CN104634935A - Preparation method of porous-silicon-based and multi-dimensional tungsten-oxide composite structure - Google Patents
Preparation method of porous-silicon-based and multi-dimensional tungsten-oxide composite structure Download PDFInfo
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- CN104634935A CN104634935A CN201510044172.3A CN201510044172A CN104634935A CN 104634935 A CN104634935 A CN 104634935A CN 201510044172 A CN201510044172 A CN 201510044172A CN 104634935 A CN104634935 A CN 104634935A
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Abstract
The invention discloses a preparation method of a porous-silicon-based and multi-dimensional tungsten-oxide composite structure, which adopts a hydrothermal method to grow a multi-dimensional nano structure of tungsten oxide on ordered porous silicon and provides the novel porous-silicon-based and multi-dimensional tungsten-oxide composite structure simple in manufacturing process and controllable in morphology. The hydrothermal method is simpler in operation and fewer in process conditions needing to be controlled and has no pollution to the environment. In addition, the prepared porous-silicon-based and multi-dimensional tungsten-oxide composite structure has higher specific surface area; simultaneously, the ordered tungsten-oxide nano-rod array is more beneficial to absorption and free diffusion of gas; and the porous-silicon-based and multi-dimensional tungsten-oxide composite structure has important practice and research values in the aspects of reducing the working temperature of a gas-sensitive sensor and improving the sensitivity and the selectivity of the sensor.
Description
Technical field
The present invention relates to a kind of preparation method of porous silicon-base multidimensional tungsten oxide composite structure.
Background technology
Along with the develop rapidly of modern industrial technology, the various harmful gases brought in production run are (as NO
2, CO, NH
3, SO
2deng) constantly increase.Wherein oxides of nitrogen (NO
x) gas is the main cause causing acid rain and photo-chemical smog, its while contaminated environment also serious threat the health and safety of the mankind.Therefore the high-performance gas sensor material and device studied for detecting oxides of nitrogen gas are significant, and become study hotspot in recent years.
Tungsten oxide, as a kind of semiconductor sensitive material having research and apply prospect, has been widely used in and has detected various poisonous and dangerous gas (as NO
2, NH
3deng).But tungsten oxide working temperature higher (150 DEG C ~ 250 DEG C), work under the high temperature conditions for a long time and not only greatly can increase the power consumption of sensor, the bad stability of sensor can be caused simultaneously.Therefore scientific and technical personnel are devoted to the research reducing tungsten oxide working temperature always, and find that one dimension tungsten oxide has larger specific surface area and stronger gas sorption ability, these features can accelerate the reaction between gas, have great importance to raising sensitivity and reduction working temperature.
Porous silicon is a kind of novel gas sensitive of the aperture size, the duct degree of depth and the adjustable porosity that are formed by etching at silicon chip surface, has higher chemical mobility of the surface at ambient temperature, can be used for detecting NO
2, NH
3, H
2s, CO
xand multiple organic gas (ethanol, acetone etc.).In addition, the manufacture craft of porous silicon easily with microelectronic process engineering compatibility.But porous silicon also also exists the low shortcoming of sensitivity, this is by its practical application of restriction.
Summary of the invention
In order to solve problems of the prior art, the invention provides a kind of preparation method of porous silicon-base multidimensional tungsten oxide composite structure, overcoming harmful gas in prior art and detecting the higher problem of tungsten oxide working temperature used.
Technical scheme of the present invention is:
A preparation method for porous silicon-base multidimensional tungsten oxide composite structure, comprises the following steps:
(1) cleaning of silicon chip:
The mixed liquor that the monocrystalline silicon substrate of P type single-sided polishing puts into the concentrated sulphuric acid and hydrogen peroxide is soaked 30 ~ 50min, 20 ~ 40min is soaked with in the mixed liquor being placed on hydrofluorite and deionized water, then ultrasonic cleaning 5 ~ 20min in acetone and ethanol respectively, finally puts into absolute ethyl alcohol by silicon chip for subsequent use;
(2) porous silicon is prepared:
Double-cell electrochemical etching is adopted to prepare porous silicon layer in the polished surface of the monocrystalline silicon piece of step (1);
(3) seed solution is prepared:
Sodium tungstate is all dissolved in deionized water, dropwise add watery hydrochloric acid subsequently, until no longer produce white precipitate, then mixed liquor is left standstill 30 ~ 60min, supernatant liquor is outwelled the precipitation of the centrifugal bottom of rear recycling low speed centrifuge, then form precipitating to dissolve in the hydrogen peroxide of 10 ~ 30ml the seed solution that concentration is the yellow transparent of 0.5 ~ 1M;
(4) Seed Layer is prepared:
The seed solution of preparation in step (3) is spun on porous silicon prepared in step (2), then heat-treats;
(5) hydro-thermal method prepares porous silicon-base multidimensional tungsten oxide composite structure:
First configure reactant liquor, take sodium tungstate, it be all dissolved in deionized water, forming concentration is the sodium tungstate solution of 0.05 ~ 0.1mol/L, utilize watery hydrochloric acid to regulate pH to acid, subsequently solution dilution is regulated pH further with oxalic acid.Then the reactant liquor that configures is pipetted in the polytetrafluoroethyllining lining of hydrothermal reaction kettle, then the level on specimen holder that is inserted in by the porous substrate being attached with Seed Layer in (4) is soared and is placed in liner, finally reactor is placed in thermostatic drying chamber isothermal reaction;
(6) cleaning of porous silicon substrate and drying after hydro-thermal reaction.
The resistivity of the monocrystalline silicon piece of the P type single-sided polishing of described step (1) is 10 ~ 15 Ω cm, and thickness is 400 μm, and crystal orientation is (100), and silicon chip substrate is of a size of 2.2 ~ 2.4cm × 0.8 ~ 0.9cm.
Described step (2) double-cell electrochemical etching electrolytic solution used by mass concentration be 40% hydrofluorite and mass concentration be that 40% dimethyl formamide forms, volume ratio is 1:2, in room temperature and not by the average pore size and the thickness that change porous silicon under the environment of illumination by changing current density and etching time, the current density of applying is 50 ~ 100mA/cm
2, etching time is 5 ~ 20min.
The number of times of the Seed Layer spin coating of described step (4) is 5 times, is placed in muffle furnace and carries out annealing in process, and annealing temperature is 550 ~ 700 DEG C, and temperature retention time is 2h, and heating rate is 2 ~ 5 DEG C/min.
In described step (5), the pH value of reaction regulates in two steps, first utilizes watery hydrochloric acid that solution ph is adjusted to 1.5 ~ 2.0, and the pH of the solution after dilution is adjusted to 1.5 ~ 3.0 by recycling oxalic acid.
Described step (5) watery hydrochloric acid regulates pH to acid, subsequently by solution dilution 10 times.
In described step (5), hydrothermal reaction condition is isothermal reaction 2h at 180 DEG C.
Described step (6) refers to the porous silicon substrate after by hydro-thermal reaction in step (5) repeatedly through deionized water and soaked in absolute ethyl alcohol cleaning, then dry 8 ~ 10h in the vacuum drying chamber of 60 ~ 80 DEG C.
The invention has the beneficial effects as follows: provide and a kind ofly low cost can control the method for porous silicon-base multidimensional tungsten oxide composite structure pattern.Hydro-thermal method operation is comparatively simple, and the process conditions of required control are few, and environmentally safe.The impact of the heat treatment temperature porous silicon-base multidimensional tungsten oxide composite structure pattern of primary study of the present invention Seed Layer.And, prepared porous silicon-base multidimensional tungsten oxide composite structure has higher specific surface area, simultaneously orderly tungsten oxide nanometer rod array is more conducive to absorption and the free diffusing of gas, and this material has important practice and researching value in the working temperature of reduction gas sensor, the sensitivity improving sensor and selectivity.
Accompanying drawing explanation
Fig. 1 is the porous silicon surface electron scanning micrograph prepared by embodiment 1;
Fig. 2 is the porous silicon cross-sectional scanning electron microphotograph prepared by embodiment 1;
Fig. 3 is the Seed Layer surface Scanning Electron microphotograph prepared by embodiment 1;
Fig. 4 is the porous silicon-base multidimensional tungsten oxide composite structure surface electron scanning micrograph prepared by embodiment 1;
Fig. 5 is the porous silicon-base multidimensional tungsten oxide composite structure cross-sectional scanning electron microphotograph prepared by embodiment 1;
Fig. 6 is the Seed Layer surface Scanning Electron microphotograph prepared by embodiment 2;
Fig. 7 is the porous silicon-base multidimensional tungsten oxide composite structure surface electron scanning micrograph prepared by embodiment 2;
Fig. 8 is the Seed Layer surface Scanning Electron microphotograph prepared by embodiment 3;
Fig. 9 is the porous silicon-base multidimensional tungsten oxide composite structure surface electron scanning micrograph prepared by embodiment 3;
Figure 10 is the porous silicon-base multidimensional tungsten oxide composite structure cross-sectional scanning electron microphotograph prepared by embodiment 3;
Figure 11 is the Seed Layer surface Scanning Electron microphotograph prepared by embodiment 4;
Figure 12 is the porous silicon-base multidimensional tungsten oxide composite structure surface electron scanning micrograph prepared by embodiment 4.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in more detail.
The present invention is raw materials used all adopts commercially available chemically pure reagent.
Embodiment 1
(1) cleaning of silicon chip
Be 10 ~ 15 Ω cm by 2 cun of P type resistivity, thickness is 400 μm, crystal orientation is the monocrystalline silicon substrate of the single-sided polishing of (100), cut into the rectangular silicon substrate being of a size of 2.4cm × 0.9cm, silicon chip is put into the concentrated sulphuric acid that volume ratio is 3:1 and hydrogen peroxide solution soaks 40min, soaking 30min with being placed in hydrofluorite and deionized water mixed liquor that volume ratio is 1:1, then ultrasonic cleaning 5min in acetone and ethanol respectively, finally silicon chip being put into absolute ethyl alcohol for subsequent use.
(2) porous silicon is prepared
Double-cell electrochemical etching is adopted to prepare porous silicon layer in the polished surface of the monocrystalline silicon piece of step (1), electrolytic solution used by mass concentration be 40% hydrofluorite and mass concentration be that 40% dimethyl formamide forms, volume ratio is 1:2, is not in room temperature and not 64mA/cm by the current density applied under the environment of illumination
2, etching time is 8min, and the forming region of porous silicon is 1.6cm × 0.4cm.As depicted in figs. 1 and 2, recording average pore size is 1.5 μm for porous silicon surface pattern prepared by embodiment 1 and section structure scanning electron microscope analysis result, and the thickness of porous silicon layer is 19 μm.
(3) seed solution is prepared
1.65g sodium tungstate is dissolved in the deionized water of 100ml, magnetic stirrer is utilized to make it whole dissolving, dropwise add watery hydrochloric acid subsequently, until no longer produce white precipitate, then mixed liquor is left standstill 1h, supernatant liquor is outwelled the precipitation of the centrifugal bottom of rear recycling low speed centrifuge, then form precipitating to dissolve in appropriate hydrogen peroxide the seed solution that concentration is the yellow transparent of 1M.
(4) Seed Layer is prepared
The seed solution of preparation in step (3) is spun on porous silicon prepared in step (2), spin coating 5 layers, is then placed in muffle furnace and heat-treats, and the heat treatment temperature of Seed Layer is 650 DEG C, temperature retention time is 2h, and heating rate is 2.5 DEG C/min.Seed Layer surface topography scanning electron microscope analysis result prepared by embodiment 1 is as Fig. 3.
(5) hydro-thermal method prepares porous silicon-base tungsten oxide nanometer rod composite structure gas sensor
First reactant liquor is configured, take 4.13g sodium tungstate, magnetic stirrer is utilized it to be all dissolved in the deionized water of 12.5ml, recycling watery hydrochloric acid regulates reacting liquid pH value to 2.0, subsequently by above-mentioned solution dilution to 125ml, add appropriate oxalic acid again, the pH value of solution is made to control 2.5, then reactant liquor that 70ml configures is pipetted in the polytetrafluoroethyllining lining of 100ml hydrothermal reaction kettle, then the level on specimen holder that is inserted in by the porous substrate being attached with Seed Layer in (4) is soared and is placed in liner, finally reactor is placed in thermostatic drying chamber in 180 DEG C of isothermal reaction 2h.
(6) cleaning of porous silicon substrate after hydro-thermal reaction
By the porous silicon substrate after hydro-thermal reaction in step (5) repeatedly through deionized water and soaked in absolute ethyl alcohol cleaning, then dry 10h in the vacuum drying chamber of 80 DEG C, the porous silicon-base multidimensional tungsten oxide composite structure of obtained different-shape.
Porous silicon-base multidimensional tungsten oxide composite structure surface prepared by embodiment 1 and cross-section morphology scanning electron microscope analysis result are as shown in Figure 4 and Figure 5, illustrate there is a large amount of one dimension tungsten oxide nanometer rods in the bottom of porous hole also length, the mean diameter of nanometer rods is 50nm, and length is 900nm.
Embodiment 2
The difference of the present embodiment and embodiment 1 is: in step (4), the heat treatment temperature of Seed Layer is 550 DEG C, as shown in Figure 6 and Figure 7, obtained tungsten oxide is the classification nanostructure of nanometer blocks-nanometer rods to the scanning electron microscope analysis result of surface topography.
Embodiment 3
The difference of the present embodiment and embodiment 1 is: in step (4), the heat treatment temperature of Seed Layer is 600 DEG C, the scanning electron microscope analysis result of surface topography as shown in Figure 8 and Figure 9, as shown in Figure 10, obtained one dimension tungsten oxide nanometer rod is almost parallel to porous silicon-base bottom growth to the scanning electron microscope analysis result of cross-section morphology.
Embodiment 4
The difference of the present embodiment and embodiment 1 is: in step (4), the heat treatment temperature of Seed Layer is 700 DEG C, the scanning electron microscope analysis result of surface topography as is illustrated by figs. 11 and 12, because temperature is too high, porous silicon surface has not had tungsten oxide nanoparticles, only there is a small amount of nanometer rods to be randomly dispersed in porous silicon surface after hydro-thermal, exist with the fusiform tungsten oxide being parallel to porous substrate growth simultaneously.
Above with reference to drawings and Examples, to invention has been schematic description, this description is not restricted.Those of ordinary skill in the art will be understood that in actual applications, and in the present invention, some change all may occur the set-up mode of each parts, and other staff also may make the similar Design of various ways under its enlightenment.It is pointed out that only otherwise depart from design aim of the present invention, all apparent changes and similar Design thereof, be all included within protection scope of the present invention.
Claims (8)
1. a preparation method for porous silicon-base multidimensional tungsten oxide composite structure, is characterized in that, comprise the following steps:
(1) cleaning of silicon chip:
The mixed liquor that the monocrystalline silicon substrate of P type single-sided polishing puts into the concentrated sulphuric acid and hydrogen peroxide is soaked 30 ~ 50min, 20 ~ 40min is soaked with in the mixed liquor being placed on hydrofluorite and deionized water, then ultrasonic cleaning 5 ~ 20min in acetone and ethanol respectively, finally puts into absolute ethyl alcohol by silicon chip for subsequent use;
(2) porous silicon is prepared:
Double-cell electrochemical etching is adopted to prepare porous silicon layer in the polished surface of the monocrystalline silicon piece of step (1);
(3) seed solution is prepared:
Sodium tungstate is all dissolved in deionized water, dropwise add watery hydrochloric acid subsequently, until no longer produce white precipitate, then mixed liquor is left standstill 30 ~ 60min, supernatant liquor is outwelled the precipitation of the centrifugal bottom of rear recycling low speed centrifuge, then form precipitating to dissolve in the hydrogen peroxide of 10 ~ 30ml the seed solution that concentration is the yellow transparent of 0.5 ~ 1M;
(4) Seed Layer is prepared:
The seed solution of preparation in step (3) is spun on porous silicon prepared in step (2), then heat-treats;
(5) hydro-thermal method prepares porous silicon-base multidimensional tungsten oxide composite structure:
First configure reactant liquor, take sodium tungstate, it be all dissolved in deionized water, forming concentration is the sodium tungstate solution of 0.05 ~ 0.1mol/L, utilize watery hydrochloric acid to regulate pH to acid, subsequently solution dilution is regulated pH further with oxalic acid.Then the reactant liquor that configures is pipetted in the polytetrafluoroethyllining lining of hydrothermal reaction kettle, then the level on specimen holder that is inserted in by the porous substrate being attached with Seed Layer in (4) is soared and is placed in liner, finally reactor is placed in thermostatic drying chamber isothermal reaction;
(6) cleaning of porous silicon substrate and drying after hydro-thermal reaction.
2. the preparation method of porous silicon-base multidimensional tungsten oxide composite structure according to claim 1, it is characterized in that, the resistivity of the monocrystalline silicon piece of the P type single-sided polishing of described step (1) is 10 ~ 15 Ω cm, thickness is 400 μm, crystal orientation is (100), and silicon chip substrate is of a size of 2.2 ~ 2.4cm × 0.8 ~ 0.9cm.
3. the preparation method of porous silicon-base multidimensional tungsten oxide composite structure according to claim 1, it is characterized in that, described step (2) double-cell electrochemical etching electrolytic solution used by mass concentration be 40% hydrofluorite and mass concentration be that 40% dimethyl formamide forms, volume ratio is 1:2, in room temperature and not by the average pore size and the thickness that change porous silicon under the environment of illumination by changing current density and etching time, the current density of applying is 50 ~ 100mA/cm
2, etching time is 5 ~ 20min.
4. the preparation method of porous silicon-base multidimensional tungsten oxide composite structure according to claim 1, it is characterized in that, the number of times of the Seed Layer spin coating of described step (4) is 5 times, be placed in muffle furnace and carry out annealing in process, annealing temperature is 550 ~ 700 DEG C, temperature retention time is 2h, and heating rate is 2 ~ 5 DEG C/min.
5. the preparation method of porous silicon-base multidimensional tungsten oxide composite structure according to claim 1, it is characterized in that, in described step (5), the pH value of reaction regulates in two steps, first utilize watery hydrochloric acid that solution ph is adjusted to 1.5 ~ 2.0, the pH of the solution after dilution is adjusted to 1.5 ~ 3.0 by recycling oxalic acid.
6. the preparation method of porous silicon-base multidimensional tungsten oxide composite structure according to claim 1, is characterized in that, described step (5) watery hydrochloric acid regulates pH to acid, subsequently by solution dilution 10 times.
7. the preparation method of porous silicon-base multidimensional tungsten oxide composite structure according to claim 1, is characterized in that, in described step (5), hydrothermal reaction condition is isothermal reaction 2h at 180 DEG C.
8. the preparation method of porous silicon-base multidimensional tungsten oxide composite structure according to claim 1, it is characterized in that, described step (6) refers to the porous silicon substrate after by hydro-thermal reaction in step (5) repeatedly through deionized water and soaked in absolute ethyl alcohol cleaning, then dry 8 ~ 10h in the vacuum drying chamber of 60 ~ 80 DEG C.
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| CN108203095A (en) * | 2018-01-24 | 2018-06-26 | 北京化工大学 | A kind of tungsten carbide nano-array material, preparation method and the usage |
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Application publication date: 20150520 |