TWI513865B - Germanium ingots/wafers having low micro-pit density (mpd) as well as systems and methods for manufacturing same - Google Patents

Description

Ingot casting/wafer with low pit density (MPD) and systems and methods for its manufacture

The systems and methods herein relate generally to single crystal germanium ingots/wafers, particularly with respect to such ingot/wafer growth with reduced micropit density (MPD).

Electronic and optoelectronic device fabrication routines require commercially grown large and uniform single semiconductor crystals that provide substrates for microelectronic device fabrication during slicing and polishing. The growth of the semiconductor crystal involves heating the feedstock to its melting point to produce a crystalline feedstock melt, contacting the melt with a high quality seed crystal, and crystallizing the melt upon contact with the seed crystal. Many different procedures are known for this purpose. These procedures include the Czochralski (Cz) program and its variants, the liquid closed diesel (LEC) program, the horizontal Bridgman and the Bridgman-Stockbarger program (HB) and their verticals. Variant (VB), as well as gradient solidification (GF) and its variant vertical gradient solidification (VGF) procedure. See, for example, "Bulk Crystal Growth of Electronic, Optical and Optoelectronic Materials", edited by P. Clapper, John Wiley and Sons Ltd, Chichester, England, 2005, which generally discusses such techniques and their use for the growth of various materials.

The crystallization of the melt forms a substantially cylindrical crystal (ingot) along the vertical axis by seeding under the crystallization material. Equipment necessary to form a semiconductor crystal includes a crystal growth furnace, an ampoule, a crucible, and sometimes a crucible support. The crucible can also have a lower narrow portion, known as a seed well.

Conventional crystal growth procedures and crystal growth apparatus have disadvantages. For example, conventional crystal growth procedures often produce crystals with too many pits or microcavities that cause defects, defective devices, and/or reduce the overall usable amount of crystals grown using such procedures. These problems and the reduction in the number of crystals that can be grown result in lower yields. Accordingly, there is a need for crystal growth systems and methods that reproducibly provide high quality ingots/wafers and that additionally overcome these shortcomings in prior systems.

Systems and methods consistent with the present invention relate to the growth of single crystal germanium.

In an exemplary implementation, a method of inserting a ampule having a raw material into a furnace having a heating source and growing the crystal using, for example, a vertical growth process is proposed, wherein a crystallization temperature gradient relative to the raw material/rhodium is moved to melt the raw material and The composition is reconstituted into a single crystal form and grown at a predetermined crystal growth length using a vertical growth procedure to melt the material and recombine it into a single crystal compound in which a single crystal ingot having a reduced pit density is reproducibly provided.

It is to be understood that both the foregoing general description and the claims Other features and/or variations may be provided in addition to the features and/or variations described herein. For example, the invention may be variously combined and subcombined with the various features and/or combinations of several other features disclosed in the Detailed Description.

Reference is made in detail to the present invention, and examples thereof are illustrated in the drawings. The implementations shown in the following descriptions do not represent all implementations consistent with the claimed invention. Rather, the implementations are only some examples consistent with the particular implementations of the invention. Where possible, the same reference numbers may be used in the drawings to refer to the same or the like.

The apparatus and method are apparatus and methods that are particularly suitable for use in germanium (Ge) crystal growth and are described herein. It should be understood, however, that the apparatus and method have greater utility as the apparatus and method can be used to produce other single crystal and/or polycrystalline ingots having low pit density.

1A is a cross-sectional view showing an example of a crystal growth apparatus 20. The example apparatus can include a crucible support 22 in the furnace 24, such as establishing a crystallization temperature that can be used for proper vertical crystal growth procedures (eg, vertical gradient solidification (VGF) procedures and/or vertical Brinell (VB) crystal growth). A gradient furnace, and/or if the furnace is movable, is a furnace that establishes a crystallization temperature gradient that can be used in the Brinell-Siehl process. In an implementation comprising a crucible support, the crucible support 22 provides physical support and enables thermal gradient control of the ampoule 26 (which may be made of quartz in one implementation) that houses the crucible 27. In some implementations, the crucible support 22 can be moved while the furnace is in operation during the crystal growth process. In other implementations, the ankle support can be fixed and the furnace in operation can be moved during the crystal growth procedure. The crucible 27 can hold the seed crystal 28, the grown single crystal crystal/compound 30 and the original molten material 32 formed on top of the seed crystal. In one implementation, the crucible 27 can be a pyrolytic boron nitride (pBN) material having a cylindrical crystal growth portion 34, a smaller diameter seed well cylinder 36, and a tapered transition portion 44. The diameter of the crystal growth portion 34 is equal to the desired diameter of the crystal product. Currently, the industry standard crystal ingots are 2 inches, 3 inches, 4 inches, 5 inches, 6 inches and 8 inches, and the ingots can be cut into wafers. The diameters of 2 inches, 3 inches, 4 inches, 5 inches, 6 inches, and 8 inches correspond to 50.80 mm, 76.20 mm, 100.00 mm, 125.00 mm, 150.00 mm, and 200.00 mm, respectively. In one implementation, at the bottom of the crucible 27, the seed well cylinder 36 can have a closed bottom and be slightly larger in diameter than the high quality seed crystal 28. In an illustrative implementation, for example, the diameter can be in the range of about 6 to 25 mm and can have a length of about 30 to 50 mm. The cylindrical crystal growth portion 34 and the seed well cylinder 36 may have straight walls or may taper outward by about 1 degree to several degrees to facilitate removal of crystals from the crucible 27. The tapered transition portion 38 between the growth portion 34 and the seed well cylinder 36 has an angled sidewall that slopes, for example, by about 45 to 60 degrees, having a larger diameter equal to the growth zone wall and connected to the growth zone wall. And a narrower diameter equal to the seed well wall and connected to the seed well wall. The angled side walls can also be other angles that are steeper or less steep than about 45 to 60 degrees. The above angle is defined as the angle between the angled side wall and the horizontal line.

Prior to insertion into the crystal growth furnace 24, the crucible 27 is filled with the raw material and inserted into the ampoule 26. The ampoule 26 can be formed from a quartz material. Ampoule 26 typically has a shape similar to 坩埚27. The crucible may be cylindrical in the crystal growth region 40, which is a cylinder having a narrower diameter in the seed well region 42 and a tapered transition region 44 between the two regions. In addition, the crucible 27 can be mated inside the ampoule 26 with a narrow boundary therebetween. The bottom of the crystal seed well area 42 of the ampoule 26 is closed, and as the crucible is sealed, the top of the crucible is filled with the crucible and the raw material. The bottom of the ampoule 26 can have the same funnel shape as 坩埚27. Arsenic (As), gallium (Ga), and/or antimony (Sb) as dopants may be added to the ampoule 26.

Without being limited by any particular structure illustrated, the apparatus for germanium crystal growth consistent with the innovations herein may include a crystal growth furnace comprising a heating source (eg, heating element 60) and a plurality of heating zones, constructed An ampoule loaded into the furnace, wherein the ampoule comprises a loading container and a crucible having a seed well; optionally including an ampoule support; and a controller coupled to the crystal growth furnace and the ampoule support, the controller controls the heating One or more of the source and the movable ampoule support are subjected to a vertical gradient solidification procedure on the crucible when the crucible is in the furnace. In addition, the crystallization temperature gradient and/or enthalpy is then moved relative to each other to melt the material and then reconstitute the material into a single crystal bismuth ingot, wherein the device is reproducibly provided with a reduction due to the vertical growth procedure performed in the apparatus锗 Ingot casting of quantum pit density. For example, a tantalum ingot having a micropore density having a range of greater than about 0.025/cm ² and less than about 0.51/cm ² ; greater than about 0.025/cm ² and less than about 0.26/cm ² ; greater than about 0.025/ is reproducibly provided. Cm ² and less than about 0.13/cm ² ; less than about 0.13/cm ² ; and greater than about 0.025/cm ² and less than about 0.26/cm ² . In addition, the pit density can be further controlled (reduced) by controlling the cooling rate and other conditions.

In an exemplary implementation, the controller coupled between the crystal growth furnace and the ampoule support may have a cooling rate of about 0.1 to about 10 ° C / hour and a temperature gradient during crystal growth through a vertical gradient solidification (VGF) program. The interface between the growing single crystal crystal/compound 30 and the original molten material 32 is cooled between about 0.5 to about 10 ° C/cm. In other example implementations, the controller may cool between about 0.1 to about 10 ° C/hour and a temperature gradient of between 0.5 and about 10 ° C/cm during crystal growth including vertical Brinell (VB) programming. Between the growing single crystal/compound 30 and the original molten material 32. In yet another example implementation, the controller may be at about 3 ° C / hour during crystal growth/cooling (including vertical gradient freeze (VGF) procedures and/or vertical Bridgman (VB) degrees). The cooling rate is 5 hours before cooling, and the remaining period of the cooling process is cooled at about 30 ° C / hour to about 45 ° C / hour to cool the interface between the grown single crystal crystal / compound 30 and the original molten material 32.

Returning to the example system of Figure 1A above, the ampoule and crucible may have a tapered (funnel) zone. The ampoule-clam combination has a funnel shape, and the crucible support 22 accommodates the funnel shape and allows the ampoule 26 to remain stable and upright within the furnace 24. In other implementations, the ampoule-twist combination can retain a different shape and the basic structure of the ankle support 22 can be varied to match a particular different shape. According to other implementations, the stability and strength of the ampoule and its contents are provided via the solid thin walled cylinder 50 of the crucible support 22. The solid thin walled cylinder 50 houses the funnel end of the ampoule structure 26. In one implementation, the crucible support cylinder 50 is made of a thermally conductive material, preferably quartz. In other implementations, tantalum carbide and ceramics can also be used to form the crucible support cylinder 50. The cylinder 50 is in circular contact with the ampoule 26 with the upper edge of the cylinder 50 contacting the shoulder of the tapered region 38 of the ampoule. This configuration results in minimal solid-solid contact, which does cause little or no uncontrolled heat transfer. Therefore, heating can be produced by other more controllable methods.

In other implementations, a low density insulating material, such as a ceramic fiber, fills most of the interior of the support cylinder 50, with only the hollow shaft core 52 about the center of the insulating material remaining clear to receive the seed well 42 of the ampoule 26. In other implementations, the low density insulating material may also comprise alumina fibers (1800 ° C), alumina-yttria fibers (1426 ° C), and/or zirconia fibers (2200 ° C). The insulating material is carefully placed in the crucible support 22. When the weight of the ampoule 26 is at the top of the cylinder 50, it presses the insulating material down and forms a slanted insulating material edge 54. The majority of the interior of the cylinder is filled with a low density insulator to reduce air flow, which does cause little or no unwanted uncontrolled convection. For example, conduction, convective system uncontrollable thermal transfer methods may be detrimental to VGF/VB and other crystal growth procedures herein.

As shown in the example system of FIG. 1A, the hollow core 52 having a diameter approximately equal to the diameter of the ampoule seed well 42 extends down to a small distance below the bottom of the ampoule seed well 42. In other implementations, the hollow core 52 can extend through the crucible support from the bottom of the seed well to the bottom of the furnace apparatus 24. The hollow core 52 provides a cooling path from the center of the crystal. It contributes to the central cooling of the seed well and the growing crystal. In this configuration, thermal energy can escape downward through the solid crystal and the center of the seed crystal, passing downwardly through the hollow core 52 in the insulating material within the crucible support 22. In the absence of the hollow core 52, the central temperature of the ingot being cooled is naturally higher than the crystalline material closer to the outer surface. In this example, the ingot in any horizontal central cross section will crystallize after it has solidified around it. Crystals having uniform electrical properties cannot be produced under these conditions. In an implementation having a hollow core 52 included in the crucible support method, thermal energy is conducted downwardly through the bottom of the ampoule 26 and the hollow core 52, and the radiation passage 56 is radiated from the hollow core 52. It is important to reduce the thermal energy from the center of the growing crystal to keep the isothermal layer throughout the crystal diameter flat. Maintaining a flat crystal melt interface enables the insulation of crystals having uniform electrical and physical properties.

In some implementations, the low density insulating material in the cylinder 50 may interfere with the flow of heat radiation from a set of furnace thermal elements 60 to the ampoule 26 in the seed well zone 42, so the method requires the need to generate a plurality of passes through the Horizontal radiant channel/opening/duct 56 of insulating material. The radiant passage 56 extends through the insulating material to provide a heat radiant outlet for controlled transfer of heat from the furnace heating element 60 to the ampoules seed well 42. The number, shape and diameter of the radiant channels 56 vary depending on the particular conditions. The radiant channel can also be inclined, curved or wavy. Since the radiant channels may only partially extend through the insulating material, they do not necessarily have to be continuous. This helps minimize convection. In one implementation, the diameter of the channels is small, about the width of the pencil, so the convective air flow is not critical. Larger apertures having a cross-sectional area of about square inches or greater may also be used in accordance with other implementations of the invention. The radiant channel 56 through the insulating material also cooperates with the hollow core 52 in the center of the insulating material to radiate thermal energy from the center of the crystal and to cool the crystal having a flat isothermal temperature gradient layer. The radiant channel 56 enables temperature control and is directly related to crystal growth rate.

The furnace 24 shown in Figure 1A is a furnace that can be used for both vertical gradient solidification (VGF) and vertical Brinell (VB) or vertical Brinell-Spear (VBS) crystal growth procedures. Other furnaces can also be used. In the VGF crystal growth procedure, as the crystal remains stationary, it moves in a crystallization temperature gradient that is itself a fixed heat source. In the VB crystal growth process, the heat source and its fixed crystallization temperature gradient remain fixed while moving the crystal. In the VBS crystal growth procedure, the heat source and its fixed crystallization temperature gradient are moved while the crystal remains fixed.

Figure 1B is a cross-sectional view of an example 坩埚99 consistent with a particular implementation of the innovations herein. Referring to FIG. 1B, an exemplary enthalpy for some of the illustrative crystal growth furnaces herein can have a tapered crystal growth region having a length of from about 25 mm to about 50 mm. Moreover, in some example implementations, the crucible 99 and the ingot may have a growth length after a taper having a length of from about 110 mm to about 200 mm ("predetermined growth length").

Figure 2 shows a region containing a crystal ingot or wafer of micropits 200 that is consistent with the particular implementation of the innovations herein. Referring to Figure 2, the presence of such micropits 200 creates significant dark spots and associated problems in the growth of the crucible material. When the number of micropits is too high, the ingot or wafer may be unusable and therefore needs to be recycled. Therefore, micropits or microcavities can reduce the yield of the crystal growth process, and it is desirable to reduce such defects. Systems, furnaces, and crystal growth procedures that overcome such micro-pit problems create higher yields.

Figure 3A broadly shows an exemplary implementation of crystal growth consistent with the particular implementation aspects associated with the innovations herein. According to such implementations, an exemplary method can include loading Ge material into crucible (280), sealing the crucible and/or holding it in a crucible vessel (282), placing the crucible into a crystal growth furnace, and melting the Ge material in the crucible A melt is produced and a vertical growth procedure is performed to form a single crystal germanium ingot (284). Additionally, the method can include one or more additional steps including controlling the crystallization temperature gradient of the melt upon contact of the melt with the seed crystal, forming a single crystal via a crystallization temperature gradient and/or movement of ruthenium relative to each other. The ingot is cast, and the single crystal germanium ingot is cooled. In addition, due to the vertical growth procedure herein, tantalum ingots having reduced quantum pit density are reproducibly provided. For example, a tantalum ingot having a micropore density having a range of greater than about 0.025/cm ² and less than about 0.51/cm ² ; greater than about 0.025/cm ² and less than about 0.26/cm ² ; greater than about 0.025/ is reproducibly provided. Cm ² and less than about 0.13/cm ² ; less than about 0.13/cm ² ; and greater than about 0.025/cm ² and less than about 0.26/cm ² . In some example implementations, the pit density can be controlled by controlling the cooling rate and other conditions. Further, the single crystal substrate according to the innovation herein may have a carrier concentration of about 9 x 10 ¹⁷ to about 4 x 10 ¹⁸ or about 5 x 10 ¹⁸ /cm ³ from the starting growth portion to the end of the growth portion, and about 7 x 10 ^-3 to 2 x 10 ^-3 or resistivity of 3 x 10 ^-3 Ω.cm, mobility of about 950cm ² / Vs to about 450cm ² / Vs. Moreover, the misalignment density can be less than about 500/cm ² , or even less than about 200/cm ² . Carrier concentration, mobility and misalignment density can also be controlled by controlling the cooling rate and other conditions. Consistent with the growth procedure shown herein, for example, the growthable carrier concentration is from about 1 x 10 ¹⁷ to about 4 x 10 ¹⁸ /cm ³ and the resistivity is from about 5 x 10 ^-3 to about 2 x 10 ^-2 Ω. Cm, and/or a p-type germanium single crystal ingot/wafer having a mobility of about 1100 to about 250 cm ² /Vs of 200 mm. Moreover, according to certain implementations, a 200 mm ingot having a dislocation density of less than about 300/cm ² can be grown.

3B shows another exemplary method 80 of growing crystals using vertical gradient solidification (VGF) and vertical Brinell (VB) program steps, which can reduce pit density and result in higher yields, which are specific to the innovations herein. The implementation is consistent. In this exemplary crystal growth procedure, a furnace (82) for crystal growth as described above is prepared. To initiate crystal growth from the seed crystal, the VGF program (84) was used. At a particular point in the crystal growth procedure, VB program (86) or VBS program can be used to complete crystal growth. When using the VB or VBS program, the melt/solid line is maintained at a level and the process is continued under fixed conditions, as the program changes typically required when the volume of the VGF program is reduced are not required. In an illustrative implementation of the procedure, for example, from about 12 mm to about 15 mm (about 1/2 inch), from about 12 mm to about 45 mm or more above the tapered region 38 as shown in FIG. 1A (such as The VB program is used from about 30 mm to about 45 mm). Consistent with the implementation and experimental results herein, the combination of VGF and VB procedures can result in better crystals with fewer micropits. The above exemplary method can be used with the furnace shown in Figure 1A, but can also be used with any other crystal growth furnace. This method can be used to grow crystals having a diameter of 2 inches to 8 inches or more.

In other vertical growth implementations, a method of growing single crystal germanium (Ge) crystals in a crystal growth furnace including a heat source, a plurality of heating zones, ampoules, and helium is proposed in accordance with the example innovations herein. In such implementations, an exemplary method can include loading a Ge feedstock into a crucible, sealing the crucible and the vessel, placing the crucible into a crystal growth furnace, melting the Ge feedstock in the crucible to produce a melt, and controlling the crystallization of the melt. The temperature gradient is simultaneously placed in contact with the seed crystal, a single crystal germanium ingot is formed via the crystallization temperature gradient and/or movement of the crucible relative to each other, and the single crystal germanium ingot is cooled. Furthermore, due to these vertical growth procedures, tantalum ingots having reduced quantum pit density are reproducibly provided. For example, a tantalum ingot having a micropore density having a range of greater than about 0.025/cm ² and less than about 0.51/cm ² ; greater than about 0.025/cm ² and less than about 0.26/cm ² ; greater than about 0.025/ is reproducibly provided. Cm ² and less than about 0.13/cm ² ; less than about 0.13/cm ² ; and greater than about 0.025/cm ² and less than about 0.26/cm ² . These dimple densities can be controlled by controlling the cooling rate and other conditions as described elsewhere herein. Additionally, the method may additionally include the addition of arsenic (As), gallium (Ga), and/or antimony (Sb) as dopants.

In an exemplary implementation, the method can include growing via a vertical gradient solidification (VGF) procedure and including a cooling rate of between about 0.1 and about 10 ° C/hour and a temperature of between about 0.5 and about 10 ° C/cm. Cooling procedure performed under gradient. In other example implementations, the method can include a vertical Brinell (VB) program crystal at a cooling rate of between about 0.1 and about 10 ° C/hour and at a temperature gradient between about 0.5 and about 10 ° C/cm. Growing. In other example implementations, the crystal growth method can include crystal growth/cooling, including cooling via a vertical gradient solidification (VGF) procedure and/or via a vertical Brinell (VB) program at a cooling rate of about 3 ° C/hour. The remaining period of the cooling procedure was cooled for 5 hours and at a cooling rate of from about 30 ° C / hour to about 45 ° C / hour.

As shown in Figure 4, the loading cassette 90 can be positioned above the cassette 27 and allows the cassette 27 to carry more material. In particular, the crucible material 92 is solid so that it cannot be stacked tightly on the crucible 27 to be melted. Thus, the loading tether is used to contain additional material that can be melted and discharged downward into the crucible, which forms a larger crucible feed in the crucible 27, which in turn forms a larger length of crucible crystals. For example, from about 35 to about 65% of the material may initially be charged to the loading crucible 90 and from about 65 to about 35% of the stock material directly loaded into the crucible 27. For example, in accordance with some of the crystal growth methods herein, about 10 kg of feed can be loaded into the furnace to produce a 200 mm 4 inch ingot having a low pit density herein.

Now, the growth of 4" (100 mm) diameter 锗 crystals grown using the above crystal growth furnace and method (in combination with VGF and VB) will be described in more detail. To grow a sample crystal, the size of the crucible is 100 mm in diameter and 200 mm in length. Crystal growth zone 40. The diameter of the crucible in the seed well zone 42 is 7 mm. In an exemplary implementation, 10 kg of ruthenium precursor material can be loaded for ingot growth. In operation, the seed crystal species are first inserted into pBN坩埚. 27 bottom portion. Next, about 10 kg of ruthenium material, and about 36 g of boron oxide may be added as a liquid sealant. Then, the loaded pBN坩埚 is inserted into the quartz ampoule. The quartz cap is sealed under reduced pressure. The quartz ampoule is then loaded into the furnace and placed on the crucible support.

Once the ampoule is loaded into the furnace, the quartz ampoule can be heated at a rate of about 150 to 200 ° C / hour. In an exemplary procedure, when the temperature of the seed portion reaches the melting point and is about 3 to 18 ° C above the melting range (~ 940 to 955 ° C) of the crystal growth region, the temperature point can be maintained until all the single crystal germanium materials Melting (eg, in some implementations, about 2 to 4 hours). Once the single crystal germanium material is melted, crystal growth is first performed using the VGF method. The temperature can then be slowly lowered in the lower temperature heating zone to initiate crystal growth from the seed portion and continue through the transition region until the crystal growth region is cooled, in association with the VGF and/or VB method, in the crystal growth procedure After completion, the first 5 hours are cooled at a cooling rate of about 3 ° C / hour, and the remainder of the cooling procedure is cooled at a cooling rate of from about 30 ° C / hour to about 45 ° C / hour. In other example implementations, the crystal growth cooling may be a cooling rate of from about 0.1 to about 10 ° C / hour and between about 0.5 to about 10 ° C / cm. Temperature gradients occur (eg, associated with VGF programs). Further, in the example VB program, a crystal growth cooling rate of 0.3 to 0.47 ° C / hr can be used while maintaining the temperature gradient at 1.2 to 1.8 ° C / cm.

According to some of the examples herein, in combination with the VGF and VB procedures, the VB procedure can be initiated when the crystal has grown in the crystal growth region from about 1 to about 3 inches. In the VB procedure, the helium descent rate is controlled to optimize the cooling/growth parameters in the crystal growth zone, such as a cooling rate of from about 0.2 to about 0.5 ° C/hr and/or a temperature gradient of from 0.3 to about 2.5 ° C/cm. Through this procedure, a crystal of high quality (i.e., low pit density or "low MPD") having a length of about 190 mm can be obtained from a 200 mm elongated ingot having a crystal yield of about 95%. By such methods, a tantalum ingot having a micropore density having a range of greater than about 0.025/cm ² and less than about 0.51/cm ² ; greater than about 0.025/cm ² and less than about 0.26/cm ² is reproducibly provided; Greater than about 0.025/cm ² and less than about 0.13/cm ² ; less than about 0.13/cm ² ; and greater than about 0.025/cm ² and less than about 0.26/cm ² .

Further, the single crystal substrate manufactured according to the innovation herein may have from about 9 x 10 ¹⁷ to about 4 x 10 ¹⁸ or about 5 x 10 ¹⁸ /cm ³ from the beginning of growth to the end of the growth portion (measured by about 9 x 10 ¹⁷ The carrier concentration to a range of about 4.86 x 10 ¹⁸ /cm ³ and about 7 x 10 ^-3 to 2 x 10 ^-3 or 3 x 10 ^-3 Ω.cm (measured to be about 7.29 x 10 ^-3 to about a range of 2.78 x 10 ^-3 Ω.cm.) the resistivity, mobility of about 950cm ² / Vs to about 450cm ² / Vs (measured 955cm ² / Vs and 467cm ² / Vs of the value). Moreover, the misalignment density can be less than about 500/cm ² , or even less than about 200/cm ² .

Consistent with Figures 4 through 5, systems and methods are provided for growing single crystal germanium (Ge) crystals in which once the original feedstock has melted but crystals grow open Prior to the start, additional feed melt can be added to the crucible (e.g., in VGF and/or VB procedures, etc.) such that a longer growing single crystal ingot is grown. Additionally, the method can include loading a first Ge feedstock into a crucible containing a seed crystal containing seed crystal, loading a second Ge feedstock into a vessel for replenishing the Ge melt material, and sealing the crucible and the vessel in the ampoule, And placing the ampoule together with the crucible into a crystal growth furnace having a movable ampoule support supporting the ampoule. Additionally, an example implementation can include melting a first Ge feedstock in the crucible to produce a melt, melting a second Ge feedstock in the vessel, and adding the molten second Ge feedstock to the melt. Other example implementations can include controlling the crystallization temperature gradient of the melt to crystallize and form a single crystal germanium ingot upon contact of the melt with the seed crystal, and optionally cooling the single crystal germanium ingot.

In an exemplary implementation, the step of forming a single crystal germanium ingot can include producing a temperature gradient in the crystal growth region of from about 0.3 to about 2.5 °C/cm. Further, the single crystal germanium ingot may be cooled at a rate of 0.2 to about 0.5 ° C / hour. In addition, the crystal can remain fixed during the crystallization temperature gradient shift.

According to a particular example implementation, the single crystal germanium ingot has a diameter of from about 50 mm to about 200 mm (about 2 inches to about 8 inches). In one implementation, for example, the single crystal germanium ingot may have a diameter of 152.4 mm (6 inches). In addition, single crystal germanium ingots and wafers having diameters ranging from about 50 mm to about 200 mm (about 2 inches to about 8 inches) made by the innovations herein are reproducibly provided with crater densities in the following ranges: Greater than about 0.025/cm ² and less than about 0.51/cm ² ; greater than about 0.025/cm ² and less than about 0.26/cm ² ; greater than about 0.025/cm ² and less than about 0.13/cm ² ; less than about 0.13/cm ² ; Greater than about 0.025/cm ² and less than about 0.26/cm ² .

Furthermore, a single crystal substrate having a diameter of from about 50 mm to about 200 mm (about 2 inches to about 8 inches) manufactured according to the innovations herein can have from about 9 x 10 ¹⁷ to about 4 from the beginning of the growth portion to the end of the growth portion. a carrier concentration of x 10 ¹⁸ or about 5 x 10 ¹⁸ /cm ³ (measured in the range of about 9 x 10 ¹⁷ to about 4.86 x 10 ¹⁸ /cm ³ ), and about 7 x 10 ^-3 to 2 x 10 ^-3 or 3 x 10 ^{-3 Ω.cm} (measured at about 7.29 x 10 ^-3 to about 2.78 x 10 ^{-3 Ω.cm} resistivity range, the mobility of about 950cm ² / Vs to about 450cm ² / Vs (measured The value of 955 cm ² /Vs and 467 cm ² /Vs is obtained. Further, the dislocation density may be less than about 500/cm ² , or even less than about 200/cm ² .

With respect to systems consistent with the innovations herein, an exemplary apparatus for growing large diameter single crystal germanium crystals can include a crystal growth furnace including a heating source and a plurality of heating zones, the ampoule being constructed into the furnace, wherein the ampoule includes The utility model comprises a loading container and a crucible having a seed crystal well, a movable ampoule support body and a controller coupled to the crystal growth furnace and the movable ampoule support body. Additionally, the controller can control one or more of the heating zones and the drivable ampoule support to perform a vertical gradient solidification procedure on the crucible when the crucible is in the crucible.

Depending on the particular implementation, the crystal growth furnace can have a plurality of heating zones, such as between 4 and 8 heating zones, between 5 and 7 heating zones, or 6 heating zones. An example crucible may be between about 50 mm and about 200 mm (about 2 to about 8 inches), or in some implementations, about 150 mm (about 6 inches), depending on the desired ingot/wafer diameter. diameter.

Figures 5A through 5D show other example implementations of erbium crystal growth consistent with the particular implementations associated with the innovations herein. Figures 5A through 5D are longitudinal cross-sectional views of an apparatus for growing single crystal germanium crystals illustrating an exemplary crystal growth procedure consistent with a particular embodiment of the present invention. Figure 5A shows a cross-sectional view of an example of a crystal growth apparatus. The apparatus may include a furnace for a vertical gradient solidification (VGF) growth procedure and/or a vertical Brinell (VB) growth procedure, and may include an ampoule support 11 in the furnace 1, wherein the heater 2 is comprised of a plurality of zones Composition, each district is individually controlled by a computer-controlled control system. The temperature of each zone can be adjusted to provide the desired overall temperature profile and the temperature gradient of the controlled solidification of the melt. The temperature profile and temperature gradient are adjusted to cause the crystalline interface to move uniformly/predictably upward through the melt, for example, to produce a temperature gradient of from about 0.3 to about 2.5 °C/cm in the crystal ingot growth zone. The ampoule support 11 can be used to provide physical support and thermal gradient control of the ampoule 3 containing the crucible 12 (i.e., in one embodiment, made of quartz), which in turn can hold the seed crystals in the seed well 18. When the furnace is in operation, the ampoule support 11 can move axially during the crystal growth process. The crucible 12 can hold the seed crystal 17 from which the single crystal formed on top of the seed crystal is grown. In one implementation, the crucible 12 can be a pyrolytic boron nitride (pBN) structure having a cylindrical crystal growth portion 13, a smaller diameter seed well cylinder 18, and a tapered transition portion 7. The crystal growth portion 13 is attached to the top opening of the crucible 12 and has a diameter equal to the desired diameter of the crystal product. Current industry standard crystal diameters are 50.8, 76.2, 100.0, and 150.0 mm (2, 3, 4, and 6 inch) diameter ingots that can be cut into wafers. In an illustrative implementation, at the bottom of the crucible 12, the seed well cylinder 18 has a closed bottom and is slightly larger in diameter than the high quality seed crystal 17, such as about 6 to 25 mm, and has a length of about 30 to 100 mm. The cylindrical crystal growth portion 13 and the seed well cylinder 18 may have straight walls or may taper outward by about 1 degree to several degrees to facilitate removal of crystals from the crucible 12. The tapered transition portion 7 between the growth portion 13 and the seed well cylinder 18 has an angled sidewall that slopes, for example, by about 45 to 60 degrees, having a larger diameter equal to the growth zone wall and connected to the growth zone wall. And a narrower diameter equal to the seed well wall and connected to the seed well wall. In other implementations, the angled sidewalls can also be other angles that are steeper or less steep than 45 to 60 degrees.

In a particular example implementation, the ampoule 3 can be made of quartz. The ampoule 3 can have a shape similar to that of the crucible 12. The ampoule 3 may be cylindrical in the seed growth zone 19, having a narrower diameter in the seed well zone 19 and a cylindrical shape with a tapered transition zone 8 between the two zones. In addition, the crucible 12 is mated inside the ampoule 3 with a narrow boundary therebetween. The second upper container 4 as a raw material container is placed on the quartz support 6. The quartz support body 6 is sealed in the middle portion of the ampoule 3. In an embodiment of the invention, the second container 4 is made of pBN. Most of the raw material 5 is filled in the second container 4. During the heating process, the material melts and drip from the bottom hole of the second vessel 4 into the main crucible 12. The bottom of the crystal seed well zone 19 of the ampoule 3 is closed and the top is sealed after the crucible and the feedstock are loaded. Arsenic (As), gallium (Ga), and/or antimony (Sb) as dopants may be added to the ampoule 12 and/or the second container 4.

In some implementations, the cylinder 16 can be shaped to form a circular contact with the ampoule 3 with the upper edge of the cylinder 16 contacting the shoulder of the tapered region 8 of the ampoule. This configuration results in minimal solid-solid contact, which does cause little or no uncontrolled heat transfer. Therefore, heating can be produced by other more controllable methods.

In an exemplary embodiment of the innovation herein, the furnace temperature may be lowered at a rate of from about 0.2 to about 0.5 ° C per hour during the growth phase of the single crystal bismuth ingot to grow the single crystal bismuth ingot.

The sequence of Figures 5A through 5D shows other example 锗 growth procedures including the characteristics of melting and supplying enthalpy. Referring to the drawings, Figure 5A shows the initial state of the exemplary procedure in which solid tethers are present in both the upper vessel 4 and the crucible 12. As an innovative heating feature and procedure, the intermediate state of the crucible melt is then shown in Figure 5B, which shows the solid state in the crucible 12 in a molten liquid state.

The heating elements of the heating zone of the furnace can be adjusted in association with the individual power supply, thus providing the required thermal energy to the upper vessel. More specifically, the upper container can be heated to cause the crucible in the upper container 4 to start to melt, and the molten crucible flows into the crucible 12 through the hole at the bottom of the container 4. In an exemplary implementation, the area of the furnace in which the upper vessel is present is heated to a temperature of from about 940 to about 955 degrees Celsius, or from about 945 to about 950 degrees Celsius. The procedure continues until all of the crucibles in the upper vessel 3 melt and flow into the crucible 12.

The furnace 1 shown in Figures 5A to 5D is an example of a furnace that can be used in a vertical gradient solidification (VGF) crystal growth procedure. Other furnaces and configurations, such as vertical Brinell. In the VGF crystal growth procedure, the crystallization temperature gradient within the fixed heat source is electrically moved while the crystal remains stationary.

For vertical gradient solidification growth (VGF), an appropriate temperature gradient curve must be established in the furnace. The furnace's heating zone is separately and independently controlled by a programmed computer for its individual power supply to heat and cool to meet the furnace crystallization temperature and temperature gradient requirements. Regarding the growth of the bismuth ingot, for example, the furnace temperature fluctuation may need to be less than about ± 0.1 °C. During the furnace preparation, the ruthenium polycrystalline material was loaded into ampoule 3 as described in more detail elsewhere herein.

As shown in the figure, the pBN loading container 4 having a hole in the tapered portion is placed on the support body 6 made of quartz above the crucible 12 in the ampoule 3. The second container 4 can be placed on the crucible 12 and within the ampoule 3. The aperture of the second container 4 can be located centrally with a tapered bottom surface that extends toward the ampoule 3. The crucible 3 may have an opening that receives the molten crystal dropped from the hole in the center of the bottom of the second container 4. The loading container 4 allows the crucible 12 to carry more material. In particular, the crucible material 5 is usually a solid thick pile or crumb and therefore cannot be stacked tightly on the crucible 12 to be melted. Thus, the loading container is adapted to contain additional material that can be melted and discharged downward into the crucible 12, which forms a larger crucible feed in the crucible 12, which in turn forms a larger length and diameter crucible crystal. For example, about 65% of the raw material can initially be loaded into the loading container 4 and 35% of the raw material can be directly loaded into the crucible 12. As a non-limiting example, 5.115 kg of feedstock feed is carried in crucible 12 and 9.885 kg of feed is carried in loading vessel 4 to form 15,000 g (15) which can produce 150 mm (6 in.) diameter cast ingots. Kg) feed.

In one example, the crucible can be doped with arsenic (As). Here, for example, a 9° offset orientation <100> seed crystal can be loaded into the crucible prior to loading the feed. A stock feed and an appropriate amount of dopant are loaded into the crucible and loaded into a loading vessel placed in a quartz ampoule 3. The ampoule and contents were evacuated to a vacuum of about 2.00 x 10 ^-4 Pascals (about 1.5 x 10 ^-6 Torr), after which the ampoule was sealed and loaded into the furnace, as shown in Figure 1A. The furnace is started and the ampoules and contents are heated to melt the material in the crucible 12. During this growth, the furnace was at a temperature of about 1000 ° C because the melting point of the crucible was about 940 ° C. The crystallization interface temperature gradient can be adjusted to between about 0.5 and about 10 ° C/cm depending on the location of the ingot. Additionally, the overall temperature profile can be adjusted to provide a crystallization rate of about 1 to 2 mm/hr. After the curing is completed, the furnace can be cooled at about 20 to 40 ° C / hour. Ge is formed from the sum of these exemplary program reproducing cocoa herein germanium ingot having a density of dimples provided the following ranges: greater than about 0.025 / cm ² and less than about 0.51 / cm ^2; greater than about 0.025 / cm ² and less than about 0.26 /cm ² ; greater than about 0.025/cm ² and less than about 0.13/cm ² ; less than about 0.13/cm ² ; and greater than about 0.025/cm ² and less than about 0.26/cm ² .

In other examples, the apparatus of the present invention is constructed of a quartz ampoule in which both a pBN loading container and a crucible can be inserted, and a support 6 is used to secure the pBN loading container. Regarding the example dimensions, the crucible may have a diameter of about 150 mm in the crystal growth section, a length of about 160 mm in the crystal growth section, and a diameter of about 7 mm in the seed section. In an exemplary implementation, <100> oriented Ge seed crystals are inserted into the seed well of pBN(R) and 96 g of boron trioxide as a liquid sealant is placed over the seed crystal in the pBN(R). Then, a total of 14,974 g of Ge polycrystalline material was loaded into the pBN(R) and pBN containers, respectively, and both the pBN container and the crucible were inserted into the quartz ampoule, and the quartz ampoule was at about 2.00 x 10 ^-4 Pascal (1.5 x 10). ^-6 Torr) is sealed with a quartz lid under reduced pressure. The sealed ampoule is then loaded into the furnace and placed on the ampoule support.

The above quartz ampoule is heated at a rate of about 270 ° C / hour. When the temperature is about 30 ° C above the melting point of the crystalline material, the heating is maintained until all of the crystalline material has melted.

As shown in Figure 6, an exemplary method for growing single crystal germanium (Ge) crystals consistent with the innovations herein is disclosed. In an exemplary implementation, a method is provided for loading a first Ge feedstock into a crucible comprising a seed crystal well, and loading a second Ge feedstock into a vessel for replenishing the feedstock to be located in the ampoule, The crucible and the container are sealed in the ampoule, and the ampoule is placed in the crystal growth furnace together with the crucible and the container therein, and the melting of the first Ge raw material in the crucible is controlled to produce a melt, and the second in the container is controlled. Melting of the Ge material. Additionally, such methods can include controlling the molten second Ge feedstock to be added to the melt, controlling the crystallization temperature gradient of the melt such that upon contact with the seed crystal the melt crystallizes and forms a single crystal bismuth ingot, and cooling the One or more of the single crystal bismuth ingots.

Other example implementations can include controlling the melting of the second Ge feedstock in the vessel, including controlling the heat applied to the second Ge feedstock and maintaining the molten second Ge feedstock within a temperature range. Additionally, controlling the molten second Ge feedstock to be added to the melt can include maintaining the melt within a specified temperature range, and the range can be from about 940 to about 955 degrees Celsius, or from about 945 to about 950 degrees Celsius. . Additionally, controlling the molten second Ge feedstock to be added to the melt can include maintaining the melt within a specified temperature range, such as the above range.

In still other example implementations, the heating power and/or one or more cooling rates may be controlled or reduced in a controlled manner to produce a Ge ingot having crystalline properties within the range provided by the reproduction. Moreover, due to such program control, single crystal germanium ingots having reduced micropit density (e.g., in any of the other ranges shown herein) are reproducibly provided.

Further, by the procedure shown herein, a germanium crystal having a micropore density in the above various ranges can be reproducibly provided without using a doping technique supplied from an external gas source. Many aspects of such shortcomings may be associated, for example, with the use of sealed ampoules (e.g., under vacuum, under pressure, and under other conditions, etc.) and avoiding the need for expensive gas supply hardware and control systems/electronic devices, etc. Complexity. In some instances, the innovations herein may be advantageously associated with systems and methods that require non-contact doping techniques. Therefore, a germanium crystal having a dislocation density within the above various ranges is reproducibly provided without using a contact doping technique and/or a doping technique supplied from an external gas source.

In certain implementations, the VGF method can be used to perform crystal growth. In addition, in a specific example 125 mm long ingot growth procedure, the heater power can be first reduced in the lowest heating zone to initiate crystal growth at the seed crystal, and then the heater power can be lowered in the transition zone where cooling The rate can be set from about 0.3 to about 0.4 ° C / hour. In addition, this cooling rate can be maintained for approximately 70 hours. Once the crystallization reaches the primary growth zone, the heater power in the appropriate zone can be reduced to provide a cooling rate of from about 0.4 to about 0.7 ° C / hour, and the crystallization interface temperature gradient is from 1.2 to about 3.0 ° C / cm, both Maintain for about 120 hours. After the crystallization is completed, the furnace is cooled at a cooling rate of about 20 to about 40 ° C / hour until it reaches room temperature.

Here, the length of the main body forming the ingot was 125 mm, and it was completely single crystal. Such crystals may have a low micropore density, for example, from the beginning of the growth portion to the end of the growth portion, and may also have from about 9 x 10 ¹⁷ to about 4 x 10 ¹⁸ or about 5 x 10 ¹⁸ /cm ³ (measured about 9 x) Free carrier concentration from 10 ¹⁷ to about 4.86 x 10 ¹⁸ /cm ³ ), and 7 x 10 ^-3 to 2 x 10 ^-3 or 3 x 10 ^-3 Ω.cm (measured approximately 7.29 x 10 ^-3 to about 2.78 x 10 ^-3 Ω.cm range of) the resistivity, mobility of about 950cm ² / Vs to about 450cm ² / Vs (measured 955cm ² / Vs and 467cm ² / Vs of the value). Moreover, the misalignment density can be less than about 500/cm ² , less than about 200/cm ² , or even less than about 100/cm ² .

In still other VGF methods, according to a particular example 200 mm long ingot growth procedure, the heater power can be first reduced in the lowest heating zone to initiate crystal growth at the seed crystal, and then the heating can be reduced in the transition zone. The power can be set to a cooling rate of from about 0.1 to about 0.3 ° C / hour. In addition, this cooling rate can be maintained for approximately 70 hours. Once the crystallization reaches the primary growth zone, the heater power in the appropriate zone can be reduced to provide a cooling rate of from about 0.4 to about 0.7 ° C / hour, and the crystallization interface temperature gradient is from 1.2 to about 3.0 ° C / cm, both Maintain for about 170 hours. After the crystallization is completed, the furnace can be cooled at a cooling rate of about 20 to about 40 ° C / hour until it reaches room temperature.

Here, the length of the main body forming the ingot was 200 mm, and it was completely single crystal. Such crystals may have a low micropore density, for example, from the beginning of growth to the end of the growth portion, and may also have from about 4 x 10 ¹⁷ to about 6 x 10 ¹⁸ or about 5 x 10 ¹⁸ /cm ³ (measured to be about 4.34 x) Free carrier concentration from 10 ¹⁷ to about 5.98 x 10 ¹⁸ /cm ³ ), and 2 x 10 ^-2 to 4 x 10 ^-3 or 3 x 10 ^-3 Ω.cm (measured approximately 2.02 x 10 ^-2 The resistivity to a range of about 3.86 x 10 ^-3 Ω·cm) has a mobility of about 800 cm ² /Vs to about 250 cm ² /Vs (measured as 713 cm ² /Vs and 271 cm ² /Vs). Moreover, the misalignment density can be less than about 300/cm ² , or even less than about 100/cm ² .

As such, it should be noted that any germanium crystal substrate (e.g., ingot, wafer, etc.) fabricated by the methods/procedures of the present disclosure is particularly within the innovations herein. In addition, any product (such as an electronic or optoelectronic device, etc.) comprising such a germanium crystal substrate manufactured by any of the methods/procedures herein is also in accordance with the innovation.

While the invention has been described with reference to the specific embodiments of the present invention, it will be understood by those skilled in the art that the invention can be practiced without departing from the spirit and scope of the invention. The scope is defined.

20. . . Crystal growth equipment

twenty two. . . Helium support

24/1. . . furnace

26/3. . . ampoule

27/99/12. . . crucible

28/17. . . Seed crystal

30. . . Single crystal/compound

32. . . Raw molten material

34/13. . . Cylindrical crystal growth section

36/18. . . Seed well column

38/44/7/8. . . Conical transition

40. . . Crystal growth zone

42. . . Crystal well area

50/16. . . cylinder

52. . . Hollow core

54. . . Tilting the edge of the insulation

56. . . Radiation channel

60. . . Furnace heating element

90. . . Loading 坩埚

92. . . Raw material

2. . . Heater

4. . . Second upper container

5. . . raw material

6. . . Quartz support

11. . . Ampoule support

19. . . Seed growth zone

BRIEF DESCRIPTION OF THE DRAWINGS The accompanying drawings, which are incorporated in FIG. In the drawings:

1A and 1B are cross-sectional views of an exemplary crystal growth apparatus and crucible, consistent with particular implementations associated with the innovations herein;

Figure 2 shows an example micropit that is consistent with the particular implementation of the innovations herein;

3A and 3B show exemplary crystal growth methods consistent with particular implementations associated with the innovations herein;

Figure 4 shows an exemplary method for loading a crucible-loaded crucible in a crystal growth furnace that is consistent with the particular implementation of the innovations herein;

Figures 5A through 5D show other example implementations of erbium crystal growth consistent with the particular implementation aspects associated with the innovations herein;

Figure 6 is a flow diagram showing other exemplary methods of crystal growth consistent with the particular implementation aspects associated with the innovations herein.

Claims (84)

A method for growing a single crystal germanium (Ge) crystal in a crystal growth furnace, the crystal growth furnace comprising a heating source, a plurality of heating zones, an ampoule and a crucible, the method comprising: loading a Ge raw material into the crucible; sealing the crucible a vessel; placing the crucible into a crystal growth furnace having a crucible support; melting the Ge material in the crucible to produce a melt; controlling a crystallization temperature gradient of the melt while contacting the melt with the seed crystal; The crystallization temperature gradient and/or movement of the crucible relative to each other to form a single crystal germanium ingot; and cooling the single crystal germanium ingot; wherein reproducibly providing a body length of about 200 mm and a micro-pit density , MPD) a single crystal germanium ingot greater than about 0.025/cm ² and less than about 0.51/cm ² , and wherein the single crystal germanium ingots are subjected to vertical gradient freeze (VGF) and vertical Brinell ( Vertical Bridgman, VB) program growth. The method of claim 1, wherein a single crystal germanium ingot having a micropit density greater than about 0.025/cm ² and less than about 0.26/cm ² is provided. The method of claim 1, wherein a single crystal germanium ingot having a micropit density greater than about 0.025/cm ² and less than about 0.13/cm ² is provided. The method of claim 1, wherein a single crystal germanium ingot having a pit density of less than about 0.13/cm ² is provided. The method of claim 1, wherein a single crystal germanium ingot having a micropit density greater than about 0.05/cm ² and less than about 0.26/cm ² is provided. The method of claim 1, wherein a single crystal germanium ingot having a carrier concentration of from about 1 x 10 ¹⁷ to about 4 x 10 ¹⁸ /cm ³ is additionally provided. The method of claim 1, wherein a single crystal germanium ingot having a resistivity of from about 5 x 10 ^-3 to about 2 x 10 ^-2 Ω·cm is provided. The method of claim 1, wherein a single crystal germanium ingot having an additional mobility of from about 1100 to about 250 cm ² /Vs is provided. The method of claim 1, wherein the crystal system is subjected to a vertical gradient freeze (VGF) procedure at a cooling rate of from about 0.1 to about 10 ° C/hr and from about 0.5 to about 10 ° C/cm. Growth between temperature gradients. The method of claim 1, wherein the crystal system has a cooling rate of from about 0.1 to about 10 ° C/hr and a temperature gradient of from about 0.5 to about 10 ° C/cm via a vertical Bridgman (VB) procedure. Under growth. The method of claim 1, wherein a single crystal germanium ingot having an additional dislocation density of less than about 300/cm ² or less than about 100/cm ² is provided. The method of claim 1, wherein the crystal growth furnace comprises a structure constructed to generate a movable temperature gradient; and wherein a controller is coupled to the crystal growth furnace, the controller controls the movable temperature gradient to The crucible is placed on the crucible when it is in the furnace Crystal growth program. The method of claim 12, wherein the movable temperature gradient is obtained by controlling a plurality of heating zones. The method of claim 12, wherein the moving temperature gradient is achieved via relative movement of one or more of a heat source, the crucible, the ampoule, and/or the crucible support. The method of claim 12, wherein a fixed heating source is controlled to move the crystallization temperature gradient relative to the fixed crucible to melt the material and reform it into a single crystal compound, and to grow in a predetermined crystal The length is subjected to a crystal growth process on the crucible, wherein the temperature gradient is moved relative to the fixed crucible to continuously melt the material and recombine it into a single crystal compound. The method of claim 12, further comprising a fixed heating source. The method of claim 12, wherein the crystal growth furnace holds a crucible having a tapered crystal growth region of from about 25 mm to about 50 mm. The method of claim 1, further comprising adding arsenic (As), gallium (Ga), and/or antimony (Sb) as a dopant to the germanium crystal. The method of claim 1, wherein the crystal growth furnace produces a crystal ingot having uniform electrical and physical properties. A method of crystal growth of a ruthenium comprising: inserting an ampoule having a seed crystal and a raw material into a furnace configured to provide a movable temperature gradient to the crucible in the crucible; growing the crystal using a vertical gradient solidification (VGF) program Wherein the crystallization temperature gradient from the heat source moves relative to the lanthanide system to melt the material and recombine it into a single crystal compound; and grows on the ampule in the furnace using a vertical Brinell procedure with a predetermined crystal growth length The crystal, wherein the ampoule is moved relative to the fixed heating source to continuously melt the material and recombine into a single crystal compound; wherein the micropore density is reproducibly provided to be greater than about 0.025/cm ² and less than about 0.51/cm ² Single crystal germanium ingots, and wherein the ingots are grown by vertical gradient solidification (VGF) and vertical Brinell (VB) procedures. The method of claim 20, wherein the movable temperature gradient is obtained via a plurality of heating zones. The method of claim 20, wherein a single crystal germanium ingot having a micropit density greater than about 0.025/cm ² and less than about 0.26/cm ² is provided. The method of claim 20, wherein a single crystal germanium ingot having a micropit density greater than about 0.025/cm ² and less than about 0.13/cm ² is provided. A method of claim 20, wherein a single crystal germanium ingot having a pit density of less than about 0.13/cm ² is provided. A method of claim 20, wherein a single crystal germanium ingot having a micropit density greater than about 0.05/cm ² and less than about 0.26/cm ² is provided. The method of claim 20, further comprising adding arsenic (As) as a dopant to the germanium crystal. For example, the method of claim 20, which additionally includes gallium (Ga) is added as a dopant to the germanium crystal. The method of claim 20, further comprising adding bismuth (Sb) as a dopant to the ruthenium crystal. The method of claim 20, wherein the crystal system is subjected to a vertical gradient solidification (VGF) procedure at a cooling rate of from about 0.1 to about 10 ° C/hr and between about 0.5 to about 10 ° C/cm. Growth under temperature gradient. The method of claim 20, wherein the crystal system is grown via the vertical Brinell (VB) program at a cooling rate of from about 0.1 to about 10 ° C/hr and at a temperature gradient of from about 0.5 to about 10 ° C/cm. . The method of claim 20, wherein the crystal growth furnace comprises a structure constructed to generate a movable temperature gradient; and wherein a controller is coupled to the crystal growth furnace, the controller controls the movable temperature gradient to The crucible is subjected to a crystal growth process on the crucible while it is in the furnace. The method of claim 30, wherein the movable temperature gradient is obtained by controlling a plurality of heating zones. The method of claim 30, wherein the moving temperature gradient is achieved via relative movement of one or more of a heat source, the crucible, the ampoule, and/or the crucible support. The method of claim 30, wherein a fixed heating source is controlled to move the crystallization temperature gradient relative to the fixed crucible to melt the material and recombine into a single crystal compound, and grow in a predetermined crystal length The crystal growth procedure is performed on the crucible, wherein the temperature gradient is moved relative to the fixed crucible to continuously melt the material and recombine it into a single crystal compound. The method of claim 30, further comprising a fixed heating source. The method of claim 30, wherein the crystal growth furnace holds a crucible having a tapered crystal growth region having a length of from about 25 mm to about 50 mm. The method of claim 30, wherein the crystal growth furnace holds a crucible having a tapered crystal growth region, and wherein the predetermined crystal growth length is from about 110 mm to about 200 mm above the conical crystal growth region. The method of claim 20, wherein the crystal growth furnace produces a crystal ingot having uniform electrical and physical properties. A single crystal germanium product produced by a method comprising: charging a Ge raw material into a crucible; sealing the crucible; placing the crucible into a crystal growth furnace having a crucible support; and melting the Ge raw material in the crucible Producing a melt; controlling a crystallization temperature gradient of the melt while placing the melt in contact with the seed crystal; forming a single crystal germanium ingot via the crystallization temperature gradient and/or movement of the crucible relative to each other; and cooling the a single crystal germanium ingot; wherein the product comprises a crucible from a single crystal germanium ingot prepared by the method to reproducibly provide a micropit density (MPD) greater than about 0.025/cm ² and less than about 0.51/cm ² , and wherein The ingots are grown by vertical gradient solidification (VGF) and vertical Brinell (VB) procedures. The product of claim 39, wherein a single crystal germanium ingot having a micropit density greater than about 0.025/cm ² and less than about 0.26/cm ² is provided. The product of claim 39, wherein a single crystal germanium ingot having a micropit density greater than about 0.025/cm ² and less than about 0.13/cm ² is provided. The product of claim 39, wherein a single crystal germanium ingot having a micropit density of less than about 0.13/cm ² is provided. A product of claim 39, wherein a single crystal germanium ingot having a micropit density greater than about 0.05/cm ² and less than about 0.26/cm ² is provided. The product of claim 39, wherein the single crystal germanium ingot is formed using arsenic (As) as a dopant of the germanium crystal. The product of claim 39, wherein the single crystal germanium ingot is formed using gallium (Ga) as a dopant of the germanium crystal. The product of claim 39, wherein the single crystal germanium ingot is formed using bismuth (Sb) as a dopant of the bismuth crystal. The product of claim 39, wherein the crystal system is subjected to a vertical gradient solidification (VGF) procedure at a cooling rate of from about 0.1 to about 10 ° C/hr and at a temperature of between about 0.5 to about 10 ° C/cm. Growth under gradient. The product of claim 39, wherein the crystal system is grown via a vertical Brinell (VB) procedure at a cooling rate of from about 0.1 to about 10 ° C/hr and at a temperature gradient of from about 0.5 to about 10 ° C/cm. The product of claim 39, wherein the crystal growth furnace comprises a structure constructed to produce a movable temperature gradient; and wherein a controller is coupled to the crystal growth furnace, the controller controls the movable temperature gradient to The crucible is subjected to a crystal growth process on the crucible while it is in the furnace. The product of claim 49, wherein the movable temperature gradient is obtained by controlling a plurality of heating zones. The product of claim 49, wherein the moving temperature gradient is achieved via relative movement of one or more of a heat source, the crucible, the ampoule, and/or the crucible support. The product of claim 49, wherein a fixed heating source is controlled to move the crystallization temperature gradient relative to the fixed crucible to melt the material and recombine into a single crystal compound, and at a predetermined crystal growth length A crystal growth procedure is performed on the crucible, wherein the temperature gradient is moved relative to the fixed crucible to continuously melt the material and recombine it into a single crystal compound. The product of claim 49, which additionally comprises a fixed heating source. The product of claim 49, wherein the crystal growth furnace holds a crucible having a tapered crystal growth region, and wherein the predetermined crystal growth The length is from about 25 mm to about 50 mm above the cone crystal growth zone. The product of claim 49, wherein the crystal growth furnace holds a crucible having a tapered crystal growth region, and wherein the predetermined crystal growth length is from about 150 mm to about 200 mm above the conical crystal growth region. The product of claim 39, wherein the crystal growth furnace produces a crystal ingot having uniform electrical and physical properties. An apparatus for crystal growth of a crucible, comprising: a crystal growth furnace comprising a heating source and a plurality of heating zones; and an ampoule configured to be loaded into the furnace, wherein the ampoule comprises a loading vessel and has a seed well And an controller that is coupled to the crystal growth furnace and the ampoule support, the controller controls one or more heating zones of the heating source and the movable ampoule support to be a vertical gradient solidification procedure is performed on the crucible when located in the furnace; wherein the crystallization temperature gradient and/or the lanthanide system moves relative to each other to melt the material and then recombine the material into a single crystal ruthenium ingot; A vertical growth procedure is performed in the apparatus that reproducibly provides tantalum ingots having a pit density greater than about 0.025/cm ² and less than about 0.51/cm ² , and wherein the ingots are solidified by vertical gradient (VGF) And vertical Brinell (VB) program growth. The apparatus of claim 57, wherein the apparatus comprises at least one heating source that is controlled to cause the crystallization temperature gradient Moving relative to the fixed crucible to melt the material and recombining it into a single crystal compound, and performing a crystal growth process on the crucible with a predetermined crystal growth length, wherein the temperature gradient is moved relative to the fixed crucible to continue melting The raw materials are recombined into a single crystal compound. The apparatus of claim 57, wherein the apparatus reproducibly provides an ingot growth temperature gradient for growing a tantalum ingot of about 0.5 degrees Celsius to about 10 degrees per centimeter of ingot. The apparatus of claim 57, which is additionally constructed to cool the crucible ingot at a rate of from about 0.1 to about 10 ° C per hour. The apparatus of claim 57, wherein the crystal growth furnace has 5 to 7 heating zones. The apparatus of claim 57, wherein the crystal growth furnace has six heating zones. The apparatus of claim 57, further comprising a loading container having a crucible loading material, the crucible material being melted in the crucible to provide a larger amount of the crucible material to the crucible. The apparatus of claim 57, wherein the tether is maintained stationary during the movement of the crystallization temperature gradient. The apparatus of claim 57, wherein the bismuth ingot has a diameter of between about 50 mm and about 150 mm. The apparatus of claim 65, wherein the bismuth ingot has a diameter of about 150 mm. A method for growing a single crystal germanium (Ge) crystal in a crystal growth furnace, the crystal growth furnace comprising a heating source, a plurality of heating zones, an ampoule and a crucible, the method comprising: loading a Ge raw material into the crucible; sealing the crucible a vessel; placing the crucible into a crystal growth furnace having a crucible support; melting the Ge material in the crucible to produce a melt; controlling a crystallization temperature gradient of the melt while contacting the melt with the seed crystal; The crystallization temperature gradient and/or movement of the crucible relative to each other to form a single crystal germanium ingot; and cooling the single crystal germanium ingot; wherein reproducibly providing a micropore density (MPD) greater than about 0.025/cm ² and less than A single crystal germanium ingot of about 0.51/cm ² , and wherein the ingots are grown by vertical gradient solidification (VGF) and vertical Brinell (VB) procedures, at about 3 ° C 5 hours before the cooling procedure. The cooling rate of the hour is cooled while cooling during the rest of the cooling procedure at a cooling rate of from about 30 ° C / hour to about 45 ° C / hour. A method of claim 67, wherein a single crystal germanium ingot having a micropit density greater than about 0.025/cm ² and less than about 0.26/cm ² is provided. A method of claim 67, wherein a single crystal germanium ingot having a micropit density greater than about 0.025/cm ² and less than about 0.13/cm ² is provided. A method of claim 67, wherein a single crystal germanium ingot having a pit density of less than about 0.13/cm ² is provided. A method of claim 67, wherein a single crystal germanium ingot having a micropit density greater than about 0.05/cm ² and less than about 0.26/cm ² is provided. The method of claim 67, further comprising adding arsenic (As) as a dopant to the germanium crystal. The method of claim 67, further comprising adding gallium (Ga) as a dopant to the germanium crystal. The method of claim 67, further comprising adding bismuth (Sb) as a dopant to the ruthenium crystal. The method of claim 67, wherein the crystal system is subjected to a vertical gradient solidification (VGF) procedure at a cooling rate of from about 0.1 to about 10 ° C/hr and a temperature of between about 0.5 to about 10 ° C/cm. Growth under gradient. The method of claim 67, wherein the crystal system is subjected to a vertical Brinell (VB) procedure at a cooling rate of from about 0.1 to about 10 ° C/hr and a temperature gradient between about 0.5 and about 10 ° C/cm. Growing. The method of claim 67, wherein the crystal growth furnace comprises a structure constructed to generate a movable temperature gradient; and wherein a controller is coupled to the crystal growth furnace, the controller controls the movable temperature gradient to The crucible is subjected to a crystal growth process on the crucible while it is in the furnace. The method of claim 77, wherein the movable temperature gradient is obtained by controlling a plurality of heating zones. The method of claim 77, wherein the moving temperature gradient is achieved via relative movement of one or more of a heat source, the crucible, the ampoule, and/or the crucible support. The method of claim 77, wherein a fixed heating source is controlled to move the crystallization temperature gradient relative to the fixed crucible to melt the material and recombine into a single crystal compound, and at a predetermined crystal growth length A crystal growth procedure is performed on the crucible, wherein the temperature gradient is moved relative to the fixed crucible to continuously melt the material and recombine it into a single crystal compound. The method of claim 77, further comprising a fixed heating source. The method of claim 77, wherein the crystal growth furnace holds a crucible having a tapered crystal growth region of from about 25 mm to about 50 mm. The method of claim 77 or 82, wherein the crystal growth furnace holds a crucible having a tapered crystal growth region, and wherein the predetermined crystal growth length is from about 110 mm to about 200 mm above the conical crystal growth region. The method of claim 67, wherein the crystal growth furnace produces a crystal ingot having uniform electrical and physical properties.