CN110423516A - Ink and preparation method thereof and gas sensor film - Google Patents
Ink and preparation method thereof and gas sensor film Download PDFInfo
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- CN110423516A CN110423516A CN201811027983.2A CN201811027983A CN110423516A CN 110423516 A CN110423516 A CN 110423516A CN 201811027983 A CN201811027983 A CN 201811027983A CN 110423516 A CN110423516 A CN 110423516A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
- C09D11/36—Inkjet printing inks based on non-aqueous solvents
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
- C09D11/38—Inkjet printing inks characterised by non-macromolecular additives other than solvents, pigments or dyes
Abstract
The present invention relates to a kind of inks and preparation method thereof and gas sensor film.Wherein, the preparation method of the ink is the following steps are included: providing has anisotropic α-Fe2O3Nano particle；In the α-Fe2O3The surface of nano particle forms the SnO with meso-hole structure2Shell obtains the α-Fe with core-shell structure2O3/SnO2Nano-complex particle；By the α-Fe with core-shell structure2O3/SnO2Nano-complex particle is dispersed in water, and obtains dispersion liquid, adds solvent, is uniformly mixed, is obtained the ink.The ink being prepared by this method is uniform, stablizes, and is suitable for inkjet printing, which is compound in one two kinds of gas sensitives, and is able to suppress coffee ring effect, improves the homogeneity and sensitivity of gas sensor film.
Description
Technical field
The present invention relates to gas sensor manufacturing technology fields, more particularly to a kind of ink and preparation method thereof and air-sensitive
Colorimetric sensor films.
Background technique
Semiconductor gas sensor is mainly using transition metal oxide semiconductor material as gas sensitive.It is commonly used for gas
The SnO of quick material2(stannic oxide) air-sensitive film has response to many gases, has many advantages, such as that detection range is wide, but also deposit
The disadvantages of selectivity is not high, job stability is not strong.α-Fe2O3(alpha-phase ferricoxide is commonly called as bloodstone) is a kind of typical case
N-shaped (depleted of electrons layer) semiconductor, have good optical band gap, corrosion resistance, it is environmental-friendly and be readily synthesized preparation etc.
Advantage, and it is widely used in the fields such as optical electro-chemistry, gas sensor, but it haves the shortcomings that sensitivity is not good enough.
Inkjet printing, which has, to be precisely controlled, is easy to operate, saving the excellent characteristics such as material, in electronic component preparation, function
Material deposition film shows special advantage.By synthesizing correlation function material, and ink is carried out to it, is beaten using ink-jet
The technology of print can easily prepare the air-sensitive film of a variety of different ingredients and thickness.But inkjet printing and its then
Drying process, it will usually the capillary flow by thin film center position points toward edge position is generated, to cause that center is thin and side
The thicker coffee ring phenomenon of edge causes film forming homogeneity bad, influences device performance.In order to inhibit this capillary flow, usually add
Add multi-solvents and pass through and adjust each solvent composition in ink, forms kalimeris brother Buddhist nun stream in the drying process, inhibit coffee ring
It is formed.
However, the addition of multi-solvents, is only capable of weakening the trend that coffee ring is formed, and form kalimeris brother Buddhist nun stream and capillary
The relative size of stream also has no way of measuring, and has certain blindness for the regulation of drying process, and molten by adding, adjusting
Agent matches to inhibit the complicated for operation of coffee ring phenomenon, and efficiency is lower.
Summary of the invention
Based on this, a kind of stable ink is provided, the influence of coffee ring can be avoided in ink curing processes, is formed equal
One air-sensitive film layer, improves the response sensitivity of gas sensor.
A kind of ink, mainly by α-Fe2O3/SnO2Nano-complex particle and solvent are prepared, the α-Fe2O3/SnO2
Nano-complex particle has core-shell structure, wherein α-Fe2O3For core, SnO2To be coated on α-Fe2O3Shell on core, SnO2Shell
Layer has meso-hole structure, the α-Fe2O3For with anisotropic α-Fe2O3。
Above-mentioned ink is in uniform colloidal dispersion system, and stability is good, is suitable for printing, and it is able to suppress ink dried
Coffee ring effect in film forming procedure improves the homogeneity of film layer, can be used for the mass printing life of gas sensor film
It produces, improves the response sensitivity of gas sensor.
The raw material for preparing the ink in one of the embodiments, further includes surfactant, the α-Fe2O3/SnO2
The 5%~30% of the ink total weight is accounted for the sum of the weight of the surfactant, the solvent accounts for the ink gross weight
The 70%~95% of amount.
Another object of the present invention is a kind of preparation method of ink, and the preparation method comprises the following steps:
There is provided has anisotropic α-Fe2O3Nano particle；
In the α-Fe2O3The surface of nano particle forms the SnO with meso-hole structure2Shell is obtained with core-shell structure
α-Fe2O3/SnO2Nano-complex particle；
By the α-Fe2O3/SnO2Nano-complex particle is dispersed in water, and obtains dispersion liquid, adds solvent, and mixing is equal
It is even, obtain the ink.
The above-mentioned preparation method of the present invention first passes through hydro-thermal method and particle purity is high, the anisotropy of good dispersion is prepared
α-Fe2O3Nano particle can weaken the influence of the capillary flow in ink curing processes, then to α-Fe2O3Nano particle table
Face carries out SnO2Cladding, forms the mesoporous α-Fe of core-shell structure2O3@SnO2Nano-complex particle, so that α-Fe2O3Particle that
This is isolated, and SnO2Cladding so that Particle surface charge density increase, the thickness of diffusion layer of micelle is increased, so that repulsion
Potential energy increases, and prevents mesoporous α-Fe2O3@SnO2Reunion between colloidal solid forms stable colloidal dispersion system；And core
Shell structure can improve SnO simultaneously2With α-Fe2O3Stability.
The ink obtained by above-mentioned preparation method is suitable for printing in uniform and stable colloidal dispersion system, is printing
In drying process, it can inhibit the uneven influence of the film forming such as coffee ring, promote the homogeneity of printing-filming thickness；And α-Fe2O3@
SnO2Particle is in loose arrangement pattern, after ink dried, uniform, loose porous film layer can be obtained, so as to mention
The response sensitivity of high gas sensor.
In one of the embodiments, in the α-Fe2O3The surface of nano particle forms the SnO with meso-hole structure2Shell
The step of layer are as follows:
By the α-Fe2O3Nano particle is scattered in ethanol water, and urea, stannate and PVP-K30 is added, and is mixed,
After the completion of 130 DEG C~110 DEG C hydro-thermal reactions, washed, drying process obtains the α-Fe with core-shell structure2O3/SnO2It receives
Rice compound particle, wherein α-Fe2O3For core, SnO2To be coated on α-Fe2O3Shell on core, SnO2Shell has meso-hole structure.
It is appreciated that PVP-K30 has space steric effect, in SnO2In synthesis process, SnO can be prevented2Not medium well
It is long, prevent its spherical surface direction from connecting completely, to densify, be easily formed the SnO of porous structure2Shell；May be used also simultaneously
To limit α-Fe2O3@SnO2The growth of particle makes its partial size maintain the requirement for meeting ink particles of solute size.
α-the Fe in one of the embodiments,2O3Nano particle, the urea, the stannate and the PVP-
The weight ratio of K30 is 1:(1.5~2.5): (2.5~3.5): (1~2).
Further include the steps that surfactant is added into the dispersion liquid in one of the embodiments,；
α-the Fe2O3/SnO2The sum of the weight of nano-complex particle and the surfactant accounts for the ink total weight
5%~30%.
The surfactant is selected from polyvinylpyrrolidone, polyethylene glycol, polyethylene glycol in one of the embodiments,
At least one of octyl phenyl ether and carboxymethyl cellulose.
By spatial stability theory it is found that the presence of high polymer surfactants can reduce the Hamaker constant between micelle, from
And reduce the Van der Waals between particle and attract energy, meanwhile, the presence of high polymer generates new repulsion position energy --- space repulsion position
Can, space steric effect is made it have, repulsion potential energy is further increased, to prevent mesoporous α-Fe2O3@SnO2Colloidal solid it
Between reunion, be capable of forming stable colloidal dispersion system.
It in one of the embodiments, further include described with anisotropic α-Fe2O3The preparation step of nano particle:
By Fe (ClO4)3Solution is added to dihydric phosphate and CO (NH2)2Mixed aqueous solution in, mix, in 100 DEG C~
After the completion of 160 DEG C of hydro-thermal reactions, separation takes solid, and washed, drying process obtains having anisotropic α-Fe2O3Nanometer
Grain.
The concentration of the ethanol water is 30vol%~50vol% in one of the embodiments,.
Yet another object of that present invention is to a kind of gas sensor film, the gas sensor film is using in the present invention
Ink is stated, or be prepared by the ink that above-mentioned preparation method is prepared.
The invention has the advantages that:
1) ink of the invention is by by anisotropic α-Fe2O3Nano grain surface carries out mesoporous SnO2Cladding is formed
With mesoporous α-Fe2O3@SnO2Nano-complex particle, while introducing dispersibility and stabilization that PVP-K30 improves colloidal particle
Property, it is then configured to be suitble to the ink of printing, two kinds of gas sensitives is not only made to be compound in one, while playing two kinds of gas sensitives
Advantage, and form mesoporous material, the contact area of gas and gas sensitive can be increased, enhance response sensitivity；And
It can also inhibit solute migration caused by capillary flow automatically, avoid the coffee ring effect in inkjet printing, improve air-sensitive film
Flatness further enhances response sensitivity.
2) in ink curing processes, mesoporous α-Fe2O3@SnO2Colloidal particle has very strong capillarity each other
Power, so that between particle stabilized be uniformly maintained near gas-liquid interface, and the strong capillarity between particle makes
It with holdback force, will not be driven easily by capillary flow, opposite holding is stablized between particle and position is fixed, and is in the ink
Now loose arrangement pattern, to improve the uniformity of film.
3) high polymer surfactants such as PVP are added in the ink, on the one hand the surface tension of adjustable ink and viscous
Power is tied, is made it is suitable for printing, another aspect high polymer can reduce mesoporous α-Fe2O3@SnO2Van der Waals between colloidal particle
Attraction, while space steric effect is generated, enhance the stability between colloidal particle, and the addition of high polymer is dry to printing
Film forming, adhesive property after dry etc. have good effect.
4) mass that the above-mentioned ink of the present invention is suitable for gas sensor film prints production, after drying resulting gas
The homogeneity of dependent sensor film is good, and compound there are two types of gas sensitives, and are in loose porous shape, can enhance gas sensor
Response sensitivity and stability.
Detailed description of the invention
Fig. 1 is the coffee ring effect schematic diagram of traditional ink in the drying process；
Fig. 2 is one embodiment of the invention ink printed drying process schematic diagram.
Specific embodiment
To facilitate the understanding of the present invention, below will to invention is more fully described, and give it is of the invention compared with
Good embodiment.But the invention can be realized in many different forms, however it is not limited to embodiment described herein.Phase
Instead, purpose of providing these embodiments is makes the disclosure of the present invention more thorough and comprehensive.
Unless otherwise defined, all technical and scientific terms used herein and belong to technical field of the invention
The normally understood meaning of technical staff is identical.Term as used herein in the specification of the present invention is intended merely to description tool
The purpose of the embodiment of body, it is not intended that in the limitation present invention.Term as used herein "and/or" includes one or more phases
Any and all combinations of the listed item of pass.
α-Fe2O3A kind of typical n-type semiconductor, have good optical band gap, corrosion resistance, it is environmental-friendly and easily
It is widely used in the fields such as optical electro-chemistry, gas sensor in be synthetically prepared the advantages that.But individual α-Fe2O3A kind of material
The gas sensing sensitivity of material is not high, and stability is also bad.SnO2Air-sensitive film has response to many gases, has detection model
The advantages that enclosing width.Therefore, by α-Fe2O3And SnO2Two kinds of Material claddings can obtain more excellent air-sensitive performance in one.
And inkjet printing technology is a kind of effective ways for realizing gas sensor film preparation.Gas-sensitive Functional Materials are matched
Ink is made, using the technology of inkjet printing, can easily carry out functional material deposition, accurately control the position of film unit
It sets, ingredient, shape and thicknesses of layers and accurate doping easy to implement etc..
But the problem of present inventor has found, inkjet printing is primarily present following two aspect at present:
(1) the granular pattern ink of inkjet printing, as shown in Figure 1, the solute in conventional inks is isotropic spherical
Grain, in evaporation of ink drying process, the vapour pressure at ink droplets edge is smaller, and intermediate vapour pressure is larger, so as to cause side
Edge divides evaporation rate of solvent very fast, and solvent evaporation in middle section is slower, causes lateral difference in flow, and middle section is to marginal portion
It compensates and intermediate extrorse compensation capillary flow occurs, along with the capillary attraction between isotropic spheric granules
Power is weaker, and the spheric granules in ink is easily brought to marginal portion, deposits at contact line, and " pinning " for generating contact line is existing
As；In further drying process, solvent is evaporated, and forms " coffee ring " structure of center thin edges thickness, and causes ink
It deposits inhomogenous, seriously affects the surface smoothness of inkjet printing film, limit its application in terms of device preparation.
(2) precondition of inkjet printing technology is that target material to be made forms the functional ink being stabilized how
Air-sensitive thin film material is formed to uniform and stable ink, this is that emphasis is also difficult point.Function of ink material is usually with nano particle
Form exist, but since nanoparticle size is small, large specific surface area, surface can be very high, and collection is easy between nano particle
Gather and deposit, stable dispersion liquid system cannot be formed, be unfavorable for the ink of functional material.
Based on this, it is necessary in conjunction with gas sensitive α-Fe2O3And SnO2The advantages of, a kind of uniform and stable ink is provided,
The influence that coffee ring can be avoided in printing and drying process forms uniform air-sensitive film layer.
A kind of ink, mainly by α-Fe2O3/SnO2Nano-complex particle and solvent are prepared, α-Fe2O3/SnO2Nanometer
Compound particle has core-shell structure, wherein α-Fe2O3For core, SnO2To be coated on α-Fe2O3Shell on core, SnO2Shell tool
There are meso-hole structure, and α-Fe2O3For with anisotropic α-Fe2O3。
According to dlvo theory, solute particles form colloid in a solvent, and colloidal particle is coagulation or stabilization in colloid
Dispersion, depending between colloidal particle mutual attractive force and electrostatic repulsion forces who strong who is weak.If repulsion is greater than gravitation, colloidal sol
Stablize, on the contrary then colloidal sol is unstable to generate coagulation.Colloidal particle has double electrical layers, when the diffusion layer between colloidal particle
When overlapping, under the action of electric double layer, electrostatic repulsion forces can be generated between colloidal particle.
Solute in the above-mentioned ink of the present invention is the α-Fe with core-shell structure2O3/SnO2Nano-complex particle, wherein α-
Fe2O3With anisotropy, the influence of the capillary flow in ink curing processes can be weakened, and there is SnO on its surface2Clad,
So that α-Fe2O3Particle isolates each other, while the charge density on particles of solute surface is increased, so as to increase micelle
Thickness of diffusion layer prevents mesoporous α-Fe so that repulsion potential energy increases2O3@SnO2Reunion between colloidal solid is formed stable
Colloidal dispersion system；And core-shell structure can improve SnO simultaneously2With α-Fe2O3Stability.
The ink is in uniform and stable colloidal dispersion system, is suitable for printing, and in printing drying process, can be inhibited automatically
The uneven influence of the film forming such as coffee ring, promotes the homogeneity of printing-filming thickness, as shown in Fig. 2, solute (the mesoporous α-in ink
Fe2O3@SnO2Colloidal solid) it is in anisotropic elliposoidal, there is very strong capillary force each other, so that particle is steady
Surely be uniformly maintained near gas-liquid interface, and the capillarity between particle make each other there are holdback forces, will not
It is driven easily by capillary flow, to keep relative stability and position is fixed, weakens the influence of capillary flow, inhibit coffee ring effect
It answers；And particle is in loose arrangement pattern, after ink dried, can obtain uniform, loose porous film layer, so as to
Improve the response sensitivity of gas sensor.
In one embodiment, the raw material for preparing ink further includes surfactant, α-Fe2O3/SnO2With surfactant
The sum of weight accounts for the 5%~30% of ink total weight, and solvent accounts for the 70%~95% of ink total weight.
Further, surfactant is selected from polyvinylpyrrolidone (PVP), polyethylene glycol (PEG), polyethylene glycol octyl
At least one of high polymer surfactants such as phenyl ether (Triton X-100) and carboxymethyl cellulose (CMC).More preferably,
Surfactant is PVP.
It is appreciated that it is theoretical by spatial stability it is found that the presence of high polymer can reduce the Hamaker constant between micelle, from
And reduce the Van der Waals between particle and attract energy, meanwhile, the presence of high polymer can also generate new repulsion position energy --- space reprimand
Power position energy, makes it have space steric effect, further increases repulsion potential energy, to prevent α-Fe2O3/SnO2Nano combined grain
Reunion between son forms stable colloidal dispersion system.Therefore, the addition of the high polymers such as PVP, improves the stability of ink
Meanwhile, it is capable to adjust the printing adaptive such as surface tension and viscosity of ink, moreover it is possible to film forming and bonding after improving ink dried
Property.
Further, α-Fe2O3/SnO2The weight ratio of nano-complex particle and PVP are (0.1~0.5): 1.
Another embodiment of the present invention provides a kind of preparation method of ink, includes the following steps S1~S3:
S1, it provides with anisotropic α-Fe2O3Nano particle.
In one embodiment, anisotropic α-Fe is prepared2O3The step of nano particle are as follows: by Fe (ClO4)3Solution adds
Enter to dihydric phosphate and CO (NH2)2It in the mixed aqueous solution of (urea), mixes, in 100 DEG C~160 DEG C hydro-thermal reactions, separation
Solid is taken, washed, drying process obtains anisotropic α-Fe2O3Nano particle.
In one embodiment, dihydric phosphate KH2PO4Or NaH2PO4。
In one embodiment, Fe (ClO4)3The concentration of solution is 0.05mol/L~0.2mol/L.
In one embodiment, dihydric phosphate and Fe (ClO4)3Molar ratio be (0.02~0.06): 1；CO(NH2)2With
Fe(ClO4)3Molar ratio be (1~1.5): 1.
In this way, being prepared each by conditions such as each raw material dosage, the hydro-thermal reaction time, temperature in control reaction process
α-the Fe of anisotropy2O3, it is in elliposoidal or spindle that not only particle purity is high, good dispersion, and crystal form is good, this respectively to different
Property nano particle in ink printed drying process, each other have very strong capillary force, enable particle steady
Surely it is uniformly maintained near gas-liquid interface, and capillarity strong between particle makes all the presence of containing each other
Power cannot be driven by capillary flow easily, to keep relative stability between particle and position is fixed, weaken the shadow of capillary flow
It rings, and loose arrangement pattern is presented, improve the uniformity of ink dried film forming.
In one embodiment, in step sl, the temperature of drying process is 40 DEG C~60 DEG C, and the time is 1h~12h.
Specifically, by Fe (ClO4)3It is added to NaH2PO4、CO(NH2)2In mixed aqueous solution, 30min~1h is mixed,
So that respectively mixing in system uniformly, yellow solution is obtained.Above-mentioned presoma yellow solution is then transferred to hydrothermal reaction kettle
In, 100 DEG C in an oven~160 DEG C heat preservation 4h~for 24 hours, room temperature is then naturally cooled to, red mixture is obtained.Wherein,
Fe(ClO4)3For 0.1mol/L, NaH2PO4With Fe (ClO4)3Molar ratio be (0.02~0.06): 1, CO (NH2)2With Fe
(ClO4)3Molar ratio be (1~1.5): 1.By red material obtained above by being centrifuged, with deionized water and/or anhydrous second
Alcohol washs 2~3 times, and obtained substance is in 40 DEG C~60 DEG C dry 1h~12h to get to anisotropic α-Fe2O3Nanometer
Grain.
S2, Yu Suoshu α-Fe2O3The surface of nano particle forms the SnO with meso-hole structure2Shell is obtained with nucleocapsid
α-the Fe of structure2O3/SnO2Nano-complex particle.
Specifically, α-Fe step S1 obtained2O3Nano particle is scattered in ethanol water, and urea, stannate is added
It with PVP-K30 (polyvinylpyrrolidone-K30), mixes, cooling after the completion of 130 DEG C~110 DEG C hydro-thermal reactions, separation takes glue
Body, washed, drying process, obtains the α-Fe with core-shell structure2O3/SnO2Nano-complex particle, wherein α-Fe2O3For core,
SnO2To be coated on α-Fe2O3Shell on core, SnO2Shell has meso-hole structure.
In one embodiment, the concentration of ethanol solution is 30vol%~50vol%.It is appreciated that α-Fe2O3Nano particle
Good dispersion in the ethanol solution of 30vol%~50vol% will not reunite, and be conducive to subsequent cladding and handle.
In one embodiment, α-Fe2O3The weight ratio of nano particle and urea is 1:(1.5~2.5), α-Fe2O3Nanometer
The weight ratio of grain and stannate is 1:(2.5~3.5), α-Fe2O3The weight ratio of nano particle and PVP-K30 are 1:(1~2).Such as
This, by the dosage of each raw material in control hydrothermal reaction process, the hydro-thermal reaction time, temperature etc. decompose generation using urea
CO2Bubble makees soft template, generates SnO by stannic acid salt hydrolysis2Nano particle, with anisotropic α-Fe2O3Nano grain surface phase
In conjunction with self assembly obtains the SnO with porous structure2Clad, and by anisotropic α-Fe2O3Nano particle coats wherein,
Form the α-Fe of PVP-K30 surface modification2O3@m-SnO2Core-shell structure.It should be noted that α-Fe2O3@m-SnO2In α-
Fe2O3For core, SnO2For clad, m indicates mesoporous, i.e. α-Fe2O3Surface cladding have porous structure SnO2Layer.
In one embodiment, the temperature of the drying process in step S2 is 70 DEG C~90 DEG C, and the time is 1h~12h.
In one embodiment, stannate is selected from one of sodium stannate and its hydrate, potassium stannate and its hydrate.
Specifically, by α-Fe2O3Nano particle is scattered in 30vol%~50vol% ethanol solution, ultrasonic disperse 20min
Then urea and Na is added in~30min2SnO3·3H2O (sodium stannate trihydrate) continues ultrasonic disperse 10mim~20mim, is added
PVP-K30 (polyvinylpyrrolidone-K30) stirs 20min~30min, after mixing, gained mixture system is transferred to water
In thermal response kettle, in 130 DEG C~110 DEG C hydro-thermal reaction 15h~20h, it is then cooled to room temperature, with deionized water and/or anhydrous
Ethanol washing 2~3 times then switches into vacuum oven, in 70 DEG C~90 DEG C dry 1h~12h, obtains α-Fe2O3@m-SnO2Glue
Body.
S3, the α-Fe for obtaining step S22O3/SnO2Nano-complex particle is dispersed in water, and obtains dispersion liquid, then plus
Enter solvent, is uniformly mixed, obtains the ink.
In one embodiment, in step s3, further include the steps that surfactant, α-Fe are added into dispersion liquid2O3/
SnO2The sum of nano-complex particle and the weight of surfactant account for the 5%~30% of ink total weight.
In one embodiment, surfactant is selected from polyvinylpyrrolidone, polyethylene glycol, Triton X-100
At least one of with the high polymer surfactants such as carboxymethyl cellulose.More preferably, PVP is selected.
Specifically, α-Fe step S2 obtained2O3/SnO2Nano-complex particle ultrasonic disperse is formed in deionized water
Uniform dispersion liquid；Then high polymer surfactants are added, after persistently stirring 12h~for 24 hours, solvent is added, is configured to ink.
In one embodiment, α-Fe2O3/SnO2The weight ratio of nano-complex particle and PVP are (0.1~0.5): 1, in this way,
By each component content in control ink, the parameters such as available surface tension, viscosity are suitable for the ink of printing.
In one embodiment, solvent is selected from least one of water, ethyl alcohol, isopropanol and ethylene glycol.
A further embodiment of this invention provides a kind of gas sensor film, for using the above-mentioned ink of the present invention or on
The ink that ink-manufacturing method is prepared is stated, is obtained after inkjet printing, drying.
Specifically, it by the above-mentioned ink of the present invention, is deposited on substrate by the way of inkjet printing, setting printing device is flat
The temperature of platform is 45 DEG C~55 DEG C, and by evaporation drying, vacuum drying is yet further forged in Muffle furnace in 300 DEG C or more
2h is burnt, accesses to gas sensor equipment then to get colorimetric sensor films uniform to film layer degree, can be sensitive to multiple gases.
The following are specific embodiments
Embodiment 1
(1) elliposoidal α-Fe2O3The preparation of nano particle
1. by Fe (ClO4)3It is added to NaH2PO4、CO(NH2)2In mixed aqueous solution, 30min is mixed, so that system
It respectively mixes uniformly.Then above-mentioned presoma yellow solution is transferred in hydrothermal reaction kettle, is kept the temperature for 24 hours for 100 DEG C in an oven,
Room temperature then is naturally cooled to, obtains red mixture.Wherein, Fe (ClO4)3For 0.1mol/L, NaH2PO4With Fe (ClO4)3
Molar ratio be 0.04:1, CO (NH2)2With Fe (ClO4)3Molar ratio be 1.2:1.
2. obtained red material is by centrifugation, after washing 3 times in dehydrated alcohol, obtained substance is in 40 DEG C of dryings
12h obtains the elliposoidal α-Fe of purity is high, good dispersion2O3Nano particle.
(2) mesoporous α-Fe2O3@m-SnO2Colloidal solid preparation
By 0.1g α-Fe2O3(dehydrated alcohol volume fraction: 30vol%) ultrasonic disperse is scattered in 90mL ethanol solution
30min；2g urea, 0.3g Na2SnO3·3H2O is added to continuation ultrasonic disperse 10min in above-mentioned dispersion liquid, and 0.1g is added
PVP (k30) stirs 30min, and then above-mentioned system is transferred in hydrothermal reaction kettle in 160 DEG C of reaction 20h, is subsequently cooled to room
Temperature is washed 2 times with dehydrated alcohol, and it is 12 hours dry in 10 DEG C to then switch into vacuum oven.
(3) preparation of ink
1. 100mg mesoporous α-Fe obtained above2O3@m-SnO2Colloid is scattered in 300mL deionization in the state of ultrasound
Water forms uniform dispersion；
2. 1g PVP is then added to above-mentioned system, 12h is persistently stirred.
3. being finally added to it isopropanol, it is configured to the ink of inkjet printable, wherein by weight percentage, mesoporous
α-Fe2O3@m-SnO2Colloid and PVP account for 30% altogether, alcohol solvent accounting 70%.
(4) inkjet printing and drying and forming-film
Above-mentioned ink is deposited on substrate by way of inkjet printing, the temperature of setting printing device platform is 50
DEG C, by evaporation drying, vacuum drying, yet further 350 DEG C of calcining 2h in Muffle furnace, obtain air-sensitive in homogeneous thickness and pass
Sensor film accesses gas sensor equipment to get the sensor film sensitive to multiple gases is arrived.
Embodiment 2
(1) elliposoidal α-Fe2O3The preparation of nano particle
1. by Fe (ClO4)3It is added to KaH2PO4、CO(NH2)2In mixed aqueous solution, 45min is mixed, so that system
It respectively mixes uniformly.Then above-mentioned presoma yellow solution is transferred in hydrothermal reaction kettle, in an oven 160 DEG C of heat preservation 4h,
Room temperature then is naturally cooled to, obtains red mixture.Wherein, Fe (ClO4)3For 0.1mol/L, KaH2PO4With Fe (ClO4)3's
Molar ratio is 0.06:1, CO (NH2)2With Fe (ClO4)3Molar ratio be 1.5:1
2. obtained red material is washed 3 times by centrifugation in dehydrated alcohol.60 DEG C of obtained substance dry 1h.
(2) mesoporous α-Fe2O3@m-SnO2Colloidal solid preparation
By 0.1g α-Fe2O3(dehydrated alcohol volume fraction: 50vol%) ultrasonic disperse is scattered in 90mL ethanol solution
30min；1.5g urea, 0.25g Na2SnO3·3H2O is added to continuation ultrasonic disperse 10min in above-mentioned dispersion liquid, and 0.1g is added
PVP-k30 stirs 30min, is then transferred in hydrothermal reaction kettle in 130 DEG C of reactions for 24 hours above-mentioned system, is subsequently cooled to room
Temperature is washed 2 times with dehydrated alcohol, and it is 12 hours dry in 70 DEG C to then switch into vacuum oven.
(3) preparation of ink
1. 300mg α-Fe obtained above2O3Nano particle is scattered in 300mL deionized water in the state of ultrasound and is formed
Uniform dispersion；
2. subsequent 2g PEG adds to above-mentioned system, lasting stirring is for 24 hours.
3. being finally added to it ethylene glycol, it is configured to the ink of inkjet printable.
Wherein by weight percentage, mesoporous α-Fe2O3@m-SnO2Colloid and PVP account for 20% altogether, alcohol solvent accounting
10%.
(4) inkjet printing and drying and forming-film
Above-mentioned ink is deposited on substrate by way of inkjet printing, the temperature of setting printing device platform is 50
DEG C, by evaporation drying, vacuum drying, yet further 400 DEG C of calcining 2h in Muffle furnace, access related gas sensor and set
It is standby, obtain the sensor film sensitive to multiple gases.
Embodiment 3
(1) elliposoidal α-Fe2O3The preparation of nano particle
1. by Fe (ClO4)3It is added to NaH2PO4、CO(NH2)2In mixed aqueous solution, 60min is mixed, so that system
It respectively mixes uniformly.Then above-mentioned presoma yellow solution is transferred in hydrothermal reaction kettle, in an oven 140 DEG C of heat preservation 20h,
Then naturally cool to room temperature.Wherein, Fe (ClO4)3For 0.1mol/L, NaH2PO4With Fe (ClO4)3Molar ratio be 0.06:1,
CO(NH2)2With Fe (ClO4)3Molar ratio be 1.5:1
2. obtained red material is washed 2 times, 50 DEG C of obtained substance dry 10h by centrifugation in dehydrated alcohol.
(2) mesoporous α-Fe2O3@m-SnO2Colloidal solid preparation
0.1gα-Fe2O3(dehydrated alcohol volume fraction: 40vol%) ultrasonic disperse is scattered in 90mL ethanol solution
30min；2.5g urea, 0.35g Na2SnO3·3H2O is added to continuation ultrasonic disperse 10min in above-mentioned dispersion liquid, is added
0.15g PVP-k30 stir 30min, then by above-mentioned system be transferred in hydrothermal reaction kettle in 160 DEG C react 20 hours, then
It is cooled to room temperature, is washed with deionized 3 times, the drying 12 hours of 10 DEG C of vacuum oven is then switched into.
(3) preparation of ink
1. 500mg α-Fe obtained above2O3Nano particle is scattered in 300mL deionized water in the state of ultrasound and is formed
Uniform dispersion；
2. subsequent 2g PVP adds to above-mentioned system, lasting stirring is for 24 hours.
3. being finally added to it ethylene glycol, it is configured to the ink of inkjet printable.
Wherein by weight percentage, mesoporous α-Fe2O3@m-SnO2Colloid and PVP account for 5% altogether, alcohol solvent accounting
95%.
(4) inkjet printing and drying and forming-film
Above-mentioned ink is deposited on substrate by way of inkjet printing, the temperature of setting printing device platform is 50
DEG C, by evaporation drying, vacuum drying, yet further in Muffle furnace 300 DEG C or more calcine 2h, access related gas sensing
Device equipment obtains the sensor film sensitive to multiple gases.
Each technical characteristic of embodiment described above can be combined arbitrarily, for simplicity of description, not to above-mentioned reality
It applies all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited
In contradiction, all should be considered as described in this specification.
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously
It cannot therefore be construed as limiting the scope of the patent.It should be pointed out that coming for those of ordinary skill in the art
It says, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to protection of the invention
Range.Therefore, the scope of protection of the patent of the invention shall be subject to the appended claims.
Claims (10)
1. a kind of ink, which is characterized in that mainly by α-Fe2O3/SnO2Nano-complex particle and solvent are prepared, the α-
Fe2O3/SnO2Nano-complex particle has core-shell structure, wherein α-Fe2O3For core, SnO2To be coated on α-Fe2O3Shell on core
Layer, SnO2Shell has meso-hole structure, the α-Fe2O3For with anisotropic α-Fe2O3。
2. ink according to claim 1, which is characterized in that the raw material for preparing the ink further includes surfactant,
α-the Fe2O3/SnO2The sum of the weight of nano-complex particle and the surfactant account for the ink total weight 5%~
30%, the solvent accounts for the 70%~95% of the ink total weight.
3. a kind of preparation method of ink, which comprises the following steps:
There is provided has anisotropic α-Fe2O3Nano particle；
In the α-Fe2O3The surface of nano particle forms the SnO with meso-hole structure2Shell obtains the α-with core-shell structure
Fe2O3/SnO2Nano-complex particle；
By the α-Fe2O3/SnO2Nano-complex particle is dispersed in water, and obtains dispersion liquid, adds solvent, is uniformly mixed, is obtained
To the ink.
4. preparation method according to claim 3, which is characterized in that Yu Suoshu α-Fe2O3The surface of nano particle forms tool
There is the SnO of meso-hole structure2The step of shell are as follows:
By the α-Fe2O3Nano particle is scattered in ethanol water, and urea, stannate and PVP-K30 is added, and is mixed, in
After the completion of 130 DEG C~180 DEG C hydro-thermal reactions, washed, drying process obtains the α-Fe with core-shell structure2O3/SnO2Nanometer
Compound particle, wherein α-Fe2O3For core, SnO2To be coated on α-Fe2O3Shell on core, SnO2Shell has meso-hole structure.
5. the preparation method according to claim 4, which is characterized in that the α-Fe2O3It is nano particle, the urea, described
The weight ratio of stannate and the PVP-K30 are 1:(1.5~2.5): (2.5~3.5): (1~2).
6. preparation method according to claim 3, which is characterized in that further include that surface-active is added into the dispersion liquid
The step of agent；
α-the Fe2O3/SnO2The sum of the weight of nano-complex particle and the surfactant accounts for the ink total weight
5%~30%.
7. preparation method according to claim 6, which is characterized in that the surfactant is selected from polyvinylpyrrolidine
At least one of ketone, polyethylene glycol, Triton X-100 and carboxymethyl cellulose.
8. preparation method according to claim 3, which is characterized in that further include described with anisotropic α-Fe2O3It receives
The preparation step of rice grain:
By Fe (ClO4)3Solution is added to dihydric phosphate and CO (NH2)2Mixed aqueous solution in, mix, in 100 DEG C~160 DEG C
After the completion of hydro-thermal reaction, separation takes solid, and washed, drying process obtains having anisotropic α-Fe2O3Nano particle.
9. according to any preparation method of claim 4~8, which is characterized in that the concentration of the ethanol water is
30vol%~50vol%.
10. a kind of gas sensor film, which is characterized in that prepare ink used in the gas sensor film and wanted for right
The ink for asking 1~2 any any preparation method of the ink or claim 3~9 to be prepared.
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| CN111137013A (en) * | 2020-01-09 | 2020-05-12 | 深圳市华星光电半导体显示技术有限公司 | Inkjet printing method, inkjet printing apparatus, inkjet printing device, and computer-readable storage medium |
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| CN1400107A (en) * | 2001-08-03 | 2003-03-05 | 中国科学院金属研究所 | Ink jet printing method for preparing metal oxide functional film |
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