TW201224228A - Germanium ingots/wafers having low micro-pit density (MPD) as well as systems and methods for manufacturing same - Google Patents

Abstract

Systems and methods are disclosed for crystal growth including features of reducing micropit cavity density in grown germanium crystals. In one exemplary implementation, there is provided a method of inserting an ampoule with raw material into a furnace having a heating source, growing a crystal using a vertical growth process wherein movement of a crystallizing temperature gradient relative to the raw material/crucible is achieved to melt the raw material, and growing, at a predetermined crystal growth length, the material to achieve a monocrystalline crystal, wherein monocrystalline ingots having reduced micro-pit densities are reproducibly provided.

Description

201224228 VI. Description of the Invention: [Technical Fields of the Invention] The systems and methods herein relate generally to single crystal germanium ingots/wafers, particularly to the growth of such ingots/wafers having reduced micropit density (MPD). . [Prior Art] Electronic and optoelectronic device fabrication routinely requires a commercially large, uniform and uniform semiconductor crystal that provides a substrate for microelectronic device fabrication during slicing and polishing. The growth of the semiconductor crystal involves heating the material to its melting point to produce a crystalline material 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 Chai (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) program. See, for example, "Buik Crystal Growth of Electronic, Optical and Optoelectronic Materials", P. Clapper, ed., 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 (prayer) along the vertical axis by seeding under the crystallization material. Equipment for forming semiconductor crystals must include crystal growth furnaces, rice, vortex, and sometimes 拍·5-201224228 埚 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 used 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. SUMMARY OF THE INVENTION Systems and methods consistent with the present invention relate to the growth of single crystal germanium. In an exemplary implementation, a method of inserting an ampoule 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 material/rhodium is obtained to melt the material and melt the material. 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 prayer having a reduced pit density is reproducibly provided. It is to be understood that the foregoing description of the invention and the claims Other features and/or variations may be provided in addition to the features and/or variations described herein. For example, the present invention may be variously combined and sub-combined with respect to various different combinations and sub-combinations of the disclosed features and/or various other features disclosed in the Detailed Description.

S -6 - 201224228 [Embodiment] Reference is made in detail to the present invention, and examples thereof are illustrated in the accompanying 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 specific 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. Figure 1 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 raft support, the ram support 22 provides physical support and enables thermal gradient control of the ampoules 26 (which may be made of quartz in one embodiment) that accommodate the rafts 27. In some implementations, during the crystal growth procedure, the support 22 can be moved while the furnace is in operation. In other implementations, the ankle support can be fixed and the furnace in operation can be moved during the crystal growth procedure. The vortex vortex 27 can accommodate 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 201224228 bulk 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. Current industry standard crystals are 2 inches, 3 inches, 4 inches, 5 inches, 6 inches and 8 inches ingots that 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 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 may be formed of a quartz material. Ampoule 26 typically has a shape similar to 埚 埚 27. The crucible may be cylindrical in the crystal growth zone 4, which is a cylindrical shape 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 to the inside of the ampoule 26 with a narrow boundary therebetween. The bottom of the crystal seed well area 42 of the Anzhen 26 series is closed, and

S -8 - 201224228 If the crucible is sealed to the top of 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 crucible ingot having a micropore density having a range of greater than about 〇.〇25/cm2 and less than about 0_51/cm2; greater than about 0.025/cm2 and less than about 0.26/cm2; greater than about 0.025/cm2 is reproducibly provided. And less than about 0.13/cm2; less than about 0.13/cm2; and greater than about 〇.〇25/cm2 and less than about 0.26/cm2. In addition, the pit density can be further controlled (decreased) by controlling the cooling rate and other conditions. In an exemplary implementation, during the growth of the crystal through the vertical gradient solidification (VGF) process, the controller coupled between the crystal growth furnace and the ampoule support can be cooled from about 1 to about 1 〇 ° C / hour. The rate and temperature gradient between about 5 and about 10 ° C / C m cools the interface between the growing single crystal/combination 201224228 30 and the original molten material 32. In other example implementations, the controller may have a cooling rate of from about 0.1 to about 10 ° C/hr and a temperature gradient of from 0.5 to 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 is cooled. In yet another example implementation, the controller may be 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 grown single crystal / compound 30 and the original molten material 3 2 The interface between the two. Returning to the example system of Figure 1A above, the ampoule and crucible may have a tapered (funnel) zone. The ampoule-twist combination has a funnel shape, and the support body 22 accommodates the funnel shape and maintains the ampoule 26 in the furnace 24 to be stable and upright. 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 embodiments, the stability and strength of the ampoule and its contents are provided by the solid thin-walled cylinder 50 of the crucible support 22. The solid thin-walled cylinder 5 〇 accommodates the amp; the funnel end of the 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 may also be used to form the crucible support cylinder 50. The cylinder 50 is in circular contact with the ampoule 26 wherein the upper edge of the cylinder 50 contacts the shoulder of the tapered region 38 of the ampoule. This configuration results in minimal solid-solid contact, which does allow little or no uncontrolled heat transfer. Therefore, heating can be produced by other more controllable methods.

S -10- 201224228 In other implementations, a low density insulating material, such as a ceramic fiber, replenishes most of the interior of the support cylinder 50, only the hollow shaft core 52 at approximately the center of the insulating material remains clear to receive the seed well of the ampoule 26 42. In other implementations, the low density insulating material may also comprise alumina fibers (1800 ° C), alumina-yttria fibers (1426 Å:), and/or chromia fibers (22 00 ° 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 low density insulators to reduce air flow, which does cause little or no unwanted uncontrolled convection. Thermal conduction methods such as conduction and convective uncontrollable methods may be detrimental to VGF/VB and other crystal growth procedures herein. As shown in the exemplary system of Figure 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 that of 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. Under these conditions, crystals having uniform electrical properties cannot be produced. In the embodiment -11 - 201224228 having a hollow core 52 included in the crucible support method, the thermal energy is conducted downward 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 crystal in the growth 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. Thus 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 passage 56 through the insulating material also cooperates with the hollow core 52 in the center of the insulating material to radiate heat energy from the center of the crystal and to cool the crystal having a flat isothermal temperature gradient layer. The radiation channel 56 enables temperature control and is directly related to crystal growth rate. The furnace 24 shown in Fig. 1A is a furnace which 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 program, when the crystal remains fixed, it moves in a junction that is itself a fixed heat source.

S -12- 201224228 Crystal temperature gradient. 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 process, 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 Figure IB, 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 that is consistent with the particular implementation of the innovations herein. According to such implementations, an exemplary method can include loading a Ge feedstock into a vortex (280), sealing the crucible and/or holding the crucible vessel (282), placing the crucible into a crystal growth furnace, and melting the Ge material in the crucible. The melt is produced and a vertical growth process is performed to form a single crystal germanium ingot (284). In addition, the method may include one or more additional steps including controlling the crystallization temperature of the melt from -13,224,228 gradients upon contact of the melt with the seed crystal, movement relative to each other via crystallization temperature gradients and/or enthalpy To form a single crystal germanium ingot, and to cool the single crystal germanium ingot. 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/cm2 and less than about 0.51/cm2; greater than about 0.025/cm2 and less than about 2626/cm2; greater than about 0.025/cm2 and reproducibly provided. Less than about 0.13/cm2; less than about 1313/cm2; and greater than about 0.025/cm2 and less than about 0.26/cm2. In some example implementations, the pit density can be controlled by controlling the rate of cooling and other conditions. Further, the single crystal substrate according to the innovation herein may have a carrier concentration of about 9 X 1017 to about 4 X 1 〇 18 or about 5 X 10 18 /cm 3 from the beginning growth portion to the end of the growth portion, and about 7 X 10·3. To 2 X 10·3 or 3 X 1 (T3 Q.cm resistivity, mobility of from about 950 cm 2 /Vs to about 450 cm 2 /Vs » further, the dislocation density may be less than about 500/cm 2 , or even less than about 200/cm2. Carrier concentration, shift and dislocation 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 lxlO17 to about 4X1018. /cm3, a resistivity of about 5χ1 (Γ3 to about 2xl (T2 n.cm, and/or a p-type germanium single crystal ingot/wafer of 200 mm having a mobility of about 1100 to about 250 cm2/Vs. Further, according to In some implementations, a 200 mm ingot having a dislocation density of less than about 300/cm2 can be grown. Figure 3B shows another exemplary method 80 for growing crystals using vertical gradient solidification (VGF) and vertical Brinell (VB) program steps, such The procedural steps reduce the density of the micropits and result in higher yields, which are consistent with the particular implementation of the innovations herein. Crystal growth process, for preparing

S -14 - 201224228 The above crystal growth furnace (82). To initiate crystal growth from the seed crystal, the VGF program (84) was used. At a particular point in the crystal growth procedure, a VB program (86) or a VBS program can be used to complete the crystal growth. When using the VB or VBS program, keep the melt/solid line at a level and then continue the process in a fixed condition, which is usually required because the volume of the VGF program is not required to be reduced. In an illustrative implementation, for example, about 12 mm to about 15 mm (about 1/2 inch), about 12 mm to about 45 mm, or more (such as about 30 mm) above the tapered region 38 as shown in FIG. 1A. Use the VB program up to approximately 45 mm). Consistent with the implementation and experimental results herein, the combination of VGF and VB procedures results in a better crystal with fewer pits. 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, in accordance with the example innovations herein, 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 krypton is proposed. 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. In addition, due to these vertical growth procedures, tantalum ingots having reduced quantum pit density are reproducibly provided. For example, a crucible ingot having a micropore density having a range of greater than about 0.025/cm2 and less than about 0.51/cm2; greater than about -15 to 201224228 0.02 5/cm2 and less than about 0.26/cm2; greater than about is reproducibly provided. 0.02 5/cm2 and less than about 0.13/cm2; less than about 1313/cm2; and greater than about 0.025/cm2 and less than about 0.26/cm2. As described elsewhere herein, such pit density can be controlled by controlling the rate of cooling and other conditions. 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 from about 0.1 to about 10 ° C / hour and between about 0.5 to about 10 ° C / cm Cooling procedure performed between temperature gradients. In other example implementations, the method can include a vertical Brinell (VB) procedure 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. Crystal growth. In other example implementations, the crystal growth method can include crystal growth/cooling, including cooling via a vertical gradient solidification (VGF) program and/or via a vertical Brinell (VB) program at a cooling rate of about 3 ° C/hour. The first 5 hours, and the remaining period of the cooling process is cooled at a cooling rate of about 30 ° C / hour to about 45 ° C / hour. As shown in FIG. 4, the loading cassette 90 can be located above the crucible 27, and the crucible 27 is made Can load more raw materials. In particular, the crucible material 92 is solid and therefore cannot be stacked tightly on the crucible 27 to be melted. Thus, the loading crucible 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 niobium crystal. For example, from about 35 to about 65% of the starting material can initially be charged to the loading crucible 90, and from about 65 to about 35% of the stock material can be directly charged to the crucible 27. For example, consistent with some of the crystal growth methods herein, about 10 kg of feed can be loaded into the furnace to

S -16- 201224228 This is a 200 mm 4 inch ingot with a low pit density. 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 10 〇mm and A crystal growth zone 40 having a length of 200 mm. 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, first The seed crystal was inserted into the bottom portion of the PBN crucible 27. Next, about 10 kg of the crucible material was placed, and about 36 g of boron oxide was added as a liquid sealant. Then, the PBN crucible loaded with the feed was inserted into the quartz ampoule. The quartz ampoule is sealed with a quartz lid 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, it can be heated at a rate of about 150 to 200 ° C / hour. Quartz ampoule. 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 is maintained until All single crystal coffins The material is melted (for example, in some embodiments, about 2 to 4 hours). Once the single crystal germanium material is melted, the VGF method is used for crystal growth. This temperature can be slowly lowered in the lower temperature heating zone to allow the seed crystal to be crystallized. Partially the initial crystal growth begins and continues through the transition zone until the crystal growth zone is cooled. When associated with the VGF and/or VB process, after the crystal growth procedure is completed, the cooling is cooled at a cooling rate of about 3 ° C / hr. The remaining period of the cooling procedure is cooled at a cooling rate of about 30 hr. (: /hr to about 4 5 t / hr. In other example implementations, 'crystal growth cooling can be from about 0.1 to about 1 〇. (: The cooling rate of /hour and the -17-201224228 temperature gradient between about 0.5 and about 10 °C/cm occur (for example, in association with the VGF program). In addition, in the example VB program, 0.3 can be used. The crystal growth cooling rate to 0.47 ° C / hour while maintaining the temperature gradient at 1.2 to 1.8 ° C / cm. According to some examples herein combined with the VGF and VB procedures, when the crystal growth region has grown about 1 in the crystal growth region Up to about 3 miles The VB program can be started. In the VB program, the helium falling speed is controlled to make the cooling/growth parameters in the crystal growth region accurate, such as a cooling rate of about 0.2 to about 0.5 ° C / hour and / or a temperature gradient of 0.3 to About 2.5 ° C / cm. Through this procedure, crystals of about 190 mm in length and high quality (ie, low pit density or "low MPD") can be obtained from a 200 mm elongated ingot, and the crystal yield is about 95%. By such methods, a bismuth ingot having a micropore density of the following range is reproducibly provided: greater than about 0.025/cm2 and less than about 0.51/cm2; greater than about 0.025/cm2 and less than about 0.26/cm2; Greater than about 0.02 5/cm 2 and less than about 0.1 3 /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 1017 to about 4 X 1018 or about 5 X 1018/cm 3 from the starting growth portion to the end of the growth portion (measured from about 9 X 1017 to about 4.86 X 1018). The carrier concentration of the range of /cm3, and about 7 X 1 〇 3 to 2 X 10·3 or 3 X 1 〇 _3 Q.cm (measured to be 7.29 X 1 〇 · 3 to about 2.78 X 10 · The resistivity of 3 Ω.cm.) has a mobility of about 950 cm2/Vs to about 450 cm2/Vs (after measuring 95 5 cm2/Vs and 467 cm2/Vs). Furthermore, the dislocation density can be less than about 500/cm2, or even less than about 200/cm2. In conjunction with Figures 4 through 5, there are provided systems and methods for growing single crystal germanium (Ge) crystals in which once the raw material feed has melted but crystal growth

S •18- 201224228 Before the start, additional feedstock melt can be added to the vortex (for example, in VGF and/or VB procedures, etc.), thus allowing the growth of longer single crystal ingots. 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 exemplary 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 exemplary implementations can include controlling the crystallization temperature gradient of the melt to crystallize and form a single crystal ruthenium ingot upon contact of the melt, and optionally cooling the single crystal ruthenium ingot. In an exemplary implementation, the step P of forming a single crystal germanium ingot may include producing a temperature gradient of from about 0.3 to about 2.5 ° C/cm in the crystal growth zone. 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 in the following ranges of micropits. Density: greater than about 〇.〇25/cm2 and less than about 0.51/cm2; greater than about 0.025/cm2 and less than about 0.26/cm2: greater than about 0.025/cm2 and less than about 0.13/cm2; less than about 0.13/cm2; Greater than about 0.025/cm2 and less than about 0.26/cm2. -19- 201224228 Further, 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 about 9 from the beginning of growth to the end of the growth portion. a carrier concentration of x 1〇17 to about 4 x 1〇18 or about 5 x 1018/cm3 (measured in the range of about 9 X 1〇17 to about 4.86 X 1018/cm3), and about 7 X 10·3 to 2 x 10·3 or 3 x 10·3 fi.cm (measured in the range of about 7.29 X 10·3 to about 2.78 X 10_3 Q.cm, mobility of about 950 cm2/Vs to about 450 cm2/ Vs (measured to 955 cm2/Vs and 467 cm2/Vs). In addition, the 'dislocation density can be less than about 500/cm2' or even less than about 200/cm2. » About the system consistent with the innovations in this paper, for large growth An exemplary apparatus for a single crystal germanium crystal may comprise a crystal growth furnace comprising a heating source and a plurality of heating zones, the ampoule being constructed into the furnace, wherein the ampoule comprises a loading vessel and a seedling well, a movable ampoule a support and a controller coupled to the crystal growth furnace and the movable ampoule support. In addition, the controller can control the heating source One or more heating zones and the drivable ampoule support for performing a vertical gradient solidification procedure on the crucible when the crucible is in the furnace. According to a particular implementation, the crystal growth furnace may have a plurality of heating zones, such as 4 to 8 heating zones, between 5 and 7 heating zones, or 6 heating zones. Depending on the desired ingot/wafer diameter, the sample 坩埚 can have a range of from about 50 mm to about 200 mm (about 2 to about 8 inches), or in some implementations, having a diameter of about 150 mm (about 6 inches). Figures 5A through 5D show other example implementations of erbium crystal growth, which are specific implementations related to the innovations herein. The state is consistent. Figures 5A to 5 D are used for students.

S -20- 201224228 A longitudinal section view of an apparatus for long single crystal germanium crystals illustrating an exemplary crystal growth procedure consistent with a particular embodiment of the present invention. Fig. 5A shows a sectional view device 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, e.g., 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 1 1 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 crystal in the seed well 18. When the furnace is in operation, the ampoule support 11 can move axially during the crystal growth process.坩埚1 2 can hold the seed crystal 17 and grow a single crystal formed on the top of the seed crystal from the seed crystal 17. 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 inches) diameter ingots that can be cut into wafers. In an illustrative implementation, at the bottom of the crucible I2, the seed well cylinder 18 has a closed bottom and is slightly larger in diameter than the high quality seed crystal 17, for example about 6 to 25 mm' and has a length of about 30 to 1 mm. The cylindrical crystal growth portion 13 and the seed well cylinder 18 may have a straight wall ' or may be outwardly reduced by about 1 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 wall equal to the growth zone wall and attached to the growth zone wall. The large diameter and the narrower diameter of the seed well wall and connected to the seed well wall. In other implementations, the angled sidewalls may 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 having 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 raw material melts and drip from the bottom hole of the second container 4 into the main crucible 12. The bottom of the crystal seed well zone 19 of the Ampoule 3 is closed and the top of the material is sealed after the crucible and the raw material 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 allow little or no controllable heat transfer. Therefore, heating can be produced by other more controllable methods. In an example implementation of the innovation of this paper, the growth order of single crystal bismuth ingots

S -22- 201224228, can be about 〇 2 to about 0 · 5. The rate of (: / hour is lowered to increase the temperature of the single crystal to grow the single crystal. The sequence of Figures 5 to 5D shows the other examples of the growth procedure 'which includes the characteristics of melting and supplying enthalpy. Figure 5A shows the initial state of the sample procedure in which the solid lanthanide is present in both the upper vessel 4 and the citrus 12. As an innovative heating feature and procedure, the intermediate state of the mash is then shown in Figure 5, which The solid state is shown to be in a molten liquid state in the crucible 12. The heating elements of the heating zone of the furnace can be adjusted in association with the individual power supply, thereby providing the desired thermal energy to the upper vessel. More specifically, 'heatable The upper container is such that the crucible in the upper container 4 begins to melt, and the molten crucible flows into the crucible 12 through the hole in the bottom of the container 4. In an exemplary embodiment, the area of the furnace in which the upper container is present is heated to about 940 to Approximately 955 degrees Celsius, or 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 through 5D is available for vertical ladders. An example of a furnace for solidification (VGF) crystal growth procedures. Other furnaces and configurations, such as vertical Brinell. In the VGF crystal growth program, the crystallization temperature in a fixed heat source is electrically moved while the crystal remains stationary. Gradient. 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 Cooling to meet the crystallization temperature and temperature gradient requirements of the furnace. For the growth of bismuth ingots, for example, the furnace temperature fluctuations may need to be less than about ± 0.11. During the preparation of the furnace -23-201224228 'more details elsewhere herein Explain that the ruthenium polycrystalline material is loaded into the ampoule 3. As shown in the figure, the pBN loading container 4 having the hole in the tapered portion is placed on the support made of quartz above the crucible 12 in the ampoule 3. 6. 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 centered on the bottom surface having a taper that extends toward the ampoule 3. The crucible 3 may have an opening for receiving molten crystal dripping from a hole in the center of the bottom of the second container 4. The loading container 4 allows the crucible 12 to be loaded with more material. In particular, the crucible material 5 is usually a solid thick pile or The pieces are therefore not stacked tightly on the crucible 12 to be melted. Therefore, the loading container is used to hold additional material that can be melted and discharged into the crucible 12, which forms a larger crucible feed in the crucible 12. Then, a larger length and diameter of the ruthenium crystal is formed. For example, about 65 % of the raw material can be initially charged into the loading capacitor 4, and 3 5% of the raw material is directly charged into the crucible 12. As a non-limiting example, A raw material feed of 5.1 15 kg was carried in crucible 12 and a feed of 9.8 8 5 kg was carried in loading vessel 4 to form 1 5000 g (15 kg) which produced a 150 mm (6 inch) diameter crucible ingot. Feeding In one example, the crucible can be doped with arsenic (As). Here, for example, a 9° offset orientation <1〇〇> seed crystal can be loaded into the crucible prior to loading the feed. The feedstock feed and the appropriate amount of dopant are loaded into the crucible and loaded into a loading vessel placed in the quartz ampoule 3. The ampoule and contents were evacuated to a vacuum of about 2.00 X 1 〇 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 ampule and contents are heated to melt the material in the crucible 12. During this growth period,

S -24 - 201224228 Since the melting point of bismuth is about 940 °C, the furnace is at a temperature of about 1 000 °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. In addition, 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(R) ingots formed from such exemplary procedures herein are reproducibly providing micropore densities having a range of greater than about 0.025/(;1112 and less than about 0.51/〇1112; greater than about 0.025/〇1112 and less than about 0.26/cm2; greater than about, 0.025/cm2 and less than about 0.13/cm2; less than about 0.13/cm2; and greater than about 0.025/cm2 and less than about 0.26/cm2. In other examples, the apparatus of the present invention is made of quartz. The ampoule is configured to insert a pBN loading container and a crucible therein, and the support 6 is used to fix the PBN loading container. With regard to the exemplary size, the crucible may have a diameter of about 150 mm in the crystal growth section for crystal growth. The segment may have a length of about 160 mm' and a diameter of about 7 mm in the seed segment. In an exemplary implementation, '<100> oriented Ge seed crystals are inserted into the pBN坩埚 seed well and 96 g Boron trioxide as a liquid sealant was placed in the pBN crucible above the seed crystal. Then, a total of 14,974 g of Ge polycrystalline material was loaded into the PBN crucible and the pBN container, and both the pBN container and the crucible were inserted into the quartz. Ampoule 'and the quartz ampoule in about 2_00 X 1 Sealed with a quartz cap under a reduced pressure of -4 Pascals (1.5 x 10·6 Torr). The sealed ampoule was then placed in a furnace and placed on an ampoule support. The above quartz ampoule was approximately 270. (: / Heating at an hourly rate. 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. -25 - 201224228 As shown in Figure 6, it is disclosed for growth in accordance with the innovations herein. An exemplary method of a single crystal germanium (Ge) crystal. In an example implementation, a method is provided for loading a first Ge material into a seed crystal comprising a seed crystal containing a seed crystal, and loading the second Ge material a container for replenishing the raw material to be placed in the ampoule, sealing the crucible and the container in the ampoule 'and placing the ampoule with the crucible and the container therein in a crystal growth furnace' to control the melting of the Ge material in the crucible Controlling the melting of the second Ge material in the vessel to produce a melt. Further, the methods may include controlling the melted second Ge material to be added to the melt, controlling the crystallization temperature gradient of the solution to cause seeding Connect The melt crystallizes and forms a single crystal germanium ingot, and cools one or more of the single crystal germanium ingots. Other example implementations can include controlling the melting of the second Ge feedstock in the vessel, including control applied to The heat of the second Ge feedstock and maintenance maintains the molten second Ge feedstock within a temperature range. Further, controlling the molten second Ge feedstock to be added to the melt can include maintaining the melt at a specified temperature range The range may 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, single crystal germanium ingots having reduced micropit density (e.g., in any of the other ranges shown herein) are reproducibly provided for such program control.

S -26- 201224228 Further, by the procedure shown herein, a germanium crystal having a pit density in the above various ranges is 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 avoid such as 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, it is reproducibly provided with a germanium having a dislocation density within the above various ranges without using a doping technique of a contact doping technique and/or 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, such a cooling rate can be maintained for about 7 hours. Once the crystallization reaches the main growth zone, the heater power in the appropriate zone can be reduced to provide a cooling rate of about 0.4 to about 0.7 ° C / hour, and the crystallization interface The temperature gradient is from 1.2 to about 3.0 ° C/cm, both of which can be maintained 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 body of the ingot is formed to have a length of 125 mm and is 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 a density of from about 9 X 1017 to about 4 X 1018 or about 5 X 1018/cm3 (measured from about 9 X 1017 to about 4.86). The free carrier concentration of X l〇18/cm3 range -27- ' 201224228 ), and 7 χ 10·3 to 2 x 10_3 or 3 χ 10·3 Ω.cm (measured to be 7.29 x 10·3 to approximately 2.78 x 1 (the range of T3 Q.cm) has a mobility of about 950 cm2/Vs to about 450 cm2/Vs (measured between 955 cm2/Vs and 467 cm2/Vs). In addition, the dislocation density It may be less than about 500/cm2, less than about 200/cm2, or even less than about 1 〇〇/cm 2. In still other VGF methods, according to the 200 mm long ingot growth procedure in a particular example, the lowest heating zone may be lowered first. The heater power is used to initiate crystal growth at the seed crystal, and then the heater power can be lowered in the transition zone, wherein the cooling rate can be set from about 0.1 to about 0.3 ° c / hr. In addition, the cooling rate can be maintained About 70 hours. Once the crystallization reaches the main growth zone, the heater power in the appropriate zone can be reduced to provide about 0.4 to about 0.7 ° C / small The cooling rate, and the crystallization interface temperature gradient is from I.2 to about 3 · 0 ° C / cm, both of which can be maintained for about 170 hours. After the crystallization is completed, it can be from about 20 to about 40 ° C / hour. The furnace is cooled at a cooling rate until it reaches room temperature. Here, the body of the ingot is formed to have a length of 200 mm and is completely single crystal. Such crystals may have, for example, low pits from the beginning of growth to the end of the growth portion. Density, and may also have a free carrier concentration of about 4 X 1017 to about 6 X 1 〇 18 or about 5 X 1018 / cm 3 (measured in the range of about 4.34 X 1017 to about 5.98 X 1018 / cm 3 ), and 2 X 1 (Γ2 to 4 X 10_3 or 3 X 10_3 Ω-cm (measured from about 2.02 X 10·2 to about 3.86 X 1 (range of T3 n.cm), mobility of about 800 cm 2 /Vs to about 250 cm2/Vs (measured at 713 cm2/Vs and 271 cm2/Vs). In addition, the dislocation density can be less than about 300/cm2, or even less than about 100/cm2.

-28-S 201224228 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. BRIEF DESCRIPTION OF THE DRAWINGS The accompanying drawings, which are incorporated in FIG. In the drawings: Figures 1A and 1B are cross-sectional views of an exemplary crystal growth apparatus and vortex vortex, which are consistent with the specific implementation aspects of the innovations herein; Figure 2 shows an exemplary micropit associated with the innovations herein Specific implementations are consistent; Figures 3A and 3B show an exemplary crystal growth method that is consistent with the particular implementation of the innovations herein; Figure 4 shows an exemplary method for loading a crucible-loaded crucible into a crystal growth furnace, It is consistent with the specific implementation aspects associated with the innovations herein; Figures 5A through 5D show other example implementations of erbium crystal growth consistent with the particular implementation aspects of the innovations herein; and -29-201224228 Figure 6 shows crystal growth A flow chart of other example methods that is consistent with the particular implementation of the innovations herein. [Description of main component symbols] 20: Crystal growth equipment 22: 坩埚 support 24/1: Furnace 26/3: Ampoule 2 7 / 9 9 /1 2 : 坩埚2 8 /1 7 : Seed crystal 30: Single crystal / Compound 32: Raw molten material 34/13: Cylindrical crystal growth portion 3 6 /1 8 : Seed well cylinder 3 8/44/7/8: Tapered transition portion 40: Crystal growth region 4 2: Seed well region 50/ 16: Cylinder 5 2 : Hollow core 54: Inclined insulating material edge 56: Radiant channel 6 〇: Furnace heating element 90: Loading 坩埚 92: Original 锗 material

S -30- 201224228 2 : Heater 4 : Second upper container 5 : Raw material 6 : Quartz support 1 1 : Ampoule support 1 9 : Seed growth zone -31

Claims (1)

201224228 VII. Patent application scope: 1. 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: Filling the crucible with the raw material; sealing the crucible and the container; placing the crucible into a crystal growth furnace having a crucible support: melting the Ge raw material in the crucible to produce a melt: controlling the crystallization temperature gradient of the melt, and simultaneously The melt is placed 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 single crystal germanium ingot; wherein reproducibly provided with about 200 mm A single crystal crucible having a body length and a micro-pit density (MPD) greater than about 〇.〇25/cm2 and less than about 0.51/cm2. 2. The method of claim 1, wherein the micro-pit is provided A single crystal germanium ingot having a pit density greater than about 0.025/cm2 and less than about 0.26/cm2. 3. The method of claim 1, wherein a single crystal germanium ingot having a micropit density greater than about 〇.〇25/cm2 and less than about 0.13/cm2 is provided. 4. The method of claim 1, wherein a single crystal germanium ingot having a micropore density of less than about 0.13/cm2 is provided. 5. The method of claim 1, wherein a single crystal germanium ingot having a micropit density greater than about 〇.〇5/cm2 and less than about 0-26/cm2 is provided. The method of claim 1, wherein a single crystal germanium ingot having a carrier concentration of from about 1 x 1 017 to about 4 x 1 018 / cm 3 is provided. 7. The method of claim 1, wherein a single crystal germanium ingot having a resistivity of between about 5 x 1 and about 2 x 1 0 2 Ω. cm is provided. 8. The method of claim 1 Providing a single crystal germanium ingot having a mobility of from about 1 100 to about 250 cm 2 /Vs. 9. The method of claim 1, wherein the crystal system is subjected to vertical gradient freeze The VGF) program is grown at a cooling rate of from about 0.1 to about 10 ° C / hour and at a temperature gradient of between about 0.5 and about 10 t / cm. 1 如 as in the method of claim 1 Wherein the crystal system is grown via a vertical Bridgman (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 method of claim 1, wherein a single crystal crucible having a dislocation density of less than about 300/cm2 or less than about 100/cm2 is provided. 12. The method of claim 1, wherein the crystal growth furnace Include a structure that is constructed to produce a movable temperature gradient; Wherein a controller is coupled to the crystal growth furnace, the controller controlling the movable temperature gradient to perform a crystal growth procedure on the crucible when the crucible is located in the furnace. 13. The method of claim 12 The movable temperature-33-201224228 gradient is obtained by controlling a plurality of heating zones. 14. The method of claim 12, wherein the moving temperature gradient is via a heat source, the crucible, the ampoule, and/or Or the relative movement of one or more of the crucible supports. 15. The method of claim 12, wherein the controlling-fixing the heating source moves the crystallization temperature gradient relative to the fixed crucible to melt The raw material is reformed into a single crystal compound, and a crystal growth process is performed on the crucible with a predetermined crystal growth length, wherein the temperature gradient is moved relative to the fixed crucible to continuously melt the raw material and recombine it into Single crystal compound 16. The method of claim 1, wherein the method further comprises a fixed heating source. The method of item 12, wherein the crystal growth furnace holds a tapered crystal growth region having a diameter of from about 25 mm to about 50 mm, as in the method of claim 1, which additionally comprises arsenic ( As), gallium (Ga) and/or antimony (Sb) is added as a dopant to the germanium crystal. The method of claim 1, wherein the crystal growth furnace produces a body lineage without a main system. Defect) crystal ingot. 20. The method of claim 1, wherein the ingots are grown by a vertical growth procedure. 21. The method of claim 2, wherein the vertical growth S-34-201224228 program is one or both of a VGF and/or VB program. 22. A method of seed crystal growth comprising: inserting an ampoule having a seed crystal and a seed material into a furnace configured to provide a movable temperature gradient to the crucible in the crucible; using vertical gradient solidification (VGF) Generating a crystal in which the crystallization temperature gradient from the heating source moves relative to the lanthanide system to melt the material and recombine it into a single crystal compound; and using a vertical Brinell procedure to predetermined crystal growth length in the furnace The crystal is grown on the ampoule, 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/cm2 and less than about 0.51/1 Cm2 single crystal introspective mirror. The method of claim 22, wherein the movable temperature gradient is obtained via a plurality of heating zones. 24. The method of claim 22, wherein a single crystal germanium ingot having a micropit density greater than about 0.025/cm2 and less than about 0.26/cm2 is provided. 25. The method of claim 22, wherein a single crystal germanium ingot having a micropore density greater than about 0.025/cm2 and less than about 1313/cm2 is provided. 26. The method of claim 22, wherein a single crystal germanium ingot having a micropit density of less than about 0.13/cm2 is provided. 27. The method of claim 22, wherein a single crystal germanium ingot having a micropit density greater than about 0.05/cm2 and less than about 2626/cm2 is provided. 28, as in the method of claim 22, In addition, arsenic (As) is added as a dopant to the germanium crystal. The method of claim 22, further comprising adding gallium (Ga) as a dopant to the germanium crystal. 30. The method of claim 22, further comprising adding bismuth (Sb) as a dopant to the ruthenium crystal. 3. The method of claim 22, wherein the crystal system is subjected to the vertical gradient solidification (VGF) procedure from about 0.1 to about 1 Torr. (:/hour cooling rate and growth at a temperature gradient between about 〇 5 and about 10 ° C / cm. 32. The method of claim 22, wherein the crystal system passes the vertical cloth The VB process is grown at a cooling rate of from about 0.1 to about 10 ° C / hour and at a temperature gradient of from about 0.5 to about 10 ° C / cm. 33. The method of claim 22: wherein The crystal growth furnace includes a structure configured 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 be performed on the crucible when the crucible is located in the furnace The method of claim 32, wherein the movable temperature gradient is obtained by controlling a plurality of heating zones. 35. The method of claim 32, wherein the moving temperature gradient system The method of claim 3, wherein the method of controlling a fixed heat source to control the heat source, the crucible, the ampoule, and/or the relative movement of the one or more of the crucible support. crystallization The gradient is moved relative to the fixed enthalpy to melt the S-36-201224228 and recombine the material into a single crystal compound, and the crystal growth process is performed on the i-glycan with a predetermined crystal growth length, wherein the temperature gradient is relative Moving on the fixed crucible to continuously melt the raw material and recombining it into a single crystal compound. 3 7. The method of claim 32, further comprising - fixing the heating source. 38. The method of the present invention, wherein the crystal growth furnace holds a crucible crystal growth region having a length of from about 25 mm to about 50 mm. The method of claim 32, wherein the crystal growth furnace holds a tapered crystal a growth zone, wherein the predetermined crystal growth length is higher than the tapered crystal growth region by about 1 l〇mm to about 200 mm 〇40. The method of claim 22, wherein the crystal growth furnace produces no The main system belongs to the crystal ingot. 41. A single crystal germanium product, which is produced by a method comprising the steps of: loading a Ge material into a crucible; sealing the crucible埚: placing the crucible into a crystal growth furnace having a crucible support: melting the Ge raw material in the crucible to produce a melt; controlling a crystallization temperature gradient of the melt while contacting the melt with the seed crystal; Forming a single crystal germanium ingot by crystallization temperature gradient and/or movement of the crucible relative to each other - 37 - 201224228; and cooling the single crystal germanium ingot; wherein the product comprises reproducibly providing micropits from the method A product having a density (MPD) greater than about 0.025/cm2 and less than about 0.51/cm2 of a single crystal germanium ingot. 42. A product according to claim 41, wherein a micropit density of greater than about 0.025/cm2 and less than about 0.26 is provided. /cm2 single crystal bismuth ingot. 43. The product of claim 41, wherein a single crystal germanium ingot having a micropit density greater than about 0.025/cm2 and less than about 0.13/cm2 is provided. 44. The product of claim 41, wherein a single crystal germanium ingot having a micropore density of less than about 1313/cni2 is provided. 45. The product of claim 41, wherein a single crystal germanium ingot having a micropit density greater than about 〇.〇5/cm2 and less than about 2626/cm2 is provided. 4. The product of claim 41, wherein the single crystal germanium ingot is formed using arsenic (As) as a dopant of the germanium crystal. 47. The product of claim 41, wherein The single crystal germanium ingot is formed using gallium (Ga) as a dopant of the germanium crystal. 4 8. The product of claim 41, wherein the single crystal germanium ingot is formed using bismuth (Sb) as a dopant of the bismuth crystal. 4. The product of claim 41, 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 from about 0.5 to about 10 ° C. 〇50. The product of the fourth aspect of the patent application, wherein the crystal system is subjected to a vertical Brinell (VB) procedure from about 0.1 to about 10 ° C via -38-S 201224228. The cooling rate is /hr and is grown at a temperature gradient of from about 0.5 to about 10 °C/cm. 51. The product of claim 41, 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 A crystal growth procedure is performed on the crucible while the crucible is in the furnace. 52. The product of claim 51, wherein the movable temperature gradient is obtained by controlling a plurality of heating zones. 53. The product of claim 51, wherein the moving temperature gradient is obtained via relative movement of one or more of a heat source, the crucible, the ampoule, and/or the crucible support. 54. The product of claim 5, 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 to grow with 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. 55. The product of claim 51, which additionally comprises a fixed heating source. 56. The product of claim 5, wherein the crystal growth furnace holds a crucible having a tapered crystal growth region, and wherein the predetermined crystal growth length is higher than the conical crystal growth region by about 25 mm to about 5 0mm. -39-201224228 57. The product of claim 5, wherein the crystal growth furnace holds a crucible having a tapered crystal growth region, and wherein the predetermined crystal growth length is about 150 mm above the conical crystal growth region. Up to about 200mm. 58. The product of claim 41, wherein the crystal growth furnace produces a crystal ingot having no main system 》 5 9. The product of claim 41, wherein the ingot is vertical Growth program growth. 60. The product of claim 59, wherein the vertical growth program is one or both of VGF and/or VB programs. 61. 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 container and a seed crystal well; an ampoule support; and a controller coupled to the crystal growth furnace and the ampoule support, the controller controlling one or more heating zones of the heating source and the movable ampoule support to Performing a vertical gradient solidification procedure on the crucible while the crucible is 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; Wherein, due to the vertical growth procedure in the apparatus, the apparatus reproducibly provides a micro-pit density greater than about 〇.〇25/〇1112 and less than about 0.5 1/(:1112 锗 ingot. 62. as claimed The apparatus of item 61, wherein the apparatus comprises at least one heating source of S-40-201224228, the heating source being controlled to move the crystallization temperature gradient relative to the fixed crucible Melting the raw 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 continuously melt the raw material and recombine it into a single crystal 63. The apparatus of claim 61, wherein the apparatus reproducibly provides an ingot casting 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 61, which is additionally constructed to cool the crucible ingot at a rate of from about 0.1 to about 10 ° C / hour. 65. The apparatus of claim 6 wherein the crystal growth furnace has 5 to 7 heating zones. 6 6. The apparatus of claim 61, wherein the crystal growth furnace has six heating zones. 67. The device of claim 61, which additionally comprises a loading crucible a loading container for the raw material, the raw material is melted in the crucible to provide a larger amount of the crucible material to the crucible. 68. The apparatus of claim 61, wherein the crystallization temperature gradient is moved The lanthanide remains fixed during the period. 69. The apparatus of claim 61, wherein the diameter of the bismuth ingot is between about 5 〇 mm and about 15 〇 mm. 70. The device, wherein the bismuth ingot has a diameter of about 15 〇mm. 71. a method for growing a single crystal germanium (Ge) crystal in a crystal growth furnace - 41 - 201224228, the crystal growth furnace includes a heating source, a plurality of heating zones, ampoules, and defects, the method comprising: loading a Ge material into the crucible; sealing the crucible and the container; placing the crucible into a crystal growth furnace having a crucible support; and melting the Ge material in the crucible To produce 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 single crystal germanium ingot; wherein a single crystal germanium ingot having a micropore density (MPD) greater than about 〇.〇25/cm2 and less than about 0.51/cm2 is reproducibly provided. 72. The method of claim 71, wherein a single crystal germanium ingot having a micropit density greater than about 0.025/cm2 and less than about 2626/cm2 is provided. 73. The method of claim 71, wherein a single crystal germanium ingot having a micropit density greater than about 〇.〇25/cm2 and less than about 〇·1 3/cm 2 is provided. 74. The method of claim 71, wherein a single crystal germanium ingot having a micropit density of less than about 0.13/cm2 is provided. 7. The method of claim 71, wherein a single crystal germanium ingot having a micropit density greater than about 0.05/cm2 and less than about 2626/cm2 is provided. 76. The method of claim 71 It additionally includes adding arsenic (As) as a dopant to the germanium crystal. 77. The method of claim 71, further comprising adding gallium S-42-201224228 (Ga) as a dopant to the germanium crystal. 78. The method of claim 71, further comprising adding bismuth (Sb) as a dopant to the ruthenium crystal. 79. The method of claim 71, wherein the crystal system is subjected to a vertical gradient solidification (VGF) procedure of from about 0.1 to about 1 Torr. a cooling rate of (:/hour) and a growth temperature of between about 0.5 and about 1 (temperature gradient between TC/cm). The method of claim 71, wherein the crystal system is via vertical Brinell The (VB) program is grown at a cooling rate of from about 0.1 to about 10 ° C / hour and at a temperature gradient between about 〇 5 and about 10 ° C / cm. 81. The method of claim 71 , wherein the grown crystals are cooled by a cooling program, via a vertical gradient solidification (VGF) program and/or a vertical Brinell (VB) program, at a cooling rate of about 3 ° C / hour for about the first 5 hours, and at about 30 ° The cooling period of C/hour to about 45 ° C / hour cools the rest of the cooling process. 8 2. The method of claim 71, wherein the crystal growth furnace comprises a structure constructed to produce a movable temperature gradient And a controller coupled to the crystal growth furnace, the controller controlling the movable temperature gradient to perform a crystal growth process on the crucible when the crucible is located in the furnace. 83. Method wherein the movable temperature gradient is 84. The method of claim 82, wherein the moving temperature -43 - 201224228 gradient is via one or more of a heat source, the crucible, the ampoule, and/or the crucible support 85. The method of claim 82, wherein the method of claim 82, 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 performing a crystal growth process on the crucible with a predetermined crystal growth length, wherein the temperature gradient moves relative to the fixed crucible to continuously melt the raw material and recombine it into a single crystal compound. 86. The method further comprising a fixed heating source. The method of claim 82, wherein the crystal growth furnace holds a crucible having a cone crystal growth region of from about 25 mm to about 50 mm. The method of item 82 or 8, wherein the crystal growth furnace holds a crucible having a tapered crystal growth region, and wherein the predetermined crystal growth The length is higher than the tapered crystal growth region by about ll 〇 mm to about 200 mm 〇 89. The method of claim 71, wherein the crystal growth furnace produces a crystal ingot which does not have a main system 。. The method of claim 71, wherein the ingots are grown by a vertical growth process. The method of claim 90, wherein the vertical growth program is a VGF and/or VB program. One or both