CN106680321B - A kind of pressure differential pressure exchange complex method being used to prepare Organic-inorganic composite semiconductor material - Google Patents
A kind of pressure differential pressure exchange complex method being used to prepare Organic-inorganic composite semiconductor material Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 152
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- 239000000463 material Substances 0.000 title claims abstract description 112
- 239000007787 solid Substances 0.000 claims abstract description 143
- 238000010438 heat treatment Methods 0.000 claims abstract description 127
- 238000005215 recombination Methods 0.000 claims abstract description 66
- 230000006798 recombination Effects 0.000 claims abstract description 66
- 239000007789 gas Substances 0.000 claims abstract description 38
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 37
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 37
- 239000010409 thin film Substances 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 239000011261 inert gas Substances 0.000 claims abstract description 14
- 150000001875 compounds Chemical class 0.000 claims abstract description 10
- 238000000137 annealing Methods 0.000 claims abstract description 4
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- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 42
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 39
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical group [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 24
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- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 13
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- 239000004305 biphenyl Substances 0.000 claims description 11
- 235000010290 biphenyl Nutrition 0.000 claims description 11
- SLIUAWYAILUBJU-UHFFFAOYSA-N pentacene Chemical compound C1=CC=CC2=CC3=CC4=CC5=CC=CC=C5C=C4C=C3C=C21 SLIUAWYAILUBJU-UHFFFAOYSA-N 0.000 claims description 11
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 claims description 11
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- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 8
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- MPMSMUBQXQALQI-UHFFFAOYSA-N cobalt phthalocyanine Chemical compound [Co+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 MPMSMUBQXQALQI-UHFFFAOYSA-N 0.000 claims description 6
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
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- PZZOEXPDTYIBPI-UHFFFAOYSA-N 2-[[2-(4-hydroxyphenyl)ethylamino]methyl]-3,4-dihydro-2H-naphthalen-1-one Chemical compound C1=CC(O)=CC=C1CCNCC1C(=O)C2=CC=CC=C2CC1 PZZOEXPDTYIBPI-UHFFFAOYSA-N 0.000 description 30
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 4
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- 229910010272 inorganic material Inorganic materials 0.000 description 4
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- RKCAIXNGYQCCAL-UHFFFAOYSA-N porphin Chemical compound N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 RKCAIXNGYQCCAL-UHFFFAOYSA-N 0.000 description 1
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- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
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- H—ELECTRICITY
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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Abstract
The present invention relates to a kind of pressure differentials for being used to prepare Organic-inorganic composite semiconductor material to force exchange complex method, it comprises the following steps that porous metal oxide semiconductor nano solid or porous metal oxide semiconductive thin film, is heat-treated under vacuum conditions；Under vacuum conditions, organic semiconductor is placed in temperature end heating, porous metal oxide semiconductor nano solid obtained above or porous metal oxide semiconductive thin film is heated in low-temperature end；Then it is passed through inert gas from temperature end, inert gas carries organic semi-conductor gas molecule and exchanges recombination reaction with porous metal oxide semiconductor nano solid or porous metal oxide semiconductive thin film；It is persistently vacuumized during the exchange recombination reaction；Product obtained above is made annealing treatment in inert gas to get.Method of the invention is simple, environmentally protective, at low cost, may be implemented material be uniformly distributed and completely it is compound.
Description
Technical field
The present invention relates to a kind of pressure differentials for being used to prepare Organic-inorganic composite semiconductor material to force exchange composite square
Method belongs to technical field of new material preparation.
Background technique
With the fast development of modern energy and information technology, people propose ten to the performance of semiconductor material and device
Divide harsh requirement.For example, semiconductor material used in manufacture opto-electronic device will not only have high mobility, adjustable band gap
And high-photoelectric transformation efficiency and it is necessary to have that preparation cost is low, processability is good, structure type is rich and varied and good
The advantages that flexibility got well.It is overcritical to meet this various aspects to comprehensive performance, simple inorganic semiconductor and organic partly leads
Body is all difficult to be competent at.For this purpose, it is intended that making it be provided simultaneously with two kinds of components by preparing organic-inorganic composite semiconductor
Advantage, and by both synergistic effect generate superior comprehensive performance, to meet wanting for modern energy and information technology
It asks.As a specific example, although traditional inorganic semiconductor gas sensor rises in the detection of toxic and harmful gas
Arrived important function, but they in the prevalence of poor selectivity, operating temperature is high the disadvantages of.It does not simply fail to be dependably distinguished not
Same gas, and high operating temperature itself is exactly a security risk when monitoring flammable explosive gas, and device is in height
It can degenerate quickly when work under temperature；In contrast, molecule organic semiconductor structure change multiplicity, and organic semiconductor gas sensing
Device operating temperature is low, and the sensor to develop many kinds of and easy to use provides more more options.But organic semiconductor
Stability is poor, mechanical strength is low, so that this kind of sensor is difficult functionization.If inorganic semiconductor partly can be led with organic
Body combines, and develops Organic-inorganic composite Semiconductor gas sensors material and sensor, then is hopeful through " association between the two
Same effect " acquisition processing performance is good, and sensitivity and selectivity are high, the low compound gas sensing materials of operating temperature.
The method for preparing organic-inorganic composite semiconductor at present mainly has in-situ compositing and ex situ complex method two big
Class.In-situ compounding process mainly in advance mixes organic semiconductor with inorganic semiconductor (or the raw material for synthesizing them)
It is even, machine-inorganic composite semiconductor is formed directly in subsequent reaction process.The advantages of this method is two kinds of component mixing
Uniformly, interfacial contact and combination are abundant.The disadvantage is that either inorganic or organic semiconductor in material, itself all is difficult to form sky
Between continuous network structure so that carrier mobility therein is hindered；Ex situ composite square rule is to prepare one kind first
Semiconductor (usually mostly is inorganic semiconductor), is then formed for " matrix " by spreading mixing or impregnating the processes such as compound with it
Composite semiconductor.The advantages of such methods is the network structure that inorganic semiconductor can form space connection, is conducive to carrier
Fast transport wherein.The disadvantage is that organic component is unevenly distributed, be in most cases " matrix " material surface it is multiple
It closes.Complex method is especially impregnated, it does not require nothing more than organic semiconductor with good dissolubility energy, and in composite semiconductor
Organic solvent is largely used in preparation process, it is easy to cause serious problem of environmental pollution.
101752499 A of Chinese patent literature CN discloses a kind of inorganic-pentacene substance composite semiconductor material
And preparation method thereof.Inorganic material is added by the way that pentacene substance to be dissolved in organic solvent in the invention, inorganic material with simultaneously
The molar ratio of five benezene materials is 10:1-1:10, sealing, and after dispersing 0.5-1h, removes organic solvent, obtains inorganic-and five
Benezene material composite semiconductor material.Composite semiconductor material provided by the invention has taken into account n-type semiconductor and p-type semiconductor
Respective advantage, preparation process is simple, at low cost.But this method needs to be unfavorable for environmental protection using organic solvent；And inorganic material
Material is largely compounded in the surface of pentacene substance, compound not uniform enough.
105842290 A of Chinese patent literature CN discloses a kind of for improving the inorganic-organic of gas sensor performance
The vacuum in situ complex method of composite air-sensitive sensor.By being carried out in high vacuum to oxide semiconductor Porous nanosolids
Heat treatment completely removes the gas molecule and other impurities of sample surfaces absorption, to obtain clean surface；Then, it is protecting
In the case of holding high vacuum state, introduces solutions of organic semiconductors and impregnate oxide semiconductor Porous nanosolids, make organic partly to lead
Body molecule and the clean surface of solids come into full contact with and bonding, and inorganic-organic hybrid is formed while modifying surface
Semiconductor gas sensors material.The inorganic-organic hybrid type gas sensor of the invention development Chemical Manufacture, environmental pollution monitoring with
And there is important application value in the fields such as automatic control.But this method need to use organic solvent, be unfavorable for environmental protection；It is partly led to organic
The solubility property of body has higher requirement；And organic component distribution is not uniform enough, most of only on the surface of inorganic material
It is compound.
For this purpose, developing a kind of method environmentally protective, simple, at low cost, to prepare, spatial connectivity is good, current-carrying
Transport factor is high, resistance is low, material internal and the uniform composite material of surface recombination are of great significance.
Summary of the invention
For existing Organic-inorganic composite semiconductor material technology of preparing there are the shortcomings that, the present invention provides a kind of use
Exchange complex method is forced in the pressure differential for preparing organic-inorganic composite semiconductor material.Method of the invention is simple, green
It is environmentally friendly, at low cost, may be implemented organic semiconductor oxide semiconductor sample interior and surface be uniformly distributed and it is completely multiple
It closes, the composite semiconductor material spatial connectivity being prepared is good, is conducive to the photo electric for increasing substantially composite semiconductor
Energy.
Technical scheme is as follows:
A kind of pressure differential pressure exchange complex method being used to prepare Organic-inorganic composite semiconductor material, including step
It is rapid as follows:
(1) by porous metal oxide semiconductor nano solid or porous metal oxide semiconductive thin film, in vacuum item
Under part, 100-300 DEG C of heat treatment 1-3h；It keeps vacuum state constant, naturally cools to room temperature, obtain the porous gold of surface cleaning
Belong to oxide semiconductor nano-solid or porous metal oxide semiconductive thin film；
(2) under vacuum conditions, organic semiconductor is placed in temperature end heating, vaporizes organic semiconductor；Meanwhile it will walk
Suddenly the porous metal oxide semiconductor nano solid or porous metal oxide semiconductive thin film for the surface cleaning that (1) obtains in
Low-temperature end heating；Then, inert gas is passed through from temperature end with 0.01-1.0 liters/min of rate, inert gas carries organic
The oxidation of the porous metal oxide semiconductor nano solid or porous metals of semi-conductor gas molecule and the surface cleaning of low-temperature end
Exchange recombination reaction occurs for object semiconductive thin film, persistently exchanges recombination reaction 8-72 hours, obtains reactant；
It is persistently vacuumized during the exchange recombination reaction, to keep organic semiconductor two sides there are pressure difference,
So that inert gas is carried organic semi-conductor gas molecule and flows to low-temperature end from temperature end；
(3) reactant for obtaining step (2) in inert gas 100-200 DEG C of annealing 0.5-2h to get it is organic-
Inorganic composite semiconductor material.
It is preferred according to the present invention, porous metal oxide semiconductor nano solid or porous gold in the step (1)
Category oxide semiconductor thin-film is zinc oxide (ZnO), stannic oxide (SnO2), titanium dioxide (TiO2), tungstic acid (WO3), three
Aoxidize two iron (Fe2O3), indium sesquioxide (In2O3) or ceria (CeO2) porous semi-conductor nano-solid or porous partly lead
Body thin film.
According to the present invention, the porous metal oxide semiconductor nano solid or porous metal oxide semiconductive thin film
Commercially available acquisition, or obtained by prior art preparation.
The porous metal oxide semiconductor nano solid is preferably according to 1431169 A (patent of Chinese patent document CN
Number: ZL 03111872.0) solvent hot-press method is prepared；The porous metal oxide semiconductive thin film is preferably according to
Sol-gel process (bibliography: Emerson A.F., Luis V.A.S., Margarida J.S., Julio through reporting
R.S.,Preparation of TiO2/SnO2Thin Films by Sol-Gel Method and Periodic B3LYP
Simulations, J.Phys.Chem.A, 2014,118,5857 and Sang H.L., David M.H., Allan J.J.,
T.R.L.,Transparent,Homogeneous Tin Oxide Thin Films Containing SnO2-Coated
Gold Nanoparticles, Chem.Mater., 2013,25,4697) it is prepared.
Preferred according to the present invention, the vacuum degree of vacuum condition is 10 in the step (1) and step (2)-3-10-6Pa.
Preferred according to the present invention, the organic semiconductor in the step (2) is that (PA, molecular weight are less than or equal to polyacetylene
5000), polyphenylacetylene (PPA, molecular weight be less than or equal to 10000), p-phenylene vinylene (PPV, molecular weight be less than or equal to 10000),
Polythiophene (10000) PTP, molecular weight are less than or equal to, Uniformpoly thiophene, bithiophene, polyselenophenes (molecular weight is less than or equal to 10000),
Biphenyl, acene, (10000) PPy, molecular weight are less than or equal to polypyrrole, (10000) PANI, molecular weight are less than or equal to polyaniline, porphin
Quinoline, metal phthalocyanine complex or naphthalene cyanines.
It is further preferred that the Uniformpoly thiophene is four thiophene of oligomerisation, five thiophene of oligomerisation, six thiophene of oligomerisation or oligomerisation second
Four thiophene of alkenyl；The bithiophene is simultaneously four thiophene, and five thiophene or hexa-thiophen；The biphenyl is quaterphenyl, 5-linked
Benzene or six biphenyl；The acene is anthracene, aphthacene, pentacene or rubrene；The metal phthalocyanine complex is CuPc
(CuPc), Phthalocyanine Zinc (ZnPc), FePC (FePc), Cobalt Phthalocyanine (CoPc) or phthalocyanine lutetium (LuPc).
It is preferred according to the present invention, the porous metal oxide of organic semiconductor and surface cleaning half in the step (2)
The mass ratio of conductor nano-solid or porous metal oxide semiconductive thin film is 1:20-1:100.
Preferred according to the present invention, step (2) the high temperature end heating temperature is 150-450 DEG C.
Preferred according to the present invention, low-temperature end heating temperature is 25-200 DEG C in the step (2).
Preferred according to the present invention, the inert gas in the step (2), (3) is argon gas or nitrogen.
Preferred according to the present invention, the speed of exhaust persistently vacuumized in the step (2) is 60 liter/min -90
Liter/min.
The present invention is in high vacuum to porous metal oxide semiconductor nano solid or porous metal oxide semiconductor
Film is heat-treated, and the gas molecule and other impurity of removal sample surfaces absorption are to obtain clean surface.It then, will be porous
Metal-oxide semiconductor (MOS) nano-solid or porous metal oxide semiconductive thin film are assembled into exchange set composite, in pressure
Difference driving under, using carrier gas carry organic semi-conductor gaseous molecular pass through porous metal oxide semiconductor nano solid or
Duct in porous metal oxide semiconductive thin film.Organic semiconductor gaseous molecular is adsorbed on channel surfaces and bonding,
Organic-inorganic composite semiconductor is formed while modifying surface.By this process, spatial connectivity can be obtained
Well, compound uniform Organic-inorganic composite semiconductor material is exchanged.These Organic-inorganic composite semiconductor materials are in photovoltaic
There is significant application value in device and gas sensor development, fieldtron preparation and the preparation of composite catalyst.
Beneficial effects of the present invention:
1, it impregnates from conventional solution and reaction method prepares that composite semiconductor material is different, method of the invention does not need
Use organic solvent.Thus two significant advantages of bring are: (1) effectively preventing problem of environmental pollution, (2) are for organic half
The solubility property of conductor does not have specific requirement, therefore method of the invention is applicable not only to the organic semiconductor of favorable solubility,
It is equally applicable for those insoluble and indissoluble organic semiconductors.
2, when preparing organic-inorganic composite semiconductor using conventional method, two kinds of the compound of component are substantially only occurred in
Superficial layer (especially solid sample).Organic semiconductor then may be implemented in oxide semiconductor sample interior in method of the invention
With surface be uniformly distributed and it is completely compound, the composite semiconductor material that carrier mobility is high, resistance is low is prepared, favorably
In the photoelectric properties for increasing substantially composite semiconductor.
3, compared with the method for usually preparing composite semiconductor, method of the invention is not only easy to get uniform component distribution
And compound complete Organic-inorganic composite semiconductor material, and inorganic semiconductor spatial connectivity therein is good, is conducive to
Increase substantially the performance of photoelectric device.
4, the Organic-inorganic composite semiconductor of the method for the present invention preparation can be used for the system of highly sensitive gas sensor
It is standby, the development of composite semiconductor photovoltaic device and composite semiconductor fieldtron, in chemical industry, environment, the energy and information
There is important application value in the fields such as technology.
5, the method for the present invention is simple, environmentally protective, cost is relatively low, is suitable for industrialized production.
Detailed description of the invention
Fig. 1 is that pressure differential forces to exchange the schematic device that complex method prepares organic-inorganic composite semiconductor material；
Wherein, 1 is high-purity argon gas, and 2 be suck-back device, and 3 be gas flowmeter, and 4 be vacuum tube furnace, and 5 be organic semiconductor, and 6 are
Metal-oxide semiconductor (MOS), 7 be vacuum pump.
Fig. 2 is the porous SnO of 1 step of embodiment (1) preparation2The stereoscan photograph of semiconductor nano solid, illustration are
Porous SnO2The macro morphology schematic diagram of semiconductor nano solid.
Fig. 3 is the porous SnO of 1 step of embodiment (1) preparation2The pore-size distribution map of semiconductor nano solid.
Fig. 4 is the porous SnO of 1 step of embodiment (1) preparation2N2 adsorption-desorption curve of semiconductor nano solid.
The CuPc-SnO that Fig. 5 is CuPc, prepared by embodiment 12Porous nanosolids composite semiconductor material and porous SnO2Half
The infrared spectrum comparison diagram of conductor nano-solid.
Fig. 6 is CuPc-SnO prepared by embodiment 12The Elemental redistribution map of Porous nanosolids composite semiconductor material.
Fig. 7 is the CuPc-SnO prepared in test example 12The knot of Porous nanosolids composite semiconductor material gas sensor
Structure schematic diagram.
Fig. 8 is different sensors in test example 1 to NO2Air-sensitive response curve.Wherein: (a) being to be prepared in embodiment 1
CuPc-SnO2The SnO prepared in Porous nanosolids composite semiconductor material and comparative example2Porous nanosolids are as air-sensitive
Sensor is to 5ppm NO2Air-sensitive respond the curve that varies with temperature；(b) SnO to be prepared in comparative example2Porous nanosolids
As gas sensor at 140 DEG C to 5ppm NO2Dynamic response curve；(c) CuPc-SnO prepared for embodiment 12It is porous
Nano-solid composite semiconductor material is as gas sensor at 140 DEG C to 5ppm NO2Dynamic response curve.
Specific embodiment:
The present invention will be further explained combined with specific embodiments below and explanation, but not limited to this.
Experimental method described in following embodiments is unless otherwise specified conventional method simultaneously；The material, such as nothing
Specified otherwise commercially obtains.
Embodiment 1:
A kind of pressure differential pressure exchange complex method being used to prepare Organic-inorganic composite semiconductor material, including step
It is rapid as follows:
(1) porous SnO2Semiconductor nano solid is prepared according to method disclosed in 1431169 A of patent document CN:
By 3.0 grams of SnO2SnO is made in nano particle2Porous nanosolids.Specific step is as follows: at room temperature, weighing 3.0 grams of SnO2It receives
Rice grain is placed in ball grinder, then measures 5 milliliters of dioxane and ball grinders are added, with 180 revs/min revolving speed ball milling 1 hour, will
Mixture is fitted into hot pressure reaction kettle, and autoclave is heated to 100 DEG C with 2.5 DEG C/min of heating rate, constant temperature 30 divides by sealing
Apply the constant pressure of 60 megapascal after clock.200 DEG C, and constant temperature 3 are heated to same heating rate under a constant later
Hour.To hot pressure reaction kettle cooled to room temperature, release stress.Sample in autoclave is taken out, is burnt in 500 DEG C of air
Knot 2 hours, obtain SnO2Porous nanosolids；
Porous SnO made from this step2The stereoscan photograph of semiconductor nano solid is as shown in Figure 2；Wherein, illustration is
Porous SnO2The macro morphology schematic diagram of semiconductor nano solid sample.As shown in Figure 2, SnO2It is interconnected to form between particle
The porous network structure being evenly distributed；
Porous SnO made from this step2The graph of pore diameter distribution of semiconductor nano solid is as shown in Figure 3.From the figure 3, it may be seen that more
Hole SnO2The aperture of semiconductor nano solid concentrates between 40-150 nanometers, even aperture distribution.
Porous SnO made from this step2The N2 adsorption of semiconductor nano solid-desorption figure is as shown in Figure 4.As shown in Figure 4,
Porous SnO2The N2 adsorption of semiconductor nano solid is very precipitous with desorption curve, and hysteresis loop is quite narrow, condensation and evaporation
Pressure is close to saturated vapor pressure；
(2) by porous SnO made from step (1)2Semiconductor nano solid is placed in three-necked flask, 2.3 × 10-4Pa's
It is heat-treated 3 hours for 150 DEG C in vacuum.It keeps vacuum state that sample is made to naturally cool to room temperature, obtains the porous of surface cleaning
SnO2Semiconductor nano solid；
(3) it weighs 0.1 gram of CuPc to be placed in aluminium oxide boat, is placed in temperature end, by table made from 0.5 gram of step (2)
The clean porous SnO in face2Semiconductor nano solid is assembled into the low-temperature end in exchange set composite shown in FIG. 1, opens vacuum
Pump vacuumizes whole device；
High-purity argon gas is passed through with 0.3 liter/min of flow velocity into exchange set composite, CuPc is then heated to 350
It DEG C is allowed to vaporize, porous SnO2The temperature of semiconductor nano solid is increased to 200 DEG C.In porous SnO2Semiconductor nano solid two
Under the driving of lateral pressure difference, argon gas carries the porous SnO that CuPc steam passes through surface cleaning2In semiconductor nano solid
Duct, and be adsorbed and bonding in channel surfaces.Entire exchange recombination process continues 24 hours, then makes whole device naturally cold
But room temperature is arrived.Stopping is passed through argon gas and closes vacuum pump, obtains reactant；
(4) 150 DEG C annealing 1 hour, further promotion in high-purity argon gas by reactant obtained in step (3)
CuPc and SnO2Bonding is to get CuPc-SnO2Porous nanosolids composite semiconductor material.
CuPc-SnO manufactured in the present embodiment2Porous nanosolids composite semiconductor material and CuPc, porous SnO2Semiconductor
The infrared spectrum comparison diagram of nano-solid is as shown in Figure 5.As shown in Figure 5, CuPc with porous SnO2Semiconductor nano solid hair
Raw effect and bonding；
CuPc-SnO manufactured in the present embodiment2Elemental redistribution map such as Fig. 6 of Porous nanosolids composite semiconductor material
It is shown.It will be appreciated from fig. 6 that CuPc and porous SnO2Semiconductor nano solid comes into full contact with, and CuPc is in porous SnO2Semiconductor nano is solid
Body surface EDS maps are uniform.
Embodiment 2:
It is a kind of be used to prepare Organic-inorganic composite semiconductor material pressure differential force exchange complex method, step with
Embodiment 1 is identical, except that:
Porous SnO in step (2)2Heat treatment temperature of the semiconductor nano solid in high vacuum is 300 DEG C, and vacuum degree is
8×10-6Pa；
High-purity argon gas changes high pure nitrogen into step (3), and CuPc has changed Phthalocyanine Zinc into, and organic semiconductor heating temperature is
450 DEG C, the exchange recombination process duration is 8 hours.
Embodiment 3:
It is a kind of be used to prepare Organic-inorganic composite semiconductor material pressure differential force exchange complex method, step with
Embodiment 1 is identical, except that:
Porous SnO in step (2)2Heat treatment temperature of the semiconductor nano solid in high vacuum is 100 DEG C, and vacuum degree is
4×10-6Pa；
CuPc has changed polyaniline into step (3), and organic semiconductor heating temperature is 150 DEG C, and exchange recombination process is held
The continuous time is 72 hours；Inert gas used is nitrogen.
Embodiment 4:
It is a kind of be used to prepare Organic-inorganic composite semiconductor material pressure differential force exchange complex method, step with
Embodiment 1 is identical, except that:
Porous SnO in step (2)2Heat treatment temperature of the semiconductor nano solid in high vacuum is 250 DEG C, and vacuum degree is
4×10-4Pa；
CuPc has changed naphthalene cyanines into step (3), and organic semiconductor heating temperature is 300 DEG C, porous SnO2Semiconductor is received
The temperature of rice solid is increased to 160 DEG C, and the exchange recombination process duration is 48 hours.
Embodiment 5:
It is a kind of be used to prepare Organic-inorganic composite semiconductor material pressure differential force exchange complex method, step with
Embodiment 1 is identical, except that:
Porous SnO in step (2)2Heat treatment temperature of the semiconductor nano solid in high vacuum is 200 DEG C, and vacuum degree is
6×10-5Pa；
CuPc has changed Cobalt Phthalocyanine into step (3), and organic semiconductor heating temperature is 250 DEG C, porous SnO2Semiconductor
The temperature of nano-solid is increased to 120 DEG C, and the exchange recombination process duration is 36 hours.
Embodiment 6:
It is a kind of be used to prepare Organic-inorganic composite semiconductor material pressure differential force exchange complex method, step with
Embodiment 1 is identical, except that:
Porous SnO in step (2)2Heat treatment temperature of the semiconductor nano solid in high vacuum is 120 DEG C, and vacuum degree is
2×10-4Pa；
CuPc has changed polythiophene into step (3), and organic semiconductor heating temperature is 200 DEG C, porous SnO2Semiconductor
The temperature of nano-solid is increased to 90 DEG C, and the exchange recombination process duration is 56 hours.
Embodiment 7:
It is a kind of be used to prepare Organic-inorganic composite semiconductor material pressure differential force exchange complex method, step with
Embodiment 1 is identical, except that:
Porous SnO in step (2)2Heat treatment temperature of the semiconductor nano solid in high vacuum is 120 DEG C, and vacuum degree is
2×10-4Pa；
CuPc has changed phthalocyanine lutetium into step (3), and organic semiconductor heating temperature is 280 DEG C, porous SnO2Semiconductor
The temperature of nano-solid is increased to 200 DEG C, and the exchange recombination process duration is 18 hours.
Embodiment 8:
It is a kind of be used to prepare Organic-inorganic composite semiconductor material pressure differential force exchange complex method, step with
Embodiment 1 is identical, except that:
Porous SnO in step (2)2Heat treatment temperature of the semiconductor nano solid in high vacuum is 160 DEG C, and vacuum degree is
1×10-3Pa；
CuPc has changed porphyrin into step (3), and organic semiconductor heating temperature is 180 DEG C, porous SnO2Semiconductor is received
The temperature of rice solid is increased to 70 DEG C, and the exchange recombination process duration is 60 hours.
Embodiment 9:
It is a kind of be used to prepare Organic-inorganic composite semiconductor material pressure differential force exchange complex method, step with
Embodiment 1 is identical, except that:
SnO in step (1)2Change ZnO into, porous ZnO semiconductor nano solid is according to Chinese patent literature CN 1431169
Embodiment 1 in A is prepared；
Heat treatment temperature of the porous ZnO semiconductor nano solid in high vacuum is 250 DEG C in step (2), vacuum degree 6
×10-4Pa；
Organic semiconductor heating temperature is 320 DEG C in step (3), and the exchange recombination process duration is 24 hours；It is high-purity
Argon gas changes high pure nitrogen into.
Embodiment 10:
It is a kind of be used to prepare Organic-inorganic composite semiconductor material pressure differential force exchange complex method, step with
Embodiment 1 is identical, except that:
SnO in step (1)2Change ZnO into；
Heat treatment temperature of the porous ZnO semiconductor nano solid in high vacuum is 100 DEG C in step (2), vacuum degree 3
×10-5Pa；
CuPc has changed polyacetylene into step (3), and organic semiconductor heating temperature is 220 DEG C, and exchange recombination process is held
The continuous time is 65 hours, and inert gas used is nitrogen.
Embodiment 11:
It is a kind of be used to prepare Organic-inorganic composite semiconductor material pressure differential force exchange complex method, step with
Embodiment 1 is identical, except that:
SnO in step (1)2Change ZnO into；
Heat treatment temperature of the porous ZnO semiconductor nano solid in high vacuum is 250 DEG C in step (2), vacuum degree 4
×10-4Pa；
CuPc has changed p-phenylene vinylene into step (3), and organic semiconductor heating temperature is 240 DEG C, and porous ZnO is partly led
The temperature of body nano-solid is increased to 160 DEG C, and the exchange recombination process duration is 56 hours.
Embodiment 12:
It is a kind of be used to prepare Organic-inorganic composite semiconductor material pressure differential force exchange complex method, step with
Embodiment 1 is identical, except that:
SnO in step (1)2Change ZnO into；
Heat treatment temperature of the porous ZnO semiconductor nano solid in high vacuum is 200 DEG C in step (2), vacuum degree 6
×10-4Pa；
CuPc has changed polypyrrole into step (3), and organic semiconductor heating temperature is 250 DEG C, and porous ZnO semiconductor is received
The temperature of rice solid is increased to 140 DEG C, and the exchange recombination process duration is 42 hours.
Embodiment 13:
It is a kind of be used to prepare Organic-inorganic composite semiconductor material pressure differential force exchange complex method, step with
Embodiment 1 is identical, except that:
SnO in step (1)2Change TiO into2, porous TiO2Semiconductor nano solid is according to Chinese patent literature CN 1431169
Embodiment 2 in A is prepared；
Porous TiO in step (2)2Heat treatment temperature of the semiconductor nano solid in high vacuum is 120 DEG C, and vacuum degree is
2×10-4Pa；
CuPc has changed polystyrene into step (3), and organic semiconductor heating temperature is 280 DEG C, porous TiO2Partly lead
The temperature of body nano-solid is increased to 130 DEG C, and the exchange recombination process duration is 32 hours.
Embodiment 14:
It is a kind of be used to prepare Organic-inorganic composite semiconductor material pressure differential force exchange complex method, step with
Embodiment 1 is identical, except that:
SnO in step (1)2Change TiO into2；
Porous TiO in step (2)2Heat treatment temperature of the semiconductor nano solid in high vacuum is 180 DEG C, and vacuum degree is
8×10-4Pa；
CuPc has changed polyselenophenes into step (3), and organic semiconductor heating temperature is 160 DEG C, porous TiO2Semiconductor
The temperature of nano-solid is increased to 100 DEG C, and the exchange recombination process duration is 64 hours.
Embodiment 15:
It is a kind of be used to prepare Organic-inorganic composite semiconductor material pressure differential force exchange complex method, step with
Embodiment 1 is identical, except that:
SnO in step (1)2Change TiO into2；
Porous TiO in step (2)2Heat treatment temperature of the semiconductor nano solid in high vacuum is 250 DEG C, and vacuum degree is
3×10-4Pa；
CuPc has changed biphenyl into step (3), and organic semiconductor heating temperature is 180 DEG C, porous TiO2Semiconductor
The temperature of nano-solid is increased to 120 DEG C, and the exchange recombination process duration is 56 hours.
Embodiment 16:
It is a kind of be used to prepare Organic-inorganic composite semiconductor material pressure differential force exchange complex method, step with
Embodiment 1 is identical, except that:
SnO in step (1)2Change TiO into2；
Porous TiO in step (2)2Heat treatment temperature of the semiconductor nano solid in high vacuum is 160 DEG C, and vacuum degree is
1×10-3Pa；
CuPc has changed pentacene into step (3), and organic semiconductor heating temperature is 250 DEG C, porous TiO2Semiconductor
The temperature of nano-solid is increased to 160 DEG C, and the exchange recombination process duration is 66 hours.
Embodiment 17:
It is a kind of be used to prepare Organic-inorganic composite semiconductor material pressure differential force exchange complex method, step with
Embodiment 1 is identical, except that:
SnO in step (1)2Change TiO into2；
Porous TiO in step (2)2Heat treatment temperature of the semiconductor nano solid in high vacuum is 200 DEG C, and vacuum degree is
5×10-4Pa；
CuPc has changed five thiophene of oligomerisation into step (3), and organic semiconductor heating temperature is 280 DEG C, porous TiO2Half
The temperature of conductor nano-solid is increased to 90 DEG C, and the exchange recombination process duration is 52 hours.
Embodiment 18:
It is a kind of be used to prepare Organic-inorganic composite semiconductor material pressure differential force exchange complex method, step with
Embodiment 1 is identical, except that:
SnO in step (1)2Change TiO into2；
Porous TiO in step (2)2Heat treatment temperature of the semiconductor nano solid in high vacuum is 160 DEG C, and vacuum degree is
5×10-4Pa；
CuPc has changed four thiophene of oligomerizing ethylene base into step (3), and organic semiconductor heating temperature is 260 DEG C, porous
TiO2The temperature of semiconductor nano solid is increased to 110 DEG C, and the exchange recombination process duration is 44 hours.
Embodiment 19:
It is a kind of be used to prepare Organic-inorganic composite semiconductor material pressure differential force exchange complex method, step with
Embodiment 1 is identical, except that:
SnO in step (1)2Change TiO into2；
Porous TiO in step (2)2Heat treatment temperature of the semiconductor nano solid in high vacuum is 160 DEG C, and vacuum degree is
5×10-4Pa；
CuPc has changed into step (3) and five thiophene, organic semiconductor heating temperature are 270 DEG C, porous TiO2Partly lead
The temperature of body nano-solid is increased to 120 DEG C, and the exchange recombination process duration is 38 hours.
Embodiment 20:
It is a kind of be used to prepare Organic-inorganic composite semiconductor material pressure differential force exchange complex method, step with
Embodiment 1 is identical, except that:
SnO in step (1)2Change TiO into2；
Porous TiO in step (2)2Heat treatment temperature of the semiconductor nano solid in high vacuum is 190 DEG C, and vacuum degree is
2×10-4Pa；
CuPc has changed quaterphenyl into step (3), and organic semiconductor heating temperature is 220 DEG C, porous TiO2Semiconductor
The temperature of nano-solid is increased to 95 DEG C, and the exchange recombination process duration is 48 hours.
Embodiment 21:
It is a kind of be used to prepare Organic-inorganic composite semiconductor material pressure differential force exchange complex method, step with
Embodiment 1 is identical, except that:
SnO in step (1)2Change TiO into2；
Porous TiO in step (2)2Heat treatment temperature of the semiconductor nano solid in high vacuum is 190 DEG C, and vacuum degree is
2×10-4Pa；
CuPc has changed anthracene into step (3), and organic semiconductor heating temperature is 260 DEG C, porous TiO2Semiconductor nano
The temperature of solid is increased to 105 DEG C, and the exchange recombination process duration is 42 hours.
Embodiment 22:
It is a kind of be used to prepare Organic-inorganic composite semiconductor material pressure differential force exchange complex method, step with
Embodiment 1 is identical, except that:
SnO in step (1)2Change TiO into2；
Porous TiO in step (2)2Heat treatment temperature of the semiconductor nano solid in high vacuum is 140 DEG C, and vacuum degree is
2×10-5Pa；
CuPc has changed rubrene into step (3), and organic semiconductor heating temperature is 220 DEG C, porous TiO2Semiconductor
The temperature of nano-solid is increased to 100 DEG C, and the exchange recombination process duration is 58 hours.
Embodiment 23:
It is a kind of be used to prepare Organic-inorganic composite semiconductor material pressure differential force exchange complex method, step with
Embodiment 1 is identical, except that:
SnO in step (1)2Change tungstic acid (WO into3), porous WO3Semiconductor nano solid is according to patent document CN
Method disclosed in 1431169 A is prepared, the specific steps are as follows: at room temperature, weighs 6.0 grams of WO3Nano particle is placed in ball
In grinding jar, then measure 5 milliliters of dioxane and ball grinders be added, with 180 revs/min revolving speed ball milling 1 hour, fill this blend into heat
It presses in reaction kettle, sealing applies 60,000,000 after autoclave is heated to 100 DEG C, constant temperature 30 minutes with 2.5 DEG C/min of heating rate
The constant pressure of pa.200 DEG C, and constant temperature 3 hours are heated to same heating rate under a constant later.It is anti-to hot pressing
Kettle cooled to room temperature is answered, is released stress.Sample in autoclave is taken out, is sintered 2 hours, obtains in 600 DEG C of air
WO3Porous nanosolids；
Porous WO in step (2)3Heat treatment temperature of the semiconductor nano solid in high vacuum is 110 DEG C, vacuum degree 5
×10-5Pa；
CuPc has changed Phthalocyanine Zinc into step (3), and organic semiconductor heating temperature is 360 DEG C, porous WO3Semiconductor is received
The temperature of rice solid is increased to 180 DEG C, and the exchange recombination process duration is 24 hours.
Embodiment 24:
It is a kind of be used to prepare Organic-inorganic composite semiconductor material pressure differential force exchange complex method, step with
Embodiment 1 is identical, except that:
SnO in step (1)2Change tungstic acid (WO into3)；
Porous WO in step (2)3Heat treatment temperature of the semiconductor nano solid in high vacuum is 150 DEG C, vacuum degree 7
×10-4Pa；
CuPc has changed polyselenophenes into step (3), and organic semiconductor heating temperature is 260 DEG C, and exchange recombination process is held
The continuous time is 55 hours.
Embodiment 25:
It is a kind of be used to prepare Organic-inorganic composite semiconductor material pressure differential force exchange complex method, step with
Embodiment 1 is identical, except that:
SnO in step (1)2Change tungstic acid (WO into3)；
Porous WO in step (2)3Heat treatment temperature of the semiconductor nano solid in high vacuum is 300 DEG C, vacuum degree 6
×10-4Pa；
CuPc has changed pentacene into step (3), and organic semiconductor heating temperature is 220 DEG C, porous WO3Semiconductor is received
The temperature of rice solid is increased to 170 DEG C, and the exchange recombination process duration is 46 hours.
Embodiment 26:
It is a kind of be used to prepare Organic-inorganic composite semiconductor material pressure differential force exchange complex method, step with
Embodiment 1 is identical, except that:
SnO in step (1)2Change tungstic acid (WO into3)；
Porous WO in step (2)3Heat treatment temperature of the semiconductor nano solid in high vacuum is 140 DEG C, vacuum degree 1
×10-4Pa；
CuPc has changed rubrene into step (3), and organic semiconductor heating temperature is 210 DEG C, porous WO3Semiconductor is received
The temperature of rice solid is increased to 120 DEG C, and the exchange recombination process duration is 48 hours.
Embodiment 27:
It is a kind of be used to prepare Organic-inorganic composite semiconductor material pressure differential force exchange complex method, step with
Embodiment 1 is identical, except that:
SnO in step (1)2Change tungstic acid (WO into3)；
Porous WO in step (2)3Heat treatment temperature of the semiconductor nano solid in high vacuum is 155 DEG C, vacuum degree 5
×10-4Pa；
CuPc has changed five thiophene of oligomerisation into step (3), and organic semiconductor heating temperature is 300 DEG C, porous WO3Partly lead
The temperature of body nano-solid is increased to 105 DEG C, and the exchange recombination process duration is 56 hours.
Embodiment 28:
It is a kind of be used to prepare Organic-inorganic composite semiconductor material pressure differential force exchange complex method, step with
Embodiment 1 is identical, except that:
SnO in step (1)2Change tungstic acid (WO into3)；
Porous WO in step (2)3Heat treatment temperature of the semiconductor nano solid in high vacuum is 100 DEG C, vacuum degree 2
×10-6Pa；
CuPc has changed four thiophene of oligomerizing ethylene base into step (3), and organic semiconductor heating temperature is 230 DEG C, porous
WO3The temperature of semiconductor nano solid is increased to 140 DEG C, and the exchange recombination process duration is 36 hours.
Embodiment 29:
It is a kind of be used to prepare Organic-inorganic composite semiconductor material pressure differential force exchange complex method, step with
Embodiment 1 is identical, except that:
SnO in step (1)2Change di-iron trioxide (Fe into2O3), porous Fe2O3Semiconductor nano solid is according to Chinese patent
Embodiment 5 in 1431169 A of document CN is prepared；
Porous Fe in step (2)2O3Heat treatment temperature of the semiconductor nano solid in high vacuum is 115 DEG C, and vacuum degree is
4×10-4Pa；
CuPc has changed polystyrene into step (3), and organic semiconductor heating temperature is 265 DEG C, porous Fe2O3Partly lead
The temperature of body nano-solid is increased to 125 DEG C, and the exchange recombination process duration is 42 hours.
Embodiment 30:
It is a kind of be used to prepare Organic-inorganic composite semiconductor material pressure differential force exchange complex method, step with
Embodiment 1 is identical, except that:
SnO in step (1)2Change di-iron trioxide (Fe into2O3)；
Porous Fe in step (2)2O3Heat treatment temperature of the semiconductor nano solid in high vacuum is 170 DEG C, and vacuum degree is
5×10-4Pa；
CuPc has changed polyselenophenes into step (3), and organic semiconductor heating temperature is 175 DEG C, and exchange recombination process is held
The continuous time is 70 hours.
Embodiment 31:
It is a kind of be used to prepare Organic-inorganic composite semiconductor material pressure differential force exchange complex method, step with
Embodiment 1 is identical, except that:
SnO in step (1)2Change di-iron trioxide (Fe into2O3)；
Porous Fe in step (2)2O3Heat treatment temperature of the semiconductor nano solid in high vacuum is 280 DEG C, and vacuum degree is
5×10-4Pa；
CuPc has changed biphenyl into step (3), and organic semiconductor heating temperature is 200 DEG C, porous Fe2O3Semiconductor
The temperature of nano-solid is increased to 150 DEG C, and the exchange recombination process duration is 26 hours.
Embodiment 32:
It is a kind of be used to prepare Organic-inorganic composite semiconductor material pressure differential force exchange complex method, step with
Embodiment 1 is identical, except that:
SnO in step (1)2Change di-iron trioxide (Fe into2O3)；
Porous Fe in step (2)2O3Heat treatment temperature of the semiconductor nano solid in high vacuum is 130 DEG C, and vacuum degree is
1×10-4Pa；
CuPc has changed pentacene into step (3), and organic semiconductor heating temperature is 240 DEG C, porous Fe2O3Semiconductor
The temperature of nano-solid is increased to 130 DEG C, and the exchange recombination process duration is 54 hours.
Embodiment 33:
It is a kind of be used to prepare Organic-inorganic composite semiconductor material pressure differential force exchange complex method, step with
Embodiment 1 is identical, except that:
SnO in step (1)2Change di-iron trioxide (Fe into2O3)；
Porous Fe in step (2)2O3Heat treatment temperature of the semiconductor nano solid in high vacuum is 230 DEG C, and vacuum degree is
5×10-4Pa；
CuPc has changed five thiophene of oligomerisation into step (3), and organic semiconductor heating temperature is 240 DEG C, Fe2O3It is porous to receive
The temperature of rice solid is increased to 95 DEG C, and the exchange recombination process duration is 44 hours.
Embodiment 34:
It is a kind of be used to prepare Organic-inorganic composite semiconductor material pressure differential force exchange complex method, step with
Embodiment 1 is identical, except that:
SnO in step (1)2Change di-iron trioxide (Fe into2O3)；
Porous Fe in step (2)2O3Heat treatment temperature of the semiconductor nano solid in high vacuum is 145 DEG C, and vacuum degree is
3×10-4Pa；
CuPc has changed four thiophene of oligomerizing ethylene base into step (3), and organic semiconductor heating temperature is 230 DEG C, porous
Fe2O3The temperature of semiconductor nano solid is increased to 145 DEG C, and the exchange recombination process duration is 32 hours.
Embodiment 35:
It is a kind of be used to prepare Organic-inorganic composite semiconductor material pressure differential force exchange complex method, step with
Embodiment 1 is identical, except that:
SnO in step (1)2Change indium sesquioxide (In into2O3), porous In2O3Semiconductor nano solid is according to patent document
Method disclosed in 1431169 A of CN is prepared, the specific steps are as follows: at room temperature, weighs 6.0 grams of In2O3Nano particle is set
In ball grinder, then measure 5 milliliters of dioxane and ball grinders be added, with 180 revs/min revolving speed ball milling 1 hour, mixture is filled
Enter in hot pressure reaction kettle, seals, autoclave is heated to 100 DEG C with 2.5 DEG C/min of heating rate, constant temperature applies after 30 minutes
The constant pressure of 60 megapascal.200 DEG C, and constant temperature 3 hours are heated to same heating rate under a constant later.To heat
Reaction kettle cooled to room temperature is pressed, is released stress.Sample in autoclave is taken out, is sintered 2 hours in 600 DEG C of air,
Obtain In2O3Porous nanosolids；
Porous In in step (2)2O3Heat treatment temperature of the semiconductor nano solid in high vacuum is 260 DEG C, and vacuum degree is
2×10-4Pa；
CuPc has changed polystyrene into step (3), and organic semiconductor heating temperature is 260 DEG C, porous In2O3Partly lead
The temperature of body nano-solid is increased to 125 DEG C, and the exchange recombination process duration is 40 hours.
Embodiment 36:
It is a kind of be used to prepare Organic-inorganic composite semiconductor material pressure differential force exchange complex method, step with
Embodiment 1 is identical, except that:
SnO in step (1)2Change indium sesquioxide (In into2O3)；
Porous In in step (2)2O3Heat treatment temperature of the semiconductor nano solid in high vacuum is 165 DEG C, and vacuum degree is
4×10-4Pa；
CuPc has changed polyselenophenes into step (3), and organic semiconductor heating temperature is 225 DEG C, and exchange recombination process is held
The continuous time is 54 hours.
Embodiment 37:
It is a kind of be used to prepare Organic-inorganic composite semiconductor material pressure differential force exchange complex method, step with
Embodiment 1 is identical, except that:
SnO in step (1)2Change indium sesquioxide (In into2O3)；
Porous In in step (2)2O3Heat treatment temperature of the semiconductor nano solid in high vacuum is 150 DEG C, and vacuum degree is
3×10-5Pa；
CuPc has changed biphenyl into step (3), and organic semiconductor heating temperature is 200 DEG C, porous In2O3Semiconductor
The temperature of nano-solid is increased to 100 DEG C, and the exchange recombination process duration is 62 hours.
Embodiment 38:
It is a kind of be used to prepare Organic-inorganic composite semiconductor material pressure differential force exchange complex method, step with
Embodiment 1 is identical, except that:
SnO in step (1)2Change indium sesquioxide (In into2O3)；
Porous In in step (2)2O3Heat treatment temperature of the semiconductor nano solid in high vacuum is 195 DEG C, and vacuum degree is
6×10-4Pa；
CuPc has changed pentacene into step (3), and organic semiconductor heating temperature is 235 DEG C, porous In2O3Semiconductor
The temperature of nano-solid is increased to 140 DEG C, and the exchange recombination process duration is 45 hours.
Embodiment 39:
It is a kind of be used to prepare Organic-inorganic composite semiconductor material pressure differential force exchange complex method, step with
Embodiment 1 is identical, except that:
SnO in step (1)2Change indium sesquioxide (In into2O3)；
Porous In in step (2)2O3Heat treatment temperature of the semiconductor nano solid in high vacuum is 205 DEG C, and vacuum degree is
3×10-4Pa；
CuPc has changed five thiophene of oligomerisation into step (3), and organic semiconductor heating temperature is 255 DEG C, porous In2O3Half
The temperature of conductor nano-solid is increased to 95 DEG C, and the exchange recombination process duration is 48 hours.
Embodiment 40:
It is a kind of be used to prepare Organic-inorganic composite semiconductor material pressure differential force exchange complex method, step with
Embodiment 1 is identical, except that:
SnO in step (1)2Change indium sesquioxide (In into2O3)；
Porous In in step (2)2O3Heat treatment temperature of the semiconductor nano solid in high vacuum is 125 DEG C, and vacuum degree is
7×10-4Pa；
CuPc has changed four thiophene of oligomerizing ethylene base into step (3), and organic semiconductor heating temperature is 270 DEG C, porous
In2O3The temperature of semiconductor nano solid is increased to 130 DEG C, and the exchange recombination process duration is 40 hours.
Embodiment 41:
It is a kind of be used to prepare Organic-inorganic composite semiconductor material pressure differential force exchange complex method, step with
Embodiment 1 is identical, except that:
SnO in step (1)2Change ceria (CeO into2), porous C eO2Semiconductor nano solid is according to patent document CN
Method disclosed in 1431169 A is prepared, and steps are as follows for specific experiment: at room temperature, weighing 4.0 grams of CeO2Nano particle is set
In ball grinder, then measure 5 milliliters of dioxane and ball grinders be added, with 180 revs/min revolving speed ball milling 1 hour, mixture is filled
Enter in hot pressure reaction kettle, seals, autoclave is heated to 100 DEG C with 2.5 DEG C/min of heating rate, constant temperature applies after 30 minutes
The constant pressure of 60 megapascal.200 DEG C, and constant temperature 3 hours are heated to same heating rate under a constant later.To heat
Reaction kettle cooled to room temperature is pressed, is released stress.Sample in autoclave is taken out, is sintered 2 hours in 600 DEG C of air,
Obtain CeO2Porous nanosolids；
Porous C eO in step (2)2Heat treatment temperature of the semiconductor nano solid in high vacuum is 120 DEG C, and vacuum degree is
6×10-4Pa；
CuPc has changed polystyrene into step (3), and organic semiconductor heating temperature is 245 DEG C, porous C eO2Partly lead
The temperature of body nano-solid is increased to 135 DEG C, and the exchange recombination process duration is 32 hours.
Embodiment 42:
It is a kind of be used to prepare Organic-inorganic composite semiconductor material pressure differential force exchange complex method, step with
Embodiment 1 is identical, except that:
SnO in step (1)2Change ceria (CeO into2)；
Porous C eO in step (2)2Heat treatment temperature of the semiconductor nano solid in high vacuum is 250 DEG C, and vacuum degree is
2×10-4Pa；
CuPc has changed polyselenophenes into step (3), and organic semiconductor heating temperature is 210 DEG C, and exchange recombination process is held
The continuous time is 46 hours.
Embodiment 43:
It is a kind of be used to prepare Organic-inorganic composite semiconductor material pressure differential force exchange complex method, step with
Embodiment 1 is identical, except that:
SnO in step (1)2Change ceria (CeO into2)；
Porous C eO in step (2)2Heat treatment temperature of the semiconductor nano solid in high vacuum is 285 DEG C, and vacuum degree is
9×10-4Pa；
CuPc has changed biphenyl into step (3), and organic semiconductor heating temperature is 175 DEG C, porous C eO2Semiconductor
The temperature of nano-solid is increased to 120 DEG C, and the exchange recombination process duration is 66 hours.
Embodiment 44:
It is a kind of be used to prepare Organic-inorganic composite semiconductor material pressure differential force exchange complex method, step with
Embodiment 1 is identical, except that:
SnO in step (1)2Change ceria (CeO into2)；
Porous C eO in step (2)2Heat treatment temperature of the semiconductor nano solid in high vacuum is 170 DEG C, and vacuum degree is
1×10-5Pa；
CuPc has changed pentacene into step (3), and organic semiconductor heating temperature is 250 DEG C, porous C eO2Semiconductor
The temperature of nano-solid is increased to 155 DEG C, and the exchange recombination process duration is 42 hours.
Embodiment 45:
It is a kind of be used to prepare Organic-inorganic composite semiconductor material pressure differential force exchange complex method, step with
Embodiment 1 is identical, except that:
SnO in step (1)2Change ceria (CeO into2)；
Porous C eO in step (2)2Heat treatment temperature of the semiconductor nano solid in high vacuum is 275 DEG C, and vacuum degree is
5×10-4Pa；
CuPc has changed five thiophene of oligomerisation into step (3), and organic semiconductor heating temperature is 230 DEG C, porous C eO2Half
The temperature of conductor nano-solid is increased to 125 DEG C, and the exchange recombination process duration is 58 hours.
Embodiment 46:
It is a kind of be used to prepare Organic-inorganic composite semiconductor material pressure differential force exchange complex method, step with
Embodiment 1 is identical, except that:
SnO in step (1)2Change ceria (CeO into2)；
Porous C eO in step (2)2Heat treatment temperature of the semiconductor nano solid in high vacuum is 235 DEG C, and vacuum degree is
4×10-4Pa；
CuPc has changed four thiophene of oligomerizing ethylene base into step (3), and organic semiconductor heating temperature is 265 DEG C, porous
CeO2The temperature of semiconductor nano solid is increased to 135 DEG C, and the exchange recombination process duration is 37 hours.
Embodiment 47:
It is a kind of be used to prepare Organic-inorganic composite semiconductor material pressure differential force exchange complex method, step with
Embodiment 1 is identical, except that:
Porous SnO in step (1)2Semiconductor nano solid is changed to SnO2Porous membrane, SnO2Porous membrane specifically prepares step
It is rapid as follows:
At room temperature, 2 milliliters of aqueous isopropanols containing 10% stannic acid tetra-isopropyl are placed in a beaker, 4 milliliters of addition is different
Propyl alcohol simultaneously stirs 30 minutes, adds 4 milliliters of acetylacetone,2,4-pentanediones, and stirring obtained the colloidal sol of stannic acid tetra-isopropyl after 2 hours；By colloidal sol
It is spin-coated on porous alumina formwork, and is dried 1 hour at 100 DEG C, then in 600 DEG C of air with 2000 revs/min of speed
SnO can be obtained in 1 hour in calcining2Porous membrane.
Embodiment 48:
It is a kind of be used to prepare Organic-inorganic composite semiconductor material pressure differential force exchange complex method, step with
Embodiment 47 is identical, except that:
SnO in step (2)2Heat treatment temperature of the film in high vacuum is 150 DEG C, and vacuum degree is 2 × 10-4Pa；
CuPc has changed low-molecular-weight polystyrene into step (3), and organic semiconductor heating temperature is 150 DEG C, SnO2
The temperature of film is increased to 100 DEG C, and the exchange recombination process duration is 42 hours.
Embodiment 49:
It is a kind of be used to prepare Organic-inorganic composite semiconductor material pressure differential force exchange complex method, step with
Embodiment 47 is identical, except that:
SnO in step (2)2Heat treatment temperature of the film in high vacuum is 180 DEG C, and vacuum degree is 6 × 10-4Pa；
CuPc has changed polyselenophenes into step (3), and organic semiconductor heating temperature is 160 DEG C, and exchange recombination process is held
The continuous time is 64 hours.
Embodiment 50:
It is a kind of be used to prepare Organic-inorganic composite semiconductor material pressure differential force exchange complex method, step with
Embodiment 47 is identical, except that:
SnO in step (2)2Heat treatment temperature of the film in high vacuum is 250 DEG C, and vacuum degree is 3 × 10-4Pa；
CuPc has changed biphenyl into step (3), and organic semiconductor heating temperature is 190 DEG C, SnO2The temperature of film
120 DEG C are increased to, the exchange recombination process duration is 56 hours.
Embodiment 51:
It is a kind of be used to prepare Organic-inorganic composite semiconductor material pressure differential force exchange complex method, step with
Embodiment 47 is identical, except that:
SnO in step (2)2Heat treatment temperature of the film in high vacuum is 285 DEG C, and vacuum degree is 5 × 10-4Pa；
CuPc has changed pentacene into step (3), and organic semiconductor heating temperature is 230 DEG C, SnO2The temperature of film
180 DEG C are increased to, the exchange recombination process duration is 44 hours.
Embodiment 52:
It is a kind of be used to prepare Organic-inorganic composite semiconductor material pressure differential force exchange complex method, step with
Embodiment 1 is identical, except that:
Porous SnO in step (1)2Semiconductor nano solid, which is changed to, changes TiO into2Porous membrane, TiO2Porous membrane is specifically made
It is standby that steps are as follows:
At room temperature, tetraisopropyl titanate is dissolved in glacial acetic acid (mass content 99.5%), by tetraisopropyl titanate
Then 1.5 milliliters of above-mentioned tetraisopropyl titanate solution are placed in a beaker to 2 mol/Ls, 2 milliliters of isopropyls are added by concentration dilution
Alcohol simultaneously stirs 1 hour, adds 1 milliliter of nitric acid and 2 milliliters of dehydrated alcohols, and stirring obtains TiO in 1 hour2Colloidal sol.It then, will be molten
Glue is spin-coated on porous alumina formwork with 3000 revs/min of speed, and is dried 1 hour at 160 DEG C, then in 600 DEG C of air
Middle calcining 1 hour, can be obtained TiO2Porous membrane.
Embodiment 53:
It is a kind of be used to prepare Organic-inorganic composite semiconductor material pressure differential force exchange complex method, step with
Embodiment 52 is identical, except that:
TiO in step (2)2Heat treatment temperature of the film in high vacuum is 120 DEG C, and vacuum degree is 5 × 10-5Pa；
CuPc has changed Cobalt Phthalocyanine into step (3), and organic semiconductor heating temperature is 280 DEG C, TiO2The temperature of film
145 DEG C are increased to, the exchange recombination process duration is 46 hours.
Embodiment 54:
It is a kind of be used to prepare Organic-inorganic composite semiconductor material pressure differential force exchange complex method, step with
Embodiment 52 is identical, except that:
TiO in step (2)2Heat treatment temperature of the film in high vacuum is 180 DEG C, and vacuum degree is 8 × 10-4Pa；
CuPc has changed polyselenophenes into step (2), and organic semiconductor heating temperature is 160 DEG C, and exchange recombination process is held
The continuous time is 68 hours.
Embodiment 55:
It is a kind of be used to prepare Organic-inorganic composite semiconductor material pressure differential force exchange complex method, step with
Embodiment 52 is identical, except that:
TiO in step (2)2Heat treatment temperature of the film in high vacuum is 260 DEG C, and vacuum degree is 5 × 10-4Pa；
CuPc has changed biphenyl into step (3), and organic semiconductor heating temperature is 180 DEG C, TiO2The temperature of film
130 DEG C are increased to, the exchange recombination process duration is 56 hours.
Embodiment 56:
It is a kind of be used to prepare Organic-inorganic composite semiconductor material pressure differential force exchange complex method, step with
Embodiment 52 is identical, except that:
TiO in step (2)2The heat treatment temperature of film in a vacuum is 280 DEG C, vacuum degree 3 × 10-4Pa；
CuPc has changed pentacene into step (3), and organic semiconductor heating temperature is 200 DEG C, TiO2The temperature of film
155 DEG C are increased to, is exchanged the recombination process duration 36 hours.
Comparative example
According to method disclosed in patent document CN1431169A, by 3.0 grams of SnO2SnO is made in nano particle2Porous nano is solid
Body.Specific step is as follows: at room temperature, weighing 3.0 grams of SnO2Nano particle is placed in ball grinder, then measures 5 milliliters of dioxies six
Ring be added ball grinder, with 180 revs/min revolving speed ball milling 1 hour, fill this blend into hot pressure reaction kettle, seal, with the speed that heats up
Autoclave is heated to 100 DEG C by 2.5 DEG C/min of rate, and constant temperature applies the constant pressure of 60 megapascal after 30 minutes.Later in constant pressure
200 DEG C, and constant temperature 3 hours are heated to same heating rate under power.To hot pressure reaction kettle cooled to room temperature, release pressure
Power.Sample in autoclave is taken out, is sintered 2 hours in 500 DEG C of air, obtains SnO2Porous nanosolids.
Test example 1
In the porous SnO of comparative example preparation2CuPc-SnO prepared by semiconductor nano solid and embodiment 12Porous nano is solid
Metal electrode is coated on bluk recombination semiconductor material surface to get gas sensor.
The CuPc-SnO of embodiment 12Gas sensor such as Fig. 7 institute of Porous nanosolids composite semiconductor material preparation
Show, wherein the small cube of four vertex positions is electrode.
CuPc-SnO prepared by embodiment 12Porous nanosolids composite semiconductor material and the SnO of comparative example preparation2It is more
Test results are shown in figure 8 for the air-sensitive of hole nano-solid.Wherein: (a) CuPc-SnO prepared for embodiment 12Porous nano is solid
The SnO prepared in bluk recombination semiconductor material and comparative example2Porous nanosolids are as gas sensor to 5ppm NO2's
Air-sensitive responds the curve varied with temperature；It (b) is the SnO of comparative example preparation2Porous nanosolids are as gas sensor 140
DEG C to 5ppm NO2Dynamic response curve；(c) CuPc-SnO prepared for embodiment 12Porous nanosolids composite semiconductor material
Material is as gas sensor at 140 DEG C to 5ppm NO2Dynamic response curve.
As shown in Figure 8, CuPc-SnO2Porous nanosolids composite semiconductor material as gas sensing response and
Response-recovery characteristic will be than pure SnO2Porous nanosolids sensor is much better.
Test example 2
Porous SnO prepared by comparative example2CuPc-SnO prepared by semiconductor nano solid and embodiment 12Porous nano is solid
Bluk recombination semiconductor material carries out Hall effect test, and test method is as follows: respectively by SnO in comparative example2Porous nanosolids
With CuPc-SnO in embodiment 12Porous nanosolids composite semiconductor material is cut into the same side of size as shown in Figure 7
Block, and rectangular gold electrode is plated at four vertex positions of the same face；Then respectively by the sample of above-mentioned comparative example and embodiment 1
It is placed in Ecopia HMS3000 Hall effect tester grips, carries out Hall effect test according to instrumentation.
Test result is as shown in table 1:
1 Hall effect result of table
As shown in Table 1, CuPc-SnO2The carrier concentration and mobility of Porous nanosolids composite semiconductor material are high
In the SnO of blank2Porous nanosolids, high carrier concentration and mobility are conducive to highly sensitive gas sensor and answer
Close the development of semiconductor photoelectric device.
Claims (6)
1. a kind of pressure differential for being used to prepare Organic-inorganic composite semiconductor material forces exchange complex method, including step
It is as follows:
(1) by porous metal oxide semiconductor nano solid or porous metal oxide semiconductive thin film, under vacuum conditions,
100-300 DEG C of heat treatment 1-3h；It keeps vacuum state constant, naturally cools to room temperature, obtain the porous metals oxygen of surface cleaning
Compound semiconductor nano solid or porous metal oxide semiconductive thin film；
(2) under vacuum conditions, organic semiconductor is placed in temperature end heating, vaporizes organic semiconductor；Meanwhile by step
(1) the porous metal oxide semiconductor nano solid or porous metal oxide semiconductive thin film of the surface cleaning obtained are in low
Warm end heating；Then, inert gas is passed through from temperature end with 0.01-1.0 liters/min of rate, inert gas carries organic half
The porous metal oxide semiconductor nano solid or porous metal oxide of conductor gas molecule and the surface cleaning of low-temperature end
Exchange recombination reaction occurs for semiconductive thin film, persistently exchanges recombination reaction 8-72 hours, obtains reactant；
It is persistently vacuumized during the exchange recombination reaction, the speed of exhaust is 60 liters/min -90 liters/min；
The organic semiconductor is the polyacetylene that molecular weight is less than or equal to 5000, or is less than or equal to 10000 polyphenyl for molecular weight
Acetylene, or the p-phenylene vinylene for molecular weight less than or equal to 10000, or the polythiophene for molecular weight less than or equal to 10000, or be
Bithiophene, or the polyselenophenes for molecular weight less than or equal to 10000, or be biphenyl, or be acene, or be less than or equal to for molecular weight
10000 polypyrrole, or the polyaniline for molecular weight less than or equal to 10000, or be porphyrin, or be metal phthalocyanine complex, or
For naphthalene cyanines；
The temperature end heating temperature is 150-450 DEG C, and low-temperature end heating temperature is 25-200 DEG C；
(3) reactant for obtaining step (2) in inert gas 100-200 DEG C of annealing 0.5-2h to get organic and inorganic
Composite semiconductor material.
2. the pressure differential according to claim 1 for being used to prepare Organic-inorganic composite semiconductor material forces exchange multiple
Conjunction method, which is characterized in that porous metal oxide semiconductor nano solid or porous metal oxide in the step (1)
Semiconductive thin film is zinc oxide (ZnO), stannic oxide (SnO2), titanium dioxide (TiO2), tungstic acid (WO3), di-iron trioxide
(Fe2O3), indium sesquioxide (In2O3) or ceria (CeO2) porous semi-conductor nano-solid or semiconductor porous film.
3. the pressure differential according to claim 1 for being used to prepare Organic-inorganic composite semiconductor material forces exchange multiple
Conjunction method, which is characterized in that the vacuum degree of vacuum condition is 10 in the step (1) and step (2)-3-10-6Pa.
4. the pressure differential according to claim 1 for being used to prepare Organic-inorganic composite semiconductor material forces exchange multiple
Conjunction method, which is characterized in that bithiophene described in step (2) is simultaneously four thiophene, and five thiophene or hexa-thiophen；The connection
Benzene is quaterphenyl, quinquephenyl or six biphenyl；The acene is anthracene, aphthacene, pentacene or rubrene；The metal phthalocyanine
Complex is CuPc (CuPc), Phthalocyanine Zinc (ZnPc), FePC (FePc), Cobalt Phthalocyanine (CoPc) or phthalocyanine lutetium (LuPc).
5. the pressure differential according to claim 1 for being used to prepare Organic-inorganic composite semiconductor material forces exchange multiple
Conjunction method, which is characterized in that the porous metal oxide semiconductor nano of organic semiconductor and surface cleaning in the step (2)
The mass ratio of solid or porous metal oxide semiconductive thin film is 1:20-1:100.
6. the pressure differential according to claim 1 for being used to prepare Organic-inorganic composite semiconductor material forces exchange multiple
Conjunction method, which is characterized in that the inert gas in the step (2), (3) is argon gas or nitrogen.
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Citations (2)
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| KR100766303B1 (en) * | 2006-05-30 | 2007-10-11 | 주식회사 풍산마이크로텍 | Methods and apparatuses for high pressure gas annealing |
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2017
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100766303B1 (en) * | 2006-05-30 | 2007-10-11 | 주식회사 풍산마이크로텍 | Methods and apparatuses for high pressure gas annealing |
| CN105842290A (en) * | 2016-03-24 | 2016-08-10 | 山东大学 | Inorganic/organic composited gas sensor vacuum on-situ composition method for improving performances of gas sensor |
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