CN110093665A - A kind of perovskite crystal growth system and preparation method thereof - Google Patents
A kind of perovskite crystal growth system and preparation method thereof Download PDFInfo
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- CN110093665A CN110093665A CN201910421874.7A CN201910421874A CN110093665A CN 110093665 A CN110093665 A CN 110093665A CN 201910421874 A CN201910421874 A CN 201910421874A CN 110093665 A CN110093665 A CN 110093665A
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/12—Halides
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
- C30B7/02—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions by evaporation of the solvent
- C30B7/06—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions by evaporation of the solvent using non-aqueous solvents
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
- C30B7/08—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions by cooling of the solution
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Abstract
A kind of perovskite crystal growth system and preparation method thereof, belongs to field of functional materials.Perovskite crystal grows system for making the monocrystal of perovskite in preferred temperature.Crystal growth system includes by the first liquid reagent and second liquid reagent of layered arrangement.First liquid reagent is made of the first molecule, and the first liquid reagent is able to maintain as liquid phase under preferred temperature.Second liquid reagent is made of the second molecule.First liquid reagent does not dissolve each other mutually with second liquid reagent, and second liquid reagent is the good solvent of perovskite and/or the raw material for making perovskite.First liquid reagent and second liquid reagent, which have, such as gives a definition: under preferred temperature, second liquid reagent can be detached from gap of second molecule across the first molecule from crystal growth system.Perovskite production method in example can realize the perovskite production of monocrystalline in a manner of high operability.
Description
Technical field
This application involves field of functional materials, grow system and its production side in particular to a kind of perovskite crystal
Method.
Background technique
In recent years, metal halide perovskite (metal halide perovskite, MHP) material is because it is with long load
It flows the excellent photoelectric properties such as sub- service life, the high absorption coefficient of light and low defect state density and has received widespread attention.
Excellent properties based on material, MHP the fields such as solar battery, optical sensor and luminescent device have been achieved for it is huge at
Function.
Currently, perovskite photoelectric device is mostly assembled by MHP polycrystal film.Compared with MHP polycrystal film, monocrystalline
Become the weight of following MHP photoelectric device due to less grain boundary defects, better stability and higher crystal quality
Want one of research direction.
The control accurate for realizing MHP crystal growth becomes the repeatability of the quality and monocrystalline growing process that improve MHP monocrystalline
It obtains particularly important.
The information disclosed in the background technology section is intended only to deepen the understanding to the general background technology of the application, and
It is not construed as recognizing or implying in any form that the information constitutes the prior art known to those skilled in the art.
Summary of the invention
Based on the deficiencies of the prior art, this application provides a kind of perovskite crystal growth system and preparation method thereof, with
Partly or entirely improve, even solution must not be stablized and repeatable make the stable monocrystalline perovskite problem of performance.
The application is achieved in that
In a first aspect, the example of the application provides a kind of perovskite crystal growth system.
Such a crystal growth system can be used for the monocrystal that perovskite is made in preferred temperature.
Crystal growth system includes by the first liquid reagent and second liquid reagent of layered arrangement.
Wherein, the first liquid reagent is made of the first molecule, and the first liquid reagent is able to maintain under preferred temperature
For liquid phase.
Wherein, second liquid reagent is made of the second molecule.
First liquid reagent does not dissolve each other mutually with second liquid reagent, and second liquid reagent is perovskite and/or for making
Make the good solvent of the raw material of perovskite.
First liquid reagent and second liquid reagent, which have, such as gives a definition:
Under preferred temperature, second liquid reagent can be raw from crystal with gap of second molecule across the first molecule
Long system is detached from.
The above crystal growth system is a kind of liquid-phase system, can dissolve perovskite or it makes raw material, and suitable
At a temperature of, is volatilized solvent and perovskite is precipitated in the form of monocrystal, realize the growth of monocrystalline perovskite.
With reference to first aspect, in some optional examples of the first possible embodiment of the first aspect of the application
In, the first liquid reagent and second liquid reagent have identical or different density.
Optionally, the first liquid reagent and second liquid reagent have different density, and the density of the first liquid reagent
Greater than the density of second liquid reagent.
According to the difference of the first liquid reagent and the ingredient of second liquid reagent, it is big that the two can have appropriate density
It is small.For example, the density of the first liquid reagent is greater than the density of second liquid reagent under normal gravity effect.In this way, in container
In, the first liquid reagent can be located at the upper layer of second liquid reagent, thus by second liquid reagent (including perovskite therein
Or it makes raw material) it closes in a reservoir under certain condition, and second liquid reagent can be made to pass through the first liquid if necessary
Body reagent reaches production monocrystalline perovskite.
With reference to first aspect, in some optional examples of second of possible embodiment of the first aspect of the application
In, the first liquid reagent includes nonpolar organic molecule.
Optionally, nonpolar organic molecule includes dimethyl silicone polymer.
With reference to first aspect or second of possible embodiment of first aspect, in the third of the first aspect of the application
In some optional examples of the possible embodiment of kind, second liquid reagent includes polar organic molecule.
Optionally, polar organic molecule includes gamma-hydroxybutyric acid lactone, n,N-Dimethylformamide or dimethyl sulfoxide.
The selection of the ingredient of first liquid reagent and second liquid reagent is mutual limitation and adapts to.According to the first liquid
The ingredient of the concrete property of the ingredient of reagent, second liquid reagent is generally being confirmed.The reasonable selection and phase interworking of the two
Conjunction can be preferably employed for making monocrystalline perovskite.
In second aspect, the example of the application provides a kind of production method of perovskite.
The production method of perovskite can be substantially carried out by crystal growth system above-mentioned.
Production method includes:
Temperature control is carried out to precursor liquid, so that the temperature of precursor liquid is in preferred temperature and is kept for the expected time；
Wherein, precursor liquid is by by perovskite or being used to make of the dissolution of raw material of perovskite in crystal growth system
Two liquid reagents and obtain.
The above production method is accurately adjusted by the solubility of solute in a solvent according to the change of the content of solvent
The degree of supersaturation of solute, to realize the crystal growth of perovskite.The production method process flow is simple, easy to implement, can be with
The product of growing large-size.
In conjunction with second aspect, in some optional examples of the first possible embodiment of the first aspect of the application
In, the method for making precursor liquid includes: the first presoma making step and the second presoma making step that successively sequence carries out.
Wherein, the first presoma making step includes: by perovskite or to be used to make the dissolution of raw material of perovskite in second
Liquid reagent, the filtration treatment optionally carried out, to obtain the first presoma；
Wherein, the second presoma making step includes: that the first liquid reagent is added in the first presoma.
Implementation difficulty or ease based on technique, the technique that can choose step by step is to implement above step.I.e. for crystalline substance above-mentioned
For body growth system, crystal growth system can be completed to construct step by step in the process that the production method of perovskite is carried out.
In conjunction with second aspect, in some optional examples of second of possible embodiment of the second aspect of the application
In, preferred temperature is 5~60 DEG C；
Optionally, preferred temperature is 12~50 DEG C；
Optionally, preferred temperature is 23~43 DEG C；
Optionally, preferred temperature is 38~47 DEG C.
According to the difference that can dissolve perovskite or its second liquid reagent for making raw material, preferred temperature also has accordingly
It is different.Normally, preferred temperature can make second liquid reagent volatilize.
In conjunction with second aspect, in some optional examples of the third possible embodiment of the second aspect of the application
In, the chemical general formula of perovskite is ABX3；
Wherein, A is the organic cation or inorganic cation of monovalence；
Alternatively, B is the metal cation of divalent；
Alternatively, X is the halide anion of monovalence；
Optionally, inorganic cation includes caesium；Organic cation includes methylamine, methyl ether, ethamine, dimethylamine, guanamines；
Optionally, metal cation includes germanium, tin, lead；
Optionally, halide anion includes iodine, bromine, chlorine.
As a kind of optinal plan of perovskite, metal halide perovskite can be used by selection.Make the list of high-quality
Brilliant metal halide perovskite can be applied to various fields, realize the high quality transformation of electronic component.
In conjunction with the third possible embodiment of second aspect, in the 4th kind of possible reality of the second aspect of the application
It applies in some optional examples of mode, the raw material for making perovskite includes the AX and BX being separately provided2。
The metal halide perovskite, which can be, to be formed and is generated during production method by its production raw material.Change speech
It, the exemplary method of the application can be used for the transformation to the polycrystalline of perovskite to monocrystalline.For directly providing, (outsourcing passes through
Other modes production) Polycrystalline Metals halogenation perovskite, can also be by the crystal growth body that is provided in the application example
System and method are remake as single-crystal metal halogenation perovskite.Or the calcium titanium that raw material is made as monocrystalline also can be directly used
Mine.
In conjunction with second aspect, in some optional examples of the 5th kind of possible embodiment of the second aspect of the application
In, perovskite is monocrystalline and size reaches millimeter.
During implementation above, the crystal growth system and production method provided in example is a kind of based on liquid phase systems
Scheme.The perovskite of monocrystalline can grow from liquid phase systems and gradually grow up.Perovskite or its reaction raw materials can dissolve
Change degree of supersaturation in liquid phase systems, and as the second liquid reagent for dissolving it gradually decreases, to realize high quality
The growth of perovskite monocrystalline.
Detailed description of the invention
In order to illustrate the technical solutions in the embodiments of the present application or in the prior art more clearly, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described.
Fig. 1 is the structural schematic diagram of the Reagent Tube in the embodiment of the present application；
Fig. 2 shows the structure cell schematic diagrames of metal halide perovskite；
Fig. 3 shows the layered structure schematic diagram of the reagent in the container of the offer of the embodiment of the present application 2；
Fig. 4 shows the monocrystalline perovskite schematic diagram of the growth in the container of the offer of the embodiment of the present application 2；
Fig. 5 shows the XRD diffracting spectrum of the monocrystalline perovskite in embodiment 2；
Fig. 6 shows the XRD diffracting spectrum of { 100 } family of crystal planes of the monocrystalline perovskite in embodiment 2.
Icon: 100- Reagent Tube；101- lid；102- tube body；The first liquid reagent of 201-；202- second liquid reagent；
301- reserved area；302- opening；303- bottom wall；The first reagent of 401-；The second reagent of 402-；403- perovskite monocrystal.
Specific embodiment
Monocrystalline perovskite has the performance for being substantially better than polycrystalline perovskite, for example, its grain boundary defects is less.Therefore, it uses
Monocrystalline perovskite making devices can obtain some pleasurable performances, be conducive to improve its application performance, the table obtained
Existing effect.
It is necessary for making high quality perovskite.Therefore, in order to obtain high-quality monocrystalline perovskite, need pair
Its preparation method carries out careful investigation.
Inventor attempts to grow in liquid phase systems, makes monocrystalline perovskite.The production method being attempted includes low temperature mistake
Saturation, inversion growth method, anti-solvent-gas phase assisting crystallisation method and seed crystal auxiliary liquid-phase growth method etc..It generally says, inventor
Increase degree of supersaturation of the MHP in precursor liquid by the way of temperature regulation and solvent regulation, to realize slowly having for MHP monocrystalline
Sequence growth.
Wherein, temperature regulation growing technology refers to: according to solubility and temperature relation of the MHP solute in different solvents,
Change the degree of supersaturation of MHP precursor liquid by the modes such as heating, cooling and spatial temperature gradient distribution, and then realizes MHP crystal
Ordering growth.
Wherein, solvent regulation growing technology refers to: the side of second liquid reagent is extracted by volatilization naturally or anti-solvent
Formula changes the degree of supersaturation of MHP precursor liquid, and then realizes the ordering growth of perovskite monocrystalline.
However, inventor recognizes above scheme, and there are the following problems in practice process:
The temperature controls growing technology such as one, cooling, heating and temperature gradient.Though its effective growth for being able to achieve MHP monocrystalline, so
And thermal convection and temperature gradient are introduced in temperature control process, defect can be not only introduced in crystal, but also influence whether crystal
The regulation of growth course, the especially control to temperature gradient distribution spatially.
Secondly, solvent volatilization and anti-solvent extract equal solvent control technique.Though growth MHP is mono- under the conditions of it is able to achieve fixed temperature
Crystalline substance, however, it is very difficult to grow large-sized MHP monocrystalline.Further, since this method is in air or anti-solvent gas phase atmosphere
Effect is lower to grow monocrystalline, so its technical process is hardly resulted in and is precisely controlled.
In view of this, inventor attempts to study and proposes a kind of scheme, to realize the accurate tune of MHP crystal growth
Control, to improve the quality of MHP monocrystalline and the repeatability of monocrystalline growing process.
It is described in detail below in conjunction with embodiment of the embodiment to the application, but those skilled in the art will
Understand, the following example is merely to illustrate the application, and is not construed as limitation scope of the present application.It is not specified in embodiment specific
Condition person carries out according to conventional conditions or manufacturer's recommended conditions.Reagents or instruments used without specified manufacturer is
The conventional products that can be obtained by commercially available purchase.
It is specifically described below for the perovskite crystal growth system and preparation method thereof of the embodiment of the present application:
It has been observed that the perovskite crystal growth system proposed in the application example can be used in making calcium under proper condition
The monocrystal of titanium ore.Felicity condition therein can usually refer to that (following its is referred to as temperature at crystal growth system
Preferred temperature).In the monocrystalline manufacturing process of perovskite, temperature can be selected as stationary temperature.But the steady temperature
It can be and arbitrarily select a determining temperature value in a wide in range range.
Perovskite crystal growth system in example is a kind of liquid phase systems (system).
For reality when carrying out the production of perovskite, the perovskite crystal growth system of the liquid phase is usually to be placed in container
In, and the production or preparation process of perovskite can be implemented under an open environment and condition (such as atmosphere).In this way
Container for example can be test tube, beaker, reagent bottle, glassware etc..
The side wall that this container usually has a bottom wall, connect with bottom wall, also with the opening of an opposing bottom wall.Liquid
Phase system is injected into container, and is retained opening and communicated with atmosphere.Alternatively, opening is closed by lid, but to a certain degree
On can be communicated with the atmosphere.Further, or opening is by lid closing and isolated from atmosphere, but wherein can be with reserved part
(being filled with liquid phase systems above-mentioned in the container of vacuum) of air either vacuum.Alternatively, the container is a closing
Shell structure, and liquid phase systems above-mentioned can be injected with through hole or notch etc..
It has been observed that the crystal growth system in the application example is a kind of liquid phase systems, and liquid phase systems are in some examples
In can also be referred to as composition for producing monocrystalline perovskite.The composition includes the first constituent and the second composition
Object.First constituent and the second constituent are different substance, and both can be the substance of one-component, can also be with multicomponent
Mixture.In the following discussion, the first constituent is by with mentioned by the first liquid reagent, the second constituent is by with second liquid
Mentioned by reagent.
Further, in conjunction with container above-mentioned, the crystal growth system being made of container and composition can also be recognized
To be a kind of for carrying out monocrystalline perovskite into the kit of production.When using the kit, perovskite related raw material is added
Into the kit, then, it is in kit at temperature appropriate and produces monocrystalline perovskite.Further, temperature control is filled
It sets the crystal growth system that (such as heater) and container, composition are bonded and is also considered one kind for carrying out monocrystalline
The production box of perovskite production.
In example, crystal growth system includes by the first liquid reagent and second liquid reagent of layered arrangement.It is layered cloth
The first liquid reagent and second liquid reagent set.And the layered mode of the two is also maintained in a reservoir.For example, in reality
It applies in scheme, the first liquid reagent is located at upper layer, and second liquid reagent is located at lower layer.A kind of container (referred to as Reagent Tube 100)
Including lid 101 and tube body 102.Second liquid reagent 202 be closed between the first liquid reagent 201 and bottom wall 303 every
From in region, and reserved area of first liquid reagent 201 between 302 (lids 101) of second liquid reagent 202 and opening
301.The reserved area 301 can be full of air.In order to make it easy to understand, such scheme is demonstrated in Fig. 1.
In example, the first liquid reagent can require selection according to following.It can be selected as the organic high score of nonpolarity
Son.Firstly, the organic polymer exists within the temperature range of monocrystalline perovskite is grown with liquid phase state；Secondly, organic high score
Sub and perovskite precursor solution (including second liquid reagent, it may also comprise and dissolved such as AX and BX2Second liquid reagent)
It is incompatible；Again, the density of organic polymer solution be less than perovskite precursor solution density, so as to its float on upper layer (or
Claim the first liquid reagent on second liquid reagent).
In example, second liquid reagent can require selection according to following.It can be selected as small organic molecule solvent.
Firstly, it can dissolve perovskite related raw material (such as subsequent AX and BX that will be mentioned2)；Secondly, small organic molecule is pole
Property molecule, prevent its with the first liquid reagent dissolving each other (such as nonpolar organic polymer).
For ease of description, the first liquid reagent restriction is made of the first molecule, and second liquid reagent is limited by second point
Son is constituted.It should be noted that the first liquid reagent and second liquid reagent either one-component purified, be also possible to
The composition that multicomponent is constituted.In other words, the first molecule for constituting the first liquid reagent can be determining compound molecule,
It can be the combination of various (at least two, such as three kinds, four kinds, five kinds) compound molecules.Similarly, second liquid is constituted
Second molecule of reagent can be determining compound molecule, be also possible to various (at least two, such as three kinds, six kinds, seven kinds
Deng) combination of compound molecule.In subsequent embodiment, the first liquid reagent and second liquid reagent are all with the object of one-component
Matter is provided and uses, but this does not imply that the two must be one-component.
In addition, the first liquid reagent is able to maintain as liquid phase under preferred temperature.I.e. in the monocrystalline manufacturing process of perovskite
In, the first liquid reagent is liquid, so as to so that second liquid reagent be all by the first liquid reagent covering and it is closed.
Further, the first liquid reagent does not dissolve each other mutually with second liquid reagent, when the two mixes, is generally divided into
Different two parts.Non-exclusively, for example, water and oil are usually that cannot dissolve each other；Water and ethyl alcohol can dissolve each other.Due to
One liquid reagent does not dissolve each other mutually with second liquid reagent, and according to the similarities and differences of the two density, the two is stored can occur in a reservoir
Autonomous layering.
Further, second liquid reagent is perovskite (the first raw material) and/or the raw material (for making perovskite
Two raw materials) good solvent.I.e. perovskite can be dissolved in second liquid reagent；Alternatively, be used to make the raw material of perovskite
It can be dissolved in second liquid reagent；Alternatively, perovskite and the raw material for making perovskite can be dissolved in second
In liquid reagent.For example, sodium chloride crystal is soluble in water, and when water is removed (such as thermal evaporation), sodium chloride is with crystalline substance
Body form is precipitated.First liquid reagent and second liquid reagent have identical or different density.In a kind of alternative example,
The first liquid reagent of selection and second liquid reagent have different density as needed, and the density of the first liquid reagent is greater than
The density of second liquid reagent.In this way, under the conditions of natural gravity, the first liquid reagent can swim in second liquid reagent it
On.For example, petroleum can swim in seawater surface.
In example, perovskite and its production dissolution of raw material remove in second liquid reagent, and in second liquid reagent
When can form the perovskite of monocrystal.The characteristic of first liquid reagent and second liquid reagent be set forth by such as giving a definition and
Limit: under preferred temperature, second liquid reagent can be with gap of second molecule across the first molecule from crystal growth
System is detached from.
Illustratively, in the system that the production raw material of the first liquid reagent and second liquid reagent, perovskite is constituted,
Under preferred temperature above-mentioned, second liquid reagent evaporates by heat, and passes through the first liquid reagent.And the production raw material of perovskite
Then monocrystalline perovskite (solid) can be formed step by step by reacting, cannot be by the first liquid reagent, and retaining (will not be by the
One liquid reagent solvent) under the first liquid reagent.Then the first liquid reagent is removed, or by the monocrystalline calcium titanium of generation
Mine is taken out from liquid can be obtained product.
In other words, second liquid reagent can be with gap of second molecule across the first molecule from crystal growth system
Be detached from can test in this way be verified, and can also test in this way screen the first liquid reagent and the second liquid
Body reagent.That is: candidate the first liquid phase substance and second liquid phase material mixing can be layered (the first liquid phase substance is on upper layer)；The
Two liquid phase substances can dissolve perovskite related raw material；Second liquid phase substance can be made to gradually eliminate and in the mistake by heating
Always there is the first liquid phase substance of appropriate amount (enough) in journey.
As a kind of example of more operability, the first liquid reagent may be selected to include nonpolar organic molecule.In this way
Nonpolar organic molecule for example can be dimethyl silicone polymer.Correspondingly, second liquid reagent may be selected to include polarity
Organic molecule.Polar organic molecule for example can be gamma-hydroxybutyric acid lactone, N,N-dimethylformamide or dimethyl sulfoxide.
In such some examples, for enabling second liquid reagent to restore, and the first liquid reagent is maintained at liquid condition
Temperature (preferred temperature) can be selected as 5~60 DEG C.Optionally, preferred temperature is 12~50 DEG C；Optionally, preferred temperature is
23~43 DEG C；Optionally, preferred temperature is 38~47 DEG C.Additionally, it should be realized that temperature can be in single crystal growth process
Any point value in aforementioned range is also possible to a value range.In other words, ensuring that temperature suitably (is able to carry out monocrystalline
Growth) in the case where, it can be suitably adjusted temperature, so as to the speed of growth and the mode etc. for controlling monocrystalline.For example, if monocrystalline
Growth temperature (preferred temperature) be selected as 30 DEG C.Temperature can be 30 DEG C in single crystal growth process, alternatively, existing as needed
Such as (intentionally) fluctuation appropriate between 29~31 DEG C, adjustment.
And for the perovskite product of monocrystalline, it can be various types, used as needed by selection.The application
In example, the chemical general formula of perovskite is ABX3。
Wherein, A is the organic cation or inorganic cation of monovalence.Optionally, inorganic cation includes caesium (Cs+)；
Organic cation includes methylamine (CH3NH3 +, MA), methyl ether (CH (NH2)2 +, FA), ethamine (CH3CH2NH3 +, EA), dimethylamine (NH2
(CH3)2 +, DEA), guanamines (C (NH2)3 +, GA) etc.；
Wherein, B is the metal cation of divalent.Optionally, metal cation includes germanium (Ge2+), tin (Sn2+), lead (Pb2 +) etc..
Wherein, X is the halide anion of monovalence.Optionally, halide anion includes iodine (I-), bromine (Br-), chlorine (Cl-)
Deng.
Therefore, as an example, perovskite for example can be MAPbBr3、FASnI3、GAGeBr3、EAGeBr3、DEAPbCl3Deng
Deng.
Such perovskite mentioned above is commonly known as metal halide perovskite (general formula ABX3), structure cell is cube
Crystal, structure are as shown in Figure 2.A cation (such as Cs+、MA+、FA+) be on eight vertex of cubic lattice；B divalent
Metal cation (such as Ge2+、Sn2+、Pb2+) it is in the body position of cubic lattice；Halide anion (such as I of X monovalencies-、
Br-、Cl-) it is in six face heart positions of cubic lattice.
The raw material of perovskite for being used to make monocrystalline can be the AX and BX that are separately provided2.Therefore, right here
Be that good solvent for making the raw material of the perovskite refers in second liquid reagent: second liquid reagent is AX and BX2's
Good solvent.
System is grown based on perovskite crystal above-mentioned, additionally provides the production method of (monocrystalline) perovskite in example.It should
Production method can be carried out by crystal growth system.It is noted that crystal growth system be used to make monocrystalline calcium
By ready in advance before titanium ore；Alternatively, what crystal growth system was fabricated during being used to make monocrystalline perovskite.
In a kind of example, the production method of perovskite includes:
Temperature control is carried out to precursor liquid, so that the temperature of precursor liquid is in preferred temperature and is kept for the expected time.
Wherein, precursor liquid is by the way that by perovskite (polycrystalline, the first raw material) or raw material for making perovskite, (second is former
Material, AX and BX as the aforementioned2) the second liquid reagent that is dissolved in crystal growth system and obtain.
In such an example, crystal growth system is prepared in advance, and second liquid reagent has also dissolved the first original
Material or the second raw material.It is placed in a reservoir by pre-prepd crystal growth system, it is subsequent for convenience to be tried in second liquid
The first raw material or the second raw material are dissolved in agent, it may be necessary to certain configuration or transformation are carried out to container.For example, in such as earlier figures
In Reagent Tube 100 in 1, the side wall that tube body 102 corresponds to receiving second liquid reagent 202 can be set to be opened by switch control
The opening closed (figure is not painted).In this way, the crystal growth system of liquid phase is injected into Reagent Tube 100, it is then logical as needed
It crosses opening above-mentioned second raw material is injected into tube body, can be mixed with second liquid reagent by dissolution.
In this scheme, the method that precursor liquid carries out temperature control can be and directly heat.Such as heat source is provided and is passed through
Thermal convection is conducted heat or is heated by modes such as such as microwaves.The mode of thermal convection heat transfer can be container corresponding to the second liquid
The part of body reagent blows hot wind；Alternatively, passing through electric-heating-wire-heating.
In another scheme, crystal growth system is fabricated during the production method of monocrystalline perovskite, and with
Afterwards in proper step, second liquid reagent dissolves the first raw material or the second raw material.In other words in such example, precursor liquid
It is by being distributed to make and be carried out during the production method of monocrystalline perovskite, such as the method for production precursor liquid includes:
Successively the first presoma making step and the second presoma making step that sequence carries out.
Wherein, the first presoma making step includes: by perovskite or to be used to make the dissolution of raw material of perovskite in second
Liquid reagent, the filtration treatment optionally carried out, to obtain the first presoma.Second presoma making step includes: by first
Liquid reagent is added in the first presoma.
In the first presoma making step, perovskite or the original for making perovskite are dissolved in second liquid reagent
Material can be to be implemented under stirring or the cooperation of ultrasound.In addition, based on the considerations of solubility and situations such as there may be impurity,
It can make the ideal solution of the first presoma in conjunction with processing is filtered.Non-exclusively, the process of dissolution can be in room temperature
Carrying out under (such as 20~27 DEG C), course of dissolution can be the completion in 24-48 hours.
By the first liquid reagent be added the first presoma in can be slowly added into the first liquid reagent as may
It is to be added dropwise.
By perovskite or it is being used to make it in second liquid reagent of the dissolution of raw material of perovskite in crystal growth system
Afterwards, by maintaining whole system under temperature appropriate (preferred temperature), as second liquid reagent gradually volatilizees and passes through
First liquid reagent and remove.In such a process, the degree of supersaturation of the solute in (remaining) second liquid reagent is controlled
System realizes the growth of high quality perovskite monocrystalline.
Predictably, in some examples, the boiling point of the first liquid reagent is above preferred temperature, second liquid
The boiling point of reagent is less than or is equal to preferred temperature.
Alternatively, the boiling point (the first boiling point) of the first liquid reagent is also likely to be less than or equal to expectation in other examples
The boiling point (the first boiling point) of temperature, second liquid reagent is less than or is equal to preferred temperature, and still, the first liquid reagent exists
Evaporation rate under preferred temperature is less than evaporation rate of the second liquid reagent under preferred temperature.In this way, under preferred temperature
During making monocrystalline perovskite, there is the first liquid reagent always and be covered on second liquid reagent, by second liquid
Reagent is kept apart with external environment (such as air).
The growth of entire perovskite monocrystalline can be the volatilization of second liquid reagent complete and stopping or, perovskite monocrystalline it is complete
It is precipitated and stops entirely.In some instances, by above step, size can be obtained by production method above-mentioned and reach millimeter
The monocrystalline perovskite of grade.The size of obtained monocrystalline perovskite is usually related to many factors, for example, constituting the raw material of perovskite
Amount (correspondingly also referring to the amount of second liquid reagent), the temperature selection during production method, the first liquid reagent and the
The component of two liquid reagents, type selection.
In the application example, based on GBL (gamma-hydroxybutyric acid lactone), DMF (N, N- dimethyl formyl in MHP precursor liquid
Amine) and the small molecule solvents (small organic molecule solvent) such as DMSO (dimethyl sulfoxide) can be effectively organic high by liquid phase nonpolarity
The molecular gap of molecular material proposes a kind of method of metal halide perovskite crystal growth.
It is influenced based on dimensional effect, concentration gradient, GBL, DMF and DMSO equal solvent small molecule can effectively pass through non-pole
Property organic macromolecule gap, and perovskite presoma solute is blocked in precursor solution, by means of molecule under different temperatures
Kinetic energy difference carrys out the evaporation rate of adjusting solvent small molecule, can be to the accurate control of system degree of supersaturation, and then realizes high-quality
Measure the growth of perovskite monocrystalline.
Based on above description, perovskite crystal growth system and production method in the application example have at least following excellent
Point:
(1) production method is simple to operate, practical.Nonpolar organic polymer solution is applied to for the first time
In the growth of MHP monocrystalline, shuttle property based on the organic solvents such as GBL, DMF and DMSO small molecule in macromolecule gap, by
, can be with the evaporation rate of adjusting solvent small molecule in influence of the temperature to small molecule kinetic energy, and then realize in MHP precursor liquid
The accurate control of small solvent molecule volatilization.
(2) in production method, ABX3Monocrystalline growing process has repeatability well.
(3) the scheme combination temperature control Crystal Growth Technique in the application example and solvent volatilization control technology, are realized for the first time
Under conditions of low temperature (such as 5 DEG C) growth of MHP monocrystalline.MHP monocrystalline is grown under cryogenic conditions, can not only effectively avoid heat right
Stream and advantageously reduces the energy loss of crystal growth to crystal defect brought by crystal growth, so reduce it is economical at
This.
In order to make those skilled in the art more easily implement the scheme in the application example, with reference to embodiments to this
Perovskite crystal growth system of application and preparation method thereof is described in further detail.
Embodiment 1
One kind is for making (monocrystalline) MAPbBr3Crystal growth system, wherein MA refers to methylamine (CH3NH3 +) cation.
The crystal growth system includes the n,N-Dimethylformamide (DMF) as second liquid reagent, as the first liquid
The dimethyl silicone polymer (PDMS) of body reagent.
Embodiment 2
Present example provides make (monocrystalline) MAPbBr using the crystal growth system in embodiment 13Method comprising
Following steps.
(1) MABr and PbBr for being 1:1 by nonstoichiometric molar ratio2Drug is put into solvent as solute, preparation mole
Concentration is the MAPbBr of 0.5-1.5mol/L3Precursor solution, i.e. the first precursor liquid sample.
(2) the first precursor liquid sample is placed in uniform stirring 32 hours under room temperature, until MAPbBr3Solute is completely dissolved
It takes and is placed in clean clean glassware in right amount in DMF solvent, after filtering, obtain (the first examination of the second precursor liquid sample
Agent 401).
(3) liquid phase dimethyl silicone polymer (PDMS, the second reagent 402) is taken to be added in the second precursor liquid sample, liquid phase
Layering, and nonpolar organic polymer PDMS solution floats on upper layer, referring to Fig. 3.
(4) sample obtained by step (3) is placed in keep the temperature at 5 DEG C and is stored, after a period of time, MAPbBr3Monocrystalline (calcium
Titanium ore monocrystal 403) occur, size can grow to millimeter magnitude, as shown in Figure 4.
Experimental example 1
It is ground to powder to the perovskite monocrystal as made by embodiment 2 to test, to obtain its XRD diffraction pattern
Spectrum.As a result as shown in figure 5, MAPbBr can be confirmed by XRD diffracting spectrum3The cubic crystal structure of monocrystalline.
MAPbBr3The obtained XRD diffracting spectrum of the largest face of monocrystal is as shown in Figure 6.Compared with Fig. 5 data, Fig. 6 is only
The diffraction maximum of remaining { 100 } family of crystal planes, and from left to right peak position is followed successively by (100), (200), (300), (400) crystal face.Fig. 5
It is MAPbBr with the long obtained crystal of Fig. 6 figure contrast table open-birth3Monocrystalline.
Although illustrate and describing the application with specific embodiment, it will be appreciated that without departing substantially from the application's
Many other change and modification can be made in the case where spirit and scope.It is, therefore, intended that in the following claims
Including belonging to all such changes and modifications within the scope of the application.
Claims (10)
1. a kind of perovskite crystal grows system, which is characterized in that the crystal growth system in preferred temperature for making
The monocrystal of perovskite；
The crystal growth system include by the first liquid reagent and second liquid reagent of layered arrangement, the first liquid reagent by
First molecule is constituted, and first liquid reagent is able to maintain as liquid phase, the second liquid reagent under the preferred temperature
It is made of the second molecule；
First liquid reagent does not dissolve each other mutually with the second liquid reagent, and the second liquid reagent is the perovskite
And/or the good solvent of the raw material for making the perovskite；
First liquid reagent and the second liquid reagent, which have, such as gives a definition:
Under the preferred temperature, the second liquid reagent can be with second molecule across first molecule
Gap is detached from from the crystal growth system.
2. perovskite crystal according to claim 1 grows system, which is characterized in that first liquid reagent and described
Second liquid reagent has identical or different density；
Optionally, first liquid reagent and the second liquid reagent have different density, and first liquid tries
The density of agent is greater than the density of the second liquid reagent.
3. perovskite crystal according to claim 1 grows system, which is characterized in that first liquid reagent includes non-
Polar organic molecule；
Optionally, the nonpolar organic molecule includes dimethyl silicone polymer.
4. perovskite crystal according to claim 1 or 3 grows system, which is characterized in that the second liquid reagent packet
Include polar organic molecule；
Optionally, the polar organic molecule includes gamma-hydroxybutyric acid lactone, n,N-Dimethylformamide or dimethyl sulfoxide.
5. a kind of production method of perovskite, the production method can pass through the crystalline substance described in any one of Claims 1 to 4
Body growth system and be carried out, which is characterized in that the production method includes:
Temperature control is carried out to precursor liquid, so that the temperature of the precursor liquid is in the preferred temperature and is kept for the expected time；
Wherein, the precursor liquid by by the perovskite or the dissolution of raw material for being used to make the perovskite in the crystalline substance
The second liquid reagent in body growth system and obtain.
6. the production method of perovskite according to claim 5, which is characterized in that make the method packet of the precursor liquid
It includes: the first presoma making step and the second presoma making step that successively sequence carries out；
The first presoma making step includes: by the perovskite or the dissolution of raw material for being used to make the perovskite
In the second liquid reagent, optionally the filtration treatment carried out, to obtain the first presoma；
The second presoma making step includes: that first liquid reagent is added in the first presoma.
7. the production method of perovskite according to claim 5, which is characterized in that the preferred temperature is 5~60 DEG C；
Optionally, the preferred temperature is 12~50 DEG C；
Optionally, the preferred temperature is 23~43 DEG C；
Optionally, the preferred temperature is 38~47 DEG C.
8. the production method of perovskite according to claim 5, which is characterized in that the chemical general formula of the perovskite is
ABX3；
Wherein, A is the organic cation or inorganic cation of monovalence；
Alternatively, B is the metal cation of divalent；
Alternatively, X is the halide anion of monovalence；
Optionally, the inorganic cation includes caesium；The organic cation includes methylamine, methyl ether, ethamine, dimethylamine, guanamines；
Optionally, the metal cation includes germanium, tin, lead；
Optionally, the halide anion includes iodine, bromine, chlorine.
9. the production method of perovskite according to claim 8, which is characterized in that described for making the perovskite
Raw material includes the AX and BX being separately provided2。
10. the production method of perovskite according to claim 5, which is characterized in that the perovskite is monocrystalline and size
Reach millimeter.
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| CN110552061A (en) * | 2019-09-16 | 2019-12-10 | 武汉大学 | Preparation method for growing perovskite single crystal by liquid-phase diffusion separation crystallization at room temperature |
| CN111994947A (en) * | 2020-08-14 | 2020-11-27 | 福建医科大学 | 125-type cesium-lead-bromine perovskite nanosheet and aqueous phase preparation method of monocrystal thereof |
| CN112981538A (en) * | 2021-02-04 | 2021-06-18 | 广西大学 | Method for growing large-size perovskite single crystal |
| CN113106535A (en) * | 2021-03-11 | 2021-07-13 | 合肥工业大学 | Preparation method of two-dimensional perovskite single crystal |
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| CN106319625A (en) * | 2016-10-18 | 2017-01-11 | 陕西师范大学 | Method for growing perovskite monocrystal with liquid-liquid two-phase method |
| CN107287656A (en) * | 2017-06-13 | 2017-10-24 | 华中科技大学 | A kind of method of III V races quantum dot induced growth perovskite crystal |
| US20180334759A1 (en) * | 2017-05-19 | 2018-11-22 | National Tsing Hua University | Method for preparing perovskite crystal |
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| CN106319625A (en) * | 2016-10-18 | 2017-01-11 | 陕西师范大学 | Method for growing perovskite monocrystal with liquid-liquid two-phase method |
| US20180334759A1 (en) * | 2017-05-19 | 2018-11-22 | National Tsing Hua University | Method for preparing perovskite crystal |
| TW201900945A (en) * | 2017-05-19 | 2019-01-01 | 國立清華大學 | Method for preparing perovskite crystal |
| CN107287656A (en) * | 2017-06-13 | 2017-10-24 | 华中科技大学 | A kind of method of III V races quantum dot induced growth perovskite crystal |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110552061A (en) * | 2019-09-16 | 2019-12-10 | 武汉大学 | Preparation method for growing perovskite single crystal by liquid-phase diffusion separation crystallization at room temperature |
| CN111994947A (en) * | 2020-08-14 | 2020-11-27 | 福建医科大学 | 125-type cesium-lead-bromine perovskite nanosheet and aqueous phase preparation method of monocrystal thereof |
| CN111994947B (en) * | 2020-08-14 | 2022-12-06 | 福建医科大学 | 125-type cesium-lead-bromine perovskite nanosheet and aqueous phase preparation method of monocrystal thereof |
| CN112981538A (en) * | 2021-02-04 | 2021-06-18 | 广西大学 | Method for growing large-size perovskite single crystal |
| CN113106535A (en) * | 2021-03-11 | 2021-07-13 | 合肥工业大学 | Preparation method of two-dimensional perovskite single crystal |
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