CN104250723B - Chemical method for in-situ large-area controlled synthesis of perovskite type CH3NH3PBI3 membrane material based on lead simple-substance membrane - Google Patents
Chemical method for in-situ large-area controlled synthesis of perovskite type CH3NH3PBI3 membrane material based on lead simple-substance membrane Download PDFInfo
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Abstract
The invention relates to a chemical method for in-situ large-area controlled synthesis of a perovskite type CH3NH3PBI3 membrane material based on a lead simple-substance membrane. The method comprises: sputtering the lead simple-substance membrane on the surface of a substrate, then horizontally immersing the substrate material possessing the lead simple-substance membrane in an organic solution containing a simple substance iodine and iodinated methylamine, and performing a constant-temperature reaction to prepare a CH3NH3PBI3 membrane material in situ; or putting the substrate possessing the lead simple-substance membrane in a steam atmosphere of a simple substance iodine to perform iodination to generate a lead iodide membrane, then immersing in an organic solution containing iodinated methylamine, and performing a constant-temperature reaction to prepare the CH3NH3PBI3 membrane material in situ. The method is simple in operation, low in energy consumption and low in cost, and has wide industrial application prospect. The obtained CH3NH3PBI3 membrane is high in purity, uniform in membrane-surface crystal and excellent in crystallinity.
Description
Technical field
The invention belongs to material chemistry technical field, more particularly, to one kind are based on metallic lead simple substance membrane on different substrates
Original position large area controls synthesis Ca-Ti ore type CH3NH3PbI3The chemical method of thin-film material.
Background technology
Early in eighties of last century, the advantageous property of perovskite is not advantageously, it has been found that but apply in solar cell device.
This kind of material mainly has advantages below：(1), because inorganic constituentss have higher charge carrier mobility and preferable light is inhaled
Receive performance, make the energy loss in photoelectric conversion process extremely low, its theoretical conversion efficiency reaches as high as 50%, be expected to be greatly reduced
The use cost of solaode；(2), building-up process is simple, and inexpensively, more suitable for industrialized production；(3), low temperature bar
Good crystallinity under part, is conducive to carrier diffusion；(4), pass through to change component, its band gap can be regulated and controled, for example, to (RNH3)
MX3The research of perovskite structure shows, the replacement of halogen atom will not change its crystal structure, but enables to its band gap
Regulation and control；(5）, perovskite structure voltage loss low, generally only 0.4eV, similar with crystalline silicon, therefore produce voltage efficiency high；
(6), do not only have higher light capture ability, and good in visual field photo absorption performance, especially absorbing blue and green photon side
Face is more preferable than silicon；(7), perovskite material not only can have been made hole mobile material but also can make electron transport material.2009, Japanese paulownia
The research group of shady Yokohama university palace slope power professor have devised first with perovskite structure CH3NH3PbI3Based on, it is to avoid liquid
The DSSC that state electrolyte uses（DSSC）, and obtained 3.8% photoelectric transformation efficiency.Here basis
On by improving synthetic method, increasing hole and fill out rate, the electron transport material selecting band-gap and the new hole transport material of synthesis
The approach such as material, this efficiency by the rapid lifting of the research groups such as Snaith, Gratzel up till now 17% about.A lot of groups are also
From interface, pattern, defect type, solvent, electrode material, hole mobile material, electron transport material, temperature to crystal structure shadow
The aspects such as sound, thermodynamics, kinetics expand and are extensively studied, to improving the efficiency of the device that perovskite is active layer.Again
When other technologies are also when for breaking through 12% competition, the solaode based on perovskite structure is just opened through a few years development
Beginning holds a safe lead, and occurs from 2009 to the first half of the year in 2014, the quantity published an article more than 165, imitate by its opto-electronic conversion
Rate is approached rapidly or even is broken through 20%, and this is unprecedented speed.People place hope on going out of this new material and are now able to swash
Encourage solaode market low at present to reactivate, and the research and development of the Fashion of Future third generation solar cell and market
Basel Ⅱ Accord.
With regard to CH3NH3PbI3The preparation of perovskite structural material mainly has 3 kinds of methods at present, and one-step method, two-step method are gentle
Phase sedimentation.The specific practice of one-step method is：It is dissolved in the lead iodide of equimolar amountss and iodate methylamine in r- butyrolactone or DMF
It is spun in substrate, 110 DEG C of annealing generate the CH of black for 1 hour3NH3PbI3Thin film.Subsequent Gratzel research group is in two steps
In titanium oxide（TiO2）Upper stacking perovskite structural material, concrete grammar is, first in TiO2Above PbI is prepared by spin coating2Thin film
Layer, is then immersed in CH3NH3Perovskite structure is built in I solution.Profit in this way, can be made with very high repeatability
The higher battery of conversion efficiency（15%）.What is particularly worth mentioning is that in September, 2013 Nature has delivered Regius professor
The newest research results of Snaith seminar, different from the liquid phase spin coating method commonly used before, are prepared for using vapour deposition process
There is the hydridization perovskite of simple flat surface heterojunction structure as absorbed layer, interface special nanostructured need not just obtain and exceed
15% efficiency.The newest research results of Yangyang seminar delivered by December, 2013 American Chemical Society JACS magazine again, with
The full gas phase process of Snaith seminar fine vacuum is different, and they are first in TiO2Upper deposition of passing through prepares PbI2Thin layer, then will
It is placed in the vapor atmosphere with the presence of 150 DEG C of nitrogen of iodate methylamine, and after 2 hours, i.e. reaction generates black
CH3NH3PbI3Thin film, and obtain 12.1% efficiency.The perovskite solaode being built by one-step method is faced with a disaster
Topic, that is, in TiO2The particle diameter of the perovskite material of upper formation is substantially uneven, leads to aberrations in property very big.Up to the present,
The perovskite thin film crystallinity of reported in literature is unsatisfactory.In addition, other methods are also subject to preparation condition up till now mostly（As rotation
Painting, vacuum vapor deposition etc.）Restriction, be difficult to produce larger perovskite continuous film, manufacture in current laboratory based on calcium
The solaode of perovskite like structure is extremely difficult to the large scale of silion cell plate.Finally, as scientists are recognized, due to rotation
Apply the unstability of deposition perovskite thin film surface topography, impact can be produced on resulting devices efficiency, especially difference is deposited into
Film method（One step spin-coating method, two-step method and vapour deposition process）Impact to resulting devices performance is most important.
Content of the invention
The technical problem to be solved is：Overcome current CH3NH3PbI3Deficiency existing for thin film preparation process：
Preparation process complex process, product are impure and are subject to preparation condition（As spin coating, vacuum vapor deposition etc.）Restriction, be difficult to big
The shortcomings of area preparation and production continuous film, device poor repeatability, provide one kind based on metallic lead simple substance membrane big face in situ
Long-pending control synthesizes Ca-Ti ore type CH3NH3PbI3The chemical method of thin-film material, the method is simple to operate, low energy consumption, cost of manufacture
Low, there is wide prospects for commercial application；Gained CH3NH3PbI3Thin film purity is high, film surface crystal is uniform, crystallinity is excellent
Good.
The present invention is adopted the technical scheme that by solving above-mentioned technical problem：
A kind of control based on metallic lead simple substance membrane original position large area synthesizes Ca-Ti ore type CH3NH3PbI3The change of thin-film material
Method it is characterised in that：Sputter lead simple substance membrane in substrate surface, then will have the base material level of lead simple substance membrane
It is soaked in the organic solution containing iodine and iodate methylamine（Iodine and iodate methylamine addition sequence in no particular order, substrate
Material is soaked in below organic solvent liquid level）, isothermal reaction can be obtained CH in situ3NH3PbI3Thin-film material；Or will have lead
The base material of simple substance membrane is put into first iodate in iodine vapor atmosphere and is generated lead iodide（PbI2）Thin film, then immerse iodate first
In the organic solution of amine, isothermal reaction is obtained CH in situ3NH3PbI3Thin-film material.
In such scheme, described reaction temperature is chosen in the range of 0 ~ 40 DEG C；Response time is 20 minutes ~ 12 hours.
In such scheme, described base material is ITO electro-conductive glass, FTO electro-conductive glass, common microscope slide etc..
In such scheme, described ITO electro-conductive glass preferably has the electro-conductive glass of dominant growth crystal face, including 222
Crystal face is the ITO electro-conductive glass of dominant growth crystal face, 400 crystal faces are the ITO electro-conductive glass of dominant growth crystal face, specifically has force
The ITO electro-conductive glass that Han Aoge company produces, dominant growth crystal face is 222 crystal faces, southern glass OLED-10 ITO electro-conductive glass, excellent
Gesture grows crystal face 400 crystal face.It is used as substrate controlledly synthesis tool by selecting the ITO electro-conductive glass with different dominant growth crystal faces
There is the CH of different advantage crystal faces3NH3PbI3Thin film.
In such scheme, affiliated lead simple substance membrane thickness range is 200 ~ 400nm.
In such scheme, the lead simple substance membrane film build method being used is magnetically controlled DC sputtering, evaporation, plating etc..
In such scheme, the described iodine and the organic solvent of iodate methylamine solution prepared is dehydrated alcohol etc..
In such scheme, in the described organic solution containing iodine and iodate methylamine, the concentration range of iodine is
0.0003~0.0007g/ml；The concentration range of iodate methylamine is 0.0050 ~ 0.0150g/ml.
In such scheme, in the organic solution of described iodate methylamine the concentration range of iodate methylamine be 0.0050 ~
0.0150g/ml.
In such scheme, the reaction temperature that described iodate forms lead iodide films is 70 DEG C.
In such scheme, described reaction vessel is the container such as glass beaker, glass culture dish of organic solvent-resistant material
Deng.
In such scheme, product is washed after the completion of including reaction by described method with isopropanol, then dry through 40 ~ 70 DEG C
Dry process.
The present invention adopts in-situ synthetic method, by sputtering have different-thickness elementary lead base material immerse containing iodine,
Iodate methylamine (CH3NH3I, in organic solution), get final product a step through simple solution soaking at room temperature and generate Ca-Ti ore type
CH3NH3PbI3Semiconductor light conductive film；Or it is first placed into simple substance iodine vapor by sputtering the base material having different-thickness elementary lead
In atmosphere, iodate generates lead iodide（PbI2）Thin film, then lead iodide films are immersed in the ethanol solution of iodate methylamine, warp
Cross two steps and generate Ca-Ti ore type CH3NH3PbI3Thin film.Almost Non-energy-consumption in the method whole preparation process, solvent is cheap and easy to get,
Nontoxic, whole process adopts the container of organic solvent-resistant material, size without using any poisonous solvent, reaction vessel
And shape is not particularly limited, the solvent being used can reuse.Gained CH3NH3PbI3Thin film purity is high, uniform, crystallinity
Excellent, surface topography and micro structure are stablized controlled, particularly can control and prepare dominant growth crystal face of thin film etc. in situ.The party
Method reaction is efficient, simple to operate, will be perovskite structure CH3NH3PbI3The application of semiconductor optoelectronic thin-film material provides important
Technical support, has extensive laboratory preparation and prospects for commercial application.
Advantages of the present invention：
1st, can react under 0 ~ 40 DEG C of room temperature condition, mild condition, course of reaction is controlled, easy to operate, reaction is quick,
Almost Non-energy-consumption.
2nd, reaction in-situ direct formation of film at surface can be passed through in substrate surface, be easy to subsequent optical electric performance test, and will not be to ITO
Damage etc. conductive substrates.Prepared thin film macroscopic view geometry controlled it is not necessary to spin coating process, can large area preparation, energy
Enough realize large-size device to make, device repeatability can significantly improve.
3rd, gained CH3NH3PbI3Thin film purity is high, film surface crystal uniformly, excellent in crystallinity, plane of crystal pattern and
Micro structure is stablized controlled.
4th, pass through to control the conditions such as lead simple substance membrane thickness, response time, temperature and different base, can control well
CH processed3NH3PbI3The pattern of thin-film material, size, thickness, crystalline phase, have different dominant growth crystal faces especially by selecting
Base material can control preparation CH in situ3NH3PbI3The dominant growth crystal face of thin film.
5th, the solvent that the method uses is cheap and easy to get, nontoxic, and whole process is held without using any poisonous solvent, reaction
Device adopts glass or organic solvent-resistant material, size and shape to be not particularly limited（As long as can seal）, made
Solvent can reuse, and the application for perovskite structure semiconductor optoelectronic thin-film material is provided important technology to prop up
Hold, there is extensive laboratory preparation and prospects for commercial application.
Brief description
Fig. 1,2：The CH of embodiment 1 preparation3NH3PbI3The XRD figure of optoelectronic thin film material, electron micrograph；
Fig. 3,4：The CH of embodiment 2 preparation3NH3PbI3The XRD figure of optoelectronic thin film material, electron micrograph；
Fig. 5,6：The CH of embodiment 3 preparation3NH3PbI3The XRD figure of optoelectronic thin film material, electron micrograph；
Fig. 7,8：The CH of embodiment 4 preparation3NH3PbI3The XRD figure of optoelectronic thin film material, electron micrograph；
Fig. 9,10：The CH of embodiment 5 preparation3NH3PbI3The XRD figure of optoelectronic thin film material, electron micrograph；
Figure 11,12：The CH of embodiment 6 preparation3NH3PbI3The XRD figure of optoelectronic thin film material, electron micrograph；
Figure 13,14：The CH of embodiment 7 preparation3NH3PbI3The XRD figure of optoelectronic thin film material, electron micrograph；
Figure 15：The CH of embodiment 8 preparation3NH3PbI3The XRD figure of optoelectronic thin film material；
Figure 16,17,18：The CH of embodiment 8 preparation3NH3PbI3The electron micrograph of optoelectronic thin film material；
Figure 19：The CH of embodiment 9 preparation3NH3PbI3The XRD figure of optoelectronic thin film material；
Figure 20,21：The CH of embodiment 9 preparation3NH3PbI3The electron micrograph of optoelectronic thin film material；
Figure 22：The CH of embodiment 10 preparation3NH3PbI3The XRD figure of optoelectronic thin film material；
Figure 23,24：The CH of embodiment 11 preparation3NH3PbI3The XRD figure of optoelectronic thin film material, electron micrograph；
Figure 25,26：The CH of embodiment 12 preparation3NH3PbI3The XRD figure of optoelectronic thin film material, electron micrograph；
Figure 27,28：The CH of embodiment 13 preparation3NH3PbI3The XRD figure of optoelectronic thin film material, electron micrograph；
Figure 29,30：The CH of embodiment 14 preparation3NH3PbI3The XRD figure of optoelectronic thin film material, electron micrograph；
Figure 31,32：The CH of embodiment 15 preparation3NH3PbI3The XRD figure of optoelectronic thin film material, electron micrograph；
Figure 33,34：(222) crystal face is that dominant growth is brilliant for the ITO-1 electro-conductive glass of dominant growth crystal face, (400) crystal face
The XRD figure of the ITO-2 electro-conductive glass in face.
Specific embodiment
Embodiment 1
（1）Preparation：By ITO electro-conductive glass（Wuhan Austria lattice：222 crystal faces are dominant growth crystal face）Vacuum be 4 ~
6×10-3During mbar, magnetically controlled DC sputtering a layer thickness is about the metallic lead simple substance membrane of 400nm, is then placed on standby in exsiccator
With；Beaker is used tap water, distilled water wash successively, stand-by after being dried；
（2）Reactions steps：In beaker, configuration iodate methylamine concentration is 0.0100g/ml, and elemental iodine concentration is 0.0007g/
Then beaker is put in constant temperature to 15 DEG C in the device such as biochemical cultivation case have temperature controlling function by the ethanol solution of ml,
The substrate of glass with metallic lead simple substance membrane surface is put in reactant liquor, and 15 DEG C are reacted 1 hour；
（3）Post processing：After reaction terminates, close biochemical cultivation case, sample is taken out, is placed in 70 DEG C of air dry oven
Dry.By the CH obtaining3NH3PbI3Thin-film material sample carefully proceeds in sample bottle, preserves in lucifuge, dry environment.Produce
Product color is black.XRD is as shown in figure 1, as seen from Figure 1：110 crystal faces are dominant growth crystal face, excellent in crystallinity；Electronic display
Fig. 2 is shown in by micro- photo, as seen from Figure 2：Film surface crystal grain is sparse, about 2 μm of size.
Embodiment 2
（1）Preparation：By ITO electro-conductive glass（Wuhan Austria lattice, 222 crystal faces are dominant growth crystal face）Vacuum be 4 ~
6×10-3During mbar, magnetically controlled DC sputtering a layer thickness is about the metallic lead simple substance membrane of 400nm, is then placed on standby in exsiccator
With；Beaker is used tap water, distilled water wash successively, stand-by after being dried；
（2）Reactions steps：In beaker, configuration iodate methylamine concentration is 0.0100g/ml, and elemental iodine concentration is 0.0007g/
Then beaker is put in constant temperature to 15 DEG C in the device such as biochemical cultivation case have temperature controlling function by the ethanol solution of ml,
The substrate of glass with metallic lead simple substance membrane surface is put in reactant liquor, and 15 DEG C are reacted 2 hours；
（3）Post processing：After reaction terminates, close biochemical cultivation case, sample is taken out, is placed in 70 DEG C of air dry oven
Dry.By the CH obtaining3NH3PbI3Thin-film material sample carefully proceeds in sample bottle, preserves in lucifuge, dry environment.Produce
Product color is black.XRD is as shown in figure 3, as seen from Figure 3：110 crystal faces are dominant growth crystal face, excellent in crystallinity；Electronic display
Fig. 4 is shown in by micro- photo, as seen from Figure 4：Film surface crystal is comparatively dense, about 2 ~ 6 μm of size.
Embodiment 3
（1）Preparation：By ITO electro-conductive glass（Wuhan Austria lattice, 222 crystal faces are dominant growth crystal face）Vacuum be 4 ~
6×10-3During mbar, magnetically controlled DC sputtering a layer thickness is about the metallic lead simple substance membrane of 400nm, is then placed on standby in exsiccator
With；Beaker is used tap water, distilled water wash successively, stand-by after being dried；
（2）Reactions steps：In beaker, configuration iodate methylamine concentration is 0.0100g/ml, and elemental iodine concentration is 0.0007g/
Then beaker is put in constant temperature to 15 DEG C in the device such as biochemical cultivation case have temperature controlling function by the ethanol solution of ml,
The substrate of glass with metallic lead simple substance membrane surface is put in reactant liquor, and 15 DEG C are reacted 3 hours；
（3）Post processing：After reaction terminates, close biochemical cultivation case, sample is taken out, is placed in 70 DEG C of air dry oven
Dry.By the CH obtaining3NH3PbI3Thin-film material sample carefully proceeds in sample bottle, preserves in lucifuge, dry environment.Produce
Product color is black.XRD is as shown in figure 5, as seen from Figure 5：110 crystal faces are dominant growth crystal face, excellent in crystallinity；Electronic display
Fig. 6 is shown in by micro- photo, as seen from Figure 6：Film surface crystal even compact, about 2 ~ 4 μm of size.
Embodiment 4
（1）Preparation：By ITO electro-conductive glass（Wuhan Austria lattice, 222 crystal faces are dominant growth crystal face）Vacuum be 4 ~
6×10-3During mbar, magnetically controlled DC sputtering a layer thickness is about the metallic lead simple substance membrane of 400nm, is then placed on standby in exsiccator
With；Beaker is used tap water, distilled water wash successively, stand-by after being dried；
（2）Reactions steps：In beaker, configuration iodate methylamine concentration is 0.0150g/ml, and elemental iodine concentration is 0.0007g/
Then beaker is put in constant temperature to 15 DEG C in the device such as biochemical cultivation case have temperature controlling function by the ethanol solution of ml,
The substrate of glass with metallic lead simple substance membrane surface is put in reactant liquor, and 15 DEG C are reacted 4 hours；
（3）Post processing：After reaction terminates, close biochemical cultivation case, sample is taken out, is placed in 70 DEG C of air dry oven
Dry.By the CH obtaining3NH3PbI3Thin-film material sample carefully proceeds in sample bottle, preserves in lucifuge, dry environment.Produce
Product color is black.XRD is as shown in fig. 7, as seen from Figure 7：110 crystal faces are dominant growth crystal face, excellent in crystallinity；Electronic display
Fig. 8 is shown in by micro- photo, as seen from Figure 8：Film surface crystal even compact, about 2 ~ 4 μm of size.
Embodiment 5
（1）Preparation：By ITO electro-conductive glass（Wuhan Austria lattice, 222 crystal faces are dominant growth crystal face）Vacuum be 4 ~
6×10-3During mbar, magnetically controlled DC sputtering a layer thickness is about the metallic lead simple substance membrane of 400nm, is then placed on standby in exsiccator
With；Beaker is used tap water, distilled water wash successively, stand-by after being dried；
（2）Reactions steps：In beaker, configuration iodate methylamine concentration is 0.0150g/ml, and elemental iodine concentration is 0.0007g/
Then beaker is put in constant temperature to 15 DEG C in the device such as biochemical cultivation case have temperature controlling function by the ethanol solution of ml,
The substrate of glass with metallic lead simple substance membrane surface is put in reactant liquor, and 15 DEG C are reacted 1 hour；
（3）Post processing：After reaction terminates, close biochemical cultivation case, sample is taken out, is placed in 70 DEG C of air dry oven
Dry.By the CH obtaining3NH3PbI3Thin-film material sample carefully proceeds in sample bottle, preserves in lucifuge, dry environment.Produce
Product color is black.XRD is as shown in figure 9, as seen from Figure 9：110 crystal faces are dominant growth crystal face, excellent in crystallinity；Electronic display
Figure 10 is shown in by micro- photo, as seen from Figure 10：Film surface crystal more even compact, particle diameter substantially diminishes, about 1 ~ 2 μm.
Embodiment 6
（1）Preparation：By ITO electro-conductive glass（Wuhan Austria lattice, 222 crystal faces are dominant growth crystal face）Vacuum be 4 ~
6×10-3During mbar, magnetically controlled DC sputtering a layer thickness is about the metallic lead simple substance membrane of 400nm, is then placed on standby in exsiccator
With；Beaker is used tap water, distilled water wash successively, stand-by after being dried；
（2）Reactions steps：In beaker, configuration iodate methylamine concentration is 0.0050g/ml, and elemental iodine concentration is 0.0007g/
Then beaker is put in constant temperature to 15 DEG C in the device such as biochemical cultivation case have temperature controlling function by the ethanol solution of ml,
The substrate of glass with metallic lead simple substance membrane surface is put in reactant liquor, and 15 DEG C are reacted 1 hour；
（3）Post processing：After reaction terminates, close biochemical cultivation case, sample is taken out, is placed in 70 DEG C of air dry oven
Dry.By the CH obtaining3NH3PbI3Thin-film material sample carefully proceeds in sample bottle, preserves in lucifuge, dry environment.Produce
Product color is black.XRD is as shown in figure 11, as seen from Figure 11：110 crystal faces are dominant growth crystal face, excellent in crystallinity；Electronics
Microphotograph is shown in Figure 12, as seen from Figure 12：Film surface crystal more even compact, about 2 ~ 3 μm of size.
Embodiment 7
（1）Preparation：By ITO electro-conductive glass（Wuhan Austria lattice, 222 crystal faces are dominant growth crystal face）Vacuum be 4 ~
6×10-3During mbar, magnetically controlled DC sputtering a layer thickness is about the metallic lead simple substance membrane of 200nm, is then placed on standby in exsiccator
With；Beaker is used tap water, distilled water wash successively, stand-by after being dried；
（2）Reactions steps：In beaker, configuration iodate methylamine concentration is 0.0150g/ml, and elemental iodine concentration is 0.0007g/
Then beaker is put in constant temperature to 25 DEG C in the device such as biochemical cultivation case have temperature controlling function by the ethanol solution of ml,
The substrate of glass with metallic lead simple substance membrane surface is put in reactant liquor, and 25 DEG C are reacted 1 hour；
（3）Post processing：After reaction terminates, close biochemical cultivation case, sample is taken out, is placed in 70 DEG C of air dry oven
Dry.By the CH obtaining3NH3PbI3Thin-film material sample carefully proceeds in sample bottle, preserves in lucifuge, dry environment.Produce
Product color is black.XRD is as shown in figure 13, as seen from Figure 13：110 crystal faces are dominant growth crystal face, excellent in crystallinity；Electronics
Microphotograph is shown in Figure 14, as seen from Figure 14：Film surface crystal more even compact, about 1 ~ 3 μm of size.
Embodiment 8
（1）Preparation：By FTO glass（Wuhan Austria lattice）It is 4 ~ 6 × 10 in vacuum-3Magnetically controlled DC sputtering one during mbar
Thickness degree is about the metallic lead simple substance membrane of 400nm, is then placed on standby in exsiccator；Beaker is used successively tap water, distillation
Water washing, stand-by after being dried；
（2）Reactions steps：In beaker, configuration iodate methylamine concentration is 0.0100g/ml, and elemental iodine concentration is 0.0007g/
Then beaker is put in constant temperature to 30 DEG C in the device such as biochemical cultivation case have temperature controlling function by the ethanol solution of ml,
The substrate of glass with metallic lead simple substance membrane surface is put in reactant liquor, and 30 DEG C are reacted 2 hours；
（3）Post processing：After reaction terminates, close biochemical cultivation case, sample is taken out, is placed in 70 DEG C of air dry oven
Dry.By the CH obtaining3NH3PbI3Thin-film material sample carefully proceeds in sample bottle, preserves in lucifuge, dry environment.Produce
Product color is black.XRD is as shown in figure 15, as seen from Figure 15：Excellent in crystallinity；Electron micrograph is shown in Figure 16,17,18,
Be can be seen that by Figure 16,17,18：Film surface crystal even compact, particle diameter is larger, about 5 μm.
Embodiment 9
（1）Preparation：By ITO electro-conductive glass（Southern glass OLED-10,400 crystal faces are dominant growth crystal face）In vacuum
For 7 × 10-3During mbar, magnetically controlled DC sputtering a layer thickness is about the metallic lead simple substance membrane of 400nm, is then placed in exsiccator
Standby；Beaker is used tap water, distilled water wash successively, stand-by after being dried；
（2）Reactions steps：In beaker, configuration iodate methylamine concentration is 0.0150g/ml, and elemental iodine concentration is 0.0007g/
Then beaker is put in constant temperature to 25 DEG C in the device such as biochemical cultivation case have temperature controlling function by the ethanol solution of ml,
The substrate of glass with metallic lead simple substance membrane surface is put in reactant liquor, and 25 DEG C are reacted 1 hour；
（3）Post processing：After reaction terminates, close biochemical cultivation case, sample is taken out, is placed in 70 DEG C of air dry oven
Dry.By the CH obtaining3NH3PbI3Thin-film material sample carefully proceeds in sample bottle, preserves in lucifuge, dry environment.Produce
Product color is black.XRD is as shown in figure 19, as seen from Figure 19：112 crystal faces are dominant growth crystal face, almost monocrystalline, crystallization
Property is excellent；Electron micrograph see Figure 20,21, by Figure 20,21 can be seen that：Film surface crystal is uniform, size about 4 ~ 6 μ
M, and single plane of crystal is porous secondary structure.
Embodiment 10
（1）Preparation：By ITO electro-conductive glass（Southern glass OLED-10,400 crystal faces are dominant growth crystal face）In vacuum
For 7 × 10-3During mbar, magnetically controlled DC sputtering a layer thickness is about the metallic lead simple substance membrane of 400nm, iodine in 70 DEG C of iodine vapors
Chemical conversion lead iodide（PbI2）Thin film, is then placed on standby in exsiccator；Beaker is used tap water, distilled water wash successively, is dried
Stand-by afterwards；
（2）Reactions steps：In beaker, configuration iodate methylamine concentration is the ethanol solution of 0.0150g/ml, then will
Beaker is put in constant temperature to 25 DEG C in the device such as biochemical cultivation case have temperature controlling function,（1）In obtain to have lead iodide thin
The substrate of glass on film surface is put in reactant liquor, and 25 DEG C are reacted 20 minutes；
（3）Post processing：After reaction terminates, close biochemical cultivation case, sample is taken out, is placed in 70 DEG C of air dry oven
Dry.By the CH obtaining3NH3PbI3Thin-film material sample carefully proceeds in sample bottle, preserves in lucifuge, dry environment.Produce
Product color is black.XRD is as shown in figure 22, as seen from Figure 22：112 crystal faces are dominant growth crystal face, excellent in crystallinity；Electronics
Microphotograph and embodiment 9 are similar.
Embodiment 11
（1）Preparation：By ITO electro-conductive glass（Wuhan Austria lattice, 222 crystal faces are dominant growth crystal face）Vacuum be 4 ~
6×10-3During mbar, magnetically controlled DC sputtering a layer thickness is about the metallic lead simple substance membrane of 400nm, is then placed on standby in exsiccator
With；Beaker is used tap water, distilled water wash successively, stand-by after being dried；
（2）Reactions steps：In beaker, configuration iodate methylamine concentration is 0.0100g/ml, and elemental iodine concentration is 0.0005g/
Then beaker is put in constant temperature to 0 DEG C in the device such as biochemical cultivation case have temperature controlling function by the ethanol solution of ml, tool
The substrate of glass having metallic lead simple substance membrane surface is put in reactant liquor, and 0 DEG C is reacted 2 hours；
（3）Post processing：After reaction terminates, close biochemical cultivation case, sample is taken out, is placed in 70 DEG C of air dry oven
Dry.By the CH obtaining3NH3PbI3Thin-film material sample carefully proceeds in sample bottle, preserves in lucifuge, dry environment.Produce
Product color is black.XRD is as shown in figure 23, as seen from Figure 23：110 crystal faces are dominant growth crystal face, excellent in crystallinity；Electronics
Microphotograph is shown in Figure 24, as seen from Figure 24：About 1 ~ 2 μm of film surface crystal particle diameter size.
Embodiment 12
（1）Preparation：By ITO electro-conductive glass（Wuhan Austria lattice, 222 crystal faces are dominant growth crystal face）Vacuum be 4 ~
6×10-3During mbar, magnetically controlled DC sputtering a layer thickness is about the metallic lead simple substance membrane of 400nm, is then placed on standby in exsiccator
With；Beaker is used tap water, distilled water wash successively, stand-by after being dried；
（2）Reactions steps：In beaker, configuration iodate methylamine concentration is 0.0100g/ml, and elemental iodine concentration is 0.0007g/
Then beaker is put in constant temperature to 25 DEG C in the device such as biochemical cultivation case have temperature controlling function by the ethanol solution of ml,
The substrate of glass with metallic lead simple substance membrane surface is put in reactant liquor, and 25 DEG C are reacted 12 hours；
（3）Post processing：After reaction terminates, close biochemical cultivation case, sample is taken out, is placed in 70 DEG C of air dry oven
Dry.By the CH obtaining3NH3PbI3Thin-film material sample carefully proceeds in sample bottle, preserves in lucifuge, dry environment.Produce
Product color is black.XRD is as shown in figure 25, as seen from Figure 25：110 crystal faces are dominant growth crystal face, excellent in crystallinity；Electronics
Microphotograph is shown in Figure 26, as seen from Figure 26：Film surface crystal grain is sparse, size about 1 ~ 6um.
Embodiment 13
（1）Preparation：By ITO electro-conductive glass（Wuhan Austria lattice, 222 crystal faces are dominant growth crystal face）Vacuum be 4 ~
6×10-3During mbar, magnetically controlled DC sputtering a layer thickness is about the metallic lead simple substance membrane of 400nm, is then placed on standby in exsiccator
With；Beaker is used tap water, distilled water wash successively, stand-by after being dried；
（2）Reactions steps：In beaker, configuration iodate methylamine concentration is 0.0100g/ml, and elemental iodine concentration is 0.0003g/
Then beaker is put in constant temperature to 40 DEG C in the device such as biochemical cultivation case have temperature controlling function by the ethanol solution of ml,
The ITO electro-conductive glass substrate with metallic lead simple substance membrane surface is put in reactant liquor, and 40 DEG C are reacted 1 hour；
（3）Post processing：After reaction terminates, close biochemical cultivation case, sample is taken out, is placed in 70 DEG C of air dry oven
Dry.By the CH obtaining3NH3PbI3Thin-film material sample carefully proceeds in sample bottle, preserves in lucifuge, dry environment.Produce
Product color is black.XRD is as shown in figure 27, as seen from Figure 27：110 crystal faces are dominant growth crystal face, excellent in crystallinity；Electronics
Microphotograph is shown in Figure 28, as seen from Figure 28：Film surface crystal even compact, about 4 μm of size.
Embodiment 14
（1）Preparation：By ITO electro-conductive glass（Wuhan Austria lattice, 222 crystal faces are dominant growth crystal face）Vacuum be 4 ~
6×10-3During mbar, magnetically controlled DC sputtering a layer thickness is about the metallic lead simple substance membrane of 400nm, is then placed on standby in exsiccator
With；Beaker is used tap water, distilled water wash successively, stand-by after being dried；
（2）Reactions steps：In beaker, configuration iodate methylamine concentration is 0.0100g/ml, and elemental iodine concentration is 0.0005g/
Then beaker is put in constant temperature to 40 DEG C in the device such as biochemical cultivation case have temperature controlling function by the ethanol solution of ml,
The substrate of glass with metallic lead simple substance membrane surface is put in reactant liquor, and 40 DEG C are reacted 1 hour；
（3）Post processing：After reaction terminates, close biochemical cultivation case, sample is taken out, is placed in 70 DEG C of air dry oven
Dry.By the CH obtaining3NH3PbI3Thin-film material sample carefully proceeds in sample bottle, preserves in lucifuge, dry environment.Produce
Product color is black.XRD is as shown in figure 29, as seen from Figure 29：110 crystal faces are dominant growth crystal face, excellent in crystallinity；Electronics
Microphotograph is shown in Figure 30, as seen from Figure 30：Film surface crystal is uniform, about 2 ~ 4 μm of size.
Embodiment 15
（1）Preparation：By sailing boat board：The common microscope slide of CAT.NO.7101 is 7 × 10 in vacuum-3Direct current during mbar
Magnetron sputtering a layer thickness is about the metallic lead simple substance membrane of 400nm, is then placed on standby in exsiccator；Beaker is used certainly successively
Water, distilled water wash, stand-by after being dried；
（2）Reactions steps：In beaker, configuration iodate methylamine concentration is 0.0100g/ml, and elemental iodine concentration is 0.0007g/
Then beaker is put in constant temperature to 25 DEG C in the device such as biochemical cultivation case have temperature controlling function by the ethanol solution of ml,
The substrate of glass with metallic lead simple substance membrane surface is put in reactant liquor, and 25 DEG C are reacted 12 hours；
（3）Post processing：After reaction terminates, close biochemical cultivation case, sample is taken out, is placed in 70 DEG C of air dry oven
Dry.By the CH obtaining3NH3PbI3Thin-film material sample carefully proceeds in sample bottle, preserves in lucifuge, dry environment.Produce
Product color is black.XRD is as shown in figure 31, as seen from Figure 31：110 crystal faces are dominant growth crystal face, excellent in crystallinity；Electronics
Microphotograph is shown in Figure 32, as seen from Figure 32：Film surface crystal is fine and close, lack of homogeneity, about 1 ~ 6 μm of size.
Two kinds of ITO electro-conductive glass used in above-described embodiment（Wuhan Austria lattice, ITO electro-conductive glass and Nan Bo OLED-10,
ITO electro-conductive glass）Corresponding XRD is shown in Figure 33 and Figure 34 respectively.By Figure 33,34 can be seen that：The ITO conduction glass that Wuhan Austria lattice produce
The dominant growth crystal face of glass is 222 crystal faces；Southern glass OLED-10：ITO electro-conductive glass dominant growth crystal face be 400 crystal faces.
Claims (11)
1. a kind of control based on metallic lead simple substance membrane original position large area synthesizes Ca-Ti ore type CH3NH3PbI3The chemistry of thin-film material
Method it is characterised in that：Sputter lead simple substance membrane in substrate surface, then the base material level with lead simple substance membrane is soaked
Steep in the organic solution containing iodine and iodate methylamine, isothermal reaction can be obtained CH in situ3NH3PbI3Thin-film material；Or
The base material with lead simple substance membrane is put into first iodate in iodine vapor atmosphere and generates lead iodide films, then immerse iodate
In the organic solution of methylamine, isothermal reaction is obtained CH in situ3NH3PbI3Thin-film material.
2. chemical method according to claim 1 it is characterised in that：Described reaction temperature is selected in the range of 0 ~ 40 DEG C
Take；Response time is 20 minutes ~ 12 hours.
3. chemical method according to claim 1 it is characterised in that：Described base material is ITO electro-conductive glass, FTO
Electro-conductive glass, common microscope slide.
4. chemical method according to claim 1 it is characterised in that：Described ITO electro-conductive glass preferably has advantage
The electro-conductive glass of growth crystal face, including（222）Crystal face be dominant growth crystal face ITO electro-conductive glass,（400）Crystal face is given birth to for advantage
The ITO electro-conductive glass of long crystal face.
5. chemical method according to claim 4 it is characterised in that：Described lead simple substance membrane thickness range be 200 ~
400nm.
6. chemical method according to claim 1 it is characterised in that：The lead simple substance membrane film build method being used is direct current
Magnetron sputtering, evaporation, plating.
7. chemical method according to claim 1 it is characterised in that：Prepare the organic molten of iodine and iodate methylamine solution
Agent is dehydrated alcohol.
8. chemical method according to claim 1 it is characterised in that：Described organic molten containing iodine and iodate methylamine
In liquid, the concentration range of iodine is 0.0003 ~ 0.0007g/ml；The concentration range of iodate methylamine is 0.0050 ~ 0.0150g/
ml.
9. chemical method according to claim 1 it is characterised in that：Iodate methylamine in the organic solution of described iodate methylamine
Concentration range be 0.0050 ~ 0.0150g/ml.
10. chemical method according to claim 1 it is characterised in that：Described iodate forms the reaction temperature of lead iodide films
Spend for 70 DEG C.
11. chemical methodes according to claim 1 it is characterised in that：Described method is included product after the completion of reaction
Washed with isopropanol, then through 40 ~ 70 DEG C of dried.
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