CN108930059A - A kind of arsenic germanium Cd monocrystal growing method can compensate for cadmium element - Google Patents
A kind of arsenic germanium Cd monocrystal growing method can compensate for cadmium element Download PDFInfo
- Publication number
- CN108930059A CN108930059A CN201811149529.4A CN201811149529A CN108930059A CN 108930059 A CN108930059 A CN 108930059A CN 201811149529 A CN201811149529 A CN 201811149529A CN 108930059 A CN108930059 A CN 108930059A
- Authority
- CN
- China
- Prior art keywords
- warm area
- crucible
- temperature
- crystal growth
- growth
- 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.)
- Pending
Links
Classifications
-
- 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
- C30B11/006—Controlling or regulating
-
- 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
- C30B11/04—Single-crystal growth by normal freezing or freezing under temperature gradient, e.g. Bridgman-Stockbarger method adding crystallising materials or reactants forming it in situ to the melt
- C30B11/06—Single-crystal growth by normal freezing or freezing under temperature gradient, e.g. Bridgman-Stockbarger method adding crystallising materials or reactants forming it in situ to the melt at least one but not all components of the crystal composition being added
- C30B11/065—Single-crystal growth by normal freezing or freezing under temperature gradient, e.g. Bridgman-Stockbarger method adding crystallising materials or reactants forming it in situ to the melt at least one but not all components of the crystal composition being added before crystallising, e.g. synthesis
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
The invention discloses a kind of arsenic germanium Cd monocrystal growing method that can compensate for cadmium element, this method uses the CdGeAs that compensates Cd element of VGF grower2The growth course of monocrystalline is controlled, VGF grower includes the crystal growth crucible being made of quartz raw material crucible and flat-bottom quartz crucible and five warm area growth furnaces, quartz raw material crucible portion is set as crystal growth area, flat-bottom quartz crucible is set as element compensating basin, element compensating basin is located at the lower section of crystal growth crucible, two regions compensate pipe by the element of growth crucible side wall and are connected, by CdGeAs2It is put into Cd raw material in two layers of crucible, warm area and step is divided to control CdGeAs2Single crystal growth temperature compensates Cd element in single crystal growth process, is uniformly distributed crystal head and the tail both ends Cd element, solves the problems, such as to increase the effective using volume of monocrystalline because monocrystalline performance caused by Cd element is inconsistent is skimble-scamble, reduce CdGeAs2Crystal growth cost.
Description
Technical field
The invention belongs to field of single crystal growth, and in particular to one kind can compensate for the arsenic germanium cadmium (CdGeAs of cadmium (Cd) element2)
Method for monocrystal growth.
Background technique
CdGeAs2Monocrystalline is a kind of mid and far infrared nonlinear optical crystal, and performance is prominent, is had a extensive future.Firstly,
CdGeAs2The nonlinear optical coefficients of monocrystalline highest in known crystal, up to 236pm/V, for known nonlinear optics now
2-3 times or more of crystal；Secondly, the crystal has suitable birefringent gradient, can be realized the wave-length coverage of phase matched compared with
It is wide；Again, CdGeAs2The hardness of monocrystalline is moderate, can be effectively machined, and laser damage threshold is high.With the crystal
Based on the device for preparing to have the characteristics that stability high, small in size, light-weight, and can be applied in high power device, this
A little advantages make CdGeAs2Monocrystalline becomes a kind of very excellent nonlinear optical crystal of performance, is even more known as II-IV-V race Huang
Best performance person in copper mine based semiconductor crystal, is concerned.
Domestic and foreign scholars attempt to grow the nonlinear optical crystal using a variety of methods, but crystal a axis and c-axis heat are swollen
Swollen difference of coefficients is big, so being limited by crystal physical property itself, it is difficult to grow large-sized CdGeAs2Monocrystalline.It is existing
It is reported that the monocrystalline of diameter 20mm can be grown using vertical bridgman-stockbarger method, CdGeAs is effectively grown to be a kind of2Monocrystalline
Method.Compared to vertical bridgman-stockbarger method, vertical gradient solidification (VGF) method has in terms of growing large-size, high quality single crystal
There is more obvious advantage, this method is by being manually set thermal field, it can be achieved that the temperature gradient and cooling rate being pre-designed, nothing
Machine error and mechanical oscillation, and have the characteristics that Temperature Distribution accurately controls in furnace body, therefore the crystal quality grown is more
Good, integrality is more preferable.However, according to the domestic and international present CdGeAs of report2The growing technology of monocrystalline is also very not perfect, brilliant
Weight is poor, especially large-sized CdGeAs2Monocrystalline, compositional difference is larger up and down for crystal, and performance difference is more, can use portion
Point shorter, single utilization rate of crystal is low.
Summary of the invention
The present invention grows CdGeAs using vertical gradient solidification (VGF)2Monocrystalline, it is therefore an objective to solve existing growth CdGeAs2
When monocrystalline, the monocrystalline top and bottom Cd changes of contents grown is big, and caused performance inconsistence problems improve growth monocrystalline
Utilization rate reduces CdGeAs2Crystal growth cost.
To achieve the above object, the technical solution used in the present invention is: a kind of arsenic germanium Cd monocrystal that can compensate for cadmium element
Growing method, which is characterized in that the CdGeAs that this method uses VGF grower to compensate Cd element2The growth course of monocrystalline
It is controlled, the VGF grower includes by quartz raw material crucible and flat-bottom quartz crucible crystal growth dimerous
Crucible and five warm area growth furnaces, quartz raw material crucible portion are set as crystal growth area, and flat-bottom quartz crucible is set as element compensating basin,
Element compensating basin is located at the lower section of crystal growth crucible, and two regions are connected by the element compensation pipe of crystal growth crucible wall
Logical, the method is completed by following growth step:
One, the preparation stage
1, the flat crucible of quartz is cleaned using deionized water, the Cd grain that the purity for weighing certain mass is 99.9999% is put into flat
In silica crucible.
2, quartz raw material crucible is cleaned using deionized water, weighs the CdGeAs that the purity of certain mass is 99.9999%2
Raw material is put into quartz raw material crucible, makes the element compensating port on element compensation pipe top after being melted down under the liquid level of liquid charging stock
Side.
3, the flat crucible of quartz and quartz raw material crucible high temperature are sealed integrally, then integrally takes out crystal growth crucible
Vacuum is sealed in crystal growth crucible top.
Two, the material stage
1, crystal growth crucible is integrally put into five warm area growth furnaces, crystal growth area is made to be located at the first warm area, the second warm area
With third warm area section, element compensating basin is located at four-temperature region and the 5th warm area section, starts to warm up material.
2, be arranged the first warm area, the second warm area and third warm area according to 1 DEG C/min-5 DEG C/min etc. heating rates heat up
To 650 DEG C -750 DEG C, four-temperature region and the 5th warm area according to 1 DEG C/min-2 DEG C/min etc. heating rates be warming up to 100 DEG C, protect
Warm -48h for 24 hours.
Three, growth phase
It keeps the first warm area temperature-resistant, with the rate of temperature fall of 0.5 DEG C/h-2 DEG C/h, the second warm area and third warm area is made to cool down,
The wherein rate of temperature fall of the second warm area < third warm area rate of temperature fall, until when third warm area is down to 600 DEG C -630 DEG C, according to 2
DEG C/h-4 DEG C/h etc. heating rates make four-temperature region and the 5th temperature-raising region temperature raising to 300 DEG C -350 DEG C, keep -48h for 24 hours；According to
With the rate of temperature fall of 0.5 DEG C/h-2 DEG C/h, make the first warm area, the second warm area and the cooling of third warm area, wherein the drop of the first warm area
Warm rate < second warm area rate of temperature fall < third warm area rate of temperature fall, until making when third warm area is down to 300 DEG C -350 DEG C
One warm area, the second warm area, third warm area, four-temperature region and the 5th warm area are down to room according to the equal rate of temperature fall of 1 DEG C/h-3 DEG C/h
Temperature takes out CdGeAs2Crystal.
The beneficial effects of the present invention are: this method can keep growth crucible position indeclinable in crystal growing process
Under state, grown CdGeAs is realized2The compensation of the Cd element of monocrystalline is uniformly distributed Cd element in growth monocrystalline, alleviates
Because in crystal Cd element it is inconsistent caused by performance difference, increase the usable volume of single monocrystalline, reduce cost.
Detailed description of the invention
Fig. 1 is the flat-bottom quartz crucible schematic diagram that the present invention uses；
Fig. 2 is the crystal growth crucible schematic diagram that the present invention uses；
Fig. 3 is the VGF grower arrangement schematic diagram that the present invention uses.
Specific embodiment
Below in conjunction with drawings and examples, the invention will be further described:
Embodiment: as shown in Figure 1, Figure 2 and Figure 3, the CdGeAs that this method uses VGF grower to compensate Cd element2Monocrystalline
Growth course controlled, VGF grower includes by 302 two parts group of quartz raw material crucible 301 and flat-bottom quartz crucible
At crystal growth crucible 3 and five warm area growth furnaces, 301 part of quartz raw material crucible be set as crystal growth area, flat quartz earthenware
Crucible 302 is set as element compensating basin, and element compensating basin is located at the lower section of crystal growth crucible 3, and two regions pass through crystal growth crucible 3
The element compensation pipe 303 of side wall is connected, and this method is completed by following growth step:
One, the preparation stage
1, clean the flat crucible 302 of quartz using deionized water, weigh the high-purity 6N(99.9999% of 6g) Cd grain be put into flat stone
In English crucible 302.
2, using deionized water clean quartz raw material crucible 301, weigh the high-purity 6N(99.9999% of 600g) CdGeAs2It is former
Material, is put into quartz raw material crucible 301, makes the element compensating port 304 on element compensation pipe 303 top liquid charging stock after being melted down
Below liquid level.
3, the flat crucible 302 of quartz and 301 high temperature of quartz raw material crucible are sealed integrally, then by crystal growth crucible
3 entirety vacuumize, and are sealed at the top of crystal growth crucible 3.
Two, the material stage
1,3 entirety of crystal growth crucible is put into five warm area growth furnaces, crystal growth area is made to be located at the first warm area, the second warm area
With third warm area section, element compensating basin is located at four-temperature region and the 5th warm area section, starts to warm up material.
2, be arranged the first warm area, the second warm area and third warm area according to 2 DEG C/min etc. heating rates be warming up to 690 DEG C,
Four-temperature region and the 5th warm area according to 1.5 DEG C/min etc. heating rates be warming up to 100 DEG C, heat preservation is for 24 hours.
Three, growth phase
It keeps the first warm area temperature-resistant, with the rate of temperature fall of 0.5 DEG C/h, the second warm area is made to cool down, with the cooling speed of 1.5 DEG C/h
Rate makes third warm area cool down, until when third warm area is down to 610 DEG C, according to 2 DEG C/h etc. heating rates make four-temperature region and the 5th
Temperature-raising region temperature raising is kept for 24 hours to 340 DEG C；According to the rate of temperature fall of 0.8 DEG C/h, the first warm area is set to cool down, according to 1.2 DEG C/h
Rate of temperature fall, so that the second warm area is cooled down, according to the rate of temperature fall of 1.5 DEG C/h, making third warm area cool down, until third warm area drops
When to 300 DEG C, make the first warm area, the second warm area, third warm area, four-temperature region and the 5th warm area according to 2 DEG C/h etc. cooling speed
Rate is down to room temperature, takes out CdGeAs2Crystal.
By the CdGeAs of high-purity 6N2It is respectively put into Cd raw material in two layers of crystal growth crucible, using the growth side of VGF
Method, the accurate temperature for controlling five each warm areas of warm area monocrystal growing furnace.In single crystal growth process, make the Cd liter of element compensating basin
Temperature evaporates into the CdGeAs dissolved2In raw material, the compensation of Cd element is carried out, crystal head and the tail both ends Cd element is uniformly distributed, from
And it solves the problems, such as because monocrystalline performance caused by Cd Elemental redistribution is inconsistent is skimble-scamble.
Claims (1)
1. a kind of arsenic germanium Cd monocrystal growing method that can compensate for cadmium element, which is characterized in that this method uses VGF grower
To the CdGeAs of Cd element compensation2The growth course of monocrystalline is controlled, and the VGF grower includes by quartz raw material crucible
(301) and flat-bottom quartz crucible (302) crystal growth crucible (3) dimerous and five warm area growth furnaces, quartz raw material earthenware
Crucible (301) is partially set as crystal growth area, and flat-bottom quartz crucible (302) is set as element compensating basin, and element compensating basin is located at monocrystalline
The lower section of growth crucible (3), two regions are connected by the element compensation pipe (303) of crystal growth crucible (3) side wall, the side
Method is completed by following growth step:
One, the preparation stage
1, the flat crucible (302) of quartz is cleaned using deionized water, the Cd grain that the purity for weighing certain mass is 99.9999% is put
Enter in flat-bottom quartz crucible (302)；
2, quartz raw material crucible (301) are cleaned using deionized water, weighs the CdGeAs that the purity of certain mass is 99.9999%2
Raw material is put into quartz raw material crucible (301), makes the element compensating port (304) on element compensation pipe (303) top liquid after being melted down
Below the liquid level of body raw material；
3, the flat crucible (302) of quartz and quartz raw material crucible (301) high temperature are sealed integrally, then by crystal growth crucible
(3) whole to vacuumize, it is sealed at the top of crystal growth crucible (3)；
Two, the material stage
1, crystal growth crucible (3) is integrally put into five warm area growth furnaces, crystal growth area is made to be located at the first warm area, the second temperature
Area and third warm area section, element compensating basin are located at four-temperature region and the 5th warm area section, start to warm up material；
2, be arranged the first warm area, the second warm area and third warm area according to 1 DEG C/min-5 DEG C/min etc. heating rates be warming up to 650
DEG C -750 DEG C, four-temperature region and the 5th warm area according to 1 DEG C/min-2 DEG C/min etc. heating rates be warming up to 100 DEG C, heat preservation
24h-48h；
Three, growth phase
It keeps the first warm area temperature-resistant, with the rate of temperature fall of 0.5 DEG C/h-2 DEG C/h, the second warm area and third warm area is made to cool down,
The wherein rate of temperature fall of the second warm area < third warm area rate of temperature fall, until when third warm area is down to 600 DEG C -630 DEG C, according to 2
DEG C/h-4 DEG C/h etc. heating rates make four-temperature region and the 5th temperature-raising region temperature raising to 300 DEG C -350 DEG C, keep -48h for 24 hours；According to
With the rate of temperature fall of 0.5 DEG C/h-2 DEG C/h, make the first warm area, the second warm area and the cooling of third warm area, wherein the drop of the first warm area
Warm rate < second warm area rate of temperature fall < third warm area rate of temperature fall, until making when third warm area is down to 300 DEG C -350 DEG C
One warm area, the second warm area, third warm area, four-temperature region and the 5th warm area are down to room according to the equal rate of temperature fall of 1 DEG C/h-3 DEG C/h
Temperature takes out CdGeAs2Crystal.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811149529.4A CN108930059A (en) | 2018-09-29 | 2018-09-29 | A kind of arsenic germanium Cd monocrystal growing method can compensate for cadmium element |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811149529.4A CN108930059A (en) | 2018-09-29 | 2018-09-29 | A kind of arsenic germanium Cd monocrystal growing method can compensate for cadmium element |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108930059A true CN108930059A (en) | 2018-12-04 |
Family
ID=64444132
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811149529.4A Pending CN108930059A (en) | 2018-09-29 | 2018-09-29 | A kind of arsenic germanium Cd monocrystal growing method can compensate for cadmium element |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108930059A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109646987A (en) * | 2019-01-10 | 2019-04-19 | 合肥欧莱迪光电技术有限公司 | A kind of continuous feeding and discharging high vacuum small organic molecule purification special equipment |
| CN112680781A (en) * | 2020-12-09 | 2021-04-20 | 清远先导材料有限公司 | Cadmium telluride crystal growth device and growth method thereof |
-
2018
- 2018-09-29 CN CN201811149529.4A patent/CN108930059A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109646987A (en) * | 2019-01-10 | 2019-04-19 | 合肥欧莱迪光电技术有限公司 | A kind of continuous feeding and discharging high vacuum small organic molecule purification special equipment |
| CN109646987B (en) * | 2019-01-10 | 2024-03-26 | 合肥百思智能装备有限公司 | Continuous feeding and discharging high-vacuum organic micromolecule purifying special equipment |
| CN112680781A (en) * | 2020-12-09 | 2021-04-20 | 清远先导材料有限公司 | Cadmium telluride crystal growth device and growth method thereof |
| CN112680781B (en) * | 2020-12-09 | 2023-10-03 | 清远先导材料有限公司 | Cadmium telluride crystal growth device and growth method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102877117B (en) | Ingot furnace thermal field structure based on multi-heater and operation method | |
| CN102289235B (en) | Heating control system and method based on top separated control polycrystalline silicon ingot casting furnace | |
| JP4203603B2 (en) | Method for producing semiconductor bulk polycrystal | |
| CN102758249B (en) | A kind of preparation method of colourless boule monocrystal | |
| CN101962798A (en) | Be used to produce the method and apparatus of sapphire single-crystal | |
| CN102191535B (en) | Manufacturing device for sapphire monocrystal | |
| CN102242392B (en) | Method for producing quasi-single crystal silicon with casting method and stabilizing crystal seed at furnace bottom after melting in ingot furnace | |
| CN202989351U (en) | Ingot furnace thermal field structure based on multiple heaters | |
| CN108930059A (en) | A kind of arsenic germanium Cd monocrystal growing method can compensate for cadmium element | |
| CN102925958A (en) | Method for improving poly-crystal quality by using re-melting technology | |
| CN110295391A (en) | The preparation method of crystalline silicon ingot | |
| CN103451726A (en) | Water chilling ingot furnace and ingot casting process thereof | |
| CN101133194B (en) | Production technique and device for float silicon wafer | |
| CN101851782A (en) | Double-cavity heat-insulation cage of second single crystal silicon ingot production furnace | |
| CN102776556B (en) | Polycrystalline silicon ingot and preparation method thereof as well as polycrystalline silicon wafer | |
| CN104073875A (en) | Preparation method of large-size sapphire crystal dynamic temperature field | |
| US5064497A (en) | Crystal growth method and apparatus | |
| CN102965727A (en) | Polycrystalline silicon ingot and casting method thereof | |
| CN203530480U (en) | Equipment for growing sapphire single crystals | |
| CN103422163A (en) | Device and method for growing sapphire single crystals | |
| CN103320857B (en) | A kind of growing method of sapphire crystal and equipment | |
| CN202175745U (en) | Heating control system of polycrystalline silicon ingot furnace based on separate control at the top | |
| CN104894637B (en) | The grower and growing method of a kind of crystal | |
| CN102691103B (en) | Method for growing sapphire crystals by double control technology | |
| CN108531985B (en) | Polycrystalline silicon semi-molten ingot casting process |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20181204 |
|
| WD01 | Invention patent application deemed withdrawn after publication |