CN102903764A - Three-layered silicon nitride antireflective film of crystalline silicon solar cell and preparation method thereof - Google Patents
Three-layered silicon nitride antireflective film of crystalline silicon solar cell and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a three-layered silicon nitride antireflective film of a crystalline silicon solar cell. The three-layered silicon nitride antireflective film is characterized in that the antireflective film is composed of three silicon nitride film layers, wherein the first silicon nitride film is formed on the surface of the crystalline silicon of the solar cell, and has a thickness of 8 to 12nm and a refractive index of 2.3 to 2.4; the second silicon nitride film has a thickness of 18 to 24nm and a refractive index of 2.0 to 2.1; and the third silicon nitride film has a thickness of 35 to 45nm and a refractive index of 1.9 to 2.0. The invention also provides a method for preparing the three-layered silicon nitride antireflective film of the crystalline silicon solar cell. The method comprises coating three silicon nitride films with different refractive indexes and thickness on a silicon wafer by plasma enhanced chemical vapor deposition using silane and ammonia gas as raw materials and adopting new process parameters, and the method has low requirement for equipment and is easy to realize. The film coating process can enhance the passivation effect of the film and reduce the reflectivity of the antireflective film, thereby improving conversion efficiency of the solar cell. The three-layered silicon nitride antireflective film provided by the invention can improve the photoelectric conversion efficiency by 0.2% to 0.3% in comparison with a single-layer antireflective film system.
Description
Technical field
The present invention relates to the production and processing technical field of solar cell, more particularly, is three layers of silicon nitride anti-reflecting film of a kind of crystal silicon solar energy battery and preparation method thereof.
Background technology
Solar energy power generating becomes one of branch with the fastest developing speed in the new forms of energy over past ten years.Crystal silicon solar energy battery is most widely used battery types in the solar energy power generating.Account for 80% the market share.Global photovoltaic adding new capacity surpassed 27GW in 2011.
For crystal silicon cell obtains higher photoelectric conversion efficiency, can start with to produce more photo-generated carrier to sun Optical Absorption from increasing battery.Industrial general employing plates antireflective coating at the later silicon chip surface of making herbs into wool, the effect of antireflective coating is exactly the optical path difference of utilizing light to produce in the reflection of antireflective coating upper and lower surface, so that interfering, two bundle reverberation disappear mutually, thereby weaken reflection, increase incident, thereby the short circuit current that increases battery improves photoelectric conversion efficiency.By regulating kind, thickness and the refractive index of antireflective coating, so that meeting certain light path condition, incident light reaches antireflecting effect.In the production technology of crystal silicon solar energy battery, antireflection layer material commonly used is by SiO
2, SiN
x, ITO etc.The crystal silicon cell industry generally adopts PEVCD to prepare SiNx and SiO at present
2As antireflective coating.By selecting different reflection-reducing material to cooperatively interact with the different deposition numbers of plies, reach best anti-reflective effect, and finally improve the photoelectric conversion efficiency of cell piece.In order better to improve the optical match degree of sunlight in antireflective coating and the visible light wave range; consider simultaneously the contradiction between the absorption of balance passivation and shortwave; duplicature or multi-layer film structure become study hotspot this year gradually, and the beginning scale is applied in the production of crystal silicon solar energy battery.But be applied in Multilayer silicon nitride antireflection film in the crystal silicon solar energy battery is that all right ripe.
Summary of the invention
The object of the present invention is to provide a kind of method that can be used in the Multilayer silicon nitride antireflection film preparation of crystal silicon solar cell sheet, solve present crystalline silicon battery plate and still adopt conventional plating individual layer silicon nitride film technique, but can not further improve the problem of photoelectric conversion efficiency.
Purpose of the present invention can be achieved through the following technical solutions:
Three layers of silicon nitride anti-reflecting film of a kind of crystal silicon solar energy battery, it is characterized in that, it is to be made of trilamellar membrane, ground floor is the silicon nitride film of solar cell surface of crystalline silicon, and thickness is 8 ~ 12nm, and refractive index is 2.3 ~ 2.4, the thickness of second layer silicon nitride film is 18 ~ 24nm, refractive index is that the thickness of the 2.0 ~ 2.1, three layer of silicon nitride film is 35 ~ 45nm, and refractive index is 1.9 ~ 2.0.
The thickness sum of described three layers of silicon nitride anti-reflecting film is 72 ~ 77nm.
The preparation method of three layers of silicon nitride anti-reflecting film of a kind of crystal silicon solar energy battery, to the process cleaning and texturing, diffusion preparation PN junction, etching is removed the PN junction around the crystalline silicon, crystalline silicon coated with antireflection film behind the treatment step of cleaning removal phosphorosilicate glass, it is characterized in that, be to utilize plasma enhanced chemical vapor deposition method to deposit successively three layers of silicon nitride film at silicon chip surface, and it comprises following step:
(1) boiler tube is vacuumized, keep 420 ℃ of the interior temperature of stove, pressure 50mTorr, the time is 4min;
(2) boiler tube is carried out preliminary treatment, temperature rises to 460 ℃, and nitrogen flow is that 10slm purges, after to be evacuated to pressure be 100mTorr and keep 2min;
(3) pressure test guarantees that device interior pressure 50mTorr is constant, keeps 0.5min;
(4) deposition the first tunic, temperature is 460 ℃, and ammonia flow is 3.8 ~ 4slm, and silane flow rate is 950 ~ 1100sccm, 5300 ~ 5600 watts of radio-frequency powers, duration 130 ~ 140s, the radio-frequency (RF) device duty ratio is set to 5ms to be opened/the 50ms pass;
(5) nitrogen 5slm purges 30s, is evacuated to 80mtor, deposits the second tunic, temperature is 450 ℃, and ammonia flow is 6.8 ~ 7.2slm, and silane flow rate is 700 ~ 750sccm, 5300 ~ 5600 watts of radio-frequency powers, duration 200 ~ 215s, the radio-frequency (RF) device duty ratio is set to 5ms to be opened/the 50ms pass;
(6) nitrogen 5slm purges 30s, is evacuated to 80mtor, deposits trilamellar membrane, temperature is 450 ℃, and ammonia flow is 7 ~ 7.2slm, and silane flow rate is 480 ~ 520sccm, 5500 watts of radio-frequency powers, duration 340 ~ 350s, the radio-frequency (RF) device duty ratio is set to 5ms to be opened/the 50ms pass;
(7) nitrogen blowing cooling, temperature is 420 ℃, and nitrogen flow is 6 ~ 10slm, and pressure is 10000mTorr, purge time 5 ~ 8min.
Beneficial effect of the present invention: the present invention utilizes silane and ammonia to be raw material, utilize plasma enhanced chemical vapor deposition method, adopt new technological parameter, be coated with the multilayer refractive index silicon nitride film system different from thickness in silicon chip substrate, have equipment requirement not high, the advantage that realizes easily.This coating process has strengthened the passivation effect of plated film, has reduced antireflective coating to the reflection of light rate, thereby improves the photoelectric conversion efficiency of solar cell.The multilayer film antireflective coating system that adopts technique of the present invention to prepare, the photoelectric conversion efficiency of battery has increased by 0.2 ~ 0.3% than monofilm antireflective system.To polycrystal silicon cell, photoelectric conversion efficiency can reach 17.5% especially.
Description of drawings
Fig. 1 is structural representation of the present invention.
Among the figure: 1, silicon chip, 2, silicon nitride film, 3, silicon nitride film, 4, silicon nitride film.
Embodiment
The invention will be further described below in conjunction with specific embodiment.
Embodiment 1
Three layers of silicon nitride anti-reflecting film of a kind of crystal silicon solar energy battery as shown in Figure 1, deposit silicon nitride film 2, silicon nitride film 3 and silicon nitride film 4 successively on silicon chip 1 surface.
The preparation method of three layers of silicon nitride anti-reflecting film of a kind of crystal silicon solar energy battery, to the process cleaning and texturing, diffusion preparation PN junction, etching is removed the PN junction around the crystalline silicon, crystalline silicon coated with antireflection film behind the treatment step of cleaning removal phosphorosilicate glass, it is characterized in that, be to utilize plasma enhanced chemical vapor deposition method to deposit successively three layers of silicon nitride film at silicon chip surface, and it comprises following step:
(1) boiler tube is vacuumized, keep 420 ℃ of the interior temperature of stove, pressure 50mTorr, the time is 4min; (2) boiler tube is carried out preliminary treatment, temperature rises to 460 ℃, and nitrogen flow is that 10slm purges, after to be evacuated to pressure be 100mTorr and keep 2min; (3) pressure test guarantees that device interior pressure 50mTorr is constant, keeps 0.5min; (4) deposition ground floor silicon nitride film, temperature is 460 ℃, ammonia flow is 3.8slm, silane flow rate is 950sccm, 5300 watts of radio-frequency powers, duration 130s, the radio-frequency (RF) device duty ratio is set to 5ms to be opened/the 50ms pass, and obtaining thickness is that 10nm, refractive index are 2.3 silicon nitride film.(5) nitrogen 5slm purges 30s, be evacuated to 80mtor, deposition second layer silicon nitride film, temperature is 450 ℃, and ammonia flow is 6.8slm, and silane flow rate is 700sccm, 5300 watts of radio-frequency powers, duration 200s, the radio-frequency (RF) device duty ratio is set to 5ms to be opened/the 50ms pass, obtaining thickness is that 18nm, refractive index are 2.0 silicon nitride film.(6) nitrogen 5slm purges 30s, be evacuated to 80mtor, deposit the 3rd layer of silicon nitride film, temperature is 450 ℃, and ammonia flow is 7slm, and silane flow rate is 480sccm, 5500 watts of radio-frequency powers, duration 350s, the radio-frequency (RF) device duty ratio is set to 5ms to be opened/the 50ms pass, obtaining thickness is that 45nm, refractive index are 1.9 silicon nitride film; (7) nitrogen blowing cooling, temperature is 420 ℃, and nitrogen flow is 6slm, and pressure is 10000mTorr, purge time 5min.
Three layers of silicon nitride anti-reflecting film of a kind of crystal silicon solar energy battery as shown in Figure 1, deposit silicon nitride film 2, silicon nitride film 3 and silicon nitride film 4 successively on silicon chip 1 surface.
The preparation method of three layers of silicon nitride anti-reflecting film of a kind of crystal silicon solar energy battery, to the process cleaning and texturing, diffusion preparation PN junction, etching is removed the PN junction around the crystalline silicon, crystalline silicon coated with antireflection film behind the treatment step of cleaning removal phosphorosilicate glass, it is characterized in that, be to utilize plasma enhanced chemical vapor deposition method to deposit successively three layers of silicon nitride film at silicon chip surface, and it comprises following step:
(1) boiler tube is vacuumized, keep 420 ℃ of the interior temperature of stove, pressure 50mTorr, the time is 4min;
(2) boiler tube is carried out preliminary treatment, temperature rises to 460 ℃, and nitrogen flow is that 10slm purges, after to be evacuated to pressure be 100mTorr and keep 2min; (3) pressure test guarantees that device interior pressure 50mTorr is constant, keeps 0.5min; (4) deposition ground floor silicon nitride film, temperature is 460 ℃, ammonia flow is 3.9slm, silane flow rate is 1000sccm, 5500 watts of radio-frequency powers, duration 135s, the radio-frequency (RF) device duty ratio is set to 5ms to be opened/the 50ms pass, and obtaining thickness is that 8nm, refractive index are 2.3 silicon nitride film; (5) nitrogen 5slm purges 30s, be evacuated to 80mtor, deposition second layer silicon nitride film, temperature is 450 ℃, and ammonia flow is 7.0slm, and silane flow rate is 730sccm, 5400 watts of radio-frequency powers, duration 208s, the radio-frequency (RF) device duty ratio is set to 5ms to be opened/the 50ms pass, obtaining thickness is that 22nm, refractive index are 2.1 silicon nitride film; (6) nitrogen 5slm purges 30s, be evacuated to 80mtor, deposit the 3rd layer of silicon nitride film, temperature is 450 ℃, and ammonia flow is 7.1slm, and silane flow rate is 495sccm, 5500 watts of radio-frequency powers, duration 345s, the radio-frequency (RF) device duty ratio is set to 5ms to be opened/the 50ms pass, obtaining thickness is that 42nm, refractive index are 2.0 silicon nitride film; (7) nitrogen blowing cooling, temperature is 420 ℃, and nitrogen flow is 8slm, and pressure is 10000mTorr, purge time 6min.
Three layers of silicon nitride anti-reflecting film of a kind of crystal silicon solar energy battery as shown in Figure 1, deposit silicon nitride film 2, silicon nitride film 3 and silicon nitride film 4 successively on silicon chip 1 surface.
The preparation method of three layers of silicon nitride anti-reflecting film of a kind of crystal silicon solar energy battery, to the process cleaning and texturing, diffusion preparation PN junction, etching is removed the PN junction around the crystalline silicon, crystalline silicon coated with antireflection film behind the treatment step of cleaning removal phosphorosilicate glass, it is characterized in that, be to utilize plasma enhanced chemical vapor deposition method to deposit successively three layers of silicon nitride film at silicon chip surface, and it comprises following step:
(1) boiler tube is vacuumized, keep 420 ℃ of the interior temperature of stove, pressure 50mTorr, the time is 4min; (2) boiler tube is carried out preliminary treatment, temperature rises to 460 ℃, and nitrogen flow is that 10slm purges, after to be evacuated to pressure be 100mTorr and keep 2min; (3) pressure test guarantees that device interior pressure 50mTorr is constant, keeps 0.5min; (4) deposition ground floor silicon nitride film, temperature is 460 ℃, ammonia flow is 4slm, silane flow rate is 1100sccm, 5600 watts of radio-frequency powers, duration 140s, the radio-frequency (RF) device duty ratio is set to 5ms to be opened/the 50ms pass, and obtaining thickness is that 12nm, refractive index are 2.4 silicon nitride film; (5) nitrogen 5slm purges 30s, be evacuated to 80mtor, deposition second layer silicon nitride film, temperature is 450 ℃, and ammonia flow is 7.2slm, and silane flow rate is 750sccm, 5600 watts of radio-frequency powers, duration 215s, the radio-frequency (RF) device duty ratio is set to 5ms to be opened/the 50ms pass, obtaining thickness is that 24nm, refractive index are 2.1 silicon nitride film; (6) nitrogen 5slm purges 30s, be evacuated to 80mtor, deposit the 3rd layer of silicon nitride film, temperature is 450 ℃, and ammonia flow is 7.2slm, and silane flow rate is 520sccm, 5500 watts of radio-frequency powers, duration 340s, the radio-frequency (RF) device duty ratio is set to 5ms to be opened/the 50ms pass, obtaining thickness is that 40nm, refractive index are 1.9 silicon nitride film; (7) nitrogen blowing cooling, temperature is 420 ℃, and nitrogen flow is 10slm, and pressure is 10000mTorr, purge time 8min.
Claims (3)
1. three layers of silicon nitride anti-reflecting film of a crystal silicon solar energy battery, it is characterized in that, it is to be made of trilamellar membrane, ground floor is the silicon nitride film of solar cell surface of crystalline silicon, and thickness is 8 ~ 12nm, and refractive index is 2.3 ~ 2.4, the thickness of second layer silicon nitride film is 18 ~ 24nm, refractive index is that the thickness of the 2.0 ~ 2.1, three layer of silicon nitride film is 35 ~ 45nm, and refractive index is 1.9 ~ 2.0.
2. three layers of silicon nitride anti-reflecting film of crystal silicon solar energy battery according to claim 1 is characterized in that, the thickness sum of described three layers of silicon nitride anti-reflecting film is 72 ~ 77nm.
3. the preparation method of three layers of silicon nitride anti-reflecting film of a crystal silicon solar energy battery, to the process cleaning and texturing, diffusion preparation PN junction, etching is removed the PN junction around the crystalline silicon, crystalline silicon coated with antireflection film behind the treatment step of cleaning removal phosphorosilicate glass, it is characterized in that, be to utilize plasma enhanced chemical vapor deposition method to deposit successively three layers of silicon nitride film at silicon chip surface, and it comprises following step:
(1) boiler tube is vacuumized, keep 420 ℃ of the interior temperature of stove, pressure 50mTorr, the time is 4min;
(2) boiler tube is carried out preliminary treatment, temperature rises to 460 ℃, and nitrogen flow is that 10slm purges, after to be evacuated to pressure be 100mTorr and keep 2min;
(3) pressure test guarantees that device interior pressure 50mTorr is constant, keeps 0.5min;
(4) deposition the first tunic, temperature is 460 ℃, and ammonia flow is 3.8 ~ 4slm, and silane flow rate is 950 ~ 1100sccm, 5300 ~ 5600 watts of radio-frequency powers, duration 130 ~ 140s, the radio-frequency (RF) device duty ratio is set to 5ms to be opened/the 50ms pass;
(5) nitrogen 5slm purges 30s, is evacuated to 80mtor, deposits the second tunic, temperature is 450 ℃, and ammonia flow is 6.8 ~ 7.2slm, and silane flow rate is 700 ~ 750sccm, 5300 ~ 5600 watts of radio-frequency powers, duration 200 ~ 215s, the radio-frequency (RF) device duty ratio is set to 5ms to be opened/the 50ms pass;
(6) nitrogen 5slm purges 30s, is evacuated to 80mtor, deposits trilamellar membrane, temperature is 450 ℃, and ammonia flow is 7 ~ 7.2slm, and silane flow rate is 480 ~ 520sccm, 5500 watts of radio-frequency powers, duration 340 ~ 350s, the radio-frequency (RF) device duty ratio is set to 5ms to be opened/the 50ms pass;
(7) nitrogen blowing cooling, temperature is 420 ℃, and nitrogen flow is 6 ~ 10slm, and pressure is 10000mTorr, purge time 5 ~ 8min.
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