CN108598216A - Temperature and pressure changing diffusion process for improving photoelectric conversion efficiency - Google Patents
Temperature and pressure changing diffusion process for improving photoelectric conversion efficiency Download PDFInfo
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- CN108598216A CN108598216A CN201810376261.1A CN201810376261A CN108598216A CN 108598216 A CN108598216 A CN 108598216A CN 201810376261 A CN201810376261 A CN 201810376261A CN 108598216 A CN108598216 A CN 108598216A
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- 238000009792 diffusion process Methods 0.000 title claims abstract description 46
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 16
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 31
- 239000010703 silicon Substances 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 25
- 238000000137 annealing Methods 0.000 claims abstract description 9
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 5
- 230000003647 oxidation Effects 0.000 claims abstract description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 56
- 229910052757 nitrogen Inorganic materials 0.000 claims description 28
- 230000009466 transformation Effects 0.000 claims description 20
- 239000001301 oxygen Substances 0.000 claims description 14
- 229910052760 oxygen Inorganic materials 0.000 claims description 14
- 229910021420 polycrystalline silicon Inorganic materials 0.000 claims description 9
- 229920005591 polysilicon Polymers 0.000 claims description 9
- 230000008439 repair process Effects 0.000 claims description 4
- 238000010792 warming Methods 0.000 claims description 4
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 7
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 7
- 239000011574 phosphorus Substances 0.000 abstract description 7
- 235000012431 wafers Nutrition 0.000 abstract 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 11
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 6
- 239000013078 crystal Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000005247 gettering Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
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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 potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table 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
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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 potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table 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
- H01L21/228—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 liquid phase, e.g. alloy diffusion processes
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- 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
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Abstract
The invention discloses a variable-temperature variable-pressure diffusion process for improving photoelectric conversion efficiency, which comprises the following steps of: step one, high-temperature oxidation; step two, variable temperature and pressure diffusion: s1, constant-temperature variable-pressure diffusion: raising the temperature in the furnace to 790 ℃, keeping the temperature unchanged, and raising the pressure in the furnace from 100mbar to 800mbar within 160 s; s2, variable-temperature constant-pressure knot pushing: keeping the pressure in the furnace unchanged, and controlling the temperature in the furnace to rise from 790 ℃ to 835 ℃ within 450 s; s3, constant temperature and pressure diffusion: adjusting the temperature in the furnace to 800 ℃ within 30s and the pressure in the furnace to 200 mbar; and diffusing under the condition for 500-650 s; and step three, annealing and cooling. In the diffusion process, the temperature and the pressure are subjected to variable control, so that the requirement on the distance between silicon wafers is reduced, the phosphorus source consumption of the diffusion process is reduced by 20%, the total time of the diffusion process is reduced by more than 10min, the yield of the battery and the photoelectric conversion efficiency of the battery can be improved, and the method is very worthy of popularization.
Description
Technical field
The present invention relates to solar battery diffusion technology technical field, specially a kind of alternating temperature improving photoelectric conversion efficiency
Transformation diffusion technique.
Background technology
PN junction is the core of crystal silicon cell, and preparing uniformity, good high square resistance emitter is to improve crystal silicon cell conversion
The important channel of efficiency, it is compound not only to reduce front surface, to improve open-circuit voltage, and can largely improve short
The spectral response of wave, to improve short circuit current.The exploitation of high square resistance silver paste constantly makes a breakthrough, and has solved to generate because of sheet resistance value height
Series resistance is excessive and problem is easily burnt in transmitting, improves the square resistance of emitter and uniformity has become raising battery efficiency
Important means.
It is main at present that phosphorus oxychloride (POCl3) is used to be prepared with constant-pressure and high-temperature diffusion way for liquid source, sheet resistance value size
And in piece between uniformity be the main characterization method of diffusion furnace diffusion property.Constant-pressure and high-temperature diffuser is generally selected in nozzle or pipe tail
Air inlet takes the other end to by big nitrogen stream, easily causes the phenomenon that one end concentration is high, other end concentration is low, and gas under normal pressure
Body molecular free path is smaller, and each region silicon chip contact phosphorus source probability gap is larger, can only control square resistance by adjusting temperature
Value, but can not still ensure in piece and uniformity between piece.
Normal pressure diffusion can reduce the consistency of diffusion PN junction longitudinal direction doping concentration, to influence PN junction depth and electrical property
Consistency prepares electrode under identical silk-screen printing sintering condition, can improve bad ratio of the larger generation of due to leakage current, together
When reduce the consistency of battery performance, improve rudimentary (B pieces) cell piece ratio, the reduction of extreme influence battery manufacturing cost.
In the prior art, application No. is a kind of high square resistance crystal silicon cell low pressure of " 201410582186.6 " to spread work
Skill is diffused by the adjustment to pressure in stove by the way of low pressure, and small nitrogen total flow and total time can be effectively reduced,
Diffusing, doping concentration genesis analysis can be preferably controlled, and can be effectively improved in piece and diffused sheet resistance uniformity between piece, still
For growing photovoltaic industry, only by the diffusion technique being adjusted to pressure, the silicon chip produced is in photoelectricity
Demand is can no longer meet in the promotion of transfer efficiency, so needing a kind of new diffusion technique.
Invention content
It is above-mentioned to solve the purpose of the present invention is to provide a kind of alternating temperature transformation diffusion technique improving photoelectric conversion efficiency
The problem of being proposed in background technology.
To achieve the above object, the present invention provides the following technical solutions：
A kind of alternating temperature transformation diffusion technique improving photoelectric conversion efficiency, includes the following steps：
Step 1: high-temperature oxydation：After silicon chip is put into diffusion furnace, pressure is 100mbar in setting stove, temperature is 780 DEG C,
Oxidation 100s -150s is carried out to silicon chip；
Step 2: alternating temperature transformation is spread：It is diffused, is as follows using gradepervasion method：
S1, the diffusion of constant temperature transformation：In-furnace temperature is risen to 790 DEG C, keeps temperature-resistant, pressure is in 160s in control stove
800mbar is boosted to from 100mbar；Big nitrogen flow is 8000ml/min -9000ml/min；Small nitrogen flow is 400ml/min-
500ml/min；Oxygen flow is 600ml/min -1500ml/min；
S2, alternating temperature constant pressure knot：Keep pressure in stove constant, control in-furnace temperature is warming up to 835 in 450s from 790 DEG C
℃；Big nitrogen flow is 5000ml/min -6000ml/min；Small nitrogen flow is 0ml/min；Oxygen flow is 0ml/min；
S3, constant temperature and pressure diffusion：In 30s by in-furnace temperature be adjusted to 800 DEG C, stove internal pressure be adjusted to 200mbar by force；And
500s -650s is spread under this condition；Big nitrogen flow is 1000ml/min -2000ml/min；Small nitrogen flow is 100ml/
min—150ml/min；Oxygen flow is 200ml/min -250ml/min；
Step 3: annealing cooling：Temperature is reduced to anneal to repair lattice and despumation.
Preferably, the technological parameter of step 3 is：Annealing temperature is 600 DEG C -700 DEG C；In 900s by pressure in stove from
200mbar rises to 800mbar, again from the near 200mbar of 800mbar.
Preferably, the silicon chip spacing is 1.5mm-1.8mm, and high square resistance value is 90-120 Ω/, sheet resistance in silicon chip
Unevenness is 2% -2.5%.
Preferably, the silicon chip is p-type polysilicon piece, and the resistivity of the p-type polysilicon piece is 1 Ω of Ω cm -2
Cm, thickness are 150 μm -180 μm.
Compared with prior art, the beneficial effects of the invention are as follows：
The present invention by the way that the diffusion process of gradepervasion is carried out process parameter control, lead to by the diffusion of first step constant temperature transformation
It crosses and pressure is incrementally increased, more nonactive phosphorus sources, second step constant pressure alternating temperature knot, in alternating temperature are formed in silicon chip surface
Gradually under temperature-rise period so that the phosphorus source gettering effect of silicon chip surface is more preferable, and knot effect is stronger, and third walks constant temperature and pressure and expands
It dissipates, can phosphorus source further be diffused into silicon chip, realize preferably doping effect.
The present invention carries out Variable Control during diffusion technique, to temperature and pressure, is wanted to silicon chip spacing to reduce
It asks so that the phosphorus source dosage of diffusion technique reduces 20%, and diffusion technique total time reduces 10min or more, and can improve electricity
Pond yield rate and cell photoelectric transfer efficiency, are highly promoted.
Description of the drawings
Fig. 1 is the process system flow diagram of the present invention.
Specific implementation mode
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete
Site preparation describes, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.It is based on
Embodiment in the present invention, it is obtained by those of ordinary skill in the art without making creative efforts every other
Embodiment shall fall within the protection scope of the present invention.
Referring to Fig. 1, the present invention provides a kind of technical solution：
A kind of alternating temperature transformation diffusion technique improving photoelectric conversion efficiency, includes the following steps：
Step 1: high-temperature oxydation：After silicon chip is put into diffusion furnace, pressure is 100mbar in setting stove, temperature is 780 DEG C,
Oxidation 100s -150s is carried out to silicon chip；
Step 2: alternating temperature transformation is spread：It is diffused, is as follows using gradepervasion method：
S1, the diffusion of constant temperature transformation：In-furnace temperature is risen to 790 DEG C, keeps temperature-resistant, pressure is in 160s in control stove
800mbar is boosted to from 100mbar；Big nitrogen flow is 8000ml/min -9000ml/min；Small nitrogen flow is 400ml/min-
500ml/min；Oxygen flow is 600ml/min -1500ml/min；
S2, alternating temperature constant pressure knot：Keep pressure in stove constant, control in-furnace temperature is warming up to 835 in 450s from 790 DEG C
℃；Big nitrogen flow is 5000ml/min -6000ml/min；Small nitrogen flow is 0ml/min；Oxygen flow is 0ml/min；
S3, constant temperature and pressure diffusion：In 30s by in-furnace temperature be adjusted to 800 DEG C, stove internal pressure be adjusted to 200mbar by force；And
500s -650s is spread under this condition；Big nitrogen flow is 1000ml/min -2000ml/min；Small nitrogen flow is 100ml/
min—150ml/min；Oxygen flow is 200ml/min -250ml/min；
Step 3: annealing cooling：Temperature is reduced to anneal to repair lattice and despumation；Technological parameter is：Annealing
Temperature is 600 DEG C -700 DEG C；Pressure in stove is risen into 800mbar, near from 800mbar again from 200mbar in 900s
200mbar。
Preferably as one, the silicon chip spacing is 1.5mm-1.8mm, and high square resistance value is 90-120 Ω/, in silicon chip
The unevenness of sheet resistance is 2% -2.5%.
Preferably as one, the silicon chip is p-type polysilicon piece, and the resistivity of the p-type polysilicon piece is 1 Ω cm-
2 Ω cm, thickness are 150 μm -180 μm.
The big nitrogen is used to keep the pressure of boiler tube, prevents ambient atmos from entering, while playing the work of mixed reaction gas
With；The small nitrogen is mainly used to carry POCl3 phosphorus sources, participates in deposition reaction；Oxygen is dry oxygen.
Embodiment：
A kind of alternating temperature transformation diffusion technique improving photoelectric conversion efficiency, includes the following steps：
Step 1: high-temperature oxydation：After silicon chip is put into diffusion furnace, pressure is 100mbar in setting stove, temperature is 780 DEG C,
Oxidation 100s is carried out to silicon chip；
Step 2: alternating temperature transformation is spread：It is diffused, is as follows using gradepervasion method：
S1, the diffusion of constant temperature transformation：In-furnace temperature is risen to 790 DEG C, keeps temperature-resistant, pressure is in 160s in control stove
800mbar is boosted to from 100mbar；Big nitrogen flow is 8000ml/min；Small nitrogen flow is 400ml/min；Oxygen flow is
600ml/min；
S2, alternating temperature constant pressure knot：Keep pressure in stove constant, control in-furnace temperature is warming up to 835 in 450s from 790 DEG C
℃；Big nitrogen flow is 5000ml/min；Small nitrogen flow is 0ml/min；Oxygen flow is 0ml/min；
S3, constant temperature and pressure diffusion：In 30s by in-furnace temperature be adjusted to 800 DEG C, stove internal pressure be adjusted to 200mbar by force；And
500s is spread under this condition；Big nitrogen flow is 1000ml/min；Small nitrogen flow is 100ml/min；Oxygen flow is 200ml/
min；
Step 3: annealing cooling：Temperature is reduced to anneal to repair lattice and despumation；Technological parameter is：Annealing
Temperature is 600 DEG C；Pressure in stove is risen into 800mbar from 200mbar in 900s, again from the near 200mbar of 800mbar.
Use silicon chip for p-type polysilicon piece, the resistivity of the p-type polysilicon piece is 1 Ω cm, and thickness is 150 μm, silicon
Piece spacing is 1.5mm -1.8mm, and high square resistance value is 120 Ω/, and the unevenness of sheet resistance is 2% in silicon chip.
Conventional diffusion processes compare：
Polysilicon chip PN junction is prepared using the alternating temperature transformation diffusion technique of above-described embodiment, is prepared through follow-up same process
The battery of the producing line output of 5000 polycrystal silicon cells and ordinary temperature routine pressure in the prior art be averaged electrical property comparison
As shown in table 1 below：
Table 1
It can be seen that according to data in table 1, the photoelectric conversion efficiency of the cell piece of the diffusion technique preparation of the embodiment of the present invention
0.08% promotion has been obtained, has there is qualitative leap, has there is positive innovation reform meaning to photovoltaic industry.
It although an embodiment of the present invention has been shown and described, for the ordinary skill in the art, can be with
Understanding without departing from the principles and spirit of the present invention can carry out these embodiments a variety of variations, modification, replace
And modification, the scope of the present invention is defined by the appended.
Claims (4)
1. a kind of alternating temperature transformation diffusion technique improving photoelectric conversion efficiency, which is characterized in that include the following steps：
Step 1: high-temperature oxydation：After silicon chip is put into diffusion furnace, pressure is 100mbar in setting stove, temperature is 780 DEG C, to silicon
Piece carries out oxidation 100s -150s；
Step 2: alternating temperature transformation is spread：It is diffused, is as follows using gradepervasion method：
S1, the diffusion of constant temperature transformation：In-furnace temperature is risen to 790 DEG C, keeps temperature-resistant, control in stove pressure in 160s from
100mbar boosts to 800mbar；Big nitrogen flow is 8000ml/min -9000ml/min；Small nitrogen flow is 400ml/min-
500ml/min；Oxygen flow is 600ml/min -1500ml/min；
S2, alternating temperature constant pressure knot：Keep pressure in stove constant, control in-furnace temperature is warming up to 835 DEG C in 450s from 790 DEG C；
Big nitrogen flow is 5000ml/min -6000ml/min；Small nitrogen flow is 0ml/min；Oxygen flow is 0ml/min；
S3, constant temperature and pressure diffusion：In 30s by in-furnace temperature be adjusted to 800 DEG C, stove internal pressure be adjusted to 200mbar by force；And at this
Under the conditions of spread 500s -650s；Big nitrogen flow is 1000ml/min -2000ml/min；Small nitrogen flow is 100ml/min-
150ml/min；Oxygen flow is 200ml/min -250ml/min；
Step 3: annealing cooling：Temperature is reduced to anneal to repair lattice and despumation.
2. a kind of alternating temperature transformation diffusion technique improving photoelectric conversion efficiency according to claim 1, which is characterized in that step
Rapid three technological parameter is：Annealing temperature is 600 DEG C -700 DEG C；Pressure in stove is risen to from 200mbar in 900s
800mbar, again from the near 200mbar of 800mbar.
3. a kind of alternating temperature transformation diffusion technique improving photoelectric conversion efficiency according to claim 1, it is characterised in that：Institute
It is 1.5mm-1.8mm to state silicon chip spacing, and high square resistance value is 90-120 Ω/, and the unevenness of sheet resistance is 2%-in silicon chip
2.5%.
4. a kind of alternating temperature transformation diffusion technique improving photoelectric conversion efficiency according to claim 1, it is characterised in that：Institute
It is p-type polysilicon piece to state silicon chip, and the resistivity of the p-type polysilicon piece is the 1 Ω cm of Ω cm -2, thickness is 150 μm -
180μm。
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Cited By (4)
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| CN109860334A (en) * | 2019-01-16 | 2019-06-07 | 晶科能源科技（海宁）有限公司 | A kind of matching HF/HNO3The high quality phosphorus diffusion method of system selective etch |
| CN110931597A (en) * | 2019-11-12 | 2020-03-27 | 浙江爱旭太阳能科技有限公司 | Diffusion process for reducing electroattenuation of PERC solar cell |
| CN113284794A (en) * | 2021-02-25 | 2021-08-20 | 宁夏隆基乐叶科技有限公司 | Doping method of silicon substrate, solar cell and manufacturing method of solar cell |
| CN115000194A (en) * | 2022-05-26 | 2022-09-02 | 普乐新能源科技(徐州)有限公司 | Simple low-cost P-type crystalline silicon IBC solar cell and preparation method thereof |
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