CN103094366A - Solar cell passivation antireflection film and preparation technology and method thereof - Google Patents
Solar cell passivation antireflection film and preparation technology and method thereof Download PDFInfo
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Abstract
The invention discloses a solar cell passivation antireflection film and a preparation technology and a method of the solar cell passivation antireflection film. The preparation technology and the method utilize a plasma enhanced chemical vapor deposition (PECVD), a layer of silicon dioxide film is deposited on the surface of a silicon slice, then a silicon nitride layer with high refractive index is deposited on the prepared silicon dioxide film, and finally a silicon nitride layer with low refractive index is deposited on the silicon nitride layer with high refractive index. The technology and the method have the advantages of being convenient to operate, low in operation cost, good in passivation and good in antireflection performance for the cell surface. The passivation antireflection film prepared by the technology can obviously improve the open circuit voltage, short circuit current and the cell efficiency of the solar cell, compared with a traditional single-layer or double-layer silicon nitride film.
Description
Technical field
The invention belongs to the cell piece processing technology field in the solar cell piece course of processing, relate in particular to a kind of technique of the solar cell piece surface being carried out coating film treatment.
Background technology
Improve the efficient of crystal-silicon solar cell, should improve silicon base to sun Optical Absorption as far as possible, reduce the reflectivity of silicon chip surface, and in order to reach this purpose, form matte except silicon chip being carried out making herbs into wool, increase light outside the incident number of times of silicon chip surface, can also plate one or more layers antireflective coating at battery surface, the method for present industrial large-scale production is to adopt the silicon chip surface cvd nitride silicon thin film of tubular type PECVD equipment after diffusion.Silicon nitride film has two Main Functions: good anti-reflective effect, reduce the silicon chip surface reflectivity; In film abundant hydrogen ion can the passivated surface dangling bonds, the defect state such as crystal boundary, the complex centre of reducing non equilibrium carrier, thus reduce recombination-rate surface, improve open circuit voltage, the short circuit current of battery.
In the PECVD process, the refractive index of silicon nitride film, extinction coefficient and passivation effect are mainly decided by the content of silicon, increase along with silane contents in reacting gas, the refractive index of film increases, extinction coefficient increases, and more light can absorb and be difficult to arrive silicon face by tunicle, has reduced the short circuit current of battery, but passivation effect has strengthened, and has reduced the surface recombination probability; Otherwise if in reaction gas, ammonia level increases, the refractive index of film and extinction coefficient diminish, and passivation effect is relatively poor, and the front surface recombination rate increases, but the transmitance of light also increases.
So, factory generally adopts two-layer coating technique at present, internal layer adopts the high index of refraction silicon nitride layer to obtain good passivation effect, the outer low-refraction silicon nitride layer that adopts is to obtain high transmission rate, disclosing application number as Shanghai Suo Ri new forms of energy Science and Technology Ltd. is 201120425191.8 patent, at the double-layer silicon nitride of silicon chip surface plating internal layer high index of refraction, outer low-refraction.Yet, the reflectivity of silicon nitride anti-reflecting film is not also very low, conventional individual layer or double-layer reflection-decreasing layer all are difficult to reach good anti-reflective effect, membrane structure is more unreasonable, make the passivation effect of battery relatively poor, and in silicon nitride deposition process, the ammonia of generation and hydrogen ion have certain corrasion to silicon chip surface, can bring certain damage, make the efficient of final battery not high.
Summary of the invention
In order to solve above-mentioned deficiency of the prior art, the object of the present invention is to provide a kind of solar cell passivated reflection reducing to penetrate film, it improves open circuit voltage, short circuit current and the battery efficiency of solar cell more significantly than conventional monolayers or double-layer silicon nitride film.
Another object of the present invention is to provide a kind of solar cell passivated reflection reducing to penetrate the process of preparing of film, it is easy to operate, operating cost is low, can carry out well passivated and good reflection preventing ability to battery surface.
The object of the invention to solve the technical problems realizes by the following technical solutions.Penetrate film according to a kind of solar cell passivated reflection reducing that the present invention proposes, comprising: a silica coating that is deposited on silicon chip surface; Be deposited on the first higher silicon nitride layer of refractive index on described silica coating; And be deposited on the second lower silicon nitride layer of refractive index on described the first silicon nitride layer.
Solar cell passivated reflection reducing of the present invention is penetrated film, and the refractive index n of described silica coating is 1.3≤n≤1.7; The refractive index n of described the first silicon nitride layer is 2.0≤n≤2.5; Refractive index 1.5≤the n of described the second silicon nitride layer＜2.0.
In addition, the invention allows for a kind of solar cell passivated reflection reducing and penetrate the film preparation process, it adopts PECVD, at silicon chip surface deposition layer of silicon dioxide film, the first higher silicon nitride layer of deposition one deck refractive index on ready-made silicon dioxide film, deposit the second lower silicon nitride layer of one deck refractive index at last again on the high index of refraction silicon nitride layer again.
Solar cell passivated reflection reducing of the present invention is penetrated the film preparation process, and it comprises the following steps:
1) silicon chip after spreading is inserted on graphite boat;
2) oar on graphite boat enters the plated film boiler tube under guide rail drives, pass into reactant gas silane in pipe, and its flow is 100-1000sccm, CO
2Flow is 1-5slm, and the radio frequency source discharge makes the concurrent biochemistry of reacting gas ionization close reaction, thereby at silicon chip surface deposition one deck SiO
2Film;
3) deposit again the first higher silicon nitride layer of one deck refractive index on above-mentioned silica coating;
4) deposit again the second lower silicon nitride layer of one deck refractive index on the first higher silicon nitride layer of above-mentioned refractive index;
5) coating process finishes, and oar enters boiler tube graphite boat is withdrawed from, and takes out from boat with vacuum pencil afterwards until silicon chip is cooling.
Solar cell passivated reflection reducing of the present invention is penetrated the film preparation process, is to carry out in tubular type PECVD equipment boiler tube.
Solar cell passivated reflection reducing of the present invention is penetrated the film preparation process, and in step 1), two silicon chip diffusingsurfaces in each lattice of graphite boat are relative, and non-diffusingsurface abuts against on the battery lead plate of graphite boat.
Solar cell passivated reflection reducing of the present invention is penetrated the film preparation process, and the Temperature Setting of described boiler tube is at 450-550 ℃, and vacuum degree is the 1000-2000 millitorr, and radio frequency source power is 5000-7000W.
Solar cell passivated reflection reducing of the present invention is penetrated film preparation process, step 2) in, the plated film time is 100-200s, and the design thickness is at 3-20nm, and refractive index is 1.3-1.7.
Solar cell passivated reflection reducing of the present invention is penetrated the film preparation process, and in step 3), coating temperature is 400-500 ℃, vacuum degree is the 1000-2000 millitorr, radio frequency source power 5000-7000W, and silane flow rate is 700-1200sccm, ammonia flow is at 4.5-5.5slm, and the plated film time is 200-350s; The refractive index n of described the first silicon nitride layer is 2.0≤n≤2.5.
Solar cell passivated reflection reducing of the present invention is penetrated the film preparation process, and in step 4), coating temperature is 400-500 ℃, vacuum degree is the 1000-2000 millitorr, radio frequency source power 5000-7000W, and silane flow rate is 250-450sccm, ammonia flow is at 4.5-5.5slm, and the plated film time is 250-450s; Refractive index 1.5≤the n of described the second silicon nitride layer＜2.0.
By technique scheme, advantage and beneficial effect that the present invention has are as follows:
1, the present invention can further reduce the reflectivity of silicon chip surface, and the conventional sheet of the luminance factor between solar spectrum 300nm-1200nm is lower, makes the photoelectric conversion efficiency of battery be improved;
2, battery absorbs further enhancing at shortwave and longwave optical, and especially short-wave band, so this technique is highly suitable for the selective emitter battery, can greatly strengthen the short wave response of battery;
3, the thin silicon dioxide layer near silicon chip surface has good passivation effect, but the dangling bonds of passivation silicon chip surface, dislocation, crystal boundary, point defect etc., reduce the compound of few son, improve carrier mobility, extend the life-span of few son, improve short circuit current and the open circuit voltage of battery, thereby improve the transformation efficiency of crystal-silicon solar cell;
4, having increased the layer of silicon dioxide film not only provides good surface passivation, and also making antireflective film is to become three layers from two-layer, has forced down the reflectivity of three wavelength, has forced down whole solar spectrum at the reflectivity of battery surface;
5, technique of the present invention does not increase extra equipment, has only increased by one road working gas and a step coating process, and the present invention and existing crystal silicon cell production technology are compatible.
Description of drawings
Fig. 1 is the film layer structure figure that passivated reflection reducing of the present invention is penetrated film.
Fig. 2 is the silicon chip of different embodiments of the invention and the reflectivity comparison diagram of common process plated film sheet.
1: front electrode
2: the second silicon nitride layers
3: the first silicon nitride layers
4: silicon dioxide layer
5: silicon chip
6: back electrode
Embodiment
As described in Figure 1, be film layer structure schematic diagram of the present invention.Passivated reflection reducing of the present invention is penetrated film, and its structure comprises: silicon chip 5; Be deposited on a silica coating 4 on this silicon chip 5 surfaces; Be deposited on the first higher silicon nitride layer 3 of refractive index on this silica coating; And be deposited on the second lower silicon nitride layer 2 of refractive index on this first silicon nitride layer 3.The refractive index n of this silica coating 4 is designed to 1.3≤n≤1.7; Refractive index 2.0≤the n of this first silicon nitride layer 3≤2.5; Refractive index 1.5≤the n of this second silicon nitride layer 2＜2.0.In addition, 1 is electrode before battery, and 6 is back electrode.
In addition, the process of preparing that passivated reflection reducing of the present invention is penetrated film is: adopt PECVD, at silicon chip surface deposition layer of silicon dioxide film, the higher silicon nitride layer of deposition one deck refractive index on ready-made silicon dioxide film, deposit the lower silicon nitride layer of one deck refractive index at last again on the high index of refraction silicon nitride layer again.
Below by concrete preferred embodiment by reference to the accompanying drawings, the present invention is described in further detail, but the present invention is not limited in following embodiment.
Embodiment 1
1. the silicon chip after spreading is inserted on graphite boat, and two silicon chips in each lattice of graphite boat want diffusingsurface relative, and non-diffusingsurface abuts against on the battery lead plate of graphite boat;
2. oar on graphite boat, enter the plated film boiler tube under guide rail drives;
3. the Temperature Setting of boiler tube is at 510 ℃, and vacuum degree is 1500 millitorrs, and radio frequency source power is 6500W, and passing into the reactant gas silane flow in pipe is 100sccm, CO
2Flow is 1slm, and the plated film time is 100s, and the radio frequency source discharge makes the concurrent biochemistry of reacting gas ionization close reaction, thereby at silicon chip surface deposition one deck SiO
2
4. deposit one deck refractive index n again and be the first silicon nitride layer of 2.3 on above-mentioned silicon dioxide layer, temperature is 510 ℃, and vacuum degree is 1500 millitorrs, radio frequency source power 6500W, and silane flow rate is 800sccm, and ammonia flow is at 4.6slm, and the plated film time is 100s;
5. deposit one deck refractive index n again and be the second silicon nitride layer of 1.6 on above-mentioned the first silicon nitride layer, temperature is 510 ℃, and vacuum degree is 1500 millitorrs, radio frequency source power 6500W, and silane flow rate is 250sccm, and ammonia flow is at 4.6slm, and the plated film time is 250s;
6. after coating process finished, oar entered boiler tube graphite boat is withdrawed from, and took out from boat with vacuum pencil afterwards until silicon chip is cooling.
1. the silicon chip after spreading is inserted on graphite boat, and two silicon chips in each lattice of graphite boat want diffusingsurface relative, and non-diffusingsurface abuts against on the battery lead plate of graphite boat;
2. oar on graphite boat, enter the plated film boiler tube under guide rail drives;
3. the Temperature Setting of boiler tube is at 510 ℃, and vacuum degree is 1500 millitorrs, and radio frequency source power is 6500W, and passing into the reactant gas silane flow in pipe is 500sccm, CO
2Flow is 3slm, and the plated film time is 150s, and the radio frequency source discharge makes the concurrent biochemistry of reacting gas ionization close reaction, thereby at silicon chip surface deposition one deck SiO
2
4. deposit one deck refractive index n again and be the first silicon nitride layer of 2.1 on above-mentioned silicon dioxide layer, temperature is 510 ℃, and vacuum degree is 1500 millitorrs, radio frequency source power 6500W, and silane flow rate is 900sccm, and ammonia flow is at 5.0slm, and the plated film time is 150s;
5. deposit one deck refractive index n again and be the second silicon nitride layer of 1.7 on the higher silicon nitride layer of above-mentioned refractive index, temperature is 510 ℃, and vacuum degree is 1500 millitorrs, radio frequency source power 6500W, silane flow rate is 300sccm, and ammonia flow is at 5.0slm, and the plated film time is 300s;
6. coating process finishes, and oar enters boiler tube graphite boat is withdrawed from, and takes out from boat with vacuum pencil afterwards until silicon chip is cooling.
1. the silicon chip after spreading is inserted on graphite boat, and two silicon chips in each lattice of graphite boat want diffusingsurface relative, and non-diffusingsurface abuts against on the battery lead plate of graphite boat;
2. oar on graphite boat, enter the plated film boiler tube under guide rail drives;
3. the Temperature Setting of boiler tube is at 510 ℃, and vacuum degree is 1500 millitorrs, and radio frequency source power is 6500W, and passing into the reactant gas silane flow in pipe is 1000sccm, CO
2Flow is 5slm, and the plated film time is 200s, and the radio frequency source discharge makes the concurrent biochemistry of reacting gas ionization close reaction, thereby at silicon chip surface deposition one deck SiO
2
4. deposit one deck refractive index n again and be the first silicon nitride layer of 2.0 on above-mentioned silicon dioxide layer, temperature is 510 ℃, and vacuum degree is 1500 millitorrs, radio frequency source power 6500W, and silane flow rate is 1000sccm, and ammonia flow is at 5.5slm, and the plated film time is 200s;
5. deposit one deck refractive index n again and be the second silicon nitride layer of 1.8 on the higher silicon nitride layer of above-mentioned refractive index, temperature is 510 ℃, and vacuum degree is 1500 millitorrs, radio frequency source power 6500W, silane flow rate is 450sccm, and ammonia flow is at 5.5slm, and the plated film time is 350s;
6. coating process finishes, and oar enters boiler tube graphite boat is withdrawed from, and takes out from boat with vacuum pencil afterwards until silicon chip is cooling.
Embodiment 4(most preferred embodiment)
1. the silicon chip after spreading is inserted on graphite boat, and two silicon chips in each lattice of graphite boat want diffusingsurface relative, and non-diffusingsurface abuts against on the battery lead plate of graphite boat;
2. oar on graphite boat, enter the plated film boiler tube under guide rail drives;
3. the Temperature Setting of boiler tube is at 510 ℃, and vacuum degree is 1500 millitorrs, and radio frequency source power is 6500W, and passing into the reactant gas silane flow in pipe is 800sccm, CO
2Flow is 4slm, and the plated film time is 190s, and the radio frequency source discharge makes the concurrent biochemistry of reacting gas ionization close reaction, thereby at silicon chip surface deposition one deck SiO
2
4. deposit one deck refractive index n again and be the first silicon nitride layer of 2.2 on above-mentioned silicon dioxide layer, temperature is 510 ℃, and vacuum degree is 1500 millitorrs, radio frequency source power 6500W, and silane flow rate is 870sccm, and ammonia flow is at 5.3slm, and the plated film time is 180s;
5. deposit one deck refractive index n again and be the second silicon nitride layer of 1.8 on the higher silicon nitride layer of above-mentioned refractive index, temperature is 510 ℃, and vacuum degree is 1500 millitorrs, radio frequency source power 6500W, silane flow rate is 350sccm, and ammonia flow is at 5.0slm, and the plated film time is 320s;
6. coating process finishes, and oar enters boiler tube graphite boat is withdrawed from, and takes out from boat with vacuum pencil afterwards until silicon chip is cooling.
The film that above-mentioned four embodiment work it out carries out the reflectivity contrast with the film that adopts conventional two-layer coating technique to work it out, as shown in Figure 2.
In addition, each embodiment and common process plated film sheet are made respectively the battery finished product at last, and its electrical performance data separately is as shown in table 1 below:
Table 1 embodiment silicon chip and the contrast of common process plated film sheet electrical property
To recently seeing, open circuit voltage, short circuit current and the conversion efficiency of the plated film sheet of embodiment 1-4 all have obvious lifting than conventional sheet by the electrical property of each embodiment in above table and conventional sheet, and average efficiency can be than high 0.2% left and right of conventional plated film sheet.
In sum, process of preparing of the present invention has further reduced the reflectivity of silicon chip surface, and is lower to the conventional sheet of the luminance factor between 1200nm at solar spectrum 300nm, makes the photoelectric conversion efficiency of battery be improved; Battery absorbs further enhancing, especially short-wave band at shortwave and longwave optical.
Therefore this technique is highly suitable for the selective emitter battery, can greatly strengthen the short wave response of battery; Thin silicon dioxide layer near silicon chip surface has good passivation effect, but the dangling bonds of passivation silicon chip surface, dislocation, crystal boundary, point defect etc., reduce the compound of few son, improve carrier mobility, extend the life-span of few son, improve short circuit current and the open circuit voltage of battery, thereby improve the transformation efficiency of crystal-silicon solar cell.
The process of preparing of the present invention damage that first ammonium ion and hydrogen ion cause silicon chip surface in silicon chip surface deposition layer of silicon dioxide film can be avoided common process deposited silicon nitride process.
The present invention is not limited to the crystal silicon battery that is applied in P type substrate, also can be applicable on the crystal silicon battery of N-type substrate.
The above, it is only preferred embodiment of the present invention, be not that the present invention is done any pro forma restriction, therefore every technical solution of the present invention content that do not break away from,, all still belong in the scope of technical solution of the present invention any simple modification, equivalent variations and modification that above embodiment does according to technical spirit of the present invention.
Claims (10)
1. a solar cell passivated reflection reducing is penetrated film, it is characterized in that it comprises: a silica coating that is deposited on silicon chip surface; Be deposited on the first higher silicon nitride layer of refractive index on described silica coating; And be deposited on the second lower silicon nitride layer of refractive index on described the first silicon nitride layer.
2. solar cell passivated reflection reducing according to claim 1 is penetrated film, it is characterized in that: the refractive index n of described silica coating is 1.3≤n≤1.7; The refractive index n of described the first silicon nitride layer is 2.0≤n≤2.5; Refractive index 1.5≤the n of described the second silicon nitride layer＜2.0.
3. the described solar cell passivated reflection reducing of claim 1 or 2 is penetrated the film preparation process, it is characterized in that: adopt PECVD, at silicon chip surface deposition layer of silicon dioxide film, the first higher silicon nitride layer of deposition one deck refractive index on ready-made silicon dioxide film, deposit the second lower silicon nitride layer of one deck refractive index at last again on the high index of refraction silicon nitride layer again.
4. solar cell passivated reflection reducing according to claim 3 is penetrated the film preparation process, it is characterized in that comprising the following steps:
1) silicon chip after spreading is inserted on graphite boat;
2) oar on graphite boat enters the plated film boiler tube under guide rail drives, pass into reactant gas silane in pipe, and its flow is 100-1000sccm, O
2Flow is 1-5slm, and the radio frequency source discharge makes the concurrent biochemistry of reacting gas ionization close reaction, thereby at silicon chip surface deposition one deck SiO
2Film;
3) deposit again the first higher silicon nitride layer of one deck refractive index on above-mentioned silica coating;
4) deposit again the second lower silicon nitride layer of one deck refractive index on the first higher silicon nitride layer of above-mentioned refractive index;
5) coating process finishes, and oar enters boiler tube graphite boat is withdrawed from, and takes out from boat with vacuum pencil afterwards until silicon chip is cooling.
5. solar cell passivated reflection reducing according to claim 3 is penetrated the film preparation process, it is characterized in that: described process of preparing is to carry out in tubular type PECVD equipment boiler tube.
6. solar cell passivated reflection reducing according to claim 1 is penetrated the film preparation process, it is characterized in that: in step 1), two silicon chip diffusingsurfaces in each lattice of graphite boat are relative, and non-diffusingsurface abuts against on the battery lead plate of graphite boat.
7. solar cell passivated reflection reducing according to claim 1 is penetrated the film preparation process, it is characterized in that: the Temperature Setting of described boiler tube is at 450-550 ℃, and vacuum degree is the 1000-2000 millitorr, and radio frequency source power is 5000-7000W.
8. solar cell passivated reflection reducing according to claim 1 is penetrated the film preparation process, it is characterized in that: step 2) in, the plated film time is 100-200s, and the design thickness is at 3-20nm, and refractive index is 1.3-1.7.
9. solar cell passivated reflection reducing according to claim 1 is penetrated the film preparation process, it is characterized in that: in step 3), coating temperature is 400-500 ℃, vacuum degree is the 1000-2000 millitorr, radio frequency source power 5000-7000W, silane flow rate is 700-1200sccm, and ammonia flow is at 4.5-5.5slm, and the plated film time is 200-350s; The refractive index n of described the first silicon nitride layer is 2.0≤n≤2.5.
10. solar cell passivated reflection reducing according to claim 1 is penetrated the film preparation process, it is characterized in that: in step 4), coating temperature is 400-500 ℃, vacuum degree is the 1000-2000 millitorr, radio frequency source power 5000-7000W, silane flow rate is 250-450sccm, and ammonia flow is at 4.5-5.5slm, and the plated film time is 250-450s; Refractive index 1.5≤the n of described the second silicon nitride layer＜2.0.
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