JP3134360B2 - Manufacturing method of thin film thermoelectric element - Google Patents
Manufacturing method of thin film thermoelectric elementInfo
- Publication number
- JP3134360B2 JP3134360B2 JP03156795A JP15679591A JP3134360B2 JP 3134360 B2 JP3134360 B2 JP 3134360B2 JP 03156795 A JP03156795 A JP 03156795A JP 15679591 A JP15679591 A JP 15679591A JP 3134360 B2 JP3134360 B2 JP 3134360B2
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- Prior art keywords
- thin film
- film pattern
- type
- thermoelectric element
- manufacturing
- Prior art date
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Description
【０００１】[0001]
【産業上の利用分野】この発明は、赤外線センサー、温
度センサー、熱センサーなどに用いられる薄膜熱電素子
の製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for manufacturing a thin film thermoelectric element used for an infrared sensor, a temperature sensor, a heat sensor, and the like.
【０００２】[0002]
【従来の技術】熱電対を多数直列接続したサーモパイル
（熱電堆）型熱電素子が赤外線センサ、温度センサ、熱
センサなどとして従来より用いられている。このような
サーモパイル型熱電素子は、温度差から生じる各熱電対
の熱起電力が加算されるため大きな熱起電力を得ること
ができ、高効率の熱電力変換素子や微小温度差を検知す
る高感度な赤外線センサ、温度センサまたは熱センサと
て利用することができる。特に、センサ用途には小型
化、高感度化、高応答速度化のために、主に薄膜型の熱
電素子が用いられている。2. Description of the Related Art A thermopile (thermopile) type thermoelectric element in which a large number of thermocouples are connected in series has been conventionally used as an infrared sensor, a temperature sensor, a heat sensor and the like. In such a thermopile type thermoelectric element, a large thermoelectromotive force can be obtained because the thermoelectromotive force of each thermocouple generated by the temperature difference is added. It can be used as a sensitive infrared sensor, temperature sensor or heat sensor. In particular, thin-film thermoelectric elements are mainly used for sensor applications in order to reduce the size, increase the sensitivity, and increase the response speed.
【０００３】従来の薄膜熱電材料としてはコンスタンタ
ン−ニクロム（特公昭６１−４０１５４号）、Ｓｉ，Ｇ
ｅ（特開昭５７−７１７２号）、Ｂｉ−Ｓｂ−Ｔｅ（特
開昭５３−１３２２８２号，特開昭６１−２２６７６
号）などの金属系または半導体系材料が用いられてき
た。Conventional thin film thermoelectric materials include Constantan-Nichrome (Japanese Patent Publication No. 61-40154), Si, G
e (JP-A-57-7172), Bi-Sb-Te (JP-A-53-132282, JP-A-61-22676)
No.) or other metal-based or semiconductor-based materials.
【０００４】[0004]
【発明が解決しようとする課題】これら従来の薄膜用熱
電材料は電気伝導率が高く熱電変換効率が高いという長
所があるが、ゼーベック係数が小さい、ゼーベック係数
の温度変化が大きい、高温下で使用できないという欠点
を備えている。また、焦電型赤外線センサに比べ赤外線
を充分検知するにはまだ感度が低い。These conventional thermoelectric materials for thin films have the advantages of high electric conductivity and high thermoelectric conversion efficiency, but have a small Seebeck coefficient, a large temperature change in the Seebeck coefficient, and are used at high temperatures. It has the disadvantage of not being able to. In addition, the sensitivity is still low for detecting infrared light sufficiently compared to a pyroelectric infrared sensor.
【０００５】この発明の目的は高感度でかつ高温域まで
使用可能な薄膜熱電素子の製造方法を提供することにあ
る。An object of the present invention is to provide a method of manufacturing a thin film thermoelectric element which has high sensitivity and can be used up to a high temperature range.
【０００６】[0006]
【課題を解決するための手段】高感度な薄膜熱電素子を
得るためには、ゼーベック係数の高い熱電材料を用いな
ければならない。珪化物半導体、特に鉄珪化物半導体は
３００〜７００μＶ／Ｋという高いゼーベック係数を有
し、耐熱性が高く、高温度下での熱電力変換素子として
注目されている。In order to obtain a highly sensitive thin film thermoelectric element, a thermoelectric material having a high Seebeck coefficient must be used. Silicide semiconductors, particularly iron silicide semiconductors, have a high Seebeck coefficient of 300 to 700 μV / K, have high heat resistance, and are attracting attention as thermoelectric power conversion elements at high temperatures.
【０００７】発明者らは、珪化物半導体材料を薄膜化す
ることによって、高温下でも使用可能な薄膜熱電材料お
よびそれを用いた高感度な薄膜熱電素子が得られること
を見出した。The inventors have found that a thin film of a silicide semiconductor material can provide a thin film thermoelectric material usable even at high temperatures and a highly sensitive thin film thermoelectric element using the same.
【０００８】この発明の請求項１に係る薄膜熱電素子の
製造方法は、Ｓｉを主体とする基板または薄膜の表面に
鉄合金によるｐ型用薄膜パターンとｎ型用薄膜パターン
を、絶縁膜を介して熱電堆状に形成し、その表面にＳｉ
を主体とする薄膜を形成し、熱処理により前記ｐ型用薄
膜パターンとｎ型用薄膜パターンをそれぞれ遷移金属珪
化物化する。According to a first aspect of the present invention, there is provided a method for manufacturing a thin-film thermoelectric element, comprising the steps of:
A p-type thin film pattern and an n-type thin film pattern made of an iron alloy are formed in the form of a thermopile through an insulating film, and a Si
Is formed, and the p-type thin film pattern and the n-type thin film pattern are each converted into a transition metal silicide by heat treatment.
【０００９】また、請求項２に係る薄膜熱電素子の製造
方法は、鉄合金によるｐ型用薄膜パターンとｎ型用薄膜
パターンを熱電堆状に形成した熱電堆単位層をＳｉを主
体とする薄膜を介して多層化し、熱処理により前記ｐ型
用薄膜パターンとｎ型用薄膜パターンをそれぞれ遷移金
属珪化物化する。A method of manufacturing a thin film thermoelectric element according to a second aspect of the present invention is a thin film mainly composed of a thermoelectric bank unit layer in which a p-type thin film pattern and an n-type thin film pattern made of an iron alloy are formed in a thermoelectric bank shape. The thin film pattern for p-type and the thin film pattern for n-type are each converted into a transition metal silicide by heat treatment.
【００１０】[0010]
【作用】この発明の請求項１に記載した薄膜熱電素子の
製造方法では、まず、Ｓｉを主体とする基板または薄膜
の表面に、鉄合金によるｐ型用薄膜パターンとｎ型用薄
膜パターンが絶縁膜を介して熱電堆状に形成され、その
表面にＳｉを主体とする薄膜が形成され、熱処理によっ
てｐ型用薄膜パターンとｎ型用薄膜パターンがそれぞれ
基板または薄膜のＳｉと反応して、遷移金属珪化物のｐ
型半導体薄膜パターンとｎ型半導体薄膜パターンとにな
る。このようにして高温下で使用可能な遷移金属珪化物
による薄膜熱電素子が得られる。また、ｐ型半導体薄膜
パターンとｎ型半導体薄膜パターンとが絶縁膜を介して
熱電堆状に構成されるため、単位面積あたりの熱電対の
対数が多くなり、小型で高感度な薄膜熱電素子が得られ
る。In the method for manufacturing a thin-film thermoelectric element according to the first aspect of the present invention, first, a p-type thin film pattern and an n-type thin film pattern made of an iron alloy are insulated on the surface of a substrate or a thin film mainly composed of Si. A thin film mainly composed of Si is formed on the surface thereof through a film, and a thin film mainly composed of Si is formed on the surface thereof. P of metal silicide
A semiconductor thin film pattern and an n-type semiconductor thin film pattern. In this manner, a thin film thermoelectric element made of a transition metal silicide that can be used at a high temperature is obtained. In addition, since the p-type semiconductor thin film pattern and the n-type semiconductor thin film pattern are formed in a thermopile shape via an insulating film, the number of thermocouples per unit area increases, and a small and highly sensitive thin-film thermoelectric element is provided. can get.
【００１１】また、請求項２に記載した薄膜熱電素子の
製造方法では、鉄合金によるｐ型用薄膜パターンとｎ型
用薄膜パターンが熱電堆状に形成され、これが熱電堆単
位層として、Ｓｉを主体とする薄膜を介して多層化さ
れ、その後の熱処理によってｐ型用薄膜パターンとｎ型
用薄膜パターンがそれぞれ薄膜のＳｉと反応して遷移金
属珪化物の半導体薄膜パターンとなる。このようにして
遷移金属珪化物半導体薄膜パターンによる熱電対が多層
化されて、単位面積あたりの熱電対の対数が非常に多い
薄膜熱電素子が得られる。In the method for manufacturing a thin-film thermoelectric device according to the second aspect, the p-type thin film pattern and the n-type thin film pattern made of an iron alloy are formed in a thermoelectric bank shape. The multi-layered structure is formed through the main thin film, and the subsequent heat treatment causes the p-type thin film pattern and the n-type thin film pattern to react with Si of the thin film to form a transition metal silicide semiconductor thin film pattern. In this way, the thermocouples using the transition metal silicide semiconductor thin film pattern are multilayered, and a thin film thermoelectric element having a very large number of thermocouples per unit area is obtained.
【００１２】[0012]
【実施例】この発明の実施例である薄膜熱電素子の製造
工程を図１〜図９に基づいて説明する。なお各図におい
て（Ａ）は上面図、（Ｂ）は断面図である。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS A manufacturing process of a thin-film thermoelectric device according to an embodiment of the present invention will be described with reference to FIGS. In each figure, (A) is a top view and (B) is a sectional view.
【００１３】まず、図１に示すようにＳｉ基板１の表面
を酸化させてＳｉＯ2 膜２を形成する。First, as shown in FIG. 1, the surface of a Si substrate 1 is oxidized to form a SiO 2 film 2.
【００１４】次に図２に示すように、後の感熱部となる
基板中央部をマスクしてＣＶＤ法によりＳｉ薄膜３を製
膜する。Next, as shown in FIG. 2, an Si thin film 3 is formed by a CVD method using a central portion of the substrate which will be a heat sensitive portion later.
【００１５】続いてアクセプタとしての不純物をドープ
した遷移金属合金を図３に示すようにｐ型用薄膜パター
ン４として形成する。ここではＦｅ ９９ｍｏｌ％、Ｍ
ｎ１ｍｏｌ％からなる鉄合金を作成し、マスクを用いて
真空蒸着により膜厚約１０μｍのｐ型用薄膜パターンを
製膜する。Subsequently, a transition metal alloy doped with an impurity as an acceptor is formed as a p-type thin film pattern 4 as shown in FIG. Here, Fe 99 mol%, M
An n1 mol% iron alloy is prepared, and a p-type thin film pattern having a thickness of about 10 μm is formed by vacuum evaporation using a mask.
【００１６】次に図４に示す破線部５の内側と外側をマ
スクして、Ｓｉ単結晶ターゲットを用いて、Ｎ2 下の反
応スパッタ法により、図５に示すように熱電対の接合部
を残してＳｉ3 Ｎ4 薄膜６を形成する。Next, the inside and outside of the dashed line portion 5 shown in FIG. 4 are masked, and the junction of the thermocouple is formed as shown in FIG. 5 by reactive sputtering under N 2 using a Si single crystal target. The Si 3 N 4 thin film 6 is formed while leaving.
【００１７】その後、ドナーとしての不純物をドープし
た遷移金属合金を図６に示すようにｎ型用薄膜パターン
７として形成する。ここでは、Ｆｅ ９９ｍｏｌ％、Ｃ
ｏ１ｍｏｌ％からなる鉄合金を作成し、マスクを用いて
真空蒸着により膜厚約１０μｍのｎ型用薄膜パターンを
製膜する。Thereafter, a transition metal alloy doped with an impurity as a donor is formed as an n-type thin film pattern 7 as shown in FIG. Here, 99 mol% of Fe, C
An iron alloy of o1 mol% is prepared, and a thin film pattern for n-type having a thickness of about 10 μm is formed by vacuum evaporation using a mask.
【００１８】そして図７に示すように、ＣＶＤ法により
全面にＳｉ薄膜８を形成する。Then, as shown in FIG. 7, a Si thin film 8 is formed on the entire surface by the CVD method.
【００１９】その後、Ａｒなどの不活性気流中または真
空中で７００℃以上、約４時間以上の熱処理を行う。こ
のことにより、ｐ型用薄膜パターンとｎ型用薄膜パター
ンである鉄合金がＳｉ薄膜３およびＳｉ薄膜８と反応し
てそれぞれ珪化鉄半導体となり、図８に示すように、ｐ
型の珪化鉄半導体薄膜パターン９とｎ型の珪化鉄半導体
薄膜パターン１０による熱電対が形成される。Thereafter, heat treatment is performed in an inert gas stream such as Ar or in a vacuum at 700 ° C. or higher for about 4 hours or longer. As a result, the iron alloys serving as the p-type thin film pattern and the n-type thin film pattern react with the Si thin film 3 and the Si thin film 8 to become iron silicide semiconductors, respectively, as shown in FIG.
A thermocouple is formed by the n-type iron silicide semiconductor thin film pattern 9 and the n-type iron silicide semiconductor thin film pattern 10.
【００２０】以上の処理によって薄膜熱電素子の主要部
が構成される。続いて図９に示すように、基板中央部の
Ｓｉ膜８の上部に白金黒などの集熱黒体１２を形成し、
またリード取付部にＮｉなどからなる電極１１を蒸着
し、さらに電極１１以外の基板表面全面にＳｉＯ2 から
なるコーティング膜１３をＣＶＤ法などにより形成す
る。最後に同図に示すように、Ｓｉ基板の裏面側中央部
をエッチングなどにより除去してダイアフラム構造とす
る。The above processing constitutes the main part of the thin film thermoelectric element. Subsequently, as shown in FIG. 9, a heat-collecting black body 12 such as platinum black is formed on the Si film 8 at the center of the substrate.
Further, an electrode 11 made of Ni or the like is deposited on the lead mounting portion, and a coating film 13 made of SiO 2 is formed on the entire surface of the substrate other than the electrode 11 by a CVD method or the like. Finally, as shown in the figure, the central portion on the back side of the Si substrate is removed by etching or the like to obtain a diaphragm structure.
【００２１】以上のようにしてＳｉ基板の中央部を受光
／受熱部とした薄膜熱電素子が得られる。As described above, a thin film thermoelectric element having the central portion of the Si substrate as the light receiving / heating portion is obtained.
【００２２】図９に示した構造で、５ｍｍ角基板で２０
０対の珪化鉄熱電対を有する薄膜熱電素子を作成し、そ
の感度を計測したところ、約２２０Ｖ／Ｗであった。In the structure shown in FIG.
When a thin film thermoelectric element having zero pairs of iron silicide thermocouples was prepared and its sensitivity was measured, it was about 220 V / W.
【００２３】図１〜図９に示した実施例では、ｐ型用半
導体薄膜パターンの形成層とｎ型用半導体薄膜パターン
の形成層を絶縁層を介してそれぞれ１層づつ形成した
が、これを多層化することによって、単位面積当たりの
熱電対の対数をさらに増すことができる。具体的には、
図７に示した状態から更に図３〜図７に示した工程を繰
り返すことにより、ｐ型用薄膜パターン、絶縁層、ｎ型
用薄膜パターンおよびＳｉ薄膜の形成工程を繰り返し行
い、熱電堆単位層を多層化した後、熱処理によって各ｐ
型用薄膜パターンとｎ型用薄膜パターンをそれぞれ珪化
物化する。これにより熱電堆層が多層化された薄膜熱電
素子が得られる。In the embodiment shown in FIGS. 1 to 9, the formation layer of the p-type semiconductor thin film pattern and the formation layer of the n-type semiconductor thin film pattern are formed one by one via an insulating layer. The number of thermocouples per unit area can be further increased by forming a multilayer structure. In particular,
By repeating the steps shown in FIGS. 3 to 7 further from the state shown in FIG. 7, the steps of forming the p-type thin film pattern, the insulating layer, the n-type thin film pattern, and the Si thin film are repeated. And then heat treating each p
The thin film pattern for the mold and the thin film pattern for the n-type are each silicidized. As a result, a thin-film thermoelectric element having a plurality of thermoelectric layers can be obtained.
【００２４】[0024]
【発明の効果】この発明によれば、遷移金属珪化物の半
導体薄膜パターンからなる薄膜熱電素子が得られるた
め、高温下での使用が可能となる。また、単位面積当た
りの熱電対の対数を多くすることができ、赤外線センサ
ーとしても充分な感度を得ることができる。According to the present invention, a thin-film thermoelectric element comprising a semiconductor thin-film pattern of a transition metal silicide can be obtained, so that it can be used at a high temperature. Further, the number of thermocouples per unit area can be increased, and sufficient sensitivity can be obtained as an infrared sensor.
【図１】薄膜熱電素子の製造途中の状態を示す図であ
り、（Ａ）は上面図、（Ｂ）は断面図である。FIGS. 1A and 1B are diagrams showing a state in the process of manufacturing a thin film thermoelectric element, wherein FIG. 1A is a top view and FIG. 1B is a cross-sectional view.
【図２】薄膜熱電素子の製造途中の状態を示す図であ
り、（Ａ）は上面図、（Ｂ）は断面図である。FIGS. 2A and 2B are diagrams showing a state in the process of manufacturing the thin-film thermoelectric element, wherein FIG. 2A is a top view and FIG.
【図３】薄膜熱電素子の製造途中の状態を示す図であ
り、（Ａ）は上面図、（Ｂ）は断面図である。FIGS. 3A and 3B are views showing a state in the process of manufacturing the thin film thermoelectric element, wherein FIG. 3A is a top view and FIG. 3B is a cross-sectional view.
【図４】薄膜熱電素子の製造途中の状態を示す図であ
り、（Ａ）は上面図、（Ｂ）は断面図である。FIGS. 4A and 4B are views showing a state in the course of manufacturing the thin-film thermoelectric element, wherein FIG. 4A is a top view and FIG.
【図５】薄膜熱電素子の製造途中の状態を示す図であ
り、（Ａ）は上面図、（Ｂ）は断面図である。FIGS. 5A and 5B are views showing a state in the process of manufacturing the thin film thermoelectric element, wherein FIG. 5A is a top view and FIG.
【図６】薄膜熱電素子の製造途中の状態を示す図であ
り、（Ａ）は上面図、（Ｂ）は断面図である。FIGS. 6A and 6B are views showing a state of the thin film thermoelectric element in the process of being manufactured, wherein FIG. 6A is a top view and FIG.
【図７】薄膜熱電素子の製造途中の状態を示す図であ
り、（Ａ）は上面図、（Ｂ）は断面図である。FIGS. 7A and 7B are views showing a state in the process of manufacturing the thin film thermoelectric element, wherein FIG. 7A is a top view and FIG.
【図８】薄膜熱電素子の製造途中の状態を示す図であ
り、（Ａ）は上面図、（Ｂ）は断面図である。FIGS. 8A and 8B are diagrams showing a state of the thin film thermoelectric element in the process of being manufactured, wherein FIG. 8A is a top view and FIG.
【図９】完成した薄膜熱電素子を示す図であり、（Ａ）
は上面図、（Ｂ）は断面図である。FIG. 9 is a view showing a completed thin-film thermoelectric element, and FIG.
Is a top view, and (B) is a sectional view.
１ Ｓｉ基板 ２ ＳｉＯ2 膜 ３ Ｓｉ膜 ４ 遷移金属合金（鉄合金）によるｐ型用薄膜パターン ５ マスク領域 ６ 絶縁膜（Ｓｉ3 Ｎ4 薄膜） ７ 遷移金属合金（鉄合金）によるｎ型用薄膜パターン ８ Ｓｉ薄膜 ９ ｐ型遷移金属珪化物（珪化鉄）半導体薄膜パターン １０ ｎ型遷移金属珪化物（珪化鉄）半導体薄膜パター
ン １１ 電極 １２ 集熱黒体 １３ ＳｉＯ2 コーティング膜Reference Signs List 1 Si substrate 2 SiO 2 film 3 Si film 4 Thin film pattern for p-type using transition metal alloy (iron alloy) 5 Mask region 6 Insulating film (Si 3 N 4 thin film) 7 Thin film for n-type using transition metal alloy (iron alloy) Pattern 8 Si thin film 9 p-type transition metal silicide (iron silicide) semiconductor thin film pattern 10 n-type transition metal silicide (iron silicide) semiconductor thin film pattern 11 electrode 12 heat-collecting black body 13 SiO 2 coating film
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 平４−258185（ＪＰ，Ａ) 特開 平３−129782（ＪＰ，Ａ) 特開 昭58−6186（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) H01L 35/32 ──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-4-258185 (JP, A) JP-A-3-129782 (JP, A) JP-A-58-6186 (JP, A) (58) Field (Int.Cl. 7 , DB name) H01L 35/32
Claims (2)
鉄合金によるｐ型用薄膜パターンとｎ型用薄膜パターン
を、絶縁膜を介して熱電堆状に形成し、その表面にＳｉ
を主体とする薄膜を形成し、熱処理により前記ｐ型用薄
膜パターンとｎ型用薄膜パターンをそれぞれ遷移金属珪
化物化する薄膜熱電素子の製造方法。1. The method according to claim 1, wherein the substrate or the thin film is composed mainly of Si.
A p-type thin film pattern and an n-type thin film pattern made of an iron alloy are formed in the form of a thermopile through an insulating film, and a Si
A method for producing a thin-film thermoelectric element, wherein a thin film mainly composed of a p-type thin film pattern and a thin-film pattern for n-type are each converted into a transition metal silicide by heat treatment.
薄膜パターンを熱電堆状に形成した熱電堆単位層をＳｉ
を主体とする薄膜を介して多層化し、熱処理により前記
ｐ型用薄膜パターンとｎ型用薄膜パターンをそれぞれ遷
移金属珪化物化する薄膜熱電素子の製造方法。2. A thermoelectric bank unit layer in which a p-type thin film pattern and an n-type thin film pattern made of an iron alloy are formed in the shape of a thermoelectric bank.
A method for producing a thin-film thermoelectric element in which a p-type thin film pattern and an n-type thin film pattern are each converted into a transition metal silicide by heat treatment.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03156795A JP3134360B2 (en) | 1991-06-27 | 1991-06-27 | Manufacturing method of thin film thermoelectric element |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03156795A JP3134360B2 (en) | 1991-06-27 | 1991-06-27 | Manufacturing method of thin film thermoelectric element |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH057021A JPH057021A (en) | 1993-01-14 |
| JP3134360B2 true JP3134360B2 (en) | 2001-02-13 |
Family
ID=15635479
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP03156795A Expired - Fee Related JP3134360B2 (en) | 1991-06-27 | 1991-06-27 | Manufacturing method of thin film thermoelectric element |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3134360B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2130668C1 (en) * | 1994-09-30 | 1999-05-20 | Акционерное общество закрытого типа "VL" | Field-effect metal-insulator-semiconductor transistor |
-
1991
- 1991-06-27 JP JP03156795A patent/JP3134360B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH057021A (en) | 1993-01-14 |
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