photoresist, first carry out face exposure 2s with mask plate after drying, then carry out reverse side entirely exposing
Light 2s；Then carry out development treatment to transfer to nano-gap electrode figure on epoxy resin layer 2；Subsequently sputtering electrode metal level
5, it is 25 nanometers of Cr and 25 nanometer of Au, peel off and remove unnecessary photoresist, as shown in Fig. 2-1, Fig. 2-2；Ethanol is finally adopted to soak
Bubble 8～10min, expands because epoxy resin layer 2 can absorb ethanol, therefore can be in two middle points of electrode metal layer 5
Produce stress concentration at angle, crack to inner side outside electrode metal layer 5, eventually forming width is w1Nano gap electricity
Pole 3, w1For 50～500 nanometers, as shown in Fig. 3-1, Fig. 3-2 and Fig. 3-3；
3rd step, dielectrophoresis assembles carboxyl-functional SWCN 4：Deca carboxyl between nano-gap electrode 3
Functionalization SWCN suspension, carboxyl-functional SWCN 4 will be along electric field line in the presence of dielectric power
Direction mobile and rotate, be eventually deposited between nano-gap electrode 3 and connect both sides nano-gap electrode 3, as Fig. 1 institute
Show, Van der Waals force can strengthen the bonding strength between carboxyl-functional SWCN 4 and nano-gap electrode 3 simultaneously,
The parameter of self assembly is 100～500KHz, 2.5～3.0Vpp, the concentration of carboxyl-functional SWCN suspension is 0.05
～0.15mg/ml, dripping quantity is 20～50 μ l, stops when voltage signal has an obvious saltus step powering up, now carboxyl work(is described
SWCN 4 can be changed successfully be assembled in nano-gap electrode 3, by adjusting voltage and frequency and carboxyl function
The quantity to control the carboxyl-functional SWCN 4 of assembling for the concentration of change SWCN suspension, thus improve
The performance of device；
4th step, flexible pH sensor pretreatment：Before carrying out pH test, first flexible pH sensor is carried out,
It is connected weaker carboxyl-functional SWCN 4 with nano-gap electrode 3 and retains and nano-gap electrode the last 3 to remove
The carboxyl-functional SWCN 4 of effect, further ensures that concordance and the stability of follow-up pH response.
The present invention solves that traditional pH sensor manufacturing cost is high, volume is big, not portable, ask more than detectable consumption etc.
Topic.Meanwhile, this flexible pH sensor construction is simple, have that flexible and applied widely, sensitivity is high, fast response time, test
Voltage is relatively low and can be compatible with integrated circuit, has vast development prospect.
Claims (1)
1. a kind of manufacture method of the flexible pH sensor based on nano-gap electrode it is characterised in that：Comprise the steps：
The first step, the surface modification of SWNTs：Weigh 5mg SWNTs and 100ml 67%HNO first3Ultrasonic mixing, subsequently will be upper
State solution to be stirred, 110 DEG C of condensing refluxes process 12h so that SWNTs surface and end introduce carboxyl simultaneously, then using going
Ionized water by above-mentioned solution with 12000r/min, 30min centrifugal treating 5～6 times until solution partial neutral, last supersound process with
Obtain scattered carboxyl-functional SWCN suspension；
Second step, prepares nano-gap electrode (3)：First in the upper spin-on epoxy layer (2) of flexible substrate (1), treat that it is complete
Spin coating photoresist after solidification, carries out positive and negative exposure respectively after drying, then carry out development treatment by nano-gap electrode figure
Transfer on epoxy resin layer (2), sputtering electrode metal level is peeled off after (5), finally using alcohol-pickled swelling go out gap
Nano-gap electrode (3) for 50～500 nanometers；
3rd step, dielectrophoresis assembling carboxyl-functional SWCN (4)：Deca carboxyl between nano-gap electrode (3)
Functionalization SWCN suspension, carboxyl-functional SWCN (4) will be along electric field in the presence of dielectric power
The direction of line is mobile and rotates, and is eventually deposited between nano-gap electrode (3) and connects both sides nano-gap electrode (3), with
When the Van der Waals force bonding strength that can strengthen between carboxyl-functional SWCN (4) and nano-gap electrode (3), from
The parameter of assembling is 100～500KHz, 2.5～3.0Vpp, the concentration of carboxyl-functional SWCN suspension is 0.05～
0.15mg/ml, dripping quantity is 20～50 μ l, by adjusting voltage and frequency and carboxyl-functional SWCN suspension
The quantity to control the carboxyl-functional SWCN (4) of assembling for the concentration；
4th step, flexible pH sensor pretreatment：Before carrying out pH test, need first flexible pH sensor to be carried out, with
Remove and be connected weaker carboxyl-functional SWCN (4) with nano-gap electrode (3) and retain and nano-gap electrode
(3) the carboxyl-functional SWCN (4) pretended.
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| CN105699429A (en) * | 2016-01-08 | 2016-06-22 | 平高集团有限公司 | Micron-order semiconductor sensor and preparation method thereof |
| CN107228881B (en) * | 2016-03-23 | 2019-08-23 | 华邦电子股份有限公司 | The soft ph value sensor of printing and its manufacturing method |
| CN106950259B (en) * | 2017-03-31 | 2019-08-09 | 北京工业大学 | One kind is based on nano wire texture flexible biological pH sensor and preparation method thereof |
| CN108584865A (en) * | 2018-05-25 | 2018-09-28 | 湖北大学 | A kind of production method of control method and its ion detector based on the arrangement of overlength molybdenum oxide nanowires array |
| CN111624248A (en) * | 2020-06-10 | 2020-09-04 | 苏州大学 | Wearable sweat pH value detection device |
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