CN105780127B - A kind of phosphorus diffusion method of crystal silicon solar energy battery - Google Patents
A kind of phosphorus diffusion method of crystal silicon solar energy battery Download PDFInfo
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- CN105780127B CN105780127B CN201610207469.1A CN201610207469A CN105780127B CN 105780127 B CN105780127 B CN 105780127B CN 201610207469 A CN201610207469 A CN 201610207469A CN 105780127 B CN105780127 B CN 105780127B
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B31/00—Diffusion or doping processes for single crystals or homogeneous polycrystalline material with defined structure; Apparatus therefor
- C30B31/06—Diffusion or doping processes for single crystals or homogeneous polycrystalline material with defined structure; Apparatus therefor by contacting with diffusion material in the gaseous state
- C30B31/08—Diffusion or doping processes for single crystals or homogeneous polycrystalline material with defined structure; Apparatus therefor by contacting with diffusion material in the gaseous state the diffusion materials being a compound of the elements to be diffused
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B31/00—Diffusion or doping processes for single crystals or homogeneous polycrystalline material with defined structure; Apparatus therefor
- C30B31/06—Diffusion or doping processes for single crystals or homogeneous polycrystalline material with defined structure; Apparatus therefor by contacting with diffusion material in the gaseous state
- C30B31/18—Controlling or regulating
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/22—Diffusion of impurity materials, e.g. doping materials, electrode materials, into or out of a semiconductor body, or between semiconductor regions; Interactions between two or more impurities; Redistribution of impurities
- H01L21/223—Diffusion of impurity materials, e.g. doping materials, electrode materials, into or out of a semiconductor body, or between semiconductor regions; Interactions between two or more impurities; Redistribution of impurities using diffusion into or out of a solid from or into a gaseous phase
Abstract
The invention discloses a kind of phosphorus diffusion methods of crystal silicon solar energy battery, include the following steps：(1) diffusion furnace is warming up to 760 ~ 780 DEG C；Into boat；(2) temperature adjustment is to 780 ~ 790 DEG C；(3) it is passed through and takes phosphorus source gas and dry oxygen, carry out low temperature diffusion；(4) stop being passed through taking phosphorus source gas and dry oxygen, in-furnace temperature is increased to 820 ~ 840 DEG C, is promoted, (5) carry out constant temperature propulsion；(6) diffusion in-furnace temperature is reduced to 700 ~ 750 DEG C, carries out cooling diffusion；(7) cool down and boat.The present invention opens the step that will anneal and is combined with secondary diffusion step, avoids the secondary problem reduced and Impurity Distribution is wide of the surface doping solubility because of caused by annealing in the prior art；So that Impurity Distribution is met shallow junction and narrow impurity demand, but also also add yield, improves photoelectric conversion efficiency.
Description
Technical field
The present invention relates to a kind of phosphorus diffusion methods of crystal silicon solar energy battery, belong to a kind of expansion of manufacture solar cell
System knot technique is dissipated, technical field of solar batteries is belonged to.
Background technology
Conventional fossil fuel is increasingly depleted, and in all sustainable energies, solar energy is undoubtedly a kind of most clear
Clean, most universal and most potential alternative energy source.Currently, in all solar cells, crystal-silicon solar cell is to obtain greatly
One of the solar cell that commerce is promoted, this is because silicon materials have extremely abundant reserves in the earth's crust, and meanwhile it is brilliant
Body silicon solar cell has excellent electric property and mechanical performance, therefore, crystalline silicon compared to other kinds of solar cell
Solar cell is occupied an important position in photovoltaic art.
The manufacturing process of current widely used crystal silicon solar energy battery is also normalized, mainly comprises the following steps：Chemistry
Cleaning and surface structuration processing (making herbs into wool)-diffusion-periphery etching-depositing antireflection film-prints electrode-are sintered.Wherein,
Diffusion is divided into phosphorus diffusion and is spread with boron, in the case where preparing solar cell using P-type wafer, needs in silicon chip surface
It carries out phosphorus diffusion and forms N layers, ultimately form PN junction, if on the contrary, when preparing using N-type silicon chip, need to carry out in silicon chip surface
Boron spreads to form PN junction.In the prior art, generally use phosphorus diffusion knot, the step are a passes in whole preparation process
Key step, quality will have a direct impact on the photoelectric conversion efficiency of battery, and in industrialized production, prepared by typical knot is divided into two
Step：Phosphorus oxychloride (the POCL that first step nitrogen passes through liquid3), by required impurity (phosphorus) current-carrying gas (nitrogen, oxygen)
It is transported to high temperature semiconductors material surface (silicon), impurity diffusion depth is about hundreds of nanometers；Second step is that high-temperature process (is driven
Enter processing), make pre-deposited continue to spread to matrix depths in the foreign atom on surface, material is thus formed one N+/N layers, this
The structure of sample is conducive to the preparation of rear electrode.
However, the high-temperature process of second step can cause in boiler tube, each warm area temperature fluctuation is larger, and difference is big, leads to PN junction not
Unanimously.
Therefore, a kind of phosphorus diffusion method of crystal silicon solar energy battery is developed, both can guarantee surface doping solubility, is made a large amount of
Impurity diffusion and meet shallow junction and narrow Impurity Distribution, and play and fractional condensation gettering effect is played to impurity, ensures PN junction consistency,
It is that those skilled in the art thirst for always the target for realizing but always failing to realize.
Invention content
The goal of the invention of the present invention is to provide a kind of phosphorus diffusion method of crystal silicon solar energy battery.
To achieve the above object of the invention, the technical solution adopted by the present invention is：A kind of phosphorus expansion of crystal silicon solar energy battery
Method is dissipated, is included the following steps：
(1) diffusion furnace is warming up to 760~780 DEG C, big nitrogen flow is 10000~30000sccm；Into boat；
(2) temperature adjustment is to 780~790 DEG C, and big nitrogen flow is 10000~30000sccm, furnace pressure control 50~
200mba；Temperature adjustment time control was at 600~800 seconds；
(3) it keeps above-mentioned temperature, pressure and big nitrogen flow constant, while being passed through and taking phosphorus source gas and dry oxygen, carry out low temperature
Diffusion, diffusion time are 600~900 seconds；
The flow of the oxygen is 1000~2000sccm；
The flow for taking phosphorus source gas is 0.8~2L/min；
(4) stop being passed through taking phosphorus source gas and dry oxygen, in-furnace temperature be increased to 820~840 DEG C, promoted in heating,
Big nitrogen flow control in 10000~30000sccm, furnace pressure control in 50~200mba, promote time control 300~
600 seconds；
(5) when in-furnace temperature is stablized at 820~840 DEG C, constant temperature propulsion is carried out, promotes time control 300~600
Second；Big nitrogen flow control is controlled in 10000~30000sccm, furnace pressure in 50~200mba；
(6) it keeps furnace pressure constant, diffusion in-furnace temperature is reduced to 700~750 DEG C, while being passed through and taking phosphorus source gas
And dry oxygen, cooling diffusion is carried out, annealing gettering is carried out while cooling, diffusion time is 1000~3000 seconds；
The flow of the oxygen is 2000~5000sccm；Big nitrogen flow is 10000~30000sccm；
The flow for taking phosphorus source gas is 0.8~2L/min；
(7) cool down and boat, complete diffusion process.
Above, step (3) spreads for constant source, this step is diffused as low temperature diffusion, and silicon chip surface is mixed rich in P after the meeting for diffusion
It is miscellaneous.Step (4) will be adulterated in pushing body, reduction surface dead layer improves internal doping to be passive, anaerobic heating propulsion step.Step
Suddenly it is passive, anaerobic propulsion in (5), this step is promoted in doping pushing body, and reduction surface dead layer is improved and adulterated in vivo, but
Under the premise of constant temperature, this step promotes can be more uniform.The diffusion source amount of step (6) is sufficient, is spread for cooling, effect has
Two：First, in conjunction with annealing process, has and segregate gettering effect, second, increase the doping of silicon chip surface, is conducive to and sintering
In conjunction with increase FF.
The source being passed through in diffusing step twice is POCl3.TongYuan's numerical value is different twice, and first time TongYuan is in silicon chip table
Face forms one layer of doping containing P, is then promoted by high temperature and is advanced to surface P doping in vivo；It can lead to surface doping in this way
It reduces, so also needing to secondary TongYuan, makes up surface doping.
In the step (6), annealing gettering is carried out while cooling, repairs lattice defect.
Preferably, in the step (1), diffusion furnace is warming up to 770~780 DEG C.
In above-mentioned technical proposal, the phosphorus source gas of taking in the step (3) and step (6) is nitrogen and POCl3。
Preferably, in the step (3), big nitrogen flow is that the flow of 18000sccm oxygen is 1500sccm；Take phosphorus source gas
The flow of body is 1L/min.
Preferably, in the step (6), diffusion in-furnace temperature is reduced to 740~750 DEG C.
Preferably, in the step (6), big nitrogen flow is 17500sccm；The flow of oxygen is 4000sccm；Take phosphorus source
The flow of gas is 1L/min.
In above-mentioned technical proposal, in the step (1), into boat time control at 600~800 seconds.
The crystal silicon solar energy battery obtained according to above-mentioned phosphorus diffusion method is claimed simultaneously in the present invention.
Since above-mentioned technical proposal is used, the present invention has following advantages compared with prior art：
1, the present invention develops a kind of phosphorus diffusion method of new crystal silicon solar energy battery, by annealing step and secondary diffusion
Step combines, and avoids the secondary reduction of the surface doping solubility because caused by being grown annealing time in the prior art and Impurity Distribution is wide
Problem；The present invention not only makes Impurity Distribution meet shallow junction and narrow impurity demand, but also also reduces the diffusion technique time, increases
Yield improves photoelectric conversion efficiency；
2, the heating of the invention by after low temperature diffusion, which promotes to walk, is refined as two steps propulsion (i.e. heating propulsion and constant temperature propulsion two
Step), promote the refinement of step to be beneficial to the uniformity of sheet resistance；It is demonstrated experimentally that comparing prior art, the silicon chip sheet resistance that the present invention obtains
Piece in, uniformity has a distinct increment between piece, complex centre is reduced, to increase out pressure and efficiency；
3, method simple possible of the invention, cost is relatively low, is suitable for popularization and application.
Specific implementation mode
The present invention is further described with reference to embodiment.
Embodiment one：
A kind of phosphorus diffusion method of crystal silicon solar energy battery, includes the following steps：
(1) diffusion furnace is warming up to 780 DEG C, big nitrogen flow is 20000sccm；Into boat, into boat time control 600~
800 seconds；
(2) 790 DEG C are warming up to, big nitrogen flow is 20000sccm, and furnace pressure is controlled in 100mba；Temperature adjustment time control
At 600~800 seconds；
(3) it keeps above-mentioned temperature, pressure and big nitrogen flow constant, while being passed through and taking phosphorus source gas and dry oxygen, carry out low temperature
Diffusion, diffusion time are 600~900 seconds；
The flow of the oxygen is 1500sccm；
The flow for taking phosphorus source gas is 1L/min；
(4) stop being passed through taking phosphorus source gas and dry oxygen, in-furnace temperature be increased to 820~840 DEG C, promoted in heating,
Big nitrogen flow control promotes time control at 300~600 seconds in 20000sccm, furnace pressure control in 50~200mba；
(5) when in-furnace temperature is stablized at 820~840 DEG C, constant temperature propulsion is carried out, promotes time control 300~600
Second；Big nitrogen flow control is controlled in 20000sccm, furnace pressure in 50~200mba；
(6) it keeps furnace pressure constant, diffusion in-furnace temperature is reduced to 750 DEG C, while being passed through and taking phosphorus source gas and do
Oxygen carries out cooling diffusion, and annealing gettering is carried out while cooling, and it is 1000~3000 seconds to repair lattice defect diffusion time；
The flow of the oxygen is 4000sccm；Big nitrogen flow control is in 17500sccm；
The flow for taking phosphorus source gas is 1.2L/min；
(7) cool down and boat, complete diffusion process.
Phosphorus source gas of taking in the step (3) and step (6) is nitrogen and POCl3。
Comparative example one
A kind of phosphorus diffusion method of crystal silicon solar energy battery, includes the following steps：
(1) diffusion furnace is warming up to 780 DEG C, big nitrogen flow is 20000sccm；Into boat, into boat time control 600~
800 seconds；
(2) 790 DEG C are warming up to, big nitrogen flow is 20000sccm, and furnace pressure is controlled in 100mba；Temperature adjustment time control
At 600~800 seconds；
(3) it keeps above-mentioned temperature and pressure constant, while being passed through and taking the dry oxygen of phosphorus source gas, carry out low temperature diffusion, when diffusion
Between be 600~900 seconds；
The flow of the oxygen is 1500sccm；Big nitrogen flow is 18000sccm；
The flow for taking phosphorus source gas is 1L/min；
(4) stop being passed through taking phosphorus source gas and dry oxygen, in-furnace temperature is increased to 820~840 DEG C, starts to promote, big nitrogen
Flow control promotes time control at 300~600 seconds in 20000sccm, furnace pressure control in 50~200mba；
(5) it when in-furnace temperature is stablized at 820~840 DEG C, while being passed through and taking phosphorus source gas and dry oxygen, carry out secondary expansion
It dissipates, diffusion time is 1000~3000 seconds；
The flow of the oxygen is 800sccm；Big nitrogen flow control is in 18500sccm；
The flow for taking phosphorus source gas is 1.2L/min；
(6) it keeps furnace pressure constant, diffusion in-furnace temperature is reduced to 700 DEG C, carries out process annealing, big nitrogen flow control
System is in 20000sccm；
(7) go out boat, complete diffusion process.
The sheet resistance of testing example and comparative example respectively, as a result such as following table：
The sheet resistance of embodiment
The sheet resistance of comparative example
From the data comparison in table：Uniformity is better than comparative example work in the diffusion technique piece of embodiment, between piece
Skill.
Then, the electrical property of testing example and comparative example, it is as a result as follows：
| EFF | Voc | Isc | FF | Rs | Rsh | |
| Embodiment one | 18.40% | 638.8 | 8.75 | 80.1 | 1.71 | 405.7 |
| Comparative example one | 18.32% | 637.2 | 8.75 | 80.0 | 1.91 | 484.9 |
By embodiment and comparative example as it can be seen that comparing prior art, in the piece of the silicon chip sheet resistance that the present invention obtains, between piece uniformly
Property have a distinct increment, complex centre reduce, the fabulous battery of sheet resistance uniformity can be obtained, technique of the invention improves out
Pressure and photoelectric conversion efficiency (promotion for having 0.08%), make Impurity Distribution meet shallow junction and narrow impurity demand.
Claims (8)
1. a kind of phosphorus diffusion method of crystal silicon solar energy battery, which is characterized in that include the following steps：
(1) diffusion furnace is warming up to 760 ~ 780 DEG C, big nitrogen flow is 10000 ~ 30000 sccm；Into boat；
(2) to 780 ~ 790 DEG C, big nitrogen flow is 10000 ~ 30000 sccm for temperature adjustment, and furnace pressure is controlled in 50 ~ 200 mbar
；Temperature adjustment time control was at 600 ~ 800 seconds；
(3) it keeps above-mentioned temperature, pressure and big nitrogen flow constant, while being passed through and taking phosphorus source gas and dry oxygen, carry out low temperature expansion
It dissipates, diffusion time is 600 ~ 900 seconds；
The flow of the oxygen is 1000 ~ 2000 sccm；
The flow for taking phosphorus source gas is 0.8 ~ 2 L/min；
(4) stop being passed through taking phosphorus source gas and dry oxygen, in-furnace temperature is increased to 820 ~ 840 DEG C, promoted in heating, big nitrogen
Flow control promotes time control at 300 ~ 600 seconds in 10000 ~ 30000 sccm, furnace pressure control in 50 ~ 200mbar；
(5) when in-furnace temperature is stablized at 820 ~ 840 DEG C, constant temperature propulsion is carried out, promotes time control at 300 ~ 600 seconds；Big nitrogen
Flow control is controlled in 10000 ~ 30000sccm, furnace pressure in 50 ~ 200mbar；
(6) it keeps furnace pressure constant, diffusion in-furnace temperature is reduced to 700 ~ 750 DEG C, while being passed through and taking phosphorus source gas and do
Oxygen carries out cooling diffusion, and annealing gettering is carried out while cooling, and diffusion time is 1000 ~ 3000 seconds；
The flow of the oxygen is 2000 ~ 5000 sccm；Big nitrogen flow is 10000 ~ 30000sccm；Take the flow of phosphorus source gas
For 0.8 ~ 2 L/min；
(7) cool down and boat, complete diffusion process.
2. the phosphorus diffusion method of crystal silicon solar energy battery according to claim 1, it is characterised in that：The step (1)
In, diffusion furnace is warming up to 770 ~ 780 DEG C.
3. the phosphorus diffusion method of crystal silicon solar energy battery according to claim 1, it is characterised in that：The step (3)
It is nitrogen and POCl with the phosphorus source gas of taking in step (6)3。
4. the phosphorus diffusion method of crystal silicon solar energy battery according to claim 1, it is characterised in that：The step (3)
In, big nitrogen flow is 18000 sccm；The flow of oxygen is 1500 sccm；The flow for taking phosphorus source gas is 1 L/min.
5. the phosphorus diffusion method of crystal silicon solar energy battery according to claim 1, it is characterised in that：The step (6)
In, diffusion in-furnace temperature is reduced to 740 ~ 750 DEG C.
6. the phosphorus diffusion method of crystal silicon solar energy battery according to claim 1, it is characterised in that：The step (6)
In, big nitrogen flow is 17500 sccm；The flow of oxygen is 4000 sccm；The flow for taking phosphorus source gas is 1 L/min.
7. the phosphorus diffusion method of crystal silicon solar energy battery according to claim 1, it is characterised in that：The step (1)
In, into boat time control at 600 ~ 800 seconds.
8. the crystal silicon solar energy battery that phosphorus diffusion method according to any one of claims 1 to 7 obtains.
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| CN107359219B (en) * | 2017-05-31 | 2019-04-09 | 中国电子科技集团公司第十三研究所 | Indium phosphide method of diffusion |
| CN107331731A (en) * | 2017-07-04 | 2017-11-07 | 合肥市大卓电力有限责任公司 | A kind of solar cell crystal silicon chip phosphorus diffusion method |
| CN109449246B (en) * | 2018-09-05 | 2021-03-05 | 浙江爱旭太阳能科技有限公司 | Silicon crystal sheet phosphorus diffusion method |
| CN109873052B (en) * | 2019-03-29 | 2021-04-20 | 山西潞安太阳能科技有限责任公司 | Annealing process after diffusion of solar cell |
| CN110265293A (en) * | 2019-05-24 | 2019-09-20 | 江苏润阳悦达光伏科技有限公司 | The P-N junction manufacture craft of solar battery |
| CN112447879A (en) * | 2019-09-05 | 2021-03-05 | 海南英利新能源有限公司 | Processing method of diffusion high sheet resistance silicon wafer |
| CN113078234B (en) * | 2020-01-03 | 2022-10-25 | 环晟光伏(江苏)有限公司 | Diffusion process for large-size silicon wafer |
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| JPH0793278B2 (en) * | 1989-07-24 | 1995-10-09 | 川崎製鉄株式会社 | Diffusion method of phosphorus into polycrystalline silicon film |
| CN100573928C (en) * | 2007-10-08 | 2009-12-23 | 苏州阿特斯阳光电力科技有限公司 | A kind of phosphorus diffusion method of making solar cell |
| CN101499501B (en) * | 2009-03-02 | 2010-08-25 | 苏州阿特斯阳光电力科技有限公司 | Phosphorus diffusion method for fabricating gallium doped monocrystaline silicon solar cell |
| CN102005502B (en) * | 2010-10-15 | 2012-10-10 | 苏州阿特斯阳光电力科技有限公司 | Method for improving phosphorus diffusion uniformity of solar cell |
| CN102005501A (en) * | 2010-10-15 | 2011-04-06 | 苏州阿特斯阳光电力科技有限公司 | Phosphorous diffusion method for producing solar cell |
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| CN102758256B (en) * | 2012-07-11 | 2015-04-22 | 苏州阿特斯阳光电力科技有限公司 | Phosphorus diffusion method for crystal silicon wafer |
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| CN102820383B (en) * | 2012-09-11 | 2015-07-01 | 江阴鑫辉太阳能有限公司 | Spread method of polycrystalline silicon solar cell |
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