CN101807616A - Back-light black-surface silicon solar battery structure and production method thereof - Google Patents
Back-light black-surface silicon solar battery structure and production method thereof Download PDFInfo
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Abstract
The invention discloses a back-light black-surface silicon solar battery structure, which comprises a silicon-based substrate, a light trapping material layer which is formed at the front side of the silicon-based substrate and a broad-spectrum absorbing black silicon material layer which is formed at the back side of the silicon-based substrate. The invention further discloses a method for producing the back-light black-surface silicon solar battery structure. The invention can adequately use the characteristic of the broad-spectrum absorption of the black silicon material, thereby leading the sunlight which enters into the battery nearly to be completely absorbed, making a contribution to light current, solving the problem that the conventional silicon-based battery can not absorb and transfer solar spectrum with the wavelength which is more than 1.1mu m under the limitation of the infrared absorption, and effectively improving the photoelectric conversion efficiency of the silicon-based solar battery.
Description
Technical field
The present invention relates to the silica-based solar cell technical field, particularly a kind of back-light black-surface silicon solar battery structure and preparation method thereof.
Background technology
Solar energy is the pollution-free renewable and clean energy resource of inexhaustible tool potentiality to be exploited, and the abundant silicon materials of content are the optimisation substance of making solar cell on the earth, but the cost of electricity-generating of present silica-based battery is also higher, and it is big to popularize civilian difficulty.The important channel that reduces silica-based solar cell generating price is the photoelectric conversion efficiency that improves battery.Currently used major technique means, the one, reduce the reflectivity of light, as adopt transparent anti-reflection electrode film, pyramid texture surface, porous silicon to fall into optical surface structure etc. at battery surface; The 2nd, improve the absorptivity of light, as back reflection structure, multijunction structure, collector lens etc. at inside battery; The 3rd, reduce photo-generated carrier compound with the surface in vivo, as carry out mixing in the subregion, surface passivation or the like.These measures make the photoelectric conversion efficiency of silica-based solar cell bring up to 24.7% new height [Prog.Photovolt:Res.Appl.7,471-474 (1999)].Will further improve the efficient of silica-based battery, as can be seen, important a followed approach is to improve the absorptivity of battery material to absorptivity, the especially near infrared light of solar spectrum from the spectrum.Because silica-based battery is subjected to the restriction of INFRARED ABSORPTION limit, the photon that has only energy to be shorter than 1.1 μ m greater than silicon energy gap, the wavelength charged son that silicon could be situated between is energized into conduction band and is absorbed, wavelength then is not absorbed substantially greater than the near-infrared photon of 1.1 μ m, has revealed away as seeing through glass.This part near infrared light that passes battery accounts for nearly 1/3 of solar spectrum.
Professor Eric Ma Zier of Harvard University in 1998 and his research team utilize superpower femtosecond laser scanning to place the silicon chip surface of sulfur hexafluoride gas, obtained a kind of forest shape micro-structural cone surfacing, it has in the almost whole solar spectrum scope of 0.25 μ m-2.5 μ m＞90% absorptivity, greatly expanded the spectral absorption scope [Appl.Phys.Lett.73,1673 (1998)] of silica-base material.Be that this new material has the almost effect of black matrix absorption to sunlight, so also be referred to as " black silicon ".Find that through further investigation the black silicon of this micro-structural has two big characteristics, the one, incident light enters the cone face can have very strong antireflective and fall into light effect constantly to the cone base refraction; The 2nd, the sulphur of the black silicon face of this micro-structural be material concentration considerably beyond its saturated concentration in silicon crystal, thereby make and produce the spectral absorption scope that a large amount of local attitude energy levels can be expanded black silicon in the silicon forbidden band.
People expect utilizing this black silicon material to make solar cell naturally.But more than ten years have gone over, and the solar cell that the black silicon wide spectrum absorption characteristics of this utilization is made also only only obtains 2.20% photoelectric conversion efficiency [PhD thesis, Harvard University, 2007], well below expection.Though the solar cell that utilizes the black silicon light trapping structure of so-called porous to make has obtained 16.8% conversion efficiency [Appl.Phys.Lett.95,123501 (2009)], in fact not as good as ripe chemical texture battery, because this battery does not utilize the wide spectrum absorption characteristic of black silicon.
Cause the reason of this phenomenon to think that the black silicon material mobility is low, carrier lifetime short, heavy doping top layer auger recombination is serious, deep energy level causes open circuit voltage reduction etc., and present research is all with the side to light of black silicon material as battery, cause these problems particularly outstanding, thereby greatly restricted the improvement of black silicon solar cell efficient.
Summary of the invention
(1) technical problem that will solve
In view of this, main purpose of the present invention is to propose a kind of back-light black-surface silicon solar battery structure and preparation method thereof, be subjected to the INFRARED ABSORPTION restriction can not absorb and transform the problem that the above wavelength sunlight of 1.1 μ m is composed to solve the traditional silicon base battery, improve the photoelectric conversion efficiency of silica-based solar cell.
(2) technical scheme
For achieving the above object, the invention provides a kind of back-light black-surface silicon solar battery structure, this structure comprises:
Silicon-based substrate;
At the positive sunken optical material layer of making of silicon-based substrate; And
The wide spectrum of making at the silicon-based substrate back side absorbs the black silicon material layer.
In the such scheme, described silicon-based substrate is monocrystalline silicon or polysilicon or amorphous silicon substrate, and its conduction type is n type or p type, and thickness is 5 μ m to 500 μ m, and positive is to have the pyramid-like of chemical texture or the silicon awl antireflective top layer of porous silicon or laser irradiation.
In the such scheme; described wide spectrum absorbs the black silicon material layer and adopts black silicon material; this black silicon material has the 20nm to 20 of being spaced apart μ m; breadth wise dimension is 20nm to 20 μ m; the degree of depth is silicon awl, silicon grain or the silicon hole of 20nm to 20 μ m, and this material has＞85% absorptivity the sunlight in 0.25 μ m to the 2.5 mum wavelength scope.
In the such scheme, it is directly to be made on the silicon-based substrate back side that described wide spectrum absorbs the black silicon material layer, perhaps is made in the mixing on the phosphorus gradient layer of the silicon-based substrate back side.
In the such scheme, the described phosphorus gradient layer of mixing is by phosphorous diffusion, or the deposit gradient mixes the polysilicon of phosphorus, or the deposit gradient mixes the amorphous silicon of phosphorus, formed from outward appearance to inner essence, the n type doped layer that successively decreases of phosphorus concentration.
In the such scheme, described sunken optical material layer is directly to be made on the silicon-based substrate front, perhaps is made on the boron-doping gradient layer in silicon-based substrate front, and its thickness is 20nm to 50 μ m.
In the such scheme, described boron-doping gradient layer is by boron diffusion, or the polysilicon of deposit gradient boron-doping, or the amorphous silicon of deposit gradient boron-doping, formed from outward appearance to inner essence, the p type doped layer that successively decreases of boron concentration.
The present invention also provides a kind of method of making back-light black-surface silicon solar battery structure, and this method comprises:
Step 1: make sunken optical material layer in the front of silicon-based substrate, with its side to light as battery;
Step 2: make wide spectrum at the back side of silicon-based substrate and absorb the black silicon material layer, with its shady face as battery;
Step 3: carry out the passivation of Si oxide medium respectively at battery side to light and shady face, form passivation layer, on passivation layer, make positive contact gate electrode and back side contact electrode and back of the body counterelectrode metal level then respectively.
In the such scheme, fall into optical material layer described in the step 1 and be the pyramid-like texture that forms by chemical corrosion or porous silicon or bore the antireflective top layer by the silicon that laser irradiation forms.
In the such scheme, it is under the sulphur based environment that wide spectrum described in the step 2 absorbs the black silicon material layer, forms by laser irradiation, and this layer material has＞85% absorptivity the sunlight in 0.25 μ m to the 2.5 mum wavelength scope.
(3) beneficial effect
From technique scheme as can be seen, the present invention has following beneficial effect:
1, the back-light black-surface silicon solar battery structure of the present invention's proposition, can overcome some shortcomings that black silicon material is brought as the battery side to light, can make full use of simultaneously the characteristics that the black silicon material wide spectrum absorbs, the sunlight that enters battery almost can all be absorbed, for photoelectric current is made contributions.Solve the traditional silicon base battery and limited by INFRARED ABSORPTION, can not absorb and transform the problem of the above wavelength sunlight spectrum of 1.1 μ m, can effectively improve the photoelectric conversion efficiency of silica-based solar cell.
2, the present invention absorbs the shady face that black silicon material is applied to silica-based solar cell with wide spectrum, can avoid the compound phenomenon of photo-generated carrier that black silicon material causes as the suffered surperficial auger recombination influence of the side to light of battery in the current programme, increases photogenerated current;
3, the present invention introduces among battery structure Fig. 5 of gradient phosphorus doping in n type silicon-based substrate battery structure Fig. 2, Fig. 3 and in p type silicon-based substrate, the pn knot of battery forms by diffusion or by deposit, be in inside battery, so, the battery open circuit voltage of these structures is not subjected to the shady face wide spectrum to absorb the influence of black silicon material substantially, has avoided black silicon side to light battery to transform the problem that reduces the solar cell open circuit voltage owing to lower energy photon;
4, the present invention is in the battery structure of introducing the gradient phosphorus doping, the n type concentration gradient from outward appearance to inner essence that back-light black-surface silicon and phosphorous diffusion form, can build the internal electric field that light induced electron and hole are separated, the separation of the photo-generated carrier that helps producing in the black silicon material and collection, but the influence that partial offset black silicon material mobility is low and carrier lifetime is short;
5, the back side of the present invention black silicon material can absorb the nearly all photon through battery, especially most near-infrared photons, collected by electrode by the photo-generated carrier that absorb to produce and to be converted into photogenerated current, can solve the traditional silicon base battery limited by INFRARED ABSORPTION, can not absorb and transform the restriction of the above near-infrared solar spectrum of 1.1 μ m, effectively improve the photoelectric conversion efficiency of silica-based solar cell.
Description of drawings
Fig. 1 is a back-light black-surface silicon solar battery structure schematic diagram of the present invention;
Fig. 2 is the back-light black-surface silicon solar battery structure figure on n type silicon-based substrate;
Fig. 3 is the back-light black-surface silicon solar battery structure figure that introduces gradient phosphorus doping layer on n type silicon-based substrate;
Fig. 4 is the back-light black-surface silicon solar battery structure on p type silicon-based substrate;
Fig. 5 is the back-light black-surface silicon solar battery structure figure that introduces gradient phosphorus doping layer on p type silicon-based substrate.
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 makes up solar cell with the black silicon material that wide spectrum absorbs as shady face, utilizes back-light black-surface silicon to absorb the infrared light that passes battery, and photoelectric current is contributed.The back-light black-surface silicon solar battery can solve the problem that the traditional silicon base battery can not absorb and transform the above near-infrared solar spectrum restriction of 1.1 μ m, improves the photoelectric conversion efficiency of silica-based solar cell.
Set forth back-light black-surface silicon solar battery structure provided by the invention below by accompanying drawing 1 to Fig. 5, its making step is as follows:
Step 1: do to fall into photosphere material 2 in the front of silicon-based substrate material 1, with its side to light as battery.Should fall into photosphere material and be the pyramid-like texture that forms by chemical corrosion or porous silicon or bore the antireflective top layer by the silicon that laser irradiation forms;
Step 2: make the black silicon material 3 that wide spectrum absorbs at the back side of silicon-based substrate material 1, with its shady face as battery.This layer material is under the sulphur based environment, forms by laser irradiation, and this layer material has＞85% absorptivity the sunlight in 0.25 μ m to the 2.5 mum wavelength scope;
Step 3: technology is done the passivation of Si oxide medium, is made positive gate electrode and the back side contact electrode and back of the body counterelectrode metal level of contacting respectively at battery side to light and shady face routinely, can finish the making of back-light black-surface silicon solar battery.
Silicon-based substrate in the above-mentioned steps 1 is monocrystalline silicon or polysilicon or amorphous silicon substrate, and its conduction type is n type or p type (being n-Si or p-Si), and its thickness d 1 is 5 μ m to 500 μ m.
It is directly to do at the positive of silicon-based substrate 1 or do on the boron-doping gradient layer that side to light in the above-mentioned steps 1 falls into photosphere material 2, and its thickness d 2 is 20nm to 50 μ m.The boron-doping gradient layer be the amorphous silicon layer by the polysilicon of boron diffusion or the boron-doping of deposit gradient or gradient boron-doping form from outward appearance to inner essence, the p type doped layer that successively decreases of boron concentration.
Back-light black-surface silicon layer 3 in the above-mentioned steps 2 is directly to do mixing on the phosphorus gradient layer at the back side or the work of silicon-based substrate 1, and its thickness d 3 is 20nm to 20 μ m, is to have the 20nm to 20 of being spaced apart μ m, and breadth wise dimension is silicon awl, silicon grain or the silicon hole of 20nm to 20 μ m.Mix the phosphorus gradient layer and be by phosphorous diffusion or deposit gradient mix that the polysilicon of phosphorus or amorphous silicon that gradient is mixed phosphorus form from outward appearance to inner essence, the n type doped layer that successively decreases of phosphorus concentration.
Back-light black-surface silicon solar battery structure on the embodiment 1:n type silicon-based substrate is seen Fig. 2, implementation process is as follows: in the front of n type silicon-based substrate, form the boron-doping gradient layer by the polysilicon of boron diffusion or the boron-doping of deposit gradient or the amorphous silicon of gradient boron-doping, on the boron-doping gradient layer, form side to light and fall into photosphere by chemical corrosion texture or laser irradiation; At the back side of n type silicon-based substrate, do to mix the black silicon that sulphur is impurity by laser irradiation, form the black silicon layer of shady face Doped n-type; Technology is done the passivation of Si oxide medium, is made positive gate electrode and back side contact electrode and the back of the body counterelectrode metal level of contacting respectively at battery side to light and shady face routinely then, has promptly finished the making of the back-light black-surface silicon solar battery structure on this n type silicon-based substrate.
The back-light black-surface silicon solar battery structure of introducing the gradient phosphorus doping on the embodiment 2:n type silicon-based substrate is seen Fig. 3, implementation process is as follows: at the n type silicon-based substrate back side, mix the polysilicon of phosphorus or amorphous silicon layer that gradient is mixed phosphorus forms from outward appearance to inner essence, phosphorus concentration successively decreases mixes the phosphorus gradient layer by phosphorous diffusion or deposit gradient, do to mix the black silicon that sulphur is impurity mixing phosphorus gradient layer surface, form the black silicon layer of shady face Doped n-type by laser irradiation; In n type silicon-based substrate front,, on the boron-doping gradient layer, make side to light and fall into photosphere by the polysilicon of boron diffusion or the boron-doping of deposit gradient or the boron-doping gradient layer that amorphous silicon forms from outward appearance to inner essence, boron concentration is successively decreased of gradient boron-doping; Technology is done the passivation of Si oxide medium, is made positive gate electrode and back side contact electrode and the back of the body counterelectrode metal level of contacting respectively at battery side to light and shady face routinely then, has promptly finished the back-light black-surface silicon solar battery of introducing the gradient phosphorus doping on this n type silicon-based substrate and has made.
Back-light black-surface silicon solar battery structure on the embodiment 3:p type silicon-based substrate is seen Fig. 4, and implementation process is as follows: in p type silicon-based substrate front, form side to light by chemical corrosion texture or laser irradiation and fall into photosphere; At the p type silicon-based substrate back side, do to mix the black silicon that sulphur is impurity by laser irradiation, form the black silicon layer of shady face Doped n-type; Technology is done the passivation of Si oxide medium, is made positive gate electrode and back side contact electrode and the back of the body counterelectrode metal level of contacting respectively at battery side to light and shady face routinely then, has promptly finished the making of the back-light black-surface silicon solar battery structure on this p type silicon-based substrate.
Introduce the back-light black-surface silicon solar battery of gradient phosphorus doping layer on the embodiment 4:p type silicon-based substrate and see Fig. 5, implementation process is as follows: at the back side of p type silicon-based substrate, mix the polysilicon of phosphorus or amorphous silicon that gradient is mixed phosphorus forms from outward appearance to inner essence, phosphorus concentration successively decreases mixes the phosphorus gradient layer by phosphorous diffusion or deposit gradient.Do to mix the black silicon that sulphur is impurity mixing phosphorus gradient layer surface, form the black silicon layer of shady face Doped n-type by laser irradiation; In the front of p type silicon-based substrate, the boron-doping gradient layer that by the polysilicon of boron diffusion or the boron-doping of deposit gradient or the amorphous silicon of gradient boron-doping, form from outward appearance to inner essence, boron concentration is successively decreased.On the boron-doping gradient layer, make side to light and fall into photosphere; Technology is done the passivation of Si oxide medium, is made positive gate electrode and back side contact electrode and the back of the body counterelectrode metal level of contacting respectively at battery side to light and shady face routinely then, has promptly finished the making of the back-light black-surface silicon solar battery structure of introducing gradient phosphorus doping layer on this p type silicon-based substrate.
In the various embodiments described above, at the boron-doping gradient layer that side to light is formed by the amorphous silicon of the polysilicon of boron diffusion or the boron-doping of deposit gradient or gradient boron-doping, its thickness range is 50nm to 100 μ m, and surperficial boron-doping concentration range is 10
17/ cm
3To 10
20/ cm
3The thickness range that the side to light of being done on boron-doping gradient layer surface falls into photosphere is 20nm to 50 μ m; Mix the phosphorus gradient layer at shady face by what phosphorous diffusion or deposit gradient mixed that the polysilicon of phosphorus or amorphous silicon that gradient is mixed phosphorus form, its thickness range is 50nm-100 μ m, and it is 10 that the phosphorus concentration scope is mixed on the surface
17/ cm
3To 10
20/ cm
3At the thickness range of mixing the black silicon layer of being done on phosphorus gradient layer surface of shady face Doped n-type is 20nm to 20 μ m.
Above-described specific embodiment; purpose of the present invention, technical scheme and beneficial effect are further described; institute is understood that; the above only is specific embodiments of the invention; be not limited to the present invention; within the spirit and principles in the present invention all, any modification of being made, be equal to replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. a back-light black-surface silicon solar battery structure is characterized in that, this structure comprises:
Silicon-based substrate;
At the positive sunken optical material layer of making of silicon-based substrate; And
The wide spectrum of making at the silicon-based substrate back side absorbs the black silicon material layer.
2. back-light black-surface silicon solar battery structure according to claim 1, it is characterized in that, described silicon-based substrate is monocrystalline silicon or polysilicon or amorphous silicon substrate, its conduction type is n type or p type, thickness is 5 μ m to 500 μ m, and positive is to have the pyramid-like of chemical texture or the silicon awl antireflective top layer of porous silicon or laser irradiation.
3. back-light black-surface silicon solar battery structure according to claim 1; it is characterized in that; described wide spectrum absorbs the black silicon material layer and adopts black silicon material; this black silicon material has the 20nm to 20 of being spaced apart μ m; breadth wise dimension is 20nm to 20 μ m; the degree of depth is silicon awl, silicon grain or the silicon hole of 20nm to 20 μ m, and this material has＞85% absorptivity the sunlight in 0.25 μ m to the 2.5 mum wavelength scope.
4. back-light black-surface silicon solar battery structure according to claim 1 is characterized in that, it is directly to be made on the silicon-based substrate back side that described wide spectrum absorbs the black silicon material layer, perhaps is made in the mixing on the phosphorus gradient layer of the silicon-based substrate back side.
5. back-light black-surface silicon solar battery structure according to claim 4, it is characterized in that the described phosphorus gradient layer of mixing is by phosphorous diffusion, or the deposit gradient is mixed the polysilicon of phosphorus, or the deposit gradient mixes the amorphous silicon of phosphorus, formed from outward appearance to inner essence, the n type doped layer that successively decreases of phosphorus concentration.
6. back-light black-surface silicon solar battery structure according to claim 1 is characterized in that, described sunken optical material layer is directly to be made on the silicon-based substrate front, perhaps is made on the boron-doping gradient layer in silicon-based substrate front, and its thickness is 20nm to 50 μ m.
7. back-light black-surface silicon solar battery structure according to claim 6, it is characterized in that described boron-doping gradient layer is by boron diffusion, or the polysilicon of deposit gradient boron-doping, or the amorphous silicon of deposit gradient boron-doping, formed from outward appearance to inner essence, the p type doped layer that successively decreases of boron concentration.
8. a method of making back-light black-surface silicon solar battery structure is characterized in that, this method comprises:
Step 1: make sunken optical material layer in the front of silicon-based substrate, with its side to light as battery;
Step 2: make wide spectrum at the back side of silicon-based substrate and absorb the black silicon material layer, with its shady face as battery;
Step 3: carry out the passivation of Si oxide medium respectively at battery side to light and shady face, form passivation layer, on passivation layer, make positive contact gate electrode and back side contact electrode and back of the body counterelectrode metal level then respectively.
9. the method for making back-light black-surface silicon solar battery structure according to claim 8, it is characterized in that, fall into optical material layer described in the step 1 and be the pyramid-like texture that forms by chemical corrosion or porous silicon or bore the antireflective top layer by the silicon that laser irradiation forms.
10. the method for making back-light black-surface silicon solar battery structure according to claim 8, it is characterized in that, it is under the sulphur based environment that wide spectrum described in the step 2 absorbs the black silicon material layer, form by laser irradiation, this layer material has＞85% absorptivity the sunlight in 0.25 μ m to the 2.5 mum wavelength scope.
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