201004003 六、發明說明·· 【發明所屬之技術領域】 本發明係關於熱電轉換模組及其製造方法，更詳細而 目’係關於可以容易地銲接由銅線等所形成的連接線之石夕 化鐵（FeSi2 )系之熱電轉換模組及其製造方法。 【先前技術】 一般而言，於將熱電轉換模組構裝於電路之際，需要 對該模組（元件）連接導線，於熱電轉換模組中，因應元 件部之溫度變化或溫度差’會產生熱感應電動勢，導線的 連接，以熱性、電性上能與熱電轉換半導體元件成爲一體 爲佳。 然而’矽化鐵（FeSh)系之熱電轉換半導體，係由 將鐵與矽之粉末予以燒結者所形成，耐熱性高，通常在 1 6 0 °C〜1 8 0 °C熔化之銲錫無法順利付著。而且—接近銲錫 作業的界限溫度（3 80 °C程度）時，基於氧化或侵蝕等，201004003 6. TECHNOLOGICAL FIELD OF THE INVENTION [Technical Field] The present invention relates to a thermoelectric conversion module and a method of manufacturing the same, and in more detail, relates to a wire which can be easily welded by a copper wire or the like. FeSi2 thermoelectric conversion module and its manufacturing method. [Prior Art] In general, when a thermoelectric conversion module is mounted on a circuit, it is necessary to connect a wire to the module (component). In the thermoelectric conversion module, depending on the temperature change or temperature difference of the component portion, The heat-induced electromotive force is generated, and the connection of the wires is preferably integrated with the thermoelectric conversion semiconductor element in terms of heat and electrical properties. However, the thermoelectric conversion semiconductor of the FeFe series is formed by sintering the powder of iron and niobium, and has high heat resistance. The solder which is usually melted at 160 ° C to 180 ° C cannot be successfully paid. With. Moreover - when it is close to the limit temperature of the soldering operation (at a temperature of 3 80 °C), it is based on oxidation or erosion, etc.
V 烙鐵前端本身的壽命變短’銲錫所含的助銲劑碳化，導致 助辉劑或靜錫之飛散。另外’ FeSia系熱電轉換半導體很 硬且脆’無法加工螺絲孔來固定連接線。 因此，以往係以由銀導電軟膏或銀的雙面捲帶等所形 成的導電性連接材來黏貼銅板等之導電材，進行對此導電 材（電極）銲接連接線之作業。 [先前技術文獻] -5- 201004003 [專利文獻] [專利文獻1]曰本專利特開2007-324500號公報 [非專利文獻] [非專利文獻1]「FeSi2系熱電轉換模組之塞貝克（ Seebeck )係數的測定」，田中勝之他，The 28th Japan Symposium on T h e r m o p h y s i c al Properties. Oct. 24-26 . 2007， Sapporo. 【發明內容】 [發明所欲解決之課題] 但是，於導電性接著材來接著前述導電材的方法中， 存在有導電性接著材的阻抗或其經年劣化，會使FeSi2系 熱電轉換模組的性能劣化之問題。 另外，雖也可以考慮以電弧熔接或雷射熔接連接線的 方法，但是，熱電轉換半導體的耐熱溫度高，熔接處所的 溫度過度上升具有熱電轉換半導體特性的組成（/3相）被 破壞，作爲熱電轉換半導體之特性（塞貝克係數）變小， 確認到並非有效的連接線連接方法。 本發明係有鑑於前述先前技術的問題點所完成者，其 目的在於提供：端子部可以容易地銲接連接線之FeSi2系 的熱電轉換模組及其製造方法。 [解決課題之手段] 爲了解決前述課題’依據本發明之第1型態之熱電轉 -6- 201004003 換模組之製ia方法’係於燒結模具內投入由p型及η型的 FeSi2系所形成的各熱電轉換半導體原料粉末、及於彼等 之至少一端部投入由特定的金屬所形成的板或粉末，藉由 放電電獎燒結法’以一階段將彼等予以燒結接合者。 於本發明中’係於由P型及η型的FeSi2系所形成的 各熱電轉換半導體原料粉末的至少一端部存在有特定的金 屬之狀態下’藉由放電電漿燒結法來燒結接合，可以形成 對於FeSi2系之熱電轉換半導體爲熱性、電性地成爲一體 化;的金屬電極’能於此電極部容易地銲接由銅等所形成的 連接線。另外’於本發明中，一階段地與p型及η型的原 料粉末一同地來燒結接合特定的金屬，可以大幅地降低熱 電轉換模組的製造成本。 於本發明的第2型態中，爲將4.1質量％之鉻（C r ) 混入FeSi2系原料粉末，來作爲p型熱電轉換半導體原料 粉末。 於本發明的第3型態中，爲將2.4質量％的鈷（Co) 混入FeSi2系原料粉末，來作爲n型熱電轉換半導體原料 粉末。 於本發明的第4型態中，前述特定的金屬，係由銀（ Ag)或銀系合金所形成。 如依據本發明，銀（Ag )之電氣阻抗小，且熱傳導 率高，最適合作爲傳導熱與電能的電極用金屬，且銀的融 點（大約962°C )比最適合於熱電轉換模組（即FeSi2系 熱電半導體原料粉末）的燒結之溫度稍高，適合於將電極 -7- 201004003 部燒結接合於熱電轉換半導體部。 於本發明之第5型離由，射f @ ^ θ ^ 土見、甲，目丨j述特定的金屬，係由鎳（V The life of the tip of the soldering iron itself is shortened. The flux contained in the solder is carbonized, causing the flux or static tin to scatter. In addition, the 'FeSia-based thermoelectric conversion semiconductor is very hard and brittle' and the screw holes cannot be processed to fix the connection line. For this reason, in the related art, a conductive material such as a copper plate is adhered to a conductive connecting material formed of a silver conductive paste or a double-sided tape of silver, and the conductive connecting wire for the conductive material (electrode) is bonded. [Prior Art Document] -5-201004003 [Patent Document 1] [Patent Document 1] Japanese Laid-Open Patent Publication No. 2007-324500 [Non-Patent Document] [Non-Patent Document 1] "Seebeck (FeSi2-based thermoelectric conversion module) "Seebeck" Coefficient Determination", The 28th Japan Symposium on T hermophysic al Properties. Oct. 24-26. 2007, Sapporo. [Summary of the Invention] However, in conductive bonding materials In the method of following the above-mentioned conductive material, there is a problem that the impedance of the conductive adhesive material or its deterioration over time deteriorates the performance of the FeSi2-based thermoelectric conversion module. Further, although a method of arc welding or laser welding of a connecting wire is also conceivable, the thermoelectric conversion semiconductor has a high heat-resistant temperature, and the temperature of the welded portion excessively rises, and the composition (/3 phase) having the characteristics of the thermoelectric conversion semiconductor is broken. The characteristics of the thermoelectric conversion semiconductor (Seebeck coefficient) become small, and it is confirmed that the connection method is not effective. The present invention has been made in view of the problems of the prior art described above, and an object thereof is to provide a FeSi2-based thermoelectric conversion module in which a terminal portion can easily weld a connecting wire and a method of manufacturing the same. [Means for Solving the Problem] In order to solve the above-mentioned problem, the thermoelectric conversion according to the first aspect of the present invention-6-201004003 ia method of replacing a module is based on the injection of p-type and n-type FeSi2 systems in a sintering mold. Each of the thermoelectric conversion semiconductor raw material powders to be formed and a plate or powder formed of a specific metal are placed on at least one end portion thereof, and they are sintered and joined in one stage by a discharge electric prize sintering method. In the present invention, 'the sintering is performed by a discharge plasma sintering method in a state in which at least one end portion of each of the thermoelectric conversion semiconductor raw material powders formed of the P-type and n-type FeSi2 systems is present in a specific metal. The FeSi2-based thermoelectric conversion semiconductor is formed to be thermally and electrically integrated; the metal electrode ' can easily solder a connection line formed of copper or the like to the electrode portion. Further, in the present invention, the specific metal is sintered and joined together with the p-type and n-type raw material powders in one stage, and the manufacturing cost of the thermoelectric conversion module can be greatly reduced. In the second aspect of the present invention, 4.1% by mass of chromium (C r ) is mixed into the FeSi 2 -based raw material powder to obtain a p-type thermoelectric conversion semiconductor raw material powder. In the third aspect of the present invention, 2.4 mass% of cobalt (Co) is mixed into the FeSi2-based raw material powder to form an n-type thermoelectric conversion semiconductor raw material powder. In the fourth aspect of the invention, the specific metal is formed of silver (Ag) or a silver alloy. According to the present invention, silver (Ag) has a small electrical impedance and a high thermal conductivity, and is most suitable as an electrode metal for conducting heat and electric energy, and a melting point of silver (about 962 ° C) is most suitable for a thermoelectric conversion module. (The FeSi2-based thermoelectric semiconductor raw material powder) has a slightly higher sintering temperature, and is suitable for sintering and bonding the electrode-7-201004003 to the thermoelectric conversion semiconductor portion. In the fifth type of the invention, the shot f @^ θ ^ is seen, the nail, the target metal, is made of nickel (
Ni )或鈦（Ti )或以彼等爲主的合金所形成。 於即使是將鎳（Ni)、欽（Ti)、或錬系或駄系的合 金作爲電極用金屬的情形時，由實驗確認到可以合適地將 電極部燒結接合於熱電轉換半導體部。 於本發明之第6型態中’係於壓力35MPa至7〇MPa 、溫度 923 K ( 65 0 〇C )至 l〇73K ( 80(rc )、時間 3〇〇sec 至3.6ksec下進行前述燒結接合。 基本上’此燒結條件雖被針對P型及η型熱電轉換半 導體的各燒結體可以顯示高塞貝克係數的結晶構造（即万 相單層）的條件所左右者，但是本發明中，進而針對電極 用金屬，於機械性且電性都可以獲得合適的接合特性的範 圍內來選擇燒結條件。 依據本發明之第7型態的熱電轉換模組，係於燒結模 具內投入由Ρ型及η型的FeSi2系所形成的各熱電轉換半 導體原料粉末、及於彼等之至少一端部投入由特定的金屬 所形成的板或粉末’藉由放電電漿燒結法’以—階段將彼 等予以燒結接合者。藉此’可以具有高的塞貝克係數之同 時，能以低成本提供容易進行導線的銲接之熱電轉換模組 〇 於本發明之第8型態中，前述特定的金屬’係由銀（ A g )、鎳（N i )、鈦（T i )或以彼等之其一爲主的合金所 形成。 -8 - 201004003 依據本發明之第9型態的熱電轉換模組，係於燒結模 具內投入由p型及η型的FeSi2系所形成的各熱電轉換半 導體原料粉末、及於彼等之至少一端部投入由p型及η型 所形成的各熱電轉換半導體原料粉末和特定的金屬粉末的 混合粉末，接著，投入由前述特定的金屬所形成的粉末， 藉由放電電漿燒結法，以一階段將彼等予以燒結接合者。 藉此’可以提供熱電轉換半導體與電極的接合強度更堅固 的熱電轉換模組。 於本發明之第1 0型態中，前述特定的金屬，係由銀 (Ag )、鎳（Ni )、鈦（Ti )或以彼等之其一爲主的合金 所形成。 [發明效果] 依據如以上所述之本發明，能於熱電轉換模組直接銲 接連接線，由使用此熱電轉換模組的裝置之製造設備費用 、製造成本面，爲極有效。 【實施方式】 以下，依據所附圖面詳細說明依據本發明之實施型態 。另外，整個說明書中，對於相同或相當的部分賦予相同 的參考號碼。第1圖係本實施型態所使用的放電電漿燒結 裝置之槪略構成圖。此放電電漿燒結裝置1，係具備：內 部可以減壓爲略真空狀態之水冷式的真空腔體2 ;及收容 於此真空腔體2的略中央部之圓環狀石墨製的燒結模具3 -9 - 201004003 ;及被投入此燒結模具3的貫穿孔內之各種原料 積體4;及由對此層積體4加壓用之上下一對的 墨所形成的衝頭（按壓件）5a、5b ;及對此等 5b通以電流之上下一對的衝壓電極6a、6b。 另外，於此真空腔體2的外部，具備有：進 實施型態之熱電轉換模組的燒結控制之控制部9 控制部9之控制下，對衝壓電極6a、6b通以電 燒結電源7 ;及同樣地在控制部9的控制下，對 6a、6b施加壓力之加壓機構部8;及將真空腔體 壓或以熱電對3 a所檢測出的燒結溫度等回饋給 之量測部1 〇。 接著，詳細說明依據使用此種放電電漿燒結 實施型態的熱電轉換模組之製造方法。第2圖係 實施型態之熱電轉換模組的製法圖，是表示關於 燒結模具3之部分的放大圖。首先，例如於平均 μ m的FeSi2系原料粉末混入例如4.1質量％之 ，做成P型熱電轉換半導體原料粉末，且於FeS 粉末混入例如2.4質量％之鈷（Co )，做成η型 半導體原料粉末。 於燒結模具3的下部插入衝頭5 b，以如插/ 所示般’於其上鋪設圓盤狀的碳紙C 1爲佳。進 結模具3的內周面將碳紙外側真空容器3 2配置 於其中將原料粉末依序地投入爲層狀。例如以 )所形成的電極用金屬粉末24，、前述所做成之 粉末的層 圓柱狀石 & 頭 5a、 行依據本 ;及於此 流之特殊 衝壓電極 2內的氣 控制部9 裝置1之 說明依據 第1圖的 f粒徑約8 鉻(Cr) 系原料 熱電轉換 人圖（a ) 而，於燒 爲筒狀， 由銀（Ag η型熱電 -10- 201004003 轉換半導體原料粉末23，、p型熱電轉換半導體原料粉末 22’、由銀（Ag )所形成的電極用金屬粉末21，的順序投 入’於其上載放碳紙C 6。然後，於其上插入衝頭5 a，如 此做成燒結模具3的套件。 將此燒結模具3的套件設置於放電電漿燒結裝置丨中 之衝壓電極6a、6b之間’將真空腔體2內的環境壓力降 低爲略真空（例如3Pa以下）。然後，一面對上下衝壓電 極6a、0b施加壓力，一面對該兩衝壓電極6a、6b之間通 以特殊燒結電流，藉由以石墨3、5a、5b爲發熱體之放電 電漿燒結法’使用以下的燒結條件，以一階段來燒結接合 各原料粉末。 加壓力以設爲35MPa~70MPa的範圍內爲佳。於燒結 接合之際，藉由對各原料粉末施加大的加壓力，物質變得 容易移動之同時，於藉由燒結之收縮初期，可以促進粉末 粒子的再排列，能夠使其急速地緻密化。加壓力如比此範 圍低，燒結體變得低密度，機械特性也低，另外，如比此 範圍高，燒結體變得高密度，確認到會變脆。 另外，燒結溫度以設爲923 K ( 6 5 0 °C )〜1 07 3K ( 800 °C )的範圍內爲佳。燒結溫度如低於此範圍，或高於此範 圍，熱電轉換半導體的熱感應電動勢（塞貝克係數）會降 低。 另外，燒結時間以設爲30〇sec~3.6ksec的範圍內爲佳 。燒結時間如比此範圍短’燒結體變得低密度’機械特性 降低，另外，如比此範圍還長’變得高密度’確認到會變 -11 - 201004003 脆。 燒結後，將真空腔體2內冷卻至5 2 3 Κ 度，同時使內部回到常壓（大氣壓），將如 狀的燒結體取出外部。藉此，由銀（Ag ) 層與熱電轉換模組的兩端面部燒結接合爲一 極，可以容易地銲接由銅等所形成的連接線 另外，關於前述之燒結條件，基本上， 及η型熱電轉換半導體的各燒結體，可以獲 熱電轉換特性（塞貝克係數）的/5相單相的 件所左右者，但是在本實施型態中，進Ϊ FeSi2系熱電半導體，銀（Ag)等之電極用 地燒結接合之範圍爲燒結條件。例如， 1 23 5 K (略962 °C)，依據本實施型態之燒 當地以比此低的製程溫度來進行。 另外，連接線對於此熱電轉換模組之連 銲接以外，電氣熔接、藉由短時間內之雷射 接等，只是是不對熱電轉換半導體的組成（ 響的溫度，皆屬可能。 另外，關於使用於此熱電轉換模組之電 前述銀（Ag )之外，即使是鎳（Ni )、鈦（ 爲主的合金，也確認到可以良好地燒結接合 ’鎳金屬的融點爲1 4 5 3 °C，鈦金屬的融點ί 爲高，在界限溫度（3 8 0 °C )前後的銲接作| 另外，電極用金屬在使用銅（Cu)板或 (25 0°C )之程 此獲得的圓柱 所形成的電極 體，對於此電 〇 雖被針對P型 得顯示有效的 結晶構造之條 ίίϊ以對於此種 金屬可被適當 Ag的融點爲 結接合，能適 接，於前述的 照射的雷射熔 /3相）造成影 極用金屬，於 Ti )或以彼等 。於此情形時 i 1 6 8 0 T：，極 I係屬可能。 銅粉末的情形 -12- 201004003 時，燒結體的電極部會產生裂痕或缺口等，無法獲得良好 的燒結接合。 接著，說明依據本發明之熱電轉換模組的實施例。 <實施例1 > 第3圖係說明實施例1之熱電轉換模組20A的圖， 且是表示將此熱電轉換模組當成檢測溫度變化用的熱電轉 換溫度感測器使用的情形。此熱電轉換模組20A例如係 以以下方法所製造。即於平均粒徑8 // m的FeSi2原料粉 末混入4.1質量％的鉻（Cr)，做成p型熱電轉換半導體 原料粉末，另外，混入2.4質量％之銘（Co)，做成η型 熱電轉換半導體原料粉末。進而，從燒結模具3的底部將 銀（Ag)粉末、η型熱電轉換半導體原料粉末、ρ型熱電 轉換半導體原料粉末、銀（Ag)粉末依序層狀地投入， 在加壓力 35MPa、燒結溫度1 023K( 750°C)、燒結時間 60〇Sec之燒結條件下，藉由放電電漿燒結法一階段地將彼 等予以燒結接合。另外，直徑20mm、ρ型層、η型層之 厚度約7mm的材料各1 〇g、直徑20mm、Ag金屬粉末的 材料爲〇.2g，此時厚度約1mm。Ag以直徑20mm來燒結 的情形時，設爲〇.2g〜2g之範圍。Ag材料很貴，以少量 爲佳，依據實驗，直徑20mm全面可以均勻地燒結之量爲 〇.2g。另外，藉由改變燒結的Ag層部的模具，使Ag層 的直徑變小，則可使Ag量變少。另外，Ag的融點爲962 °C，與燒結溫度接近，在多量的情形時，Ag會混入η型 -13- 201004003 層、P型層，依據實驗’有效果的Ag層，在直徑20mm 的情形時，爲2g。 第3 ( A )圖係實施例1之熱電轉換模組2〇a的正視 圖’第3 ( B )係表示其之斜視圖。於此熱電轉換模組 20A中，銀（Ag)電極21、與p型熱電轉換半導體22、 與η型熱電轉換半導體23、與銀（Ag )電極24係被燒結 接合爲一體。如舉一例之尺寸來說，圓柱的直徑爲2〇mm 、p型層22及η型層23的厚度共約7mm，各Ag電極21 、24的厚度約lmm。於此熱電轉換模組2〇a中，上下的 電極21、24都是由銀（Ag)所形成，成爲可以容易地銲 接由銅（Cu)等所形成的連接線32a、32b。此處，31a、 3 1 b係銲錫。 接著，參照第4圖說明將實施例1的熱電轉換模組 20A當成檢測溫度變化的熱電轉換溫度感測器使用的情形 之動作。第4圖係表示將熱電轉換模組20A橫放之情形 的正視圖，且表示從下將熱此熱電轉換模組20A的全體 之狀態。一般得知，在導體或半導體的一端如被施加不同 溫度時，物質中的帶電載子（金屬中的電子、半導體中的 電子、電洞等）會依據其之熱梯度而擴散。即位於熱端的 熱載子（電洞、電子）有朝熱載子的密度稀薄的冷端擴散 之性質。 以第4圖的例子具體來說明此時，兩端部的Ag電極 2 1、24，熱傳導率高（即熱容量小），快速地其整體暖和 。另一方面，ρ-η界面相偕的半導體接合部，由熱容量大 -14- 201004003 的陶瓷所形成，熱傳導慢，相對地成爲冷溫部。其結果爲 在P型區域22中，被溫暖而變得活潑的電洞朝能量低的 冷溫端（接合面）側移動，電極21側因電洞不足而成爲 一極，接合面側因電洞集合而成爲+極。另外，於η型區 域2 3中，被溫暖的電子朝冷溫端（接合面）側移動，電 極24側因電子不足而成爲+極，結合面側因電子集中而 成爲一極。然後，P-η接合的整體中，此等之熱電轉換作 用電性地重疊，電極24側成爲+極，電極2 1側成爲一極 。在此情形，銀（Ag )電極21、24，由於電氣阻抗小， 沒有損失地將所產生的熱感應電動勢傳達於外部。 第5圖係表示實施例1之熱電轉換溫度感測器20A 的熱感應電動勢測定結果圖。圖係測量使此熱電轉換溫度 感測器20A整體比室溫高30°C、投入風速85cm/秒的垂 直氣流，伴隨時間經過之熱感應電動勢的變化者。如第5 圖所示般，此熱電轉換溫度感測器20A的熱感應電動勢 ，於熱氣流的投入後約30秒後，達到最大之約0.97mV， 熱被傳達至感測器整體後，熱感應電動勢逐漸降低。作爲 此熱電轉換溫度感測器20A，可以藉由熱感應電動勢上升 之區間的變化率，來推算投入的溫度差。 <實施例2 > 第6圖係說明實施例2之熱電轉換模組2 0 B之圖，且 是表示於藉由本發明對熱電轉換模組連接連接線之其他的 情形。第6 ( A )圖係表示原料粉末層積時之正視圖。於 -15- 201004003 此熱 2 1，、 半導 型原 於電 穿孔 上某 鑽頭 極 2 34a、 部至 長度 20B ，插 表面 例2 熱電 <實 表示 器使 模組 電轉換模組之製造時’於由Ag所形成的兩電極粉末 24’、及由p型及η型的FeSi2系所形成的熱電轉換 體原料粉末22，、23,的層積後，於電極粉末21，與p 料粉末22,之中心部加工貫穿孔33a至中途，另外， 極粉末24,與η型原料粉未23,的中心部，也加工貫 33b至中途。此種貫穿孔33a、33b，可以在事先加 種程度壓力的固體狀態之各原料粉末的層積部，利用 等來鑽孔，或插入圓柱棒等來形成。 第6 ( B )圖係於實施例2的熱電轉換模組2 〇 B的電 1、2 4銲接導線端子之狀態的正視圖。此導線端子 '3 4 b係以銅或黃銅等之導電性素材所製作，從前端 特定長度的位置固定有凸緣部35a、35b。此特定的 係因應貫穿孔3 3 a、3 3 b的深度。於熱電轉換模組 的貫穿孔33a、33b插入導線端子34a、34b的前端部 入至此等之凸緣部35a、35b抵接Ag電極21、24的 爲止，且將此等銲接於Ag電極2 1、24。關於此實施 之熱電轉換模組2 0 B的動作，可以與前述實施例1之 轉換模組2 0 A所敘述者相同。 施例3 > 第7圖係說明實施例3之熱電轉換模組20C之圖’且 將ρ - η - p - η型的熱電轉換模組當成熱電轉換溫度感測 用的情形。依據第7 ( A )圖，槪略說明此熱電轉換 2 0 C的製法。於此例子中，從未圖示出的燒結楔具3 -16- 201004003 的底部，將Ag 24,、η型熱電轉換半導體26’、p型熱電 轉換半導體25’、η型熱電轉換半導體23’、p型熱電轉換 半導體22’、Ag 21’之順序將各原料粉末投入爲層狀。通 常已在上部及下部衝頭與粉末的境界面設置碳紙，將如此 獲得的燒結模具3於加壓力35MPa、燒結溫度1 023 K ( 7 5 0°C )、燒結時間600sec的條件下，藉由放電電漿燒結 法以一階段予以燒結接合爲佳。 第7 ( B )圖係表示實施例3之熱電轉換模組20C的 斜視圖。以前述之製法所獲得之燒結體中，Ag電極2 1、 及P型熱電轉換半導體22、及η型熱電轉換半導體23、 及Ρ型熱電轉換半導體25、及η型熱電轉換半導體26、 及Ag電極24係被燒結接合爲一體。 於此實施例3中，進而對於此燒結體，如第7 ( B ) 圖所示般，藉由將包含中央部的接觸面s3的η型區域23 的下半部與Ρ型區域2 5的上半部以線切刀等來切削加工 ，如圖示般，形成中間部變細的形狀之熱電轉換模組20C 。如舉一例之尺寸而言，圓柱部的直徑φ 1爲2 0mm、小 圓柱的直徑Φ 2爲10mm、ρ型層及n型層的厚度都是約 7mm、中央的變細部的厚度約7mm、各Ag電極的厚度都 是約1 mm。進而’作爲熱電轉換溫度感測器2 0 C使用的 情形時’於上下端面的Ag電極21、24藉由銲錫3 1 a、 31b來銲接由銅線等所形成的連接線32a、32b，而構裝於 未圖示出的電路。 接著，槪略說明此種熱電轉換溫度感測器2 0 C的熱電 201004003 轉換動作。另外，關於Ag電極21、24，熱傳導率高且厚 度薄，熱容量極小。因此，關於熱傳導，將Ag電極2 1、 24當成不存在來說明。 對於此熱電轉換溫度感測器2 0 C之整體，如從外部施 加熱時，於P型半導體區域22中，接合面s 1側接近外氣 之故，溫度快速上升，但是接合面s2側與η型半導體區 域23相接，溫度延遲緩慢上升。即成爲（接合面s 1的熱 容量）<(接合面s2的熱容量）的關係。因此，接合面 s 1與s2暫時性地成爲「溫」、「冷」的關係，接合面s 1 側，電洞少而成爲一極，接合面s2側，電洞多而成爲+ 極。另外，n型半導體區域23中，由於是（接合面s2的 面積）>(接合面s3的面積），成爲（接合面s2的熱容量 )>(接合面S3的熱容量）的關係。因此，接合面s2與S3 成爲「冷」、「溫」的關係，接合面s2側，電子多而成 爲一極，接合面S3側，電子少而成爲+極。 接著，於P型半導體區域25中，（接合面S3的面積 ) <(接合面s4的面積），成爲（接合面S3的熱容量）<(接 合面s4的熱容量）之關係。因此，接合面S3與s4成爲「 溫」、「冷」的關係，接合面s3側，電洞少而成爲一極 ，接合面s4側，電洞多而成爲+極。進而，於η型半導 體區域2 6中，接合面s 5側接近外氣，溫度快速上升，但 是接合面s4側，與ρ型半導體區域25相接，溫度延遲緩 慢上升。即成爲（接合面s5的熱容量）<(接合面s4的熱 容量）之關係。因此，接合面s4與s5成爲「冷」、「溫 -18- 201004003 」之關係，接合面s4側，電子多而成爲一極，接合面s5 側，電子少而成爲+極。 如此一·來，於p-n-p-n接合之整體中，藉由各層的熱 電轉換作用電性地重疊，Ag電極21側成爲一極，Ag電 極24側成爲+極。在此情形，銀（Ag )電極2 1、24因 爲電氣阻抗小，無損失地將熱感應電動勢傳達於外部。 另外，基於前述之熱電轉換作用，接合面s2或S4的 面積與接合面S3的面積之比，以盡可能變大爲佳。如使 此面積比變大，基於熱容量，會產生大的差異，變得更容 易產生大的溫度差，可以獲得更大的熱感應電動勢。 <實施例4 > 第8圖係說明實施例4之熱電轉換模組20D的製法 圖，此圖係表示關於燒結模具1 1的部分之放大圖。第8 (A)圖係其平剖面圖，第8 ( B )圖係表示側剖面圖。此 燒結模具1 1係呈現圓柱狀石墨的中央部挖空爲矩形的形 狀，於此燒結模具1 1的內部收容箱型狀的下側燒結模具 1 2a與蓋狀的上側燒結模具1 2b，成爲於其上下插入一對 的矩形狀衝頭13a、13b之形狀。 關於P型及η型之各熱電轉換半導體原料粉末42’、 43’，可以使用與前述第2圖所敘述的同樣者。以覆蓋下 側燒結模具1 2 a的內壁面之方式來設置碳紙之同時，於其 地面鋪設碳紙，於其上投入Ag粉末4 1 ’與44 ’成爲層狀。 進而，於Ag粉末41’之上塡充p型熱電轉換半導體原料 -19- 201004003 粉末42’。另外’於Ag粉末44,之上塡充η型熱電轉換半 導體原料粉末43，。然後’於此等ρ型及η型之各熱電轉 換半導體原料粉末42 ’、43 ’之上鋪設碳紙，於其上搭載上 側燒結模具1 2b。將如此獲得之燒結模具1 1之套件設置 於放電電漿燒結裝置1，於與第2圖所述同樣的燒結條件 下，以一階段來燒結接合各原料粉末。 第9圖係實施例4之熱電轉換模組2 0 D的斜視圖， 且表示對可以檢測溫度差之熱電轉換模組的適用例子。於 此熱電轉換模組20D中，Ag電極41、及ρ型熱電轉換半 導體42、及n型熱電轉換半導體43 '及Ag電極44係被 燒結接合爲一體。於此例子中，熱電轉換模組的兩端電極 4 1、44細微金屬（Ag )，能容易地銲接導線等。另外， 也可以將Ag電極4 1、44的部分載放於印刷配線上而直 接地銲接。或以電氣熔接、藉由短時間之雷射照射的雷射 熔接等’只要是不對熱電轉換半導體組成造成影響的溫度 ，此等方法都可以連接。 接著，說明使用此種熱電轉換模組20D來測定溫度 差之情形的動作。如第9圖所示般，從上加熱此熱電轉換 模組20D’從下將其冷卻時，於ρ型熱電轉換半導體42 中，基於電洞朝冷溫（電極41 )側移動，加熱側成爲一 極’冷溫側成爲+極。另外，於η型熱電轉換半導體4 3 中’基於電子朝向冷溫（電極44 )側移動，加熱側成爲 +極’冷溫側成爲一極。然後，於熱電轉換模組20D之 整體中，基於此等之熱電轉換作用電性地重疊，Ag電極 -20- 201004003 41側成爲+極，Ag電極4 4側成爲一極。在此情形時， 各Ag電極41、44其電氣阻抗小，熱傳導率高，最適合 作用爲傳達熱與電能之電極用金屬。 <實施例5 > 第1 〇圖係說明實施例5之熱電轉換模組之製法圖， 且表示關於第1圖的燒結模具3之部分的放大圖。實施例 5之熱電轉換模組’係個別投入：由p型及η型的F e S i 2 系所形成的熱電轉換半導體原料粉末22 ’、23，、及於此等 的一端部與電極用之金屬粉末2 1 ’、2 4，之間，作爲中間層 之原料的P型熱電轉換半導體原料粉末22,與金屬粉末 21’之混合粉末215’、及n型熱電轉換半導體原料粉末 23’與金屬粉末2V的混合粉末235’，接著，投入由特定 的金屬所形成的金屬粉末21’、24’，於從前之燒結條件下 ，藉由放電電漿燒結法，以一階段來燒結接合者。於以下 當中，將Ρ型熱電轉換半導體與電極間的中間層稱爲ρ側 中間層、將η型熱電轉換半導體與電極間的中間層稱爲η 側中間層。因此’實施例5之熱電轉換模組，係具有電極 、η側中間層、η型熱電轉換半導體、ρ型熱電轉換半導 體、Ρ側中間層、電極所層積的構造。 如第1 〇圖所示般’於燒結模具3的下部插入衝頭5 b ，以如插入頭（a )所示般’於衝頭5 b上鋪設圓盤狀的碳 紙C 1爲佳。進而於燒結模具3的內周面配置碳紙^ 2爲 筒狀，於其中依序投入原料粉末成爲層狀。例如以由銀（ -21 - 201004003Ni) or titanium (Ti) or an alloy mainly composed of them. In the case where a nickel (Ni), a bismuth (Ti), or a lanthanide or lanthanide alloy is used as the electrode metal, it has been experimentally confirmed that the electrode portion can be sintered and bonded to the thermoelectric conversion semiconductor portion as appropriate. In the sixth form of the present invention, the foregoing sintering is carried out at a pressure of 35 MPa to 7 MPa, a temperature of 923 K (65 0 〇C) to 10 〇 73 K (80 (rc), and a time of 3 〇〇sec to 3.6 ksec. In the present invention, it is basically the case that the sintering conditions of the P-type and n-type thermoelectric conversion semiconductors can exhibit a high-seebeck coefficient crystal structure (that is, a single-phase single layer). Further, the electrode metal is selected in a range in which mechanical properties and electrical properties can be obtained with suitable bonding characteristics. The thermoelectric conversion module according to the seventh aspect of the present invention is incorporated in a sintering mold. And each of the thermoelectric conversion semiconductor raw material powders formed by the η-type FeSi2 system and the plates or powders formed by the specific metal at at least one end portion thereof are subjected to the discharge plasma sintering method to By sintering the bonder, it is possible to provide a thermoelectric conversion module which can easily perform wire bonding at a low cost while having a high Seebeck coefficient. In the eighth aspect of the present invention, the aforementioned specific metal Formed by silver (A g ), nickel (N i ), titanium (T i ) or an alloy based on one of them. -8 - 201004003 A thermoelectric conversion module according to a ninth aspect of the present invention, Each of the thermoelectric conversion semiconductor raw material powders formed of the p-type and n-type FeSi2 systems is introduced into the sintering mold, and each of the thermoelectric conversion semiconductor raw material powders formed of the p-type and the n-type is introduced into at least one end portion thereof. a powder of a specific metal powder, followed by a powder formed of the above-mentioned specific metal, which is sintered by a discharge plasma sintering method in one stage. Thus, a thermoelectric conversion semiconductor and an electrode can be provided. The thermoelectric conversion module having a stronger joint strength. In the first aspect of the present invention, the specific metal is made of silver (Ag), nickel (Ni), titanium (Ti) or one of them. According to the present invention as described above, the connection line can be directly soldered to the thermoelectric conversion module, and the manufacturing equipment cost and manufacturing cost of the apparatus using the thermoelectric conversion module are Extremely effective. DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings, wherein the same reference numerals are given to the same or corresponding parts throughout the specification. FIG. 1 is a discharge used in the present embodiment. A schematic diagram of a plasma sintering apparatus. The discharge plasma sintering apparatus 1 is provided with a water-cooled vacuum chamber 2 in which a vacuum can be reduced to a slightly vacuum state, and a slightly central portion of the vacuum chamber 2 a sintered mold made of annular graphite 3 -9 - 201004003; and various raw material bodies 4 which are put into the through holes of the sintering mold 3; and a pair of upper and lower inks pressed by the laminated body 4 The formed punches (pressing members) 5a, 5b; and the pair of punching electrodes 6a, 6b for which the current is passed through the pair 5b. Further, outside the vacuum chamber 2, a control unit 9 for performing sintering control of the thermoelectric conversion module of the embodiment is provided, and the electric sintering power source 7 is connected to the press electrodes 6a and 6b under the control of the control unit 9; Similarly, under the control of the control unit 9, the pressurizing mechanism unit 8 that applies pressure to the 6a and 6b; and the measuring unit 1 that feeds the vacuum chamber or the sintering temperature detected by the thermoelectric pair 3 a is fed back to the measuring unit 1 Hey. Next, a method of manufacturing a thermoelectric conversion module according to the embodiment in which such a discharge plasma is sintered will be described in detail. Fig. 2 is a plan view showing a thermoelectric conversion module of the embodiment, showing an enlarged view of a portion of the sintering mold 3. First, for example, the FeSi 2 -based raw material powder having an average μ m is mixed with, for example, 4.1% by mass to form a P-type thermoelectric conversion semiconductor raw material powder, and the FeS powder is mixed with, for example, 2.4% by mass of cobalt (Co ) to form an n-type semiconductor raw material. powder. The punch 5b is inserted into the lower portion of the sintering mold 3, and it is preferable to lay a disk-shaped carbon paper C1 thereon as shown in Fig. The carbon paper outer side vacuum container 32 is disposed in the inner peripheral surface of the joining die 3, and the raw material powders are sequentially introduced into a layer shape. For example, the electrode metal powder 24 formed, the layered cylindrical stone & head 5a of the powder formed above, and the gas control unit 9 in the special stamping electrode 2 flowing therethrough According to Fig. 1, the f-particle size of about 8 chrome (Cr)-based raw material thermoelectric conversion diagram (a) is burned into a cylindrical shape, and silver (Ag η-type thermoelectricity-10-201004003 converts semiconductor raw material powder 23, The p-type thermoelectric conversion semiconductor raw material powder 22' and the metal powder 21 for electrodes formed of silver (Ag) are sequentially placed on the carbon paper C 6 which is placed thereon. Then, the punch 5a is inserted thereon, A kit for forming the sintering mold 3. The kit of the sintering mold 3 is placed between the stamping electrodes 6a and 6b in the discharge plasma sintering apparatus ' 'Reducing the environmental pressure in the vacuum chamber 2 to a slight vacuum (for example, 3 Pa or less) Then, a pressure is applied to the upper and lower stamping electrodes 6a, 0b, and a special sintering current is applied between the two stamping electrodes 6a, 6b, and the discharge plasma is made of graphite 3, 5a, 5b as a heating element. Sintering method 'Use the following sintering conditions, one In the range of 35 MPa to 70 MPa, it is preferable to apply the pressure to the raw material powder. In the case of sintering bonding, the material is easily moved by applying a large pressing force to each raw material powder. In the initial stage of the shrinkage of the sintering, the rearrangement of the powder particles can be promoted, and the powder can be rapidly densified. The pressing force is lower than this range, the sintered body becomes low in density, and the mechanical properties are also low, and if it is higher than this range, The sintered body becomes high in density and is confirmed to be brittle. In addition, the sintering temperature is preferably in the range of 923 K (650 ° C) to 1 07 3 K (800 ° C). The sintering temperature is lower than this. In the range, or higher than this range, the thermally induced electromotive force (Seebeck coefficient) of the thermoelectric conversion semiconductor is lowered. In addition, the sintering time is preferably in the range of 30 〇 sec to 3.6 sec. The sintering time is shorter than this range. The sintered body becomes low in density, and the mechanical properties are lowered. In addition, if it is longer than this range, it becomes "high density" and it is confirmed that it will become -11 - 201004003. After sintering, the inside of the vacuum chamber 2 is cooled to 5 2 3 Κ Degree while making the interior At normal pressure (atmospheric pressure), the sintered body is removed from the outside, whereby the silver (Ag) layer and the both end faces of the thermoelectric conversion module are sintered and joined as one pole, and can be easily welded by copper or the like. In addition to the sintering conditions described above, basically, each sintered body of the n-type thermoelectric conversion semiconductor can obtain a thermoelectric conversion characteristic (Seebeck coefficient) of the /5-phase single-phase member, but in the present embodiment, In the type, the range of sintering bonding of the FeSi2-based thermoelectric semiconductor, silver (Ag) or the like is sintering conditions. For example, 1 23 5 K (slightly 962 ° C), according to the embodiment, the local burning ratio is This low process temperature is carried out. In addition, the connection of the connection wire to the thermoelectric conversion module, the electric welding, the laser connection in a short time, etc., is not the composition of the thermoelectric conversion semiconductor (the temperature is loud, it is possible. In addition to the above-mentioned silver (Ag) of the thermoelectric conversion module, even if it is nickel (Ni) or titanium (mainly alloy, it is confirmed that the melting point of the nickel metal can be satisfactorily joined is 1 4 5 3 °). C, the melting point of titanium is high, and the welding is performed before and after the boundary temperature (380 ° C). In addition, the metal for the electrode is obtained by using a copper (Cu) plate or (25 0 ° C). The electrode body formed by the cylinder is adapted to the P-type to show an effective crystal structure for the electrode, so that the metal can be bonded by the melting point of the appropriate Ag, and can be adapted to the aforementioned irradiation. Laser melting / 3 phase) causes the shadow metal to be used in Ti) or in them. In this case, i 1 6 8 0 T:, the pole I is possible. In the case of copper powder -12-201004003, cracks or nicks are formed in the electrode portion of the sintered body, and good sintering bonding cannot be obtained. Next, an embodiment of a thermoelectric conversion module according to the present invention will be described. <Embodiment 1> Fig. 3 is a view showing a thermoelectric conversion module 20A of the first embodiment, and shows a case where the thermoelectric conversion module is used as a thermoelectric conversion temperature sensor for detecting a temperature change. This thermoelectric conversion module 20A is manufactured, for example, by the following method. In other words, the FeSi2 raw material powder having an average particle diameter of 8 // m is mixed with 4.1% by mass of chromium (Cr) to form a p-type thermoelectric conversion semiconductor raw material powder, and 2.4% by mass of the indium (Co) is mixed to form an n-type thermoelectric. The semiconductor raw material powder is converted. Further, silver (Ag) powder, n-type thermoelectric conversion semiconductor raw material powder, p-type thermoelectric conversion semiconductor raw material powder, and silver (Ag) powder are sequentially supplied in a layered manner from the bottom of the sintering mold 3, and a pressing pressure of 35 MPa and a sintering temperature are applied. Under the sintering conditions of 1 023 K (750 ° C) and sintering time 60 〇 Sec, they were sintered and joined in one stage by a discharge plasma sintering method. Further, a material having a diameter of 20 mm, a p-type layer, and an n-type layer of about 7 mm each having a thickness of 1 mm, a diameter of 20 mm, and a material of the Ag metal powder was 0.2 g, and the thickness was about 1 mm. When Ag is sintered at a diameter of 20 mm, it is set to a range of 〇. 2g to 2g. The Ag material is very expensive, preferably in small amounts. According to the experiment, the total amount of the 20 mm diameter can be uniformly sintered to 〇.2g. Further, by changing the mold of the sintered Ag layer portion to reduce the diameter of the Ag layer, the amount of Ag can be reduced. In addition, the melting point of Ag is 962 °C, which is close to the sintering temperature. In the case of a large amount, Ag will be mixed into the n-type-13-201004003 layer and the P-type layer, according to the experimental 'effective layer of Ag, at a diameter of 20 mm. In the case of 2g. Fig. 3(A) is a front elevational view of the thermoelectric conversion module 2A of the first embodiment, and Fig. 3(B) is a perspective view thereof. In the thermoelectric conversion module 20A, the silver (Ag) electrode 21, the p-type thermoelectric conversion semiconductor 22, the n-type thermoelectric conversion semiconductor 23, and the silver (Ag) electrode 24 are sintered and integrated. As an example, the diameter of the cylinder is 2 mm, the thickness of the p-type layer 22 and the n-type layer 23 is about 7 mm, and the thickness of each of the Ag electrodes 21 and 24 is about 1 mm. In the thermoelectric conversion module 2A, the upper and lower electrodes 21 and 24 are made of silver (Ag), and the connection wires 32a and 32b formed of copper (Cu) or the like can be easily welded. Here, 31a, 3 1 b are solders. Next, an operation in the case where the thermoelectric conversion module 20A of the first embodiment is used as a thermoelectric conversion temperature sensor for detecting a temperature change will be described with reference to Fig. 4. Fig. 4 is a front view showing a state in which the thermoelectric conversion module 20A is placed laterally, and shows a state in which the entire thermoelectric conversion module 20A is heated from the lower side. It is generally known that when a different temperature is applied to one end of a conductor or a semiconductor, charged carriers (electrons in the metal, electrons in the semiconductor, holes, etc.) in the material diffuse according to the thermal gradient thereof. That is, the hot carriers (holes, electrons) located at the hot end have the property of diffusing toward the thin end of the hot carrier. Specifically, in the case of the example of Fig. 4, the Ag electrodes 2 1 and 24 at both ends have a high thermal conductivity (i.e., a small heat capacity), and the whole is quickly warmed. On the other hand, the semiconductor junction portion at the ρ-η interface is formed of a ceramic having a large heat capacity of -14 to 201004003, and the heat conduction is slow, and relatively becomes a cold temperature portion. As a result, in the P-type region 22, the heated and energized hole moves toward the cold-temperature end (joining surface) side where the energy is low, and the electrode 21 side becomes one pole due to insufficient hole, and the joint surface side is electrically The holes are assembled and become the + pole. Further, in the n-type region 23, the warmed electrons move toward the cold-temperature end (joining surface) side, the electrode 24 side becomes a +-electrode due to insufficient electrons, and the bonding surface side becomes a pole due to concentration of electrons. Then, in the entire P-η junction, these thermoelectric conversion functions are electrically overlapped, the electrode 24 side becomes a + pole, and the electrode 2 1 side becomes a pole. In this case, the silver (Ag) electrodes 21 and 24 transmit the generated thermally induced electromotive force to the outside without loss due to the small electrical impedance. Fig. 5 is a graph showing the results of measurement of the thermally induced electromotive force of the thermoelectric conversion temperature sensor 20A of the first embodiment. The measurement of the thermoelectric conversion temperature sensor 20A is 30 ° C higher than the room temperature, and the vertical air flow of the input wind speed of 85 cm / sec, with the change of the thermal induced electromotive force with the passage of time. As shown in Fig. 5, the thermally induced electromotive force of the thermoelectric conversion temperature sensor 20A reaches a maximum of about 0.97 mV after about 30 seconds after the input of the hot air current, and the heat is transmitted to the entire sensor, and the heat is applied. The induced electromotive force gradually decreases. As the thermoelectric conversion temperature sensor 20A, the temperature difference of the input can be estimated by the rate of change of the section in which the thermo-induced electromotive force rises. <Embodiment 2> Fig. 6 is a view showing the thermoelectric conversion module 20B of the second embodiment, and showing other cases in which the connection line is connected to the thermoelectric conversion module by the present invention. Figure 6 (A) shows a front view of the raw material powder when it is laminated. -15-201004003 This heat 2 1, semi-conducting type is on the electroporation of a drill bit 2 34a, part to length 20B, insert surface example 2 thermoelectric < real display to make the module electrical conversion module manufacturing The two-electrode powder 24' formed of Ag and the thermoelectric converter raw material powders 22 and 23 formed of p-type and n-type FeSi2-based layers are laminated on the electrode powder 21 and the p-powder powder. 22, the center portion is machined through the hole 33a to the middle, and the center portion of the electrode powder 24 and the n-type material powder 23 is also processed 33b to the middle. The through-holes 33a and 33b can be formed by drilling a hole or a cylindrical rod or the like in a layered portion of each raw material powder in a solid state in which a predetermined degree of pressure is applied. Fig. 6(B) is a front view showing the state of the electric welding terminal of the thermoelectric conversion module 2 〇 B of the second embodiment. The lead terminal '3 4 b is made of a conductive material such as copper or brass, and flange portions 35a and 35b are fixed from a position of a predetermined length of the tip end. This particular factor is due to the depth of the holes 3 3 a, 3 3 b. The through holes 33a and 33b of the thermoelectric conversion module are inserted into the distal end portions of the lead terminals 34a and 34b, and the flange portions 35a and 35b are abutted against the Ag electrodes 21 and 24, and are soldered to the Ag electrodes 2 1 . ,twenty four. The operation of the thermoelectric conversion module 20B in this embodiment can be the same as that described in the conversion module 20A of the first embodiment. Example 3 > Fig. 7 is a view showing the thermoelectric conversion module 20C of the third embodiment and the π-η - p - η type thermoelectric conversion module is used for thermoelectric conversion temperature sensing. According to the 7th (A) diagram, the method of manufacturing this thermoelectric conversion 20 C is briefly explained. In this example, the Ag 24, the n-type thermoelectric conversion semiconductor 26', the p-type thermoelectric conversion semiconductor 25', and the n-type thermoelectric conversion semiconductor 23' are shown at the bottom of the sintered wedge 3-16-201004003, which is not shown. In the order of the p-type thermoelectric conversion semiconductor 22' and Ag 21', each raw material powder is put into a layer shape. Carbon paper is usually placed at the interface between the upper and lower punches and the powder, and the thus obtained sintered mold 3 is borrowed under the conditions of a pressing pressure of 35 MPa, a sintering temperature of 1,023 K (750 ° C), and a sintering time of 600 sec. It is preferred to perform sintering bonding in one stage by a discharge plasma sintering method. Fig. 7(B) is a perspective view showing the thermoelectric conversion module 20C of the third embodiment. In the sintered body obtained by the above-described production method, the Ag electrode 2 1 and the P-type thermoelectric conversion semiconductor 22, the n-type thermoelectric conversion semiconductor 23, the Ρ-type thermoelectric conversion semiconductor 25, and the n-type thermoelectric conversion semiconductor 26, and Ag are Ag. The electrode 24 is sintered and joined together. In the third embodiment, the sintered body is further formed by the lower half of the n-type region 23 including the contact surface s3 at the center portion and the Ρ-shaped region 25 as shown in the seventh (B) diagram. The upper half is cut by a wire cutter or the like, and as shown in the figure, a thermoelectric conversion module 20C having a tapered shape in the middle portion is formed. As an example, the diameter φ 1 of the cylindrical portion is 20 mm, the diameter Φ 2 of the small cylinder is 10 mm, the thickness of the p-type layer and the n-type layer are both about 7 mm, and the thickness of the central tapered portion is about 7 mm. Each Ag electrode has a thickness of about 1 mm. Further, when the thermoelectric conversion temperature sensor 20 C is used, the Ag electrodes 21 and 24 on the upper and lower end faces are welded to the connecting wires 32a and 32b formed of copper wires or the like by the solders 3 1 a and 31 b. Constructed in a circuit not shown. Next, the thermal power 201004003 conversion operation of the thermoelectric conversion temperature sensor 20 C will be briefly described. Further, regarding the Ag electrodes 21 and 24, the thermal conductivity is high and the thickness is small, and the heat capacity is extremely small. Therefore, regarding the heat conduction, the description of the Ag electrodes 2 1 and 24 as absent. For the whole of the thermoelectric conversion temperature sensor 20 C, when heat is applied from the outside, in the P-type semiconductor region 22, the junction surface s 1 side is close to the outside air, and the temperature rises rapidly, but the joint surface s2 side is The n-type semiconductor regions 23 are in contact with each other, and the temperature delay is slowly increased. That is, the relationship (the heat capacity of the joint surface s 1) < (the heat capacity of the joint surface s2). Therefore, the joint faces s 1 and s2 temporarily become "warm" and "cold", and the joint surface s 1 side has a small number of holes and becomes one pole, and the joint surface s2 side has a large number of holes and becomes a + pole. In the n-type semiconductor region 23, (the area of the bonding surface s2) > (the area of the bonding surface s3), the relationship (the heat capacity of the bonding surface s2) > (the heat capacity of the bonding surface S3). Therefore, the joint surfaces s2 and S3 have a relationship of "cold" and "warm", and on the joint surface s2 side, electrons are often formed as one pole, and on the joint surface S3 side, electrons are small and become + poles. Then, in the P-type semiconductor region 25, (the area of the bonding surface S3) < (the area of the bonding surface s4) becomes the relationship (the heat capacity of the bonding surface S3) < (the heat capacity of the bonding surface s4). Therefore, the joint surfaces S3 and s4 have a relationship of "warm" and "cold", and the joint surface s3 side has a small number of holes and becomes one pole, and the joint surface s4 side has a large number of holes and becomes a + pole. Further, in the n-type semiconductor region 26, the junction surface s5 side is close to the outside air, and the temperature rises rapidly. However, the junction surface s4 side is in contact with the p-type semiconductor region 25, and the temperature delay is slowly increased. That is, the relationship (the heat capacity of the joint surface s5) < (the heat capacity of the joint surface s4). Therefore, the joint faces s4 and s5 are in a relationship of "cold" and "warm -18-201004003", and the side of the joint surface s4 has a large number of electrons and becomes a pole, and the side of the joint surface s5 has few electrons and becomes a + pole. As a result, in the entire p-n-p-n junction, the thermoelectric conversion action of each layer is electrically overlapped, the side of the Ag electrode 21 becomes one pole, and the side of the Ag electrode 24 becomes a + pole. In this case, the silver (Ag) electrodes 2 1 and 24 have a small electrical impedance and transmit the thermally induced electromotive force to the outside without loss. Further, based on the aforementioned thermoelectric conversion action, the ratio of the area of the joint surface s2 or S4 to the area of the joint surface S3 is preferably as large as possible. If this area ratio is made larger, a large difference is generated based on the heat capacity, and it becomes easier to generate a large temperature difference, and a larger heat-induced electromotive force can be obtained. <Embodiment 4> Fig. 8 is a view showing a method of manufacturing the thermoelectric conversion module 20D of the fourth embodiment, which is an enlarged view showing a portion of the sintering mold 11. Fig. 8(A) is a plan sectional view, and Fig. 8(B) is a side sectional view. In the sintered mold 11, the central portion of the cylindrical graphite is hollowed out in a rectangular shape, and the box-shaped lower side sintering mold 1 2a and the lid-shaped upper side sintering mold 1 2b are accommodated in the inside of the sintering mold 1 1 . The shape of a pair of rectangular punches 13a, 13b is inserted above and below. The respective thermoelectric conversion semiconductor raw material powders 42' and 43' of the P-type and the η-type can be used in the same manner as described in the second drawing. Carbon paper was placed on the floor surface so as to cover the inner wall surface of the lower side sintering mold 1 2 a, and carbon paper was placed on the floor, and Ag powders 4 1 ' and 44 ' were placed thereon to form a layer. Further, a p-type thermoelectric conversion semiconductor material -19 - 201004003 powder 42' is filled on the Ag powder 41'. Further, the n-type thermoelectric conversion semiconductor raw material powder 43 is filled on the Ag powder 44. Then, carbon paper is placed on each of the p-type and n-type thermoelectric conversion semiconductor raw material powders 42' and 43', and the upper side sintering mold 12b is mounted thereon. The kit of the sintered mold 1 thus obtained was placed in the spark plasma sintering apparatus 1, and each raw material powder was sintered and joined in one stage under the same sintering conditions as described in Fig. 2 . Fig. 9 is a perspective view of the thermoelectric conversion module 20 D of the fourth embodiment, and shows an example of application to a thermoelectric conversion module capable of detecting a temperature difference. In the thermoelectric conversion module 20D, the Ag electrode 41, the p-type thermoelectric conversion semiconductor 42, and the n-type thermoelectric conversion semiconductor 43' and the Ag electrode 44 are integrally joined by sintering. In this example, the electrodes 4 1 and 44 of the thermoelectric conversion module have fine metal (Ag), which can easily solder wires and the like. Further, a portion of the Ag electrodes 41 and 44 may be placed on the printed wiring and soldered to the ground. Either electric welding, laser welding by short-time laser irradiation, etc. can be connected as long as it does not affect the composition of the thermoelectric conversion semiconductor. Next, an operation of measuring the temperature difference using such a thermoelectric conversion module 20D will be described. As shown in Fig. 9, when the thermoelectric conversion module 20D' is heated from above, the p-type thermoelectric conversion semiconductor 42 is moved toward the cold temperature (electrode 41) side by the hole, and the heating side becomes One pole 'cold temperature side becomes + pole. Further, in the n-type thermoelectric conversion semiconductor 4 3, the electrons move toward the cold temperature (electrode 44) side, and the heating side becomes the + pole' cold temperature side becomes one pole. Then, in the entire thermoelectric conversion module 20D, the thermoelectric conversion action based on these is electrically overlapped, the side of the Ag electrode -20-201004003 41 becomes a + pole, and the side of the Ag electrode 4 4 becomes a pole. In this case, each of the Ag electrodes 41 and 44 has a small electrical impedance and a high thermal conductivity, and is most suitable as an electrode metal for transmitting heat and electric energy. <Embodiment 5> Fig. 1 is a view showing a method of manufacturing a thermoelectric conversion module of the fifth embodiment, and showing an enlarged view of a portion of the sintering mold 3 of Fig. 1. The thermoelectric conversion module of the fifth embodiment is an individual input: a thermoelectric conversion semiconductor raw material powder 22', 23 formed of a p-type and an n-type F e S i 2 system, and one end portion and an electrode for the same The P-type thermoelectric conversion semiconductor raw material powder 22 as a raw material of the intermediate layer, the mixed powder 215' with the metal powder 21', and the n-type thermoelectric conversion semiconductor raw material powder 23' and the metal powder 2 1 ', 2 4 The metal powder 2V is mixed powder 235', and then the metal powders 21' and 24' formed of a specific metal are introduced, and the joint is sintered in one stage by a discharge plasma sintering method under the previous sintering conditions. In the following, an intermediate layer between the Ρ-type thermoelectric conversion semiconductor and the electrode is referred to as a ρ-side intermediate layer, and an intermediate layer between the η-type thermoelectric conversion semiconductor and the electrode is referred to as an η-side intermediate layer. Therefore, the thermoelectric conversion module of the fifth embodiment has a structure in which an electrode, an n-side intermediate layer, an n-type thermoelectric conversion semiconductor, a p-type thermoelectric conversion semiconductor, a crucible intermediate layer, and an electrode are laminated. It is preferable to insert the punch 5b into the lower portion of the sintering mold 3 as shown in Fig. 1 to form a disk-shaped carbon paper C1 on the punch 5b as shown in the insertion head (a). Further, carbon paper 2 is placed in a cylindrical shape on the inner circumferential surface of the sintering mold 3, and the raw material powder is sequentially introduced into a layered shape. For example, by silver ( -21 - 201004003
Ag)所形成的電極用之金屬粉末24’、金屬粉末24,與前 述所做成的η型熱地轉換半導體原料粉末23,的混合粉末 23 5’、η型熱電轉換半導體原料粉末23，、前述做成之Ρ 型熱電轉換半導體原料粉末22’、由銀（Ag)所形成之電 極用的金屬粉末21與ρ型熱電轉換半導體原料粉末22’ 的混合粉末2 1 5 ’、金屬粉末2 Γ之順序投入筒狀的碳紙 C2的內部’於金屬粉末21’之上載放碳紙C6。然後，從 其上將衝頭5 a插入燒結模具3的上部，如此做成燒結模 具3的套件。 另外，也可以於各粉末層間配置碳紙。例如如第1〇 圖所示般’於金屬粉末24’與混合粉末23 5,之間配置碳紙 C3、於混合粉末235’與n型熱電轉換半導體原料粉末23, 間配置碳紙C 8。於η型熱電轉換半導體原料粉末2 3，與ρ 型熱電轉換半導體原料粉末22’間配置碳紙C4。進而於ρ 型熱電轉換半導體原料粉末22’與混合粉末215,間配置碳 紙C7 ’於混合粉末21 5’與金屬粉末21，間配置碳紙C5。 例如在與第2圖所述相同的燒結條件下，以一階段將 燒結模具3的各原料粉末予以燒結接合，製作實施例5之 熱電轉換模組。混合粉末2 1 5，被燒結，形成ρ側中間層 ，混合粉末23 5 ’被燒結，形成η側中間層。即於燒結金 屬粉末24’所形成的電極與燒結^型熱電轉換半導體原料 粉末23 ’所形成的η型熱電轉換半導體之間，形成有η側 中間層。然後’於燒結ρ型熱電轉換半導體原料粉末22 ’所形成之ρ型熱電轉換半導體與燒結金屬粉末2 i，所形 -22- 201004003 成的電極之間，形成有P側中間層。 於P型熱電轉換半導體粉末與Ag電極的例子之情形 時’ P側中間層在p型熱電轉換半導體粉末與Ag粉末的 質量比爲3 : 1之情形，成爲良好的燒結結合。另一方面 ，在P型熱電轉換半導體粉末與Ag粉末的質量比爲1: 1 之情形或1 : 3之情形時，產生裂痕或缺口，無法獲得良 好的燒結結合。此係p側中間層的Ag比率多時，推測由 於Ag的濡濕性的關係，於p側中間層與Ag電極間，無 法充分地進行燒結結合。 另外，在η型熱電轉換半導體粉末與Ag電極的例子 之情形時，η側中間層在n型熱電轉換半導體粉末與Ag 粉末的質量比爲1 : 1之情形時，成爲良好的燒結結合。 另一方面，η型熱電轉換半導體粉末與Ag粉末之質量比 爲3 : 1的情形時，產生裂痕或缺口，無法獲得良好的燒 結結合。 藉由形成P側中間層與η側中間層，電極與熱電轉換 半導體間的強度變得更爲堅固，導線與模組間之強度和沒 有Ρ側中間層、η側中間層者相比，以實驗確認到變得更 爲堅固。 於實驗中，將A g電極0 · 4 g、η側中間層的混合粉末 〇.8g、n型熱電轉換半導體粉末21g燒結結合爲Φ20ιηιη 圓桶狀，並加以確認。另外，將Ag電極〇.4g、ρ側中間 層之混合粉末〇.8g、p型熱電轉換半導體粉末17.2g燒結 結合爲Φ 20mm圓桶狀，並加以確認。 -23- 201004003 另外，中間層以1層爲佳。於做成改變熱電轉換半導 體粉末與金屬粉末的混合比率的2層、3層的中間層之實 驗中，基於裂痕、缺口，無法獲得良好的燒結接合。 具有如前述之特徵的本發明之熱電轉換模組，於作爲 利用將熱轉換爲電氣之塞貝克效果的溫泉廢熱發電、生質 熱利用發電、發電廠廢熱發電、汽車廢熱發電等中之熱電 轉換模組，或空調機、工廠、火災警報設備等中，可以作 爲檢測溫度變化的熱電轉換溫度感測器使用。另外，本發 明之熱電轉換模組’也可以作爲利用從電氣轉換爲熱之珀 耳帖（Peltier )效應之C P U冷卻、電子機器冷卻、道路 的防凍結、冬季期間之融雪對策、非聚四氟乙烯冷凍庫等 中之熱電轉換模組來利用。 另外’於前述各實施例中，雖具體地敘述包含1對或 2對的p-n接合之熱電轉換模組，但是關於包含3對以上 的P - η接合之熱電轉換模組，也可以同樣地構成。另外， 不單是p-n接合’關於η_ρ接合之熱電轉換模組，也可以 適用本發明。 另外’於前述各實施例中，雖將構成電極部用之A g 粉末層積爲層狀，但是並不限定於此。藉由改變Ag粉末 等之層積形狀’也可以形成其他各種形狀的電極。 【圖式簡單說明】 第1圖係放電電漿燒結裝置的槪略構成圖。 第2圖係說明依據實施型態之熱電轉換模組之製法圖 -24- 201004003 第3圖係說明實施例1之熱電轉換模組圖。 第4圖係說明實施例1之熱電轉換模組的動作圖。 第5圖係表示實施例1之熱電轉換模組的熱感應電動 勢測定結果圖。 第6圖係說明實施例2之熱電轉換模組圖。 第7圖係說明實施例3之熱電轉換模組圖。 第8圖係說明實施例4之熱電轉換模組之製法圖。 第9圖係實施例4之熱電轉換模組之斜視圖。 第1 〇圖係說明實施例5之熱電轉換模組之製法圖。 【主要元件符號說明】 1 :放電電漿燒結裝置 2 :真空腔體 3 :燒結模具 3 a :熱電對 4 :原料粉末 5 :衝頭（按壓件） 5 a ' 5 b :衝頭 6 :衝壓電極 7 :特殊燒結電源 8 :加壓機構部 9 :控制部 1 〇 :量測部 -25- 201004003 1 1 :燒結模具 1 2 a :下側燒結模具 1 2 b :上側燒結模具 1 3 a、1 3 b :矩形狀衝頭 2 0 A〜2 0 D :熱電轉換模組 21、 24、41、44:電極用金屬（Ag) 22、 25、42 : p型熱電轉換半導體 23、 26、43 : η型熱電轉換半導體 3 1 a、3 1 b :銲錫 3 2 a、3 2 b :連接線 3 4 a、3 4 b :導線端子 3 5 a、3 5 b :凸緣部 21’：由銀（Ag)所形成的電極用金屬粉末 22’： p型熱電轉換半導體原料粉末 23 ’ ： η型熱電轉換半導體原料粉末 24’：由銀（Ag)所形成的電極用金屬粉末 C :碳紙 -26-a metal powder 24' for an electrode formed of Ag), a metal powder 24, a mixed powder 23 5' of the n-type thermally conductive semiconductor raw material powder 23, and an n-type thermoelectric conversion semiconductor raw material powder 23, The Ρ-type thermoelectric conversion semiconductor raw material powder 22', the mixed powder of the metal powder 21 for the electrode formed of silver (Ag) and the p-type thermoelectric conversion semiconductor raw material powder 22', the metal powder 2 Γ In the order of the inside of the cylindrical carbon paper C2, the carbon paper C6 is placed on the metal powder 21'. Then, the punch 5a is inserted therefrom into the upper portion of the sintering mold 3, thus forming a kit of the sintering mold 3. Further, carbon paper may be disposed between the respective powder layers. For example, carbon paper C3, mixed powder 235' and n-type thermoelectric conversion semiconductor raw material powder 23 are disposed between metal powder 24' and mixed powder 235 as shown in Fig. 1, and carbon paper C 8 is disposed therebetween. Carbon paper C4 is disposed between the n-type thermoelectric conversion semiconductor raw material powder 23 and the p-type thermoelectric conversion semiconductor raw material powder 22'. Further, between the p-type thermoelectric conversion semiconductor raw material powder 22' and the mixed powder 215, carbon paper C7' is disposed between the mixed powder 21 5' and the metal powder 21, and carbon paper C5 is disposed therebetween. For example, in the same sintering conditions as described in Fig. 2, the raw material powders of the sintering mold 3 are sintered and joined in one stage to produce the thermoelectric conversion module of the fifth embodiment. The mixed powder 2 15 was sintered to form a p-side intermediate layer, and the mixed powder 23 5 ' was sintered to form an n-side intermediate layer. That is, an n-side intermediate layer is formed between the electrode formed of the sintered metal powder 24' and the n-type thermoelectric conversion semiconductor formed by the sintered thermoelectric conversion semiconductor raw material powder 23'. Then, a P-side intermediate layer is formed between the p-type thermoelectric conversion semiconductor formed by sintering the p-type thermoelectric conversion semiconductor raw material powder 22' and the sintered metal powder 2i, and the electrode formed by the shape of -22-201004003. In the case of the P-type thermoelectric conversion semiconductor powder and the Ag electrode, the P-side intermediate layer has a good sintered bond in the case where the mass ratio of the p-type thermoelectric conversion semiconductor powder to the Ag powder is 3:1. On the other hand, in the case where the mass ratio of the P-type thermoelectric conversion semiconductor powder to the Ag powder is 1:1 or 1:3, cracks or nicks are generated, and a good sintered bond cannot be obtained. When the ratio of Ag in the p-side intermediate layer is large, it is presumed that due to the wettability of Ag, sintering bonding cannot be sufficiently performed between the p-side intermediate layer and the Ag electrode. Further, in the case of the n-type thermoelectric conversion semiconductor powder and the Ag electrode, the n-side intermediate layer becomes a good sintered bond when the mass ratio of the n-type thermoelectric conversion semiconductor powder to the Ag powder is 1:1. On the other hand, when the mass ratio of the n-type thermoelectric conversion semiconductor powder to the Ag powder is 3:1, cracks or notches are generated, and good sintering bonding cannot be obtained. By forming the P-side intermediate layer and the η-side intermediate layer, the strength between the electrode and the thermoelectric conversion semiconductor becomes stronger, and the strength between the wire and the module is compared with that of the intermediate layer without the Ρ side and the η side intermediate layer. The experiment confirmed that it became stronger. In the experiment, a mixed powder of 0.8 g of the A g electrode, 〇. 8 g of the intermediate layer of the η side, and 21 g of the n-type thermoelectric conversion semiconductor powder were sintered and combined into a Φ20 ιηιη round barrel shape, and confirmed. Further, the Ag electrode 〇4 g, the ρ side intermediate layer mixed powder 〇8 g, and the p-type thermoelectric conversion semiconductor powder 17.2 g were sintered and combined into a Φ 20 mm round barrel shape, and were confirmed. -23- 201004003 In addition, the middle layer is preferably 1 layer. In the experiment of changing the two-layer and three-layer intermediate layers of the thermoelectric conversion semiconductor powder and the metal powder, it was not possible to obtain a good sintered joint based on cracks and notches. The thermoelectric conversion module of the present invention having the characteristics as described above is used as a thermoelectric conversion in hot spring waste heat power generation, biomass heat utilization power generation, power generation waste heat power generation, automobile waste heat power generation, etc., which utilizes the effect of converting heat into electric Seebeck. Modules, or air conditioners, factories, fire alarm devices, etc., can be used as thermoelectric conversion temperature sensors that detect temperature changes. In addition, the thermoelectric conversion module 'of the present invention can also be used as a CPU cooling using an Peltier effect from electrical to thermal, electronic machine cooling, road freezing prevention, snow melting countermeasures during winter, non-polytetrafluoroethylene. The thermoelectric conversion module in an ethylene freezer or the like is used. Further, in the above embodiments, the thermoelectric conversion module including one or two pairs of pn junctions is specifically described. However, the thermoelectric conversion module including three or more pairs of P - η junctions may be configured in the same manner. . Further, the present invention can also be applied not only to the p-n junction 'the thermoelectric conversion module for the η_ρ junction. Further, in each of the above embodiments, the A g powder constituting the electrode portion is laminated in a layer shape, but the invention is not limited thereto. Other electrodes of various shapes can also be formed by changing the laminated shape of Ag powder or the like. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic diagram of a schematic configuration of a discharge plasma sintering apparatus. Fig. 2 is a diagram showing the method of thermoelectric conversion module according to the embodiment. -24- 201004003 Fig. 3 is a diagram showing the thermoelectric conversion module of the first embodiment. Fig. 4 is a view showing the operation of the thermoelectric conversion module of the first embodiment. Fig. 5 is a graph showing the results of measurement of the thermally induced electromotive force of the thermoelectric conversion module of the first embodiment. Fig. 6 is a view showing the thermoelectric conversion module of the second embodiment. Fig. 7 is a view showing the thermoelectric conversion module of the third embodiment. Fig. 8 is a view showing the recipe of the thermoelectric conversion module of the fourth embodiment. Fig. 9 is a perspective view showing the thermoelectric conversion module of the fourth embodiment. Fig. 1 is a diagram showing the recipe of the thermoelectric conversion module of the fifth embodiment. [Description of main components] 1 : Discharge plasma sintering device 2 : Vacuum chamber 3 : Sintering mold 3 a : Thermoelectric pair 4 : Raw material powder 5 : Punch (pressing member) 5 a ' 5 b : Punch 6 : Stamping Electrode 7 : Special sintering power source 8 : Pressurizing mechanism portion 9 : Control portion 1 量: Measuring portion - 25 - 201004003 1 1 : Sintering mold 1 2 a : Lower side sintering mold 1 2 b : Upper side sintering mold 1 3 a, 1 3 b : Rectangular punch 2 0 A to 2 0 D : Thermoelectric conversion module 21, 24, 41, 44: Metal for electrode (Ag) 22, 25, 42 : p-type thermoelectric conversion semiconductor 23, 26, 43 : n-type thermoelectric conversion semiconductor 3 1 a, 3 1 b : solder 3 2 a, 3 2 b : connection line 3 4 a, 3 4 b : wire terminal 3 5 a, 3 5 b : flange portion 21': Metal powder 22' for electrode formed of silver (Ag): p-type thermoelectric conversion semiconductor raw material powder 23' : n-type thermoelectric conversion semiconductor raw material powder 24': metal powder for electrode formed of silver (Ag) C: carbon paper -26-