!"

#$ %& ' '

%( ( )*+ , -. */( 01 2 -3%4/ -%5/ ( (

(1( " , (

" " )4+ ( ( - 1 (1 -. */ , 2 2 ( ( -

2 /,

(

!""! 6 7 4884 9!:(; < ; = # 9 8?@A(*?8BC84C87*4(845B D *BE8FE8C8 45B

0

)+ ' ' &G 6 '1

, % % H I %&" % %*5 ?' -I#/!($ J1

K & H , %H # H9B 4>: -I#/

)+ '& 1 !'H I % '&

HCH,H H,%

Zn MeMe In

Me

Me Me

Mg

O O

F

F

F

F

F

F

Cu

Si

Me

MeMe

a)b)

c) d)

. * H $ / 2 / / %4 / -,%H/

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! # $ %

! &

!"" #

. -';5/ -;4H/ -;4H/ (

-/ L -%./ (

-. 4/)5+ ,

45A 4884 9!:(; < ; = # 9 8?@A(*?8BC84C87*4(845A D *BE8FE8C8 !""! 6 7

C H

$ $ $ % & & ' & & $ ( $ ") $ * $ $ $ ' "+,-. / $ ' $ 0. $$ "+, .

$ 1 2 3 ' $ ((. 4

& 0$

54&06 "+ 7 "++7 % "++- %

$ 1. 2 &

5%12&6 $ $ % 18121 $ $ & 5"++,6 9

: $ # % $ 2( 5"++;

E8 %.

78 M 8* ,

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)@+ > %. ( %. ( !"( " " 2 ( ( 2 0 (

%& 0 0 (

)E+

!"! > 5=6

H 1 %)7+

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E058

,

,

;

.

1 ( H ( ' . 2 % (

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&

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6

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!""! 6 7 4884 9!:(; < ; = # 9 8?@A(*?8BC84C87*4(845? D *BE8FE8C8 45?

C H

. 4 ,

. 5 ,

L -H/ 2 (

-HH/ 2 ( ->>H/ (

!!" >

> %@ 5%6$ (%&

, 2 L

-. E/)B+ (

,

L (

" 1 2

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)B+

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2 > 2

C2

"

;

(

% ( > 1 516$ > H -. 7/

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1 (

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4@8 4884 9!:(; < ; = # 9 8?@A(*?8BC84C87*4(84@8 D *BE8FE8C8 !""! 6 7

C H

. @ H% (

MFCAr

Exhaust

MFCO2

Infrared Heating

Substrate

Injector

Evaporator

Heaters

Vaporiser

Precursor SolutionFlash Evaporator

Heaters

MFC

MFC

VaporiserInfrared Heating

Injector

Exhaust

Precursor

SolutionSubstrate

Ar

O2

. E H L %& )B +

1"

( ,

2 ( : 1$

% ( (L ( L 2 ,

L NO I , ( L(

L L (

)A?+

, H

" L > ( ( ( ( 9 (

- / "

( 2 )*8+ , - /

!!! :(: 1

, ( ->>/ L ! > (( 2 (

> , -/ (2 2 > ( (

2 )***4+

, ( L(

;

(

& " >> :& : -/4 :-/5 -/4-P 4477(

(5E(/ - ,;.

&4/

)*5+

!!A 1 1

H ;

'1 . B , (

, ( ( , :& -/4 :-/5 -/4 ; 1 >> (

!""! 6 7 4884 9!:(; < ; = # 9 8?@A(*?8BC84C87*4(84@* D *BE8FE8C8 4@*

C H

Flash VaporizationMatrix Structure

CarrierGas

ProcessGas

LiquidReservoir

. 7 H >,% -H/

'1 - !)7 A"7 @C48C?5

. B H ;

'1 -HH/ ( )*@+ *??* > '

, " '" -4E0588 M/ -4 / , ( 2 (

)*@+

( ( L , ( - / , (

2 2

, ( . A)*E*7+

'

, ( (-/ 2 2 1 , 2 (

' 2H

, H '

; (

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' %$( $ $ (

> " - / (

, (

-/ ,

( - (/$)*B+

3P - 0 9/ F 4 0 3P F 4 0 3P

- " /

P - 0 9/ -/ (

-9/ - ( " /

P - /,

"

, ( " - / )*B+ ,

( .

$ P 4 -

/

4@4 4884 9!:(; < ; = # 9 8?@A(*?8BC84C87*4(84@4 D *BE8FE8C8 !""! 6 7

C H

Precursor solution

Injector

Solvent out

Coldtrap

Coldtrap

To pumpTo pump

PrecursorvaporSubstrate

holder

Porous conveyer belt

Cold zoneEvaporation zone

Direction of gas

Precursor solution

Injector

Solvent outlet

Coldtrap

Coldtrap

To pumpTo pump

PrecursorvaporSubstrate

holder

Porous conveyer belt

Cold zone

Direction of gas

. A L ( )*E*7+

3P 4 - ( /

P 4 ,

1

" )*A+

A"" 2( 1

. ( $ P5 -

/ 3P 4 P 4 ,

% " -2/ "

0 , 01 %43Q6!5 %4QH-;4/@ 9 )*?+ , ( )48045+

( 0(1 - / - (/)4@047+ )44B+ 1

- / 1 2 C 2)4A4?+ . ? 2 (2 ( N O

*4 1 )58+ 2

;

( ,

" 01 , " 20 -%30,!>%/ (

)58+ % (

4$*

" %3 ,!>% ,!>%

- (

/ %3 " (

2( , (

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)5*+ > 201 1 > ( ,1 (

( *$* " (2)54+

,1

" %3 ,!>% - / -

"/ ( ! *

P *%3 %3 F *,!>% ,!>% -*/

*%3 %3 !(

4

*%3P%3C-%3 F ,!>% F >I,/ -4/

%3 %3 (

,!>% 9 *$* , ,

*$* " ,!>% %3 )55+ **@-5/ 8 M -@

(

!""! 6 7 4884 9!:(; < ; = # 9 8?@A(*?8BC84C87*4(84@5 D *BE8FE8C8 4@5

C H

. ? 2 2

/)5@+ > "(

! 5

%3-/ F ,!>%-/ %3C,!>%-*0/ -5/

" ! @

P %3-C-* F // F ,!>%-C-* F // -@/

, -" / ! E

BP -* 0 /-* F /C4 -E/

,

1 *E4> " (

" (

H (

)%3+C),!>%+ *$*E-*P 8@/ *8@ 8 M , -6%/ -1 ER/S ( > (

%3 ,!>%

1 "

" (

, (

* - / *%3 -1 / ,

! 7

0*B-*%3/4 F -4 *B 0 B 0 */*%3 F *P 8 -7/

I (

( , B . *8

, ( 1 " 1 ( ;

B 8@ T * T 87 >

B

" (

" % 1 %3 ,!>% ,!>% %3 ; " "

9 - /

%3C,!>% *$* % " %3 %3C,!>% (

%3

" (

" I *$* " B

BB

%3 5E *P 8@7 ,

" 54 %3 -

!/)5@+

%3 " " *$* *B %3)54+ , ( %3 " B

%3 4E05E , " (

! )5@+ ; " ()5@+

A"! & * 1

, %3C,!>% (

" " ,!>% "

4@@ 4884 9!:(; < ; = # 9 8?@A(*?8BC84C87*4(84@@ D *BE8FE8C8 !""! 6 7

C H

K = 84

0.0

20.0

40.0

60.0

80.0

100.0

120.0

140.0

00.20.40.60.81

Mole fraction of DMZ

Vap

ou

r P

ress

ure

/Torr

. *8 " 2 ( 1

-%&%!/ )5E+ -!%/)57+ "H

01 !% !%4 )5E+ ! )5B+ !% )5A+ -%H/ !% !(%4

)5E5?+ & )@8+ 6%

!% " ;

01 , (

!%4 !(

B -,%/ -!%/

4%5 F !4% 5!%4 -B/

(

!5 %3C,!>% $ P5 -

/ 3P 4 -

/ P 4 -! B/

1 ; 1 1 ,%!% -,!/ ! A

4%4!%5 F %!4 -A/

5%4!%5 F 4 !4 -A /

6 ,! 2 (

*,% ,% P *!% !% P *%! %! -?/

, ( 2 !% )5E+

,% (

,

" " ( ",

( (

,

"I1 " -,% !% ,! !(6/ ( % " 01

01 0(1 1 ( " " - / 1 )@*+ -! A/ , 1 (

, ( 9 , 0 " -%&'!/

" 01

-5/

( ( " ( ( , -

07E M)@5+ " -078 M 0AE M/

)@@+ "(

*4 1 )@E+ % ( ( " #

)@7+ 3, %&'! ( 2 ( " 1 ( 2 2 , " )>;5(6-;5/5+ ( 1 1 %&'!)@B@A+ , 1 ( " 0 " " , ( "

' !

,% ( >

1 &

> (

. (1)@?E8+

,% ( ( . *4 ,

( ( 1 % " ,% (

( (

, . *5 1 - / 9

( $ P 5 3P 4 -

0 3 P 5S /

P 5 , ,% "

, ( H (,% ( -/

!" ,% *$* ,%( ()@?E8+ ! E ,% (

, "( ,%,

1 .

1 - / ,

( " ,% )E*+

. *@ (

,% 48 M- / P *B -48 M/ ,% *75 C ( -1 /

4@7 4884 9!:(; < ; = # 9 8?@A(*?8BC84C87*4(84@7 D *BE8FE8C8 !""! 6 7

C H

Bubbles of entraining gas

Solid Phase B

. *4 > ,% (

N2 in N2 / Me3In out

Me3In vapour

Me3Indmda 1:1 adductsolid Me3In

. *5 ,% ,%

' ' &

% )( *

(1 -. */

% ; .4 , C (

( 1 4 " 2 6;5 ( (1 )@-/A+ )E4+

,

( $ P4 -P 5/

3P 4 -

/

P 4 ,

)-/4+ ) P + & > 1 ( ( & 1

6;5 " "

>

(2 4H44&* H-/4-/4 -/4 )-'/5+ ( ,

" 488 M (

2 1

( )E5+

I " ( H-/4 -/4 , (

@80E8 M ,

-/4 (,

;

H-/4 -/4 -/4 ( -. *E/ ; (

2 , 1 ( 2 (

-! *8/

5-/7-/ 5-/4-/ 5-/4-/ -*8/

( 0 0 , ( ( 2 -! **/

5-/7-/ 5-/4-/?5

5-/4-6;5/-/ -**/

> " )5-/7+ , -. *E/ ( )E@+ & (

( ( ( )-/4-/+ ( P -. *E / , )-/4-/+ ( (

" )5-/7+

)EE+

!""! 6 7 4884 9!:(; < ; = # 9 8?@A(*?8BC84C87*4(84@B D *BE8FE8C8 4@B

C H

0

0.5

1

1.5

0 0.1 0.2 0.3 0.4 0.5Mole Fraction of Dodecyl Amine

Liquid

+

Solid

Liquid + Vapor

x = 0.62

at 22 C

Solid+ Liquid

+ Vapor

1.0 mole fraction of TMI 0

T

VP

[T

orr

]

. *@ ,% 48 M - / P *B -48 M/ ( ,% *75 C )575B+ ( - 1 /

+

> ( (

( ,

( % & 1 (

, -/ (

$ K *7 4884. $ % 4* 4884

0)*+ > K ' &G $ 1 9(

; 9 ,,-)4+ K (; ,," !; AE4)5+ / K . K K H 1 % ,,. " 45? / > H(

; 1 1 2 ,,/ A+ ?*)@+ K K H . 2 !""" 83/)E+ & 3 1 H!%>,!;

?584*@?5>(,

' K 9 % K > '

1( > K , K # ,,0 "+! @4@/ % K ' > ' K 9 K 9 > K, K K K # !""" !"+ 5?8

)A+ % % > . 9 K ' HV ! ( K ; 2 1 3 !"" 7)) A*

)?+ % ; . 9 K ' HV K ; : !"" ,+ *4@7

)*8+ K . , ; H % > # ; H ; H '1 H H

%% ,, ! 4@5)45+ . . K '

K K (;

6 > ; % : > 9 K & 9 :& = ,,+ A *75

)4@+ 6 '1

. K H > ' &G K 9 %

:& = ,,+ 7 5@5

4@A 4884 9!:(; < ; = # 9 8?@A(*?8BC84C87*4(84@A D *BE8FE8C8 !""! 6 7

C H

a)

b)

. *E / )5-/7+ )E@+ / )-/4-/+ ( )EE+

)58+ ' K 9 ' K ' 1 1 > K ' ! & # ,, ") E4E

)5*+ & . 3 # ' &G ' > ; K 9 > K ,0, 7 4@@

)54+ # ; , C : : ,/' A!- *E7)55+ ' &G K 9 > K H > %

& ,,' A B5?)5@+ H H K 6 % > K

% H H > : ,,/ ; *4?@)5E+ > K H > K ; , K 91 , %

' &G % $ & =* ,,/&W5

)57+ # . ' # > % % =& ,0/ "- ?*

)5B+ / % & ; # : # ,, ""-4E@ / % & # H : # : ,,! ;)*4*B / %