CN100422730C - Nano-structural ordered porous thin-film type gas sensor and method for preparing same - Google Patents
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- CN100422730C CN100422730C CNB2005100956069A CN200510095606A CN100422730C CN 100422730 C CN100422730 C CN 100422730C CN B2005100956069 A CNB2005100956069 A CN B2005100956069A CN 200510095606 A CN200510095606 A CN 200510095606A CN 100422730 C CN100422730 C CN 100422730C
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Abstract
The invention discloses a nano-structure orderly porous thin film gas-sensing element and preparation method. The element includes the substrate, the electrode and the thin file on it, especially the substrate being curved surface, and the thin film formed by spherical hole-shaped metal oxide, its aperture size 200~1000nm, thin film thickness 100~5000nm. The method includes the single layer colloidal crystal template, with steps (1) putting the single layer colloidal crystal template into the metal oxide precursor solution or sol of concentration 0.1~0.5M, and waiting for it detached from the substrate and floating on the surface of the precursor solution or sol, with the required shape electrode substrate to salvage the single layer colloidal crystals and covering it on the substrate surface; (2) first putting it under the temperature 80~120DEG C for heating 1~2 hours, then raising under the temperature 200~500DEG C for sintering 2~3 hours; (3) repeat the above (1) and (2) steps for more than 0 times, to make the nano-structure orderly porous thin film gas-sensing element. It can be widely used for environmental monitoring, chemical industry and many other fields.
Description
Technical field
The present invention relates to a kind of gas sensor and method for making, especially nano-structural ordered porous thin-film type gas sensor and preparation method thereof.
Background technology
At present, using gas sensor in large quantities in various fields such as environmental monitoring, chemical industry, as one of them thin film type gas-sensitive element because of it is quick on the draw, volume is little and working stability reliably enjoys favor, as various commercially available.It is by substrate and electrode, and the film that covers thereon constitutes.People often use chemical methodes such as physical methods such as vacuum evaporation, sputter, plasma reinforced chemical vapour deposition and sol-gel process in order to obtain it.But this thin film type gas-sensitive element and its method for making all exist weak point, and at first, the specific surface area of element is little, makes its sensitivity low, and are difficult to improve, and can not be used for the higher occasion of ask for something; Secondly, the apparatus expensive of physical method, complicated operation, and mainly be used on the smooth substrate and make; Once more, when sol-gel process is carried out the element making as a kind of common chemical method, mainly be that mode by artificial coating is coated in colloidal sol on the substrate in advance, heat-treat then, though this method can be made on the substrate-ceramic pipe of curved surface,, because of artificial factor, the uneven film thickness of element surface is even, gas sensitive easily comes off, thereby the stability of gas sensor and repeatability are seriously influenced.For overcoming an above-mentioned difficult problem, people have done some trials and effort, attempt to increase by the size that changes particle in the film specific surface area of film, and the measure of employing has photoetching process, electron beam lithography, little contact printing technology etc.; Yet, exist the costing an arm and a leg of equipment, complicated operation equally, and be difficult to defective directly synthetic on non-smooth surface, the synthesis nano porous thin-film type gas sensor on curved substrate of particularly failing.
Summary of the invention
The technical problem to be solved in the present invention provides a kind of highly sensitive, easy to make nano-structural ordered porous thin-film type gas sensor and preparation method thereof for overcoming weak point of the prior art.
Nano-structural ordered porous thin-film type gas sensor comprises substrate and electrode, and cover thereon film, particularly said substrate is a curved surface shape or plane, said film is made of the poroid metal oxide of sphere, the bore dia of said spherical pore is 200～1000nm, and the thickness of said film is 100～5000nm.
As the further improvement of nano-structural ordered porous thin-film type gas sensor, described curved surface shape is convex surface or concave surface, and said convex surface is a sphere; Described substrate is metal or glass or pottery or monocrystalline silicon or mica or quartz; Described spherical pore be two-layer more than, Kong Chengliu side's solid matter type, and being interconnected between the hole; Between three spherical hole walls of described six side's solid matter types triangular apertures is arranged; Described metal oxide is tin ash or di-iron trioxide or zinc paste.
It is that the colloidal spheres of 200～1000nm invests the planar substrate surface and forms colloid monolayer crystal template that the preparation method of nano-structural ordered porous thin-film type gas sensor comprises diameter, particularly it is finished according to the following steps: (1), colloid monolayer crystal template is immersed concentration is in the metal oxide precursor solution or colloidal sol of 0.1～0.5M, treat the colloid monolayer crystal break away from substrate and swim in precursor solution or the surface of colloidal sol after, pick up the colloid monolayer crystal and make it be covered in substrate surface with the substrate that has pair of electrodes of required form; The substrate that will be covered with the colloid monolayer crystal (2), earlier and be soaked with metal oxide precursor solution or colloidal sol places 80～120 ℃ of heating 1～2 hour down, is placed on 200～500 ℃ of following sintering again 2～3 hours; (3), repeat to make nano-structural ordered porous thin-film type gas sensor more than the step 0 time of above-mentioned (1) and (2).
Further improvement as the preparation method of nano-structural ordered porous thin-film type gas sensor, described metal oxide precursor solution is butter of tin solution or iron nitrate solution or zinc acetate solution, and metal oxide precursor colloidal sol is tin oxide sol or di-iron trioxide colloidal sol or zinc paste colloidal sol; Intensification step-length when the described substrate that is covered with the colloid monolayer crystal and is soaked with metal oxide precursor solution or colloidal sol sinters to 200～500 ℃ is 3～10 ℃/minute; Describedly repeat to immerse successively, pick up, the step of heating and sintering is 2～5 times.
Beneficial effect with respect to prior art is, one, use field emission scanning electron microscope and x-ray diffractometer to characterize respectively to the gas sensor that makes, from the stereoscan photograph that obtains and X-ray diffracting spectrum (XRD) and analytical calculation as can be known, the surface of gas sensor is a film, and six sides are compact arranged by being for it, be interconnected between the hole, have the orderly spherical pore of single or multiple lift triangular apertures, that hole on framework (wall) is fine and close to constitute between per three spherical hole walls.It is covered in the surface of curved surface or plane substrate, its bore dia is 200～1000nm, the thickness of film is 100～5000nm, hole wall is by metal oxide, be that tin ash or di-iron trioxide or zinc paste constitute, curved surface shape substrate be shaped as convex surface or concave surface, said convex surface is a sphere, substrate is metal or glass or pottery or monocrystalline silicon or mica or quartz; Its two, after tested, gas sensor has wider universality, and sensitivity and response time are all far above existing thin film type gas-sensitive sensor; They are three years old, adopt butter of tin solution or tin oxide sol or iron nitrate solution or di-iron trioxide colloidal sol or zinc acetate solution or zinc paste colloidal sol, by the colloidal crystal template method, on different substrates, be made into colloid monolayer crystal template as long as choose the polystyrene colloid ball of different-diameter, just can synthesize the orderly tin ash of large-area individual layer or the di-iron trioxide or the spherical hole of the zinc paste film in different apertures, and then obtain different sensitivity and the gas sensor of response time; They are four years old, colloid monolayer crystal template is immersed in butter of tin solution or tin oxide sol or iron nitrate solution or di-iron trioxide colloidal sol or zinc acetate solution or the zinc paste colloidal sol, treat its break away from former substrate and swim in precursor solution or the surface of colloidal sol after, the substrate that has electrode with required form picks up the colloid monolayer crystal and makes it be covered in the technology of substrate surface, both be easy to curved substrate previous step put in place ground synthesizing porous thin film type gas-sensitive element, can guarantee its quality of stability again; They are five years old, exist the triangle hole of orderly arrangement in the whole colloid monolayer of formation colloid monolayer crystal template, after it is dipped into precursor solution or colloidal sol, these holes just have been full of solution or colloidal sol, when being picked up by other substrates, because acting force capillaceous, solution in the hole or colloidal sol can not run off, after the process first step is heating and curing, solute in these solution or the colloidal sol can be separated out gradually and be formed a kind of shell structurre around colloidal spheres, the sintering processes that is higher than polystyrene colloid ball melting temperature again through second step, remove and burnt colloidal spheres, remaining shell structurre will become outside the film of orderly hole, has also obtained needed material thing phase, i.e. tin ash or di-iron trioxide or zinc paste.As for the triangular apertures between per three spherical hole walls, then be the result that precursor solution or colloidal sol shrink in the process of being heating and curing, its existence has greatly increased the specific surface area of film; They are six years old, repeatedly repeat to immerse successively, pick up, the step of heating and sintering, both increased the specific surface area of film, improved the sensitivity of element, eliminated the phenomenon that very easily occurs a lot of crackles when on tubular substrate, constructing single thin film again because of the difference of thermal expansivity, electric conductivity and gas-sensitive property are all improved greatly, also obtained stable pore structure; Its seven, equipment used in the preparation process is few, inexpensive, technology is simple, cost is low, and is pollution-free, is suitable for suitability for industrialized production.
Description of drawings
Below in conjunction with accompanying drawing optimal way of the present invention is described in further detail.
Fig. 1 be to gas sensor take the photograph after with the observation of Japanese JEOL 6700 type field emission scanning electron microscopes photo, wherein, figure (A) can be found out the shape of substrate for being that colloidal crystal template, metal oxide precursor solution or colloidal sol that the polystyrene colloid ball of 200nm is made are that butter of tin solution or tin oxide sol, substrate are the pore structure of the orderly spherical pore film of individual layer that forms of convex surface with the diameter by the little figure in the upper right corner among the figure.Figure (B) is for being that colloidal crystal template, metal oxide precursor solution or colloidal sol that the polystyrene colloid ball of 600nm is made are that iron nitrate solution or di-iron trioxide colloidal sol, substrate are the pore structure of the orderly spherical pore film of individual layer that forms of concave surface with the diameter, and the little figure in the upper right corner is the shape of substrate among the figure.Figure (C) is for being that colloidal crystal template, metal oxide precursor solution or colloidal sol that the polystyrene colloid ball of 1000nm is made are that zinc acetate solution or zinc paste colloidal sol, substrate are the pore structure of the orderly spherical pore film of individual layer that forms of sphere with the diameter, and the little figure in the upper right corner is the shape of substrate among the figure.Figure (D) is for being that colloidal crystal template, metal oxide precursor solution or colloidal sol that the polystyrene colloid ball of 200nm is made are that butter of tin solution or tin oxide sol, substrate are the pore structure of the orderly spherical pore film of individual layer that forms of plane with the diameter.By figure (A), figure (B), figure (C) and figure (D), can see that pore structure is by spherical macropore and triangular apertures composition;
Fig. 2 be to gas sensor take the photograph after with the observation of Japanese JEOL 6700 type field emission scanning electron microscopes photo, wherein, the pore structure shape appearance figure that figure (A4) attaches most importance to and obtains after the step 4 time of the orderly spherical pore film of individual layer shown in the figure (A) that duplicates Fig. 1 fully, the pore structure shape appearance figure that the pore structure shape appearance figure that figure (B4) attaches most importance to and obtains after the step 4 time of the orderly spherical pore film of individual layer shown in the figure (B) that duplicates Fig. 1 fully, figure (C4) are attached most importance to and obtained after the step 4 time of the orderly spherical pore film of individual layer shown in the figure (C) that duplicates Fig. 1 fully.Can find out that by figure (A4), figure (B4) and figure (C4) after constructing through multilayer, the surface of nanostructure ordered hole film is rare or do not had crackle;
Fig. 3 is to the figure among Fig. 1 (A), figure (B) and the orderly spherical pore film of figure (C) pairing individual layer, with the X-ray diffracting spectrum (XRD) that obtains after the test of Phillips X ' Pert type x-ray diffractometer, wherein, horizontal ordinate is an angle of diffraction, ordinate is a relative intensity, by the position of each diffraction peak of XRD and relative intensity as can be known, (a) the orderly spherical pore film of the individual layer shown in the figure is made of tin ash, (b) the orderly spherical pore film of the individual layer shown in the figure is made of di-iron trioxide, and (c) the orderly spherical pore film of the individual layer shown in the figure is made of zinc paste;
Fig. 4 is respectively with the figure among Fig. 3 (a), figure (b) with scheme the orderly spherical pore film of (c) pairing individual layer places 100ppm as gas sensor alcohol atmosphere, measured sensitivity characteristic curve map, wherein, horizontal ordinate is the time, ordinate is a resistance value, on among the figure is an injected gas in container, and off discharges gas from container.Figure (As) is the sensitivity characteristic curve map of SnO 2 gas-sensitive element, and figure (Bs) is the sensitivity characteristic curve map of di-iron trioxide gas sensor, and figure (Cs) is the sensitivity characteristic curve map of zinc paste gas sensor.As can be seen from Figure, the sensitivity of gas sensor increases along with reducing of aperture, and the response time shortens along with reducing of aperture, and the specific surface area of this and film has confidential relation.In like manner, the number of plies of film is many more, its sensitivity will be high more and the response time will be short more.
Embodiment
At first make or buy the polystyrene colloid ball that the monodispersed diameter of commercialization is 200～1000nm, again substrate is cleaned up in advance from market with conventional method.Then,
1), select the monodispersed polystyrene colloid ball of commercialization suspending liquid for use embodiment 1: finish preparation according to the following steps:, adopting spin-coating method is that the polystyrene colloid ball of 200nm invests and forms colloid monolayer crystal template on the flat glass with diameter.Then, it is in the butter of tin solution of 0.1M that colloid monolayer crystal template is immersed concentration, after treating that the colloid monolayer crystal breaks away from glass substrate and swims in the surface of butter of tin solution, pick up the colloid monolayer crystal and make it be covered in this ceramic substrate surface with the ceramic substrate that has pair of electrodes of convex-shaped; The ceramic substrate that will be covered with the colloid monolayer crystal 2), earlier and be soaked with butter of tin solution places 80 ℃ of heating 2 hours down, is placed on 200 ℃ of following sintering again 3 hours, and wherein, the step-length when being warming up to 200 ℃ is 3 ℃/minute; 3) repeat above-mentioned 1, successively) and 2) step 0 time, make the nano-structural ordered porous thin-film type gas sensor shown in the curve among Fig. 1 (A), Fig. 3 (a) and Fig. 4 (As).
1), be that the polystyrene colloid ball of 400nm invests and forms colloid monolayer crystal template on the flat glass with spin-coating method with diameter embodiment 2: finish preparation according to the following steps:.Then, it is in the butter of tin solution of 0.2M that colloid monolayer crystal template is immersed concentration, after treating that the colloid monolayer crystal breaks away from glass substrate and swims in the surface of butter of tin solution, pick up the colloid monolayer crystal and make it be covered in this ceramic substrate surface with the ceramic substrate that has pair of electrodes of convex-shaped; The ceramic substrate that will be covered with the colloid monolayer crystal 2), earlier and be soaked with butter of tin solution places 90 ℃ of heating 1.7 hours down, is placed on 280 ℃ of following sintering again 2.8 hours, and wherein, the step-length when being warming up to 280 ℃ is 5 ℃/minute; 3) repeat above-mentioned 1, successively) and 2) step 2 time, make and be similar to Fig. 2 (A4), the nano-structural ordered porous thin-film type gas sensor shown in the curve among Fig. 3 (a) and Fig. 4 (As).
1), be that the polystyrene colloid ball of 600nm invests and forms colloid monolayer crystal template on the flat glass with spin-coating method with diameter embodiment 3: finish preparation according to the following steps:.Then, it is in the butter of tin solution of 0.3M that colloid monolayer crystal template is immersed concentration, after treating that the colloid monolayer crystal breaks away from glass substrate and swims in the surface of butter of tin solution, pick up the colloid monolayer crystal and make it be covered in this ceramic substrate surface with the ceramic substrate that has pair of electrodes of convex-shaped; The ceramic substrate that will be covered with the colloid monolayer crystal 2), earlier and be soaked with butter of tin solution places 100 ℃ of heating 1.5 hours down, is placed on 350 ℃ of following sintering again 2.5 hours, and wherein, the step-length when being warming up to 350 ℃ is 6 ℃/minute; 3) repeat above-mentioned 1, successively) and 2) step 3 time, make and be similar to Fig. 2 (A4), the nano-structural ordered porous thin-film type gas sensor shown in the curve among Fig. 3 (a) and Fig. 4 (As).
1), be that the polystyrene colloid ball of 800nm invests and forms colloid monolayer crystal template on the flat glass with spin-coating method with diameter embodiment 4: finish preparation according to the following steps:.Then, it is in the butter of tin solution of 0.4M that colloid monolayer crystal template is immersed concentration, after treating that the colloid monolayer crystal breaks away from glass substrate and swims in the surface of butter of tin solution, pick up the colloid monolayer crystal and make it be covered in this ceramic substrate surface with the ceramic substrate that has pair of electrodes of convex-shaped; The ceramic substrate that will be covered with the colloid monolayer crystal 2), earlier and be soaked with butter of tin solution places 110 ℃ of heating 1.3 hours down, is placed on 430 ℃ of following sintering again 2.2 hours, and wherein, the step-length when being warming up to 430 ℃ is 8 ℃/minute; 3) repeat above-mentioned 1, successively) and 2) step 4 time, make the nano-structural ordered porous thin-film type gas sensor shown in the curve among Fig. 2 (A4), Fig. 3 (a) and Fig. 4 (As).
1), be that the polystyrene colloid ball of 1000nm invests and forms colloid monolayer crystal template on the flat glass with spin-coating method with diameter embodiment 5: finish preparation according to the following steps:.Then, it is in the butter of tin solution of 0.5M that colloid monolayer crystal template is immersed concentration, after treating that the colloid monolayer crystal breaks away from glass substrate and swims in the surface of butter of tin solution, pick up the colloid monolayer crystal and make it be covered in this ceramic substrate surface with the ceramic substrate that has pair of electrodes of convex-shaped; The ceramic substrate that will be covered with the colloid monolayer crystal 2), earlier and be soaked with butter of tin solution places 120 ℃ of heating 1 hour down, is placed on 500 ℃ of following sintering again 2 hours, and wherein, the step-length when being warming up to 500 ℃ is 10 ℃/minute; 3) repeat above-mentioned 1, successively) and 2) step 5 time, make and be similar to Fig. 2 (A4), the nano-structural ordered porous thin-film type gas sensor shown in the curve among Fig. 3 (a) and Fig. 4 (As).
Select iron nitrate solution or zinc acetate solution in the metal oxide precursor solution more respectively for use, tin oxide sol in the metal oxide precursor colloidal sol or di-iron trioxide colloidal sol or zinc paste colloidal sol, and as metal or glass or monocrystalline silicon or the mica or the quartz of curved surface shape or plane substrate, curved surface shape wherein is respectively concave surface or convex surface, said convex surface is a sphere, repeat the foregoing description 1～5, make equally as or be similar to Fig. 1 (A)～(C), Fig. 2 (A4)～(C4), nano-structural ordered porous thin-film type gas sensor shown in the curve among Fig. 3 (a)～(c) and Fig. 4 (As)～(Cs).
Obviously, those skilled in the art can carry out various changes and modification to nano-structural ordered porous thin-film type gas sensor of the present invention and preparation method thereof and not break away from the spirit and scope of the present invention.Like this, if of the present invention these are revised and modification belongs within the scope of claim of the present invention and equivalent technologies thereof, then the present invention also is intended to comprise these changes and modification interior.
Claims (10)
1. nano-structural ordered porous thin-film type gas sensor, comprise substrate and electrode, and cover thereon film, it is characterized in that said substrate is a curved surface shape or plane, said film is made of the poroid metal oxide of sphere, the bore dia of said spherical pore is 200～1000nm, and the thickness of said film is 100～5000nm.
2. nano-structural ordered porous thin-film type gas sensor according to claim 1 is characterized in that the curved surface shape is convex surface or concave surface.
3. nano-structural ordered porous thin-film type gas sensor according to claim 2 is characterized in that substrate is metal or glass or pottery or monocrystalline silicon or mica or quartz.
4. nano-structural ordered porous thin-film type gas sensor according to claim 1, it is characterized in that spherical pore be two-layer more than, Kong Chengliu side's solid matter type, and being interconnected between the hole.
5. nano-structural ordered porous thin-film type gas sensor according to claim 4 is characterized in that between three spherical hole walls of six side's solid matter types triangular apertures being arranged.
6. nano-structural ordered porous thin-film type gas sensor according to claim 5 is characterized in that metal oxide is tin ash or di-iron trioxide or zinc paste.
7. the preparation method of nano-structural ordered porous thin-film type gas sensor according to claim 1, comprise with diameter being that the colloidal spheres of 200～1000nm invests the planar substrate surface and forms colloid monolayer crystal template, it is characterized in that finishing according to the following steps:
7.1, colloid monolayer crystal template is immersed concentration is in the metal oxide precursor solution or colloidal sol of 0.1～0.5M, treat the colloid monolayer crystal break away from substrate and swim in precursor solution or the surface of colloidal sol after, pick up the colloid monolayer crystal and make it be covered in substrate surface with the substrate that has pair of electrodes of required form;
7.2, the substrate that will be covered with the colloid monolayer crystal and be soaked with metal oxide precursor solution or colloidal sol earlier places 80～120 ℃ of heating 1～2 hour down, is placed on 200～500 ℃ of following sintering again 2～3 hours;
7.3, repeat to make nano-structural ordered porous thin-film type gas sensor more than above-mentioned 7.1 and 7.2 the step 0 time.
8. the preparation method of nano-structural ordered porous thin-film type gas sensor according to claim 7, it is characterized in that metal oxide precursor solution is butter of tin solution or iron nitrate solution or zinc acetate solution, metal oxide precursor colloidal sol is tin oxide sol or di-iron trioxide colloidal sol or zinc paste colloidal sol.
9. the preparation method of nano-structural ordered porous thin-film type gas sensor according to claim 7 is characterized in that the intensification step-length the when substrate that is covered with the colloid monolayer crystal and is soaked with metal oxide precursor solution or colloidal sol sinters to 200～500 ℃ is 3～10 ℃/minute.
10. the preparation method of nano-structural ordered porous thin-film type gas sensor according to claim 7 is characterized in that repeating immersing successively, picks up, the step of heating and sintering is 2～5 times.
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