CN108502918A - A kind of synthetic method of inorganic perovskite nano wire - Google Patents
A kind of synthetic method of inorganic perovskite nano wire Download PDFInfo
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Abstract
The present invention is a kind of synthetic method of inorganic perovskite nano wire.Length has been made up to several millimeters using solvent-thermal method and anion exchange method in this method at a lower temperature, and diameter is only the CsPbBr of the superelevation draw ratio of 10 rans3Nano wire, and obtain CsPbI by simple anion exchange procedures3And CsPbCl3Nano wire.This largely prepares inorganic perovskite nano wire with effect is greatly facilitated for industrialization, is expected to be further implemented in the application of photodetection, laser and solar cell etc..The present invention is simply controllable, and yield is high, and pattern is uniform, and reaction temperature is relatively low, is suitble to large-scale production.
Description
Technical field
The present invention relates to a kind of synthetic method of inorganic perovskite nano wire, specially a kind of CsPbX of superelevation draw ratio3
The synthetic method of (X=Cl, Br, I) nano wire belongs to new material preparation and field of nanometer technology.
Background technology
Inorganic perovskite CsPbX3(X=Cl, Br, I) is nanocrystalline because having higher fluorescence quantum efficiency, and emission wavelength can
It adjusts and covers the excellent photoelectric characteristics such as entire visible spectrum (400-700nm) and high absorption coefficient in light emitting diode, too
Positive energy battery and photodetection etc. fields have a wide range of applications.Wherein one-dimensional inorganic perovskite nano wire is because of its unique structure
Feature, such as the features such as light conductive performance is excellent, and transverse conduction is good either in solar cell still in photodetection side
Face all has larger application prospect, therefore probes into inorganic perovskite nano wire synthetic method grinding as numerous researchers
Study carefully direction.Inorganic perovskite CsPbX is prepared at present3The synthetic method of nano wire mainly has hot injection method, recrystallization and chemistry
Vapour deposition process (CVD).Wherein hot injection method (Muhammad I, Francesco Di S, Zhiya Dang, et
Al.Chem.Mater.2016,28,6450 it is on the basis of synthesizing inorganic perovskite quantum dot) to be prepared into perovskite nano wire
Change reaction condition acquisition (Dandan Z, Samuel W.E, Yi Yu, et al.J.Am.Chem.Soc.2015,137,
9230).The synthetic method is limited in that：Experimental implementation is comparatively laborious, needs dehydration and inert atmosphere, and be prepared
Nano wire yield it is relatively low, therefore, it is difficult to realize prepare with scale.Patent《A kind of recrystallization prepares lead halogen perovskite nano wire
Method》(patent publication No. CN 106629835A) reports recrystallization and prepares lead halogen perovskite CsPbI3Nano wire, first
The presoma of nano wire is spin-coated in substrate, the mixed solvent of undesirable solvent and polar non-solute is then added, with
Perovskite CsPbI is prepared under high temperature annealing condition afterwards3Nano wire.But this recrystallization mode does not prepare
CsPbBr3And CsPbCl3Nano wire, and the preparation process needs higher annealing temperature, and can be due to rotation in a large amount of prepare
Apply final pattern that is uneven and influencing nano wire.Chemical vapor deposition CVD method prepares perovskite nano wire《A kind of nanometer of ruler
Spend the preparation method of laser array》Diameter 200-800nm has been prepared in (patent publication No. CN 107104357A), and length is
The perovskite nano wire of 10-80 μm of plane interior orientation arrangement.Pan An practices seminar's also system in the way of chemical vapor deposition
It is standby to have obtained the CsPbBr of planar directed alignment3Overlong nanowire (Muhammad S, Xuehong Z, Xiaoxia W, et
Al.J.Am.Chem.Soc, 2017,139,15592), and assemble and obtained the photodetector with quick response.But it should
Method will use the sapphire of price costly as substrate, need higher heating temperature and venting process, therefore the party
Method still has certain limitation for largely preparing inorganic perovskite nano wire.
Patent " a kind of synthetic method of inorganic perovskite nanometer sheet " (publication number CN107522225A), uses solvent heat
Method, cesium carbonate is added in mixed solution to (volume ratio of octadecylene and oleic acid is 7 first:1) presoma of caesium, is formed
Solution, the wherein molar concentration of caesium are 0.15-0.20mol/L；Metal halide lead is then added in mixed solution (18
Alkene：Oleic acid：The volume ratio of oleyl amine is 7:1:1) precursor solution of lead halide, is formed, the molar concentration of wherein lead halide is
0.07-0.10mol/L；Then by the precursor solution of the presoma of above-mentioned caesium and lead halide with volume ratio 1:9-1:15 mixing,
It reacts in a kettle, has obtained the perovskite CsPbX of sheet3Nanometer sheet.Although the patent realizes CsPbX3Nanometer sheet can
Control synthesis, but the CsPbX obtained3Nanometer tablet stability is poor, and can not realize one by existing technical parameter
Victoria C sPbX3The controlledly synthesis of nano wire.A kind of patent " caesium lead halogen Cs4PbX6Nanocrystalline synthetic method " (application number
201810126310.6) solvent-thermal method, is also used, wherein cesium carbonate is added in mixed solution (octadecylene and oil first
The volume ratio of acid is 4:1) precursor solution of caesium, is formed, the wherein molar concentration of caesium is 0.30-0.45mol/L；It then will be golden
Belong to lead halide and is added in mixed solution (octadecylene：Oleic acid：The volume ratio of oleyl amine is 10:1:1) presoma of lead halide, is formed
Solution, the wherein molar concentration of lead halide are 0.08-0.12mol/L；Then by the forerunner of the presoma of above-mentioned caesium and lead halide
Liquid solution is with volume ratio 1:4-1:2 mixing, react in a kettle, then centrifuge, washing, and drying has simultaneously obtained solid powder
Cs4PbX6It is nanocrystalline.The patent is realized to Cs4PbX6Nanocrystalline controlledly synthesis, but existing technical parameter reality can not be passed through
The controlledly synthesis of existing one-dimensional nano line.
Invention content
The present invention is directed to and prepares perovskite CsPbX at present3The low-yield of nanowire approach, the complexity of experimentation are high
The deficiencies of warm processing procedure and high cost, provides a kind of inorganic perovskite CsPbX3The synthesis side of (X=Cl, Br, I) nano wire
Method.Length has been made up to several millimeters using solvent-thermal method and anion exchange method in this method at a lower temperature, and diameter is only
The nano wire of the superelevation draw ratio of 10 rans, and obtain CsPbI by simple anion exchange procedures3And CsPbCl3
Nano wire, this largely prepares inorganic perovskite nano wire with effect is greatly facilitated for industrialization, is expected to further realize
In the application of photodetection, laser and solar cell etc..The present invention is simply controllable, and yield is high, and pattern is uniform, reaction temperature
Spend relatively low, suitable large-scale production.
The technical scheme is that：
A kind of synthetic method of inorganic perovskite nano wire, includes the following steps：
Step 1, by cesium carbonate (Cs2CO3) be added in mixed liquor A, 15-35min is stirred at 110-160 DEG C, then certainly
It is so cooled to room temperature, forms the precursor solution of caesium；
Wherein, mixed solution A is made of oleic acid and octadecylene, wherein volume ratio oleic acid：Octadecylene=1:8；Before caesium
It drives in liquid solution, the molar concentration of caesium is 0.12-0.25mol/L；
Step 2, by lead bromide (PbBr2) be added in mixed solution B, 15-35min is stirred at 90-130 DEG C, then
It is cooled to room temperature under conditions of ice-water bath, forms the precursor solution of lead bromide；
Wherein, mixed solution B is made of oleyl amine, oleic acid and octadecylene, wherein volume ratio oleyl amine：Oleic acid：Octadecylene=
1:1:8, in the precursor solution of lead bromide, the molar concentration of lead bromide is 0.09-0.15mol/L；
Step 3, the precursor solution of the caesium is heated to 60-100 DEG C, is transferred in reaction kettle and naturally cools to room
Wen Hou, is added the precursor solution of lead bromide, and is ultrasonically treated 15-35min at room temperature, obtains mixed solution D；
Wherein, the precursor solution of volume ratio lead bromide：Precursor solution=7 of caesium:1-16:1；
Step 4, the mixed solution D that will be obtained in upper step 3, reacts 30-90h, then in 80-150 DEG C of range temperature
Reactant solution E is obtained through Temperature fall；
Step 5, the reactant E upper step obtained washs after centrifugal treating, obtains the inorganic perovskite of final product
CsPbBr3Nano wire.
When product is CsPbCl3、CsPbClxBr3-x、CsPbBrxI3-xOr CsPbI3Nano wire (wherein, 0<x<3) when, also
Include the following steps：
Step 6, by CsPbBr obtained above3Nano wire, which is added in nonpolar solvent, obtains dispersion liquid F；Wherein, non-
Polar solvent is generally toluene, n-hexane or normal octane；A concentration of 0.015mmol/L-0.025mmol/L of dispersion liquid F；
Obtained dispersion liquid F is added in 40-85 DEG C of lead iodide or the precursor solution of lead chloride, obtains mixing molten
Liquid G；
Wherein, the precursor solution of volume ratio lead iodide or lead chloride：Dispersion liquid F=1：1-5：1；
The preparation method of the precursor solution of the lead iodide or lead chloride, includes the following steps：By lead iodide
(PbI2) or lead chloride (PbCl2) be added in mixed solution C, 15-35min is stirred at 100-170 DEG C, then in ice-water bath
Under conditions of be cooled to room temperature, form the precursor solution of lead iodide or lead chloride；
Wherein, if by lead iodide (PbI2) when being added to mixed solution C, C solution is made of oleyl amine, oleic acid and octadecylene,
Wherein volume ratio oleyl amine：Oleic acid：Octadecylene=1:1:8, in the precursor solution of lead iodide, the molar concentration of lead iodide is
0.09-0.15mol/L；If by lead chloride (PbCl2) when being added to mixed solution C, C solution by tri octyl phosphine, oleic acid, oleyl amine and
Octadecylene forms, wherein volume ratio tri octyl phosphine：Oleic acid：Oleyl amine：Octadecylene=1:1:1:8, in the precursor solution of lead chloride,
The molar concentration of lead chloride is 0.09-0.15mol/L；
Step 7, the mixed solution G upper step obtained washs after centrifugal treating, obtains the inorganic perovskite of final product
CsPbCl3、CsPbClxBr3-x、CsPbBrxI3-xOr CsPbI3Nano wire；
Centrifugal rotational speed in step 5 and step 7 is 5000-10000r/min, centrifugation time 5-10min；Washing reagent
For acetone, toluene or ethyl acetate.
The nonpolar solvent is one or both of n-hexane, toluene and normal octane.
The present invention substantive distinguishing features be：
The present invention is successfully prepared perovskite CsPbX by the way of solvent-thermal method and anion exchange3(X=Cl, Br,
I) nano wire.The longer reaction time under lower temperature during solvent thermal reaction so that presoma can be in surface ligand
It plays one's part to the full under effect, nano wire can finally obtain the preferable CsPbBr of crystallization degree along specific direction continued propagation3It receives
Rice noodles；And with CsPbBr3Nano wire is that have prepared superelevation in the way of anion exchange at a lower temperature long for template
Diameter than CsPbI3And CsPbCl3Nano wire.
Cesium carbonate and lead bromide are dissolved in the solvent for the octadecylene for being mixed with surface ligand (steps 1 and 2) respectively first,
So that surface ligand is uniformly wrapped in presoma surface, can preferably control reaction process；At room temperature by cesium carbonate forerunner
Body and lead bromide presoma are sufficiently mixed and are transferred to (step 3) in reaction kettle, control heat of solution reaction time and reaction temperature,
So that the abundant forming core of two kinds of presomas and slowly growing up, reactant is obtained after centrifugal treating, using ethyl acetate wash it is extra not
The organic matter of reaction, finally obtains CsPbBr3Overlong nanowire (step 4,5).Using preparing CsPbBr3Overlong nanowire
For template, CsPbBr will be dispersed with by the method for anion exchange3The dispersion liquid of nano wire continuously adds lead iodide or chlorine
Change in lead precursor solution, anion exchange speed is controlled using the temperature of presoma, gradually by Br element portions or complete
Total exchange will obtain reactant and carry out centrifugal treating, after being handled with reagent wash such as acetone at I elements or Cl element (steps 6)
Obtain CsPbCl3、CsPbClxBr3-x、CsPbBrxI3-xOr CsPbI3Nano wire (step 7).The method is anti-by controlling solvent heat
It answers temperature and reaction time that oleic acid oleyl amine surfactant is made to play one's part to the full, promotes perovskite and given birth to along specific direction
It is long, and ultimately generated the CsPbBr with superelevation draw ratio3Perovskite nano wire, and obtained in the way of anion exchange
The perovskite nano wires of other halogens of identical pattern.
Beneficial effects of the present invention are：
It is inorganic calcium titanium 1. the diffraction maximum of the XRD spectra of the inorganic perovskite nano wire synthesized by the method for the present invention is clear
Mine CsPbBr3Structure, crystal structure meet CsPbBr3- PDF#54-752 occurs without the diffraction maximum of other dephasigns, and purity is up to
97%；Perovskite CsPbBr3Nano wire SEM is shown in Fig. 2, shows ultra-fine threadiness, length is up to several millimeters；CsPbBr3Nanometer
Line TEM is shown in Fig. 3, a diameter of 12nm, the draw ratio with superelevation；CsPbBr3The fluorescence spectra of nano wire is shown in Fig. 8, have compared with
Narrow half-peak breadth, maximum emission peak is in 519nm；CsPbBr3The ultravioletvisible absorption collection of illustrative plates of nano wire is shown in Fig. 9, characteristic absorption
Peak is in 508nm.
2. the present invention makes oleic acid oleyl amine surfactant give full play to by controlling solvent thermal reaction temperature and reaction time
The effect for regulating and controlling crystal growth, causes perovskite along specific direction continued propagation, ultimately forms receiving with superelevation draw ratio
Rice noodles.
3. the present invention realizes CsPbBr by the way of solvent-thermal method and anion exchange3, CsPbCl3And CsPbI3Calcium
The preparation of titanium ore nano wire synthesizes, and equipment is simple needed for experiment, is not necessarily to harsh experiment condition, and reaction controllability is suitble to by force industrial
Metaplasia is produced.
4. prepared by the present invention, the inorganic perovskite nano wire half-peak breadth synthesized is relatively narrow, and purity is higher, and crystallization degree well may be used
For photodetector, the fields such as solar cell.
Description of the drawings
Fig. 1 is the inorganic perovskite CsPbBr that embodiment 1 obtains3The XRD diagram of nano wire.
Fig. 2 is the inorganic perovskite CsPbBr that embodiment 1 obtains3The SEM of nano wire schemes.
Fig. 3 is the inorganic perovskite CsPbBr that embodiment 1 obtains3The TEM of nano wire schemes.
Fig. 4 is the inorganic perovskite CsPbI that embodiment 2 obtains3The SEM of nano wire schemes.
Fig. 5 is the inorganic perovskite CsPbI that embodiment 2 obtains3The TEM of nano wire schemes.
Fig. 6 is the inorganic perovskite CsPbCl that embodiment 3 obtains3The SEM of nano wire schemes.
Fig. 7 is the inorganic perovskite CsPbCl that embodiment 3 obtains3The TEM of nano wire schemes.
Fig. 8 is the inorganic perovskite CsPbBr that embodiment 1-3 is obtained3, CsPbI3And CsPbCl3The fluorescent emission of nano wire
Spectrum.
Fig. 9 is the inorganic perovskite CsPbBr that embodiment 1-3 is obtained3, CsPbI3And CsPbCl3The UV, visible light of nano wire
Absorption spectrum.
Figure 10 is the inorganic perovskite CsPbBr that embodiment 4 obtainsxI3-xThe SEM of nano wire schemes.
Figure 11 is the inorganic perovskite CsPbCl that embodiment 5 obtainsxBr3-xThe SEM of nano wire schemes.
Specific implementation mode
Further explanation and explanation are made to invention with reference to embodiment and attached drawing
Embodiment 1
Step 1 weighs 0.7mmol cesium carbonates (Cs2CO3) it is added to the flask equipped with 1.0mL oleic acid and 8.0mL octadecylenes
In, stirring 25min makes cesium carbonate powder be completely dissolved at 120 DEG C, then naturally cools to room temperature, it is molten to form caesium presoma
Liquid.
Step 2 weighs 2.0mmol lead bromides and is added to equipped with 2.0mL oleic acid, 2.0mL oleyl amines and 16mL octadecylene flasks
In, stirring 25min makes lead bromide powder be completely dissolved at 110 DEG C, is then cooled to room temperature using ice-water bath, forms lead bromide
Precursor solution.
Step 3 measures 2mL after the oleic acid caesium precursor solution obtained by step 1 is heated to 80 DEG C and is added in reaction kettle,
The 20mL lead bromide presoma room temperatures obtained in step 2 are added again after being cooled to room temperature, are ultrasonically treated 15min.
Step 4, by the mixed solution obtained by step 3, react 70h at 120 DEG C of heating temperature, it is naturally cold after reaction
But to room temperature.
Upper layer organic matter layer is discarded step 4 products therefrom by 8000r/min centrifugal treatings 7min by step 5 later,
After obtained bottom sediment object is washed with acetone, product CsPbBr is obtained3Nano wire (0.3mmol, that is, 0.174g), and by its
It is dispersed in 20mL n-hexanes and preserves.
Above-mentioned all operating process are open environment, without inertia protection gas and the processing of stringent dehydration and deoxidation.
The CsPbBr that the present embodiment 1 obtains3The XRD of nano wire is shown in attached drawing 1, and crystal structure meets CsPbBr3-PDF#54-
752, and perovskite nano wire crystallinity is preferable；Perovskite CsPbBr3Nano wire SEM is shown in Fig. 2, shows ultra-fine threadiness,
Length is up to several millimeters；CsPbBr3Nano wire TEM is shown in Fig. 3, a diameter of 12nm, the draw ratio with superelevation；CsPbBr3Nano wire
Fluorescence spectra see Fig. 8, have relatively narrow half-peak breadth, maximum emission peak is in 519nm；CsPbBr3The ultraviolet of nano wire can
See that absorbing collection of illustrative plates sees Fig. 9, characteristic absorption peak is in 508nm.
Embodiment 2
Step 1 weighs 0.7mmol cesium carbonates and is added in the flask equipped with 1.0mL oleic acid and 8.0mL octadecylenes, 120
25min is stirred at DEG C makes cesium carbonate powder be completely dissolved, and then naturally cools to room temperature, forms caesium precursor solution.
Step 2 weighs 2.0mmol lead bromides and is added to equipped with 2.0mL oleic acid, 2.0mL oleyl amines and 16mL octadecylene flasks
In, stirring 25min makes lead bromide powder be completely dissolved at 110 DEG C, is then cooled to room temperature using ice-water bath, forms lead bromide
Precursor solution.
Step 3 weighs 2.0mmol lead iodides and is added to equipped with 2.0mL oleic acid, 2.0mL oleyl amines and 16mL octadecylene flasks
In, stirring 25min makes lead iodide powder be completely dissolved at 110 DEG C, is then cooled to room temperature using ice-water bath, forms lead iodide
Precursor solution.
Step 4 measures 2mL after the oleic acid caesium precursor solution obtained by step 1 is heated to 80 DEG C and is added in reaction kettle,
The 20mL lead bromide presoma room temperatures obtained in step 2 are added again after being cooled to room temperature, are ultrasonically treated 15min.
Step 5, by the mixed solution obtained by step 4, react 70h at 120 DEG C of heating temperature, it is naturally cold after reaction
But to room temperature.
Upper layer organic matter layer is discarded step 5 products therefrom by 8000r/min centrifugal treatings 7min by step 6 later,
After obtained bottom sediment object is washed with acetone, product CsPbBr is obtained3Nano wire (0.3mmol), and be dispersed in
In 20mL n-hexanes.
Step 7, the CsPbBr for taking step 6 to obtain3What nanowire dispersion 5mL was added to that step 3 obtains is heated to 80
DEG C 20mL lead iodide precursor solutions in, wait for obtaining thick liquid after reaction.
Upper layer organic matter layer is discarded thick liquid obtained by step 7 by 8000r/min centrifugal treatings 7min by step 8 later,
After obtained bottom sediment object is washed with acetone, product CsPbI is obtained3Nano wire, and be dispersed in 10mL n-hexanes.
Above-mentioned all operating process are open environment, without inertia protection gas and the processing of stringent dehydration and deoxidation.
The CsPbI that the present embodiment 2 obtains3Nano wire SEM is shown in Fig. 4, shows ultra-fine threadiness, length is up to several millis
Rice；CsPbI3Nano wire TEM is shown in Fig. 3, a diameter of 12nm, the draw ratio with superelevation.CsPbI3The fluorescence spectra of nano wire is shown in
Fig. 8, maximum emission peak is in 685nm；CsPbI3The ultravioletvisible absorption collection of illustrative plates of nano wire is shown in that Fig. 9, characteristic absorption peak exist
678nm。
Embodiment 3
Step 1 weighs 0.7mmol cesium carbonates and is added in the flask equipped with 1.0mL oleic acid and 8.0mL octadecylenes, 120
25min is stirred at DEG C makes cesium carbonate powder be completely dissolved, and then naturally cools to room temperature, forms caesium precursor solution.
Step 2 weighs 2.0mmol lead bromides and is added to equipped with 2.0mL oleic acid, 2.0mL oleyl amines and 16mL octadecylene flasks
In, stirring 25min makes lead bromide powder be completely dissolved at 110 DEG C, is then cooled to room temperature using ice-water bath, forms lead bromide
Precursor solution.
Step 3, weigh 2.0mmol lead chlorides be added to equipped with 2.0mL oleic acid, 2.0mL oleyl amines, 2.0mL tri octyl phosphines and
In 16mL octadecylene flasks, stirring 25min makes lead chloride powder be completely dissolved at 110 DEG C, is then cooled to using ice-water bath
Room temperature forms lead chloride precursor solution.
Step 4 measures 2mL after the oleic acid caesium precursor solution obtained by step 1 is heated to 80 DEG C and is added in reaction kettle,
The lead bromide presoma room temperature obtained in step 2 is added again after being cooled to room temperature, is ultrasonically treated 15min.
Step 5, by the mixed solution obtained by step 4, react 70h at 120 DEG C of heating temperature, it is naturally cold after reaction
But to room temperature.
Upper layer organic matter layer is discarded step 5 products therefrom by 8000r/min centrifugal treatings 7min by step 6 later,
After obtained bottom sediment object is washed with acetone, product CsPbBr is obtained3Nano wire (0.3mmol), and be dispersed in
In 20mL n-hexanes.
Step 7, the CsPbBr for taking step 6 to obtain3What nanowire dispersion 5mL was added to that step 3 obtains is heated to 60
DEG C 22mL lead chloride precursor solutions in, wait for obtaining thick liquid after reaction.
Upper layer organic matter layer is discarded thick liquid obtained by step 7 by 8000r/min centrifugal treatings 7min by step 8 later,
After obtained bottom sediment object is washed with acetone, product CsPbCl is obtained3Nano wire, and it is dispersed in 10mL n-hexanes
In.Above-mentioned all operating process are open environment, without inertia protection gas and the processing of stringent dehydration and deoxidation.
CsPbCl is made in the present embodiment 33Nano wire SEM is shown in Fig. 6, shows ultra-fine threadiness, length is up to several millimeters；
CsPbCl3Nano wire TEM is shown in Fig. 7, a diameter of 12nm, the draw ratio with superelevation；CsPbCl3The fluorescence spectra of nano wire is shown in
Fig. 8 has relatively narrow half-peak breadth, and maximum emission peak is in 410nm；CsPbCl3The ultravioletvisible absorption collection of illustrative plates of nano wire is shown in figure
9, characteristic absorption peak is in 404nm.
Embodiment 4
By CsPbBr in step 7 in embodiment 23Nanowire dispersion 5mL is changed to 15mL, other operations with reality
It is identical to apply example 2, obtains CsPbBrxI3-xNano wire.CsPbBr is made in the present embodiment 4xI3-xNano wire SEM is shown in Figure 10, and excess of export is presented
Thin threadiness, length is up to several millimeters.
Embodiment 5
By CsPbBr in step 7 in embodiment 33Nanowire dispersion 5mL is changed to 15mL, other operations with reality
It is identical to apply example 3, obtains CsPbClxBr3-xNano wire.CsPbCl is made in the present embodiment 5xBr3-xNano wire SEM is shown in Figure 11, shows
Ultra-fine threadiness, length is up to several millimeters.
The perovskite CsPbBr with superelevation draw ratio has been obtained by adjusting solvent thermal reaction temperature and reaction time3It receives
Rice noodles (length reaches several millimeters, diameter only 10 rans), and with CsPbBr3Nano wire is template by way of ion exchange
Prepare CsPbCl3、CsPbClxBr3-x、CsPbBrxI3-xAnd CsPbI3Nano wire remains CsPbBr3The superelevation of nano wire
Major diameter ratio characteristic.The presoma PbI in ion exchange process2Or PbCl2The speed of anion exchange that can influence of temperature, point
Dissipating has CsPbBr3The solution of nano wire and presoma PbI2Or PbCl2Ratio also influence whether the progress of exchange reaction, change
The ratio of the two can obtain the perovskite nano wire with different luminous peak positions and different component, this is for the controllable of nano wire
Synthesis provides experiment basis, has important impetus to its application in photodetection and solar cell etc..
Unaccomplished matter of the present invention is known technology.
Claims (4)
1. a kind of synthetic method of inorganic perovskite nano wire, it is characterized in that this method comprises the following steps：
Step 1, by cesium carbonate（Cs2CO3）It is added in mixed liquor A, 15-35 min is stirred at 110-160 DEG C, it is then natural
It is cooled to room temperature, forms the precursor solution of caesium；
Wherein, mixed solution A is made of oleic acid and octadecylene, wherein volume ratio oleic acid：Octadecylene=1:8；The presoma of caesium
In solution, the molar concentration of caesium is 0.12-0.25 mol/L;
Step 2, by lead bromide（PbBr2）It is added in mixed solution B, 15-35 min is stirred at 90-130 DEG C, then in ice
It is cooled to room temperature under conditions of water-bath, forms the precursor solution of lead bromide；
Wherein, mixed solution B is made of oleyl amine, oleic acid and octadecylene, wherein volume ratio oleyl amine：Oleic acid：Octadecylene=1:1:
8, in the precursor solution of lead bromide, the molar concentration of lead bromide is 0.09-0.15 mol/L；
Step 3, the precursor solution of the caesium is heated to 60-100 DEG C, is transferred to cooled to room temperature in reaction kettle
Afterwards, the precursor solution of lead bromide is added, and is ultrasonically treated 15-35 min at room temperature, obtains mixed solution D；
Wherein, the precursor solution of volume ratio lead bromide：Precursor solution=7 of caesium:1-16:1；
Step 4, the mixed solution D that will be obtained in upper step 3 reacts 30-90 h in 80-150 DEG C of range temperature, then passes through certainly
So cooling obtains reactant solution E；
Step 5, the reactant E upper step obtained washs after centrifugal treating, obtains the inorganic perovskite CsPbBr of final product3It receives
Rice noodles.
2. the synthetic method of inorganic perovskite nano wire as described in claim 1, it is characterized in that when product is CsPbCl3、
CsPbClxBr3-x、CsPbBrxI3-xOr CsPbI3Further include following steps when nano wire：
Step 6, by CsPbBr obtained above3Nano wire, which is added in nonpolar solvent, obtains dispersion liquid F；Wherein, nonpolarity is molten
Agent is generally toluene, n-hexane or normal octane；A concentration of 0.015 mmol/L-0.025 mmol/L of dispersion liquid F；
Obtained dispersion liquid F is added in 40-85 DEG C of lead iodide or the precursor solution of lead chloride, mixed solution G is obtained；
Wherein, the precursor solution of volume ratio lead iodide or lead chloride：Dispersion liquid F=1：1-5：1；
The preparation method of the precursor solution of the lead iodide or lead chloride, includes the following steps：By lead iodide（PbI2）Or
Lead chloride（PbCl2）It is added in mixed solution C, 15-35 min is stirred at 100-170 DEG C, then in the condition of ice-water bath
Under be cooled to room temperature, form the precursor solution of lead iodide or lead chloride；
Wherein, if by lead iodide（PbI2）When being added to mixed solution C, C solution is made of oleyl amine, oleic acid and octadecylene, wherein body
Product compares oleyl amine：Oleic acid：Octadecylene=1:1:8, in the precursor solution of lead iodide, the molar concentration of lead iodide is 0.09-0.15
mol/L；If by lead chloride（PbCl2）When being added to mixed solution C, C solution is by tri octyl phosphine, oleic acid, oleyl amine and octadecylene group
At wherein volume ratio tri octyl phosphine：Oleic acid：Oleyl amine：Octadecylene=1:1:1:8, in the precursor solution of lead chloride, lead chloride
Molar concentration is 0.09-0.15 mol/L；
Step 7, the mixed solution G upper step obtained washs after centrifugal treating, obtains the inorganic perovskite of final product
CsPbCl3、CsPbClxBr3-x、CsPbBrxI3-xOr CsPbI3Nano wire；Wherein, 0<x<3.
3. the synthetic method of inorganic perovskite nano wire as claimed in claim 2, it is characterized in that the step 5 and step 7
In centrifugal rotational speed be 5000-10000 r/min, centrifugation time be 5-10 min；Washing reagent is acetone, toluene or acetic acid second
Ester.
4. the synthetic method of inorganic perovskite nano wire as claimed in claim 2, it is characterized in that the nonpolar solvent is
One or both of n-hexane, toluene and normal octane.
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