CN109037395B - Diffusion process for improving sheet resistance uniformity - Google Patents

Diffusion process for improving sheet resistance uniformity Download PDF

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CN109037395B
CN109037395B CN201810658370.2A CN201810658370A CN109037395B CN 109037395 B CN109037395 B CN 109037395B CN 201810658370 A CN201810658370 A CN 201810658370A CN 109037395 B CN109037395 B CN 109037395B
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oxidation
flow rate
oxygen
diffusion process
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CN109037395A (en
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章天瑜
张文锋
胡玉婷
张文超
范启泽
张雄伟
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Risen Energy Co Ltd
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00Semiconductor 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
    • H01L31/18Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
    • H01L31/1804Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof comprising only elements of Group IV of the Periodic Table
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04Manufacture 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
    • H01L21/18Manufacture 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
    • H01L21/22Diffusion 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
    • H01L21/223Diffusion 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
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50Manufacturing or production processes characterised by the final manufactured product

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Abstract

The invention discloses a diffusion process for improving sheet resistance uniformity, which comprises the following steps: (1) and (3) heating: inserting the silicon wafer after texturing into a quartz boat, loading the quartz boat, and heating a furnace tube to 750-795 ℃ after the quartz boat is loaded; (2) dry oxygen oxidation: introducing dry oxygen for oxidation, wherein the flow rate of the dry oxygen is 1800-2200 ml/min, and the oxidation time is 100-sec; (3) wet oxygen oxidation: introducing wet oxygen for oxidation, wherein the flow rate of the wet oxygen is 1400-1600 ml/min, and the oxidation time is 200 sec; (4) and (3) diffusion, namely introducing dry oxygen, small nitrogen and large nitrogen for precipitation diffusion, wherein the flow of the dry oxygen is 600-900 ml/min, the flow of the small nitrogen is 1200-1500 ml/min, the flow of the large nitrogen is 10000 ml/min-15000 ml/min, and the diffusion is carried out for 1200sec at the temperature of 750-795 ℃.

Description

Diffusion process for improving sheet resistance uniformity
Technical Field
The invention relates to the technical field of crystalline silicon cell solar cell production, in particular to a diffusion process for improving sheet resistance uniformity.
Background
In the aspect of crystalline silicon cell industrialization, a high-temperature diffusion method is generally adopted to prepare PN junctions, and the industrial preparation of high sheet resistance emitters with good uniformity among and in sheets is an important way for improving the conversion efficiency and the electrical property stability of cells, so that not only can the diffusion process optimization space be integrally improved, but also the grading quantity of the cell efficiency can be reduced, and according to the prior art, the silicon wafer spacing is continuously reduced in order to improve the productivity. The adjacent distance of the silicon chip is small, the partial pressure ratio of the doped atoms is small, the difference between the doping concentration in the middle of the silicon chip and the edge is large, the diffusion process quality is poor, the uniformity is low, and in a production line of high sheet resistance production, the sheet resistance is high, so that the non-uniform phenomenon is increased, and the edge of the diffused silicon chip and the peripheral sheet resistance are more non-uniform.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the defects of the prior art are overcome, and the diffusion process for improving the sheet resistance uniformity is good in diffusion process quality, high in uniformity and good in sheet resistance uniformity of the edge and the periphery of the diffused silicon wafer.
The technical scheme adopted by the invention is as follows: a diffusion process for improving sheet resistance uniformity comprises the following steps:
(1) and (3) heating: inserting the silicon wafer after texturing into a quartz boat, loading the quartz boat, and heating a furnace tube to 750-795 ℃ after the quartz boat is loaded;
(2) dry oxygen oxidation: introducing dry oxygen for oxidation, wherein the flow rate of the dry oxygen is 1800-2200 ml/min, and the oxidation time is 100 sec;
(3) wet oxygen oxidation: introducing wet oxygen for oxidation, wherein the flow rate of the wet oxygen is 1400-1600 ml/min, and the oxidation time is 200 sec;
(4) diffusing, namely introducing dry oxygen, small nitrogen and large nitrogen for precipitation diffusion, wherein the flow rate of the dry oxygen is 600-900 ml/min, the flow rate of the small nitrogen is 1200-1500 ml/min, the flow rate of the large nitrogen is 10000 ml/min-15000 ml/min, and the diffusion is carried out for 1200sec at the temperature of 750-795 ℃;
(5) heating and propelling, wherein the temperature of the furnace tube is increased to 800-830 ℃, and the propelling time is 500-700 sec;
(6) dry oxygen oxidation: introducing dry oxygen for oxidation again, wherein the flow rate of the dry oxygen is 1200-1600 ml/min, the flow rate of the large nitrogen is 20000-25000 ml/min, and the oxidation is carried out for 200sec at the temperature of 820-840 ℃;
(7) wet oxygen oxidation: and introducing wet oxygen for oxidation again, wherein the flow rate of the wet oxygen is 1200-1600 ml/min, the flow rate of the large nitrogen is 20000-25000 ml/min, and the oxidation is carried out for 550sec at the temperature of 820-840 ℃.
The small nitrogen is the source-carrying nitrogen, the large nitrogen is the nitrogen, the dry oxygen is the dry oxygen, and the wet oxygen is the oxygen with water vapor.
After adopting the structure, compared with the prior art, the invention has the following advantages: the invention improves the diffusion process in the solar cell manufacturing, shortens the single tube process time by 3000s, reduces the average unevenness by 4 percent, well controls the depth and the surface concentration of the PN junction, and improves the average photoelectric conversion efficiency by 0.15 percent. It can be seen that the present invention is very helpful to improve the yield per unit time, the diffusion uniformity and the photoelectric conversion efficiency.
Preferably, the process parameters in the step (2) are as follows: the dry oxygen flow is 1900-2100 ml/min, the oxidation time is 100sec, a layer of SiO2 with the nanometer thickness grows, and the dry oxygen flow is preferably 1950, 2000 and 2050 ml/min.
Preferably, the process parameters in the step (3) are as follows: and (3) growing a layer of SiO2 with the nanometer thickness again with the wet oxygen flow of 1450-1550 ml/min and the oxidation time of 200sec, wherein the wet oxygen flow is preferably 1450, 1500 and 1550 ml/min.
Preferably, the process parameters of the step (4) are as follows: introducing dry oxygen at a flow rate of 700-800 ml/min, small nitrogen at a flow rate of 1300-1400 ml/min, large nitrogen at a flow rate of 11000-14000 ml/min, and diffusing at 770-793 ℃ for 1200sec, wherein the dry oxygen at a flow rate of 700, 750 and 800ml/min, the small nitrogen at a flow rate of 1300, 1350 and 1400ml/min, the large nitrogen at a flow rate of 12000, 13000 and 13500ml/min, and the temperature at a flow rate of 770, 780 and 790 ℃ are preferred.
Preferably, the process parameters in the step (6) are as follows: introducing dry oxygen flow of 1300-1500 ml/min, large nitrogen flow of 21000-24000 ml/min, oxidizing for 200sec at the temperature of 825-835 ℃, wherein the dry oxygen flow is preferably 1300, 1400 and 1500ml/min, the large nitrogen flow is preferably 21000, 22000 and 23000ml/min, and the temperature is preferably 825, 830 and 835 ℃.
Preferably, the process parameters in the step (7) are as follows: the wet oxygen flow is 1300-1500 ml/min, the large nitrogen flow is 21000-24000 ml/min, the oxidation is carried out for 550sec at the temperature of 825-835 ℃, the wet oxygen flow is preferably 1300, 1400 and 1500ml/min, the large nitrogen flow is preferably 21000, 22000 and 23000ml/min, and the temperature is preferably 825, 830 and 835 ℃.
Preferably, the silicon wafer has a wafer spacing of 1.0-2.0 mm, the sheet square resistance value of the silicon wafer obtained after diffusion is 85-130 omega/□, the sheet square resistance unevenness of the silicon wafer after diffusion is less than 3%, the temperature difference between the furnace mouth and the furnace tail temperature zone of the diffusion tube is less than or equal to 10 ℃, the wafer spacing of the silicon wafer is preferably 1.0, 1.5 and 2.0mm, and the sheet square resistance value of the silicon wafer is preferably 90, 100 and 110 omega/□.
Preferably, the silicon wafer is a P-type polycrystalline silicon wafer, the P-type polycrystalline silicon wafer has a resistivity of 1 Ω · cm to 3 Ω · cm and a thickness of 100 μm to 200 μm, the P-type polycrystalline silicon wafer preferably has a resistivity of 1, 2, and 3 Ω · cm and a thickness of 100, 150, and 200 μm.
Detailed Description
The present invention will be further described with reference to the following embodiments.
A diffusion process for improving sheet resistance uniformity comprises the following steps:
(1) and (3) heating: inserting the textured silicon wafer into a quartz boat, loading the quartz boat, and heating a furnace tube to 750-795 ℃ after the quartz boat is loaded, wherein the temperature is preferably 770, 780 and 790 ℃;
(2) dry oxygen oxidation: introducing dry oxygen for oxidation, wherein the flow rate of the dry oxygen is 1800-2200 ml/min, and the oxidation time is 100 ecs;
(3) wet oxygen oxidation: introducing wet oxygen for oxidation, wherein the flow rate of the wet oxygen is 1400-1600 ml/min, and the oxidation time is 200 sec;
(4) and (3) diffusion, namely introducing dry oxygen, small nitrogen and large nitrogen for precipitation diffusion, wherein the flow of the dry oxygen is 600-900 ml/min, the flow of the small nitrogen is 1200-1500 ml/min, the flow of the large nitrogen is 10000 ml/min-15000 ml/min, and the diffusion is carried out for 1200sec at the temperature of 750-795 ℃.
(5) Heating and propelling, wherein the temperature of the furnace tube is increased to 800-830 ℃, and the propelling time is 500-700 sec;
(6) dry oxygen oxidation: introducing dry oxygen for oxidation again, wherein the flow rate of the dry oxygen is 1200-1600 ml/min, the flow rate of the large nitrogen is 20000-25000 ml/min, and the oxidation is carried out for 200sec at the temperature of 820-840 ℃;
(7) wet oxygen oxidation: and introducing wet oxygen for oxidation again, wherein the flow rate of the wet oxygen is 1200-1600 ml/min, the flow rate of the large nitrogen is 20000-25000 ml/min, and the oxidation is carried out for 550sec at the temperature of 820-840 ℃.
The small nitrogen is the source-carrying nitrogen, the large nitrogen is the nitrogen, the dry oxygen is the dry oxygen, and the wet oxygen is the oxygen with water vapor.
After adopting the structure, compared with the prior art, the invention has the following advantages: the invention improves the diffusion process in the solar cell manufacturing, shortens the single tube process time by 3000s, reduces the average unevenness by 4 percent, well controls the depth and the surface concentration of the PN junction, and improves the average photoelectric conversion efficiency by 0.15 percent. It can be seen that the present invention is very helpful to improve the yield per unit time, the diffusion uniformity and the photoelectric conversion efficiency.
The technological parameters in the step (2) are as follows: the dry oxygen flow is 1900-2100 ml/min, the oxidation time is 100sec, a layer of SiO2 with the nanometer thickness grows, and the dry oxygen flow is preferably 1950, 2000 and 2050 ml/min.
The technological parameters in the step (3) are as follows: and (3) growing a layer of SiO2 with the nanometer thickness again with the wet oxygen flow of 1450-1550 ml/min and the oxidation time of 200sec, wherein the wet oxygen flow is preferably 1450, 1500 and 1550 ml/min.
The technological parameters of the step (4) are as follows: introducing dry oxygen flow of 700-800 ml/min, small nitrogen flow of 1300-1400 ml/min, large nitrogen flow of 11000 ml/min-14000 ml/min, diffusing at 770-793 ℃ for 1200sec, dry oxygen flow of 700, 750 and 800ml/min, small nitrogen flow of 1300, 1350 and 1400ml/min, large nitrogen flow of 12000, 13000 and 13500ml/min, and temperature of 770, 780 and 790 ℃ preferably.
The technological parameters in the step (6) are as follows: introducing dry oxygen flow of 1300-1500 ml/min, large nitrogen flow of 21000-24000 ml/min, oxidizing for 200sec at the temperature of 825-835 ℃, wherein the dry oxygen flow is preferably 1300, 1400 and 1500ml/min, the large nitrogen flow is preferably 21000, 22000 and 23000ml/min, and the temperature is preferably 825, 830 and 835 ℃.
The technological parameters in the step (7) are as follows: the wet oxygen flow is 1300-1500 ml/min, the large nitrogen flow is 21000-24000 ml/min, the oxidation is carried out for 550sec at the temperature of 825-835 ℃, the wet oxygen flow is preferably 1300, 1400 and 1500ml/min, the large nitrogen flow is preferably 21000, 22000 and 23000ml/min, and the temperature is preferably 825, 830 and 835 ℃.
The silicon wafer spacing is 1.0-2.0 mm, the sheet resistance value of the silicon wafer obtained after diffusion is 85-130 omega/□, the sheet-to-sheet resistance unevenness of the silicon wafer after diffusion is less than 3%, the temperature difference between a furnace mouth and a furnace tail temperature zone of the diffusion tube is less than or equal to 10 ℃, the sheet spacing of the silicon wafer is preferably 1.0, 1.5 and 2.0mm, and the sheet resistance value of the silicon wafer is preferably 90, 100 and 110 omega/□.
The silicon wafer is a P-type polycrystalline silicon wafer, the resistivity of the P-type polycrystalline silicon wafer is 1 omega-cm-3 omega-cm, the thickness of the P-type polycrystalline silicon wafer is 100 mu m-200 mu m, the resistivity of the P-type polycrystalline silicon wafer is preferably 1, 2 and 3 omega-cm, and the thickness of the P-type polycrystalline silicon wafer is preferably 100, 150 and 200 mu m
The technical scheme of the invention is further described below, and the diffusion process for improving the sheet resistance uniformity is a diffusion process of a crystalline silicon solar cell, the diffusion process of the crystalline silicon solar cell of the invention adopts a tube type diffusion furnace created by Jiefa on the basis of keeping other original processes unchanged, and the process parameter format edited by us is also according to the format of the diffusion furnace.
The dry oxygen oxidation growth rate in the front oxidation and the back oxidation is slow, the square resistance uniformity is poor, but the dry oxygen oxidation structure has good compactness, strong impurity masking capability and uniform growth; the invention adopts dry oxygen oxidation firstly and wet oxygen oxidation, not only maintains the advantages of dry oxygen oxidation, but also shortens the oxidation time, improves the sheet resistance uniformity, and has shallow junction depth and low surface concentration.
The total process time of the traditional process is 5850sec, the process time of the invention is 5450sec, the time is saved by 400s, and the productivity is greatly improved.
The following table shows the sheet resistance comparison between the conventional process and the process of the present invention:
Figure BDA0001706014780000041
unevenness calculation method: the non-uniformity is (max-min)/(max + min) × 100%), and as can be seen from the data, the process of the present invention can improve the sheet resistance uniformity and reduce the sheet resistance range.
The following table shows the electrical performance parameters of the conventional process compared to the process of the present invention:
Uoc Isc FF Ncell
conventional process 0.6301 9.1148 80.19 18.745%
Invention process 0.6332 9.1235 80.22 18.861%
As can be seen from the data, the electrical property of the process is improved, and the photoelectric conversion efficiency is improved.
The foregoing has described preferred embodiments of the present invention and is not to be construed as limiting the claims. The present invention is not limited to the above embodiments, and the specific structure thereof is allowed to vary, and various changes made within the scope of the independent claims of the present invention are within the scope of the present invention.

Claims (7)

1. A diffusion process for improving sheet resistance uniformity comprises the following steps: (1) and (3) heating: inserting the silicon wafer after texturing into a quartz boat, loading the quartz boat, and heating a furnace tube to 750-795 ℃ after the quartz boat is loaded; (2) dry oxygen oxidation: introducing dry oxygen for oxidation, wherein the flow rate of the dry oxygen is 1800-2200 ml/min, and the oxidation time is 100 sec; (3) wet oxygen oxidation: introducing wet oxygen for oxidation, wherein the flow rate of the wet oxygen is 1400-1600 ml/min, and the oxidation time is 200 sec; (4) diffusing, namely introducing dry oxygen, small nitrogen and large nitrogen for precipitation diffusion, wherein the flow rate of the dry oxygen is 600-900 ml/min, the flow rate of the small nitrogen is 1200-1500 ml/min, the flow rate of the large nitrogen is 10000 ml/min-15000 ml/min, and the diffusion is carried out for 1200sec at the temperature of 750-795 ℃; (5) heating and propelling, wherein the temperature of the furnace tube is increased to 800-830 ℃, and the propelling time is 500-700 sec; (6) dry oxygen oxidation: introducing dry oxygen for oxidation again, wherein the flow rate of the dry oxygen is 1200-1600 ml/min, the flow rate of the large nitrogen is 20000-25000 ml/min, and the oxidation is carried out for 200sec at the temperature of 820-840 ℃; (7) wet oxygen oxidation: introducing wet oxygen for oxidation again, wherein the flow of the wet oxygen is 1200-1600 ml/min, the flow of large nitrogen is 20000-25000 ml/min, the oxidation is carried out for 550sec at the temperature of 820-840 ℃, the inter-sheet distance of the silicon wafers is 1.0-2.0 mm, the sheet resistance value of the silicon wafers obtained after diffusion is 85-130 omega/□, the inter-sheet resistance unevenness of the silicon wafers after diffusion is less than 3%, and the temperature difference between a furnace mouth and a furnace tail temperature zone is less than or equal to 10 ℃.
2. The diffusion process of claim 1, wherein the diffusion process comprises: the technological parameters in the step (2) are as follows: the flow rate of dry oxygen is 1900-2100 ml/min, the oxidation time is 100sec, and a layer of SiO2 with the nanometer thickness grows.
3. The diffusion process of claim 1, wherein the diffusion process comprises: the technological parameters in the step (3) are as follows: and (3) the flow rate of the wet oxygen is 1450-1550 ml/min, the oxidation time is 200sec, and a layer of SiO2 with the nanometer thickness is grown.
4. The diffusion process of claim 1, wherein the diffusion process comprises: the technological parameters of the step (4) are as follows: introducing dry oxygen at a flow rate of 700-800 ml/min, introducing small nitrogen at a flow rate of 1300-1400 ml/min, introducing large nitrogen at a flow rate of 11000-14000 ml/min, and diffusing at a temperature of 770-793 ℃ for 1200 sec.
5. The diffusion process of claim 1, wherein the diffusion process comprises: the technological parameters in the step (6) are as follows: introducing dry oxygen flow of 1300-1500 ml/min and large nitrogen flow of 21000-24000 ml/min, and oxidizing at 825-835 ℃ for 200 sec.
6. The diffusion process of claim 1, wherein the diffusion process comprises: the technological parameters in the step (7) are as follows: the wet oxygen flow is 1300-1500 ml/min, the large nitrogen flow is 21000-24000 ml/min, and the oxidation is carried out for 550sec at the temperature of 825-835 ℃.
7. The diffusion process of claim 1, wherein the diffusion process comprises: the silicon wafer is a P-type polycrystalline silicon wafer, the resistivity of the P-type polycrystalline silicon wafer is 1-3 omega-cm, and the thickness of the P-type polycrystalline silicon wafer is 100-200 mu m.
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