JP2012019205A5 - - Google Patents
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- JP2012019205A5 JP2012019205A5 JP2011124805A JP2011124805A JP2012019205A5 JP 2012019205 A5 JP2012019205 A5 JP 2012019205A5 JP 2011124805 A JP2011124805 A JP 2011124805A JP 2011124805 A JP2011124805 A JP 2011124805A JP 2012019205 A5 JP2012019205 A5 JP 2012019205A5
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開示する一観点からは、複数の熱電変換材料微結晶粒子と、前記複数の熱電変換材料微結晶粒子間の空孔とからなる柱状或いは格子状の熱電変換材料構造体と前記熱電変換材料構造体の一方の端面に設けられた第１の電極と、前記熱電変換材料構造体の他方の端面に設けられた第２の電極とを有する熱電変換素子が提供される。 From one aspect disclosed, a plurality of thermoelectric conversion material fine crystal grains, a columnar or grid thermoelectric conversion material structure and the thermoelectric conversion material structure consisting of pores between the plurality of thermoelectric conversion material microcrystal grains There is provided a thermoelectric conversion element having a first electrode provided on one end surface of the thermoelectric conversion material structure and a second electrode provided on the other end surface of the thermoelectric conversion material structure.
また、開示する別の観点からは、基板に複数の孔を形成する孔形成工程と、前記孔の内部にエアロゾルデポジション法を用いて熱電変換材料を充填して熱電変換材料構造体を形成する充填工程とを有することを特徴とする熱電変換素子の製造方法が提供される。 From another viewpoint to be disclosed, a hole forming step for forming a plurality of holes in the substrate , and a thermoelectric conversion material structure is formed by filling the holes with a thermoelectric conversion material using an aerosol deposition method. A method for manufacturing a thermoelectric conversion element comprising a filling step is provided.
ここで、実施例１乃至実施例４を含む本発明の実施の形態に関して、以下の付記を開示する。
（付記１）複数の熱電変換材料微結晶粒子と、前記複数の熱電変換材料微結晶粒子間の空孔とからなる柱状或いは格子状の熱電変換材料構造体と前記熱電変換材料構造体の一方の端面に設けられた第１の電極と、前記熱電変換材料構造体の他方の端面に設けられた第２の電極とを有する熱電変換素子。
（付記２）前記熱電変換材料構造体は、高さが５０μｍ乃至５００μｍであり、水平断面の最短径が５μｍ乃至１００μｍであり、且つ、アスペクト比が２以上であることを特徴とする付記１に記載の熱電変換素子。
（付記３）前記熱電変換材料が、金属酸化物半導体からなることを特徴とする付記２または付記３に記載の熱電変換素子。
（付記４）前記熱電変換材料構造体の側壁の少なくとも一部が、電気抵抗及び熱抵抗が前記熱電変換材料の電気抵抗及び熱抵抗より高い補強部材で被覆されることを特徴とする付記１乃至付記３のいずれか１に記載の熱電変換素子。
（付記５）前記補強部材が、電気抵抗及び熱抵抗が前記熱電変換材料の電気抵抗及び熱抵抗より高い補強材料微結晶粒子と、前記複数の補強部材微結晶間の空孔とからなることを特徴とする付記４に記載の熱電変換素子。
（付記６）前記複数の熱電変換材料構造体が互いに導電型の異なった二種類の熱電変換材料構造体からなり、前記熱電変換材料構造体の一方の端面において、一導電型の前記熱電変換材料構造体と反対導電型の前記熱電変換材料構造体を第１の電極で交互に接続するとともに、前記熱電変換材料構造体の他方の端面において、一導電型の前記熱電変換材料構造体と反対導電型の前記熱電変換材料構造体を第２の電極で交互に接続して、前記第１の導電型の熱電変換材料構造体と前記第２の熱電変換材料構造体を交互に直列接続することを特徴とする付記１乃至付記５のいずれか１に記載の熱電変換素子。
（付記７）基板に複数の孔を形成する孔形成工程と、前記孔の内部にエアロゾルデポジション法を用いて熱電変換材料を充填して熱電変換材料構造体を形成する充填工程とを有することを特徴とする熱電変換素子の製造方法。
（付記８）前記熱電変換材料構造体を形成したのち、前記基板の少なくとも一部を除去して前記熱電変換材料構造体の少なくとも一部の側壁を露呈する工程と、前記露呈した熱電変換材料構造体の側壁を、電気抵抗及び熱抵抗が前記熱電変換材料の電気抵抗及び熱抵抗より高い補強材料で被覆する工程とを有することを特徴とする付記７に記載の熱電変換素子の製造方法。
（付記９）前記孔形成工程の前に、前記基板に格子状の開口を形成する開口形成工程と、前記開口の内部にエアロゾルデポジッション法を用いて電気抵抗及び熱抵抗が前記熱電変換材料の電気抵抗及び熱抵抗より高い補強材料を充填して補強部を形成する充填工程とを有し、前記孔形成工程において、格子状に充填された前記補強部の内部に孔を形成することを特徴とする付記７に記載の熱電変換素子の製造方法。
（付記１０）前記基板が、シリコン基板、シリコン基板上に絶縁膜を介してシリコン層を設けたシリコン複合基板、或いは、シリコン基板上に有機物層を設けた複合基板のいずれかであることを特徴とする付記７乃至付記９のいずれか1に記載の熱電変換素子の製造方法。
（付記１１）前記基板に複数の孔を形成する孔形成工程及び前記孔の内部にエアロゾルデポジション法を用いて熱電変換材料を充填して熱電変換材料構造体を形成する充填工程が、前記基板に複数の第１の孔を形成する第１の孔形成工程及び前記第１の孔の内部に一導電型の熱電変換材料構造体を設ける第１の充填工程と、前記基板の前記一導電型の熱電変換材料構造体の存在しない領域に複数の第２の孔を形成する第２の孔形成工程及び前記第２の孔の内部に反対導電型の熱電変換材料構造体を設ける第２の充填工程と、からなることを特徴とする付記７乃至付記１０のいずれか１に記載の熱電変換素子の製造方法。
Here, the following additional notes are disclosed regarding the embodiment of the present invention including Examples 1 to 4.
(Supplementary Note 1) and a plurality of thermoelectric conversion material microcrystalline particles, one of the columnar or grid thermoelectric conversion material structure and the thermoelectric conversion material structure consisting of pores between the plurality of thermoelectric conversion material microcrystal grains A thermoelectric conversion element having a first electrode provided on an end face and a second electrode provided on the other end face of the thermoelectric conversion material structure.
(Supplementary note 2) The supplementary note 1, wherein the thermoelectric conversion material structure has a height of 50 μm to 500 μm, a shortest horizontal cross-sectional diameter of 5 μm to 100 μm, and an aspect ratio of 2 or more. The thermoelectric conversion element as described.
(Additional remark 3) The thermoelectric conversion element of Additional remark 2 or Additional remark 3 characterized by the said thermoelectric conversion material consisting of a metal oxide semiconductor.
(Additional remark 4) At least one part of the side wall of the said thermoelectric conversion material structure is coat | covered with the reinforcing member whose electrical resistance and thermal resistance are higher than the electrical resistance and thermal resistance of the said thermoelectric conversion material, The additional notes 1 thru | or characterized by the above-mentioned. The thermoelectric conversion element according to any one of appendix 3.
(Supplementary Note 5) The reinforcing member is composed of reinforcing material microcrystalline particles whose electrical resistance and thermal resistance are higher than the electrical resistance and thermal resistance of the thermoelectric conversion material, and pores between the plurality of reinforcing member microcrystals. The thermoelectric conversion element according to appendix 4, which is characterized.
(Supplementary Note 6) The plurality of thermoelectric conversion material structures are composed of two types of thermoelectric conversion material structures having different conductivity types, and one thermoelectric conversion material is provided on one end face of the thermoelectric conversion material structure. The thermoelectric conversion material structures of the opposite conductivity type to the structure are alternately connected by the first electrodes, and the other end surface of the thermoelectric conversion material structure is opposite to the one conductivity type of the thermoelectric conversion material structure. The thermoelectric conversion material structures of the mold are alternately connected by the second electrodes, and the thermoelectric conversion material structures of the first conductivity type and the second thermoelectric conversion material structures are alternately connected in series. The thermoelectric conversion element according to any one of Supplementary Note 1 to Supplementary Note 5, which is characterized.
(Additional remark 7) It has the hole formation process which forms a some hole in a board | substrate , and the filling process which fills the thermoelectric conversion material inside the said hole using the aerosol deposition method, and forms a thermoelectric conversion material structure. The manufacturing method of the thermoelectric conversion element characterized by these.
(Supplementary note 8) After forming the thermoelectric conversion material structure, removing at least a part of the substrate to expose at least a part of the side wall of the thermoelectric conversion material structure; and the exposed thermoelectric conversion material structure The method of manufacturing a thermoelectric conversion element according to appendix 7, further comprising: covering a side wall of the body with a reinforcing material having an electric resistance and a thermal resistance higher than the electric resistance and thermal resistance of the thermoelectric conversion material.
(Additional remark 9) Before the said hole formation process, the opening formation process which forms a grid | lattice-like opening in the said board | substrate , and the electrical resistance and thermal resistance of the said thermoelectric conversion material are used for the inside of the said opening using the aerosol deposition method. Filling a reinforcing portion with a reinforcing material higher than electrical resistance and thermal resistance to form a reinforcing portion, and in the hole forming step, holes are formed inside the reinforcing portions filled in a lattice shape. The manufacturing method of the thermoelectric conversion element of Additional remark 7.
(Additional remark 10) The said board | substrate is either a silicon substrate, the silicon composite substrate which provided the silicon layer through the insulating film on the silicon substrate, or the composite substrate which provided the organic substance layer on the silicon substrate. The method for manufacturing a thermoelectric conversion element according to any one of appendix 7 to appendix 9.
(Appendix 11) A hole forming step of forming a plurality of holes in the substrate , and a filling step of filling the thermoelectric conversion material into the holes using an aerosol deposition method to form a thermoelectric conversion material structure are performed on the substrate. A first hole forming step of forming a plurality of first holes in the substrate, a first filling step of providing a one-conductivity-type thermoelectric conversion material structure inside the first hole, and the one-conductivity type of the substrate A second hole forming step of forming a plurality of second holes in a region where the thermoelectric conversion material structure does not exist, and a second filling in which a thermoelectric conversion material structure of an opposite conductivity type is provided inside the second hole The method for manufacturing a thermoelectric conversion element according to any one of Supplementary Note 7 to Supplementary Note 10, characterized by comprising the steps of:
Claims (8)
前記複数の熱電変換材料微結晶粒子間の空孔と
からなる柱状或いは格子状の熱電変換材料構造体と
前記熱電変換材料構造体の一方の端面に設けられた第１の電極と、
前記熱電変換材料構造体の他方の端面に設けられた第２の電極と
を有する熱電変換素子。 A plurality of thermoelectric conversion material microcrystalline particles;
A columnar or lattice-shaped thermoelectric conversion material structure composed of pores between the plurality of thermoelectric conversion material microcrystalline particles ; and a first electrode provided on one end face of the thermoelectric conversion material structure;
The thermoelectric conversion element which has a 2nd electrode provided in the other end surface of the said thermoelectric conversion material structure.
電気抵抗及び熱抵抗が前記熱電変換材料の電気抵抗及び熱抵抗より高い補強材料微結晶粒子と、
前記複数の補強部材微結晶粒子間の空孔と
からなることを特徴とする請求項２に記載の熱電変換素子。 The reinforcing member is
Reinforcement material microcrystalline particles having electrical resistance and thermal resistance higher than the electrical resistance and thermal resistance of the thermoelectric conversion material;
The thermoelectric conversion element according to claim 2, comprising holes between the plurality of reinforcing member microcrystalline particles.
前記孔の内部にエアロゾルデポジション法を用いて熱電変換材料を充填して熱電変換材
料構造体を形成する充填工程と
を有することを特徴とする熱電変換素子の製造方法。 A hole forming step of forming a plurality of holes in the substrate ;
A method for manufacturing a thermoelectric conversion element, comprising: a filling step of forming a thermoelectric conversion material structure by filling a thermoelectric conversion material into the hole using an aerosol deposition method.
一導電型の前記熱電変換材料構造体を充填する工程と、Filling the thermoelectric conversion material structure of one conductivity type;
前記一導電型と反対の導電型の前記熱電変換材料構造体を充填する工程とFilling the thermoelectric conversion material structure having a conductivity type opposite to the one conductivity type;
を有することを特徴とする請求項５に記載の熱電変換素子の製造方法。The manufacturing method of the thermoelectric conversion element of Claim 5 characterized by the above-mentioned.
前記露呈した熱電変換材料構造体の側壁を、電気抵抗及び熱抵抗が前記熱電変換材料の電気抵抗及び熱抵抗より高い補強材料で被覆する工程と
を有していることを特徴とする請求項５または請求項６に記載の熱電変換素子の製造方法。 After forming the thermoelectric conversion material structure, removing at least a part of the substrate to expose at least a part of the side wall of the thermoelectric conversion material structure;
6. A step of covering the exposed side wall of the thermoelectric conversion material structure with a reinforcing material whose electric resistance and thermal resistance are higher than the electric resistance and thermal resistance of the thermoelectric conversion material. Or the manufacturing method of the thermoelectric conversion element of Claim 6 .
前記基板に格子状の開口を形成する開口形成工程と、
前記開口の内部にエアロゾルデポジッション法を用いて電気抵抗及び熱抵抗が前記熱電
変換材料の電気抵抗及び熱抵抗より高い補強材料を充填して補強部を形成する充填工程と
を有し、
前記孔形成工程において、格子状に充填された前記補強部の内部に孔を形成することを
特徴とする請求項５または請求項６に記載の熱電変換素子の製造方法。 Before the hole forming step,
An opening forming step of forming a lattice-like opening in the substrate ;
Filling the inside of the opening with a reinforcing material having an electrical resistance and thermal resistance higher than the electrical resistance and thermal resistance of the thermoelectric conversion material by using an aerosol deposition method; and
In the hole forming step, the manufacturing method of the thermoelectric conversion element according to claim 5 or claim 6, characterized in that to form the interior hole of the reinforcing portion filled in a grid pattern.
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| JP2011124805A JP2012019205A (en) | 2010-06-10 | 2011-06-03 | Thermoelectric conversion element and manufacturing method thereof |
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| JP2011124805A JP2012019205A (en) | 2010-06-10 | 2011-06-03 | Thermoelectric conversion element and manufacturing method thereof |
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| JP5672079B2 (en) * | 2011-03-08 | 2015-02-18 | 富士通株式会社 | Manufacturing method of ceramic structure and manufacturing method of thermoelectric conversion element |
| WO2014064755A1 (en) | 2012-10-22 | 2014-05-01 | 富士通株式会社 | Semiconductor device, method for manufacturing semiconductor device, and electronic thermoelectric power generation device |
| JP6405604B2 (en) * | 2013-07-08 | 2018-10-17 | 富士通株式会社 | Thermoelectric element and manufacturing method thereof |
| JP6240514B2 (en) * | 2014-01-22 | 2017-11-29 | 株式会社アツミテック | Thermoelectric conversion module |
| KR101517784B1 (en) * | 2014-03-27 | 2015-05-06 | 서울시립대학교 산학협력단 | Thermoelectric materials having high figure of merit and manufacturing method thereof |
| JP6785459B2 (en) * | 2016-03-28 | 2020-11-18 | パナソニックＩｐマネジメント株式会社 | Thermoelectric conversion element and thermoelectric conversion module |
| CN112038478B (en) * | 2020-09-15 | 2023-09-26 | 上海商皓电子科技有限公司 | Manufacturing process of semiconductor refrigeration element and element |
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| JP2777508B2 (en) * | 1991-10-07 | 1998-07-16 | 松下電器産業株式会社 | Electronic cooling element |
| JPH1098216A (en) * | 1996-09-20 | 1998-04-14 | Seiko Epson Corp | Manufacturing method of thermoelectric generating device |
| JPH10209509A (en) * | 1997-01-24 | 1998-08-07 | Ngk Insulators Ltd | Thermoelectric transducer and its manufacture |
| JP3724133B2 (en) * | 1997-08-26 | 2005-12-07 | 松下電工株式会社 | Method for manufacturing thermoelectric conversion module |
| JP2001210879A (en) * | 1999-11-17 | 2001-08-03 | Sumitomo Metal Ind Ltd | High-output porous thermoelectric conversion element |
| JP2003229607A (en) * | 2002-02-01 | 2003-08-15 | Hiroshima Pref Gov | Thermomodule and method for manufacturing the same |
| JP4301827B2 (en) * | 2003-02-03 | 2009-07-22 | パナソニック株式会社 | Thermoelectric module manufacturing method |
| JP2011129832A (en) * | 2009-12-21 | 2011-06-30 | Denso Corp | Thermoelectric conversion element and method of manufacturing the same |
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