CN101540346A - Method for manufacturing polysilicon thin film solar battery - Google Patents
Method for manufacturing polysilicon thin film solar battery Download PDFInfo
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- CN101540346A CN101540346A CN200810049380A CN200810049380A CN101540346A CN 101540346 A CN101540346 A CN 101540346A CN 200810049380 A CN200810049380 A CN 200810049380A CN 200810049380 A CN200810049380 A CN 200810049380A CN 101540346 A CN101540346 A CN 101540346A
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The invention provides a method for manufacturing a polysilicon thin film solar battery, which comprises the following steps: treating a 3N-grade-purity polysilicon chip, particularly a 3N-grade-purity heavily-doped polysilicon chip substrate having large-grain columnar crystals; forming a first semiconductor layer and a second semiconductor layer on the substrate through outward extending; forming a contact electrode; and forming an anti-reflection film on the second semiconductor layer. The method of the invention has the advantages of simple process, low cost, easy industrialization, and high efficiency of the manufactured solar battery.
Description
Technical field
The invention belongs to technical field of solar batteries, particularly a kind of method of on low-purity 3N level polysilicon substrate, making multi-crystal silicon film solar battery.
Relevant background technology
Solar energy is a kind of clean, cleaning, pollution-free, inexhaustible natural energy resources, is that electric energy is the important technology basis that utilizes solar energy on a large scale with solar energy converting, is subjected to the generally attention of countries in the world.Be subjected to the influence of single crystal silicon material price and monocrystalline silicon battery preparation process, substitute products as monocrystaline silicon solar cell, thin-film solar cells is with advantages such as its low cost, high conversion efficiency, suitable large-scale production, cause the extensive interest of manufacturer, the output of thin-film solar cells increases rapidly.Polycrystalline silicon thin film solar cell had both had efficient, stable, the nontoxic and resourceful advantage of crystal silicon cell, have the advantage that hull cell technology is simple, material is saved, cost reduces significantly again, the research and development of polycrystalline silicon thin film solar cell have become focus in recent years.And the key technology of polycrystalline silicon thin film solar cell research is the inexpensive substrate material of development function admirable.Under the common situation, people select cheap glass as substrate, and reaction generates silicon atom and is deposited on substrate surface under certain protection atmosphere then.But, directly form bigger crystal grain than difficult, and form hole at intergranule easily with CVD method deposit spathic silicon on glass, unfavorable to the battery of preparation greater efficiency.Therefore crystallization technique is more further improved, to improve crystallite dimension, its concrete grammar is: form the thin amorphous silicon layer of one deck with the chemical vapor deposition (CVD) method at substrate surface earlier, with high temperature this layer amorphous silicon layer annealed again, obtain bigger crystal grain, as inculating crystal layer, use the polysilicon film of CVD method grow thick with the thin large scale polysilicon layer of this layer in the above.As can be seen, the method that this CVD legal system is equipped with polysilicon thin-film solar battery also will be sought a kind of crystallization technique more preferably, such method also can form the high polycrystalline silicon thin film solar cell of efficient, but it has increased the complexity of technology, thereby increased the manufacturing battery cost, the raising of efficient can not remedy the cost that technology increases.Meanwhile,, thereby make epitaxial loayer produce defectives such as a large amount of dislocations, distinguish the clinkering crystalline substance once more and can not eliminate owing to not matching of substrate and the epitaxial loayer lattice and the coefficient of expansion.
Summary of the invention
The purpose of this invention is to provide a kind of low cost, high efficiency, be easy to the manufacture method of the multi-crystal silicon film solar battery of industrialization.
For reaching above-mentioned purpose, the present invention adopts following technical scheme: the multi-crystal silicon film solar battery manufacture method, be included on the substrate extension and form first semiconductor layer and the second semiconductor layer step, form the contact electrode step and form one deck antireflective coating step on second semiconductor layer, substrate is selected 3N level purity polysilicon chip.
Substrate is selected the highly doped polysilicon chip with big crystal grain column crystal of 3N level purity.
Polysilicon chip forms the impurity depletion layer through high-temperature process on the surface.
The polysilicon chip high temperature processing step is: polysilicon chip is put on the pedestal that reative cell has the radio frequency induction heater coil, in 1200 ± 20 ℃ of heating 15 ± 5 minutes, meanwhile fed hydrogen.
After the polysilicon chip high-temperature process in 1150 ± 5 ℃ of annealing in process 10 ± 5 minutes.
Extension forms the first semiconductor layer step: reactive component silane or trichlorosilane are diluted to volumetric concentration 1%-10%, doping component B through high-purity hydrogen
2H
6Be diluted to volumetric concentration 1%-5% through high-purity hydrogen, feed reative cell respectively simultaneously and carry out chemical vapour deposition (CVD) in 1150 ℃, be deposited into epitaxial loayer substrate is slightly stopped feed behind the lid, logical hydrogen to the impurity in the boundary layer drains, and continues feed again and is deposited into specific thickness.
Extension forms the second semiconductor layer step: in first semiconductor layer surface with liquid state diffusion source POCl
3Concentration is 10
19/ cm
3Diffuse to form second semiconductor layer to specific thickness, the formation p-n junction in 850-900 ℃.
Take out the polysilicon chip of band p-n junction and remove the impurity of edge deposit, carry out the antireflective coating deposit, form the solar cell upper/lower electrode again.
In the process of the present invention, both can carry out the extension of p N-type semiconductor N earlier, carry out the extension of p N-type semiconductor N then, and also can carry out the extension of n type semiconductor layer earlier, carry out the extension of p N-type semiconductor N then, only electrode direction changes.
The present invention uses the polysilicon of low-purity as substrate, because the epitaxial loayer semiconductor also is a silicon semiconductor layer, time-delay outside carrying out, the lattice energy of epitaxial loayer and substrate layer well mates, there are not crystal defect and internal stress, and epitaxial loayer can be seeded growth with the substrate, grows the polycrystal layer of big crystal grain.By polysilicon chip is carried out high-temperature heating treatment, the impurity that the polysilicon surface layer of low-purity is contained is able to diffusive evaporation and removes, thereby reduce to delay time outside epitaxial loayer is carried out diffuse pollution.If carry out annealing in process again, can also make substrate carry out the polysilicon that secondary crystallization forms big crystal grain.The epitaxial growth radio frequency induction coil heats of wide adaptability, can guarantee to form in the silicon chip effective temperature gradient, make the temperature of silicon chip surface be higher than the temperature at the back side, thereby the impurity that reduces outer time-delay substrate surface spreads to epitaxial loayer, make in the epitaxial loayer Impurity Distribution very steep, transition zone is very thin, make epitaxial loayer grow along the direction and the size of substrate crystal grain, epitaxial loayer can form the column crystal of good coarsegrain, each column crystal is a solar cell, a plurality of column crystals are equivalent to a plurality of solar cell parallel connections, thereby realize the high efficiency of solar cell.
The used equipment of the present invention is the CVD system equipment of popularizing very much, use this method source material to make high-purity material with physico-chemical process in advance, and equipment is fairly simple, and is easy to operate.The present invention's work simplification compared to existing technology in addition is easy to realize producing in enormous quantities, thereby can be used widely in industry, thereby promotes the industrialized development of solar cell.
Device therefor of the present invention should satisfy following operation requirement:
(1) can provide the process environments of a cleaning, condition of high vacuum degree;
(2) can controlledly be heated to 1200 ℃ to substrate;
(3) can be controlledly the gas delivery of reaction source gas and doping to substrate location, and better controlled flow, protection gas and carrier gas can be good at control;
(4) can controlledly intrasystem temperature gradient be set by load coil heating and radiation heating;
(5) can controlledly coordinate bi-product gas removal and the safety problem that technology produces.
The battery efficiency test that the product that utilizes the present invention to obtain carries out is as follows:
Laboratory apparatus comprises: solar photovoltaic assembly, 300 watts of tungsten halogen lamps of radiating light source, and 2 of digital multimeter, terminal block, load resistance, solar cell can be used pn junction diode D, constant-current source I
Ph, solar cell the series resistance R that causes such as electrode
sWith the parallel resistance R that is equivalent to the pn junction leakage current
ShThe circuit of forming represents that this circuit is the equivalent electric circuit of solar cell, as shown in Figure 4.
Solar photovoltaic assembly, digital multimeter, load resistance are connected into the loop by terminal block, change load resistance R, measure the flow through electric current I of load and the voltage V in the load, can obtain the E-I characteristic of this photovoltaic module.The distance of radiating light source and photovoltaic module will remain unchanged in the measuring process, carries out under identical intensity of illumination to guarantee whole measuring process.
Measure after two ends add load resistance, load R can be from zero to infinity.As load R
mWhen making the power of solar cell be output as maximum, the maximum power P of its correspondence
m=I
m* V
m, I
mAnd V
mBe respectively recommended current and optimum operating voltage.
The efficiency eta of solar cell is defined as the peak power output P of solar cell
mWith the integrated radiant emittance P that shines solar cell
InThe ratio.
When solar cell connected load R, the load E-I characteristic of gained as shown in Figure 5.The power output P of photovoltaic module is with the variation of load resistance R.Determine the short circuit current Isc of photovoltaic module under the different condition, open circuit voltage Voc, maximum power Pm, recommended current Im, operating voltage Vm and load resistance Rm, fill factor, curve factor FF, and these experimental datas are listed in the form compare.
| V oc(Mv) | J SC(mA/cm 2) | Fill factor, curve factor FF (%) | Efficient (%) |
| 618 | 25.5 | 76.0 | 12.1 |
| 611 | 28.9 | 78.8 | 13.9 |
| 621 | 26.2 | 75.6 | 12.3 |
The minority carrier life time experiments of measuring that the product that utilizes the present invention to obtain carries out is as follows:
The pulsed laser irradiation that infrared semiconductor laser sends is on silicon chip, thereby it is right to produce free electron-hole in sample.The optical maser wavelength that adopts in the measurement is 904nm, and its depth of penetration at silicon materials is about 30 μ m, thereby only just has the free carrier generation in the coating region of distance silicon chip upper surface≤30 μ m.After illumination stopped, because free electron and hole is compound, the sample carrier concentration reduced, and conductivity reduces thereupon.Because the microwave power of (from sample) reflection is directly proportional with the conductivity of sample, thereby, by record microwave reflection rate over time, can monitor (index in time) decay of sample conductivity.The microwave reflection rate that records concerned over time fit to an exponential curve that obtain its time constant, this constant is the few sub-useful life in sample measurement zone.Recording numerical value is 10.4us.
Sample： 001
Raster： 2mm
Size：
Scanradius： 38.73mm，57.01mm
Lifetime：
Average： 10.36us
Median： 7.8391us
Deviation： 104.74％
Minimum： 1.758us
Maximum： 143.18us
Time Range： 0.1ms
Time Cursor： Auto
Sensitivity： 50mV
Averaging： 16
MW Frequency： 10.463GHz
Laser Power： 120E11
Pulse Width： 200ns
Excited Area： 1mm2
Laser Wavelength：904nm
Head Height： 11mm
Description of drawings
Fig. 1 for the polysilicon chip substrate through after the high-temperature process by temperature gradient substrate impurity movement tendency distribution situation is set;
Fig. 2 is the device schematic diagram with solar cell character that utilizes the present invention to form;
Wherein, 1-electrode, 2-antireflective coating, 3-n type layer, 4-p type layer, 5-substrate, 6-back side ohmic contact.
Fig. 3 is the schematic diagram of epitaxial loayer crystal grain along substrate grain growth situation;
Wherein, 7-epitaxially grown layer crystal grain distributes, and 8-substrate crystal grain distributes.
Fig. 4 is the solar cell schematic equivalent circuit;
Fig. 5 is the load current-voltage diagram of solar cell.
Embodiment
A kind of manufacture method of multi-crystal silicon film solar battery, deposition p type layer deposits n type layer then earlier, comprises following implementation step:
(1) because the semi-conductive system of manufacturing epitaxial loayer is the system of airtight relatively cleaning, so at first charge into highly purified hydrogen cleaning reaction chamber.Fill hydrogen repeatedly, put the hydrogen operation, make whole system be in high clean state.
(2) 3N level purity silicon slice placed on the pedestal that has the radio frequency induction heater coil, to guarantee the whole area homogeneous heating of pedestal, then silicon chip is carried out high-temperature process, heating-up temperature to 1200 ℃ maintenance 20 minutes, the impurity of substrate surface is overflowed from substrate surface, meanwhile feed hydrogen and drive the impurity of overflowing in substrate edge interlayer surface, form the impurity depletion layer at substrate surface like this.Owing to there is temperature gradient, the dispersal direction of impurity and extension direction opposite tendency are kept the cleaning action of substrate surface impurity, do not influence the growth of extension.
(3) system is cleaned after, carry out the extension of p type semiconductor layer 1150 ℃ of preparations.Reactive component silane or trichlorosilane are 1%-10% through highly purified diluted in hydrogen to volumetric concentration, doping component B
2H
6Is 1%-5% through highly purified diluted in hydrogen to volumetric concentration, and the stainless steel conveying pipe that adopts inwall to polish is imported reative cell respectively simultaneously and carried out the epitaxial loayer deposit.The control of flow is realized by FMC (flow masscontroll, flow mass control) electromagnetically operated valve and pneumatic operated valve, feeds reative cell then.The growth rate of epitaxial loayer can be controlled by the flow of gas.Extension adopts two step epitaxial growth methods, the epitaxial growth of short time is only carried out in beginning, epitaxial loayer is slightly covered substrate, can stop substrate impurity further to be overflowed effectively from substrate, feed stops after during this period of time, only logical hydrogen is driven the impurity that remains in the boundary layer, and the impurity in the epitaxial loayer also can evaporate a part.Behind certain hour, the impurity in the boundary layer drains, and carries out the second stage epitaxial growth again, and up to the desired thickness of epitaxial loayer, the impurity that so just reduces in the substrate spreads to epitaxial loayer, and the impurity transition region is narrowed down.
(4) the diffusion system of carrying out the n type semiconductor layer is tied.With POCl
3Liquid source is a diffuse source, and diffusion temperature is 850-900 ℃, POCl
3Concentration be 10
19/ cm
3, the junction depth of making p-n junction is 0.3 μ m.
(5) silicon chip with p-n junction character that takes out deposit formation cleans, and removes the impurity of edge deposit, thereby can carry out the antireflective coating deposit, forms the solar cell upper/lower electrode again.Adopt antireflection layer to reduce the reflection of solar battery surface, and reduce surface recombination, can significantly improve the conversion efficiency of solar energy.
(6) carry out epitaxial layer quality detection and battery efficiency test at last.Detection, impurities concentration distribution detection, epitaxy layer thickness detection, fault and the dislocation density that resistivity is mainly carried out in the detection of epitaxial layer quality detects, the epitaxial loayer minority carrier life time is measured, the observation of epi-layer surface defective etc.With battery sheet and terminal block load resistance and digital multimeter formation circuit, thereby shine the efficient that the battery sheet is measured battery with the standard radiovoltaic generator then.The high energy of the battery efficiency that makes in this way reaches 12-14%.
In the above-mentioned implementation step, at first to prepare silicon substrate, under the prerequisite that guarantees enough low series resistance, mixing should not be too high to guarantee that the intact of substrate lattice and minimizing impurity spread to epitaxial loayer, then substrate is cleaned to eliminate impurities on surface of silicon chip, reduce autodoping at substrate backside deposition layer of silicon dioxide film with the evaporation of restraining back side impurity again.
Claims (8)
1, multi-crystal silicon film solar battery manufacture method, being included on the substrate extension forms first semiconductor layer and the second semiconductor layer step, forms the contact electrode step and form one deck antireflective coating step on second semiconductor layer, it is characterized in that substrate is selected 3N level purity polysilicon chip.
2, multi-crystal silicon film solar battery manufacture method according to claim 1 is characterized in that, substrate is selected the highly doped polysilicon chip with big crystal grain column crystal of 3N level purity.
3, multi-crystal silicon film solar battery manufacture method according to claim 1 and 2 is characterized in that, polysilicon chip forms the impurity depletion layer through high-temperature process on the surface.
4, multi-crystal silicon film solar battery manufacture method according to claim 3, it is characterized in that, the polysilicon chip high temperature processing step is: polysilicon chip is put on the pedestal that reative cell has the radio frequency induction heater coil, in 1200 ± 20 ℃ of heating 15 ± 5 minutes, meanwhile feed hydrogen.
5, multi-crystal silicon film solar battery manufacture method according to claim 4 is characterized in that, after the polysilicon chip high-temperature process in 1150 ± 5 ℃ of annealing in process 10 ± 5 minutes.
6, according to claim 4 or 5 described multi-crystal silicon film solar battery manufacture methods, it is characterized in that extension forms the first semiconductor layer step and is: reactive component silane or trichlorosilane are diluted to volumetric concentration 1%-10%, doping component B through high-purity hydrogen
2H
6Be diluted to volumetric concentration 1%-5% through high-purity hydrogen, feed reative cell respectively simultaneously and carry out chemical vapour deposition (CVD) in 1150 ℃, be deposited into epitaxial loayer substrate is slightly stopped feed behind the lid, logical hydrogen to the impurity in the boundary layer drains, and continues feed again and is deposited into specific thickness.
7, multi-crystal silicon film solar battery manufacture method according to claim 6 is characterized in that, extension forms the second semiconductor layer step and is: in first semiconductor layer surface with liquid state diffusion source POCl
3Concentration is 10
19/ cm
3Diffuse to form second semiconductor layer to specific thickness, the formation p-n junction in 850-900 ℃.
8, multi-crystal silicon film solar battery manufacture method according to claim 7 is characterized in that, takes out the polysilicon chip of band p-n junction and removes the impurity of edge deposit, carries out the antireflective coating deposit, forms the solar cell upper/lower electrode again.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102244143A (en) * | 2011-06-27 | 2011-11-16 | 光为绿色新能源有限公司 | Preparation method of crystalline silicon solar cell |
| CN114784148A (en) * | 2022-06-15 | 2022-07-22 | 浙江晶科能源有限公司 | Preparation method of solar cell, solar cell and photovoltaic module |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100416863C (en) * | 2006-10-13 | 2008-09-03 | 中国科学院上海技术物理研究所 | Cheap polysilicon thin film solar cell |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102244143A (en) * | 2011-06-27 | 2011-11-16 | 光为绿色新能源有限公司 | Preparation method of crystalline silicon solar cell |
| CN102244143B (en) * | 2011-06-27 | 2013-10-23 | 光为绿色新能源股份有限公司 | Preparation method of crystalline silicon solar cell |
| CN114784148A (en) * | 2022-06-15 | 2022-07-22 | 浙江晶科能源有限公司 | Preparation method of solar cell, solar cell and photovoltaic module |
| US11848397B1 (en) | 2022-06-15 | 2023-12-19 | Zhejiang Jinko Solar Co., Ltd. | Method for preparing solar cell and solar cell, photovoltaic module |
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