CN102738307A - Method for manufacturing spectrum scattering resonance modulation high-efficiency crystalline silicon solar cell - Google Patents
Method for manufacturing spectrum scattering resonance modulation high-efficiency crystalline silicon solar cell Download PDFInfo
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- CN102738307A CN102738307A CN2012102380858A CN201210238085A CN102738307A CN 102738307 A CN102738307 A CN 102738307A CN 2012102380858 A CN2012102380858 A CN 2012102380858A CN 201210238085 A CN201210238085 A CN 201210238085A CN 102738307 A CN102738307 A CN 102738307A
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Abstract
The invention discloses a method for manufacturing a spectrum scattering resonance modulation high-efficiency crystalline silicon solar cell by utilizing surface Si nanocrystalline and metal silicide nanocrystalline. The method comprises the following technical steps of: etching the surface of a crystalline silicon wafer by acid or alkali, forming a PN junction through the diffusion of phosphorus oxychloride, depositing a Si thin film on the surface, forming Si nanocrystalline through quick thermal annealing, depositing a metal thin film/silicon thin film on the surface, forming metal silicide nanocrystalline through quick thermal annealing, manufacturing Si3N4 antireflection film, forming a positive electrode and a negative electrode through screen printing on the back surface and the front surface, and annealing alloy to finish the manufacturing of the cell. The invention fully utilizes traditional production devices, physical principles and processes, and has the characteristics of simple production process, fewer additional devices, easiness for industrial production and reduced production cost.
Description
[technical field]
The present invention relates to a kind of solar cell fabrication process, be specifically related to a kind of efficient crystal silicon solar batteries preparation method of spectral dispersion resonance modulation that surperficial Si is nanocrystalline, metal silicide is nanocrystalline that utilizes, belong to technical field of new energies.
[background technology]
Along with rapid increase and various countries' rapid economy development of world population, more and more to demands for energy; Energy problem has become the permanent fast-developing strategic problem of a country.Extensive at present traditional energy that uses such as oil and coal are because reserves are limited; By present consumption will be exhausted after to more than 100 years after decades; Frequent use fossil energy causes serious air pollution and greenhouse effect at present simultaneously, and is therefore also more and more urgent to the demand of clean reproducible energy; Solar cell has obtained fast development thus as clean energy resource a kind of.Since AT&T Labs in 1954 reported first commercial Si solar cell, various solar cells were come out one after another.Through the continuous development of recent decades, solar cell is from the thin-film solar cells of the monocrystaline silicon solar cell of the first generation, the second generation high performance solar batteries of the third generation till now, and its cost of manufacture progressively reduces, and conversion efficiency improves constantly.
At present crystal silicon battery be faced with conversion efficiency be not very high (large-scale production can monocrystalline at 18-18.5%; Polycrystalline is between 16.5-17.2%), shortcoming such as expensive; But crystal silicon (monocrystalline and polycrystalline) battery is at present in various solar cells; Its market proportion has accounted for more than 90%, withdraws from the market on a large scale also to take day; Therefore improving conversion efficiency is a kind of effective means that reduces cost.From the light absorption angle, energy is greater than the photon of above photon, particularly high-energy (short wavelength is such as about 450nm) of Si energy gap (1.1eV), greatly owing to lattice vibration loses.According to report, aspect the short wavelength, cause with a toll of 33%, how effectively utilizing that these spectrum that lose raise the efficiency is an important content.
Therefore, for solving the problems of the technologies described above, the necessary efficient crystal silicon solar batteries preparation method of spectral dispersion resonance modulation that a kind of advanced person is provided is to overcome said defective of the prior art.
[summary of the invention]
For addressing the above problem; The object of the present invention is to provide the efficient crystal silicon solar batteries preparation method of spectral dispersion resonance modulation, it utilizes conventional crystal silicon production line, in the process of preparation crystal silicon cell; Surface preparation at battery goes out the mixed structure that Si is nanocrystalline, metal silicide is nanocrystalline; Utilize the nanocrystalline quantum limitation effect of Si, absorb high-octane photon and reduce thermal loss, utilize the nanocrystalline resonance scattering effect of metal silicide again; Make light generation resonance scattering and be coupled to nanocrystalline and the pn knot; Utilize the nanocrystalline narrow band gap characteristic absorption long wavelength photons of metal silicide simultaneously, make the utilance of light greatly improve, and then reach the purpose of efficient opto-electronic conversion.
For realizing above-mentioned purpose, the technical scheme that the present invention takes is: the efficient crystal silicon solar batteries preparation method of spectral dispersion resonance modulation, and it comprises following processing step:
1), the positive and negative matte of preparation on P type crystalline silicon substrate;
2), positive and negative two sides all has the crystal silicon substrate of suede structure to be placed in the stopped pipe type diffusion furnace, and P type crystalline silicon substrate is carried out phosphorous diffusion, forms PN junction;
3), utilize dull and stereotyped plasma-reinforced chemical vapor deposition, carry out the deposition of amorphous silicon membrane on the surface;
4), utilize annealing furnace that the crystalline silicon substrate with amorphous silicon membrane is carried out rapid thermal annealing, annealing process forms silicon nanocrystal;
5), at crystal silicon substrate surface deposit skim metallic film, utilize dull and stereotyped plasma-reinforced chemical vapor deposition deposition of amorphous silicon films again, thereby form metallic film/amorphous silicon membrane;
6), utilize the mode of annealing furnace thermal annealing that the silicon substrate with metallic film/amorphous silicon membrane is annealed and to form Si nanocrystalline;
7), utilize tubular type or flat plasma-reinforced chemical vapor deposition method at substrate face deposit Si
3N
4Antireflective film;
8), utilize screen process press at the crystalline silicon substrate back side with positive carry out the silk screen printing of positive and negative electricity respectively, form the positive pole and the negative pole of battery respectively;
9), to positive pole and negative pole annealing in process, accomplish the efficient crystal silicon solar batteries of this spectral dispersion resonance modulation.
The efficient crystal silicon solar batteries preparation method of spectral dispersion resonance modulation of the present invention further is: the P type crystalline silicon substrate in the said step 1) is p type 125mm * 125mm monocrystalline silicon piece, 156mm * 156mm monocrystalline silicon piece or 156 * 156mm polysilicon chip; Its thickness is between 180 microns to 250 microns, and it is positioned over NaOH, Na
2SiO
3Carry out anisotropic etch in the Woolen-making liquid that mixes with absolute ethyl alcohol.
The efficient crystal silicon solar batteries preparation method of spectral dispersion resonance modulation of the present invention further is: the diffuse source that is adopted when carrying out phosphorous diffusion said step 2) is liquid POCl
3, utilize nitrogen as carrier gas to POCl
3Carry out gas delivery, the junction depth of the double-sided PN junction that diffuses out utilizes pickling to remove the phosphorosilicate glass of positive and negative between the 200-500 micron after having spread.
The efficient crystal silicon solar batteries preparation method of spectral dispersion resonance modulation of the present invention further is: the thickness of the said amorphous silicon membrane in the said step 3) is at 1nm-30nm, and depositing temperature is not higher than 600 degree.
The efficient crystal silicon solar batteries preparation method of spectral dispersion resonance modulation of the present invention further is: use the nitrogen atmosphere protection in the annealing process of said step 4), annealing temperature is between 700-900 ℃, and annealing time is 20-500s.
The efficient crystal silicon solar batteries preparation method of spectral dispersion resonance modulation of the present invention further is: the deposition process that said step 5) adopts is magnetron sputtering or electron beam evaporation, and the thickness of its sheet metal film is 1nm-30nm; The thickness of said metallic film/amorphous silicon membrane is 1nm-30nm.
The efficient crystal silicon solar batteries preparation method of spectral dispersion resonance modulation of the present invention further is: use the nitrogen atmosphere protection in the annealing process of said step 6), annealing temperature is 400-650 ℃, and annealing time is 30-1000s.
The efficient crystal silicon solar batteries preparation method of spectral dispersion resonance modulation of the present invention further is: said Si
3N
4Antireflective film thickness is between 70nm-120nm.
The efficient crystal silicon solar batteries preparation method of spectral dispersion resonance modulation of the present invention further is: in the said step 8) silk screen printing aluminum paste material is carried out at the back side, at positive printed silver slurry.
Spectral dispersion resonance modulation of the present invention is efficient crystal silicon solar batteries preparation method also can be: the negative electrode in front, the positive electrode at the back side are annealed simultaneously in the said step 9), no special atmosphere protection in the annealing process.
Compared with prior art; The present invention has following beneficial effect: quantum limitation effect, the resonance scattering effect that the efficient crystal silicon solar batteries preparation method of spectral dispersion resonance modulation of the present invention is nanocrystalline through surperficial Si, metal silicide is nanocrystalline, come to absorb fully short-wavelength light; And the light of scattering resonance 350-650nm wave band; And utilize the long wavelength light of characteristic absorption 900-1200nm of the narrow band gap of metal silicide, and make light absorbed fully and utilize, improve the inside and outside quantum efficiency of crystal silicon cell; Increase short circuit battery, finally reach aim of efficient conversion.Processing step with increase is few, can with the process compatible on the big production line, be easy to realize characteristics such as large-scale production.
[description of drawings]
Fig. 1 is the efficient crystal silicon solar batteries preparation method's of a spectral dispersion resonance modulation of the present invention flow chart.
Fig. 2 is the sketch map of P type crystalline silicon substrate.
Fig. 3 is for making the sketch map of matte at the substrate positive and negative.
Fig. 4 is for forming the sketch map of PN junction after the phosphorous diffusion on the surface.
Fig. 5 forms the nanocrystalline sketch map of Si for crystalline silicon substrate.
Fig. 6 is for forming the sketch map of metallic film/amorphous silicon membrane.
Fig. 7 is growth Si
3N
4The sketch map of antireflective film.
Fig. 8 prints negative electrode and positive electrode sketch map for utilizing screen printing technique respectively at front and back.
[embodiment]
See also shown in the Figure of description 1, the present invention is a kind of efficient crystal silicon solar batteries preparation method of spectral dispersion resonance modulation that surperficial Si is nanocrystalline, metal silicide is nanocrystalline that utilizes, and it comprises following processing step:
Step 101: the positive and negative matte of preparation on P type crystalline silicon substrate;
Step 102: positive and negative two sides all has the crystal silicon substrate of suede structure to be placed in the stopped pipe type diffusion furnace, and P type crystalline silicon substrate is carried out phosphorous diffusion, forms PN junction;
Step 103: utilize dull and stereotyped plasma-reinforced chemical vapor deposition, carry out the deposition of amorphous silicon membrane on the surface;
Step 104: utilize annealing furnace that the crystalline silicon substrate with amorphous silicon membrane is carried out rapid thermal annealing, annealing process forms silicon nanocrystal;
Step 105: at crystal silicon substrate surface deposit skim metallic film, utilize dull and stereotyped plasma-reinforced chemical vapor deposition deposition of amorphous silicon films again, thereby form metallic film/amorphous silicon membrane;
Step 106: the mode of utilizing the annealing furnace thermal annealing is annealed to the silicon substrate with metallic film/amorphous silicon membrane and to form Si nanocrystalline;
Step 107: utilize tubular type or flat plasma-reinforced chemical vapor deposition method at substrate face deposit Si3N4 antireflective film;
Step 108: utilize screen process press to carry out the silk screen printing of positive and negative electricity respectively with positive, form the positive pole and the negative pole of battery respectively at the crystalline silicon substrate back side;
Step 109:, accomplish the efficient crystal silicon solar batteries of this spectral dispersion resonance modulation to anodal and negative pole annealing in process.
Fig. 2 to Fig. 8 is the sketch map that is used for explaining a specific embodiment of the present invention.
Shown in step 201 among Fig. 2, the crystal silicon substrate of choosing is asked and is p type 125mm * 125mm monocrystalline silicon piece, 156mm * 156mm monocrystalline silicon piece or 156 * 156mm polysilicon chip.Monocrystalline resistivity is 0.5-3 Ω cm, and polycrystalline resistivity is 0.5-6 Ω cm.Thickness is between 180 microns to 250 microns.
Shown in step 202 among Fig. 3, utilize the method for preparing matte on the large-scale production line, be that crystal silicon substrate between 180 microns to 250 microns is positioned over NaOH, Na with thickness
2SiO
3In the Woolen-making liquid that mixes with absolute ethyl alcohol, because chemical reaction takes place, can carry out anisotropic etch to crystal silicon and form matte, the shape of matte presents inverted pyramid shape.Because substrate positive and negative in the preparation process are because all place corrosive liquid, so the matte characteristic basically identical prepared of tow sides.
Shown in step 303 among Fig. 4, the crystal silicon substrate that tow sides is prepared suede structure is placed in the diffusion furnace, spreads.The diffusion furnace temperature can be 300 ℃ to 1300 ℃ variations.Get diffusion temperature between 850-950 ℃, diffuse source is liquid POCl
3Can realize the diffusion of single face PN junction, also can realize the double-sided PN junction diffusion.In this example, be diffused as example with the single face PN junction, its junction depth of the PN junction that diffuses out is between 200-500nm, and junction depth is by confirming that diffusion finishes the formed square resistance in back about 20-120 Ω/ variation diffusion time.Because in the diffusion process, can form phosphorosilicate glass at battery surface, it can influence the efficient of battery, therefore with HF acid, HNO
3The acid and the hybrid corrosion liquid of water are eliminated phosphorosilicate glass, clean up and dry with deionized water after having removed phosphorosilicate glass.
Shown in step 401 among Fig. 5, it is nanocrystalline to prepare Si.Before preparation, substrate must be put into the work of carrying out crystal silicon substrate surface deoxidation layer in the buffered HF acid.After having gone oxide layer; To as soon as possible substrate be put in the flat plasma-reinforced chemical vapor deposition equipment and go; With silane and hydrogen is deposited gas, and power selection is at 80KW, and gas flow ratio is between 1: 4 to 1: 10; Underlayer temperature is chosen in 400 degree, and thickness is at the amorphous silicon membrane of 2-30nm.The mode of utilizing the chain type rapid thermal annealing after evaporating is between 700-900 ℃, and annealing time is 20-500s, and rapid thermal annealing forms silicon nanocrystal.The size of silicon nanocrystal, density can be come Comprehensive Control by thickness, annealing temperature and the annealing time of Si film.
Shown in step 501 among Fig. 6, utilize the thick metallic film of magnetron sputtering or electron beam evaporation equipment evaporation 1-30mm again.In order to realize metal silicide better, and realize resonance scattering, and the adjusting to be with, preferentially the metal of selection is respectively Ni, Ag, Au, Pt, Cu here.Again substrate being put into flat plasma-reinforced chemical vapor deposition equipment, is deposited gas with silane and hydrogen, and underlayer temperature is a precursor gas with silane and hydrogen, and deposition temperature is chosen in 400 degree, the amorphous silicon membranes of deposit one deck 2-30nm again.Owing to be metal and amorphous silicon forms, it forms the nanocrystalline transformation temperature of metal silicide and falls between, so the mode of rapid thermal annealing is controlled at 400-650 ℃ in temperature, and annealing time is 30-1000s, and the formation metal silicide is nanocrystalline.
Shown in step 601 among Fig. 7,, the crystal silicon substrate is put in the plasma enhanced chemical vapor deposition equipment again growth Si in order to prepare antireflective film
3N
4Film, film thickness monitoring is between 70-120nm.For the individual layer antireflective film situation of crystal silicon battery, it is best that its anti-reflection effect to light can reach.This moment, antireflective film can cover Si nanometer crystal layer and metal silicide nanometer crystal layer.
Shown in step 701 among Fig. 8, utilize silk screen printing that aluminum slurry is printed in cell backside, form aluminium back of the body field plate, finish printing the back and also solidify 200 ℃ of heat treatments.Then for another example shown in the step 702, at front surface coated negative electrode silver paste, form grid line and busbar, finish printing the back and also solidify 200 ℃ of heat treatments with screen process press.
Last annealed alloy mode according to large-scale production line; The negative electrode of frontal, the positive electrode at the back side carry out the staged thermal anneal process from 300 ℃ to 900 ℃; No special atmosphere protection in the annealing process accomplishes finally that surperficial Si is nanocrystalline, the preparation of the efficient crystal silicon solar batteries of the nanocrystalline spectral dispersion resonance modulation of metal silicide.
The above preparation technology only is preferred embodiment of the present invention, is not the present invention is done any pro forma restriction; Though the present invention discloses as above with preferred embodiment; Yet be not in order to limiting the present invention, anyly be familiar with the professional and technical personnel, in not breaking away from technical scheme scope of the present invention; When the technology contents of above-mentioned announcement capable of using is made a little change or is modified to the equivalent embodiment of equivalent variations; In every case be the content that does not break away from technical scheme of the present invention, to any simple modification, equivalent variations and modification that above embodiment did, all still belong in the scope of technical scheme of the present invention according to technical spirit of the present invention.
Claims (10)
1. the efficient crystal silicon solar batteries preparation method of spectral dispersion resonance modulation, it is characterized in that: it comprises following processing step:
1), the positive and negative matte of preparation on P type crystalline silicon substrate;
2), positive and negative two sides all has the crystal silicon substrate of suede structure to be placed in the stopped pipe type diffusion furnace, and P type crystalline silicon substrate is carried out phosphorous diffusion, forms PN junction;
3), utilize dull and stereotyped plasma-reinforced chemical vapor deposition, carry out the deposition of amorphous silicon membrane on the surface;
4), utilize annealing furnace that the crystalline silicon substrate with amorphous silicon membrane is carried out rapid thermal annealing, annealing process forms silicon nanocrystal;
5), at crystal silicon substrate surface deposit skim metallic film, utilize dull and stereotyped plasma-reinforced chemical vapor deposition deposition of amorphous silicon films again, thereby form metallic film/amorphous silicon membrane;
6), utilize the mode of annealing furnace thermal annealing that the silicon substrate with metallic film/amorphous silicon membrane is annealed and to form Si nanocrystalline;
7), utilize tubular type or flat plasma-reinforced chemical vapor deposition method at substrate face deposit Si
3N
4Antireflective film;
8), utilize screen process press at the crystalline silicon substrate back side with positive carry out the silk screen printing of positive and negative electricity respectively, form the positive pole and the negative pole of battery respectively;
9), to positive pole and negative pole annealing in process, accomplish the efficient crystal silicon solar batteries of this spectral dispersion resonance modulation.
2. the efficient crystal silicon solar batteries preparation method of spectral dispersion resonance modulation as claimed in claim 1; It is characterized in that: the P type crystalline silicon substrate in the said step 1) is p type 125mm * 125mm monocrystalline silicon piece, 156mm * 156mm monocrystalline silicon piece or 156 * 156mm polysilicon chip; Its thickness is between 180 microns to 250 microns, and it is positioned over NaOH, Na
2SiO
3Carry out anisotropic etch in the Woolen-making liquid that mixes with absolute ethyl alcohol.
3. the efficient crystal silicon solar batteries preparation method of spectral dispersion resonance modulation as claimed in claim 1 is characterized in that: the diffuse source that is adopted when carrying out phosphorous diffusion said step 2) is liquid POCl
3, utilize nitrogen as carrier gas to POCl
3Carry out gas delivery, the junction depth of the double-sided PN junction that diffuses out utilizes pickling to remove the phosphorosilicate glass of positive and negative between the 200-500 micron after having spread.
4. the efficient crystal silicon solar batteries preparation method of spectral dispersion resonance modulation as claimed in claim 1 is characterized in that: the thickness of the said amorphous silicon membrane in the said step 3) is at 1nm-30nm, and depositing temperature is not higher than 600 degree.
5. the efficient crystal silicon solar batteries preparation method of spectral dispersion resonance modulation as claimed in claim 1 is characterized in that: use the nitrogen atmosphere protection in the annealing process of said step 4), annealing temperature is between 700-900 ℃, and annealing time is 20-500s.
6. the efficient crystal silicon solar batteries preparation method of spectral dispersion resonance modulation as claimed in claim 1 is characterized in that: the deposition process that said step 5) adopts is magnetron sputtering or electron beam evaporation, and the thickness of its sheet metal film is 1nm-30nm; The thickness of said metallic film/amorphous silicon membrane is 1nm-30nm.
7. the efficient crystal silicon solar batteries preparation method of spectral dispersion resonance modulation as claimed in claim 1 is characterized in that: use the nitrogen atmosphere protection in the annealing process of said step 6), annealing temperature is 400-650 ℃, and annealing time is 30-1000s.
8. the efficient crystal silicon solar batteries preparation method of spectral dispersion resonance modulation as claimed in claim 1 is characterized in that: said Si
3N
4Antireflective film thickness is between 70nm-120nm.
9. the efficient crystal silicon solar batteries preparation method of spectral dispersion resonance modulation as claimed in claim 1 is characterized in that: in the said step 8) silk screen printing aluminum paste material is carried out at the back side, at positive printed silver slurry.
10. the efficient crystal silicon solar batteries preparation method of spectral dispersion resonance modulation as claimed in claim 1 is characterized in that: the negative electrode in front, the positive electrode at the back side are annealed simultaneously in the said step 9), no special atmosphere protection in the annealing process.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2024059012A1 (en) * | 2022-09-15 | 2024-03-21 | Lam Research Corporation | Backside layer for a semiconductor substrate |
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| CN101840953A (en) * | 2009-03-18 | 2010-09-22 | 中国科学院微电子研究所 | Method for preparing surface hybrid modulation crystal silicon solar battery |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102356466A (en) * | 2009-01-30 | 2012-02-15 | 可再生能源公司 | Method for producing contact, contact and solar cell comprising contact |
| CN101840953A (en) * | 2009-03-18 | 2010-09-22 | 中国科学院微电子研究所 | Method for preparing surface hybrid modulation crystal silicon solar battery |
Non-Patent Citations (1)
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| WO2024059012A1 (en) * | 2022-09-15 | 2024-03-21 | Lam Research Corporation | Backside layer for a semiconductor substrate |
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Application publication date: 20121017 |