CN102272361A - Systems, methods and substrates of monocrystalline germanium crystal growth - Google Patents
Systems, methods and substrates of monocrystalline germanium crystal growth Download PDFInfo
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Abstract
Systems, methods, and substrates directed to growth of monocrystalline germanium (Ge) crystals are disclosed. In one exemplary implementation, there is provided a method for growing a monocrystalline germanium (Ge) crystal. Moreover, the method may include loading first raw Ge material into a crucible, loading second raw Ge material into a container for supplementing the Ge melt material, sealing the crucible and the container in an ampoule, placing the ampoule with the crucible into a crystal growth furnace, as well as melting the first and second raw Ge material and controlling the crystallizing temperature gradient of the melt to reproducibly provide monocrystalline germanium ingots with improved/desired characteristics.
Description
The mutual reference of related application data
The application is based on the U.S. Patent application No.12/544 of No.200810177006.0 of Chinese patent application formerly that submitted on November 10th, 2008 and submission on September 5th, 2009,902, and require to enjoy its rights and interests/right of priority, the full content of described application is included this paper by reference in.
Technical field
The present invention relates to growth of monocrystalline germanium (Ge) crystalline and relevant system, method and substrate thereof.
Background technology
Electric installation and optoelectronic equipment manufacturers need the big and electrical property homogeneous semiconductor monocrystalline of size usually, and described monocrystalline is after section and polishing, as the substrate of producing little electric installation.The growth of semiconductor crystal comprises: polycrystal raw material is heated to its fusing point (surpasses 1 usually, 200 ℃) thus a kind of polycrystal raw material melt produced, this melt is contacted with the high-quality seed crystal of this material, and make this melt on the contact surface of itself and described seed crystal, carry out crystallization.Being used for finishing the multiple diverse ways of this purpose all is that document is known.Described method comprises and lifts (Czochralski, Cz) method and modification thereof, LEC (liquid encapsulation Czochralski) (Liquid Encapsulated Czochralski, LEC) method, horizontal Bridgman and crucible decline (Horizontal Bridgman and Bridgman-Stockbarger, HB) method and vertical modification (VB) thereof, and gradient freezing (gradient freeze, GF) method and modification thereof, vertical gradient condensation (VGF) method.Referring to, for example " Bulk Crystal Growth of Electronic; Optical and Optoelectronic Materials ", P.Clapper, Ed., John Wiley and Sons Ltd, Chichester, England, 2005, wherein these technology and their application in the growth of multiple material have been carried out extensive argumentation.
About known method, commercial by using the technology of lifting to produce the low dislocation germanium single crystal of diameter as 150mm (6 inches).The wafer of larger diameter is discussed, but do not confirmed (Vanhellemont and Simoen, J.Electrochemical Society, 154 (7) H572-H583 (2007)) as yet.In addition, diameter is that the germanium single crystal of 100mm (4 inches) is come out by VGF and VB technology growth, described in document (Ch.Frank-Rotsch, et al., J.Crystal Growth (2008), doi:10.1016, J.Crys Growth 2007.12.020).
Show as the many institutes that report in the document, compare with the Cz/LEC technology, the VB/VGF growing technology generally is to utilize lower thermal gradient and lower growth velocity, produce monocrystalline thus (referring to A.S.Jordan et al. with much lower dislocation desity, J.Cryst.Growth 128 (1993) 444-450,2), M.Jurisch et al., J.Cryst.Growth 275 (2005) 283-291 and S.Kawarabayashi, 6th Intl.Conf.on InP and Related Materials (1994), 227-230).Therefore, in some applications, the preferred VB/VGF method germanium of diameter, low-dislocation-density (or dislocation-free) of growing up next life.
In commercial single crystal growing operation, crystal ingot (ingot) is the target of pursuing with the high production of possible least cost growth and crystal ingot section, promptly by cutting out wafer as much as possible on the single crystal bar.Thereby, if wish under other restricted conditions that method adopts, to grow possible long crystal ingot, then need to use a large size crucible usually.Usually, because the general shape of polycrystalline piece material to be installed does not wait, the space that does not contain material remaining between the raw material is very big, and stacking factor is very low.When described add material fusing after, melt is the filling part crucible only.Considering that the volume of melt needs and have now the structure of crucible, replenish the important step that melt is the whole growth method with additional material, also is the step of a complexity.For example germanium is especially true for some material: (thermal conductivity and density are respectively 1.358Wcm with Si
-1℃
-1And 2.3332gcm
-3) compare, germanium has lower thermal conductivity (0.58Wcm
-1℃
-1) and higher density (5.32gcm
-3), thereby be subjected to special method restriction.
The known existing several still immature modes of melt of in crystal growth, replenishing.For example in the silicon growth system, polycrystalline piece material is added to the mode of the Si melt that is used for growing single-crystal Si, and in system, with pack into mode in the crucible of Cz method growing single-crystal of raw material.Similar these technology is all practicable, because Cz (or LEC) system is an open system, and relatively easily adds material to crucible.But, being encapsulated in VGF and VB technology in the ampoule for crucible, described method then can not be used.In addition, for the particular requirement of special adulterated Ge mono crystal growth, also can limit the use of aforesaid method.If for example use arsenic (As), then because arsenic has high vapour pressure and toxicity is restricted the arsenic method of mixing of this germanium single crystal as doping agent.
Summary of the invention
System of the present invention, method and substrate relate to the growth of monocrystalline germanium (Ge) crystalline.
In an exemplary, provide a kind of growing single-crystal germanium (Ge) crystalline method.In addition, this method can comprise packs a Ge raw material in the crucible into, the 2nd Ge raw material pack into one in order in the container that replenishes the Ge melt material, with described crucible and container sealing in an ampoule, the ampoule that described crucible is housed is put into a crystal growth smelting furnace, except controlling the first and second Ge melting raw materials, also control the crystallization temperature gradient of melt, thereby the crystal ingot of the monocrystalline germanium with required crystal property can repeatedly be provided.
It should be understood that above general description and detailed description hereinafter only are exemplary and explanat, and do not limit the present invention, as mentioned above.Except that feature and/or modification that this paper provides, also can provide other features and/or modification.For example, the present invention can relate to disclosed feature multiple combination and inferior in conjunction with and/or detailed description hereinafter in the combination and the inferior combination of disclosed several other features.
Description of drawings
Accompanying drawing constitutes the part of this specification sheets, and it illustrates a plurality of embodiment of the present invention and many aspects, and explains principle of the present invention together with describing.In the accompanying drawings:
Figure 1A-1D is the longitudinal cutting face diagrammatic sketch of the monocrystalline germanium crystal growing apparatus of an exemplary crystal process of growth of some aspect of the relevant the present invention of explanation.
Fig. 2 is the exemplary status diagrammatic sketch that pBN (pyrolitic boron nitride) container of the use loading raw material of some aspect of the relevant the present invention of displaying carries out crystal growth.
Fig. 3 is the example of EPD (etch-pit density) figure (57 EPD, average EPD:186) of germanium crystal ingot head that meets the diameter 150mm that is grown of some aspect of relevant the present invention.
Fig. 4 is the example of EPD figure (57 EPD, average EPD:270) of germanium crystal bar afterbody that meets the diameter 150mm that is grown of some aspect of relevant the present invention.
Fig. 5 is a schema of showing an illustrative methods of the crystal growth that meets some aspect of relevant the present invention.
Embodiment
Now will describe the present invention in detail, the example has the example explanation in the accompanying drawings.The embodiment that provides in the following specification sheets is not represented and is met all of the embodiments of the present invention of being protected.But they only are some examples that meet some aspect of relevant the present invention.As possible, use identical Reference numeral to refer to same or analogous part in the whole accompanying drawing.
Aspects more of the present invention are particularly suitable for the germanium crystal ingot crystalline apparatus and method that growth diameter is 150mm (6 inches), in this article described apparatus and method are described.Yet should be understood that aspects more of the present invention have bigger use, for example can use relevant apparatus and method to produce diameter and be above germanium (Ge) crystal ingot of 50mm (2 inches) that for example diameter is the crystal ingot of 100mm (4 inches) and 200mm (8 inches).
Consistent with Figure 1A-Fig. 2, provide and be used for growing single-crystal germanium (Ge) crystalline system and method, in case wherein initial feed adds material and melts---but before crystal growth begins---and (for example additional raw material melt can be added to crucible, carry out with VGF and/or VS method etc.), thus make the monocrystalline crystal ingot grow longlyer.In addition, this method can comprise: in the crucible of at first a Ge raw material being packed into, described crucible comprises a seed crystal well of depositing seed crystal, the 2nd Ge raw material pack into one in order in the container that replenishes the Ge melt material, in an ampoule, the ampoule that will have crucible is then put into a crystal growth smelting furnace with the removable ampoule bearing that supports described ampoule with described crucible and container sealing.In addition, exemplary embodiment can comprise: the Ge raw material in the fusion crucible to be generating a kind of melt, the 2nd Ge raw material in the melting vessel, and the 2nd Ge raw material that will melt adds to described melt.Other exemplary embodiment can comprise: the crystallization temperature gradient of control melt, crystallization and form monocrystalline germanium crystal ingot when melt is contacted with seed crystal then randomly, is cooled off the monocrystalline germanium crystal ingot.
In an exemplary, the step that forms the monocrystalline germanium crystal ingot can be included in the crystal growth district and form about 0.3 thermograde to about 2.5 ℃/cm.In addition, can be with about 0.2 to about 0.5 ℃/hour speed cooling monocrystalline germanium crystal ingot.In addition, can in the crystallization temperature gradient moving process, keep crucible to fix.
According to some exemplary, the diameter of monocrystalline germanium crystal ingot can be about 50mm to about 200mm (about 2 inches to about 8 inches).In one embodiment, for example, the diameter of monocrystalline germanium crystal ingot can be 152.4mm (6 inches).In addition, monocrystalline germanium crystal ingot and wafer can have less than about 350 dislocations/cm at this
3, less than about 300 dislocations/cm
3, less than about 250 dislocations/cm
3Or even less than about 200 dislocations/cm
3
For the system that conforms to the present invention, the exemplary means of the major diameter single crystal germaniumcrystal that is used to grow can comprise a crystal growth smelting furnace, and described crystal growth smelting furnace comprises a thermal source and a plurality of heating zone; One is configured to put into the smelting furnace ampoule, and wherein said ampoule comprises the crucible of a container and a band seed crystal well; An ampoule bearing movably; With a controller that is connected with removable ampoule bearing with the crystal growth smelting furnace.In addition, one or more heating zone of described controller may command thermal source and removable ampoule bearing are so that crucible is implemented the vertical gradient condensation method in smelting furnace the time on crucible.
According to some embodiment, described crystal growth smelting furnace can have a plurality of heating zone, 4 to 8 heating zone for example, 5 to 7 heating zone or 6 heating zone.Be that the internal diameter of exemplary crucible can be about 50mm to about 200mm (about 2 to about 8 inches), perhaps, in some embodiments, is about 150mm (about 6 inches) with required crystal ingot/wafer diameter conforms to.
Get back to accompanying drawing, Figure 1A-1D is the longitudinal cutting face diagrammatic sketch of the monocrystalline germanium crystal growing apparatus of an exemplary crystal process of growth of some aspect of the relevant the present invention of explanation.Figure 1A has illustrated the sectional view of an example of crystal growing apparatus.This device can comprise a smelting furnace that is used for vertical gradient condensation (VGF) growth method or vertical Bridgman (VB) growth method, and can comprise an ampoule bearing 11 that is arranged in smelting furnace 1, wherein well heater 2 is made up of a plurality of districts, and each district is by a computer independent control via Controlling System control.Regulate the temperature in each district, solidify required temperature distribution and thermograde so that the control melt to be provided.Adjust temperature distribution and thermograde, crystalizing interface is moved up by expection run through melt, for example form about 0.3 thermograde to about 2.5 ℃/cm in the crystal ingot vitellarium.Ampoule bearing 11 provides physical support and thermal gradient control for the ampoule 3 (in one embodiment, being made by quartz) that contains crucible 12, and crucible can leave seed crystal in the seed crystal well 18 in.During the smelting furnace operation, ampoule bearing 11 is moved vertically in crystal growing process.Crucible 12 can contain a seed crystal 17, is gone out the monocrystalline that forms at the seed crystal top by described seeded growth.In one embodiment, crucible 12 can be a pyrolitic boron nitride (pBN) structure, has a cylindric crystal growth part 13, a seed crystal well cylinder 18 and a tapered intermediate portion 7 than minor diameter.Crystal growth part 13 is open at the top of crucible 12, and its diameter equals the diameter of required crystalline product.The crystal diameter of standard is 50.8,76.2,101.6 and the crystal ingot of the be cut into wafer of 152.4mm (2 inches, 3 inches, 4 inches and 6 inches) on the current industrial.In an exemplary, the seed crystal well cylinder 18 in the bottom of crucible 12 can have the bottom of a sealing and be a bit larger tham the diameter of high-quality seed crystal 17, for example about 6-25mm, and the length of about 30-100mm.Cylindric crystal growth part 13 and seed crystal well cylinder 18 can have straight wall, or tapered about one mass dryness fraction as for that outwards is tapered, and are beneficial to shift out crystal from crucible 12.Tapered intermediate portion 7 between growth part 13 and the seed crystal well cylinder 18 has the sidewall with angle of a for example about 45-60 degree of inclination, its bigger diameter equals the diameter of vitellarium and is connected in the vitellarium wall, and less diameter equals the diameter of seed crystal well and is connected in the seed crystal borehole wall.This sidewall with angle also can be other angles steeper than 45-60 degree or that steepness is littler.
In an exemplary, ampoule 3 can be made by quartz.Ampoule 3 has a shape that is similar to crucible 12.Ampoule 3 is cylindric in seeded growth zone 19---cylinder has narrow and small diameter in the seed crystal well area 19 at ampoule 3, and has a tapering transition zone 8 between described two zones.Crucible 12 adapts to the inside of ampoule 3 and have a narrow gap between them.As material container, second container 4 on top is positioned on the quartzy bearing 6.Quartzy bearing 6 is encapsulated in the middle portion of ampoule 3.In one embodiment of the invention, this second container 4 is made of pBN.Most of raw material 5 is packed in this second container 4.In heat-processed, raw material fusing also splashes into the main crucible 12 from the hole of the bottom of second container 4.Ampoule 3 seals in the bottom of its seed crystal well area 19, and after pack into crucible and raw material at top seal.
In some embodiments, wherein ampoule-crucible molectron is a doline, needs ampoule bearing 11 to adapt to this doline and keeps ampoule 12 stable and stand on inside furnace.In other embodiments, ampoule-crucible molectron can be different shapes, and the basic structure of ampoule bearing 11 can change according to different shapes.According to an embodiment, the stability of ampoule and content thereof and the thin cylinder 16 of its holding strength that provides by the brute force of ampoule bearing 11 provided.The thin cylinder 16 of described brute force holds the funnel-form bottom of ampoule structure 3.In one embodiment, crucible bearing cylinder 16 is made of thermally conductive material, preferred quartz.In other embodiments, silicon carbide or pottery also can be used for forming crucible bearing cylinder 16.Described cylinder 16 contacts with ampoule 3 circumference, wherein the shoulder branch of the conical region 8 of the top edge of cylinder 16 contact ampoule.This configuration causes solid that solid contact is minimized, can guarantee so seldom in addition do not have undesirable, uncontrollable relatively thermal conduction to take place.Therefore, available other more controlled method heating.
In other embodiments, the low density insulating material, ceramic fiber for example can be filled the major part of bearing cylinder 11 inside, only has the axle center 20 of a hollow to keep empty state in about center of described insulating material, in order to hold the seed crystal well 19 of ampoule 3.In other embodiments, the low density insulating material also can contain sapphire whisker (1,800 ℃), aluminium oxide-silicon oxide fibre (1,426 ℃), and/or Zirconium oxide fibre (2,200 ℃).Insulating material is placed in the ampoule bearing 11 carefully.The weight of ampoule 3---when it places the top of cylinder 16---promotes insulating material downwards and forms the insulating material edge 9 of inclination.The major part of filling in the cylinder with the low density isolator can reduce air flowing, this can guarantee seldom or do not have a generation unwanted, uncontrollable relatively convection current.Similar with conduction, convection current is a kind of to VGF and the disadvantageous uncontrollable heat transfer method of other growing methods.
Diameter approximates the hollow 20 of ampoule seed crystal well 19, extends the following a bit of distance in ampoule seed crystal well 19 bottoms downwards.In another embodiment, hollow 20 passes the bottom that the crucible bearing extends to smelting furnace device 1 from the bottom of seed crystal well.It is a kind of from crystal center refrigerative approach that hollow 20 provides.This approach helps the cooling at seed crystal well and institute growing crystal center.Adopt this structure, heat energy can escape downwards the center of passing solid crystals and seed crystal, be passed down through the hollow in the insulating material 20 in the crystal bearing 11.Do not have hollow 20, cool off the crystal ingot center temperature will be higher than crystalline material in the nature of things near outside surface.In the case, the center in the arbitrary horizontal square section of crystal ingot will just crystallization more behindhand after this crystal ingot periphery has solidified.Under such condition, can not prepare crystal with homogeneous electrical property.By comprising hollow 20 in crystal support method, the bottom of ampoule 3 and hollow 20 is passed in heat energy conduction downwards, and the width of cloth is penetrated back and passed the width of cloth and penetrates path 10 thus.Importantly reduce heat energy, to keep the isothermal layer straight (flat) on the whole crystal diameter from the growing crystal center.Keep straight crystal-molten mass interfacial energy to produce crystal with homogeneous electrical property and physicals.
Low density insulating material in the cylinder 11 hinder thermal radiation and flow to the seed crystal well area 19 of ampoule 3 from one group of furnace heats element 2, so this method need form a plurality of horizontal radiation passage/opening/pipelines 10 that run through insulating material.Thereby running through insulating material, radiation channel 10 provides the thermal radiation outlet, controllably heat is transferred to ampoule seed crystal well 19 from furnace heats element 2.The quantity of radiation channel 10, shape and diameter become as the case may be.Radiation channel also can be that tilt, bending or wavy.Radiation channel also not necessarily must be a successive, because they can only partly extend through insulating material.This helps convection current to minimize.In one embodiment, the diameter of these passages is very little, and the width of an about pencil is so convection current is not remarkable.According to a further embodiment of the present invention, also can use the about 6.4516cm of cross-sectional area
2(one square inch) or bigger macropore.The radiation channel 10 that passes insulating material also can with the hollow 20 at insulating material center in conjunction with working, thereby radiation from the heat energy of germ nucleus, and cooling has the crystal of plane isothermal temperature gradient layer.Radiation channel 10 can controlled temperature and directly relevant with the productive rate of crystal growth.
In an exemplary of the present invention, at monocrystalline germanium crystal ingot growth phase, furnace temperature is grown the monocrystalline germanium crystal ingot with about 0.2 to the cooling of about 0.5 ℃/hour speed.
The exemplary fusing of drafting sequence explanation of Figure 1A to Fig. 1 D and the method for supply germanium.Figure 1A illustrates original state, and wherein solid-state germanium is present in upper container 4 and the crucible 12.As the Heating Characteristics and the method for innovation, the intermediateness of germanium melt then is shown among Figure 1B, and Figure 1B illustrates that solid-state germanium has been molten into liquid a kind of state in crucible 12.
Adjust the power that smelting furnace different heating district heating unit is supplied with separately, so that required heat to be provided to upper container.Particularly, can heat upper container, make the germanium in the upper container 3 begin fusing, the germanium of this fusing advances crucible 12 through the orifice flow that is positioned at container 3 bottoms then.In an exemplary, the smelting furnace zone that has upper container is heated to about 940 to about 955 degrees centigrade or about 945 to about 950 degrees centigrade.This process continues to germanium in the upper container 3 and all melts and flow to crucible 12.
Smelting furnace shown in Figure 1A-1D 1 is an example that can be used for the smelting furnace of vertical gradient condensation (VGF) crystal growth.Also can use other smelting furnaces and configuration, for example vertical Bridgman method.In the VGF crystal growth, fixedly the crystallization temperature gradient in the thermal source moves through the electric control mode, and crystal is fixed.
For implementing vertical gradient condensation growth (VGF) (32), need in stove, to set up required temperature gradient distribution.The heating zone of smelting furnace power is separately controlled respectively individually by computer, and this computer is programmed to heating and lowers the temperature to be fit to smelting furnace Tc and thermograde needs.For growth germanium crystal ingot, for example, the temperature fluctuation of smelting furnace may need to be controlled at less than ± 0.1 ℃.In the smelting furnace set-up procedure, the germanium polycrystal raw material is packed in the ampoule 3, in more detail referring to Fig. 2.
As shown in the figure, will be fixed at the pBN container 4 that tapered section has a hole place in the ampoule 3 make by quartz, be positioned on the bearing 6 on the crucible 12.Container 4 makes crucible 12 can load more raw materials.Particularly, germanium raw material 5 is generally solid-state piece or sheet, therefore can not closely be packed in the crucible 12 and melt.Therefore, described container is used to deposit extra carried out raw material melted, then it is drained into downwards in the crucible 12, and this makes, and more germanium adds material in the crucible 12, thereby forms length and all bigger germaniumcrystal of diameter.For example, about 65% raw material can be packed into when initial in the container 4, the raw material with 35% is directly packed in the crucible 12.As a non-limiting example, the 5.115kg material quantity is packed in the crucible 12, the 9.885kg material quantity packed in the container 4, produced 15000g (15kg) can form diameter be 152.4mm (6 inches) the germanium crystal ingot add material.
In one embodiment, germanium can use arsenic (As) to mix.For example, can be with orientation＜100 of departing from 9 ° at this〉seed crystal of (9 ° of off-orientation) is packed in the crucible, and then charging.The doping agent of raw material and appropriate amount is added in the crucible of expecting to pack into and in the container, and crucible and container are put into quartz ampoule 3.Ampoule and content be evacuated to be about 2.00 * 10
-4Pascal (1.5 * 10
-6Holder), then with ampoule sealing and put into smelting furnace, as shown in fig. 1.Open smelting furnace, heating ampoule and content are so that the fusing of the raw material in the crucible 12.In the crystal growing process, the temperature of smelting furnace is about 1000 ℃, because the fusing point of germanium is about 940 ℃.The thermograde of crystalizing interface can be adjusted to about 0.5 according to the different positions of crystal ingot to about 10 ℃/cm.In addition, regulating whole temperature distribution, to make crystallization rate be 1-2mm/ hour.After curing is finished, with about 20-40 ℃/hour speed cooling smelting furnace.The Ge crystal ingot that is obtained by this illustrative methods can have following feature at this: the dislocation amount of Zhi Bei germaniumcrystal can be less than about 300 dislocations/cm in this way
2, or be 150/cm
2To about 300/cm
2, or for about 180/cm
2To about 270/cm
2, or for about 60/cm
2To about 300/cm
2, or for about 80/cm
2To about 280/cm
2, or for about 100/cm
2To about 260/cm
2, or in other this type of numerical value window (numerical number) of 10%, 20% or 30% of measured herein or the amount that provides.
In another embodiment, device of the present invention constitutes by the quartz ampoule that wherein can embed pBN container and crucible with in order to the bearing 6 of depositing the pBN container.Described crucible is of a size of: the diameter of growing crystal section is about 150mm, and the length of growing crystal section is 160mm, and the diameter of seed crystal section is 7mm.In an exemplary, will＜100〉the Ge seed crystal of orientation embeds in the seed crystal well of pBN crucible, and 96g added in the pBN crucible of seed crystal top as the boron trioxide of fluid sealant.Then, will be altogether 14, the Ge polycrystalline material of 974g is put into pBN crucible and pBN container respectively, pBN container and crucible are all embedded in the quartz ampoule, and with this quartz ampoule about 2.00 * 10
-4Pascal (1.5 * 10
-6Holder) seals with quartz cover under the reduced pressure.Pack into the ampoule of sealing in the smelting furnace then and be placed on the ampoule bearing.
Heat above-mentioned quartz ampoule with about 270 ℃/hour speed.When temperature is higher than about 30 ℃ of the fusing point of crystalline material, keep heating until all polycrystalline materials fusings.
As shown in Figure 5, the illustrative methods of growing single-crystal germanium (Ge) crystalline that is used for according to the invention is disclosed.In an exemplary, provide a kind of following method: a Ge raw material is packed in the crucible, and described crucible comprises a seed crystal well of depositing seed crystal; With the 2nd Ge raw material pack into one in order to replenish raw material, wait to place the container in the ampoule; With described crucible and container sealing in described ampoule; The described ampoule that wherein has described crucible and described container is put into a crystal growth smelting furnace; Ge melting raw materials in the control crucible is to generate a kind of melt; Control the 2nd Ge melting raw materials in the described container.In addition, described method also can comprise one or more following processes: the crystallization temperature gradient of interpolation process, control melt that the 2nd Ge raw material that control will fusing adds to described melt crystallization and form the monocrystalline germanium crystal ingot and cool off monocrystalline germanium crystal ingot when melt is contacted with seed crystal.
Other exemplary can comprise the two Ge melting raw materials of control in the described container, comprises that control is to the heating of the 2nd Ge raw material and the 2nd Ge raw material of fusing is remained in the temperature range.In addition, the interpolation process that the 2nd Ge raw material that control will fusing adds to described melt can comprise remains in the given temperature range described melt, and described scope can be about 940 to about 955 degrees centigrade, or about 945 to about 950 degrees centigrade.In addition, the interpolation process that the 2nd Ge raw material that control will fusing adds to described melt can comprise remains in the given temperature range described melt, for example above listed scope.
In another exemplary, the mode of available a kind of control is controlled or is reduced power and/or one or more rate of cooling, and the Ge crystal ingot of the crystalline nature in the scope that can repeat to provide is provided with production.In addition, because the control of this method can repeatedly provide dislocation amount less than about 300 dislocations/cm
3, or the listed interior monocrystalline germanium crystal ingot of any other scope of this paper.
In addition, by the method that this paper enumerates, need not to use the doping techniques of supply external air source that the germaniumcrystal of dislocation desity in above-mentioned each scope just can repeatedly be provided.Some aspects of these advantages can relate to for example have been used sealed ampoule (for example sealing down in vacuum, pressure or other condition etc.) and has avoided relevant complicacy, for example needs expensive air feed hardware and Controlling System/electronics etc.In some cases, the present invention can advantageously combine with the system and method for the contactless doping techniques of needs.So, need not the contact doping techniques or the supply external air source doping techniques the germaniumcrystal of dislocation desity in above-mentioned each scope just can repeatedly be provided.
In some embodiments, the VGF method can be used for implementing crystal growth.In addition, can earlier the heater power in the minimum heating zone be reduced so that begin crystal growth at the seed crystal place, and then the heater power in the zone of transition is reduced, wherein rate of cooling is about 0.3 to about 0.4 ℃/hour.Kept this rate of cooling about 70 hours.In case crystallization arrives main vitellarium, then the heater power in the suitable zone is reduced providing about 0.4, and to make the crystalizing interface thermograde be about 1.2 to about 3.0 ℃/cm that the two all kept about 120 hours to about 0.7 ℃/hour rate of cooling.After crystallization is finished, to about 40 ℃/hour speed smelting furnace is cooled off with about 20 and reach room temperature until it.
The body of the exemplary crystal ingot of gained is long to be 125mm, and is monocrystalline fully.To the terminal growth part, it is 9.05 * 10 that crystal has concentration from the initial growth part
17To 4.86 * 10
18/ cm
3Free carrier (carrier) and 7.29 * 10
-3To 2.78 * 10
-3The resistivity of Ω cm and 955cm
2/ Vs to 467cm
2The mobility of/Vs.Dislocation desity is 186/cm at start-up portion
2, as shown in Figure 3, be 270/cm at the end of growth part
2, as shown in Figure 4.
Therefore, it should be noted that all clearly within the scope of the invention with any germaniumcrystal substrate (for example crystal ingot, wafer etc.) of method disclosed by the invention/process preparation.In addition, any product (for example electronics or optoelectronic device etc.) that comprises this germaniumcrystal substrate with one of the inventive method preparation also meets the present invention.
Though foregoing is illustrated with reference to specific embodiments more of the present invention, but those skilled in the art should understand that, can change described embodiment under the situation that does not depart from principle of the present invention and purport, scope of the present invention limits by appended claims.
Claims (30)
1. a growing single-crystal germanium (Ge) crystalline method, described method comprises:
The one Ge raw material is packed in the crucible, and described crucible comprises a seed crystal well of depositing seed crystal;
With the 2nd Ge raw material pack into one in order to replenish raw material, wait to place the container in the ampoule;
With described crucible and container sealing in described ampoule;
The described ampoule that wherein has described crucible and described container is put into a crystal growth smelting furnace with the removable ampoule bearing that supports described ampoule;
Ge raw material in the fusion crucible is to generate a kind of melt;
Melt the 2nd Ge raw material in the described container, and the 2nd Ge raw material that will melt adds to described melt;
The crystallization temperature gradient of control melt, crystallization and form monocrystalline germanium crystal ingot when melt is contacted with seed crystal; And
Cooling monocrystalline germanium crystal ingot.
2. the process of claim 1 wherein that the process that forms the monocrystalline germanium crystal ingot is included in the thermograde that the crystal growth district forms 0.3-2.5 ℃/cm.
3. the process of claim 1 wherein and cool off the monocrystalline germanium crystal ingot with 0.2-0.5 ℃/hour speed.
4. the method for claim 1 also is included in and keeps crucible to fix in the crystallization temperature gradient moving process.
5. the process of claim 1 wherein that the diameter of described monocrystalline germanium crystal ingot is that about 50mm (about 2 inches) is to about 200mm (about 8 inches).
6. the method for claim 5, the diameter of wherein said monocrystalline germanium crystal ingot is about 150mm (about 6 inches).
7. the process of claim 1 wherein that described monocrystalline germanium crystal ingot has less than about 300 dislocations/cm
3
8. device that is used for growing single-crystal germanium comprises:
A crystal growth smelting furnace, it comprises a thermal source and a plurality of heating zone;
Ampoule in smelting furnace that is configured to pack into, wherein said ampoule comprises the crucible of a container and a band seed crystal well;
An ampoule bearing movably; With
A controller that is connected with removable ampoule bearing with the crystal growth smelting furnace, the one or more heating zone and the removable ampoule bearing of this controller control thermal source are implemented the vertical gradient condensation method on crucible when being arranged in smelting furnace with convenient crucible.
9. the device of claim 8, wherein said crystal growth smelting furnace has 5 to 7 heating zone.
10. the device of claim 8, wherein said crystal growth smelting furnace has six heating zone.
11. the device of claim 8, the internal diameter of wherein said crucible are that about 5mm (about 2 inches) is to about 200mm (about 8 inches).
12. the device of claim 8, the internal diameter of wherein said crucible are about 150mm (about 6 inches).
13. a growing single-crystal germanium (Ge) crystalline method, described method comprises:
The one Ge raw material is packed in the crucible, and described crucible comprises a seed crystal well of depositing seed crystal;
With the 2nd Ge raw material pack into one in order to replenish raw material, wait to place the container in the ampoule;
With described crucible and container sealing in described ampoule;
The described ampoule that wherein has described crucible and described container is put into a crystal growth smelting furnace;
Ge melting raw materials in the control crucible is to generate a kind of melt;
Control the 2nd Ge melting raw materials in the described container;
The 2nd Ge raw material of interpolation/control fusing is to described melt;
The crystallization temperature gradient of control melt, crystallization and form monocrystalline germanium crystal ingot when melt is contacted with seed crystal; And
Cooling monocrystalline germanium crystal ingot.
14. the method for claim 13 is wherein controlled the 2nd Ge melting raw materials in the described container and is comprised that control is to the heating of the 2nd Ge raw material and the 2nd Ge raw material of fusing is remained in the temperature range.
15. the method for claim 13, wherein the 2nd Ge raw material of the control fusing interpolation process that adds to described melt comprises described melt is remained in the given temperature range.
16. the method for claim 14, wherein said temperature range are about 940 to about 955 degrees centigrade.
17. the method for claim 14, wherein said temperature range are about 945 to about 950 degrees centigrade.
18. the method for claim 13, wherein the 2nd Ge raw material of the control fusing interpolation process that adds to described melt comprises described melt is remained in the given temperature range.
19. the method for claim 18, wherein said given temperature range are about 940 to about 955 degrees centigrade.
20. the method for claim 18, wherein said given temperature range are about 945 to about 950 degrees centigrade.
21. the method for one of claim 13-20 is wherein controlled or is reduced heating power and/or one or more rate of cooling in the mode of control, has the Ge crystal ingot of the crystalline nature that can repeat in the scope with production.
22. the method for one of claim 13-21 wherein owing to one or more controlled step, can repeatedly provide less than about 300 dislocations/cm
3The monocrystalline germanium crystal ingot.
23. the method for claim 13, wherein said crystal growth smelting furnace can make ampoule and/or smelting furnace/device on every side move relative to each other.
24. the method for claim 13 or 23, wherein said crystal growth smelting furnace have a removable ampoule bearing that supports described ampoule.
25. the method for one of claim 13-24 wherein because described crystal manufacture method can repeatedly provide the germaniumcrystal of dislocation desity in setting range, and is not used the doping techniques of supply external air source.
26. the method for claim 25, wherein setting range is less than about 300 dislocations/cm
3
27. the method for one of claim 13-24 wherein because described crystal manufacture method can repeatedly provide the germaniumcrystal of dislocation desity in setting range, and is not used the doping techniques of contact doping techniques or supply external air source.
28. the method for claim 27, wherein said setting range is less than about 300 dislocations/cm
3
29. a germaniumcrystal substrate, it is by the method for one of claim 1-7 or by the method for one of claim 13-28 or any means preparation of enumerating by this paper.
30. a product that comprises a kind of germaniumcrystal substrate, described germaniumcrystal substrate is by the method for one of claim 1-7 or by the method for one of claim 13-28 or any means preparation of enumerating by this paper.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810177006.0 | 2008-11-10 | ||
| US12/554,902 US8506706B2 (en) | 2008-11-08 | 2009-09-05 | Systems, methods and substrates of monocrystalline germanium crystal growth |
| US12/554,902 | 2009-09-05 | ||
| PCT/US2009/006052 WO2010053586A2 (en) | 2008-11-10 | 2009-11-09 | Systems, methods and substrates of monocrystalline germanium crystal growth |
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| CN102272361A true CN102272361A (en) | 2011-12-07 |
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| CN2009801543267A Pending CN102272361A (en) | 2008-11-10 | 2009-11-09 | Systems, methods and substrates of monocrystalline germanium crystal growth |
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| CN (1) | CN102272361A (en) |
| TW (1) | TW201109483A (en) |
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| CN102517624A (en) * | 2011-12-16 | 2012-06-27 | 华中科技大学 | Multi-segment temperature control crystal growing furnace |
| CN104032370A (en) * | 2013-03-05 | 2014-09-10 | 太阳世界创新有限公司 | Device for producing silicon blocks |
| CN104328483A (en) * | 2014-11-13 | 2015-02-04 | 吴晟 | Single crystal growth method and device |
| CN108091708A (en) * | 2017-12-08 | 2018-05-29 | 北京通美晶体技术有限公司 | Single germanium wafer, its preparation method, the purposes of the preparation method of crystal bar and single-chip |
| CN108277528A (en) * | 2018-02-28 | 2018-07-13 | 昆明凯航光电科技有限公司 | A kind of method of germanium single crystal annealing process resistance control |
| CN110195256A (en) * | 2019-06-10 | 2019-09-03 | 苏州亚傲鑫企业管理咨询有限公司 | Monocrystalline silicon repeatedly feeds the device continuously grown and technique |
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| CN107620123B (en) * | 2016-07-13 | 2020-09-08 | 清华大学 | Preparation method of semimetal compound of metal platinum |
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- 2009-11-09 CN CN2009801543267A patent/CN102272361A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102517624A (en) * | 2011-12-16 | 2012-06-27 | 华中科技大学 | Multi-segment temperature control crystal growing furnace |
| CN104032370A (en) * | 2013-03-05 | 2014-09-10 | 太阳世界创新有限公司 | Device for producing silicon blocks |
| CN104328483A (en) * | 2014-11-13 | 2015-02-04 | 吴晟 | Single crystal growth method and device |
| CN108091708A (en) * | 2017-12-08 | 2018-05-29 | 北京通美晶体技术有限公司 | Single germanium wafer, its preparation method, the purposes of the preparation method of crystal bar and single-chip |
| CN108091708B (en) * | 2017-12-08 | 2020-08-14 | 北京通美晶体技术有限公司 | Germanium single crystal wafer, method for producing the same, method for producing crystal bar, and use of single crystal wafer |
| CN108277528A (en) * | 2018-02-28 | 2018-07-13 | 昆明凯航光电科技有限公司 | A kind of method of germanium single crystal annealing process resistance control |
| CN110195256A (en) * | 2019-06-10 | 2019-09-03 | 苏州亚傲鑫企业管理咨询有限公司 | Monocrystalline silicon repeatedly feeds the device continuously grown and technique |
| CN112176399A (en) * | 2020-09-21 | 2021-01-05 | 广东先导先进材料股份有限公司 | Preparation method and preparation device of single crystal containing doping elements |
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