CN1060234C - High-temperature heat treatment method for mercury cadmium telluride material - Google Patents
High-temperature heat treatment method for mercury cadmium telluride material Download PDFInfo
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- CN1060234C CN1060234C CN97106663A CN97106663A CN1060234C CN 1060234 C CN1060234 C CN 1060234C CN 97106663 A CN97106663 A CN 97106663A CN 97106663 A CN97106663 A CN 97106663A CN 1060234 C CN1060234 C CN 1060234C
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Abstract
The present invention relates to a high-temperature heat treatment method for mercury-cadmium-tellurium materials. The heat treatment is completed in a quartz ampoule, and the heat treatment source is a source containing tellurium and mercury; protective gas is added in the ampoule, and the absolute evaporation for atoms on the surfaces of the mercury-cadmium-tellurium materials is effectively restrained by using tellurium partial pressure provided by a tellurium source in a heat treatment system and the protective gas. After high-temperature heat treatment is carried out on the mercury-cadmium-tellurium materials by using the method, the dislocation of the mercury-cadmium-tellurium materials is reduced by about one order of magnitude, and meanwhile the integrity of surface morphology of the materials is well kept. The method is also suitable for electrical property activation of blended atoms in the mercury-cadmium-tellurium materials under high temperatures.
Description
Handle after the present invention relates to monocrystalline or having the homogeneous polycrystalline material of a fixed structure, especially for reducing the high-temperature heat treatment method of tellurium every mercury semiconductor material dislocation desity, this method also is applicable to the electrical activation of foreign atom in the Hg-Cd-Te material.
In fields such as space flight and airborne remote sensing, military photoelectron countermeasure techniques, information technology and industrial thermometric, infrared eye has a wide range of applications.Development along with the infrared focus plane Detection Techniques, the big area tellurium has obtained a large amount of use in preparation in the infrared eye every mercury (HgCdTe) thin-film material, and the requirement that the quality that how to improve material satisfies infrared focal plane device is a key link in this technical field.
The big area tellurium is to be prepared from certain substrate material with epitaxy technology every the mercury thin-film material, because the lattice mismatch between substrate and the tellurium cadmium mercury epitaxial layer, can there be dislocation defects in the epitaxial material, reduces misfit dislocation density and generally need pass through high-temperature heat treatment process.In addition, the infrared focal plane device of the P-on-N structure of researching and developing at present also requires to come active ions to inject the arsenic atom that mixes with high-temperature heat treatment, and the arsenic atom that is about to inject is sent into the crystallographic site of tellurium atom, makes its one-tenth be subjected to the principal mode foreign atom.At present, all adopt the thermal treatment unit of high-pressure type abroad in the Te-Cd-Hg high-temperature heat treatment, as: J.M.Arias, et.at J.Vac.Sci.Technol B9 (3), 1646 (1991), C.C.Wang et.al J.Electrochem.Soc.127 (8), 175 (1980), compare with traditional mercury source thermal treatment process of carrying out with quartz ampoule, the high-pressure type equipment requirements has improved a lot.
The objective of the invention is to provides a kind of novel high-temperature heat treatment method same with hot high pressure treatment process effect by improving traditional quartz ampoule heat treating method.
Purpose of the present invention reaches by following technical solution: present method splits ampoule two with sample and source earlier; sample temperature is a little more than 3～5 ℃ of source temperature; its heat treatment source is for containing tellurium mercury source and adding protective gas (Forming Gas); as: argon gas, nitrogen or hydrogen; utilize tellurium source and protective gas to suppress the absolute steam output of Hg-Cd-Te material self under the high temperature, in 400～500 ℃ of temperature ranges, heat-treat.Said Hg-Te heat treatment source contains the atomic ratio of tellurium greater than the maxima solubility of mercury to tellurium, less than 50%; Pressure under the used protective gas room temperature is 4 * 10
4～6 * 10
4The Pa scope can be pressed for thermal treatment provides enough mercury, can satisfy the requirement of quartz ampoule pipe sealing simultaneously again.
For setting forth conveniently, elder generation is as follows to description of drawings of the present invention:
Fig. 1. be traditional Te-Cd-Hg quartz ampoule mercury source thermal treatment unit synoptic diagram.
Fig. 2. be the shape appearance figure of the 490 ℃ of thermal treatments in the pure mercury of tradition source to the destruction situation on Hg-Cd-Te material surface.
Fig. 3. for using the mercury source Hg-Cd-Te material surface topography map after 490 ℃ of thermal treatment that contains tellurium, the degree of being damaged in its surface has been subjected to certain inhibition.
Fig. 4. fill protective gas and tellurium-mercury source quartz ampoule Te-Cd-Hg high-temperature heat treatment device synoptic diagram for what the present invention adopted.
Fig. 5. for adopting behind the present invention Hg-Cd-Te material surface Nomarski shape appearance figure before 490 ℃ of thermal treatment in 30 minutes.
Fig. 6. for adopting behind the present invention Hg-Cd-Te material surface Nomarski shape appearance figure after 490 ℃ of thermal treatment in 30 minutes, surface integrity obtains fine maintenance.
Fig. 7. add protective gas Hg-Cd-Te material surface topography map after 490 ℃ of thermal treatment in 30 minutes for adopting pure mercury, still can't keep the integrity on surface.
Fig. 8. be the shape appearance figure of Hg-Cd-Te material surface dislocation pit density before the employing thermal treatment process of the present invention.
Fig. 9. be to adopt the shape appearance figure of Hg-Cd-Te material surface dislocation pit density after the thermal treatment process of the present invention, shown the dislocation desity in the material lower effectively.
Below in conjunction with accompanying drawing method of the present invention is further elaborated and analyzes.
See also Fig. 1, the synoptic diagram of traditional quartz ampoule mercury source thermal treatment unit, source and sample split ampoule two, and the mercury source temperature is a little less than 3～5 ℃ in sample.Find in the experiment, traditional mercury source thermal treatment process is more than 400 ℃ the time, the surface of Hg-Cd-Te material will be subjected to havoc, Theoretical Calculation shows, as: Yang Jianrong, J.Crystal Growth, 126,695 (1993), the required tellurium atom of Hg-Cd-Te material and the equilibrium vapour pressure of cadmium atom will be brought up to the 10-3Pa magnitude under the high temperature, and the evaporation line of surface atom reaches 10
15/ cm
2S, traditional mercury source thermal treatment process has generally all been ignored this effect, the vapour pressure of corresponding tellurium and cadmium is not provided in ampoule, therefore, when this technology is used for high-temperature heat treatment, because the continuous volatilization of Hg-Cd-Te material surface tellurium and cadmium atom has caused the structure of Hg-Cd-Te material upper layer to be subjected to destruction.See also Fig. 2, shown the situation that the surface is damaged at Fig. 2.
According to this thought, the inventor uses the instead of pure mercury source, mercury source that contains 10～20% telluriums instead, this source is in 400 ℃～500 ℃ scopes, form by the HgTe solid with its equilibrated Hg-Te liquid, in principle, all be identical greater than mercury to the maxima solubility of tellurium, less than 50% effect as long as the Hg-Te heat treatment source contains the atomic ratio of tellurium.According to the P-T phasor of Hg-Cd-Te material, under same temperature, the equilibrium vapour pressure of HgTe is greater than Hg1-
xCd
xThe equilibrium vapour pressure of Te crystalline material, after employing contained the mercury source of tellurium, after 490 ℃ of thermal treatment, the degree of being damaged in the Hg-Cd-Te material surface had been subjected to certain inhibition (see figure 3), the density of surface imperfection obviously descends to some extent, but does not eliminate the destruction of thermal treatment to material surface yet fully.
If further use the Hg-Cd-Te source instead; also be expected to improve surface quality; but choosing and preparing of source is all cumbersome; the inventor found before the quartz ampoule vacuum sealing tube in the experiment; in ampoule, charge into a certain amount of protective gas, as: argon gas, nitrogen or hydrogen, can suppress the evaporation at high temperature of Hg-Cd-Te material surface atom effectively; its principle is identical with the principle of hot high pressure treatment process, promptly suppresses the evaporation line of material surface by high pressure.See also Fig. 4, the inventor has introduced 4 * 10 in quartz ampoule in Fig. 4
4Pa～6 * 10
4The protective gas of Pa, and adopt the mercury source that contains 15% tellurium as heat treated source, Hg-Cd-Te material is after 490 ℃ of thermal treatment in 30 minutes as a result, and surface integrity has obtained keeping well (seeing Fig. 5 and Fig. 6).But the technology that adopts pure mercury to add the protective gas of low pressure still can't keep the integrity (see figure 7) on Hg-Cd-Te material surface.Therefore, the present invention proposes to adopt and contains ampoule heat treating method that tellurium mercury source adds protective gas and finished high-temperature heat treatment to Hg-Cd-Te material.
Inventor's aforesaid method on probation is to using the Hg1-of molecular beam epitaxial growth on the GaAs substrate
xCd
xThe Te material reduces the effect of dislocation to be tested, and the result is as shown in the table:
| Heat-treat condition dislocation desity (cm -2) before ℃ time thermal treatment of sample number into spectrum component temperature after the thermal treatment (branch) |
| gamct039 0．23 490℃ 30 2×10 7 3×10 6gamct060 0．228 490℃ 20 1．5×10 7 2×10 6 |
The result shows that the present invention can reduce the dislocation desity in the Hg-Cd-Te material effectively.Fig. 8 and Fig. 9 show the correlated situation of thermal treatment front and back material surface dislocation pit density.
Beneficial effect of the present invention has been to provide and has contained the ampoule heat treating method that tellurium-mercury source adds protective gas; this method can avoid traditional mercury source thermal treatment at high temperature to the destruction on Hg-Cd-Te material surface; after with this method Te-Cd-Hg being come out to carry out high-temperature heat treatment; the dislocation of the Hg-Cd-Te material order of magnitude nearly that descended; simultaneously, the integrity of material surface is well kept.Behind the HgCdTe arsenic doping, need high-temperature heat treatment that former occupying at the arsenic atom of V family on the mercury lattice point adjusted on the VI family tellurium atom lattice point, the arsenic atom that mixes could form P type foreign atom, its high-temperature heat treatment process is identical with the technology of falling dislocation, as: S.H.Shin, et.at J.Electronic Materials, 22 (8), 1039 (1993).Therefore, present method is suitable for foreign atom electrical activation at high temperature in the Hg-Cd-Te material too.
Claims (2)
1, a kind of high-temperature heat treatment method for mercury cadmium telluride material; sample and source split ampoule two; sample temperature is a little more than 3～5 ℃ of the temperature in source; heat treatment source is for containing tellurium mercury source; it is characterized in that: add protective gas in the ampoule, utilize argon gas, nitrogen or hydrogen to suppress the absolute steam output of Hg-Cd-Te material self atom under the high temperature, the described tellurium atom ratio that contains tellurium mercury source is greater than the maxima solubility of mercury to tellurium; in 50% scope, heat treated temperature is 490 ℃.
2,, it is characterized in that pressure under the used protective gas room temperature is 4 * 10 by the high-temperature heat treatment method for mercury cadmium telluride material of claim 1 defined
4～6 * 10
4In the Pa scope.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97106663A CN1060234C (en) | 1997-10-17 | 1997-10-17 | High-temperature heat treatment method for mercury cadmium telluride material |
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| CN97106663A CN1060234C (en) | 1997-10-17 | 1997-10-17 | High-temperature heat treatment method for mercury cadmium telluride material |
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| CN1195038A CN1195038A (en) | 1998-10-07 |
| CN1060234C true CN1060234C (en) | 2001-01-03 |
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| CN104532356A (en) * | 2014-12-09 | 2015-04-22 | 中国科学院上海技术物理研究所 | Heat treatment apparatus for eliminating tellurium-zinc-cadmium material precipitate-phase defects |
| CN105908254B (en) * | 2016-06-12 | 2018-07-06 | 中国科学院上海技术物理研究所 | A kind of bushing type cavity body structure for being used to prepare semi-conducting material |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2720891A1 (en) * | 1976-06-11 | 1977-12-22 | Cominco Ltd | METHOD FOR IMPROVING THE PROPERTIES OF CADMIUM MERCURY TELLURIDE |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2720891A1 (en) * | 1976-06-11 | 1977-12-22 | Cominco Ltd | METHOD FOR IMPROVING THE PROPERTIES OF CADMIUM MERCURY TELLURIDE |
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