Polycrystalline silicon ingot, preparation method thereof, and polycrystalline silicon wafer

Abstract

Disclosed is a preparation method of a polycrystalline silicon ingot. The preparation method comprises: providing a silicon nucleation layer at the bottom of a crucible, and filling a silicon material above the silicon nucleation layer; heating the silicon material to melt same, adjusting the thermal field inside the crucible to make the melted silicon material to start crystallization on the basis of the silicon nucleation layer; and when the crystallization is finished, performing annealing and cooling to obtain a polycrystalline silicon ingot. By adopting the preparation method, a desirable initial nucleus can be obtained for a polycrystalline silicon ingot, so as to reduce dislocation multiplication during the growth of the polycrystalline silicon ingot. Further disclosed are a polycrystalline silicon ingot obtained through the preparation method and a polycrystalline silicon wafer made using the polycrystalline silicon ingot as a raw material.

Claims

1. A method for preparing polycrystalline silicon ingot, comprising: (1) laying a microcrystalline nucleating source layer at the bottom of the crucible, the microcrystalline nucleating source layer is microcrystalline silicon and/or amorphous silicon; thickness of the microcrystalline nucleating source layer is a first height; the microcrystalline nucleating source layer is the nucleating source of silicon material layer; (2) feeding silicon onto the microcrystalline nucleating source layer, melting the silicon to form molten silicon by heating, wherein a solid-liquid interface formed after the silicon is melted completely reaches the surface of the microcrystalline nucleating source layer or is deep into the microcrystalline nucleating source layer and the height to the bottom of the crucible is greater than or equal to 1 mm, regulating a thermal field to achieve supercooled state to grow crystals from the molten silicon on the base of the microcrystalline nucleating source layer; (3) after the crystallization of molten silicon is completely finished, performing annealing and cooling to obtain polycrystalline silicon ingot.

2. The method for preparing polycrystalline silicon ingot according to claim 1, when solid-liquid interface formed after the silicon is melted completely is deep into the microcrystalline nucleating source layer and the height to the bottom of the crucible is greater than or equal to 5 mm, regulating the thermal field to achieve supercooled state to grow crystals from the molten silicon on the base of the microcrystalline nucleating source layer.

3. The method for preparing polycrystalline silicon ingot according to claim 1, wherein the first height is in a range of 1-150 mm.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 is a schematic view showing the crucible after feeding feedstock, according to Example 1.

(2) FIG. 2 is a map of minority carrier lifetime of the silicon ingot, according to Example 1.

(3) FIG. 3 is a dislocation test pattern of the bottom of silicon ingot, according to Example 1.

(4) FIG. 4 is a dislocation test pattern of the top of silicon ingot, according to Example 1.

(5) FIG. 5 is a schematic view showing the crucible after feeding feedstock, according to Example 6.

(6) FIG. 6 is a map of minority carrier lifetime of the polycrystalline silicon ingot, according to Example 6.

(7) FIG. 7 is a photoluminescence spectrum of polycrystalline silicon wafer according to Example 6.

(8) FIG. 8 is a schematic view showing the preparation according to Example 9.

(9) FIG. 9 is an image showing prevention of dislocation observed by photoluminescence silicon wafer inspection system, according to Example 9.

(10) FIG. 10 is a map of minority carrier lifetime of the polycrystalline silicon ingot, according to Example 9.

(11) FIG. 11 is a map of minority carrier lifetime of the quasi-single crystal, according to comparative experiment 1.

(12) FIG. 12 is a map of minority carrier lifetime of the polycrystalline silicon ingot, according to comparative experiment 2.

DETAILED DESCRIPTION OF ILLUSTRATED EMBODIMENTS

(13) The invention will now be described in detail on the basis of preferred embodiments. It is to be understood that various changes may be made without departing from the spirit and scope of the inventions.

EXAMPLE 1

(14) A method for preparing polycrystalline silicon ingot.

(15) A layer of silicon nitride was provided on inner wall of a quartz crucible by spray coating, followed by laying a layer of crushed polycrystalline silicon having a size of 1-5 cm at the bottom of the crucible. The layer of crushed polycrystalline silicon was 1 cm. Then various chunk silicon was fed onto crushed polycrystalline silicon until the crucible was full. FIG. 1 is a schematic view of one embodiment, showing the crucible after feeding. 1 is crucible, 2 is crushed polycrystalline silicon and 3 is silicon.

(16) The crucible filled with silicon was then placed into a casting furnace. Starting a casting ingot program and vacuuming. And the temperature was elevated to the melting point of silicon by heating so as to melt the silicon slowly. During the melting process, solid-liquid interface formed by molten silicon and unmelted silicon was detected by using quartz rob. In preliminary stage of the melting process, the position was detected once every 2 hours (at 1 hour intervals). In later stage of the melting process, the position was detected at 0.5 hour intervals.

(17) When solid-liquid interface formed by molten silicon and unmelted silicon was detected to be just in the layer of crushed polycrystalline silicon, heat shield was open, thus reducing the temperature and cooling the molten silicon. Temperature was reduced at a speed of 10 K/min. A somewhat supercooled state was achieved. Molten silicon started to grow crystals on the base of unmelted silicon.

(18) After the crystallization of molten silicon was completely finished, performing annealing and cooling to obtain polycrystalline silicon ingot.

(19) The polycrystalline silicon ingot as prepared was then cooled and sectioned to produce chunk polycrystalline silicon, followed by slicing and cleaning, polycrystalline silicon wafer was obtained. The polycrystalline silicon wafer was used as raw material to manufacture solar cell by screen printing technique.

(20) Minority carrier lifetime of the polycrystalline silicon ingot was tested using WT2000, the test results are shown in FIG. 2. It can be seen from the FIG. 2 that minority carrier lifetime of polycrystalline silicon ingot distributes uniformly from the bottom (right) to the top (left), area for short minority carrier lifetime is small, silicon ingot is of good quality.

(21) As for the obtained polycrystalline silicon ingot, dislocation was observed by using optical microscope (magnified 100 times). Test results showed that: average dislocation density at the bottom of the silicon ingot was 2.9610.sup.4 (1/cm.sup.2), average dislocation density at the top of the silicon ingot was 3.4110.sup.4 (1/cm.sup.2). FIG. 3 shows test results of dislocation at the bottom of the silicon ingot. FIG. 4 shows test results of dislocation at the top of the silicon ingot.

(22) Photoelectric conversion efficiency of the solar cell was tested by using a test system for solar cells (Halm, a German company). Test results showed that the photoelectric conversion efficiency of the solar cell was 17.3%.

EXAMPLE 2

(23) A method for preparing polycrystalline silicon ingot.

(24) A layer of silicon nitride was provided on inner wall of a quartz crucible by spray coating. And then a layer of chunk polycrystalline silicon was laid at the bottom of the crucible, followed by laying a layer of crushed polycrystalline material having a size of 1-5 cm. Thickness of the layer of chunk polycrystalline silicon was 1 cm. Thickness of the layer of crushed polycrystalline material was 2 cm. After that, various chunk silicon was fed onto crushed polycrystalline material until the crucible was full.

(25) The crucible filled with silicon was then placed into a casting furnace. Starting a casting ingot program and vacuuming. And the temperature was elevated to the melting point of silicon by heating so as to melt the silicon slowly. During the melting process, solid-liquid interface formed by molten silicon and unmelted silicon was detected by using quartz rob. In preliminary stage of the melting process, the position was detected once every 2 hours (at 1 hour intervals). In later stage of the melting process, the position was detected at 0.5 hour intervals.

(26) When solid-liquid interface formed by molten silicon and unmelted silicon was detected to be deep into the layer of crushed polycrystalline silicon a distance of 0.5 cm, heat shield was open, thus reducing the temperature and cooling the molten silicon. Temperature was reduced at a speed of 20 K/min. A somewhat supercooled state was achieved. Molten silicon started to grow crystals on the base of unmelted silicon.

(27) After the crystallization of molten silicon was completely finished, performing annealing and cooling to obtain polycrystalline silicon ingot.

(28) The polycrystalline silicon ingot as prepared was then cooled and sectioned to produce chunk polycrystalline silicon, followed by slicing and cleaning, polycrystalline silicon wafer was obtained. The polycrystalline silicon wafer was used as raw material to manufacture solar cell by screen printing technique.

(29) As for the obtained polycrystalline silicon ingot, dislocation was observed by using optical microscope (magnified 200 times). Test results showed that: average dislocation density at the bottom of the silicon ingot was 2.810.sup.4 (1/cm.sup.2), average dislocation density at the top of the silicon ingot was 3.4010.sup.4 (1/cm.sup.2).

(30) Photoelectric conversion efficiency of the solar cell was tested by using a test system for solar cells (Halm, a German company). Test results showed that the photoelectric conversion efficiency of the solar cell was 17.46%.

EXAMPLE 3

(31) A method for preparing polycrystalline silicon ingot.

(32) A layer of silicon nitride was provided on inner wall of a quartz crucible by spray coating. And then a layer of graphite plate of high strength, high density and high purity was laid at the bottom of the crucible, followed by laying a layer of crushed polycrystalline material having a size of 1-5 cm. Thickness of the layer of graphite plate was 1 cm. Thickness of the layer of crushed polycrystalline material was 0.5 cm. After that, various chunk silicon was fed onto crushed polycrystalline material until the crucible was full.

(33) The crucible filled with silicon was then placed into a casting furnace. Starting a casting ingot program and vacuuming. And the temperature was elevated to the melting point of silicon by heating so as to melt the silicon slowly. During the melting process, solid-liquid interface formed by molten silicon and unmelted silicon was detected by using quartz rob. In preliminary stage of the melting process, the position was detected once every 2 hours (at 1 hour intervals). In later stage of the melting process, the position was detected at 0.5 hour intervals.

(34) When solid-liquid interface formed by molten silicon and unmelted silicon was detected to be deep into the layer of crushed polycrystalline silicon a distance of 0.2 cm, heat shield was open, thus reducing the temperature and cooling the molten silicon. Temperature was reduced at a speed of 15 K/min. A somewhat supercooled state was achieved. Molten silicon started to grow crystals on the base of unmelted silicon.

(35) After the crystallization of molten silicon was completely finished, performing annealing and cooling to obtain polycrystalline silicon ingot.

(36) The polycrystalline silicon ingot as prepared was then cooled and sectioned to produce chunk polycrystalline silicon, followed by slicing and cleaning, polycrystalline silicon wafer was obtained. The polycrystalline silicon wafer was used as raw material to manufacture solar cell by screen printing technique.

(37) As for the obtained polycrystalline silicon ingot, dislocation was observed by using optical microscope (magnified 200 times). Test results showed that: average dislocation density at the bottom of the silicon ingot was 3.110.sup.4 (1/cm.sup.2), average dislocation density at the top of the silicon ingot was 3.5610.sup.4 (1/cm.sup.2).

(38) Photoelectric conversion efficiency of the solar cell was tested by using a test system for solar cells (Halm, a German company). Test results showed that the photoelectric conversion efficiency of the solar cell was 17.53%.

EXAMPLE 4

(39) A method for preparing polycrystalline silicon ingot.

(40) A layer of silicon nitride was provided on inner wall of a quartz crucible by spray coating, followed by feeding various chunk silicon onto the crucible from the bottom to the top until the crucible was full.

(41) The crucible filled with silicon was then placed into a casting furnace. Starting a casting ingot program and vacuuming. And the temperature was elevated to the melting point of silicon by heating so as to melt the silicon slowly. During the melting process, solid-liquid interface formed by molten silicon and unmelted silicon was detected by using quartz rob. In preliminary stage of the melting process, the position was detected once every 2 hours (at 1 hour intervals). In later stage of the melting process, the position was detected at 0.5 hour intervals.

(42) When the distance between the bottom of the crucible and the solid-liquid interface formed by molten silicon and unmelted silicon was detected to be 0.2 cm, heat shield was open, thus reducing the temperature and cooling the molten silicon. Temperature was reduced at a speed of 15 K/min. A somewhat supercooled state was achieved. Molten silicon started to grow crystals on the base of unmelted silicon.

(43) After the crystallization of molten silicon was completely finished, performing annealing and cooling to obtain polycrystalline silicon ingot.

(44) The polycrystalline silicon ingot as prepared was then cooled and sectioned to produce chunk polycrystalline silicon, followed by slicing and cleaning, polycrystalline silicon wafer was obtained. The polycrystalline silicon wafer was used as raw material to manufacture solar cell by screen printing technique.

(45) As for the obtained polycrystalline silicon ingot, dislocation was observed by using optical microscope (magnified 200 times). Test results showed that: average dislocation density at the bottom of the silicon ingot was 3.1210.sup.4 (1/cm.sup.2), average dislocation density at the top of the silicon ingot was 3.5810.sup.4 (1/cm.sup.2).

(46) Photoelectric conversion efficiency of the solar cell was tested by using a test system for solar cells (Halm, a German company). Test results showed that the photoelectric conversion efficiency of the solar cell was 17.48%.

EXAMPLE 5

(47) A method for preparing polycrystalline silicon ingot.

(48) (1) Nucleating source was provided at the bottom of a crucible to form a nucleating source layer, wherein the step of providing nucleating source at the bottom of a crucible was: applying 200 g of silicon powder at the bottom of a crucible which had been coated with a layer of silicon nitride in advance. Then the crucible was roasted in an oven at 600 C. for 2 hours. Particle size of the silicon powder was 1 mm.

(49) (2) Molten silicon was provided above the nucleating source layer, wherein the step of providing molten silicon above the nucleating source layer was: feeding 450-800 kg of solid silicon above the nucleating source layer, then melting the solid silicon by heating the crucible and elevating the temperature to 1560 C. At that moment, molten silicon was provided on the surface of the nucleating source layer.

(50) (3) controlling the temperature inside the crucible, the temperature raising along the direction perpendicular to the bottom of the crucible to form temperature gradient, making the molten silicon nucleating and forming crystals by using the nucleating source, then obtaining polycrystalline silicon ingot. Herein, open heat shield and control the bottom temperature at 1360 C. to make the molten silicon liquid in a supercooled state, then nucleating and growing crystals by using nucleating source. Polycrystalline silicon ingot was obtained.

(51) Dislocation density of the polycrystalline silicon ingot prepared according to this embodiment was in a range of 3.610.sup.3-4.810.sup.3 (1/cm.sup.2), minority carrier lifetime was 18 microseconds (ms).

(52) Polycrystalline silicon wafer prepared by using the polycrystalline silicon ingot of this embodiment was suitable for manufacturing solar cell. Conversion efficiency of the obtained solar cell was 17.6%.

EXAMPLE 6

(53) A method for preparing polycrystalline silicon ingot.

(54) (1) Amorphous rob silicon of high purity produced by Siemens was laid at the bottom of a crucible to form microcrystalline nucleating source layer. Silicon was fed onto the microcrystalline nucleating source layer until the crucible was full. FIG. 5 is a schematic view of this embodiment, showing the crucible after feeding. Thickness of the microcrystalline nucleating source layer was 120 mm.

(55) (2) The crucible filled with silicon was then placed into a casting furnace. Starting a casting ingot program and vacuuming. And the temperature was elevated to 1530 C. by heating so as to melt the silicon slowly and form molten silicon. During the melting process, solid-liquid interface formed by molten silicon was detected by using quartz rob. In preliminary stage of the melting process, the position was detected once every 2 hours (at 1 hour intervals). In later stage of the melting process, the position was detected at 0.5 hour intervals.

(56) (3) When distance between the bottom of the crucible and the solid-liquid interface formed by melting molten silicon was detected to be 15 mm, heat shield was open, thus reducing the temperature and cooling the molten silicon. Temperature was reduced at a speed of 5 K/min. A somewhat supercooled state was achieved. Molten silicon started to grow crystals on the base of the amorphous rob silicon of high purity.

(57) (4) after the crystallization of molten silicon was completely finished, performing annealing and cooling to obtain polycrystalline silicon ingot.

(58) The polycrystalline silicon ingot as prepared was then cooled and sectioned to produce chunk polycrystalline silicon, followed by slicing and cleaning, polycrystalline silicon wafer was obtained. The polycrystalline silicon wafer was used as raw material to manufacture solar cell by screen printing technique.

(59) Minority carrier lifetime of the obtained polycrystalline silicon ingot was tested by using WT2000. Test results were shown in FIG. 6. It can be seen from FIG. 6 that the polycrystalline silicon ingot was of long minority carrier lifetime and small dislocations.

(60) As for the obtained polycrystalline silicon ingot, dislocation was observed by using optical microscope (magnified 200 times). Test results showed that: average dislocation density at the bottom of the silicon ingot was 2.210.sup.4 (1/cm.sup.2).

(61) Dislocations of polycrystalline silicon wafer were inspected by using photoluminescence spectra. Test results were shown in FIG. 7. It can be seen from FIG. 7 that the polycrystalline silicon wafer was of small dislocations and fine and uniform crystalline grains.

(62) Photoelectric conversion efficiency of the solar cell was tested by using a test system for solar cells (Halm, a German company). Test results showed that the photoelectric conversion efficiency of the solar cell was 17.8%.

EXAMPLE 7

(63) A method for preparing polycrystalline silicon ingot.

(64) (1) Amorphous rob silicon of high purity produced by Siemens was crushed and then laid at the bottom of a crucible to form microcrystalline nucleating source layer. Silicon was fed onto the microcrystalline nucleating source layer. Thickness of the microcrystalline nucleating source layer was 50 mm.

(65) (2) The crucible filled with silicon was then placed into a casting furnace. Starting a casting ingot program and vacuuming. And the temperature was elevated to 1540 C. by heating so as to melt the silicon slowly and form molten silicon. During the melting process, solid-liquid interface formed by molten silicon was detected by using quartz rob. In preliminary stage of the melting process, the position was detected once every 2 hours (at 1 hour intervals). In later stage of the melting process, the position was detected at 0.5 hour intervals.

(66) (3) When distance between the bottom of the crucible and the solid-liquid interface formed by molten silicon is detected to be 30 mm, heat shield was open, thus reducing the temperature and cooling the molten silicon. Temperature was reduced at a speed of 6 K/min. A somewhat supercooled state was achieved. Molten silicon started to grow crystals on the base of the amorphous rob silicon of high purity.

(67) (4) after the crystallization of molten silicon was completely finished, performing annealing and cooling to obtain polycrystalline silicon ingot.

(68) The polycrystalline silicon ingot as prepared was then cooled and sectioned to produce chunk polycrystalline silicon, followed by slicing and cleaning, polycrystalline silicon wafer was obtained. The polycrystalline silicon wafer was used as raw material to manufacture solar cell by screen printing technique.

(69) As for the obtained polycrystalline silicon ingot, dislocation was observed by using optical microscope (magnified 200 times). Test results showed that: average dislocation density at the bottom of the silicon ingot was 8.510.sup.3 (1/cm.sup.2).

(70) Photoelectric conversion efficiency of the solar cell was tested by using a test system for solar cells (Halm, a German company). Test results showed that the photoelectric conversion efficiency of the solar cell was 18.0%.

EXAMPLE 8

(71) A method for preparing polycrystalline silicon ingot.

(72) (1) Silicon of high purity produced by Fluidized-bed method was laid at the bottom of a crucible to form microcrystalline nucleating source layer. Silicon was fed onto the microcrystalline nucleating source layer until the crucible was full. Thickness of the microcrystalline nucleating source layer was 15 mm.

(73) (2) The crucible filled with silicon was then placed into a casting furnace. Starting a casting ingot program and vacuuming. And the temperature was elevated to 1500 C. by heating so as to melt the silicon slowly. During the melting process, solid-liquid interface formed by molten silicon was detected by using quartz rob. In preliminary stage of the melting process, the position was detected once every 2 hours (at 1 hour intervals). In later stage of the melting process, the position was detected at 0.5 hour intervals.

(74) (3) When distance between the bottom of the crucible and the solid-liquid interface formed by molten silicon was detected to be 10 mm, heat shield was open, thus reducing the temperature and cooling the molten silicon. Temperature was reduced at a speed of 15 K/min. A somewhat supercooled state was achieved. Molten silicon started to grow crystals on the base of the microcrystalline silicon.

(75) (4) after the crystallization of molten silicon was completely finished, performing annealing and cooling to obtain polycrystalline silicon ingot.

(76) The polycrystalline silicon ingot as prepared was then cooled and sectioned to produce chunk polycrystalline silicon, followed by slicing and cleaning, polycrystalline silicon wafer was obtained. The polycrystalline silicon wafer was used as raw material to manufacture solar cell by screen printing technique.

(77) As for the obtained polycrystalline silicon ingot, dislocation was observed by using optical microscope (magnified 200 times). Test results showed that: average dislocation density at the bottom of the silicon ingot was 3.510.sup.4 (1/cm.sup.2).

(78) Photoelectric conversion efficiency of the solar cell was tested by using a test system for solar cells (Halm, a German company). Test results showed that the photoelectric conversion efficiency of the solar cell was 17.6%.

EXAMPLE 9

(79) A method for preparing polycrystalline silicon ingot.

(80) (1) randomly laying seed crystals with unlimited crystal orientation at the bottom of crucible to form a layer of seed crystals;

(81) Seed crystals herein were pieces of single crystals produced in the manufacture of semiconductor. Seed crystals were single crystals in a form of plate. The maximum side-length was 20 mm, dislocation density is less than or equal to 10.sup.3 (1/cm.sup.2), thickness of the layer of seed crystals was 50 mm.

(82) (2) providing molten silicon above the layer of seed crystals, controlling the temperature at the bottom of the crucible below melting point of the seed crystals, making the layer of seed crystals not completely melted not completely melted;

(83) FIG. 8 shows the preparation according to this embodiment, wherein 1 is crucible, 2 is layer of seed crystals, 3 is silicon. The step of providing molten silicon above the layer of seed crystals was: feeding solid silicon, melting the silicon by heating the crucible and elevating the temperature to 1530 C. At that moment, molten silicon was provided on the surface of the layer of seed crystals. Temperature at the bottom of the crucible was 1412 C. Percentage of unmelted seed crystals of initial seed crystals in step (1) was 60%.

(84) (3) controlling the temperature inside the crucible, the temperature raising along the direction perpendicular to the bottom of the crucible to form temperature gradient, making the molten silicon growing above the seed crystals, the molten silicon inheriting the structure of the seed crystals, then obtaining polycrystalline silicon ingot.

(85) FIG. 9 is an image showing prevention of dislocation observed by photoluminescence silicon wafer inspection system, according to this embodiment. As shown in FIG. 9, 1 is grain boundary, 2 is no-dislocation area, 3 is dislocation area, dislocations of grain boundary 1 moving is refrained obviously, and no-dislocation area 2 and dislocation area 3 formed at two sides of grain boundary 1.

(86) Dislocation density of the polycrystalline silicon ingot prepared according to this embodiment was in a range of 1.510.sup.3-1.810.sup.3 (1/cm.sup.2), minority carrier lifetime was 25 microseconds (ms).

(87) Polycrystalline silicon wafer prepared by using the polycrystalline silicon ingot of this embodiment was suitable for manufacturing solar cell. Conversion efficiency of the obtained solar cell was 17.8%.

EXAMPLE 10

(88) A method for preparing polycrystalline silicon ingot.

(89) (1) randomly laying seed crystals with unlimited crystal orientation at the bottom of crucible to form a layer of seed crystals;

(90) Seed crystals herein were pieces of single crystals produced in the manufacture of semiconductor. Seed crystals were single crystals in a form of chunk. The maximum side-length was 100 mm, dislocation density was less than or equal to 10.sup.3 (1/cm.sup.2), thickness of the layer of seed crystals was 50 mm.

(91) (2) providing molten silicon above the layer of seed crystals, controlling the temperature at the bottom of the crucible below melting point of the seed crystals, making the layer of seed crystals not completely melted not completely melted;

(92) The step of providing molten silicon above the layer of seed crystals was: feeding solid silicon, melting the silicon by heating the crucible and elevating the temperature to 1560 C. At that moment, molten silicon was provided on the surface of the layer of seed crystals. Temperature at the bottom of the crucible was 1412 C. Percentage of unmelted seed crystals of initial seed crystals in step (1) was 95%.

(93) (3) controlling the temperature inside the crucible, the temperature raising along the direction perpendicular to the bottom of the crucible to form temperature gradient, making the molten silicon growing above the seed crystals, the molten silicon inheriting the structure of the seed crystals, then obtaining polycrystalline silicon ingot.

(94) Dislocation density of the polycrystalline silicon ingot prepared according to this embodiment was in a range of 7.510.sup.3-8.010.sup.3 (1/cm.sup.2), minority carrier lifetime was 18 microseconds (ms).

(95) Polycrystalline silicon wafer prepared by using the polycrystalline silicon ingot of this embodiment was suitable for manufacturing solar cell. Conversion efficiency of the obtained solar cell was 17.8%.

EXAMPLE 11

(96) A method for preparing polycrystalline silicon ingot.

(97) (1) randomly laying seed crystals with unlimited crystal orientation at the bottom of crucible to form a layer of seed crystals;

(98) Seed crystals herein were pieces of single crystals produced in the manufacture of semiconductor. Seed crystals were single crystals in a form of granule. The maximum side-length was 1 mm, dislocation density was less than or equal to 10.sup.3 (1/cm.sup.2), thickness of the layer of seed crystals was 5 mm.

(99) (2) providing molten silicon above the layer of seed crystals, controlling the temperature at the bottom of the crucible below melting point of the seed crystals, making the layer of seed crystals not completely melted not completely melted;

(100) The step of providing molten silicon above the layer of seed crystals was: feeding solid silicon, melting the silicon by heating the crucible and elevating the temperature to 1500 C. At that moment, molten silicon was provided on the surface of the layer of seed crystals. Temperature at the bottom of the crucible was 1412 C. Percentage of unmelted seed crystals of initial seed crystals in step (1) was 5%.

(101) (3) controlling the temperature inside the crucible, the temperature raising along the direction perpendicular to the bottom of the crucible to form temperature gradient, making the molten silicon growing above the seed crystals, the molten silicon inheriting the structure of the seed crystals, then obtaining polycrystalline silicon ingot.

(102) Dislocation density of the polycrystalline silicon ingot prepared according to this embodiment was in a range of 3.510.sup.4-4.810.sup.4 (1/cm.sup.2), minority carrier lifetime was 10 microseconds (ms).

(103) Polycrystalline silicon wafer prepared by using the polycrystalline silicon ingot of this embodiment was suitable for manufacturing solar cell. Conversion efficiency of the obtained solar cell was 17.1%.

EXAMPLE 12

(104) A method for preparing polycrystalline silicon ingot.

(105) (1) randomly laying seed crystals with unlimited crystal orientation at the bottom of crucible to form a layer of seed crystals;

(106) Seed crystals herein were pieces of single crystals produced in the manufacture of semiconductor. Seed crystals were single crystals in a form of granule. The maximum side-length was 50 mm, dislocation density was less than or equal to 10.sup.3 (1/cm.sup.2), thickness of the layer of seed crystals was 50 mm.

(107) (2) providing molten silicon above the layer of seed crystals, controlling the temperature at the bottom of the crucible below melting point of the seed crystals, making the layer of seed crystals not completely melted;

(108) The step of providing molten silicon above the layer of seed crystals was: heating solid silicon in another crucible to prepare molten silicon, followed by pouring the molten silicon into the crucible with a layer of seed crystals. At that moment, the molten silicon was provided on the surface of the layer of seed crystals. Temperature at the bottom of the crucible was 1413 C. Percentage of unmelted seed crystals of initial seed crystals in step (1) was 95%.

(109) (3) controlling the temperature inside the crucible, the temperature raising along the direction perpendicular to the bottom of the crucible to form temperature gradient, making the molten silicon growing above the seed crystals, the molten silicon inheriting the structure of the seed crystals, then obtaining polycrystalline silicon ingot.

(110) Dislocation density of the polycrystalline silicon ingot prepared according to this embodiment was in a range of 3.210.sup.4-3.810.sup.4 (1/cm.sup.2), minority carrier lifetime was 15 microseconds (ms).

(111) Polycrystalline silicon wafer prepared by using the polycrystalline silicon ingot of this embodiment was suitable for manufacturing solar cell. Conversion efficiency of the obtained solar cell was 17.5%.

EXAMPLE 13

(112) A method for preparing polycrystalline silicon ingot.

(113) (1) randomly laying seed crystals with unlimited crystal orientation at the bottom of crucible to form a layer of seed crystals;

(114) Seed crystals herein were pieces of single crystals produced in the manufacture of semiconductor. Seed crystals were polycrystals in a form of granule. The maximum side-length was 1 mm, dislocation density was less than or equal to 10.sup.3 (1/cm.sup.2), thickness of the layer of seed crystals was 5 mm.

(115) (2) providing molten silicon above the layer of seed crystals, controlling the temperature at the bottom of the crucible below melting point of the seed crystals, making the layer of seed crystals not completely melted;

(116) The step of providing molten silicon above the layer of seed crystals was: feeding solid silicon, melting the silicon by heating the crucible and elevating the temperature to 1500 C. At that moment, molten silicon was provided on the surface of the layer of seed crystals. Temperature at the bottom of the crucible was 1412 C. Percentage of unmelted seed crystals of initial seed crystals in step (1) was 60%.

(117) (3) controlling the temperature inside the crucible, the temperature raising along the direction perpendicular to the bottom of the crucible to form temperature gradient, making the molten silicon growing above the seed crystals, the molten silicon inheriting the structure of the seed crystals, then obtaining polycrystalline silicon ingot.

(118) Dislocation density of the polycrystalline silicon ingot prepared according to this embodiment was in a range of 1.210.sup.4-1.810.sup.4 (1/cm.sup.2), minority carrier lifetime was 10 microseconds (ms).

(119) Polycrystalline silicon wafer prepared by using the polycrystalline silicon ingot of this embodiment was suitable for manufacturing solar cell. Conversion efficiency of the obtained solar cell was 17.2%.

EXAMPLE 14

(120) A method for preparing polycrystalline silicon ingot.

(121) (1) randomly laying seed crystals with unlimited crystal orientation at the bottom of crucible to form a layer of seed crystals;

(122) Seed crystals herein were pieces of single crystals produced in the manufacture of semiconductor. Seed crystals were single crystals in a form of chunk. The maximum side-length was 40 mm, dislocation density was less than or equal to 10.sup.3 (1/cm.sup.2), thickness of the layer of seed crystals was 40 mm.

(123) (2) providing molten silicon above the layer of seed crystals, controlling the temperature at the bottom of the crucible below melting point of the seed crystals, making the layer of seed crystals not completely melted;

(124) The step of providing molten silicon above the layer of seed crystals was: heating solid silicon in another crucible to prepare molten silicon, followed by pouring the molten silicon into the crucible with a layer of seed crystals. At that moment, the molten silicon was provided on the surface of the layer of seed crystals. Temperature at the bottom of the crucible was 1413 C. Percentage of unmelted seed crystals of initial seed crystals in step (1) was 5%.

(125) (3) controlling the temperature inside the crucible, the temperature raising along the direction perpendicular to the bottom of the crucible to form temperature gradient, making the molten silicon growing above the seed crystals, the molten silicon inheriting the structure of the seed crystals, then obtaining polycrystalline silicon ingot.

(126) Dislocation density of the polycrystalline silicon ingot prepared according to this embodiment was in a range of 5.010.sup.3-5.610.sup.3 (1/cm.sup.2), minority carrier lifetime was 12 microseconds (ms).

(127) Polycrystalline silicon wafer prepared by using the polycrystalline silicon ingot of this embodiment was suitable for manufacturing solar cell. Conversion efficiency of the obtained solar cell was 17.4%.

EXAMPLE ILLUSTRATING THE EFFECTS

(128) In order to support benefits of the present invention, comparative experiment data are provided below.

(129) Comparative experiment 1: A complete single crystal rob was provided. After removing portions at the top or the end or the edge, it was sectioned into seed crystal cubes having a size of 156 mm156 mm. The monocrystalline cubes were laid at the bottom of crucible regularly, until the bottom of crucible was completely covered, followed by laying silicon onto seed crystals. Melting at high temperature and controlling seed crystals at the bottom not completely melted.

(130) Controlling temperature gradient and cooling the bottom first. Molten silicon liquid grows crystals on the surface of seed crystals, and quasi-monocrystalline silicon ingot having a monocrystalline structure was obtained.

(131) Comparative experiment 2: Growth of an ordinary polycrystalline silicon ingot comprising: feeding silicon into crucible, melting silicon by heating the crucible to control the thermal field in the crucible, so as to make molten silicon grows at the bottom of crucible and obtain polycrystalline silicon ingot.

(132) Comparison of Example 9, Example 10, comparative experiment 1 and comparative experiment 2 are shown below:

(133) TABLE-US-00001 TABLE 1 Comparison of Example 9, Example 10, comparative experiment 1 and comparative experiment 2 Comparative Comparative Example 9 Example 10 experiment 1 experiment 2 Characteristic In a form of Fragment from the Large area No of seed fragment edge of single crystals crystals Source Waste material Crushed fragment Complete single No of seed produced during from the edge of crystal rob obtained crystals the manufacture single crystals by sectioning after of semiconductor removing portions at the top and the end and the edge Price No cost in 2 RMB/kg High, 400-800 No non-silicon (non-silicon RMB/kg material material) (non-silicon material) Characteristic Multycrystals of Multycrystals of Quasi-single Ordinary of product high efficiency high efficiency crystals multycrystals dislocation dislocation dislocation dislocation density lower density lower density lower density lower than 10.sup.5 1/cm.sup.2, than 10.sup.5 1/cm.sup.2, than 10.sup.5 1/cm.sup.2, than 10.sup.5-10.sup.6 1/cm.sup.2, minority carrier minority carrier minority carrier minority carrier lifetime is lifetime is lifetime is lifetime is 15~25 ms 10~20 ms 15~25 ms 5~10 ms

(134) FIG. 10 is a map of minority carrier lifetime of the polycrystalline silicon ingot, according to Example 9. FIG. 11 is a map of minority carrier lifetime of the quasi-single crystal, according to comparative experiment 1. FIG. 12 is a map of minority carrier lifetime of the polycrystalline silicon ingot, according to comparative experiment 2. It can be seen from FIGS. 10-12 that, one embodiment of the present invention prepares polycrystalline silicon ingot of long minority carrier lifetime and few central area for minority carriers (area of high dislocation in a certain extent). Comparative experiment 1 prepares central area of quasi-single crystals exhibits a divergent pattern (indicating that dislocations are prone to expand). Comparative experiment 2 prepares polycrystalline silicon ingot of short minority carrier lifetime, large area for minority carrier having short lifetime in the center, and high dislocations.

(135) Above all, layer of seed crystals of the present invention is nucleating source of silicon material layer. The obtained polycrystalline silicon ingot having a dislocation density less than 10.sup.5 l/cm.sup.2, minority carrier lifetime is in a range of 10-25 ms. However, silicon ingot obtained by traditional method has a dislocation density in a range of 10.sup.5-10.sup.6 l/cm.sup.2, minority carrier lifetime is in a range of 5-10 ms. Thus the polycrystalline silicon wafer prepared by using polycrystalline silicon ingot is suitable for manufacturing solar cell. The prepared solar cell has a conversion efficiency in a range of 17.1%17.8%, whereas solar cell prepared by using ordinary polycrystalline silicon wafer has a conversion efficiency in a range of 16.516.9%. Efficiency of quasi-single crystals is in a range of 17.2%-18.5%.

(136) While the present invention has been described with reference to particular embodiments, it will be understood that the embodiments are illustrative and that the invention scope is not so limited. Alternative embodiments of the present invention will become apparent to those having ordinary skill in the art to which the present invention pertains. Such alternate embodiments are considered to be encompassed within the spirit and scope of the present invention. Accordingly, the scope of the present invention is described by the appended claims and is supported by the foregoing description.