Atomic-scale processes at the fluorite-water interface visualized by frequency modulation atomic force microscopy

(1)

Atomic‑scale processes at the fluorite‑water interface visualized by frequency modulation atomic force microscopy

著者 Kobayashi Naritaka, Itakura Shiro, Asakawa Hitoshi, Fukuma Takeshi

journal or

publication title

Journal of Physical Chemistry C

volume 117

number 46

page range 24388‑24396

year 2013‑11‑21

URL http://hdl.handle.net/2297/36478

doi: 10.1021/jp4076228

(2)

†

‡

†

¶

∗

†

¶

§

!"" ## $

%& '"! ()* # +,-. - /

!"" # ,' #

' , 0 )" 11 !!" #

!"#!$%& '!(&# %%&#)*+)

∗

†

‡

¶

!"#$%$&

§

# "

(3)

2

! "

! #

$%$

&&& ' ( ) *+ ' ( )

* ' ( *

σ =

^&, ^&,, ^-

.

/ ' 0 !

! '

/! 1 1!

1 ! !

2+

−

!

/

(4)

2

!

"

#

$%

#

& & '

!

%!

( )

*** & '

*+,-++

( ! . ***

& '

$

/

***0

) .

!1

x

²⁾

2x−y

y

^!3

# ***

)

$

4

& ' 5 6

(5)

!

"##$%

& '

( ) *

"""

) *(

*(

+ *"""

) )

) ,

) -

,

+ ! )

+ *"""

& ! .

*(

!

)

& '

! *(

*"""

,/) ,

(6)

0.315 nm 0.386 nm (a) Cleaved (111) surface

-

[111]

[211]

[011]

-

[011]

[211]

[111]

- -

-

(b) [011] projection (A-A’ cross section)

Ca ²⁺ F ^- (upper) F ^- (lower) 0.386 nm

A A’

! " #$%#$ #$

&'

¯1

⁽ ⁾

" #$

#$ '*+, -

−

%

2+

−

. &( '/* 0

" #$ 1

−

%

2+

'/2,

(7)

×

³

^!

" # $ ! % &

$#'

μ

^! ^()*(

# # !

" & + , -!' +

, - + , -

σ =

^!

σ

^#

. &

σ = (c − c eq )/c eq

c c eq

# # $&!

! " & !' #/ #)+

2 18 ^◦ C

!0 (! 12(

2

^3- ⁽

4 ! 5

σ =

^! ^"

σ =

& # ! . + ,

& # +! 6

c eq

^!' ⁽ ^& ^#⁺ ^! ^"

+ & 7 # !

% 5 ) 8 ) $ ()*( ))

< 10

^/

√

Hz

^! ^*^&^$⁾

7 9:: ;9< # $

8 &

f 0

A

^# ^{8 &}

Δf

$ & ) ! * #

Δf

^! ^" ⁾ ^# ^& ^&

$ *( =; ;9<! $ *7

#6+*>6 ! "&

f 0

⁸ ^#

k

^'⁷⁺

(8)

!

"#

A B

0.386 nm

A B

Distance [nm]

0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 0

60 40 Height [pm] 20 (c)

(a) (b)

$ % & %& ' (%"""& ! %) * +,& % &

Δf = +122

^)- ^. ^* ^"## ^%&

Δf = +1.89

^!)- ^. ^* ^" ^%& ⁾

/ 0'1 %&

' (%"""& '

% % && (

!

−

'2

2+

'

−

%#3", & %& '

4 '

' /%%&& 0'1 %&

2

2+

(9)

−

445:40

(a) 0 min (b) 14 min

(c) 28 min (d) 46 min

!"#! $% &&&$ ' () * +

, $ (( '

&- . - $

Δf = +122

^)/ ^* ^&

(

) $ " ($ $

!"#! , $

($

(( , ( $

# ( (

.

±

^$

#$ $

±

^/ ^$ ^&

±

((

0( #!1 ( $ $

( (

# 2)

−

$$

−

$ $

(10)

2+

−

! "# "

$%&'

$(

±

^)*

$%&' + ,

-

−

. / 0

-

−

-

−

0

!-1 . /

2 " 3)

0

-

−

3)

! ,0

-

−

4 5

-

−

-

(11)

−

!

"

2+

#$

−

!

% !

"

2+

#$

−

!

#$

−

! $% !&

' ($ ) *+

, ! ' ($ ) *+

-( +.-(+ ' (

+ /0

' $1

$!

% !

( -(++

% !

% !&

2 ' 2 (///+

(12)

(a) 0 min (b) 37 min

(c) 52 min (d) 55 min

!" # #$ "% &' (

) * +, " - ' %

Δf = +1.0

^.% ^# ^* ⁽⁽^%

"### %

Δf = +2.5

^.% ^#^*^% ^&'

"" *$ ' "" # ' ##"" # ' $#

%

(13)

!

" !

"#

−

$

% # #

−

& %

%

'( #)

((*+(

(*, -

.#/

- %

( 0

%

# , #/.#/ 1 2

! #/.#/

! #, %%

% ! # ,+,

(14)

(a) 0 min (b) 29 min

(c) 44 min (d) 59 min

(e) 74 min (f)

! " #$ % &' (

)* ' ++ ' * ,+ $ "

Δf = +122

^-"

( && " "

Δf = +500

^-"

( & "

(15)

±

!

"# $ %

& & $ "

! ' !! (

$ )

! )

& !

!&

! & $ # ! *

%

! +

(

% ! ! ,-

−

$

−

& +

$

−

$

−

& & ,-

−

! . $

−

. ! & (

! % ! !

% ! & !& "#

! & $

/ ( $0($0 ! !

( $ !

(16)

!

! "

!#

2+

$%

−

! & ' ('

)

*

! ! !

!

( ! !

!

+

!

!!

! !

,-, ' ('

!%. / !!

* ! ++ &

!% . , !

!

>

⁰¹

! !% !! !

,-, ' ('

&

(17)

(b) 52 min (a) 0 min

(c) 96 min (d) 86 min

(e) 87 min (f) 88 min

!" # $ %&

' () *+ , & $

Δf = +122

-$ * (( $ !"

$ %& ' . ) * ./ ..

& $

Δf = +1.46

^-$ ^* ^$

(18)

!"

# $ %

&

∼

$

&

−

'

−

(

%" % '

&

−

)

2+

'

−

σ =

** +(+

& ,

σ =

^"! ^#-

# - * .

/

(19)

(a) 0 min (b) 48 min

(c) 66 min (d)

(e) (f)

nm

8 nm 1 nm

4.6 nm 4.6 nm

!

σ =

^" ^# ^$ ^%& ^' ^"

! ( )* & $

Δf = +500

^+$ ⁽ ^""^$

$

Δf = +2.5

^+$ ⁽ ^$,^$ ^!

Δf = +1.0

^+$ ⁽ ^-^$ ^.^& ^& ^&' ^(#

/0'$

(20)

∼

! "

# # $ # #

%

&

>

^'

( &

) "

& &

"

*

2+

−

+

,+

−

* % " *

2+

,+

−

, " - .-).

+ " -

! "

" /

) & -

" & !

" (& + "

-

$ &

&

& & # ! & &

"

# $" "

& " &

(21)

!"# $%

!" &%

'

" &!% '

(

−

"

−

σ =

)!%*)! % + + "

! % ,

(22)

(a) 0 min (b) 70 min

(c) 73 min (d) 77 min

(e) (f)

A

B

A

B

B C

!

σ =

^"" ^# ^$ ^%& ^'

" ! ( )" )* )) & $

Δf = +500

^+$

( ""$ %& ' '& & ( & $ !

$

Δf = +2.0

^+$ ⁽ ^*^$

(23)

∼

σ =

σ

^!

!

"!#$! !

%& ! !

$! ' !

( ! !

!! !

) * % $!

%+,- $ . ,-

/ *

! ,% +,-- ! ! !!

! !! ! !

! !

σ =

*

* ! !

0 *

1 ! $!

! ! ( * *

!

$! ,

>

^- ² ^, ^% ^3,--

! !

(24)

2+

−

!" # $ $ %

& '" # % % $

( " )* $ $ %

& ( '" )* % % $

( +

σ

^,-" ^% ^$ ^%

( +

σ

^,--" ^% ^% ^%

. + // 0 1 2 3

404 2 ,,," /

5 ' !"+ 5 ' "

5 +

σ =

^,- ^,--" ⁶ ^/

7 6 , 8 7 + /

9 &

+ 0 1

:" "; " . /

+ 0 2 ,,,"

/

6 0

/ 0

(+

<"+ :";:" =";=" 8 / +

1 >1 +

/

−

(25)

σ =

^!" #$" ##

!

! " %

&

2+

!

−

'(

−

&)

!

−

!

−

* + ,

-!. '

!.,-!. /

,

!.,-!.

-+ .0 ,

-& ,& 1 +

-

- ,

2 !.,-!.&!3 #

(26)

σ = 10

σ = 100

! " # $ % & '

() * )"% '"

+,-.+,,

- ! / & 0*

3

¹² ^)*

2

^)" ^{) 1}

( 0

3+

30

2+

) +45.+46

7 89 *" 0 0 09 0 /: ; " !

# 9 2 09 )" & /1

)12 ) ' )< *

4-=.47-

+ > 0 ? ? 8 8 ; @ )*

2

^$ ^$

)A" @ -465.-467

6 /( ' & $ # )"( * )

* ! -7.-+5

, !$!$A'&# ) *

" ,47.,B

4 *:9%2*C )"D"#$% &#

66.45

B /"9% 9 E / A! )"( *

2 F ' +=B.

65,

(27)

! "# $%&'

$%()

%* "+ , - . /0 .

(1'2**

%% 34 5 # - 678 / 5 # 9:

/ "8 ;# - -

! < 8 < 4 < "8

)(')1%

%) < = /0 <0: 8 /0 - >? :

; %*'%%@

%$ <=-<</0

2

^"^8:^:;

(12'(@&

%& A7 5 5 - B4 > > " /4/ "

AC9 <D494 <-8

2

⁴

2

⁴ ⁴ ⁸ ^!

%*&'%%)

%( ;4/ E /. "8 "#

$*'$$

%2 - A - / " 5 " 8 "

F0< 44/0 - $! %& %%'%1

%1 ;. 5 /9 6 /0

/8 " 4 8 ' (

) )21')12

(28)

2

^!"#

$ "% & ' (% )*+),

- ' & '% . .

(&/ &0,,0

0, 1 2 ' 2" % 2 ' &23 4$(

5 6 $ 7 '$ 8 %#'

9 ' (% ! ",:)*,;

0 1 2" % 2 ' & 2 3 4 9

58"%8 %#' 9 ' (%#$%

,);,

00 4&" < 4&4 = 3 ' > = 5 ' #

.&9? $% #' & ' (%58

# $ %% -),-

0) 4&&' = 1'1 6 1 % 3 $ =

5 % 9@ <& '" & ' ( 0:)0+0:;0

0; 3 42" % 21 4 32 @ ' &2' #

A && = ' 58 B& 8 % '

9 ' (%

0: 9 1 4 1 ' # 9 & ' &

=((C '> < % A$& "% 8 % '

9 ' (% 58 )* 0D;,,

0D 6 & 29"'' !% "6 2" % 23 4! '

21 ' ' 4 ' A$&

(29)

!

"# $% &' % $' % (' ) * +

( , *+ *

"-#-."-#/

"0 $% $' % 1 ( 2, $

* -/.-0

"3 $% &' % $' % 1 ( % (' ( +

$ $+ ( 4 ( 5 6

2

⁽⁺^$+ ^"-7!#

- $% $' % 1( ( $ +

! $/.$/!

- 89 % $' ' +

8 "! 3/

-" (' &% 89 % $ : ' +

# $ #$ % /./0

-- 89% (' &$ 4 + :4

# $ &7!#-

-! 89 % &9; % $' ( + 8 (

$ # $ # $ & "70!."73!

-7 9 % <, $ = 5, + :,

;' ; 1 5>$ + , + ?

5 '$ (( !-#

(30)

%& '" (%)"*"+",

-./-/

/ "*!0 ")# 0!#1"*!"" 2'3"'

*" 4,"1 " + # !"' ' * % "# "

5 61 , #", 7789.7

: # *0;<1=0>";442" !,''5"" "

*" # 5

2

⁷⁷⁷ ^!"' ^8?:

@ A0 + ," B 0 = "' %0 + , % C" , $#" !",

!,' "*"

2

⁷⁷⁷ ⁵

2

⁷⁷⁷^!"'

79:.?79:/

(31)

Atomic-scale processes at the fluorite-water interface visualized by frequency modulation atomic force microscopy