CN101132029A - Aluminum based crystal silicon particle solar battery and preparation method thereof - Google Patents
Aluminum based crystal silicon particle solar battery and preparation method thereof Download PDFInfo
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- CN101132029A CN101132029A CNA200710061207XA CN200710061207A CN101132029A CN 101132029 A CN101132029 A CN 101132029A CN A200710061207X A CNA200710061207X A CN A200710061207XA CN 200710061207 A CN200710061207 A CN 200710061207A CN 101132029 A CN101132029 A CN 101132029A
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Abstract
The present invention relates to aluminum-based-silicon-particle solar cell and its processing method. The solar cell includes N-type crystalline silicon particles (01), aluminum substrate (02), middle insulating layer (05), surface transparent conductive layer (06) and antireflection layer (07). The N-type crystalline silicon particles are evenly paved on the aluminum substrate, and a layer of reducing agent (03) is evenly paved on then to be sintered under condition of 580 to 600 centigrade. A layer of Al-Si alloy (04) is formed on the contact region of silicon particles and aluminum substrate, and alloy PN junctions are formed on the silicon particle surface. The silicon particles are grinded to have a small height. Insulating material is filled into gaps between the silicon particles. The transparent conductive layer as upper surface electrode is deposited on the silicon surface which has been washed off the insulating material and been exposed. An antireflection layer is deposited on the transparent conductive layer then.
Description
Technical field
The present invention relates to solar cell, particularly solar cell that on the aluminium substrate, prepares and preparation method thereof with crystal silicon particle.
Background technology
In this manual, the one side that solar cell is received light be called upper surface or above, face on the other side is called lower surface, the back side or claims substrate.The electrode of being drawn by upper surface is called top electrode, and the electrode of being drawn by substrate claims to become bottom electrode or back electrode.
Traditional crystal-silicon solar cell comprises single crystal silicon solar cell and polycrystalline silicon solar cell, this solar cell adopts the monocrystalline or the polysilicon chip that are mixed with boron to make, its resistivity between 10 ohmcms, forms PN junction at the upper surface of battery diffusion phosphorus at 0.2 ohmcm.In order to reduce the reflection of battery surface, evaporate one or more layers antireflective coating at upper surface, at the upper surface of battery the extraction electrode of palisade is arranged, there is back electrode to draw at lower surface.
Though the crystal-silicon solar cell of prior art manufacturing has high conversion rate, in manufacture process, consumed a large amount of energy, raw-material utilance is low, makes that the manufacturing cost of solar cell is very high.To could regain through the generator operation of decades and make the energy that is consumed.In the solar cell field, reduce the energy consumption in the manufacture process, improving stock utilization is the problem that presses for solution.
U.S. Patent number 4514580 has been introduced a kind of preparation method of silicon grain solar cell.With P type silicon grain sintering on metal substrate.Metal substrate plays a part supporter and bottom electrode in the method.At the gap of silicon grain fill insulant, form PN junction at the upper surface deposition N of silicon grain layer.In this method,, make the preparation method of PN junction be subjected to certain restriction because the silicon grain surface is polluted in the existence of insulating barrier easily.
China Patent No. ZL00806689.2 has introduced a kind of aluminium alloy back side connection solar cell.General solar cell is made in upper surface with PN junction, help incident light like this and absorbed by the PN junction zone, and this solar cell is done PN junction overleaf, has equally also obtained high conversion rate.
Summary of the invention
The purpose of this invention is to provide a kind of new crystal silicon particle solar battery and preparation method thereof, can overcome the shortcoming of prior art.
With aluminium flake as substrate, N type crystal silicon particle sintering on the aluminium flake surface, is formed silicon-aluminum type PN junction in the contact position of silicon grain and aluminium flake simultaneously, and silicon grain is by the surface of soldering at aluminium flake, aluminium flake plays a part supporter, also is the back electrode of solar cell simultaneously.Fill out the slit of silicon grain with insulating material and locate, make the place, slit of silicon grain all be insulated the material covering, make the silicon grain surface exposure simultaneously.Constitute the upper surface electrode of solar cell at silicon grain surface deposition transparency conducting layer.On transparency conducting layer, deposit one deck antireflection layer again.
Described aluminium flake thickness is 0.1mm to 0.5mm, and purity is at the high-purity aluminium flake more than 99.9%.
Described N type body crystal silicon body particle is to be obtained through crushing and screening by the monocrystalline silicon or the polycrystalline silicon material of resistivity at 0.2 Ω cm to 10 Ω cm, and particle size is between 1mm to 0.3mm.
Described insulating material is organic insulation resin or inorganic insulating material, can tolerate the temperature more than 150 ℃, can tolerate the corrosion of HF acid simultaneously.
Described transparency conducting layer is that zinc oxide, tin oxide, tin indium oxide or other transparent conductive material constitute.
Described antireflection layer material is magnesium fluoride or silicon nitride.
The preparation method of crystal silicon particle solar battery of the present invention comprises the steps:
With aluminium flake as substrate, N type crystal silicon particle evenly is layered on the aluminium flake surface, and evenly spread in the above and spill the reducing agent that one deck can destroy the aluminium surface oxide layer, in 577 ℃ to 600 ℃ stove, carry out sintering, contact position at silicon grain and aluminium flake forms silicon-aluminum, forms the alloy-type PN junction on the silicon grain surface simultaneously, and silicon grain is by the surface of soldering at aluminium flake, aluminium flake plays a part supporter, also is the bottom electrode of solar cell simultaneously.With the silicon grain surface rubbing, make all silicon grains have identical height with abrasive method.With selective corrosion liquid aluminium is corroded, make the aluminium flake surface have certain height poor with the silicon grain surface.Insert the slit of silicon grain with insulating material and locate, make the place, slit of silicon grain all be insulated the material covering, make the silicon grain surface exposure simultaneously.Constitute the upper surface induced labor electrode of solar cell at silicon grain surface deposition transparency conducting layer.On transparency conducting layer, deposit one deck antireflection layer again.
Described reducing agent can be molten into liquid state between 500 ℃ to 600 ℃, the surface that covers aluminium in the oxide layer erosion removal with the aluminium surface is oxidized once more to prevent the aluminium surface.Reducing agent also will have the removal effect to the oxide layer of silicon face.Reducing agent generally is made of the mixture of chloride and fluoride.
Described selective corrosion liquid has corrosion rate faster to aluminium and silicon-aluminum, and to silicon do not corrode or corrosion rate very low.10% sodium hydroxide solution can be used as selective corrosion liquid.
Now the present invention is described in detail as follows:
Silicon materials itself are easy to form crystalline state, polysilicon itself after process is purified just has the crystalline state of centimeter scale, when polysilicon is pulverized, and the easier fracture in crystal boundary place, if it is ground into particle below 1 millimeter, each particle can be regarded as by monocrystal and constitute.Silicon grain after the pulverizing has various size, through screening, the particle that varies in size is separated, size all can be used for preparing solar cell from 1 millimeter to 0.3 millimeter silicon grain, but during specific to preparation a slice solar cell, then to select the close particle of size for use, in subsequent handling, guarantee full wafer battery performance unanimity easily like this.
The silicon grain that the present invention selects for use is the solar level N type monocrystalline or the polycrystalline silicon material of resistivity 0.5 to 10 ohmcm, the silicon grain that screening is good is through after cleaning, be layered on the surface of aluminium flake equably, the thickness of aluminium flake is between 0.1mm to 0.5mm, and representative value is 0.3mm.Aluminium and silicon just can form silicon-aluminum more than 577 ℃, but because aluminium and silicon face all have layer of oxide layer, and the existence of oxide layer has stoped the direct contact between aluminium and the silicon, though to the melting temperature of 660 ℃ of aluminium can not form silicon-aluminum yet.Making silicon and aluminium form silicon-aluminum below the fusing point of aluminium will reduce to the oxide layer of aluminium and silicon face with reducing agent, make fresh aluminium can directly contact the formation alloy with silicon atom.Sintering temperature generally is controlled between 580 ℃ to 600 ℃.Requiring reducing agent is liquid in this temperature range.Liquid reducing agent covers the surface of aluminium and silicon grain after oxide layer is removed, make the not oxidation once more of aluminium and silicon grain surface.
Generally speaking, sintering temperature can not surpass the fusing point of aluminium, and above behind the fusing point of aluminium, aluminium flake can be in balling-up under the surface tension effects.In sintering process, silicon grain and aluminium constantly form alloy, and the volume of silicon grain is constantly reducing, will lower the temperature in due course, when certain thickness alloy-layer is arranged, also have the crystalline silicon of certain volume, could between silicon and alloy-layer, form PN junction like this.
Silicon grain can be divided in the sintering process on aluminium surface: intensification → thawing → cooling → crystallization again.The recrystallization process of wherein lowering the temperature is the committed step of decision PN junction performance.Particularly near 577 ℃, cooling will be tried one's best slowly, and rate of temperature fall will be controlled at below 0.5 ℃/minute.
The silicon grain that sintering is finished evenly covers the surface of aluminium flake.But the shape of silicon grain differs, and height is different.Adopt abrasive method that the silicon grain polishing is extremely highly identical.Bruting process is as the criterion with minimum particle, the silicon grain that exceeds all polishing to minimum particle sustained height, form the upper surface of neat and consistent.At this moment the height from the aluminium substrate surface to the silicon grain surface can not accurately be controlled.Adopt selective corrosion liquid that aluminium and silicon-aluminum are corroded, make the aluminium substrate surface that the distance of 100 μ m to 150 μ m be arranged to the silicon grain surface.It is fast to aluminium and silicon-aluminum corrosion rate that corrosive liquid requires, to silicon do not corrode or corrosion rate very slow.10% sodium hydroxide solution is very fast to aluminium and silicon-aluminum speed under 40 ℃, and silica-based is not corroded.
Insulating layer material can adopt organic resin or inorganic material.Requirement can tolerate 150 ℃ high temperature.With the surface of insulator-coating, and make insulating material penetrate into the place, slit of each silicon grain at silicon grain.After insulating material solidifies, will grind off attached to the insulating material on silicon grain surface with abrasive method, expose the silicon face of cleaning.At the place, slit of silicon grain, to the distance that 100 μ m to 150 μ m are arranged the aluminium substrate, filling insulating material wherein plays good insulating effect from silicon face.Remove the affected layer of the silicon face that causes when grinding with the mixed liquor of hydrofluoric acid and nitric acid.At silicon face deposition layer of transparent conductive layer, as ITO, perhaps zinc oxide, in order to improve the absorptivity of light, can be in surface evaporation one deck reflection-reducing material, as magnesium fluoride etc.Fig. 6 is complete particle solar.
Description of drawings:
Fig. 1 is that silicon grain evenly is layered on the aluminium flake surface, above evenly the shop spill reducing agent.
Fig. 2 is that the silicon grain soldering forms silicon-aluminum on the aluminium surface behind the sintering in the contact position.
Fig. 3 grinds to form sustained height with the different silicon grain of height.
Fig. 4 is with behind the selective corrosion corrosion, makes the aluminium substrate surface that the distance of 100 μ m to 150 μ m be arranged to the silicon grain surface.
Fig. 5 is on the silicon grain surface and slit place with insulator-coating.
Fig. 6 removes the insulating material on silicon grain surface, and the insulating material at place, slit keeps
Fig. 7 is a complete crystal silicon particle solar battery behind deposit transparent conductive layer and the antireflection layer.
Embodiment
As shown in the figure, 01 represent N type crystal silicon particle; 02 represents the aluminium substrate; 03 represents reducing agent; 04 silicon-aluminum that between crystal silicon particle and aluminium substrate, forms; 05 represents insulating material; 06 represents the electrically conducting transparent top electrode; 07 represents antireflection layer.
Embodiment:
The preparation process of aluminium base silicon grain solar cell is:
With resistivity is that the N type polycrystalline silicon material of 5 ohmcms is ground into silicon grain, through screening, selects size at 0.3 millimeter to 0.5 millimeter particle.
After the silicon grain process cleaning of choosing, be tiled in the surface of aluminium flake equably.Aluminium flake purity is 99.9%, and thickness is 0.3mm.One deck reducing agent is spilt in even shop on silicon grain, and reducing agent can adopt 201 commercially available aluminum brazing flux.
The print of completing silicon grain and reducing agent pushed carry out sintering in the tube furnace.Furnace temperature is set in 585 ℃, and sintering time is 10 minutes, cooling lentamente then, and rate of temperature fall is 0.5 ℃/minute, when temperature drops to below 570 ℃ print is taken out from stove.With clear water reducing agent is thoroughly washed when treating that the print temperature is reduced to room temperature.
With the silicon grain surface rubbing, make all silicon grains have identical height with No. 1000 waterproof abrasive papers.
Sodium hydroxide solution with 10% corrodes aluminium and silicon-aluminum under 40 ℃, and after about 20 minutes, the difference in height of measuring silicon face and aluminium substrate can stop corrosion when 100 μ m to 150 μ m.With pure water the print surface is thoroughly cleaned up.
Be coated in the surface of silicon grain with the Synthesized with Thermal Polymerization acrylic resin, guarantee that resin is filled into each place, slit of silicon grain, and not have bubble.
After the resin natural air drying, grind off substantially earlier with No. 3000 sand paper resin with the silicon grain surface, be stained with abrasive pastes with soft cloth then the resin on silicon grain surface is thoroughly ground off, reduce the destruction of grinding to the silicon grain surface as far as possible.Abrasive pastes can adopt common toothpaste.
With the print surface clean clean after, put into 180 baking ovens acrylic resin carried out polymerization, the time approximately is 20 minutes
HF acid with 5% is carried out erosion removal to the oxide layer on silicon grain surface, about 3 minutes of time.
Method with vacuum sputtering deposits one deck Al-Doped ZnO as transparency conducting layer at surface sputtering.
Final evaporation one deck magnesium fluoride antireflection layer.
Claims (10)
1. solar cell with crystal silicon particle preparation, it is characterized in that: with aluminium flake as substrate, with N type crystal silicon particle sintering on the aluminium flake surface, form silicon-aluminum type PN junction in the contact position of silicon grain and aluminium flake simultaneously, silicon grain is by the surface of soldering at aluminium flake, aluminium flake plays a part supporter, also is the back electrode of solar cell simultaneously.Insert the slit of silicon grain with insulating material and locate, make the place, slit of silicon grain all be insulated the material covering, make the silicon grain surface exposure simultaneously.Constitute the upper surface electrode of solar cell at silicon grain surface deposition transparency conducting layer.On transparency conducting layer, deposit one deck antireflection layer again.
2. according to the described crystal silicon particle solar battery of claim 1, it is characterized in that described aluminium flake thickness is 0.1mm to 0.3mm, purity is at the high-purity aluminium flake more than 99.9%.
3. according to the described crystal silicon particle solar battery of claim 1, it is characterized in that described N type body crystal silicon body particle is to be obtained through crushing and screening by the monocrystalline silicon or the polycrystalline silicon material of resistivity at 0.2 Ω cm to 10 Ω cm, particle size is between 1mm to 0.3mm.
4. according to the described crystal silicon particle solar battery of claim 1, it is characterized in that described insulating material is organic insulation resin or inorganic insulating material, can tolerate the temperature more than 150 ℃, can tolerate the corrosion of HF acid simultaneously.
5. according to the described crystal silicon particle solar battery of claim 1, it is characterized in that described surface transparent conductive layer is that zinc oxide, tin oxide, tin indium oxide or other transparent conductive material constitute.
6. according to the described crystal silicon particle solar battery of claim 1, it is characterized in that described antireflection layer material is magnesium fluoride or silicon nitride.
7. according to the preparation method of the described crystal silicon particle solar battery of claim 1, it is characterized in that it comprises the steps: with aluminium flake as substrate, N type crystal silicon particle evenly is layered on the aluminium flake surface, and evenly spread in the above and spill the reducing agent that one deck can destroy the aluminium surface oxide layer, in 577 ℃ to 600 ℃ stove, carry out sintering, contact position at silicon grain and aluminium flake forms silicon-aluminum, form the alloy-type PN junction on the silicon grain surface simultaneously, silicon grain is by the surface of soldering at aluminium flake, aluminium flake plays a part supporter, also is the bottom electrode of solar cell simultaneously.With the silicon grain surface rubbing, make all silicon grains have identical height with abrasive method.With selective corrosion liquid aluminium is corroded, make the aluminium flake surface have certain height poor with the silicon grain surface.Insert the slit of silicon grain with insulating material and locate, make the place, slit of silicon grain all be insulated the material covering, make the silicon grain surface exposure simultaneously.Constitute the upper surface extraction electrode of solar cell at silicon grain surface deposition transparency conducting layer.On transparency conducting layer, deposit one deck antireflection layer again.
8. according to the preparation method of the described crystal silicon particle solar battery of claim 7, it is characterized in that described reducing agent can be molten into liquid state between 500 ℃ to 600 ℃, the surface that covers aluminium in the oxide layer erosion removal with the aluminium surface is oxidized once more to prevent the aluminium surface.Reducing agent also will have the removal effect to the oxide layer of silicon face.
9. according to the described reducing agent of claim 8, it is characterized in that described reducing agent is the mixture of chloride and fluoride.
10. according to the preparation method of the described crystal silicon particle solar battery of claim 7, it is characterized in that described selective corrosion liquid has corrosion rate faster to aluminium and silicon-aluminum, and to silicon do not corrode or corrosion rate very low.
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| CNA200710061207XA CN101132029A (en) | 2007-09-27 | 2007-09-27 | Aluminum based crystal silicon particle solar battery and preparation method thereof |
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| CNA200710061207XA CN101132029A (en) | 2007-09-27 | 2007-09-27 | Aluminum based crystal silicon particle solar battery and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102439736A (en) * | 2009-04-02 | 2012-05-02 | 斯戴勒公司 | Electronic structure comprising an epitaxial layer on sintered silicon |
| CN113790538A (en) * | 2021-08-27 | 2021-12-14 | 中南大学 | Photo-thermal conversion film and preparation method and application thereof |
-
2007
- 2007-09-27 CN CNA200710061207XA patent/CN101132029A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102439736A (en) * | 2009-04-02 | 2012-05-02 | 斯戴勒公司 | Electronic structure comprising an epitaxial layer on sintered silicon |
| CN113790538A (en) * | 2021-08-27 | 2021-12-14 | 中南大学 | Photo-thermal conversion film and preparation method and application thereof |
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Open date: 20080227 |