AgI

1 1

1

2

3

1

3

3

2 4

1

2

3

Debye

4

11

12

3 15

1

2

3

AgI

15

15

16

4 20

5 X 24

6 25

1

2

25

29

7 30

1

2

3

4

5

6

AgI X

ColeCole

-AgI

-AgI

-AgI

-AgIX

30

33

34

35

36

37

8 39

40

41

1

1

framework

framework

Fig.1-1

Li+ framework

Fig.1-1 framework

2

Poly ethylene terephthalate (PET)

PET

PET

(1) Poly ethylene terephthalate (PET)

(2)

-AgI

3

2

1961B. S. H. ROYCEK+

KCl[1]B. S. H. ROYCE

KCl 10 0.2 eV

2000S. FurusawaK+KTiOPO4 (;KTP)

S. FurusawaKTP

GPa

KTPc-

framework

[2]

[3-10]

frameworkframework

2

framework

-AgI

4

()

mobile ion

thermal activated

barrierU(x)

a

ZZe

0

P

hopping

T1P

Pk TB

exp

(2-1)

kB

[s-1]0

0 0P

k TBexp (2-2)

xx

5

Fig.2-1-1 HollanditeK+

Ze0

a

x

U(x)

Fig.2-1-2 E=0

site

1hopping1

10attempt

frequencyhopping

rate

6

xE

U'(x)U(x)

(x)

U'(x)=U(x)+Ze(x)=U(x)ZeEx+k k(2-3)

x

U(x)

Ze0

+Zea

2E

Zea

2E

E

Fig.2-1-3 E0

x

EZea

2

x

EZea

2

E

xhoppingx(2-2)

Tk

ZeaE

B

0x

/2exp

Tk

ZeaE(

B

/2exp (2-4)

1v(2-4)hopping rate +xa

av x

Tk

ZeaE

Tk

ZeaE

Tk

a

BBB

02

exp2

expexp

7

Tk

ZeaE

Tk

a

BB

02

sinh2exp (2-5)

EakBT

12

Tk

ZeaE

B

Tk

ZeaE

Tk

ZeaE

BB 22sinh

(2-6)

Tk

Tk

Zeav

BB

exp2

0 (2-7)

ZeNi

ETk

Tk

ZeaNvNZei

BB

exp

2

0(2-8)

i

Ei = (2-9)

(2-8)(2-9)

Tk

Tk

aZeN

BB

22

exp0 (2-10a)

(2-10a)f

Tk

f

Tk

aZeN

BB

22

exp0 (2-10b)

(2-10)

(2-10b)T

T

ek

T

1logloglog

B

0

fk

aZN 0

B

22

0

e

(2-11)

T

e

k

T

3

3

B

0

10

10

logloglog

(2-12)

8

log(

ek

B

log10 3

Arrenius plot

log(

T)

1000/T

kB10-3log10e

Fig.2-1-4

[11]

(1)

Li 1

9

(2)

(1)(2)

(3)(7)

(3)

(4)

Li

AgI

Table 2-1-1 [12,13]

Table 2-1-1 e=Pe/E

ion e=Pe/E [cm3] ion e=Pe/E [cm

3]

Li+ 0.0310-24 O2- 0.53.210-24

Na+ 0.4110-24 I- 6.4310-24

K+ 1.3310-24 Si4+ 0.0210-24

Rb+ 1.9810-24 Sn4+ 3.410-24

Cs+ 3.3410-24 Ge4+ 1.0010-24

Ag+ 2.410-24

(5)

(6)

(7)

10

D*=fDrandom f

Haven ratio1/31

11

Debye

0

12

Fig.2-1-6

Z'

RB

RB

CB

max

-Z" (a)

Fig.2-1-6 Cole-Cole

RB CB

Z*()

BB

B

RCi

RZ

1)(* (2-15a)

2

BB

B

RC

RZZ

)(1)('Re *

(2-15b)

2

2*

)(1)("Im

BB

BB

RC

RCZZ

(2-15c)

(1-b)(1-c)

2

2

2

2"

2'

BB R

ZR

Z (2-16)

(2-16) ZZCole-Cole

(RB/2, 0) RB/2

Z RBCole-Cole

Z0=RB

max 1/(RB CB) RBmax

13

CB

RB

14

RB

CB

Rg

Cg-Z"

Z'

RB

(c)

Rb

Cb

Re

Ce

or

RB+Rgor

RB+Re

Fig.2-1-8 Cole-Cole

2

2 Ri

Ci

Z'

RB

RB

CB

max

-Z" (f)

RB

Fig.2-1-9

15

1 AgI

AgI

PET (Ag)(Fig.3-2 )

(I2)(Ag)(I2) 2

X -AgI

2

-AgI 3D (OLYMPUS OLS4000 LEXT)

Ag2 mAg -AgI 8.5 m

16

3

Ag Ag

Fig.3-1 Table 3-1

VPC-260F

ROUGH

FORE

Fig. 3-1 VPC-260F

17

Table 3-1 VPC-260F

110-5 Torr1.310-3 Pa

310-5 Torr4.010-3 Pa20

100 V 5060 Hz 1.2 kW

010 VMax 150 A

200 V 5060 Hz 1.5 kW

Fig. 3-2 (Ag)

Ag AgI

Ag AgI

1 AgI

AgIAg

AgIAg

Fig. 3-2

18

Fig. 3-3 (a),(b)

Fig. 3-3 (b)

Fig. 3-3 (b) Table 3-2

Fig. 3-3

(a) (b)

Table 3-2 Fig. 3-3(b)

PET film AgI thin film

x [mm] 20 17

y [mm] 60 10

z [m] 100 8.5 8.7

(a) (b)

19

d l d/l1 E

l l=1.0 mm

d=9 m d/l= 910-31

[][film ][Sample ](Fig. 3-4)

S = d W

W

S

l

sample film

d ()

= filmsample

E

A

AA

A

A

d

l

10 mm17 mm 8

Fig. 3-4

20

4

Fig. 4-1

LCB04K150K Table 4-1 LOAD CELL

Fig. 4-2

Fig. 4-3

Fig. 4-1 (a)(b) (

(a)

(b)

21

Fig. 4-2

-

+

0 V

+12 V

Fig. 4-3

Table 4-1 LOAD CELL

LCB04K150L

1.5 kN

2 mV/V10 %

DC12 V

100 ][ L

L (4-1)

L L

22

1878

Tomlinson

[14]

LOAD CELL

LOAD CELL 12 V 2 mV/V

24 mV 1.5 kN

1.5 kN 24mV 2mV/V mV2

1 mV F0[N] 24

1500 [N/mV]

measureVFF 0 measureV LOAD CELL [mV]

23

PET

Fig. 4-4 0 ~ 20 N

20 N

0 ~ 20 N PET

20 N

PET PET

0 N 0

PET

PET

0

20

40

60

80

100

0 0.2 0.4 0.6 0.8 1

[%]

F [

N]

Fig. 4-4 PET

24

5 X

Fig. 5-1

Table 5-1

X

X

X

()

(R185mm)

2

2

Fig.5-1 X

Table 5-1 X

RIGAKU RINT2000

CuK= 1.5406 )

-2

40 kV

20 mA

-2

2390

0.010

25

6

.

1

HP4194A Impedance/Gain-Phase

AnalyzerHEWLETT PACKARDHP4194A

RDUTDevice Under Test

IDUTFig. 6-1-1L(

=0)Fig. 6-1-1

L

DUTZx

IRZx

V1V2IRV2=RI

V1V2

2

1

2

11

V

VR

R

V

V

I

VZx

(6-1-1)

ZxV1

V212

1111111 sincose 1

iVVVVi

(6-1-2)

2222222 sincose 2

iVVVVi

(6-1-3)

21212

1

2

1

2

1 sincosee

e21

2

1

i

V

VR

V

VR

V

VRZ

i

i

i

x (6-1-4)

26

LFHF20 Hz110 MHz

Fig. 6-1-2

()

HP4194A 50

31440A

HP4194A 31440A GP-IB 1)

PC-9821V13

IANAZ

1GP-IB

IEEE 488 HP-IB (Hewlett-Packard Instrument Bus)GP-IB

V1 V2

H L

DUT

Zx R

Fig. 6-1-1

27

Fig. 6-1-2 Table. 6-1-1

Fig. 6-1-2

28

Table 6-1-1

HP4194A ImpedanceGain-Phase AnalyzerHEWLETT PACKARD

100 Hz 15 MHz( 1 m)

1 mHz

20 ppm(235 )

|Z |, |Y |, , R, X, G, B, L, C, D, Q

10 m100 M

100

31440AAgilent

Alumel Chromel

PC-9821V13NEC

IANAZ

OS MS-DOS N88BASIC

29

2

Table 6-2-1

Table 6-2-1

0120 N (5 N )

290325 K

100 Hz10 MHz

N2

Ag

AgI S l

Table 6-2-2 -AgI S l

l [mm] S [mm2]

OHP Film (PET) 1.0 0.69

30

7

1 AgI X

AgI X

Fig.7-1-1 Fig.7-1-1

Table 7-1-1 -AgI PDF (No. 01-078-1613) -AgI

-AgI

PDF -AgI

(002)(102)(110)(103)(112)

26

PET

0 10 20 30 40 50 60 70 80 90

2 [deg]

102

103

112

-AgI thin film

Substrate:PET

Thickness 2 m

CuK

PDF2Plus No.01-078-1613

-AgI

110

002

002

102

110 103

112

PET

Inte

nsi

ty [

Arb

. U

nit

s]

100

101

203

213

Fig.7-1-1 -AgI X

31

Table 7-1-1 -AgI PDF

01-078-1613 QM=*

AgI

Silver Iodide

Rad: CuKa1 Lambda: 1.5406 Filter: d-sp: Calculated

Cutoff: Int: Calculated I/Icor: 6.81

Ref. Anharmonic thermal vibrations in wurtzite-type Ag I., Yoshiasa, A., Koto,

K., Kanamaru, F., Emura, S., Horiuchi, H., Acta Crystallogr., Sec. B:

Struct. Sci., 43, 434 (1987), Calculated from ICSD using POWD-12++

Sys: Hexagonal S.G.: P63mc(186) Aspect:

a: 4.591(1) b: c: 7.511(4) A: C: 1.636027

A: B: C: Z: 2.00

mp:

Ref. Ibid.

Dx: 5.687 Dm: SS/FOM: F30=1000(.000,32)

ANX: AX. Analysis: Ag1 I1. Formula from original source: Ag I. Delete

duplicate: Delete: see 01-078-1614, JMB 7/00. ICSD Collection Code: 62789.

Temperature of Data Collection: 123 K. Wyckoff Sequence: b2 (P63MC). Unit

Cell Data Source: Single Crystal. Peak height intensities. Single-crystal

data used.

2 [de] Int h k l 2 [de] Int h k l

22.34241 100 100 92.94596 7 215

23.67217 57 002 93.29958 1 206

25.32536 63 101 93.44423 2 312

32.77674 34 102 96.07385 1 107

39.21436 77 110 99.51207 6 313

42.64136 73 103 101.6038 1 305

45.59591 12 200 102.8368 1 401

46.31888 44 112 103.7345

32

63.03395 6 211 114.9206 1 108

64.00974

33

2 -AgI Cole-Cole

Fig. 7-2-1 -AgI 0.0 %Cole-Cole (at 300 K)

0

5000

1 104

1.5 104

0 5000 1 104

1.5 104

2 104

-Z''

[cm

]

Z' [cm]

-AgI thin film

Thickness 8.7 m

0.0 %

300 K

Fig. 7-2-1-AgI 0.0 %Cole-Cole

i

1

ZZZZ 0* (2-13)

Z0 Z

Z=0

34

3 -AgI

Fig. 7-3-1 -AgI

0

1 10-5

2 10-5

3 10-5

4 10-5

5 10-5

6 10-5

7 10-5

0 0.2 0.4 0.6 0.8 1

[%]

-AgI thin film

thickness 8.7 m

at 300 K

[

-1cm

-1]

Fig. 7-3-1-AgI

PET -AgI

-AgI

X

35

4 -AgI

-AgI

Fig. 7-4-1

0.001

0.01

0.1

3.1 3.2 3.3 3.4

T

[

-1cm

-1K

]

1000/T [K-1]

-AgI thin film

Thickness 8.7 m

0.00% 0.19% 0.44% 0.69% 0.94%

Fig. 7-4-1 -AgI

Tk

TB

exp0 (7-4-1)

fk

aZeN

B

0

22

0

)( (7-4-2)

fittingN

a

fittingfitting2

36

5 -AgI

Fig. 7-5-1 -AgI

0.2

0.25

0.3

0.35

0.4

0.45

0.5

102

103

104

105

106

0 0.2 0.4 0.6 0.8 1

[

eV]

0 [

-1cm-1]

[%]

1000/T=3.27-3.4 [K-1]

1000/T=3.1-3.4 [K-1]

1000/T=3.1-3.27 [K-1]

-AgI thin film

Thickness 8.7 m

Fig. 7-5-1 AgI

framework

framework X

X

37

6 -AgI X

X

( EXTRA4020)

2

-AgIXFig.7-6-1

2 = 22.524.5 Fig. 7-6-3

20 30 40 50

(b)

2[deg]

(a)Inte

nsi

ty [

Arb

. U

nit

s]

00

2

10

2

11

0

10

3

11

2

1.0 %

0.0 %

Fig. 7-6-1 -AgI X

(a)( 0.0 %) (b)( 1.0 %)

22.5 23 23.5 24 24.5

1.0 %

2[deg]

00

2

Inte

nsi

ty [

Arb

. U

nit

s]

0.0 %

Fig. 7-6-2 Fig. 7-6-1 2 = 22.524.5

Fig. 7-6-1 Fig. 7-6-2

Table 7-6-1

38

-AgI -AgI

framework

Table 7-6-1 -AgI

dhkl []

h k l *0.0 *1.0 [%]

002 3.766 3.748 0.499

102 2.736 2.728 0.297

110 2.300 2.295 0.196

103 2.120 2.118 0.134

112 1.961 1.958 0.163

*

39

8

-AgI

(1) -AgI

(2) -AgI

(3) XRD

-AgI-AgI framework

-AgI

(Fig.

3-3(b) x )(Fig. 3-3(b) z )

(Fig. 8-1(a))(Fig. 8-1(b), 8-1(c))

AgI

(1)(Fig. 3-3(b) x )(Fig. 3-3(b) z )

(2)(Fig. 8-1(a))(Fig. 8-1(b),8-1(c))

(3)

(4)

Fig. 8-1 (a) (b) (c)

(b)

(c)

(a)

40

[1] B. S. H. ROYCE, R. SMOLUCNOWSKI, Effect of Plastic Deformation on the

Low-Temperature Ionic Conductivity of Potassium Chloride, Physical Review Vol. 122, No.4,

(1961) pp.1125-1128

[2] S. Furusawa, H. Sugiyama, F. Itoh, A. Miyamoto and T. Sasaki; Ionic Conductivity of

Quasi-One-Dimensional Ionic Conductor KTiOPO4 (KTP) Single Crystal at High Pressure J. Phys.

Soc Jpn., 69 (2000) pp. 2087-2091

[3] B. Morosin and P. S. Peercy; Physcs Letters A, Vol.53 (1975) pp. 147-148.

[4] G.A. Samara; Pressure and temperature dependences of the ionic conductivities of cubic and

orthorhombic lead fluoride (PbF2) Journal of Physics and Chemistry of Solids, Volume 40, Issue 7,

1979, Pages 509522

[5] G.A. Samara; High-Pressure Studies of Ionic Conductivity in Solids Solid State Physics, Vol38,

(1984) pp. 180

[6] J. Zhang, J. Ko, R. M. Hazen, C. T. Prewitt; High-pressure crystal chemistry of KAlSi3O8

hollandite American Mineralogist, Vol.78 (1993) pp. 493-499

[7] A. Yagi, T. Suzuki, M. Akaogi; High Pressure Transitions in the System KAlSi3O8-NaAlSi3O8

Phys Chem Minerals 21 (1994) pp. 12-17

[8] Aimin Hao et al.; Conductivity of AgI under high pressure J. Appl. Phys. 101 (2007) pp.

053701

[9] T. Katsumata, Y. Inaguma, M. Itoh, and K. Kawamura; Influence of Covalent Character on High

Li Ion Conductivity in a Perovskite-Type Li Ion Conductor: Prediction from a Molecular Dynamics

Simulation of La0.6Li0.2TiO3 Chem. Mater. 2002, 14, 3930-3936

[10] Fabrice Bruneta, Nikolai Bagdassarov, Ronald Miletich Na3Al2(PO4)3, a fast sodium conductor

at high pressure Solid State Ionics 159 (2003) 35 47

[11] JME

[12] p.212e=Pe/E

[13]p.8 11

[14] ,

http://www.aandd.co.jp/adhome/products/loadcell/introduction/cell_intro02_01.html

41

29 3 6