CN114394597A - Method for preparing silicon film by using silicon tetrafluoride as raw material - Google Patents
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- CN114394597A CN114394597A CN202210076267.3A CN202210076267A CN114394597A CN 114394597 A CN114394597 A CN 114394597A CN 202210076267 A CN202210076267 A CN 202210076267A CN 114394597 A CN114394597 A CN 114394597A
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 60
- 239000010703 silicon Substances 0.000 title claims abstract description 60
- ABTOQLMXBSRXSM-UHFFFAOYSA-N silicon tetrafluoride Chemical compound F[Si](F)(F)F ABTOQLMXBSRXSM-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title claims abstract description 27
- 239000002994 raw material Substances 0.000 title claims abstract description 9
- 239000011856 silicon-based particle Substances 0.000 claims abstract description 66
- 239000007789 gas Substances 0.000 claims abstract description 41
- 239000000758 substrate Substances 0.000 claims abstract description 40
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- 238000010438 heat treatment Methods 0.000 claims abstract description 24
- 239000012159 carrier gas Substances 0.000 claims abstract description 16
- 238000001514 detection method Methods 0.000 claims abstract 3
- 238000001035 drying Methods 0.000 claims description 42
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- 238000004140 cleaning Methods 0.000 claims description 22
- 238000002791 soaking Methods 0.000 claims description 22
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims 5
- 229910001873 dinitrogen Inorganic materials 0.000 claims 1
- PUUOOWSPWTVMDS-UHFFFAOYSA-N difluorosilane Chemical compound F[SiH2]F PUUOOWSPWTVMDS-UHFFFAOYSA-N 0.000 abstract description 16
- 238000007323 disproportionation reaction Methods 0.000 abstract description 5
- 239000006227 byproduct Substances 0.000 abstract description 4
- 239000002686 phosphate fertilizer Substances 0.000 abstract description 2
- 238000012512 characterization method Methods 0.000 abstract 1
- 238000010926 purge Methods 0.000 abstract 1
- 238000005303 weighing Methods 0.000 description 30
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 21
- 239000010409 thin film Substances 0.000 description 15
- 229910004014 SiF4 Inorganic materials 0.000 description 14
- 239000010408 film Substances 0.000 description 11
- 238000005265 energy consumption Methods 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- 235000012239 silicon dioxide Nutrition 0.000 description 8
- 239000010453 quartz Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- 229910000831 Steel Inorganic materials 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- 239000010959 steel Substances 0.000 description 6
- 230000002194 synthesizing effect Effects 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 5
- 229910004016 SiF2 Inorganic materials 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000005229 chemical vapour deposition Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002210 silicon-based material Substances 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 2
- 238000001755 magnetron sputter deposition Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000011435 rock Substances 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- MGNHOGAVECORPT-UHFFFAOYSA-N difluorosilicon Chemical compound F[Si]F MGNHOGAVECORPT-UHFFFAOYSA-N 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005328 electron beam physical vapour deposition Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000004050 hot filament vapor deposition Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 239000012788 optical film Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000002367 phosphate rock Substances 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/02—Silicon
- C01B33/021—Preparation
Abstract
The invention discloses a method for preparing a silicon film by using silicon tetrafluoride as a raw material. The method comprises the following steps: (1) placing silicon particles and a substrate in constant temperature areas at the left end and the right end of a double-temperature-area tubular furnace respectively, and setting the final temperature and the heating rate of the constant temperature area of the tubular furnace; (2) connecting the tube furnace and the gas path part, introducing carrier gas, and starting temperature programming of the tube furnace; (3) after the set temperature is reached, closing the carrier gas, and opening the silicon tetrafluoride gas for reaction; (4) after the reaction is finished, closing the silicon tetrafluoride gas, opening the carrier gas for purging, and performing program cooling on the double-temperature-zone tube furnace; (5) and after the temperature is reduced to room temperature, taking out the sample substrate for detection and characterization. The invention relates to a process method for preparing a silicon film by effectively utilizing silicon tetrafluoride gas which is a byproduct of phosphate fertilizer to generate intermediate silicon difluoride and then carrying out disproportionation reaction on the silicon difluoride.
Description
The technical field is as follows:
the invention relates to the field of nano materials, in particular to a method for preparing a silicon film by using silicon tetrafluoride as a raw material.
Background art:
silicon is the second highest element in the earth's crust, and occurs in nature only rarely in the form of simple substance, and mostly in the form of silicon dioxide and silicate. Silicon present in rocks in 1787 was first discovered by lavatin, and in 1823 silicon was first discovered in elemental form by beilliwus, a swedish chemist, and then elemental silicon began its lengthy course of development. The silicon material is mainly used for manufacturing semiconductor materials, solar cells, integrated circuits, optical fibers, metal ceramics and the like due to the excellent performance of the silicon material, and is widely applied to various industries such as chemical industry, buildings, food, aerospace, electronics and electricity. Although more and more materials can replace silicon in some aspects with the advance of the technology level, the market scale and application of the current silicon materials still hold a great position. The Guizhou province is a big province of phosphorite resources, associated fluorine and silicon resources are rich in the production process of phosphate fertilizers, the derived silicon tetrafluoride brings huge problems of environment, storage and resource waste, and the method has important significance for converting silicon elements in the silicon tetrafluoride into simple substance silicon through technical means.
The silicon film is a commonly used infrared band optical film material, has the advantages of small infrared absorption coefficient, good thermal property and the like, and is commonly applied to the aspects of solar cells, displays, sensors and the like. At present, there are many reports on the preparation methods of silicon thin films, mainly including physical methods such as magnetron sputtering method, electron beam physical vapor deposition technique, etc., and chemical methods such as chemical vapor deposition method, plasma enhanced chemical vapor deposition method, hot filament chemical vapor deposition method, sol-gel method, etc. The method can prepare the silicon film with good performance, but has certain limitations, such as expensive equipment and higher cost required by magnetron sputtering and plasma enhanced technology, and SiH adopted by some chemical vapor deposition technology4Adding H as silicon source2To prepare silicon thin films, there is a certain experimental risk and SiH4Is unstable and active.
The invention content is as follows:
the invention aims to provide a consumption path for a byproduct silicon tetrafluoride of a phosphate fertilizer, namely a process method for preparing a silicon film by reacting silicon tetrafluoride gas with silicon particles to generate an intermediate silicon difluoride and then carrying out disproportionation reaction on the silicon difluoride, and has the advantages of simple preparation process and low cost.
The method for preparing the silicon film by using the silicon tetrafluoride as the raw material comprises the following steps:
(I) silicon tetrafluoride reacts with silicon particles to produce silicon difluoride
1. Weighing silicon particles with a certain mass, soaking the silicon particles in ethanol, cleaning the silicon particles by ultrasonic waves, drying the silicon particles, placing the silicon particles in a constant-temperature area at the left end of a double-temperature-area tubular furnace, wherein the temperature of the area is set at 1200-1300 ℃, the heating rate is 8-10 ℃/min, and a certain amount of inert gas is used for blowing in the heating process;
2. after reaching the set temperature, silicon tetrafluoride gas is introduced to react with silicon particles to generate SiF4+Si→SiF2To obtain intermediate silicon difluoride.
Silicon film prepared by silicon difluoride reaction disproportionation reaction
1. The substrate suitable for the pipe diameter of the tubular furnace is soaked in ethanol, ultrasonically cleaned and dried, and then vertically placed in a constant-temperature area at the right end of the tubular furnace with a double-temperature area, wherein the temperature of the area is set at 400-;
2. after reaching the set temperature, the silicon difluoride generates SiF2→SiF4And + Si to obtain the silicon thin film of the present invention. Description of the drawings: the step (I) and the step (II) are not carried out in sequence and are carried out in the same tube furnace; and (3) introducing silicon tetrafluoride gas for reaction after the temperature of the first step and the second step reaches the set temperature.
The invention has the beneficial effects that: in the process, SiF4For the stabilization of the silicon source properties, SiF is used at high temperatures4React with Si to form SiF2Using SiF at lower temperatures2Si simple substance is separated out by disproportionation reaction to form a silicon film. Due to intermediate SiF2The preparation of the silicon film is very active, and the preparation can be completed within minutes to tens of minutes, so that the preparation period of the silicon film can be greatly shortened, and the whole processSimple and high-efficiency. Meanwhile, the chemical vapor deposition equipment adopted by the invention is simple, the process is stable, and tail gas SiF is4Can be recycled, is beneficial to environmental protection and full utilization of raw materials, and has low production cost and high added value of products. Furthermore, since the raw material SiF4Is a byproduct of phosphorus chemical industry, can be obtained in large quantity and has low price, and SiF is not treated in the industry at present4The invention is beneficial to the by-product SiF4High added value industrial application.
Description of the drawings:
FIG. 1 is an SEM photograph of a silicon thin film prepared by synthesizing intermediate silicon difluoride from silicon tetrafluoride in example 1;
FIG. 2 is an SEM photograph of a silicon thin film prepared by synthesizing intermediate silicon difluoride from silicon tetrafluoride in example 2;
FIG. 3 is an SEM photograph of a silicon thin film prepared by synthesizing intermediate silicon difluoride from silicon tetrafluoride in example 3;
FIG. 4 is an SEM photograph of a silicon thin film prepared by synthesizing intermediate silicon difluoride from silicon tetrafluoride in example 4;
FIG. 5 is an SEM photograph of a silicon thin film prepared by synthesizing intermediate silicon difluoride from silicon tetrafluoride in example 5;
FIG. 6 is an SEM photograph of a silicon thin film prepared by synthesizing intermediate silicon difluoride from silicon tetrafluoride in example 6;
FIG. 7 is a schematic representation of the experimental operation of the present invention.
The specific implementation mode is as follows:
the method for preparing a silicon thin film by using silicon tetrafluoride as a raw material gas and reacting the silicon tetrafluoride with silicon particles to generate an intermediate silicon difluoride, and then performing a disproportionation reaction on the silicon difluoride will be described in detail in the following examples, but is not limited to the examples. The equipment and reagents used in the present invention are, unless otherwise specified, conventional and commercially available products in the art.
Example 1:
(1) soaking purchased silicon particles with the content of 99.99 percent in absolute ethyl alcohol, cleaning the silicon particles for 30 minutes by using ultrasonic waves, drying the silicon particles in a constant-temperature drying oven at 120 ℃, and weighing 150g of the silicon particles by using a balance and placing the silicon particles in a constant-temperature area at the left end of a double-temperature-area tubular furnace; soaking a 4N-purity monocrystalline silicon wafer <111> in absolute ethyl alcohol, cleaning for 30 minutes in ultrasonic waves, drying at 120 ℃ in a constant-temperature drying box, weighing the mass of the monocrystalline silicon wafer with an electronic balance to be 0.9802g, vertically placing the monocrystalline silicon wafer in a constant-temperature area at the right end of a double-temperature-area tubular furnace, and connecting the double-temperature-area tubular furnace with a gas circuit;
(2) setting a temperature rise program: the left end of the double-temperature-zone tube furnace is heated to 1300 ℃ from 20 ℃ at the heating rate of 10 ℃/min, and the right end is heated to 400 ℃ from 20 ℃ at the heating rate of 10 ℃/min; opening carrier gas N2Bottle (purity)>99.5%), the flow rate is set to 150 ml/min; simultaneously, a temperature-raising program is operated, wherein the temperature-raising program at the right end is started after the temperature at the left end is raised to 900 ℃ (energy consumption is reduced);
(3) after the dual-temperature-zone tube furnace reaches 1300 ℃ and 400 ℃ set by the program, the N2 bottle is closed, and the SiF is opened4The flow of the gas cylinder is set to be 150ml/min, and the reaction lasts for 60 min;
(4) after the reaction is finished, the SiF is closed4Gas cylinder, open N2And (3) starting program cooling in a bottle and a double-temperature-zone tube furnace, taking out the silicon wafer substrate after the temperature is reduced to room temperature, weighing the silicon wafer substrate to 1.0482g, and then detecting and characterizing the silicon wafer substrate, wherein the result is shown in figure 1. As can be seen from FIG. 1, the surface of the silicon thin film deposited on the silicon wafer has a large number of particles and is piled up in a chain shape.
Example 2
(1) Soaking purchased silicon particles with the content of 99.99 percent in absolute ethyl alcohol, cleaning the silicon particles for 30 minutes by using ultrasonic waves, drying the silicon particles in a constant-temperature drying oven at 120 ℃, and weighing 150g of the silicon particles by using a balance and placing the silicon particles in a constant-temperature area at the left end of a double-temperature-area tubular furnace; soaking a 4N-purity monocrystalline silicon wafer <111> in absolute ethyl alcohol, cleaning for 30 minutes in ultrasonic waves, drying at 120 ℃ in a constant-temperature drying box, weighing the mass of the monocrystalline silicon wafer with an electronic balance to be 0.6591g, vertically placing the monocrystalline silicon wafer in a constant-temperature area at the right end of a double-temperature-area tube furnace, and connecting the tube furnace with a gas circuit;
(2) setting a temperature rise program: the left end of the double-temperature-zone tube furnace is heated to 1300 ℃ from 20 ℃ at the heating rate of 10 ℃/min, and the right end is heated to 600 ℃ from 20 ℃ at the heating rate of 10 ℃/min; opening carrier gas N2Bottle (purity)>99.5%), the flow rate is set to 150 ml/min; simultaneously, a temperature-raising program is operated, wherein the temperature-raising program at the right end is started after the temperature at the left end is raised to 700 ℃ (energy consumption is reduced);
(3) after the double-temperature-zone tube furnace reaches the programmed temperature of 1300 ℃ and 600 ℃, N is closed2Bottle, open SiF4The flow of the gas cylinder is set to be 150ml/min, and the reaction lasts for 60 min;
(4) after the reaction is finished, the SiF is closed4Gas cylinder, open N2And (3) starting program cooling in a bottle and a double-temperature-zone tube furnace, taking out the silicon wafer substrate after the temperature is reduced to room temperature, weighing the silicon wafer substrate to 0.7403g, and detecting and characterizing the silicon wafer substrate, wherein the result is shown in figure 2. It can be seen from fig. 2 that a large amount of needle-like substances are formed on the surface of the silicon thin film deposited on the substrate in this example.
Example 3
(1) Soaking purchased silicon particles with the content of 99.99 percent in absolute ethyl alcohol, cleaning the silicon particles for 30 minutes by using ultrasonic waves, drying the silicon particles in a constant-temperature drying oven at 120 ℃, and weighing 150g of the silicon particles by using a balance and placing the silicon particles in a constant-temperature area at the left end of a double-temperature-area tubular furnace; soaking a 4N-purity monocrystalline silicon wafer <111> in absolute ethyl alcohol, cleaning for 30 minutes in ultrasonic waves, drying at 120 ℃ in a constant-temperature drying box, weighing the mass of the monocrystalline silicon wafer with an electronic balance to be 1.1495g, vertically placing the monocrystalline silicon wafer in a constant-temperature area at the right end of a double-temperature-area tube furnace, and connecting the tube furnace with a gas circuit;
(2) setting a temperature rise program: the left end of the double-temperature-zone tube furnace is heated to 1300 ℃ from 20 ℃ at the heating rate of 10 ℃/min, and the right end is heated to 800 ℃ from 20 ℃ at the heating rate of 10 ℃/min; opening carrier gas N2Bottle (purity)>99.5%), the flow rate is set to 150 ml/min; simultaneously, a temperature-raising program is operated, wherein the temperature-raising program at the right end is started after the temperature at the left end is raised to 500 ℃ (energy consumption is reduced);
(3) after the double-temperature-zone tube furnace reaches the programmed temperature of 1300 ℃ and 800 ℃, N is closed2Bottle, open SiF4The flow of the gas cylinder is set to be 150ml/min, and the reaction lasts for 60 min;
(4) after the reaction is finished, the SiF is closed4Gas cylinder, open N2Bottle, and simultaneously, starting program cooling of the double-temperature-zone tube furnace, taking out the silicon wafer substrate after cooling to room temperature,the mass of the sample was 1.2381g, and the sample was analyzed and characterized, and the results are shown in FIG. 3. It can be seen from fig. 3 that under the conditions of this example there is a dense silicon film on the substrate.
Example 4
(1) Soaking purchased silicon particles with the content of 99.99 percent in absolute ethyl alcohol, cleaning the silicon particles for 30 minutes by using ultrasonic waves, drying the silicon particles in a constant-temperature drying oven at 120 ℃, and weighing 150g of the silicon particles by using a balance and placing the silicon particles in a constant-temperature area at the left end of a double-temperature-area tubular furnace; soaking a quartz plate (with the purity of more than 99.9%) in absolute ethyl alcohol, cleaning for 30 minutes in ultrasonic waves, drying at 120 ℃ in a constant-temperature drying box, weighing the quartz plate by using an electronic balance to obtain 1.2659g of quartz plate, vertically placing the quartz plate in a constant-temperature area at the right end of a double-temperature-zone tube furnace, and connecting the tube furnace with a gas circuit;
(2) setting a temperature rise program: the left end of the double-temperature-zone tube furnace is heated to 1300 ℃ from 20 ℃ at the heating rate of 10 ℃/min, and the right end is heated to 600 ℃ from 20 ℃ at the heating rate of 10 ℃/min; opening carrier gas N2Bottle (purity)>99.5%), the flow rate is set to 150 ml/min; simultaneously, a temperature-raising program is operated, wherein the temperature-raising program at the right end is started after the temperature at the left end is raised to 700 ℃ (energy consumption is reduced);
(3) after the double-temperature-zone tube furnace reaches the programmed temperature of 1300 ℃ and 600 ℃, N is closed2Bottle, open SiF4The flow of the gas cylinder is set to be 150ml/min, and the reaction lasts for 60 min;
(4) after the reaction is finished, the SiF is closed4Gas cylinder, open N2And (3) starting program cooling of the bottle and the double-temperature-zone tube furnace, taking out the quartz plate substrate after the temperature is reduced to room temperature, weighing the quartz plate substrate to have the mass of 1.2939g, and detecting and characterizing the quartz plate substrate, wherein the result is shown in fig. 4. It can be seen from FIG. 4 that a large number of particles are accumulated on the surface of the silicon thin film under the conditions of this example.
Example 5
(1) Soaking purchased silicon particles with the content of 99.99 percent in absolute ethyl alcohol, cleaning the silicon particles for 30 minutes by using ultrasonic waves, drying the silicon particles in a constant-temperature drying oven at 120 ℃, and weighing 150g of the silicon particles by using a balance and placing the silicon particles in a constant-temperature area at the left end of a double-temperature-area tubular furnace; soaking a copper sheet in absolute ethyl alcohol, cleaning for 30 minutes in ultrasonic waves, drying at 120 ℃ in a constant-temperature drying box, weighing the copper sheet by an electronic balance to 0.6186g, vertically placing the copper sheet in a constant-temperature area at the right end of a double-temperature-area tubular furnace, and connecting the tubular furnace with a gas circuit;
(2) setting a temperature rise program: the left end of the double-temperature-zone tube furnace is heated to 1300 ℃ from 20 ℃ at the heating rate of 10 ℃/min, and the right end is heated to 600 ℃ from 20 ℃ at the heating rate of 10 ℃/min; opening carrier gas N2Bottle (purity)>99.5%), the flow rate is set to 150 ml/min; simultaneously, a temperature-raising program is operated, wherein the temperature-raising program at the right end is started after the temperature at the left end is raised to 700 ℃ (energy consumption is reduced);
(3) after the double-temperature-zone tube furnace reaches the programmed temperature of 1300 ℃ and 600 ℃, N is closed2Bottle, open SiF4The flow of the gas cylinder is set to be 150ml/min, and the reaction lasts for 60 min;
(4) after the reaction is finished, the SiF is closed4Gas cylinder, open N2And (3) starting program cooling in a bottle and a double-temperature-zone tube furnace, taking out the copper sheet substrate after the temperature is reduced to room temperature, weighing the copper sheet substrate to 0.7096g, and detecting and characterizing the copper sheet substrate, wherein the result is shown in fig. 5. It can be seen from FIG. 5 that under the conditions of this example, a large number of particles are accumulated on the surface of the silicon thin film and are present in a lump like a rock.
Example 6
(1) Soaking purchased silicon particles with the content of 99.99 percent in absolute ethyl alcohol, cleaning the silicon particles for 30 minutes by using ultrasonic waves, drying the silicon particles in a constant-temperature drying oven at 120 ℃, and weighing 150g of the silicon particles by using a balance and placing the silicon particles in a constant-temperature area at the left end of a double-temperature-area tubular furnace; soaking the steel sheet in absolute ethyl alcohol, cleaning for 30 minutes in ultrasonic waves, drying at 120 ℃ in a constant-temperature drying box, weighing the steel sheet by an electronic balance to 0.8350g, vertically placing the steel sheet in a constant-temperature area at the right end of a double-temperature-area tubular furnace, and connecting the tubular furnace with a gas circuit;
(2) setting a temperature rise program: the left end of the double-temperature-zone tube furnace is heated to 1300 ℃ from 20 ℃ at the heating rate of 10 ℃/min, and the right end is heated to 600 ℃ from 20 ℃ at the heating rate of 10 ℃/min; opening carrier gas N2Bottle (purity)>99.5%), the flow rate is set to 150 ml/min; simultaneously, a temperature-raising program is operated, wherein the temperature-raising program at the right end is started after the temperature at the left end is raised to 700 ℃ (energy consumption is reduced);
(3) dual temperature zone tube furnaceAfter the programmed temperature of 1300 and 600 ℃, N is closed2Bottle, open SiF4The flow of the gas cylinder is set to be 150ml/min, and the reaction lasts for 60 min;
(4) after the reaction is finished, the SiF is closed4Gas cylinder, open N2And (3) starting program cooling in a bottle and a double-temperature-zone tube furnace, taking out the steel sheet substrate after the temperature is reduced to room temperature, weighing the steel sheet substrate to 0.8736g, and detecting and representing the steel sheet substrate, wherein the result is shown in fig. 6. It can be seen from fig. 6 that the silicon thin film surface has a large amount of particles stacked and exhibits clusters under the conditions of this example.
Example 7
(1) Soaking purchased silicon particles with the content of 99.99 percent in absolute ethyl alcohol, cleaning the silicon particles for 30 minutes by using ultrasonic waves, drying the silicon particles in a constant-temperature drying oven at 120 ℃, and weighing 150g of the silicon particles by using a balance and placing the silicon particles in a constant-temperature area at the left end of a double-temperature-area tubular furnace; soaking a 4N-purity monocrystalline silicon wafer <111> in absolute ethyl alcohol, cleaning for 30 minutes in ultrasonic waves, drying at 120 ℃ in a constant-temperature drying box, weighing the mass of the monocrystalline silicon wafer with an electronic balance to be 1.1493g, vertically placing the monocrystalline silicon wafer in a constant-temperature area at the right end of a double-temperature-area tube furnace, and connecting the tube furnace with a gas circuit;
(2) setting a temperature rise program: the left end of the double-temperature-zone tube furnace is heated to 1300 ℃ from 20 ℃ at the heating rate of 10 ℃/min, and the right end is heated to 600 ℃ from 20 ℃ at the heating rate of 10 ℃/min; opening carrier gas N2Bottle (purity)>99.5%), the flow rate is set to 150 ml/min; simultaneously, a temperature-raising program is operated, wherein the temperature-raising program at the right end is started after the temperature at the left end is raised to 700 ℃ (energy consumption is reduced);
(3) after the double-temperature-zone tube furnace reaches the programmed temperature of 1300 ℃ and 600 ℃, N is closed2Bottle, open SiF4The flow of the gas cylinder is set as 100ml/min, and the reaction lasts for 60 min;
(4) after the reaction is finished, the SiF is closed4Gas cylinder, open N2And (5) starting program cooling in a bottle and a double-temperature-zone tube furnace, taking out the silicon wafer substrate after the temperature is reduced to room temperature, weighing the silicon wafer substrate with the mass of 1.1984g, and detecting and characterizing the silicon wafer substrate.
Example 8
(1) Soaking purchased silicon particles with the content of 99.99 percent in absolute ethyl alcohol, cleaning the silicon particles for 30 minutes by using ultrasonic waves, drying the silicon particles in a constant-temperature drying oven at 120 ℃, and weighing 150g of the silicon particles by using a balance and placing the silicon particles in a constant-temperature area at the left end of a double-temperature-area tubular furnace; soaking a 4N-purity monocrystalline silicon wafer <111> in absolute ethyl alcohol, cleaning for 30 minutes in ultrasonic waves, drying at 120 ℃ in a constant-temperature drying box, weighing the mass of the monocrystalline silicon wafer with an electronic balance to be 1.1142g, vertically placing the monocrystalline silicon wafer in a constant-temperature area at the right end of a double-temperature-area tube furnace, and connecting the tube furnace with a gas circuit;
(2) setting a temperature rise program: the left end of the double-temperature-zone tube furnace is heated to 1300 ℃ from 20 ℃ at the heating rate of 10 ℃/min, and the right end is heated to 600 ℃ from 20 ℃ at the heating rate of 10 ℃/min; opening carrier gas N2Bottle (purity)>99.5%), the flow rate is set to 150 ml/min; simultaneously, a temperature-raising program is operated, wherein the temperature-raising program at the right end is started after the temperature at the left end is raised to 700 ℃ (energy consumption is reduced);
(3) after the double-temperature-zone tube furnace reaches the programmed temperature of 1300 ℃ and 600 ℃, N is closed2Bottle, open SiF4The flow of the gas cylinder is set to be 200ml/min, and the reaction time is 60 min;
(4) after the reaction is finished, the SiF is closed4Gas cylinder, open N2And (5) starting program cooling in a bottle and a double-temperature-zone tube furnace, taking out the silicon wafer substrate after the temperature is reduced to room temperature, weighing the silicon wafer substrate with the mass of 1.1605g, and detecting and characterizing the silicon wafer substrate.
Example 9
(1) Soaking purchased silicon particles with the content of 99.99 percent in absolute ethyl alcohol, cleaning the silicon particles for 30 minutes by using ultrasonic waves, drying the silicon particles in a constant-temperature drying oven at 120 ℃, and weighing 150g of the silicon particles by using a balance and placing the silicon particles in a constant-temperature area at the left end of a double-temperature-area tubular furnace; soaking a 4N-purity monocrystalline silicon wafer <111> in absolute ethyl alcohol, cleaning for 30 minutes in ultrasonic waves, drying at 120 ℃ in a constant-temperature drying box, weighing the mass of the monocrystalline silicon wafer with an electronic balance to be 0.8975g, vertically placing the monocrystalline silicon wafer in a constant-temperature area at the right end of a double-temperature-area tube furnace, and connecting the tube furnace with a gas circuit;
(2) setting a temperature rise program: the left end of the double-temperature-zone tube furnace is heated to 1300 ℃ from 20 ℃ at the heating rate of 10 ℃/min, and the right end is heated to 600 ℃ from 20 ℃ at the heating rate of 10 ℃/min; opening carrier gas N2Bottle (purity)>99.5%), flow rate set to 150ml/min; simultaneously, a temperature-raising program is operated, wherein the temperature-raising program at the right end is started after the temperature at the left end is raised to 700 ℃ (energy consumption is reduced);
(3) after the double-temperature-zone tube furnace reaches the programmed temperatures of 1300 and 600, N is closed2Bottle, open SiF4The flow of the gas cylinder is set to be 150ml/min, and the reaction time is 120 min;
(4) after the reaction is finished, the SiF is closed4Gas cylinder, open N2And (5) starting program cooling in a bottle and a double-temperature-zone tube furnace, taking out the silicon wafer substrate after the temperature is reduced to room temperature, weighing the silicon wafer substrate with the mass of 0.9391, and detecting and characterizing the silicon wafer substrate.
Example 10
(1) Soaking purchased silicon particles with the content of 99.99 percent in absolute ethyl alcohol, cleaning the silicon particles for 30 minutes by using ultrasonic waves, drying the silicon particles in a constant-temperature drying oven at 120 ℃, and weighing 150g of the silicon particles by using a balance and placing the silicon particles in a constant-temperature area at the left end of a double-temperature-area tubular furnace; soaking a 4N-purity monocrystalline silicon wafer <111> in absolute ethyl alcohol, cleaning for 30 minutes in ultrasonic waves, drying at 120 ℃ in a constant-temperature drying box, weighing the mass of the monocrystalline silicon wafer with an electronic balance to be 0.8677g, vertically placing the monocrystalline silicon wafer in a constant-temperature area at the right end of a double-temperature-area tube furnace, and connecting the tube furnace with a gas circuit;
(2) setting a temperature rise program: the left end of the double-temperature-zone tube furnace is heated to 1200 ℃ from 20 ℃ at the heating rate of 10 ℃/min, and the right end is heated to 600 ℃ from 20 ℃ at the heating rate of 10 ℃/min; opening carrier gas N2Bottle (purity)>99.5%), the flow rate is set to 150 ml/min; simultaneously, a temperature-raising program is operated, wherein the temperature-raising program at the right end is started after the temperature at the left end is raised to 700 ℃ (energy consumption is reduced);
(3) after the dual-temperature-zone tube furnace reaches the programmed temperature of 1200 and 600 ℃, N is closed2Bottle, open SiF4The flow of the gas cylinder is set to be 150ml/min, and the reaction lasts for 60 min;
(4) after the reaction is finished, the SiF is closed4Gas cylinder, open N2And (5) starting program cooling in a bottle and a double-temperature-zone tube furnace, taking out the silicon wafer substrate after the temperature is reduced to room temperature, weighing the silicon wafer substrate with the mass of 0.9173g, and detecting and characterizing the silicon wafer substrate.
Claims (5)
1. A method for preparing a silicon film by using silicon tetrafluoride as a raw material is characterized by comprising the following steps: the method comprises the following steps:
(1) taking silicon particles, and taking a substrate with a proper pipe diameter;
(2) silicon particles are placed in a constant temperature area at the left end of the dual-temperature-zone tubular furnace, a substrate is vertically placed in a constant temperature area at the right end of the dual-temperature-zone tubular furnace, the final temperatures of the constant temperature areas at the left end and the right end of the dual-temperature-zone tubular furnace are respectively 1200-1300 ℃ and 400-800 ℃, and the heating rates are 8-10 ℃/min;
(3) opening carrier gas nitrogen with the flow rate of 100-; after the temperature is raised to the reaction temperature, the nitrogen gas of the carrier gas is closed, and the silicon tetrafluoride gas is opened for reaction for 30-150 min;
(4) and after the reaction is finished, closing the silicon tetrafluoride gas, opening the carrier gas nitrogen, starting the program cooling of the double-temperature-zone tube furnace, and taking out the substrate for detection after the temperature is reduced to the room temperature.
2. The method of claim 1, wherein: and (2) pretreating the silicon particles and the substrate, soaking the silicon particles and the substrate in ethanol, ultrasonically cleaning the silicon particles and the substrate, and drying the silicon particles and the substrate.
3. The method of claim 1, wherein: the step (2) adopts a double-temperature-zone tube furnace, and the temperature-raising programs at the left end and the right end operate independently.
4. The method of claim 1, wherein: the flow rate of the silicon tetrafluoride in the step (3) is 50-300 ml/min.
5. The method of claim 1, wherein: and (4) the detection in the step (4) comprises scanning electron microscope analysis.
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