METHOD FOR PRODUCING SEMICONDUCTOR WAFERS FROM SILICON

Abstract

Silicon single crystals having an oxygen concentration of greater than 2×10.sup.17 at/cm.sup.3, a concentration of pinholes having a diameter of greater than 100 μm of less than 1.0×10.sup.−5 l/cm.sup.3, a carbon concentration of less than 5.5×10.sup.14 at/cm.sup.3, an iron concentration of less than 5.0×10.sup.9 at/cm.sup.3, a COP concentration of fewer than 1000 defects/cm.sup.3, a LPIT concentration of fewer than 1 defect/cm.sup.2 and a crystal diameter of greater than 200 mm, are produced by the Czochralski method employing a purge gas at specified pressures and flow rates.

Claims

1.-8. (canceled)

9. A method for producing silicon wafers, comprising: melting polysilicon in a crucible, pulling a single crystal in a Czochralski pulling system, dividing the single crystal into crystal pieces and cutting the crystal pieces into wafers, further comprising: purging the pulling system with a purge gas, wherein the following relationship applies to the flow rate f of the purge gas and the pressure p in the pulling system during the melting of the polysilicon:
flow rate f [l/h]>400×pressure p [mbar] wherein the pressure p in the pulling system is less than 7 mbar.

10. The method of claim 9, wherein the following relationship partially applies to the flow rate of the purge gas f and the pressure in the pulling system p during at least a portion of the melting of the polysilicon:
flow rate f [l/h]>720×pressure p [mbar].

11. The method of claim 9, wherein the crucible is set up with polysilicon having, on average, a mass-based specific surface area of less than 2 cm.sup.2/g.

12. The method of claim 9, wherein the polysilicon has a chlorine content of greater than 1 ppba.

13. A silicon single crystal having an oxygen concentration of greater than 2×10.sup.17 at/cm.sup.3, a concentration of pinholes having a diameter of greater than 100 μm of less than 1.0×10.sup.−5 l/cm.sup.3, a carbon concentration of less than 5.5×10.sup.14 at/cm.sup.3, an iron concentration of less than 5.0×10.sup.9 at/cm.sup.3, a COP concentration of fewer than 1000 defects/cm.sup.3, a concentration of agglomerates composed of interstitial silicon atoms of fewer than 1 defect/cm.sup.2 and a crystal diameter of greater than 200 mm.

14. The silicon single crystal of claim 13, wherein the carbon concentration is less than 4×10.sup.14 at/cm.sup.3.

15. The silicon single crystal of claim 13, wherein the iron concentration is less than 1.0×10.sup.9 at/cm.sup.3.

16. The silicon single crystal of claim 13, wherein the carbon concentration is less than 4×10.sup.14 at/cm.sup.3, and the iron concentration is less than 1.0×10.sup.9 at/cm.sup.3.

17. The single crystal of claim 13, wherein the concentration of pinholes having a diameter of greater than 50 μm is less than 1.0×10.sup.−5 l/cm.sup.3.

18. The single crystal of claim 16, wherein the concentration of pinholes having a diameter of greater than 50 μm is less than 1.0×10.sup.−5 l/cm.sup.3.

19. The single crystal of claim 13, wherein the crystal diameter is greater than 300 mm.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0025] FIG. 1 shows the relationship between the flow rate f [l/h] of the inert gas and the applied pressure p [mbar].

[0026] FIG. 2 shows a typical profile of the brightness, measured with a camera, during silicon heating in brightness values b over time in relative units in each case.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0027] The features specified in relation to the above-mentioned embodiments of the method according to the invention can be applied mutatis mutandis to the products according to the invention. Conversely, the features specified in relation to the above-mentioned embodiments of the products according to the invention can be applied mutatis mutandis to the method according to the invention. These and other features of the embodiments according to the invention are elucidated in the description of the figures and in the claims. The individual features can be realized either separately or in combination as embodiments of the invention. Furthermore, they can describe advantageous embodiments which are independently protectable. A person skilled in the art understands the unit (litres per hour) to mean standard litres per hour, i.e. the volume per hour that the gas would have at standard pressure.

[0028] As shown in FIG. 2, during heating of the silicon in the crucible, the brightness measured remains initially constant within the limit of error tolerance (201). With the onset of the solid-to-liquid phase transition, the brightness signal rises sharply (202).

[0029] Once the silicon has completely melted, the brightness measured is again constant (203), but at a higher level than at the start (201).

[0030] Polysilicon melting is to be understood to mean the process in which polysilicon is brought from room temperature in a solid state to a temperature greater than the melting temperature in a liquid state. The end of the melting process is defined as the time point of placing the seedling for crystal-pulling. Crystal-pulling starts afterwards.

[0031] Table 1 summarizes the measurement results concerning the concentrations of pinholes, carbon and iron in the pulled crystals, which were pulled both according to the prior art (Comparative Examples 1 and 2) and according to the invention (Examples 3, 4 and 5).

[0032] Rods were pulled according to the Czochralski method, having a nominal diameter of either 300 mm or 200 mm. This involved polycrystalline silicon being stacked into a quartz crucible known from the prior art and being provided for crystal-pulling.

[0033] Means for producing defect-free crystals were used for crystal-pulling. In principle, this can be achieved with a CUSP magnetic field, a horizontal magnetic field or with a travelling magnetic field. Furthermore, crystal rotation and crucible rotation are set appropriately for this purpose.

[0034] The results shown in Table 1 come from crystals which were pulled using a horizontal magnetic field. In addition, crystal rotation and crucible rotation were varied such that a different oxygen concentration was achieved in each case.

[0035] For what is further described, the type of magnetic field used is irrelevant; what is essential is that a centrally upwardly directed melt flow is achieved so that a defect-free crystal is pulled.

[0036] Each monocrystalline rod thus pulled was, in addition, divided into rod pieces using a band saw and cut into wafers in accordance with the prior art, and these were examined both for pinholes and defect properties and for impurities (carbon, iron).

[0037] Carbon concentration in silicon was measured with the aid of gas fusion analysis, which, for example, has been described in DE 1020 14217514 A1.

[0038] Iron concentration was measured with the aid of the ICPMS (Inductively Coupled Plasma Mass Spectrometry) method. It can also be measured using NAA (neutron activation analysis) with suitable calibration.

[0039] Example 1 in Table 1 shows the results achievable with conventional means known from the prior art. In this case, the concentration of pinholes was identified as excessively high.

[0040] With the aim of decreasing the concentration of pinholes in the monocrystalline rod, what was first attempted by the inventors was to reduce the pressure during polysilicon melting to the extent that—as described in JP-5009097 A2—the gases which possibly form cannot cause pinholes. In this connection, the inventors have discovered that this measure is only suitable to a limited extent for appropriately reducing the concentration. The results are summarized in Example 2 in Table 1.

[0041] It became apparent that the measure brings about a clearly additional increased contamination of the monocrystalline rods with carbon and iron (Table 1: Example 2).

[0042] The inventors have therefore discovered that additional measures should be carried out in order to solve these problems.

[0043] When setting up the crucible, care is taken that polysilicon having very low impurity levels is preferably used, as described in DE 10 2010 040 293 A1 for example.

[0044] Preferably, silicon having an average mass-based specific surface area of less than 2 cm.sup.2/g is used. Very particularly preferably, the crucible is set up with polysilicon having a mass-specific surface area of less than 1 cm.sup.2/g at a distance of less than 5 cm and greater than 2 cm from the crucible wall. The remainder of the crucible volume is set up with polysilicon having a mass-specific surface area of greater than 1 cm.sup.2/g and less than 5 cm.sup.2/g.

[0045] During polysilicon melting, a pressure in the crystal-pulling system of preferably not greater than 10 mbar is set. At the same time, the total flow rate f [l/h] of a purge gas through the pulling system is preferably set such that it is greater than the pressure p [mbar] multiplied by 160.

[0046] FIG. 1 shows the preferred area of pressure p and flow rate f in (102).

[0047] Preferably, the total flow rate f [l/h] of a purge gas through the pulling system is set such that it is greater than the pressure p [mbar] multiplied by 400, more preferably 720. At the same time, the pressure is preferably set not greater than 10 mbar.

[0048] FIG. 1 shows the preferred area of pressure p and flow rate f in (101).

[0049] In general, it is advantageous to keep the flow rate f as high as possible and, simultaneously, to keep the pressure as low as possible. The maximum flow rate at a given pressure is, then, only dependent on the pump output.

[0050] The purge gas used during melting comprises gases from the list of the gases argon, helium, nitrogen or combinations thereof. Preferably, argon having a degree of purity of greater than 99.99% by volume is used.

[0051] Example 3 in Table 1 shows the results of crystals that were achieved with above-described means according to the invention.

[0052] In a further embodiment, the pressure (and thus also the flow rate of the purge gas) was increased once the first polysilicon had become liquid. The pressure increase was, in this connection, 4 mbar, preferably 8 mbar and more preferably 12 mbar.

[0053] The melting process was, in this connection, observed using a camera which determines, by means of suitable digital image processing methods, the time point from which the first silicon has become liquid.

[0054] The inventors have discovered that the time point at which a significant increase in the brightness of the evaluated image data can be established can be correlated very well with the time point of the start of the solid-to-liquid phase transition.

[0055] FIG. 2 shows, for example, brightness as a function of time. It became apparent that the pressure should preferably be increased in the time point between the regions (201) and (202) in order to achieve a further positive effect with respect to the density of pinholes and the concentration of carbon and iron.

[0056] Example 4 in Table 1 shows the results of crystals that were achieved with above-described means according to the invention.

[0057] In an additional embodiment, polysilicon which had a chlorine content of 1 ppba was used for setup.

[0058] The inventors have discovered in this case that, surprisingly, the use of polysilicon having a chlorine content of greater than 1 pbba has further positive effects on iron contamination, even though a person skilled in the art would make the assumption that chlorine at high temperatures ought to release iron from the system and to contaminate the silicon.

[0059] Example 5 in Table 1 shows the results of crystals that were achieved with above-described means according to the invention.

[0060] The above description of exemplary embodiments is to be understood exemplarily. The disclosure made thereby firstly allows a person skilled in the art to understand the present invention and the associated advantages and secondly also encompasses alterations and modifications to the described structures and methods that are obvious in the understanding of a person skilled in the art. Therefore, all such alterations and modifications and also equivalents are intended to be covered by the scope of protection of the claims.

TABLE-US-00001 Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Comparative Inventive Inventive Inventive Pinholes 1 0.30 0.10 0.06 0.05 [10.sup.4/cm.sup.3] Carbon 6 143 5.2 5.1 3.4 [10.sup.14 at/cm.sup.3] Iron 7 10 4 3 1 [10.sup.9 at/cm.sup.3] COP Concentration <1000 <1000 <1000 <1000 <1000 [1/cm.sup.3] Lpit Concentration none none none none none [1/cm.sup.2] Oxygen 0, 5 2 2.1 5.8 4.5 [10.sup.17 at/cm.sup.3] Nominal Diameter 300 300 300 300 300 [mm]