㊀ὐ↥ᬺ೑↪⺖㗴ႎ๔ᦠ䇼ታᣉ⺖㗴⇟ภ䇽
2007A1922䇼ታᣉ⺖㗴ฬ䇽Ⱟశ EXAFS 䈮䉋䉎 high-k 䉭䊷䊃⛘✼⤑ HfSiON ਛ Hf ේሶ๟ㄝ䈱ዪᚲ᭴ㅧ⸃ᨆ䇼ታ㛎⠪ᚲዻᯏ㑐䈍䉋䈶ฬ೨䇽᧲੩ᄢቇᎿቇ⎇ⓥ⑼ ᔕ↪ൻቇኾ᡹ የ᎑ᱜᴦ䋨⽷䋩㜞ノᐲశ⑼ቇ⎇ⓥ䉶䊮䉺䊷 ↥ᬺ೑↪ផㅴቶ㩷 ᄢᷨඳት䇼૶↪䊎䊷䊛䊤䉟䊮䇽
BL01B1㩷 䋨ഀᒰ䉲䊐䊃ᢙ䋺6 䉲䊐䊃䋩䇼ታ㛎⋡⊛䇽ㅢᏱ LSI-CMOS 䊒䊨䉶䉴䈪䈲䇮ਇ⚐‛ᵴᕈൻ䈱䈢䉄䈮 1000㷄એ਄䈱㜞᷷䉝䊆䊷䊥䊮䉫䈏ᔅⷐਇนᰳ䈪䈅䉎䇯䈚䈎䈚䈭䈏䉌㜞᷷ਅ䈪䈲䇮HfO2 䈫 Si 䈫䈱෻ᔕ䈮䉋䉍 SiOx 䉇 HfSi2 䈭䈬䉲䊥䉰䉟䊄䈱ᒻᚑ䉇䇮䉝䊝䊦䊐䉜䉴 HfO2 ጀ䈱⚿᥏ൻ䈱䈢䉄䇮䊥䊷䉪㔚ᵹ䈏Ⴧᄢ䈜䉎䈫䈇䈉ᬺ⇇౒ㅢ䈱⺖㗴䈏ታ↪ൻ䈻䈱ᄢ䈐䈭㓚ኂ䈫䈭䈦䈩䈇䉎䇯䈖䈱໧㗴䈮ኻ䈚䇮HfSiO 䈱⓸ൻಣℂ䈮䉋䉎 HfSiON ⤑䈱ᒻᚑ䈫䈇䈉ᚻᴺ䈏㐿⊒䈘䉏䇮䈖䉏䈮䉋䉍㔚᳇⊛․ᕈ(㔚ሶ䊃䊤䉾䊒ኒᐲ)䈏ᡷༀ䈘䉏䉎䈖䈫䈏᣿䉌䈎䈫䈭䈦䈢䇯䈚䈎䈚䈭䈏䉌䇮䉲䊥䉰䉟䊄ᒻᚑ䉇⚿᥏ൻ䈭䈬䈱໧㗴䈲ቢో䈮䈲⸃᳿䈘䉏䈩䈇䈭䈇䇯䉁䈢䇮⓸ൻಣℂ䈱㓙䇮㉄⚛ᰳ៊䈏ᒻᚑ䈚䉇䈜䈇䈫䈇䈉ᣂ䈢䈭໧㗴䈏↢䈛䉎䇯䈖䈱䈢䉄૞⵾᧦ઙ䈱ᦨㆡൻ䈏ᕆോ䈫䈭䈦䈩䈇䉎䇯੹࿁䈱ታ㛎䈪䈲䇮⇣䈭䉎᧦ઙ䈪૞⵾䈘䉏䈢 HfSiON/SiON/Si ⤑䈮䈧䈇䈩䇮HfSiON ጀ䈱㉄⚛ᰳ៊䈱ഀว䇮෸䈶⚿᥏ൻ䈱ᐲว䈇䉕Ⱟశ EXAFS ᴺ䈮䉋䉍ቯ㊂䈜䉎䈖䈫䉕⹜䉂䈢䇯䇼ታ㛎ᣇᴺ䇽(1) XAFS ᷹ቯ᧦ઙ૶↪䊎䊷䊛䊤䉟䊮: BL01B1
ಽశེ⚿᥏: Si(111)䊚䊤䊷ⷺᐲ: 3.5 mrad
᷹ቯᣇᴺ: Ⱟశᴺ䇮ㅘㆊᴺᬌ಴ེ: 19 ⚛ሶ䉭䊦䊙䊆䉡䊛ඨዉ૕ᬌ಴ེ
᷹ቯๆ෼┵: Hf LΥ 9.22䌾10.30 keV䉴䊁䉾䊒᏷: 0.0005䌾0.005deg.
Ⓧ▚ᤨ㑆: 1 ὐ䈅䈢䉍 20䌾80 ⑽᷹ቯ᷷ᐲ䋺ቶ᷷
䉣䊈䊦䉩䊷ᩞᱜ: Cu-foil 䉴䊕䉪䊃䊦䈪䇮䉣䉾䉳䉳䊞䊮䊒䈱ਛὐ䉕 12.7185deg.䈫䈚䈢䇯(2) ᷹ቯ⹜ᢱ੹࿁᷹ቯ䈚䈢 HfSiON ⹜ᢱ䈱૞⵾᧦ઙ䉕⴫ 1 䈮␜䈜䇯A ␠䈱⹜ᢱ䈲䉲䊥䉬䊷䊃ൻ䈍䉋䈶⓸ൻಣℂ䉕ᣉ䈚䈢䉅䈱䈪䈅䉎䇯䉁䈢䇮B ␠䈱⹜ᢱ䈲⤑ෘ䈱⇣䈭䉎 HfSiON ਄䈮 poly-Si ጀ䉕ၸⓍ䈘䈞䈢䉅䈱
䈫䇮HfSiON ጀ䈱⓸ൻ䈱ᐲว䈇䉕ᄌൻ䈘䈞䈢䉅䈱䈪䈅䉎䇯䈇䈝䉏䈱 HfSiON ⹜ᢱ䉅Ⱟశᴺ䈮䈩᷹ቯ䈚䈢䇯䉁䈢䇮ᮡḰ⹜ᢱ䈫䈚䈩 BN 䈪Ꮧ㉼䈚䊕䊧䉾䊃⁁䈮䈚䈢 HfO2 ☳ᧃ⹜ᢱ䉕ㅘㆊᴺ䈮䈩᷹ቯ䈚䈢䇯䇼ታ㛎⚿ᨐ෸䈶⠨ኤ䇽(1)A ␠⹜ᢱ䈱 EXAFS ⸃ᨆ⚿ᨐA ␠⹜ᢱ䈱ⷙᩰൻ EXAFS 䉕࿑ 1䇮േᓘಽᏓ䉕࿑ 2 䈮␜䈜䇯䈇䈝䉏䈱⹜ᢱ䉅ᮡḰ⹜ᢱ䈫䈚䈩᷹ቯ䈚䈢 HfO2 ☳ᧃ⹜ᢱ䈱䉴䊕䉪䊃䊦䈮㘃ૃ䈚䈩䈇䉎䈖䈫䈏ಽ䈎䉎䇯䈖䈱䈖䈫䈎䉌䇮੹࿁᷹ቯ䈚䈢
HfSiON ⹜ᢱ䈲䇮HfO2 䈫ห᭽䇮ၮᧄ⊛䈮 Hf ๟ㄝ䈮 O 䈏㈩૏䈚䈢᭴ㅧ䉕ᒻᚑ䈚䈩䈇䉎䈫⠨䈋䉌䉏䉎䇯ฦ⹜ᢱ䈱䉦䊷䊑䊐䉞䉾䊁䉞䊮䉫⚿ᨐ䉕⴫ 2(a)䈮␜䈜䇯⸃ᨆ䈱⚿ᨐ䇮HfSiO 䈍䉋䈶 HfSiON ⹜ᢱ䈱㉄⚛䈱㈩૏ᢙ䈏 HfO2 ⹜ᢱ䈮Ყ䈼䈩ዊ䈘䈒䈭䉎䈖䈫䈏ಽ䈎䈦䈢䇯䈖䈱⚿ᨐ䈲䇮䉲䊥䉬䊷䊃ൻ䈍䉋䈶⓸ൻಣℂ䈮䉋䉍㉄⚛ᰳ៊䈏↢䈛䉎䈖䈫䉕␜ໂ䈜䉎䉅䈱䈪䈅䉎䇯䉁䈢䇮Debye-Waller ࿃ሶ䈮䈧䈇䈩䈲᦭ᗧ䈭㆑䈇䈲⷗䉌䉏䈝䇮⚿᥏ൻ䈱ᐲว䈇䈮ᄢ䈐䈭㆑䈇䈲䈭䈇䉅䈱䈫ᕁ䉒䉏䉎䇯(2)B ␠⹜ᢱ䈱 EXAFS ⸃ᨆ⚿ᨐ
B ␠⹜ᢱ䈱ⷙᩰൻ EXAFS 䉕࿑ 3-4䇮േᓘಽᏓ䉕࿑ 5-6 䈮␜䈜䇯A ␠⹜ᢱ䈫ห᭽䇮HfO2 ☳ᧃ⹜ᢱ䈱䉴䊕䉪䊃䊦ᒻ⁁䈫㘃ૃ䈚䈩䈇䉎䈖䈫䈎䉌䇮ၮᧄ⊛䈮 Hf ๟ㄝ䈮䈲 O 䈏㈩૏䈚䈩䈇䉎䈫⠨䈋䉌䉏䉎䇯ฦ⹜ᢱ䈱䉦䊷䊑䊐䉞䉾䊁䉞䊮䉫⚿ᨐ䉕⴫ 2(b)䈮␜䈜䇯HfSiON ጀ 1nm 䈱⹜ᢱ B1 䈱㈩૏ᢙ䈲
B2,B3 䈮Ყ䈼䈩ዊ䈘䈒䈭䈦䈩䈍䉍䇮⤑ෘ䈏⭯䈇⹜ᢱ䈪䈲㉄⚛ᰳ៊䈱ഀว䈏Ⴧട䈜䉎䈖䈫䉕␜ໂ䈚䈩䈇䉎䇯䉁䈢䇮⓸ൻಣℂ 20%䈱⹜ᢱ B6 䈱㈩૏ᢙ䈏ઁ䈱⹜ᢱ䈮Ყ䈼䈩ዊ䈘䈒䈭䈦䈩䈇䉎䈖䈫䈏ಽ䈎䈦䈢䇯䈖䈱⚿ᨐ䈲䇮⓸ ൻ ಣ ℂ 䈮 䉋 䉍 ㈩ ૏ ᢙ 䈏 ዊ 䈘䈒䈭䉎 䈫䈇䈉 A ␠䈱⹜ᢱ䈱⸃ᨆ⚿ᨐ䈫৻⥌䈜䉎䇯
Debye-Waller ࿃ሶ䈏⓸ൻ䈱ഀว䈱Ⴧട䈮ኻ䈚ᄢ䈐䈒䈭䈦䈩䈇䉎䈖䈫䈏䇮⓸ൻಣℂ䈏ㅴ䉃䈮䈧䉏䈩⚿᥏ൻ䈱ᐲว䈇䈏ᄢ䈐䈒䈭䈦䈩䈇䉎䈖䈫䈏␜ໂ䈘䉏䉎䇯(3)EXAFS ᷹ቯᴺ䈱ᡷༀὐ੹࿁䈱ታ㛎䈲ቶ᷷䈮䈩᷹ቯ䉕ⴕ䈦䈢䈢䉄䇮േᓘಽᏓ䈮䈍䈇䈩╙ੑㄭធએ㒠䈱䊏䊷䉪䈏ਇ᣿⍎䈫䈭䉍䇮⚿᥏ൻ䈱ᐲว䈇䉕චಽ䈮ᬌ⸛䈜䉎䈖䈫䈏䈪䈐䈭䈎䈦䈢䇯䈖䉏䈲䇮Debye-Waller ࿃ሶ䈏ᄢ䈐䈒䈭䈦䈢䈢䉄䈪䈅䉎䈫⠨䈋䉌䉏䉎䇯ᰴ࿁䈱 EXAFS ᷹ቯ䈪䈲䉪䊤䉟䉥䉴䉺䉾䊃䉕↪䈇䈩⹜ᢱ䉕಄ළ䈚䈩᷹ቯ䈜䉎䈖䈫䈪 Debye-Waller ࿃ሶ䉕ዊ䈘䈒䈚䇮EXAFS ᝄേ䈱ᝄ᏷䉕ᄢ䈐䈒䈜䉎䈖䈫䈪േᓘಽᏓ䈱╙ੑㄭធએ㒠䈱䊏䊷䉪䉕䉋䉍᣿⍎䈮䈜䉎䈖䈫䈏䈪䈐䉎䈫ᦼᓙ䈚䈩䈇䉎䇯

⴫ 1 ੹࿁᷹ቯ䈚䈢 HfSiON ⹜ᢱ䈱૞⵾᧦ઙ(a) A ␠⹜ᢱSample No.

Structure

A1

HfO2(2nm)/SiO2/Si(001)

A2

HfSiO (3nm)/SiO2/Si(001)

A3

HfSiON(3nm)/SiO2/Si(001)(b) B ␠⹜ᢱSample No.

Structure

Nitridation (%)

B1

poly-Si/HfSiON(1nm)/SiON/Si(001)20

B2

poly-Si/HfSiON(2nm)/SiON/Si(001)20

B3

poly-Si/HfSiON(3nm)/SiON/Si(001)

20B4HfSiON(2nm)/SiON/Si(001)

0B5

HfSiON(2nm)/SiON/Si(001)10

B6

HfSiON(2nm)/SiON/Si(001)20

Hf LIII-edge

HfO2 2nm (A1)

k 3F(k) (arb. units)

HfSiO 3nm (A2)

HfSiON 3nm (A3)

HfO2 powder

2345678910

WAVE NUMBER : k (Å-1)࿑ 1 ⷙᩰൻ EXAFS(HfSiON(A ␠⹜ᢱ), Hf LIII-edge)1112

Hf LIII-edge

F.T.{k 3F(k)} (arb. unit)

HfO2 2nm (A1)

HfSiO 3nm (A2)

HfSiON 3nm (A3)

HfO2 powder
01234

RADIAL DISTANCE (Å)࿑ 2 േᓘಽᏓ(HfSiON(A ␠⹜ᢱ), Hf LIII-edge)(䊐䊷䊥䉣ᄌ឵▸࿐䋺3.0䌾12.0Å-1)56

Hf LIII-edge
HfSiON 1nm (B1)

k 3F(k) (arb. units)

HfSiON 2nm (B2)

HfSiON 3nm (B3)

HfO2 powder

234567891011

WAVE NUMBER : k (Å-1)࿑ 3 ⷙᩰൻ EXAFS(HfSiON(B ␠⹜ᢱ䇮⤑ෘଐሽᕈ), Hf LIII-edge)12

Hf LIII-edge
poly-Si/HfSiON
nitridation 0% (B4)k 3F(k) (arb. units)

nitridation 10% (B5)nitridation 20% (B6)

HfO2 powder

234567891011WAVE NUMBER : k (Å-1)
࿑ 4 ⷙᩰൻ EXAFS(HfSiON(B ␠⹜ᢱ䇮⓸⚛࿶ଐሽᕈ), Hf LIII-edge)12

Hf LIII-edge

F.T.{k 3F(k)} (arb. unit)

HfSiON 1nm (B1)

HfSiON 2nm (B2)

HfSiON 3nm (B3)

HfO2 powder012345RADIAL DISTANCE (Å)࿑ 5 േᓘಽᏓ(HfSiON(B ␠⹜ᢱ䇮⤑ෘଐሽᕈ), Hf LIII-edge)(䊐䊷䊥䉣ᄌ឵▸࿐䋺3.0䌾12.0Å-1)6

Hf LIII-edge
poly-Si/HfSiON

F.T.{k 3F(k)} (arb. unit)

nitridation 0% (B4)

nitridation 10% (B5)nitridation 20% (B6)

HfO2 powder012345RADIAL DISTANCE (Å)࿑ 6 േᓘಽᏓ(HfSiON(B ␠⹜ᢱ䇮⓸⚛࿶ଐሽᕈ), Hf LIII-edge)(䊐䊷䊥䉣ᄌ឵▸࿐䋺3.0䌾12.0Å-1)6⴫ 2 䉦䊷䊑䊐䉞䉾䊁䉞䊮䉫⚿ᨐ(a) A ␠⹜ᢱ(䊐䊷䊥䉣ᄌ឵▸࿐䋺3.0䌾11.65Å-1䇮ㅒ䊐䊷䊥䉣ᄌ឵▸࿐䋺0.95䌾2.27Å)
⹜ᢱ⚿ว⒳

ේሶ㑆〒㔌

㈩૏ᢙ

Debye-Wallerr (Å)

N࿃ሶ V (Å)

A1

Hf-O

2.15

5.9

0.110

A2

Hf-O

2.10

4.8

0.100

A3

Hf-O

2.12

4.4

0.107

(b) B ␠⹜ᢱ(䊐䊷䊥䉣ᄌ឵▸࿐䋺3.0䌾11.65Å-1䇮ㅒ䊐䊷䊥䉣ᄌ឵▸࿐䋺0.95䌾2.27Å)
⹜ᢱ⚿ว⒳

ේሶ㑆〒㔌

㈩૏ᢙ

Debye-Waller ࿃ሶr (Å)

NV (Å)

B1

Hf-O

2.08

3.50.088

B2Hf-O

2.09

6.50.119

B3

Hf-O

2.09

5.5

0.104

B4

Hf-O

2.06

5.7

0.098

B5

Hf-O

2.08

6.6

0.112

B6

Hf-O

2.10

4.00.118

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