㋕㍑Ꮏ႐ᑄᾲ⊒㔚↪㜞ᕈ⢻ᾲ㔚ᄌ឵᧚ᢱߩഃ⵾㩷⎇ⓥઍ⴫⠪㩷 㠽ขᄢቇᄢቇ㒮Ꮏቇ⎇ⓥ⑼㩷 ᢎ᝼㩷 㩷 㩷 㒸㩷 ਛᤐ㩷㩷✜⸒䉣䊈䊦䉩䊷໧㗴䉇࿾⃿᷷ᥦൻ໧㗴䈱ᷓೞൻ䈮䈧䉏䈩䇮㋕㍑Ꮏ႐╬↥ᬺಽ㊁䈎䉌ᝥ䈩䉌䉏䈩䈇䉎ᑄᾲ䉕㔚᳇䉣䊈䊦䉩䊷䈮⋥ធᄌ឵䈜䉎ᾲ㔚⊒㔚䈲䇮⋭䉣䊈䊦䉩䊷ᛛⴚ䈫䈚䈩ᵈ⋡䈘䉏䈩䈇䉎䇯Ꮏ႐ᑄᾲ䉕㔚ജ䈮ᄌ឵䈘䈞䉎䈢䉄䈮䈲䇮ᑄᾲ᷷ᐲ䈮䉋䉍ᐢ▸࿐䈱ᾲ㔚᧚ᢱ䈏ⷐ᳞䈘䉏䉎䈏䇮㋕㍑Ꮏ႐䈱႐ว䇮ᾲᑧടᾲἹឃᾲ╬ 300䌾600oC 䈱䉋䈉䈭ਛ᷷▸࿐䈪ല₸䈱⦟䈇ᾲ㔚ᄌ឵᧚ᢱ䈏ਇนᰳ䈪䈅䉎䇯ᓥ᧪䇮ਛ᷷㗔ၞ䈪㜞䈇ᕈ⢻䉕␜䈜 PbTe ♽᧚ᢱ䈏ᬌ⸛䈘䉏䈩䈇䈢䈏䇮Pb 䈲ⅣႺᳪᨴ‛⾰䈫䈚䈩૶↪䈏೙㒢䈘䉏䈩䈇䉎䈢䉄䇮ᣂ䈚䈇㜞ᕈ⢻ⅣႺ⺞๺ဳᾲ㔚᧚ᢱ䈱㐿⊒䈏ⷐ᳞䈘䉏䉎䇯
ㄭᐕ䇮ඨዉ૕ൻว‛ Zn4Sb3 䈲 p ဳᾲ㔚᧚ᢱ䈫䈚䈩ਛ᷷㗔ၞ䈪ఝ䉏䈢ᾲ㔚ᕈ⢻䉕␜䈜䈖䈫䈏᣿䉌䈎䈮䈘䉏䈩䈇䉎䇯଀䈋䈳䇮400oC 䈪䈲 Zn4Sb3 ൻว‛䈱ήᰴరᾲ㔚ᕈ⢻ᜰᢙ ZT=1.3 䈫䈇䈉㜞䈇୯䉕␜䈚䈩䈍䉍 1)䇮㋕㍑Ꮏ႐╬↥ᬺ䉇᳃↢ಽ㊁䈎䉌ᝥ䈩䉌䉏䈩䈇䉎ᑄᾲ䉕㔚᳇䉣䊈䊦䉩䊷䈮⋥ធᄌ឵䈜䉎ᔕ↪䈏ᦼᓙ䈘䉏䈩䈇䉎䇯Zn4Sb3 䊋䊦䉪᧚䈱૞⵾䈮䈧䈇䈩䇮䈖䉏䉁䈪ṁ⵾ᴺ 2,3)䉇䊖
䉾䊃䊒䊧䉴ᴺ 1,4-7)䉕ਛᔃ䈮⎇ⓥ䈏ㅴ䉄䉌䉏䈩䈇䉎䇯䈚䈎䈚䈭䈏䉌䇮䈖䉏䉌䈱ᚑᒻᛛⴚ䈪䈲䇮㜞᷷䈪
Zn4Sb3 䈱⋧ᄌᘒ䈮䉋䉎૕Ⓧᄌൻ䉇ᾲ⤘ᒛ₸䈱㆑䈇䈏↢䈛䉎䈢䉄䇮⹜ᢱ䈮䉪䊤䉾䉪䈏౉䉍䉇䈜䈇 8)䇯
䉁䈢䇮㐳ᤨ㑆㜞᷷ㆊ⒟䈮䉋䉎 Zn4Sb3 ⋧䈱ಽ⸃䇮䈠䉏䈮઻䈉 Zn 䈫 ZnSb ⋧䈱↢ᚑ䇮Zn 䈱⫳⊒䈮䉋䉎⚵ᚑ䉇⚵❱䈱ᄌൻ䇮ᾲ㔚ᕈ⾰䈱ૐਅ䈭䈬䈏ᄢ䈐䈭໧㗴䈫䈭䈦䈩䈇䉎䇯䈘䉌䈮䇮䈇䈝䉏䈱ᣇᴺ䈮
䈍䈇䈩䉅䇮วᚑ䈘䉏䈢᧚ᢱ䈱ᒝᐲ䈲ૐ䈒䇮⣀䈒䈩⎕უ䈚䉇䈜䈇໧㗴ὐ䈏䈅䉎䇯㋕㍑Ꮏ႐ᑄᾲ䉕೑↪䈜䉎ᾲ㔚ᄌ឵ᛛⴚ䉕ታ↪ൻ䈜䉎䈢䉄䈮䈲䇮ⅣႺ⽶⩄ర⚛䉕฽䉁䈭䈇㜞ᕈ⢻ᾲ㔚᧚ᢱ䈍䉋䈶䈠䈱ᚑᒻടᎿ䊒䊨䉶䉴䉕㐿⊒䈚䈭䈔䉏䈳䈭䉌䈭䈇䇯䈠䈖䈪䇮ᧄ⎇ⓥ䈪䈲䇮☳ᧃ䈱䇸෻ᔕ㪄᛼಴䈚䊒䊨䉶䉴䇹䉕ឭ᩺䈚䇮ᾲ㑆᛼಴䈚䈮䈍䈇䈩 Zn 䈫 Sb ☳ᧃ㑆䈱෻ᔕ䈮䉋䉎 Zn4Sb3ᾲ㔚ൻว‛䈱วᚑ䇮䈍䉋䈶႟ᕈടᎿ䈮䉋䉎ᒻ⁁ઃਈ䈫✺ኒൻ䉕หᤨ䈮ታ⃻䈜䉎䈖䈫䉕࿑䉎䇯
Zn4Sb3 䊋䊦䉪᧚䈱᛼಴䈚ᚑᒻ᜼േ䇮⋧䊶⚵❱䇮䈍䉋䈶ᾲ㔚ᕈ⾰䊶ᯏ᪾⊛ᕈ⾰䈮෸䈿䈜᛼಴䈚ടᎿ䊌䊤䊜䊷䉺䉇ᒝൻ╙ੑ⋧䈱ᓇ㗀䉕᣿䉌䈎䈮䈜䉎䈖䈫䉕⋡⊛䈫䈚䈢䇯ታ㛎᧦ઙ߅ࠃ߮ᣇᴺ
ᧄ⎇ⓥ䈪䈲䇮಴⊒ේᢱ䈫䈚䈩䇮੝㋦(Zn)䈫䉝䊮䉼䊝䊮(Sb)䈱 2 ⒳㘃䈱㊄ዻ☳ᧃ䉕↪䈇䈢䇯Zn 䈫Sb ☳ᧃ䈱ᐔဋ☸ᓘ䈲䈠䉏䈡䉏 45 Pm 䈫 9Pm 䈪䈅䉎䇯䉁䈢䇮ᯏ᪾⊛ᕈ⾰䉕ᡷༀ䈜䉎䈖䈫䉕ਥ䈭⋡⊛䈫䈚䈩䇮ᐔဋ☸ᓘ 50nm 䈱 SiC ☳ᧃ䉕ᒝൻ⋧䈫䈚䈩↪䈇䈢䇯ήᷝട᧚䈱႐ว䇮Zn 䈫 Sb ☳ᧃ䉕䊗䊷䊦䊚䊦䈮䉋䉍ᷙว䈚䈢䈏䇮SiC 䊅䊉☸ሶ䉕ᷝട䈚䈢႐ว䇮䉣䉺䊉䊷䊦ਛ䈪⿥㖸ᵄಽᢔ䈮䉋䉍
SiC ☸ሶ䉕ಽᢔ䊶ᷙว䈚䈢䇯ੇ῎ᓟ䈱ᷙว☳ᧃ䉕㊄ဳ䈮䉋䉍࿶☳䈚䇮㊄ዻ䉲䊷䉴䈮⌀ⓨኽ౉䈚䈢䇯⌀ⓨኽ౉䈚䈢䊎䊧䉾䊃䉕
673䌾723 K䇮᛼಴䈚Ყ 5䌾25䇮᛼಴䈚ㅦᐲ 1䌾10 mm/min 䈱᧦ઙ䈪ᾲ㑆᛼಴䈚䉕ⴕ䈦䈢䇯䈖䈖䈪䈲᛼಴䈚ᠲ૞䉕ᣉ䈜೨䈱ടᾲᲑ㓏䈪䉮䊮䊁䊅ౝ䈮䈍䈔䉎 Zn 䈫 Sb 䈫䈱ൻቇ෻ᔕ䈮䉋䉍 Zn4Sb3 ൻว‛䉕วᚑ䈚䇮䈠䈱ᓟ䇮ᾲ㑆᛼಴䈚䈮䉋䉍 Zn4Sb3 ൻว‛䈱✺ኒൻ䈫ᒻ⁁ઃਈ䉕หᤨ䈮ታ⃻䈜䉎㧙㧙⹜䉂䉕ⴕ䈦䈩䈇䉎䇯᛼಴䈚ᚑᒻ䈚䈢⹜ᢱ䈮䈧䈇䈩䇮X ✢࿁᛬䈮䉋䉍⚿᥏⋧䈱หቯ䇮SEM 䈮䉋䉍⚵❱ⷰኤ䇮䉝䊦䉨䊜䊂䉴ᴺ䈮䉋䉍ኒᐲ䈱᷹ቯ䉕ⴕ䈦䈢䇯䉁䈢䇮䉷䊷䊔䉾䉪ଥᢙ䉕ቯ᷷௑ᢳᴺ䇮㔚᳇ᛶ᛫₸䉕 4 ┵ሶᴺ䇮ᾲવዉ₸䉕䊧䊷䉱䊐䊤䉾䉲䊠ᴺ䈮䉋䉍䈠䉏䈡䉏᷹ቯ䈚䇮ήᰴరᾲ㔚ᕈ⢻ᜰᢙ(ZT)䉕ᰴᑼ䈮䉋䉍᳞䉄䈢䇯

ZTD 2TUN(1)䈖䈖䈪䇮D 䈲䉷䊷䊔䉾䉪ଥᢙ䇮U䈲㔚᳇ᛶ᛫₸䇮N䈲ᾲવዉ₸䇮T 䈲⛘ኻ᷷ᐲ䈪䈅䉎䇯䈘䉌䈮䇮䊎䉾䉦䊷䉴⎬䈘䇮4 ὐᦛ䈕⹜㛎䈮䉋䉍ᦛ䈕ᒝᐲ䇮࿶ሶ࿶౉ᴺ(IF ᴺ)䈮䉋䉍⎕უ㕤ᕈ╬ᯏ᪾⊛ᕈ⾰䉅⹏ଔ䈚䈢䇯ታ㛎⚿ᨐ߅ࠃ߮⠨ኤ
Fig. 1 䈮䇮᛼಴䈚᷷ᐲ T = 723 K䇮᛼಴䈚Ყ R = 7 䈱᧦ઙ䈪᛼಴䈚ᚑᒻ䈚䈢႐ว䈱࿶ജ䋭䉴䊃䊨䊷䉪ᦛ✢䉕␜䈜䇯1%SiC ☸ሶ䉕ᷝട䈚䈢ᣇ䈏䇮ήᷝട䈱䉅䈱䉋䉍ᦨᄢ᛼಴䈚࿶ജ䈲䉇䉇㜞䈇䈏䇮ਔ⠪䈱ᦛ✢䈲㕖Ᏹ䈮ૃ䈩䈇䉎䇯᛼಴䈚࿶ജ䋭䉴䊃䊨䊷䉪ᦛ✢䈮䈲 B䇮C䇮D䇮E 䈱䈠䉏䈡䉏䈱ὐ䉕Ⴚ䈫䈚䈩㆑䈦䈢௑ะ䈏⷗䉌䉏䉎䇯A ὐ䈎䉌 B ὐ䉁䈪䈲䇮᛼಴䈚ᠲ૞䉕ᣉ䈜⋥೨䈱ടᾲᲑ㓏䈪

Extrusion Pressure (MPa)Zn4Sb3 ࡃ࡞ࠢ᧚ߩ᛼಴ߒ᜼േߣ⚵❱

300CD200B100
A00Zn 䈫 Sb ☳ᧃ㑆䈱ൻቇ෻ᔕ䈮䉋䉍↢ᚑ䈚䈢
Zn4Sb3 ൻว‛☳ᧃ䈏࿶ኒ䈘䉏䉎䈫หᤨ䈮䇮㊄ዻ䉲䊷䉴䈏႟ᕈᄌᒻ䈜䉎䈖䈫䈮䉋䉍࿶ജ䈏ᕆỗ䈮Ⴧട䈚䈢䇯䈠䈱ᓟ䇮B ὐ䈪䈲㊄ዻ

E

1020Stroke (mm)30Fig. 1 Extrusion pressure vs. stroke curves under
the conditions of R = 7 at 723 K. The solid anddotted lines correspond to the curves without andwith 1%SiC addition, respectively.

䉲䊷䉴᧚䈏᛼䈚಴䈘䉏䇮䊏䊷䉪࿶ജ䈱 C ὐ䈎䉌 Zn4Sb3 ൻว‛䈏᛼䈚಴䈘䉏䈲䈛䉄䇮C䌾D 䈪䈲 Zn4Sb3 䈫䉲䊷䉴᧚䈏หᤨ䈮᛼䈚಴䈘䉏䈢䇯䉁䈢䇮᛼಴䈚䈱ㅴⴕ䈮䈚䈢䈏䈦䈩䇮䊎䊧䉾䊃䈫䉮䊮䊁䊅䈫䈱ធ⸅㕙Ⓧ䈱ᷫዋ䈮䉋䉍៺ᡂജ䈏ૐਅ䈚䇮⚿ᨐ䈫䈚䈩᛼಴䈚࿶ജ䈏ᷫዋ䈚䈩䈇䉎䇯Dὐ䈪䈲 Zn4Sb3 ൻว‛䈏䈜䈼䈩᛼䈚಴䈘䉏䈢䈢䉄࿶ജ䈲ᕆỗ䈮⪭䈤䇮䈠䈱ᓟ䇮E ὐએ㒠䈲䉲䊷䉴᧚䈱䉂䈏᛼䈚಴䈘䉏䈩䈇䉎䈖䈫䈮ኻᔕ䈚䈩䈇䉎䇯䈭䈍䇮᛼಴䈚Ყ䈱Ⴧട䉇᛼಴䈚᷷ᐲ䈱ᷫዋ䈮઻䈦䈩᛼಴䈚࿶ജ䈱䊧䊔䊦䈏਄᣹䈜䉎䈖䈫䈏䉒䈎䈦䈢 9),10)䇯
৻ᣇ䇮᛼಴䈚ᚑᒻ䈚䈢⹜ᢱ䈱ኒᐲ䈮䈧䈇䈩䈲䇮R 㻠㩷 7䇮T = 723 K 䈱᧦ઙਅ䈪䇮SiC ☸ሶᷝട䈱᦭ή䈮䈎䈎䉒䉌䈝䇮99%એ਄䈱㜞䈇⋧ኻኒᐲ䉕᦭䈜䉎᛼಴䈚䊋䊦䉪᧚䈏ᓧ䉌䉏䈢䇯䉁䈢䇮ᚑᒻ䈚䈢⹜ᢱ䈲䇮ᄖⷰ਄ᰳ㒱䈏䈭䈒䇮ஜో䈪䈅䉎䈖䈫䈏⏕⹺䈘䉏䈢䇯
Fig. 2 䈮䇮⇣䈭䉎 SiC ᷝട㊂䉕᦭䈚䇮723 K 䈪᛼಴䈚䈮䉋䉍ᚑᒻ䈚䈢⹜ᢱ䈱 XRD 䊌䉺䊷䊮䉕␜㧙㧙E: E-Zn4Sb3

Intensity (a.u.)

(d)

(c)

(b)
E
EE

(a)

2025E30EEE

EEEE

E354045

EE502ǰ(deg.)
Fig. 2 XRD patterns of hot-extruded Zn4Sb3 bulk samples containing (a) 0%,(b) 1%, (c) 3%, and (d) 5%SiC.

䈚䈢䇯ᧄታ㛎᧦ઙਅ䈪䇮SiC ☸ሶ䉕ᷝട䈚䈢⹜ᢱ䈲䇮ήᷝട䈱䉅䈱䈫䈾䈿ห᭽䈭 XRD 䊌䉺䊷䊮䉕␜䈚䇮න৻䈱E-Zn4Sb3 ⋧䈱䊏䊷䉪䈎䉌᭴ᚑ䈘䉏䈩䈇䉎䇯䈚䈢䈏䈦䈩䇮Zn 䈫 Sb 䈱ᷙว☳ᧃ䈏᛼಴䈚䈱Ბ㓏䈪⏕䈎䈮(2)ᑼ䈮␜䈚䈢ൻቇ෻ᔕ䈏⿠䈖䉍䇮Zn4Sb3 ⋧䈏↢ᚑ䈘䉏䈢䈖䈫䉕␜䈚䈩䈇䉎䇯䈭䈍䇮᣿⍎䈭 SiC ⋧䈱䊏䊷䉪䈏⷗䉌䉏䈭䈎䈦䈢䈖䈫䈲䇮SiC ☸ሶ䈱⚦䈎䈇䈖䈫䈍䉋䈶ᷝട㊂䈏ዋ䈭䈇䈖䈫䈮⿠࿃䈜䉎䈫⠨䈋䉌䉏䉎䇯
4 Zn + 3 Sb ĺ Zn4Sb3(2)ᾲ㑆᛼಴䈚䈪ᚑᒻ䈚䈢 Zn4Sb3 ൻว‛䈱⚵❱䈮䈧䈇䈩䈲䇮᛼಴䈚䈮䉋䉍ᄢ䈐䈭႟ᕈ䈵䈝䉂䉕ਈ䈋䈢䈮䉅᜔䉌䈝䋬᛼಴䈚ᣇะ䈮㗼⪺䈮ᑧ䈶䈢⚿᥏☸䈏ⷰኤ䈘䉏䈝䋬ᓸ⚦䈭╬ゲ⚿᥏☸䉕᦭䈜䉎⚵❱䈏ᒻᚑ䈘䉏䈢䈖䈫䉕⏕⹺䈚䈢䋮䈖䉏䈲ᾲ㑆᛼಴䈚䈮䈍䈔䉎േ⊛ౣ⚿᥏䈍䉋䈶᛼಴䈚⋥ᓟ䈱㕒⊛ౣ⚿᥏䈮䉋䉎䉅䈱䈫ᕁ䉒䉏䉎䇯Fig. 3(a)䈫(b)䈲䇮䈠䉏䈡䉏ήᷝട䇮1%SiC 䉕ᷝട䈚䈢᛼಴䈚᧚䉕 4 ὐᦛ䈕⹜㛎ᓟ䈱⎕ᢿ㕙䈱 SEM ౮⌀䈪䈅䉎䇯ήᷝട᧚䈱⎕㕙䈲Ყセ⊛Ṗ䉌䈎䈪䈅䉎䈱䈮ኻ䈚䇮1%SiC ☸ሶ䉕ᷝട䈚䈢⹜ᢱ䈱⎕㕙䈏☻䈒䈭䈦䈢䇯䉁䈢䇮䈠䉏䈡䉏䈱᜛ᄢ౮⌀(Fig. 3(c)䈫
(d))䈎䉌⷗䉌䉏䉎䉋䈉䈮䇮SiC ☸ሶ䉕ᷝട䈚䈢႐ว䇮⚿᥏☸䈱䉰䉟䉵䈏ዊ䈘䈒䈭䉍䇮⚿᥏☸ౝ䈍䉋䈶☸⇇䈪 SiC 䊅䊉☸ሶ䈏ಽᢔ䈚䈩䈇䉎䈖䈫䈏ಽ䈎䉎䇯䈖䉏䉌䈱䈖䈫䈲䇮ᓟㅀ䈜䉎 SiC 䊅䊉☸ሶ䈱ᷝട
䈮䉋䉎 Zn4Sb3 ൻว‛䈱⎕უ㕤ᕈ䈱ᡷༀ䈮ነਈ䈜䉎䈫ᕁ䉒䉏䉎䇯 Zn4Sb3 ࡃ࡞ࠢ᧚ߩᾲ㔚ᕈ⾰ߦ෸߷ߔ᛼಴ߒࡄ࡜ࡔ࡯࠲߅ࠃ߮ SiC ☸ሶᷝടߩᓇ㗀
 Fig. 4 䈲䇮⇣䈭䉎᧦ઙ䈪᛼಴䈚ᚑᒻ䈚䈢 Zn4Sb3 䊋䊦䉪᧚䈱䉷䊷䊔䉾䉪ଥᢙ䈫㔚᳇ᛶ᛫₸̓䈱᷷㧙㧙

(a)(b)(c)(d)

䊔䉾䉪ଥᢙ䇮㔚᳇ᛶ᛫₸䈫䉅䈮᷷ᐲ䈱਄᣹䈮઻䈦䈩Ⴧട䈜䉎௑ะ䈏⷗䉌䉏䉎䈏䇮᛼಴䈚⵾ຠ䈱䉷䊷䊔䉾䉪ଥᢙ䈮෸䈿䈜᛼಴䈚Ყ䉇᛼಴䈚ㅦᐲ╬᧦ઙ䈱ᓇ㗀䈏ዊ䈘䈇䈖䈫䉕␜䈚䈩䈇䉎䇯䈚䈎䈚䈭䈏䉌䇮㔚᳇ᛶ᛫₸䈻䈱᛼಴䈚ടᎿ䊌䊤䊜䊷䉺䈱ᓇ㗀䈏ᄢ䈐䈇䈖䈫䈏 Fig. 4 䈎䉌ಽ䈎䉎䇯᛼಴䈚Ყ

250

3200

2.5

150

21001.5‫ڈ‬٨ R=7, V=1mm/min٠䂹 R=7, V=10mm/min
䂦䂥 R=25, V=1mm/min

500300400䈏৻ቯ䈱႐ว䇮᛼಴䈚ㅦᐲ䈏ዊ䈘䈇䈾䈬䇮㔚᳇ᛶ᛫₸䈏ૐ䈇䇯䈖䉏䈲᛼಴䈚䈮䈍䈔䉎ౣ⚿᥏䈫࿁ᓳ䈮㑐ଥ䈜䉎䈫ᕁ䉒䉏䉎䇯᛼಴䈚ㅦᐲ䈏ㆃ䈒䈭䉎䈫䇮᛼䈚಴䈘䉏䉎᧚ᢱ䈮ሽ࿷䈜䉎ᩰ

500

Temperature (K)6001Electrical resistivity (m : cm)

ᐲଐሽᕈ䉕␜䈚䈢䉅䈱䈪䈅䉎䇯䉷䊷

Seebeck coefficient (PV/K)

Fig. 3 SEM images of the Fracture surfaces of extruded Zn4Sb3 samples after 4-point bending
tests. (a) 0%SiC and (b) 1%SiC. (c) and (d) are magnified images for the areas of the whiteframes shown in (a) and (b), respectively.

0.5

Fig. 4 Temperature dependence of the Seebeck coefficient and electrical resistivity of extruded Zn4Sb3 samples.
The filled and unfilled symbols indicate electricalresistivity and Seebeck coefficient, respectively.

ሶᰳ㒱䈏䉋䉍ዋ䈭䈒䈭䉍䇮⚿ᨐ䈫䈚䈩䇮㔚᳇ᛶ᛫₸䈏ૐ䈒䈭䉎䇯
৻ᣇ䇮Fig. 4 䈎䉌ಽ䈎䉎䉋䈉䈮䇮᛼಴䈚Ყ䈏ᄢ䈐䈇႐ว(R = 25)䈪䉅䇮ᚑᒻ䈚䈢 Zn4Sb3 䊋䊦䉪᧚䈱㔚᳇ᛶ᛫₸䈏ዊ䈘䈒䈭䈦䈢䇯೨ㅀ䈚䈢䉋䈉䈮䇮᛼಴䈚䈮䈍䈔䉎േ⊛䈍䉋䈶㕒⊛ౣ⚿᥏䈮䉋䈦䈩䇮㧙㧙⚦䈎䈇⚿᥏☸䉕᦭䈜䉎⚵❱䈏ᒻᚑ䈘䉏䈢䇯䉁䈢䇮᛼಴䈚Ყ䈏ᄢ䈐䈇䈾䈬䇮⚿᥏☸ᓘ䈏ዊ䈘䈒䈭䉎௑ะ䉅䈅䈦䈢䇯⚿᥏☸⇇ᢔੂ䊜䉦䊆䉵䊛䈮䉋䉎䈫䇮ᄙ⚿᥏᧚ᢱ䈮䈍䈇䈩䇮㔚᳇ᛶ᛫₸䈏⚿᥏☸ᓘ䈱ᷫዋ䈮઻䈦䈩Ⴧട䈜䉎䈫䈇䈉䈖䈫䈏䉋䈒⍮䉌䉏䈩䈇䉎䇯Ueno 䉌 7)䈲䇮䊖䉾䊃䊒䊧䉴䈮䉋䉍૞⵾䈚䈢
Zn4Sb3 ൻว‛䈱႐ว䇮⚿᥏☸⇇䈱㔚᳇ᛶ᛫₸䈻䈱⽸₂䈏ᭂ䉄䈩ዊ䈘䈇䈖䈫䉕␜䈚䈢䇯ᧄታ㛎䈱႐ว䇮㜞᛼಴䈚Ყ䈪ᚑᒻ䈚䈢 Zn4Sb3 䊋䊦䉪᧚䈱㔚᳇ᛶ᛫₸䈱ૐਅ䈲䇮ᾲ㑆᛼಴䈚䈮䈍䈇䈩ᒻᚑ䈚䈢᭽䇱䈭ᩰሶᰳ㒱(଀䈋䈳䇮ⓨ㓗䉇ㅒ䉰䉟䊃ᰳ㒱(anti-site defects 11,12)䇮ォ૏䇮ᄌᒻ⺃⿠᭴ㅧᰳ㒱 13)╬)䈮㑐ㅪ䈜䉎䈫⠨䈋䉌䉏䉎䇯ᾲવዉ₸䈮㑐䈚䈩䈲䇮᛼಴䈚Ყ䈏 1 mm/min 䈱႐ว䇮᷷ᐲ䈱Ⴧട䈮઻䈦䈩ᾲવዉ₸䈱୯䈏ᄢ䈐䈒ᄌൻ䈞䈝䇮⚂ 0.75 W/mK 䈪䈅䈦䈢䇯᛼಴䈚ㅦᐲ䈏ㅦ䈒䈭䉎䈫䇮଀䈋䈳 10 mm/min 䈱႐ว䇮423 K એ਄䈪ᾲવዉ₸䈏᷷ᐲ䈱Ⴧട䈫䈫䉅䈮਄᣹䈚䈩䈇䉎௑ะ䈏⷗䉌䉏䉎䇯
Fig. 5 䈮ήᰴరᾲ㔚ᕈ⢻ᜰᢙ ZT 䈱2䊂䊷䉺䈮Ყ䈼䇮᷹ቯ䈱᷷ᐲ▸࿐䈮䈍䈇䈩䇮ᧄታ㛎䈪ᓧ䉌䉏䈢 Zn4Sb3 ᛼಴䈚䊋䊦䉪᧚䈱ᣇ䈏㜞䈇 ZT ୯䉕␜䈚䈩䈇䉎䇯᛼಴䈚ㅦᐲ䈱㆑䈇䈮䈧䈇䈩䇮423 K એਅ䈪䈲䇮ㅦᐲ䈱㆑䈇䈮䉋䉎 ZT䈻䈱ᓇ㗀䈏䈾䈫䉖䈬⷗䉌䉏䈭䈇䈏䇮䈠䈱ᓟ䇮ㅦᐲ䈱ૐ䈇(1 mm/min)ᣇ䈏㜞䈇 ZT ୯䉕␜䈚䈢䇯․䈮䇮623 K 䈪 ZT =1.77 䈫䈇䈉ᦨᄢ୯䉕ᓧ䈩䈇䉎䇯䈖䈱୯

Figure of merit, ZT᷷ᐲᄌൻ䉕␜䈚䈢䇯Caillat 䉌 1)䈱ታ㛎

1.5‫ ڈ‬V=1mm/min٠ V=10mm/min

1Ref. [1]

0.5
0300

᛼಴䈚ᚑᒻ䈚䈢 Zn4Sb3 䊋䊦䉪᧚䈲䊖䉾䊃䊒䊧䉴᧚䉋䉍ᾲવዉ₸䈱୯䈏䉇䉇ᄢ䈐䈇䈮䉅᜔䉌䈝䇮䉋䉍㜞䈇 ZT ୯䉕᦭䈜

500

600

Temperature (K)䈲䇮ᓥ᧪䈱䊖䉾䊃䊒䊧䉴᧚(673 K 䈪 ZT= 1.3)䉋䉍⚂ 36%਄᣹䈚䈢䇯ᧄታ㛎䈪

400

Fig. 5 Temperature dependence of dimensionlessthermoelectric figure of merit of extruded Zn4Sb3samples. The inserted curve indicates the resultsreported by Caillat et al 1).

䉎䈱䈲䇮䉷䊷䊔䉾䉪ଥᢙ䈏ᄢ䈐䈇䈖䈫䇮䈍䉋䈶㔚᳇ᛶ᛫₸䈏ૐ䈇䈖䈫䈮䉋䉎䉅䈱䈪䈅䉎䇯䈖䉏䈲᛼಴䈚ᚑᒻ䈚䈢⵾ຠ䈱㜞ኒᐲ䈮⿠࿃䈜䉎䈫ᕁ䉒䉏䉎䇯䉅䈉৻䈧䈱ℂ↱䈲䇮ᧄታ㛎䈱႐ว䇮ේᢱ☳ᧃ䈏㊄ዻ䉲䊷䉴䈮ኽ౉䈘䉏䈢䈢䉄䇮ᾲ㑆᛼಴䈚Ბ㓏䈪䈱㉄ൻ䈏ዋ䈭䈒䇮ᚑᒻ䈚䈢 Zn4Sb3 ൻว‛䈮䈍䈔䉎㉄⚛฽᦭㊂䈏ᭂ䉄䈩ૐ䈇䈖䈫䈮䉋䉎䈫ᕁ䉒䉏䉎䇯೨ㅀ䈚䈢䉋䈉䈮䇮Zn4Sb3 ൻว‛䈲ఝ䉏䈢ᾲ㔚ᕈ⾰䉕᦭䈜䉎䈏䇮ᯏ᪾ᒝᐲ䈏ૐ䈒䇮⣀䈒䈩⎕უ䈚䉇䈜䈇໧㗴ὐ䈏䈅䉎䇯ᧄታ㛎䈪䈲ᯏ᪾⊛ᕈ⾰䈱ᡷༀ䈮⌕⋡䈚䇮ᒝൻ೷䈫䈚䈩䊅䊉䉰䉟䉵䈱 SiC☸ሶ䉕↪䈇䈢䇯Fig. 6 䈮 SiC 䈱ᷝട㊂䈗䈫䈱䉷䊷䊔䉾䉪ଥᢙ䈫㔚᳇ᛶ᛫䈱᷷ᐲଐሽᕈ䉕␜䈚䈢䇯
SiC ☸ሶ䉕ᷝട䈚䈢⹜ᢱ䈱䉷䊷䊔䉾䉪ଥᢙ䈲䇮ήᷝട䈱䉅䈱䈮Ყ䈼䈩㜞䈒䈭䉎௑ะ䉕␜䈚䈢䇯․䈮䇮⚂ 450K એ਄䈪 SiC 䈱ᷝട䈮䉋䉎䉷䊷䊔䉾䉪ଥᢙ䈱Ⴧട䈏㗼⪺䈪䈅䉎䇯ήᷝട䈱䉅䈱䉋䉍Ⴧട䈚䈢ේ࿃䈫䈚䈩䈲䇮ේᢱ☳ᧃ䈱☸ᓘ䈍䉋䈶 SiC ☸ሶ䈱ሽ࿷䈮䉋䉎⚿᥏☸䈱ᓸ⚦ൻ䈮䉋䉎䉅䈱䈫⠨䈋䉌䉏䉎䇯ᧄታ㛎䈪䈲䇮⿥㖸ᵄಽᢔ㪄䊗䊷䊦䊚䊦䈫䈇䈉☳ᧃᷙว䊒䊨䉶䉴䉕↪䈇䉎䈖䈫䈮䉋䉍䇮☳㧙㧙ᣇ䇮㔚᳇ᛶ᛫₸䈮䈧䈇䈩䈲䇮
1%SiC ☸ሶ䉕ᷝട䈚䈢⹜ᢱ䈪䈲⧯ᐓૐਅ䈚䈢䈏䇮5%䈱႐ว䇮㔚᳇ᛶ᛫₸䈏㜞䈒䈭䈦䈢䇯㔚᳇ᛶ᛫₸䈱Ⴧട䈲䇮SiC ☸ሶ䈮䉋䉎ᢔੂ䈍䉋䈶⚿᥏☸ᓘ䈱ᓸ⚦ൻ䈮䉋䉎☸⇇ᢔੂ䈏↢䈛䉎䈢䉄

250

3200

2.5

150

2100

1.50䈫ℂ⸃䈪䈐䉎䈏䇮1%SiC ᷝട䈮䇳䃂 0%SiC
䂺䂹 1%SiC
䂦䂥 5%SiC50䉋䉎㔚᳇ᛶ᛫₸䈱ૐਅ䈲䇮Fig.

300

400
500
600
Temperature (K)4 䈮␜䈚䈢᛼಴䈚Ყ䈱Ⴧട䈮䉋䉎ૐਅ䈮ૃ䈩䈍䉍䇮੹ᓟᦝ䈭䉎

1Electrical resistivity 䋨m: cm䋩䈦䈩䈇䉎䈖䈫䈏⏕⹺䈘䉏䈢䇯৻

Seebeck coefficient (PV/K)ᧃ☸ᓘ䈲ඨಽ䈾䈬䉁䈪ዊ䈘䈒䈭

0.5

Fig. 6 Temperature dependence of the Seebeck coefficientand electrical resistivity of extruded Zn4Sb3 samples withdifferent amounts of SiC particles. The filled and unfilled
symbols indicate electrical resistivity and Seebeck coefficient,
respectively.

ᬌ⸛䈏ᔅⷐ䈪䈅䉎䇯
Fig. 7 䈮ᾲવዉ₸䈱᷹ቯ⚿ᨐ䉕␜䈜䇯ᾲવዉ₸䈲 SiC ☸
ሶ䈱ᷝട䈮䉋䉍Ⴧട䈚䈢䇯SiC䈱ᾲવዉ₸䈲 100W/mK એ਄䈫䇮

Zn4Sb3 䈮Ყ䈼䉎䈫䈲䉎䈎䈮㜞䈇୯䉕␜䈜䇯䈠䈱䈢䉄䇮SiC ☸ሶ䈱ዉ౉䉇䇮⚿᥏☸ᓘ䈏ዊ䈘䈒䈭䈦䈢䈖䈫╬䈮䉋䉎䊐䉤䊉䊮ᢔੂ䈱ᓇ㗀䉋䉍䉅䇮න⚐䈭ⶄวᾲવዉ₸䈱ᄢ䈐䈘䈱ᓇ㗀䈱ᣇ䈏ᄢ䈐䈒䈭䉍䇮ో૕䈫䈚䈩ᾲવዉ₸䈲Ⴧട䈚䈢䉅䈱䈫⠨䈋䉌䉏䉎䇯䈚䈎䈚䈭䈏䉌䇮1%ᷝട䈫 5%ᷝട䈪䈘䈋䈠䉏䈾䈬ᄢ䈐䈭㆑䈇䈲䈭䈒䇮Zn4Sb3 䈱․ᱶ䈭⚿᥏᭴ㅧ䈮⿠࿃䈜䉎ᾲવዉ₸䈻䈱ᓇ㗀䈏ᄢ䈐䈇䉅䈱䈫⠨䈋䉌䉏䉎䇯

1.2

2

1
0.8
0.6
䇳 0%SiC
䂺 1%SiC
䂦 5%SiC

0.40.2

300

400
500
Temperature (K)Figure of merit, ZT

Thermal conductivity (W/mK)

1
䇳 0%SiC
䂺 1%SiC
䂦 5%SiC

0.50600

Fig. 7 Temperature dependence of thermal conductivity of Zn4Sb3 samples with different
amounts of SiC particles.

1.5300400500
Temperature (K)600

Fig. 8 Temperature dependence of dimensionlessthermoelectric figure of merit of extruded Zn4Sb3samples with different amounts of SiC particles.

㧙㧙

Fig. 8 䈲䇮ήᰴరᾲ㔚ᕈ⢻ᜰᢙ ZT 䈱᷷ᐲଐሽᕈ䉕␜䈚䈢䉅䈱䈪䈅䉎䇯1%ᷝട⹜ᢱ䈮䈧䈇䈩
䈲䇮500K એ਄䈪ήᷝട⹜ᢱ䈮Ყ䈼䈩 ZT 䈏Ⴧട䈚䇮623K 䈪 ZT=1.84 䈫䈭䈦䈢䇯Fig. 6䇮Fig. 7 䈮␜䈚䈢䉋䈉䈮䇮ᾲવዉ₸䈏Ⴧട䈚䈩䈇䈢䈏䇮䉷䊷䊔䉾䉪ଥᢙ䈱Ⴧട䈍䉋䈶㔚᳇ᛶ᛫₸䈱ૐਅ䈱ᓇ㗀䈪䇮ో૕䈫䈚䈩 ZT 䈲Ⴧട䈚䈢䇯䈚䈎䈚䈭䈏䉌䇮5%ᷝട⹜ᢱ䈪䈲ᄢ䈐䈭 ZT 䈱ૐਅ䉕␜䈚䈢䇯 Zn4Sb3 ࡃ࡞ࠢ᧚ߩᯏ᪾⊛ᕈ⾰ߦ෸߷ߔ SiC ࠽ࡁ☸ሶᷝടߩᓇ㗀
Fig. 9 䈮᛼಴䈚ᚑᒻ䈚䈢 Zn4Sb3 䊋䊦䉪᧚䈱䊎䉾䉦䊷䉴⎬䈘䈫 SiC ☸ሶ䈱ᷝട㊂䈫䈱㑐ଥ䉕␜䈚䈢䇯SiC ᷝട㊂䈱Ⴧട䈮䈧䉏䈩䇮䊎䉾䉦䊷䉴⎬䈘䈲਄᣹䈚䈩䈇䉎䈖䈫䈏䉒䈎䉎䇯䈖䉏䈲 SiC ☸ሶ⥄り䈱ಽᢔᒝൻലᨐ䇮䈍䉋䈶 SiC ☸ሶ䈱ሽ࿷䈮䉋䉎 Zn4Sb3 ⚿᥏☸ᚑ㐳䈱ᛥ೙䈮઻䈉ᓸ⚦ൻ䈮⿠࿃䈜䉎䈫ᕁ䉒䉏䉎䇯Fig. 10 䈲䇮4 ὐᦛ䈕⹜㛎䈮䉋䉍᳞䉄䈢ᦛ䈕ᒝᐲ䈱ᄌൻ䉕␜䈚䈢䉅䈱䈪䈅䉎䇯
1%SiC ☸ሶ䉕ᷝട䈜䉎䈖䈫䈮䉋䉍ᦛ䈕ᒝᐲ䈏ᄢ䈐䈒ะ਄䈚䈢䈏䇮䈠䈱ᓟ䈘䉌䈮 SiC ☸ሶ䉕ᷝട䈜䉎䈫ᦛ䈕ᒝᐲ䈻䈱⽸₂䈏ዊ䈘䈒䈭䈦䈢䇯䈖䉏䈲䇮SiC ☸ሶ䈱䉰䉟䉵䈏ዊ䈘䈇䈱䈪䇮ᷝട㊂䈱Ⴧട䈮઻䈦䈩ಝ㓸䈏↢䈛䉇䈜䈒䈭䉎䈢䉄䈫⠨䈋䉌䉏䉎䇯
140
Flexural strength (MPa)Vickers hardness (HV)

280
260
240
220
012
3
4Volume fraction of SiC (%)

5Fig. 9 Vickers hardness of extruded Zn4Sb3
samples as a function of volume fraction ofSiC particles.

120
100
80
6001234Volume fraction of SiC (%)

5Fig. 10 Variation of flexural strength ofextruded Zn4Sb3 samples with volume
fraction of SiC particles.

䈭䈍䇮᛼಴䈚ᚑᒻ䈚䈢 Zn4Sb3 䊋䊦䉪᧚䈱⎕უ㕤ᕈ䈮䈧䈇䈩䈲䇮IF ᴺ䈮䉋䉍᷹ቯ䈚䈢⚿ᨐ䈎䉌䇮
1%SiC 䊅䊉☸ሶ䉕ᷝട䈜䉎䈖䈫䈮䉋䈦䈩䇮⎕უ㕤ᕈ䈏⚂ 50%ะ਄䈚䈢䈏䇮䈘䉌䈮 SiC ☸ሶ䈱㊂䉕Ⴧ䉇䈜䈫⎕უ㕤ᕈᡷༀ䈱ലᨐ䈏ዊ䈘䈒䈭䉎䈖䈫䉕␜䈚䈢䇯䈖䈱䉋䈉䈮䇮䊅䊉䉰䉟䉵䈱 SiC ☸ሶ䈱ዉ౉䈮䉋䉍㕤ᕈะ਄䈱௑ะ䈏⷗䉌䉏䉎䈏䇮⎕უ㕤ᕈ୯䈫䈚䈩䈲䉁䈣ዊ䈘䈒䇮䈘䉌䈭䉎ᡷༀ䈏ⷐ᳞䈘䉏䉎䇯੹ᓟ䈲䇮Zn4Sb3 䊋䊦䉪᧚䈱⎕უ㕤ᕈ䈮෸䈿䈜 SiC ☸ሶ䉰䉟䉵䈱ᓇ㗀䉕⸃᣿䈜䉎ᔅⷐ䈏䈅䉎䈫ᕁ䉒䉏䉎䇯એ਄䈱⚿ᨐ䈎䉌䇮䊅䊉䉰䉟䉵䈱 SiC ☸ሶ䉕 Zn4Sb3 䈮 1%ዉ౉䈜䉎䈖䈫䈮䉋䈦䈩䇮ᾲ㔚ᕈ⾰䈏ᡷༀ䈘䉏䉎䈫หᤨ䈮䇮⎬䈘䉇ᦛ䈕ᒝᐲ䉅ะ਄䈚䈢䇯ᷝട㊂䈏䈘䉌䈮Ⴧട䈜䉎䈫䇮ᾲ㔚ᕈ⾰䈮ᖡᓇ㗀䉕ਈ䈋䉎䈖䈫䈏ಽ䈎䈦䈢䇯㧙㧙⚿⸒ᧄ⎇ⓥ䈪䈲䇮Zn 䈫 Sb ☳ᧃ䉕಴⊒ේᢱ䈫䈚䈩↪䈇䇮☳ᧃ䈱䇸෻ᔕ㪄᛼಴䈚䊒䊨䉶䉴䇹䉕ᬌ⸛䈚䇮
Zn4Sb3 䊋䊦䉪᧚䈱᛼಴䈚ᚑᒻ᜼േ䈍䉋䈶ᾲ㔚ᕈ⾰䊶ᯏ᪾⊛ᕈ⾰䈮෸䈿䈜᛼಴䈚䊌䊤䊜䊷䉺䉇ᒝൻ╙ੑ⋧䈱ᓇ㗀䈮䈧䈇䈩⺞䈼䈢䇯ᾲ㑆᛼಴䈚䈱৻Ꮏ⒟䈪 Zn 䈫 Sb ☳ᧃ㑆䈱ൻቇ෻ᔕ䈮䉋䉎
Zn4Sb3 ൻว‛䈱วᚑ䇮䈍䉋䈶႟ᕈടᎿ䈮䉋䉎ᒻ⁁ઃਈ䈫✺ኒൻ䉕หᤨ䈮ታ⃻䈜䉎䈖䈫䈏⏕⹺䈘䉏䈢䇯᛼಴䈚Ყ䉇᛼಴䈚ㅦᐲ╬䈱ടᎿ䊌䊤䊜䊷䉺䈲䇮Zn4Sb3 䊋䊦䉪᧚䈱ᾲ㔚ᕈ⾰䈮ᄢ䈐䈭ᓇ㗀䉕ਈ䈋䇮ᄢ䈐䈇᛼಴䈚Ყ䈍䉋䈶ㆃ䈇᛼಴䈚ㅦᐲ䈲᛼಴䈚⵾ຠ䈱ᾲ㔚ᕈ⾰䈱ะ਄䈮ነਈ䈜䉎䇯ᧄ⎇ⓥ䈱᧦ઙਅ䈪᛼಴䈚ᚑᒻ䈚䈢 Zn4Sb3 䊋䊦䉪᧚䈲䇮ᓥ᧪䈱䊖䉾䊃䊒䊧䉴᧚䈮Ყ䈼䇮ήᰴరᾲ㔚ᕈ⢻ᜰᢙ䈏⚂ 36%ะ਄䈚䈢䇯䉁䈢䇮䊅䊉䉰䉟䉵䈱 SiC ☸ሶ䉕 1%ዉ౉䈜䉎䈖䈫䈮䉋䈦䈩䇮ᾲ㔚ᕈ⾰䈏⧯ᐓᡷༀ䈘䉏䇮⎬䈘䉇ᦛ䈕ᒝᐲ䈭䈬ᯏ᪾⊛ᕈ⾰䉅ะ਄䈚䈢䇯੹ᓟ䇮᛼಴䈚ᚑᒻ䈚䈢 Zn4Sb3 䊋䊦䉪᧚䈱⎕უ㕤ᕈ䈱ᦝ䈭䉎ะ਄䈏ᔅⷐ䈪䈅䉎䇯⻢ㄉ㩷 㩷 㩷 ᧄ⎇ⓥ䉕ㆀⴕ䈜䉎䈮䈅䈢䉍䇮⽷࿅ᴺੱJFE21਎♿⽷࿅䈎䉌ᛛⴚ⎇ⓥഥᚑ䈱䈗ᡰេ䉕⾦䉍䉁䈚䈢䇯䈖䈖䈮⸥䈚䈩ᷓ⻢䈱ᗧ䉕⴫䈚䉁䈜䇯ෳ⠨ᢥ₂1) T. Caillat, J.-P. Fleurial and A. Borshchevsky, J. Phys. Chem. Solids, 58 (1997), 1119-1125.
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