CN103236467A - Method for preparing efficient si-based nano-structural solar batteries - Google Patents
Method for preparing efficient si-based nano-structural solar batteries Download PDFInfo
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- CN103236467A CN103236467A CN2013101234986A CN201310123498A CN103236467A CN 103236467 A CN103236467 A CN 103236467A CN 2013101234986 A CN2013101234986 A CN 2013101234986A CN 201310123498 A CN201310123498 A CN 201310123498A CN 103236467 A CN103236467 A CN 103236467A
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Abstract
The invention discloses a method for preparing efficient si-based nano-structural solar batteries. The method includes: cleaning a silicon wafer; generating a monolayer silicon nitride film on the back side of the silicon wafer; forming a nano ultra-small textured structure on the front side of the silicon wafer via wet etching; heating concentrated acid to process the silicon wafer so as to remove rest metal; etching an electrode pattern on the silicon textured surface via the laser ablation method; utilizing an alkali solution to process the silicon wafer so as to remove surface damage of the silicon wafer; cleaning the silicon wafer; preparing a PN junction via heat diffusion; removing PSG (phospho silicate glass) by hydrofluoric acid; generating a silicon nitride passivation layer on the front side of the silicon wafer; preparing an aluminum-back surface field via silk-screen printing, and preparing a front electrode via secondary aligned silk-screen printing; and sintering to finish the preparation of a solar battery. The solar battery prepared by the method is ultra-low in emissivity, high in light trapping capability, and good in electrode contact while surface recombination of charge carriers can be effectively reduced, and service life of the solar battery can be effectively prolonged.
Description
Technical field
The invention belongs to new and effective filed of crystal silicon solaode technique, relate in particular to a kind of method for preparing silicon-based nano structure efficient solar battery.
Background technology
In recent years, the environmental problem of energy scarcity problem and global warming is serious day by day, and human regenerative resource demand to cleaning is unprecedentedly eager.Many advantages such as photovoltaic solar is a kind of important renewable energy, and it is extensive to have the energy, and the region restriction is few, and is safe and reliable.
Use so far from first silicon solar cell in 1954, solar cell has passed through first generation single crystal silicon solar cell, the development of second generation hull cell, and from the development of present photovoltaic solar battery, its technology trends is that cost reduces, efficient improves.
The solar cell that existing market is used is based on crystal silicon cell, though the photovoltaic industry is relative and other new forms of energy have many advantages, but current high cost of electricity-generating has seriously limited the further extensive use of crystal-silicon solar cell, therefore reduces the emphasis that the solar cell cost becomes current research.
From the absorption angle of present crystal silicon battery to sunlight, battery absorbs high-energy photon and produces " heat " charge carrier, and at the bottom of " heat " carrier relaxation conduction band or top of valence band, this part energy is thermal loss with the form loss of lattice heat.Energy can not be absorbed by battery less than the photon of battery band gap, and directly sees through battery, is and sees through loss.Even at visible waveband, the reflection of silicon face is also bigger, has lost suitable light.If the light of these losses is effectively utilized, then can realize significantly improving of battery efficiency.
Summary of the invention
(1) technical problem that will solve
In view of this, main purpose of the present invention is to provide a kind of method for preparing silicon-based nano structure efficient solar battery, reduces the solar cell cost to improve, and improves the efficient of solar cell.
(2) technical scheme
For achieving the above object, the invention provides a kind of method for preparing silicon-based nano structure efficient solar battery, comprising: silicon chip is cleaned; At silicon chip back side growth individual layer silicon nitride film; At the positive wet etching of using of silicon chip, form the extra small suede structure of nanometer; With concentrated acid heat treated silicon chip, remove metal catalytic and corrode remaining metal behind the little suede; Use laser that the one side that silicon chip has the extra small suede structure of nanometer is carried out etching, carve electrode pattern; Silicon chip is put into aqueous slkali boil, remove damage; Again silicon chip is cleaned; Thermal diffusion prepares PN junction in the back side diffusion in the front of silicon chip; And the PSG of removal front and back, at positive grown silicon nitride passivation layer; Formerly in silk screen printing aluminium back of the body field, then at front secondary screen printing electrode, make electrode position and previous laser draw the position alignment at quarter after finishing; Final alloy sintering is finished cell preparation.
(3) beneficial effect
From technique scheme as can be seen, the present invention has following beneficial effect:
1, the preparation method of silicon-based nano structure efficient solar battery provided by the invention, effectively preparation size evenly, the nanostructure of distribution rule, and prepared and had good electrodes in contact.This battery structure can increase battery effectively to absorption of incident light and utilization, reduces the compound of charge carrier, improves the transport capability of charge carrier, has increased photogenerated current,, effectively improve battery conversion efficiency.
2, silicon-based nano structure efficient solar battery provided by the invention the preparation method, under the prerequisite of part and existing solar cell preparation technology compatibility, innovation structure has been proposed, and provide effective preparation method, to improve the conversion efficiency of crystal silicon solar batteries, reduce the production cost of solar cell.
The aspect that the present invention adds and advantage part in the following description provide, and part will become obviously from the following description, or recognize by practice of the present invention.
Description of drawings
Above-mentioned and/or additional aspect of the present invention and advantage are from obviously and easily understanding becoming the description of embodiment below in conjunction with accompanying drawing, wherein:
Fig. 1 is the method flow diagram according to the preparation silicon-based nano structure efficient solar battery of the embodiment of the invention;
Fig. 2 to Fig. 7 is the process chart according to each production phase of the preparation silicon-based nano structure efficient solar battery of the embodiment of the invention.
Embodiment
For making the purpose, technical solutions and advantages of the present invention clearer, below in conjunction with specific embodiment, and with reference to accompanying drawing, the present invention is described in more detail.
The present invention relates generally to a kind of preparation method of silicon-based nano structure efficient solar battery.Disclosing hereinafter provides many different embodiment or example to be used for realizing different structure of the present invention.Of the present invention open in order to simplify, hereinafter parts and the setting to specific examples is described.Certainly, they only are example, and purpose does not lie in restriction the present invention.In addition, the present invention can be in different examples repeat reference numerals and/or letter.This repetition is in order to simplify and purpose clearly, itself not indicate the relation between the various embodiment that discuss of institute and/or the setting.In addition, various specific technology and the examples of material that the invention provides, but those of ordinary skills can recognize the property of can be applicable to of other technologies and/or the use of other materials.In addition, first feature described below second feature it " on " and/or the structure of " top " can comprise that first and second features form the embodiment of direct contact, can comprise that also additional features is formed on the embodiment between first and second features, such first and second features may not be direct contacts.
The present invention utilizes wet etching, has prepared a kind of silicon-based nano structure that is applied to solar cell; Adopt the preceding electrode of laser ablation zygomite reticulated printing preparation, effectively improved the problem of extra small textured cell electrode loose contact.This battery structure has ultralow reflectivity and falls into luminous energy power efficiently, be applied on the crystal silicon solar battery, thereby reduce reflection, and will see through the long wavelength threshold system of battery easily in vivo, strengthen light absorption, effective reduction of while charge carrier is compound battery surface, finally is converted to photoelectric current, realizes higher battery efficiency.
As shown in Figure 1, Fig. 1 shows the flow chart according to the preparation silicon-based nano structure efficient solar battery method of the embodiment of the invention, and this method may further comprise the steps:
In step 101, at first silicon chip 201 is cleaned.
Wherein silicon substrate can be the p-type silicon chip, also can n type silicon chip.Preferably, adopt P type silicon substrate.
Then in step 102, at the back side of silicon substrate grown silicon nitride film 202, as shown in Figure 2.
Preferably, the depositing operation of the silicon nitride film in the step 102 can include but not limited to PECVD, and the thickness of silicon nitride film is 200nm～400nm.
In step 103, the silicon chip 201 that the described back side of Fig. 2 is coated with silicon nitride film 202 carries out wet etching, forms nanostructure, as shown in Figure 3.
What preferably, the technology of the wet etching in the step 103 can include but not limited to is the auxiliary wet etching of metal.
For example in specific embodiment, it is 40% AgNO that the silicon chip 201 that the back side is coated with silicon nitride film 202 places molar concentration
3With corrosion in the mixed liquor of HF solution equal proportion 10 minutes-120 minutes.
In step 104, the silicon chip 201 that will have nanostructure places the dense H of boiling
2SO
4With clean in the hydrogen peroxide mixed liquor, use HF and washed with de-ionized water again, nitrogen dries up.
In step 105, the silicon chip 201 that will have nanostructure carries out laser ablation, forms electrode pattern, as Fig. 4.Preferably, etching depth is 1 μ m～10 μ m in the step 105.
In step 106, the silicon chip 201 that etching is finished electrode pattern places aqueous slkali to boil, and removes damage.Preferably, the aqueous slkali that adopts in the step 106 is that molar concentration is 20% NaOH solution, boils 1 minute～5 minutes.
In step 107, in step 107, the silicon chip 201 that will have nanostructure is used washed with de-ionized water, and nitrogen dries up.
In step 108, the silicon chip 201 that cleans is spread, preparation PN junction 203 is as Fig. 5.
In step 109, acid solution is removed the PSG on silicon chip 201 surfaces.Preferably, what adopt in the step 109 is that molar concentration is 30% HF solution, washed with de-ionized water, and nitrogen dries up.
In step 109, with removing the silicon chip 201 positive grown silicon nitride passivation layers 204 of PSG, as Fig. 6.Preferably, the depositing operation of the silicon nitride film in the step 109 can include but not limited to PECVD, and the thickness of silicon nitride film is 50nm～100nm.
In step 110, to silicon chip 201 printing aluminium back of the body fields 205, secondary is aimed at the preceding electrode 206 of silk screen printing, as Fig. 7.
In step 111, silicon chip 201 is carried out sintering, finish cell preparation.
It is pointed out that the above-mentioned specific embodiment mode that arrives step 111 about step 101 only for the simple clear schematic example of describing the principle of the invention, is not that the present invention is done any pro forma restriction, more especially can pass through the step that existing technology realizes.
Though the present invention discloses as above with preferred embodiment, yet is not in order to limit the present invention.Those of ordinary skills obviously as can be known, in not breaking away from the technical solution of the present invention scope, when the technology contents that can utilize above-mentioned announcement 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 solution of the present invention,, 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.
The present invention compared with prior art has following tangible advantage and beneficial effect:
1, the silicon-based nano structure is compared with traditional crystalline silicon structure, can effectively reduce the battery surface reflectivity, and good sunken light effect is arranged, and improves absorbing visible light and infrared band light;
2, the silicon-based nano structure has auxiliaring effect to solar cell carrier transport aspect, can reduce the carrier transport path, improves carrier collection efficient, increases photogenerated current density;
3, long silicon nitride before the wet etching has protected cell backside not corroded, and is conducive to the contact of the aluminium back of the body, and the reduction back side is compound;
4, laser forms electrode pattern, and secondary is aimed at the silk-screen electrode again, has solved the problem of extra small textured cell electrode loose contact;
5, damage is gone in the aqueous slkali corrosion, is conducive to reduce the surface recombination of textured cell, improves battery efficiency.
Than other technologies following practical advantage is arranged in technology aspect preparing:
1, the present invention adopts wet etching to prepare matte, is conducive to large-scale production, reduces cost;
2, the present invention adopts laser to form electrode pattern, and secondary is aimed at the silk-screen electrode again, adopts this technology to have the potentiality of industrialization;
3, the basic full silica-base material that adopts of Zhi Bei structure, the raw material abundance, cost is lower, and silicon process technology is quite ripe, is conducive to applying of large-scale production.
In sum, the present invention is silicon-based nano structure of being used for new and effective solar cell and preparation method thereof, under the prerequisite of part and existing solar cell preparation technology compatibility, has proposed innovation structure, to improve the conversion efficiency of crystal silicon solar batteries, reduce the production cost of solar cell.Thereby move towards practicability, the creation of value.The present invention has above-mentioned many advantages and practical value, has large improvement technically, and has produced handy and practical effect, thereby be suitable for practicality more.
Though describe in detail about example embodiment and advantage thereof, be to be understood that under the situation of the protection range that does not break away from the restriction of spirit of the present invention and claims, can carry out various variations, substitutions and modifications to these embodiment.For other examples, when those of ordinary skill in the art should understand easily in keeping protection range of the present invention, the order of processing step can change.
In addition, range of application of the present invention is not limited to technology, mechanism, manufacturing, material composition, means, method and the step of the specific embodiment of describing in the specification.From disclosure of the present invention, to easily understand as those of ordinary skill in the art, for the technology, mechanism, manufacturing, material composition, means, method or the step that have existed or be about to later on develop at present, wherein they are carried out the corresponding embodiment cardinal principle identical functions of describing with the present invention or obtain identical substantially result, can use them according to the present invention.Therefore, claims of the present invention are intended to these technology, mechanism, manufacturing, material composition, means, method or step are included in its protection range.
Claims (17)
1. a method for preparing silicon-based nano structure efficient solar battery is characterized in that, comprising:
Silicon chip is cleaned;
At silicon chip back side growth individual layer silicon nitride film;
At the positive wet etching of using of silicon chip, form the extra small suede structure of nanometer;
With concentrated acid heat treated silicon chip, remove silicon chip surface because after corrosion of metals finishes;
Use laser that the one side that silicon chip has the extra small suede structure of nanometer is carried out etching, carve electrode pattern;
Silicon chip is put into aqueous slkali boil, remove damage;
Again silicon chip is cleaned;
Thermal diffusion prepares PN junction at the silicon chip front and back;
Remove the PSG of front and back, and at positive grown silicon nitride passivation layer;
Overleaf behind the silk screen printing aluminium back of the body, the recycling secondary is aimed at electrode before the silk screen printing, makes the pattern alignment that position and aforementioned laser carve that prints electrode; Final high temperature alloy sintering is finished cell preparation.
2. preparation method according to claim 1 is characterized in that, in the described step that silicon chip is cleaned, is to use dense H
2SO
4Boiling is cleaned silicon chip with the hydrogen peroxide Hybrid Heating, uses HF solution and washed with de-ionized water then respectively, and dries up with nitrogen.
3. the method for preparing silicon-based nano structure efficient solar battery according to claim 1 is characterized in that, and is described in the step of silicon chip back side growth individual layer silicon nitride film, is to adopt the PECVD method to realize.
4. the method for preparing silicon-based nano structure efficient solar battery according to claim 3 is characterized in that, the thickness of described individual layer silicon nitride film is 200nm～400nm.
5. the method for preparing silicon-based nano structure efficient solar battery according to claim 1, it is characterized in that, described in the step of silicon chip front with the extra small suede structure of wet etching formation nanometer, being to use molar concentration is that the hydrofluoric acid of 5-40% and the equal proportion mixed liquor of silver nitrate carry out wet etching.
6. the method for preparing silicon-based nano structure efficient solar battery according to claim 5 is characterized in that, the etching time of described wet etching is 10 minutes～120 minutes.
7. the method for preparing silicon-based nano structure efficient solar battery according to claim 5 is characterized in that, the length of nano-pillar is 0.3 μ m～3 μ m in the extra small suede structure of described nanometer.
8. the method for preparing silicon-based nano structure efficient solar battery according to claim 1 is characterized in that, describedly removes in the step of remaining metal with concentrated acid heat treated silicon chip, is to adopt dense H
2SO
4Boiling is cleaned with the hydrogen peroxide Hybrid Heating, uses HF and washed with de-ionized water again, and dries up with nitrogen.
9. the method for preparing silicon-based nano structure efficient solar battery according to claim 1, it is characterized in that, described use laser carries out in the step of etching the one side that silicon chip has the extra small suede structure of nanometer, and the degree of depth of the electrode pattern that etches is 1 μ m～10 μ m.
10. the method for preparing silicon-based nano structure efficient solar battery according to claim 1 is characterized in that, described silicon chip is put into the step that aqueous slkali boils, and used alkali lye is that molar concentration is the NaOH solution of 2-20%, and the time is 1 minute～5 minutes.
11. the method for preparing silicon-based nano structure efficient solar battery according to claim 1 is characterized in that, in the described step of again silicon chip being cleaned, is to use deionized water that silicon chip is cleaned, and dries up with nitrogen.
12. the method for preparing silicon-based nano structure efficient solar battery according to claim 1 is characterized in that, described thermal diffusion prepares in the step of PN junction, and used phosphorus source is POCl
3
13. the method for preparing silicon-based nano structure efficient solar battery according to claim 12 is characterized in that, described thermal diffusion prepares 600 ℃～800 ℃ of the temperature of PN junction, and the time is 30 minutes.
14. the method for preparing silicon-based nano structure efficient solar battery according to claim 1, it is characterized in that in the step of described removal PSG grown silicon nitride passivation layer, solutions employed is that molar concentration is the hydrofluoric acid of 2-5%, temperature is room temperature, and the time is 2 minutes～5 minutes.
15. the method for preparing silicon-based nano structure efficient solar battery according to claim 1 is characterized in that, in the step of described removal PSG grown silicon nitride passivation layer, the employed method of grown silicon nitride passivation layer is PECVD.
16. the method for preparing silicon-based nano structure efficient solar battery according to claim 15 is characterized in that, the thickness of described grown silicon nitride passivation layer is 50nm～100nm.
17. the method for preparing silicon-based nano structure efficient solar battery according to claim 1 is characterized in that, described sintering is finished in the step of cell preparation, and sintering temperature is 800 ℃, and the time is 5 seconds～20 seconds.
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Application publication date: 20130807 |