CN115432731B - Inversion Cs 8 Sn 3 GaI 24 /Cs 8 Sn 3 InI 24 Hybrid composite material and preparation method thereof - Google Patents
Inversion Cs 8 Sn 3 GaI 24 /Cs 8 Sn 3 InI 24 Hybrid composite material and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of organic-inorganic hybrid semiconductor materials, and particularly relates to an inversion type Cs 8 Sn 3 GaI 24 /Cs 8 Sn 3 InI 24 Hybrid composite materials and methods of making the same; in the present invention, the inversion Cs 8 Sn 3 GaI 24 /Cs 8 Sn 3 InI 24 The morphology of the hybrid composite material is a thin film structure formed by nanocubes, and the hybrid composite material consists of Ga 3+ And In 3+ Ion-mediated energy level formation of inverse Cs 2 SnI 6 The crystal form is a face-centered cubic structure, the surface morphology is a nanocube, and hollow structures are distributed on the surface; the surface of the hybrid film prepared by the invention is uniform and compact, and simultaneously has good crystallographic characteristics and photoelectric properties, and has good application prospects in the fields of solar photovoltaic devices, light-emitting diodes, sensors and the like; in addition, the preparation method does not need high-temperature calcination, has simple production process, good production efficiency, low synthesis cost, environmental protection and energy saving, and is suitable for large-scale industrial manufacturing.
Description
Technical Field
The invention belongs to the technical field of organic-inorganic hybrid semiconductor materials, and particularly relates to an inversion type Cs 8 Sn 3 GaI 24 /Cs 8 Sn 3 InI 24 Hybrid composite materials and methods of making the same.
Background
In recent years, a novel organic-inorganic hybrid calcium H has appeared 3 NH 3 MX 3 The application research of the solar cell module in the field of solar cells has been greatly advanced; the highest efficiency reported at present has exceeded 23% and this record is still in constant refresh. The perovskite thin film solar cell has a structure similar to a silicon-based p-i-n cell, and the perovskite thin film is used as a light absorption layer, namely an i-type layer, and is deposited between a p-type perovskite semiconductor material hole selective transmission layer (called a hole transmission layer or HTL for short) and an n-type electron selective transmission layer (called an electron transmission layer or ETL for short); perovskiteThe film absorbs incident light and excites electron-hole pairs in the film, the photo-generated electrons and the holes diffuse to reach the surfaces of the p-type layer and the n-type layer and are respectively collected by the p-type layer and the n-type layer, so that the photoelectric conversion process is completed; the efficient extraction of photo-generated carriers by the carrier selective transport layers (HTL and ETL) is critical to reduce energy losses.
Cs 2 SnI 6 Belonging to an inorganic perovskite metamorphic structure, the eigenstate of the perovskite metamorphic structure is usually in an n-type direct band gap (1.3 eV) structure, and the energy level structure of the perovskite metamorphic structure is matched with that of a perovskite solar cell; the synthetic raw materials of the semiconductor material exist in a large amount in nature, are nontoxic and convenient to process, and are novel semiconductor compound materials in the research of solar photovoltaic devices. Due to the interaction of strong excitons, the light absorption coefficient of the material is very large (104 cm -1 ) The method comprises the steps of carrying out a first treatment on the surface of the However, it is notable that the inverted (p-type) Cs 2 SnI 6 Hole mobility of the material (42 cm) 2 V -1 s -1 ) Far higher than CuI (0.5-2.0 cm) 2 V -1 s -1 ) And CuSCN (0.01-0.1 cm) 2 V -1 s -1 ) Other common hybridized materials, adopts inverse Cs 2 SnI 6 As a hole transport layer material in the perovskite solar cell, the collection efficiency of holes can be effectively improved, the absorption spectrum range can be expanded, the utilization rate of incident light can be increased, and the photoelectric conversion efficiency of the device can be improved.
At present, it has been reported that Cs is achieved by adding lithium salt (Li-TFSI) and tetra-tert-butylpyridine (TBP) 2 SnI 6 Optimization of valence band position (actually for Cs 2 SnI 6 Li+ ion p-type doping) and using the doped material as a hole transport material to prepare a solar cell device, compared with intrinsic Cs 2 SnI 6 The battery prepared from the material has a remarkable improvement in device performance, such as the documents 'J.Zhang, C.Yu, L.Wang, Y.Li, Y.Ren, K.Shum, sci.Rep.,2014,4,6954' and 'B.Lee, C.C.Stoumpos, N.Zhou, F.Hao, C.Malliakas, C. -Y.Yeh, T.J.Marks, M.G.Kanatzidis, R.P.H.Chang, J.Am.Chem.Soc.,2014,136,15379-15385'. From this, it can be seen that the inversion Cs 2 SnI 6 The basic properties of the material directly influence the photogenerated carriers in the hole transport layer and perovskiteMicroscopic transport conditions of the film interface, and microscopic transport characteristics of carriers directly determine macroscopic properties (open circuit voltage, short circuit current, filling factor, stability and the like) of the battery device; however, currently, inverted Cs 2 SnI 6 The report of the hybridized material and the preparation thereof is very limited, and Ga-based materials have not been found yet 3+ And In 3+ Inverse Cs of ion 8 Sn 3 GaI 24 /Cs 8 Sn 3 InI 24 Report on hybrid composite materials.
Disclosure of Invention
The invention aims to solve the problems or disadvantages of the prior art and provide an inversion Cs 8 Sn 3 GaI 24 /Cs 8 Sn 3 InI 24 Hybrid composite materials and methods of making the same; the material is specifically Ga-based 3+ And In 3+ Inverse Cs of ion 8 Sn 3 GaI 24 /Cs 8 Sn 3 InI 24 The hybrid composite material has a thin film structure formed by nanocubes, is low in preparation cost, is suitable for large-area and large-scale manufacturing, has a crucial effect on improving the performance of perovskite thin film solar cells, and has wide application prospects in the fields of light emitting diodes, semiconductor lasers, photoelectric detectors and the like.
In order to achieve the above purpose, the invention adopts the following technical scheme:
inversion Cs 8 Sn 3 GaI 24 /Cs 8 Sn 3 InI 24 The hybrid composite material is characterized by comprising the following chemical expression: cs (cells) 8 Sn 3 GaI 24 /Cs 8 Sn 3 InI 24 From Ga 3+ With In 3+ Ion-mediated energy level formation of inverse Cs 2 SnI 6 The crystal form of the structure is a face-centered cubic structure, the surface appearance of the structure is a nanocube, and the surface of the structure is distributed with a hollow structure.
The above-mentioned inverse Cs 8 Sn 3 GaI 24 /Cs 8 Sn 3 InI 24 The preparation method of the hybrid composite material comprises the following steps:
step 1, gaI is carried out 3 、InI 3 With SnI 4 Respectively dissolving in DMF to form mixed solution; wherein Ga 3+ With In 3+ The molar ratio of the ions is 1:1, ga 3+ 、In 3+ Ions are co-located with Sn 4+ Stoichiometric ratio of ions (Ga 3+ +In 3+ :Sn 4+ ) 1 to 5 percent;
step 2, adding CsI into the mixed solution according to the proportion of 0.2mol/L, and stirring until the CsI is completely dissolved to form a precursor solution;
step 3, spraying the precursor solution on the substrate by adopting ultrasonic spraying, and baking the substrate at 130-180 ℃ for 5-10min; the ultrasonic spraying parameters are set as follows: working distance is 10cm, flow velocity is 20 mu L/s, spray head moving speed is 5mm/s, spraying times are 4 times, working air pressure is 0.2MPa, and substrate temperature is 130-180 ℃;
step 4, placing the substrate into SnI 4 Soaking in absolute ethanol solution, taking out, washing with absolute ethanol, and blow-drying to obtain inverse Cs 8 Sn 3 GaI 24 /Cs 8 Sn 3 InI 24 Hybrid composite materials.
Further, in step 1, the total concentration of metal ions in the mixed solution was 0.1mol/L.
Further, in step 4, snI 4 The concentration of the absolute ethyl alcohol solution is 0.1g/mL, and the soaking time is 1-5 minutes.
In terms of working principle:
the invention adopts a plane wave super-soft pseudo-potential method based on density functional theory to calculate and discover Ga 3+ 、In 3+ The ion is III group transition metal ion, and the ionic radius and Cs of the ion are 2 SnI 6 Sn in (i) 4+ Ion approach, when Ga 3+ And In 3+ Ion p-type co-doped Cs 2 SnI 6 Predominantly substitution, co-existence of substitution and interstitials, and resulting in Cs 2 SnI 6 Inversion of form Cs 8 Sn 3 GaI 24 /Cs 8 Sn 3 InI 24 Hybrid composite materials. The invention adopts wet chemical method to prepare Cs first 2 SnI 6 Spraying the precursor on the substrate by ultrasonic spraying method, and baking to obtain Ga 3+ And In 3+ Ion entry into Cs 2 SnI 6 Inside the crystal, the transformation from the intrinsic state n-type to p-type is realized, namely the inversion Cs with microcosmic cube structure is prepared 8 Sn 3 GaI 24 /Cs 8 Sn 3 InI 24 Hybrid composite materials. The inversion Cs prepared by the invention 8 Sn 3 GaI 24 /Cs 8 Sn 3 InI 24 The hybrid composite material has a crystal form of a face-centered cubic structure, and has high crystal purity and no impurity phase; at the same time, ga 3+ 、In 3+ Ion-combined synergized-regulation Cs 2 SnI 6 All exhibit p-type semiconductor conductivity type with Ga 3+ 、In 3 + Rise in ion concentration, inversion Cs 8 Sn 3 GaI 24 /Cs 8 Sn 3 InI 24 The Hall mobility of the hybrid composite material is also greatly improved, and the carrier transport performance of the sample is improved mainly due to the fact that a large number of Ga-I or In-I bonds exist. In addition, the invention adopts an ultrasonic spraying method, and has the advantages of high production efficiency, low synthesis cost, simple process requirement and the like.
In summary, the beneficial effects of the invention are as follows:
the invention provides an inversion Cs 8 Sn 3 GaI 24 /Cs 8 Sn 3 InI 24 The surface of the hybrid composite material is uniform and compact, and the hybrid composite material has good crystallographic characteristics and photoelectric properties; the preparation method does not need high-temperature calcination, has the advantages of simple production process, good production efficiency, low synthesis cost, environmental protection and energy conservation, is suitable for large-scale industrial manufacture, and has wide application prospect in the fields of solar photovoltaic devices, light-emitting diodes, semiconductor lasers, photoelectric detectors, sensors and the like.
Drawings
FIG. 1 shows the preparation of inverted Cs in examples 1 to 5 8 Sn 3 GaI 24 /Cs 8 Sn 3 InI 24 SEM image of hybrid composite.
FIG. 2 is example 1Preparation of inverse Cs in 5 8 Sn 3 GaI 24 /Cs 8 Sn 3 InI 24 XRD pattern of the hybrid composite.
FIG. 3 shows the preparation of inverted Cs in examples 1 to 5 8 Sn 3 GaI 24 /Cs 8 Sn 3 InI 24 Raman spectrum of hybrid composite.
FIG. 4 shows the preparation of inverted Cs in examples 1 to 5 8 Sn 3 GaI 24 /Cs 8 Sn 3 InI 24 Visible-infrared spectrum absorption profile of hybrid composite.
FIG. 5 shows the preparation of inverted Cs in examples 1 to 5 8 Sn 3 GaI 24 /Cs 8 Sn 3 InI 24 Time resolved photoluminescence spectra (TRPL) profiles of hybrid composites.
Detailed Description
In order to make the objects, technical solutions and advantageous effects of the present invention more apparent, the present invention will be described in further detail with reference to the accompanying drawings and examples.
Example 1
The present embodiment provides an inversion Cs 8 Sn 3 GaI 24 /Cs 8 Sn 3 InI 24 The hybrid composite material is prepared by the following steps:
step 1, gaI is carried out 3 、InI 3 With SnI 4 Respectively dissolving in DMF, ga 3+ With In 3+ The molar ratio of the ions is 1:1, and a mixed solution is formed, wherein Ga is contained in the solution 3+ 、In 3+ Ions are co-located with Sn 4+ Stoichiometric ratio of ions (Ga 3+ +In 3+ :Sn 4+ ) 1% of metal ions and 0.1mol/L of total concentration;
step 2, adding 0.2mol/L CsI into the mixed solution, and stirring until the CsI is completely dissolved to form a reddish brown mixed solution;
step 3, spraying the precursor solution on a common glass slide (substrate) cleaned by a base plate by adopting ultrasonic spraying, and baking the substrate at 130 ℃ for 5min after the spraying is finished; the ultrasonic spraying parameters are set as follows: working distance is 10cm, flow velocity is 20 mu L/s, spray head moving speed is 5mm/s, spraying times are 4 times, working air pressure is 0.2MPa, and substrate temperature is 130 ℃;
step 4, placing the substrate into SnI with the concentration of 0.1g/mL 4 Soaking in absolute ethanol solution for 1 min, taking out, washing with absolute ethanol, and blow-drying to obtain inverse Cs 8 Sn 3 GaI 24 /Cs 8 Sn 3 InI 24 Hybrid composite samples.
Example 2
The present embodiment provides an inversion Cs 8 Sn 3 GaI 24 /Cs 8 Sn 3 InI 24 The only difference from example 1 is the hybrid composite: in step 1, ga in solution 3+ 、In 3+ Ions are co-located with Sn 4+ Stoichiometric ratio of ions (Ga 3+ +In 3+ :Sn 4+ ) 2%.
Example 3
The present embodiment provides an inversion Cs 8 Sn 3 GaI 24 /Cs 8 Sn 3 InI 24 The only difference from example 1 is the hybrid composite: in step 1, ga in solution 3+ 、In 3+ Ions are co-located with Sn 4+ Stoichiometric ratio of ions (Ga 3+ +In 3+ :Sn 4+ ) 3%.
Example 4
The present embodiment provides an inversion Cs 8 Sn 3 GaI 24 /Cs 8 Sn 3 InI 24 The only difference from example 1 is the hybrid composite: in step 1, ga in solution 3+ 、In 3+ Ions are co-located with Sn 4+ Stoichiometric ratio of ions (Ga 3+ +In 3+ :Sn 4+ ) 4%.
Example 5
The present embodiment provides an inversion Cs 8 Sn 3 GaI 24 /Cs 8 Sn 3 InI 24 The only difference from example 1 is the hybrid composite: in step 1, ga in solution 3+ 、In 3+ Ion(s)Together with Sn 4+ Stoichiometric ratio of ions (Ga 3+ +In 3+ :Sn 4+ ) 5%.
The present invention is based on Ga in each of examples 1 to 5 3+ 、In 3+ Inverse Cs synthesized by ion concentration 8 Sn 3 GaI 24 /Cs 8 Sn 3 InI 24 SEM surface morphology observation is carried out on the hybrid composite material, and the result is shown in figure 1; the results show that the ultrasonic spraying method can obtain compact Cs with uniform surface 8 Sn 3 GaI 24 /Cs 8 Sn 3 InI 24 A hybrid film; and it can be seen from the figure that cubic phase crystallization is clearly observed on all sample surfaces when Ga 3+ 、In 3+ When the ion concentration is increased, although the morphology of the crystal is distorted and also forms a hollow morphology, the surface particle morphology can still be clearly observed to maintain cubic phase crystallization, and the particle size is along with Ga 3+ 、In 3+ The concentration increases with an increase in concentration. Meanwhile, for examples 1 to 5, the respective Ga is based on 3+ 、In 3+ Inverse Cs synthesized by ion concentration 8 Sn 3 GaI 24 /Cs 8 Sn 3 InI 24 XRD testing was performed on the hybrid composite, and the results are shown in fig. 2; as can be seen, the diffraction peak of all sample lines is equal to Cs in the ICSD crystal library 2 SnI 6 The theoretical diffraction peak positions of standard PDF card #73-0330 are identical, which indicates Ga 3+ 、In 3+ Ion entry does not alter Cs 2 SnI 6 The crystal morphology of the face-centered cubic structure is only different in the relative intensities of the diffraction peaks, and these differences may be the effect of the morphology changes in fig. 1; in addition, in FIG. 2, in addition to Cs 2 SnI 6 No other impurity diffraction peaks other than the standard diffraction peak of (2), indicating Ga 3+ 、In 3+ Ions enter Cs 2 SnI 6 The crystal lattice forms substitutional or interstitial spaces without changing its intrinsic crystalline phase, and Ga 3+ 、In 3+ The ions also do not form other compound impurities. Therefore, the invention successfully prepares the Cs with the cubic structure by adopting the ultrasonic spraying method 8 Sn 3 GaI 24 /Cs 8 Sn 3 InI 24 Hybrid composite materials.
Further, the present invention adopts Raman spectrum pairs to the Ga-based on each of examples 1-5 3+ 、In 3+ Inverse Cs synthesized by ion concentration 8 Sn 3 GaI 24 /Cs 8 Sn 3 InI 24 The hybrid composite was analyzed and the results are shown in FIG. 3; as can be seen, ga 3 + 、In 3+ Ion in the inversion form Cs 8 Sn 3 GaI 24 /Cs 8 Sn 3 InI 24 Four raman peaks of the hybrid material are at positions 76, 90, 124 and 246cm, respectively -1 A place; control intrinsic Cs 2 SnI 6 Is 76cm -1 The peak at the position is Cs 2 SnI 6 Delta (F) 2g ) Vibration peak, 90cm -1 Is v (E) g ) Vibration peak, main peak 124cm -1 Is v (A) 1g ) Vibration peak, 245-246cm -1 Also Cs 2 SnI 6 Is not present except for other impurity peaks, which also confirms XRD test results, ga 3+ 、In 3+ Ions enter Cs 2 SnI 6 Lattice, and no impurities are formed. Furthermore, with Ga 3+ 、In 3+ Gradually increasing ion concentration, 124cm -1 The main peak is also shifted, which can be attributed to Ga 3+ 、In 3+ Ions change the morphology of the crystal. The results further demonstrate that Ga in the methods disclosed by the invention 3+ 、In 3+ The ions do not form the corresponding impurity phases.
Further, the present invention is based on Ga in each of examples 1 to 5 3+ 、In 3+ Inverse Cs synthesized by ion concentration 8 Sn 3 GaI 24 /Cs 8 Sn 3 InI 24 The hybrid composite material was subjected to visible-infrared spectrum testing, and the results are shown in fig. 4; as can be seen, ga 3+ 、In 3+ The ions do not cause Cs 8 Sn 3 GaI 24 /Cs 8 Sn 3 InI 24 The absorption coefficient of the hybrid material deteriorates in the visible-infrared light band,only the absorption edge is slightly blue shifted. Also, as can be seen from the time resolved photoluminescence spectrum (TRPL) curve as shown in fig. 5, ga 3+ 、In 3+ Ion concentration vs. Cs 8 Sn 3 GaI 24 /Cs 8 Sn 3 InI 24 The lifetime of carriers in the hybrid material has a certain influence. As can be seen from the carrier quenching curves in the inset of FIG. 5, ga 3+ And In 3+ At an ion level of 1% (sample prepared in example 1), the sample carrier lifetime was most significantly prolonged.
At the same time, the invention also relates to the preparation of the respective Ga-based alloy in examples 1 to 5 3+ 、In 3+ Inverse Cs synthesized by ion concentration 8 Sn 3 GaI 24 /Cs 8 Sn 3 InI 24 The hybrid composite material was subjected to Hall effect tests, and the test results show that the samples obtained in examples 1 to 5 are all p-type semiconductor conductivity types, ga 3+ 、In 3+ Combined regulation of ions can control Cs 2 SnI 6 Conversion from original n-type semiconductor to p-type Cs 8 Sn 3 GaI 24 /Cs 8 Sn 3 InI 24 A semiconductor; second, with Ga 3+ 、In 3+ The Hall mobility of the sample is also greatly improved due to the increase of the ion concentration, and the carrier transport performance of the sample is improved mainly due to the large number of Ga-I or In-I bonds.
In conclusion, the invention can obtain compact Cs with uniform surface by ultrasonic spraying 8 Sn 3 GaI 24 /Cs 8 Sn 3 InI 24 Hybrid film, surface grain morphology maintains cubic phase crystallization, grain size can be obtained from Ga 3+ 、In 3+ Ion concentration regulation; the method does not need high-temperature calcination, is simple and feasible, is environment-friendly and energy-saving, and has low cost; inversion s prepared 8 Sn 3 GaI 24 /Cs 8 Sn 3 InI 24 The hybrid composite material has good crystallographic characteristics and photoelectric properties, and has good application prospects in the fields of solar photovoltaic devices, light-emitting diodes, sensors and the like.
While the invention has been described in terms of specific embodiments, any feature disclosed in this specification may be replaced by alternative features serving the equivalent or similar purpose, unless expressly stated otherwise; all of the features disclosed, or all of the steps in a method or process, except for mutually exclusive features and/or steps, may be combined in any manner.
Claims (4)
1. Inversion Cs 8 Sn 3 GaI 24 /Cs 8 Sn 3 InI 24 The hybrid composite material is characterized by comprising the following chemical expression: cs (cells) 8 Sn 3 GaI 24 /Cs 8 Sn 3 InI 24 From Ga 3+ With In 3+ Ion-mediated energy level formation of inverse Cs 2 SnI 6 The crystal form of the structure is a face-centered cubic structure, the surface appearance of the structure is a nanocube, and the surface of the structure is distributed with a hollow structure.
2. The inversion Cs of claim 1 8 Sn 3 GaI 24 /Cs 8 Sn 3 InI 24 The preparation method of the hybrid composite material is characterized by comprising the following steps:
step 1, gaI is carried out 3 、InI 3 With SnI 4 Respectively dissolving in DMF to form mixed solution; wherein Ga 3+ With In 3+ The molar ratio of the ions is 1:1, ga 3+ 、In 3+ Ions are co-located with Sn 4+ Stoichiometric ratio of ions (Ga 3+ +In 3+ :Sn 4+ ) 1 to 5 percent;
step 2, adding CsI into the mixed solution according to the proportion of 0.2mol/L, and stirring until the CsI is completely dissolved to form a precursor solution;
step 3, spraying the precursor solution on the substrate by adopting ultrasonic spraying, and baking the substrate at 130-180 ℃ for 5-10min; the ultrasonic spraying parameters are set as follows: working distance is 10cm, flow velocity is 20 mu L/s, spray head moving speed is 5mm/s, spraying times are 4 times, working air pressure is 0.2MPa, and substrate temperature is 130-180 ℃;
step 4, baseTablet is put into SnI 4 Soaking in absolute ethanol solution, taking out, washing with absolute ethanol, and blow-drying to obtain inverse Cs 8 Sn 3 GaI 24 /Cs 8 Sn 3 InI 24 Hybrid composite materials.
3. The inversion Cs of claim 2 8 Sn 3 GaI 24 /Cs 8 Sn 3 InI 24 The preparation method of the hybrid composite material is characterized in that in the step 1, the total concentration of metal ions in the mixed solution is 0.1mol/L.
4. The inversion Cs of claim 2 8 Sn 3 GaI 24 /Cs 8 Sn 3 InI 24 The preparation method of the hybrid composite material is characterized in that in the step 4, snI 4 The concentration of the absolute ethyl alcohol solution is 0.1g/mL, and the soaking time is 1-5 minutes.
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