CN106906518A - A kind of adjustable organic inorganic hybridization alloy perovskite of band gap - Google Patents

A kind of adjustable organic inorganic hybridization alloy perovskite of band gap Download PDF

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CN106906518A
CN106906518A CN201710198862.3A CN201710198862A CN106906518A CN 106906518 A CN106906518 A CN 106906518A CN 201710198862 A CN201710198862 A CN 201710198862A CN 106906518 A CN106906518 A CN 106906518A
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尚明辉
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Ningbo University of Technology
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Abstract

A kind of adjustable organic inorganic hybridization alloy perovskite of band gap, it is characterised in that：Chemical formula is CH3NH3SrxPb1‑xI3, wherein x=0.25,0.5,0.75 or 1；CH3NH3SrxPb1‑xI3Structure cell in 8.834 angstroms≤a≤8.869 angstrom, 8.847 angstroms≤b≤8.878 angstrom, 12.81 angstroms≤c≤12.863 angstrom, 89.6 °≤α≤89.622 °, 90.384 °≤β≤90.402 °, 90.082 °≤γ≤90.088 °, 1001.2 angstroms3≤ V≤1012.73 angstrom3.Using Sr2+Substitution Pb2+Mode adulterate CH3NH3PbI3.The incorporation of strontium element significantly improves CH3NH3SrxPb1‑xI3Stability；Strontium element doping simultaneously have adjusted band structure especially Fermi's energy and neighbouring conduction band bottom and top of valence band, increased CH3NH3SrxPb1‑xI3Band gap, and have adjusted electric charge effective mass.

Description

A kind of adjustable organic inorganic hybridization alloy perovskite of band gap
Technical field
The present invention relates to a kind of perovskite, particularly a kind of adjustable organic inorganic hybridization alloy perovskite of band gap.
Background technology
Organic metal halide perovskite material (ABX3) it was used for solar cell from 2009, surpass to current efficiency 22% is crossed, 5 times of battery efficiency when being initial, novel thin films such as DSSC, organic solar batteries Solar cell is got rid of after one's death, and perovskite solar cell is to develop very fast inexpensive thin film solar electricity over nearly 3 years Pond.
The high efficiency of perovskite solar cell is derived mainly from organic metal halide (ABX3) excellent absorbing properties.Its Middle A is mostly methylamino (CH3NH3 +), B is metallic lead bivalent cation (Pb2+), and X be the halogen monovalence such as chlorine, bromine, iodine it is cloudy from Son (X-).At present in terms of relevant efficient Ca-Ti ore type solar cell research, with methylamine lead iodine perovskite (CH3NH3PbI3, MAPbI3) of greatest concern.Main cause has：
I) material belongs to direct band-gap semicondictor, and optical band gap is about 1.5eV.Conduction band bottom mostlys come from Pb 6p rails Road, top of valence band is mainly contributed by I 5p electronics, so top of valence band belongs to p-p transition to conduction band bottom electron transition, therefore the material disappears Backscatter extinction logarithmic ratio is high, and hundreds of nanometers of thick films can fully absorb the sunshine of below 800nm.
Ii) Pb 6p and I 5p tracks are discrete substantially, and conduction band bottom and top of valence band nearby can be stronger with dispersion, and then so that should The existing superior hole transmission of material has the electric transmission i.e. bipolarity charge transmission of brilliance concurrently again.
Iii) this material prepares simple and with low cost.
Above-mentioned characteristic causes perovskite structure CH3NH3PbI3Can not only realize to visible ray and part near infrared light Absorb, then photo-generated carrier is difficult to be combined, and energy loss is small, it is efficient that this is that Ca-Ti ore type solar cell can be realized Basic reason.But the big intrinsic defect of methylamine lead iodine perovskite material two seriously constrains the battery large-scale application：First, first The photostability extreme difference of amine lead iodine perovskite material and easily meet water decomposition；Second, methylamine lead iodine perovskite it is soluble in water and then Accelerating the toxic element in the material --- the dispersion of lead is simultaneously caused environment pollution.
Current researcher is attempted by organic inorganic hybridization perovskite (ABX3) A, B and X element replace or Person's doping adjusts its performance, realizes optimization perovskite material opto-electronic conversion performance and improves the purpose of stability.B is two at present The work that the metal ion of valency is replaced doping is only limitted to Sn2+And Ge2+.Wherein Sn2+Replace Pb2+Become materials optical band gap The narrow sun light absorbs further widened, but have lost battery device open-circuit voltage；Additionally, Sn2+Easily turn under normal circumstances Turn to Sn4+Cause device performance degradation.
In sum, the problem of prior art presence is：
I) stability of methylamine lead iodine perovskite is badly in need of improving；
Toxic element --- lead in methylamine lead iodine perovskite material, is a big hidden danger for environment.
Applicant employs substitute elements of the Ba as Pb in the patent 2017100640459 applied before, has reached ratio Preferable effect.But the effect of Ba is mainly in view of it with Pb in same period, and atomic radius is similar, using other cycles Can element reach same effect has greatly uncertainty, in order to solve the above problems, it is necessary to the unit of different cycles Element doping is verified and analyzed.
The content of the invention
In order to solve the above problems, the invention provides one kind there is crystal structure more to stablize, band gap tune can be enriched Whole option, can be used in preparing the adjustable organic inorganic hybridization alloy calcium titanium of band gap of bigger photoelectric transformation efficiency solar cell Ore deposit.Application before the present invention is compared further optimizes data, reduces experimental error, while finding Sr and Ba in perovskite knot Performance in structure possesses very big difference.
The present invention provide technical scheme be：A kind of adjustable organic inorganic hybridization alloy perovskite of band gap, its feature exists In：Chemical formula is CH3NH3SrxPb1-xI3, wherein x=0.25,0.5,0.75 or 1；CH3NH3SrxPb1-xI3Structure cell in 8.834 Angstrom≤a≤8.869 angstrom, and 8.847 angstroms≤b≤8.878 angstrom, 12.81 angstroms≤c≤12.863 angstrom, 89.6 °≤α≤89.622 °, 90.384 °≤β≤90.402 °, 90.082 °≤γ≤90.088 °, 1001.2 angstroms3≤ V≤1012.73 angstrom3, wherein a, b and c point Wei not have three ribs on same summit on structure cell, angle is γ between a and b, and angle is α between b and c, angle between a and c It is β, V is unit cell volume；CH3NH3SrxPb1-xI3Structure cell body-centered be Sr2+；The summit of structure cell vertical direction incline is Sr2+Or Pb2+；The midpoint of structure cell vertical direction incline is Sr2+Or Pb2+；It is Sr at the structure cell bottom surface center of area2+Or Pb2+；On structure cell The bottom surface center of area is Sr2+Or Pb2+；Pass through I between the center of area of the upper surface of structure cell and the summit of upper surface-It is connected, under structure cell Pass through I between the center of area on surface and the summit of lower surface-It is connected；Pass through between the body-centered of structure cell and the midpoint of vertical direction incline I-It is connected；Pass through I between the summit of any vertical direction incline and the incline midpoint-It is connected；Between body-centered and the center of area of upper surface By I-It is connected, I is passed through between body-centered and the center of area of lower surface-It is connected；The preceding surface of structure cell, rear surface, left surface and right surface On respectively have the CH of two3NH3 +, the I of adjacent two inclines on structure cell vertical direction-By CH3NH3 +It is connected.It is not doped Pure CH3NH3PbI3Structure cell be the tetragonal crystal system of standard, the uneven doping of whole sample can be had a strong impact on subsequently to be made The stability and carrier mobility of the perovskite material during.In view of cell configuration, x=0.25,0.5,0.75 can The organic inorganic hybridization stabilization broad-band gap alloy perovskite higher to obtain structure cell uniformity, to the actually used mistake of perovskite material Chemical stability in journey and can be effectively improved with its solar cell photoelectric conversion efficiency for preparing.Because special Different electronic structure, lead ensure that the photoelectric transformation efficiency higher of the solar cell based on the material in perovskite material.Sr2+ Chemical stability is higher, and toxicity compares Ba2+It is lower.The calculated results are disclosed with Sr2+Substitute or part substitutes CH3NH3PbI3 In Pb2+Sr-Pb alloying perovskites are formed, stability of material is improved, optical band gap is widened, while Pb contains in reducing material Amount, so as to reduce environmental pollution and reduce cost recovery, and causes that perovskite structure possesses chemical stability higher, while Because band gap variation is different from the perovskite of doping Ba, the leeway of band gap selection is enriched, and it was found that, Sr is widened for band gap Effect it is close with Ba.First-principles calculations are the Ab initio method based on density functional theory (DFT), because of Sr2+With Ba2+ It is same main group, Ba2+With Pb2+Ionic radius relatively, so Sr2+Substitution CH3NH3PbI3In Pb2+Calculate relatively easy. Atom replaces the doping of form, Sr2+Electron affinity energy is compared with Pb2+It is smaller, therefore can be with I-、(CH3NH3)+Combine to form it is ionic more Strong ionic crystals, can further improve perovskite material self stability.Sr2+And Pb2+Valence electron arrangement and number Difference, therefore and I-、(CH3NH3)+The electronic band structure for combining to form ionic crystals will occur significant change, especially conduction band The change of bottom and valence band roof construction will cause the increase of band gap and the change of electric charge effective mass.
Work as x=0.25, the summit and midpoint of four inclines of structure cell vertical direction are Pb2+, the center of area of the upper bottom surface of structure cell The center of area with the bottom surface of structure cell is Pb2+；Work as x=0.5, the summit and midpoint of four inclines of structure cell vertical direction are Pb2 +, the center of area of the center of area of the upper bottom surface of structure cell and the bottom surface of structure cell is Sr2+, or, work as x=0.5, the upper bottom surface of structure cell Four summits of the center of area and upper bottom surface are Pb2+, the center of area of the bottom surface of structure cell and the four of bottom surface summits are Pb2+, erect Nogata is to be Sr to four midpoints of incline2+；Work as x=0.75, four midpoints of incline of structure cell vertical direction are to be Sr2+, The summit of four inclines of structure cell vertical direction is Pb2+, the center of area of the upper bottom surface of structure cell and the center of area of bottom surface are Sr2+；When X=1, the summit and midpoint of four inclines of structure cell vertical direction are Sr2+, the center of area of the upper bottom surface of structure cell and the bottom surface of structure cell The center of area be Sr2+.Substituted by the atom under x correspondence values, form the Pb of structure cell body-centered, the center of area and structure cell apex2+By Level substitution, forms the less crystal of defect, has huge raising to the stability of perovskite structure, while forming what is adjusted step by step Can band band gap, coordinate with the perovskite of original perovskite structure or the other element of adulterating can adapt to prepare more multiple level and The perovskite solar cell of different efficiency class, is specially adapted to prepare lamination perovskite solar cell.Calcium is reduced step by step Pb in perovskite like structure2+Content, maintain and ensure using strontium element adulterate perovskite structure can be used in make opto-electronic conversion Perovskite solar cell in hgher efficiency.
When x=0.25,0.5 or 0.75, the Pb of the upper surface of structure cell2+With the I of the upper surface of structure cell-Between ionic bond key A length of RPbIs, 3.164 angstroms≤RPbIs≤ 3.221 angstroms；Pb on structure cell vertical direction incline2+With the I on same incline-Between Ionic bond bond distance is RPbIc, 3.22 angstroms≤RPbIc≤ 3.264 angstroms, in crystal structure, Pb2+I adjacent with its horizontal direction-Formed Angle be ∠ IPbIs, 174.809 °≤∠ IPbIs≤ 175.468 °, Pb2+I adjacent with its vertical direction-The angle of formation It is ∠ IPbIc, 168.436 °≤∠ IPbIc≤173.419°.The excursion of bond distance has reacted the change of energy level, while can The change of band gap is adjusted, for the level-density parameter important role in the perovskite solar cell using perovskite material, Rational level structure can be formed simultaneously, the raising of transmission and open-circuit voltage beneficial to electronics.(CH simultaneously3NH3)+Or I- Replacement can equally change RPbIcAnd RPbIsBond distance, influence perovskite material level structure, it is necessary to and Sr2+And Pb2+Knot Structure energy level is adapted, and forms the perovskite structure of stabilization.While Sr2+With Ba2+With different level structures, in order to probe into it Specific energy level variations trend, the present invention is calculated energy level variations.
I between structure cell body-centered and the upper surface center of area-With the Sr of structure cell body-centered2+Between ionic bond bond distance be RSrIc, 3.252 angstroms≤RSrIc≤ 3.257 angstroms, the I between structure cell body-centered and vertical direction incline-With the Sr of structure cell body-centered2+Between from Sub-key bond distance is RSrIs, 3.22 angstroms≤RSrIs≤ 3.26 angstroms, in crystal structure, Sr2+I adjacent with its horizontal direction-The folder of formation Angle is ∠ ISrIs, 157.824 °≤∠ ISrIs≤ 176.008 °, Sr2+I adjacent with its vertical direction-The angle of formation is ∠ ISrIc, 167.695 °≤∠ ISrIc≤167.701°.The excursion of bond distance has reacted the change of energy level, while can adjust The change of band gap, for the level-density parameter important role in the perovskite solar cell using perovskite material, while Rational level structure can be formed, the raising of transmission and open-circuit voltage beneficial to electronics.While CH3NH3 +Or I-Replacement R can equally be changedSrIcAnd RSrIsBond distance, influence perovskite material level structure, it is necessary to and Sr2+And Pb2+Structure energy level It is adapted, forms the perovskite structure of stabilization.Bond distance has together decided on crystal structure and crystal parameter, different elements with bond angle Doping is also different to the variation pattern and trend of crystal structure, and the crystal stability that it brings is different.
CH3NH3SrxPb1-xI3Band gap width be Eg, 1.98eV≤Eg≤4.03eV.Different band gap widths are applied to Different electron transfer layers and the energy level of hole mobile material, effectively lifting level-density parameter degree.
Compared with prior art, the advantage of the invention is that：Using Sr2+Substitution Pb2+Mode adulterate CH3NH3PbI3.Strontium Unit
The incorporation of element significantly improves CH3NH3SrxPb1-xI3Stability；It is outstanding that strontium element doping simultaneously have adjusted band structure Its Fermi can and
Neighbouring conduction band bottom and top of valence band, increased CH3NH3SrxPb1-xI3Band gap, and have adjusted electric charge effective mass.
Brief description of the drawings
Fig. 1 is the sample XRD on the same day after the completion of the sample preparation of embodiment of the present invention 1-4 and contrast groups.
Fig. 2 is embodiment of the present invention 1-4 energy diagrams.
Fig. 3 is the crystal structure schematic diagram of the embodiment of the present invention 1.
Fig. 4 is the crystal structure schematic diagram of the embodiment of the present invention 3.
In Fig. 1, XRD, the XRD of embodiment 1, the XRD of embodiment 2, the implementation of contrast groups are respectively from lower road
The XRD of example 3 and the XRD of embodiment 4.
In Fig. 2, from left to right respectively the level structure figure of embodiment 1, the level structure figure of embodiment 2, the level structure of embodiment 3
Figure and the level structure figure of embodiment 4.
In Fig. 3 and Fig. 4,It is RPbIs,It is RSrIs,It is RPbIc,It is RSrIc, ∠ IPbIequatorialIt is ∠ IPbIs, ∠ ISrIequatorialIt is ∠ ISrIs, ∠ IPbIapicalIt is ∠ IPbIc, ∠ ISrIapicalIt is ∠ ISrIc。
Specific embodiment
The present invention is described in further detail below in conjunction with the accompanying drawings and by embodiment, and following examples are to this hair Bright explanation and the invention is not limited in following examples.Preparation method in contrast groups and in embodiment only provides one kind can Option, preparation method of the invention is not limited to the method provided in embodiment and contrast groups.It is real for concise explanation Apply (the CH in example and contrast groups3NH3)+, i.e. methylamine group represented using MA.Wherein a, b and c are respectively on single cell and have together One the three of summit rib, angle is γ between a and b, and angle is α between b and c, and angle is β between a and c, and V is single cell Volume, RSrIcIt is Sr on structure cell vertical direction2+With I-Ionic bond bond distance.RSrIsIt is Sr on structure cell horizontal plane2+With I-Ionic bond Bond distance.RPbIcIt is Pb on structure cell vertical direction2+With I-Ionic bond bond distance.RPbIsIt is Pb on structure cell horizontal plane2+With I-Ionic bond Bond distance.Pb2+I adjacent with its horizontal direction-The angle of formation is ∠ IPbIs, Pb2+I adjacent with its vertical direction-Formed Angle is ∠ IPbIc, Sr2+I adjacent with its horizontal direction-The angle of formation is ∠ ISrIs, Sr2+With phase on its vertical direction Adjacent I-The angle of formation is ∠ ISrIc。
Contrast groups.
Referring to Fig. 1.
The chemical formula of perovskite is MASr in this contrast groupsxPb1-xI3, the chemical formula of perovskite in x=0, i.e. this contrast groups It is MAPbI3.The chemical formula cell configuration is as follows：Structure cell body-centered, the summit of upper bottom surface, the upper bottom surface center of area, the summit of bottom surface, Four incline midpoints of the bottom surface center of area and vertical direction are Pb2+.Adjacent Pb on vertical direction same incline2+By I- Bonding.Body-centered Pb2+With vertical direction incline midpoint Pb2+Between pass through I-Bonding.Upper bottom surface center of area Pb2+With the top of upper bottom surface Point Pb2+Between pass through I-Bonding.Bottom surface center of area Pb2+With the summit Pb of bottom surface2+Between pass through I-Bonding.Body-centered Pb2+With it is upper Bottom surface center of area Pb2+By I-Bonding.Body-centered Pb2+With bottom surface center of area Pb2+By I-Bonding.MA into key position be existing skill Art.
The preparation method of this contrast groups is as follows：By PbCl2Add to DMF, then MAI added into DMF, form solution, Wherein add PbCl2Material amount with add MAI material amount ratio be 1:3.Then it is sufficiently stirred for solution and forms stabilization Perovskite solution.PbCl in perovskite solution2Substance withdrawl syndrome be 0.8mol/L.Then by perovskite solution with 3000 Revolutions per second speed rotate 30 seconds, be deposited on substrate surface, then crystallized under the conditions of 60 DEG C -95 DEG C, form homogeneous MAPbI3 Crystal.
By MAPbI3Crystal geometry calculation its electronic band structure.
I) MAPbI is built3Crystal unit cell geometry, relaxation optimization is carried out to its lattice parameter and atom site, is sought Look for Ground-state Structures
Ii above-mentioned Ground-state Structures) are based on, are set up and is included 4 MAPbI3Super cell (the MAPbI of unit cell3)4, and it is brilliant to optimize it Lattice constant and atom relative position.
Iii) crystal XRD of the theoretical modeling with ground state super cell as construction unit；
Iv electronics) is carried out to above-mentioned crystal structure from being in harmony calculatings, the wave function and charge density of acquisition Ground-state Structures；
V) wave function and charge density are based on, electronic band structure, charge density distribution, optical dielectric constant and mould is calculated Intend absorption spectrum.
Vi) in this contrast groups, structural relaxation is divided into two steps, first, the optimization of lattice parameter；Second, atom site Relaxation.
Vii) in Geometrical optimization and electronic structure calculating process, electron exchange association functional uses generalized gradient approximation (GGA, specially PBE).It can be 400eV that plane wave function is blocked, and calculating energy convergence is in harmony certainly for 1.01.0 × 10-7eV/ Atom. using the K points of Monkhorst-Pack grid configurations come approximate simulation MA crystal to space Brillouin zone.Ion relaxation mistake Energy convergence is 1.0 × 10 in journey-3The eV/ angstroms of convergence of correspondence each atomic force is 0.03eV/ angstroms of electron energy band Approximate simulation Brillouin zone is set using line style K points in calculating process.
A=8.913 angstroms in this contrast groups, b=8.913 angstroms, c=13.117 angstroms, α=90 °, β=90 °, γ=90 °, V= 1041.942 angstroms3, RPbIs=3.221 angstroms, RPbIc=3.307 angstroms, ∠ IPbIs=175.446 °, ∠ IPbIc=168.712 °.
Embodiment 1.
Referring to Fig. 1, Fig. 2 and Fig. 3.
The chemical formula of perovskite is MASr in the present embodimentxPb1-xI3, the chemistry of perovskite in x=0.25, i.e. this contrast groups Formula is MASr0.25Pb0.75I3.The chemical formula cell configuration is as follows：Structure cell body-centered is Sr2+.The summit of upper bottom surface, the upper bottom surface center of area, The summit of bottom surface, four incline midpoints of the bottom surface center of area and vertical direction are Pb2+.Phase on vertical direction same incline Adjacent Pb2+By I-Bonding.Body-centered Sr2+With vertical direction incline midpoint Pb2+Between pass through I-Bonding.Upper bottom surface center of area Pb2+ With the summit Pb of upper bottom surface2+Between pass through I-Bonding.Bottom surface center of area Pb2+With the summit Pb of bottom surface2+Between pass through I-Bonding. Body-centered Sr2+With upper bottom surface center of area Pb2+By I-Bonding.Body-centered Sr2+With bottom surface center of area Pb2+By I-Bonding.MA into key mapping It is set to prior art.
The preparation method of this contrast groups is as follows：By SrCl2And PbCl2Add to DMF, add SrCl2Material amount with plus Enter PbCl2Material amount ratio be 1:3.MAI is added into DMF again, solution is formed, wherein the SrCl for adding2With PbCl2Total material amount with add MAI material amount ratio be 1:3.Then it is sufficiently stirred for solution and forms stabilization perovskite Solution.Wherein SrCl2And PbCl2Total material amount concentration be 0.8mol/L.Then by perovskite solution with 3000 revolutions per seconds Speed rotates 30 seconds, is deposited on substrate surface, is then crystallized under the conditions of 60 DEG C -95 DEG C, forms homogeneous MAPbI3Crystal.
By MAPbI3Crystal geometry calculation its electronic band structure.
I) it is based on super cell (MAPbI3)4, 4 Pb atoms therein are replaced one by one with 1 Sr atom builds Sr-Pb alloys Perovskite MASr0.25Pb0.75I3(totally four kinds of configurations), and lattice parameter optimization and atom site relaxation are carried out to each structure, than Compared with four total energys of configuration (Etot), determine minimum energy is configured as ground state；
Ii) the XRD of crystal of the theoretical modeling with ground state super cell as construction unit；
Iii electronics) is carried out to above-mentioned crystal structure from being in harmony calculatings, the wave function and charge density of acquisition Ground-state Structures；
Iv) based on wave function and charge density, calculating electronic band structure, charge density distribution, optical dielectric constant is simultaneously Simulation absorption spectrum.
MASr0.25Pb0.75I3Band gap width Eg be 1.98eV.A=8.834 angstroms, b=8.747 angstroms, c=12.81 angstroms, α =89.622 °, β=90.384 °, γ=90.085 °, V=1001.2 angstroms3, RPbIs=3.164 angstroms, RPbIc=3.264 angstroms, RSrIs =3.253 angstroms, RSrIc=3.257 angstroms.∠IPbIs=174.809 °, ∠ IPbIc=169.241 °, ∠ ISrIs=157.824 °, ∠ISrIc=167.695 °.
Embodiment 2.
Referring to Fig. 1 and Fig. 2.
The chemical formula of perovskite is MASr in the present embodimentxPb1-xI3, the chemistry of perovskite in x=0.5, i.e. this contrast groups Formula is MASr0.5Pb0.5I3.The chemical formula cell configuration is as follows：Structure cell body-centered, the upper bottom surface center of area and the bottom surface center of area are Sr2+.On The summit of bottom surface, the four incline midpoints in the summit of bottom surface and vertical direction are Pb2+.Phase on vertical direction same incline Adjacent Pb2+By I-Bonding.Body-centered Sr2+With vertical direction incline midpoint Pb2+Between pass through I-Bonding.Upper bottom surface center of area Sr2+ With the summit Pb of upper bottom surface2+Between pass through I-Bonding.Bottom surface center of area Sr2+With the summit Pb of bottom surface2+Between pass through I-Bonding. Body-centered Sr2+With upper bottom surface center of area Sr2+By I-Bonding.Body-centered Sr2+With bottom surface center of area Sr2+By I-Bonding.MA into key mapping It is set to prior art.
The preparation method of this contrast groups is as follows：By SrCl2And PbCl2Add to DMF, add SrCl2Material amount with plus Enter PbCl2Material amount ratio be 1:1.MAI is added into DMF again, solution is formed, wherein the SrCl for adding2With PbCl2Total material amount with add MAI material amount ratio be 1:3.Then it is sufficiently stirred for solution and forms stabilization perovskite Solution.Wherein SrCl2And PbCl2Total material amount concentration be 0.8mol/L.Then by perovskite solution with 3000 revolutions per seconds Speed rotates 30 seconds, is deposited on substrate surface, is then crystallized under the conditions of 60 DEG C -95 DEG C, forms homogeneous MAPbI3Crystal.
By MAPbI3Crystal geometry calculation its electronic band structure.
I) it is based on super cell (MAPbI3)4, 2 Pb atoms therein are replaced one by one with 2 Sr atoms builds Sr-Pb alloys Perovskite MASr0.75Pb0.25I3(totally four kinds of configurations), and lattice parameter optimization and atom site relaxation are carried out to each structure, than Compared with four total energys of configuration (Etot), determine minimum energy is configured as ground state；
Ii) crystal XRD of the theoretical modeling with ground state super cell as construction unit；
Iii electronics) is carried out to above-mentioned crystal structure from being in harmony calculatings, the wave function and charge density of acquisition Ground-state Structures；
Iv) based on wave function and charge density, calculating electronic band structure, charge density distribution, optical dielectric constant is simultaneously Simulation absorption spectrum.
MASr0.5Pb0.5I3Band gap width Eg be 3.06eV.A=8.848 angstroms, b=8.863 angstroms, c=12.831 angstroms, α =89.617 °, β=90.402 °, γ=90.088 °, V=1006.1 angstroms3, RPbIs=3.221 angstroms, RPbIc=3.22 angstroms, RSrIs =3.26 angstroms, RSrIc=3.256 angstroms.∠IPbIs=175.298 °, ∠ IPbIc=173.419 °, ∠ ISrIs=176.008 °, ∠ISrIc=167.701 °.
Embodiment 3.
Referring to Fig. 1, Fig. 2 and Fig. 4.
The chemical formula of perovskite is MASr in the present embodimentxPb1-xI3, the chemistry of perovskite in x=0.75, i.e. this contrast groups Formula is MASr0.75Pb0.25I3.The chemical formula cell configuration is as follows：Structure cell body-centered, the upper bottom surface center of area, the bottom surface center of area and vertically Four, direction incline midpoint is Sr2+.The summit of upper bottom surface and the summit of bottom surface are Pb2+.Phase on vertical direction same incline Adjacent Sr2+And Pb2+By I-Bonding.Body-centered Sr2+With vertical direction incline midpoint Sr2+Between pass through I-Bonding.Upper bottom surface face Heart Sr2+With the summit Pb of upper bottom surface2+Between pass through I-Bonding.Bottom surface center of area Sr2+With the summit Pb of bottom surface2+Between pass through I-Bonding.Body-centered Sr2+With upper bottom surface center of area Sr2+By I-Bonding.Body-centered Sr2+With bottom surface center of area Sr2+By I-Bonding.MA's It is prior art into key position.
The preparation method of this contrast groups is as follows：By SrCl2And PbCl2Add to DMF, add SrCl2Material amount with plus Enter PbCl2Material amount ratio be 3:1.MAI is added into DMF again, solution is formed, wherein the SrCl for adding2With PbCl2Total material amount with add MAI material amount ratio be 1:3.Then it is sufficiently stirred for solution and forms stabilization perovskite Solution.Wherein SrCl2And PbCl2Total material amount concentration be 0.8mol/L.Then by perovskite solution with 3000 revolutions per seconds Speed rotates 30 seconds, is deposited on substrate surface, is then crystallized under the conditions of 60 DEG C -95 DEG C, forms homogeneous MAPbI3Crystal.
I) it is based on super cell (MAPbI3)4, 3 Pb atoms therein are replaced one by one with 3 Sr atoms builds Sr-Pb alloys Perovskite MASr0.75Pb0.25I3(totally four kinds of configurations), and lattice parameter optimization and atom site relaxation are carried out to each structure, than Compared with four total energys of configuration (Etot), determine minimum energy is configured as ground state；
Ii) crystal XRD of the theoretical modeling with ground state super cell as construction unit；
Iii electronics) is carried out to above-mentioned crystal structure from being in harmony calculatings, the wave function and charge density of acquisition Ground-state Structures；
Iv) based on wave function and charge density, calculating electronic band structure, charge density distribution, optical dielectric constant is simultaneously Simulation absorption spectrum.
MASr0.75Pb0.25I3Band gap width Eg be 3.33eV.A=8.863 angstroms, b=8..871 angstroms, c=12.847 angstroms, α=89.6 °, β=90.396 °, γ=90.088 °, V=1010.04 angstroms3, RPbIs=3.169 angstroms, RPbIc=3.229 angstroms, RSrIs =3.234 angstroms, RSrIc=3.253 angstroms.∠IPbIs=175.468 °, ∠ IPbIc=168.436 °, ∠ ISrIs=174.564 °, ∠ISrIc=169.348 °.
Embodiment 4.
Referring to Fig. 1 and Fig. 2.
The chemical formula of perovskite is MASr in the present embodimentxPb1-xI3, the chemical formula of perovskite in x=1, i.e. this contrast groups It is MASrI3.The chemical formula cell configuration is as follows：Structure cell body-centered, the summit of upper bottom surface, the upper bottom surface center of area, the summit of bottom surface, Four incline midpoints of the bottom surface center of area and vertical direction are Sr2+.Adjacent Sr on vertical direction same incline2+By I- Bonding.Body-centered Sr2+With vertical direction incline midpoint Sr2+Between pass through I-Bonding.Upper bottom surface center of area Sr2+With the top of upper bottom surface Point Sr2+Between pass through I-Bonding.Bottom surface center of area Sr2+With the summit Sr of bottom surface2+Between pass through I-Bonding.Body-centered Sr2+With it is upper Bottom surface center of area Sr2+By I-Bonding.Body-centered Sr2+With bottom surface center of area Sr2+By I-Bonding.MA into key position be existing skill Art.
The preparation method of this contrast groups is as follows：By SrCl2Add to DMF.MAI is added into DMF again, forms solution, The SrCl for wherein adding2The amount of material is 1 with the amount ratio of the material for adding MAI:3.Then solution is sufficiently stirred for be formed surely Determine perovskite solution.Wherein SrCl2Substance withdrawl syndrome is 0.8mol/L.Then by perovskite solution with 3000 revolutions per seconds of speed Degree rotation 30 seconds, is deposited on substrate surface, is then crystallized under the conditions of 60 DEG C -95 DEG C, forms homogeneous MAPbI3Crystal.
I) it is based on super cell (MAPbI3)4, wherein will all replace with Sr atoms structure Sr-Pb alloy perovskites by Pb atoms MASrI3, and lattice parameter optimization and atom site relaxation are carried out to each structure, compare four total energys of configuration (Etot), really That determines minimum energy is configured as ground state
Ii) crystal XRD of the theoretical modeling with ground state super cell as construction unit；
Iii electronics) is carried out to above-mentioned crystal structure from being in harmony calculatings, the wave function and charge density of acquisition Ground-state Structures；
Iv) based on wave function and charge density, calculating electronic band structure, charge density distribution, optical dielectric constant is simultaneously Simulation absorption spectrum.
MASrI3Band gap width Eg be 4.03eV.A=8.869 angstroms, b=8..878 angstroms, c=12.863 angstroms, α= 89.601 °, β=90.393 °, γ=90.082 °, V=1012.73 angstroms3, RSrIs=3.22 angstroms, RSrIc=3.252 angstroms.∠ ISrIs=175.184 °, ∠ ISrIc=169.392 °.
It is the cell configuration variation relation between clear explanation contrast groups and embodiment 1-4, is said using Tables 1 and 2 It is bright.Tables 1 and 2 is the geometric parameter contrast of contrast groups and each structure cell in embodiment 1-4, and wherein geometric parameter includes a, b, c, α, beta, gamma, V, RPbIs, RPbIc, RSrIs, RSrIc, ∠ IPbIs, ∠ IPbIc, ∠ ISrIs, ∠ ISrIc。
Table 1
Table 2
, it is apparent that substantially being eliminated in the miscellaneous peak that 2theta is 28.5 ° or so and 32 ° or so from Fig. 1, Sr is illustrated The doping of element effectively improves the stability of perovskite structure.
Furthermore, it is necessary to explanation, the specific embodiment described in this specification, is named the shape of its parts and components Claiming etc. can be with difference, and the above content described in this specification is only to structure example explanation of the present invention.It is all according to The equivalence changes or simple change done according to the construction described in inventional idea of the present invention, feature and principle, are included in this hair In the protection domain of bright patent.Those skilled in the art can do various to described specific embodiment The modification of various kinds or supplement are substituted using similar mode, without departing from structure of the invention or surmount present claims Scope defined in book, all should belong to protection scope of the present invention.

Claims (5)

1. the adjustable organic inorganic hybridization alloy perovskite of a kind of band gap, it is characterised in that：Chemical formula is CH3NH3SrxPb1-xI3, Wherein x=0.25,0.5,0.75 or 1；CH3NH3SrxPb1-xI3Structure cell in 8.834 angstroms≤a≤8.869 angstrom, 8.847 angstroms≤b≤ 8.878 angstroms, 12.81 angstroms≤c≤12.863 angstrom, 89.6 °≤α≤89.622 °, 90.384 °≤β≤90.402 °, 90.082 °≤ γ≤90.088 °, 1001.2 angstroms3≤ V≤1012.73 angstrom3, wherein a, b and c be respectively on structure cell with three of same summit Rib, angle is γ between a and b, and angle is α between b and c, and angle is β between a and c, and V is unit cell volume；CH3NH3SrxPb1- xI3Structure cell body-centered be Sr2+；The summit of structure cell vertical direction incline is Sr2+Or Pb2+；The midpoint of structure cell vertical direction incline It is Sr2+Or Pb2+；It is Sr at the structure cell bottom surface center of area2+Or Pb2+；The structure cell upper bottom surface center of area is Sr2+Or Pb2+；Structure cell Pass through I between the center of area of upper surface and the summit of upper surface-It is connected, between the center of area of the lower surface of structure cell and the summit of lower surface By I-It is connected；Pass through I between the body-centered of structure cell and the midpoint of vertical direction incline-It is connected；The summit of any vertical direction incline Pass through I between the incline midpoint-It is connected；Pass through I between body-centered and the center of area of upper surface-It is connected, the center of area of body-centered and lower surface Between pass through I-It is connected；Respectively there is the CH of two on the preceding surface of structure cell, rear surface, left surface and right surface3NH3 +, structure cell erect The I of upward adjacent two inclines of Nogata-By CH3NH3 +It is connected.
2. the adjustable organic inorganic hybridization alloy perovskite of band gap according to claim 1, it is characterised in that：Work as x= 0.25, the summit and midpoint of four inclines of structure cell vertical direction are Pb2+, the center of area of the upper bottom surface of structure cell and the bottom surface of structure cell The center of area be Pb2+；Work as x=0.5, the summit and midpoint of four inclines of structure cell vertical direction are Pb2+, the upper bottom surface of structure cell The center of area of the bottom surface of the center of area and structure cell is Sr2+, or, work as x=0.5, the center of area of the upper bottom surface of structure cell and the four of upper bottom surface Summit is Pb2+, the center of area of the bottom surface of structure cell and the four of bottom surface summits are Pb2+, in four inclines of vertical direction Point is to be Sr2+；Work as x=0.75, four midpoints of incline of structure cell vertical direction are to be Sr2+, four sides of structure cell vertical direction The summit of rib is Pb2+, the center of area of the upper bottom surface of structure cell and the center of area of bottom surface are Sr2+；Work as x=1, structure cell vertical direction four The summit and midpoint of bar incline are Sr2+, the center of area of the center of area of the upper bottom surface of structure cell and the bottom surface of structure cell is Sr2+。
3. the adjustable organic inorganic hybridization alloy perovskite of band gap according to claim 2, it is characterised in that：Work as x= 0.25th, 0.5 or 0.75, the Pb of structure cell upper surface2+With the I of structure cell upper surface-Between ionic bond bond distance be RPbIs, 3.164 angstroms ≤RPbIs≤ 3.221 angstroms；Pb on structure cell vertical direction incline2+With the I on same incline-Between ionic bond bond distance be RPbIc, 3.22 angstroms≤RPbIc≤ 3.264 angstroms, in crystal structure, Pb2+I adjacent with its horizontal direction-The angle of formation is ∠ IPbIs, 174.809°≤∠IPbIs≤ 175.468 °, Pb2+I adjacent with its vertical direction-The angle of formation is ∠ IPbIc, 168.436°≤∠IPbIc≤173.419°。
4. the adjustable organic inorganic hybridization alloy perovskite of band gap according to claim 1 or 2 or 3, it is characterised in that：It is brilliant I between the cell space heart and the upper surface center of area-With the Sr of structure cell body-centered2+Between ionic bond bond distance be RSrIc, 3.252 angstroms≤RSrIc ≤ 3.257 angstroms, the I between structure cell body-centered and vertical direction incline-With the Sr of structure cell body-centered2+Between ionic bond bond distance be RSrIs, 3.22 angstroms≤RSrIs≤ 3.26 angstroms, in crystal structure, Sr2+I adjacent with its horizontal direction-The angle of formation is ∠ ISrIs, 157.824 °≤∠ ISrIs≤ 176.008 °, Sr2+I adjacent with its vertical direction-The angle of formation is ∠ ISrIc, 167.695°≤∠ISrIc≤167.701°。
5. the adjustable organic inorganic hybridization alloy perovskite of band gap according to claim 1, it is characterised in that： CH3NH3SrxPb1-xI3Band gap width be Eg, 1.98eV≤Eg≤4.03eV.
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