CN117684265A - Vertical perovskite sheet layer grown on silicon substrate and preparation method and application thereof - Google Patents
Vertical perovskite sheet layer grown on silicon substrate and preparation method and application thereof Download PDFInfo
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- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 47
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- 238000002360 preparation method Methods 0.000 title abstract description 10
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 52
- 239000010453 quartz Substances 0.000 claims abstract description 42
- 238000000034 method Methods 0.000 claims abstract description 39
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- 229910052786 argon Inorganic materials 0.000 claims description 23
- 238000004519 manufacturing process Methods 0.000 claims description 5
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Abstract
The invention discloses an upright perovskite sheet layer growing on a silicon substrate, and a preparation method and application thereof, and relates to the technical field of semiconductor materials. The method comprises the steps of 2 And CsBr powder is placed in a quartz boat and is placed in a heating area of a tube furnace; placing a substrate in a corundum boat, and placing the substrate on one side of a quartz boat of a tube furnace; and vacuumizing the tube furnace, continuously introducing inert gas from the quartz boat to the corundum boat, wherein the growth temperature is 570 ℃, and the heating time is 15min, namely the vertical perovskite sheet layer growing on the silicon substrate. The invention grows the vertical all-inorganic CsSnBr with good crystal quality on the silicon substrate by a chemical vapor deposition method 3 The single crystal perovskite can be used for high-efficiency perovskite luminescence and development of photovoltaic devices.
Description
Technical Field
The invention relates to the technical field of semiconductor materials, in particular to an upright perovskite sheet layer growing on a silicon substrate, and a preparation method and application thereof.
Background
Perovskite (perovskie) was at the earliest a compound found by Gustav Rose in 1839 and named by russian mineralogist LevAlekseevich Perovski. Perovskite has a general structural formula of AMX 3 Wherein A is a monovalent cation, M is a divalent metal cation, and X is a monovalent halide anion. Perovskite generally has the structure: eight cations are located at the vertices of the cube, one metal cation is located at the center of the cube, and six halide anions are distributed in the face center of the cube. The metal ion and 6 halide anions located in the central position of the cube constitute the basic framework of the perovskite: [ MX ] 6 ] 4﹣ An octahedral structure. Halide perovskite can be classified into organic-inorganic hybrid perovskite and all-inorganic perovskite according to monovalent cation. The all-inorganic metal halide perovskite material has the characteristics of continuously adjustable band gap, long carrier migration distance, balanced carrier injection rate, high quantum yield, high defect tolerance and the like because of excellent photoelectric properties, and has great application potential in the fields of photovoltaics, illumination, display, laser, imaging, detection and the like, and has attracted great attention in recent years.
In particular, since the advent of lasers, with the development of photonic technology and micro-nano processing technology, laser technology has been widely used in various fields such as biological imaging, optical communication, integrated optics, and the like. In order to solve the problems of high power consumption, low operation speed and the like of the traditional electronic chip, the optoelectronic device needs to be miniaturized and integrated. Micro-nano lasers are an important component of photonic chips, which are key devices for generating optical signals. The laser mainly comprises 3 important parts: pump source, resonant cavity and gain material. Perovskite is used as a direct band gap semiconductor material, has excellent characteristics of high quantum yield, low non-radiative recombination rate, low manufacturing cost, tunable band gap width and the like, and is widely applied to micro-nano lasers as an important gain material. Through development researches in recent years, researchers at home and abroad prepare perovskite with different shapes and sizes such as nanowires, nanoplatelets, microdisks and the like based on high-gain perovskite materials, and various micro-nano lasers are formed, such as: fabry-perot Luo Weina lasers, whispering gallery micronano lasers, array micronano lasers, and the like.
In recent years, perovskite micro-nano lasers have the defects of high threshold value, large line width, stability deviation and the like despite great progress, and realizing electrically pumped micro-nano lasers and on-chip integration still is a great challenge. Therefore, based on the synthesis method of perovskite materials, micro-nano processing technology and the like still need to be improved to expire the development of on-chip integration. The high quality of the sample determines the space and upper limit of application of the material. The prepared perovskite sample has the problems of small grain size, low crystallization quality, high grain boundary density, high defect density and the like, and the improvement of the performance of the all-inorganic perovskite-based photoelectric device is limited. In order to obtain high-quality perovskite materials, researchers at home and abroad develop various preparation methods, such as: spin coating, antisolvent crystallization, vapor phase epitaxial growth, and the like. For various solution methods, many organic solvents are needed, which are not beneficial to environmental protection and also cause harm to human bodies. In addition, various lead-containing perovskites have been most recently reported, and although they have achieved great performance, the problem of lead toxicity has also been attracting increasing attention. Therefore, the development of a synthesis method which is easy to regulate and control, is environment-friendly and avoids the harm of toxic reagents to human beings is important to grow high-quality lead-free perovskite single crystals.
Disclosure of Invention
Aiming at the defects in the background technology, the invention mainly solves the technical problems: the problems of complex process, poor quality of the grown crystals and the like faced by the growth and preparation of all-inorganic single crystal perovskite sheet layers. The invention provides an upright perovskite sheet layer growing on a silicon substrate, and a preparation method and application thereof. The method grows vertical all-inorganic CsSnBr with good crystal quality on a silicon substrate by a chemical vapor deposition method 3 A method of single crystal perovskite. And it is worth noting that the method is general. It is not limited to CsSnBr 3 Growth of single crystal perovskite, csPbBr 3 And CsPbI 3 Single crystal perovskite lamellae are also equally suitable, and are not onlySuch vertical single crystal perovskite sheet growth can also be achieved on a sapphire substrate on a silicon substrate.
The first object of the present invention is to provide a method for preparing an upstanding perovskite sheet layer grown on a silicon substrate, comprising the steps of:
SnBr is prepared 2 And CsBr powder is placed in a quartz boat and is placed in a heating area of a tube furnace;
placing a substrate in a corundum boat, and placing the substrate on one side of a quartz boat of a tube furnace;
vacuumizing the tube furnace, continuously introducing inert gas from the quartz boat to the corundum boat, wherein the growth temperature is 565-580 ℃, and the heating time is 10-20min, namely the vertical perovskite sheet layer growing on the silicon substrate.
Preferably, the SnBr 2 And CsBr is 1:1.
preferably, a rectangular corundum boat is further covered on the corundum boat provided with the substrate;
wherein, the open area of the corundum boat with the substrate is partially shielded by a covered rectangular corundum boat.
Preferably, the inert gas is argon, the purity is 99.999 percent, and the flow rate is 100-200 sccm.
Preferably, the heating to the growth temperature is for a period of 80-120min.
Preferably, the heating rate of the tube furnace is 5-10 ℃/min.
Preferably, the geometric center of the quartz boat and the geometric center of the corundum boat are on the same straight line, and the distance between the center of the quartz boat and the center of the corundum boat is 13-15cm.
Preferably, the SnBr 2 The purity of the powder is 99.1 to 99.99 percent; the CsBr powder had a purity of 99.99%.
A second object of the present invention is to provide a vertical perovskite sheet layer grown on a silicon substrate.
A third object of the present invention is to provide the use of an upstanding perovskite sheet layer grown on a silicon substrate in a photovoltaic device.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides an upright perovskite sheet layer growing on a silicon substrate, and a preparation method and application thereof. The vertical perovskite sheet layer grown on the silicon substrate is prepared by adopting a chemical vapor deposition method, and the method has the advantages of simple process, safe and pollution-free experimental process. The single-temperature zone tube furnace greatly reduces the production cost, and the repeatability of the experiment is high, and the quality of the grown crystals is excellent. Chemical Vapor Deposition (CVD), one of the key technologies for preparing a variety of advanced semiconductor materials with excellent properties, can precisely control the growth of materials through the regulation of gas flow rate and composition, deposition temperature, pressure, vacuum chamber shape, deposition time, substrate materials, and the like. Particularly, the vapor pressure and the diffusion rate of the gas can be effectively regulated through the optimal combination of temperature and pressure, the deposition distance of the reaction gas on the substrate is reasonably designed, and the morphology of the material can be further regulated and controlled. CsSnBr of the present invention 3 The perovskite crystal uses a space finite field method in the growth process, a layer of corundum boat is covered on the corundum boat with the growth substrate, and the design avoids deposition and growth of a continuous thick layer sample on the substrate by using the growth gas with too high concentration. After confinement, the sample can be deposited on the surface of the substrate in a dispersed manner, which is beneficial to the formation of independent single crystals with high crystallization quality.
According to the invention, the silicon substrate is selected as the growth substrate, and compared with the well-known mica substrate, sapphire substrate and the like, the silicon substrate is low in price, and the production cost is effectively reduced. Generally, researchers use dangerous chemicals such as acetone to treat the substrate to remove impurities, so as to ensure the surface of the substrate to be clean. In the invention, the silicon substrate is not specially treated, and the cleaning of the silicon substrate by using the ear-washing ball only can be achieved. The method not only avoids the use of dangerous chemicals in the experiment and reduces the risk of the experiment, but also simplifies the experimental steps to a great extent and saves the time cost.
CsSnBr prepared by the invention 3 Unlike conventional perovskite crystals grown along the surface of a substrate, which have a variety of morphologies, perovskite crystals canTo achieve vertical growth in a direction perpendicular to the surface of the silicon substrate. The method greatly enriches the diversity and controllability of the morphology of perovskite crystal preparation and promotes the thermodynamic and kinetic research of perovskite crystal growth.
The invention provides application of an upright perovskite sheet layer grown on a silicon substrate in a photovoltaic device. Mainly based on the prepared vertical single crystal CsSnBr 3 The perovskite sheet layer has high crystallization quality, and the contact area with the substrate is greatly reduced due to the vertical growth of the perovskite sheet layer. As a good gain medium for the preparation of micro-nano lasers, the vertical single crystal CsSnBr 3 The micro-nano laser prepared by the perovskite sheet layer has small structure size, and can meet the requirement of laser emission direction facing in the plane, so that the laser can be coupled into an adjacent optical waveguide device, and the requirement of on-chip integration is better met.
Drawings
FIG. 1 shows the growth of vertical single crystal CsSnBr at low pressure by chemical vapor deposition 3 Schematic of experimental setup of perovskite sheets.
FIG. 2 is an upright single crystal CsSnBr grown in example 1 3 SEM pictures of perovskite lamellae.
FIG. 3 is an upright single crystal CsSnBr grown in example 1 3 Optical photographs of perovskite platelets.
FIG. 4 is an upright single crystal CsSnBr grown in example 1 3 Photoluminescence spectra of perovskite platelets.
FIG. 5 is an upright single crystal CsSnBr grown in example 1 under a 50X lens 3 Optical pictures of perovskite sheets and their corresponding Mapping pictures.
FIG. 6 is an upright single crystal CsSnBr grown in example 1 3 Peak position distribution Mapping graph of perovskite sheet.
FIG. 7 is an upright single crystal CsSnBr grown in example 1 3 Fluorescence lifetime plot of perovskite platelets.
FIG. 8 is an upright single crystal CsSnBr grown along example 1 at the same excitation power 3 Photoluminescence spectra at different positions of perovskite sheet layer from low to high in Z direction.
FIG. 9 is an upright single crystal CsSnBr grown in example 1 3 Photoluminescence spectra of perovskite platelets at different excitation powers.
Fig. 10 is a graph showing the trend of peak position, peak intensity and half-width with power, which is obtained by fitting from the variable power emission spectrum in fig. 9.
Detailed Description
In order that those skilled in the art will better understand the technical solution of the present invention, the present invention will be further described with reference to the specific examples and the accompanying drawings, but the examples are not intended to be limiting.
The invention provides a method for growing vertical all-inorganic CsSnBr with good crystal quality on a silicon substrate by a chemical vapor deposition method 3 A method of single crystal perovskite. And it is worth noting that the method is general. It is not limited to CsSnBr 3 Growth of single crystal perovskite, csPbBr 3 And CsPbI 3 The single crystal perovskite sheet is also applicable, and the vertical single crystal perovskite sheet growth can be realized on a sapphire substrate as well as a silicon substrate.
The first aspect of the present invention provides a method of preparing a layer of upstanding perovskite platelets grown on a silicon substrate, comprising the steps of:
SnBr is prepared 2 And CsBr powder is placed in a quartz boat and is placed in a heating area of a tube furnace;
placing a substrate in a corundum boat, and placing the substrate on one side of a quartz boat of a tube furnace;
vacuumizing the tube furnace, continuously introducing inert gas from the quartz boat to the corundum boat, wherein the growth temperature is 565-580 ℃, and the heating time is 10-20min, namely the vertical perovskite sheet layer growing on the silicon substrate.
The SnBr 2 And CsBr is 1:1. a rectangular corundum boat is covered on the corundum boat with the substrate; wherein, the open area of the corundum boat with the substrate is partially shielded by a covered rectangular corundum boat. The SnBr 2 The purity of the powder is 99.1 to 99.99 percent; the CsBThe purity of the r powder was 99.99%.
Wherein the tube furnace is vacuumized, which is to vacuumize the tube furnace to ensure that the growth pressure is controlled to be 1.7X10 2 pa。
It should be noted that, a small rectangular corundum boat is covered on the corundum boat with the substrate to play a role of a certain space limitation, so that a large amount of growth elements are not deposited on the substrate under a higher growth concentration, and the crystal growth density on the substrate is overlarge and is connected into slices. After the finite field, the CsSnBr can be dispersed on a substrate, and has good crystal quality 3 Perovskite crystals.
The silicon substrate dimensions were: 2 cm. Times.0.8 cm, the surface of the substrate was cleaned with an ear-washing ball prior to the experiment.
In one embodiment, snBr 2 And CsBr powder is uniformly mixed with CsBr powder according to the molar ratio of 1:1 and placed in a quartz boat, so that the quartz boat is ensured to be placed in the center of a tube furnace, and the highest heating temperature is achieved. The corundum boat is provided with a silicon substrate and is covered with a small rectangular corundum boat. The quartz boat has the following dimensions: length x width: 50mm by 16mm; the corundum boat has the following dimensions: length x width x height: 97mm by 17mm by 12mm; the rectangular corundum boat has the following dimensions: length x width x height: 45mm by 22mm by 14mm; the growth substrate is a silicon substrate plated with 300nm single-sided polished silicon dioxide.
In one embodiment, snBr is weighed 2 Powder: 27.8mg, csBr powder: 21.3mg. On this basis, if the amount of the precursor powder is as low as 10mg or less, perovskite crystals cannot be obtained on the substrate, and if an excessive amount of the precursor is used, thick and uneven crystals cannot be obtained, and also dispersed independent crystals with good growth quality cannot be obtained.
Specifically, the inert gas is argon, the purity is 99.999%, and the flow rate is 100-200 sccm.
In one embodiment, the tube furnace was purged with 40sccm argon for 15 minutes before the experiment was started so that no other miscellaneous gases in the furnace interfere with the experiment, avoiding air ingress affecting the crystallization quality. And then argon with the purity of 99.999 percent and the flow rate of 100-200 sccm is continuously introduced into the whole experiment, and the whole tube furnace is filled with high-purity inert gas, so that the growth process can be protected, and the precursor is conveyed to the substrate to grow crystals.
According to the invention, the heating to the growth temperature is carried out for a period of 80-120min. The heating rate of the tube furnace is 5-10 ℃/min.
In one embodiment, the maximum growth temperature is set at 570 ℃, the heating time from room temperature to 570 ℃ is 100min, and then the temperature is reduced to room temperature after maintaining the maximum temperature for 15 min.
Specifically, a single temperature zone tube furnace is used to reduce growth costs. The single-temperature zone tube furnace is a miniature 1200 ℃ open type tube furnace with a Kejing type OTF-1200X-S, the quartz tube of the tube furnace is 800mm in length and 25mm in diameter.
According to the invention, the geometric center of the quartz boat and the geometric center of the corundum boat are on the same straight line, and the distance between the center of the quartz boat and the center of the corundum boat is 13-15cm.
In one embodiment, the geometric center of the quartz boat is kept in line with the geometric center of the corundum boat, and the distance between the center of the quartz boat and the center of the corundum boat on the left side is 13-15cm. Neither too close nor too far distance can result in CsSnBr on the substrate 3 Perovskite crystals.
A second aspect of the invention provides an upstanding perovskite sheet layer grown on a silicon substrate.
A third aspect of the invention provides the use of an upstanding perovskite sheet layer grown on a silicon substrate in a photovoltaic device.
It should be noted that, the experimental methods adopted in the invention are all conventional methods unless otherwise specified; the reagents and materials employed, unless otherwise specified, are commercially available.
Example 1
This example provides a method of growing a layer of upstanding single crystal perovskite platelets on a silicon substrate, as shown in figure 1, comprising the steps of:
(1) Weighing SnBr2 powder according to a molar ratio of 1:1: 27.8mg, csBr powder: 21.3mg are placed in a quartz boat, wherein SnBr 2 The purity of the powder is 99.2%; the purity of the CsBr powder is 99.99%. The silicon substrate coated with 300nm single-sided polished silica was then cut into 2cm by 0.8cm sizes with a diamond cutter and placed in a corundum boat.
(2) The quartz boat containing the precursor powder is placed in the center of the tube furnace, the corundum boat containing the growth substrate is placed at a position about 13cm away from the left side of the quartz boat, the geometric center of the quartz boat and the geometric center of the corundum boat are kept on the same straight line, and a small rectangular corundum boat is covered on the quartz boat. The covered rectangular boat can play a role in limiting a certain space, so that a large amount of growth elements are not deposited on the substrate under a higher growth concentration, and the crystal growth density on the substrate is overlarge and is connected into a sheet. After the space limitation, the CsSnBr can be dispersed on a substrate, and has good crystal quality 3 Perovskite crystals.
(3) After the furnace is assembled, the gas flow is controlled, and inert gas argon is continuously introduced into the tubular furnace. Before the experiment starts, the tubular furnace is cleaned by argon with the purity of 99.999 percent and the flow rate of 40sccm for 15 minutes, so that other mixed gases in the furnace do not interfere with the experiment, and the influence of air entering on the crystallization quality is avoided. After cleaning the tube furnace, starting the pump to pump at low pressure to stabilize the pressure at 1.0X10 2 After a period of time pa, the argon flow rate was again adjusted to 200sccm while maintaining the pressure at 1.7X10 2 pa. The argon flow rate was maintained at 200sccm and the pressure was stabilized at 1.7X10 during the whole of the experiment thereafter 2 pa。
(4) Setting a heating program, setting the highest growth temperature to 570 ℃, setting the heating time from room temperature to 570 ℃ to 100min, maintaining the highest temperature for 15min, and then cooling to room temperature. And (5) after the tube furnace is cooled to room temperature, opening the furnace for sampling, and observing the sample.
(5) First, the prepared CsSnBr is subjected to an optical microscope 3 As shown in FIG. 3, csSnBr can be observed under an optical microscope 3 Perovskite crystals are grown vertically on silicon substrates. From the lowest end to the topmost end, not on the same focal plane, and can be roughly measured to obtain CsSnBr 3 The perovskite crystal size is mostly distributed inAbout 20 microns.
(6) As shown in FIG. 2, SEM shows the prepared CsSnBr 3 The perovskite crystal is a triangular plate vertically grown on the surface of the silicon substrate, and the edge of the triangular plate is sharp, so that the perovskite crystal has better crystallization quality. As shown in FIG. 4 and FIG. 5, csSnBr 3 The perovskite was observed to have a strong PL peak at 675nm under 200. Mu.w of 100ms laser irradiation. Then selecting an upright perovskite grown on the substrate, scanning the whole crystal to obtain a Mapping graph of the crystal, as shown in FIG. 6, showing that the luminescence of the whole crystal is relatively uniform and also reflects the prepared CsSnBr to a certain extent 3 Perovskite has good crystal quality and excellent optical properties.
(7) For the prepared vertical single crystal CsSnBr 3 The perovskite sheet was subjected to optical characterization test, as shown in FIG. 7, to measure CsSnBr 3 The fluorescence lifetime of perovskite was 0.291ns, and excitation was performed under 100. Mu.w.200 ms laser light at the same position for the same sample, and the PL peak position was shifted with the Z axis, i.e. the focus position, shifted up and down, as shown in FIG. 8. As shown in fig. 9 and 10, the peak PL shifts blue with increasing excitation power from 100 μw to 900 μw, and the half-peak width increases with increasing power. According to the power law formulas I-P k Can be fitted to obtain the prepared vertical single crystal CsSnBr 3 Perovskite sheet k=0.7, indicating that energy transfer from free excitons to defect states occurs throughout the photoluminescence process.
Example 2
The present example provides a method of growing a layer of upstanding single crystal perovskite platelets on a sapphire substrate, comprising the steps of:
(1) Weighing SnBr2 powder according to a molar ratio of 1:1: 27.8mg, csBr powder: 21.3mg are placed in a quartz boat, wherein the purity of SnBr2 powder is 99.2%; the CsBr powder had a purity of 99.99%. The 300nm single-sided polished silicon dioxide coated C-M sapphire substrate was then cut into 1cm by 1cm sizes using a diamond cutter and placed in a corundum boat.
(2) The quartz boat containing the precursor powder is placed in the center of the tube furnace, the corundum boat containing the growth substrate is placed at a position about 15cm away from the left side of the quartz boat, the geometric center of the quartz boat and the geometric center of the corundum boat are kept on the same straight line, and a small rectangular corundum boat is covered on the quartz boat. The covered rectangular boat can play a role in limiting a certain space, so that a large amount of growth elements are not deposited on the substrate under a higher growth concentration, and the crystal growth density on the substrate is overlarge and is connected into a sheet.
(3) After the furnace is assembled, the gas flow is controlled, and inert gas argon is continuously introduced into the tubular furnace. Before the experiment starts, the tubular furnace is cleaned for 20min by argon with the purity of 99.999 percent and the flow rate of 40sccm, so that other mixed gases in the furnace do not interfere with the experiment, and the influence of air entering on the crystallization quality is avoided. After cleaning the tube furnace, starting a vacuum pump to pump low pressure to ensure that the pressure is stabilized at 1.0 multiplied by 10 2 After a period of time pa, the argon flow rate was again adjusted to 100sccm, while the pressure was maintained at 1.5X10 2 pa. The argon flow rate was maintained at 100sccm throughout the experiment thereafter, and the pressure was stabilized at 1.5X10 2 pa。
(4) Setting a heating program, setting the highest growth temperature to be 580 ℃, setting the heating time from room temperature to 580 ℃ to be 120min, then keeping the highest temperature for 15min, and then cooling to room temperature. And (5) after the tube furnace is cooled to room temperature, opening the furnace for sampling, and observing the sample.
Example 1 differs from example 2 in that the growth substrate selected is different, and the experimental parameters selected accordingly, such as argon flow rate and growth temperature, and the position of the corundum boat from the precursor, are different.
Example 3
The present example provides a method of growing a single crystal perovskite bulk on a silicon substrate comprising the steps of:
(1) Weighing SnBr2 powder according to a molar ratio of 1:1: 27.8mg, csBr powder: 21.3mg are placed in a quartz boat, wherein SnBr 2 The purity of the powder is 99.2%; the CsBr powder had a purity of 99.99%. The silicon substrate coated with 300nm single-sided polished silicon dioxide was then cut into 2cm x 2cm sizes with a diamond cutter and placed in a corundum boat.
(2) The quartz boat containing the precursor powder is placed in the center of the tube furnace, the corundum boat containing the growth substrate is placed at a position about 13cm away from the left side of the quartz boat, and the geometric center of the quartz boat and the geometric center of the corundum boat are kept on the same straight line.
(3) After the furnace is assembled, the gas flow is controlled, and inert gas argon is continuously introduced into the tubular furnace. Before the experiment starts, the tubular furnace is cleaned by argon with the purity of 99.999 percent and the flow rate of 40sccm for 15 minutes, so that other mixed gases in the furnace do not interfere with the experiment, and the influence of air entering on the crystallization quality is avoided. After cleaning the tube furnace, starting the pump to pump at low pressure to stabilize the pressure at 1.0X10 2 After a period of time pa, the argon flow rate was again adjusted to 200sccm while maintaining the pressure at 1.7X10 2 pa. The argon flow rate was maintained at 200sccm and the pressure was stabilized at 1.7X10 during the whole of the experiment thereafter 2 pa。
(4) Setting a heating program, setting the highest growth temperature to 570 ℃, setting the heating time from room temperature to 570 ℃ to 100min, maintaining the highest temperature for 15min, and then cooling to room temperature. And (5) after the tube furnace is cooled to room temperature, opening the furnace for sampling, and observing the sample.
Example 3 differs from example 1 in that a rectangular corundum boat was not covered on the corundum boat on which the growth substrate was placed, and that although the same growth substrate was selected, the experimental parameters selected, such as argon flow rate and growth temperature, and the position of the corundum boat from the precursor, were all the same, but the upright single crystal perovskite could not be obtained, but a more dense perovskite block was obtained.
Example 4
The present example provides a method of growing a thick layer single crystal perovskite thin film on a sapphire substrate comprising the steps of:
(1) Weighing SnBr2 powder according to a molar ratio of 1:1: 27.8mg, csBr powder: 21.3mg are placed in a quartz boat, wherein the purity of SnBr2 powder is 99.2%; the purity of the CsBr powder is 99.99%. The 300nm single-sided polished silicon dioxide coated C-M sapphire substrate was then cut into 1cm by 1cm sizes using a diamond cutter and placed in a corundum boat.
(2) The quartz boat containing the precursor powder is placed in the center of the tube furnace, the corundum boat containing the growth substrate is placed at a position about 15cm away from the left side of the quartz boat, and the geometric center of the quartz boat and the geometric center of the corundum boat are kept on the same straight line.
(3) After the furnace is assembled, the gas flow is controlled, and inert gas argon is continuously introduced into the tubular furnace. Before the experiment starts, the tubular furnace is cleaned for 20min by argon with the purity of 99.999 percent and the flow rate of 40sccm, so that other mixed gases in the furnace do not interfere with the experiment, and the influence of air entering on the crystallization quality is avoided. After cleaning the tube furnace, starting a vacuum pump to pump low pressure to ensure that the pressure is stabilized at 1.0 multiplied by 10 2 After a period of time pa, the argon flow rate was again adjusted to 100sccm, while the pressure was maintained at 1.5X10 2 pa. The argon flow rate was maintained at 100sccm throughout the experiment thereafter, and the pressure was stabilized at 1.5X10 2 pa。
(4) Setting a heating program, setting the highest growth temperature to be 580 ℃, setting the heating time from room temperature to 580 ℃ to be 120min, then keeping the highest temperature for 15min, and then cooling to room temperature. And (5) after the tube furnace is cooled to room temperature, opening the furnace for sampling, and observing the sample.
Example 4 differs from example 2 in that the same growth substrate and growth parameters were selected but a rectangular corundum boat was not covered on the corundum boat on which the growth substrate was placed, and the space-limiting effect was not achieved, so that too much precursor gas reached the substrate for deposition growth, and thus an upstanding single crystal perovskite could not be obtained, but a thick single crystal perovskite film was obtained as shown in fig. 3 (b). In fig. 3 (a), the presence of the upper rectangular boat can serve a good space-limiting function, so that a dispersed single crystal perovskite can be grown.
In conventional CVD growth processes, deposition growth of crystals on a substrate is typically regulated by adjusting the growth temperature, carrier gas flow rate, pressure, and the position of the substrate from the precursor. At a suitable growth temperature, the precursor is converted from a solid state to a gaseous state and transported in the tube by the carrier gas, and as the temperature begins to decrease away from the heating center, the precursor nucleates on the substrate and the crystal grows as it is transported to the substrate at a certain distance. Typically, the substrate is placed parallel to the precursor along the direction of transport of the carrier gas stream, and the precursor is transported with the carrier gas stream to directly perform chemical reactions on the substrate surface to grow crystals. Thus, although the crystal growth can be controlled by adjusting the flow of the carrier gas and the distance between the substrate and the precursor, the influence on the concentration of the precursor is still weak. The precursor concentration above the substrate is still easily too high, so that nucleation growth occurs at multiple locations on the substrate, and crystals are easily connected to form a large-area thick layer crystal. Based on the method, a space-limited method growth mode is innovatively designed, the space of the upper layer of the substrate is limited on the basis of original growth regulation, and the concentration of a precursor contacted with the substrate is well controlled, so that the purpose of regulating and controlling the crystal growth is achieved. A layer of boat with a certain thickness is covered on the boat with the substrate, the partial pressure of the precursor and the flow speed of the air flow at the boat are changed, and the contact mode of the air flow and the substrate is changed by the boat on the upper layer, so that the air does not act on the substrate in the original parallel direction, but is additionally introduced into a section of air flow path, and a section of vertical distance is increased. Under such conditions, the concentration and partial pressure of gas flowing to the surface of the substrate are controlled, and the precursor deposited on the substrate is greatly reduced, thus achieving the purpose of the dispersed growth of crystals on the substrate.
From the above examples, it is known that the use of a spatial confinement method to regulate the concentration of the growth gas during the growth of the perovskite is a key factor in forming the vertical perovskite single-wafer layer.
The present invention describes preferred embodiments and effects thereof. Additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. It is therefore intended that the following claims be interpreted as including the preferred embodiments and all such alterations and modifications as fall within the scope of the invention.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (10)
1. A method of producing a layer of upstanding perovskite platelets grown on a silicon substrate, comprising the steps of:
SnBr is prepared 2 And CsBr powder is placed in a quartz boat and is placed in a heating area of a tube furnace;
placing a substrate in a corundum boat, and placing the substrate on one side of a quartz boat of a tube furnace;
vacuumizing the tube furnace, continuously introducing inert gas from the quartz boat to the corundum boat, wherein the growth temperature is 565-580 ℃, and the heating time is 10-20min, namely the vertical perovskite sheet layer growing on the silicon substrate.
2. The method of producing a layer of upstanding perovskite platelets grown on a silicon substrate as claimed in claim 1, wherein the SnBr is 2 And CsBr is 1:1.
3. the method for producing an upstanding perovskite sheet layer grown on a silicon substrate according to claim 1, wherein a rectangular corundum boat is further covered on the corundum boat on which the substrate is placed;
wherein, the open area of the corundum boat with the substrate is partially shielded by a covered rectangular corundum boat.
4. The method of producing a layer of upstanding perovskite sheets grown on a silicon substrate according to claim 1, wherein the inert gas is argon with a purity of 99.999% and a flow rate of 100 to 200sccm.
5. The method of producing an upstanding perovskite sheet layer grown on a silicon substrate according to claim 1, wherein the period of heating to the growth temperature is 80 to 120 minutes.
6. The method of producing a layer of upstanding perovskite sheets grown on a silicon substrate according to claim 1, wherein the heating rate of the tube furnace is 5-10 ℃/min.
7. The method of producing a vertical perovskite sheet layer grown on a silicon substrate according to claim 1, wherein the geometric center of the quartz boat is on a straight line with the geometric center of the corundum boat, and the distance between the center of the quartz boat and the center of the corundum boat is 13-15cm.
8. The method of producing a layer of upstanding perovskite platelets grown on a silicon substrate as claimed in claim 1, wherein the SnBr is 2 The purity of the powder is 99.1 to 99.99 percent; the CsBr powder had a purity of 99.99%.
9. An upstanding perovskite sheet layer grown on a silicon substrate produced by the production process of any one of claims 1 to 8.
10. Use of an upstanding perovskite platelet layer grown on a silicon substrate as claimed in claim 9 in a photovoltaic device.
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