CN105702749B - The polycrystalline multilayer passivated reflection reducing of high PID resistances penetrates film and preparation method thereof - Google Patents
The polycrystalline multilayer passivated reflection reducing of high PID resistances penetrates film and preparation method thereof Download PDFInfo
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- 230000001603 reducing effect Effects 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 229910004205 SiNX Inorganic materials 0.000 claims abstract description 45
- 230000003287 optical effect Effects 0.000 claims abstract description 25
- 238000005457 optimization Methods 0.000 claims abstract description 25
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 21
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000001301 oxygen Substances 0.000 claims abstract description 15
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 15
- 229910021420 polycrystalline silicon Inorganic materials 0.000 claims abstract description 15
- 238000005530 etching Methods 0.000 claims abstract description 14
- 229920005591 polysilicon Polymers 0.000 claims abstract description 14
- 229910020286 SiOxNy Inorganic materials 0.000 claims abstract description 13
- 239000007789 gas Substances 0.000 claims abstract description 11
- 230000008569 process Effects 0.000 claims abstract description 9
- 239000000758 substrate Substances 0.000 claims abstract description 5
- 208000002925 dental caries Diseases 0.000 claims description 5
- 238000000151 deposition Methods 0.000 claims description 4
- 238000007747 plating Methods 0.000 claims description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 2
- 230000003247 decreasing effect Effects 0.000 claims description 2
- 238000012545 processing Methods 0.000 claims description 2
- 229910021419 crystalline silicon Inorganic materials 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 94
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 13
- 229910052710 silicon Inorganic materials 0.000 description 13
- 239000010703 silicon Substances 0.000 description 13
- 238000002161 passivation Methods 0.000 description 9
- 230000000694 effects Effects 0.000 description 7
- 239000006117 anti-reflective coating Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 238000002310 reflectometry Methods 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 229910052814 silicon oxide Inorganic materials 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 230000009466 transformation Effects 0.000 description 4
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000006698 induction Effects 0.000 description 3
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 235000008216 herbs Nutrition 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- 210000002268 wool Anatomy 0.000 description 2
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 230000003667 anti-reflective effect Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 235000013842 nitrous oxide Nutrition 0.000 description 1
- -1 refractive index 2.2 Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 230000005641 tunneling Effects 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- 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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- H01L31/02—Details
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- 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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- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
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Abstract
The present invention relates to a kind of polycrystalline multilayer passivated reflection reducing of high PID resistances to penetrate film and preparation method thereof, after entering PECVD bodies of heater including polysilicon chip after etching, after first leading to the oxygen-containing gas such as oxygen or air, redeposited multilayer passivated reflection reducing penetrates film layer, the bottom SiN that polysilicon chip substrate front surface is set gradually from bottom to top and refractive index is successively decreasedxLayer, intermediate layer SiNxLayer, single or multiple lift optical optimization layer SiNxLayer and top layer optical optimization layer SiOxNyLayer；Its total film thickness is 70~135nm, and total refractive index is 1.95~2.20.The present invention is based on conventional multi-crystalline silicon battery process, and the preparation method and passivated reflection reducing when only changing PECVD penetrate the film quality structure of film, can be compatible with conventional crystalline silicon battery process, can be produced after being transformed directly using common etching apparatus and PECVD device or slightly.
Description
Technical field
The present invention relates to solar energy crystal silicon battery manufacturing field, the polycrystalline multilayer passivation of especially a kind of high PID resistances subtracts
Reflectance coating and preparation method thereof.
Background technology
As environmental problem and energy problem obtain the concern of more and more people, solar cell as a kind of clean energy resource,
People research and develop to it has had been introduced into a new stage.PID (potential induced degradation) is imitated
It should refer under long-term action of high voltage, leaky in component between glass and encapsulating material be present, cause surface passivation before this
Antireflective coating fails, and then PN junction fails, and finally assembly property is reduced.The p-type solar energy crystal silicon component of traditional handicraft is all
In the presence of certain PID Problem of Failure, so research PID phenomenons, the solar cell for developing PID Free is vast solar energy factory
One of target of business research and development department and part research institutions.More general and stricter at present is that double 85PID are tested, its test condition
For 1000V negative voltage, 85 DEG C of environment temperature, 85% humidity, 96h testing time, the final peak power output of component
Attenuation ratio, which is less than 5%, can be determined as PID test passes, i.e. PID Free.
The SiNx passivated reflection reducings of traditional solar energy polycrystal battery surface penetrate film layer nearly all because refractive index is relatively low so that PID declines
Subtract more serious；Existing market is in order to pursue PID Free, and main method is to improve the refractive index of SiNx film layers, but battery is changed
The more conventional technique of efficiency reduces 1-2%；Also method is exactly the ozone O generated using ultraviolet ionization, high frequency ozone generator3Oxygen
Change silicon chip surface, generate relatively thin SiOxLayer uses laughing gas N2OPECVD methods directly deposit one layer of SiO in silicon chip surfacexFilm,
Make battery that there is certain PID resistances.
On the other hand, the conventional antireflective coating of polycrystalline battery surface is mostly two to three layers of nitridation in large-scale production at present
Silicon, its usual optical thickness are a quarter or half of specific wavelength.For single-layer silicon nitride silicon antireflective coating, its
Only there is preferable anti-reflective effect to single wavelength, there is of a relatively high reflectivity and poor passivation effect.It can drop
Antiradar reflectivity and improve passivation effect antireflective coating be solar cell research focus.
The content of the invention
The technical problem to be solved in the present invention is：It is proposed a kind of polycrystalline multilayer passivated reflection reducing of high PID resistances penetrate film and its
Preparation method, this method need not use ozone devices or other method, and silicon chip top layer specially increases SiOx layers after etching,
After directly being transformed using common etching apparatus and PECVD device or slightly.Passivated reflection reducing prepared by this method penetrates film can
Reflectivity is reduced, improves passivation effect, improves efficiency of solar cell, and there is very excellent anti-PID attenuation characteristics.
The technical solution adopted in the present invention is：A kind of polycrystalline multilayer passivated reflection reducing of high PID resistances penetrates film, is included in more
The bottom SiN that crystal silicon chip substrate front surface is set gradually from bottom to topxLayer, intermediate layer SiNxLayer, single or multiple lift optical optimization layer
SiNxLayer and top layer optical optimization layer SiOxNyLayer；Described bottom SiNxLayer, intermediate layer SiNxLayer, single or multiple lift optics are excellent
Change layer SiNxLayer and top layer optical optimization layer SiOxNyThe refractive index of layer is successively decreased；Described bottom SiNxLayer, intermediate layer SiNxLayer,
Single or multiple lift optical optimization layer SiNxLayer and top layer optical optimization layer SiOxNyThe total film thickness of layer is 70~135nm, total refraction
Rate is 1.95~2.20.
Further, bottom SiN of the present inventionxLayer, intermediate layer SiNxLayer and single or multiple lift optical optimization layer
SiNxLayer is prepared using PECVD；Described bottom SiNxThe refractive index of layer is 2.15~2.35, and thickness is 4~15nm；Institute
The intermediate layer SiN statedxThe refractive index of layer is 2.10~2.30, and thickness is 10~25nm；Described single or multiple lift optical optimization
Layer SiNxThe refractive index of layer is 1.95~2.25, and thickness is 20~65nm.
Further say, top layer optical optimization layer SiO of the present inventionxNyLayer using PECVD by oxygen-containing gas with
SiH4、NH3Deposition forms together；Its thickness is 15~60nm, and refractive index is 1.6~1.95.
Meanwhile present invention also offers the preparation method that a kind of polycrystalline multilayer passivated reflection reducing of high PID resistances penetrates film, including
Following steps：
1) performed etching after the processing of polysilicon chip common process；
2) polysilicon chip is sent into the PECVD cavitys 300 DEG C to 550 DEG C by carrier after etching, and is passed through oxygen-containing gas
3min to 20min；
3) film is penetrated using PECVD device plating multilayer passivated reflection reducing；Be included in polysilicon chip substrate front surface from bottom to top according to
The bottom SiN of secondary settingxLayer, intermediate layer SiNxLayer, single or multiple lift optical optimization layer SiNxLayer and top layer optical optimization layer
SiOxNyLayer；
4) using conventional batteries typography printing back electrode, Al-BSF, positive grid line and positive electrode, and sinter.
The present invention principle be：Polysilicon chip enters in the PECVD cavitys between 300 DEG C to 550 DEG C after etching, is passed through oxygen
For the oxygen-containing gas such as gas or air with after certain time, silicon chip surface grown a thin layer of hot SiO2Layer, the SiOx layers relatively cause
It is close, there is preferable passivation effect, can effectively reduce the recombination-rate surface of cell piece；And the fine and close relatively thin (0.1nm- of SiOx layers
2nm), clearly, a part of electric charge that can be enriched with battery surface guides from preventing because of electric charge heap the tunneling effect of electronics
Product potential induction attenuation (PID) caused by battery surface, makes battery have anti-PID attenuation characteristics.
Multilayer passivated reflection reducing penetrates the SiN of film bottom high index of refractionxThe introducing of layer can both strengthen film layer passivation effect, again may be used
With the free positively charged ion in effective barrier assembly, the anti-PID attenuation characteristics of battery are effectively improved；According to certain rules successively
Reduce multilayer SiNxThe reflectivity of cell piece side to light, Neng Gouyou can also be greatly reduced in layer while having certain PID resistances
Effect reduces the reflectivity of intermediate waves wave band, improves the short circuit current of cell piece；In conjunction with the SiO of top layer low-refractionxNyLayer, makes
Overall film layer refractive index it is lower, continue increase incident ray ratio, improve short circuit current, and cell piece lamination after color compared with
Secretly, overall uniform colorless is poor.The polycrystalline multilayer film battery PID resistances prepared using this method are splendid, and the component of preparation can lead to
The PID tests crossed under the conditions of the non-resistance EVA of in the market double 85, and battery conversion efficiency is higher than the conventional PECVD coating process of tradition.
The beneficial effects of the invention are as follows：Based on conventional polysilicon battery process, only preparation method during change PECVD and passivation
The film quality structure of antireflective coating, can be compatible with conventional crystalline silicon battery process, directly using common etching apparatus and PECVD device or
It can be produced after slightly transforming.This method to equipment and polysilicon chip without particular/special requirement, be easily achieved and due to depositional coating before
The oxygen-containing gas such as oxygen or air are passed through, safety problem when being not in vent gas treatment, suitable for large-scale production, can also be transported
For some advanced battery process, such as：Carry on the back passivation cell, N-type double-side cell, MWT battery etc..
Brief description of the drawings
The present invention is further described with reference to the accompanying drawings and examples.
Fig. 1 is the structural representation of the present invention；
In figure：1st, bottom SiNx layer；2nd, intermediate layer SiNxLayer；3rd, single or multiple lift optical optimization layer SiNxLayer；4th, top layer light
Learn optimization layer SiOxNyLayer.
Embodiment
Presently in connection with accompanying drawing and preferred embodiment, the present invention is further detailed explanation.These accompanying drawings are simplified
Schematic diagram, only illustrate the basic structure of the present invention in a schematic way, therefore it only shows the composition relevant with the present invention.
A kind of polycrystalline multilayer passivated reflection reducing of high PID resistances as shown in Figure 1 penetrates membrane structure, is included in polysilicon chip substrate
The bottom SiN that front surface is set gradually from bottom to topxLayer 1, intermediate layer SiNxLayer 2, single or multiple lift optical optimization layer SiNxLayer 3
And top layer optical optimization layer SiOxNyLayer 4.These film layers from bottom to top successively decrease by refractive index, and its total film thickness is 70~135nm, always
Refractive index is 1.95~2.20.
It is further described below by two groups of embodiments：
Embodiment 1
1) original silicon chip is pre-processed, the pretreatment includes the techniques such as making herbs into wool, diffusion and the etching in battery process；
2) silicon chip is into being warming up to 500 DEG C after 380 DEG C of PECVD device after etching, first lead in PECVD cavitys oxygen or
The oxygen-containing gas such as air 15min；The multilayer that refractive index reduces successively according to certain rules is sequentially depositing on polysilicon chip surface again
SiNxLayer, wherein bottom SiNxLayer, refractive index 2.35, thicknesses of layers 10nm；Intermediate layer SiNxLayer, refractive index 2.2, film
Thickness degree is 20nm；Individual layer SiNxLayer, refractive index 2.10, thicknesses of layers 30nm；It is surplus in diffusingsurface plating using PECVD device
Remaining SiOxNyLayer, refractive index 1.75, thicknesses of layers 30nm；
4) using conventional batteries typography printing back electrode, Al-BSF, positive grid line and positive electrode, and sinter.
Found by detection, the photoelectric transformation efficiency for the solar battery sheet that the present embodiment obtains increases and PID resistances have
Larger lifting.Specific data see the table below 1：
The photoelectric transformation efficiency and PID for the solar cell that the present embodiment of table 1 obtains
As can be seen from Table 1：Double-layer reflection reducing coating process efficiency gain 0.11% prepared by this method, mainly due to short circuit
50 milliamperes of current gain, filling FF increases by 0.05；Double 85 condition PID (potential induction attenuation) power attenuations in 96 hours only have simultaneously
1.3%, PID decays to 2.8% within 192 hours.
Embodiment 2
1) original silicon chip is pre-processed, the pretreatment includes the techniques such as making herbs into wool, diffusion and the etching in battery process；
2) silicon chip is into being warming up to 550 DEG C after 380 DEG C of PECVD device after etching, first lead in PECVD cavitys oxygen or
The oxygen-containing gas such as air 5min；The multilayer SiN that refractive index reduces successively according to certain rules is sequentially depositing on polysilicon chip surface againx
Layer, wherein bottom SiNxLayer, refractive index 2.4, thicknesses of layers 8nm；Intermediate layer SiNxLayer, refractive index 2.20, thicknesses of layers
For 15nm；Individual layer SiNxLayer, refractive index 2.05, thicknesses of layers 30nm；Using PECVD device residue is plated in diffusingsurface
SiOxNyLayer, refractive index 1.75, thicknesses of layers 40nm；
4) using conventional batteries typography printing back electrode, Al-BSF, positive grid line and positive electrode, and sinter.
Found by detection, the photoelectric transformation efficiency for the solar battery sheet that the present embodiment obtains increases and PID resistances have
Larger lifting.Specific data see the table below 2：
The photoelectric transformation efficiency and PID for the solar cell that the present embodiment of table 2 obtains
As can be seen from Table 1：Double-layer reflection reducing coating process efficiency gain 0.18% prepared by this method, mainly due to short circuit
80 milliamperes of current gain, filling FF increases by 0.05；PID (potential induction attenuation) power attenuation in 96 hours simultaneously only has 0.7%,
192 hours PID decay to 2.8%, and battery PID pad values are very low.
The embodiment of the simply present invention described in description above, various illustrations are not to the reality of the present invention
Matter Composition of contents limits, and person of an ordinary skill in the technical field can be to described in the past specific after specification has been read
Embodiment is made an amendment or deformed, without departing from the spirit and scope of the invention.
Claims (4)
1. a kind of polycrystalline multilayer passivated reflection reducing of high PID resistances penetrates the preparation method of film, it is characterised in that：Comprise the following steps：
1) performed etching after the processing of polysilicon chip common process；
2) polysilicon chip is sent into the PECVD cavitys 300 DEG C to 550 DEG C by carrier after etching, and is passed through oxygen-containing gas 3min
To 20min；
3) film is penetrated using PECVD device plating multilayer passivated reflection reducing；It is included in polysilicon chip substrate front surface to set successively from bottom to top
The bottom SiN putxLayer, intermediate layer SiNxLayer, single or multiple lift optical optimization layer SiNxLayer and top layer optical optimization layer SiOxNy
Layer；
4) using conventional batteries typography printing back electrode, Al-BSF, positive grid line and positive electrode, and sinter.
2. the polycrystalline multilayer passivated reflection reducing of high PID resistances as claimed in claim 1 penetrates the preparation method of film, it is characterised in that：
Described bottom SiNxLayer, intermediate layer SiNxLayer, single or multiple lift optical optimization layer SiNxLayer and top layer optical optimization layer
SiOxNyThe refractive index of layer is successively decreased；Described bottom SiNxLayer, intermediate layer SiNxLayer, single or multiple lift optical optimization layer SiNxLayer with
And top layer optical optimization layer SiOxNyThe total film thickness of layer is 70~135nm, and total refractive index is 1.95~2.20.
3. the polycrystalline multilayer passivated reflection reducing of high PID resistances as claimed in claim 1 penetrates the preparation method of film, it is characterised in that：
Described bottom SiNxLayer, intermediate layer SiNxLayer and single or multiple lift optical optimization layer SiNxLayer is prepared using PECVD；
Described bottom SiNxThe refractive index of layer is 2.15~2.35, and thickness is 4~15nm；Described intermediate layer SiNxThe refractive index of layer
For 2.10~2.30, thickness is 10~25nm；Described single or multiple lift optical optimization layer SiNxThe refractive index of layer for 1.95~
2.25, thickness is 20~65nm.
4. the polycrystalline multilayer passivated reflection reducing of high PID resistances as claimed in claim 1 penetrates the preparation method of film, it is characterised in that：
Described top layer optical optimization layer SiOxNyLayer uses PECVD by oxygen-containing gas and SiH4、NH3Deposition forms together；Its thickness
For 15~60nm, refractive index is 1.6~1.95.
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| CN102903764A (en) * | 2012-09-27 | 2013-01-30 | 东方电气集团(宜兴)迈吉太阳能科技有限公司 | Three-layered silicon nitride antireflective film of crystalline silicon solar cell and preparation method thereof |
| CN103794658A (en) * | 2014-01-27 | 2014-05-14 | 镇江大全太阳能有限公司 | Composite membrane efficient crystalline silicon solar cell and manufacturing method of composite membrane efficient crystalline silicon solar cell |
| CN104916710A (en) * | 2015-06-30 | 2015-09-16 | 江苏顺风光电科技有限公司 | High-efficiency polycrystalline multilayer passivation anti-reflection film structure with high PID resistance |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102903764A (en) * | 2012-09-27 | 2013-01-30 | 东方电气集团(宜兴)迈吉太阳能科技有限公司 | Three-layered silicon nitride antireflective film of crystalline silicon solar cell and preparation method thereof |
| CN103794658A (en) * | 2014-01-27 | 2014-05-14 | 镇江大全太阳能有限公司 | Composite membrane efficient crystalline silicon solar cell and manufacturing method of composite membrane efficient crystalline silicon solar cell |
| CN104916710A (en) * | 2015-06-30 | 2015-09-16 | 江苏顺风光电科技有限公司 | High-efficiency polycrystalline multilayer passivation anti-reflection film structure with high PID resistance |
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