CN102534547A - Preparation process for gradient antireflection silicon nitride thin film of crystalline silicon solar cell - Google Patents
Preparation process for gradient antireflection silicon nitride thin film of crystalline silicon solar cell Download PDFInfo
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Abstract
The invention discloses a preparation process for a gradient antireflection silicon nitride thin film of a crystalline silicon solar cell. A phosphorus-diffused crystalline silicon chip is selected, and different microwave powers, different temperatures and different gas flow ratios are set in the heading direction of the silicon chip by adopting a plasma enhanced chemical vapor deposition (PECVD) process, so that the gradient antireflection silicon nitride thin film is formed, and the refractivity of the thin film is sequentially decreased from bottom to top, but does not have a remarkable boundary. The silicon nitride thin film prepared by the process has high gradient silicon nitride bottom layer refractivity, and directly contacts the surface of the silicon chip to achieve a good passivation effect; the silicon nitride thin film with the high bottom layer refractivity is thin, so that light absorption loss is low, and influence on the conversion efficiency of the crystalline silicon solar cell is low; and due to the adoption of the silicon nitride thin film with gradient refractivity, the reflection of light is reduced, an antireflection effect is improved, and the conversion efficiency of the crystalline silicon solar cell can be improved.
Description
Technical field
The invention belongs to technical field of solar cells, be specifically related to a kind of gradual change antireflective silicon nitride film preparation technology of crystal-silicon solar cell.
Background technology
A kind of scheme that improves the crystal silicon solar energy battery efficiency of conversion is reflectivity that reduces silicon chip surface and the passivation effect that increases the surface.As shown in Figure 1, the commercialization solar cell adopts the PECVD mode to deposit one deck silicon nitride film at present, because be rich in the H+ key in this silicon nitride, uses SiN again
X: H representes, can play and reduce reflectivity and the effect that increases passivation effect.Simultaneously, SiN
X: H contains positive charge, can push the minority carrier hole in the diffusion layer to the PN junction direction, has good passivation effect.
Consider when solar cell uses need be encapsulated in the packaged materials such as glass or EVA that best specific refractory power reaches best anti-reflective effect when 2.3 left and right sides, specific refractory power can reach good passivation effect 2.0 when above.But the silicon nitride of high refractive index can cause serious extinction loss, can reduce outward current on the contrary, makes the efficiency of conversion step-down.The individual layer SiN that adopts at present
X: the H film can't solve this contradiction, can only compromise and choose optimum point.
Summary of the invention
The object of the present invention is to provide a kind of preparation technology of gradual change antireflective silicon nitride film of crystal-silicon solar cell; It is little that the film that adopts this prepared to obtain has the extinction loss; Surface passivation effect is good; Have good anti-reflective effect simultaneously, can improve the efficiency of conversion of crystal silicon solar energy battery.
Above-mentioned purpose of the present invention realizes through following technical scheme: a kind of preparation technology of gradual change antireflective silicon nitride film of crystal-silicon solar cell; Choose the crystal silicon chip after the phosphorous diffusion; Adopt pecvd process on the silicon chip direct of travel, to set different microwave power, temperature and gas flow ratio, thereby form the gradual change silicon nitride antireflective coating that reduces successively of specific refractory power from down to up.
Gas according to the invention is silane and ammonia, and the throughput ratio of said silane and ammonia is 1:1 ~ 7.
Microwave power according to the invention is 2000 ~ 4000w.
Temperature according to the invention is 400 ~ 500 ℃.
As of the present invention preferred embodiment a kind of: set among the present invention microwave power in 2000 ~ 4000w scope in arbitrary value and arbitrary value of temperature in 400 ~ 500 ℃ of scopes maintenance constant; The throughput ratio that adopts pecvd process on the silicon chip direct of travel, to adjust silane and ammonia progressively increases; As from 1:1 ~ 1:7 etc., thus form one from down to up specific refractory power reduce successively but do not have the gradual change silicon nitride antireflective coating of obvious boundary.
Wherein the throughput ratio of silane and ammonia mainly influences the specific refractory power of antireflective coating, and the content of silane is high more, and specific refractory power is big more, and microwave power mainly influences the thickness of antireflective coating, and microwave power is big more, and thickness is thick more.
As a kind of preferred implementation of the present invention: the arbitrary value of design temperature in above-mentioned 400 ~ 500 ℃ of scopes keeps constant; Adopting pecvd process on the silicon chip direct of travel, to adjust microwave power progressively increases; As from 2000w to 4000w etc.; The throughput ratio of adjusting silane and ammonia simultaneously progressively increases, as from 1:1 ~ 1:7 etc., thereby form one from down to up specific refractory power reduce successively but do not have the gradual change silicon nitride antireflective coating of obvious boundary.
Other operations such as the surface-texturing of preparation sun power, phosphorous diffusion, adopt silk screen printing aluminium paste and silver slurry, positive silk screen printing silver slurry, sintering to form metallic contact, the mode that testing, sorting etc. can adopt those skilled in that art to know at the silicon chip back side.
As as one embodiment of the present invention, the preparation technology of the gradual change antireflective silicon nitride film of crystal-silicon solar cell provided by the invention contains following steps:
(1) chooses silicon substrate, remove the affected layer of silicon chip surface, clean after the making herbs into wool;
(2) at POCl
3Carry out phosphorous diffusion in the atmosphere and form the n+ diffusion layer;
(3) carry out dry method or wet edge etching, remove phosphorosilicate glass;
(4) adopt online pecvd process on the silicon chip direct of travel, to set different microwave power and gas flow ratio, thus form one from down to up specific refractory power reduce successively but do not have the gradual change silicon nitride antireflective coating of obvious boundary;
(5) use silk screen printing aluminium paste and silver slurry at the silicon chip back side, and at positive silk screen printing silver slurry;
(6) sintering forms metallic contact;
(7) testing, sorting.
Compared with prior art, the present invention has following beneficial effect:
(1) silicon nitride film of bottom high refractive index directly contacts silicon chip surface, forms good passivation effect;
(2) silicon nitride film layer of bottom high refractive index is thinner, and the extinction loss is less, and is less to the efficiency of conversion influence of solar cell;
(3) adopt the just silicon nitride film of gradually changed refractive index, reduced reflection of light, improved anti-reflective effect, the efficiency of conversion that helps solar cell promotes.
Description of drawings
Fig. 1 is a commercialization crystal-silicon solar cell structural representation;
Fig. 2 is the crystal silicon solar energy battery structural representation that contains the application's gradual change silicon nitride film;
Fig. 3 is the synoptic diagram that carries out plated film that adopts Roth&Rau plate P 3200+ among the embodiment 1-4, wherein 1, heating unit; 2, graphite frame (being used to adorn crystal silicon chip); 3, silica tube.
Embodiment
The present invention will be described below to enumerate specific embodiment.It is pointed out that following examples only are used for the present invention is described further, do not represent protection scope of the present invention, nonessential modification and adjustment that other people prompting according to the present invention is made still belong to protection scope of the present invention.
Embodiment 1
The gradual change antireflective silicon nitride film preparation technology of the crystal silicon solar energy battery that present embodiment provides is following
:Adopt the P mold base, form n through phosphorous diffusion
+Diffusion layer, utilizing Roth&Rau plate P 3200+ equipment (its part-structure descends together as shown in Figure 3) to adopt the pecvd process setting power is 3500W; 450 ℃ of temperature, air pressure are 226Pa, and first and second root silica tube silane and ammonia flow compare 1:2; Third and fourth root silica tube silane and ammonia flow be than being 1:4, the 5th, six roots of sensation silica tube silane and ammonia flow be than being 1:6, deposition one deck specific refractory power gradual change silicon nitride antireflective coating from high to low; As shown in Figure 2, on the silicon chip back side, adopt silk screen printing aluminium paste and silver slurry again, at positive silk screen printing silver slurry; Form metallic contact through sintering, carry out testing, sorting at last and get final product.
The specific refractory power of the gradual change silicon nitride antireflective coating that obtains of mode (as shown in Figure 2, down with) is respectively 2.4,2.18,2.04 from down to up like this, and thickness is respectively 26nm, 27nm, 29nm; Silicon nitride antireflective coating (as shown in fig. 1, the down together) specific refractory power that adopts common process to obtain is 2.06, thickness 80nm; The rete of gradual change silicon nitride antireflective coating bottom high refractive index plays good passivation effect; Because the thickness that it is thin can effectively reduce the extinction loss of silicon nitride, the rete of different refractivity stack simultaneously; Can reduce reflection of light, improve anti-reflective effect.
The gradual change antireflective silicon nitride film preparation technology of the crystal silicon solar energy battery that present embodiment provides is following
:Adopt the P mold base, form n through phosphorous diffusion
+Diffusion layer utilizes Roth&Rau plate P 3200+ equipment to adopt 430 ℃ of pecvd process design temperatures, and air pressure is 239Pa; First silica tube power be 2900W, silane and ammonia flow than 1:2, second silica tube power be 2900W, silane and ammonia flow than being 1:3, the 3rd silica tube power is that 3000W, silane and ammonia flow are than being 1:4; The 4th silica tube power is that 3000W, silane and ammonia flow are than being 1:5; The 5th silica tube power is that 3100W, silane and ammonia flow ratio are 1:6, and six roots of sensation silica tube power is that 3100W, silane and ammonia flow are than being 1:7, deposition one deck specific refractory power gradual change silicon nitride antireflective coating from high to low; On the silicon chip back side, adopt silk screen printing aluminium paste and silver slurry again; At positive silk screen printing silver slurry, form metallic contact through sintering, carry out testing, sorting at last and get final product.
The specific refractory power of the gradual change silicon nitride antireflective coating that obtains of mode is respectively 2.4,2.3,2.18,2.1,2.04,2 from down to up like this; Thickness is respectively 12nm, 12nm, 14nm, 14nm, 15nm, 15nm, and the silicon nitride antireflective coating specific refractory power that obtains according to common process is 2.06, thickness 80nm; The rete of gradual change silicon nitride antireflective coating bottom high refractive index plays good passivation effect; Because the thickness that it is thin can effectively reduce the extinction loss of silicon nitride, the rete of different refractivity stack simultaneously; Can reduce reflection of light, improve anti-reflective effect.
The gradual change antireflective silicon nitride film preparation technology of the crystal silicon solar energy battery that present embodiment provides is following
:Adopt the N mold base, form n through phosphorous diffusion
+Diffusion layer; Utilize Roth&Rau plate P 3200+ equipment to adopt 400 ℃ of pecvd process design temperatures, air pressure is 239Pa, and first silica tube power is that 2900W, silane and ammonia flow compare 1:2; Second silica tube power is that 2900W, silane and ammonia flow are than being 1:3; The 3rd silica tube power is that 3000W, silane and ammonia flow ratio are 1:4, and the 4th silica tube power is that 3000W, silane and ammonia flow ratio are 1:5, and the 5th silica tube power is that 4000W, silane and ammonia flow are than being 1:6; Six roots of sensation silica tube power is that 4000W, silane and ammonia flow are than being 1:7; Deposition one deck specific refractory power gradual change silicon nitride antireflective coating from high to low republishes aluminium paste and forms metallic contact with the silver slurry through sintering, carries out testing, sorting at last and gets final product.
The specific refractory power of the gradual change silicon nitride antireflective coating that obtains of mode is respectively 2.4,2.3,2.18,2.1,2.04,2 from down to up like this; Thickness is respectively 12nm, 12nm, 14nm, 14nm, 18nm, 18nm, and the silicon nitride antireflective coating specific refractory power that obtains according to common process is 2.06, thickness 80nm; The rete of gradual change silicon nitride antireflective coating bottom high refractive index plays good passivation effect; Because the thickness that it is thin can effectively reduce the extinction loss of silicon nitride, the rete of different refractivity stack simultaneously; Can reduce reflection of light, improve anti-reflective effect.
Embodiment 4
The gradual change antireflective silicon nitride film preparation technology of the crystal silicon solar energy battery that present embodiment provides is following
:Adopt the N mold base, form n through phosphorous diffusion
+Diffusion layer utilizes Roth&Rau plate P 3200+ equipment to adopt 500 ℃ of pecvd process design temperatures, and air pressure is 239Pa; First silica tube power is that 2000W, silane and ammonia flow compare 1:2; Second silica tube power is that 2000W, silane and ammonia flow ratio are 1:3, and the 3rd silica tube power is that 3000W, silane and ammonia flow ratio are 1:4, and the 4th silica tube power is that 3000W, silane and ammonia flow are than being 1:5; The 5th silica tube power is that 3100W, silane and ammonia flow are than being 1:6; Six roots of sensation silica tube power is that 3100W, silane and ammonia flow ratio are 1:7, and deposition one deck specific refractory power gradual change silicon nitride antireflective coating from high to low republishes aluminium paste and starches with silver; Form metallic contact through sintering, carry out testing, sorting at last and get final product.
The specific refractory power of the gradual change silicon nitride antireflective coating that obtains of mode is respectively 2.4,2.3,2.18,2.1,2.04,2 from down to up like this; Thickness is respectively 9nm, 9nm, 14nm, 14nm, 15nm, 15nm, and the silicon nitride antireflective coating specific refractory power that obtains according to common process is 2.06, thickness 80nm; The rete of gradual change silicon nitride antireflective coating bottom high refractive index plays good passivation effect; Because the thickness that it is thin can effectively reduce the extinction loss of silicon nitride, the rete of different refractivity stack simultaneously; Can reduce reflection of light, improve anti-reflective effect.
The present invention will be described more than to enumerate specific embodiment.It is pointed out that the foregoing description only is used for the present invention is described further, do not represent protection scope of the present invention, nonessential modification and adjustment that other people prompting according to the present invention is made still belong to protection scope of the present invention.
Claims (6)
1. the preparation technology of the gradual change antireflective silicon nitride film of a crystal-silicon solar cell; It is characterized in that: choose the crystal silicon chip after the phosphorous diffusion; Adopt pecvd process on the silicon chip direct of travel, to set different microwave powers, temperature and gas flow ratio parameter, thus form one from down to up specific refractory power reduce successively but do not have the gradual change silicon nitride antireflective coating of obvious boundary.
2. the preparation technology of the gradual change antireflective silicon nitride film of crystal-silicon solar cell according to claim 1, it is characterized in that: said gas is silane and ammonia, the throughput ratio of said silane and ammonia is 1:1 ~ 7.
3. the preparation technology of the gradual change antireflective silicon nitride film of crystal-silicon solar cell according to claim 1 and 2, it is characterized in that: said microwave power is 2000 ~ 4000w.
4. the preparation technology of the gradual change antireflective silicon nitride film of crystal-silicon solar cell according to claim 3, it is characterized in that: said temperature is 400 ~ 500 ℃.
5. the preparation technology of the gradual change antireflective silicon nitride film of solar cell according to claim 4; It is characterized in that: set microwave power and homo(io)thermism; The throughput ratio that adopts pecvd process on the silicon chip direct of travel, to adjust silane and ammonia progressively increases, thus form one from down to up specific refractory power reduce successively but do not have the gradual change silicon nitride antireflective coating of obvious boundary.
6. the preparation technology of the gradual change antireflective silicon nitride film of crystal-silicon solar cell according to claim 4; It is characterized in that: design temperature is constant; Adopting pecvd process on the silicon chip direct of travel, to adjust microwave power progressively increases; The throughput ratio of adjusting silane and ammonia simultaneously progressively increases, thus form one from down to up specific refractory power reduce successively but do not have the gradual change silicon nitride antireflective coating of obvious boundary.
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| CN103579379A (en) * | 2013-11-08 | 2014-02-12 | 英利集团有限公司 | Crystal silicon solar cell and manufacturing method thereof |
| 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 |
| CN104716085A (en) * | 2013-12-17 | 2015-06-17 | 中芯国际集成电路制造(上海)有限公司 | Semiconductor device and manufacturing method thereof |
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| 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 |
| CN103579379A (en) * | 2013-11-08 | 2014-02-12 | 英利集团有限公司 | Crystal silicon solar cell and manufacturing method thereof |
| CN103579379B (en) * | 2013-11-08 | 2016-08-17 | 英利集团有限公司 | Crystal silicon solar batteries and preparation method thereof |
| CN104716085B (en) * | 2013-12-17 | 2018-09-21 | 中芯国际集成电路制造(上海)有限公司 | A kind of semiconductor devices and its manufacturing method |
| CN104716085A (en) * | 2013-12-17 | 2015-06-17 | 中芯国际集成电路制造(上海)有限公司 | Semiconductor device and manufacturing method thereof |
| 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 |
| CN104952978A (en) * | 2015-05-26 | 2015-09-30 | 江苏荣马新能源有限公司 | Solar cell coating technology |
| 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 |
| CN107275190A (en) * | 2017-06-30 | 2017-10-20 | 韩华新能源（启东）有限公司 | A kind of method for preparing dual-layer silicon nitride film on a semiconductor substrate |
| CN107338424A (en) * | 2017-08-07 | 2017-11-10 | 苏州阿特斯阳光电力科技有限公司 | A kind of gas control method and equipment of PECVD plated films |
| CN107492576A (en) * | 2017-08-07 | 2017-12-19 | 苏州阿特斯阳光电力科技有限公司 | A kind of antireflective coating and polycrystalline silicon solar cell |
| CN107338424B (en) * | 2017-08-07 | 2020-03-03 | 苏州阿特斯阳光电力科技有限公司 | Gas control method and equipment for PECVD (plasma enhanced chemical vapor deposition) coating |
| CN109243969A (en) * | 2018-08-31 | 2019-01-18 | 常州亿晶光电科技有限公司 | Tubular type PECVD silicon nitride gradual change membrane process |
| CN109360866A (en) * | 2018-09-25 | 2019-02-19 | 韩华新能源（启东）有限公司 | A kind of preparation method of three layers of silicon nitride film |
| CN109360866B (en) * | 2018-09-25 | 2021-07-20 | 韩华新能源（启东）有限公司 | Preparation method of three-layer silicon nitride film |
| CN110391304A (en) * | 2019-07-02 | 2019-10-29 | 天津爱旭太阳能科技有限公司 | A kind of solar battery multilayer antireflective graded films and its preparation process |
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Application publication date: 20120704 |