CN108166061A - A kind of method for reducing Insb Single Crystals dislocation - Google Patents
A kind of method for reducing Insb Single Crystals dislocation Download PDFInfo
- Publication number
- CN108166061A CN108166061A CN201711424693.7A CN201711424693A CN108166061A CN 108166061 A CN108166061 A CN 108166061A CN 201711424693 A CN201711424693 A CN 201711424693A CN 108166061 A CN108166061 A CN 108166061A
- Authority
- CN
- China
- Prior art keywords
- single crystals
- insb single
- dislocation
- reducing
- insb
- 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
- 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
- C30B29/40—AIIIBV compounds wherein A is B, Al, Ga, In or Tl and B is N, P, As, Sb or Bi
-
- 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
- C30B33/00—After-treatment of single crystals or homogeneous polycrystalline material with defined structure
- C30B33/02—Heat treatment
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
The present invention relates to a kind of methods for reducing Insb Single Crystals dislocation, belong to optoelectronic materials technology.The method of the invention is to carry out in-situ annealing processing to the Insb Single Crystals prepared using Czochralski methods, so as to reduce Insb Single Crystals dislocation.Relative to the method for reducing dislocation density by regulating and controlling temperature in Insb Single Crystals growth course, technical solutions according to the invention are easy to operate, and the condition of annealing process is easier, the dislocation density of Insb Single Crystals can be significantly reduced, the dislocation density of large scale indium antimonide crystal that diameter is about 50mm is enable to be less than 50/cm2, so as to which the large scale Insb Single Crystals haveing excellent performance are prepared.
Description
Technical field
The present invention relates to a kind of methods for reducing Insb Single Crystals dislocation, belong to optoelectronic materials technology.
Background technology
Indium antimonide is that energy gap is most narrow in III-V a small bundle of straw, etc. for silkworms to spin cocoons on compound semiconductor, the material of mobility maximum, physics, change
It learns performance to stablize, is widely used in infrared detector and hall device etc..The quantum efficiency of infrared detector and selection
Infrared-sensitive material it is closely related, and indium antimonide 3 μm~5 mu m wavebands have very high quantum efficiency, in addition indium antimonide exists
It prepares and possesses low cost on infrared detector, infrared detector of indium antimonide is with its important application in military aspect and in civilian side
The extensive prospect in face, causes more and more extensive concern.In addition, in order to adapt to indium antimonide infrared focal plane array device to big
The trend of scale development, meanwhile, in order to reduce infrared detector device development cost and improve production efficiency, exist always both at home and abroad
Research and development large scale Insb Single Crystals growing technology.
Mainly using conventional Czochralski (cutting krousky) method growth, this is one for Insb Single Crystals growth at present
Kind prepares the important means of semiconductor bulk single crystal materials.This method can not be constrained by crucible and grow crystal, outside crystal
Shape size may be selected in a certain range, meanwhile, prepared crystal has higher integrality.The growth of Czochralski methods is single
Brilliant equipment mainly includes heater, quartz ampoule, crucible and lifting rod, and heater adds the quartz ampoule region for placing crucible
Heat melts the polycrystalline material inside crucible, seed crystal is made to be inserted into melt by lifting rod, then again slowly lifts seed crystal,
New crystal is constantly grown in seed crystal lower part, is filled with protective gas inside quartz ampoule during the crystal growth.
However, Czochralski methods growth Insb Single Crystals have a shortcoming, i.e., there are one very high longitudinal temperatures for tool in stove
Gradient easily generates dislocation in crystal growing process.Particularly in the single crystal rod for drawing a diameter of more than 20mm, improve brilliant
The integrality of body reduces dislocation density, many difficulties is occurred as soon as in technique.And about the research of indium antimonide crystal integrality,
More particularly to the research of dislocation, has more elaborate report in recent years.There are two types of viewpoint, Yi Zhongshi for relevant bibliography
The radial direction thermal stress of near surface and the paraxial dislocation that can cause crystal to thermal stress, when the diameter increase of crystal, the position of crystal
Mistake also increases, and when the degree of heat radiation variation of crystal, the dislocation density of crystals can also change, and thinks when environment heating is brilliant
It is advantageous to reducing dislocation during body；Another viewpoint is to eliminate thermal stress to reduce dislocation, it is believed that as long as axial-temperature gradient is
One constant, radial symmetry gradient zero can pull out the monocrystalline of low dislocation.The basic ideas of above two viewpoint are all consistent
, it is provided to reduce the axial-temperature gradient of crystal, reduces radial flow heat, the thermal stress in crystal is reduced, so as to reduce
The dislocation density of monocrystalline.Indoor appropriate thermal field mainly also is grown in the process by designing crystal pulling at present, reduces monocrystalline
Dislocation.But in actual mechanical process, the temperature of growth room is difficult to accuracy controlling, has for the degree for reducing dislocation density
Dislocation density, can only generally be reduced to every square centimeter hundreds of by limit.
Invention content
The problem of reducing Insb Single Crystals dislocation density limitation for the prior art, the purpose of the present invention is to provide
A kind of method for reducing Insb Single Crystals dislocation, this method are by the Insb Single Crystals to being prepared using Czochralski methods
In-situ annealing processing is carried out, reduces Insb Single Crystals dislocation, easy to operate, the condition of annealing easily regulates and controls, and makes a diameter of
The large scale Insb Single Crystals dislocation density of 50mm or so is less than 50/cm2。
The purpose of the present invention is what is be achieved through the following technical solutions.
A kind of method for reducing Insb Single Crystals dislocation, the method step is as follows,
(1) Insb Single Crystals are prepared using Czochralski methods；
(2) after Insb Single Crystals crystal pulling, the temperature on Insb Single Crystals surface is controlled at 350 DEG C~450 DEG C, and is protected
Warm more than 20h, preferably 20h~40h；
(3) after keeping the temperature, continue to be cooled to room temperature, and place more than for 24 hours and further take out at room temperature, obtain low dislocation antimony
Change indium monocrystalline；Wherein, cooled down with the rate of temperature fall of 15 DEG C/h~25 DEG C/h, place preferably for 24 hours~50h at room temperature.
Advantageous effect：
The method of the invention is to carry out in-situ annealing processing to the Insb Single Crystals after crystal pulling, so as to avoid in antimony
Change in indium single crystal growth process to regulate and control to reduce the dislocation of Insb Single Crystals, in-situ annealing processing of the present invention into trip temperature
It is easy to operate, and condition easily regulates and controls, and can significantly reduce the dislocation density of Insb Single Crystals, makes large scale (about
The dislocation density of indium antimonide crystal 50mm) can be less than 50/cm2, and then large scale Insb Single Crystals can be significantly improved
Performance.
Specific embodiment
The present invention will be further described With reference to embodiment.
Embodiment 1
A kind of low dislocation indium antimonide<211>The preparation process of direction monocrystalline is as follows,
(1) by purity be 6N indium and antimony according to 1:1 molar ratio carries out dispensing, and the mixture of the two is placed on quartz boat
It is interior, it transfers in the quartz ampoule filled with hydrogen and sealing, heating is completely melt the solid in quartz boat, and keeps the temperature 5h and ensure
Antimony and indium are uniformly mixed, then are solidified, and obtain indium antimonide polycrystalline material；
(2) after the zone-refine of 20 times is carried out to indium antimonide polycrystalline material, using Hall effect to the ingot after zone-refine
Item is tested, and intercepts carrier concentration N≤1 × 10 in ingot14cm-3(77K), electron mobility u >=5 × 105/V·S
The indium antimonide polycrystalline material of the part of (77K), as high-purity；
(3) polishing cleaning is carried out to the indium antimonide polycrystalline material surface of high-purity, and using CP4 corrosive agent (by volume ratio
It is 5:3:3 nitric acid, hydrofluoric acid and glacial acetic acid composition) corrosion treatment is carried out, it is then charged into the dry silica crucible of cleaning, and
Silica crucible is transferred in the quartz ampoule filled with hydrogen and sealing, and the quartz ampoule region for placing silica crucible is added
Heat makes the indium antimonide polycrystalline material of high-purity in silica crucible be completely melt into liquid；
(4) heating power is reduced, it, will by lifting rod after forming nucleus after liquid surface area<211>The antimony in direction
Indium seed crystal is inserted into 4mm below liquid levels, and it is 120 DEG C to treat the temperature difference between the temperature of liquid surface and liquid surface upper air
When, then with the rate of climb of the rotating speed of 15r/min and 45mm/h lift seed crystal, while silica crucible with the rotating speed of 15r/min into
Row rotation, and heating power is continuously decreased with the rate of 5mW/min~30mW/min during lifting, forming shouldering angle is
30oShouldering section；Heating power is uniformly reduced later, forms isometrical section of a diameter of 50mm；Finally increase heating power, formed
Taper finishes up section to get to an indium antimonide<211>Direction monocrystalline；
(5) indium antimonide<211>After the monocrystalline crystal pulling of direction, stop the rotation of crucible, the rotation of seed crystal and to seed crystal
Lifting, and reduce heating power, make indium antimonide<211>The temperature of direction single-crystal surface is down to 400 DEG C, and is protected at 400 DEG C
Warm 30h；
(6) after keeping the temperature, continue to reduce heating power, with the rate of temperature fall of 20 DEG C/h by indium antimonide<211>Direction is single
Brilliant surface temperature is cooled to room temperature, then is placed and taken out afterwards for 24 hours, obtains low dislocation indium antimonide<211>Direction monocrystalline.
To prepared low dislocation indium antimonide<211>Isometrical section of direction monocrystalline is sliced, and use CP4 corrosive agent (by
Volume ratio is 5:3:3 nitric acid, hydrofluoric acid and glacial acetic acid composition) the slice progress corrosion treatment of channel angular section, it is placed on optics later
Micro- Microscopic observation and statistics obtain dislocation density as 50/cm2。
Comparative example 1
On the basis of embodiment 1, antimony is prepared using the process conditions identical with (1)~step (4) the step of embodiment 1
Change indium<211>Direction monocrystalline.
To prepared indium antimonide<211>Isometrical section of direction monocrystalline is sliced, and is cut using CP4 corrosive agent channel angular sections
Piece carries out corrosion treatment, puts observe and count to obtain dislocation density under an optical microscope as 2000/cm later2。
In conclusion the foregoing is merely a prefered embodiment of the invention, it is not intended to limit the scope of the present invention.
All within the spirits and principles of the present invention, any modification, equivalent replacement, improvement and so on should be included in the present invention's
Within protection domain.
Claims (4)
- A kind of 1. method for reducing Insb Single Crystals dislocation, it is characterised in that：The method step is as follows,(1) Insb Single Crystals are prepared using Czochralski methods；(2) after Insb Single Crystals crystal pulling, the temperature on Insb Single Crystals surface is controlled at 350 DEG C~450 DEG C, and is kept the temperature More than 20h；(3) after keeping the temperature, continue to be cooled to room temperature, and place more than for 24 hours and further take out at room temperature, obtain low dislocation indium antimonide Monocrystalline.
- 2. a kind of method for reducing Insb Single Crystals dislocation according to claim 1, it is characterised in that：In step (2), 20h~40h is kept the temperature at 350 DEG C~450 DEG C.
- 3. a kind of method for reducing Insb Single Crystals dislocation according to claim 1, it is characterised in that：In step (3), with The rate of temperature fall of 15 DEG C/h~25 DEG C/h is cooled to room temperature.
- 4. a kind of method for reducing Insb Single Crystals dislocation according to claim 1, it is characterised in that：In step (3), It is further taken out after placing for 24 hours~50h at room temperature.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711424693.7A CN108166061A (en) | 2017-12-25 | 2017-12-25 | A kind of method for reducing Insb Single Crystals dislocation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711424693.7A CN108166061A (en) | 2017-12-25 | 2017-12-25 | A kind of method for reducing Insb Single Crystals dislocation |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108166061A true CN108166061A (en) | 2018-06-15 |
Family
ID=62520752
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711424693.7A Pending CN108166061A (en) | 2017-12-25 | 2017-12-25 | A kind of method for reducing Insb Single Crystals dislocation |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108166061A (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55109300A (en) * | 1979-02-09 | 1980-08-22 | Toshiba Corp | Evaluation of insb single crystal |
| JPS55138228A (en) * | 1979-04-12 | 1980-10-28 | Toshiba Corp | Manufacture of semiconductor device |
| CN102534771A (en) * | 2010-12-29 | 2012-07-04 | 北京有色金属研究总院 | Method for growing gallium phosphide single crystals |
-
2017
- 2017-12-25 CN CN201711424693.7A patent/CN108166061A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55109300A (en) * | 1979-02-09 | 1980-08-22 | Toshiba Corp | Evaluation of insb single crystal |
| JPS55138228A (en) * | 1979-04-12 | 1980-10-28 | Toshiba Corp | Manufacture of semiconductor device |
| CN102534771A (en) * | 2010-12-29 | 2012-07-04 | 北京有色金属研究总院 | Method for growing gallium phosphide single crystals |
Non-Patent Citations (1)
| Title |
|---|
| 徐向东等: "较大直径、低位错锑化铟单晶的研制", 《红外与激光技术》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108166060A (en) | A kind of indium antimonide<211>The preparation method of direction monocrystalline | |
| CN109280978A (en) | A kind of preparation method of low dislocation indium antimonide<111>direction monocrystalline | |
| CZ303673B6 (en) | Preparation of doped garnet structure single crystals with diameters of up to 500 mm | |
| CN107541776A (en) | A kind of growth apparatus and method of large scale gallium oxide single crystal | |
| CN102409395B (en) | Gallium element doping device and method for Czochralski silicon | |
| WO2016123866A1 (en) | Method for preparing large-sized slablike ce3+ ion doped rare-earth orthosilicate-series scintillation crystals by means of horizontal directional solidification | |
| CN105247115B (en) | monocrystalline silicon manufacturing method | |
| CN102011187B (en) | Bismuth silicate-germanate mixed crystal and preparation method thereof | |
| TWI699464B (en) | Compound semiconductor and compound semiconductor single crystal manufacturing method | |
| CN111809229B (en) | Preparation method and device of indium antimonide single crystal | |
| CN102703970A (en) | Kyropous method growth of titanium doped sapphire crystals | |
| WO2020238646A1 (en) | Germanium single-crystal wafer, method for preparing germanium single-crystal wafer, method for preparing crystal bar, and use of single-crystal wafer | |
| CN113957537A (en) | Growth device and method for rapidly growing low-dislocation gallium arsenide single crystal by combining VB method and VGF method | |
| US20180347071A1 (en) | Systems and methods for low-oxygen crystal growth using a double-layer continuous czochralski process | |
| CN102758244A (en) | Compound heating-type Czochralski polycrystalline silicon or monocrystal silicon preparation technology | |
| Lan et al. | Multicrystalline silicon crystal growth for photovoltaic applications | |
| CN104073875A (en) | Preparation method of large-size sapphire crystal dynamic temperature field | |
| CN102002754B (en) | Method for growing bismuth silicate (BSO) scintillation crystal by shaping and lifting | |
| CN101260563A (en) | Seed crystal free vertical gas phase growth method for thallium bromide single-crystal | |
| CN109576777A (en) | Crystal growth double crucible and crystal growth technique | |
| CN108166061A (en) | A kind of method for reducing Insb Single Crystals dislocation | |
| CN115341284B (en) | High-concentration gradient neodymium doped gadolinium yttrium aluminum garnet laser crystal and preparation method thereof | |
| CN111304736A (en) | Method for eliminating influence of scum on dislocation-free germanium single crystal crystallization | |
| CN102817071A (en) | Preparation technology of heat radiation resistant Czochralski polysilicon or monocrystalline silicon | |
| CN204779916U (en) | Iraurite ring apron that iraurite crucible was used |
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 | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20180615 |
|
| RJ01 | Rejection of invention patent application after publication |