CN1125199C - Method of mfg. single crystal and apparatus for mfg. single crystal - Google Patents
Method of mfg. single crystal and apparatus for mfg. single crystal Download PDFInfo
- Publication number
- CN1125199C CN1125199C CN 97180857 CN97180857A CN1125199C CN 1125199 C CN1125199 C CN 1125199C CN 97180857 CN97180857 CN 97180857 CN 97180857 A CN97180857 A CN 97180857A CN 1125199 C CN1125199 C CN 1125199C
- Authority
- CN
- China
- Prior art keywords
- liquation
- granular
- raw material
- monocrystalline
- crystal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Abstract
The present invention discloses a method and an apparatus for manufacturing single crystals, which is a technology that molten liquid by melting raw materials becomes a super-cooled state of granular liquid and a part of surface free energy of a suspended state of molten liquid is reduced under a micro-gravity environment to grow single crystals so as to manufacture granular single crystals. A single crystal manufacturing apparatus (31) has a gold image furnace (35), a chamber (33), a raw material supplying and retaining mechanism (38), fall pipelines (36, 37), a rotary plate (39), a recovery tank (40), etc. A raw material (32a) composed of heated semiconductor materials is molten and then is fallen freely in the vacuum of the fall pipelines (36, 37). In the course of fall, a part of the surface of a super cooled state of spherical molten liquid (32b) contacts with the solid surface of the rotary plate (39) to generate a crystal nucleus from which a single crystal grows into a single crystal as a spherical single crystal (32c). The spherical single crystal (32c) enters the recovery tank (40).
Description
Technical field
The present invention relates to a kind of monocrystalline manufacture method and device, this method and device make the liquation of fused raw material, in microgravity environment, become the overcooling state with suspended state, then, generate crystal grain, make it to solidify, thus without seed crystal (crystal seed), and direct crystallization becomes monocrystalline; Relate in particular to a kind of technology that is suitable for making single-element semi-conductor granular single crystal and compound semiconductor granular single crystal.
Background technology
Single-element such as silicon or germanium semiconductor crystal, Binary compound semiconductor crystal such as GaAs, GaP, GaSb, InAs, InP, InSb, ZnSe, CdTe or two Binary compound semiconductor blended alloy semiconductors can be used as electronic device material, and the quality of these semiconductor crystals is very big to the device performance influence.Therefore, lattice defect is few, and the manufacturing technology of elementary composition ratio of composition and the controllable high-quality bulk-shaped monocrystal of impurities concentration distribution (single crystal) is epochmaking.
On the other hand,, then can improve the performance of electron device, also be expected to reduce manufacturing cost if can make monocrystalline thereby this liquation is directly solidified without seed crystal by by the direct synthetic compound liquation of raw semiconductor.At present, as the method that the liquation that makes raw semiconductor solidifies, grows into bulk-shaped monocrystal, known have CZ method, FZ method, Bridgman (Bridgman) method.
But, in these methods,, thereby must prepare the high-quality seed crystal at first all from the seeded growth monocrystalline.Usually the method that adopts is to cut out seed crystal from the bulk-shaped monocrystal that other method is made.But,, also be difficult to make the high-quality monocrystalline sometimes because of semi-conductive kind difference.In this case,, the monocrystalline than big crystal grain in this polycrystal partly is cut into seed crystal, is difficult to obtain the high-quality seed crystal though can be the seeded growth polycrystal with sintered compact or precious metal rod.
In the past from liquation growing crystal method, the known influence of gravity that is subjected to produces complicated flowing in liquation, very big to the quality influence of growing crystal.The most fatal shortcoming is, the crucible of dress liquation must be arranged, and since chemistry, the physical action of crucible can produce crystal purity and reduce and lattice defect.And, along with the temperature difference can produce thermal convection in liquation,, form the quality instability, form crystal inhomogeneous, that crystal defect is many because the change of solid-liquid interface temperature and composition is easy to generate lattice defect.
In order to eliminate the detrimentally affect that this gravity produces, various experiments have been carried out, growing crystal under the microgravity environment of realizing by space station, space shuttle, rocket, aircraft.But not only the crystal manufacturing expense becomes greatly, and material applicatory also is restricted, and owing to be called the small gravity disturbance of G fluctuation (jitter), makes crystal growth produce fluctuation, and is at this moment unfavorable.Recently, in about 10 seconds short period of time, in the freely falling body facility on ground, realized the little microgravity environment of G fluctuation, though to utilizing this facility to place on hope, do not propose any scheme by the method for liquation direct growth monocrystalline.
For example, in No. 4021323 communique of United States Patent (USP), a kind of technology of making the silicon spherulite has been described, has sprayed melted silicon,, made the silicon spherulite from spray tower freely falling body air from the small nozzle that is arranged on the spray tower upper end.But, in this technology, leave over following problems: because the atmospheric drag when falling thereby can not obtain sufficient microgravity state, and can mix impurity from nozzle.
The present invention be according to the contriver under the microgravity environment that produces with the freely falling body facility, make spherulite and the new phenomenon found in all experiments of carrying out is that the basis proposes by the semi-conductor liquation.
The object of the present invention is to provide liquation by various semiconductor materials (the multiple semi-conductor of the semi-conductor of single-element, single-element, compound semiconductor), without seed crystal make monocrystalline technology, make the technology of the few high quality single crystal of lattice defect, make the technology of monocrystalline by the liquation of other various materials without seed crystal.
Summary of the invention
Monocrystalline manufacture method of the present invention, thus be to solidify the method for making monocrystalline with making it after the raw materials melt, and this method comprises following operation: heating raw makes it fused the 1st operation; The temperature that reduces described raw material liquation makes liquation become the 2nd operation of the granular liquation of overcooling state; Make the granular liquation of described overcooling state under microgravity environment, keep suspended state, reduce the surface free energy of this granular liquation part surface, in granular liquation, generate the 3rd operation of nucleus; Make granular liquation be frozen into the 4th operation of monocrystalline with nucleus.
The liquation that raw materials melt such as semi-conductor is generated is about 10 at universal gravity constant
-3-10
-5The microgravity environment of G keeps suspended state down, because of surface tension effects becomes the granular liquation with free surface, keeping that temperature is reduced, becomes the overcooling state.Since under microgravity environment, be in non-contacting suspended state, thereby can not generate uneven nucleus, because temperature and density fluctuation in the liquation are little, thereby even caryogenic free energy barrier height height, become but state of high undercooling.Thereby generate nucleus in case reduce the surface free energy of granular liquation part surface under the big state of overcooling degree, then along with the generation of this nucleus, the granular liquation of overcooling state is frozen into granular single crystal rapidly.In order to reduce the surface free energy of above-mentioned granular liquation part surface, for example can make an end of the high granular molten surface of solid short-time contact of the chemical stability in karyogenesis place.
Germanium (Ge), gallium antimonide (GaSb), indium antimonide semi-conductors such as (InSb) are tested this method, can make the granular single crystal that granular liquation is frozen into.Thus,, the semiconductor material of various single-elements can be used, also the various kinds of compound semiconductors material can be used as raw material.With polynary semiconductor compound elementary composition more than three kinds during, can use polycrystal raw material or by the stoichiometric composition raw material formed of the semiconductor material that is in harmonious proportion of each composition element of weighing in advance with these stoichiometric compositions as raw material.But be not limited to semiconductor monocrystal, also can make the monocrystalline of various metallic substance and various insulating material.
Though scientifically do not make explanation completely as yet for can generate this fact of monocrystalline with this method, but can think: in case under microgravity environment, do not contact with other materials, it is spherical to only depend on surface tension to become, become the overcooling state of free energy minimum, then the structure of granular liquation is actually loose atomic bond, becomes the correct atomic arrangement of rule equally with the solid monocrystalline, thus, deducibility generates because of nucleus, begins growing single-crystal hastily.
When above-mentioned raw materials contains the high semiconductor material of vapour pressure, preferably raw material is contained in and carries out the 1st～the 4th operation in the sealed cabin.At this moment, other semiconductor materials except that the high semiconductor material of vapour pressure are pre-installed in the main chamber in the sealed cabin, and the high semiconductor material of vapour pressure is pre-installed in in the sealed cabin and the concubine that the main chamber is communicated with, also comprises the step that the semiconductor material in the main chamber and the semiconductor material in the concubine is heated to differing temps in the 1st operation.The the 1st～the 4th operation is preferably in vacuum atmosphere, carries out in arbitrary atmosphere among inert gas atmosphere, the oxidizing gas atmosphere.Again, the part surface of the granular liquation by ionic fluid short irradiation overcooling state also can reduce surface free energy.
According to monocrystalline manufacture method of the present invention, can make monocrystalline without seed crystal by the semiconductor material liquation of various single-elements, multiple semiconductor material or compound semiconductor materials liquation by single-element are made compound semiconductor single crystal without seed crystal, simple method that can enough abundant application microgravity environments and make monocrystalline without seed crystal by the liquation of various materials.
Single-crystal manufacturing apparatus of the present invention is to be suitable for being applied to the single-crystal manufacturing apparatus that microgravity environment is realized means, be to cooperate with the microgravity environment of microgravity environment realization means realization, be used for making the single-crystal manufacturing apparatus of monocrystalline by raw material, this device comprises: the chamber housing that forms sealed chamber, be configured in described indoor, the material container of placing raw material, heat the heater means of raw material in the described material container, and described material container is supported in the while can drive the actuator that material container moves with respect to the chamber housing in the housing of chamber.
The raw material that heats in the described material container with heater means makes it fusion, make this liquation in material container, in microgravity environment, keep the contactless state that suspends, and under this state, be cooled to the granular liquation of overcooling state, drive material container by actuator under the contactless state that in microgravity environment, keeps suspending and do moving mutually moving with respect to the chamber housing, thus, the part surface of the granular liquation of this overcooling state contacts with the solid face of material container, in granular liquation, generate nucleus, granular liquation is solidified, make granular single crystal.
Again, described heater means also can be made of the tungsten-iodine lamp that has oval plane of reflection and be configured in this ellipse plane of reflection focus.
Can be applicable to the single-crystal manufacturing apparatus that various microgravity environments are realized means according to this, the single-crystal manufacturing apparatus of simple structure can be provided, can have the effect same with the monocrystalline manufacture method.
Another single-crystal manufacturing apparatus of the present invention is that heating raw makes it to become liquation, makes this liquation freely falling body, in microgravity environment, solidify, thus the single-crystal manufacturing apparatus of manufacturing monocrystalline, it comprises: the gastight that extends in vertical direction falls pipeline; Can keep raw material also can remove the raw material maintenance means of maintenance in the described pipeline upper end that falls; The raw material that heats described raw material maintenance means maintenance makes it the fused heater means; Nucleus generates means, this means limit makes the granular liquation of described fused freely falling body limit in falling pipeline become the overcooling state, in freely falling body, reduce falling the free energy of granular liquation part surface in the pipeline middle portion, generate nucleus thereby make in the granular liquation; And recovery is the monocrystalline recoverer of examining the monocrystalline that is frozen into the nucleus.
Can be provided with and extract the extraction means that the described air that falls in the pipeline makes it to form vacuum, make in the vacuum of granular liquation in falling pipeline to fall.Described heater means also can be made of the tungsten-iodine lamp that has oval plane of reflection and be configured on this ellipse plane of reflection focus.Available configuration in falling pipeline granular liquation fall in the path and the swivel plate of the solid material system that chemical stability is high constitutes described nucleus and generates means.According to this single-crystal manufacturing apparatus, owing to realize microgravity environment, thereby become and to be arranged on ground device by freely falling body.In addition, it also can obtain the effect identical with the monocrystalline manufacture method.
Single-crystal manufacturing apparatus as other also can followingly constitute: the sealed cabin maintenance means of using the sealed cabin that raw material is housed and Gong falls are set replace raw material to keep means, under the state that raw material is contained in the sealed cabin, heating makes it fusion, and the granular liquation of fused is fallen with sealed cabin.At this moment, owing to the granular liquation that falls in the process can not contact with the swivel plate of solid material system, the described nucleus that therefore constitutes generates means and preferably contains the deceleration means that the sealed cabin that falls in the pipeline falls in the path, is used for making the sealed cabin deceleration that falls that are configured in.
According to this single-crystal manufacturing apparatus, can contain the compound semiconductor single crystal of the high semiconductor material of decomposition pressure without the seed crystal manufacturing.In addition, also can obtain the effect same with the monocrystalline manufacture method.
Summary of drawings
Fig. 1 is the longitudinal diagram of the single-crystal manufacturing apparatus of example 1, Fig. 2 is the longitudinal diagram of the single-crystal manufacturing apparatus of example 2, Fig. 3 is the longitudinal diagram of the single-crystal manufacturing apparatus of example 3, Fig. 4 is the longitudinal diagram of upper end one side part of the single-crystal manufacturing apparatus of Fig. 3, and Fig. 5 is the longitudinal diagram of remainder of the single-crystal manufacturing apparatus of Fig. 3.Fig. 6 (a)～(e) is the interior feed states of ampoule (ampule) in 5 stages when making monocrystalline by the single-crystal manufacturing apparatus of Fig. 3 and the explanatory view of action.
Preferable example of the present inventionExample 1 (with reference to Fig. 1)
The single-crystal manufacturing apparatus of this example is to be suitable for being applied to the single-crystal manufacturing apparatus that microgravity environment is realized means, is that a kind of microgravity environment of realizing with microgravity environment realization means cooperates, and is made the single-crystal manufacturing apparatus of monocrystalline by raw material.
Realize means as microgravity environment, have object to be fallen realize the falling pipeline, fall tower of microgravity environment form, aircraft and pencil rocket etc. and in orbit with spaceship, spacelab, recovery sealed cabin (capsule) and the space station etc. of gravity with centrifugal force balance realization microgravity environment form.
Being shown in the single-crystal manufacturing apparatus of Fig. 1, is a kind of device that the microgravity environment in space and time utilization less-restrictive in all microgravity environment realization means is realized means that is suitable for being applied to.Earlier this single-crystal manufacturing apparatus is illustrated.
As shown in Figure 1, this single-crystal manufacturing apparatus 1 comprises: form the gastight chamber housing 3 of section for the stainless steel of circular chamber (chamber) 2, be configured in this chamber 2, the material container 5 of the graphite system of raw material 4a is housed, this material container 5 is supported in steady arm 6 on the chamber housing 3, stainless steel, drive the solenoid actuator 7 that material containers 5 relative chamber shell spares 3 relatively move up and down through this steady arm 6, and as the golden image furnace (gold image furnace) 8 of the heater means of the interior raw material 4a of heating raw container 5.
Material container 5 by the lower end bracket part 5a that is used to place raw material 4a, many supporting rod 5b, and upper end wall 5a constitute, the supporter 6b of the stainless steel that the 6a of smaller diameter rods portion of steady arm 6 bottoms is connected with the upper end wall 5c of material container 5 is fixedly connected.9 granulous raw material 4a are placed on bracket part 5a and go up among the recess 5d of a plurality of circles that are provided with (diameter 2.2mm, dark 1.5mm, spacing 3mm in length and breadth, totally 9).The thermopair 9 that is used to measure temperature be installed in bracket part 5a below, its lead (not shown) is drawn to the outside through the wiring path of steady arm 6 inside along the supporting rod 5b cabling of material container 5, is connected to control unit (not shown).Solenoid actuator 7 its formations are can drive steady arm 6 by solenoid coil only to move up and down predetermined stroke (for example about 2mm), drive control by control unit.
Chamber housing 3 is made of with the top board 36 that clogs the upper end cylindrical shell 3a cylindraceous, forms the openning (not shown) of observing raw material 4a in the side of cylindrical shell 3a.In order to make the atmosphere in the chamber 2 is rare gas element (for example argon gas), on the cylindrical shell 3a of chamber housing 3, be provided for bleeding by vacuum pump and provide rare gas element mouth 10, make the open and close valve 12 of rare gas element mobile relief outlet 11 and switching relief outlet 11 chamber 2 in.And its formation makes at least can be cut off inert gas flows, keep airtight conditions until solidificating period in raw material 4a fusion.
The good vitreous silica plate 13 of photopermeability that chamber 2 and golden image furnace 8 are separated is set, and O shape ring 14 is set on the two sides of the peripheral part of this quartz plate 13.Gold image furnace 8 comprises the furnace body 16 of aluminum magnesium alloy system, be formed on the internal surface of this furnace body 16, gold-plated oval plane of reflection 17, the luminous site is in the tungsten-iodine lamp 18 (peak power 1KW) of these ellipse plane of reflection 17 focal positions, the micro-adjusting mechanism 19 of fine setting tungsten-iodine lamp 18 positions, and the passage forming body 21 that forms cooling water path 20.
In case provide electric current from the lamp terminal 22 of tungsten-iodine lamp 18, the infrared light that sends from the luminescent part of tungsten-iodine lamp 18 sees through quartz plate 13 by oval plane of reflection 17 reflections, is concentrated on oval plane of reflection 17 the opposing party's focus.At the bracket part 5a of this focal position configuration material container 5, thereby can be the raw material 4a in the material container 5 with the preset temperature fusion.Again, in this single-crystal manufacturing apparatus 1, material container 5 and steady arm 6 and solenoid actuator 7 are equivalent to nucleus and generate means.Also can use the actuator that drives up and down except that solenoid actuator 7 again.
What this single-crystal manufacturing apparatus 1 was contained in agravic experimental center, (strain) ground (be arranged in the Hokkaido, Japan sky and know sand Chuan Ding on the prefecture) falls the employed falling bodies sealed cabin of tower, when the falling bodies sealed cabin falls with universal gravity constant, produce 10
-4In the microgravity environment below the G (10 seconds time length), enforcement crystal growth experiment as described below can be without the granular liquation direct growth granular single crystal of seed crystal by raw semiconductor.
Beginning is contained in the Ge crystalline length of side 1.47mm cubes raw material 4a more than the purity 9N among 9 recess 5d of bracket part 5a, and 1 of each recess amounts to 9.Then, the air of discharging in the chamber 2 makes it to become vacuum, and the limit flows into the argon gas limit by tungsten-iodine lamp 18 heating and melting raw material 4a then.The temperature of gold image furnace 8 is set for than the complete fused temperature of Visual Confirmation is high 2～3 ℃ in advance under the 1G gravity environment.Then, close open and close valve 12 after the raw material 4a fusion, make in the chamber 2 to be the static atmosphere of argon gas, keep about 15 seconds with melt temperature after, the falling bodies sealed cabin then begins to fall.Cuts off the power supply of tungsten-iodine lamp 18 after second from falling beginning 1-3, makes solenoid actuator 7 actions simultaneously, with material container with the speed of 20mm/sec (falling bodies sealed cabin fall direction) mobile about 0.2mm downwards.The result, liquation 4b upwards floats with respect to material container 5 from the recess 5d of bracket part 5a, become spherical liquation, naturally cooling limit, limit becomes the overcooling state, because inertial motion, in several seconds, the upper wall portions 5c of spherical liquation 4b and material container 5 and the collision of the solid wall surface of supporting rod 5b, by contacting with its solid wall surface, reduce the surface free energy of the granular liquation 4b of overcooling state part surface, in the granular liquation of part, generate nucleus.With the pick up camera real time record state of liquation 4b at this moment.After this, fall in the process at the falling bodies sealed cabin, liquation 4b continues heat release, the limit is solidified by the nucleus growth crystal limit of granular liquation 4b, become material shape monocrystalline, through the microgravity time length (time that the falling bodies sealed cabin falls with universal gravity constant) of 10 seconds kinds, the falling bodies sealed cabin is subjected to the damping force of stopper, is blocked in the bottom that falls tower and stops.After this from the falling bodies sealed cabin, take out single-crystal manufacturing apparatus 1, take out monocrystalline from single-crystal manufacturing apparatus 1.
Monocrystalline have with the bottom surface of returning bracket part 5a after solid wall surface contacts, what have is attached to solid wall surface.The vestige no matter as seen the sort of monocrystalline all contacts with solid wall surface.With solid wall surface slowly the monocrystalline of collision be the shape of almost spherical, and with the monocrystalline of the fierce collision of solid wall surface be the shape of shell shape.But, no matter in the sort of monocrystalline, during with its crystal property of X-ray diffraction studies, can be observed the laue spot in cycle, thereby confirm to have formed monocrystalline.
In Fig. 1, schematically represent raw material 4a over time, Rong Xie raw material 4a is not shown in the right-hand member of bracket part 5a, enter the liquation 4b that has fused before the microgravity environment and be shown in its left side, enter the granular liquation 4b that contacts with the upper wall surface 5c of material container 5 owing to limit suspension limit inertial motion behind the microgravity environment and be shown in the upper wall surface downside.
Except that germanium (Ge) as the raw material, also use gallium antimonide (GaSb), indium antimonide (InSb) to test equally as raw material.The raw material size all cuts into 0.4mm
3, 1-4 is placed in each recess 5d, make its fusion, each self-generating liquation.The heating and melting temperature is set according to raw material, is in 1～5 second scope from falling after the beginning to making time till material container 5 moves downwards, is in 2～3 seconds to making the granular liquation on floating with suspension time till wall contacts.After the falling bodies sealed cabin falls and finishes, reclaim monocrystalline, when doing research, can confirm that it has formed monocrystalline with X-ray diffraction.
The monocrystalline manufacturing technology of above-mentioned explanation is characterized in that single-crystal manufacturing apparatus 1 is applied to microgravity environment and realizes means, makes the granular liquation 4b of overcooling state be frozen into monocrystalline under microgravity environment.
According to this monocrystalline manufacturing technology, owing to make full use of the microgravity environment that microgravity environment realization means realize, can obtain following effect: be subjected to the room and time restriction few, can set various crystal formation conditions, be suitable for as the technology of in the microgravity environment in universe, making monocrystalline, can directly make monocrystalline by the raw material liquation without seed crystal, can make the monocrystalline of various materials (semi-conductor of single-element, compound semiconductor, metallic substance, insulating material etc.), available packaged unit is made monocrystalline.Example 2 (with reference to Fig. 2)
The single-crystal manufacturing apparatus of this example is the device that makes full use of the microgravity environment manufacturing monocrystalline of freely falling body generation on the ground, and the monocrystalline manufacture method of this device is more easily implemented.
With reference to Fig. 2, this single-crystal manufacturing apparatus is illustrated earlier.
As shown in Figure 2, this single-crystal manufacturing apparatus 31 comprises: form the chamber housing 34 of chamber 33, this chamber 33 is equipped with raw material 32a and is formed vacuum atmosphere; Be configured in the golden image furnace 35 of these chamber 33 upsides as heater means; Be connected chamber housing 34 lower end edge vertical direction definite length extended (for example, about 4m), make the top of the vertical freely falling body of granular liquation 32b of raw material 32a fusion fall pipeline 36; The lower ends downward side that falls pipeline 36 from top extends, have the necessary bottom that falls length (for example about 10m) of liquation 32b setting time falls pipeline 37; To 33 inside, chamber supply raw materials 32a, can keep raw material and can remove the raw material supplying maintaining body 38 of maintenance; Be arranged on the bottom fall near pipeline 37 upper ends, with fall in liquation 32b rotor plate 39 short-time contact, graphite system; And be connected, have the collision that absorbs the monocrystalline after the liquation 32b crystallization and the accumulator tank 40 etc. of refrigerative liquid bath in addition with lower end side that the bottom falls pipeline 37.
As shown in the figure, separate with vitreous silica plate 41 between chamber housing 34 and the golden image furnace 35, chamber housing 34 and top fall between the pipeline 36 and separate with vent plug (air lock) 42, and top falls pipeline 36 and bottom and falls between the pipeline 37 and separate with vent plug 43.If open vent plug 42, then chamber 33 falls 36 interior connections of pipeline with top; If open vent plug 43, then top falls pipeline 36 and falls pipeline 37 with the bottom and be communicated with.Gold image furnace 35 is identical with the structure of above-mentioned example 1, forms single oval plane of reflection 45 in the lower face side of furnace body 44, and its focal position is provided with tungsten-iodine lamp 46, converges at another interior focal position of chamber 33 by the infrared rays of these lamp 46 emissions.At the raw material 32a of this downside focal position configuration by 38 maintenances of raw material supplying maintaining body.
Raw material supplying maintaining body 38 has: the rotation pole 47 of quartzy system, be formed on the holding chamber 47a of these rotation pole 47 left end portion and maintenance raw material 32a, the sleeve 48 of quartzy system, the raw material of quartzy system inserts rod 49, make the revolving actuator 50 of rotation pole 47 Rotate 180 degree, back and forth drive reciprocal driving that raw material inserts rod with actuator 51, and be formed at raw material input port 52 on the sleeve 48 etc.The right side wall portions that rotation pole 47 passes chamber housing 34, insert 33 inside, chamber, form circular section segment, the open maintenance tube of left end in its left part, in this keeps tube, keep raw material 32a, form holding chamber 47, form the opening 47b. that liquation 32b is fallen in the upper end that keeps tube
Sleeve 48 passes the left side wall portion of chamber housing 34, inserts 33 inside, chamber, and the right-hand member rotation of sleeve 48 embeds freely and keeps in the tube.Raw material inserts left end insertion sleeve 48 inside of rod 49 from sleeve 48, and the raw material 32a that provides in sleeve 48 from raw material input port 52 inserts rod 49 by raw material and pushes holding chamber 47a.Raw material input port 52 can seal with cover 53 and O shape ring, and gas-tight seal is carried out with box nut 54 and O shape ring in the left part of sleeve 48.
For in the chamber 33 inside switch vacuum or inert gas atmosphere, venting port 58 is set on chamber housing 34 and can opens and closes the open and close valve 59 of venting port 58, on venting port 58, switch ground and connect vacuum pump and rare gas element generator.Equally, switch vacuum or inert gas atmosphere in the pipeline 36, fall the open and close valve 61 that venting port 60 is set on the pipeline 36 and can opens and closes venting port 60, on venting port 60, switchably connect vacuum pump and rare gas element feedway on top in order to fall on top.Equally, switch vacuum or inert gas atmosphere in pipeline 37 and the accumulator tank 40 in order to fall in the bottom, fall the valve 63 that venting port 62 is set on the pipeline 37 and can opens and closes venting port 62 in the bottom, on venting port 62, switchably connect vacuum pump and rare gas element feedway.Above-mentioned rotor plate 39 is arranged to make in granular liquation 32b freely falling body way and can be contacted with granular liquation 32b.Again, rotor plate 39 also is provided with and adjusts and the angle of granular liquation 32b collision and mechanism's (not shown) of rotor plate 39 speed of rotation.
The silicone cooling fluid 65 that is used to cushion the collision of fallen monocrystalline 32c and cools off monocrystalline 32c is housed in the fluid container 64 of accumulator tank 40 bottoms, has designed the vent plug 67 that is used to take out the openning 66 of monocrystalline 32c and opens and closes this openning 66 at accumulator tank 40 side wall portions.Also be provided with and drive the above-mentioned tungsten-iodine lamp 46 of control, revolving actuator 50, the reciprocal control unit (not shown) that drives with actuator 51, open and close valve 59,61,63, vent plug 42,43,67, vacuum pump, rare gas element feedway etc. again.In this single-crystal manufacturing apparatus 31, rotor plate 39 is equivalent to nucleus and generates means.
Then, to adopting single-crystal manufacturing apparatus 31, the method for being made granular single crystal by raw semiconductor is illustrated.
The feature of this monocrystalline manufacture method is, make the liquation 32b freely falling body of the raw material 32a fusion of forming by semiconductor material, under the microgravity environment in it falls, the granular liquation 32b of overcooling state is contacted with solid surface, generate nucleus, thereafter, further freely falling body limit, limit makes it to solidify, thereby crystallizes into monocrystalline 32c.
Beginning, behind the vent plug 42 of close chamber's 33 downsides, drop in the sleeve 48 from raw material input port 52 the raw material 32a of pre-determined volume and shape, insert rod 49 by raw material raw material 32a is pushed to holding chamber 47a, tighten and cover 53 and make into airtight conditions with box nut 54, the air of discharging in the chamber 33 make it to become vacuum.Equally, also top is fallen pipeline 36 and bottom and fall in pipeline 37 and the accumulator tank 40 and be evacuated, ready making when raw material 32a falls, open vent plug 42,43, granular liquation 32b falls in a vacuum.
Be heated to preset temperature by tungsten-iodine lamp 46, the raw material 32a in the fusion holding chamber 47a.This liquation 32b keeps certain hour to this liquation at a certain temperature because surface tension effects becomes hemispheric liquation.Then, make rotation pole 47 Rotate 180 degree, openning 47b is downward, makes liquation 32b freely falling body.
Liquation 32b is complete globular liquation 32b because of surface tension effects becomes, in top falls pipeline 36 during the freely falling body, and heat radiation rapidly under microgravity environment, temperature reduces and becomes the overcooling state.The liquation 32b of this overcooling state and the solid surface short-time contact of rotor plate 39.As a result, the part surface at the liquation 32b of overcooling state generates nucleus.Thereafter, deflection takes place and continues freely falling body in the direction that falls of liquation 32b, still remain under the microgravity environment, keep spherical former state to solidify rapidly and grow into monocrystalline, become spherical monocrystalline 32c, and in statu quo fall into silicone cooling fluid 65 in the accumulator tank 40 bottom liquid containers 64, by quick cooling and stop at the bottom of fluid container 64.
In this monocrystalline manufacture method, the temperature of liquation is controlled by the output of adjusting tungsten-iodine lamp 46 before falling, and sets the optimum temps corresponding to material for.The kind of temperature, the liquation 32b of liquation 32b and size before falling, to contacting the time till the rotor plate 39 or fall distance etc. because of relevant with the overcooling degree, thereby these parameters must be reflected in during device designs.Again, preferably controlling rotor plate 39 makes angle when contacting with spherical liquation 32b, contact pressure, its duration of contact etc. also for best.The material of rotor plate 39 contact surfaces must be chemically stable material, and the material of this contact surface is preferably also selected according to kind of liquation etc.Moreover preferably the distance that falls of setting device makes with after rotor plate 39 contact, solidifies before the liquation 32b arrival cooling fluid 65.
Be difficult for the pyrolysated material in the low and vacuum of the most handy vapour pressure of this monocrystalline manufacture method and make raw material.Available silicon, germanium, SiGe mixed crystal, indium antimonide, gallium antimonide or its mixed crystal etc.Self-evident, make raw material with metallic substance and insulating material, also can make the monocrystalline of these materials.
Can obtain following effect according to this monocrystalline manufacturing technology: can be without seed crystal from raw material liquation direct crystallization glomeration monocrystalline, can make the few high quality single crystal of spherulite defective, form with adulterated discrete little according to the density official post of material in the liquation, can make the monocrystalline of various materials (semi-conductor of single-element, compound semiconductor, metallic substance, insulating material etc.), availablely be arranged on ground device and make monocrystalline, the formation that nucleus generates means is simple, but also supplies raw materials thereby the scale production monocrystalline from raw material supplying maintaining body 38 serially.Example 3 is (with reference to Fig. 3～Fig. 6)
In composition, have in the compound semiconductor crystal of high score decompress(ion) element, decompose in order to prevent liquation or solidified crystal, growing crystal in ampoule or sealed cabin adopts Bridgman method mostly.But, in prior art, can directly crystallize into monocrystalline to liquation with seed crystal.The monocrystalline manufacturing technology of this example is characterized in that the liquation of synthetic compound semiconductor crystal directly crystallizes into monocrystalline to this liquation without seed crystal.
Earlier single-crystal manufacturing apparatus is illustrated.
Fig. 3 represents the integral body of single-crystal manufacturing apparatus 71, and Fig. 4 represents the upper end one side part of single-crystal manufacturing apparatus 71, and Fig. 5 represents the rest part of single-crystal manufacturing apparatus 71.As Fig. 3～shown in Figure 5, single-crystal manufacturing apparatus 71 comprises the ampoule 72 (being equivalent to sealed cabin) with the in addition vacuum-packed quartzy system of raw material (not shown), bielliptic(al) shape gold image furnace 73, the furnace side pipeline 74 of the weak point that links to each other with these gold image furnace 73 downsides, link to each other with these furnace side pipeline 74 lower ends, in the vertical direction definite length extended (for example, about 14m) fall pipeline 75, connect the accumulator tank 76 that this falls pipeline 75 lower ends, the copper messenger wire 78 (be equivalent to sealed cabin and keep means) that in the chamber 77 of golden image furnace 73, keeps ampoule 72, temperature detection thermopair 79, be arranged on the retarding mechanism 80 that falls pipeline 75 inner height directions middle part, and control unit (not shown) etc.The vent plug 81 of separating furnace side pipeline 74 and falling pipeline 75 also is set, separates the vent plug 82 that falls pipeline 75 and accumulator tank 76.
Above-mentioned bielliptic(al) shape gold image furnace 73 is the oval golden image furnace 73a of the relative list of a pair of horizontal direction, makes it that common focus be arranged.Shown in Figure 72, keep ampoule 72 with copper messenger wire 78, make the raw material that is loaded in the ampoule 72 be positioned at this public focus, thus but heating and melting raw material.In golden image furnace 73 upper ends airtight terminal 83 is set, copper messenger wire 78 is from these airtight terminal 83 extensions, and the thermopair 79 that connects platinum-platinum rhodium (Pt-PtRh) system from airtight terminal 83 extensions simultaneously is to detect the temperature of ampoule 72 concubine 72b.The outside terminal 84 that is connected with copper messenger wire 78, the outside terminal 85 that is connected with thermopair 79 are set on airtight terminal 83.
Be provided with mouthfuls 86 and can open and close the open and close valve 87 of this mouthful 86 on the furnace side pipeline 74 that golden image furnace 73 is connected, mouthful 86 its formations can connect vacuum pump, extract the air in the chamber 77 out, as required, can import air to inside.On being installed, the terminal installation parts 98 of airtight terminal 83 forms the transparent gas dam (not shown) that monitors raw material and liquation in the ampoule 72.As shown in Figure 3, Figure 4, be provided with mouthfuls 88 and can open and close the open and close valve 89 of this mouthful 88 on the sidewall that falls pipeline 75, mouthful 88 its formations can connect vacuum pump, extract the air in the chamber 77 out, as required, can import air to inside.Retarding mechanism 80 is used for making and falls the ampoule that falls in the pipeline 75 72 and slow down, and it is arranged on and falls pipeline 75 inner height directions middle part.This retarding mechanism 80 has pair of right and left rotor plate 80a, leans on to the opposite direction of direction shown in the arrow by weak spring, and upper end and the side wall portion of each rotor plate 80a are connected through the hinge.In a single day the ampoule 72 that falls contacts this rotor plate 80a is just slowed down, but does not stop and continuing to fall.
In the fluid container 90 of accumulator tank 76 bottoms, silicone oil 91 that has 72 impacts of buffering ampoule and refrigerating function concurrently and the cushioning material 92 that absorbs ballistic silicone rubber and so on are housed.Be provided for taking out the openning 93 of ampoule 72 at the sidewall of accumulator tank 76, it constitutes this openning 93 available vent plug 94 and opens and closes.
Be provided with mouthfuls 96 and can open and close mouthfuls 96 open and close valve 97 on the sidewall of accumulator tank 76, mouthful 96 its formations can connect vacuum pump, extract the air in the accumulator tank 76 out, also can import air to inside as required.
As shown in Figure 4, the ampoule 72 of quartzy system has by raw material liquation 95b to be made the 72a of main chamber of monocrystalline and is arranged in the 72a of this main chamber top, makes the high elements vaporization of vapour pressure and dissolves in the concubine 72b of the 72a of main chamber liquation 95b, between 72a of main chamber and concubine 72b, diffusion partitions 72d is set, forms vapor diffusion on it and adjust aperture 72c.When manufacturing contains the compound semiconductor single crystal of the high element of decomposition pressure, in this ampoule 72, enclose raw material and make it then to fall.
At this moment, in the 72a of main chamber, pack into to each constitute element in advance weighing make the raw material that becomes in its compound semiconductor stoichiometric composition of fusing point, perhaps in the 72a of main chamber, pack into by having the raw material that polycrystalline that this compound semiconductor forms constitutes, by golden this raw material of image furnace 73 heating and meltings, make the compound semiconductor liquation.
On the other hand, in concubine 72b, pack into the raw material of the high element of decomposition pressure.And raw material quantity that provides and Heating temperature only produce and the suitable vapour pressure of the necessary decomposition pressure of stoichiometric composition the liquation at the 72a of fusing point main chamber.Again, ampoule 72 is equivalent to nucleus generation means with retarding mechanism 80.
Then, illustrate with single-crystal manufacturing apparatus 71 manufacturing In
0.97Ga
0.03The example of As semiconductor monocrystal.
In is put in bottom at the 72a of the main chamber of ampoule 72
0.97Ga
0.03The As semi-conductor is formed element Ga and In.The amount of packing into is In
0.97Ga
0.03The liquation of As fusing point is formed the predetermined amount of pairing germanium (Ga) and indium (In).Equally, in secondary 72b, put into generation and In
0.97Ga
0.03Arsenic decomposition pressure equilibrated arsenic (As) during the As fusing point is pressed necessary As amount.After putting into the raw material of these components, ampoule 72 is evacuated to be sealed.
This ampoule 72 passes its upper end ring portion 73e with copper messenger wire 78, winches to the public focus place of golden image furnace 73.After the 77 inner vacuum exhausts of chamber, make electric current flow through tungsten-iodine lamp 73b, the bottom of the 72a of main chamber of ampoule 72 is heated to compares In
0.97Ga
0.031070 ℃ of the high slightly temperature of the fusing point of As, concubine 72b is heated to about 600 ℃ simultaneously.By heating, at first form the liquation of forming by In and Ga in the bottom of the 72a of main chamber, at concubine 72b, the distillation of the part of AS becomes gas, diffuses among the 72a of main chamber, and the liquation of forming with In and Ga reacts, and synthesizes to have In
0.97Ga
0.03The liquation 95b that As forms.Ampoule 72 before liquation 95b is synthetic, make vent plug 81,82 become open state, so that can fall freely falling body in pipeline 75 and the accumulator tank 76 pre-evacuated.Then, at In
0.97Ga
0.03As liquation 95b is synthetic to be finished constantly, makes electric current flow through copper messenger wire 78 and makes it fusing, allows ampoule 72 freely falling bodies, the power supply that cuts off tungsten-iodine lamp 73b simultaneously.
Fall in the ampoule 72 that begins the back freely falling body and become microgravity environment, In
0.97Ga
0.03As liquation 95b is in suspended state, becomes spherical fully under surface tension effects.Spherical liquation 95b dispels the heat in falling becomes the overcooling state, and ampoule 72 contacts with a pair of rotor plate 80a then, and speed of fall is slowed down, ampoule 72 in owing to action of gravity, the solid surface short-time contact of the liquation 95b of suspension and 72a bottom surface, main chamber.Thus, the part surface at spherical liquation 95b generates nucleus.Thereafter because ampoule 72 continues freely falling bodies and heat radiation, the nucleus by the liquation 95b of suspended state in the 72a of main chamber carries out crystal growth rapidly, and whole spherical liquation 95b become In
0.97Ga
0.03The As monocrystalline is fallen into silicone oil 91 then and is cooled off.
With reference to Fig. 6 above-mentioned action of solidifying that is blended into by liquation that remarks additionally.Fig. 6 (a) is the state of ampoule 72 before golden image furnace 73 just will begin to fall, and by golden image furnace 73 heating, In is made in the mutual fusion of the raw material of each component
0.97Ga
0.03As synthesizes liquation 95b.Fig. 6 (b) expression ampoule 72 freely falling body in falling pipeline 75 produces microgravity environment in inside, and liquation 95b suspends, because of surface tension effects becomes the globular state.Can infer that in this spherical liquation 95b identical with monocrystalline, a large amount of atoms that constitute element are done the arrangement of systematicness.Fig. 6 (c) expression ampoule 72 contacts with a pair of rotor plate 80a of retarding mechanism 80 and state when slowing down.Spherical liquation 95b and 72a bottom surface, main chamber (solid surface) collision, the part surface contact bottom surface of spherical liquation 95b because its surface free energy reduces, generates nucleus in this part.Fig. 6 (d) expression ampoule 72 becomes free falling body state once more by retarding mechanism 80, the state of the spherical monocrystalline 95c of spherical liquation 95b solidify out into of suspension.State when Fig. 6 (e) expression ampoule 72 is fallen into silicone cooling fluid 91.This monocrystalline manufacture method can be used for making the monocrystalline that above-mentioned various kinds of compound semiconductors in addition promptly contains the compound semiconductor of the high element of decomposition pressure.But self-evident, also the raw material of available metal material and insulating material is made the spherical monocrystalline of these materials.
According to this monocrystalline manufacturing technology, can obtain following effect: can directly make spherical monocrystalline from liquation without seed crystal, can be by multiple element raw material synthetic compound semi-conductor, under microgravity environment, keep the spheroidal monocrystalline with suspended state, thereby can make the considerably less high-quality monocrystalline of lattice defect, form with adulterated impurity discrete little according to the density official post of material in the liquation, the above compound semiconductor single crystal of ternary can be made, and the various materials (semi-conductor of single-element can be made, compound semiconductor, metallic substance, insulating material etc.) spherical monocrystalline etc.At last, in the also available above-mentioned example 1～3 in addition the form that changes of following part implement.
(1) heater meanses such as available resistive heating device, high-frequency electromagnetic induction heating unit, electron beam heating unit, laser heating device replace tungsten-iodine lamp.
(2) as implementing shown in the form 3, ampoule is fallen when making monocrystalline, wish that the low concubine of temperature of making the high-temperature main of liquation and making muddy property elements vaporization heats respectively.For this reason, preferably can heat main chamber and concubine by the independent separately thermal source of controlling by temperature.This also is fully possible in prior art.
(3) known faster when under microgravity environment, gravity being arranged by the velocity ratio of granular liquation that is in suspended state or spherical liquation crystal growth.Supposition according to relevant therewith contriver can be thought, the liquation structure of overcooling state is different with the liquation structure under the gravity state, but make regular atomic arrangement equally with monocrystalline, in case thereby nucleus is a point or local the generation, because the chemical potential energy of liquid phase is big, therefore from nucleus growing crystal rapidly, become monocrystalline.Thereby, can change an end that makes granular liquation in the above-mentioned example and contact the step that generates nucleus with other solid matters, replace, an end or the part of granular liquation in falling on the way with ion beam irradiation are to reduce surface free energy, thus, generate nucleus, by this nucleus growth monocrystalline.
Claims (18)
1. a fused raw material makes it to solidify the method for making monocrystalline then, it is characterized in that comprising following operation:
Heating raw makes it fused the 1st operation;
Reducing described raw material melt temperature makes liquation become the 2nd operation of the granular liquation of overcooling state;
In microgravity environment, make the granular liquation of described overcooling state keep suspended state, by making the high solid surface of part surface short-time contact chemical stability of this granular liquation, reduce this granular liquation part surface surface free energy, make the 3rd operation that in granular liquation, generates nucleus;
Under microgravity environment, make granular liquation be frozen into the 4th operation of granular single crystal with described nucleus.
2. monocrystalline manufacture method as claimed in claim 1 is characterized in that, the semiconductor material of using single-element is as described raw material.
3. monocrystalline manufacture method as claimed in claim 1 is characterized in that, makes compound semiconductor single crystal with compound semiconductor materials as described raw material.
4. monocrystalline manufacture method as claimed in claim 1 is characterized in that, makes compound semiconductor single crystal with the semiconductor material of multiple element as described raw material.
5. monocrystalline manufacture method as claimed in claim 4 is characterized in that, when described raw material contains the high semiconductor material of vapour pressure, raw material is placed on carries out the 1st～the 4th operation in the sealed cabin.
6. monocrystalline manufacture method as claimed in claim 5, it is characterized in that, in the main chamber of sealed cabin, pack in advance semiconductor material except that the high semiconductor material of described vapour pressure, in the close cabin of envelope with concubine that the main chamber is communicated with in the high semiconductor material of vapour pressure of packing in advance, in the 1st operation, semiconductor material in the main chamber and the semiconductor material in the concubine are heated to differing temps.
7. as each described monocrystalline manufacture method in the claim 1～6, it is characterized in that, carry out the 1st～the 4th operation in the arbitrary atmosphere in vacuum atmosphere, inert gas atmosphere, oxidizing gas atmosphere.
8. one kind is suitable for the single-crystal manufacturing apparatus that microgravity environment is realized means, cooperates by raw material manufacturing monocrystalline with the microgravity environment that microgravity environment realization means realize, it is characterized in that this single-crystal manufacturing apparatus comprises:
Form the chamber housing of resistance to air loss chamber;
Be configured in the material container of described indoor placement raw material;
Heat the heater means of the raw material in the described material container;
Described material container is supported on the housing of chamber can drives the actuator that material container moves with respect to the chamber housing simultaneously.
9. single-crystal manufacturing apparatus as claimed in claim 8, it is characterized in that, it constitutes the raw material that heats in the described material container with heater means and makes it fusion, make the noncontact shape suspension in microgravity environment in material container of this liquation, cooling becomes the granular liquation of overcooling state under this state, in microgravity environment under noncontact shape suspended state, driving material container by described actuator moves relative to the chamber housing, the granular liquation part surface of this overcooling state is contacted with the solid face of material container, in granular liquation, generate nucleus, make granular liquation solidify the manufacturing granular single crystal.
10. single-crystal manufacturing apparatus as claimed in claim 8 or 9 is characterized in that described heater means comprises oval plane of reflection and is configured in the tungsten-iodine lamp of this ellipse plane of reflection focus.
11. a heating raw makes it to become liquation, makes this liquation freely falling body solidify the single-crystal manufacturing apparatus of making monocrystalline in microgravity environment, it is characterized in that this manufacturing installation comprises:
Extend in vertical direction, gastight falls pipeline;
Keep means at the described raw material that keeps raw material in the ducted upper end and can remove maintenance that falls;
Heating described raw material keeps the raw material that means kept to make it the fused heater means;
The granular liquation of described fused freely falling body in falling pipeline becomes the overcooling state, reduces granular liquation part surface free energy in freely falling body in falling the pipeline way, makes the nuclei of crystallization that generate nucleus in granular liquation generate means;
Being recovered in the further freely falling body with the nucleus is the recoverer of the monocrystalline that solidifies of nuclear.
12. single-crystal manufacturing apparatus as claimed in claim 11 is characterized in that, the described extraction means that ducted air makes it to form vacuum that fall that extract also are set.
13. single-crystal manufacturing apparatus as claimed in claim 12 is characterized in that, described heater means has oval plane of reflection and is configured in the tungsten-iodine lamp of this ellipse plane of reflection focus.
14. as each described single-crystal manufacturing apparatus in the claim 11～13, it is characterized in that, described crystal grain generation means be configured in the granular liquation that falls in the pipeline fall in the path and the rotor plate of being made by the high solid material of chemical stability constitutes.
15. a heating raw makes it to become liquation, makes this liquation freely falling body solidify the single-crystal manufacturing apparatus of making monocrystalline in microgravity environment, it is characterized in that this device comprises:
The gastight that extends in vertical direction falls pipeline;
The sealed cabin that charging feedstock can Gong fall;
Sealed cabin is remained on the described sealed cabin maintenance means that fall the pipeline upper end and can remove maintenance;
Heating described sealed cabin keeps the interior raw material of sealed cabin that means kept to make it the fused heater means;
The granular liquation of described fused becomes the overcooling state with sealed cabin freely falling body in falling pipeline, falls free energy that the pipeline middle part divides granular liquation part surface generates nucleus in granular liquation nucleus generation means in the freely falling body thereby reduce;
Reclaim the recoverer that the further monocrystalline that when freely falling with the nucleus is nuclear is frozen into reclaims sealed cabin simultaneously.
16. single-crystal manufacturing apparatus as claimed in claim 15 is characterized in that, the described extraction means that ducted air makes it to form vacuum that fall that extract also are set.
17. single-crystal manufacturing apparatus as claimed in claim 16 is characterized in that, described heater means has oval plane of reflection and is configured in the tungsten-iodine lamp of this ellipse plane of reflection focus.
18., it is characterized in that described nucleus generation means are configured in the deceleration means that the sealed cabin that falls in the pipeline falls in the path and comprises the sealed cabin deceleration that makes in falling as each described single-crystal manufacturing apparatus among the claim 15-17.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 97180857 CN1125199C (en) | 1997-10-23 | 1997-10-23 | Method of mfg. single crystal and apparatus for mfg. single crystal |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 97180857 CN1125199C (en) | 1997-10-23 | 1997-10-23 | Method of mfg. single crystal and apparatus for mfg. single crystal |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1241222A CN1241222A (en) | 2000-01-12 |
| CN1125199C true CN1125199C (en) | 2003-10-22 |
Family
ID=5177916
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 97180857 Expired - Fee Related CN1125199C (en) | 1997-10-23 | 1997-10-23 | Method of mfg. single crystal and apparatus for mfg. single crystal |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1125199C (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107695359B (en) * | 2017-09-06 | 2020-03-31 | 西北工业大学 | Microgravity and liquid quenching integrated metal droplet solidification method |
| CN108168994B (en) * | 2017-11-27 | 2020-03-20 | 西北工业大学 | Device for solidifying metal liquid drops under free falling condition |
-
1997
- 1997-10-23 CN CN 97180857 patent/CN1125199C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1241222A (en) | 2000-01-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP3287579B2 (en) | Single crystal manufacturing method and single crystal manufacturing apparatus | |
| Schilz et al. | Bulk growth of silicon-germanium solid solutions | |
| JP3053958B2 (en) | Crystal production equipment by the floating zone melting method | |
| CN102260903A (en) | Method for growing thin silicon crystals | |
| US20210222320A1 (en) | Method of Producing a Single-Crystal | |
| Triboulet | The travelling heater method (THM) for Hg1− xCdxTe and related materials | |
| CN1125199C (en) | Method of mfg. single crystal and apparatus for mfg. single crystal | |
| CN105133004B (en) | A kind of USb2The flux growth method of monocrystalline and the product of preparation | |
| CN116334759A (en) | Seed crystal dissolving method and device for growing tellurium-zinc-cadmium crystals based on THM | |
| Hurle | Crystal Growth | |
| JP6607652B1 (en) | Single crystal manufacturing equipment | |
| CN100408731C (en) | Method and appts. of using molten lead iodide to grow monocrystal | |
| EP1013801A1 (en) | Process and apparatus for synthesizing and growing crystals | |
| KR100349872B1 (en) | Method of manufacturing single crystal and apparatus for manufacturing single crystal | |
| JPH089520B2 (en) | Method of manufacturing thin film single crystal | |
| JP2013537511A (en) | Method for doping semiconductor materials | |
| US3999950A (en) | Apparatus for crystal growth in outer space | |
| JP2006036581A (en) | Method for producing granular crystal | |
| JP2010030847A (en) | Production method of semiconductor single crystal | |
| JP2000226300A (en) | Method and apparatus for synthesizing and growing crystal | |
| JP3951009B2 (en) | Manufacturing method of spherical semiconductor | |
| CN117626440A (en) | Device for releasing latent heat of tellurium-zinc-cadmium monocrystal crystallization and growth method | |
| Nelson et al. | Advances In (Hg, Cd) Te Materials Technology | |
| Capper et al. | Growert | |
| JP2732573B2 (en) | Manufacturing method of compound semiconductor single crystal |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| REG | Reference to a national code |
Ref country code: HK Ref legal event code: GR Ref document number: 1045907 Country of ref document: HK |
|
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20031022 Termination date: 20121023 |