CN109360866B - Preparation method of three-layer silicon nitride film - Google Patents
Preparation method of three-layer silicon nitride film Download PDFInfo
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- CN109360866B CN109360866B CN201811112871.7A CN201811112871A CN109360866B CN 109360866 B CN109360866 B CN 109360866B CN 201811112871 A CN201811112871 A CN 201811112871A CN 109360866 B CN109360866 B CN 109360866B
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- 229910052581 Si3N4 Inorganic materials 0.000 title claims abstract description 76
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000000151 deposition Methods 0.000 claims abstract description 260
- 230000008021 deposition Effects 0.000 claims abstract description 237
- 238000000034 method Methods 0.000 claims abstract description 28
- 239000004065 semiconductor Substances 0.000 claims abstract description 10
- 239000000758 substrate Substances 0.000 claims abstract description 10
- 239000000463 material Substances 0.000 claims abstract description 6
- 239000007789 gas Substances 0.000 claims description 17
- 239000012495 reaction gas Substances 0.000 claims description 15
- 239000001257 hydrogen Substances 0.000 claims description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- 230000003247 decreasing effect Effects 0.000 claims description 5
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 3
- 230000008569 process Effects 0.000 abstract description 14
- 230000000694 effects Effects 0.000 abstract description 11
- 238000002161 passivation Methods 0.000 abstract description 8
- 229910021419 crystalline silicon Inorganic materials 0.000 abstract description 5
- 238000005265 energy consumption Methods 0.000 abstract description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 18
- 229910052710 silicon Inorganic materials 0.000 description 18
- 239000010703 silicon Substances 0.000 description 18
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 15
- 150000002431 hydrogen Chemical class 0.000 description 6
- 238000009792 diffusion process Methods 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 238000002310 reflectometry Methods 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910000077 silane Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000013082 photovoltaic technology Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
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- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/1804—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof comprising only elements of Group IV of the Periodic System
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
- H01L21/67005—Apparatus not specifically provided for elsewhere
- H01L21/67242—Apparatus for monitoring, sorting or marking
- H01L21/67248—Temperature monitoring
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
- H01L21/67005—Apparatus not specifically provided for elsewhere
- H01L21/67242—Apparatus for monitoring, sorting or marking
- H01L21/67253—Process monitoring, e.g. flow or thickness monitoring
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- H—ELECTRICITY
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0216—Coatings
- H01L31/02161—Coatings for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/02167—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells
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- H—ELECTRICITY
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0216—Coatings
- H01L31/02161—Coatings for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/02167—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells
- H01L31/02168—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells the coatings being antireflective or having enhancing optical properties for the solar cells
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/547—Monocrystalline silicon PV cells
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The invention discloses a preparation method of a three-layer silicon nitride film, which comprises the following steps: (1) preparing materials: preparing a semiconductor substrate; (2) preparing a first layer of film: putting the semiconductor substrate into deposition equipment, setting a first deposition condition, wherein the deposition temperature in the first deposition condition is uniformly reduced, and depositing a first layer of silicon nitride film; (3) preparing a second film layer: setting a second deposition condition, wherein the deposition temperature in the second deposition condition is uniformly reduced to form a second layer of silicon nitride film; (4) preparing a third film: and setting a third deposition condition, wherein the deposition temperature in the third deposition condition is uniformly reduced to form a third layer of silicon nitride film. The preparation method of the three-layer silicon nitride film can effectively improve the passivation effect and the antireflection effect of the silicon nitride film on the crystalline silicon solar cell, reduce the process time, gradually reduce the deposition temperature, save the energy consumption and reduce the power consumption cost.
Description
Technical Field
The invention relates to the technical field of solar cell manufacturing, in particular to a preparation method for depositing three layers of silicon nitride films on a semiconductor substrate.
Background
With the continuous development of photovoltaic technology, crystalline silicon solar cells have been rapidly developed as a clean energy product for converting solar energy into electric energy.
The silicon nitride film has the functions of passivating the surface of a silicon wafer and reducing reflection, and the Deposition of silicon nitride on the surface of an emitter by using a Plasma Enhanced Chemical Vapor Deposition (PECVD) method is an important part in the preparation process of a crystalline silicon solar cell. However, the silicon nitride deposition method in the prior art is basically constant in temperature and constant in power supply power, uneven temperature field is easy to occur, the proportion of reworked chips is increased, and the production cost is increased.
Disclosure of Invention
In view of the above, in order to overcome the defects of the prior art, the present invention aims to provide a method for preparing a three-layer silicon nitride film, which can reduce energy consumption, save cost, reduce damage of plasma on the surface of a silicon wafer, and has a good passivation effect.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a three-layer silicon nitride film comprises the following steps:
(1) preparing materials: preparing a semiconductor substrate;
(2) preparing a first layer of film: putting the semiconductor substrate into deposition equipment, and introducing SiH (hydrogen oxygen) reaction gas into a deposition cavity of the deposition equipment4And NH3Setting a first deposition condition, wherein the deposition temperature in the first deposition condition is uniformly reduced, and depositing a first layer of silicon nitride film on the semiconductor substrate;
(3) preparing a second film layer: continuously introducing SiH (hydrogen oxygen) reaction gas into the deposition cavity after the step (2) is finished4And NH3Setting a second deposition condition, wherein the deposition temperature in the second deposition condition is uniformly reduced, and forming a second layer of silicon nitride film on the outer surface of the first layer of silicon nitride film;
(4) preparing a third film: continuously introducing SiH (hydrogen oxygen) reaction gas into the deposition cavity after the step (3) is finished4And NH3And setting a third deposition condition, wherein the deposition temperature in the third deposition condition is uniformly reduced, and a third layer of silicon nitride film is formed on the outer surface of the second layer of silicon nitride film, so that a three-layer silicon nitride film structure is finally formed.
Preferably, the deposition temperature in the first deposition condition, the deposition temperature in the second deposition condition, and the deposition temperature in the third deposition condition are decreased at the same rate.
Preferably, the deposition temperature in the first deposition condition is higher than the deposition temperature in the second deposition condition, which is higher than the deposition temperature in the third deposition condition. More preferably, the deposition temperature in the first deposition condition is reduced from 480-500 ℃; the final deposition temperature in the first deposition condition is the initial deposition temperature in the second deposition condition, and the final deposition temperature in the second deposition condition is the initial deposition temperature in the third deposition condition.
Preferably, the power supply power in the first deposition condition is lower than the power supply power in the second deposition condition, which is lower than the power supply power in the third deposition condition.
More preferably, the power supply used in the first deposition condition is 5000-6500W, the power supply used in the second deposition condition is 6500-7000W, and the power supply used in the third deposition condition is 7500-8000W.
Preferably, the deposition time in the first deposition condition is 110 to 150s, the deposition time in the second deposition condition is 70 to 120s, and the deposition time in the third deposition condition is 170 to 220 s.
More preferably, NH is in the first deposition condition3And SiH4Is less than NH in the second deposition condition3And SiH4Gas flow ratio of (1), NH in the second deposition condition3And SiH4Is less than NH in the third deposition condition3And SiH4The gas flow ratio of (2). Because when a dielectric film with the refractive index of n1 is inserted between two dielectric films with the refractive indexes of n0 and n2, the refractive index satisfies
The lowest reflectivity can be obtained; similarly, a second film is inserted between the first film and the third film, and the refractive index of the second film is required to satisfy
The lowest reflectance can be obtained where n0 is the refractive index of the silicon wafer, n1 is the refractive index of the first film, n2 is the refractive index of the second film, and n3 is the refractive index of the third film. So that NH in the first deposition condition is set3And SiH4The gas flow ratio of (1) is 4-5, and NH is present under the second deposition condition3And SiH4The gas flow ratio of (a) is 6.5 to 7.5, NH in the third deposition condition3And SiH4The gas flow ratio of (2) is 8.5～9.5。
Namely, the deposition temperature in the first deposition condition is reduced from 480-500 ℃ to 470-490 ℃, the power supply power is 5000-6500W, the deposition time is 110-150 s, and the gas flow ratio of ammonia gas to silane is 4-5; the deposition temperature in the second deposition condition is reduced from 470-490 ℃ to 460-480 ℃, the power supply power is 6500-7000W, the deposition time is 70-120 s, and the gas flow ratio of ammonia gas to silane is 6.5-7.5; and the deposition temperature in the third deposition condition is reduced from 460-480 ℃ to 440-460 ℃, the power of the used power supply is 7500-8000W, the deposition time is 170-220 s, and the gas flow ratio of ammonia gas to silane is 8.5-9.5.
Preferably, the pressure for depositing the silicon nitride in the preparation method is 1500-2000 mTorr. mTorr is the unit of pressure in millitorr of pressure, i.e. one thousandth of a milli-mercury column pressure, 1mTorr being equal to 0.133 Pa. Both slm and sccm are gas mass flow units, sccm (standard capacitive center meter per minute) is a flow of 1 cubic centimeter (1mL/min) per minute under standard conditions (i.e., 1 atmosphere at 25 ℃), and slm (standard tolerance per minute) is a flow of 1 liter (1L/min) under standard conditions.
Preferably, the power supply switching ratio during silicon nitride deposition in the preparation method is 1/7-1/10. Specifically, a power supply Pulse on is set to be 3-5 ms, and Pulse off is set to be 21-50 ms, so that proper silicon nitride film layer deposition rate is ensured, the smaller the power supply switch is, the larger the deposition rate is, the film thickness is easy to be uneven due to overlarge deposition rate, and the rework proportion is increased; too low a deposition rate can result in extended process times and increased production costs.
Compared with the prior art, the invention has the advantages that: according to the preparation method of the three-layer silicon nitride film, the deposition temperature used in the process of depositing the silicon nitride film is gradually and uniformly reduced, the energy consumption can be saved, the electricity consumption cost is reduced, the power supply power used in the process of depositing the first layer of silicon nitride film is lower than the power supply power used in the process of depositing the second layer of silicon nitride film, the power supply power used in the process of depositing the second layer of silicon nitride film is lower than the power supply power used in the process of depositing the third layer of silicon nitride film, the inward diffusion of H is promoted, the damage of plasma to the surface of a silicon wafer is reduced, and the passivation effect and the antireflection effect of the silicon nitride film to a crystalline silicon solar cell can be effectively improved.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
FIG. 1 is a flow chart illustrating the steps of preparing a three-layer silicon nitride film according to a preferred embodiment of the present invention;
FIG. 2 is a graph showing the variation of power and temperature of a power supply in accordance with a first preferred embodiment of the present invention;
FIG. 3 is a diagram showing the variation of power and temperature of the power supply in the second preferred embodiment of the present invention;
fig. 4 is a diagram showing the variation of power and temperature of the power supply in the third preferred embodiment of the present invention.
Detailed Description
In order to make those skilled in the art better understand the technical solution of the present invention, the technical solution in the embodiment of the present invention will be clearly and completely described below with reference to the drawings in the embodiment of the present invention, and it is obvious that the described embodiment is only a part of the embodiment of the present invention, and not a whole embodiment. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It should be noted that the terms "first," "second," and the like in the description and claims of the present invention and in the drawings described above are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order. It is to be understood that the data so used is interchangeable under appropriate circumstances such that the embodiments of the invention described herein are capable of operation in sequences other than those illustrated or described herein. Furthermore, the terms "comprises," "comprising," and "having," and any variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, apparatus, article, or device that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed, but may include other steps or elements not expressly listed or inherent to such process, method, article, or device.
In the following examples, the semiconductor substrate used was a silicon wafer, which was a silicon wafer commercially available from xixin new energy control ltd; the deposition equipment used was model E2000HT 410-4, available from Centrotherm; the instrument for detecting the light absorption effect is a reflectivity tester, and can test the reflectivity of the silicon wafer within the wavelength range of 300-1100nm (the reflectivity is low, which indicates that the antireflection effect is good).
Example one
Referring to fig. 1 to 2, a method for preparing a three-layer silicon nitride film of the present embodiment includes the following steps:
step S1: preparing the material
And preparing a clean silicon wafer which is finished with the processes of texturing, diffusion, etching and the like.
Step S2: preparing the first film
Putting a silicon wafer into deposition equipment, and introducing SiH (hydrogen) reaction gas into a deposition cavity4And NH3And depositing a first layer of silicon nitride film on the silicon wafer by setting a first deposition condition.
The first deposition conditions were: the deposition temperature is uniformly reduced from 480 ℃ at the speed of 5 ℃/min, the power of the used power supply is 5000W, the deposition time is 150s, and NH is added3Flow 4.53slm, SiH4The flow rate is 1130sccm, the pressure is 2000mTorr, and the power switch ratio is 4/28. mTorr is the unit of pressure in millitorr of pressure, i.e. one thousandth of a milli-mercury column pressure, 1mTorr being equal to 0.133 Pa. Both slm and sccm are gas mass flow units, sccm (standard capacitive center meter per minute) is a flow of 1 cubic centimeter (1mL/min) per minute under standard conditions (i.e., 1 atmosphere at 25 ℃), and slm (standard tolerance per minute) is a flow of 1 liter (1L/min) under standard conditions.
The temperature for depositing the first layer of silicon nitride film is higher, which is beneficial to obtaining better passivation effect. And the power of the used power supply is low, the damage of the plasma to the surface of the silicon wafer is reduced, and the reduction of recombination centers is facilitated. And the thickness of the film is controlled by controlling the deposition time, and the thickness of the first layer of silicon nitride film in the embodiment is controlled to be 15-25 nm.
Step S3: preparation of the second film
After the step S2 is finished, SiH serving as a reaction gas is continuously introduced into the deposition chamber4And NH3And setting a second deposition condition to form a second layer of silicon nitride film on the outer surface of the first layer of silicon nitride film.
The second deposition conditions were: the deposition temperature is started at the temperature when the first deposition condition is finished, the speed of 5 ℃/min is kept to be uniformly reduced, the power supply is 7000W, the deposition time is 70s, and NH is added3Flow 5.9slm, SiH4The flow rate is 900sccm, the pressure is 2000mTorr, and the power switch ratio is 4/28.
The refractive index of the deposited second layer of silicon nitride film needs to be between the refractive indexes of the first layer of silicon nitride film and the third layer of silicon nitride film, so that the interface difference between the bottom layer and the outer layer of silicon nitride film is favorably reduced, the defects are fewer, the internal stress is smaller, the propagation path of light in the film is increased, the light absorption is further improved, and the passivation and antireflection effects are improved. In this embodiment, the refractive index of the first silicon nitride film is set to be 2.3-2.4, the refractive index of the second silicon nitride film is set to be 2.1-2.3, and the refractive index of the third silicon nitride film is set to be 2.0-2.1.
Step S4: preparation of the third film
Continuously introducing SiH (hydrogen oxygen) reaction gas into the deposition cavity after the step (3) is finished4And NH3Setting a third deposition condition, forming a third layer of silicon nitride film on the outer surface of the second layer of silicon nitride film, and finally forming a three-layer silicon nitride film structure.
The third deposition conditions were: the deposition temperature is started at the temperature when the second deposition condition is finished and is uniformly reduced at a rate of 5 ℃/min, and the used electricitySource power 8000W, deposition time 200s, NH3Flow 6slm, SiH4The flow rate is 700sccm, the pressure is 2000mTorr, and the power switch ratio is 4/28.
The power supply power for depositing the third layer of silicon nitride film is higher than the power supply power for depositing the first layer of silicon nitride film and the second layer of silicon nitride film, so that the deposition rate can be improved, the process time can be shortened, and the productivity can be improved.
As can be obtained by the detailed description of the above steps, in the present embodiment, the deposition temperature in the first deposition condition is uniformly decreased, the deposition temperature in the second deposition condition is uniformly decreased, the deposition temperature in the third deposition condition is uniformly decreased, and the rates of decrease of the deposition temperature in the first deposition condition, the deposition temperature in the second deposition condition, and the deposition temperature in the third deposition condition are the same. The deposition temperature is uniformly reduced, so that the passivation effect can be ensured, the yield of products is improved, and the rework proportion is reduced.
The final deposition temperature in the first deposition condition is the initial deposition temperature in the second deposition condition, and the final deposition temperature in the second deposition condition is the initial deposition temperature in the third deposition condition, i.e., the deposition temperature in the first deposition condition is higher than the deposition temperature in the second deposition condition, and the deposition temperature in the second deposition condition is higher than the deposition temperature in the third deposition condition. Controlling the deposition temperature of the first layer to be higher, and promoting the inward diffusion of H to improve the passivation effect; the natural reduction of temperature can reduce energy consumption and save cost.
In this embodiment, the power source power in the first deposition condition is lower than the power source power in the second deposition condition, and the power source power in the second deposition condition is lower than the power source power in the third deposition condition. The power supply power used for depositing the first layer of film is lower than that used for depositing other film layers, so that the damage of plasma to the surface of the silicon wafer can be reduced.
NH in the first deposition condition3And SiH4Is less than NH in the second deposition condition3And SiH4Gas flow ratio of (1), NH in the second deposition condition3And SiH4Is less than NH in the third deposition condition3And SiH4The gas flow ratio of (2).
Example two
Referring to fig. 1 and 3, a method for preparing a three-layer silicon nitride film according to this embodiment includes the following steps:
step S1: preparing the material
And preparing a clean silicon wafer which is finished with the processes of texturing, diffusion, etching and the like.
Step S2: preparing the first film
Putting a silicon wafer into deposition equipment, and introducing SiH (hydrogen) reaction gas into a deposition cavity4And NH3And depositing a first layer of silicon nitride film on the silicon wafer by setting a first deposition condition.
The first deposition conditions were: the deposition temperature is uniformly reduced from 500 ℃ at a rate of 5 ℃/min, the power of the used power supply is 6500W, the deposition time is 130s, NH3Flow 5.6slm, SiH4The flow rate is 1130sccm, the pressure is 1500mTorr, and the power switching ratio is 4/36.
Step S3: preparation of the second film
After the step S2 is finished, SiH serving as a reaction gas is continuously introduced into the deposition chamber4And NH3And setting a second deposition condition to form a second layer of silicon nitride film on the outer surface of the first layer of silicon nitride film.
The second deposition conditions were: the temperature at the end of the first deposition condition is used as the initial deposition temperature in the second deposition condition, the speed of 5 ℃/min is kept to be uniformly reduced, the power supply is 7000W, the deposition time is 80s, and NH is added3Flow 6.2slm, SiH4The flow rate is 900sccm, the pressure is 1500mTorr, and the power switch ratio is 4/36.
Step S4: preparation of the third film
Continuously introducing SiH (hydrogen oxygen) reaction gas into the deposition cavity after the step (3) is finished4And NH3Setting a third deposition condition, forming a third layer of silicon nitride film on the outer surface of the second layer of silicon nitride film, and finally forming a three-layer silicon nitride film structure.
The third deposition conditions were: the temperature at the end of the second deposition condition is taken as the third depositionThe initial deposition temperature in the product condition is kept at the rate of 5 ℃/min and is uniformly reduced, the power supply power is 8000W, the deposition time is 220s, and NH is added3Flow 6.3slm, SiH4The flow rate is 700sccm, the pressure is 1500mTorr, and the power switch ratio is 4/36.
EXAMPLE III
Referring to fig. 1 and 4, a method for preparing a three-layer silicon nitride film according to this embodiment includes the following steps:
step S1: preparing the material
And preparing a clean silicon wafer which is finished with the processes of texturing, diffusion, etching and the like.
Step S2: preparing the first film
Putting a silicon wafer into deposition equipment, and introducing SiH (hydrogen) reaction gas into a deposition cavity4And NH3And depositing a first layer of silicon nitride film on the silicon wafer by setting a first deposition condition.
The first deposition conditions were: the deposition temperature is uniformly reduced from 490 ℃ at a rate of 5 ℃/min, the power supply used is 5500W, the deposition time is 140s, NH3Flow 5.4slm, SiH4The flow rate is 1200sccm, the pressure is 2000mTorr, and the power switch ratio is 3/30.
Step S3: preparation of the second film
After the step S2 is finished, SiH serving as a reaction gas is continuously introduced into the deposition chamber4And NH3And setting a second deposition condition to form a second layer of silicon nitride film on the outer surface of the first layer of silicon nitride film.
The second deposition conditions were: the temperature of the first deposition condition is the initial deposition temperature of the second deposition condition and is uniformly reduced at a rate of 5 ℃/min, the power supply power is 6800W, the deposition time is 120s, and NH is added3Flow 6.7slm, SiH4The flow rate is 900sccm, the pressure is 2000mTorr, and the power switch ratio is 3/30.
Step S4: preparation of the third film
Continuously introducing SiH (hydrogen oxygen) reaction gas into the deposition cavity after the step (3) is finished4And NH3Setting third deposition condition on the second layer of silicon nitride filmAnd forming a third layer of silicon nitride film on the outer surface, and finally forming a three-layer silicon nitride film structure.
The third deposition conditions were: the temperature at the end of the second deposition condition is the initial deposition temperature in the third deposition condition, the speed of 5 ℃/min is kept to be uniformly reduced, the power supply power is 7500W, the deposition time is 170s, and NH is maintained to be uniformly reduced3Flow 5.7slm, SiH4The flow rate is 600sccm, the pressure is 2000mTorr, and the power switch ratio is 3/30.
Comparative example 1
And (3) depositing the silicon nitride film by adopting the existing preparation process, namely, respectively depositing for three times while keeping the corresponding deposition temperature and the used power supply constant when depositing each layer of silicon nitride film to obtain three layers of silicon nitride films.
Example four results and discussion
The test was performed on the cell fabricated in the example and the cell fabricated in the conventional process of the first comparative example, where Eta is the conversion efficiency, Uoc is the open-circuit voltage, Isc is the short-circuit current, FF is the fill factor, Rs is the series resistance, Rsh is the parallel resistance, IRev1 is the reverse current, and R is the reflectance to light after the film plating, and the results are as follows:
TABLE 1 test results
From the electrical property test results of table 1, it can be derived: the gain of the photoelectric conversion efficiency of the cell mainly comes from the improvement of the Uoc, mainly because the high temperature in the first deposition condition is favorable for improving the hydrogen passivation, and the power supply power in the first condition is lower, so that the damage to the surface of the crystalline silicon is reduced, and the recombination center is reduced, thereby improving the photoelectric conversion efficiency.
The above embodiments are merely illustrative of the technical concept and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the content of the present invention and implement the invention, and not to limit the scope of the invention, and all equivalent changes or modifications made according to the spirit of the present invention should be covered by the scope of the present invention.
Claims (8)
1. A preparation method of a three-layer silicon nitride film is characterized by comprising the following steps:
(1) preparing materials: preparing a semiconductor substrate;
(2) preparing a first layer of film: putting the semiconductor substrate into deposition equipment, and introducing SiH (hydrogen oxygen) reaction gas into a deposition cavity of the deposition equipment4And NH3Setting a first deposition condition, wherein the deposition temperature in the first deposition condition is uniformly reduced, and depositing a first layer of silicon nitride film on the semiconductor substrate;
(3) preparing a second film layer: continuously introducing SiH (hydrogen oxygen) reaction gas into the deposition cavity after the step (2) is finished4And NH3Setting a second deposition condition, wherein the deposition temperature in the second deposition condition is uniformly reduced, and forming a second layer of silicon nitride film on the outer surface of the first layer of silicon nitride film;
(4) preparing a third film: continuously introducing SiH (hydrogen oxygen) reaction gas into the deposition cavity after the step (3) is finished4And NH3Setting a third deposition condition, wherein the deposition temperature in the third deposition condition is uniformly reduced, and a third layer of silicon nitride film is formed on the outer surface of the second layer of silicon nitride film, so as to finally form a three-layer silicon nitride film structure;
the deposition temperature in the first deposition condition, the deposition temperature in the second deposition condition, and the deposition temperature in the third deposition condition are decreased at the same rate; a final deposition temperature in the first deposition condition is an initial deposition temperature in the second deposition condition, and a final deposition temperature in the second deposition condition is an initial deposition temperature in the third deposition condition;
a deposition temperature in the first deposition condition is higher than a deposition temperature in the second deposition condition, which is higher than a deposition temperature in the third deposition condition; the source power in the first deposition condition is lower than the source power in the second deposition condition, which is lower than the source power in the third deposition condition.
2. The method as claimed in claim 1, wherein the deposition temperature in the first deposition condition is reduced from 480 to 500 ℃.
3. The method according to claim 1, wherein the power used in the first deposition condition is 5000-6500W, the power used in the second deposition condition is 6500-7000W, and the power used in the third deposition condition is 7500-8000W.
4. The method as claimed in claim 1, wherein the deposition time under the first deposition condition is 110-150 s, the deposition time under the second deposition condition is 70-120 s, and the deposition time under the third deposition condition is 170-220 s.
5. The method of claim 1, wherein NH is present in the first deposition condition3And SiH4Is less than NH in the second deposition condition3And SiH4Gas flow ratio of (1), NH in the second deposition condition3And SiH4Is less than NH in the third deposition condition3And SiH4The gas flow ratio of (2).
6. The method of claim 5, wherein NH is present under the first deposition condition3And SiH4The gas flow ratio of (1) is 4-5, and NH is present under the second deposition condition3And SiH4The gas flow ratio of (a) is 6.5 to 7.5, NH in the third deposition condition3And SiH4The gas flow rate ratio of (A) is 8.5 to 9.5.
7. The method of claim 1, wherein the pressure of depositing the silicon nitride is 1500-2000 mTorr.
8. The method of claim 1, wherein the power on/off ratio of the deposited silicon nitride is 1/7-1/10.
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