FUSED QUARTZ CRUCIBLE FOR PRODUCING SILICON CRYSTALS, AND METHOD FOR PRODUCING A FUSED QUARTZ CRUCIBLE

Abstract

A fused quartz crucible for pulling a single crystal of silicon by the Czochralski technique, has an inner side with an inner layer of fused quartz that forms a surface, the inner layer being provided with a crystallization promoter which on heating of the fused quartz crucible during use, in crystal pulling, causes crystallization of fused quartz to form b-cristobalite, wherein the concentration C of synthetically obtained SiO.sub.2 at a distance d from the surface is greater than the concentration of synthetically obtained SiO.sub.2 at a distance d2 from the surface, where d2 is greater than d. Multiple crystals can be grown while maintaining high crystal quality.

Claims

1.-15. (canceled)

16. A fused quartz crucible for pulling a single crystal of silicon according to the Czochralski technique, comprising: an inner side on which there is located an inner layer of fused quartz, forming a surface, the inner layer being provided with a crystallization promoter which on heating of the fused quartz crucible during a crystal pulling, brings about crystallization of fused quartz to form β-cristobalite, wherein the concentration C of synthetically obtained SiO.sub.2 at a distance d from the surface is greater than the concentration of synthetically obtained SiO.sub.2 at a distance d2 from the surface, where d2 is greater than d, and the concentration C of synthetically obtained SiO.sub.2 as a function of the distance d is subject to the following relationships:
C[%]<=100−(d[mm]−0.25)×30 and
C[%]>=100−(d[mm]+0.25)×80.

17. The fused quartz crucible of claim 16, wherein said crystallization promoter comprises barium or strontium.

18. The fused quartz crucible of claim 16, wherein the concentration C of synthetically obtained SiO.sub.2 is greater than 90% when the distance d to the surface is less than 0.4 mm.

19. The fused quartz crucible of claim 16, wherein the concentration C of synthetically obtained SiO.sub.2 as a function of the distance d is subject to the following relationships:
C[%]<=100−(d[mm]+0.1)×80, and
C[%]>=100−(d[mm]−0.05)×36.

20. The fused quartz crucible of claim 16, wherein the concentration C of synthetically obtained SiO.sub.2 as a function of the distance d is subject to the following relationships:
C[%]<=100−(d[mm]+0.1)×80, and
C[%]>=100−(d[mm]−0.05)×36.

21. The fused quartz crucible of claim 16, wherein the concentration of the crystal promoter is less than 1 ppba and greater than 0.05 ppba, based on silicon in the fused quartz crucible.

22. The fused quartz crucible of claim 16, wherein the crystal promoter comprises barium.

23. A method for producing a fused quartz crucible comprising a crystallization promotor of claim 16, comprising: producing a crucible base body which has an inner side and comprises naturally obtained SiO.sub.2, and coating the inner side with a layer comprising synthetically obtained SiO.sub.2, the concentration C of the synthetically obtained SiO.sub.2 increasing with increasing layer thickness, wherein the material for the coating is mixed continuously in a mixing vessel in order to prevent separation, with fractions of synthetically obtained and naturally obtained SiO.sub.2 in the mixing vessel being altered over time and at the same time withdrawing material from the mixing vessel for the coating.

24. The method of claim 23, wherein the crystallization promoter is added during the production of the crucible base body.

25. The method of claim 23, wherein during said coating of the inner side, a crystallization promoter is added.

26. The method of claim 23, wherein subsequent to the coating with the layer comprising synthetically obtained SiO.sub.2, the crucible is filled with polysilicon and is heated to above 1400° C. in order to melt the polysilicon.

27. The method of claim 24, wherein the polysilicon is additionally admixed with a crystallization promoter having a concentration greater than 0.5 ppba and less than 10 ppba, based on the polysilicon.

28. The method of claim 23, wherein the crystallization promoter comprises barium.

29. A method for producing semiconductor wafers, characterized in that an ingot is pulled in a crystal pulling unit using a fused quartz crucible of claim 16, the ingot is cut into wafers by means of a wire saw, the wafers are polished, optionally subjected to epitaxy.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0015] FIG. 1 shows a minimum and maximum concentration C, in accordance with the invention, of the synthetically obtained SiO.sub.2, as a function of the distance d from the internal surface of the quartz crucible.

[0016] FIGS. 2, 3, and 4 illustrate results of measurements obtained when pulling a number of crystals (abscissa) from a crucible

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0017] FIG. 1 shows a minimum and maximum concentration C, in accordance with the invention, of the synthetically obtained SiO.sub.2, as a function of the distance d from the internal surface of the quartz crucible. The preferred concentration profile is located between curve 1 and curve 2, and the particularly preferred concentration profile is located between curve 3 and curve 4.

[0018] An empirical imaging protocol for the respective limits was developed from experimental data.

[0019] Curve 1, accordingly, may be mathematically described with the imaging protocol C [%]<=100−(d [mm]−0.25)×30, and curve 2 with the imaging protocol C [%]>=100−(d [mm]+0.25)×80.

[0020] The inventors have recognized that even greater effect can be found in the region between curve 3 and curve 4. These curves 3 and 4 can be well described using the respective mathematical protocols C [%]>=100−(d [mm]−0.05)×36 and C [%]<=100−(d [mm]+0.1)×80.

[0021] The graphs in FIGS. 2, 3 and 4 illustrate results of measurements obtained when pulling a number of crystals (abscissa) from a crucible.

[0022] The ordinates designated “SPV” convey the characteristic mean free path length of the minority charge carriers (SPV) of the respective crystal (abscissa) in relative units based on the maximum value.

[0023] The ordinates designated “L” convey the length of the dislocation-free portion of the respective crystal (abscissa).

[0024] Crystals for which data is shown in FIGS. 2a and 2b were pulled using a crucible which—as described in the prior art—was produced from naturally obtained SiO.sub.2, and whose inside was coated with a barium-containing component.

[0025] While it is found that the length of the dislocation-free portion of the crystals remains high, there is nevertheless a considerable drop apparent in the mean free path length. The mean free path length, then, drops on average to 70% of the initial value. There is therefore no assurance that crystals of uniform quality can be produced with this crucible.

[0026] Crystals for which data is shown in FIGS. 3a and 3b were pulled using a crucible which—as described in the prior art—was produced from synthetically obtained SiO.sub.2, and whose inside was coated with a barium-containing component.

[0027] The normalized values (FIG. 3a) for the free path length show a significantly increased scatter. Even the first crystal from the crucible used shows a mean free path length which is smaller by an average of 10%. Crystals of this quality are inadequate for the semiconductor industry. The length of the dislocation-free portion of the crystals as well (FIG. 3b) exhibits an unacceptable scatter and would result in economic damage for a corresponding crucible.

[0028] FIGS. 4a and 4b show the results for crystals pulled with a crucible produced in accordance with the invention.

[0029] It is clearly apparent that not only the mean free path length (FIG. 4a) but also the portion of the dislocation-free length of the crystals (FIG. 4b) exhibit no more than minimum (zero) scatter. Both in terms of quality and economics, the crucibles of the invention are optimal.

[0030] A plurality of crystals were pulled in each case from a crucible by means of the Czochralski pulling method and measurements were made both of the mean free path length of the minority charge carriers (SPV) and of the length of the undislocated crystal. The length of the undislocated portion of the crystal was placed in relation to the theoretically attainable overall length.

[0031] Similarly, the characteristic mean free path length of the minority charge carriers was placed in relation to the maximum mean free path length measured. This statistic is used below as a quality criterion for any impurities that might be present in the crystal that adversely affect the components subsequently fabricated on the silicon. It would also be possible theoretically to use other statistics for the quality of the crystals. Examples of such include a μPCD lifetime measurement or else a chemical analysis of the resulting silicon by ICP-MS. A number of suitable methods are available here to the skilled person.

[0032] The inventors have identified the above-described measurement techniques as being the most suitable and, in particular, readily accessible.

[0033] The inventors here have recognized that the use of crucibles manufactured according to the prior art is subject to distinct disadvantages when a crucible is used to pull a number of crystals in succession according to the Czochralski technique. Moreover, crystal pulling appeared to be more difficult the longer the pulling process lasted.

[0034] The results of the studies are conveyed in FIG. 2 and FIG. 3.

[0035] Crystals for which data is shown in FIGS. 2a and 2b were pulled using a crucible which—as described in the prior art—was produced from naturally obtained SiO.sub.2, and whose inside was coated with a barium-containing component.

[0036] While it is found that the length of the dislocation-free portion of the crystals remains high, there is nevertheless a considerable drop apparent in the mean free path length. The mean free path length, then, drops on average to 70% of the initial value. There is therefore no assurance that crystals of uniform quality can be produced with a crucible.

[0037] Crystals for which data is shown in FIGS. 3a and 3b were pulled using a crucible which—as described in the prior art—was produced from synthetically obtained SiO.sub.2, and whose inside was coated with a barium-containing component.

[0038] The normalized values (FIG. 3a) for the free path length show a significantly increased scatter. Even the first crystal from the crucible used shows a mean free path length which is smaller by an average of 10%. Crystals of this quality are inadequate for the semiconductor industry. The length of the dislocation-free portion of the crystals as well (FIG. 3b) exhibits an unacceptable scatter and would result in economic damage for a corresponding crucible.

[0039] The inventors have identified crucible material as being a cause of the measured deficiencies and have undertaken extensive trials to eliminate the deficiencies.

[0040] It is known from the literature that β-cristobalite has a higher melting temperature than quartz. It is also known that there are certain crystallization promoters which sometimes favor the generation of β-cristobalite.

[0041] Another piece of knowledge is that quartz crucibles made from synthetically obtained SiO.sub.2 differ in their properties from those quartz crucibles made from naturally obtained SiO.sub.2. The results of the experiments are shown for example in FIGS. 2 and 3.

[0042] Surprisingly, the inventors found that a fused quartz crucible having an inner side located on which there is an inner layer of fused quartz that forms a surface, the inner layer being provided with a crystallization promoter, exhibits positive properties in relation to the multiple pulling of crystals from a crucible, specifically when the concentration C of synthetically obtained SiO.sub.2 at one distance from the surface is greater than the concentration of synthetically obtained SiO.sub.2 at another distance from the surface.

[0043] Acting as crystallization promoters here with particular preference are the substances barium or strontium, with barium being especially preferred.

[0044] The inventors have recognized that it is preferential if the concentration C of synthetically obtained SiO.sub.2 is greater than 90% when the distance to the surface is less than 0.4 mm.

[0045] Further trials revealed, unexpectedly, that if the concentration of synthetically obtained SiO.sub.2 as a function of the distance d is subject to the following relationships:

C[%]<=100−(d[mm]−0.25)×30 and

C[%]>=100−(d[mm]+0.25)×80

[0046] there are advantages in relation both to the quality (SPV) and to the portion of dislocation-free length of the crystal. The range just described is depicted in FIG. 1, and relates to the shaded region between curve 1 and curve 2.

[0047] Results are depicted, for example, in FIGS. 4a and 4b.

[0048] The inventors were able to narrow down the region somewhat, through further experiments, and found that, when the concentration of synthetically obtained SiO.sub.2 as a function of the distance d is subject to the following relationships

C[%]<=100−(d[mm]+0.1)×80

and C[%]>=100−(d[mm]−0.05)×36,

[0049] there are further advantages in relation both to the quality (SPV) and to the portion of dislocation-free length of the crystal.

[0050] This region described is also illustrated in FIG. 1, and relates to the shaded region between curve 3 and curve 4.

[0051] With particular preference the concentration of the crystal promoter here is less than 1 ppba and greater than 0.05 ppba, based on silicon.

[0052] Preferred for producing the fused quartz crucibles of the invention, comprising a crystallization promoter, is a method which involves producing a crucible base body having an inner side and comprising naturally obtained SiO.sub.2, and coating the inner side with a layer comprising synthetically obtained SiO.sub.2, the concentration C of the synthetically obtained SiO.sub.2 increasing with increasing layer thickness.

[0053] It is particularly preferred here if the crystallization promoter is added during the actual production of the crucible base body.

[0054] For the method it is preferable if the material intended for the coating is mixed continuously in a mixing vessel in order to prevent separation. The proportions of synthetically obtained and naturally obtained SiO.sub.2 in the mixing vessel here are altered over time. At the same time, material for the coating is withdrawn from the mixing vessel. The fraction of the synthetically obtained material in the vessel is ideally increased over time.

[0055] It has proven to be particularly advantageous for a crystallization promoter to be added during the actual coating of the inner side.

[0056] It is particularly preferred if, subsequent to the coating, the crucible is filled with polysilicon and is heated to above 1400° C. in order to melt the polysilicon.

[0057] It is especially preferred for the polysilicon to be admixed additionally with a crystallization promoter, preferably comprising barium, with a concentration of greater than 0.5 ppba and less than 10 ppba, based on the polysilicon.