1. 電子セラミックスと固体化学 Electroceramics and Solid State Cheminstry 格子欠陥の利用 Application of Lattice Defects 工学部 応用化学科 片山 恵一

2. Today's subjects 電子セラミックスと は？ What is Electroceramics? 固体化学とは？ What is Solid State Chemistry? これらの関係は？ What is the relationship between these two subjects ? この関係は何に利用されている？ What has this relationship been utilized for? The interdisciplinary study of these two subjects has developed technology, and has been producing lots of sophisticated products underpinned modern society.

3. 講義の流れ Flow of today's talk 電子セラミックスとは？ What is Electroceramics? 固体化学 Solid State Chemistry 実用例 Application

4. 電子セラミックスとは？ What is Electroceramics ?

5. セラミックスとは？ What is a ceramic? 加熱して作製される非金属無機固体化合物 A ceramic is an inorganic, non-metallic solid prepared by heating. 例：陶磁 器 pottery 半導体材料として広範に利用されてい る。 In the 20th century, new ceramic materials were developed for use in advanced ceramic engineering; for example, in semiconductors.

6. Definition of Ceramics セラミックスの定義 The term ‘ceramics’ is restricted to polycrystalline, inorganic, non-metallic materials that can acquire their mechanical strength through a firing or sintering process. Glass and single crystals are sometimes included as a matter of convenience. 厳密には多結晶を対象とするが、単結晶･ガラスを含 む場合もある

7. 電子セラミックス Classification of Electroceramics Insulators ( 絶縁体 ) 基板、点火プラグ Magnetics ( 磁性体 ) 磁石、記録装置 Dielectrics ( 誘電体 ) ｺﾝﾃﾞﾝｻ、メモリー Conductors ( 導電体 ) 抵抗、ｻｰﾐｽﾀ、発熱体、ｶﾞｽｾ ﾝｻ Piezoelectrics ( 圧電体 ) ｽﾋﾟｰｶ、ﾌｨﾙﾀ、超音波診断装 置 Pyroelectrics ( 焦電体 ) 赤外線ｾﾝｻ Optics ( 光学材料 ) 光ﾌｧｲﾊﾞｰ、透明電極 ・

8. 固体化学の基礎 Fundamental Solid State Chemistry

9. 固体化学って何？ What is Solid State Chemistry? Preparative methods Crystal chemistry Phase diagrams Phase transition Electrical properties Magnetic properties Optical properties Crystal defects Non-stoichiometry Solid solution Electroceramics

10. Crystal defects Point Defects  Schottky defect  Frenkel defect  intrinsic and extrinsic defects  Interchanged Atoms

11. Perfect and Imperfect Crystals Perfect Crystals in which all atoms are at rest on their correct lattice positions. Imperfect Crystals which contain random defects, resulting in the deficiency of one element. At all real temperatures, crystals are imperfect.

12. Stoichiometry and Non-stoichiometry Stoichiometric compounds （化学量論組成化合物） Non-stoichiometric compounds （非化学量論組成化合物）

13. Example of Non-stoichiometric compounds Ideal formula : FeO Actual formula : Fe 1-X O (X≈0.05) In the latter formula, Fe 3+ ions are present and O 2− vacancies are formed. Ferrous oxide: FeO （酸化鉄 (  ) ）

14. Why non-stoichiometry exists? Since the solid needs to be overall electrically neutral, the missing atom's charge needs to be compensated by a change in the charge for another atom in the solid, by changing the oxidation state, or by replacing it with an atom of a different element with a different charge.

15. Types of Defect Schottky defect （ショットキー欠陥） : A pair of vacant sites, a cation defect and an anion defect （一対の陽イオンと陰イオンが抜ける） Frenkel defect （フレンケル欠陥） : An atom displaced off its lattice site into an interstitial site （片方のイオンが格子間位置に移動） These defects are described using the Kroger-Vink notation.

16. Types of Defect Schottky defect At room temperature, only one in 10 15 of both ion sites in NaCl is vacant. Na Cl Na Cl Na

17. Types of Defect Frenkel defect

18. Kroger-Vink notation クレーガー･ビンク記号 The symbol for the atom involved, or “V” if the site is vacant （空孔は V で表す） A superscript indicating the net charge: “  ” for charge  1, “  ” for zero net charge, “ ” for charge  1 （元に比べて “ ＋ ” の場 合 “  ” 、 ” － “ の場合は “ ” 、変化なしの場合 は “  ” ） A subscript to indicated the nature of the site in an ideal crystal, with ” i” for an interstitial site and “s” for a surface site （格子間位置は ” i” )

19. Kroger-Vink notation Na , Cl  : Na + and Cl  ions on regular lattice sites, zero net charge V : a Na + ion vacancy, net charge  1 V  : a Cl  ion vacancy, net charge  1 Mg  : a substitutional Mg 2+ ion on a Na site, charge +1 Ag  : an interstitial Ag + ion in AgCl, charge  1 F : an interstitial F  ion in CaF 2, charge  1 i i Na Cl Na Cl

20. Examples of Kroger-Vink notation NaCl null → V Na ’+V Cl 無 空の Na + 格子点 空の Cl – 格子点 (Na x Na +Cl x Cl → V Na ’+V Cl +Na x s +Cl x s ) AgCl Ag Ag x → Ag i + V Ag ’ 空の Ag + 格子点 格子間位置にある Ag + 本来の格子点にある Ag + (Ag x Ag +Cl x Cl → Ag i +V’ Ag +Cl x Cl )

21. Other examples of Defects Intrinsic defects: defects which are thermally created Example: ZnO(Zn 1+x O), NiO(Ni 1-x O) Extrinsic defects: defects which are associated with dopants or impurities Example 1: Al 2 O 3 including Cr 2 O 3 Example 2: ZnO including Al 2 O 3

22. Solid Solutions （固溶体） A crystalline phase that can have variable composition ( 規則性なく組成が変化する結晶相） 水とエタノールの混合と 同じ！ Examples Fe 0.95 O : Mixtures of FeO and Fe 2 O 3 Problem 1: Calculate the molar fraction of each compounds in Fe 0.95 O.

23. Answer to the problem The formation of Fe 0.95 O is; x FeO + y Fe 2 O 3 →Fe 0.95 O (x: mols of FeO in SS, y: mols of Fe 2 O 3 in SS) x+2y=0.95 ·····(1) x+3y=1.00 ·····(2) (2) – (1); y=0.05, x=0.85 Answer: FeO = 0.85 / 0.90 = 94.4 mol% Fe 2 O 3 = 100 – 94.4 = 5.6 mol%

24. Types of Solid Solutions Substitutional solid solutions ( 置換型 )  The atoms or ions that is being introduced directly replaces an atom or ion in the parent structure Interstitial solid solutions （格子間型）  The introduced species occupies a site that is normally empty and no ions or atoms are left out

25. Substitutional solid solutions Al 2-x Cr x O 3 (0≤x ≤ 2) (derived from Al 2 O 3 )  Al 3+ and Cr 3+ ions are distributed at random  the probability that it is one or the other is related to the composition x. (each site is occupied by an ‘average cation’)  Average cation whose properties, atomic number, size, etc., are intermediate between those of Al 3+ and Cr 3+ ions ( 固溶体の物性値は、それぞれの値 の平均！ ) Example Ionic radius of a cation in Al 1.6 Cr 0.4 O 3 is calculated to be 69.1 nm from ionic radii of Al 3+ : 67.5 nm and Cr 3+ : 75.5 nm.

26. Interstitial solid solutions If the solute atoms are small, they may dissolve interstitially in the host crystal.  YF 3 in CaF 2 Y 3+ is interstitially located in the lattice, and V Ca is created.  PdH x (0 ≤ x ≤ 0.7) Pd metal occludes( 吸蔵する ) H 2 gas, and H atoms occupy interstitial sites.

27. 応用例 1 ： BaTiO 3 系サーミスタ PTC thernistor

28. Temperature-sensitive Resistors (Thermal Resistors :Thermistors) Negative temperature coefficient of resistance (NTC) Positive temperature coefficient of resistance (PTC) 04080120160 0 1 2 3 4 5 6 log(ρ/Ω m) T/ºC PTC Thermistor Pt wire NTC Thermistor

29. Transformation of BaTiO 3 04080120160 0 1 2 3 4 5 6 log(ρ/Ω m) T/ºC PTC Thermistor Pt wire NTC Thermistor 相変態 立方晶 正方晶 単斜晶 菱面体晶

30. PTC Thermistors Lanthanum-doped BaTiO 3 (Ba 1-X La X TiO 3 ) or Niobium-doped BaTiO 3 (BaTi 1-X Nb X O 3 )

31. Defect chemistry of BaTiO 3 In case of addition of La 2 O 3 and forming non- stoichiometric BaTiO 3  BaO is formed or vacancies of Ti are formed. La 2 O 3 → 2La Ba + 2BaO +2e’ + 1/2O 2 La 2 O 3 → 2La Ba + 2V Ti + 10e’ + 1/2O 2 In case of addition of La 2 O 3 and forming stoichiometric BaTiO 3  La 2 O 3 (+2TiO 2 ) La 2 O 3 → 2La Ba + 2O X O +2e’ + 1/2O 2 La Ba is compensated by an electron ( 2TiO 2 + 2BaO → 2Ba X Ba + 2Ti X Ti + 6O X O ).

32. Defect chemistry of BaTiO 3 In case of another stoichiometric BaTiO 3  Nb 2 O 5 (+2BaO) Nb 2 O 5 → 2Nb Ti + 4O X O +2e’ + 1/2O 2 In case of stoichiometric BaTiO 3 –Al 2 O 3 (+2TiO 2 ) Al 2 O 3 → 2Al’ Ti + 3O X O +V O or Al 2 O 3 + 1/2O 2 +2e - → 2Al’ Ti + 4O X O

33. Solid state chemistry 固体化学 Solid state chemistry 固体化学 Electroceramics 電子セラミックス Electroceramics 電子セラミックス

34. The End Electroceramics and Solid State Cheminstry 電子セラミックスと固体化学 Application of Lattice Defects 格子欠陥の利用 工学部 応用化学科 片山 恵一

35. Assignment Explain the relationship between electroceramics and crystal defects within 200 words or less. （日本語の場合は 500 字以 内） Submission deadline: Feb. 27 E-mail to: Katayama Keiichi