CN1412152A - Hole-conductive semiconductor ceramic refrigerating material and its preparation method - Google Patents
Hole-conductive semiconductor ceramic refrigerating material and its preparation method Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 39
- 239000004065 semiconductor Substances 0.000 title claims abstract description 32
- 239000000919 ceramic Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 238000005057 refrigeration Methods 0.000 claims abstract description 30
- 239000000203 mixture Substances 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 9
- 238000005516 engineering process Methods 0.000 claims abstract description 7
- 238000004814 ceramic processing Methods 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 239000002019 doping agent Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 239000012300 argon atmosphere Substances 0.000 claims 2
- 238000005245 sintering Methods 0.000 claims 2
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 239000013078 crystal Substances 0.000 abstract description 3
- 238000011056 performance test Methods 0.000 abstract description 3
- 238000001816 cooling Methods 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- 238000011160 research Methods 0.000 abstract description 2
- 239000004615 ingredient Substances 0.000 description 4
- 238000011161 development Methods 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000004663 powder metallurgy Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004857 zone melting Methods 0.000 description 1
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Abstract
一种空穴传导型半导体陶瓷制冷材料及其制备方法。其材料组成为Bi2Te3、Sb2Te3、Sb2Se3、Te。将上述组成的各种成份按设定的比例混合后，采用陶瓷加工技术制备半导体陶瓷制冷材料。性能测试结果证明：可制备出与单晶半导体制冷材料性能相当的半导体陶瓷制冷材料，其主要指标达到P型半导体陶瓷性能水平。塞贝克系数：220μV/K，电导率：96Ω－1·cm－1，热导率：13.3mW/cm·K，优值系数：3.50×10－3K－1。本发明制法简单，制造成本较低，可应用在科学研究、军事、工业生产、日常生活等众多领域，特别是在大规模集成线路、光敏器件、功率元件、高频晶体管、电子仪器等元件和设备的冷却方面具有较广泛的实用性。A hole conduction semiconductor ceramic refrigeration material and a preparation method thereof. Its material composition is Bi 2 Te 3 , Sb 2 Te 3 , Sb 2 Se 3 , Te. After mixing various components of the above-mentioned composition according to the set ratio, the semiconductor ceramic refrigeration material is prepared by using ceramic processing technology. The performance test results prove that the semiconductor ceramic refrigeration material with the same performance as the single crystal semiconductor refrigeration material can be prepared, and its main indicators reach the performance level of P-type semiconductor ceramics. Seebeck coefficient: 220μV/K, electrical conductivity: 96Ω -1 ·cm -1 , thermal conductivity: 13.3mW/cm·K, figure of merit: 3.50×10 -3 K -1 . The method of the invention is simple, the manufacturing cost is low, and can be applied in scientific research, military affairs, industrial production, daily life and many other fields, especially in large-scale integrated circuits, photosensitive devices, power components, high-frequency transistors, electronic instruments and other components. And the cooling of equipment has a wider range of practicability.
Description
技术领域technical field
本发明涉及一种空穴传导型(P型)半导体陶瓷制冷材料及其制备方法，属半导体陶瓷材料领域。The invention relates to a hole conduction type (P type) semiconductor ceramic refrigeration material and a preparation method thereof, belonging to the field of semiconductor ceramic materials.
背景技术Background technique
目前，空穴传导型半导体制冷材料及其应用技术已引起众多科研工作者和生产厂家的高度重视。但半导体制冷材料生产所存在的一些困难在很大程度上限制了半导体制冷材料及其应用技术的进一步发展。其中，材料的生产成本高、制造工艺复杂是半导体制冷材料广泛应用的最大障碍。现有的半导体制冷材料的传统制备工艺主要有区熔法和粉末冶金法，这两种方法都需在700℃左右进行高温熔炼，工艺过程复杂，生产条件苛刻，消耗大，成本高，导致P型半导体制冷材料制造成本较高。这是造成半导体制冷技术尚未广泛应用于民用这一广阔领域的主要原因之一，同时也在很大程度上限制和制约了该技术的进一步发展。At present, hole-conducting semiconductor refrigeration materials and their application technologies have attracted the attention of many researchers and manufacturers. However, some difficulties in the production of semiconductor refrigeration materials limit the further development of semiconductor refrigeration materials and their application technology to a large extent. Among them, the high production cost of materials and complex manufacturing process are the biggest obstacles to the wide application of semiconductor refrigeration materials. The existing traditional preparation techniques of semiconductor refrigeration materials mainly include zone melting method and powder metallurgy method. Both of these methods require high-temperature melting at about 700°C. The process is complicated, the production conditions are harsh, the consumption is large, and the cost is high, resulting in P The manufacturing cost of semiconductor refrigeration materials is relatively high. This is one of the main reasons why semiconductor refrigeration technology has not been widely used in the civil field, and it also limits and restricts the further development of this technology to a large extent.
发明内容Contents of the invention
本发明所要解决的问题是提供一种性能优良、且制造成本较低的空穴传导型(P型)半导体陶瓷制冷材料及其制备方法。The problem to be solved by the present invention is to provide a hole conduction type (P type) semiconductor ceramic refrigeration material with excellent performance and low manufacturing cost and a preparation method thereof.
本发明提供的技术方案是：一种空穴传导型半导体陶瓷制冷材料，该陶瓷制冷材料由重量百分数为20％～25％Bi2Te3、72％～75％Sb2Te3、3％～6％Sb2Se3三项成份百分数之和为100％的混合物，和该混合物重量1.8％～2.5％Te的外加掺杂剂组成。The technical solution provided by the invention is: a hole-conducting semiconductor ceramic refrigeration material, the ceramic refrigeration material is composed of 20% to 25% Bi 2 Te 3 , 72% to 75% Sb 2 Te 3 , 3% to 6% Sb 2 Se 3 is a mixture in which the sum of the percentages of the three components is 100%, and the weight of the mixture is composed of 1.8%-2.5% Te as an external dopant.
所述的空穴传导半导体陶瓷制冷材料的掺杂剂为Te。The dopant of the hole-conducting semiconductor ceramic refrigeration material is Te.
上述的空穴传导型半导体陶瓷制冷材料的制备方法，是将所述的组成各成份混合后采用陶瓷加工技术制备半导体陶瓷制冷材料，其步骤为：The preparation method of the above-mentioned hole-conducting semiconductor ceramic refrigeration material is to prepare the semiconductor ceramic refrigeration material by using ceramic processing technology after mixing the various components of the composition. The steps are:
(1)按所述的组成范围内设定组成计算出Bi、Te、Se、Sb及掺杂剂Te的量，并分别称量后充分混合研磨，压片成型，预烧；(1) Calculate the amount of Bi, Te, Se, Sb and dopant Te according to the composition set within the composition range, and fully mix and grind after weighing respectively, press into tablets, and calcinate;
(2)预烧后的物料经粉碎、研磨、压片成型后，进行二烧，制得所需要的空穴传导型半导体陶瓷制冷材料。(2) After the pre-fired material is pulverized, ground, and pressed into tablets, it is second-fired to obtain the required hole-conducting semiconductor ceramic refrigeration material.
上述制备工艺的特征是：压片成型压力为19MPa，预烧最高温度410℃，升温速率5℃/min，270℃保温1小时，410℃保温6小时，二烧前物料颗粒度控制在2.5μm～3.0μm，二烧最高温度420℃，升温速率6℃/min，420℃保温2小时。The characteristics of the above-mentioned preparation process are: the pressure of tablet forming is 19MPa, the highest temperature of pre-calcination is 410°C, the heating rate is 5°C/min, the temperature is kept at 270°C for 1 hour, and the temperature is kept at 410°C for 6 hours. The particle size of the material before the second firing is controlled at 2.5 μm ～3.0μm, the maximum temperature of the second firing is 420°C, the heating rate is 6°C/min, and the temperature is kept at 420°C for 2 hours.
性能测试结果证明：采用陶瓷制备工艺可制备出与单晶半导体制冷材料性能相当的P型半导体陶瓷制冷材料，其主要性能指标达到以下水平：
本发明所用原材料的利用率高，且制法简单，因而本发明的制造成本较低。The utilization rate of raw materials used in the invention is high, and the preparation method is simple, so the manufacturing cost of the invention is relatively low.
本发明的P型半导体陶瓷制冷材料性能优良，可应用在科学研究、军事、工业生产、日常生活等众多领域，特别是在大规模集成线路、光敏器件、功率元件、高频晶体管、电子仪器等元件和设备的冷却方面具有较强的实用性。The P-type semiconductor ceramic refrigeration material of the present invention has excellent performance, and can be applied in many fields such as scientific research, military affairs, industrial production, and daily life, especially in large-scale integrated circuits, photosensitive devices, power components, high-frequency transistors, electronic instruments, etc. It has strong practicality in the cooling of components and equipment.
具体实施方式Detailed ways
实施例1：按重量25％Bi2Te3+72％Sb2Te3+3％Sb2Se3，外加前三项成份量总和的2.0wt％Te的配方，将各种成份混合，研磨3-5小时。在压力机上以19MPa左右的压力压制成型，在Ar气氛中410℃进行预烧1小时。预烧后样品粉碎、研磨1-3小时，压片后，在Ar气氛中420℃左右二烧2小时，最后得到所需要的P型半导体陶瓷制冷材料。Example 1: According to the formula of 25% Bi 2 Te 3 +72% Sb 2 Te 3 +3% Sb 2 Se 3 by weight, plus 2.0wt% Te of the total amount of the first three ingredients, the various ingredients were mixed and ground for 3 -5 hours. It is pressed and formed on a press at a pressure of about 19MPa, and pre-fired at 410°C for 1 hour in an Ar atmosphere. After pre-fired, the sample is pulverized and ground for 1-3 hours, and after being pressed into tablets, it is fired in an Ar atmosphere at about 420°C for 2 hours, and finally the required P-type semiconductor ceramic refrigeration material is obtained.
性能测试结果证明：采用陶瓷制备工艺可制备出与单晶半导体制冷材料性能相当的P型半导体陶瓷制冷材料，所制备材料的主要性能指标如下：
实施例2～实施例5：
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| CNB021477655A CN1181012C (en) | 2002-11-29 | 2002-11-29 | Hole conduction semiconductor ceramic refrigeration material and preparation method thereof |
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| CNB021477655A CN1181012C (en) | 2002-11-29 | 2002-11-29 | Hole conduction semiconductor ceramic refrigeration material and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100419130C (en) * | 2004-11-03 | 2008-09-17 | 中国科学技术大学 | Sb2Te3 monocrystalline nanometer line ordered array and its preparation method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100419130C (en) * | 2004-11-03 | 2008-09-17 | 中国科学技术大学 | Sb2Te3 monocrystalline nanometer line ordered array and its preparation method |
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