CN1684276A

CN1684276A - Serial tellurium-cadmium-mercury infrared material and its preparing method and use

Info

Publication number: CN1684276A
Application number: CNA2004100305701A
Authority: CN
Inventors: 陈文通; 郭国聪; 徐玲; 李强; 黄锦顺
Original assignee: Fujian Institute of Research on the Structure of Matter of CAS
Current assignee: Fujian Institute of Research on the Structure of Matter of CAS
Priority date: 2004-04-13
Filing date: 2004-04-13
Publication date: 2005-10-19
Anticipated expiration: 2024-04-13
Also published as: CN100508220C

Abstract

A series kind TeCdHg infrared material and its preparation method and usage relate to the series kind TeCdHg infrared material and its composition. This invention is aimed at finding out a semiconductor material capable of being cut out and selects element Se of VIA group, Br of VIIA group and Cd and Hg of IIB group to composite new type of series kind TeCdHg infrared material compound: CdHg4O4x6(Q=S, Se, Te, X=Cl, Br I) by solid phase reaction method, which is used in infrared detector and emitter, thermoelectric material and infrared laser.

Description

Series tellurium-cadmium-mercury infrared material and its preparation method and use

Technical Field

The invention relates to a novel infrared material and a preparation method thereof, in particular to a series of tellurium-cadmium-mercury infrared materials and synthesis thereof.

Technical Field

The semiconductor is a basic material of modern information technology and is also a key material of modern national defense. The development and application of semiconductor materials greatly improve the quality of life of human beings. Since the invention of mercury cadmium telluride (Hg1-xCdxTe) crystal (MCT) in 1958, the MCT material has become the third most important semiconductor material after Si and GaAs for more than 40 years.

The silicon germanium semiconductor is not wide enough in forbidden band and the semiconductor energy gap is indirect transition type, so that the silicon germanium semiconductor is out of the field of optoelectronics for a long time, the GaAs has low thermal conductivity and cannot be used for high-power electronic devices, and the MCT has numerous advantages: intrinsic excitation, high absorption coefficient and high quantum efficiency (greater than 80%) with high detectivity. The MCT has higher working temperature and wide working temperature range, and is suitable for military variable working temperature. Currently, MCT-based products account for more than half of the infrared device market. The sales of infrared detectors alone worldwide reach more than billions of us per year, and the scale of industries such as infrared instruments and infrared systems is larger. MCTs, however, also have their disadvantages, such as: poor crystal structure integrity, non-uniform alloy composition, difficulty in preparing large-sized single crystals, and the like. Developed countries tend to impose strict export restrictions due to the underlying status and use of MCTs. Therefore, the design and synthesis of the novel semiconductor material capable of replacing MCT have remarkable significance for developing the high-tech industry of infrared semiconductor materials and devices in China and enhancing the national defense strength in China.

The physical properties of the material can change along with the change of components, the energy band structure of the solid solution has dependency on the components, and the 'cutting' of the energy band structure of the material can be realized by controlling the components. In view of this principle, quaternary compound semiconductor materials have been tried in order to obtain materials having specified properties. Quaternary compoundA typical example of a semiconductor is yellow tin ore (Cu)₂FeSnS₄) And its analogous compound Cu₂CdSnTe₄And is called a cassiterite type semiconductor.

It is desirable to improve lasers and light emitting diodes and field effect transistors that require higher electron saturation drift velocities with materials that can be "tailored" for band structure. For these applications, the quaternary semiconducting material may have a greater degree of freedom in "tailoring" the material properties due to its addition of a composition control parameter. Therefore, the research on quaternary compound semiconductor materials has recently become a new highlight in the field of semiconductor materials.

Disclosure of Invention

The object of the present invention is to find a semiconductor material with a greater "tailorability" of the energy band. For this reason, it is necessary to select appropriate elements for synthesizing a class of quaternary compound semiconductors.

We select VIA group element Se, VIIA group element Br and IIB group Cd and Hg, and synthesize a novel MCT-like compound CdHg by a solid-phase reaction method₄Se₄Br₆. Because the same group elements in the periodic table have similar properties, S or Te elements can be selected to replace Se, Cl or I to replace Br elements, and a heterogeneous and isomorphous series compound CdHg is obtained under the preparation conditions₄Q₄X₆(Q ═ S, Se, Te; X ═ Cl, Br, I), e.g. CdHg₄S₄Br₆，CdHg₄Te₄Br₆，CdHg₄Se₄Cl₆And the like. Meanwhile, due to the difference of the elements in the same group, the energy band bandwidths of the series of semiconductor materials are different, so that the semiconductor materials with different energy band bandwidths can be obtained by adjusting the components of the materials so as to meet the requirements of different application fields.

Cdyhg of quaternary MCT compound₄Q₄X₆(Q ═ S, Se, Te; X ═ Cl, Br, I) has the following advantages: compared with the preparation and purification of other infrared materials, the preparation of the compound is simpler and easier. Impurities are not introduced in the reaction process, and purification is not needed as long as a sufficiently pure reagent is used; can be prepared under relatively mild conditions without complex equipment; the single crystal can be directly obtained without further growth of the single crystal.

Detailed Description

Cdyhg for MCT-like compounds₄Se₄Br₆Synthesis and single crystals ofGrowth ofMCT-like compound Cdyg Hg₄Se₄Br₆The synthesis and the single crystal growth are simultaneously completed by a solid-phase reaction method. The reaction formula is as follows:

the chemical reagents and the manufacturers are as follows:

HgBr₂ May&baker (England) purity is more than or equal to 99.95 percent

The purity of the Se powder Sichuan semiconductor material factory is more than or equal to 99.95 percent

CdBr₂The purity of Shanghai pavilion new chemical reagent factory is more than or equal to 99.95 percent

The material feeding amount of the three reagents is as follows:

HgBr₂ 0.05mol 0.1820g

se powder 0.1mol 0.0789g

CdBr₂ 0.05mol 0.1361g

The specific operation steps are as follows:

accurately weighing reactants with corresponding mass according to the molar ratio of each reactant in the reaction formula, putting the reactants into a mortar for uniform grinding, tabletting the ground mixture, and filling the tabletting mixture into a glass tube. The glass tube was evacuated and then closed with a flame. And (3) putting the sealed glass tube into a muffle furnace, controlling the temperature by using a temperature controller, raising the temperature to 200 ℃ within 6 hours from room temperature, keeping the temperature at 200 ℃ for 24 hours, raising the temperature to 300 ℃ within 6 hours, keeping the temperature at 300 ℃ for 144 hours, lowering the temperature to 100 ℃ within 33 hours, lowering the temperature to 35 ℃ within 5 hours, and then turning off the power supply. The glass tube is taken out of the muffle furnace and opened to obtain yellow block crystals with the maximum size of 1.6mm multiplied by 1.4mm multiplied by 1.0 mm.

The compound CdHg is determined by the single crystal structure₄Se₄Br₆The space group of (1) is Cmm2(No35), the unit cell parameters are a-9.409 (8) Å, b-17.53 (1) Å, c-9.775 (6) Å - β - γ -90 °, Z-4, the unit cell volume V-1612 (2) Å³. Ultraviolet-visible spectrum test shows that the compound CdHg₄Se₄Br₆The forbidden band width is about 2.15eV。

Claims

1. The series tellurium-cadmium-mercury infrared materials are characterized in that: the chemical formula is CdHg₄Q₄X₆Wherein Q ═ S, Se, Te; x ═ Cl, Br, I; its space group is Cmm2(No 35).

2. The material of claim 1, wherein: the chemical formula is CdHg₄S₄Br₆。

3. The material of claim 1, wherein: the chemical formula is CdHg₄Te₄Br₆。

4. The material of claim 1, wherein: the chemical formula is CdHg₄Se₄Cl₆。

5. The material of claim 1, wherein: the chemical formula is CdHg₄Se₄Br₆The space group is Cmm2(No35), the unit cell parameters are a-9.409 (8) Å, b-17.53 (1) Å, c-9.775 (6) Å - β - γ -90 °, Z-4, the unit cell volume V-1612 (2) Å³The forbidden band width is 2.15 eV.

6. A method of preparing the material of claim 5, characterized by: the material is synthesized by a solid-phase reaction method, reactants with corresponding mass are accurately weighed according to the molar ratio of each reactant in a reaction formula, the reactants are put into a mortar for uniform grinding, and then the ground mixture is pressed into tablets and filled into a glass tube; vacuumizing the glass tube, sealing the glass tube by using flame, putting the sealed glass tube into a muffle furnace, controlling the temperature by using a temperature controller, heating the glass tube to 200 ℃ within 6h of room temperature, keeping the temperature at 200 ℃ for 24 hours, heating the glass tube to 300 ℃ within 6h, keeping the temperature at 300 ℃ for 144 hours, cooling the glass tube to 100 ℃ within 33h, and cooling the glass tube to 35 ℃ within 5 h.

7. Use of a material according to claim 1, characterized in that: the material is used for infrared detectors and emitters.

8. Use of a material according to claim 1, characterized in that: the material is used for thermoelectric materials.

9. Use of a material according to claim 1, characterized in that: the crystal is used for infrared lasers.