CN103632934B - The Boron diffusion methods of N type silicon chips, crystal silicon solar energy battery and preparation method thereof - Google Patents
The Boron diffusion methods of N type silicon chips, crystal silicon solar energy battery and preparation method thereof Download PDFInfo
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- CN103632934B CN103632934B CN201310627344.0A CN201310627344A CN103632934B CN 103632934 B CN103632934 B CN 103632934B CN 201310627344 A CN201310627344 A CN 201310627344A CN 103632934 B CN103632934 B CN 103632934B
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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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- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention discloses a kind of Boron diffusion method of N-type silicon chip, crystal silicon solar energy battery and preparation method thereof.Boron diffusion method comprises the following steps：Depositional phase, the silicon chip after wet etching is put into diffusion furnace and is warming up to predetermined depositing temperature, and being passed through boron source, oxygen and nitrogen makes it be deposited in silicon chip surface；Diffusion phase is promoted, the post-depositional silicon chip in surface is warming up to predetermined diffusion temperature, diffusion is promoted, and oxygen and nitrogen are passed through during heating up and promoting diffusion；And the rear oxidation stage, the silicon chip after diffusion is cooled, and be passed through during cooling oxygen and nitrogen.The deposit and spread technique reduces the boron atom concentration of silicon chip surface, reduce the recombination rate and lattice damage on surface, by sheet resistance standard deviation (STDEV) control 2.0 or so, improve boron diffused sheet resistance uniformity, improve battery conversion efficiency, also reduce boron source consumption, it is to avoid excessive Pyrex of generation (BGS), save cost.
Description
Technical field
The present invention relates to technical field of solar cell manufacturing, in particular to a kind of boron diffused sheet of N-type silicon chip
Method, crystal silicon solar energy battery and preparation method thereof.
Background technology
Conventional fossil fuel is increasingly depleted, and in existing sustainable energy, solar energy is undoubtedly a kind of most clear
Clean, most universal and most potential alternative energy source.At present, in all solar cells, silicon solar cell is to obtain big
One of solar cell that commerce is promoted, this is due to that silicon materials have extremely abundant reserves in the earth's crust, while silicon
Solar cell compares other kinds of solar cell, there is excellent electric property and mechanical performance, silicon solar cell
In photovoltaic art in occupation of consequence.Therefore, the silicon solar cell of research and development high performance-price ratio has become photovoltaic enterprise of various countries
One of main direction of studying of industry.
In the manufacturing process of crystal silicon solar energy battery, the boron diffusion technique of N-type crystalline silicon battery forms P-N junction
Core process, because solid solubility of the boron atom in crystalline silicon is far below the solid solubility of phosphorus atoms, and boron diffusion is required at 900 DEG C
It is diffused, chemically reacts more complicated at a high temperature of above, is difficult to control, thus it is more difficult to the optimization of diffusion technique.It is existing
(one is more than 930 DEG C) deposits to silicon chip surface under some Boron diffusion methods are typically high temperature, while to miscellaneous under high temperature
Matter atom is diffused propulsion.But high temperature deposition, High temperature diffusion mode complex process, it is difficult to control, and single tube single is produced
Can be relatively low, the yield of every boiler tube only has 80%, and boron source consumption is larger, and excessive boron source reacts to form a large amount of boron with Quartz stove tube
Silica glass (BGS), not only the equipment such as heavy corrosion diffusion furnace, also creates the serious waste of boron source.Most of all, using
The uniformity for the diffused sheet resistance that the technique of high temperature deposition High temperature diffusion is obtained is poor, its standard deviation (STDEV) more than 4.0, from
And making p-n junction uneven, the built in field intensity of formation produces influence on the migration velocity of minority carrier, and in silicon chip table
Face generates thicker b-rich layer (SiB compounds), and etching, heavy damage silicon chip surface are difficult in subsequent wet chemical reaction
Lattice, adds recombination-rate surface, reduces the life-span of minority carrier, has had a strong impact on the conversion efficiency of battery.
Therefore, how boron diffusion technique is improved, with produce the solar battery sheet with uniform sheet resistance and then
Battery conversion efficiency is improved into the important directions of current research.
The content of the invention
The present invention is intended to provide a kind of Boron diffusion method of N-type silicon chip, crystal silicon solar energy battery and preparation method thereof, should
Method of diffusion reduces boron source consumption, improves the uniformity of silicon chip sheet resistance, and then improve battery conversion efficiency.
To achieve these goals, according to an aspect of the invention, there is provided a kind of Boron diffusion method of N-type silicon chip,
Comprise the following steps：Depositional phase, the silicon chip after wet etching is put into diffusion furnace and is warming up to predetermined depositing temperature, and is passed through
Boron source, oxygen and nitrogen make it be deposited in silicon chip surface；Diffusion phase is promoted, the post-depositional silicon chip in surface is warming up to pre-
Determine diffusion temperature, promote diffusion, and oxygen and nitrogen are passed through during heating up and promoting diffusion；And the rear oxidation stage,
By the silicon chip cooling after diffusion, and it is passed through during cooling oxygen and nitrogen.
Further, in the depositional phase, the temperature of deposition is 890 DEG C~940 DEG C, and the time of deposition is 15~40 minutes,
The flow of nitrogen is 22~24slm, and the flow of oxygen is 30sccm~320sccm, the flow of boron source for 120sccm~
1000sccm。
Further, in the depositional phase, the temperature of deposition is 900 DEG C~930 DEG C, and the time of deposition is 20~30 minutes,
The flow of nitrogen is 22~23slm, and the flow of oxygen is 30sccm~160sccm, the flow of boron source for 120sccm~
450sccm。
Further, in the depositional phase, the temperature of deposition is 925 DEG C, and the time of deposition is 25 minutes, and the flow of nitrogen is
22.5slm, the flow of oxygen is 65sccm, and the flow of boron source is 200sccm.
Further, the post-depositional silicon chip in surface is warming up to 950 DEG C~1000 DEG C, constant temperature diffusion with 5~15 DEG C/min
20~30 minutes.
Further, the post-depositional silicon chip in surface is warming up to 960 DEG C with 10 DEG C/min, constant temperature spreads 25 minutes.
Further, in heating diffusion phase, the flow of oxygen is 30~1000sccm, preferably 30~100sccm.
Further, the post-depositional silicon chip in surface is cooled to 750 DEG C~850 DEG C with 4~5.2 DEG C/min, preferably cooled
Most 800 DEG C.
Further, in the rear oxidation stage, the flow of oxygen is 10~20slm, and the flow of nitrogen is 5slm~10slm.
According to another aspect of the present invention there is provided a kind of preparation method of crystal silicon solar energy battery, including boron diffusion
Step, wherein boron diffusing step use any of the above-described kind of Boron diffusion method.
According to another aspect of the present invention there is provided a kind of crystal silicon solar energy battery, the crystal silicon solar energy battery is
It is made using above-mentioned preparation method.
Apply the technical scheme of the present invention, the technique promoted in N-type silicon chip boron diffusion process using low temperature depositing high temperature,
And optimising and adjustment is carried out to depositing temperature, diffusion temperature, boron source flow etc., the boron atom concentration of silicon chip surface is reduced, is reduced
The recombination-rate surface and the lattice damage of silicon chip surface of solar cell so that the average of sheet resistance is poor (STDEV)
Control is 2.0 or so, the problem of improving boron diffused sheet resistance lack of homogeneity, so that the p-n junction being evenly distributed.Using this
The there is provided method of invention is so that the qualification rate of silicon chip rises to 99.7% from current 90.8%, and the conversion for improving battery is imitated
Rate, while it also avoid generation Pyrex (BGS), reduces boron source consumption, has saved cost.
Brief description of the drawings
The Figure of description for constituting the part of the application is used for providing a further understanding of the present invention, and of the invention shows
Meaning property embodiment and its illustrate be used for explain the present invention, do not constitute inappropriate limitation of the present invention.In the accompanying drawings：
Fig. 1 is the distribution schematic diagram of the diffused sheet resistance of the silicon chip obtained using boron diffusion technique of the prior art；And
Fig. 2 is the distribution schematic diagram of the diffused sheet resistance of the silicon chip obtained using the boron diffusion technique of the present invention.
Embodiment
It should be noted that in the case where not conflicting, the feature in embodiment and embodiment in the application can phase
Mutually combination.Describe the present invention in detail below with reference to the accompanying drawings and in conjunction with the embodiments.
In order to solve the silicon chip side existed during using the Boron diffusion method for using high temperature deposition High temperature diffusion in the prior art
The problem of hindering lack of homogeneity, excessive boron source consumption and low battery conversion efficiency, the invention provides a kind of expansion of the boron of N-type silicon chip
Method is dissipated, is comprised the following steps：Depositional phase, the silicon chip after wet etching is put into diffusion furnace and heated up, and is passed through nitrogen, oxygen
Gas and boron source carry out surface deposition to silicon chip；Diffusion phase is promoted, the post-depositional silicon chip in surface is warming up to predetermined temperature, is promoted
Diffusion, and it is passed through oxygen and nitrogen during heating up and promoting diffusion；And the rear oxidation stage, the silicon chip after diffusion is dropped
Temperature, and it is passed through during cooling oxygen and nitrogen.
In the boron diffusion process of N-type silicon chip, the technique promoted using low temperature depositing high temperature, and to depositing and spreading temperature
Degree, boron source flow etc. are regulated and controled, and reduce the boron atom concentration of silicon chip surface, reduce the surface recombination speed of solar cell
The lattice damage of rate and silicon chip surface so that the average poor (STDEV) of sheet resistance is controlled 2.0 or so, improves boron expansion
The problem of dissipating sheet resistance lack of homogeneity, so that the p-n junction being evenly distributed.Silicon chip is caused using method provided by the present invention
Qualification rate rise to 98% from current 80%, improve the conversion efficiency of battery, at the same it also avoid generate Pyrex
(BGS) boron source consumption, is reduced, cost has been saved.
Silicon chip is the carrier of solar battery sheet, is needed before the boron diffusing procedure of solar cell is made to N-type silicon chip
Si wafer quality is detected, afterwards etched away the damage pollution layer of silicon chip surface, using the anisotropic etch of silicon, in silicon chip
Surface forms up-and-down matte.Due to incident light on surface by multiple reflections and refraction, matte can increase the suction of light
Receive, improve the short circuit current flow and conversion efficiency of battery.Silicon chip is washed and pickling after making herbs into wool, to remove silicon chip surface
Metal impurities, it is preferred to use do not influence silicon chip boron diffusion effect and can be the chemical combination for being dissolved in water by silicon chip surface converting metal impurities
The reagent of thing is cleaned to silicon chip, preferably to remove the metal impurities of silicon chip surface residual.Because silicon chip surface
The presence of metal impurities can influence boron at high temperature to the diffusion inside silicon chip, be formed in Carrier recombination center, reduction silicon chip
The life-span of the few son in portion, and then reduce the photoelectric transformation efficiency of N-type solar cell.Silicon chip after making herbs into wool is cleaned is put into diffusion furnace
Quartz boat in, there is in one quartz boat cutting, silicon chip is put into the cutting of quartz boat and make it that silicon chip is placed vertically, with guarantor
Demonstrate,prove the uniformity and yield rate of boron diffusion.
Silicon chip is warming up to depositing temperature, after after equitemperature stable a few minutes, starts to be passed through nitrogen, oxygen and boron source to silicon
Piece surface is deposited.Boron tribromide mainly has cost relatively as boron source in view of Boron tribromide employed in it
The of a relatively high advantage of low, purity.Boron tribromide is liquid under normal temperature and pressure, and one carries Boron tribromide using nitrogen and entered
In diffusion furnace, wherein boron source flow is the nitrogen flow for referring to carry Boron tribromide.
In order that obtaining in boiler tube, two-part mixed gas is evenly distributed unanimously up and down, largely improves away from boron source
The temperature control of deposition phase deposits is 890 DEG C~940 DEG C by the sheet resistance uniformity of silicon chip at the fire door region in area, the present invention,
The time control of deposition is 15~40 minutes, and the control of the flow of nitrogen is 22~24slm, the flow control of oxygen for 30sccm~
320sccm, the flow control of boron source is 120sccm~1000sccm.Wherein depositing temperature can influence silicon chip surface post-depositional
The thickness of boron atom concentration and b-rich layer, if depositing temperature is higher than 940 DEG C, can cause on the silicon chip surface in boron source region
The boron atom concentration of deposition is higher, and the concentration of boron atom is relatively low on the silicon chip surface away from boron source region, causes identical boiler tube
Sheet resistance difference is larger after the silicon chip diffusion of interior different warm areas；If depositing temperature is less than 890 DEG C, the anti-of boron source and oxygen can be caused
Answer speed slower, cause the process time to extend so that the boron atom concentration reduction of silicon chip surface deposition, made within the defined time
Into the waste of part boron source.
If sedimentation time is more than 40 minutes in above-mentioned deposition temperature range, boron atom diffusion inside silicon chip can be caused dense
Degree is larger, and the P-N junction of formation is deeper, and the destruction to silicon chip internal crystal framework is aggravated；If sedimentation time is less than 10 minutes, can
Cause the sheet resistance uniformity on surface after silicon chip diffusion poor, and diffusion depth is shallower, the boron atom diffusion concentration on surface is larger.Cause
This, the present invention considers, and it is 15 that depositing temperature, which is controlled simultaneously to control sedimentation time in the range of 890 DEG C~940 DEG C,
~40 minutes, surface boron atomic concentration was relatively low after being spread, the preferable boron diffusion silicon chip of inner homogeneous.
The present invention is by nitrogen flow control in 22~24slm, and oxygen flux control is in 30sccm~320sccm, boron source stream
Amount control is in 120sccm~1000sccm.Wherein the size of nitrogen flow mainly influences the silicon chip sheet resistance away from boron source region, such as
Fruit nitrogen flow is more than 24slm, then the boron source of source region can be caused to be advanced near fire door, cause the silicon in quartz boat
The boron source deposited on piece is relatively low, and only silicon chip edge position has a small amount of boron source, and intervening deposition amount is lower, diffused sheet resistance it is uniform
Property is poor；If nitrogen flow is less than 22slm, the boron atom concentration in fire door area can be caused relatively low, cause the uniform of diffused sheet resistance
Property is poor.If the flow of oxygen is more than 320sccm, the Pyrex of generation can be caused blocked up, and cause to expand inside silicon chip
Dissipate the boron atom concentration entered smaller；If the flow of oxygen be less than 30sccm, can cause generation boron oxide level it is relatively low and
Boron source can not react completely, but be discharged in the form of tail gas, cause the waste of boron source.If boron source flow is more than
1000sccm, then can lead to not reaction completely because boron source flow is excessive so that excessive boron source easily with quartz boat or boiler tube
Inwall reacts, the material such as generation boron oxide, causes the waste of boron source, and etch quartz boat and boiler tube；If boron source flow is less than
120sccm, then can cause silicon chip spread after sheet resistance uniformity it is very poor, the boron atom concentration of silicon chip surface is less.
Through considering, the present invention by the flow restriction of nitrogen, oxygen and boron source within the above range, largely
Reduce silicon chip surface boron atom concentration, diffusion after silicon chip recombination-rate surface and the lattice damage of silicon chip surface, compared with
The poor defect of boron diffused sheet resistance uniformity is improved well, so as to obtain the more uniform p-n junction of distribution, adds silicon chip
Minority carrier lifetime, significantly improve the conversion efficiency of battery.Using the low temperature depositing with condition in above range
And high-temperature diffusion process, significantly improve the conversion efficiency of battery.
Preferably, in the depositional phase, the temperature of deposition is 900 DEG C~930 DEG C, and the time of deposition is 20~30 minutes, nitrogen
The flow of gas is 22~23slm, and the flow of oxygen is 30sccm~100sccm, and the flow of boron source is 120sccm~450sccm.
Most preferably, in the depositional phase, the temperature of deposition is 925 DEG C, and the time of deposition is 25 minutes, and the flow of nitrogen is 22.5slm,
The flow of oxygen is 65ccm, and the flow of boron source is 200sccm.
Because solid solubility of the boron atom in crystalline silicon is far below the solid solubility of phosphorus atoms, it can pass through in low temperature depositing
Temperature is controlled to control the deposited concentration of silicon chip surface.The Boron tribromide being passed through generates boron oxide and bromine gas with oxygen reaction, and
Boron oxide and silicon atom reaction generation boron atom and silica, the boron-rich area of silicon chip surface one floor of formation of low temperature depositing, surface is in
It is light brown, and thickness is in tens nanometer ranges.In the depositional phase, there is also a small amount of boron source showing to silicon chip diffusion inside
As, but be due to that temperature is relatively low, diffusion rate is slower, and one is ignored.
In order that must be enriched in b-rich layer thicker on silicon chip surface continues uniform to form sheet resistance to silicon chip diffusion inside
P-n junction, complete surface deposition after, the post-depositional silicon chip in surface is warming up to 950 DEG C~1000 DEG C with 5~15 DEG C/min,
Constant temperature spreads 20~30 minutes.Stop being passed through boron source in heating and constant temperature diffusion process, and keep same with the depositional phase
Nitrogen flow, continue to be passed through the oxygen that flow is 30~1000sccm, the purpose for continuing to be passed through oxygen is easy to control silicon chip table
The degree of oxidation in face, be conducive to increase silicon chip surface Pyrex uniformity, by the flow of oxygen from the depositional phase when 30
~320sccm increases are 30~1000sccm, and remaining boron source is further reacted after the oxygen and deposition of big flow, are conducive to pair
Make up after deposition on silicon chip surface the problem of Pyrex uneven distribution.
It is higher than 15 DEG C/min if up speed, then Quartz stove tube can be caused because the coefficient of expansion is different and crackle occur；
If heating rate is less than 5 DEG C/min, the process time can be extended.If diffusion temperature is higher than 1000 DEG C, it can cause big
Measure boron atom to enter inside silicon chip, increase the concentration of boron atom at its internal lattice defect, increase complex centre；If diffusion
Temperature is less than 950 DEG C, then the concentration of boron atom inside silicon chip can be caused too low, be unfavorable for setting up stronger built in field so that
The migration velocity of carrier is restricted, so as to add the recombination probability of carrier.Therefore, through considering, the present invention is with 5
The post-depositional silicon chip in surface is warming up to 950 DEG C~1000 DEG C by~15 DEG C/min.It is further preferred that in a nitrogen atmosphere, with
The post-depositional silicon chip in surface is warming up to 980 DEG C, constant temperature diffusion into the surface 25 minutes by 10 DEG C/min.
Boron diffusion method after being improved using the present invention, and by oxygen and Boron tribromide flow, nitrogen flow and sink
Product and the time control of diffusion can be obtained by the silicon chip with uniform sheet resistance within the above range, while reducing silicon chip surface
B-rich layer, reduce the recombination rate of silicon chip surface carrier, improve the conversion efficiency of battery.
After diffusion is finished, silicon chip is cooled to 750 DEG C~850 DEG C, preferably 800 DEG C, and to stove during cooling
Nitrogen is passed through in pipe and oxygen is aoxidized to silicon chip.Wherein rate of temperature fall is 4~5.2 DEG C/min, nitrogen in temperature-fall period
Flow is 5~10slm, and the flow of oxygen is 10~20slm.In the rear oxidation stage, the effect of nitrogen is to promote and transport other
Gas, the effect of oxygen is the b-rich layer reaction generation Pyrex with silicon chip surface, to reduce the dense of silicon chip surface boron atom
Degree.If stopping being passed through oxygen in follow-up temperature-fall period, the concentration of silicon chip surface boron atom can not be reduced, and then can not reduce
The thickness of the b-rich layer of silicon chip surface, so that thicker b-rich layer is not thorough in wet chemical technology removal, and then reduces
Solar cell opens piezoelectricity pressure, short circuit current flow and fill factor, curve factor.The present invention in the rear oxidation stage by reducing the boron of silicon chip surface
Atomic concentration, is conducive to matching subsequent wet chemical technique.
The boiler tube of diffusion furnace of the present invention is divided into five warm areas, i.e. the first humidity province to the from boiler tube door area to boiler tube source region
Five humidity provinces, the different rate of temperature fall in cooling according to humidity province are also different.Preferably, the rate of temperature fall of the first humidity province is
4.7~5.2 DEG C/min, the rate of temperature fall in second temperature area is 4.5~4.7 DEG C/min, and the rate of temperature fall of the 3rd humidity province is
4.3~4.5 DEG C/min, the rate of temperature fall of the 4th humidity province is 4.15~4.3 DEG C/min, and the rate of temperature fall of the 5th humidity province is
4 DEG C/min.Using contributing to control the uniformity of silicon chip in each warm area in oxidizing process by the way of subregion cools.
There is provided a kind of preparation method of crystal silicon solar energy battery, including silicon chip are pre- according to another aspect of the present invention
Processing, surface wool manufacturing, phosphorus diffusion, wet etching, boron diffusion, plasma etching, wet chemical etching, coated with antireflection film, silk screen
Printing, sintering and encapsulation step, using any of the above-described kind of Boron diffusion method wherein in boron diffusing step.
In accordance with a further aspect of the present invention there is provided a kind of crystal silicon solar energy battery, the crystal silicon solar energy battery is
It is made using above-mentioned preparation method.
Beneficial effects of the present invention are further illustrated with reference to specific embodiment and comparative example.
Embodiment 1
1) depositional phase：N-type silicon chip is taken to carry out phosphorus diffusion, wet etching successively, by the silicon chip after wet etching (by Baoding
YINGLI SOLAR new energy Co., Ltd provides) it is placed in the boiler tube of diffusion furnace, silicon chip is placed perpendicular to quartz boat, and every boiler tube is put
Enter 500.925 DEG C are warming up to 10 DEG C/min, nitrogen, oxygen and the nitrogen reactive deposition 25 for carrying Boron tribromide is passed through
Minute, wherein oxygen flow is 65sccm, and the nitrogen flow for carrying Boron tribromide is 200sccm, and nitrogen flow is 22.5slm.
2) diffusion phase：Stopping is passed through oxygen and boron source, continues to be passed through the nitrogen that flow is 22.5slm, at the same with 10 DEG C/
Minute is warming up to 960 DEG C, is spread 25 minutes in 960 DEG C of lower surfaces.
3) the rear oxidation stage：Silicon chip is cooled into 800 DEG C (in such a way to cool：First humidity province is 4.7 DEG C/minute
Clock, second temperature area is 4.5 DEG C/min, and the 3rd humidity province is 4.3 DEG C/min, and the 4th humidity province is 4.15 DEG C/min, the 5th
Humidity province is 4 DEG C/min to cool), while continuing to be passed through nitrogen with 5slm flow, being passed through oxygen with 10slm flow enters
Row rear oxidation, the time is 20 minutes.
4) cooling is finished, and goes out boat, takes out silicon chip, completes boron diffusing step.
Embodiment 2
1) depositional phase：N-type silicon chip is taken to carry out phosphorus diffusion, wet etching successively, by the silicon chip after wet etching (by Baoding
YINGLI SOLAR new energy Co., Ltd provides) it is placed in the boiler tube of diffusion furnace, silicon chip is placed perpendicular to quartz boat, and every boiler tube is put
Enter 500.900 DEG C are warming up to 10 DEG C/min, nitrogen, oxygen and the nitrogen for carrying Boron tribromide, wherein oxygen stream is passed through
Measure as 160sccm, the nitrogen flow for carrying Boron tribromide is 450sccm, nitrogen flow is 23slm, and sedimentation time is 20 minutes.
2) diffusion phase：Stopping is passed through oxygen and boron source, continues to be passed through the nitrogen that flow is 23slm, while with 5 DEG C/minute
Clock is warming up to 950 DEG C, is spread 20 minutes in 950 DEG C of lower surfaces.
3) the rear oxidation stage：Silicon chip is cooled into 750 DEG C, and (cooling is in such a way：First humidity province is 5.2 DEG C/minute
Clock, second temperature area is 4.7 DEG C/min, and the 3rd humidity province is 4.5 DEG C/min, and the 4th humidity province is 4.3 DEG C/min, the 5th
Humidity province is 4 DEG C/min to cool), while continuing to be passed through nitrogen with 10slm flow, being passed through oxygen with 20slm flow enters
Row rear oxidation, the time is 30 minutes.
4) cooling is finished, and goes out boat, takes out silicon chip, completes boron diffusing step.
Embodiment 3
1) depositional phase：N-type silicon chip is taken to carry out phosphorus diffusion, wet etching successively, by the silicon chip after wet etching (by Baoding
YINGLI SOLAR new energy Co., Ltd provides) it is placed in the boiler tube of diffusion furnace, silicon chip is placed perpendicular to quartz boat, and every boiler tube is put
Enter 500.930 DEG C are warming up to 10 DEG C/min, nitrogen, oxygen and the nitrogen for carrying Boron tribromide, wherein oxygen stream is passed through
Measure as 30sccm, the nitrogen flow for carrying Boron tribromide is 120sccm, nitrogen flow is 22slm, and sedimentation time is 30 minutes.
2) diffusion phase：Stopping is passed through oxygen and boron source, continues to be passed through the nitrogen that flow is 24slm, while with 15 DEG C/minute
Clock is warming up to 1000 DEG C, is spread 30 minutes in 1000 DEG C of lower surfaces.
3) the rear oxidation stage：Silicon chip is cooled into 850 DEG C, and (cooling is in such a way：First humidity province is 5.0 DEG C/minute
Clock, second temperature area is 4.6 DEG C/min, and the 3rd humidity province is 4.4 DEG C/min, and the 4th humidity province is 4.2 DEG C/min, the 5th
Humidity province is 4 DEG C/min to cool), while continuing to be passed through nitrogen with 8slm flow, being passed through oxygen with 10slm flow enters
Row rear oxidation, the time is 10 minutes.
4) cooling is finished, and goes out boat, takes out silicon chip, completes boron diffusing step.
Embodiment 4
1) depositional phase：N-type silicon chip is taken to carry out phosphorus diffusion, wet etching successively, by the silicon chip after wet etching (by Baoding
YINGLI SOLAR new energy Co., Ltd provides) it is placed in the boiler tube of diffusion furnace, silicon chip is placed perpendicular to quartz boat, and every boiler tube is put
Enter 500.890 DEG C are warming up to 10 DEG C/min, nitrogen, oxygen and the nitrogen for carrying Boron tribromide, wherein oxygen stream is passed through
Measure as 30sccm, the nitrogen flow for carrying Boron tribromide is 120sccm, nitrogen flow is 24slm, and sedimentation time is 15 minutes.
2) diffusion phase：Stopping is passed through oxygen and boron source, continues to be passed through the nitrogen that flow is 24slm, while with 12 DEG C/minute
Clock is warming up to 960 DEG C, is spread 20 minutes in 960 DEG C of lower surfaces.
3) the rear oxidation stage：Silicon chip is cooled into 780 DEG C, and (cooling is in such a way：First humidity province is 5.0 DEG C/minute
Clock, second temperature area is 4.6 DEG C/min, and the 3rd humidity province is 4.4 DEG C/min, and the 4th humidity province is 4.2 DEG C/min, the 5th
Humidity province is 4 DEG C/min to cool), while continuing to be passed through nitrogen with 5slm flow, being passed through oxygen with 10slm flow enters
Row rear oxidation, the time is 10 minutes.
4) cooling is finished, and goes out boat, takes out silicon chip, completes boron diffusing step.
Embodiment 5
1) depositional phase：N-type silicon chip is taken to carry out phosphorus diffusion, wet etching successively, by the silicon chip after wet etching (by Baoding
YINGLI SOLAR new energy Co., Ltd provides) it is placed in the boiler tube of diffusion furnace, silicon chip is placed perpendicular to quartz boat, and every boiler tube is put
Enter 500.940 DEG C are warming up to 10 DEG C/min, nitrogen, oxygen and the nitrogen for carrying Boron tribromide, wherein oxygen stream is passed through
Measure as 320sccm, the nitrogen flow for carrying Boron tribromide is 1000sccm, nitrogen flow is 22.5slm, and sedimentation time is 40 points
Clock.
2) diffusion phase：Stopping is passed through oxygen and boron source, continues to be passed through the nitrogen that flow is 22.5slm, at the same with 5 DEG C/
Minute is warming up to 1080 DEG C, is spread 22 minutes in 1080 DEG C of lower surfaces.
3) the rear oxidation stage：Silicon chip is cooled into 830 DEG C, and (cooling is in such a way：First humidity province is 5.0 DEG C/minute
Clock, second temperature area is 4.6 DEG C/min, and the 3rd humidity province is 4.4 DEG C/min, and the 4th humidity province is 4.2 DEG C/min, the 5th
Humidity province is 4 DEG C/min to cool), while continuing to be passed through nitrogen with 10slm flow, being passed through oxygen with 18slm flow enters
Row rear oxidation, the time is 18 minutes.
4) cooling is finished, and goes out boat, takes out silicon chip, completes boron diffusing step.
Embodiment 6
1) depositional phase：N-type silicon chip is taken to carry out phosphorus diffusion, wet etching successively, by the silicon chip after wet etching (by Baoding
YINGLI SOLAR new energy Co., Ltd provides) it is placed in the boiler tube of diffusion furnace, silicon chip is placed perpendicular to quartz boat, and every boiler tube is put
Enter 500.860 DEG C are warming up to 10 DEG C/min, nitrogen, oxygen and the nitrogen for carrying Boron tribromide, wherein oxygen stream is passed through
Measure as 25sccm, the nitrogen flow for carrying Boron tribromide is 100sccm, nitrogen flow is 18slm, and sedimentation time is 10 minutes.
2) diffusion phase：Stopping is passed through oxygen and boron source, continues to be passed through the nitrogen that flow is 18slm, while with 3 DEG C/minute
Clock is warming up to 920 DEG C, is spread 15 minutes in 920 DEG C of lower surfaces.
3) the rear oxidation stage：Silicon chip is cooled into 700 DEG C, and (cooling is in such a way：First humidity province is 4.5 DEG C/minute
Clock, second temperature area is 4.3 DEG C/min, and the 3rd humidity province is 4.1 DEG C/min, and the 4th humidity province is 4.0 DEG C/min, the 5th
Humidity province is 3 DEG C/min to cool), while continuing to be passed through 3slm nitrogen and 8slm oxygen progress rear oxidation, the time is 8
Minute.
4) cooling is finished, and goes out boat, takes out silicon chip, completes boron diffusing step.
Embodiment 7
1) depositional phase：N-type silicon chip is taken to carry out phosphorus diffusion, wet etching successively, by the silicon chip after wet etching (by Baoding
YINGLI SOLAR new energy Co., Ltd provides) it is placed in the boiler tube of diffusion furnace, silicon chip is placed perpendicular to quartz boat, every boiler tube
It is put into 500.960 DEG C are warming up to 10 DEG C/min, nitrogen, oxygen and the nitrogen for carrying Boron tribromide, wherein oxygen is passed through
Flow is 340sccm, and the nitrogen flow for carrying Boron tribromide is 1100sccm, and nitrogen flow is 28slm, and sedimentation time is 45 points
Clock.
2) diffusion phase：Stopping is passed through oxygen and boron source, continues to be passed through the nitrogen that flow is 28slm, while with 20 DEG C/minute
Clock is warming up to 1200 DEG C, is spread 45 minutes in 1200 DEG C of lower surfaces.
3) the rear oxidation stage：Silicon chip is cooled into 900 DEG C, and (cooling is in such a way：First humidity province is 5.5 DEG C/minute
Clock, second temperature area is 5.3 DEG C/min, and the 3rd humidity province is 5.0 DEG C/min, and the 4th humidity province is 4.7 DEG C/min, the 5th
Humidity province is 5 DEG C/min and cooled), while continue to be passed through 25slm nitrogen and 15slm oxygen carries out rear oxidation, the time is
8 minutes.
4) cooling is finished, and goes out boat, takes out silicon chip, completes boron diffusing step.
Comparative example 1
1) the high temperature deposition High temperature diffusion stage：N-type silicon chip is taken to carry out phosphorus diffusion, wet etching successively, after wet etching
Silicon chip be placed in the boiler tube of diffusion furnace, silicon chip is placed perpendicular to quartz boat, and every boiler tube is put into 400.Risen with 10 DEG C/min
Temperature is passed through nitrogen, oxygen and the nitrogen for carrying Boron tribromide, wherein oxygen flow is 160sccm, carries tribromo to 938 DEG C
The nitrogen flow for changing boron is 500sccm, and nitrogen flow is 16.5slm, and sedimentation time is 43 minutes.
2) the rear oxidation stage：Silicon chip is down to by 750 DEG C, temperature-fall period with 10 DEG C/min of speed according to each warm area
The middle nitrogen and 5.5slm oxygen for continuing to be passed through 10slm, is kept for 20 minutes.
The silicon chip obtained after being spread in embodiment 1 to 7 and comparative example 1 is tested, using minority carrier lifetime tester
WT-2000 detects minority carrier life time, using four probes in a line pin sheet resistance resistivity tester (4P automatic four point
Probe meter model 280) sheet resistance uniformity is detected, specific data are shown in Table 1.Wherein, Fig. 1 is silicon chip in comparative example 1
Diffused sheet resistance distribution map, Fig. 2 is the diffused sheet resistance distribution map of silicon chip in embodiment 1.
By the silicon chip made in embodiment 1 to 7 and comparative example 1 through plasma etching, coated with antireflection film, silk-screen printing,
The step such as sintering and encapsulation, obtains solar battery sheet, determines the electrical property of solar battery sheet.Surveyed using Halm testers
Determine the Uoc of solar battery sheet, Isc, FF, Eff.Specific performance data are shown in Table 2.
Table 1
Table 2
From table 1 and Fig. 1~2 as can be seen that compared with comparative example 1, after technical scheme deposit and spread
The minority carrier life time and boron source consumption of obtained silicon chip are relatively low, and yield rate is higher, and the uniformity of diffused sheet resistance is preferable.Diffusion
Standard deviation (STDEV) that the uniformity of sheet resistance is distributed with diffused sheet resistance represents, that is, sheet resistance distribution situation on silicon chip after spreading,
STDEV=(sheet resistance maximum-sheet resistance minimum value)/(sheet resistance maximum+sheet resistance minimum value), standard deviation is smaller, illustrates to spread rear
Hinder uniformity better, it is on the contrary then poorer.
Diffused sheet resistance is slightly above the standard deviation that diffused sheet resistance is distributed in the average value of Fig. 1 diffused sheet resistances, Fig. 2 in Fig. 2
(STDEV) it is significantly less than the standard deviation that diffused sheet resistance is distributed in Fig. 1, illustrates that the sheet resistance uniformity of silicon chip in Fig. 2 is preferable, sheet resistance is equal
Even property directly influences energy band and the built in field distribution of doped energy-band in p-n junction, causes the boron atom concentration in Fig. 2 less than figure
1 boron atom concentration.
From Table 2, it can be seen that relative to existing high temperature deposition high-temperature diffusion process, using the low temperature depositing of the present invention
The technique that high temperature is promoted so that the minority carrier lifetime of solar cell piece has larger lifting, and diffused sheet resistance, which is evenly distributed, to be had
Beneficial to the built in field in p-n junction to producing stronger migration velocity during the carrier transport in each region of silicon chip, so as to subtract
Lack recombination probability of the defect level to carrier, it will be apparent that improve the open-circuit voltage and short circuit current flow of solar battery sheet,
And the fill factor, curve factor of cell piece is increased, improve the photoelectric transformation efficiency of solar battery sheet
As can be seen from the above description, following effect is achieved using the technique of the present invention：In the diffusion of N-type silicon chip boron
During, the technique promoted using low temperature depositing high temperature, and deposition and diffusion temperature, boron source flow etc. are regulated and controled, reduce
The boron atom concentration of silicon chip surface, reduces the recombination-rate surface of solar cell and the lattice damage of silicon chip surface so that
The average poor (STDEV) of sheet resistance is controlled 2.0 or so, improves the problem of boron diffused sheet resistance uniformity is poor, so that
To the p-n junction being evenly distributed.The qualification rate for causing silicon chip using method provided by the present invention rises from current 90.8%
To 99.7%, the conversion efficiency of battery is improved, while it also avoid generation Pyrex (BGS), boron source consumption is reduced, saved
About cost.
The preferred embodiments of the present invention are the foregoing is only, are not intended to limit the invention, for the skill of this area
For art personnel, the present invention can have various modifications and variations.Within the spirit and principles of the invention, that is made any repaiies
Change, equivalent substitution, improvement etc., should be included in the scope of the protection.
Claims (8)
1. a kind of Boron diffusion method of N-type silicon chip, it is characterised in that comprise the following steps：
Depositional phase, the silicon chip after wet etching is put into diffusion furnace and is warming up to predetermined depositing temperature, and is passed through boron source, oxygen
It is set to be deposited in the silicon chip surface with nitrogen, in the depositional phase, the temperature of the deposition is 890 DEG C~940 DEG C,
The time of the deposition is 15~40 minutes, and the flow of the nitrogen is 22~24slm, the flow of the oxygen for 30sccm~
320sccm, the flow of the boron source is 120sccm~1000sccm；
Diffusion phase is promoted, stopping is passed through oxygen and boron source, continues to be passed through nitrogen, while by the post-depositional silicon chip liter in surface
Temperature promotes diffusion to predetermined diffusion temperature, with 5~15 DEG C/min by the post-depositional silicon chip in surface be warming up to 950 DEG C~
1000 DEG C, constant temperature spreads 20~30 minutes；And
In the rear oxidation stage, the silicon chip after diffusion is cooled, and the oxygen is passed through and described during the cooling
Nitrogen, oxidation stage in the rear, the flow of the oxygen is 10~20slm, and the flow of the nitrogen is 5slm~10slm.
2. Boron diffusion method according to claim 1, it is characterised in that in the depositional phase, the temperature of the deposition
For 900 DEG C~930 DEG C, the time of the deposition is 20~30 minutes, and the flow of the nitrogen is 22~23slm, the oxygen
Flow be 30sccm~160sccm, the flow of the boron source is 120sccm~450sccm.
3. Boron diffusion method according to claim 2, it is characterised in that in the depositional phase, the temperature of the deposition
For 925 DEG C, the time of the deposition is 25 minutes, and the flow of the nitrogen is 22.5slm, and the flow of the oxygen is
65sccm, the flow of the boron source is 200sccm.
4. Boron diffusion method according to claim 1, it is characterised in that with 10 DEG C/min that surface is post-depositional described
Silicon chip is warming up to 960 DEG C, and constant temperature spreads 25 minutes.
5. Boron diffusion method according to claim 1, it is characterised in that with 4~5.2 DEG C/min that surface is post-depositional
The silicon chip is cooled to 750 DEG C~850 DEG C.
6. Boron diffusion method according to claim 5, it is characterised in that with 4~5.2 DEG C/min that surface is post-depositional
The silicon chip is cooled to 800 DEG C.
7. a kind of preparation method of crystal silicon solar energy battery, including boron diffusing step, it is characterised in that the boron diffusing step
Using the Boron diffusion method any one of claim 1 to 6.
8. a kind of crystal silicon solar energy battery, it is characterised in that be made using the preparation method described in claim 7.
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| CN105304753A (en) * | 2015-09-25 | 2016-02-03 | 中国电子科技集团公司第四十八研究所 | N-type cell boron diffusion technology |
| CN106129177B (en) * | 2016-07-18 | 2017-12-12 | 保定天威英利新能源有限公司 | A kind of solar cell boron diffusion device |
| CN107706269B (en) * | 2017-09-25 | 2019-05-03 | 江西展宇新能源股份有限公司 | A kind of diffusion technique and front surface processing method of solar energy polycrystal battery P-N junction |
| CN109559982A (en) * | 2018-10-23 | 2019-04-02 | 开封大学 | A kind of boron diffusion technique of N-type crystalline silicon solar cell |
| CN110518091A (en) * | 2019-08-12 | 2019-11-29 | 阜宁苏民绿色能源科技有限公司 | Oxygen technique after a kind of boron expands |
| CN114068758A (en) * | 2020-07-30 | 2022-02-18 | 一道新能源科技(衢州)有限公司 | Boron diffusion treatment control method and device and furnace tube |
| CN112599410B (en) * | 2020-12-16 | 2022-12-13 | 上海玻纳电子科技有限公司 | Method for improving boron diffusion of N-type monocrystalline silicon wafer |
| CN113571411B (en) * | 2021-07-12 | 2024-04-05 | 江苏顺风新能源科技有限公司 | Manufacturing method of N-type TOPCON solar cell |
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