CN106757371A - A kind of organo-mineral complexing perovskite monocrystalline induced conversion method and device based on methylamine atmosphere - Google Patents
A kind of organo-mineral complexing perovskite monocrystalline induced conversion method and device based on methylamine atmosphere Download PDFInfo
- Publication number
- CN106757371A CN106757371A CN201611176317.6A CN201611176317A CN106757371A CN 106757371 A CN106757371 A CN 106757371A CN 201611176317 A CN201611176317 A CN 201611176317A CN 106757371 A CN106757371 A CN 106757371A
- Authority
- CN
- China
- Prior art keywords
- methylamine
- single crystal
- organic
- inorganic composite
- pbi
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 title claims abstract description 191
- 238000000034 method Methods 0.000 title claims abstract description 35
- 238000006243 chemical reaction Methods 0.000 title abstract description 7
- 230000000536 complexating effect Effects 0.000 title abstract 3
- 229910052500 inorganic mineral Inorganic materials 0.000 title abstract 3
- 239000011707 mineral Substances 0.000 title abstract 3
- 239000013078 crystal Substances 0.000 claims abstract description 164
- 239000000463 material Substances 0.000 claims abstract description 29
- 238000010521 absorption reaction Methods 0.000 claims abstract description 28
- 230000003287 optical effect Effects 0.000 claims abstract description 18
- 238000011282 treatment Methods 0.000 claims abstract description 7
- 239000002131 composite material Substances 0.000 claims description 49
- 230000006698 induction Effects 0.000 claims description 42
- 239000000243 solution Substances 0.000 claims description 23
- 238000011426 transformation method Methods 0.000 claims description 12
- -1 amine halide Chemical class 0.000 claims description 10
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 10
- 229940071870 hydroiodic acid Drugs 0.000 claims description 9
- LLWRXQXPJMPHLR-UHFFFAOYSA-N methylazanium;iodide Chemical compound [I-].[NH3+]C LLWRXQXPJMPHLR-UHFFFAOYSA-N 0.000 claims description 9
- LEBNOLJDIRXMJN-UHFFFAOYSA-N [Pb].[I] Chemical compound [Pb].[I] LEBNOLJDIRXMJN-UHFFFAOYSA-N 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- CALQKRVFTWDYDG-UHFFFAOYSA-N butan-1-amine;hydroiodide Chemical compound [I-].CCCC[NH3+] CALQKRVFTWDYDG-UHFFFAOYSA-N 0.000 claims description 5
- 229910052732 germanium Inorganic materials 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 125000000962 organic group Chemical group 0.000 claims description 5
- 238000011084 recovery Methods 0.000 claims description 5
- 229910052718 tin Inorganic materials 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- 229910052745 lead Inorganic materials 0.000 claims description 4
- XHFGWHUWQXTGAT-UHFFFAOYSA-N dimethylamine hydrochloride Natural products CNC(C)C XHFGWHUWQXTGAT-UHFFFAOYSA-N 0.000 claims description 3
- IQDGSYLLQPDQDV-UHFFFAOYSA-N dimethylazanium;chloride Chemical group Cl.CNC IQDGSYLLQPDQDV-UHFFFAOYSA-N 0.000 claims description 3
- 230000005669 field effect Effects 0.000 claims description 3
- 230000001939 inductive effect Effects 0.000 claims description 3
- BFHRMYJJIMKAFV-UHFFFAOYSA-N 2-iodoguanidine Chemical compound NC(N)=NI BFHRMYJJIMKAFV-UHFFFAOYSA-N 0.000 claims description 2
- 229960000789 guanidine hydrochloride Drugs 0.000 claims description 2
- PJJJBBJSCAKJQF-UHFFFAOYSA-N guanidinium chloride Chemical compound [Cl-].NC(N)=[NH2+] PJJJBBJSCAKJQF-UHFFFAOYSA-N 0.000 claims description 2
- VNAAUNTYIONOHR-UHFFFAOYSA-N hexylazanium;iodide Chemical compound [I-].CCCCCC[NH3+] VNAAUNTYIONOHR-UHFFFAOYSA-N 0.000 claims description 2
- JMXLWMIFDJCGBV-UHFFFAOYSA-N n-methylmethanamine;hydroiodide Chemical group [I-].C[NH2+]C JMXLWMIFDJCGBV-UHFFFAOYSA-N 0.000 claims description 2
- HBZSVMFYMAOGRS-UHFFFAOYSA-N octylazanium;iodide Chemical compound [I-].CCCCCCCC[NH3+] HBZSVMFYMAOGRS-UHFFFAOYSA-N 0.000 claims description 2
- 230000007704 transition Effects 0.000 abstract description 3
- 230000009466 transformation Effects 0.000 description 13
- 239000010409 thin film Substances 0.000 description 10
- 238000000862 absorption spectrum Methods 0.000 description 9
- 238000011160 research Methods 0.000 description 6
- 230000015556 catabolic process Effects 0.000 description 5
- 238000006731 degradation reaction Methods 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 230000008439 repair process Effects 0.000 description 5
- 230000005693 optoelectronics Effects 0.000 description 4
- 238000000103 photoluminescence spectrum Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000000634 powder X-ray diffraction Methods 0.000 description 3
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 238000011419 induction treatment Methods 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 150000002892 organic cations Chemical class 0.000 description 2
- 230000000717 retained effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000002211 ultraviolet spectrum Methods 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000005067 remediation Methods 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
Classifications
-
- 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
- C30B29/54—Organic compounds
-
- 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
- C30B7/14—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions the crystallising materials being formed by chemical reactions in the solution
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Photovoltaic Devices (AREA)
Abstract
Description
技术领域technical field
本发明涉及一种有机无机复合钙钛矿单晶到单晶的转变方法，尤其涉及一种基于甲胺气氛的有机无机复合钙钛矿单晶诱导转变方法及装置，属于半导体晶体材料技术领域。The invention relates to a conversion method from an organic-inorganic composite perovskite single crystal to a single crystal, in particular to a methylamine-based atmosphere-based organic-inorganic composite perovskite single crystal induced transformation method and device, and belongs to the technical field of semiconductor crystal materials.
背景技术Background technique
2009年，日本桐荫横滨大学Miyasaka等首次将钙钛矿材料CH3NH3PbBr3和CH3NH3PbI3用在太阳能电池上，拉开了钙钛矿材料研究的序幕，使得有机无机复合钙钛矿材料获得了深入的研究发展。有机无机复合钙钛矿材料，尤其是有机无机复合铅基钙钛矿材料作为一类新型半导体材料，表现出特殊的光电及相变性能。基于其诸多优点，在太阳能电池，光电探测器，LED等领域具有潜在的应用价值，是目前世界各国研究的重点。但是，关于该类材料报道的多数为薄膜材料，例如，CN105098080A公开了一种制造有机无机钙钛矿晶体薄膜的方法，包括在柔性衬底上形成有机无机钙钛矿薄膜，然后进行退火处理，使得该晶体薄膜的晶粒平均尺寸增加，且可得到更多[220]晶向的晶粒，因此延长其载流子寿命，减少晶界复合，从而提高有机无机钙钛矿太阳能电池的光电转换效率。但是，薄膜材料稳定性一般低于单晶材料，且薄膜多晶存在更多缺陷，不利于材料本征性能的研究应用。In 2009, Miyasaka of Toin Yokohama University in Japan used perovskite materials CH 3 NH 3 PbBr 3 and CH 3 NH 3 PbI 3 in solar cells for the first time, which opened the prelude to the research on perovskite materials, making organic-inorganic composites Perovskite materials have been intensively researched and developed. Organic-inorganic composite perovskite materials, especially organic-inorganic composite lead-based perovskite materials, as a new type of semiconductor material, exhibit special photoelectric and phase transition properties. Based on its many advantages, it has potential application value in the fields of solar cells, photodetectors, LEDs, etc., and is currently the focus of research in various countries in the world. However, most of the reports on this type of material are thin film materials, for example, CN105098080A discloses a method for manufacturing organic-inorganic perovskite crystal thin films, including forming organic-inorganic perovskite thin films on a flexible substrate, and then performing annealing treatment, The average grain size of the crystal film is increased, and more [220] crystal grains can be obtained, thereby prolonging its carrier life and reducing grain boundary recombination, thereby improving the photoelectric conversion of organic-inorganic perovskite solar cells efficiency. However, the stability of thin film materials is generally lower than that of single crystal materials, and thin film polycrystals have more defects, which is not conducive to the research and application of intrinsic properties of materials.
目前，有少数有机无机复合钙钛矿单晶生长的报道，例如CN104911705A提供一种低温溶液中生长ABX3(A为CH3NH3 +、H2N-CH＝NH2 +、(CH3)4N+、C7H7 +、Cs+或C3H11SN3 2+，B为Pb、Ge或Sn；X为Cl、Br或I)钙钛矿单晶的方法，将卤代物和能溶解该金属化合物的溶剂混合配制成溶液，将铅源、锡源或锗源金属化合物加入后配成单晶生长液，采用连续多周期分阶段在低温溶液中快速生长ABX3钙钛矿单晶，所用溶液浓度大，生长所需原料溶解均匀，增加生长周期和对生长条件的精细控制，得到大尺寸的ABX3钙钛矿单晶，从而促进对钙钛矿材料及相关光电器件(包括太阳电池、光探测器、LED及激光器等)的基础机理理论研究。该方法步骤繁琐，需多周期分阶段进行生长，不利于高品质单晶的可控生长。相比于有机无机复合钙钛矿单晶薄膜的丰富研究成果来说，有机无机复合钙钛矿晶体材料的研究相对薄弱，尤其是对于有机无机复合钙钛矿单晶材料的可控生长以及对所得单晶进行特殊处理得到优化的单晶的转变方法，迄今为止在国内外尚未见报道。At present, there are a few reports on the growth of organic-inorganic composite perovskite single crystals. For example, CN104911705A provides a low-temperature solution to grow ABX 3 (A is CH 3 NH 3 + , H 2 N-CH=NH 2 + , (CH 3 ) 4 N + , C 7 H 7 + , Cs + or C 3 H 11 SN 3 2+ , B is Pb, Ge or Sn; X is Cl, Br or I) perovskite single crystal method, the halide and Solvents that can dissolve the metal compound are mixed to make a solution, and the metal compound of lead source, tin source or germanium source is added to make a single crystal growth solution, and the ABX 3 perovskite single crystal is rapidly grown in the low temperature solution in stages by continuous multi-cycle Crystal, the concentration of the solution used is large, the raw materials required for growth are uniformly dissolved, the growth cycle is increased and the growth conditions are finely controlled, and a large-sized ABX 3 perovskite single crystal is obtained, thereby promoting the development of perovskite materials and related optoelectronic devices (including Theoretical research on the basic mechanism of solar cells, photodetectors, LEDs and lasers, etc.). The steps of this method are cumbersome, and multi-cycle and stage-by-stage growth is required, which is not conducive to the controllable growth of high-quality single crystals. Compared with the rich research results of organic-inorganic composite perovskite single crystal thin films, the research on organic-inorganic composite perovskite crystal materials is relatively weak, especially for the controllable growth of organic-inorganic composite perovskite single crystal materials and the controllable growth of organic-inorganic composite perovskite single crystal materials. The conversion method of the obtained single crystal through special treatment to obtain an optimized single crystal has not been reported at home and abroad so far.
发明内容Contents of the invention
针对现有技术的不足，本发明提供一种对有机无机复合钙钛矿单晶材料进行诱导优化处理得到光学吸收范围更宽的有机无机复合钙钛矿单晶的转变方法。特别是，基于甲胺气氛的有机无机复合钙钛矿单晶诱导转变方法。经过该方法诱导之后，有机无机复合钙钛矿单晶既保留原有的单晶性，又能改善其本征特性，扩大光学吸收范围，提高其在太阳能电池、光电探测器等方面应用性能，扩大应用范围。Aiming at the deficiencies of the prior art, the present invention provides a method for transforming an organic-inorganic composite perovskite single crystal material into an organic-inorganic composite perovskite single crystal with a wider optical absorption range by inductive optimization treatment. In particular, an organic-inorganic composite perovskite single crystal-induced transition method based on a methylamine atmosphere. After induced by this method, the organic-inorganic composite perovskite single crystal not only retains the original single crystal, but also improves its intrinsic characteristics, expands the optical absorption range, and improves its application performance in solar cells, photodetectors, etc. Expand the scope of application.
本发明还提供用于以上所述方法的单晶诱导转变装置。The present invention also provides a single crystal induced transformation device used in the above method.
术语说明：Terminology Explanation:
有机无机复合钙钛矿，具有LMX3或L2MX4分子通式，其中，L为C2H6NH2、C4H9NH3、C6H13NH3、C8H17NH3、CN3H4或CH3NH3；M为Pb、Ge或Sn；X为Cl、Br或I。其中，C2H6NH2简称DA，C4H9NH3简称BA，C6H13NH3简称HA，C8H17NH3简称OA，CN3H4简称GA，CH3NH3简称MA。Organic-inorganic composite perovskite, with the general molecular formula of LMX 3 or L 2 MX 4 , where L is C 2 H 6 NH 2 , C 4 H 9 NH 3 , C 6 H 13 NH 3 , C 8 H 17 NH 3 , CN 3 H 4 or CH 3 NH 3 ; M is Pb, Ge or Sn; X is Cl, Br or I. Among them, C 2 H 6 NH 2 is referred to as DA, C 4 H 9 NH 3 is referred to as BA, C 6 H 13 NH 3 is referred to as HA, C 8 H 17 NH 3 is referred to as OA, CN 3 H 4 is referred to as GA, and CH 3 NH 3 is referred to as MA.
本发明的技术方案如下：Technical scheme of the present invention is as follows:
一、基于甲胺气氛的有机无机复合钙钛矿单晶诱导转变方法1. Induced transformation method of organic-inorganic composite perovskite single crystal based on methylamine atmosphere
一种基于甲胺气氛的有机无机复合钙钛矿单晶诱导转变方法，所述有机无机复合钙钛矿，具有LMX3或L2MX4分子通式，其中，L为有机基团，L＝C2H6NH2、C4H9NH3、C6H13NH3、C8H17NH3、CN3H4或CH3NH3，M为Pb、Ge或Sn；X为Cl、Br或I；包括步骤如下：An organic-inorganic composite perovskite single crystal induced transformation method based on a methylamine atmosphere, the organic-inorganic composite perovskite has a general molecular formula of LMX 3 or L 2 MX 4 , wherein, L is an organic group, L= C 2 H 6 NH 2 , C 4 H 9 NH 3 , C 6 H 13 NH 3 , C 8 H 17 NH 3 , CN 3 H 4 or CH 3 NH 3 , M is Pb, Ge or Sn; X is Cl, Br or I; including steps as follows:
将所述有机无机复合钙钛矿单晶置于甲胺气氛下，在40-150℃温度下诱导处理3-36h。The organic-inorganic composite perovskite single crystal is placed under a methylamine atmosphere, and induced at a temperature of 40-150° C. for 3-36 hours.
经以上诱导后，甲胺分子部分取代单晶中的有机基团，所得转变后的单晶是一种完全单晶，既保留原有的晶体结构，又在紫外-可见光区具有更宽的光学吸收范围。After the above induction, methylamine molecules partially replace the organic groups in the single crystal, and the resulting transformed single crystal is a complete single crystal, which not only retains the original crystal structure, but also has a wider optical range in the ultraviolet-visible region. absorption range.
所述有机无机复合钙钛矿单晶经甲胺诱导转变后，完全保留原有的单晶性，但其光学吸收范围大大扩展，光电性能大大提高。诱导后，原单晶中的有机基团被甲胺分子部分取代，形成混合有机阳离子单晶，使单晶带隙降低。根据本发明优选的，所述有机无机复合钙钛矿单晶是有机无机复合碘铅基钙钛矿单晶，分子通式LPbI3或L2PbI4，L＝C2H6NH2、C4H9NH3、C6H13NH3、C8H17NH3、CN3H4或CH3NH3。After the organic-inorganic composite perovskite single crystal undergoes transformation induced by methylamine, the original single crystal property is completely retained, but its optical absorption range is greatly expanded, and the photoelectric performance is greatly improved. After induction, the organic groups in the original single crystal were partially replaced by methylamine molecules to form a mixed organic cation single crystal, which reduced the band gap of the single crystal. Preferably according to the present invention, the organic-inorganic composite perovskite single crystal is an organic-inorganic composite iodine-lead-based perovskite single crystal, with a general molecular formula of LPbI 3 or L 2 PbI 4 , L=C 2 H 6 NH 2 , C 4H9NH3 , C6H13NH3 , C8H17NH3 , CN3H4 or CH3NH3 . _ _ _
进一步优选的，所述有机无机复合碘铅基钙钛矿单晶选自：C2H6NH2PbI3、(C4H9NH3)2PbI4、(C6H13NH3)2PbI4、(C8H17NH3)2PbI4或CN3H4PbI3。Further preferably, the organic-inorganic composite iodine-lead-based perovskite single crystal is selected from: C 2 H 6 NH 2 PbI 3 , (C 4 H 9 NH 3 ) 2 PbI 4 , (C 6 H 13 NH 3 ) 2 PbI 4 , (C 8 H 17 NH 3 ) 2 PbI 4 or CN 3 H 4 PbI 3 .
其中，以实施例1的C2H6NH2PbI3和实施例3的(C4H9NH3)2PbI4为例，经甲胺气氛诱导之后，C2H6NH2PbI3、(C4H9NH3)2PbI4单晶中部分C2H6NH2(简称DA)、C4H9NH3(简称BA)离子被甲胺离子取代，分别转变为混合单晶MA0.1DA0.9PbI3、(MA0.66BA0.34)2PbI4。单晶转变后，保留原有的晶体结构，但该类混合单晶具有CH3NH3PbI3(简称MAPbI3)的性质，表现为半导体带隙降低，光学吸收范围大大扩展，光电性能大大提高。例如，Wherein, taking C 2 H 6 NH 2 PbI 3 in Example 1 and (C 4 H 9 NH 3 ) 2 PbI 4 in Example 3 as examples, after being induced by a methylamine atmosphere, C 2 H 6 NH 2 PbI 3 , In (C 4 H 9 NH 3 ) 2 PbI 4 single crystal, part of C 2 H 6 NH 2 (DA for short) and C 4 H 9 NH 3 (BA for short) ions were replaced by methylamine ions, respectively converted into mixed single crystal MA 0.1 DA 0.9 PbI 3 , (MA 0.66 BA 0.34 ) 2 PbI 4 . After single crystal transformation, the original crystal structure is retained, but this type of mixed single crystal has the properties of CH 3 NH 3 PbI 3 (MAPbI 3 for short), which is characterized by a reduced semiconductor band gap, greatly expanded optical absorption range, and greatly improved optoelectronic properties. . E.g,
a.C2H6NH2PbI3晶体其光学吸收范围在200-500nm范围全吸收；甲胺气体诱导之后单晶转变为MA0.1DA0.9PbI3，其光学吸收范围扩展到800nm。The optical absorption range of aC 2 H 6 NH 2 PbI 3 crystal is fully absorbed in the range of 200-500nm; the single crystal transforms into MA 0.1 DA 0.9 PbI 3 after methylamine gas induction, and its optical absorption range extends to 800nm.
b.(C4H9NH3)2PbI4晶体其光学吸收范围在200-530nm范围全吸收。甲胺气体诱导之单晶转变为(MA0.66BA0.34)2PbI4后其光学吸收范围扩展到800nm。b. The optical absorption range of (C 4 H 9 NH 3 ) 2 PbI 4 crystal is totally absorbed in the range of 200-530nm. The optical absorption range extends to 800nm after methylamine gas-induced single crystal transformation to (MA 0.66 BA 0.34 ) 2 PbI 4 .
根据本发明优选的，所述诱导处理温度为100-120℃。Preferably according to the present invention, the induction treatment temperature is 100-120°C.
根据本发明优选的，所述的甲胺气氛是用质量分数为20～40wt％的甲胺水溶液发生并经干燥得到的甲胺气体。Preferably, according to the present invention, the methylamine atmosphere is a methylamine gas obtained by using a methylamine aqueous solution with a mass fraction of 20-40wt% and drying.
根据本发明，所述的晶体诱导时间需要根据所述有机无机复合钙钛矿单晶的尺寸大小和诱导温度确定；当温度50-100℃时，诱导时间约为8-36h，当温度为100-150℃时，诱导时间约为3-8h。优选诱导温度为100-120℃。According to the present invention, the crystal induction time needs to be determined according to the size of the organic-inorganic composite perovskite single crystal and the induction temperature; when the temperature is 50-100°C, the induction time is about 8-36h, and when the temperature is 100 At -150°C, the induction time is about 3-8h. Preferably the induction temperature is 100-120°C.
本发明的诱导方法具有普适性，适用于多种宽带隙钙钛矿晶体材料，如C2H6NH2PbI3、(C4H9NH3)2PbI4、(C6H13NH3)2PbI4、(C8H17NH3)2PbI4或CN3H4PbI3等。The induction method of the present invention has universal applicability and is applicable to various wide bandgap perovskite crystal materials, such as C 2 H 6 NH 2 PbI 3 , (C 4 H 9 NH 3 ) 2 PbI 4 , (C 6 H 13 NH 3 ) 2 PbI 4 , (C 8 H 17 NH 3 ) 2 PbI 4 or CN 3 H 4 PbI 3 , etc.
本发明的方法还能用于有机无机复合钙钛矿单晶制成的薄膜的诱导转变，将所述薄膜置于甲胺气氛下诱导转变，诱导之后所述薄膜的光响应性能大幅度提高。The method of the present invention can also be used for the induced transformation of the thin film made of organic-inorganic composite perovskite single crystal, and the thin film is placed under the atmosphere of methylamine to induce the transformation, and the photoresponse performance of the thin film is greatly improved after induction.
二、本发明还提供一种用于表面降解的碘铅甲胺(MAPbI3)晶体材料修复的方法Two, the present invention also provides a kind of method for the restoration of lead iodide methylamine (MAPbI 3 ) crystal material used for surface degradation
一种表面降解的碘铅甲胺(MAPbI3)晶体材料的修复方法，将表面降解的碘铅甲胺晶体，置于甲胺气氛下，在40-150℃温度下诱导处理3-36h。碘铅甲胺晶体表面由降解后的黄色逐渐变为黑色。优选100-120℃下，诱导5-7h。A method for repairing surface-degraded lead iodide methylamine (MAPbI 3 ) crystal material, including placing the surface-degraded lead iodide methylamine crystal under methylamine atmosphere, and inducing treatment at a temperature of 40-150° C. for 3-36 hours. The surface of lead iodide methylamine crystals gradually changed from yellow to black after degradation. Preferably at 100-120°C, induction for 5-7h.
该方法用于修复降解了的太阳能电池等器件。The method is used to repair degraded solar cells and other devices.
三、本发明所述的有机无机复合钙钛矿单晶可以按现有技术制备。本发明优选的制备方法，以LPbI3或L2PbI4为例，步骤如下：3. The organic-inorganic composite perovskite single crystal described in the present invention can be prepared according to the prior art. The preferred preparation method of the present invention, taking LPbI 3 or L 2 PbI 4 as an example, the steps are as follows:
一种有机无机复合钙钛矿单晶的制备方法，按照LPbI3或L2PbI4(L＝C2H6NH2、C4H9NH3、C6H13NH3、C8H17NH3或CN3H4)的化学计量比称量卤化胺或胺盐、PbO，溶于氢碘酸(HI)溶液中，升温至70-100℃使完全溶解形成透明澄清溶液，降至饱和点后，缓慢降温至有单晶析出。A method for preparing an organic-inorganic composite perovskite single crystal, according to LPbI 3 or L 2 PbI 4 (L=C 2 H 6 NH 2 , C 4 H 9 NH 3 , C 6 H 13 NH 3 , C 8 H 17 Stoichiometric ratio of NH 3 or CN 3 H 4 ) Weigh amine halide or amine salt, PbO, dissolve in hydroiodic acid (HI) solution, raise the temperature to 70-100°C to completely dissolve to form a transparent and clear solution, and reduce to saturation After the point, the temperature was slowly lowered until a single crystal was precipitated.
优选的，所述卤化胺为碘化二甲胺、碘化丁胺、碘化己胺、碘化辛胺或碘化胍。其中上述卤化胺亦可用相应的胺盐替代，例如：二甲胺盐酸盐、盐酸胍。Preferably, the amine halide is dimethylamine iodide, butylamine iodide, hexylamine iodide, octylamine iodide or guanidine iodide. Wherein the above-mentioned amine halides can also be replaced by corresponding amine salts, for example: dimethylamine hydrochloride, guanidine hydrochloride.
优选的，所述氢碘酸溶液质量分数为30-45wt％。Preferably, the mass fraction of the hydriodic acid solution is 30-45wt%.
四、基于甲胺气氛的有机无机复合钙钛矿单晶诱导转变方法的专用装置4. Special device for the induced transformation method of organic-inorganic composite perovskite single crystal based on methylamine atmosphere
一种用于本发明方法的装置，包括：A device for the method of the present invention, comprising:
-甲胺气体发生器，用于盛装甲胺水溶液，- a methylamine gas generator for containing an aqueous solution of methylamine,
-通气管，用于连通甲胺气体发生器与甲胺气氛晶体处理器，-A vent pipe for connecting the methylamine gas generator with the methylamine atmosphere crystal processor,
-温控加热台，用于放置并加热甲胺气体发生器、甲胺气氛晶体处理器，-Temperature-controlled heating table for placing and heating the methylamine gas generator, methylamine atmosphere crystal processor,
-气体干燥器，安装于通气管中段，用于干燥甲胺气体，- gas dryer, installed in the middle of the vent pipe, for drying methylamine gas,
-有机无机复合钙钛矿单晶放置在甲胺气氛晶体处理器内。- The organic-inorganic composite perovskite single crystal is placed in the methylamine atmosphere crystal processor.
根据本发明优选的，在甲胺气氛晶体处理器上部设有气体输出管通入气体回收装置，用于回收逸出的甲胺气体。优选的，在气体回收装置盛放有甲胺气体吸收剂，如酸性溶液，使其与甲胺中和。Preferably according to the present invention, a gas output pipe is provided on the upper part of the methylamine atmosphere crystal processor to lead into a gas recovery device for recovering the escaped methylamine gas. Preferably, a methylamine gas absorbent, such as an acidic solution, is placed in the gas recovery device to neutralize the methylamine.
根据本发明，所述有机无机复合钙钛矿单晶经甲胺诱导转变后的单晶的应用，基于诱导后的晶体光学吸收范围增加、光学带隙显著减小、光电性能提高，用于光电探测器、太阳能电池、场效应晶体管材料等领域。According to the present invention, the application of the organic-inorganic composite perovskite single crystal induced by methylamine is based on the increase of the optical absorption range of the induced crystal, the significant reduction of the optical band gap, and the improvement of photoelectric performance. Detectors, solar cells, field effect transistor materials and other fields.
尤其是，C2H6NH2PbI3、(C4H9NH3)2PbI4、(C6H13NH3)2PbI4或(C8H17NH3)2PbI4等单晶经本发明方法诱导后，用于太阳能电池的应用、作为光电探测器的应用；或者作为场效应晶体管材料的应用。In particular, single crystals such as C 2 H 6 NH 2 PbI 3 , (C 4 H 9 NH 3 ) 2 PbI 4 , (C 6 H 13 NH 3 ) 2 PbI 4 or (C 8 H 17 NH 3 ) 2 PbI 4 After being induced by the method of the present invention, it can be used in the application of solar cells, as a photodetector, or as a field effect transistor material.
本发明的技术特点及优良效果：Technical characteristics and excellent effects of the present invention:
1、采用本发明的方法，对有机无机复合钙钛矿宽带隙单晶进行诱导，在诱导过程中，单晶中的有机基团部分被甲胺分子取代，形成混合有机阳离子单晶，使单晶带隙降低，光学吸收范围扩大，从而改善其光学性能。随着光学吸收范围的扩大，晶体的光电性能随之改变。1. Adopt the method of the present invention to induce the organic-inorganic composite perovskite wide-bandgap single crystal. During the induction process, the organic groups in the single crystal are partially replaced by methylamine molecules to form a mixed organic cation single crystal, so that the single crystal The crystal band gap is reduced, and the optical absorption range is expanded, thereby improving its optical properties. As the optical absorption range expands, the optoelectronic properties of the crystal change accordingly.
2、采用本发明的方法诱导制得的C2H6NH2PbI3等晶体其光电性能大幅度提高，如图8所示。2. The optoelectronic properties of crystals such as C 2 H 6 NH 2 PbI 3 induced by the method of the present invention are greatly improved, as shown in FIG. 8 .
3、采用本方法可修复降解了的晶体，甲胺气体分子可补充由于晶体降解缺失的有机分子基团。本发明的方法还可以诱导修复降解了的太阳能电池等器件。3. The degraded crystal can be repaired by this method, and the methylamine gas molecules can supplement the organic molecular groups missing due to crystal degradation. The method of the present invention can also induce the repair of degraded solar cells and other devices.
4、本发明诱导制备的C2H6NH2PbI3、(C4H9NH3)2PbI4等晶体作为半导体晶体材料，在紫外-可见光区具有很好吸光范围(如图6和图13所示)，可以应用于光导以及光探测领域。4. Crystals such as C 2 H 6 NH 2 PbI 3 , (C 4 H 9 NH 3 ) 2 PbI 4 prepared by induction in the present invention are used as semiconductor crystal materials, and have a good light absorption range in the ultraviolet-visible light region (as shown in Figure 6 and Figure 6 13), it can be applied to the field of light guide and light detection.
5、本发明所述的方法实现从单晶到单晶的转变且具有普适性，本方法设备简单，价格低廉，材料制备高效。5. The method of the present invention realizes the transformation from single crystal to single crystal and has universal applicability. The method has simple equipment, low price, and efficient material preparation.
附图说明Description of drawings
图1是本发明的甲胺诱导单晶转变装置，1.甲胺气体发生器(盛装甲胺水溶液)，2.温控加热台，3.气体干燥器，4.通气管，5、甲胺气氛晶体处理器，6.有机无机复合钙钛矿单晶，7.气体输出管，8、甲胺气体回收装置，9、甲胺气体吸收液。Fig. 1 is the methylamine-induced single crystal conversion device of the present invention, 1. methylamine gas generator (contains methylamine aqueous solution), 2. temperature-controlled heating platform, 3. gas dryer, 4. ventilation pipe, 5. methylamine Atmosphere crystal processor, 6. Organic-inorganic composite perovskite single crystal, 7. Gas output tube, 8. Methylamine gas recovery device, 9. Methylamine gas absorption liquid.
图2是实施例1甲胺气体诱导前的DAPbI3晶体照片；Fig. 2 is the DAPbI3 crystal photo before methylamine gas induction of embodiment 1;
图3是实施例1甲胺气体诱导后的MA0.1DA0.9PbI3晶体照片；Fig. 3 is the MA 0.1 DA 0.9 PbI crystal photo of Example 1 after methylamine gas induction;
图4是实施例1甲胺气体诱导前后的DAPbI3、MA0.1DA0.9PbI3的XRD谱图；横坐标是2θ，单位：度(°)；纵坐标是强度，任意单位。Fig. 4 is the XRD spectrum of DAPbI 3 , MA 0.1 DA 0.9 PbI 3 before and after methylamine gas induction in Example 1; the abscissa is 2θ, unit: degree (°); the ordinate is intensity, arbitrary unit.
图5是实施例1甲胺气体诱导前的DAPbI3的紫外-可见吸收光谱及PL吸收光谱；横坐标是吸收波长(nm)；左边纵坐标是吸收(O.D.)，右边纵坐标是PL强度，任意单位。Fig. 5 is the ultraviolet-visible absorption spectrum and the PL absorption spectrum of DAPbI3 before embodiment 1 methylamine gas induction; The abscissa is the absorption wavelength (nm); The left ordinate is absorption (OD), and the right ordinate is the PL intensity, any unit.
图6是实施例1甲胺气体诱导后的MA0.1DA0.9PbI3的紫外-可见吸收光谱及PL吸收光谱；横坐标是吸收波长(nm)；左边纵坐标是吸收(O.D.)，右边纵坐标是PL强度，任意单位。Fig. 6 is the ultraviolet-visible absorption spectrum and the PL absorption spectrum of MA 0.1 DA 0.9 PbI 3 after the methylamine gas induction of embodiment 1; The abscissa is the absorption wavelength (nm); The left ordinate is absorption (OD), and the right ordinate is the PL intensity, in arbitrary units.
图7是是实施例1甲胺气体诱导前的DAPbI3光电性能图；横坐标是时间，单位秒；纵坐标是电流，单位μA。7 is a photoelectric performance diagram of DAPbI 3 before methylamine gas induction in Example 1; the abscissa is time, in seconds; the ordinate is current, in μA.
图8是是实施例1甲胺气体诱导后的MA0.1DA0.9PbI3光电性能图；横坐标是时间，单位秒；纵坐标是电流，单位μA。图9是实施例3甲胺气体诱导前的BA2PbI4晶体照片。Fig. 8 is a photoelectric performance diagram of MA 0.1 DA 0.9 PbI 3 after methylamine gas induction in Example 1; the abscissa is time, in seconds; the ordinate is current, in μA. Fig. 9 is a photograph of BA 2 PbI 4 crystals before methylamine gas induction in Example 3.
图10是实施例3甲胺气体诱导后的(MA0.66BA0.34)2PbI4晶体照片。Fig. 10 is a photograph of (MA 0.66 BA 0.34 ) 2 PbI 4 crystals after methylamine gas induction in Example 3.
图11是实施例3甲胺气体诱导前后的BA2PbI4和(MA0.66BA0.34)2PbI4的XRD谱图；横坐标是2θ，单位：度(°)；纵坐标是强度，任意单位。Figure 11 is the XRD spectrum of BA 2 PbI 4 and (MA 0.66 BA 0.34 ) 2 PbI 4 before and after methylamine gas induction in Example 3; the abscissa is 2θ, unit: degree (°); the ordinate is intensity, arbitrary unit .
图12是实施例3甲胺气体诱导前的BA2PbI4的紫外-可见吸收光谱及PL吸收光谱；横坐标是吸收波长(nm)；左边纵坐标是吸收(O.D.)，右边纵坐标是PL强度，任意单位。Fig. 12 is the ultraviolet-visible absorption spectrum and the PL absorption spectrum of BA 2 PbI 4 before embodiment 3 methylamine gas induction; The abscissa is the absorption wavelength (nm); The left ordinate is absorption (OD), and the right ordinate is PL Intensity, in arbitrary units.
图13是实施例3甲胺气体诱导后的(MA0.66BA0.34)2PbI4的紫外-可见吸收光谱及PL吸收光谱；横坐标是吸收波长(nm)；左边纵坐标是吸收(O.D.)，右边纵坐标是PL强度，任意单位。Fig. 13 is the ultraviolet-visible absorption spectrum and PL absorption spectrum of (MA 0.66 BA 0.34 ) 2 PbI 4 after methylamine gas induction in Example 3; the abscissa is the absorption wavelength (nm); the left ordinate is the absorption (OD), The right ordinate is the PL intensity, in arbitrary units.
图14是实施例4对若干种有机无机复合碘铅基钙钛矿单晶的诱导转变前后的单晶照片；上一排是转变前的单晶，下一排是转变后的单晶，由左往右依次是：(C4H9NH3)2PbI4、(C6H13NH3)2PbI4、C2H6NH2PbI3、(C8H17NH3)2PbI4和CN3H3PbI3。Fig. 14 is the single crystal photo before and after the induced transformation of several kinds of organic-inorganic composite iodine-lead-based perovskite single crystals in embodiment 4; the upper row is the single crystal before the transformation, and the next row is the single crystal after the transformation, by From left to right: (C 4 H 9 NH 3 ) 2 PbI 4 , (C 6 H 13 NH 3 ) 2 PbI 4 , C 2 H 6 NH 2 PbI 3 , (C 8 H 17 NH 3 ) 2 PbI 4 and CN 3 H 3 PbI 3 .
图15是实施例5甲胺气体对降解后不同尺寸的MAPbI3进行不同时间诱导修复的照片；上排依次是小尺寸MAPbI3晶体在诱导时间0、0.5h、3h、7h时的照片，下排依次是大尺寸MAPbI3晶体在诱导时间0、0.5h、3h、7h时的照片。Figure 15 is a photo of different time-induced repairs of MAPbI 3 of different sizes after degradation by methylamine gas in Example 5; the upper row is the photos of small-sized MAPbI 3 crystals at induction times of 0, 0.5h, 3h, and 7h, and the lower row is Rows are photos of large-sized MAPbI 3 crystals at induction times of 0, 0.5h, 3h, and 7h.
图16是实施例5甲胺气体修复降解MAPbI3前后的XRD图谱；横坐标是2θ，单位：度(°)；纵坐标是强度，任意单位。Fig. 16 is the XRD spectrum of Example 5 before and after methylamine gas remediation degradation of MAPbI 3 ; the abscissa is 2θ, unit: degree (°); the ordinate is intensity, arbitrary unit.
具体实施方式detailed description
下面通过实施例对本发明作进一步的说明，但本发明并不限于以下实施例。The present invention will be further described below through the examples, but the present invention is not limited to the following examples.
实施例1、甲胺气体诱导一维DAPbI3单晶的转变Embodiment 1, methylamine gas induces the transformation of one-dimensional DAPbI 3 single crystal
一、DAPbI3单晶制备1. Preparation of DAPbI 3 single crystal
(a)按照化学计量比准确称量二甲胺盐酸盐，将其加入到45wt％的HI溶液中，得到黄色透明溶液。(a) Accurately weigh dimethylamine hydrochloride according to the stoichiometric ratio, and add it into 45wt% HI solution to obtain a yellow transparent solution.
(b)按照化学计量比准确称量PbO，加入到步骤(a)的黄色透明溶液中，产生淡黄色沉淀，在油浴锅中升温至沉淀完全溶解，得到黄色澄清的溶液，降至饱和点后，缓慢降温，自发结晶出DAPbI3黄色单晶，照片如图2所示，晶体尺寸约为1mm。(b) Accurately weigh PbO according to the stoichiometric ratio, add it to the yellow transparent solution of step (a), produce a light yellow precipitate, raise the temperature in an oil bath until the precipitate is completely dissolved, obtain a yellow clear solution, and drop to the saturation point After that, the temperature was lowered slowly, and a yellow single crystal of DAPbI 3 was spontaneously crystallized. The photo is shown in Figure 2, and the crystal size is about 1mm.
二、甲胺气体诱导DAPbI3单晶2. DAPbI 3 single crystal induced by methylamine gas
将以上所制备的DAPbI3单晶置于甲胺气氛下，在120℃温度下诱导处理3h-5h，得到黑色MA0.1DA0.9PbI3单晶，晶体照片如图3所示。The above-prepared DAPbI 3 single crystal was placed in a methylamine atmosphere and induced at 120°C for 3h-5h to obtain a black MA 0.1 DA 0.9 PbI 3 single crystal. The crystal photo is shown in Figure 3.
此诱导方法得到的晶体粉末XRD与纯相DAPbI3粉末XRD不同，在甲胺气体诱导之后，DA+离子被MA+部分取代，形成MA0.1DA0.9PbI3单晶，如图4所示。The crystal powder XRD obtained by this induction method is different from the pure phase DAPbI 3 powder XRD, after methylamine gas induction, DA + ions are partially replaced by MA + to form MA 0.1 DA 0.9 PbI 3 single crystal, as shown in Fig. 4.
将实施例1得到的纯相DAPbI3单晶与甲胺气体诱导之后的黑色MA0.1DA0.9PbI3单晶研磨成粉末测试其固体-紫外光谱及光致发光光谱(PL光谱)。纯相DAPbI3晶体吸收截止边在500nm左右(图5)，甲胺气体诱导之后，MA0.1DA0.9PbI3单晶吸收截止边扩展到800nm，其PL吸收光谱亦扩展到800nm。表明诱导之后其化合物带隙宽度降低为1.53eV，如图6所示。The pure-phase DAPbI 3 single crystal obtained in Example 1 and the black MA 0.1 DA 0.9 PbI 3 single crystal after methylamine gas induction were ground into powder to test their solid-state-ultraviolet spectrum and photoluminescence spectrum (PL spectrum). The absorption cut-off edge of pure DAPbI 3 crystal is around 500nm (Figure 5). After methylamine gas induction, the absorption cut-off edge of MA 0.1 DA 0.9 PbI 3 single crystal extends to 800nm, and its PL absorption spectrum also extends to 800nm. It shows that the bandgap width of the compound decreases to 1.53eV after induction, as shown in FIG. 6 .
将实施例1得到纯相DAPbI3单晶溶于DMF，并在转速为2000r/min下旋涂40s，获得其薄膜。将薄膜置于甲胺气氛下诱导。诱导之后其光响应性能大幅度提高，如图7-8所示。The pure-phase DAPbI 3 single crystal obtained in Example 1 was dissolved in DMF, and spin-coated at a rotation speed of 2000r/min for 40s to obtain its thin film. The films were induced under an atmosphere of methylamine. After induction, its photoresponse performance is greatly improved, as shown in Figure 7-8.
实施例2、如实施例1所述，所不同的是，甲胺气体诱导DAPbI3单晶时，在100℃温度下诱导处理8-10h，得到黑色MA0.1DA0.9PbI3单晶。Example 2. As described in Example 1, the difference is that when the DAPbI 3 single crystal is induced by methylamine gas, the induction treatment is performed at 100° C. for 8-10 hours to obtain a black MA 0.1 DA 0.9 PbI 3 single crystal.
实施例3、甲胺气体诱导二维BA2PbI4单晶Example 3. Two-dimensional BA 2 PbI 4 single crystal induced by methylamine gas
一、BA2PbI4单晶的制备1. Preparation of BA 2 PbI 4 single crystal
(a)碘化丁胺CH3(CH2)3NH3I的合成制备：(a) Synthesis and preparation of butylamine iodide CH 3 (CH 2 ) 3 NH 3 I:
在冰水浴中将CH3(CH2)3NH3溶液加入到HI溶液中，反应3.5h；CH3(CH2)3NH2:HI＝1.5:1摩尔比。丁胺溶液的质量百分浓度为99wt％，HI溶液的质量百分浓度为45wt％。经过真空旋转蒸发仪旋蒸，得到白色的碘化丁胺，并将其置于真空干燥箱干燥2h，得到干燥碘化丁胺晶体。CH 3 (CH 2 ) 3 NH 3 solution was added to HI solution in an ice-water bath, and reacted for 3.5 h; CH 3 (CH 2 ) 3 NH 2 :HI=1.5:1 molar ratio. The mass percent concentration of the butylamine solution is 99wt%, and the mass percent concentration of the HI solution is 45wt%. Rotary evaporation by a vacuum rotary evaporator was performed to obtain white butylamine iodide, which was dried in a vacuum oven for 2 hours to obtain dry butylamine iodide crystals.
(b)按照化学计量比准确称量PbO，将其加入到45wt％HI溶液中，得到黄色透明溶液。(b) Accurately weigh PbO according to the stoichiometric ratio, and add it into the 45wt% HI solution to obtain a yellow transparent solution.
(c)按照化学计量比准确称量CH3(CH2)3NH3I，将其加入到步骤(b)的黄色透明溶液中，产生淡黄色沉淀，在油浴锅中升温至沉淀完全溶解，得到黄绿色澄清的溶液，降至饱和点后，缓慢降温，自发结晶出BA2PbI4单晶，照片如图9所示，其尺寸约为7mm。(c) Accurately weigh CH 3 (CH 2 ) 3 NH 3 I according to the stoichiometric ratio, add it to the yellow transparent solution in step (b), and produce a light yellow precipitate, heat up in an oil bath until the precipitate is completely dissolved , a yellow-green clear solution was obtained. After reaching the saturation point, the temperature was lowered slowly, and a BA 2 PbI 4 single crystal spontaneously crystallized. The photo is shown in Figure 9, and its size is about 7 mm.
二、甲胺气体诱导二维BA2PbI4单晶的转变2. Transformation of two-dimensional BA 2 PbI 4 single crystal induced by methylamine gas
将所制备的BA2PbI4单晶置于甲胺气氛下，在120℃温度下诱导处理3h-5h(或100℃时8-10h)，得到黑色(MA0.66DA0.34)2PbI4单晶，晶体照片如图10所示。Put the prepared BA 2 PbI 4 single crystal in an atmosphere of methylamine, induce treatment at 120°C for 3h-5h (or 8-10h at 100°C), and obtain a black (MA 0.66 DA 0.34 ) 2 PbI 4 single crystal , the crystal photo is shown in Figure 10.
此诱导转变后(MA0.66DA0.34)2PbI4单晶的晶体粉末XRD与诱导前纯相BA2PbI4粉末XRD不同，在甲胺气体诱导之后，BA+离子被MA+部分取代，形成(MA0.66DA0.34)2PbI4单晶，如图11所示。The crystal powder XRD of (MA 0.66 DA 0.34 ) 2 PbI 4 single crystal after this induced transformation is different from the XRD of pure phase BA 2 PbI 4 powder before induction. After methylamine gas induction, BA + ions are partially replaced by MA + to form ( MA 0.66 DA 0.34 ) 2 PbI 4 single crystal, as shown in FIG. 11 .
将实施例3得到的纯相BA2PbI4单晶与甲胺气体诱导之后的黑色(MA0.66DA0.34)2PbI4单晶研磨成粉末测试其固体-紫外光谱及光致发光光谱(PL光谱)。纯相BA2PbI4晶体吸收截止边在530nm左右(图12)，甲胺气体诱导之后，(MA0.66DA0.34)2PbI4单晶吸收截止边扩展到800nm。表明诱导之后其化合物带隙宽度降低为1.55eV，如图13所示。The pure phase BA 2 PbI 4 single crystal obtained in Example 3 and the black (MA 0.66 DA 0.34 ) 2 PbI 4 single crystal after induction with methylamine gas were ground into powder to test its solid-ultraviolet spectrum and photoluminescence spectrum (PL spectrum ). The absorption cut-off edge of the pure phase BA 2 PbI 4 crystal is around 530nm (Figure 12), and after methylamine gas induction, the absorption cut-off edge of the (MA 0.66 DA 0.34 ) 2 PbI 4 single crystal extends to 800nm. It shows that the bandgap width of the compound decreases to 1.55eV after induction, as shown in FIG. 13 .
实施例4、普适性实验Embodiment 4, universality experiment
分别利用实施例1和2中的方法，制备(C4H9NH3)2PbI4、(C6H13NH3)2PbI4、C2H6NH2PbI3、(C8H17NH3)2PbI4和CN3H4PbI3等有机无机复合钙钛矿单晶材料，并在120℃温度下诱导处理3h-5h，(C4H9NH3)2PbI4、(C6H13NH3)2PbI4、C2H6NH2PbI3、(C8H17NH3)2PbI4和CN3H4PbI3等纯相晶体变黑，表明其光学吸收范围扩大，带隙变窄，如图14所示。Using the methods in Examples 1 and 2, prepare (C 4 H 9 NH 3 ) 2 PbI 4 , (C 6 H 13 NH 3 ) 2 PbI 4 , C 2 H 6 NH 2 PbI 3 , (C 8 H 17 ( C 4 H 9 NH 3 ) 2 PbI 4 , ( C Pure phase crystals such as 6 H 13 NH 3 ) 2 PbI 4 , C 2 H 6 NH 2 PbI 3 , (C 8 H 17 NH 3 ) 2 PbI 4 and CN 3 H 4 PbI 3 turned black, indicating that their optical absorption range expanded , the band gap narrows, as shown in Figure 14.
实验表明本方法是一种普适性的甲胺气体诱导有机无机复合钙钛矿单晶到单晶转变的方法。Experiments show that this method is a universal methylamine gas-induced organic-inorganic composite perovskite single-crystal-to-single-crystal transformation method.
实施例5、表面降解的碘铅甲胺(MAPbI3)晶体材料修复Example 5, repair of surface-degraded lead iodide methylamine (MAPbI 3 ) crystal material
将表面降解的大小两个尺寸的碘铅甲胺MAPbI3晶体，在100-120℃下，置于甲胺气氛中诱导，0.5h后，表面即发生变化，由降解后的黄色逐渐变为黑色，随着诱导时间的延长(3h、7h)，晶体表面并未出现溶解状态，如图15所示，晶体颜色的转变表明其表面的修复。图15中，上一排是小尺寸(长约2.5mm)MAPbI3晶体在诱导时间0、0.5h、3h、7h时的照片，下一排是大尺寸(长约15mm)MAPbI3晶体在诱导时间0、0.5h、3h、7h时的照片。The surface-degraded lead iodide methylamine MAPbI 3 crystals of two sizes were induced at 100-120°C in an atmosphere of methylamine. After 0.5h, the surface changed, and the degraded yellow gradually changed to black. , as the induction time prolongs (3h, 7h), the crystal surface does not appear in a dissolved state, as shown in Figure 15, the change of crystal color indicates the repair of its surface. In Fig. 15, the upper row is the photos of small size (about 2.5mm in length) MAPbI 3 crystals at induction time 0, 0.5h, 3h, 7h, and the lower row is the photos of large size (about 15mm in length) MAPbI 3 crystals in induction time Photos at time 0, 0.5h, 3h, 7h.
降解的碘铅甲胺晶体粉末XRD(如图16(a)上曲线)表明其峰位完全区别于MAPbI3的XRD标准图谱(如图16(a)下曲线)。在进行甲胺气体诱导恢复之后，其XRD峰位(如图16(b)上曲线)与标准XRD图谱(如图16(b)下曲线)完全匹配，表明甲胺气体诱导之后降解的MAPbI3得到恢复，如图16所示。The XRD of the degraded lead iodide methylamine crystal powder (as shown in the upper curve of Figure 16(a)) shows that its peak position is completely different from the XRD standard spectrum of MAPbI 3 (as shown in the lower curve of Figure 16(a)). After methylamine gas-induced recovery, its XRD peak position (as shown in Fig. 16(b) upper curve) completely matches the standard XRD pattern (as shown in Fig. 16(b) lower curve), indicating that the degraded MAPbI 3 is restored, as shown in Figure 16.
实验表明本发明甲胺气体诱导有机无机复合钙钛矿单晶到单晶转变的方法，对表面降解的有机无机复合碘铅基钙钛矿晶体材料具有一定的修复性。Experiments show that the methylamine gas-induced organic-inorganic composite perovskite single-crystal to single-crystal transformation method of the present invention has certain repairability for surface-degraded organic-inorganic composite iodine-lead-based perovskite crystal materials.
Claims (10)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611176317.6A CN106757371A (en) | 2016-12-19 | 2016-12-19 | A kind of organo-mineral complexing perovskite monocrystalline induced conversion method and device based on methylamine atmosphere |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611176317.6A CN106757371A (en) | 2016-12-19 | 2016-12-19 | A kind of organo-mineral complexing perovskite monocrystalline induced conversion method and device based on methylamine atmosphere |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106757371A true CN106757371A (en) | 2017-05-31 |
Family
ID=58890118
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611176317.6A Pending CN106757371A (en) | 2016-12-19 | 2016-12-19 | A kind of organo-mineral complexing perovskite monocrystalline induced conversion method and device based on methylamine atmosphere |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106757371A (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107359251A (en) * | 2017-07-26 | 2017-11-17 | 湖北大学 | A kind of organic inorganic hybridization perovskite photodetector and preparation method thereof |
| CN107534088A (en) * | 2015-05-29 | 2018-01-02 | 学校法人冲绳科学技术大学院大学学园 | Gas induced perovskite is formed |
| CN108389967A (en) * | 2018-02-27 | 2018-08-10 | 华南理工大学 | The extinction layer material of solar cell, broad-band gap perovskite solar cell and preparation method thereof |
| CN108550700A (en) * | 2018-04-13 | 2018-09-18 | 苏州协鑫纳米科技有限公司 | Perovskite photosensitive layer and preparation method thereof, perovskite battery |
| CN109148690A (en) * | 2018-08-27 | 2019-01-04 | 领旺（上海）光伏科技有限公司 | A kind of surface treatment method of organic inorganic hybridization perovskite thin film |
| CN109950409A (en) * | 2019-02-28 | 2019-06-28 | 深圳市先进清洁电力技术研究有限公司 | A perovskite atmosphere treatment device |
| CN112062680A (en) * | 2020-08-25 | 2020-12-11 | 南京工业大学 | Organic matter type ionic liquid, two-dimensional perovskite pure-phase quantum well structure film, preparation method and application thereof |
| KR20210080471A (en) * | 2018-10-22 | 2021-06-30 | 옥스포드 유니버시티 이노베이션 리미티드 | How to prepare a layer with a mixed solvent system |
| CN115044982A (en) * | 2022-05-23 | 2022-09-13 | 南昌大学 | Low-defect-state-density methylamine-free perovskite single crystal with synergistic effect of dopant and auxiliary dopant, and preparation method and application thereof |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102915908A (en) * | 2011-08-03 | 2013-02-06 | 中芯国际集成电路制造(上海)有限公司 | Pretreatment method for silanization and silanization method comprising the method |
| CN104662625A (en) * | 2012-05-18 | 2015-05-27 | 埃西斯创新有限公司 | Optoelectronic devices with organometal perovskites with mixed anions |
| CN104787747A (en) * | 2015-04-10 | 2015-07-22 | 宁波诺丁汉大学 | Method for preparing multiwalled carbon nanotube through microwave enhanced fast pyrolysis of biomass and/or carbonaceous organic waste |
| CN105024012A (en) * | 2015-06-13 | 2015-11-04 | 中国科学院青岛生物能源与过程研究所 | A method for manufacturing a high-quality perovskite thin film |
| CN105336856A (en) * | 2015-10-14 | 2016-02-17 | 中国科学院青岛生物能源与过程研究所 | Novel method for preparing perovskite thin film |
| CN105702869A (en) * | 2016-01-25 | 2016-06-22 | 上海科技大学 | Mixed cation perovskite and preparation method therefor |
| CN106159097A (en) * | 2015-04-19 | 2016-11-23 | 中国科学院青岛生物能源与过程研究所 | A kind of new method improving perovskite thin film quality |
| WO2016194317A1 (en) * | 2015-05-29 | 2016-12-08 | Okinawa Institute Of Science And Technology School Corporation | Gas-induced perovskite formation |
| CN106229412A (en) * | 2016-08-03 | 2016-12-14 | 浙江悦昇新能源科技有限公司 | A kind of novel solar battery material |
-
2016
- 2016-12-19 CN CN201611176317.6A patent/CN106757371A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102915908A (en) * | 2011-08-03 | 2013-02-06 | 中芯国际集成电路制造(上海)有限公司 | Pretreatment method for silanization and silanization method comprising the method |
| CN104662625A (en) * | 2012-05-18 | 2015-05-27 | 埃西斯创新有限公司 | Optoelectronic devices with organometal perovskites with mixed anions |
| CN104787747A (en) * | 2015-04-10 | 2015-07-22 | 宁波诺丁汉大学 | Method for preparing multiwalled carbon nanotube through microwave enhanced fast pyrolysis of biomass and/or carbonaceous organic waste |
| CN106159097A (en) * | 2015-04-19 | 2016-11-23 | 中国科学院青岛生物能源与过程研究所 | A kind of new method improving perovskite thin film quality |
| WO2016194317A1 (en) * | 2015-05-29 | 2016-12-08 | Okinawa Institute Of Science And Technology School Corporation | Gas-induced perovskite formation |
| CN105024012A (en) * | 2015-06-13 | 2015-11-04 | 中国科学院青岛生物能源与过程研究所 | A method for manufacturing a high-quality perovskite thin film |
| CN105336856A (en) * | 2015-10-14 | 2016-02-17 | 中国科学院青岛生物能源与过程研究所 | Novel method for preparing perovskite thin film |
| CN105702869A (en) * | 2016-01-25 | 2016-06-22 | 上海科技大学 | Mixed cation perovskite and preparation method therefor |
| CN106229412A (en) * | 2016-08-03 | 2016-12-14 | 浙江悦昇新能源科技有限公司 | A kind of novel solar battery material |
Non-Patent Citations (1)
| Title |
|---|
| MING-JIA ZHANG,ET AL.: "Carrier Transport Improvement of CH3NH3PbI3 Film by Methylamine Gas Treatment", 《ACS APPLIED MATERIALS INTERFACES 》 * |
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107534088B (en) * | 2015-05-29 | 2020-08-18 | 学校法人冲绳科学技术大学院大学学园 | Gas induced perovskite formation |
| CN107534088A (en) * | 2015-05-29 | 2018-01-02 | 学校法人冲绳科学技术大学院大学学园 | Gas induced perovskite is formed |
| CN107359251A (en) * | 2017-07-26 | 2017-11-17 | 湖北大学 | A kind of organic inorganic hybridization perovskite photodetector and preparation method thereof |
| CN108389967A (en) * | 2018-02-27 | 2018-08-10 | 华南理工大学 | The extinction layer material of solar cell, broad-band gap perovskite solar cell and preparation method thereof |
| CN108550700A (en) * | 2018-04-13 | 2018-09-18 | 苏州协鑫纳米科技有限公司 | Perovskite photosensitive layer and preparation method thereof, perovskite battery |
| CN108550700B (en) * | 2018-04-13 | 2022-02-22 | 昆山协鑫光电材料有限公司 | Perovskite photosensitive layer, preparation method thereof and perovskite battery |
| CN109148690A (en) * | 2018-08-27 | 2019-01-04 | 领旺（上海）光伏科技有限公司 | A kind of surface treatment method of organic inorganic hybridization perovskite thin film |
| KR102813729B1 (en) | 2018-10-22 | 2025-05-27 | 옥스포드 유니버시티 이노베이션 리미티드 | Method for producing layers with mixed solvent systems |
| KR20210080471A (en) * | 2018-10-22 | 2021-06-30 | 옥스포드 유니버시티 이노베이션 리미티드 | How to prepare a layer with a mixed solvent system |
| JP2022505430A (en) * | 2018-10-22 | 2022-01-14 | オックスフォード ユニバーシティ イノベーション リミテッド | Method of manufacturing a layer using a mixed solvent system |
| JP7627211B2 (en) | 2018-10-22 | 2025-02-05 | オックスフォード ユニバーシティ イノベーション リミテッド | Method for Producing Layers Using Mixed Solvent Systems - Patent application |
| CN109950409A (en) * | 2019-02-28 | 2019-06-28 | 深圳市先进清洁电力技术研究有限公司 | A perovskite atmosphere treatment device |
| CN109950409B (en) * | 2019-02-28 | 2023-01-06 | 深圳市先进清洁电力技术研究有限公司 | A perovskite atmosphere treatment device |
| CN112062680B (en) * | 2020-08-25 | 2021-06-22 | 南京工业大学 | An organic proton ionic liquid, two-dimensional perovskite pure-phase quantum well structure film, preparation method and application thereof |
| CN112062680A (en) * | 2020-08-25 | 2020-12-11 | 南京工业大学 | Organic matter type ionic liquid, two-dimensional perovskite pure-phase quantum well structure film, preparation method and application thereof |
| CN115044982B (en) * | 2022-05-23 | 2023-08-22 | 南昌大学 | A low defect density of states-free perovskite single crystal with synergistic effect of dopant and auxiliary dopant, preparation method and application thereof |
| CN115044982A (en) * | 2022-05-23 | 2022-09-13 | 南昌大学 | Low-defect-state-density methylamine-free perovskite single crystal with synergistic effect of dopant and auxiliary dopant, and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106757371A (en) | A kind of organo-mineral complexing perovskite monocrystalline induced conversion method and device based on methylamine atmosphere | |
| CN107195710A (en) | A kind of method that the inorganic perovskite thin film of high-luminous-efficiency is prepared based on one-step method | |
| CN108034989B (en) | Method and device for growing large-size lead methylamine bromide crystal by controllable anti-solvent diffusion method | |
| CN108329912A (en) | A method of improving the fluorescent yield and stability of non-lead halogen perovskite material | |
| CN105350078B (en) | A kind of method of quick preparation large area perovskite crystal | |
| CN103397382A (en) | Preparation method of zinc-oxide nanorod array film | |
| CN106938854A (en) | A kind of preparation method of large scale lead halide caesium perovskite crystal | |
| CN108389967A (en) | The extinction layer material of solar cell, broad-band gap perovskite solar cell and preparation method thereof | |
| CN101927983B (en) | CuInSe2 nanometer material and its preparation method and application | |
| CN114464739B (en) | A method for preparing high-performance near-infrared perovskite film in air | |
| CN105624771A (en) | Preparation method of CH3NH3PbBr3 nanowires with perovskite structure | |
| CN106058060A (en) | Method for preparing high-quality perovskite crystal thin film | |
| CN107460535A (en) | The preparation method of growth in situ monocrystalline perovskite organic metal halide thin-film material | |
| CN110862702A (en) | Lead-free tin-based halide perovskite thin film, preparation method and application thereof | |
| CN110635050A (en) | A pressure-assisted approach to fabricate high-quality perovskite thin films | |
| Mei et al. | Polymer additive assisted crystallization of perovskite films for high-performance solar cells | |
| CN110194718A (en) | A kind of highly stable lead base hybrid inorganic-organic perovskite nanometer piece preparation method | |
| CN110938432A (en) | A kind of preparation method of perovskite quantum dot material | |
| Han et al. | Recent progress of organic–inorganic hybrid perovskite quantum dots: preparation, optical regulation, and application in light‐emitting diodes | |
| CN112375566B (en) | CsPbCl 3 Yb quantum dot and preparation method thereof | |
| CN101619487B (en) | A kind of cuprous iodide single crystal with P-type conductivity and hydrothermal growth method thereof | |
| CN110010769A (en) | A kind of preparation method of oriented growth organic-inorganic hybrid perovskite thin film | |
| CN111509129B (en) | Method for preparing high-crystallinity perovskite and product application thereof | |
| CN115651652B (en) | All-inorganic quaternary metal halide with waterproof function and preparation method thereof | |
| CN107180914A (en) | A kind of preparation method of perovskite thin film battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20170531 |