CN114921846B - Method for reducing impurity stripes of heavily stibium <100> doped single crystal - Google Patents
Method for reducing impurity stripes of heavily stibium <100> doped single crystal Download PDFInfo
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- 239000012535 impurity Substances 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 title claims abstract description 26
- 239000013078 crystal Substances 0.000 title claims description 154
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 17
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims abstract description 17
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 32
- 229910052786 argon Inorganic materials 0.000 claims description 16
- 238000004321 preservation Methods 0.000 claims description 11
- 238000007711 solidification Methods 0.000 claims description 11
- 230000008023 solidification Effects 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 6
- 230000005484 gravity Effects 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 18
- 229910052710 silicon Inorganic materials 0.000 abstract description 18
- 239000010703 silicon Substances 0.000 abstract description 18
- 238000002474 experimental method Methods 0.000 description 32
- 235000012431 wafers Nutrition 0.000 description 21
- 210000003128 head Anatomy 0.000 description 9
- 201000010099 disease Diseases 0.000 description 8
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 8
- 238000010621 bar drawing Methods 0.000 description 6
- 239000013256 coordination polymer Substances 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 230000004075 alteration Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000005204 segregation Methods 0.000 description 3
- 235000014347 soups Nutrition 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
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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
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/02—Elements
- C30B29/06—Silicon
-
- 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
- C30B15/00—Single-crystal growth by pulling from a melt, e.g. Czochralski method
- C30B15/20—Controlling or regulating
-
- 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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- Engineering & Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
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- Organic Chemistry (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
The invention provides a method for reducing heavily doped antimony <100> monocrystal impurity stripes, which belongs to the technical field of silicon Wafer processing.
Description
Technical Field
The invention relates to the technical field of silicon wafer processing, in particular to a method for reducing stripes of heavily doped antimony <100> single crystal impurities.
Background
After the crystal bar is pulled, the crystal bar is cut into a silicon wafer, impurity stripes appear on the surface of the silicon wafer, the impurity stripes are regular concentric circular stripes or eccentric circular stripes or irregular stripes (the regularity refers to color difference stripes visible on the surface of the silicon wafer), if the impurity stripes on the surface of the silicon wafer are irregular stripes, the impurity stripes are generally oxygen stripes, and if the impurity stripes on the surface of the silicon wafer are regular concentric circular stripes or eccentric circular stripes, the impurity stripes on the surface of the silicon wafer are generally resistivity stripes.
In the prior art, concentric circles or eccentric circular patterns appear on the surface of a Wafer (Wafer) after mixed acid corrosion (Chemical Polishing, CP) of a crystal bar heavily doped with antimony in a crystal orientation, because of the segregation effect of doping, the impurity concentration shows a trend of low head and high tail, and the resistivity shows a trend of low head and tail, so that the tail resistivity of the crystal bar is lower, the probability of appearance of the concentric circles or eccentric circular patterns on the tail of the crystal bar is higher, after the crystal bar is cut into silicon wafers, part of the silicon wafers are subjected to visual observation to obtain samples with ring color difference exceeding the limit (the limit samples show that the surface of the silicon wafers has unclear stripes and are difficult to be observed by naked eyes), the silicon wafers are scrapped, and the yield is affected.
Disclosure of Invention
In view of the above, the invention provides a method for reducing the impurity stripes of heavily-doped antimony <100> single crystals, which aims to solve the technical problems that after a crystal bar heavily doped with antimony with a <100> crystal orientation is cut into silicon wafers in the prior art, part of the silicon wafers are scraped due to the fact that ring-shaped color difference exceeds a limit sample by naked eyes, and the yield is affected.
The technical scheme adopted for solving the technical problems is as follows:
a method for reducing the streak of heavily doped Sb <100> monocrystal impurity features that when the crystal rod is pulled, the pull speed of crystal rod is controlled to control the growth interface of crystal rod, and the concave-to-solution growth interface is controlled to be horizontal or convex for the same solidification time.
Preferably, after the crystal bar is pulled by 70%, the crystal bar is pulled at a pulling speed of 0-0.6mm/min, and the pulling speed gradually decreases along with the pulling of the crystal bar, and the average pulling speed fluctuation is-10%, so that the growth interface of the concave solution is controlled to be horizontal or convex.
Preferably, the upper and lower pulling rates of the crystal bar are set to be-0.25 mm/min before the crystal bar is pulled.
Preferably, when the crystal rod is pulled, the ratio of the rotation speed of the crystal rod to the rotation speed of the crucible is controlled to be more than 1, namely: SR/CR >1.0 to stabilize the solid-liquid interface.
Preferably, argon gas is introduced at a predetermined flow rate while the ingot is being pulled.
Preferably, the predetermined flow rate of the argon gas is 0-80slm.
Preferably, before the furnace is opened, the deviation of the center shaft center in the single crystal furnace from the cross direction of the furnace barrel, the heat preservation barrel and the heater is ensured to be smaller than a first preset distance, and the deviation of the center shaft center and the gravity center of the heavy hammer is ensured to be smaller than a second preset distance.
Preferably, the first predetermined distance is 3mm.
Preferably, the second predetermined distance is 3mm.
Preferably, during the ingot drawing process, if a large change in ingot diameter occurs, the ingot diameter is controlled only by adjusting the temperature.
Compared with the prior art, the invention has the beneficial effects that:
according to the invention, when the crystal bar is pulled, the growth interface concave to the solution is controlled to be horizontal or convex by controlling the growth interface of the crystal bar, so that the solidification time of the growth interface of the crystal bar is the same, and further, the radial solidification time is the same in the cutting direction perpendicular to the growth axis direction, so that the concentration of impurities at each point is consistent, and further, concentric circles or eccentric circular lines cannot appear on the Wafer surface after CP corrosion, and the yield of products cannot be reduced.
Detailed Description
The technical scheme and technical effects of the present invention are further described in detail below.
A method for reducing the streak of heavily doped Sb <100> monocrystal impurity features that when the crystal rod is pulled, the pull speed of crystal rod is controlled to control the growth interface of crystal rod, and the concave-to-solution growth interface is controlled to be horizontal or convex for the same solidification time.
Compared with the prior art, the invention has the beneficial effects that:
according to the invention, when the crystal bar is pulled, the growth interface concave to the solution is controlled to be horizontal or convex by controlling the growth interface of the crystal bar, so that the solidification time of the growth interface of the crystal bar is the same, and further, the radial solidification time is the same in the cutting direction perpendicular to the growth axis direction, so that the concentration of impurities at each point is consistent, and further, concentric circles or eccentric circular lines cannot appear on the Wafer surface after CP corrosion, and the yield of products cannot be reduced.
Further, after the crystal bar is pulled by 70%, the crystal bar is pulled at a pulling speed of 0-0.6mm/min, the pulling speed gradually decreases along with the pulling of the crystal bar, and the average pulling speed fluctuation is-10%, so that the growth interface of the concave solution is controlled to be horizontal or convex.
Specifically, the average pull speed is an average value in unit time, the unit time is set to be 2h, and the calculation method of the fluctuation value is as follows: the pull rate fluctuation of the constant diameter head may not be counted in (average pull rate-set pull rate)/set pull rate is 100%.
Furthermore, before the crystal bar is pulled, the upper limit pulling speed and the lower limit pulling speed of the crystal bar are set to be-0.25 mm/min, so that the pulling speed is not too large in the changing process, and the diameter of the crystal bar is not affected.
Further, when the crystal bar is pulled, the ratio of the rotation speed of the crystal bar to the rotation speed of the crucible is controlled to be more than 1, namely: SR/CR is greater than 1.0, and the direction of crystal bar rotation is different with the direction of crucible rotation, and the crystal bar rotation is rotated with the crucible and is brought the forced convection of two kinds of directions different, and wherein the forced convection that the crystal bar rotated arouses can restrain natural convection, increases crystal rotation/crucible rotation can be better steady solid-liquid interface (CZ), and radial impurity distribution is evenly distributed to effectual control.
Further, argon gas with a preset flow rate is introduced during the process of pulling the crystal bar
Further, the preset flow rate of the argon is 0-80slm, and the surface of the molten soup is stabilized by introducing the preset flow rate of the argon and a Gap value.
Specifically, the resistivity of the heavily doped antimony (6 inch) is distributed between 0.01 and 0.02 omega cm, and the concentration of antimony in silicon is 3.6E18 to 9.4E18atom/cm 3 The impurity stripes are resistivity stripes, concentric or eccentric circular ring stripes are shown, the resistivity can show a trend of high head and low tail due to the segregation effect of doping, the impurity concentration shows a trend of low head and low tail, the probability of the impurity stripes appearing at the tail of the crystal bar is higher, and in the prior art, the trend of low head and tail is shown due to the resistivity, and the impurity stripes are containedThe method is easy to think about reducing the occurrence probability of ring marks by improving the resistivity, but by setting the process parameters, after 70% of crystal bar drawing, lower drawing speed is set, so that the concave-to-solution growth interface is controlled to be horizontal or convex, average drawing speed fluctuation is controlled to be within-10%, the crystal transformation and crucible transformation ratio is controlled, proper argon flow and Gap values are set, so that the surface of molten soup is stable, and the solid-liquid interface is stable, so that the solidification time of the crystal bar growth interface is the same, the radial solidification time is the same in the cutting direction perpendicular to the growth axis direction, the concentration of impurities at each point is consistent, and concentric circles or eccentric ring marks are not generated on the Wafer surface after CP corrosion, so that the yield of products is not reduced.
Further, before the furnace is opened, the deviation of the center shaft axis in the single crystal furnace from the cross direction of the furnace barrel, the heat preservation barrel and the heater is ensured to be smaller than a first preset distance, and the deviation of the center shaft axis and the gravity center of the heavy hammer is ensured to be smaller than a second preset distance, so that the center of a circle of a growth interface is consistent with the center shaft axis in the single crystal furnace, and further, the occurrence of eccentric ring lines is avoided.
Specifically, the precision of the single crystal furnace is as follows, SR: + -0.05 rpm; CR: + -0.05 rpm; seed crystal ascent Speed (SL): (+ -0.05 mm/min); crucible elevation speed (CL): (+ -0.01 mm/min); argon (Ar) flow rate: 1slm; liquid Gap: 2mm.
Further, the first predetermined distance is 3mm.
Further, the second predetermined distance is 3mm.
Further, in the process of drawing the crystal rod, if the diameter of the crystal rod is changed greatly, the diameter of the crystal rod is controlled only by adjusting the temperature, but not by adjusting the drawing speed, and the shape of a crystal rod growth interface can be influenced by adjusting the drawing speed.
Further, the resistivity is improved within the resistivity specification so that the occurrence position of the ring is close to the tail of the crystal bar; because the existing resistivity specification and the segregation coefficient of antimony (k=0.023) cannot eliminate the occurrence of ring patterns by increasing the resistivity, the occurrence position of the ring patterns can be close to the tail of the crystal bar only by increasing the resistivity within the resistivity specification, so that the defect rate of the ring patterns can be reduced by solving the ring pattern occurrence rate and serious conditions of the tail.
Specifically, the occurrence position of the ring is changed by improving the resistivity within the resistivity specification, and the specific experimental process is shown in experiment 1.
Experiment 1: the precision in the single crystal furnace is as follows, SR: + -0.05 rpm; CR: + -0.05 rpm; SL: (+ -0.05 mm/min); CL: (+ -0.01 mm/min); ar: 1slm; gap: detecting that the cross direction of the center shaft center in the single crystal furnace and the furnace cylinder, the heat preservation cylinder and the heater is smaller than 3mm, confirming that the center-of-gravity deviation of the center shaft center and the heavy hammer is smaller than 3mm, after the length of the crystal bar is 70%, SL=0.80 mm/min, the fluctuation range of pulling speed is-10-10%, the upper limit and the lower limit of pulling speed are-0.25-0.25 mm/min, SR/CR=1.5, when the specific resistance specification is 0.008-0.02 Ω cm under 80slm, drawing the crystal bar, dividing the experiment into 3 groups according to the head resistivity, carrying out 5 experiments on each group, and obtaining data shown in table 1, wherein other parameters are the same except the specific resistance.
TABLE 1
| Group of | Sequence number | Head resistivity | The ring grain generating position accounts for the proportion of the crystal bar | Severity of disease |
| A | 1 | 0.016 | 61% | Unacceptable |
| A | 2 | 0.016 | 60% | Unacceptable |
| A | 3 | 0.016 | 59% | Unacceptable |
| A | 4 | 0.016 | 64% | Unacceptable |
| A | 5 | 0.016 | 63% | Unacceptable |
| B | 1 | 0.0175 | 65% | Unacceptable |
| B | 2 | 0.0175 | 67% | Unacceptable |
| B | 3 | 0.0175 | 69% | Unacceptable |
| B | 4 | 0.0175 | 65% | Unacceptable |
| B | 5 | 0.0175 | 66% | Unacceptable |
| C | 1 | 0.0185 | 70% | Unacceptable |
| C | 2 | 0.0185 | 71% | Unacceptable |
| C | 3 | 0.0185 | 74% | Unacceptable |
| C | 4 | 0.0185 | 72% | Unacceptable |
| C | 5 | 0.0185 | 72% | Unacceptable |
According to the experimental data in table 1, it can be seen that concentric circular ring patterns still appear on the surface of the silicon wafer with simple increase of resistivity, and the chromatic aberration of the ring patterns is higher than that of a limit sample, so that rejection is caused, the yield is affected, but the increase of resistivity can enable the position where the ring patterns occur to be closer to the tail of the crystal bar, so that the utilization rate of the crystal bar is improved, and the rejection is reduced.
Specifically, the process of the invention is determined, and the specific experimental process is shown in experiments 2-6.
Experiment 2: the precision of the single crystal furnace is as follows, SR: + -0.05 rpm; CR: + -0.05 rpm; SL: (+ -0.05 mm/min); CL: (+ -0.01 mm/min); ar: 1slm; gap: detecting that the cross direction of the center shaft center in the single crystal furnace and the furnace barrel, the heat preservation barrel and the heater is less than 3mm, confirming that the center-of-gravity deviation of the center shaft center and the heavy hammer is less than 3mm, performing experiments under the condition of TOP Res=0.0185, performing crystal bar drawing, dividing the experiments into 5 groups according to the set value of the pull rate of the crystal bar after 70%, performing 5 times of experiments on each group, and obtaining data shown in table 2, wherein other parameters except the resistivity are the same.
TABLE 2
| Group of | Sequence number | Pull rate setting after 70% | The ring grain generating position accounts for the proportion of the crystal bar | Severity of disease |
| A | 1 | 0.80mm/min | 60% | Unacceptable |
| A | 2 | 0.80mm/min | 61% | Unacceptable |
| A | 3 | 0.80mm/min | 59% | Unacceptable |
| A | 4 | 0.80mm/min | 58% | Unacceptable |
| A | 5 | 0.80mm/min | 62% | Unacceptable |
| B | 1 | 0.70mm/min | 67% | Unacceptable |
| B | 2 | 0.70mm/min | 69% | Unacceptable |
| B | 3 | 0.70mm/min | 70% | Unacceptable |
| B | 4 | 0.70mm/min | 71% | Unacceptable |
| B | 5 | 0.70mm/min | 69% | Unacceptable |
| C | 1 | 0.60mm/min | 78% | Can be connected withIs subject to |
| C | 2 | 0.60mm/min | 79% | Acceptable for |
| C | 3 | 0.60mm/min | 79% | Acceptable for |
| C | 4 | 0.60mm/min | 80% | Acceptable for |
| C | 5 | 0.60mm/min | 81% | Acceptable for |
| D | 1 | 0.55mm/min | 82% | Acceptable for |
| D | 2 | 0.55mm/min | 83% | Acceptable for |
| D | 3 | 0.55mm/min | 80% | Acceptable for |
| D | 4 | 0.55mm/min | 79% | Acceptable for |
| D | 5 | 0.55mm/min | 81% | Acceptable for |
| E | 1 | 0.52mm/min | 82% | Acceptable for |
| E | 2 | 0.52mm/min | 83% | Acceptable for |
| E | 3 | 0.52mm/min | 84% | Acceptable for |
| E | 4 | 0.52mm/min | 82% | Acceptable for |
| E | 5 | 0.52mm/min | 81% | Acceptable for |
| F | 1 | 0.50mm/min | 84% | Acceptable for |
| F | 2 | 0.50mm/min | 85% | Acceptable for |
| F | 3 | 0.50mm/min | 85% | Acceptable for |
| F | 4 | 0.50mm/min | 84% | Acceptable for |
| F | 5 | 0.50mm/min | 83% | Acceptable for |
As shown in Table 2, when the pulling rate of the ingot after the length of the ingot is 70% is set to be 0.7mm/min-0.8mm/min, the color difference of the ring marks generated by the whole ingot is higher than that of a limit sample, and the ingot is scrapped, so that the yield is affected, but when the pulling rate of the ingot after the length of the ingot is 70% is set to be 0.6mm/min-0.5mm/min, the growth interface of the whole ingot during growth is horizontal or convex, so that the color difference of the ring marks generated by the whole ingot is lower than that of the limit sample, the whole ingot is available and can not be scrapped, but when the pulling rate of the ingot after the length of the ingot is 70% is set to be 0.50mm/min, the crystal pulling is not smooth and is easy to fail, so that the optimal pulling rate of the ingot after the length of the ingot is 70% is set to be 0.6-0.52mm/min.
Experiment 3: the precision of the single crystal furnace is as follows, SR: + -0.05 rpm; CR: + -0.05 rpm; SL: (+ -0.05 mm/min); CL: (+ -0.01 mm/min); ar: 1slm; gap: detecting that the cross direction of the center shaft center in the single crystal furnace and the furnace barrel, the heat preservation barrel and the heater is less than 3mm, confirming that the center-of-shaft center deviation is less than 3mm, performing experiments on the TOP res=0.0185 and the length of the crystal bar after 70% of the length of the crystal bar with SL=0.60 mm/min, performing crystal bar drawing to ensure that the growth interface of the whole crystal bar is horizontal or convex when growing, dividing the experiments into 2 groups according to the fluctuation range of the drawing speed, performing 5 experiments on each group, and obtaining data with the same other parameters as shown in table 3.
TABLE 3 Table 3
| Group of | Sequence number | Fluctuation range | The ring grain generating position accounts for the proportion of the crystal bar | Severity of disease |
| A | 1 | ±10% | 78% | Acceptable for |
| A | 2 | ±10% | 79% | Acceptable for |
| A | 3 | ±10% | 80% | Acceptable for |
| A | 4 | ±10% | 79% | Acceptable for |
| A | 5 | ±10% | 81% | Acceptable for |
| B | 1 | ±5% | 84% | Acceptable for |
| B | 2 | ±5% | 83% | Acceptable for |
| B | 3 | ±5% | 84% | Acceptable for |
| B | 4 | ±5% | 83% | Acceptable for |
| B | 5 | ±5% | 82% | Acceptable for |
As can be seen from Table 3, the pull rate fluctuation range is within the range of-10% -10%, the chromatic aberration of the ring grain generated by the whole crystal bar is lower than the limit sample, so that the whole crystal bar is available and can not be scrapped, when the pull rate fluctuation range is larger, although the chromatic aberration of the ring grain is lower than the limit sample, the quality of the crystal bar can be influenced when the ratio of the ring grain generation position to the crystal bar is closer to the head of the crystal bar, when the pull rate fluctuation range is smaller, the ring grain generation position is closer to the tail of the crystal bar, the use range of the crystal bar is wider and the use frequency is higher, and no experiment for smaller pull rate fluctuation is performed due to the limited precision of equipment, but according to the experiment, the fact that the ring grain generation position is smaller when the pull rate fluctuation is closer to the tail of the crystal bar can be obtained.
Experiment 4: the precision of the single crystal furnace is as follows, SR: + -0.05 rpm; CR: + -0.05 rpm; SL: (+ -0.05 mm/min); CL: (+ -0.01 mm/min); ar: 1slm; gap: detecting that the cross direction of the center shaft center in the single crystal furnace and the furnace barrel, the heat preservation barrel and the heater is less than 3mm, confirming that the center-of-gravity deviation of the center shaft center and the heavy hammer is less than 3mm, carrying out experiments under the conditions that TOP Res=0.0185, SL=0.60 mm/min after the length of the crystal bar is 70%, and the fluctuation range of the pulling speed is-5-5%, carrying out crystal bar drawing, so that the growth interface of the whole crystal bar is horizontal or convex when growing, dividing the experiments into 2 groups according to the setting of the upper limit and the lower limit of the pulling speed, carrying out 5 experiments on each group, and obtaining data as shown in table 4, wherein other parameters are the same.
TABLE 4 Table 4
| Group of | Sequence number | Upper and lower limits of pull speed/mm/min | The ring grain generating position accounts for the proportion of the crystal bar | Severity of disease |
| A | 1 | -0.25-0.25 | 84% | Acceptable for |
| A | 2 | -0.25-0.25 | 83% | Acceptable for |
| A | 3 | -0.25-0.25 | 84% | Acceptable for |
| A | 4 | -0.25-0.25 | 82% | Acceptable for |
| A | 5 | -0.25-0.25 | 84% | Acceptable for |
| B | 1 | -0.2-0.2 | 85% | Acceptable for |
| B | 2 | -0.2-0.2 | 85% | Acceptable for |
| B | 3 | -0.2-0.2 | 86% | Acceptable for |
| B | 4 | -0.2-0.2 | 85% | Acceptable for |
| B | 5 | -0.2-0.2 | 84% | Acceptable for |
As can be seen from Table 4, the upper and lower limits of the pulling speed are set at-0.25-0.25 mm/min, and the color difference of the ring patterns generated by the whole crystal bar is lower than that of a limit sample, so that the whole crystal bar is usable and can not be scrapped, and the upper and lower limits of the pulling speed are set to be approximate to be better, and the ring patterns are generated at a position closer to the tail of the crystal bar.
Experiment 5: the precision of the single crystal furnace is as follows, SR: + -0.05 rpm; CR: + -0.05 rpm; SL: (+ -0.05 mm/min); CL: (+ -0.01 mm/min); ar: 1slm; gap: detecting that the cross direction of the center shaft center in the single crystal furnace and the furnace barrel, the heat preservation barrel and the heater is less than 3mm, confirming that the center-of-shaft center deviation is less than 3mm, carrying out experiments at TOP Res=0.0185, SL=0.60 mm/min after the length of the crystal bar is 70%, the fluctuation range of pulling speed is-5-5%, the upper limit and the lower limit of the pulling speed are-0.2-0.2 mm/min, carrying out crystal bar drawing, enabling the growth interface of the whole crystal bar to be horizontal or convex when growing, dividing the experiments into 3 groups according to the difference of SR/CR, carrying out 5 experiments for each group, and carrying out other parameters identically, wherein the obtained data are shown in Table 5.
TABLE 5
| Group of | Sequence number | SR/CR | The ring grain generating position accounts for the proportion of the crystal bar | Severity of disease |
| A | 1 | 1.5 | 85% | Acceptable for |
| A | 2 | 1.5 | 85% | Acceptable for |
| A | 3 | 1.5 | 85% | Acceptable for |
| A | 4 | 1.5 | 84% | Acceptable for |
| A | 5 | 1.5 | 84% | Acceptable for |
| B | 1 | 1.7 | 86% | Acceptable for |
| B | 2 | 1.7 | 85% | Acceptable for |
| B | 3 | 1.7 | 86% | Acceptable for |
| B | 4 | 1.7 | 85% | Acceptable for |
| B | 5 | 1.7 | 86% | Acceptable for |
| C | 1 | 2.0 | 87% | Acceptable for |
| C | 2 | 2.0 | 86% | Acceptable for |
| C | 3 | 2.0 | 88% | Acceptable for |
| C | 4 | 2.0 | 88% | Acceptable for |
| C | 5 | 2.0 | 87% | Acceptable for |
As can be seen from Table 5, when SR/CR is greater than 1, the color difference of the ring patterns generated by the whole crystal bar is lower than a limit sample, so that the whole crystal bar is available and can not be scrapped, the higher the value of SR/CR is, the closer the ring pattern generation position is to the tail part of the crystal bar, the higher the yield of the crystal bar is, and the larger the SR/CR is not tested because the precision of the equipment is limited, but according to the experiment, the larger the SR/CR is, the closer the ring pattern generation position is to the tail part of the crystal bar, and the higher the quality of the silicon wafer is; and the resonance point is avoided when the specific crystal rotation value and the pot rotation value are set according to the ratio of SR/CR.
Experiment 6: the precision of the single crystal furnace is as follows, SR: + -0.05 rpm; CR: + -0.05 rpm; SL: (+ -0.05 mm/min); CL: (+ -0.01 mm/min); ar: 1slm; gap: detecting that the cross direction of the center shaft center in the single crystal furnace and a furnace cylinder, a heat preservation cylinder and a heater is less than 3mm, confirming that the center-of-shaft center deviation is less than 3mm, carrying out experiments on the center shaft center and the center of gravity of a heavy hammer in TOP Res=0.0185, SL=0.60 mm/min after the length of the crystal bar is 70%, the fluctuation range of pulling speed is-5-5%, the upper limit and the lower limit of the pulling speed are-0.2-0.2 mm/min, carrying out crystal bar drawing under SR/CR=2.0, so that the growth interface of the whole crystal bar is horizontal or convex, dividing the experiments into 3 groups according to the difference of argon flow, carrying out 5 experiments on each group, and obtaining data shown in Table 6.
TABLE 6
| Group of | Sequence number | Argon flow/slm | The ring grain generating position accounts for the proportion of the crystal bar | Severity of disease |
| A | 1 | 40 | 85% | Acceptable for |
| A | 2 | 40 | 86% | Acceptable for |
| A | 3 | 40 | 85% | Acceptable for |
| A | 4 | 40 | 85% | Acceptable for |
| A | 5 | 40 | 86% | Acceptable for |
| B | 1 | 60 | 88% | Acceptable for |
| B | 2 | 60 | 89% | Acceptable for |
| B | 3 | 60 | 89% | Acceptable for |
| B | 4 | 60 | 90% | Acceptable for |
| B | 5 | 60 | 88% | Acceptable for |
| C | 1 | 80 | 85% | Acceptable for |
| C | 2 | 80 | 83% | Acceptable for |
| C | 3 | 80 | 84% | Acceptable for |
| C | 4 | 80 | 84% | Acceptable for |
| C | 5 | 80 | 85% | Acceptable for |
As can be seen from Table 6, when the argon flow is 40-80slm, the argon flow and Gap value enable the surface of molten soup to be stable, fluctuation is small, impurities at the solid-liquid interface of the crystal bar are distributed, the color difference of the ring lines of the whole crystal bar is lower than a limit sample, the whole crystal bar is available and can not be scrapped, and when the argon flow is 60slm, the ring lines are located closer to the tail of the crystal bar, and the yield of the crystal bar is higher.
In summary, the best growth conditions for the ingot obtained from experiments 2 to 6 were: the upper limit resistivity, SL=0.60 mm/min, pull rate fluctuation range + -5%, pull rate upper and lower limits + -0.2mm, SR/CR=2.0, argon 50-70slm within the resistivity specification.
Specifically, the present scheme is further illustrated by the following example 1, comparative example 1.
Example 1
The precision of the single crystal furnace is as follows, SR: + -0.05 rpm; CR: + -0.05 rpm; SL: (+ -0.05 mm/min); CL: (+ -0.01 mm/min); ar: 1slm; gap: detecting that the cross direction of the center shaft center in the single crystal furnace and the furnace cylinder, the heat preservation cylinder and the heater is less than 3mm, confirming that the center-of-shaft center deviation is less than 3mm, carrying out 10 experiments on the whole crystal bar when the crystal bar grows, wherein the TOP Res=0.0185, SL=0.60 mm/min after the crystal bar length is 70%, the fluctuation range of the pulling speed is-5-5%, the upper limit and the lower limit of the pulling speed are-0.2-0.2 mm/min, SR/CR=2.0, and the growth interface of the whole crystal bar is horizontal or convex when the crystal bar grows, and obtaining the data shown in table 7.
TABLE 7
| Sequence number | The ring grain generating position accounts for the proportion of the crystal bar | Severity of disease |
| 1 | 88% | Acceptable for |
| 2 | 87% | Can be connected withIs subject to |
| 3 | 85% | Acceptable for |
| 4 | 89% | Acceptable for |
| 5 | 88% | Acceptable for |
| 6 | 85% | Acceptable for |
| 7 | 86% | Acceptable for |
| 8 | 90% | Acceptable for |
| 9 | 88% | Acceptable for |
| 10 | 89% | Acceptable for |
Comparative example 1
The precision of the single crystal furnace is as follows, SR: + -0.05 rpm; CR: + -0.05 rpm; SL: (+ -0.05 mm/min); CL: (+ -0.01 mm/min); ar: 1slm; gap: detecting that the cross direction of the center shaft center in the single crystal furnace and the furnace cylinder, the heat preservation cylinder and the heater is less than 3mm, confirming that the center-of-shaft center deviation is less than 3mm, carrying out 10 experiments on the whole crystal bar in a concave growth interface during growth, and obtaining the data shown in table 8, wherein SL=0.80 mm/min after TOP Res=0.0185 and the length of the crystal bar is 70%, the fluctuation range of the pulling speed is-10-10%, the upper and lower limits of the pulling speed are-0.25-0.25 mm/min, SR/CR=1.5 and the argon flow is 80slm.
TABLE 8
| Sequence number | The ring grain generating position accounts for the proportion of the crystal bar | Severity of disease |
| 1 | 72% | Unacceptable |
| 2 | 71% | Unacceptable |
| 3 | 70% | Unacceptable |
| 4 | 73% | Unacceptable |
| 5 | 72% | Unacceptable |
| 6 | 69% | Unacceptable |
| 7 | 71% | Unacceptable |
| 8 | 70% | Unacceptable |
| 9 | 68% | Unacceptable |
| 10 | 73% | Unacceptable |
Experiments of the embodiment 1 and the comparative example 1 show that the process is improved, so that the growth interface of the whole crystal bar concave to the solution body is controlled to be horizontal or convex during growth, the solidification time of the growth interface of the crystal bar is identical, the radial solidification time is identical in the cutting direction perpendicular to the growth axis direction, the concentration of impurities at each point is consistent, the color difference of ring lines on the surface of a silicon wafer is lower than that of a limit sample, and the whole crystal bar is available and cannot be scrapped.
The foregoing disclosure is illustrative of the preferred embodiments of the present invention, and is not to be construed as limiting the scope of the invention, as it is understood by those skilled in the art that all or part of the above-described embodiments may be practiced with equivalents thereof, which fall within the scope of the invention as defined by the appended claims.
Claims (9)
1. A method for reducing the streak of heavily doped antimony <100> single crystal impurity is characterized in that when a crystal bar is pulled, the pulling speed of the crystal bar is controlled to control the growth interface of the crystal bar, and the growth interface concave to a solution is controlled to be horizontal or convex, so that the solidification time of the growth interface of the crystal bar is the same;
and when the crystal bar is pulled to 70%, pulling the crystal bar at a pulling speed of 0-0.6mm/min, gradually reducing the pulling speed along with the pulling of the crystal bar, and controlling the average pulling speed fluctuation to be-10% so as to control the growth interface of the concave solution to be horizontal or convex.
2. The method for reducing streaks of heavily doped antimony <100> single crystal impurities according to claim 1, wherein the upper and lower pull rates of the ingot are set to-0.25 to 0.25mm/min before the ingot is pulled.
3. The method for reducing the streaks of heavily doped antimony <100> single crystal impurities according to claim 2, wherein the ratio of the ingot rotation speed to the crucible rotation speed is controlled to be greater than 1 during ingot pulling, namely: SR/CR >1.0 to stabilize the solid-liquid interface.
4. The method for reducing streaks of heavily doped antimony <100> single crystal impurities according to claim 3, wherein a predetermined flow rate of argon is introduced during ingot pulling.
5. The method for reducing fringing of heavily doped antimony <100> single crystal impurity according to claim 4, wherein the predetermined flow rate of argon is 0 to 80slm.
6. The method for reducing streaks of heavily doped antimony <100> single crystal impurities according to claim 5, wherein before the single crystal furnace is opened, the deviation of the center axis of the single crystal furnace from the cross direction of the furnace barrel, the heat preservation barrel and the heater is ensured to be smaller than a first preset distance, and the deviation of the center axis of the center of gravity of the heavy hammer is ensured to be smaller than a second preset distance.
7. The method for reducing fringing of heavily doped antimony <100> single crystal impurity according to claim 6, wherein the first predetermined distance is 3mm.
8. The method for reducing fringing of heavily doped antimony <100> single crystal impurity according to claim 7, wherein the second predetermined distance is 3mm.
9. The method for reducing the fringing of heavily doped antimony <100> single crystal impurities according to claim 8, wherein the diameter of the ingot is controlled by adjusting the temperature only when a large variation in the diameter of the ingot occurs during the drawing of the ingot.
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