CN104313681A - Device for growth of multinary compound crystals and application thereof - Google Patents
Device for growth of multinary compound crystals and application thereof Download PDFInfo
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- CN104313681A CN104313681A CN201410624831.6A CN201410624831A CN104313681A CN 104313681 A CN104313681 A CN 104313681A CN 201410624831 A CN201410624831 A CN 201410624831A CN 104313681 A CN104313681 A CN 104313681A
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Abstract
The invention discloses a device for the growth of multinary compound crystals and application thereof. The device comprises a furnace body, a lifting device and a growing ampoule, wherein the growing ampoule successively consists of a hanger, a main body part, a shoulder placing part and a seed crystal bag from top to bottom, and the inner diameter of a column of the main body part is gradually decreased from top to bottom; the seed crystal bag is a cylinder of which the lower part is sealed, and the shape of the combination of the shoulder placing part and the seed crystal bag is similar to a funnel; and the inner part of the device is divided into an upper furnace low-temperature area, a middle furnace high-temperature area and a lower furnace low-temperature area by a heating element. For the device and the application thereof, disclosed by the invention, the growth of the crystals is carried out in a real-time supply manner, and the condition that parts of components are gathered in a melting body close to a growing interface because of the component segregation is effectively avoided, so that the components of the growing crystals are more uniform.
Description
Technical field
The present invention relates to a kind of crystal technique, be specifically related to a kind of equipment for multi-element compounds crystal growth and application thereof.
Background technology
Bridgeman crystal growth method is that people are exploring the method that extensively adopts of novel semi-conductor crystal material growth method initial stage in recent years.Because the method technique is simple, can without the need to the guiding of seed crystal, crystal grows in airtight ampoule simultaneously, is not subject to the advantages such as environmental pollution, and bridgeman crystal growth method becomes current people in the primary selection exploring the melt method for growing novel crystal initial stage.
In long-term research practice, people, by improving to some extent the method, achieve the growth to dissimilar crystal, obtain the multiple novel crystal that can meet national product demand, as gallium arsenide, S-Ga-Ag, selenium gallium silver, phosphorus germanium zinc.
Bridgeman crystal growth method is mainly divided into vertical Bridgman and horizontal Bridgman two kinds of methods.Its basic ideas are all be encapsulated in the growth ampoule of a particular design by the polycrystal raw material of growing crystal, first at high temperature by polycrystal raw material melting, and then slow mobile growth ampoule is to low-temperature zone, in moving process, polycrystalline melt in ampoule starts crystallization and grows up gradually, after whole ampoule all moves to low-temperature zone, crystal growth terminates.Under normal circumstances, crystal all has certain exhausting impurity function in process of growth.Particularly in the process of growth of some multi-element compounds crystal, the uneven key factor affecting crystal practical application often of the stoichiometric ratio that the solute segregation that its exhausting impurity function causes causes.
The homogeneity of growing crystal in order to improve, the method that people generally adopt has two kinds, and one is the mass transfer accelerating melt inside by rotating ampoule, reduces the gathering of impurities removal component; Two is carry out crystal growth by the mode of real-time feed, namely constantly supplements the quantity of polycrystal raw material according to the speed of crystal growth, reduces the melt thickness at solid-liquid interface place.Although be in a relatively uniform state by the mode component that can realize in melt rotating ampoule, but the component of discharging in process of growth due to crystal still can be assembled in melt, the homogeneity question that solute segregation causes therefore fundamentally cannot be solved.And grown by the mode of real-time feed, due to melt very thin thickness more than solid-liquid interface, the scope that solute segregation can act on is also just very little, therefore fundamentally can improve the homogeneity of institute's growing crystal.
But feed is owing to relating to the matching problem of feeding system and growing system in real time, also have the airtight problem of whole environment, therefore actual using not is a nothing the matter.Traditional bridgeman growth method is all in same ampoule due to melt and crystal, is realized the growth of crystal by the mode of directional freeze, and the mode that cannot meet real-time feed grows.
Summary of the invention
[technical problem that will solve]
The object of the invention is to solve the component uniformity difference and the problems referred to above thereof that cause because of solute segregation in traditional bridgeman crystal growth process, provide crystal growth equipment and the application thereof of real-time feed in a kind of crystal growing process.
[technical scheme]
In order to reach above-mentioned technique effect, the present invention takes following technical scheme:
The present invention devises a kind of bridgeman growth method that can realize real-time feed in process of growth.The method can be supplemented in real time according to the amount of the polycrystal raw material consumed in single crystal growth process, makes the melt quantity of more than growth interface remain on a less level, reduces the scope that solute segregation can affect.
A kind of equipment for multi-element compounds crystal growth, it comprises body of heater, pulling apparatus and growth ampoule, boiler tube is provided with in described body of heater, and the central shaft of body of heater overlaps with the central shaft of boiler tube, one deck stove inner thermal insulating layer is covered between body of heater and boiler tube, described stove inner thermal insulating layer is embedded in heating unit, and heating unit is near boiler tube; Described growth ampoule is connected by lifting line with pulling apparatus, and growth ampoule moves up and down under the traction of pulling apparatus in boiler tube, and described growth ampoule is followed successively by hook, main body section, shouldering position and seed crystal bag from top to bottom; The top that described hook is placed in main body section between two parties and connect lift line growth ampoule is connected with pulling apparatus; The column internal diameter of described main body section diminishes from top to bottom gradually; Described seed crystal bag is the right cylinder of lower seal, the combination likeness in form funnel of described shouldering position and seed crystal bag; Described heating unit makes to be divided into stove cold zone, middle stove high-temperature zone and lower stove cold zone in boiler tube from top to bottom.
According to a preferred embodiment of the present invention, upper part of described main body section is for placing the polycrystalline stock column consistent with its shape size, and this polycrystalline stock column does not fill up upper part of main body section; Described seed crystal bag is used for filling seed crystal.
According to another preferred embodiment of the present invention, the column internal diameter at described shouldering position is reduced to size the same as the column internal diameter of seed crystal bag gradually from size the same as the column internal diameter bottom main body section.
According to another preferred embodiment of the present invention, the temperature of described upper stove cold zone is from top to bottom in the trend raised gradually, and on this, the temperature of stove cold zone is lower than the fusing point of multi-element compounds crystal used.
According to another preferred embodiment of the present invention, the temperature of described lower stove cold zone is from top to bottom in downward trend gradually, and the temperature of this lower stove cold zone is lower than the fusing point of multi-element compounds crystal used.
According to another preferred embodiment of the present invention, the temperature of described middle stove high-temperature zone is from top to bottom in downward trend after first raising, and in this, the temperature of stove high-temperature zone is higher than the fusing point of multi-element compounds crystal used; The area size of described middle stove high-temperature zone is consistent with the region between described polycrystalline stock column lower end to seed crystal upper end.
According to another preferred embodiment of the present invention, described growth ampoule is prepared from by high purity quartz or pyrolitic boron nitride.
Described equipment is applied to the method for multi-element compounds crystal growth, and the method comprises the following steps:
First, polycrystal is pressed into the consistent polycrystalline stock column of main body section upper part shape size, then polycrystalline stock column is loaded in growth ampoule;
Then, the growth ampoule loading polycrystalline stock column is put into boiler tube by lift line and pulling apparatus, and make upper part that the main body section of growth ampoule is equipped with polycrystalline stock column be positioned at stove cold zone, region between polycrystalline stock column lower end to seed crystal upper end is arranged in stove high-temperature zone, and the seed crystal bag that seed crystal is housed is positioned at lower stove cold zone;
Secondly, set warm curvature of field line, equipment is heated up, insulation for some time;
Then, open pulling apparatus, slow degrowth ampoule, polycrystalline stock column starts fusing, and the polycrystal melt after fusing is added dropwise to seed crystal surface area and starts to carry out the growth of crystal; Treat that polycrystalline stock column is gradually consumed complete, after the polycrystal melt in growth ampoule all drops to lower stove cold zone, stop declining, crystal growth terminates;
Finally, equipment is lowered the temperature, take out crystal.
The present invention will be explained below.
A kind of equipment for multi-element compounds crystal growth, it comprises boiler tube, pulling apparatus and growth ampoule, boiler tube is provided with in described boiler tube, and the central shaft of body of heater overlaps with the central shaft of boiler tube, one deck stove inner thermal insulating layer is covered between body of heater and boiler tube, described stove inner thermal insulating layer is embedded in heating unit, and heating unit is near boiler tube; Described growth ampoule is connected by lifting line with pulling apparatus, and growth ampoule moves up and down under the traction of pulling apparatus in boiler tube, and described growth ampoule is followed successively by hook, main body section, shouldering position and seed crystal bag from top to bottom; The top that described hook is placed in main body section between two parties and connect lift line growth ampoule is connected with pulling apparatus; The column internal diameter of described main body section diminishes from top to bottom gradually; Described seed crystal bag is the right cylinder of lower seal, the combination likeness in form funnel of described shouldering position and seed crystal bag; Described heating unit makes to be divided into stove cold zone, middle stove high-temperature zone and lower stove cold zone in boiler tube from top to bottom.
Described heating unit is looped around in stove inner thermal insulating layer, heats to boiler tube near boiler tube, makes to form certain warm curvature of field line in boiler tube.
The column internal diameter of the described main body section Main Function that diminishes gradually is from top to bottom fixing polycrystalline stock column.Described main body section makes main body section be certain taper from the setting diminished gradually under upper, and this range of taper is at 3 ~ 5 °.In growth ampoule decline process, polycrystal bottom is constantly melted, and after this structure design of main body section can ensure that polycrystalline stock column bottom is melted, polycrystalline stock column top relative displacement can not occur in growth ampoule inside.Be conducive to the fusing controlling polycrystalline stock column like this, be also beneficial to the realization of real-time feed simultaneously.
The opening of whole growth ampoule is located at the top of main body section.
According to a preferred embodiment of the present invention, upper part of described main body section is for placing the polycrystalline stock column consistent with its shape size, and this polycrystalline stock column does not fill up upper part of main body section; Described seed crystal bag is used for filling seed crystal.
The shape size of polycrystalline stock column is consistent with upper part of main body section refer to the tapering of this polycrystal and diameter be placed on the tapering of the position of main body section with it and column internal diameter in the same size.Ensure that the shape size of polycrystalline stock column is consistent with upper part shape size of main body section, refer to the position that will to be placed on according to polycrystalline stock column in growth ampoule, utilize particular mold that powder polycrystal is pressed into corresponding size shape, can ensure that polycrystal is fitted closely with growth ampoule inwall after putting into growth ampoule like this, along with the fusing of polycrystalline stock column bottom, relative displacement not occur.
According to another preferred embodiment of the present invention, polycrystal column bottom and shouldering position distance have 3 ~ 5cm.
Seed crystal used has specific orientation and the single crystal identical with the multi-element compounds crystalline component of synthesis, is the seed of growing single-crystal.The seed crystal of growing single-crystal is the single crystal identical with polycrystal composition, and only one is polycrystalline, and one is monocrystalline.With polycrystalline as raw material, single crystal seed guides growth, the corresponding seed crystal of growth needs of different crystal.Such as long silicon single-crystal needs to do seed crystal with silicon single crystal, long sapphire then needs to do seed crystal with sapphire single-crystal.
According to another preferred embodiment of the present invention, the column internal diameter at described shouldering position is reduced to size the same as the column internal diameter of seed crystal bag gradually from size the same as the column internal diameter bottom main body section.
The effect at shouldering position is the diameter of being grown up by seed crystal to the same with crystalline body position column internal diameter, and its slant range needs to be optimized according to the specific object of institute's growing crystal.
According to another preferred embodiment of the present invention, the temperature of described upper stove cold zone is from top to bottom in the trend raised gradually, and on this, the temperature of stove cold zone is lower than the fusing point of multi-element compounds crystal used.The thermograde of described upper stove cold zone is arranged on 1 ~ 10 DEG C/cm, and the distribution of its thermograde shows as slow lower steep trend.
According to another preferred embodiment of the present invention, the temperature of described lower stove cold zone is from top to bottom in downward trend gradually, and the temperature of this lower stove cold zone is lower than the fusing point of multi-element compounds crystal used.The thermograde of described lower stove cold zone is arranged on 1 ~ 10 DEG C/cm, and the distribution of its thermograde shows as steep lower slow trend.
According to another preferred embodiment of the present invention, the temperature of described middle stove high-temperature zone is from top to bottom in downward trend after first raising, and in this, the temperature of stove high-temperature zone is higher than the fusing point of multi-element compounds crystal used; The interval size of described middle stove high-temperature zone is consistent with the region between described polycrystalline stock column lower end to seed crystal upper end.The temperature head of described middle stove high-temperature zone is generally 5 ~ 30 DEG C.
The area size of described middle stove high-temperature zone can not be too short, because under normal conditions, utilizes tubular type to add the warm field gradient of thermosetting smaller, need more reserved spaces to adapt to warm field control overflow.Therefore the area size of middle stove high-temperature zone specifically need be arranged according to the melting temperature of polycrystalline stock column, the control making the design of its area size can melt polycrystalline stock column fully to adapt to again warm field.The placement location of corresponding polycrystalline stock column is also relevant with the melting temperature of polycrystalline stock column used.The crystallisation process of crystal completes in temperature gradient zone, and maintaining a stable thermograde is temperature controlled key in crystal growing process.Consider from the angle maintaining plane crystalizing interface, thermograde should be comparatively large, middle stove high-temperature zone of the present invention area size relative to upper stove cold zone and lower stove cold zone shorter.Therefore, the present invention need the fusing point needed for concrete multi-element compounds crystal growth regulate simultaneously in the temperature province of stove high-temperature zone and the placement location of polycrystalline stock column, to obtain best warm field gradient.
According to another preferred embodiment of the present invention, described growth ampoule is prepared from by high purity quartz or pyrolitic boron nitride.
Growth ampoule is directly with the crystal grown and melt contacts thereof, and has important impact to the heat transfer characteristic of crystal growing process.Therefore, the selection of growth ampoule material is that can crystal growing process realize and one of the controlling factor of crystal structure quality good or not.The selection of growth ampoule material is determined by grown crystal and character in the molten state thereof.Selected material will have higher chemical stability, not with crystal or melt generation chemical reaction; There is sufficiently high purity, impurity, the pollution crystalline material harmful to crystal can not be discharged in crystal growing process, or occur bonding with crystal; There is higher fusing point and hot strength, under crystal growth temperature, still keep sufficiently high intensity, and at high temperature can not decompose, oxidation etc.; There is certain capacity of heat transmission, be convenient in high-temperature zone melt heating or the cooling carrying out crystal in cold zone; But it is disadvantageous to crystal growth that the capacity of heat transmission is crossed strong; There is workability, be convenient to according to crystal growth need be processed into different shapes; There is the thermal expansion character of mating with crystalline material, can not to crystal formation larger stress in crystal growing process, and be easy to take out after crystal growth terminates.
Described equipment is applied to the method for multi-element compounds crystal growth, and the method comprises the following steps:
First, polycrystal is pressed into the consistent polycrystalline stock column of main body section upper part shape size, then polycrystalline stock column is loaded in growth ampoule;
Multi-element compounds single crystal growing is all generally first with the simple substance raw material through chemical reaction synthesised polycrystalline material of this crystal of synthesis, and then carrys out growing crystal with polycrystal as raw material.The synthesis of polycrystalline needs to carry out chemical reaction, utilizes polycrystal growing single-crystal to be a physical process being melted to crystallization.Certainly, the growth needs of often kind of monocrystalline synthesizes the polycrystal of corresponding composition.For example, growth arsenide gallium monocrystal, first generate gallium arsenide with elemental arsenic and Metallic Gallium by chemical reaction, and the gallium arsenide that chemical reaction generates is all the polycrystal powder or particle that crystal grain is tiny, then utilizes this polycrystal powder or particle to carry out fusion-crystallization again as raw material and grow into a large single crystal.
Then, the growth ampoule loading polycrystalline stock column is put into boiler tube by lift line and pulling apparatus, and make upper part that the main body section of growth ampoule is equipped with polycrystalline stock column be positioned at stove cold zone, region between polycrystalline stock column lower end to seed crystal upper end is arranged in stove high-temperature zone, and the seed crystal bag that seed crystal is housed is positioned at lower stove cold zone;
Secondly, set warm curvature of field line, equipment is heated up, insulation for some time; The setting of its warm curvature of field line specifically sets according to the thermograde of upper stove cold zone, lower stove cold zone and the temperature difference of middle stove high-temperature zone.
Insulation for some time is to allow polycrystalline stock column lower end and seed crystal upper end portion fully melt.Substantially a kind of steady state is reached.
Then, open pulling apparatus, slow degrowth ampoule, polycrystalline stock column starts fusing, and the polycrystal melt after fusing is added dropwise to seed crystal surface area and starts to carry out the growth of crystal; Treat that polycrystalline stock column is gradually consumed complete, after the polycrystal melt in growth ampoule all drops to lower stove cold zone, stop declining, crystal growth terminates;
Degrowth ampoule slowly, is utilize the slow mobile growth ampoule of pulling apparatus, makes it steady uniform descent.In decline process, seed crystal and above region down enter lower stove cold zone and carry out crystallization, and the region of polycrystalline stock column lower end enters middle stove high-temperature zone and melts.The amount of seed crystal above position melt crystallization is less than or equal to the amount of polycrystalline stock column lower end fusing, can ensure that the position of more than growth interface has skim polycrystalline melt to exist all the time like this, be dropped on crystalizing interface the disturbance that growth interface causes after reducing the fusing of polycrystalline stock column lower end.
Finally, equipment is lowered the temperature, after temperature is down to room temperature in boiler tube, take out growth ampoule, cut growth ampoule and take out crystal.
[beneficial effect]
The present invention compared with prior art, has following beneficial effect:
The single crystal growing that described growth method of the present invention is carried out, due to the melt very thin thickness near growth interface, simultaneously in process of growth, polycrystal adds to growth interface place by the mode of real-time supply, effectively prevent the gathering of constituent part near growth interface in melt because solute segregation causes, and make the component of institute's growing crystal more even.Particularly for the crystal that some solute segregations are more serious, the effect of the method is more obvious.
Accompanying drawing explanation
The growth ampoule structural representation that Fig. 1 adopts for the embodiment of the present invention 1;
The structural representation of the equipment for multi-element compounds crystal growth that Fig. 2 adopts for the embodiment of the present invention 1;
Fig. 3 is the warm curvature of field line distribution schematic diagram of equipment in Fig. 2, and wherein, X-coordinate represents temperature, and ordinate zou is height consistent with Fig. 2 equipment;
Wherein, the region length of middle stove high-temperature zone is consistent with the interval length below polycrystalline stock column in growth ampoule to seed crystal;
Fig. 4 is the XRD figure spectrum of the In component of the selenium indium gallium silver crystal different sites that the embodiment of the present invention 2 adopts traditional Bridgman method to grow;
Fig. 5 is the XRD figure spectrum that the embodiment of the present invention 2 adopts the In component of the selenium indium gallium silver crystal different sites of present device and method growth thereof;
Illustrate as shown in the figure below,
1 is hook; 10 is growth ampoule;
2 is polycrystalline stock column; 11 is stove inner thermal insulating layer;
3 is main body section; 12 is warm curvature of field line;
4 is shouldering position; 13 is upper stove cold zone;
5 is seed crystal bag; 14 is middle stove high-temperature zone;
6 is seed crystal; 15 is lower stove cold zone;
7 is pulling apparatus; 16 is body of heater;
8 is lift line; 17 is boiler tube.
9 is heating unit;
Embodiment
Below in conjunction with embodiments of the invention, the invention will be further elaborated.
Embodiment 1:
Fig. 2 is a kind of equipment for multi-element compounds crystal growth, it comprises body of heater 16, pulling apparatus 7 and growth ampoule 10, boiler tube 17 is provided with in described body of heater 16, and the central shaft of body of heater 16 overlaps with the central shaft of boiler tube 17, one deck stove inner thermal insulating layer 11 is covered between body of heater 16 and boiler tube 17, described stove inner thermal insulating layer 11 is embedded in heating unit 9, and heating unit 9 is near boiler tube 17; Described growth ampoule 10 is connected by lifting line 8 with pulling apparatus 7, and growth ampoule 10 moves up and down under the traction of pulling apparatus 7 in boiler tube 17.
Fig. 1 is growth ampoule, and described growth ampoule 10 is prepared from by high purity quartz or pyrolitic boron nitride.It is made up of hook 1, main body section 3, shouldering position 4 and seed crystal bag 5 from top to bottom successively; The top that described hook 1 is placed in main body section (3) between two parties and connect lift line 8 growth ampoule 10 is connected with pulling apparatus 7; The column internal diameter of described main body section (3) diminishes from top to bottom gradually; Described seed crystal bag 5 is the right cylinder of lower seal, the combination likeness in form funnel of described shouldering position 4 and seed crystal bag 5; Described heating unit 9 makes to be divided into stove cold zone 13, middle stove high-temperature zone 14 and lower stove cold zone 15 in boiler tube 17 from top to bottom.
Upper part of described main body section 3 is for placing the polycrystalline stock column 2 consistent with its shape size, and this polycrystalline stock column 2 does not fill up upper part of main body section 3; Described seed crystal bag 5 is for filling seed crystal 6.
The column internal diameter at described shouldering position 4 is reduced to size the same as the column internal diameter of seed crystal bag 5 gradually from the same size of column internal diameter bottom main body section 3.
Fig. 3 is the warm curvature of field line matched with Fig. 2 equipment, and the temperature of described upper stove cold zone 13 is from top to bottom in the trend raised gradually, and on this, the temperature of stove cold zone 13 is lower than the fusing point of multi-element compounds crystal used; The temperature of described lower stove cold zone 15 is from top to bottom in downward trend gradually, and the temperature of this lower stove cold zone 15 is lower than the fusing point of multi-element compounds crystal used; Downward trend after the temperature of described middle stove high-temperature zone 14 first raises from top to bottom, in this, the temperature of stove high-temperature zone 14 is higher than the fusing point of multi-element compounds crystal used; The area size of described middle stove high-temperature zone 14 is consistent with the region between described polycrystalline stock column 2 lower end to seed crystal 6 upper end.
Described equipment is applied to a method for multi-element compounds crystal growth, and the method comprises the following steps:
First, polycrystal is pressed into the consistent polycrystalline stock column 2 of main body section 3 upper part shape size, then polycrystalline stock column 2 is loaded in growth ampoule 10;
Then, the growth ampoule 10 loading polycrystalline stock column 2 is put into boiler tube 17 by lift line 8 and pulling apparatus 7, and make upper part that the main body section 3 of growth ampoule 10 is equipped with polycrystalline stock column 2 be positioned at stove cold zone 13, region between polycrystalline stock column 2 lower end to seed crystal 6 upper end is arranged in stove high-temperature zone 14, and the seed crystal bag 5 that seed crystal 6 is housed is positioned at lower stove cold zone 15;
Secondly, set warm curvature of field line 12, boiler tube 17 is heated up, insulation for some time;
Then, open pulling apparatus 7, slow degrowth ampoule 10, polycrystalline stock column starts fusing, and the polycrystal melt after fusing is added dropwise to seed crystal 6 surface area and starts to carry out the growth of crystal; Treat that polycrystalline stock column 2 is gradually consumed complete, after the polycrystal melt in growth ampoule 10 all drops to lower stove cold zone 15, stop declining, crystal growth terminates;
Finally, equipment is lowered the temperature, take out crystal.
Embodiment 2
The invention provides a kind of method for monocrystal growth of self-adding formula, specifically comprise following steps:
First, by AgGa
0.2in
0.8se
2polycrystal is pressed into the polycrystalline stock column consistent with main body section 3 upper part shape size, ensures that this polycrystal is fitted closely with growth ampoule 3 inwall after putting into growth ampoule 3, along with the fusing of polycrystal bottom, relative displacement does not occur.
Then, AgGa will be housed
0.2in
0.8se
2the growth ampoule 3 of polycrystalline stock column 2 puts into boiler tube 17 by lift line 8 and pulling apparatus 7.Need ensure during blowing that the lower end of polycrystalline stock column 2 and the upper end of seed crystal 6 are in the position of middle stove high-temperature zone 14, and the upper end of polycrystalline stock column 2 is in stove cold zone, the lower end of seed crystal 6 is in lower stove cold zone.Adjustment and the optimization of polycrystal post placement location is carried out according to the actual growth of crystal.
Then, set warm curvature of field line 12, body of heater is heated up, the temperature wherein going up stove cold zone 13 controls between 750 DEG C-800 DEG C, the temperature of middle stove high-temperature zone 14 controls between 800 DEG C-820 DEG C, the temperature of lower stove cold zone 15 controls between 750 DEG C-800 DEG C, carries out insulation 48 hours after having heated up;
Then, open pulling apparatus 7 and slowly declined by growth ampoule 10, fall off rate controls at 1-10mm/day, and in the process declined, growth ampoule 10 slowly enters lower stove cold zone 15, and the melt of seed crystal 6 and top thereof enters lower stove cold zone 15 and starts growth.The lower end of polycrystalline stock column 2 slowly enters middle stove high-temperature zone 14 and starts to melt and drop onto the participation growth of growth interface place.Drop onto below growth ampoule 10 in melt when polycrystalline stock column 2 all melts, stop after waiting the melt in growth ampoule 10 all to enter into lower stove cold zone 15 declining, crystal growth is complete.
Finally, equipment is lowered the temperature, take out crystal, obtain chalcopyrite structure semiconductor crystal selenium indium gallium silver (AgGa
0.2in
0.8se
2) crystal.
For chalcopyrite structure semiconductor crystal selenium indium gallium silver (AgGa
0.2in
0.8se
2) crystal, utilize traditional Bridgman method to carry out the growth of this crystal, because the In in component very easily assembles in process of growth in melt, in the crystal causing late growing stage to go out, In concentration is greater than the crystal grown in advance.Fig. 4 be utilize traditional Bridgman method to grow selenium indium gallium silver single crystal different sites (112) face go out peak position, as can be seen from the figure, the closer to crystal afterbody, (112) face to go out peak position lower, illustrate that the In content in component is more.The change of In component can cause the change of crystal attribute, makes institute's growing crystal cannot be used for practical application at all.
Fig. 5 be utilize the present invention program to grow selenium indium gallium silver single crystal different sites (112) face go out peak position, as can be seen from the figure, the peak position difference that goes out in crystal different sites (112) face reduces a lot, illustrates that the homogeneity of the selenium indium gallium silver single crystal utilizing growth method of the present invention to grow is greatly improved.Show to adopt growth method of the present invention can effectively reduce the difference of In component in crystal simultaneously.
In sum, Apparatus for () and method therefor of the present invention efficiently avoid the gathering of constituent part near growth interface in melt because solute segregation causes, and makes the component of institute's growing crystal more even.The present invention also can adopt method of the present invention to grow for the multi-element compounds crystal that component Segregation is more serious.
Although with reference to explanatory embodiment of the present invention, invention has been described here, above-described embodiment is only the present invention's preferably embodiment, embodiments of the present invention are not restricted to the described embodiments, should be appreciated that, those skilled in the art can design a lot of other amendment and embodiment, these amendments and embodiment will drop within spirit disclosed in the present application and spirit.
Claims (8)
1. the equipment for multi-element compounds crystal growth, it comprises body of heater (16), pulling apparatus (7) and growth ampoule (10), boiler tube (17) is provided with in described body of heater (16), and the central shaft of body of heater (16) overlaps with the central shaft of boiler tube (17), one deck stove inner thermal insulating layer (11) is covered between body of heater (16) and boiler tube (17), described stove inner thermal insulating layer (11) is embedded in heating unit (9), and heating unit (9) is near boiler tube (17); Described growth ampoule (10) is connected by lifting line (8) with pulling apparatus (7), growth ampoule (10) moves up and down under the traction of pulling apparatus (7) in boiler tube (17), it is characterized in that described growth ampoule (10) is followed successively by hook (1), main body section (3), shouldering position (4) and seed crystal bag (5) from top to bottom; The top that described hook (1) is placed in main body section (3) between two parties and connect lift line (8) growth ampoule (10) is connected with pulling apparatus (7); The column internal diameter of described main body section (3) diminishes from top to bottom gradually; The right cylinder that described seed crystal bag (5) is lower seal, the combination likeness in form funnel of described shouldering position (4) and seed crystal bag (5); Described heating unit (9) makes to be divided into stove cold zone (13), middle stove high-temperature zone (14) and lower stove cold zone (15) in boiler tube (17) from top to bottom.
2. equipment according to claim 1, it is characterized in that upper part of described main body section (3) is for placing the polycrystalline stock column (2) consistent with its shape size, this polycrystalline stock column (2) does not fill up upper part of main body section (3); Described seed crystal bag (5) is for filling seed crystal (6).
3. equipment according to claim 2, is characterized in that the column internal diameter of described shouldering position (4) is reduced to the same size of column internal diameter with seed crystal bag (5) gradually from the same size of column internal diameter of main body section (3) bottom.
4. equipment according to claim 3, the temperature that it is characterized in that described upper stove cold zone (13) is from top to bottom in the trend raised gradually, and on this, the temperature of stove cold zone (13) is lower than the fusing point of multi-element compounds crystal used.
5. equipment according to claim 3, the temperature that it is characterized in that described lower stove cold zone (15) is from top to bottom in downward trend gradually, and the temperature of this lower stove cold zone (15) is lower than the fusing point of multi-element compounds crystal used.
6. equipment according to claim 3, the temperature that it is characterized in that described middle stove high-temperature zone (14) is from top to bottom in downward trend after first raising, and in this, the temperature of stove high-temperature zone (14) is higher than the fusing point of multi-element compounds crystal used; The interval size of described middle stove high-temperature zone (14) is consistent with the region between described polycrystalline stock column (2) lower end to seed crystal (6) upper end.
7. equipment according to claim 1, is characterized in that described growth ampoule (10) is prepared from by high purity quartz or pyrolitic boron nitride.
8. the equipment described in claim 1 to 7 any one is applied to a method for multi-element compounds crystal growth, it is characterized in that the method comprises the following steps:
First, polycrystal is pressed into the consistent polycrystalline stock column (2) of main body section (3) upper part shape size, then polycrystalline stock column (2) is loaded in growth ampoule (10);
Then, the growth ampoule (10) loading polycrystalline stock column (2) is put into boiler tube (17) by lift line (8) and pulling apparatus (7), and make upper part that the main body section of growth ampoule (10) (3) is equipped with polycrystalline stock column (2) be positioned at stove cold zone (13), region between polycrystalline stock column (2) lower end to seed crystal (6) upper end is arranged in stove high-temperature zone (14), and the seed crystal bag (5) that seed crystal (6) is housed is positioned at lower stove cold zone (15);
Secondly, set warm curvature of field line (12), equipment is heated up, insulation for some time;
Then, open pulling apparatus (7), slow degrowth ampoule (10) polycrystalline stock column starts fusing, and the polycrystal melt after fusing is added dropwise to seed crystal (6) surface area and starts to carry out the growth of crystal; Treat that polycrystalline stock column (2) is gradually consumed complete, after the polycrystal melt in growth ampoule (10) all drops to lower stove cold zone (15), stop declining, crystal growth terminates;
Finally, equipment is lowered the temperature, take out crystal.
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| CN105369343A (en) * | 2015-12-08 | 2016-03-02 | 中国工程物理研究院化工材料研究所 | Single temperature zone crystal growth device, and single temperature zone crystal growth method |
| CN105543953A (en) * | 2015-12-28 | 2016-05-04 | 中国工程物理研究院化工材料研究所 | Polycompound polycrystal nucleating control device and method |
| CN105803518A (en) * | 2016-05-31 | 2016-07-27 | 中国工程物理研究院化工材料研究所 | Czochralski-method-like monocrystal growing device and method |
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