CN106149046A - The polycrystal synthesis method of gallium selenide and method for monocrystal growth - Google Patents
The polycrystal synthesis method of gallium selenide and method for monocrystal growth Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/46—Sulfur-, selenium- or tellurium-containing compounds
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B11/00—Single-crystal growth by normal freezing or freezing under temperature gradient, e.g. Bridgman-Stockbarger method
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B11/00—Single-crystal growth by normal freezing or freezing under temperature gradient, e.g. Bridgman-Stockbarger method
- C30B11/002—Crucibles or containers for supporting the melt
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B28/00—Production of homogeneous polycrystalline material with defined structure
- C30B28/12—Production of homogeneous polycrystalline material with defined structure directly from the gas state
- C30B28/14—Production of homogeneous polycrystalline material with defined structure directly from the gas state by chemical reaction of reactive gases
Abstract
The polycrystal synthesis method of gallium selenide and method for monocrystal growth, it relates to polycrystal synthesis and the method for monocrystal growth of mid and far infrared nonlinear material.It is intended to solve, and the stoichiometry skew of existing GaSe polycrystal synthesis is big and productivity is low and the spontaneous nucleation stage is easily formed invalid nuclei and the uncertain technical problem in crystal growth direction.Polycrystal synthesis: simple substance Ga is placed in bateau, then drop it off one end of quartz ampoule, Se is placed on the other end of quartz ampoule, vacuumize rear sealing by fusing, be placed in horizontal dual temperature district tube type resistance furnace synthesis, obtain GaSe polycrystalline, its stoichiometric proportion is 1:(1～1.05), productivity is more than 97%.Crystal growth: join GaSe polycrystalline in PBN crucible, be then vertically placed on PBN crucible in quartz ampoule, vacuumizes rear sealing by fusing, then is placed in vertical dual temperature district tube type resistance furnace, and crystal growth obtains GaSe monocrystalline after terminating.Can be used as mid and far infrared laser material and realize 8～10 μm of laser outputs.
Description
Technical field
The present invention relates to polycrystal synthesis and the method for monocrystal growth of mid and far infrared nonlinear material.
Background technology
Mid and far infrared laser (particularly 3-5 μm and 8-10 μm of infrared band) is at military field or civil area all
Having very important application, gallium selenide (GaSe) crystal has the big (d of nonlinear factor22=54pm/V), transmission region width
The excellent non-linear optical properties such as (0.65-18 μm), birefringence big (Δ n=0.36), are that mid and far infrared laser frequency turns
Change optimal dielectric material, it is possible to achieve 8-10 μm of laser output.
At present, the method synthesizing GaSe polycrystal raw material has single warm area method and dual temperature district method.Single warm area method only need to arrange one
Constant temperature zone, technique is simple, easy to operate.Dual temperature district method, owing to being provided with high-temperature region and low-temperature space, effectively reduces Se mono-
Matter vapour pressure in the reactor, it is to avoid the quartz ampoule causing due to Se high-vapor-pressure bursts.Two are had in Ga-Se system
Individual stable compound GaSe (fusing point 938 DEG C) and Ga2Se3(fusing point 1005 DEG C), and unstable product Ga3Se2And Ga2Se, above-mentioned
Two kinds of methods all can have higher vapor pressure due to GaSe when temperature is higher than more than 900 DEG C, and occurs component to offset, and more
Be deposited on reaction quartz ampoule inwall, cause product non-stoichiometric and productivity to decline.
Growth mid and far infrared crystal (such as germanium zinc phosphide, sulfuration gallium silver, gallium selenide silver, gallium selenide and cadmium selenide etc.) all can be adopted
With Bridgman-Stockbarger method or vertical gradient condensation method.Bridgman-Stockbarger method is to make polycrystal material melt by high temperature by the crucible moving down
District shifts to low-temperature space and solidifies, and vertical gradient condensation method is by reducing furnace body temperature, making whole polycrystal raw material melt from bottom
It is solidified to top and form monocrystal.Two kinds of growing technologies all have preferable effect for seed-grain method growth monocrystalline, and GaSe crystal is
Layer structure, combines by Van der Waals force between layers, and mechanical performance is poor, is not suitable for using conventional seed-grain method growth, logical
Frequently with the spontaneous nucleation growth without seed crystal.Obtain the nucleus of bulk in order to ensure crystal in the spontaneous nucleation stage, and utilize several
What eliminative mechanism grows into the monocrystal with crucible shape, needs to design suitable growth crucible shape.GaSe crystal growth
The silica crucibles using front end to be thin taper, but this silica crucible not easy cleaning having compared with apicule end, outside being readily incorporated more
The impurity coming forms invalid nuclei, reduces and is grown to the probability of bulky single crystal body, and uses the crystal growth that this method grows
Direction is uncertain, is unfavorable for crystal-cut and the element manufacturing in later stage.
Content of the invention
The present invention is to solve the non-stoichiometric of existing GaSe polycrystal synthesis and productivity is low and GaSe spontaneous nucleation
Stage is easily formed invalid nuclei and the uncertain technical problem in crystal growth direction, and provides polycrystal synthesis method and the list of GaSe
Crystals growth method.
The polycrystal synthesis method of the GaSe of the present invention, sequentially includes the following steps:
First, with quartzy bateau or the boron nitride bateau of chloroazotic acid immersion quartz ampoule and charge, then clean with ultra-pure water, dry
Dry；According to mol ratio Ga:Se=1:(1+n) weigh simple substance raw material Ga and Se, wherein n=PV/RT, P are 1 atmospheric pressure, and V is quartz
Pipe inner cylinder voidage, T is (600+273) K, and R is gas constant；
2nd, it is positioned over Ga in bateau, the bateau filling Ga is placed into the blind end of quartz ampoule, Se is directly placed at
The other end of quartz ampoule；Quartz ampoule is vacuumized, then with oxyhydrogen flame sealing by fusing quartz ampoule, is then placed in horizontal dual temperature district tubular type electricity
In resistance stove, the bateau filling Ga is positioned at high-temperature region, and Se is positioned at low-temperature space, is gradient zones between bateau and Se；
3rd, the temperature of high-temperature region is first made to rise to t1=950～1000 DEG C, make low-temperature space temperature rise to t simultaneously2=500～
700 DEG C, being incubated 10～15h, this is the first stage；Then maintain high-temperature region temperature-resistant, the temperature of low-temperature space is increased to t2’
=t1+ (10～20) DEG C, are incubated 3～5h, and this is second stage；The temperature of last whole resistance furnace drops with 20～40 DEG C/h speed
To room temperature, obtain GaSe polycrystalline.
The method for monocrystal growth of the GaSe of the present invention, sequentially includes the following steps:
Soak growth quartz ampoule with chloroazotic acid and contain the PBN crucible of polycrystal raw material, then clean with ultra-pure water, dry；
Wherein PBN crucible is the cylinder with seed crystal trap；
2nd, GaSe polycrystalline is joined in PBN crucible, be then vertically placed on PBN crucible in quartz ampoule, quartz ampoule is taken out
Vacuum, finally uses oxyhydrogen flame sealing by fusing quartz ampoule；
3rd, putting into the quartz ampoule of sealing by fusing in vertical dual temperature district tube type resistance furnace, vertical dual temperature district tube type resistance furnace is from upper
Be high-temperature region, gradient zones and low-temperature space to lower low order, in quartz ampoule the seed crystal trap bottom of PBN crucible bottom be positioned at gradient zones initiate
Position；
4th, first making high-temperature region temperature be increased to 1010～1020 DEG C, low-temperature space temperature is increased to 950～960 DEG C simultaneously,
The thermograde of gradient zones is 5～7 DEG C/cm, is incubated 15～20h, and this is the first stage；Then the temperature of high-temperature region is reduced by 7
～10 DEG C, the temperature of low-temperature space reduces by 7～10 DEG C simultaneously, keeps 1～2h, and this is second stage；Again the temperature of high-temperature region is carried
High 5～8 DEG C, the temperature of low-temperature space improves 5～8 DEG C simultaneously, keeps 2～3h, and this is the phase III；Again the temperature of high-temperature region is dropped
Low 50～70 DEG C, the temperature of low-temperature space reduces by 50～70 DEG C simultaneously, and this is fourth stage；Finally the temperature of whole resistance furnace is dropped
To room temperature, obtain GaSe monocrystalline.
The GaSe polycrystal raw material synthesis of the present invention uses dual temperature district method, in initial reaction stage according to traditional dual temperature district method Ga
Being positioned over high-temperature region, Se is positioned over low-temperature space, and by gas phase transmission, Se steam is transferred to high-temperature region and Ga reaction by low-temperature space
Generate GaSe, in the reaction the later stage add drive reactant Se steam drive program, i.e. (place Se by improving low-temperature space
One end) temperature, make the temperature of the low-temperature space temperature higher than high-temperature region (placing one end of Ga), reactant Se is all transported to height
Warm area simultaneously generates product.Same this temperature trend that keeps in temperature-fall period, i.e. low-temperature space (placing one end of Se) temperature begin
Eventually higher than the temperature generating product one end, adopt and can ensure that product vapor is all generating the cohesion of product district in this way, produce
Thing composition improves close to stoichiometric proportion, productivity.
When GaSe crystal growth, the spontaneous nucleation using vertical gradient condensation technology to combine with temperature oscillation technology is raw
Long method.Vertical gradient condensation technology requires that bottom temp is lower than upper temp, forms longitudinal temperature gradient, and crystal becomes in bottom
Core.After material, the temperature of melt is incubated 4～24 hours higher than melting temperature 10～50 DEG C, it is ensured that all molten matter particles by heat are equal
Even, nucleation stage rate of temperature fall is slow, so advantageously reduces nucleus number, improves the average dimension of crystal；Use temperature oscillation
Technology limits crystal nucleation number, the i.e. circulation by repeatedly fall-intensification, and each fall-ramp cycle temperature is less than upper one
Individual circulating temperature, makes crystal growth and melts alternately, and each temperature-rise period can melt a upper temperature-fall period and be formed
Invalid small crystal nucleus, leave slightly larger crystal grain, finally by geometry eliminative mechanism obtain bulky single crystal.The growth that the method uses
Crucible is boron nitride (PBN) growth crucible with seed crystal trap.Before there is the less cylindrical seed crystal trap of internal diameter due to this crucible
End, not only improves geometry eliminative mechanism, also easily cleans.Its solution absciss layer of GaSe crystal using this crucible to grow is indulged with crucible
Parallel to direction, direction determines, crystal is more regular, and dissociate during cutting face and cutting machine panel attachment, it is easy to cutting, and crystal utilizes
Rate is high.
Brief description
Fig. 1 be polycrystal synthesis in embodiment 1 quartz ampoule in raw material place and temperature field schematic diagram；
Fig. 2 is quartz ampoule and the growth temperature field schematic diagram thereof of crystal growth in embodiment 1；
Fig. 3 is the photo of the GaSe monocrystalline obtaining in embodiment 1；
Fig. 4 be the GaSe monocrystalline that obtains in embodiment 1 pass through spectrogram.
Fig. 5 is the photo of the GaSe monocrystalline obtaining in embodiment 2.
Detailed description of the invention
Detailed description of the invention one: the polycrystal synthesis method of the GaSe of present embodiment, sequentially includes the following steps:
First, with quartzy bateau or the boron nitride bateau of chloroazotic acid immersion quartz ampoule and charge, then clean with ultra-pure water, dry
Dry；According to mol ratio Ga:Se=1:(1+n) weigh simple substance raw material Ga and Se, wherein n=PV/RT, P are 1 atmospheric pressure, and V is quartz
Pipe inner cylinder voidage, T is (600+273) K, and R is gas constant；
2nd, it is positioned over Ga in bateau, the bateau filling Ga is placed into the blind end of quartz ampoule, Se is directly placed at
The other end of quartz ampoule；Quartz ampoule is vacuumized, then with oxyhydrogen flame sealing by fusing quartz ampoule, is then placed in horizontal dual temperature district tubular type electricity
In resistance stove, the bateau filling Ga is positioned at high-temperature region, and Se is positioned at low-temperature space, is gradient zones between bateau and Se；
3rd, the temperature of high-temperature region is first made to rise to t1=950～1000 DEG C, make low-temperature space temperature rise to t simultaneously2=500～
700 DEG C, being incubated 10～15h, this is the first stage；Then maintain high-temperature region temperature-resistant, the temperature of low-temperature space is increased to t2’
=t1+ (10～20) DEG C, are incubated 3～5h, and this is second stage；The temperature of last whole resistance furnace drops with 20～40 DEG C/h speed
To room temperature, obtain GaSe polycrystalline.
Detailed description of the invention two: present embodiment and quartz ampoule and charge in step one unlike detailed description of the invention one
Quartzy bateau or boron nitride (PBN) bateau chloroazotic acid soak time be 6～8h.Other and detailed description of the invention one phase
With.
Detailed description of the invention three: present embodiment is taken out from quartz ampoule in step 2 unlike detailed description of the invention one or two
Vacuum is to 10-4Pa～10-6Pa.Other are identical with detailed description of the invention one or two.
Detailed description of the invention four: present embodiment and in step 3 unlike one of detailed description of the invention one to three first
In stage, the programming rate of high-temperature region is 180～200 DEG C/h, and the programming rate of low-temperature space is 100～140 DEG C/h.Other with tool
One of body embodiment one to three is identical.
Detailed description of the invention five: present embodiment and in step 3 unlike one of detailed description of the invention one to four second
In stage, the programming rate of low-temperature space is 100～140 DEG C/h.Other are identical with one of detailed description of the invention one to four.
Detailed description of the invention six: the method for monocrystal growth of the GaSe of present embodiment, sequentially includes the following steps:
First, soak growth quartz ampoule with chloroazotic acid and contain the PBN crucible of polycrystal raw material, then cleaning with ultra-pure water, dry
Dry；Wherein PBN crucible is the cylinder with seed crystal trap；
2nd, GaSe polycrystalline is joined in PBN crucible, be then vertically placed on PBN crucible in quartz ampoule, quartz ampoule is taken out
Vacuum, finally uses oxyhydrogen flame sealing by fusing quartz ampoule；
3rd, putting into the quartz ampoule of sealing by fusing in vertical dual temperature district tube type resistance furnace, vertical dual temperature district tube type resistance furnace is from upper
Be high-temperature region, gradient zones and low-temperature space to lower low order, in quartz ampoule the seed crystal trap bottom of PBN crucible bottom be positioned at gradient zones initiate
Position；
4th, first making high-temperature region temperature be increased to 1010～1020 DEG C, low-temperature space temperature is increased to 950～960 DEG C simultaneously,
The thermograde of gradient zones is 5～7 DEG C/cm, is incubated 15～20h, and this is the first stage；Then the temperature of high-temperature region is reduced by 7
～10 DEG C, the temperature of low-temperature space reduces by 7～10 DEG C simultaneously, keeps 1～2h, and this is second stage；Again the temperature of high-temperature region is carried
High 5～8 DEG C, the temperature of low-temperature space improves 5～8 DEG C simultaneously, keeps 2～3h, and this is the phase III；Again the temperature of high-temperature region is dropped
Low 50～70 DEG C, the temperature of low-temperature space reduces by 50～70 DEG C simultaneously, and this is fourth stage；Finally the temperature of whole resistance furnace is dropped
To room temperature, obtain GaSe monocrystalline.
Detailed description of the invention seven: present embodiment is from step 2 unlike detailed description of the invention six, and quartz ampoule is taken out very
Empty to 10-4Pa-10-6Pa.Other are identical with detailed description of the invention six.
Detailed description of the invention eight: present embodiment from unlike detailed description of the invention six or seven: the first rank in step 4
Programming rate in Duan is 50～80 DEG C/h.Other are identical with detailed description of the invention six or seven.
Detailed description of the invention nine: present embodiment from unlike one of detailed description of the invention six to eight: in step 4
Cooling rate in two-stage is 0.1～0.2 DEG C/h.Other are identical with one of detailed description of the invention six to eight.
Detailed description of the invention ten: present embodiment from unlike one of detailed description of the invention six to nine: in step 4
Triphasic programming rate is 5～10 DEG C/h.Other are identical with one of detailed description of the invention six to nine.
Detailed description of the invention 11: present embodiment from unlike one of detailed description of the invention six to ten: in step 4
The cooling rate of fourth stage is 0.1～0.2 DEG C/h.Other are identical with one of detailed description of the invention six to ten.
Detailed description of the invention 12: present embodiment from unlike one of detailed description of the invention six to ten one: step 4
In the cooling rate of last whole resistance furnace be 20～40 DEG C/h.Other are identical with one of detailed description of the invention six to ten one.
Verify beneficial effects of the present invention by following example:
Embodiment 1: the polycrystal synthesis method of the GaSe of the present embodiment, sequentially includes the following steps:
First, soak the boron nitride bateau 8h of quartz ampoule and charge with chloroazotic acid, then clean with ultra-pure water, dry；Weigh
70 grams of simple substance raw material Ga and 80 grams of simple substance raw material Se, Se therein is according to stoichiometric proportion Ga:Se=1: 1 calculates excessive 1.1 grams；
2nd, it is positioned over Ga in bateau, the bateau filling Ga is placed into the blind end of quartz ampoule, Se is directly placed at
The other end of quartz ampoule；Quartz ampoule is evacuated to 10-5Pa, with oxyhydrogen flame sealing by fusing quartz ampoule, is then placed in horizontal dual temperature district
In tube type resistance furnace, the bateau filling Ga is positioned at high-temperature region, and a length of 20cm of high-temperature region, Se are positioned at low-temperature space, low-temperature space
A length of 20cm, is gradient zones between bateau and Se；Gradient zones length 40cm；As shown in Figure 1；
3rd, first make the temperature of high-temperature region with 200 DEG C/h ramp to 980 DEG C, make low-temperature space temperature with 140 simultaneously
DEG C/h ramp to 600 DEG C, be incubated 12h, this be the first stage；Then maintain high-temperature region temperature-resistant, continue with 140 DEG C/h
The temperature of low-temperature space is increased to 1000 DEG C by speed, is incubated 3h, and this is second stage；The temperature of last whole resistance furnace is with 30
DEG C/h speed is down to room temperature, obtains GaSe polycrystalline.
The warm field of the first stage in the present embodiment step 3 and second stage is as shown in Figure 1.
The metering of the product GaSe polycrystalline composition that the present embodiment obtains is than 1:1.02, close to stoichiometric proportion, productivity 98%.
The method for monocrystal growth of the GaSe of the present embodiment, sequentially includes the following steps:
First, soak growth quartz ampoule with chloroazotic acid and contain the PBN crucible of polycrystal raw material, then cleaning with ultra-pure water, dry
Dry；Wherein PBN crucible is the cylinder with seed crystal trap, PBN crucible length 30cm, internal diameter 2cm, the internal diameter of the seed crystal trap of front end
5mm, length 2.5cm；
2nd, GaSe polycrystalline is joined in PBN crucible, be then vertically placed on PBN crucible in quartz ampoule, quartz ampoule is taken out
Vacuum is to 10-5Pa, finally uses oxyhydrogen flame sealing by fusing quartz ampoule；
3rd, putting into the quartz ampoule of sealing by fusing in vertical dual temperature district tube type resistance furnace, vertical dual temperature district tube type resistance furnace is from upper
It is high-temperature region, gradient zones and low-temperature space to lower low order, a length of 10 centimetres of a length of 20mm in high-temperature region, gradient zones, the low temperature head of district
Degree is 20mm, and in quartz ampoule, the seed crystal trap bottom of PBN crucible bottom is positioned at gradient zones original position；As shown in Figure 2；
4th, making high-temperature region temperature be increased to 1020 DEG C initially with 60 DEG C/h heating rate, low-temperature space temperature raises simultaneously
To 950 DEG C, the thermograde of gradient zones is 7 DEG C/cm, is incubated 20h, and this is the first stage；Then with 0.2 DEG C/h speed by high temperature
The temperature in district is reduced to 1010 DEG C, and the temperature of low-temperature space is reduced to 940 DEG C simultaneously, keeps 1h；Again with 5 DEG C/h speed by high-temperature region
Temperature improve to 1015 DEG C, simultaneously low-temperature space temperature improve to 945 DEG C, keep 2h；Again with 0.2 DEG C/h speed by high-temperature region
Temperature be reduced to 960 DEG C, the temperature of low-temperature space is reduced to 890 DEG C simultaneously；Finally with 40 DEG C/h speed by whole resistance furnace
Temperature is down to room temperature, obtains GaSe monocrystalline.The growth temperature field of first stage is as shown in Figure 2.
The photo of GaSe monocrystalline prepared by the present embodiment is as it is shown on figure 3, GaSe single crystal diameter 2cm, length 4.5cm, crystal
Volume is big, and color is homogeneous brownish red, and its solution absciss layer of GaSe crystal using this crucible to grow is put down with crucible longitudinal direction
OK, crystal is more regular, and face of dissociating during cutting is combined with cutting machine panel, it is easy to cutting, and crystal utilization rate is high.
Fig. 4 is that the thick wafer of 6mm of GaSe monocrystalline passes through spectrum, from fig. 4, it can be seen that in the range of wave band 1-13 μm,
The transmitance of monocrystalline reaches 60%.
Embodiment 2: the polycrystal synthesis method of the GaSe of the present embodiment, sequentially includes the following steps:
First, soak the boron nitride bateau 6h of quartz ampoule and charge with chloroazotic acid, then clean with ultra-pure water, dry；Weigh
70 grams of simple substance raw material Ga and 80 grams of simple substance raw material Se, Se therein is according to stoichiometric proportion Ga:Se=1: 1 calculates excessive 1.1 grams；
2nd, it is positioned over Ga in bateau, the bateau filling Ga is placed into the blind end of quartz ampoule, Se is directly placed at
The other end of quartz ampoule；Quartz ampoule is evacuated to 10-5Pa, with oxyhydrogen flame sealing by fusing quartz ampoule, is then placed in horizontal dual temperature district
In tube type resistance furnace, the bateau filling Ga is positioned at high-temperature region, and a length of 20cm of high-temperature region, Se are positioned at low-temperature space, low-temperature space
A length of 20cm, is gradient zones between bateau and Se；Gradient zones length 40cm；
3rd, first make the temperature of high-temperature region with 190 DEG C/h ramp to 1000 DEG C, make low-temperature space temperature with 120 simultaneously
DEG C/h ramp to 700 DEG C, be incubated 12h, this be the first stage；Then maintain high-temperature region temperature-resistant, continue with 120 DEG C/h
The temperature of low-temperature space is increased to 1010 DEG C by speed, is incubated 3h, and this is second stage；The temperature of last whole resistance furnace is with 30
DEG C/h speed is down to room temperature, obtains GaSe polycrystalline.The metering ratio 1: 1.05 of this GaSe polycrystalline composition, close to stoichiometric proportion, produces
Rate 97.8%.
The method for monocrystal growth of the GaSe of the present embodiment, sequentially includes the following steps:
First, soak growth quartz ampoule with chloroazotic acid and contain the PBN crucible of polycrystal raw material, then cleaning with ultra-pure water, dry
Dry；Wherein PBN crucible is the cylinder with seed crystal trap, PBN crucible length 30cm, internal diameter 2cm, the internal diameter of the seed crystal trap of front end
5mm, length 2.5cm；
2nd, GaSe polycrystalline is joined in PBN crucible, be then vertically placed on PBN crucible in quartz ampoule, quartz ampoule is taken out
Vacuum is to 10-5Pa, finally uses oxyhydrogen flame sealing by fusing quartz ampoule；
3rd, putting into the quartz ampoule of sealing by fusing in vertical dual temperature district tube type resistance furnace, vertical dual temperature district tube type resistance furnace is from upper
It is high-temperature region, gradient zones and low-temperature space to lower low order, a length of 10 centimetres of a length of 20mm in high-temperature region, gradient zones, the low temperature head of district
Degree is 20mm, and in quartz ampoule, the seed crystal trap bottom of PBN crucible bottom is positioned at gradient zones original position；
4th, making high-temperature region temperature be increased to 1010 DEG C initially with 50 DEG C/h heating rate, low-temperature space temperature raises simultaneously
To 960 DEG C, the thermograde of gradient zones is 5 DEG C/cm, is incubated 20h, and this is the first stage；Then with 0.2 DEG C/h speed by high temperature
The temperature in district is reduced to 1000 DEG C, and the temperature of low-temperature space is reduced to 950 DEG C simultaneously, keeps 1h；Again with 5 DEG C/h speed by high-temperature region
Temperature improve to 1018 DEG C, simultaneously low-temperature space temperature improve to 958 DEG C, keep 2h；Again with 0.2 DEG C/h speed by high-temperature region
Temperature be reduced to 958 DEG C, the temperature of low-temperature space is reduced to 898 DEG C simultaneously；Finally with 30 DEG C/h speed by whole resistance furnace
Temperature is down to room temperature, obtains GaSe monocrystalline.
The photo of GaSe monocrystalline prepared by the present embodiment, as it is shown in figure 5, GaSe single crystal diameter 2cm, length 4cm, uses this
Its solution absciss layer of GaSe crystal planting crucible growth is parallel with crucible longitudinal direction, and crystal is more regular, dissociate during cutting face and cutting
Machine side hardens conjunction, it is easy to cutting, and crystal utilization rate is high.
Claims (10)
- The polycrystal synthesis method of 1.GaSe, it is characterised in that the method sequentially includes the following steps:First, with quartzy bateau or the boron nitride bateau of chloroazotic acid immersion quartz ampoule and charge, then clean with ultra-pure water, dry； According to mol ratio Ga:Se=1:(1+n) weigh simple substance raw material Ga and Se, wherein n=PV/RT, P are 1 atmospheric pressure, and V is quartz ampoule Inner cylinder voidage, T is (600+273) K, and R is gas constant；2nd, it is positioned over Ga in bateau, the bateau filling Ga is placed into the blind end of quartz ampoule, Se is directly placed at quartz The other end of pipe；Quartz ampoule is vacuumized, then with oxyhydrogen flame sealing by fusing quartz ampoule, is then placed in horizontal dual temperature district tube type resistance furnace In, the bateau filling Ga is positioned at high-temperature region, and Se is positioned at low-temperature space, is gradient zones between bateau and Se；3rd, the temperature of high-temperature region is first made to rise to t1=950～1000 DEG C, make low-temperature space temperature rise to t simultaneously2=500～700 DEG C, it is incubated 10～15h, this is the first stage；Then maintain high-temperature region temperature-resistant, the temperature of low-temperature space is increased to t2'=t1 + (10～20) DEG C, are incubated 3～5h, and this is second stage；The temperature of last whole resistance furnace is down to room with 20～40 DEG C/h speed Temperature, obtains GaSe polycrystalline.
- 2. the polycrystal synthesis method of GaSe according to claim 1, it is characterised in that in step one, quartz ampoule and charge are used Quartzy bateau or boron nitride bateau chloroazotic acid soak time be 6～8h.
- 3. the polycrystal synthesis method of GaSe according to claim 1 and 2, it is characterised in that in step 2, quartz ampoule vacuumizes To 10-4Pa～10-6Pa。
- 4. the polycrystal synthesis method of GaSe according to claim 1 and 2, it is characterised in that in step 3 in the first stage, The programming rate of high-temperature region is 180～200 DEG C/h, and the programming rate of low-temperature space is 100～140 DEG C/h.
- 5. the polycrystal synthesis method of GaSe according to claim 1 and 2, it is characterised in that in step 3 in second stage, The programming rate of low-temperature space is 100～140 DEG C/h.
- The method for monocrystal growth of 6.GaSe, it is characterised in that the method sequentially includes the following steps:First, soak growth quartz ampoule with chloroazotic acid and contain the PBN crucible of polycrystal raw material, then cleaning with ultra-pure water, dry；Its Middle PBN crucible is the cylinder with seed crystal trap；2nd, GaSe polycrystalline is joined in PBN crucible, be then vertically placed on PBN crucible in quartz ampoule, quartz ampoule is taken out very Sky, finally uses oxyhydrogen flame sealing by fusing quartz ampoule；3rd, putting into the quartz ampoule of sealing by fusing in vertical dual temperature district tube type resistance furnace, vertical dual temperature district tube type resistance furnace is from top to bottom Low order is high-temperature region, gradient zones and low-temperature space, and in quartz ampoule, the seed crystal trap bottom of PBN crucible bottom is positioned at gradient zones start bit Put；4th, first making high-temperature region temperature be increased to 1010～1020 DEG C, low-temperature space temperature is increased to 950～960 DEG C simultaneously, gradient The thermograde in district is 5～7 DEG C/cm, is incubated 15～20h, and this is the first stage；Then the temperature of high-temperature region is reduced by 7～10 DEG C, the temperature of low-temperature space reduces by 7～10 DEG C simultaneously, keeps 1～2h, and this is second stage；Again the temperature of high-temperature region is improved 5～ 8 DEG C, the temperature of low-temperature space improves 5～8 DEG C simultaneously, keeps 2～3h, and this is the phase III；Again the temperature of high-temperature region is reduced by 50 ～70 DEG C, the temperature of low-temperature space reduces by 50～70 DEG C simultaneously, and this is fourth stage；Finally the temperature of whole resistance furnace is down to room Temperature, obtains GaSe monocrystalline.
- 7. the method for monocrystal growth of GaSe according to claim 6, it is characterised in that in step 2, quartz ampoule is evacuated to 10-4Pa-10-6Pa。
- 8. the method for monocrystal growth of the GaSe according to claim 6 or 7, it is characterised in that in step 4 in the first stage Programming rate is 50～80 DEG C/h.
- 9. the method for monocrystal growth of the GaSe according to claim 6 or 7, it is characterised in that in step 4 in second stage Cooling rate is 0.1～0.2 DEG C/h.
- 10. the method for monocrystal growth of the GaSe according to claim 6 or 7, it is characterised in that phase III in step 4 Programming rate is 5～10 DEG C/h.
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