DEVICE AND METHOD OF MANUFACTURING AIII-BV-CRYSTALS AND SUBSTRATE WAFERS MANUFACTURED THEREOF FREE OF RESIDUAL STRESS AND DISLOCATIONS
20220106702 · 2022-04-07
Inventors
- Stefan Eichler (Dresden, DE)
- Michael ROSCH (Freiberg, DE)
- Dmitry SUPTEL (Dresden, DE)
- Ulrich KRETZER (Chemnitz, DE)
- Berndt Weinert (Freiberg, DE)
Cpc classification
C30B11/002
CHEMISTRY; METALLURGY
C30B29/40
CHEMISTRY; METALLURGY
International classification
C30B11/00
CHEMISTRY; METALLURGY
C30B29/40
CHEMISTRY; METALLURGY
Abstract
A device (1′, 1″, 1′″) for manufacturing III-V-crystals and wafers (14) manufactured therefrom, which are free of residual stress and dislocations, from melt (16) of a raw material optionally supplemented by lattice hardening dopants comprises a crucible (2′, 2″, 2′″) for receiving the melt (16) having a first section (4′, 4″) including a first cross-sectional area and a second section (6′) for receiving a seed crystal (12) and having a second cross-sectional area, wherein the second cross-sectional area is smaller than the first cross-sectional area and the first and second sections are connected with each other directly or via third section (8, 8′) which tapers from the first section towards the second section, in order to allow a crystallization starting from the seed crystal (12) within the directed temperature field (T) into the solidifying melt. The first section (4′, 4″) of the crucible (2′, 2″, 2′″) has a central axis (M), and the second section (6′) is arranged being offset (v) with regard to the central axis (M) of the first section (4′, 4″).
Claims
1. A device for manufacturing a crystal from a melt of a raw material, comprising: a crucible for receiving the melt having a first section including a first cross-sectional area and having a second section for receiving a seed crystal and including a second cross-sectional area, wherein the second cross-sectional area is smaller than the first cross-sectional area and the first and the second section of connected with each other directly or via a third section which tapers from the first to the second section, in order to allow a crystallization starting from the seed crystal within a directed temperature field into the solidifying melt, wherein the first section of the crucible has a central axis, and the second section is arranged to be laterally offset from the central axis of the first section.
2. The device according to claim 1, wherein the second section includes a longitudinal axis, which, when it is extended into a region of the first section, extends in a distance of 15 mm or less from an inner wall of the crucible within the first section.
3. The device according to claim 2, wherein the second section is at least partially formed in cylindrical shape and has an inner diameter of 15 mm or less.
4. The device according to claim 1, wherein the first section is at least partially formed in cylindrical shape.
5-6. (canceled)
7. The device according to claim 1, wherein the second section has a length along a direction of the central axis, wherein the length amounts to between 40 mm and 120 mm.
8. The device according to claim 1, further comprising a heating device which includes one or more heating elements, the heating device configured to generate the directed temperature field having a temperature gradient, wherein the crucible is arranged in the temperature field.
9. The device according to claim 1, wherein the crucible is formed from boron nitride (BN) or pyrolytically deposited boron nitride (pBN), which is suitable to receive a melt formed from gallium arsenide (GaAs) or indium phosphide (InP).
10. The device according to claim 1, wherein in addition to the crucible, further identical crucibles are provided being arranged symmetrically and in parallel and at the same height, and wherein the one direction, in which the second section is offset from the central axis, is oriented towards the symmetry axis of the arrangement of crucibles.
11-19. (canceled)
20. An AIII-BV-single-crystal or wafer obtained by separation therefrom, comprising an average density of dislocations in the lattice of the crystal determined as an average edge pit density (EPD.sub.av) within the cross-sectional area of the single-crystal perpendicular to its central axis (M) in amount of 10 cm.sup.−2 or less.
21. The AIII-BV-single-crystal or wafer obtained by separation therefrom according to claim 20, wherein boron, silicon, zinc, sulphur, or indium, are incorporated in the lattice of the single-crystal alone or in combination.
22. The AIII-BV-single-crystal or wafer obtained by separation therefrom according to claim 20, comprising a distribution of the residual stress at maximum of +/−30 kPa or less on a cross-sectional area of the single-crystal or of the wafer, obtained by a spatially resolved measurement according to the SIRD method.
23. The AIII-BV-single-crystal or wafer obtained by separation therefrom according to claim 20, wherein within a cross-sectional area of the single-crystal or of the wafer, a fraction of measurement fields sized as 0.25 mm.sup.2 within the measurement grid, all measurement fields completely covering the cross-sectional area, the fraction of measurement fields being completely free of dislocations, amounts to 99% of total area of the cross-sectional area, or more.
24. An AIII-BV-single-crystal or wafer obtained by separation therefrom, comprising a distribution of the residual stress at maximum of +/−30 kPa or less, preferably of +/−25 kPa or less, on a cross-sectional area of the single-crystal (14) or of the wafer, obtained by a spatially resolved measurement according to the SIRD method.
25. The AIII-BV-single-crystal or wafer obtained by separation therefrom according to claim 24, wherein the lateral resolution of the spatially resolved measurement amounts to 100 μm.
26. The AIII-BV-single-crystal or wafer obtained by separation therefrom according to claim 24, wherein the diameter of the single-crystal or of the wafer amounts to 150 mm or more.
27. An AIII-BV-single-crystal or wafer obtained by separation therefrom comprising an average density of dislocations in the lattice of the crystal determined as an average edge pit density (EPD.sub.av) within the cross-sectional area of the single-crystal (14) perpendicular to its central axis (M) in amount of 1000 cm.sup.−2 or less, wherein a charge carrier concentration including lattice hardening dopants, in particular boron, silicon, zinc, sulphur, indium, each alone or in combination, amounts to 7×10.sup.16 Atoms/cm.sup.3 or less, preferably 1×10.sup.16 atoms/cm.sup.3 or less.
28. (canceled)
29. The AIII-BV-single-crystal according to claim 20, wherein the single crystal comprises Gallium arsenide (GaAs) or Indium phosphide (InP).
30. The AIII-BV-single-crystal according to claim 24, wherein the single crystal comprises Gallium arsenide (GaAs) or Indium phosphide (InP).
31. The AIII-BV-single-crystal according to claim 27, wherein the single crystal comprises Gallium arsenide (GaAs) or Indium phosphide (InP).
Description
BRIEF DESCRIPTION OF THE DRAWINGS
[0040] Further features, advantages, and purposive embodiments will be described in more detail below by virtue of a description of non-limiting embodiments pertaining to preferred embodiments taken in conjunction with drawings. Therein:
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DETAILED DESCRIPTION OF THE INVENTION
[0055] A first embodiment of a device for manufacturing single-crystal from a raw melt pursuant to the present invention is depicted in
[0056] The crucible 2 is formed from boron nitride or pyrolytically deposited boron nitride (pBN) and comprises a first cylindrically shaped section 4, which receives the raw melt 16—herein composed of gallium arsenide GaAs—and a second section 6 formed as a seed channel and the third section 8 which forms the transition between the first 4 and the second section 6 and connects these sections. In a region of its second section, the crucible 2 has an inner diameter of at least 152 mm, which is composed of a nominal diameter d of 150 mm that is to be minutely yielded or achieved for the finished single-crystal and of an oversize of up to 2 mm that is conventionally added in the growth process, and which accounts for a grinding step that is subsequently applied to an outer cylinder shell portion of the single-crystal to be manufactured (and that is sacrificed during that step). This grinding step serves for providing a positional accurate, high quality cylinder surface of the crystal required for subsequent alignment steps with regard to the subsequently separated wafer.
[0057] In this specific embodiment the seed channel, or the second section 6 respectively, is also shaped cylindrically and has a diameter of for example 10 mm and a length k′ of 100 mm. Seed channels according to the invention may also require spatial shapes different from cylindrical and the invention is not limited to the specific shape. The seed channel may also be of a cuboid shape, or may have a polygonal or oval shape in cross-section, etc.
[0058] A seed crystal 12 (herein formed from GaAs) is received in the second section 6 having a length of 20 mm and a diameter of slightly less than 10 mm (e.g., 8 or 9 mm) in order to ensure that the distance from the crucible wall is present within the seed channel. The gap in the seed channel maybe filled with liquid boron oxide (B.sub.2O.sub.3) such that the melt and crystal is floating in the liquid during crystallization. Due to the considerable difference between the length of the seed crystal 12 and the length k′ of the seed channel, the seed crystal 12 is arranged deeply at the bottom in the second section 6. The top face or seed face of the seed crystal is thus distant from the upper end of the second section 6, or the seed channel respectively, by 80 mm. A ratio of the length to the inner diameter of the free space portion not occupied by the seed crystal thus amounts to 8:1.
[0059] In the state shown in
[0060] In the corresponding method (VGF) an amount of silicon is for example added to the melt before or after heating the same (or to its compact or granular precursor). Above the raw melt 16 and between the crystal and the crucible wall there is a layer 18 of liquid (molten) diboron trioxide (B.sub.2O.sub.3) because of its lower density, that serves to protect the GaAs melt below as described above. By means of the heating device, a directed temperature field T is generated (the arrow in
[0061] Due to the large ratio between the free length open to crystallization and the inner diameter in the narrow seed channel, the central dislocations 101 as shown in
[0062] After the dislocations 101 have vanished in the cross-sectional areas of the single-crystal still within the second section 6 (seed channel) of the crucible 2, a single crystal 14 is grown upon further propagation of the crystallization front which is substantially free of dislocations considering an exclusion of the edge areas (80 cm.sup.2). A listing of relevant parameters of several samples shown in table 1. Therein sample 1a is a GaAs single-crystal manufactured using a crucible with conventional seed channel, sample 1a serving as a comparative example, while samples 2-5 are manufactured according to the method of the invention in a crucible as shown in
TABLE-US-00001 TABLE 1 Sample 1a (comparative example) Sample 2 Sample 3 Sample 4 Sample 5 EPD.sub.av 235 cm.sup.−2 12 cm.sup.−2 4 cm.sup.−2 0 cm.sup.−2 2 cm.sup.−2 EPC.sub.total 18.000 960 320 0 640
[0063] A second embodiment of a device 1′ according to the invention is shown in
[0064] The crucible 2′ of the second embodiment includes, similar to the first embodiment, a first section 4′ for receiving raw melt 16, a second section 6′ serving as a seed channel, and a third section 8′ serving as the transition region between the seed channel and the first section 4′. The second section 6′ has a diameter of 10 mm like in the first embodiment, its length k amounts, however, like in conventional crystal growth devices to 30 mm, for example, such that the seed face of the seed crystal 12 inserted into the seed channel and having a length of 20 mm has a distance from an upper end of the seed channel 12 of only 10 mm. Without general limitation the seed channel in this embodiment is also formed being cylindrical as a mere example. The third section is not provided with rotational symmetry any more in view of the offset v of the second section 6′ with regard to the first section 4′, and rather tapers laterally outwards in an asymmetrical manner when viewed from the cylindrical first section 4′ having the larger inner diameter towards the second section 6′ having the smaller diameter.
[0065] Instead, the second section 6′ is arranged laterally offset with regard to the central axis M of the first section. In other words, a central axis M′ of the second section is parallel to the central axis M of the first section 4′ based on a mutual offset v between both. In this embodiment, the offset v has a sufficient dimension, such that the central axis M′ of the second section 6′, or of the sea channel, respectively, extends through an edge exclusion area of cross-sectional areas of the first section 4′, when such central axis M′ is extended into the first section 4′.
[0066] In the second embodiment the first section has an inner diameter d′″ of 172 mm. However, the nominal diameter d of the single-crystal 14 to be manufactured also in the present embodiment amounts to only 152 mm. The crucible 2′ is thus provided with a considerably larger diameter d′″ as compared with the crucible 2 of the first embodiment but also with respect to conventional crucibles, with which a single-crystal is to be manufactured having the given nominal diameter. In this second embodiment, the (extended) central axis M′ of the second section 6′, or of the seed channel, respectively, thus extends through an edge area of the cross-sectional area as shown in
[0067] The method for manufacturing the single-crystal is similar to that in the previous embodiment (for example including the addition of one or more lattice hardening dopants to the melt). However, the subsequent grinding step of the post-processing for smoothing and finishing the cylinder surface of the optionally doped GaAs single-crystal 14 according to prior art is supplemented or even replaced by a further step, in which the oversize of herein 20 mm in diameter (or herein 10 mm in radius) is reduced or removed by drilling or another step capable of more strongly removing material from the cylindrical surface of the single-crystal. Thereby, in the second embodiment material is removed from the cylindrical surface of the single-crystal in symmetrical manner about the central axis of the single-crystal 14 (which coincides with the centre axis M of the first section of the crucible 2′). Advantageously, edge areas of the single-crystal 14 are removed, which had been close to the walls during growth and thus were—as shown in
[0068] Since moreover due to the specific arrangement, or the offset v respectively, the dislocations 101 (cf.
TABLE-US-00002 TABLE 2 Sample 1b (comparative example) Sample 6 Sample 7 Sample 8 Sample 9 EPD.sub.av 56 cm.sup.−2 8 cm.sup.−2 1 cm.sup.−2 0 cm.sup.−2 2 cm.sup.−2 EPC.sub.total 8.400 1.200 150 0 300
[0069] A third embodiment of a device 1″ according to the invention is shown in
[0070] In this embodiment, it is accepted that edge dislocations 102 particularly positioned at the bottom on the left side in
TABLE-US-00003 TABLE 3 Sample 1c (comparative example) Sample 10 EPD.sub.av 56 cm.sup.−2 7 cm.sup.−2 EPC.sub.total 8.400 1.000
[0071] A fourth embodiment of a device 1″ according to the invention is shown in
[0072] The advantages and effects are the same as those described above with reference to the first through third embodiments, wherein the advantages are accumulated. Relevant parameters of a sample of single-crystal 14 manufactured using the device are provided in table 4. Therein, a sample 1d is a GaAs single-crystal manufactured using a crucible having a conventional seat channel, and serves as a comparative example, while the sample 11 has been manufactured using the crucible as shown in
TABLE-US-00004 TABLE 4 Sample 1d (comparative example) Sample 11 EPD.sub.av 56 cm.sup.−2 0 cm.sup.−2 EPC.sub.total 8.400 0
[0073] Embodiments of the device 1″″ or 1″″″ comprising multiple crucible arrangement including 3 or 5 crucibles 2″ as shown in
[0074] In these two embodiments the crucible arrangement has a symmetry axis Z, which extends in parallel to the corresponding central axes M of the crucibles 2″ through the centre of the arrangement. As viewed from the respective central axes the direction of the offset v is exactly oriented towards the symmetry axis Z. In other words, the corresponding second sections 6′ of the crucibles 2″ are offset towards the centre of the arrangement.
[0075] Such a multiple crucible arrangement allows to generate excellent, stable and homogeneous temperature fields, in particular in a direction towards its centre. By providing offsets of the seed channels in the same manner, the conditions of crystallization are the same in each crucible. Due to the combination of the features of the device 1″ according to the invention shown in
[0076] The above-described embodiments relate to a device configured to perform the VGF-method. However, the invention is not limited to the specific device, and attentive devices may for example also be based on the Vertical Bridgeman method.
[0077] The above-described crucibles include in the first section the cylindrical shape. Attentively, there may, however, also be used other shapes such as cuboid-shaped crucibles having a square or rectangular cross-sectional area, or those shapes in which circular segments are separated from generally round cross-sectional areas (for example for the formation of flats).
[0078] Modifications of the above described embodiments are possible within the scope of embodiments of the disclosure. Also, as in the fourth embodiment, single elements of the embodiments may be combined with those of other embodiments. For example it is conceivable and possible to put into practice, to arrange in the first embodiment having the symmetrically arranged seed channel first crucible section which is expanded in diameter according to aspects of the invention, .i.e., being provided with an increased inner diameter (e.g., d′″=172 mm) in order to perform a post-processing step (drilling, polishing, lapping, or grinding etc.) also therein yielding a corresponding removal of material in a cylinder-wall-shaped or tubular wall-shaped edge area of the single-crystal 14.
[0079] For the post-processing step, drilling, polishing, lapping, or grinding are cited as examples in the above embodiments. However, it is a matter of course for the person skilled in the art, that attentively also other methods known in the technical field of materials science for removing material may be applied.
[0080] It was also surprisingly found that the reduction of the dislocation density in the described range with respect to the reference values is connected with a further significant reduction of the amount of shear stress of the crystals and the wafers manufactured therefrom. For this purpose, the measurement method of SIRD as described above has been employed.
[0081] In order to obtain a unified parameter for the concrete single-crystal/wafer, values of the shear stress obtained for each position on the surface of the wafer (frequency versus shear stress under consideration of the sign) are recorded (see for example
[0082]
[0083] As shown in
[0084] This means that measurements performed at wafers according to embodiments, which were obtained from reference crystals, revealed significantly reduced residual stress as compared with wafers examined in Geiler et al. (2006), according to the SIRD-method, see in this regard also a comparison shown in Table 5 between a comparative example and an embodiment.
TABLE-US-00005 TABLE 5 Comparative Parameter unit example Embodiment EPD.sub.av from full surface cm.sup.−2 130 3 measurement acc. to SEMI M83 EPD.sub.av from measurement of 69 cm.sup.−2 82 0 measurement fields according to SEMI M36 P(EPD.sub.L = 0 cm.sup.−2) from full % 94.0 99.7 surface measurement according to SEMI M83 Maximum value of shear stress kPa 200 <25
[0085] In the comparative example of Table 5, a conventionally manufactured GaAs wafer (as described in Geiler et al. (2006)) having a diameter of 150 mm and separated from a corresponding GaAs single-crystal is concerned.
[0086] The corresponding values of maximum shear stress are displayed in Table 5, and in particular for the comparative example as well as for the embodiment. In
[0087] It is noted, that in practice up to nowadays vanishing values of the shear stress, i.e., maximum values of the shear stress of about 0 kPa (throughout this analysis, only the absolute amount of shear stress is given, if no sign as stated), has not been reached. This value, or those equal to 0.1 kPa or less, or further even those equal to or less 1 kPa may thus optionally be excluded or disclaimed.
[0088] In the various aspects and embodiments explained in the forgoing, the second section includes a longitudinal axis, which, when it is extended into a region of the first section, may extend in a distance of 15 mm or less from an inner wall of the crucible within the first section, but preferably in a distance of 10 mm or less, and even more preferably in a distance of 5 mm or less.
[0089] Furthermore, with respect to such aspects and embodiments, the second section 6′ may at least partially formed in cylindrical shape and may have an inner diameter of 15 mm or less, in particular in a range from 10 mm to 15 mm, or from 5 mm to 10 mm.
[0090] In the various aspects and embodiments explained in the forgoing, the device 1 is configured for manufacturing a crystal having a nominal diameter, which is to be achieved in a post-processing step following a step of growing the crystal, wherein the first section has an inner diameter which is associated with its cross-sectional area perpendicular to the central axis. This inner diameter maybe larger than the nominal diameter by equal to or more than 2 mm, preferably by equal to or more than 3 mm, more preferably by equal to or more than 5 mm, and the inner diameter is larger than the nominal diameter by 10 mm at maximum.
[0091] In the various aspects and embodiments explained in the forgoing, the second section 6, 6′ has a length k′ along a direction of its central axis M, wherein the length may amount to between 40 mm and 120 mm, preferably between 50 mm and 90 mm, more preferably between 60 mm and 80 mm, each range including the boundary values.
[0092] Various aspects and embodiments explained in the forgoing concern an AIII-BV-single-crystal or wafer obtained by separation therefrom, i.e., in particular semiconductor compound materials. These may specifically comprise, for example, gallium arsenide (GaAs) or Indium phosphide (InP), etc.
[0093] In some of the various aspects and embodiments explained in the forgoing, lattice hardening dopants are included in the single crystal manufactured. In such a case, the lattice hardening dopants may be selected from at least one the group composed of: boron, silicon, zinc, sulphur, indium. However, alternative suitable elements may be encompassed as well and the aspects and embodiments are not limited to those specific dopants listed above.