Abstract
The present invention discloses a method for preparing a multilayer metal oxide nano-porous thin film gas sensitive material, in which the microsphere aqueous solution is self-assembled on a substrate covered with an insulating layer, to form a compact single-layer array template; the surface of these microspheres are etched by using a plasma etching method to reduce the pitches between the microspheres; the metal oxide thin film is deposited by a physical deposition method; the template is removed by ultrasonic treatment with a solvent to prepare a porous array metal oxide thin film; and annealing is performed in air atmosphere to obtain the metal oxide porous thin film gas sensitive material. The present invention can be used for preparing a regular porous array thin film gas sensitive material; the pore size of the prepared porous thin film material is uniform and controllable; and the combination of these materials is controllable.
Claims
1. A method for preparing a multilayer metal oxide nano-porous film gas sensitive material, comprising the following steps: Step 1-self-assembling the polystyrene microsphere single-layer template on a Si substrate covered with SiO.sub.2 by using a solution evaporation method; Step 2-etching the polystyrene microsphere template by using a reactive ion etching method, to reduce the pitches between PSs; Step 3-depositing, on the substrate processed in Step 2, 40 nm Cu.sub.2O+40 nm In.sub.2O.sub.3 with indium oxide being in the bottom layer, and cuprous oxide being in the top layer, 40 nm In.sub.2O.sub.3+40 nm Cu.sub.2O with cuprous oxide being in the bottom layer, and indium oxide being in the top layer, 30 nm Cu.sub.2O+20 nm In.sub.2O.sub.3, +30 nm Cu.sub.2O with indium oxide being in the intermediate layer, and 30 nm In.sub.2 O.sub.3+20 nm Cu.sub.2O+30 nm In.sub.2O.sub.3 with cuprous oxide being in the intermediate layer, using a magnetron sputter physical deposition method; and Step 4-placing the processed substrate of step 3 in toluene for ultrasonic treatment to remove the polystyrene microsphere template, and performing annealing for 4 h in air atmosphere at the temperature of 550 C.
2. The method for preparing a multilayer metal oxide nano-porous film gas sensitive material according to claim 1, wherein the thickness of SiO.sub.2 in Step 1 is between 100 nm and 10 m.
3. The method for preparing a multilayer metal oxide nano-porous film gas sensitive material according to claim 1, wherein in Step 2, the flow rate of the fed plasma gas O.sub.2 is controlled to be 40 sccm, the pressure in the reaction cavity is controlled to be 37 mTorr, the power applied to excite the O.sub.2 plasma is controlled to be 90 W, and the O.sub.2 plasma etching time is controlled to be 1 min.
4. The method for preparing a multilayer metal oxide nano-porous film gas sensitive material according to claim 1, wherein in Step 3, the target material used for magnetron sputtering is a ceramics target material of indium oxide or cuprous oxide, the power for exciting the Ar plasma is 80 W, and the pressure in the cavity is 3 mTorr.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
(1) FIG. 1 is a schematic diagram of steps for preparing a single-layer metal oxide porous film gas sensitive material;
(2) FIG. 2 is a schematic diagram of steps for preparing a double-layer and multilayer metal oxide porous film gas sensitive materials;
(3) FIG. 3 is a morphology from a scanning electron microscope (SEM) after polystyrene microspheres are self-assembled into a single-layer film in Example 1;
(4) FIG. 4 is a morphology from the SEM after plasma etching is performed on the polystyrene microspheres in Example 1;
(5) FIG. 5 is a morphology from the SEM after the polystyrene microspheres are etched and then metal oxide films are sequentially deposited in Example 1;
(6) FIG. 6 is a morphology from the SEM of a double-layer metal oxide porous film prepared after removal of the template and then annealing in Example 1:
(7) FIG. 7 is a 2D morphology from an atomic force microscope (AFM) of the double-layer metal oxide porous film prepared in Example 1;
(8) FIG. 8 is an X-ray diffraction (XRD) spectrum of different metal oxide porous films prepared in Example 1;
(9) FIG. 9 is a comparison diagram of sensitivity curves of different metal oxide porous films prepared in Example 1 with respect to ethanol of 1000 ppm at different temperatures;
(10) FIG. 10 is a diagram of a sensitivity curve of a multilayer metal oxide porous film prepared in Example 1 of the present invention with respect to ethanol of different concentrations at the temperature of 150 C.;
(11) FIG. 11 is a diagram of selectivity of the multilayer metal oxide porous film prepared in Example 1 with respect to ethanol of 1000 ppm at the temperature of 150 C.;
(12) FIG. 12 is a morphology from the SEM of a three-layer metal oxide porous film, prepared in Example 2, which is similar to that of the multilayer metal oxide porous film prepared in Example 1; and
(13) FIG. 13 is a comparison diagram of sensitivity of different multilayer metal oxide porous films prepared in Example 2 with respect to ethanol of 1000 ppm at the temperature of 150 C.
DETAILED DESCRIPTION OF THE INVENTION
(14) The present invention is illustrated in detail below with reference to the embodiments and the accompanying drawings.
(15) A method for preparing a multilayer metal oxide nano-porous film gas sensitive material includes the following steps:
(16) Step 1) self-assembling a microsphere template on a substrate covered kith an insulating layer by means of an LB membrane method, a solution evaporation method, a spin-coating method or a dip-coating method, to form a compact single-layer array template;
(17) Step 2) reducing the pitches between microspheres by etching, the pitch being in the range of 1 nm to 1 m;
(18) Step 3) depositing a metal oxide film by means of physical deposition; and
(19) Step 4) removing the template to prepare a porous array metal oxide film, and performing annealing to obtain a metal oxide porous film gas sensitive material.
(20) Further, the insulating layer in Step 1 is preferably made of SiO.sub.x, where 1x2, the thickness of the insulating layer is between 100 nm and 10 m, and the substrate is one selected from Si, SiC, Si.sub.3N.sub.4, and ceramics substrates, preferably a Si substrate made of SiO.sub.2.
(21) Further, the microsphere template in Step 1 is a polystyrene microsphere aqueous solution or a silicon dioxide microsphere aqueous solution, preferably the polystyrene microsphere aqueous solution; the volume-mass concentration of the polystyrene microsphere aqueous solution is 0.5% to 3% mg/ml, preferably 1% mg/ml; and the diameter of the microsphere template is 100 nm to 5 m, preferably 500 nm.
(22) Further, the etching method in Step 2 includes plasma dry etching or HF solution wet etching; when the microsphere template is the polystyrene microsphere aqueous solution, plasma dry etching is selected, and when the microsphere template is the silicon dioxide microsphere aqueous solution, HF solution wet etching or plasma dry etching is selected; and the plasma in plasma dry etching comes from a plasma etching machine or a reactive ion etching machine.
(23) Further, the, physical deposition in Step 3 is magnetron sputter physical deposition or electron beam evaporation physical deposition.
(24) Further, when the microsphere template is the polystyrene microsphere aqueous solution, an organic solvent is selected to perform ultrasonic treatment so as to remove the template, and when the microsphere template is the silicon dioxide microsphere aqueous solution, an HF solution is selected to perform ultrasonic treatment. The annealing temperature in Step 4 is 200 C. to 1000 C., and the annealing time is 0.5 h to 10 h.
EXAMPLE 1
(25) FIG. 1 is a diagram of steps for preparing a single-layer metal oxide porous film, FIG. 2 is a schematic diagram of steps for preparing a double-layer metal oxide porous film, and in the figures, the substrate of the obtained metal oxide porous film is a silicon wafer substrate covered with a monocrystal SiO.sub.2 oxide layer with a thickness of 150 nm. The used PS microsphere template is a non-functional PS aqueous solution having a diameter of 500 nm, and the mass-volume concentration of the aqueous solution is 1% mg/ml. The polystyrene microsphere single-layer template was self-assembled on a Si substrate covered with SiO.sub.2 by using a solution evaporation method, the PS template was etched by using a reactive ion etching method so as to reduce the pitches between PS, and in the process of using a reactive ion etching machine, the flow rate of the fed O.sub.2 was controlled to be 40 sccm, the pressure in the cavity was controlled to be 37 mTorr, the power applied to excite the O.sub.2 plasma was controlled to be 90 W, and the O.sub.2 plasma etching time was controlled to be 1 min. A magnetron sputter physical deposition method was used to deposit, on four processed substrates, 80 nm ZnO, 80 nm TiO.sub.2, 40 nm ZnO+40 nm TiO.sub.2 (with titanium oxide being in the bottom layer, and zinc oxide being in the top layer), and 40 nm TiO.sub.2+40 nm ZnO (with zinc oxide being in the bottom layer, and titanium oxide being in the top layer) respectively. In the process of depositing a metal oxide film by means of magnetron sputter physical deposition, the power for exciting the Ar plasma was 80 W, and the pressure in the cavity was 3 mTorr. A sample was placed in toluene for ultrasonic treatment for 2 min to remove the PS template, and annealing was performed for 4 h in air atmosphere at the temperature of 550 C. The target materials used in magnetron sputter were respectively ceramics target materials of titanium oxide and zinc oxide.
(26) The morphology after self-assembly of the PS template, the morphology of the PSs after processing of the plasma, the morphology after deposition of the metal oxide, and the morphology of the porous film after removal of the PS template that are obtained in the process of preparing the metal oxide porous film gas sensitive material by using this method are shown in FIGS. 3, 4, 5, 6, and 7, and it can be seen from these figures that, the diameter of the pores in the prepared metal oxide porous film is quite uniform and is around 450 nm. The X-ray film diffraction of various types of metal oxide porous film gas sensitive materials prepared by using this method is shown in FIG. 8, and it can be seen from the figure that, the prepared metal oxide porous film has a good crystal form. The diagrams of the gas sensitive responses of the metal oxide porous film gas sensitive material prepared by using this method with respect to ethanol at different temperatures, the gas sensitive responses of the double-layer metal oxide porous film with respect to ethanol of different concentrations, and the selectivity of the double-layer metal oxide porous film with respect to ethanol of a certain concentration at a certain temperature are shown in FIGS. 9, 10, and 11. It can be seen from FIG. 9 that, the gas sensitive response of the prepared single-layer metal oxide porous film is lower than the gas sensitive response of the double-layer metal oxide porous film, and it can also be seen that the gas sensitive response of the material is improved with the increase of the temperature within a certain temperature range, the gas sensitive responses of the three metal oxide porous films all satisfy the above condition, and the higher the temperature within the temperature range is, the higher the gas sensitive responses of the metal oxide porous films are. It can be seen from FIG. 10 that, the gas sensitive response of the, prepared metal oxide porous film is improved with the increase of the gas concentration. It can be seen from FIG. 11 that, the prepared double-layer metal oxide porous film has a preferable selectivity to ethanol.
EXAMPLE 2
(27) In the schematic diagram of steps for preparing a multilayer metal oxide porous film shown in FIG. 2, the substrate of the obtained metal oxide porous film is a silicon wafer substrate covered with a monocrystal SiO.sub.2 oxide layer having a thickness of 150 nm. The used PS microsphere template is a non-functional polystyrene sphere (PS) aqueous solution having a diameter of 500 nm, and the mass-volume concentration of the aqueous solution is 1% mg/ml. The polystyrene microsphere single-layer template was self-assembled on a Si substrate covered with SiO.sub.2 by using a solution evaporation method, the PS template was etched by using a reactive ion etching method so as to reduce the pitches between PS, and the flow rate of the fed O.sub.2 was controlled to be 40 sccm, the pressure in the cavity was controlled to be 37 mTorr, the power applied to excite the O.sub.2 plasma was controlled to be 90 W, and the O.sub.2 plasma etching time was controlled to be 1 min. A magnetron sputtering physical deposition method was used to deposit, on four processed substrates, 40 nm Cu.sub.2O+40 nm In.sub.2O.sub.3 (with indium oxide being in the bottom layer, and cuprous oxide being in the top layer), 40 nm In.sub.2O.sub.3+40 nm Cu.sub.2O (with cuprous oxide being in the bottom and indium oxide being in the top layer), 30 nm Cu.sub.2O+20 nm In.sub.2O.sub.3+30 nm Cu.sub.2O (with indium oxide being in the intermediate layer) and 30 nm In.sub.2O.sub.3+20 nm Cu.sub.2O+30 nm In.sub.2O.sub.3 (with cuprous oxide being in the intermediate layer) respectively. The target materials used for magnetron sputter were respectively ceramics target materials of indium oxide and cuprous oxide, h power for exciting the Ar plasma was 80 W, and the pressure in the cavity was 3 mTorr. A sample was placed in toluene for ultrasonic treatment to remove the PS template, and annealing was performed for 4 h in air atmosphere at the temperature of 550 C.
(28) The morphology of the metal oxide porous film gas sensitive material pared by using this method is shown in FIG. 13, and it can be seen from FIG. 12 that the morphology of the prepared multilayer metal oxide porous film gas sensitive material is similar to the morphology of the metal oxide porous film prepared by using the method in Example 1. The comparison diagram of the gas sensitive responses of the double-layer metal oxide porous film gas sensitive material and the three-layer metal oxide porous film prepared by using this method is shown in FIG. 13, and it can be seen from FIG. 13 that, the gas sensitive response of the three-layer metal oxide porous film gas sensitive material is higher than the gas sensitive response of the double-layer metal oxide porous film.
