CN106601917B - A kind of preparation method of unleaded organic-inorganic cationic hydridization perovskite material and its film jointly - Google Patents
A kind of preparation method of unleaded organic-inorganic cationic hydridization perovskite material and its film jointly Download PDFInfo
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Abstract
The invention discloses the preparation methods of a kind of cationic common hydridization perovskite material of unleaded organic-inorganic and its film, the unleaded common hydridization perovskite material of organic-inorganic cation is obtained by the common hydridization BiI3 of the inorganic cations such as the organic cations such as methylamino or ethylamino and Rb or Cs, and the unleaded common hydridization perovskite thin film of organic-inorganic cation is made using magnetron sputtering method.The present invention relates to solar energy electric materials, field of semiconductor materials, replace Pb as the central ion of perovskite material with Bi, avoid perovskite material to the potential pollution of environment, furthermore, the perovskite material that Bi and the common hydridization of organic-inorganic cation obtain has lower band gap, be conducive to electron transition, improve incident photon-to-electron conversion efficiency.
Description
Technical field
The present invention relates to solar energy electric material, field of semiconductor materials more particularly to a kind of unleaded organic-inorganic sun from
The preparation method of sub common hydridization perovskite material and its film.
Background technique
With the development of human society, energy consumption increasingly increases, and the development of solar-photovoltaic technology is undoubtedly by the mankind
Concern.Perovskite material, as one of 2013 " the big technological breakthrough in the world ten ", it is considered to be develop high-efficiency solar
The most potential new material of battery.The highest transformation efficiency of perovskite solar battery has been up to 22.1% at present.
Perovskite in perovskite solar battery is usually the ABX3 type compound of organic inorganic hybridization, wherein A
For methylamino, ethylamino- or inorganic K, Rb, Cs plasma；B is the metal ions such as Pb, Sn or Ti, X
For anion such as Cl, Br, I.If all inorganic ions of A, the perovskite material are known as inorganic perovskite material,
If A is the small organic molecules, referred to as organic inorganic hybridization perovskite material such as methylamino, ethylamino-.
Perovskite material research the most widely be methylamino, ethylamino- hydridization PbI2 and the iodine methylamine lead that obtains and
Iodine ethamine lead.But the central ion of this organic inorganic hybridization perovskite material is Pb, there are potential environmental pollutions to ask
Topic.
Document [Anna J. Lehner et.al, Chenistry Materials, 2015,27,7137-7148.
Crystal and Electronic Structures of Complex Bismuth Iodides A3Bi2I9(A = K,
Rb, Cs) Related to Perovskite:Aiding the Rational Design of Photovoltaics] report
The road crystal structure of A3Bi2I9 (A=K, Rb, Cs) finds that the band gap of RbBi2I9 is 2.1eV；Document [
Michael Saliba. et.al,Science.aah5557 (2016), Incorporation of rubidium
Cations into perovskite solar cellsimproves photovoltaic performance] it reports
The research of Rb ion doping methiodide amine lead perovskite material, and 20.4% photoelectric conversion is obtained on the area of 0.5cm2
Efficiency.Document [354 ISSUE 6308 of Abhishek Swarnkaret.al, Science, OCT.2016, VOL,
Quantum dot-induced phasestabilization of a-CsPbI3 perovskite for high-
Efficiency photovoltaics] report the heat injection synthetic method and performance study result of CsPbI3 quantum dot.
Above-mentioned literature method has a problem that that is, the band gap of RbBi2I9 is 2.1eV, and methiodide amine lead perovskite material
Material is leaded perovskite material, and there are potential problem of environmental pollutions.The present invention proposes a kind of using Bi as the nothing of center ion
Lead organic inorganic hybridization perovskite material.It is well known that the stability of pure inorganic ions hydridization perovskite material is more preferable, but light
Electrical property is slightly poor；The photoelectric properties of the perovskite material of organic-inorganic ion hydridization are prominent, but stability is slightly worse.Meanwhile text
The hydridization perovskite material of organic-inorganic ion described in offering is that anode ion is organic methylamino or ethylamino- while using
Anion is inorganic halogen ion.The main reason for stability is poor is that organic anion is combined into central ion
Substance meet the photoelectric properties sharp-decay that can be decomposed reaction after water or air and lead to perovskite material.
Summary of the invention
The present invention is to overcome at least one described in the above-mentioned prior art insufficient, and it is prominent, stable to provide a kind of photoelectric properties
Property the high environmentally friendly common hydridization perovskite material of unleaded organic-inorganic cation.
In order to solve the above-mentioned technical problem, the present invention is achieved by the following technical programs:
A kind of unleaded common hydridization perovskite material of organic-inorganic cation, the unleaded organic-inorganic cation are common miscellaneous
Change perovskite material to be obtained by the common hydridization BiI3 of the inorganic cations such as the organic cations such as methylamino or ethylamino and Rb or Cs.
The present invention is using common hydridization BiI3 of the inorganic cations such as organic cations and Rb or Cs such as methylamino or ethylaminos
The unleaded common hydridization perovskite material of organic-inorganic cation is obtained, becomes the central ion of perovskite material with Bi substitution Pb,
Avoid perovskite material to the potential pollution of environment, in addition, the perovskite material that Bi and the common hydridization of organic-inorganic cation obtain
Material has lower band gap, is conducive to electron transition, improves incident photon-to-electron conversion efficiency.Organic inorganic hybridization perovskite material of the invention
Material is different from traditional organic inorganic hybridization perovskite material, and commonly called organic inorganic hybridization perovskite refers to that cation is
Organic methylamino or ethylamino- organic ion, anion be inorganic iodide ion, organic inorganic hybridization of the present invention be then sun from
Subdivision is other than organic methylamino, ethylamino-, and there are also the inorganic ions such as inorganic potassium, rubidium, caesium.By being introduced in cationic side
Inorganic ions, so that the stability of perovskite material of the present invention is greatly improved.The inorganic cations such as Rb or Cs with have
The perovskite material that the common hydridization BiI3 of machine cation is obtained has excellent photoelectric properties, and the doping of Rb, Cs plasma
The incident photon-to-electron conversion efficiency of perovskite material is improved, Rb, Cs ion are by the influence to perovskite material structure, so that its forbidden band
Width is adjusted；Rubidium, the suitable outer electronic structure of cesium ion are but also these ions have better photoelectric conversion simultaneously
Performance.
The method of the cationic common hydridization perovskite material of unleaded organic-inorganic and its film, includes the following steps:
S1. by BiI3, iodine methylamine or iodine ethamine, RbI or CsI or KI, stoichiometrically 1:1.8 ~ 2.2:0.8 ~ 1.2 are matched
Than mixed grinding, the unleaded common hydridization perovskite material of organic-inorganic cation is obtained；
S2. the obtained perovskite material of step S1 is put into mold and is pressed into perovskite target under 5 ~ 150MPa pressure
Material；
S3. the perovskite target that step S2 is obtained is put into vacuum magnetic-control sputtering platform and carries out magnetron sputtering, film thickness reaches
It deflates after to 50 ~ 1500nm, obtains the unleaded common hydridization perovskite thin film of organic-inorganic cation.
The present invention is put into vacuum magnetic-control sputtering platform for the perovskite material prepared in advance as target using magnetron sputtering method
Magnetron sputtering is carried out to obtain and substrate binding force is strong, the dense uniform common hydridization perovskite of unleaded organic-inorganic cation is thin
Film is advantageously implemented large area preparation to further increase its photoelectric properties.
In step S1, be added before BiI3, iodine methylamine or iodine ethamine, RbI or CsI or KI grinding DMF or isopropanol or its
Its alcohols is dried after grinding, obtains the unleaded common hydridization perovskite material of organic-inorganic cation.DMF is added before grinding
Or isopropanol or other alcohols are conducive to the synthesis of perovskite material.
In step S1, stoichiometrically 1:1:1 is matched by BiI3, iodine methylamine or iodine ethamine, RbI or CsI or KI, is conducive to
Each raw material sufficiently reacts.
In step S1, after BiI3, iodine methylamine or iodine ethamine, RbI or CsI or KI mixed grinding, 100 ~ 300 DEG C are heated to,
It is cooling to take out, obtain the unleaded common hydridization perovskite material of organic-inorganic cation.Heating is so that perovskite material knot after grinding
It is brilliant more perfect, more perfect crystal structure is obtained, to further increase the photoelectric properties of perovskite material.
In step S1, after BiI3, iodine methylamine or iodine ethamine, RbI or CsI or KI mixed grinding, heat under protection of argon gas
It is cooling to take out to 100 ~ 600 DEG C, obtain the unleaded common hydridization perovskite material of organic-inorganic cation.Argon gas can anti-block
Change, especially prevents the decomposition of iodide.
In step S2, vacuum sealing is carried out after perovskite material compacting and obtains perovskite target.
In step S2, the perovskite material is suppressed under 10 ~ 100MPa pressure.
In step S3, vacuum magnetic-control sputtering platform is evacuated to 10 before progress magnetron sputtering-4~10-6Pa is filled with argon gas extremely
0.5~0.8Pa。
In step S3, deflation is taken out after Magnetron Sputtering Thin Film reaches 100 ~ 1000nm.
Compared with prior art, the invention has the following beneficial effects:
The present invention with Bi replace Pb become perovskite material central ion, using methylamino or ethylamino etc. it is organic sun from
The common hydridization BiI3 of the inorganic cations such as son and Rb or Cs obtains the unleaded common hydridization perovskite material of organic-inorganic cation, keeps away
Exempt from perovskite material to the potential pollution of environment, in addition, the perovskite material that Bi and the common hydridization of organic-inorganic cation obtain
With lower band gap, be conducive to electron transition, improve incident photon-to-electron conversion efficiency.Organic inorganic hybridization of the present invention is cation
Part is other than organic methylamino, ethylamino-, and there are also the inorganic ions such as inorganic potassium, rubidium, caesium, by introducing nothing in cationic side
Machine ion, so that the stability of perovskite material of the present invention is greatly improved.The inorganic cations such as Rb or Cs with it is organic
The perovskite material that cationic common hydridization BiI3 is obtained has excellent photoelectric properties, and the doping of Rb, Cs plasma improves
The incident photon-to-electron conversion efficiency of perovskite material.The present invention is put the perovskite material prepared in advance as target using magnetron sputtering method
Enter vacuum magnetic-control sputtering platform and carry out magnetron sputtering to obtain and substrate binding force is strong, dense uniform unleaded organic-inorganic cation is total
With hydridization perovskite thin film, to further increase its photoelectric properties, it is advantageously implemented large area preparation.
Detailed description of the invention
Fig. 1 is the X-ray diffractogram of the common hydridization perovskite material of unleaded organic-inorganic cation of the invention.
Specific embodiment
In order to allow those skilled in the art to more fully understand technical solution of the present invention, below with reference to the present invention make into
One step illustrates, but embodiment does not limit in any form the present invention.
Embodiment 1
A kind of unleaded common hydridization perovskite material of organic-inorganic cation, by methylamino organic cation and the inorganic sun of Rb
The common hydridization BiI3 of ion is obtained.
The preparation method of the cationic common hydridization perovskite material of the unleaded organic-inorganic and its film, including walk as follows
It is rapid:
S1. by BiI3, iodine methylamine, RbI, stoichiometrically the mixing of 1:2:1 proportion is put into mortar and grinds 15 minutes, obtains
To the unleaded common hydridization perovskite material of organic-inorganic cation of brownish black；
S2. the obtained perovskite material of step S1 is put into mold the compression moulding under 45MPa pressure, then vacuum is close
It seals up to perovskite target；
S3. the perovskite target that step S2 is obtained is put into vacuum magnetic-control sputtering platform, is evacuated to 10-5Pa is filled with argon
Gas opens radio-frequency power supply and carries out magnetron sputtering, deflation is taken out after film thickness reaches 550nm, is obtained unleaded organic to 0.65Pa
The common hydridization perovskite thin film of inorganic cation.
Embodiment 2
A kind of unleaded common hydridization perovskite material of organic-inorganic cation, by methylamino organic cation and the inorganic sun of Cs
The common hydridization BiI3 of ion is obtained.
The preparation method of the cationic common hydridization perovskite material of the unleaded organic-inorganic and its film, including walk as follows
It is rapid:
S1. by BiI3, iodine methylamine, CsI, stoichiometrically the mixing of 1:2:1 proportion is put into mortar and grinds 15 minutes, obtains
To the unleaded common hydridization perovskite material of organic-inorganic cation of brownish black；
S2. the obtained perovskite material of step S1 is put into mold the compression moulding under 45MPa pressure, then vacuum is close
It seals up to perovskite target；
S3. the perovskite target that step S2 is obtained is put into vacuum magnetic-control sputtering platform, is evacuated to 10-5Pa is filled with argon
Gas opens radio-frequency power supply and carries out magnetron sputtering, deflation is taken out after film thickness reaches 550nm, is obtained unleaded organic to 0.65Pa
The common hydridization perovskite thin film of inorganic cation.
Embodiment 3
A kind of unleaded common hydridization perovskite material of organic-inorganic cation, by methylamino organic cation and the inorganic sun of K
The common hydridization BiI3 of ion is obtained.
The preparation method of the cationic common hydridization perovskite material of the unleaded organic-inorganic and its film, including walk as follows
It is rapid:
S1. by BiI3, iodine methylamine, KI, stoichiometrically the mixing of 1:2:1 proportion is put into mortar and grinds 15 minutes, obtains
The unleaded common hydridization perovskite material of organic-inorganic cation of brownish black；
S2. the obtained perovskite material of step S1 is put into mold the compression moulding under 55MPa pressure, then vacuum is close
It seals up to perovskite target；
S3. the perovskite target that step S2 is obtained is put into vacuum magnetic-control sputtering platform, is evacuated to 10-5Pa is filled with argon
Gas opens radio-frequency power supply and carries out magnetron sputtering, deflation is taken out after film thickness reaches 550nm, is obtained unleaded organic to 0.65Pa
The common hydridization perovskite thin film of inorganic cation.
Embodiment 4
A kind of unleaded common hydridization perovskite material of organic-inorganic cation, by ethylamino organic cation and the inorganic sun of Rb
The common hydridization BiI3 of ion is obtained.
The preparation method of the cationic common hydridization perovskite material of the unleaded organic-inorganic and its film, including walk as follows
It is rapid:
S1. by BiI3, iodine ethamine, RbI, stoichiometrically the mixing of 1:2:1 proportion is put into mortar and grinds 15 minutes, obtains
To the unleaded common hydridization perovskite material of organic-inorganic cation of brownish black；
S2. the obtained perovskite material of step S1 is put into mold the compression moulding under 55MPa pressure, then vacuum is close
It seals up to perovskite target；
S3. the perovskite target that step S2 is obtained is put into vacuum magnetic-control sputtering platform, is evacuated to 10-5Pa is filled with argon
Gas opens radio-frequency power supply and carries out magnetron sputtering, deflation is taken out after film thickness reaches 550nm, is obtained unleaded organic to 0.65Pa
The common hydridization perovskite thin film of inorganic cation.
Embodiment 5
A kind of unleaded common hydridization perovskite material of organic-inorganic cation, by ethylamino organic cation and the inorganic sun of Cs
The common hydridization BiI3 of ion is obtained.
The preparation method of the cationic common hydridization perovskite material of the unleaded organic-inorganic and its film, including walk as follows
It is rapid:
S1. by BiI3, iodine ethamine, CsI, stoichiometrically the mixing of 1:2:1 proportion is put into mortar and grinds 15 minutes, obtains
To the unleaded common hydridization perovskite material of organic-inorganic cation of brownish black；
S2. the obtained perovskite material of step S1 is put into mold the compression moulding under 55MPa pressure, then vacuum is close
It seals up to perovskite target；
S3. the perovskite target that step S2 is obtained is put into vacuum magnetic-control sputtering platform, is evacuated to 10-5Pa is filled with argon
Gas opens radio-frequency power supply and carries out magnetron sputtering, deflation is taken out after film thickness reaches 550nm, is obtained unleaded organic to 0.65Pa
The common hydridization perovskite thin film of inorganic cation.
Embodiment 6
A kind of unleaded common hydridization perovskite material of organic-inorganic cation, by ethylamino organic cation and the inorganic sun of K
The common hydridization BiI3 of ion is obtained.
The preparation method of the cationic common hydridization perovskite material of the unleaded organic-inorganic and its film, including walk as follows
It is rapid:
S1. by BiI3, iodine ethamine, KI, stoichiometrically the mixing of 1:2:1 proportion is put into mortar and grinds 15 minutes, obtains
The unleaded common hydridization perovskite material of organic-inorganic cation of brownish black；
S2. the obtained perovskite material of step S1 is put into mold the compression moulding under 55MPa pressure, then vacuum is close
It seals up to perovskite target；
S3. the perovskite target that step S2 is obtained is put into vacuum magnetic-control sputtering platform, is evacuated to 10-5Pa is filled with argon
Gas opens radio-frequency power supply and carries out magnetron sputtering, deflation is taken out after film thickness reaches 550nm, is obtained unleaded organic to 0.65Pa
The common hydridization perovskite thin film of inorganic cation.
Embodiment 7
The present embodiment the difference from embodiment 1 is that, in preparation step S1, BiI3, iodine methylamine, RbI mixed grinding 15 divide
Zhong Hou is put into water heating kettle and is heated to 200 DEG C, cooling to take out, and obtains crystallizing the unleaded organic-inorganic cation of perfect black total
With hydridization perovskite material, other are the same as embodiment 1.
Embodiment 8
The present embodiment and the difference of embodiment 7 are, in preparation step S1,100 DEG C of coolings are heated in water heating kettle and are taken
Out, other are the same as embodiment 7.
Embodiment 9
The present embodiment and the difference of embodiment 7 are, in preparation step S1,300 DEG C of coolings are heated in water heating kettle and are taken
Out, other are the same as embodiment 7.
Embodiment 10
The present embodiment the difference from embodiment 1 is that, in preparation step S1, BiI3, iodine methylamine, RbI mixed grinding 15 divide
Zhong Hou, is put into the heating furnace of argon gas protection and is heated to 350 DEG C, and it is common miscellaneous to obtain unleaded organic-inorganic cation for cooling taking-up
Change perovskite material.
Embodiment 11
The present embodiment and the difference of embodiment 10 are, in preparation step S1, are heated in the heating furnace of argon gas protection
100 DEG C of cooling taking-ups, other are the same as embodiment 10.
Embodiment 12
The present embodiment and the difference of embodiment 11 are, in preparation step S1, are heated in the heating furnace of argon gas protection
600 DEG C of cooling taking-ups, other are the same as embodiment 10.
Embodiment 13
The present embodiment the difference from example 2 is that, in preparation step S1, BiI3, iodine methylamine, CsI grinding before be added
DMF is dried after 15 minutes as abrasive media, grinding, obtains the unleaded common hydridization perovskite material of organic-inorganic cation
Material.
Embodiment 14
The present embodiment and the difference of embodiment 13 are that the abrasive media being added in preparation step S1 is isopropanol, other
With embodiment 13.
Embodiment 15
The present embodiment and the difference of embodiment 13 are that the abrasive media being added in preparation step S1 is dehydrated alcohol,
He is the same as embodiment 13.
Embodiment 16
A kind of unleaded common hydridization perovskite material of organic-inorganic cation, by ethylamino organic cation and the inorganic sun of K
The common hydridization BiI3 of ion is obtained.
The preparation method of the cationic common hydridization perovskite material of the unleaded organic-inorganic and its film, including walk as follows
It is rapid:
S1. by BiI3, iodine ethamine, KI, stoichiometrically the mixing of 1:1.9:0.9 proportion is put into mortar and grinds 15 minutes,
Obtain the unleaded common hydridization perovskite material of organic-inorganic cation of brownish black；
S2. the obtained perovskite material of step S1 is put into mold the compression moulding under 10MPa pressure, then vacuum is close
It seals up to perovskite target；
S3. the perovskite target that step S2 is obtained is put into vacuum magnetic-control sputtering platform, is evacuated to 10-5Pa is filled with argon
Gas opens radio-frequency power supply and carries out magnetron sputtering, deflation is taken out after film thickness reaches 100nm, obtains unleaded organic nothing to 0.6Pa
The common hydridization perovskite thin film of machine cation.
Embodiment 17
A kind of unleaded common hydridization perovskite material of organic-inorganic cation, by ethylamino organic cation and the inorganic sun of K
The common hydridization BiI3 of ion is obtained.
The preparation method of the cationic common hydridization perovskite material of the unleaded organic-inorganic and its film, including walk as follows
It is rapid:
S1. by BiI3, iodine ethamine, KI, stoichiometrically the mixing of 1:2.1:1.1 proportion is put into mortar and grinds 15 minutes,
Obtain the unleaded common hydridization perovskite material of organic-inorganic cation of brownish black；
S2. the obtained perovskite material of step S1 is put into mold the compression moulding under 100MPa pressure, then vacuum
It seals up to perovskite target；
S3. the perovskite target that step S2 is obtained is put into vacuum magnetic-control sputtering platform, is evacuated to 10-5Pa is filled with argon
Gas opens radio-frequency power supply and carries out magnetron sputtering, deflation is taken out after film thickness reaches 1000nm, is obtained unleaded organic to 0.7Pa
The common hydridization perovskite thin film of inorganic cation.
Embodiment 17
A kind of unleaded common hydridization perovskite material of organic-inorganic cation, by ethylamino organic cation and the inorganic sun of K
The common hydridization BiI3 of ion is obtained.
The preparation method of the cationic common hydridization perovskite material of the unleaded organic-inorganic and its film, including walk as follows
It is rapid:
S1. by BiI3, iodine ethamine, KI, stoichiometrically the mixing of 1:1.8:0.8 proportion is put into mortar and grinds 15 minutes,
Obtain the unleaded common hydridization perovskite material of organic-inorganic cation of brownish black；
S2. the obtained perovskite material of step S1 is put into mold the compression moulding under 5MPa pressure, then vacuum is close
It seals up to perovskite target；
S3. the perovskite target that step S2 is obtained is put into vacuum magnetic-control sputtering platform, is evacuated to 10-4Pa is filled with argon
Gas opens radio-frequency power supply and carries out magnetron sputtering, deflation is taken out after film thickness reaches 50nm, obtains unleaded organic nothing to 0.5Pa
The common hydridization perovskite thin film of machine cation.
Embodiment 18
A kind of unleaded common hydridization perovskite material of organic-inorganic cation, by ethylamino organic cation and the inorganic sun of K
The common hydridization BiI3 of ion is obtained.
The preparation method of the cationic common hydridization perovskite material of the unleaded organic-inorganic and its film, including walk as follows
It is rapid:
S1. by BiI3, iodine ethamine, KI, stoichiometrically the mixing of 1:2.2:1.2 proportion is put into mortar and grinds 15 minutes,
Obtain the unleaded common hydridization perovskite material of organic-inorganic cation of brownish black；
S2. the obtained perovskite material of step S1 is put into mold the compression moulding under 150MPa pressure, then vacuum
It seals up to perovskite target；
S3. the perovskite target that step S2 is obtained is put into vacuum magnetic-control sputtering platform, is evacuated to 10-6Pa is filled with argon
Gas opens radio-frequency power supply and carries out magnetron sputtering, deflation is taken out after film thickness reaches 1500nm, is obtained unleaded organic to 0.8Pa
The common hydridization perovskite thin film of inorganic cation.
Test method
Perovskite material made from Example 1 ~ 18 does X-ray diffraction respectively, obtains X-ray as shown in drawings and spreads out
Figure is penetrated, the X-ray diffractogram of the figure and traditional leaded perovskite material is almost the same, shows to replace Pb to become perovskite with Bi
The central ion of material utilizes the common hydridization BiI3 of the inorganic cations such as the organic cations such as methylamino or ethylamino and Rb or Cs
It is feasible for obtaining the common hydridization perovskite material of unleaded organic-inorganic cation, therefore can be prepared and unleaded have using the formula
It the common hydridization perovskite material of machine inorganic cation and can be prepared using polishing, the perovskite material pressure being prepared
Target of the manufactured perovskite target as magnetron sputtering, the unleaded organic-inorganic of large-area high-quality is made by magnetron sputtering method
Cationic common hydridization perovskite thin film.
Claims (9)
1. a kind of preparation method of the unleaded common hydridization perovskite thin film of organic-inorganic cation, which is characterized in that including as follows
Step:
S1. by BiI3, iodine ethamine, RbI stoichiometrically 1:1.8 ~ 2.2:0.8 ~ 1.2 match mixed grinding 15 minutes, obtain
The unleaded common hydridization perovskite material of organic-inorganic cation；
S2. the obtained perovskite material of step S1 is put into mold under 5 ~ 150MPa pressure and is pressed into perovskite target material；
S3. the perovskite target that step S2 is obtained being put into vacuum magnetic-control sputtering platform and carries out magnetron sputtering, film thickness reaches 50 ~
It deflates after 1500nm, obtains the unleaded common hydridization perovskite thin film of organic-inorganic cation.
2. the preparation method of the unleaded common hydridization perovskite thin film of organic-inorganic cation according to claim 1, special
Sign is, in step S1, in BiI3, iodine ethamine, DMF or isopropanol is added before RbI grinding, dried after grinding, obtain nothing
The common hydridization perovskite material of lead organic-inorganic cation.
3. the preparation method of the unleaded common hydridization perovskite thin film of organic-inorganic cation according to claim 1, special
Sign is, in step S1, BiI3, iodine ethamine, after RbI mixed grinding, be heated to 100 ~ 300 DEG C, it is cooling to take out, obtain unleaded having
The common hydridization perovskite material of machine inorganic cation.
4. the preparation method of the unleaded common hydridization perovskite thin film of organic-inorganic cation according to claim 1, special
Sign is, in step S1, BiI3, iodine ethamine, after RbI mixed grinding, be heated to 100 ~ 600 DEG C under protection of argon gas, cooling takes
Out, the unleaded common hydridization perovskite material of organic-inorganic cation is obtained.
5. the preparation side of described in any item unleaded common hydridization perovskite thin films of organic-inorganic cation according to claim 1 ~ 4
Method, which is characterized in that in step S1, BiI3, iodine ethamine, RbI stoichiometrically 1:2:1 match.
6. the preparation method of the unleaded common hydridization perovskite thin film of organic-inorganic cation according to claim 1, special
Sign is, in step S2, carries out vacuum sealing after perovskite material compacting and obtains perovskite target.
7. the preparation method of the common hydridization perovskite thin film of unleaded organic-inorganic cation according to claim 1 or 6,
It is characterized in that, in step S2, the perovskite material is suppressed under 10 ~ 100MPa pressure.
8. the preparation method of the unleaded common hydridization perovskite thin film of organic-inorganic cation according to claim 1, special
Sign is, vacuum magnetic-control sputtering platform is evacuated to 10 before progress magnetron sputtering in step S3-4~10-6Pa is filled with argon gas to 0.5
~0.8Pa。
9. the preparation method of the common hydridization perovskite thin film of unleaded organic-inorganic cation according to claim 1 or 8,
It is characterized in that, in step S3, deflation is taken out after Magnetron Sputtering Thin Film reaches 100 ~ 1000nm.
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