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WO2010083706A1 - 一种温差电池及其制造方法 - Google Patents

一种温差电池及其制造方法 Download PDF

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Publication number
WO2010083706A1
WO2010083706A1 PCT/CN2009/075422 CN2009075422W WO2010083706A1 WO 2010083706 A1 WO2010083706 A1 WO 2010083706A1 CN 2009075422 W CN2009075422 W CN 2009075422W WO 2010083706 A1 WO2010083706 A1 WO 2010083706A1
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WO
WIPO (PCT)
Prior art keywords
type thermoelectric
film layer
thermoelectric material
insulating substrate
material film
Prior art date
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PCT/CN2009/075422
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English (en)
French (fr)
Inventor
范平
张东平
郑壮豪
粱广兴
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深圳大学
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Application filed by 深圳大学 filed Critical 深圳大学
Priority to JP2011545614A priority Critical patent/JP5554786B2/ja
Priority to US13/145,207 priority patent/US8748208B2/en
Priority to EP09838673.3A priority patent/EP2410584B1/en
Publication of WO2010083706A1 publication Critical patent/WO2010083706A1/zh

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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
    • H10N10/01—Manufacture or treatment
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
    • H10N10/10—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects operating with only the Peltier or Seebeck effects
    • H10N10/17—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects operating with only the Peltier or Seebeck effects characterised by the structure or configuration of the cell or thermocouple forming the device

Definitions

  • the present invention relates to the field of thermoelectric power technology, and in particular, to a temperature difference battery and a manufacturing method thereof.
  • Thermoelectric cells are devices that use temperature differences to convert thermal energy directly into electrical energy due to the Seebeck effect.
  • the thermoelectric cell works by combining two different metals or two different types of thermoelectric conversion materials, one end of the ⁇ type and the ⁇ type semiconductor, and placing them at a high temperature, and the other end is open and given a low temperature. Since the thermal excitation at the high temperature end is strong, the hole and electron concentrations are also higher than the low temperature end. Under the carrier concentration gradient, holes and electrons diffuse toward the low temperature end, thereby forming a potential difference at the low temperature open end; By connecting a number of pairs of ⁇ -type and ⁇ -type thermoelectric conversion materials to form a module, a sufficiently high voltage can be obtained to form a thermoelectric generator.
  • the temperature difference battery As a clean energy source, the temperature difference battery has a series of advantages such as no noise, no harmful substances, high reliability and long life. It can provide stable power output for a long time, safely and continuously.
  • the main purpose is to cut the thermoelectric material wire into pieces and then solder it to form a temperature difference battery.
  • thermoelectric single The body substrate and the ⁇ -type thermoelectric unit substrate are separately manufactured separately, so that in the manufacturing process of the micro-film temperature difference battery, the conductive layer connecting the ⁇ -type and the ⁇ -type thermoelectric unit is fabricated on the substrate and the thermoelectric unit. It can be carried out without peeling.
  • the process for manufacturing the temperature difference battery by the above method is complicated, and there are processes for connecting the ⁇ type and the ⁇ type temperature difference electric unit, and the performance of the temperature difference battery is also limited.
  • An object of the present invention is to provide a temperature difference battery and a method of fabricating the same, which are advantageous in the above prior art, wherein the performance of the temperature difference battery is improved, and the manufacturing process is simple.
  • thermoelectric battery comprising an insulating substrate, the insulating substrate is coated with a P-type thermoelectric material film layer
  • the underside of the insulating substrate is plated with a film layer of an N-type thermoelectric material, and one of the sides of the insulating substrate is plated with a P-type and N-type material film to form a P-type thermoelectric material film layer and an N-type thermoelectric material film layer.
  • the connection end, the P-type thermoelectric material film layer and the N-type thermoelectric material film layer respectively lead to the electrode.
  • the thickness of the insulating substrate is: 0.1 mm to 100 mm
  • the thickness of the P-type thermoelectric material film layer is: lnm to ⁇
  • the thickness of the ⁇ -type thermoelectric material film layer is: lnm to 10 ⁇ .
  • the shape of the insulating substrate material is a regular rectangle or a square.
  • the exposed side shape of the insulating substrate is a plane or a curved surface.
  • a method for manufacturing a temperature difference battery comprising the steps of:
  • a thin film of a ruthenium-type thermoelectric material is plated on the other side of the insulating substrate, and has a thickness ranging from 1 nm to ⁇
  • thermoelectric material film Both the ⁇ -type thermoelectric material film and the ⁇ -type thermoelectric material film are deposited and joined on the exposed side of the insulating substrate;
  • the electrodes are taken out from the thin film layer of the ⁇ -type thermoelectric material and the thin film layer of the ⁇ -type thermoelectric material, respectively, to form a main structure of the temperature difference battery.
  • the beneficial effects of the present invention are as follows:
  • the method for preparing a thermoelectric battery provided by the present invention is to separately deposit a thin film of a ruthenium-type thermoelectric material and a film of a ruthenium-type thermoelectric material on both sides of the insulating substrate, and in the process of plating, insulation a bare side of the substrate, a thin film of a germanium type thermoelectric material and a thin film of a germanium type thermoelectric material are deposited there, and a thin film layer of a germanium type thermoelectric material and a thin film layer of a germanium type thermoelectric material are connected at the side to form a knot;
  • There is no need to have a process of specifically connecting the thin film layer of the ⁇ -type thermoelectric material and the thin film layer of the ⁇ -type thermoelectric material so that the process for manufacturing the temperature difference battery is relatively simple.
  • thermoelectric material film layer of a ruthenium-type thermoelectric material and a film layer of a ruthenium-type thermoelectric material are used to form a thermocouple, and the performance of the temperature difference battery is greatly improved due to the characteristics of the film thermoelectric material. Since the ⁇ -type thermoelectric material and the ⁇ -type thermoelectric material are deposited on the exposed side of the substrate to form one end of the ⁇ -type thermoelectric material film layer and the ⁇ -type thermoelectric material film layer, the end is not soldered, and the end is used as the end of the substrate. At the hot end, the hot surface operating temperature of the thermoelectric cell will also be greatly improved.
  • FIG. 2a and FIG. 2b are diagrams showing a manufacturing process of a temperature difference battery according to Embodiment 1 of the present invention.
  • FIG. 3 is a schematic cross-sectional structural view of a temperature difference battery according to Embodiment 2 of the present invention.
  • FIG. 4a and FIG. 4b are diagrams showing a manufacturing process of a thermoelectric battery according to Embodiment 2 of the present invention.
  • the present invention provides a temperature difference battery and a method of fabricating the same, and the present invention will be further described in detail below with reference to the accompanying drawings and embodiments.
  • a temperature difference battery provided in the first embodiment includes: an insulating substrate 110, and a P-type plated on one side of the insulating substrate.
  • the thermoelectric material thin film layer 120 is plated on the other side of the insulating substrate to form an N-type thermoelectric material thin film layer 130. From the P-type thermoelectric material film layer 120
  • the electrodes 140, 150 are taken out separately from the N-type thermoelectric material film layer 130.
  • a P-type thermoelectric material film layer 120 is plated on one side of the insulating substrate 110 to form a structure as shown in FIG. 2a, and then a N-type thermoelectric material film layer 130 is formed on the other surface of the insulating substrate 110 to form a film.
  • the structure shown in Fig. 2b; the P-type thermoelectric material film layer 120 and the N-type thermoelectric material film layer 130 are all deposited and joined on the exposed side of the insulating substrate.
  • the P-type thermoelectric material film layer 120 and the N-type thermoelectric material film layer 130 on the structure shown in Fig. 2b lead the electrodes 140, 150, respectively, to form the temperature difference cell.
  • the P-type thermoelectric material film layer 120 and the N-type thermoelectric material film layer 130 are completely overlapped on one side of the insulating substrate 110.
  • the temperature difference battery provided in the second embodiment includes: an insulating substrate 210, and a P-type plated on one side of the insulating substrate.
  • the thermoelectric material thin film layer 220 is plated on the other side of the insulating substrate to form an N-type thermoelectric material thin film layer 230. From the P-type thermoelectric material film layer 220
  • the electrodes 240 and 250 are taken out separately from the N-type thermoelectric material thin film layer 230.
  • a P-type thermoelectric material film layer 220 is plated on one surface of the insulating substrate 210 to form a structure as shown in FIG. 4a, and then a N-type thermoelectric material film layer 230 is formed on the other surface of the insulating substrate 210 to form a film.
  • the structure shown in Figure 4b Both the P-type thermoelectric material film layer 220 and the N-type thermoelectric material film layer 230 are deposited and joined on the exposed side of the insulating substrate.
  • the P-type thermoelectric material film layer 220 and the N-type thermoelectric material film layer 230 on the structure shown in Fig. 4b lead the electrodes 240, 250, respectively, to form the temperature difference battery. Wherein the P-type thermoelectric material film layer 220 and the N-type thermoelectric material are thin
  • the film layer 230 is just joined on one side of the insulating substrate 210.
  • the materials of the temperature difference battery in the above embodiments are generally metal and semiconductor.
  • the P-type and N-type thermoelectric materials may also be two different metal materials, that is, two different metal material films are plated to form thermocouples.
  • the shape of the insulating substrate material is a regular rectangle, or a square shape, or an arbitrary irregular shape.
  • the exposed side shape of the insulating substrate can be either a flat surface or a curved surface.
  • the temperature difference battery proposed in the above embodiment has a simple manufacturing process, low manufacturing cost, and greatly improved performance.
  • the temperature difference batteries provided in the above embodiments can generate a sufficiently large voltage output with a small temperature difference by a large number of series connection.
  • the device used in the third embodiment to fabricate the thermoelectric battery is a three-target magnetron sputtering coating machine.
  • Sb, Bi and Te were selected as targets, and the purity of the target was 99.99%.
  • Sb and Bi were respectively placed on two DC sputtering targets, and Te was placed in the RF sputtering target.
  • the substrate is ultrasonically cleaned by an organic solvent, and then placed on a jig in the coating chamber; the jig is designed to flip the substrate to facilitate the coating of the two substrates on the substrate.
  • One side of the insulating substrate 110 is exposed, the other sides are shielded, and the substrate 110 is placed at a certain inclination so that the exposed sides of the substrate 100 are plated with Sb, Bi and Te films.
  • a two-layer film of Sb and Te is plated on one side of the insulating substrate 110 by direct current sputtering and radio frequency sputtering, and a P-type thermoelectric material Sb 2 Te 3 is formed after the subsequent heat treatment.
  • the film layer 120 has a thickness of 700 nm as shown in FIG. 2a; then Bi and Te are plated on the other side of the insulating substrate 110 by adjusting the target and inverting the substrate by DC sputtering and RF sputtering, respectively.
  • an N-type thermoelectric material Bi 2 Te 3 film layer 130 was formed to have a thickness of 700 nm, as shown in Fig. 2b.
  • the film is annealed at 200 ° C for a certain period of time.
  • the background vacuum of the deposited film was 2.8xl0 4 Pa ' working vacuum ⁇ . ⁇ ⁇
  • the working gas is 99.99% high-purity Ar gas with a flow rate of 50sccm.
  • the electrodes are taken out from the Sb 2 Te 3 thin film layer 120 and the Bi 2 Te 3 thin film layer 130, respectively.
  • a main structure of the temperature difference battery as shown in FIG. 1 or as shown in FIG. 3 is formed.
  • thermoelectric material thin film layer in this embodiment, a magnetron sputtering method is used, and in other embodiments, various processes for preparing a thermoelectric material thin film can be used.
  • various processes for preparing a thermoelectric material thin film can be used.
  • vacuum evaporation coating molecular beam epitaxy (MBE), ion beam sputtering, pulsed laser deposition, electrochemical atomic layer epitaxy (ECALE), metal organic compound vapor deposition (MOCVD) and continuous ion layer adsorption And reaction method (SILAR) and so on.
  • MBE molecular beam epitaxy
  • ECALE electrochemical atomic layer epitaxy
  • MOCVD metal organic compound vapor deposition
  • SILAR continuous ion layer adsorption And reaction method
  • the P-type thermoelectric material film 120 may be first plated, and then the N-type thermoelectric material film 130 may be plated; or the N-type thermoelectric material film 130 may be plated first, and then the P-type thermoelectric material film 120 may be plated.
  • the apparatus is an ultra-high vacuum ion beam sputtering coating machine for preparing P-type and N-type thermoelectric material thin film layers by ion beam sputtering. Selecting the Seebeck coefficients for the P-type and N-type metals Sb and Bi as targets, the target purity is 99.99%, and placing the P-type and N-type metal Sb and Bi targets on the rotatably selective sputtering target. Target position.
  • the substrate is ultrasonically cleaned with an organic solvent and then placed on the coating chamber fixture; the fixture is designed to flip the substrate, facilitating the coating of the substrate on both sides, and insulating the substrate
  • One side of the sheet 110 is exposed, the other sides are shielded, and the substrate 110 is placed at a certain inclination so that the exposed side of the substrate 110 is plated with an overlap of Sb and Bi.
  • the Sb film layer 120 is first plated on one side of the insulating substrate 110 by ion beam sputtering to a thickness of 30 Onm, as shown in Fig.
  • a Bi film layer 130 is plated on the other side of the insulating substrate 110 to a thickness of 300 nm as shown in Fig. 2b.
  • the background vacuum of the deposited film was 4. 5xlO" 4 Pa, and the working vacuum was 4.1xlO- 2 Pa.
  • the working gas is 99.99% high-purity Ar gas with a flow rate of 4 S ccm.
  • the process parameters of ion beam deposition are: screen voltage 1KV, anode voltage 75V, acceleration voltage 220V, cathode voltage 7V, cathode current 11A, beam current
  • the electrodes 140 and 150 are respectively extracted from the Sb thin film layer 120 and the Bi thin film layer, thereby forming The main structure of the temperature difference battery shown in FIG. 1 or FIG.
  • the deposition of P-type and N-type materials on the exposed side of the insulating substrate may also partially overlap during the plating process.
  • the thickness of the insulating substrate is from 0.1 mm to 100 mm, and a thicker or thinner substrate may also be used.
  • the method for manufacturing a temperature difference battery provided by the above embodiment is not only simple and easy to manufacture, but also has low manufacturing cost, and the performance of the produced temperature difference battery is also greatly improved.
  • the fabricated cell temperature difference cells are connected in a large number of series to produce a sufficiently large voltage output with a small temperature difference.
  • thermoelectric phenomenon itself is reversible.
  • Semiconductor temperature difference power generation and semiconductor cooling are two aspects of the thermoelectric phenomenon and are mutually reversible.
  • the main structure of the thermoelectric battery of this embodiment is the main structure of the thermoelectric cooler.

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Measuring Temperature Or Quantity Of Heat (AREA)
  • Physical Deposition Of Substances That Are Components Of Semiconductor Devices (AREA)
  • Secondary Cells (AREA)
  • Physical Vapour Deposition (AREA)

Description

说明书
Title of Invention: —种温差电池及其制造方法
[1] 或
[2] 本发明涉及温差电技术领域， 特别涉及一种温差电池及其制作方法。
[3]
[4] 温差电池就是利用温度差异制成的电池， 由于塞贝克效应， 使热能直接转化为 电能的装置。 温差电池的工作原理是， 将两种不同的金属或两种不同类型的热 电转换材料 Ρ型和 Ν型半导体的一端结合并将其置于高温状态， 另一端开路并给 以低温。 由于高温端的热激发作用较强， 空穴和电子浓度也比低温端高， 在这 种载流子浓度梯度的驱动下， 空穴和电子向低温端扩散， 从而在低温开路端形 成电势差； 如果将许多对 Ρ型和 Ν型热电转换材料连接起来组成模块， 就可得到 足够高的电压， 形成一个温差发电机。
[5] 温差电池作为一种清洁能源， 具有无噪音、 无有害物质排放、 可靠性高、 寿命 长等一系列优点， 它能长期、 安全、 连续地提供稳定的电能输出。 目前， 主要 是将热电材料线切割成片， 再焊接， 形成温差电池； 制作微型温差电池的方法 中， 主要有两类， 一类方法是： 在同一个基片上涂敷感光胶， 通过两次光刻的 方法在感光胶上先后形成 Ρ型和 Ν型微区， 之后又先后在 Ρ型和 Ν型微区内沉积 Ρ 型和 Ν型温差电材料。 这种制造方法难度大， 特别是在连接温差电单体的导电层 制造工序中， 需要把基片与其上已沉积好的温差电单体整个剥离； 另一类方法 是： Ρ型温差电单体基片和 Ν型温差电单体基片分开独立制造， 使得在微型薄膜 温差电池的制造过程中， 连接 Ρ型和 Ν型温差电单体的导电层的制造在基片与温 差电单体不剥离的条件下就可以进行。 利用上述方法制造温差电池的工艺复杂 ， 都有连接 Ρ型和 Ν型温差电单体的过程， 温差电池的性能也受到了限制。
[6] 咖容
[7] 本发明的目的是， 针对上述现有技术存在的缺陷提供了一种温差电池及其制作 方法， 该温差电池的性能得到了提高， 且该制作工艺简单。
[8] 本发明的技术方案如下： [9] 一种温差电池， 包括绝缘基片， 所述绝缘基片的上面镀有 P型热电材料薄膜层
， 所述绝缘基片的下面镀有 N型热电材料薄膜层， 所述绝缘基片侧面中的一面镀 有 P型和 N型材料薄膜成为 P型热电材料薄膜层和 N型热电材料薄膜层的连接端， 所述 P型热电材料薄膜层和所述 N型热电材料薄膜层分别引出电极。
[10] 其中， 所述绝缘基片的厚度为： 0.1mm至 100mm, 所述 P型热电材料薄膜层的 厚度为： lnm至 ΙΟμηι; 所述 Ν型热电材料薄膜层的厚度为： lnm至 10μηι。
[11] 其中， 所述绝缘基片材料的形状是规则的矩形、 或者方形。
[12] 其中， 所述绝缘基片裸露的侧面形状是平面或者是曲面。
[13] 一种温差电池的制作方法， 包括步骤：
[14] 将绝缘基片的一侧面在镀制过程中裸露， 其他侧面被遮档；
[15] 在所述绝缘基片的一面镀制 Ρ型热电材料薄膜层， 厚度范围为 lnm至 ΙΟμηι;
[16] 在所述绝缘基片的另一面镀制 Ν型热电材料薄膜层， 厚度为范围 lnm至 ΙΟμηι
[17] Ρ型热电材料薄膜和 Ν型热电材料薄膜都在绝缘基片裸露的一侧面沉积连接起 来；
[18] 分别从所述 Ν型热电材料薄膜层和所述 Ρ型热电材料薄膜层引出电极， 形成温 差电池的主体结构。
[19] 本发明的有益效果为： 本发明提供的温差电池的制备方法是在绝缘基片的两面 分别镀制 Ρ型热电材料薄膜层和 Ν型热电材料薄膜层， 在镀制过程中， 绝缘基片 裸露一侧面， Ρ型热电材料薄膜层和 Ν型热电材料薄膜层都在此有沉积， 而使 Ρ型 热电材料薄膜层和 Ν型热电材料薄膜层在该侧面处连接， 形成 ΡΝ结； 无需再有 专门连接 Ρ型热电材料薄膜层和 Ν型热电材料薄膜层的过程， 使得制造温差电池 的工艺比较简单。 本发明釆用镀制 Ρ型热电材料薄膜层和 Ν型热电材料薄膜层来 形成温差电偶， 由于薄膜热电材料的特性， 制作出的温差电池的性能也大幅度 提高。 由于利用镀制过程中 Ρ型热电材料和 Ν型热电材料都会在基片裸露侧面沉 积成为连接 Ρ型热电材料薄膜层和 Ν型热电材料薄膜层的一端， 因此， 该端无焊 接， 该端作为热面端， 则制成温差电池的热面工作温度也将大幅提高。
[20] 國綱 [21] 图 1为本发明实施例一提供的温差电池的断面结构示意图；
[22] 图 2a和图 2b为本发明实施例一提供的温差电池的制作过程图；
[23] 图 3为本发明实施例二提供的温差电池的断面结构示意图；
[24] 图 4a和图 4b为本发明实施例二提供的温差电池的制作过程图。
[25] t ^
[26] 本发明提供了一种温差电池及其制作方法， 为使本发明的目的、 技术方案及优 点更加清楚、 明确， 以下参照附图并举实施例对本发明进一步详细说明。
[27] 图 1是本发明实施例一提供的温差电池的断面结构示意图， 参照该图， 本实施 例一提供的温差电池包括： 绝缘基片 110， 镀制在该绝缘基片一面的 P型热电材料 薄膜层 120、 镀制在该绝缘基片另一面的 N型热电材料薄膜层 130。 从该 P型热电 材料薄膜层 120
和 N型热电材料薄膜层 130分别引出电极 140、 150。 在绝缘基片 110的一面镀制一 层 P型热电材料薄膜层 120， 形成如图 2a所示的结构， 然后在绝缘基片 110的另一 面镀制一层 N型热电材料薄膜层 130， 形成如图 2b所示的结构； P型热电材料薄膜 层 120和 N型热电材料薄膜层 130都在绝缘基片裸露的一侧面沉积连接起来。 在图 2b所示的结构上的 P型热电材料薄膜层 120和 N型热电材料薄膜层 130分别引出电 极 140、 150， 形成该温差电池。 其中 P型热电材料薄膜层 120和 N型热电材料薄 膜层 130在绝缘基片 110的一侧面完全重叠连接。
[28] 图 3是本发明实施例二提供的温差电池的断面结构示意图， 参照该图， 本实施 例二提供的温差电池包括： 绝缘基片 210， 镀制在该绝缘基片一面的 P型热电材料 薄膜层 220、 镀制在该绝缘基片另一面的 N型热电材料薄膜层 230。 从该 P型热电 材料薄膜层 220
和 N型热电材料薄膜层 230分别引出电极 240、 250。 在绝缘基片 210的一面镀制一 层 P型热电材料薄膜层 220， 形成如图 4a所示的结构， 然后在绝缘基片 210的另一 面镀制一层 N型热电材料薄膜层 230， 形成如图 4b所示的结构。 P型热电材料薄膜 层 220和 N型热电材料薄膜层 230都在绝缘基片裸露的一侧面沉积连接起来。 在图 4b所示的结构上的 P型热电材料薄膜层 220和 N型热电材料薄膜层 230分别引出电 极 240、 250, 形成该温差电池。 其中 P型热电材料薄膜层 220和 N型热电材料薄 膜层 230在绝缘基片 210的一侧面刚好连接。
[29] 上述实施例中的温差电池的材料一般有金属和半导体两种。 所述的 P型和 N型 热电材料， 也可以是两种不同的金属材料， 即釆用镀制两种不同的金属材料薄 膜来形成温差电偶。 绝缘基片材料的形状是规则的矩形、 或者方形， 或者是任 意的不规则形状。
[30] 绝缘基片裸露的侧面形状可以是平面， 也可以是曲面。
[31] 上述实施例提出的温差电池， 制造过程简便易行， 制造成本低， 而且性能也大 幅度提高。 上述实施例提供的温差电池通过大量串联连接， 可以在很小的温差 下产生足够大的电压输出。
[32] 下面利用实施例三和实施例四来详细描述该温差电池制作方法的过程。
[33] 实施例三：
[34] 实施例三制作该温差电池使用的设备为三靶磁控溅射镀膜机。 选用 Sb、 Bi与 Te 为靶材， 靶材纯度为 99.99% , Sb、 Bi分别安置在两个直流溅射靶位， Te安置在 射频溅射靶位。 以普通钠钙玻璃作为基片， 有机溶剂对该基片进行超声波清洗 ， 然后放入镀膜室内的夹具上； 该夹具被设计为可以对基片进行翻转， 便于对 基片进行两底面镀膜， 将绝缘基片 110的一侧面裸露， 其他侧面遮档住， 基片 11 0放置有一定的倾角， 使在基片 100裸露的侧面镀上 Sb、 Bi与 Te薄膜。 在室温条 件下， 分别釆用直流溅射和射频溅射方法， 在绝缘基片 110的一面上镀制 Sb与 Te 两层膜， 在后面进行的热处理后， 形成 P型热电材料 Sb2Te3
薄膜层 120， 厚度为 700nm， 如图 2a所示； 然后通过调整靶材和翻转基片， 分别 釆用直流溅射和射频溅射方法， 在绝缘基片 110的另一面上镀制 Bi与 Te两层膜， 进行的热处理后， 形成 N型热电材料 Bi2Te3薄膜层 130， 厚度为 700nm， 如图 2b。 完成在绝缘基片 110的一面上镀制 Sb与 Te两层膜和在绝缘基片 110的另一面上镀制 Bi与 Te两层膜后， 在 200°C下退火一定吋间。 沉积制备薄膜的本底真空度 2.8xl04Pa ' 工作真空 β. ΙχΙΟ Ψα
。 工作气体为 99.99%的高纯 Ar气， 流量为 50sccm。
[35] 完成绝缘基片 110的一面上镀制 Sb2Te3薄膜层 120和另一面上镀制 Bi2Te3
薄膜层 130的结构后， 分别从 Sb2Te3薄膜层 120和 Bi2Te3薄膜层 130弓 |出电极， 就 形成了如图 1所示或如图 3所示的温差电池的主体结构。
[36] 之后可进行划片、 装架、 封装等常规后续工艺步骤。
[37] P型和 N型热电材料薄膜层的制备技术， 在本实施例中釆用的是磁控溅射法， 在其他的实施例中还可以釆用热电材料薄膜制备的各种工艺。 如： 真空蒸发镀 膜法、 分子束外延法 （MBE) 、 离子束溅射法、 脉冲激光沉积法、 电化学原子 层外延法 （ECALE) 、 金属有机化合物气相沉积法 （MOCVD) 和连续离子层吸 附与反应法 （SILAR) 等。
[38] 制作过程中， 可以先镀制 P型热电材料薄膜 120，后镀制 N型热电材料薄膜 130; 也可以先镀制 N型热电材料薄膜 130，后镀制 P型热电材料薄膜 120。
[39] 实施例四：
[40] 实施例四使用设备为超高真空离子束溅射镀膜机， 为离子束溅射法制备 P型和 N型热电材料薄膜层。 选用塞贝克系数分别为 P型和 N型的金属 Sb与 Bi为靶材， 靶材纯度为 99.99%， 分别将 P型和 N型的金属 Sb与 Bi的靶材安置在可转动选择溅 射靶的靶位。 以普通钠钙玻璃作为基片， 使用有机溶剂对基片进行超声波清洗 ， 然后放入镀膜室内夹具上； 夹具被设计为可以对基片进行翻转， 便于对基片 进行两底面镀膜， 将绝缘基片 110的一侧面裸露， 其他侧面遮档住， 基片 110放 置有一定的倾角， 使在基片 110裸露的侧面镀上 Sb与 Bi的交叠层。 在室温条件下 ， 釆用离子束溅射方法， 先在绝缘基片 110的一面上镀制 Sb薄膜层 120， 厚度为 30 Onm, 如图 2a所示； 然后通过调整靶材和翻转基片， 在绝缘基片 110的另一面上 镀制 Bi薄膜层 130， 厚度为 300nm， 如图 2b所示。 沉积制备薄膜的本底真空度为 4 .5xlO"4Pa， 工作真空为 4.1xlO-2Pa
。 工作气体为 99.99%的高纯 Ar气， 流量为 4Sccm。 离子束沉积的工艺参数为： 屏 极电压 1KV, 阳极电压 75V， 加速电压 220V, 阴极电压 7V, 阴极电流 11A, 束流
[41] 得到绝缘基片 110—面上镀制 Sb薄膜层 120和另一面上镀制 Bi薄膜层 130的结构 后， 分别从 Sb薄膜层 120和 Bi薄膜层引出电极 140、 150， 就形成了如图 1或图 3所 示的温差电池的主体结构。
[42] 之后可进行划片、 装架、 封装等常规后续工艺步骤， 完成本发明温差电池的制 作。
[43] 在其他的实施例中， 镀制过程中， P型和 N型材料在绝缘基片裸露侧面的沉积 ， 也可以部分重叠。 所述绝缘基片的厚度为： 0.1mm至 100mm, 也可以选用更厚 或更薄的基片。
[44] 上述实施例提供的温差电池制作方法， 不仅制作过程简便易行， 制作成本低， 而且制作出的温差电池的性能也大幅度提高。 制作出的单体温差电池通过大量 串联连接， 可以在很小的温差下产生足够大的电压输出。
[45] 热电现象本身是可逆的，半导体温差发电和半导体致冷是热电现象的两个方面， 互相可逆。 对于同一个 PN结，若施加温差则可用来发电，若对其通电，则可用于在 一端致冷。 因此， 本实施例的温差电池的主体结构， 同吋也就是温差电致冷器 的主体结构。
[46] 应说明的是， 以上实施例仅用以说明本发明的技术方案而非限制， 尽管参照较 佳实施例对本发明进行了详细说明， 本领域的普通技术人员应当理解， 可以对 本发明的技术方案进行修改或者等同替换， 而不脱离本发明技术方案的精神和 范围， 其均应涵盖在本发明的权利要求范围当中。

Claims

权利要求书
一种温差电池， 其特征在于， 包括绝缘基片， 所述绝缘基片的上 面镀有 P型热电材料薄膜层， 所述绝缘基片的下面镀有 N型热电材 料薄膜层， 所述绝缘基片侧面中的一面镀有 P型和 N型材料薄膜成 为 P型热电材料薄膜层和 N型热电材料薄膜层的连接端， 所述 P型 热电材料薄膜层和所述 N型热电材料薄膜层分别引出电极。
如权利要求 1所述温差电池， 其特征在于， 所述绝缘基片的厚度为 ： 0.1mm至 100mm, 所述 P型热电材料薄膜层的厚度为： lnm至 10μ m; 所述 N型热电材料薄膜层的厚度为： lnm至 10μηι。
如权利要求 1所述温差电池， 其特征在于， 所述绝缘基片材料的形 状是规则的矩形、 或者方形。
如权利要求 1所述温差电池， 其特征在于， 所述绝缘基片裸露的侧 面形状是平面或者是曲面。
一种温差电池的制作方法， 其特征在于， 包括步骤：
将绝缘基片的一侧面在镀制过程中裸露， 其他侧面被遮档； 在所述绝缘基片的一面镀制 Ρ型热电材料薄膜层， 厚度范围为 lnm 至 ΙΟμπΐ;
在所述绝缘基片的另一面镀制 Ν型热电材料薄膜层， 厚度为范围 In m至 ΙΟμπΐ;
所述 Ρ型热电材料薄膜层和 Ν型热电材料薄膜层都在绝缘基片裸露 的一侧面沉积连接起来；
分别从所述 Ν型热电材料薄膜层和所述 Ρ型热电材料薄膜层引出电 极， 形成温差电池的主体结构。
PCT/CN2009/075422 2009-01-20 2009-12-09 一种温差电池及其制造方法 WO2010083706A1 (zh)

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