CN102912424B - Method for improving uniformity of axial resistivity of czochralski silicon and obtained monocrystalline silicon - Google Patents
Method for improving uniformity of axial resistivity of czochralski silicon and obtained monocrystalline silicon Download PDFInfo
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- CN102912424B CN102912424B CN201210382987.9A CN201210382987A CN102912424B CN 102912424 B CN102912424 B CN 102912424B CN 201210382987 A CN201210382987 A CN 201210382987A CN 102912424 B CN102912424 B CN 102912424B
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Abstract
The invention discloses a method for improving the uniformity of axial resistivity of czochralski silicon. The method comprises the steps as follows: (1) melting a polycrystalline silicon raw material and a solid doping agent in an argon atmosphere to obtain stable molten silicon; (2) introducing seed crystals into the stable molten silicon, and conducting constant diameter growth on the crystals after necking and shouldering processes; and (3) during the constant diameter growth period, adding dopant gas with the conductive type opposite to that of the solid doping agent until the growth of the czochralski silicon is fulfilled. According to the method, the type and the usage amount of the dopant gas are convenient to control, various required impurity concentration distributions can be obtained, the utilization rate of the czochralski silicon is increased, and the uniformity of the resistivity of the czochralski silicon is remarkably improved.
Description
Technical field
The present invention relates to field of semiconductor materials, the silicon single crystal being specifically related to a kind of method by the axial resistivity evenness of gas phase doping method raising pulling of silicon single crystal and obtaining.
Background technology
In a foreseeable future, photovoltaic generation is most important renewable energy technologies.According to EPIA (EPIA) prediction, the year two thousand thirty, photovoltaic generation was by the electricity needs of nearly for the satisfied whole world 10%.
Current solar cell mainly manufactures based on the single crystal silicon material of boron-doping, but this battery is because simultaneously containing boron and oxygen in silicon single crystal, in use can form boron oxygen complex body, cause the photoelectric transformation efficiency of solar cell to decline more than 10%, the performance of solar cell significantly reduces.For solving this problem, researchist has invented the single crystal silicon solar cell mixing gallium.
Although the single crystal silicon solar cell mixing gallium is unglazed relaxation phenomenon, but there is very large defect in it, due to the segregation coefficient of gallium in silicon extremely low (about 0.008), which results in and mix in gallium pulling of silicon single crystal process of growth, axial resisitivity is very large, in pulling of silicon single crystal, the resistivity of the silicon single crystal of last growth does not reach requirement, makes the practical efficiency mixing gallium pulling of silicon single crystal only have about 80%.
In addition, the resistivity distribution of mixing gallium pulling of silicon single crystal is wider, causes the efficiency distribution of solar cell also wide, has had a strong impact on the consistence of solar module power stage.
It is with high costs that these defects cause mixing gallium solar cell, meets difficulty in industry member large-scale application.Up to the present, not yet announce both at home and abroad a kind of effective means can obtain axial uniform resistivity distribution mix gallium pulling of silicon single crystal.
The advantages such as at microelectronic, reblended antimony pulling of silicon single crystal is also a kind of important materials, and the n/n+ epitaxial wafer be made up of it has that zone of transition is narrow, knot gradient is steep, the spread coefficient of antimony is little under high temperature, making to mix antimony single crystal silicon becomes a kind of important substrate.
But similar with gallium doped monocrystaline silicon, antimony equilibrium segregation coefficient in silicon also very little (about 0.023), causes the axial resistivity evenness mixing antimony pulling of silicon single crystal very poor equally.
Summary of the invention
The invention provides a kind of method improving the axial resistivity evenness of pulling of silicon single crystal, by the method for gas phase doping, substantially increase the homogeneity of the axial resistivity of pulling of silicon single crystal, simple and practical, there is good prospects for commercial application.
Improve a method for the axial resistivity evenness of pulling of silicon single crystal, comprise the steps:
(1) by polycrystalline silicon raw material and solid dopants melting under an argon atmosphere, stable molten silicon is obtained;
(2) in stable molten silicon, introduce seed crystal, crystal growth, through necking down, shouldering process, enters the isodiametric growth stage;
(3) in the isodiametric growth stage, the impurity gas contrary with described solid dopants conduction type is passed into, until pulling of crystals silicon growth completes.
In the normal isodiametric growth process of czochralski silicon monocrystal, pass into impurity gas continuous uniform and realize gas phase doping, following equation is obeyed in the distribution of gaseous impurities in silicon single-crystal that impurity gas is introduced:
Wherein,
C
sfor the doping content of the impurity in silicon single-crystal;
A is the doping speed of impurity gas;
V is the growth velocity of pulling of silicon single crystal;
K is the segregation coefficient of the impurity that impurity gas is introduced;
G is solid fraction.
If there is p-type impurity and N-shaped impurity when mixing altogether, in silicon crystal, following equation (mixing altogether for the phosphorus of the gallium of p-type and N-shaped) is obeyed in the distribution of current carrier:
Wherein,
P is the concentration of current carrier in silicon crystal;
C
0for the initial melt concentration of gallium;
K
1for the segregation coefficient of gallium;
G is solid fraction;
A is the doping speed (impurity level introduced in the unit time, the flow control by impurity gas) of impurity gas;
V is the growth velocity of pulling of silicon single crystal;
K
2for the segregation coefficient of phosphorus;
represent the impurity concentration that solid dopants is introduced;
represent the impurity concentration that impurity gas is introduced.
By regulating concentration and the flow of impurity gas, best gas phase doping amount can be obtained, making the axial resistivity of czochralski silicon monocrystal keep being uniformly distributed.
Wherein best gas doping amount is:
Wherein,
C
0for the initial melt concentration of solid dopants;
K
1for the segregation coefficient of solid dopants;
A is the doping speed of impurity gas;
V is the growth velocity of pulling of silicon single crystal;
K
2for the segregation coefficient of impurity in impurity gas.
According to this formula, in the compensated crystal of gallium and phosphorus, the suitable doping of phosphine is 0.0268C
0(C
0initial melt concentration for gallium), no more than 0.0326C
0, more than 0.0404C
0there will be small part transoid; For antimony and boron compensation crystal, the suitable doping of borine is 0.0463C
0(C
0initial melt concentration for antimony), no more than 0.0569C
0, more than 0.0775C
0there will be small part transoid.In fact optimal gas doping can change in next scope on Appropriate.
In czochralski silicon monocrystal manufacturing processed, polycrystalline silicon raw material is placed in quartz crucible, the solid phase dopants of respective amount is dropped into according to target resistivity, after pulling of crystals silicon growth completes, the resistivity of its crystal head (position of crystal grow first) and afterbody (position of crystal growth ending) can be variant, causes axial resistivity distribution uneven.
In order to improve the axial resistivity of czochralski silicon monocrystal; in the czochralski silicon monocrystal isodiametric growth stage; continue to pass into the impurity gas contrary with solid dopants conduction type evenly; after isodiametric growth terminates; stop passing into impurity gas; continue to carry out finishing up under the protection of argon gas and the process such as cooling, complete the process of growth of whole silicon crystal.The doping of described impurity gas is 0.001 ~ 0.1 times of the initial melt concentration of solid dopants.Concrete value calculates according to formula (3).
As preferably, when described solid dopants is gallium, described impurity gas is phosphine, and the doping of phosphine is 0.025 ~ 0.03 times of the initial melt concentration of gallium.
The czochralski silicon monocrystal utilization ratio produced is close to 100% (removing crystal head and afterbody), and comparing does not have 80% czochralski silicon monocrystal utilization ratio of impurity gas to have to significantly improve, and the resistivity in more than 90% region controls within the scope of 0.5 ~ 3 Ω .cm.
As preferably, when described solid dopants is antimony, described impurity gas is diborane, and the doping of diborane is 0.045 ~ 0.055 times of the initial melt concentration of antimony.
The axial change in resistance in czochralski silicon monocrystal more than 80% region produced controls in the scope of 25%.
As preferably, in the impurity gas in described step (3), be mixed with rare gas element.
Rare gas element is used for dopingtank gas, should select the gas not affecting crystal growth, such as, be used as the argon gas of crystal growth shielding gas under normal circumstances, or the nitrogen of stable in properties.
Directly the impurity gas mixed can be passed into crystal growth indoor, as shown in Figure 1, also can by arranging noble gas source 2 and impurity gas source of the gas 4 respectively, by regulating the under meter 5 of rare gas element gas meter 1, dopant gas flow meter 3 and mixed gas, after obtaining determining the mixed gas of ratio, by purity quartz glass pipe for high road 7, pass in crystal growing chamber 6.
As preferably, in described impurity gas, the percent by volume of rare gas element is 1 ~ 99.9%.In impurity gas, the volume percent of rare gas element does not strictly limit, and rare gas element dilutes impurity gas, avoids impurity gas excessive concentration, because of the excessive transoid caused of local impurity gas concentration in the czochralski silicon monocrystal that may cause.
As preferably, the flow that described impurity gas passes into growth room is 1 ~ 1000sccm (mark condition milliliter per minute).
The flow of impurity gas is according to the kind of solid dopants in the kind of impurity gas, concentration and crystal, concentration and determining, need to ensure that the speed of mixing of impurity gas and the speed of growth of crystal adapt, the impurity gas making conduction type contrary compensates solid phase dopants, obtains the czochralski silicon monocrystal of axial uniform resistivity.
The axial resistivity in more than 90% region of the gallium phosphorus compensation pulling of silicon single crystal of the solar cell utilizing the method for the axial resistivity evenness of raising pulling of silicon single crystal of the present invention to prepare is 0.5 ~ 3 Ω cm, and the axial change in resistance in more than 80% region of the reblended antimony boron compensation pulling of silicon single crystal of microelectronics is less than 25%.
Pulling of silicon single crystal manufacture method provided by the invention, has the following advantages:
(1) kind of impurity gas and consumption is convenient controls, can obtain various required impurities concentration distribution;
(2) improve the utilization ratio of czochralski silicon monocrystal;
(3) resistivity evenness of crystal is significantly improved.
Accompanying drawing explanation
Fig. 1 implements the device schematic diagram that the inventive method manufactures czochralski silicon monocrystal;
Fig. 2 is the czochralski silicon monocrystal resistivity distribution figure that embodiment 1 prepares;
Fig. 3 is the czochralski silicon monocrystal resistivity distribution figure that embodiment 2 prepares.
Embodiment
Embodiment 1
In quartz crucible, add the high-purity polycrystalline silicon raw material of 60kg, mix simultaneously 2.982g high purity gallium (controlling head target resistivity is 1.8 ohm. centimetre).
Under argon shield, heat to more than 1420 DEG C gradually and high purity polycrystalline silicon is melted completely.Conveniently crystal growth parameters seeding, shouldering, enters the isodiametric growth stage, and control pulling rate 1.2mm/min, crystal diameter is 150mm.
Control furnace pressure 20Torr, argon flow amount is 70slpm (standard liters per minute).
The parameter of setting impurity gas:
1) adopt the phosphine of argon-dilution as impurity gas, the volume ratio 1: 1000 of phosphine and argon gas;
2) suppose doping efficiency 100% (impurity of impurity gas introducing can all enter in czochralski silicon monocrystal), setting doping airshed is 21.14sccm.
Isodiametric growth terminates rear closedown impurity gas, normally finishes up, cooling.
Complete the czochralski silicon monocrystal different sites sampling of growth, use the distribution of four point probe resistivity meter test resistance rate, result as shown in Figure 2.
If controlled at 0.5 ~ 3 ohm according to solar cell silicon chip resistivity. centimetre requirement, the silicon single-crystal utilization ratio of only mixing gallium is 75%; But for gallium and phosphor codoping silicon single crystal (namely passing into the silicon single crystal of impurity gas), its utilization ratio can be increased to 93%, after this meaning removes head and afterbody, the silicon single crystal of gallium phosphor codoping can all be utilized.Meanwhile, only its resistivity distribution of gallium-mixing silicon monocrystal is very uneven.And for the silicon single-crystal of gallium and phosphor codoping, its most of resistivity is very even, only decline to some extent in afterbody small part resistivity, and these silicon chips obtained can both prepare high-level efficiency, the solar cell of unglazed decay.
Embodiment 2
In quartz crucible, add the high-purity polycrystalline silicon raw material of 60kg, mix simultaneously 416.64g high purity antimony (controlling head target resistivity is 0.016 ohm. centimetre).
Under argon shield, heat to more than 1420 DEG C gradually and polysilicon is melted completely.Conveniently crystal growth parameters seeding, shouldering, enters the isodiametric growth stage, and control pulling rate 0.8mm/min, crystal diameter is 150mm.
Control furnace pressure 20Torr, argon flow amount is 70slpm.
The parameter of setting impurity gas:
1) diborane of argon-dilution is adopted, the volume ratio 1: 100 of diborane and argon gas;
2) suppose doping efficiency 100%, setting doping airshed is 97.58sccm.
After isodiametric growth terminates, close impurity gas, normally finish up, cooling.
Complete the silicon single crystal different sites sampling of growth, use the distribution of four point probe resistivity meter test resistance rate, result as shown in Figure 3.
If floated to change in resistance according to microelectronics manufacturer 25% requirement, for the silicon single crystal only mixing antimony, utilization ratio is only about 40%, and for the silicon single crystal (namely having passed into the silicon single crystal of impurity gas) that antimony boron is mixed altogether, utilization ratio can reach about 80%, increases nearly 1 times, improves the utilization ratio of silicon single crystal significantly, and significantly improve resistivity evenness, have the quality control utilizing unicircuit.
Claims (6)
1. improve a method for the axial resistivity evenness of pulling of silicon single crystal, comprise polycrystalline silicon raw material and solid dopants melting under an argon atmosphere, obtain stable molten silicon; In stable molten silicon, introduce seed crystal, crystal growth, through necking down, shouldering process, enters the isodiametric growth stage; It is characterized in that, in the isodiametric growth stage, pass into the impurity gas contrary with described solid dopants conduction type, until pulling of crystals silicon growth completes; The doping of described impurity gas is 0.001 ~ 0.1 times of the initial melt concentration of solid dopants.
2. the method improving the axial resistivity evenness of pulling of silicon single crystal as claimed in claim 1, it is characterized in that, when described solid dopants is gallium, described impurity gas is phosphine, and the doping of phosphine is 0.025 ~ 0.03 times of the initial melt concentration of gallium.
3. the method improving the axial resistivity evenness of pulling of silicon single crystal as claimed in claim 1, it is characterized in that, when described solid dopants is antimony, described impurity gas is diborane, and the doping of diborane is 0.045 ~ 0.055 times of the initial melt concentration of antimony.
4. the method for the axial resistivity evenness of the raising pulling of silicon single crystal as described in as arbitrary in claims 1 to 3, is characterized in that, be mixed with rare gas element in described impurity gas.
5. the method improving the axial resistivity evenness of pulling of silicon single crystal as claimed in claim 4, it is characterized in that, in described impurity gas, the percent by volume of rare gas element is 1 ~ 99.9%.
6. the method improving the axial resistivity evenness of pulling of silicon single crystal as claimed in claim 5, it is characterized in that, the flow that described impurity gas passes into growth room is 1 ~ 1000sccm.
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| CN101654804A (en) * | 2009-09-24 | 2010-02-24 | 浙江大学 | Method for controlling specific resistance of gallium-doped Czochralski silicon in crystal growth process |
| CN102534752A (en) * | 2012-03-08 | 2012-07-04 | 天津市环欧半导体材料技术有限公司 | Czochralski zone melting gas doping method for preparing zone-melted silicon single crystal |
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