CN102280526A - Method for improving solar cell efficiency and preparing efficient solar cell - Google Patents
Method for improving solar cell efficiency and preparing efficient solar cell Download PDFInfo
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- CN102280526A CN102280526A CN201110218925XA CN201110218925A CN102280526A CN 102280526 A CN102280526 A CN 102280526A CN 201110218925X A CN201110218925X A CN 201110218925XA CN 201110218925 A CN201110218925 A CN 201110218925A CN 102280526 A CN102280526 A CN 102280526A
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Abstract
The invention discloses a method for improving the efficiency of a solar cell. The method comprises: irradiating a solar cell doped region by using a pulse laser, enabling impurities in the doped region to form a saturated substitutional impurity which is activated, and reducing the clearance doping amount, thereby improving the semiconductor junction quality, and reducing the carrier recombination to achieve the aim of improving a short-circuit current and an open-circuit voltage and finally improving the solar cell efficiency.
Description
Technical field
The present invention relates to technical field of solar batteries, relate in particular to a kind of method that improves solar battery efficiency, and preparing the method for high efficiency solar cell based on this method, this solar cell includes but not limited to it is crystalline silicon, polysilicon, microcrystal silicon, receive solar cells such as crystal silicon, amorphous silicon, Copper Indium Gallium Selenide, cadmium sulfide or GaAs.
Background technology
Silicon solar cell is current production rate maximum, most widely used product, the laboratory tidemark of crystal silicon solar energy battery photovoltaic efficiency has reached 24.7%, and the commercial level of photovoltaic efficiency has only 18%, the polysilicon solar cell photovoltaic efficiency also has only 16%, people are constantly making great efforts to improve technology, improve the photovoltaic efficiency of battery, to reduce its gap
[1]Improved major technique means have: the one, and reduce the reflectivity of light, as adopt light trapping structures such as sphere, pyramid, taper, cylindricality, metal nanoparticle at battery surface, these measures can drop to the reflectivity of sunlight below 10%; The 2nd, the absorptivity of raising solar cell material is as backside reflection structure, multijunction structure, optically focused etc.; The 3rd, strengthen effective collection of photo-generated carrier, as thickening gate electrode, attenuate substrate, molten (FC) silicon substrate in employing district etc.For a long time, people pay attention to increasing the absorption of battery to sunlight always, and by photo-generated carrier being collected to improve short circuit current, and then improve battery efficiency.Yet, but ignored the raising of battery open circuit voltage, ignored the raising of semiconductor junction quality.The appearance of black silicon has then brought another kind of thinking to us.
The Eric Mazur professor of Harvard University in 1998 and his research team utilize femtosecond laser scanning to place sulphur hexafluoride (SF
6) silicon chip surface in the gas
[2], accident has obtained a kind of surperficial micro-structure cone material, and it has in the almost full solar spectrum scope of 0.25～2.5 μ m＞90% absorptivity, the effect that similar black matrix absorbs is so also be referred to as " deceiving silicon ".The black silicon of this surperficial micro-structure has following characteristics: the one, and incident light can have very strong wide spectrum anti-reflective effect constantly to the cone base refraction after entering cone structure; The 2nd, in the thick layer of the black silicon face nanometer scale of this micro-structure, sulphur is that material concentration is considerably beyond its saturated concentration in silicon crystal; The 3rd, this black silicon material has very high photoelectric respone, and the photoelectric respone of black silicon photoelectric diode at 850nm wavelength place that diameter is 250 μ m reaches 0.77A/W0V, 60A/W1V, 79A/W2V, the high value of 92A/W3V
[3], this will exceed more than 100 times than common silicon pin photodetector response, and the internal quantum efficiency when calculating its short circuit in view of the above has the obvious gain feature greater than 100%.
Although the cost of manufacture height of black silicon wafer awl, material surface exists lattice damage, defective and the complex centre of being introduced by laser in a large number, has hindered the output of photo-generated carrier, and the gain characteristic of black silicon photodetector is mathematical.Recently, we utilize ion injection+laser irradiation, successfully prepare the photodetector that gain is arranged under the low pressure, and its photoelectric respone at the 1000nm wave band is 100A/W5V.According to our research and understanding, the essence of black silicon just is the supersaturation displacement doping under the laser action, and this supersaturation displacement doping has promoted fermi level position, has formed the pumping to majority carrier under illumination.Therefore, black silicon provides a method that improves doping content of semiconductor (being that the supersaturation displacement is mixed) with laser irradiation for us, opened up a new thought and an approach that improves battery open circuit voltage, make battery open circuit voltage break away from the restriction of impurity solid solubility in the silicon, the theoretical upper limit of silion cell 30% efficient can be broken through on the principle, the maximized new round upsurge of research silicon photovoltaic effect will be caused.
List of references:
[1]Martin?A.Green，Solar?Cells：Operating?Principles，Technology，andSystem?Applications，University?of?New?South?Wales(1986).
[2] Xiong Shaozhen, Zhu Meifang, " solar cell basis and application ", chapter 5: silicon-based film solar cells, Science Press, front page, in October, 2009.
[3]Her?T?H，Finlay?R?J，Wu?C，Deliwala?S?and?Mazur，E，Microstructuringof?silicon?with?femtosecond?laser?pulses，Applied?Physics?Letters，73，1673(1998).
Summary of the invention
(1) technical problem that will solve
Along with the raising of impurity concentration in the silicon, the ratio that mix in the gap and displacement is mixed will be more and more higher, and 3 * 10
20/ cm
3Form under the displacement doping content in " dead band ", promptly more doping can not be activated, and only can form a large amount of gaps and mix, and be transformed into the complex centre, make battery performance worse and worse, and then quasi-Fermi level is defined.The problem that solves is: how with laser interstitial impurity to be transformed into substitutional impurity as much as possible in heavily doped region.
(2) technical scheme
For achieving the above object, technical scheme of the present invention is as follows:
A kind of method that improves solar cell open circuit voltage and efficient, this method is to adopt pulse laser that the solar cell doped region is carried out irradiation, make the impurity formation supersaturation displacement in the doped region mix and be activated, reduce gap doping quantity, thereby improve the semiconductor junction quality, it is compound to reduce charge carrier, reaches to improve short circuit current and open circuit voltage the final efficient that realizes improving solar cell.
In the such scheme, described solar cell is by crystalline silicon, polysilicon, microcrystal silicon, receives the solar cell that crystal silicon, amorphous silicon, Copper Indium Gallium Selenide, cadmium sulfide or GaAs be made.
In the such scheme, described pulse laser be pulse duration femtosecond, psec and nanosecond the order of magnitude high-power ultrafast laser, its pulse power density is at 10mJ/cm
2To 1000mJ/cm
2Between, its wavelength is between 1064 nanometer to 200 nanometers.
In the such scheme, described irradiation is to adopt the mode of single pass or repeatedly scanning to carry out, or adopt irradiation of large spot or repeatedly irradiation carry out, and scanning or irradiation do not destroy the surface topography of solar cell.
In the such scheme, impurity in the described doped region forms supersaturation displacement doping and is activated and is meant the given displacement doping content of static heat balance that the lattice displacement rate of impurity in solar cell base material top layer is higher than, and by discharging out more charge carrier after these oversaturated substitutional impurity ionization.
A kind of method for preparing high efficiency solar cell, this method comprises:
Adopt diffusion facilities that p type silicon substrate side to light is expanded phosphorus, form heavily doped n type silicon layer on the surface;
Adopt ultrafast laser that doped n type silicon layer is carried out irradiation;
Adopt screen process press that aluminium paste and baking are stenciled in the p type silicon substrate back side, on n type silicon layer, stencil silver slurry gate electrode and sintering again, finish the preparation of a solar battery sheet.
A kind of method for preparing high efficiency solar cell, this method comprises:
The first conduction type silicon substrate side to light is mixed, form heavily doped second conductivity type silicon layers on the surface; The first conduction type silicon substrate shady face is mixed, form heavily doped first conductivity type silicon layers on back of the body surface;
Adopt ultrafast laser that second conductivity type silicon layers that side to light has mixed is carried out irradiation, first conductivity type silicon layers that shady face has mixed is carried out irradiation;
Adopt screen process press that electrocondution slurry and baking are stenciled in the first conduction type silicon substrate back side, on second conductivity type silicon layers, stencil slurry gate electrode and sintering again, finish the preparation of a solar battery sheet.
A kind of method for preparing high efficiency solar cell, this method comprises:
The first conduction type silicon substrate side to light is mixed, form heavily doped first conductivity type silicon layers on the surface; The first conduction type silicon substrate shady face is mixed, form semiconductor junction on back of the body surface, and the heavily doped first conduction type silicon area and the second conduction type silicon area are arranged;
Adopt ultrafast laser that first conductivity type silicon layers that side to light has mixed is carried out irradiation, the first conduction type silicon area and the second conduction type silicon area that shady face has been mixed carry out irradiation;
Adopt screen process press to shady face printing conductive slurry and baking, adopt high energy laser beam that the substrate back first conduction type silicon area and the second conduction type silicon area are isolated, finish the preparation of a solar battery sheet.
In the such scheme, described silicon is crystalline silicon, or polysilicon.
In the such scheme, described employing ultrafast laser is carried out in the step of irradiation silicon substrate side to light and the shady face that has mixed, the pulse laser of this ultrafast laser be pulse duration femtosecond, psec and nanosecond the order of magnitude high-power ultrafast laser, its pulse power density is at 10mJ/cm
2To 1000mJ/cm
2Between, its wavelength makes the interstitial impurity in the n type silicon layer change the displacement activator impurity between 1064 nanometer to 200 nanometers, forms the carrier concentration of extraordinary heavily doped layer, and the carrier concentration behind its irradiation should be 1 * 10
19/ cm
3To 1 * 10
21/ cm
3Between, and determine by the peak of battery conversion efficiency.
(3) beneficial effect
From technique scheme as can be seen, the present invention has following beneficial effect:
1, utilizes the present invention, can improve the junction characteristic of photovoltaic cell, increase short circuit current and open circuit voltage, thereby improve the efficient of solar cell.
2, utilize the present invention, only increase the laser of a high-power large beam spot, exposure time is a nanosecond order, and the expense increase is not high, does not also influence existing speed of production, and holds between existing production technology.
Description of drawings
Fig. 1 is the schematic diagram that the present invention adopts the side of ultrafast laser irradiation solar cell substrates;
Fig. 2 is the static energy band diagram of the battery after the one-sided laser irradiation (unglazed according to static), mixes because n type doped region one side is subjected to ultrafast laser, and its Fermi level surpasses conduction band;
Fig. 3 is the dynamic energy band diagram of the battery after the one-sided laser irradiation (sun lights is dynamic), quasi-Fermi level E
FBecause of laser irradiation has surpassed conduction band, the quasi-Fermi level E between p, the n type district
NFAnd E
PFDifference be open circuit voltage.Because the raising of Fermi level has illustrated that more interstitial impurity changes substitutional impurity into, i.e. the improvement of semiconductor junction quality.
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.
At first realization principle of the present invention is carried out brief description below.
1, the supersaturation displacement under the laser action is mixed
Adopt ultrafast pulse laser irradiation, promptly light energy is by high concentration, and decides the top layer to absorb the degree of depth according to wavelength, form a non-equilibrium ultrafast heat treatment process of transient state, in this process, high-octane light is enough to interrupt lattice, and fills in impurity, and then formation supersaturation displacement is mixed, reduce interstitial impurity, improve displacement/gap doping ratio, improve the quality of semiconductor junction, reduce saturation current, the charge carrier that reduces between being with is compound.
Based on above-mentioned realization principle, the method of this raising solar battery efficiency provided by the invention, be to adopt pulse laser that irradiation is carried out in the battery doping zone, make the impurity formation supersaturation displacement in the doped region mix and be activated, reduce gap doping quantity, thereby thereby improve the semiconductor junction quality, it is compound to reduce charge carrier, reach and improve short circuit current and open circuit voltage, the final purpose that realizes improving battery efficiency.
Wherein, described solar cell is by crystalline silicon, polysilicon, microcrystal silicon, receives the solar cell that crystal silicon, amorphous silicon, Copper Indium Gallium Selenide, cadmium sulfide or GaAs etc. are made.Described pulse laser be pulse duration femtosecond, psec and nanosecond the order of magnitude high-power ultrafast laser, its pulse power density is at 10mJ/cm
2To 1000mJ/cm
2Between, its wavelength is between 1064 nanometer to 200 nanometers.Described irradiation is to adopt the mode of single pass or repeatedly scanning to carry out, or adopt irradiation of large spot or repeatedly irradiation carry out, and scanning or irradiation do not destroy the surface topography of solar cell.It is the given displacement doping content of static heat balance that the lattice displacement rate of impurity in solar cell base material top layer in the doped region is higher than that impurity in the described doped region forms supersaturation displacement activation, and by discharging out more charge carrier after these oversaturated substitutional impurity ionization.
Fig. 1 shows the schematic diagram that the present invention adopts the side of ultrafast laser irradiation solar cell substrates.Fig. 2 shows the static energy band diagram of battery (unglazed according to static) after the one-sided laser irradiation, mixes because n type doped region one side is subjected to ultrafast laser, and its Fermi level surpasses conduction band; Fig. 3 shows the dynamic energy band diagram of battery (sun lights is dynamic) after the one-sided laser irradiation, quasi-Fermi level E
FBecause of laser irradiation has surpassed conduction band, the quasi-Fermi level E between p, the n type district
NFAnd E
PFDifference be open circuit voltage.
Based on the method for above-mentioned raising solar battery efficiency, the embodiment of the invention provides a kind of method for preparing high efficiency solar cell, and this method comprises:
Step 1: adopt diffusion facilities that p type silicon substrate side to light is expanded phosphorus; Wherein, adopt diffusion facilities that p type silicon substrate side to light is expanded phosphorus, form normal n type silicon layer.
Step 2: adopt ultrafast laser that doped p type surface of silicon n type silicon layer is carried out irradiation; Wherein, the pulse laser of this ultrafast laser be pulse duration femtosecond, psec and nanosecond the order of magnitude high-power ultrafast laser, its pulse power density is at 10mJ/cm
2To 1000mJ/cm
2Between, its wavelength makes the interstitial impurity in the n type silicon layer change substitutional impurity between 1064 nanometer to 200 nanometers, forms extraordinary heavily doped n
+The doping content of type layer.
Step 3: adopt screen process press that aluminium paste and baking are stenciled in the p type silicon substrate back side, stencil silver slurry gate electrode and sintering again in p type silicon substrate front, finish the preparation of a solar battery sheet.
Based on the method for above-mentioned raising solar battery efficiency, the embodiment of the invention also provides a kind of method for preparing high efficiency solar cell, and this method comprises:
The first conduction type silicon substrate side to light is mixed, form heavily doped second conductivity type silicon layers on the surface; The first conduction type silicon substrate shady face is mixed, form heavily doped first conductivity type silicon layers on back of the body surface;
Adopt ultrafast laser that second conductivity type silicon layers that side to light has mixed is carried out irradiation, first conductivity type silicon layers that shady face has mixed is carried out irradiation; And
Adopt screen process press that electrocondution slurry and baking are stenciled in the first conduction type silicon substrate back side, on second conductivity type silicon layers, stencil slurry gate electrode and sintering again, finish the preparation of a solar battery sheet.
Based on the method for above-mentioned raising solar battery efficiency, the embodiment of the invention provides a kind of method for preparing high efficiency solar cell again, and this method comprises:
The first conduction type silicon substrate side to light is mixed, form heavily doped first conductivity type silicon layers on the surface; The first conduction type silicon substrate shady face is mixed, form semiconductor junction on back of the body surface, and the heavily doped first conduction type silicon area and the second conduction type silicon area are arranged;
Adopt ultrafast laser that first conductivity type silicon layers that side to light has mixed is carried out irradiation, the first conduction type silicon area and the second conduction type silicon area that shady face has been mixed carry out irradiation; And
Adopt screen process press to shady face printing conductive slurry and baking, adopt high energy laser beam that the substrate back first conduction type silicon area and the second conduction type silicon area are isolated, finish the preparation of a solar battery sheet.
In the above-mentioned method for preparing high efficiency solar cell, described silicon is crystalline silicon, or polysilicon.Described employing ultrafast laser is carried out in the step of irradiation silicon substrate side to light and the shady face that has mixed, the pulse laser of this ultrafast laser be pulse duration femtosecond, psec and nanosecond the order of magnitude high-power ultrafast laser, its pulse power density is at 10mJ/cm
2To 1000mJ/cm
2Between, its wavelength makes the interstitial impurity in the n type silicon layer change the displacement activator impurity between 1064 nanometer to 200 nanometers, forms the carrier concentration of extraordinary heavily doped layer, and the carrier concentration behind its irradiation should be 1 * 10
19/ cm
3To 1 * 10
21/ cm
3Between, and determine by the peak of battery conversion efficiency.
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. method that improves solar battery efficiency, it is characterized in that, this method is to adopt pulse laser that the solar cell doped region is carried out irradiation, make the impurity formation supersaturation displacement in the doped region mix and be activated, reduce gap doping quantity, thereby improve the semiconductor junction quality, it is compound to reduce charge carrier, reach and improve short circuit current and open circuit voltage, the final efficient that realizes improving solar cell.
2. the method for raising solar battery efficiency according to claim 1, it is characterized in that described solar cell is by crystalline silicon, polysilicon, microcrystal silicon, receives the solar cell that crystal silicon, amorphous silicon, Copper Indium Gallium Selenide, cadmium sulfide or GaAs be made.
3. the method for raising solar battery efficiency according to claim 1 is characterized in that, described pulse laser be pulse duration femtosecond, psec and nanosecond the order of magnitude high-power ultrafast laser, its pulse power density is at 10mJ/cm
2To 1000mJ/cm
2Between, its wavelength is between 1064 nanometer to 200 nanometers.
4. the method for raising solar battery efficiency according to claim 1, it is characterized in that, described irradiation is to adopt the mode of single pass or repeatedly scanning to carry out, or adopt irradiation of large spot or repeatedly irradiation carry out, and scanning or irradiation do not destroy the surface topography of solar cell.
5. the method for raising solar battery efficiency according to claim 1, it is characterized in that, impurity in the described doped region forms supersaturation displacement doping and is activated and is meant the given displacement doping content of static heat balance that the lattice displacement rate of impurity in solar cell base material top layer is higher than, and by discharging out more charge carrier after these oversaturated substitutional impurity ionization.
6. one kind prepares the method for high efficiency solar cell based on the described method of claim 1, it is characterized in that this method comprises:
Adopt diffusion facilities that p type silicon substrate side to light is expanded phosphorus, form heavily doped n type silicon layer on the surface;
Adopt ultrafast laser that doped n type silicon layer is carried out irradiation;
Adopt screen process press that aluminium paste and baking are stenciled in the p type silicon substrate back side, on n type silicon layer, stencil silver slurry gate electrode and sintering again, finish the preparation of a solar battery sheet.
7. one kind prepares the method for high efficiency solar cell based on the described method of claim 1, it is characterized in that this method comprises:
The first conduction type silicon substrate side to light is mixed, form heavily doped second conductivity type silicon layers on the surface; The first conduction type silicon substrate shady face is mixed, form heavily doped first conductivity type silicon layers on back of the body surface;
Adopt ultrafast laser that second conductivity type silicon layers that side to light has mixed is carried out irradiation, first conductivity type silicon layers that shady face has mixed is carried out irradiation;
Adopt screen process press that electrocondution slurry and baking are stenciled in the first conduction type silicon substrate back side, on second conductivity type silicon layers, stencil slurry gate electrode and sintering again, finish the preparation of a solar battery sheet.
8. one kind prepares the method for high efficiency solar cell based on the described method of claim 1, it is characterized in that this method comprises:
The first conduction type silicon substrate side to light is mixed, form heavily doped first conductivity type silicon layers on the surface; The first conduction type silicon substrate shady face is mixed, form semiconductor junction on back of the body surface, and the heavily doped first conduction type silicon area and the second conduction type silicon area are arranged;
Adopt ultrafast laser that first conductivity type silicon layers that side to light has mixed is carried out irradiation, the first conduction type silicon area and the second conduction type silicon area that shady face has been mixed carry out irradiation;
Adopt screen process press to shady face printing conductive slurry and baking, adopt high energy laser beam that the substrate back first conduction type silicon area and the second conduction type silicon area are isolated, finish the preparation of a solar battery sheet.
9. according to each described method in the claim 6,7 or 8, it is characterized in that described silicon is crystalline silicon, or polysilicon.
10. according to each described method in the claim 6,7 or 8, it is characterized in that, described employing ultrafast laser is carried out in the step of irradiation silicon substrate side to light and shady face, the pulse laser of this ultrafast laser be pulse duration femtosecond, psec and nanosecond the order of magnitude high-power ultrafast laser, its pulse power density is at 10mJ/cm
2To 1000mJ/cm
2Between, its wavelength makes the interstitial impurity in the n type silicon layer change the displacement activator impurity between 1064 nanometer to 200 nanometers, forms the carrier concentration of extraordinary heavily doped layer, and the carrier concentration behind its irradiation should be 1 * 10
19/ cm
3To 1 * 10
21/ cm
3Between, and determine by the peak of battery conversion efficiency.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103268852A (en) * | 2013-05-02 | 2013-08-28 | 中国科学院半导体研究所 | Method for preparing supersaturated-doping semiconductor thin film |
| CN106449863A (en) * | 2015-08-06 | 2017-02-22 | 上海凯世通半导体股份有限公司 | Processing method of photovoltaic device |
| CN109175728A (en) * | 2018-09-30 | 2019-01-11 | 大族激光科技产业集团股份有限公司 | It is a kind of for being cut by laser the device and method of low-temperature co-fired ceramics |
| CN116885049A (en) * | 2023-09-07 | 2023-10-13 | 武汉帝尔激光科技股份有限公司 | Laser doping method and TOPCON solar cell |
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| CN101403094A (en) * | 2008-10-28 | 2009-04-08 | 浙江大学 | Method for growth of type n ZnMgO Ga semiconductor film on flexible substrate |
| CN101570312A (en) * | 2009-06-11 | 2009-11-04 | 南京大学 | Method for realizing controlled doping of nano silicon quantum dots |
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| CN101403094A (en) * | 2008-10-28 | 2009-04-08 | 浙江大学 | Method for growth of type n ZnMgO Ga semiconductor film on flexible substrate |
| CN101570312A (en) * | 2009-06-11 | 2009-11-04 | 南京大学 | Method for realizing controlled doping of nano silicon quantum dots |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103268852A (en) * | 2013-05-02 | 2013-08-28 | 中国科学院半导体研究所 | Method for preparing supersaturated-doping semiconductor thin film |
| CN103268852B (en) * | 2013-05-02 | 2015-10-21 | 中国科学院半导体研究所 | A kind of preparation method of over-saturation doped semiconductor films |
| CN106449863A (en) * | 2015-08-06 | 2017-02-22 | 上海凯世通半导体股份有限公司 | Processing method of photovoltaic device |
| CN109175728A (en) * | 2018-09-30 | 2019-01-11 | 大族激光科技产业集团股份有限公司 | It is a kind of for being cut by laser the device and method of low-temperature co-fired ceramics |
| CN116885049A (en) * | 2023-09-07 | 2023-10-13 | 武汉帝尔激光科技股份有限公司 | Laser doping method and TOPCON solar cell |
| CN116885049B (en) * | 2023-09-07 | 2023-11-28 | 武汉帝尔激光科技股份有限公司 | Laser doping method and TOPCON solar cell |
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