CN100379902C - Low-temperature solvent heat growth method of cadmium telluride single-crystal - Google Patents

Low-temperature solvent heat growth method of cadmium telluride single-crystal Download PDF

Info

Publication number
CN100379902C
CN100379902C CNB2006100409771A CN200610040977A CN100379902C CN 100379902 C CN100379902 C CN 100379902C CN B2006100409771 A CNB2006100409771 A CN B2006100409771A CN 200610040977 A CN200610040977 A CN 200610040977A CN 100379902 C CN100379902 C CN 100379902C
Authority
CN
China
Prior art keywords
cadmium
crystal
low
growth method
cadmium telluride
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
CNB2006100409771A
Other languages
Chinese (zh)
Other versions
CN1920123A (en
Inventor
谢毅
李本侠
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
University of Science and Technology of China USTC
Original Assignee
University of Science and Technology of China USTC
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by University of Science and Technology of China USTC filed Critical University of Science and Technology of China USTC
Priority to CNB2006100409771A priority Critical patent/CN100379902C/en
Publication of CN1920123A publication Critical patent/CN1920123A/en
Application granted granted Critical
Publication of CN100379902C publication Critical patent/CN100379902C/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

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
    • C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)

Abstract

The invention relates the cadmium telluride single-crystal low-temperature solvent thermal growth method, comprising the following steps: dissolving the water-soluble cadmium salt, tellurium and reduced agent in the 20-30% ammonial solution, which is 30-45mL, the mole ratio of cadmium salt, tellurium and reduced agent being 1: 1: 2-3, sealing them at 160-200Deg.C, and reacting for 3 days. The invention can produce cadmium telluride single-crystal material at low temperature, without adopting vacuum or protective atmosphere condition. The method has the advantages of low cost and simple technology.

Description

The low-temperature solvent growth method of cadmium telluride single-crystal
Technical field:
The invention belongs to non-oxidized substance single crystal preparation technical field, particularly the low-temperature solvent growth method of cadmium telluride single-crystal.
Background technology:
Cadmium telluride (CdTe) monocrystalline has a wide range of applications at aspects such as room temperature X ray, gamma detector, electron optics setter and solar cells as a kind of semiconductor material.How to realize that technology is simple, low-cost and can mass-produced preparation method be the problem that at first faces." crystal growth magazine " (Journal of Crystal Growth of Holland, 1989 the 98th volume 595-609 pages or leaves and 1994 the 138th volume 168-174 pages or leaves) reported and adopted mobile heating method (Traveling HeaterMethod is called for short THM) preparation II-VI semiconductor material CdTe, Cd from the source of solvent that is rich in Te 1-xZn xTe and Hg 1-xCd xThe crystal of Te, but the thermograde that this method is had relatively high expectations, technology cost height, growth velocity is very slow, and the used time is long.Holland " crystal growth magazine " (Journal of Crystal Growth, 1993 the 130th volume 181-187 pages or leaves) reported use Accelerate Crucible rotation technique (Accelerated Crucible Rotation Technique in mobile heating method, be called for short ACRT) the relevant crystal of preparation II-VI semiconductor material CdTe, but because this technology must rely on many conditions: minimum and maximum speed of rotation, pick-up period and geometry condition, complex operation is difficult to find optimum experimental condition.Holland " crystal growth magazine " (Journal of Crystal Growth, 1996 the 159th volume 171-174 pages or leaves) reported vertical Bridgman (Vertical Bridgman, be called for short VB) and physical vapor transmission (PhysicalVapor Transport, be called for short PVT) method growth CdTe monocrystalline, but these methods all need very high temperature, the crystalline growth temperature is higher than its fusing point, causes defective in process of cooling easily.
Summary of the invention:
The present invention proposes a kind of low-temperature solvent growth method of cadmium telluride single-crystal, to overcome that existing method temperature of reaction is higher, experimental implementation is complicated and easily to cause the shortcoming of lattice defect.
The low-temperature solvent growth method of cadmium telluride single-crystal of the present invention, it is characterized in that: with reactants water dissolubility cadmium salt, tellurium source and reductive agent according to 1: 1: the mol ratio of 2-3 is dissolved in the aqueous ammonia solvent that the 30-45mL massfraction is 20%-30%, reaction is no less than 3 days under being enclosed in 160-200 ℃, naturally cool to room temperature, promptly get the CdTe monocrystalline.
Described water-soluble cadmium salt can be chosen from Cadmium chloride fine powder, Cadmium Sulphate or cadmium acetate; Described tellurium source can be tellurium dioxide (TeO 2) or sodium tellurite (Na 2TeO 3); Described reductive agent is sodium borohydride (NaBH 4) or POTASSIUM BOROHYDRIDE (KBH 4).
Adopt commentaries on classics target X-ray powder diffraction (XRD), scanning electronic microscope (SEM) that product is characterized, the XRD test result shows that product is well-crystallized's a face-centered cubic phase CdTe monocrystalline, the SEM photo shows that monocrystalline is prism-shaped, and diameter dimension is at 1mm, and length arrives 4mm at 2mm.
Mechanism of the present invention is: TeO in aqueous ammonia solvent 3 2-Be reduced agent and be reduced to simple substance Te, simple substance Te disproportionation under alkaline condition generates Te 2-And TeO 3 2-Simultaneously, NH 3And Cd 2+Form title complex ion [Cd (NH 3) 4] 2+By the Te of Te simple substance in the generation of alkaline condition disproportionation 2-With title complex ion [Cd (NH 3) 4] 2+The Cd that discharges 2+Final in conjunction with generating product C dTe.This reaction process can be expressed as follows:
TeO 3 2-+BH 4 -+H 2O→Te+BO 2 -+2OH -+2H 2(1)
3Te+6OH -→TeO 3 2-+2Te 2-+3H 2O (2)
[Cd(NH 3) 4] 2++Te 2-→CdTe+4NH 3(3)
Adopt ammoniacal liquor as solvent among the present invention, it has two vital role: the one, and higher alkalescence (the pH value is 14) helps Te 2-Formation reaction (2), and the TeO that generates simultaneously 3 2-Can be used as the tellurium source and continue to be reduced generation simple substance Te; The 2nd, NH 3Can and Cd 2+Form title complex ion [Cd (NH 3) 4] 2+Thereby, slowly release Cd 2+, help crystal growth.These 2 generations to the CdTe monocrystalline are all extremely important.
Ammoniated mass percent all has certain influence to the final product of reaction in mol ratio between temperature of reaction, reaction times, the reactant and the ammoniacal liquor.The present invention adopts reactant cadmium source: the tellurium source: the mol ratio of reductive agent is 1: 1: 2 to 1: 1: 3, under 160-200 ℃ of temperature, react, usually the reaction times is in 3-7 days, can obtain quality cadmium telluride single-crystal preferably, if the reaction times is less than 3 days, contain a large amount of polycrystal powders in the less and product of the monocrystalline size that obtains; Surpass 7 days if prolong the reaction times, the monocrystalline size that finally obtains does not obviously change; If temperature of reaction is lower than 160 ℃, contain simple substance tellurium impurity in the product that obtains; If temperature of reaction is higher than 200 ℃, contain a large amount of cadmium telluride polycrystal powders in the product of acquisition, the monocrystalline productive rate is lower.In reaction system, add excessive reductive agent NaBH 4Or KBH 4It is oxygen free condition in order to ensure reaction system.In addition, the concentration of ammoniacal liquor also should meet some requirements, and it is that 20%-30% (contains NH that the present invention adopts massfraction 3) aqueous ammonia solvent, because if ammonia concentration is lower than 20%, reaction system alkalescence reduces, and is unfavorable for Te 2-Generation, can contain impurity Te in the final product that obtains; If the ammonia excessive concentration, then reaction system is dangerous, and the effusion of a large amount of ammonias easily causes the danger of exploding under the high temperature.
For preventing that reaction system is subjected to the reactor material contamination to introduce impurity, generally can select the teflon-lined reactor for use.
Compared with prior art, adopting the inventive method to prepare cadmium telluride single-crystal has the following advantages:
Because the present invention adopts the method carry out the reaction of solution phase chemistry in closed reactor, thereby can under the temperature more much lower, realize the preparation of cadmium telluride single-crystal, and can avoid adopting the condition of high vacuum or specific protective atmosphere than THM, VB and PVT method.In addition, compare with the method for " crystal growth magazine " (2002 the 236th volume 165-170 pages or leaves) report, the present invention adopts common tellurium source and cadmium source and suitable reductive agent direct reaction in aqueous ammonia solvent to obtain the CdTe monocrystalline, raw material cheaply is easy to get and is relatively stable to air, preparation technology simply, does not relate to complicated loaded down with trivial details operation, and cost is lower.Adopt the inventive method, can grow monocrystal material near the stoichiometric ratio component; In addition, recrystallization process also can be used as a purification step, thereby obtains the higher monocrystalline of purity.
Description of drawings:
The product of single crystal that Fig. 1 prepares for the present invention is ground into the XRD style figure behind the powder;
Fig. 2 is the XRD diffraction pattern figure of the product of single crystal of the present invention's preparation;
Fig. 3 is the rocking curve of (111) crystal face of the CdTe monocrystalline of the present invention's preparation;
Fig. 4 is the low power SEM photo of product C dTe monocrystalline of the present invention;
The SEM photo that Fig. 5 amplifies for the high power of product C dTe monocrystalline of the present invention.
Embodiment:
Embodiment 1:
The pre-configured CdCl that contains 25mmol, TeO 25mmol, NaBH 440mL ammoniacal liquor (25wt.%) mixing solutions of 10mmol is packed into and is had in the teflon-lined reactor, after airtight, in 45min, be elevated to 160 ℃ from room temperature, be reflected at and carry out stopping after 7 days heating under 160 ℃, after waiting to naturally cool to room temperature monocrystalline is taken out, with distilled water and absolute ethanol washing, 60 ℃ of dryings 3 hours in vacuum drying oven promptly get product then.
Embodiment 2:
With CdSO 4Replace the CdCl among the embodiment 1 2As the cadmium source, (25wt.%) is solvent with ammoniacal liquor, gets CdSO 4, TeO 2And NaBH 4Amount of substance be respectively 5mmol, 5mmol and 10mmol; This mixing solutions is packed in the reactor of inner liner polytetrafluoroethylene, and airtight back stops heating 200 ℃ of constant temperature 3 days, and its aftertreatment is identical with embodiment 1, obtains product.
Embodiment 3:
Use Na 2TeO 3Replace the TeO among the embodiment 1 2As the tellurium source, (25wt.%) is solvent with ammoniacal liquor, gets Na 2TeO 3, CdCl 2And NaBH 4Amount of substance be respectively 5mmol, 5mmol and 10mmol; Identical among operation steps and the embodiment 1, be reflected at 180 ℃ of following constant temperature and stop heating after 5 days, monocrystalline is taken out after waiting to naturally cool to room temperature, with distilled water and absolute ethanol washing, 60 ℃ of dryings 3 hours in vacuum drying oven promptly get product then.
Adopt commentaries on classics target X-ray powder diffraction (XRD) and scanning electronic microscope (SEM) that product is characterized:
Fig. 1 has provided the XRD style figure after products therefrom in the foregoing description is ground into powder, shows among the figure: each diffraction peak can index to face-centered cubic phase CdTe, do not find the diffraction peak of impurity.Calculate lattice constant a=6.386 with this
Figure C20061004097700051
, with literature value very near (a=6.410
Figure C20061004097700052
JCPDS Card No.75-2086).
Fig. 2 is the XRD diffraction pattern of gained bar-like single crystal in the foregoing description, and Fig. 3 is the rocking curve of (111) crystal face of the monocrystalline that obtained, only occurs three respectively corresponding 111,311,511 crystal faces of sharp-pointed diffraction peaks in the XRD diffraction pattern; (111) the crystal face rocking curve is presented at 10.887 ° and locates to have a symmetric diffraction peak, and its halfwidth is 0.06 °, shows that product has higher degree of crystallinity.
Fig. 4 and Fig. 5 are respectively the low power of products therefrom in the foregoing description and the SEM photo that high power is amplified.Photo shows that monocrystalline is bar-shaped, and its diameter dimension is at 1mm, and length arrives 4mm at 2mm.Bar-like single crystal is actual as can be seen under high x magnification is prism-shaped.
Because TeO 2Easily dissolving generates TeO in aqueous ammonia solvent 3 2-, and Na 2TeO 3Have similarity, therefore can adopt TeO respectively 2And Na 2TeO 3For utilizing the inventive method, the tellurium source prepares a cube phase CdTe monocrystalline.Because temperature of reaction is below 200 ℃, the inner liner of reaction kettle material generally can be selected tetrafluoroethylene for use.When temperature of reaction at 180-200 ℃, the reaction times is 3-5 days; When temperature of reaction at 160-180 ℃, the reaction times was generally 5-7 days.

Claims (4)

1. the low-temperature solvent growth method of a cadmium telluride single-crystal, it is characterized in that: with reactants water dissolubility cadmium salt, tellurium source and reductive agent according to 1: 1: the mol ratio of 2-3 is dissolved in the aqueous ammonia solvent that the 30-45mL massfraction is 20%-30%, reaction is no less than 3 days under being enclosed in 160-200 ℃, naturally cool to room temperature, promptly get the CdTe monocrystalline.
2. the low-temperature solvent growth method of cadmium telluride single-crystal according to claim 1 is characterised in that described water-soluble cadmium salt comprises Cadmium chloride fine powder, Cadmium Sulphate or cadmium acetate.
3. the low-temperature solvent growth method of cadmium telluride single-crystal according to claim 1 is characterised in that described tellurium source is tellurium dioxide or sodium tellurite.
4. the low-temperature solvent growth method of cadmium telluride single-crystal according to claim 1 is characterised in that described reductive agent is sodium borohydride or POTASSIUM BOROHYDRIDE.
CNB2006100409771A 2006-08-16 2006-08-16 Low-temperature solvent heat growth method of cadmium telluride single-crystal Expired - Fee Related CN100379902C (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CNB2006100409771A CN100379902C (en) 2006-08-16 2006-08-16 Low-temperature solvent heat growth method of cadmium telluride single-crystal

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CNB2006100409771A CN100379902C (en) 2006-08-16 2006-08-16 Low-temperature solvent heat growth method of cadmium telluride single-crystal

Publications (2)

Publication Number Publication Date
CN1920123A CN1920123A (en) 2007-02-28
CN100379902C true CN100379902C (en) 2008-04-09

Family

ID=37777958

Family Applications (1)

Application Number Title Priority Date Filing Date
CNB2006100409771A Expired - Fee Related CN100379902C (en) 2006-08-16 2006-08-16 Low-temperature solvent heat growth method of cadmium telluride single-crystal

Country Status (1)

Country Link
CN (1) CN100379902C (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102071453B (en) * 2010-12-14 2012-05-02 吉林大学 Method for preparing high-quality aqueous phase semiconductor nanocrystals by one pot method at room temperature
JP5836497B2 (en) * 2011-12-07 2015-12-24 イースト チャイナ ユニバーシティ オブ サイエンス アンド テクノロジー Method for producing cadmium selenide multi-legged nanocrystal
CN112573490A (en) * 2020-11-09 2021-03-30 青海大学 Method for macro-preparation of uniform single crystal cadmium telluride nanorods

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6287499A (en) * 1985-10-14 1987-04-21 Nippon Mining Co Ltd Heat treatment of single crystal cdte
JPH03131599A (en) * 1989-10-17 1991-06-05 Nippon Mining Co Ltd Production of ii-vi group compound semiconductor crystal
JPH05270995A (en) * 1992-03-27 1993-10-19 Ngk Insulators Ltd Production of cadmium-tellurium based single crystal
JPH08119797A (en) * 1994-10-27 1996-05-14 Nec Corp Production of rare earth metal vanadate single crystal
CN1524783A (en) * 2003-09-18 2004-09-01 吉林大学 Method and apparatus for preparing water-soluble CdTe nanocrystalline
CN1524782A (en) * 2003-09-17 2004-09-01 中国科学院长春应用化学研究所 Manufacturing method of cadmium selenide and cadmium telluride nanometer rod
US20050115489A1 (en) * 2001-08-06 2005-06-02 Triboulet Robert G.L. Method of obtaining a cdte or cdznte single crystal and the single crystal thus obtained
CN1710154A (en) * 2005-04-22 2005-12-21 吉林大学 Method for water-phase rapid synthesis of CdTe nano crystal at warm condition

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6287499A (en) * 1985-10-14 1987-04-21 Nippon Mining Co Ltd Heat treatment of single crystal cdte
JPH03131599A (en) * 1989-10-17 1991-06-05 Nippon Mining Co Ltd Production of ii-vi group compound semiconductor crystal
JPH05270995A (en) * 1992-03-27 1993-10-19 Ngk Insulators Ltd Production of cadmium-tellurium based single crystal
JPH08119797A (en) * 1994-10-27 1996-05-14 Nec Corp Production of rare earth metal vanadate single crystal
US20050115489A1 (en) * 2001-08-06 2005-06-02 Triboulet Robert G.L. Method of obtaining a cdte or cdznte single crystal and the single crystal thus obtained
CN1524782A (en) * 2003-09-17 2004-09-01 中国科学院长春应用化学研究所 Manufacturing method of cadmium selenide and cadmium telluride nanometer rod
CN1524783A (en) * 2003-09-18 2004-09-01 吉林大学 Method and apparatus for preparing water-soluble CdTe nanocrystalline
CN1710154A (en) * 2005-04-22 2005-12-21 吉林大学 Method for water-phase rapid synthesis of CdTe nano crystal at warm condition

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
CdTe and CdZnTe growth. Triboulet, R.Crystal Growth Technology, [International School on Crystal Growth Technology ISCTG-1], 1st, Beatenberg, Switzerland. 1998 *
Control of composition and conduction type of CdTe filmelectrodeposited from ammonia alkaline aqueous solutions. Murase, Kuniaki, Watanabe, Hiroto, Mori, Shiro, Hirato,Tetsuji, Awakura, Yasuhiro.Journal of the Electrochemical Society,Vol.146 No.12. 1999 *
Preparation and photoluminescence characterization ofhigh-purity CdTe single crystals: purification effect of normalfreezing on tellurium and cadmium telluride.. Song, S. H., Wang, J., Isshiki, M.Journal of Crystal Growth,Vol.236 No.1-3. 2002 *

Also Published As

Publication number Publication date
CN1920123A (en) 2007-02-28

Similar Documents

Publication Publication Date Title
CN102337524B (en) Preparation method of Bi-based chalcogenide thermoelectric thin film
Fearheiley The phase relations in the Cu, In, Se system and the growth of CuInSe2 single crystals
CN110467165B (en) Method for preparing high-purity black phosphorus by adopting fixed bed catalysis
CN101560693A (en) Preparation method of solar-grade silicon crystal containing doping elements
CN110184654A (en) A kind of Bi2O2Se crystal and preparation method thereof
CN106365128A (en) Preparation method of magic-size nanocrystal substance
CN100379902C (en) Low-temperature solvent heat growth method of cadmium telluride single-crystal
CN103137720B (en) A kind of photovoltaic film material of doped with rare-earth elements
Bouznit et al. New co-spray way to synthesize high quality ZnS films
CN101597790A (en) The method of preparing cast polycrystalline silicon through melting silicon and doping nitrogen under nitrogen
Parikh et al. Two-dimensional halide perovskite single crystals: principles and promises
US8679445B1 (en) Synthesis of CsSnI3 by temperature gradient solid-phase sintering method
CN113430650B (en) Middle and far infrared crystal LiGaGe 2 Se 6 Polycrystalline raw material synthesis method and monocrystal growth method thereof
CN102766905B (en) Erbium ion activated 1.55 micron waveband gallate laser crystalss and preparation method thereof
CN102766906B (en) Erbium ion activated 3 micron waveband gallate laser crystals and preparation method thereof
CN102168299A (en) Method for growing phosphorus-silicon-cadmium single crystal
CN113186590B (en) Preparation method of centimeter-level molybdenum trioxide single crystal
KR101509332B1 (en) Preparation of copper selenide compound controlling particle size and composition
US20120146189A1 (en) Quaternary chalcogenide wafers
CN101597792A (en) Under nitrogen, cast the method for the controlled doped polysilicon of nitrogen concentration
JP6008282B2 (en) Method for producing Ge clathrate
John et al. Comprehensive Review on CdTe Crystals: Growth, Properties, and Photovoltaic Application
CN113481597B (en) Preparation method of Zn-P-As single crystal
JP2003137535A (en) Rare earth borosilicide and its manufacturing method
CN112956033A (en) Semiconductor material, infrared light receiving element, and method for manufacturing semiconductor material

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
C19 Lapse of patent right due to non-payment of the annual fee
CF01 Termination of patent right due to non-payment of annual fee