CN1173878C - High pressure synthesis of lump nano semiconductor PbTe material - Google Patents
High pressure synthesis of lump nano semiconductor PbTe material Download PDFInfo
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- CN1173878C CN1173878C CNB021093679A CN02109367A CN1173878C CN 1173878 C CN1173878 C CN 1173878C CN B021093679 A CNB021093679 A CN B021093679A CN 02109367 A CN02109367 A CN 02109367A CN 1173878 C CN1173878 C CN 1173878C
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- pressure
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- high pressure
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- pbte
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B19/00—Selenium; Tellurium; Compounds thereof
- C01B19/007—Tellurides or selenides of metals
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/76—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by a space-group or by other symmetry indications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/32—Thermal properties
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
Abstract
The present invention belongs to a high-temperature high-pressure synthetic method of a block-shaped nanometer semiconductor PbTe material. The thermoelectric conversion performance of the material is mainly increased, and the material is beneficial for practical application. The present invention uses lead powder (Pb) and tellurium powder (Te) as raw materials which are prepared into the PbTe material by carrying out the technical processes of material mixture and block press, assembly, high-temperature high-pressure synthesis, cooling, etc. The material mixture and block press process is formed by that the lead powder and the tellurium powder are mixed according to a molar ratio of 1: 1, and are pressed into blocks according to the size of a synthesis cavity. The high-temperature high-pressure synthesis process is carried out on a presser, the synthesis pressure is from 1.0 to 6.0 Gpa, and the temperature is from 850 to 1400K. After the material carries out pressure maintenance and heat insulation, the material is cooled by the temperature falling rate of 50 to 200 K/s. The synthetic PbTe material of the present invention has a NaCl structure, the crystal size is nanometer magnitude, the value of the heat conductivity is below 1.5 w/m. k, the value of the electrical conductivity is above 10<-4> omega. M magnitude, and the present invention is suitable for practical application.
Description
Technical field
The invention belongs to a kind of preparation method of semiconductor material, particularly the High Temperature High Pressure synthetic method of lead telluride (PbTe) material.
Background technology:
PbTe is a kind of good thermoelectric material.Adopt different preparation methods, very big influence is arranged for its thermoelectricity capability.In many methods for preparing thermoelectric material, mainly be by the raising conductivity of electrolyte materials, the thermal conductivity (mainly being the lattice thermal conductivity that reduces material) that reduces material simultaneously improves the thermoelectricity capability of material.
The background technology relevant with present technique is to be raw material with Pb powder and Te powder, by stoichiometric ratio (Pb: Te=0.49: 0.51) mix, then 10
-3Sintering is about 12 hours under high vacuum more than the Pa, the 1200K hot conditions.The PbTe material of preparing mostly is monocrystalline or the polycrystalline of crystal grain in micron dimension, and the value of thermal conductivity is about 2.3w/m.k, and the value of resistivity is 10
-4Ω m magnitude.This material is used to prepare thermo-electric device, and its thermoelectricity capability is lower.
Summary of the invention
The present invention adopts the new method for preparing the PbTe material---high pressure synthetic method, mainly solves this technical problem of thermo-electric conversion performance that improves material, is beneficial to practical application.The thermal conductivity of PbTe material and its grain size have certain relation, and the present invention is with control High Temperature High Pressure synthetic condition, particularly pressure size, allow the crystal size of PbTe material in nanometer scale, and thermal conductivity descends, resistivity reduces thereby make.
The high pressure synthetic method of of the present invention block of Nano semiconductor PbTe material is a raw material with lead powder (Pb) and tellurium powder (Te), and technological processs such as, cooling synthetic through batch mixing briquetting, assembling, High Temperature High Pressure make the PbTe material.Said batch mixing briquetting is that lead powder and tellurium powder were mixed in 1: 1 in molar ratio, is pressed into bulk by the synthetic cavity size.Said assembling is that block raw material is packed in the heating container.Said High Temperature High Pressure is synthetic, is at high-tension unit, and such as what carry out on the six-plane piercer, synthesis condition is that pressure is that 1.0～6.0Gpa, temperature are 850～1400K, and heat-insulation pressure keeping stops heating after 20～40 minutes, and pressurize is 3～8 minutes again.Said cooling is that the rate of temperature fall with 50～200K/S cools off.
Compound experiment of the present invention is finished on homemade DS029B type six-plane piercer.Experiment shows that the size of synthesis pressure is to influence PbTe material mean particle size, and then influences the important factor of the thermal conductivity of PbTe material, and optimal pressure range is 2.5～6.0Gpa.The size of synthesis temperature is the important factor that influences the PbTe material purity, and optimum temperature range is 1100～1250K.Rate of temperature fall during cooling is the principal element that influences the PbTe material particle size, and best rate of temperature fall is 130～200K/S.
In order to keep the sample chamber temperature homogeneity, assembling can be the heater-type type of heating; In order to make synthetic PbTe material and raw material not oxidized in preparation, can the applying argon gas protection in the synthetic cavity.
It is good that the present invention has the synthetic materials performance, and production cost is low, is convenient to advantages such as enforcement.The PbTe crystal growth is good, and the X light analysis result shows that PbTe has the NaCl structure, and electron microscopic analysis shows that the crystal grain size is a nanometer scale.The value of the PbTe thermal conductivity that synthesizes is lower than 1.5w/m.k, and the value of resistivity is 10
-5～10
-6Ω m magnitude.
Embodiment
Embodiment 1
High-purity Pb powder is mixed by chemical dosage ratio (1: 1) with the Te powder, after powder is molded, sample is packed in the high-pressure chamber.Make heating tube with graphite in the assembling cavity, do insulation tube with agalmatolite, synthesis pressure is 4.0GPa, temperature 1200K, and the rate of cooling 60K/s of sample after stopping to heat, synthesizing the PbTe average grain size is 1000nm.The specific conductivity of sample is 6 * 10
-5Ω m, heat conductivity value are 1.4w/m.k.
Embodiment 2
Adopt the assembling identical with embodiment 1, insulation tube is changed do hexagonal nitrogenize roc, synthesis pressure is 4.0GPa, and temperature 1200K stops to heat afterwards that the rate of cooling of sample is 150K/s, and synthetic sample grain size is 300 nanometers.The specific conductivity of sample is 4 * 10
-5Ω m, heat conductivity value are 0.8w/m.k.
Embodiment 3
Adopt the assembling identical with embodiment 2, synthesis pressure is 1.0GPa, temperature 1200K, and synthetic sample grain size is 700 nanometers.The specific conductivity of sample is 7 * 10
-5Ω m, heat conductivity value are 1.3w/m.k.
Comparing embodiment 2 and 3, just synthesis pressure is variant, and the PbTe material crystals granularity that makes when pressure is big is little, and has influence on the performance of PbTe material, and the thermal conductivity that granularity is little is low.
Embodiment 4
Adopt the assembling identical with embodiment 2, synthesis pressure is 6.0GPa, temperature 1200K, and synthetic sample grain size is 100 nanometers.The specific conductivity of sample is 3 * 10
-6Ω m, heat conductivity value are 0.7w/m.k.
Embodiment 5
Adopt the assembling identical with embodiment 2, synthesis pressure is 4.0GPa, and temperature 700K can not synthesize the PbTe sample.
Claims (3)
1, the high pressure synthetic method of a kind of block of Nano semiconductor lead telluride material is a raw material with lead powder and tellurium powder, it is characterized in that,, process for cooling process synthetic through batch mixing briquetting, assembling, High Temperature High Pressure makes the PbTe material; Said batch mixing briquetting is that lead powder and tellurium powder were mixed in 1: 1 in molar ratio, is pressed into bulk by the synthetic cavity size; Said assembling is that block raw material is packed in the heating container; Said High Temperature High Pressure is synthetic, carries out on high-tension unit, and synthesis condition is that pressure is that 1.0～6.0GPa, temperature are 850～1400K, and heat-insulation pressure keeping stops heating after 20～40 minutes, and pressurize is 3～8 minutes again; Said cooling is that the rate of temperature fall with 50～200K/S cools off.
According to the high pressure synthetic method of described block of Nano semiconductor lead telluride of claim 1 material, it is characterized in that 2, said High Temperature High Pressure synthesis condition is that pressure is that 2.5～6.0Gpa, temperature are 1100～1250K; Said cooling is that the rate of temperature fall with 130～200K/S cools off.
According to the high pressure synthetic method of claim 1 or 2 described blocks of Nano semiconductor lead telluride materials, it is characterized in that 3, said assembling is the heater-type type of heating, the protection of synthetic cavity applying argon gas.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021093679A CN1173878C (en) | 2002-03-27 | 2002-03-27 | High pressure synthesis of lump nano semiconductor PbTe material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021093679A CN1173878C (en) | 2002-03-27 | 2002-03-27 | High pressure synthesis of lump nano semiconductor PbTe material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1375450A CN1375450A (en) | 2002-10-23 |
| CN1173878C true CN1173878C (en) | 2004-11-03 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB021093679A Expired - Fee Related CN1173878C (en) | 2002-03-27 | 2002-03-27 | High pressure synthesis of lump nano semiconductor PbTe material |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100344802C (en) * | 2005-07-28 | 2007-10-24 | 上海大学 | Process for preparing lead sulfur family compound semiconductor single crystal |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7465871B2 (en) | 2004-10-29 | 2008-12-16 | Massachusetts Institute Of Technology | Nanocomposites with high thermoelectric figures of merit |
| US8865995B2 (en) | 2004-10-29 | 2014-10-21 | Trustees Of Boston College | Methods for high figure-of-merit in nanostructured thermoelectric materials |
| CN100363132C (en) * | 2005-09-23 | 2008-01-23 | 北京科技大学 | High pressure method for preparing Bi-Te alloy series thermoelectric material |
| US9048004B2 (en) | 2010-12-20 | 2015-06-02 | Gmz Energy, Inc. | Half-heusler alloys with enhanced figure of merit and methods of making |
| CN104674046B (en) * | 2015-02-03 | 2017-11-03 | 河南理工大学 | A kind of preparation method of BiCu ζ O thermoelectric materials |
| CN106379872B (en) * | 2016-11-01 | 2018-07-03 | 吉林大学 | A kind of hexagonal structure TaSe of quick preparation pure phase2Method |
| CN112062153A (en) * | 2020-09-15 | 2020-12-11 | 吉林大学 | Improve BaZrO3Method of electrical conductivity |
-
2002
- 2002-03-27 CN CNB021093679A patent/CN1173878C/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100344802C (en) * | 2005-07-28 | 2007-10-24 | 上海大学 | Process for preparing lead sulfur family compound semiconductor single crystal |
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| CN1375450A (en) | 2002-10-23 |
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