CN114873639B - Ba (Bay) 3 Zr 2 S 7 Film, preparation method and application thereof - Google Patents
Ba (Bay) 3 Zr 2 S 7 Film, preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a Ba 3 Zr 2 S 7 The preparation method and application of the film are used for solving the technical problems of poor stability, environmental pollution and uncomfortable forbidden bandwidth of the current perovskite film, and the preparation method comprises the following steps: baCO is carried out 3 And ZrO(s) 2 Vulcanizing the raw material powder to generate BaZrS 3 Powder, baZrS 3 Powder preparation of BaZrS 3 A target material; baSO is carried out 4 Vulcanizing the raw material powder to generate BaS powder, and preparing the BaS powder into a BaS target; sputtering and coating the two targets to obtain a precursor film; recrystallizing the precursor film to obtain Ba 3 Zr 2 S 7 A film. The invention obtains the Ba which does not contain lead, is environment-friendly, has stable performance and excellent photoelectric performance 3 Zr 2 S 7 A film; the material has an optical forbidden bandwidth of 1.5eV and has a good application prospect in the field of photovoltaic cells.
Description
Technical Field
The invention belongs to the technical field of novel semiconductor materials, and particularly relates to a Ba (barium) semiconductor material 3 Zr 2 S 7 Film, and preparation method and application thereof.
Background
In the modern society, the realization of effective utilization of clean solar energy is the target of the human cumin. In recent years, organic or inorganic hybrid lead-halide perovskite solar cells have been rapidly developed, which have an efficiency of more than 25%, thanks to the advantages of high efficiency and low temperature solution preparation.
However, the instability of organic or inorganic hybrid lead halide perovskite and the presence of the biotoxic element lead are two major problems that are not negligible, and become a problem limiting its large-scale commercial application. There is a lack of a method for preparing a perovskite film with a proper forbidden bandwidth (about 1.5eV of the optimal absorption forbidden bandwidth of a solar cell) and being stable and environment-friendly.
Sulfide perovskite materials have unique chemical and physical characteristics, have better stability than halide perovskite materials and are environment-friendly; for example, patent CN105914296a discloses a method for preparing a perovskite thin film by using radio frequency magnetron sputtering technology, and the prepared organic metal halide perovskite thin film contains lead element; compared with oxide perovskite, the perovskite has a proper forbidden bandwidth as a solar energy absorption layer; is easier to synthesize than nitride. However, there is currently less research on sulfide perovskite thin film preparation. Therefore, how to develop a method for preparing a sulfide perovskite thin film with high stability, environmental friendliness and proper forbidden bandwidth is always one of the problems to be solved by the technicians in the field.
Disclosure of Invention
Aiming at the technical problems of poor stability, environmental pollution and uncomfortable forbidden bandwidth of the current perovskite film, the invention provides a Ba 3 Zr 2 S 7 The prepared sulfide perovskite film achieves the purposes of high stability, environmental friendliness and proper forbidden bandwidth, and has a good application prospect in the field of photovoltaic cells.
In order to achieve the above purpose, the technical scheme of the invention is realized as follows:
ba (Bay) 3 Zr 2 S 7 The preparation method of the film comprises the following steps:
s1, baCO is carried out 3 And ZrO(s) 2 Vulcanizing the raw material powder to generate BaZrS 3 Powder, baZrS 3 Powder preparation of BaZrS 3 A target material;
s2, baSO is carried out 4 The raw material powder is subjected to vulcanization reactionGenerating BaS powder, and preparing the BaS powder into a BaS target;
s3, performing sputter coating on the target material obtained in the step S1 and the step S2 to obtain a precursor film;
s4, recrystallizing the precursor film obtained in the step S3 to obtain Ba 3 Zr 2 S 7 A film.
The BaZrS is prepared in the step S1 3 The specific steps of the target material are as follows:
s11, baCO with the mass ratio of 1:1 is added 3 And ZrO(s) 2 Placing the reaction raw material powder into a high-temperature reaction furnace, pumping the high-temperature reaction furnace to background vacuum, and vacuum-pumping<0.1Pa；
S12, introducing CS into the high-temperature reaction furnace in the step S11 2 Steam, the flow is 20-30SCCM;
s13, heating the high-temperature reaction furnace in the step S12 to 1000-1100 ℃, keeping the air pressure in the high-temperature reaction furnace at 20-30Pa for 1-2h, and cooling to room temperature to obtain BaZrS 3 A powder;
s14, the BaZrS prepared in the step S13 is processed 3 Grinding the powder, placing into a tabletting mold to obtain tablet, placing the tablet into a high temperature reaction furnace, and sintering at 1000-1400 deg.C to obtain BaZrS 3 And (3) a target material.
The grinding process in the step S14 is manual grinding, and the grinding time is 1h; the pressure in the process of preparing the tabletting is 50-100Mpa, and the diameter of a tabletting mold is 50mm.
The specific steps for preparing the BaS target in the step S2 are as follows:
s21, baSO 4 Placing raw material powder into a high-temperature reaction furnace, pumping the high-temperature reaction furnace to background vacuum, and vacuum-pumping<0.1Pa；
S22, introducing CS into the high-temperature reaction furnace in the step S21 2 Steam, the flow is 20-30SCCM;
s23, heating the high-temperature reaction furnace in the step S22 to 900-1000 ℃, keeping the air pressure in the high-temperature reaction furnace at 20-30Pa for 1-2h, and cooling to room temperature to obtain BaS powder;
s24, grinding the BaS powder obtained in the step S23, then placing the ground BaS powder into a tabletting mold to obtain tablets, placing the tablets into a high-temperature reaction furnace, and sintering at 900-1000 ℃ to obtain the BaS target.
The grinding process in the step S24 is manual grinding, and the grinding time is 1h; the pressure in the process of preparing the tabletting is 50-100Mpa, and the diameter of a tabletting mold is 50mm.
The specific steps of the sputtering coating in the step S3 are as follows: baZrS obtained in the step S1 3 The target material and the BaS target material prepared in the step S2 are placed into a magnetron sputtering cavity in a magnetron sputtering system, the background of the sputtering cavity is pumped to vacuum, and the vacuum degree is achieved<0.001Pa; the substrate is a quartz substrate, the temperature of the substrate is 400-500 ℃, and the precursor film is obtained by low-temperature deposition on the substrate.
The BaZrS 3 And the power of the two BaS sputtering guns is 40-80W, the sputtering pressure is 0.5-2Pa, the sputtering flow is 5-30SCCM, the sputtering time is 2-3h, and simultaneously, the radio frequency sulfur source is turned on to supplement sulfur loss.
The specific steps of the recrystallization in the step S4 are as follows: putting the precursor film obtained in the step S3 into a high-temperature reaction furnace, vacuumizing the high-temperature reaction furnace to a vacuum degree<0.001Pa; heating the high temperature furnace to 900-1100 ℃, preserving heat for 1h, and then cooling to room temperature to obtain Ba 3 Zr 2 S 7 A film.
Ba (Bay) 3 Zr 2 S 7 Film of Ba 3 Zr 2 S 7 The film is prepared by the preparation method.
Ba 3 Zr 2 S 7 Application of film, said Ba 3 Zr 2 S 7 The thin film is applied to the field of solar photovoltaic devices, and can be used as a light absorption layer in a single junction solar cell or as an absorption layer material of a top cell in a laminated solar cell.
The invention has the beneficial effects that: the invention uses BaCO 3 、ZrO 2 And BaSO 4 As a reaction raw material, prepared Ba 3 Zr 2 S 7 Has unique chemical and physical characteristics, has better stability than halide perovskite and is environment-friendly; as compared with oxide perovskiteThe positive energy absorption layer has a proper forbidden bandwidth; is easier to synthesize than nitride. The preparation method prepares the Ba through the processes of target material preparation, secondary vulcanization, sputter coating and recrystallization 3 Zr 2 S 7 The chemical bond between the three atoms of Ba-Zr-S in the film is strong, and the film is not easy to oxidize and decompose in an air atmosphere aging experiment at 400 ℃, and the film has excellent stability; the material has excellent photoelectric performance due to the special Ruddlesden-pop er crystal structure, and the optical forbidden band width is 1.5 eV; simultaneously prepared Ba 3 Zr 2 S 7 The film does not contain lead and is environment-friendly, thus, ba 3 Zr 2 S 7 The film has good application prospect in the field of photovoltaic cells.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, it being obvious that the drawings in the following description are only some embodiments of the invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic diagram of a high temperature vulcanizing and recrystallizing apparatus according to the present invention;
FIG. 2 is a schematic diagram of a magnetron sputtering system according to the present invention;
FIG. 3 shows Ba prepared in example 1 of the present invention 3 Zr 2 S 7 Thin film X-ray diffraction patterns;
FIG. 4 shows Ba prepared in example 1 3 Zr 2 S 7 Film absorption coefficient map;
FIG. 5 shows Ba prepared in example 1 3 Zr 2 S 7 A film scanning electron microscope morphology map;
FIG. 6 shows Ba prepared in example 1 3 Zr 2 S 7 Film energy dispersion spectrum.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without any inventive effort, are intended to be within the scope of the invention.
Example 1
Ba (Bay) 3 Zr 2 S 7 The preparation method of the film comprises the following steps:
(1)BaZrS 3 preparing a target material:
s1, using BaCO 3 And ZrO(s) 2 For reacting raw material powder, preparing according to the mass ratio of 1:1, and carrying out vulcanization reaction to obtain BaZrS 3 Powder and preparing target material, and the vulcanization reaction equation is 2BaCO 3 +2ZrO 2 +3CS 2 ＝2BaZrS 3 +10CO 2 The high-temperature vulcanizing device is shown in fig. 1, and comprises a carbon disulfide supplying device, a flow control device, a high-temperature furnace and a vacuum device, wherein the devices are connected through an air valve. The method comprises the following specific steps:
s11, using BaCO 3 And ZrO(s) 2 For reacting raw material powder, the raw material powder is placed into a high-temperature reaction furnace, a vacuum pumping device is opened, the high-temperature reaction furnace is pumped to background vacuum, and the vacuum degree is kept<0.1Pa。
S12, opening the flowmeter to enable CS 2 The steam was introduced into the high temperature reactor in step S11, and the flow rate thereof was set to 30SCCM.
S13, setting and executing a temperature program for the high-temperature reaction furnace in the step S12, gradually heating to 1000, preserving heat for 1h, and then cooling to room temperature to obtain BaZrS 3 And (3) powder.
S14, the BaZrS prepared in the step S13 is processed 3 Taking out the powder, grinding, tabletting in a tabletting mold, and sintering at 1400 deg.C in a high temperature reaction furnace to obtain BaZrS 3 And (3) a target material.
(2) Preparation of a BaS target:
s2, using BaSO 4 To react the raw material powder, it is subjected to a vulcanization reaction,generating BaS powder, preparing target material, and vulcanizing to obtain BaSO 4 +CS 2 ＝BaS+CO 2 +SO 2 The high-temperature vulcanizing device is shown in fig. 1, and comprises a carbon disulfide supplying device, a flow control device, a high-temperature furnace and a vacuum device, wherein the devices are connected through an air valve. The method comprises the following specific steps:
s21, using BaSO 4 For reacting raw material powder, the raw material powder is placed into a high-temperature reaction furnace, a vacuum pumping device is opened, the high-temperature reaction furnace is pumped to background vacuum, and the vacuum degree is kept<0.1Pa。
S22, opening the flowmeter to enable CS 2 The steam was introduced into the high temperature reactor in step S21, and the flow rate thereof was set to 30SCCM.
S23, setting and executing a temperature program for the high-temperature reaction furnace in the step S21, gradually heating to 900 ℃, preserving heat for 1h, and then cooling to room temperature to obtain BaS powder.
S24, taking out and grinding the BaS powder prepared in the step S23, putting the powder into a tabletting mold for tabletting, and putting the powder into a high-temperature reaction furnace for sintering at the temperature of 1000 ℃ to form tablets to prepare the BaS target.
(3) Preparing a precursor film:
s3, performing co-sputtering coating on the target material obtained in the step 1 and the step 2 to obtain a precursor film; the method comprises the following specific steps: baZrS obtained in the step S1 3 And (2) placing the BaS target material prepared in the step (S2) into a magnetron sputtering cavity in a magnetron sputtering system, and vacuumizing the background of the sputtering cavity to ensure that the vacuum degree of the sputtering cavity is maintained<0.001Pa, and a magnetron sputtering system shown in FIG. 2, selecting quartz substrate, setting substrate temperature to 500 deg.C, and sputtering BaZrS 3 And (3) the target material and the BaS target material, and opening a radio frequency sulfur source to supplement sulfur deficiency, and performing low-temperature deposition on the substrate to obtain the precursor film.
(4)Ba 3 Zr 2 S 7 Film preparation:
s4, recrystallizing the precursor film obtained in the step 3 to obtain Ba 3 Zr 2 S 7 A film; the method comprises the following specific steps: putting the precursor film obtained in the step S3 into a high-temperature reaction furnace, and opening a vacuumizing devicePumping the high-temperature reaction furnace to background vacuum of 0.001Pa, setting and executing a temperature program for the high-temperature furnace to gradually raise the temperature to 900 ℃, preserving heat for 1h, and then cooling to room temperature to obtain Ba 3 Zr 2 S 7 A film.
As shown in FIG. 3, for Ba prepared in example 1 3 Zr 2 S 7 The films were subjected to XRD testing and subjected to thermal annealing at 400℃for 1 hour, and then the XRD was further tested for stability. It can be seen that the prepared Ba 3 Zr 2 S 7 After the film is subjected to a thermal annealing experiment in an air environment at 400 ℃, XRD of the film can be matched with a reference peak, and the film has good c-axis growth orientation characteristic, which shows that the film in the embodiment Ba 3 Zr 2 S 7 The film has high purity and high stability.
FIG. 4 shows Ba prepared according to example 1 3 Zr 2 S 7 The film optical absorption data test result shows that the forbidden band width is 1.5eV, and the forbidden band width is suitable to be used as an absorption layer of a single junction solar cell according to the limit theory of a Shockley-Queisser solar cell. At the same time, it can be seen that for the portion greater than 1.5eV, the absorption coefficient is greater than 10 -5 cm -1 Exhibiting high absorption of photons.
FIG. 5 shows Ba prepared according to example 1 3 Zr 2 S 7 Thin film scanning electron microscopy surface topography (SEM). The film forming agent has uniform, regular and flat appearance under an electron microscope, and shows good film forming quality.
FIG. 6 shows Ba prepared according to example 1 3 Zr 2 S 7 Film energy dispersive spectroscopy (EDX). The figure clearly shows the spectral peaks of the Ba-Zr-S elements with the element proportions in stoichiometric ratio, no other impurity peaks, si and O peaks from the substrate background.
Example 2
Ba (Bay) 3 Zr 2 S 7 The preparation method of the film comprises the following steps:
(1)BaZrS 3 preparing a target material:
s11, weighing BaCO 3 And ZrO(s) 2 Powder is prepared according to the mass ratio of 1:1, and after being fully ground and uniformly mixed, the powder is placed into a high-temperature reaction furnace, a vacuum device is opened for air extraction, the high-temperature reaction furnace is pumped to background vacuum, and the vacuum degree is kept<0.1Pa。
S12, opening a gas flow control device to enable CS 2 The steam was introduced into the high temperature reactor in step S11, and the flow rate thereof was set to 30SCCM.
S13, setting and executing a temperature program for the high-temperature reaction furnace in the step S11, controlling a vacuum pump to enable the air pressure in the high-temperature reaction furnace to be 30Pa, gradually heating to 1000 ℃, preserving heat for 1h, cooling to room temperature, and closing a vacuum device and a flowmeter to obtain BaZrS 3 And (3) powder.
S14, the BaZrS prepared in the step S13 is processed 3 Taking out the powder, and manually grinding the powder for 1h; putting the powder into a tabletting mould with the diameter of 50mm, and tabletting under the pressure of 100 MPa; placing the pressed sheet into a high-temperature reaction furnace, vacuumizing the high-temperature reaction furnace, and heating the high-temperature reaction furnace to 1300 ℃ for sintering; baZrS to be sintered into a sheet 3 Bonding indium to copper back plate to obtain BaZrS for magnetron sputtering 3 And (3) a target material.
(2) Preparation of a BaS target:
s21, weighing BaSO 4 The method comprises the steps of fully grinding raw material powder, placing the raw material powder into a high-temperature reaction furnace, opening a vacuum device to perform air suction, and pumping the high-temperature reaction furnace to background vacuum to ensure the vacuum degree<0.1Pa。
S22, opening a gas flow control device to enable CS 2 The steam was introduced into the high temperature reactor in step S21, and the flow rate thereof was set to 30SCCM.
S23, setting and executing a temperature program for the high-temperature reaction furnace in the step S21, controlling a vacuum pump to enable the air pressure in the high-temperature reaction furnace to be 30Pa, gradually heating to 1000 ℃, preserving heat for 1h, cooling to room temperature, and closing a vacuum device and a flowmeter to obtain BaS powder.
S24, taking out the BaS powder prepared in the step S23, and manually grinding the BaS powder for 1h; putting the powder into a tabletting mould with the diameter of 50mm, and tabletting under the pressure of 50 MPa; then placing the powder into a high-temperature reaction furnace, vacuumizing the high-temperature reaction furnace, and heating the powder to 1000 ℃ for sintering; and bonding the sintered sheet of BaS with indium to a copper back plate to prepare the BaS target material for magnetron sputtering.
(3) Preparing a precursor film:
s3, the BaZrS prepared in the step (1) and the step (2) is processed 3 The target material and the BaS target material are placed into a magnetron sputtering cavity in a magnetron sputtering system, and background vacuum of the sputtering cavity is pumped to ensure that the vacuum degree is maintained<0.001Pa, wherein the sputtering time is 2h, the sputtering gas is argon, the sputtering flow is 5SCCM, the sputtering pressure is 0.5Pa, and the sputtering power of the two targets is 60W; selecting a quartz substrate, sequentially performing ultrasonic cleaning on the quartz substrate by acetone, deionized water, isopropanol and deionized water, setting a substrate heating program, setting the temperature to 400 ℃, and sputtering BaZrS in a magnetron sputtering cavity 3 And (3) the target material and the BaS target material, and opening a radio frequency sulfur source to supplement sulfur deficiency, and performing low-temperature deposition on the substrate to obtain the precursor film.
(4)Ba 3 Zr 2 S 7 Film preparation:
s4, placing the precursor film obtained in the step 3 into a high-temperature reaction furnace, opening a vacuum pumping device, pumping the high-temperature reaction furnace to background vacuum of 0.001Pa, setting and executing a temperature program for the high-temperature reaction furnace, gradually heating to 950 ℃, preserving heat for 1h, and then cooling to room temperature to obtain Ba 3 Zr 2 S 7 A film.
Example 3
Ba (Bay) 3 Zr 2 S 7 The preparation method of the film comprises the following steps:
(1)BaZrS 3 preparing a target material:
s11, weighing BaCO 3 And ZrO(s) 2 Powder is prepared according to the mass ratio of 1:1, and after being fully ground and uniformly mixed, the powder is placed into a high-temperature reaction furnace, a vacuum device is opened for air extraction, the high-temperature reaction furnace is pumped to background vacuum, and the vacuum degree is kept<0.1Pa。
S12, opening a gas flow control device to enable CS 2 The steam was introduced into the high temperature reactor in step S11, and the flow rate thereof was set to 30SCCM.
S13, setting and executing a temperature program for the high-temperature reaction furnace in the step S11, controlling a vacuum pump to enable the air pressure in the high-temperature reaction furnace to be 20Pa, gradually heating to 1050 ℃, preserving heat for 1h, cooling to room temperature, and closing a vacuum device and a flowmeter to obtain BaZrS 3 And (3) powder.
S14, the BaZrS prepared in the step S13 is processed 3 Taking out the powder, and manually grinding the powder for 1h; putting the powder into a tabletting mould with the diameter of 50mm, and tabletting under the pressure of 80 MPa; then placing the powder into a high-temperature reaction furnace, vacuumizing the high-temperature reaction furnace, and heating the powder to 1400 ℃ for sintering; baZrS to be sintered into a sheet 3 Bonding indium to copper back plate to obtain BaZrS for magnetron sputtering 3 And (3) a target material.
(2) Preparation of a BaS target:
s21, weighing BaSO 4 The method comprises the steps of fully grinding raw material powder, placing the raw material powder into a high-temperature reaction furnace, opening a vacuum device to perform air suction, and pumping the high-temperature reaction furnace to background vacuum to ensure the vacuum degree<0.1Pa。
S22, opening a gas flow control device to enable CS 2 The steam was introduced into the high temperature reactor in step S21, and the flow rate thereof was set to 30SCCM.
S23, setting and executing a temperature program for the high-temperature reaction furnace in the step S21, controlling a vacuum pump to enable the air pressure in the high-temperature reaction furnace to be 30Pa, gradually heating to 900 ℃, preserving heat for 1h, cooling to room temperature, and closing a vacuum device and a flowmeter to obtain BaS powder.
S24, taking out the BaS powder prepared in the step S23, and manually grinding the BaS powder for 1h; putting the powder into a tabletting mould with the diameter of 50mm, and tabletting under the pressure of 80 MPa; then placing the powder into a high-temperature reaction furnace, vacuumizing the high-temperature reaction furnace, and heating the powder to 900 ℃ for sintering; and bonding the sintered sheet of BaS with indium to a copper back plate to prepare the BaS target material for magnetron sputtering.
(3) Preparing a precursor film:
s3, the BaZrS prepared in the step (1) and the step (2) is processed 3 The target material and the BaS target material are placed into a magnetron sputtering cavity in a magnetron sputtering system, and background vacuum of the sputtering cavity is pumped to ensure that the vacuum degree is maintained<0.001Pa, wherein the sputtering time is 3h, the sputtering gas is argon, the sputtering flow is 10SCCM, the sputtering pressure is 1.5Pa, and the sputtering power of the two targets is 40W; selecting a quartz substrate, sequentially performing ultrasonic cleaning on the quartz substrate by acetone, deionized water, isopropanol and deionized water, setting a substrate heating program, setting the temperature of the substrate to 500 ℃, and sputtering BaZrS in a magnetron sputtering cavity 3 And (3) the target material and the BaS target material, and opening a radio frequency sulfur source to supplement sulfur deficiency, and performing low-temperature deposition on the substrate to obtain the precursor film.
(4)Ba 3 Zr 2 S 7 Film preparation:
s4, placing the precursor film obtained in the step 3 into a high-temperature reaction furnace, opening a vacuum pumping device, pumping the high-temperature reaction furnace to background vacuum of 0.001Pa, setting and executing a temperature program for the high-temperature reaction furnace, gradually heating to 1000 ℃, preserving heat for 1h, and then cooling to room temperature to obtain Ba 3 Zr 2 S 7 A film.
Example 4
Ba (Bay) 3 Zr 2 S 7 The preparation method of the film comprises the following steps:
(1)BaZrS 3 preparing a target material:
s11, weighing BaCO 3 And ZrO(s) 2 Powder is prepared according to the mass ratio of 1:1, and after being fully ground and uniformly mixed, the powder is placed into a high-temperature reaction furnace, a vacuum device is opened for air extraction, the high-temperature reaction furnace is pumped to background vacuum, and the vacuum degree is kept<0.1Pa。
S12, opening a gas flow control device to enable CS 2 The steam was introduced into the high temperature reactor in step S11, and the flow rate thereof was set to 30SCCM.
S13, setting and executing a temperature program for the high-temperature reaction furnace in the step S11, controlling a vacuum pump to enable the air pressure in the high-temperature reaction furnace to be 30Pa, and gradually changing the air pressureHeating to 1100 ℃, preserving heat for 1h, cooling to room temperature, and closing the vacuum device and the flowmeter to obtain BaZrS 3 And (3) powder.
S14, the BaZrS prepared in the step S13 is processed 3 Taking out the powder, and manually grinding the powder for 1h; putting the powder into a tabletting mould with the diameter of 50mm, and tabletting under the pressure of 60 MPa; then placing the powder into a high-temperature reaction furnace, vacuumizing the high-temperature reaction furnace, and heating the powder to 1200 ℃ for sintering; baZrS to be sintered into a sheet 3 Bonding indium to copper back plate to obtain BaZrS for magnetron sputtering 3 And (3) a target material.
(2) Preparation of a BaS target:
s21, weighing BaSO 4 The method comprises the steps of fully grinding raw material powder, placing the raw material powder into a high-temperature reaction furnace, opening a vacuum device to perform air suction, and pumping the high-temperature reaction furnace to background vacuum to ensure the vacuum degree<0.1Pa。
S22, opening a gas flow control device to enable CS 2 The steam was introduced into the high temperature reactor in step S21, and the flow rate thereof was set to 30SCCM.
S23, setting and executing a temperature program for the high-temperature reaction furnace in the step S21, controlling a vacuum pump to enable the air pressure in the high-temperature reaction furnace to be 30Pa, gradually heating to 950 ℃, preserving heat for 1h, cooling to room temperature, and closing a vacuum device and a flowmeter to obtain BaS powder.
S24, taking out the BaS powder prepared in the step S23, and manually grinding the BaS powder for 1h; putting the powder into a tabletting mould with the diameter of 50mm, and tabletting under the pressure of 50 MPa; then placing the powder into a high-temperature reaction furnace, vacuumizing the high-temperature reaction furnace, and heating the powder to 950 ℃ for sintering; and bonding the sintered sheet of BaS with indium to a copper back plate to prepare the BaS target material for magnetron sputtering.
(3) Preparing a precursor film:
s3, the BaZrS prepared in the step (1) and the step (2) is processed 3 The target material and the BaS target material are placed into a magnetron sputtering cavity in a magnetron sputtering system, and background vacuum of the sputtering cavity is pumped to ensure that the vacuum degree is maintained<0.001Pa, wherein the sputtering time is 2h, and the sputtering gas is argonThe sputtering flow is 20SCCM, the sputtering pressure is 2Pa, and the sputtering power of the two targets is 80W; selecting a quartz substrate, sequentially performing ultrasonic cleaning on the quartz substrate by acetone, deionized water, isopropanol and deionized water, setting a substrate heating program, setting the temperature to 450 ℃, and sputtering BaZrS in a magnetron sputtering cavity 3 And (3) the target material and the BaS target material, and opening a radio frequency sulfur source to supplement sulfur deficiency, and performing low-temperature deposition on the substrate to obtain the precursor film.
(4)Ba 3 Zr 2 S 7 Film preparation:
s4, placing the precursor film obtained in the step 3 into a high-temperature reaction furnace, opening a vacuum pumping device, pumping the high-temperature reaction furnace to background vacuum of 0.001Pa, setting and executing a temperature program for the high-temperature reaction furnace, gradually heating to 1050 ℃, preserving heat for 1h, and then cooling to room temperature to obtain Ba 3 Zr 2 S 7 A film.
Example 5
Ba (Bay) 3 Zr 2 S 7 The preparation method of the film comprises the following steps:
(1)BaZrS 3 preparing a target material:
s11, weighing BaCO 3 And ZrO(s) 2 Powder is prepared according to the mass ratio of 1:1, and after being fully ground and uniformly mixed, the powder is placed into a high-temperature reaction furnace, a vacuum device is opened for air extraction, the high-temperature reaction furnace is pumped to background vacuum, and the vacuum degree is kept<0.1Pa。
S12, opening a gas flow control device to enable CS 2 The steam was introduced into the high temperature reactor in step S11, and the flow rate thereof was set to 30SCCM.
S13, setting and executing a temperature program for the high-temperature reaction furnace in the step S12, controlling a vacuum pump to enable the air pressure in the high-temperature reaction furnace to be 30Pa, gradually heating to 1000 ℃, preserving heat for 1h, cooling to room temperature, and closing a vacuum device and a flowmeter to obtain BaZrS 3 And (3) powder.
S14, the BaZrS prepared in the step S13 is processed 3 Taking out the powder, and manually grinding the powder for 1h; putting the mixture into a tabletting mold with the diameter ofTabletting at 50mm and 50 MPa; then placing the powder into a high-temperature reaction furnace, vacuumizing the high-temperature reaction furnace, and heating the powder to 1000 ℃ for sintering; baZrS to be sintered into a sheet 3 Bonding indium to copper back plate to obtain BaZrS for magnetron sputtering 3 And (3) a target material.
(2) Preparation of a BaS target:
s21, weighing BaSO 4 The method comprises the steps of fully grinding raw material powder, placing the raw material powder into a high-temperature reaction furnace, opening a vacuum device to perform air suction, and pumping the high-temperature reaction furnace to background vacuum to ensure the vacuum degree<0.1Pa。
S22, opening a gas flow control device to enable CS 2 The steam was introduced into the high temperature reactor in step S21, and the flow rate thereof was set to 30SCCM.
S23, setting and executing a temperature program for the high-temperature reaction furnace in the step S21, controlling a vacuum pump to enable the air pressure in the high-temperature reaction furnace to be 30Pa, gradually heating to 900 ℃, preserving heat for 1h, cooling to room temperature, and closing a vacuum device and a flowmeter to obtain BaS powder.
S24, taking out the BaS powder prepared in the step S23, and manually grinding the BaS powder for 1h; putting the powder into a tabletting mould with the diameter of 50mm, and tabletting under the pressure of 60 MPa; then placing the powder into a high-temperature reaction furnace, vacuumizing the high-temperature reaction furnace, and heating the powder to 950 ℃ for sintering; and bonding the sintered sheet of BaS with indium to a copper back plate to prepare the BaS target material for magnetron sputtering.
(3) Preparing a precursor film:
s3, the BaZrS prepared in the step (1) and the step (2) is processed 3 The target material and the BaS target material are placed into a magnetron sputtering cavity in a magnetron sputtering system, and background vacuum of the sputtering cavity is pumped to ensure that the vacuum degree is maintained<0.001Pa, wherein the sputtering time is 2.5h, the sputtering gas is argon, the sputtering flow is 30SCCM, the sputtering pressure is 1Pa, and the sputtering power of the two targets is 60W; selecting a quartz substrate, sequentially performing ultrasonic cleaning on the quartz substrate by acetone, deionized water, isopropanol and deionized water, setting a substrate heating program, setting the temperature to 400 ℃, and sputtering BaZrS in a magnetron sputtering cavity 3 And (3) the target material and the BaS target material, and opening a radio frequency sulfur source to supplement sulfur deficiency, and performing low-temperature deposition on the substrate to prepare the precursor film.
(4)Ba 3 Zr 2 S 7 Film preparation:
s4, placing the precursor film obtained in the step 3 into a high-temperature reaction furnace, opening a vacuum pumping device, pumping the high-temperature reaction furnace to background vacuum of 0.001Pa, setting and executing a temperature program for the high-temperature reaction furnace, gradually heating to 1100 ℃, preserving heat for 1h, and then cooling to room temperature to obtain Ba 3 Zr 2 S 7 A film.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (7)
1. Ba (Bay) 3 Zr 2 S 7 The preparation method of the film is characterized by comprising the following steps:
s1, carrying out vulcanization reaction on raw materials to prepare BaZrS respectively 3 Powder and BaS powder, and then preparing the two into BaZrS 3 Target and BaS target;
s2, performing sputter coating on the target material obtained in the step S1 to obtain a precursor film;
s3, recrystallizing the precursor film obtained in the step S2 to obtain Ba 3 Zr 2 S 7 A film;
the step of sputtering coating in the step S2 is as follows: baZrS obtained in the step S1 3 The target material and the BaS target material are placed into a magnetron sputtering cavity in a magnetron sputtering system to carry out magnetron sputtering, so that a precursor film is prepared;
in the process of magnetron sputtering, baZrS in the magnetron sputtering system 3 And the power of the two BaS sputtering guns is 40-80W, and the vacuum degree of a sputtering cavity in the magnetron sputtering system<The substrate in the magnetron sputtering system is a quartz substrate, the temperature of the substrate is 400-500 ℃, the sputtering pressure is 0.5-2Pa, the sputtering flow is 5-30SCCM, the sputtering time is 2-3h,simultaneously, a radio frequency sulfur source in the magnetron sputtering system is turned on;
the step of recrystallization in the step S3 is as follows: putting the precursor film obtained in the step S2 into a high-temperature reaction furnace, and sintering in a vacuum environment to obtain Ba 3 Zr 2 S 7 A film; vacuum degree of high temperature reaction in sintering process<0.001Pa, sintering temperature of 900-1100 ℃ and heat preservation time of 1-2h.
2. Ba according to claim 1 3 Zr 2 S 7 The preparation method of the film is characterized in that the vulcanization reaction in the step S1 is operated as follows: placing raw material powder into a high-temperature reaction furnace, and introducing CS under vacuum condition 2 The steam is heated up to react.
3. Ba according to claim 2 3 Zr 2 S 7 The preparation method of the film is characterized in that: the CS is introduced into 2 The flow rate of the steam is 20-30SCCM, the temperature of the heating reaction is 900-1100 ℃, the reaction time is 1-2h, and the pressure is 20-30Pa; wherein BaZrS is prepared 3 The raw material of the powder is BaCO with the mass ratio of 1:1 3 Powder and ZrO 2 Powder composition mixed powder, wherein the raw material for preparing the BaS powder is BaSO 4 And (3) powder.
4. Ba according to claim 1 3 Zr 2 S 7 A method for producing a film, characterized in that in the step S1, baZrS is produced 3 The steps of the target material and the BaS target material are as follows: baZrS 3 Grinding the powder and BaS powder respectively, preparing a tablet by using a tablet die, and then placing the tablet into a high-temperature reaction furnace for sintering to prepare the BaZrS 3 Target and BaS target.
5. Ba according to claim 4 3 Zr 2 S 7 The preparation method of the film is characterized in that: the pressure of the tabletting mold in the tabletting preparation process is 50-100Mpa, and the diameter of the tabletting mold is 50mm; wherein, baZrS is prepared 3 The sintering temperature of the target material is 1000-1400 ℃, and the sintering temperature of the BaS target material is 900-1000 ℃.
6. Ba (Bay) 3 Zr 2 S 7 The film is characterized in that: the Ba is 3 Zr 2 S 7 A film produced by the production method according to any one of claims 1 to 5.
7. The method of claim 6 wherein Ba 3 Zr 2 S 7 The application of the film in the field of solar photovoltaic devices.
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