CN101022135A - Silicon solar battery antireflective thin film - Google Patents
Silicon solar battery antireflective thin film Download PDFInfo
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- CN101022135A CN101022135A CN 200710019794 CN200710019794A CN101022135A CN 101022135 A CN101022135 A CN 101022135A CN 200710019794 CN200710019794 CN 200710019794 CN 200710019794 A CN200710019794 A CN 200710019794A CN 101022135 A CN101022135 A CN 101022135A
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Abstract
This invention discloses an anti-reflection film of silicon solar cell used in solar cells by depositing a rich silicon SiN film on the positive surface of a silicon chip and a SiN film with ideal match on the rich silicon SiN film, in which, and the film content closing to the Si chip surface is high and the surface pasivation effect is better than the SiN film approaching to the idea match, the surface composition speed is more than one time less than the normal matched SiN film, and the rich Si film is thin and only absorbs 20%-30% short waves with the wavelength about 300nm and does not absorb long-middle lightwaves and other composition approaches to ideal chemical match.
Description
Technical field
The present invention relates to a kind of silicon nitride antireflection film that is used for solar cell.
Background technology
The silicon nitride antireflection film is widely used in crystalline silicon (comprising monocrystalline silicon, the polysilicon) solar cell, and the method for preparing silicon nitride usually is plasma reinforced chemical vapour deposition (PECVD) or sputter, and wherein PECVD's is most widely used general.When PECVD deposits, also can comprise the accessory substance hydrogen of reaction in the silicon nitride film.Silicon nitride film mainly contains following effect in crystal silicon solar energy battery:
1) antireflective effect.The refractive index of general silicon nitride is 1.9～2.3, adopts the suitable refractive index and the silicon nitride film of thickness, and solar cell is significantly reduced reflection of light, thereby improves the photoelectric conversion rate of solar cell.
2) surface passivation effect.Silicon nitride film can reduce the outstanding key of silicon face, thereby plays certain surface passivation effect.Particularly in silicon nitride deposition and follow-up sintering/annealing process, the hydrogen release in the silicon nitride is come out, and the outstanding bond of part hydrogen and silicon face is closed, thus the interface state density of minimizing silicon/silicon nitride.Because the surface passivation of silicon nitride, the surface recombination of solar cell reduces, and battery performance makes moderate progress.
3) body passivation.For polysilicon solar cell, there is a large amount of crystal boundaries in the cell body.These crystal boundaries have negative effect to battery performance.In sintering/annealing process, the hydrogen release in the silicon nitride is come out, and the part hydrogen molecule transfers hydrogen atom or hydrogen-double-void to by mode such as combine with room in the silicon, diffuses in the polysilicon body.Outstanding key on hydrogen and the crystal boundary or other defective, the impurity in the cell body combine, and can play the effect of passivation crystal boundary, defective or impurity.The body passivation of silicon nitride has important effect to polysilicon solar cell, can obviously improve the minority carrier lifetime of polycrystal silicon cell, thereby improves battery efficiency.For monocrystaline silicon solar cell, the defect and impurity of the hydrogen in the silicon nitride in also can passivation, this point is particularly important to the low monocrystalline silicon battery of quality of materials.
The desirable stoicheiometry of silicon nitride film is Si
3N
4The silicon nitride film component of practical application departs from desirable stoicheiometry sometimes, notes by abridging to be SiN
X, when X greater than 1.33 the time, rich nitrogen in the silicon nitride; X is less than 1.33 o'clock, Silicon-rich in the silicon nitride.Because hydrogeneous usually in the silicon nitride, note by abridging and be SiN
X: H.
The refractive index of silicon nitride film and film composition (being the silicon nitrogen ratio in the film) have much relations.Usually, the silicone content among the SiNx is high more, and then the refractive index of film is high more; Nitrogen content is high more, and then the refractive index of film is low more.In addition, whether film refractive index also with in film compactness extent, the film has oxygen impurities etc. relevant.When desirable stoicheiometry, the refractive index of silicon nitride film is 1.95～2.0.
The surface passivation performance of silicon nitride film also has much relations with film composition.The common high thin film passivation better effects if of silicone content.
Consider from antireflecting angle, concern that the best refractive index of silicon nitride is 2.3 if consider the refractive index match between air, encapsulating material (glass and EVA), the silicon materials.Consider that from the angle of surface passivation silicon nitride should be Silicon-rich, corresponding refractive index is more than 2.0.
But there is raise problems in terms of light absorption in the silicon nitride of Silicon-rich.After content exceeded stoichiometric(al) in the silicon nitride, the extinction coefficient of film was non-vanishing, therefore had certain light absorption.Silicone content is high more, and corresponding light absorption is also high more.This part has been lost fully by the light that silicon nitride film absorbs.Can reduce the efficient of solar cell.
Therefore, in common silicon solar cell, use nitrogenize film (refractive index 1.95～2.05) one-component, approaching desirable stoicheiometry.Though this film does not almost have optical absorption loss, the surface passivation performance is weak (surface recombination velocity doubles above than the silicon nitride film of Silicon-rich), and refractive index is also also imperfect.
Summary of the invention
The objective of the invention is to provide a kind of silicon solar battery antireflective thin film, and this film surface good passivation effect, optical absorption loss are less, possess good reflection preventing ability simultaneously.
The object of the present invention is achieved like this: this antireflection film is to deposit silicon-rich silicon nitride thin films at the silicon chip front surface, deposits on silicon-rich silicon nitride thin films near the stoichiometric(al) silicon nitride film.
Thickness 2 ~ 35 nanometers of silicon-rich silicon nitride thin films, chemical constituent are SiNx:H (0.9＜x＜1.33), and refractive index is 2.0 ~ 2.5.
Thickness near the stoichiometric(al) silicon nitride film is 35 ~ 75 nanometers, and chemical constituent is SiNx:H, (1.8＞x＞1.25), and refractive index is 1.8 ~ 2.05.
Also deposit the silicon nitride transition zone between silicon-rich silicon nitride thin films and the stoichiometric(al) silicon nitride film.
The thickness of silicon nitride transition zone is 2 ~ 75 nanometers, and refractive index is between silicon-rich silicon nitride thin films and the refractive index near the stoichiometric(al) silicon nitride film, and silicone content is also between silicon-rich silicon nitride thin films with between near the stoichiometric(al) silicon nitride film.
Silicon-rich silicon nitride thin films, silicon nitride transition zone and near gross thickness 65 ~ 90 nanometers of stoichiometric(al) silicon nitride film, silicone content reduces gradually.
Employed silicon chip is for finishing the monocrystalline silicon or the polysilicon chip of surface-texturing and diffusion system knot.Employed depositional mode can be a Chemical Physics deposition process arbitrarily such as PECVD, magnetron sputtering.
The present invention adopts the antireflection film of the silicon nitride of multilayer component difference or graded component as solar cell, wherein, adopts the silicon nitride film of Silicon-rich (refractive index height) at silicon/silicon nitride interface place, to improve the surface passivation effect of silicon nitride.On the nitrogenize film of Silicon-rich, the preparation component reduces optical absorption loss near the silicon nitride film of stoichiometric(al).
The present invention is because near the silicon nitride film content height of silicon chip surface, so surface passivation effect is better than the silicon nitride film near stoichiometric(al), and surface recombination velocity is lower more than one times than the silicon nitride film of normal proportioning.Simultaneously, the silicon nitride film of Silicon-rich is thinner, and the optical absorption loss that causes is less, only absorbs the short wavelength light of 20%～30% wavelength about 300 nanometers, and the centering longwave optical does not almost absorb.All the other silicon nitride film components almost do not have optical absorption loss near desirable stoicheiometry.In addition, adopt after the silicon nitride film of multilayer or graded index, the silicon nitride surface light reflection minimizing 2%～4% than single refractive index (refractive index is 1.9～2.1) also helps improving battery efficiency.
Embodiment
Embodiment one, adopts the different silicon nitride film of two layer components.The different silicon nitride film of front surface (diffusingsurface) deposition two layer components at described silicon chip.Depositional mode can adopt PECVD.Deposit silicon-rich silicon nitride thin films earlier, thickness 5 nanometers, chemical constituent are SiNx:H, X=0.9, and respective indices of refraction is 2.5.Deposition component is near the stoichiometric(al) silicon nitride film on described silicon-rich silicon nitride thin films then, and thickness 65 nanometers, chemical constituent are SiNx:H, X=1.33, and respective indices of refraction is 2.0.The thickness of above-mentioned bilayer film, the relation between the refractive index satisfy makes surface light reflect few principle of trying one's best.
Embodiment two, adopt the different silicon nitride film of two-layer above component.Wherein, the film of the high Silicon-rich of first depositing silicon content, thickness 10 nanometers, chemical constituent are SiNx:H, X=1.1, respective indices of refraction is 2.2.Deposit one deck silicon nitride transition zone then.Last deposition component is near the silicon nitride film of stoichiometric(al), and thickness 50 nanometers, chemical constituent are SiNx:H, X=1.8, and respective indices of refraction is 1.8.Described silicon nitride transition zone refractive index between the refractive index of orlop and the superiors' silicon nitride film, thickness 25 nanometers, silicone content is also between orlop and the superiors' silicon nitride film.Embodiment three, adopt the silicon nitride film of content gradually variational.The film chemical component that deposits earlier at silicon chip surface is SiNx:H, X=1.0, and respective indices of refraction is 2.4.Progressively increase nitrogen content in the film by the mode of X=1.01, X=1.02, x=1.03... then, respective indices of refraction also reduces.Chen Ji film chemical component is SiNx:H at last, X=1.4, and respective indices of refraction is 1.9.The gross thickness of above-mentioned film is 75 nanometers.
Regulate the concrete grammar (is example with PECVD) of chemical constituent in the film: the stoicheiometry (control film chemical proportioning has different modes, as regulate microwave power in microwave remote PECVD) that can control film by source gas (silane and ammonia) the air-flow ratio of regulating PECVD.When the air-flow of silane was higher, the film of deposition tended to Silicon-rich.During desire deposition silicon-rich silicon nitride thin films, by regulating parameters such as air-flow ratio, power, air pressure, depositing temperature and time, can obtain thickness 2 ~ 35 nanometers, chemical constituent is SiNx:H (0.9＜x＜1.33), and respective indices of refraction is 2.0 ~ 2.5 silicon nitride films.When desire deposits near the film of stoichiometric(al), can reduce the throughput of silane, at this moment Chen Ji silicon nitride tends to desirable stoicheiometry.The same parameters such as adjusting air-flow ratio, power, air pressure, depositing temperature and time of passing through can obtain thickness 35 ~ 75 nanometers, and chemical constituent is SiNx:H, 1.8＞x＞1.25, and respective indices of refraction is 1.8 ~ 2.05 silicon nitride film.
After the silicon nitride deposition was finished, silicon chip can become the crystal solar cell through prepared such as silk screen printing metal electrode, sintering.
Claims (6)
1. silicon solar battery antireflective thin film is characterized in that depositing at the silicon chip front surface silicon nitride film of Silicon-rich depositing the silicon nitride film near stoichiometric(al) on silicon-rich silicon nitride thin films.
2. silicon solar battery antireflective thin film according to claim 1 is characterized in that thickness 2～35 nanometers of silicon-rich silicon nitride thin films, and chemical constituent is SiNx:H, 0.9＜x＜1.33, and respective indices of refraction is 2.0～2.5.
3. silicon solar battery antireflective thin film according to claim 1 is characterized in that the thickness near the stoichiometric(al) silicon nitride film is 35～75 nanometers, and chemical constituent is SiNx:H, 1.8＞x＞1.25, and respective indices of refraction is 1.8～2.05.
4. silicon solar battery antireflective thin film according to claim 1 is characterized in that silicon-rich silicon nitride thin films and near also depositing the silicon nitride transition zone between the stoichiometric(al) silicon nitride film.
5. silicon solar battery antireflective thin film according to claim 4, the thickness that it is characterized in that the silicon nitride transition zone is 2～75 nanometers, refractive index is between silicon-rich silicon nitride thin films and the refractive index near the stoichiometric(al) silicon nitride film, and silicone content is also between silicon-rich silicon nitride thin films with between near the stoichiometric(al) silicon nitride film.
6. silicon solar battery antireflective thin film according to claim 4 is characterized in that gross thickness 65～90 nanometers of silicon-rich silicon nitride thin films, silicon nitride transition zone and stoichiometric(al) silicon nitride film, and each layer silicone content reduces gradually.
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| CN101533861B (en) * | 2009-03-18 | 2010-05-12 | 厦门市三安光电科技有限公司 | Three-layer antireflective film for solar battery and preparation method thereof |
| CN101866982A (en) * | 2010-05-11 | 2010-10-20 | 电子科技大学 | Method for surface regulation of silicon material for solar cells |
| CN102064237A (en) * | 2010-11-29 | 2011-05-18 | 奥特斯维能源（太仓）有限公司 | Double-layer passivating method for crystalline silicon solar battery |
| CN102071407A (en) * | 2011-01-25 | 2011-05-25 | 山东舜亦新能源有限公司 | Method for forming anti-reflecting film on PN junction silicon chip |
| WO2011091587A1 (en) * | 2010-01-27 | 2011-08-04 | Xu Zhen | Solar cell apparatus having light-modulating function |
| CN102185006A (en) * | 2010-11-11 | 2011-09-14 | 江阴浚鑫科技有限公司 | Method for preparing antireflective film of polycrystalline silicon solar cell as well as polycrystalline silicon solar cell |
| CN102222733A (en) * | 2011-07-01 | 2011-10-19 | 宁波尤利卡太阳能科技发展有限公司 | Preparation method of double-layer silicon nitride anti-reflecting film |
| CN102222718A (en) * | 2010-04-19 | 2011-10-19 | 浙江索日光电科技有限公司 | Film coating process for solar cell slice |
| CN102299185A (en) * | 2010-06-24 | 2011-12-28 | 北京北方微电子基地设备工艺研究中心有限责任公司 | Solar cell structure and preparation method thereof |
| CN102492936A (en) * | 2011-12-23 | 2012-06-13 | 保定天威英利新能源有限公司 | Method for depositing antireflection film |
| CN102534547A (en) * | 2011-12-16 | 2012-07-04 | 合肥晶澳太阳能科技有限公司 | Preparation process for gradient antireflection silicon nitride thin film of crystalline silicon solar cell |
| CN101989623B (en) * | 2009-08-07 | 2012-09-26 | 比亚迪股份有限公司 | Solar battery reducing reflection coating and preparation method thereof |
| CN102723371A (en) * | 2012-06-29 | 2012-10-10 | 苏州嘉言能源设备有限公司 | Antireflection film for trough type solar collector tube |
| CN103022254A (en) * | 2012-12-21 | 2013-04-03 | 浙江正泰太阳能科技有限公司 | Graduated-refractive-index antireflection-film solar cell and preparation method thereof |
| CN103132084A (en) * | 2011-11-29 | 2013-06-05 | 中国科学院苏州纳米技术与纳米仿生研究所 | Preparation method of high refractive index semiconductor surface anti-reflection passivation composite structure |
| CN103165685A (en) * | 2011-12-13 | 2013-06-19 | 三星Sdi株式会社 | Photovoltaic device and method of manufacturing the same |
| CN103928536A (en) * | 2014-04-25 | 2014-07-16 | 中利腾晖光伏科技有限公司 | Electric potential induced attenuation prevention crystalline silicon battery and preparation method thereof |
| CN103985781A (en) * | 2013-02-07 | 2014-08-13 | 大日本网屏制造株式会社 | Crystalline silicon solar cell and manufacture method thereof |
| CN103981508A (en) * | 2014-04-25 | 2014-08-13 | 武汉新芯集成电路制造有限公司 | Silicon oxynitride gradient anti-reflection thin film and preparation process thereof |
| CN104051572A (en) * | 2014-06-09 | 2014-09-17 | 山东力诺太阳能电力股份有限公司 | High-temperature annealing method for silicon nitride film |
| CN104241402A (en) * | 2013-06-20 | 2014-12-24 | 晶科能源有限公司 | Solar cell antireflection film and manufacturing method thereof |
| CN104409338A (en) * | 2014-11-14 | 2015-03-11 | 英利集团有限公司 | Solar cell and manufacturing method of silicon nitride film and solar cell |
| CN104952978A (en) * | 2015-05-26 | 2015-09-30 | 江苏荣马新能源有限公司 | Solar cell coating technology |
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-
2007
- 2007-02-09 CN CN 200710019794 patent/CN101022135A/en active Pending
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| CN101533861B (en) * | 2009-03-18 | 2010-05-12 | 厦门市三安光电科技有限公司 | Three-layer antireflective film for solar battery and preparation method thereof |
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| CN107154437A (en) * | 2017-06-30 | 2017-09-12 | 国家电投集团西安太阳能电力有限公司 | The preparation method of solar battery antireflective film |
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| CN110416363A (en) * | 2019-08-07 | 2019-11-05 | 山西潞安太阳能科技有限责任公司 | A kind of matching alkali throws the front passivation technology of selective emitter |
| CN110416363B (en) * | 2019-08-07 | 2020-12-22 | 山西潞安太阳能科技有限责任公司 | Front passivation technology matched with alkali polishing selectivity emitter |
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