US010615287B2

(12) United States Patent ( 10 ) Patent No.: US 10,615,287 B2

Sano et al. (45 ) Date of Patent: * Apr. 7, 2020
(54 ) AMORPHOUS OXIDE AND FIELD EFFECT HOIL 27/1225 ( 2013.01); HOIL 29/66969
TRANSISTOR (2013.01); HOIL 29/7869 (2013.01 ); HOIL
29/78696 ( 2013.01)
(71) Applicants : CANON KABUSHIKI KAISHA , (58 ) Field of Classification Search
Tokyo ( JP ) ; TOKYO INSTITUTE OF CPC HOIL 29/786 ; HOLL 29/772; HOIL
TECHNOLOGY, Kanagawa-ken (JP ); 29/78603; HOIL 29/247 ; HOLL 29/2006 ;
Japan Science and Technology HOIL 29/263; HOLL 29/06 ; HOIL 29/36 ;
Agency , Saitama (JP ) HO1L 29/43 ; HO1L 29/4908; HOIL
29/78693; HO1L 27/1225; HO1L 27/124 ;
(72) Inventors: Masafumi Sano , Kanagawa-ken (JP ); HO1L 29/66969; HO1L 29/78696 ; HOIL
Katsumi Nakagawa, Kanagawa-ken 21/02422 ; HO1L 21/02554 ; HOLL
21/02565 ; HOIL 21/02592 ; HOIL
(JP ); Hideo Hosono, Kanagawa -ken 21/02631; HO1L 21/428 ; HO1L 29/7869;
(JP ); Toshio Kamiya , Kanagawa-ken HO1L 29/26
(JP ) ; Kenji Nomura , Kanagawa-ken USPC 257/57 , 52, 65 , E31.034 ; 438/149, 166 ;
( JP ) 252 /519.51, 500 , 519.12 , 519.13 , 520.1 ,
252/520.21 , 519.1
(73 ) Assignees : CANON KABUSHIKI KAISHA , See application file for complete search history.
Tokyo (JP ); TOKYO INSTITUTE OF
TECHNOLOGY, Tokyo (JP ) ; JAPAN (56 ) References Cited
SCIENCE AND TECHNOLOGY
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(Continued )
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(60 ) Continuation of application No. 14 /806,108 , filed on EP 1313134 5/2003
Jul. 22 , 2015 , now Pat. No. 9,583,637, which is a EP 1 443 130 A1 8/2004
continuation of application No. 13 /923,009 , filed on (Continued )
Jun . 20 , 2013 , now Pat. No. 9,130,049 , which is a
division of application No. 12 /406,464 , filed on Mar. OTHER PUBLICATIONS
18, 2009, now abandoned , which is a division of
application No. 11/269,600 , filed on Nov. 9, 2005, Indian Office Action dated Apr. 26 , 2017 , issued in counterpart IN
now Pat. No. 7,601,984 . application 1378/CHENP /2012 (8 pages).
Brazilian Office Action dated May 2, 2017, issued in counterpart BR
( 30 ) Foreign Application Priority Data application PI0517568-2 ( 10 pages).
Patent Abstracts of Japan , vol. 2000 , No. 5 , Sep. 2000 for JP2000
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(51) Int. CI. 2002-076356 .
HOIL 29/786 ( 2006.01 ) (Continued )
HOIL 29/66 ( 2006.01)
HOIL 21/428 ( 2006.01) Primary Examiner Douglas J Mc Ginty
HOIL 21/02 (2006.01) (74 ) Attorney, Agent, or Firm — Venable LLP
HOIL 27/12 ( 2006.01)
(52) U.S. CI. (57) ABSTRACT
CPC .. HOIL 29/78693 (2013.01); HOIL 21/02422 A novel amorphous oxide applicable, for example, to an
(2013.01); HOIL 21/02554 (2013.01); HOIL active layer of a TFT is provided . The amorphous oxide
21/02565 (2013.01 ); HOIL 21/02592 comprises microcrystals .
(2013.01); HOIL 21/02631 (2013.01); HOIL
21/428 ( 2013.01); HOIL 27/124 ( 2013.01) ; 28 Claims, 5 Drawing Sheets
 US 10,615,287 B2
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* cited by examiner
U.S. Patent Apr. 7 , 2020 Sheet 1 of 5 US 10,615,287 B2

FIG . 1
1020
1019
CECLARTIEORN/cONEmTRA3ION 1018
O

1017
1016
??
1015 0 1 2 3 4 5 6 7
Lu

OXYGEN PARTIAL PRESSURE / Pa

FIG . 2
TTTTTTH TIITENUTTTTTIETTITUT TITLE

EM/
V5
(
cm2
**
)
LOEBCITLRIOTNY 10 g OO
o

???? ??????????????????????????????
1015 1016 1017 1018 1019 1020 1021
ELECTRON CARRIER
CONCENTRATION / cm -3
U.S. Patent Apr. 7, 2020 Sheet 2 of 5 US 10,615,287 B2

FIG . 3
102 O 0

100 ?I F?I oo
CE/Scm-1OLNDUCTIRVOTNY 10-2
10-4
ME
?Iilaru?_
10-6
humuman m
10-8
10-1010-3 10-2 10-1
Qm
100
OXYGEN PARTIAL PRESSURE / Pa
U.S. Patent Apr. 7, 2020 Sheet 3 of 5 US 10,615,287 B2

FIG . 4A
ELCTRI
C/Scm-1ONDUCTIV TY
0
?? 0
O

0
?
O

FIG . 4B cECLARTIEONR/CONEmTRA3ION ? ? 0

O
?? ?
O

101 o

FIG . 40 MOBILITY
cm2
/
**
)
V5
( ?? 0

ELCTRON
o

0
O

100 1

0.2 0.4 0.6 0.8 1.0

X in InGaZn1-XMgx04
U.S. Patent Apr. 7, 2020 Sheet 4 of 5 US 10,615,287 B2

FIG . 5
4

3
5 6

FIG . 6
15

GATE
VOLTAGE /
10 6.0
DC/UAURARIENT 5.5
5.0
4.5
or 4.0
3,5
3.0
2.5
2.0
TI
o
2.0 TO 01
0 5 10 15
DRAIN VOLTAGE /
U.S. Patent Apr. 7 , 2020 Sheet 5 of 5 US 10,615,287 B2

FIG . 7 718 719 720

716
718 719 704 721 705
706

703 707
708
-717
713
709 710
702 -714
711
a
701 715
718 719

818 819
FIG . 8 805

821 830

808 807
O2 -817
Ar

-814

815
 US 10,615,287 B2
1 2
AMORPHOUS OXIDE AND FIELD EFFECT increases. According to further aspect of the present
TRANSISTOR invention , there is provided a field effective transistor com
prising an active layer formed of an amorphous oxide
The present application is a continuation of Ser. No. containing a microcrystal, and a gate electrode formed so as
14 /806,108 , filed on Jul. 22 , 2015 , which is a continuation 5 to face the active layer via a gate insulator.
of U.S. application Ser. No. 13 /923,009 , filed on Jun . 20 , The transistor is preferably a normally -off type transistor.
2013 , now issued as U.S. Pat. No. 9,130,049, which is a According to a still further aspect of the present invention ,
divisional of U.S. application Ser . No. 12/ 406,464 , filed on there is provided an amorphous oxide whose composition
Mar. 18, 2009 , which is a divisional of U.S. application Ser. changes in a layer thickness direction and having an electron
No. 11/ 269,600 , filed on Nov. 9 , 2005 , now issued as U.S. 10 carrier concentration of less than 1018 /cm .
Pat. No. 7,601,984 , which claims priority to JP 2004 The amorphous oxide preferably contains at least one
326687, filed Nov. 10 , 2004, the entire disclosure of each of element selected from the group consisting of In , Zn and Sn .
which is incorporated by reference herein . Alternatively , the amorphous oxide is preferably any one
BACKGROUND OF THE INVENTION 15 selected from the group consisting of an oxide containing In ,
Zn and Sn ; an oxide containing In and Zn; an oxide
Field of the Invention containing In and Sn ; and an oxide containing In .
The present invention relates to an amorphous oxide . The In ,Alternatively
Ga and Zn .
, the amorphous oxide preferably contains
present invention also relates to a field effect transistor using 20
an amorphous oxide. According to a still further aspect of the present invention ,
Related Background Art there is provided a field effect transistor comprising
In recent years , flat panel display (FPD ) is commercial an active layer ofan amorphous oxidewhose composition
ized as the results of progress of liquid crystal techniques , changes in a layer thickness direction , and
electroluminescence (EL ), and the related techniques . The a gate electrode formed so as to face the active layer via
FPD is driven by an active matrix circuit comprising a 25 a gate insulator,
field -effect thin film transistor ( TFT) employing an amor wherein the active layer comprises a first region and a
phous silicon thin film or polycrystalline silicon thin film as second region , which is closer to the gate insulator than the
the active layer formed on a glass substrate . first region , and the oxygen concentration of the first region
For smaller thickness , lighter weight, and higher impact is higher than that of the second region .
strength of the FPD , use of a lightweight and a flexible resin 30 According to a still further aspect of the present invention ,
substrate is investigated in place of the glass substrate. there is provided a field effect transistor comprising
However, the transistor employing the silicon thin film an active layer of an amorphous oxide having at least one
cannot by directly formed on a less heat-resistant resin element selected from the group consisting of In and Zn, and
substrate, since the production of the silicon thin film a gate electrode formed so as to face the active layer
transistor requires a relatively high - temperature in the pro- 35 through a gate insulator,
cess , wherein the active layer comprises a first region and a
Therefore , for the TFT, use of an oxide semiconductor second region , which is closer to the gate insulator than the
thin film such as a ZnO thin film is actively investigated first region , and the In concentration of the second region is
which enables film formation at a lower temperature ( Japa higher than that of the first region , or the Zn concentration
nese Patent Application Laid -Open No. 2003-298062). 40 of the second region is higher than that of the first region .
However, TFTs using conventional oxide semiconductor According to a still further aspect of the present invention ,
thin filmshave not provided performances on the same level there is provided an amorphous oxide whose composition
as of TFTs using silicon . changes in a layer thickness direction ,
The present invention relates to an amorphous oxide , and wherein electron mobility increases as electron carrier
also , to a field effect transistor using the amorphous oxide. 45 concentration increases.
According to a still further aspectof the present invention ,
SUMMARY OF THE INVENTION there is provided a field effect transistor comprising
an active layer of an amorphous oxide and having at least
An object of the present invention is to provide an one element selected from the group consisting of In and Zn ,
amorphous oxide for use in the active layer of a semicon- 50 and
ductor device such as a thin film transistor ( TFT) and serving a gate electrode formed so as to face the active layer via
as a suitable semiconductor, and a field effect transistor. a gate insulator,
According to an aspect of the present invention , there is wherein the active layer comprises a first region and a
provided a amorphous oxide comprising a microcrystal and second region , which is closer to the gate insulator than the
having an electron carrier concentration of less than 1018 / 55 first region , and the In concentration of the second region is
cm . higher than that of the first region , or the Zn concentration
The amorphous oxide preferably comprises at least one of the second region is higher than that of the first region .
element selected from the group consisting of In , Zn and Sn . According to a still further aspect of the present invention ,
Alternatively, the amorphous oxide is preferably any one there is provided an amorphous oxide comprising one type
selected from the group consisting ofan oxide containing In , 60 of element or a plurality of types of elements selected from
Zn and Sn ; an oxide containing In and Zn ; an oxide the group consisting of Li, Na, Mn, Ni, Pd , Cu , Cd , C , N , P ,
containing In and Sn ; and an oxide containing In . Ti, Zr, V, Ru , Ge, Sn , and F and having an electron carrier
Alternatively, the amorphous oxide preferably comprises concentration of less than 1x1018 /cm3.
In , Ga, and Zn . The amorphous oxide preferably comprises at least one
According to another aspect of the present invention , 65 element selected from the group consisting of In , Zn and Sn .
there is provided an amorphous oxide , wherein electron Alternatively, the amorphous oxide is preferably any one
mobility increases as electron carrier concentration selected from the group consisting of an oxide containing In ,
 US 10,615,287 B2
3 4
Zn and Sn ; an oxide containing In and Zn ; an oxide In the above, mention is mostly made of a case where an
containing In and Sn ; and an oxide containing In . amorphous oxide is used as the active layer serving as the
Alternatively , the amorphous oxide preferably comprises channel of a TFT. However, the present invention is not
In , Zn and Ga. limited to the case .
According to a still further aspectof the present invention , 5 According to the present invention , there is provided an
there is provided an amorphous oxide comprising at least amorphous oxide that is suitably used in the channel layer of
one type of element selected from group consisting of Li, a transistor, for example, a TFT . The present invention also
Na, Mn, Ni, Pd , Cu, Cd , C , N , P , Ti, Zr, V , Ru, Ge, Sn , and provides a field effect transistor having excellent properties.
F, wherein electron mobility increases as electron carrier 10
concentration increases . BRIEF DESCRIPTION OF THE DRAWINGS
According to a still further aspect of the present invention , FIG . 1 is a graph showing the relationship between the
there is provided a field effect transistor comprising electron carrier concentration of an In - Ga - Zn- based
an active layer of an amorphous oxide containing at least amorphous film formed by a pulse laser deposition method
one type of element selected from the group consisting of Li
Na, Mn, Ni, Pd , Cu, Cd, C , N , P , Ti, Zr, V , Ru , Ge, Sn , and
, 15 and the oxygen partial pressure during film formation time;
F ; and FIG . 2 is a graph showing the relationship between the
a gate electrode formed so as to face the active layer via phous film formed by ofa sputtering
electric conductivity an In — GaZn – O based amor
method using argon gas
a gate insulator. and the oxygen partial pressure during film formation time;
Further, in the present invention , the amorphous oxide is 20
FIG . 3 is a graph showing the relationship between the
preferably selected from the group consisting of an oxide number of electron carriers of an In — Ga - Zn - C based
containing In , Zn and Sn ; an oxide containing In and Zn; an amorphous film formed by a pulse laser deposition method
oxide containing In and Sn ; and an oxide containing In. and the electron mobility ;
As the results of investigation on the oxide semiconduc FIGS. 4A , 4B and 4C show graphs showing respectively
tors by the inventors of the present invention , it was found 25 changes of electric conductivity, carrier concentration , and
that the above -mentioned ZnO is formed in a state of a electron mobility versus value x of a film having a compo
polycrystalline phase , causing scattering of carriers at the sition of InGaOz(Zn - Mg. O ) formed by a pulse laser depo
interface between the polycrystalline grains to lower the sition method in an oxygen atmosphere having an oxygen
electron mobility . Further it was found that ZnO is liable to 30
partial pressure of 0.8 Pa;
cause oxygen defect therein to produce many carrier elec FIG . 5 is a schematic illustration showing the structure of
trons , which makes difficult to lower the electrical conduc a top - gate type metal insulator semiconductor field effect
tivity . Thereby, even when a gate voltage is not applied to the transistor (MISFET) device ;
transistor, a large electric current flow is caused between the FIG . 6 is a characteristic graph showing the electric
current versus voltage of a top - gate type MISFET device;
source terminal and the drain terminal, making impossible 35 FIG . 7 is a schematic illustration of a film formation
the normally -off state of the TFT and a larger on -off ratio of apparatus employing the pulse laser deposition method ; and
the transistor.
The inventors of the present invention investigated the FIG . 8 is a schematic illustration of a film formation
apparatus employing the sputtering method .
amorphous oxide film Zn,M , In O (x+3y/2+3z/2) (M : at least
one element of Al and Ga) mentioned in Japanese Patent 40 DETAILED DESCRIPTION OF THE
Application Laid -Open No. 2000-044236 . This material PREFERRED EMBODIMENTS
contains electron carriers at a concentration not less than
1x1018/cm " , and is suitable as a simple transparent elec Now , the first to third inventions will be explained in
trode . However , the oxide containing the electron carrier at accordance with first to third embodiments , respectively.
a concentration of not less than 1x1018 /cm2 used in a 45 After that, an amorphous oxide material applicable to the
channel layer of TFT cannot give a sufficient on -off ratio , present invention will be explained . In the embodiments
and is not suitable for the normally -off TFT. Thus a con below , an In Ga - Zn- based oxide will be mainly
ventional amorphous oxide film cannot provide a film of a explained in the embodiments below ; however, the present
carrier concentration of less than 1x1018/cm3. invention is not limited to such material.
50
The inventors of the present invention prepared a TFT by First Embodiment: Amorphous Oxide Having a
use of an amorphous oxide of a carrier concentration of less Microcrystals
than 1x1018/cm as an active layer of a field -effect transistor.
The TFT was found to have desired properties and to be The invention according to the first embodimentrelates to
useful for an image display apparatus like a light emission 55 an amorphous oxide, characterized in that the amorphous
apparatus . contains a microcrystal(s ). Where a microcrystal(s) are
Further, the inventors of the present invention investi contained or not in the amorphous oxide is determined by
gated a material InGaOz(ZnO )m and the film forming con taking a TEM (transmission electron microscopic ) photo
ditions of this material, and found that the carrier concen graph of a section of a formed amorphous oxide film . An
tration of this material can be controlled to be less than 60 amorphous oxide film according to the present invention
1x1018 /cm by controlling the oxygen atmosphere condi comprises In — Ga - Zn- and the composition of the
tions in the film formation . amorphous oxide film in a crystalline state is represented by
The above explanation is given with a view to a case of InGa03(ZnO )m (m is a natural number of less than 6 ).
using the amorphous oxide as an active layer serving as e.g. Oxides represented by the term “ amorphous oxide” in the
a channel layer of TFT. The present invention is , however, 65 specification has an electron carrier concentration is less
not so limited to the case wherein such an active layer is than 1018 /cm or shows a tendency that the electron mobility
used . increases as the electron carrier concentration increases , or
 US 10,615,287 B2
5 6
and so forth . Although depending on the kind of use of a heated and therefore maintained approximately at room
TFT , it is preferable to use the amorphous TFT for fabri temperature . When a plastic film is used as a substrate, the
cating normally off type TFT. temperature of the plastic film is preferably maintained at
Alternatively , an amorphous oxide film according to the less than 100 ° C.
present invention comprises In — Ga - Zn - Mg - O and the 5 According to the invention of this embodiment, an amor
composition of the amorphous oxide film in a crystalline phous oxide comprises In Ga - Zn 0 and formed by a
state is represented by InGaOz( Zn - Mg, 0 ) m (m is a natural pulse laser deposition method under light irradiation. More
number of less than 6 , 0 < xsl ). It is preferable that these specifically, the invention is directed to a transparent amor
amorphous oxide films have an electron mobility exceeding phous oxide thin film containing a microcrystal(s ) repre
1 cm ?N.sec . 10 sented by a crystalline state composition of InGaOz(Zn )
The present inventors found that use of such a film (m is a natural number of less than 6 ). A normally -off
mentioned above as a channel layer makes it possible to transistor can be formed by use of such a thin film .
form a flexible TFT having transistor characteristics: a gate In such a thin film , it is possible to obtain an electron
current of less than 0.1 micro ampere when the TFT is off mobility exceeding 1 cm²/V •sec and a large on /off ratio
(normally -off) and an on /off ratio exceeding 1x107, and 15 exceeding 1x10 %.
being permeable to visible light. Furthermore, the present invention is directed to an amor
Such a transparent film is characterized in that the elec phous oxide comprising InGaZn 0 and formed by a
tron mobility increases with an increase of the number of sputtering method using argon gas under light irradiation.
conductive electrons. As a substrate for forming the trans More specifically, the present invention is directed to a
parent film , use can be made of a glass substrate , plastic 20 transparent amorphous oxide thin film containing a micro
substrate and plastic film . crystal(s) represented by a crystalline state composition ,
When the transparent oxide film is used as the channel InGaOz (ZnO )m (m is a natural number of less than 6 ). Such
layer of a transistor, it is preferable to employ, as the gate a film can be obtained by a sputtering method using the
insulator, one type of compound selected from the group apparatus shown in FIG . 8 in an atmosphere having a high
consisting of A120 - Y203 and HfO2 or a mixed crystal 25 oxygen partial pressure in excess of 1x10-2 Pa . In this case ,
compound containing at least two types selected from the the temperature of the substrate is not purposely heated and
group consisting of Al2O3 , Y203 and HfO2. thus maintained approximately at room temperature. When
It is preferable that the film ( transparent oxide film ) is a plastic film is used as a substrate , the substrate temperature
formed in an atmosphere containing oxygen under light is preferably maintained at less than 100° C. The number of
irradiation without adding impurity ions for enhancing elec- 30 electron carriers can be reduced by further increasing oxy
tric resistance on purpose . gen partial pressure .
< Film Composition > More specifically , the present invention is directed to an
In a transparent amorphous oxide thin which has a amorphous oxide comprising In GaZn O prepared by
composition in a crystalline state represented by InGaOz a sputtering deposition method under light irradiation .
(ZnO )m (m is a natural number of less than 6 ), the amor- 35 According to the present invention , a normally -off transistor
phous state can be stably maintained to a temperature as high having an on /off ratio exceeding 1x103 can be formed by
as 800° C. or more if the value m is less than 6. However, using a transparent amorphous oxide thin film containing a
as the value m increases, in other words, the ratio of ZnO to microcrystal (s ) represented by a crystalline state composi
InGaOz increases ( that is, the composition of the film tion of InGaOz(ZnO )m (m is a natural number of less than 6 ).
becomes closer to ZnO ), the film comes to be easily crys- 40 In the thin film prepared by a pulse laser deposition
tallized method and a sputtering method under light irradiation , the
For this reason , it is preferable that the value m is less than electron mobility increases with an increase of the number
6 when the amorphous film is used as the channel layer of of conductive electrons.
an amorphous TFT. However , it is found that when the film In this case, if a polycrystalline InGaO ; (Zn - Mg, 0 )m (m
is formed under light irradiation , microcrystals can be 45 is a naturalnumber of less than 6,0 < xsl) is used as a target,
formed even though the value m is small . a high resistance amorphous film having a composition of
The film may be formed by a vapor-phase film formation InGaOz( Zn - Mg, 0 )m can be obtained even under a partial
method with a polycrystalline-sintered body having a com oxygen pressure of less than 1 Pa.
position of InGaOz(ZnO )m used as a target . Of the vapor As explained above , oxygen defect can be overcome by
phase film formation methods, a sputtering method and a 50 controlling oxygen partial pressure . As a result, the electron
pulse laser deposition method are suitable. Moreover , the carrier concentration can be reduced without adding prede
sputtering method is most preferable in view of large-scale termined impurity ions. An amorphous oxide according to
production . the present invention can be obtained by forming a thin film
However, such an amorphous film is formed in general according to any one of FIGS. 1 to 5 under light irradiation .
conditions, mainly oxygen defect occurs. Therefore , an 55 When apparatuses according to FIGS. 7 and 8 are used , a
electron carrier concentration has not yet been reduced to film can be formed at an oxygen partial pressure , for
less than 1x1018 /cm ", in other words, 10 S/cm or less in example , within the predetermined range described later. In
terms of electric conductivity. When such a conventional the amorphous state containing a microcrystal (s ), the grain
thin film is used , a normally -off transistor cannot be formed . boundary interface of a microcrystal is covered with (sur
However, when a transparent amorphous oxide film , which 60 rounded by ) an amorphous structure. Therefore , the grain
has a composition of In — Ga - Zn - O and a crystalline state boundary interface capable of trapping mobile electrons and
composition represented by InGaOz(ZnO )m (m is a natural holes does not virtually exist, unlike the polycrystalline state
number of less than 6 ), is formed by a pulse laser deposition like zinc oxide. As a result, an amorphous thin film having
method using the apparatus shown in FIG . 7, in an atmo high electron mobility can be obtained . Furthermore , the
sphere having a high oxygen partial pressure in excess of 3.2 65 number of conductive electrons can be reduced without
Pa, the electron carrier concentration can be reduced to less adding predetermined impurity ions. Since electrons are not
than 1x1018/ cm3. In this case, the substrate is not purposely scattered by the impurity ions, high electron mobility can be
 US 10,615,287 B2
7 8
maintained . The microcrystals according to the present That is, in case of using the above amorphous oxide as an
invention are not limited to that having a composition active layer of the transistor, it is preferable to design the
represented by InGaO3(ZnO )m (m is a natural number of less active layer so as to be comprised of the first region and the
than 6 ) . second region more adjacent to the gate insulator than the
In a thin film transistor employing the transparent film 5 first region , the concentration of oxygen in the second region
mentioned above , the gate insulator is preferably formed of is greater than the that in the first region . Incidentally , the
a mixed crystal compound containing at least two com two regions are not necessary to be distinguishable at a
pounds selected from the group consisting of A120 - Y203 boundary of them but may change their respective compo
and HfO2. When a defect (deficiency ) is present in the sitions gradually or step by step .
interface between the gate insulating thin film and the 10 In particular, the electron carrier concentration of the
channel layer thin film , the electron mobility decreases and amorphous oxide is preferably less than 118 /cm3.
hysteresis as a transistor characteristic , takes place . Further A direction of the film formed on the substrate means any
more , if the ty of gate insulators differs , leak current direction which is not in the direction in plane of the
greatly varies. For this reason , it is necessary to select a substrate , e.g. the direction perpendicular to the direction in
suitable gate insulator for the channel layer. If an Al2O3 film 15 plane of the substrate . Furthermore, in a transistor having an
is used ( as the gate insulator), the leak current can be active layer formed of an amorphous oxide having at least
reduced . If an Y203 film is used , the hysteresis can be one element selected from the group consisting of In and Zn
reduced . If an HfO , film having a high dielectric constant is and a gate insulator in contact with the active layer at the
used , the electron mobility can be increased . Furthermore , if interface , the concentration of In or Zn contained in the
a mixed crystal of these compounds is used (as a gate 20 region of the amorphous oxide layer (active layer) close to
insulator), leak current, it is possible to form a TFT having the interface is higher than the region away from the
a small leak current and hysteresis, and large electron interface. In this case, the electron field -effect mobility can
mobility . Since a gate insulator formation process and a be enhanced .
channel layer formation process can be performed at room That is, in case of using the above amorphous oxide as an
temperature , not only a stagger -structure TFT but also an 25 active layer of the transistor, it is preferable to design the
inverse- stagger structure TFT may be formed . active layer so as to be comprised of the first region and the
A TFT is a device having three terminals , namely, a gate second region more adjacent to the gate insulator than the
terminal, source terminal and drain terminal . In the TFT, a first region , the concentration of In or Zn in the second
semiconductor thin film formed on an insulating substrate region is greater than the that in the first region .
such as ceramic , glass, or plastic substrate is used as a 30 According to the second invention , an oxide film com
channel layer for migrating electrons and holes there prises In Ga - Zn- and its composition changes in the
through . The current flowing through the channel layer is film -thickness direction, and characterized in that the com
controlled by applying a voltage to the gate terminal, thereby position of a crystalline -state portion is represented by
switching the current between the source terminal and the InGaOz(ZnO ) m (m is a naturalnumber of less than 6 ) and an
drain terminal. Since the TFT has such a switching function , 35 electron carrier concentration is less than 1x1018/ cm3.
it is an active device. Note that microcrystals contained in an Alternatively , an oxide film according to the second
amorphous oxide may be formed by light irradiation (spe invention is a transparent amorphous oxide film comprising
cifically, light irradiation by a halogen lamp or UV irradia In — Ga - Zn - Mg - O and characterized in that the com
tion ) as mentioned above and may be formed by other position changes in a film -thickness direction and the com
methods except for light irradiation . 40 position of a crystalline state portion is represented by
InGaOz(Zn1-xMg, 0 )m (m is a natural number of less than 6 ,
Second Embodiment: Compositional Distribution of O <xsl ) and an electron carrier concentration is less than
Amorphous Oxide 1x1018/cm². Note that, it is also preferable that these films
have an electron mobility exceeding 1 cm²/V sec .
According to this embodiment, an amorphous oxide is 45 When the aforementioned film is used as the channel
characterized by a composition varying in a film -thickness layer , it is possible to obtain a flexible TFT having transistor
direction . characteristics : a gate current of less than 0.1 micro ampere
The phrase " composition varying in a film -thickness when TFT is off (normally -off ), an on /off ratio exceeding
direction ” means that the oxygen amount contained in an 1x104, and being permeable to visible light.
oxide changes in the film thickness direction and elements 50 Note that, such a transparent film is characterized in that
constituting an oxide changes in the middle (that is , the the electron mobility increases with an increase of the
composition changes ), and the contents of the elements number of conductive electrons. As a substrate for forming
constituting an oxide change . the transparent film , use can be made of a glass substrate,
Therefore , when the amorphous oxide is used as the active plastic substrate or plastic film .
layer (also called channel layer ) of a field effect transistor, 55 When the transparent oxide film is used as the channel
for example , the following constitution is preferable . In a layer of a transistor, it is preferable to employ one type of
transistor having an active layer containing an amorphous compound selected from the group consisting of A120
oxide and a gate insulator in contact with each other at an Y202 and HfO , or a mixed crystal compound containing at
interface , the amorphous oxide layer is constituted such that least two types of compounds selected from the group
the concentration of oxygen near the interface is set higher 60 consisting of Al2O3, Y203 and HfO , as the gate insulator.
than the region away from the interface . In this case, since It is preferable that the film ( transparent oxide film ) is
the electric resistance of the amorphous oxide layer near the formed in an atmosphere containing oxygen without adding
interface is high , the so -called channel of the transistor is impurity ions for enhancing electric resistance on purpose.
formed within the amorphous oxide layer away from the The present inventors found a specific feature of the
interface . Such a constitution is preferable when the inter- 65 semi-insulating amorphous oxide thin film . That is , the
face is a rough surface , because current leakage can be electron mobility increases with an increase of the number
reduced . of conductive electrons. They formed a TFT using this film
 US 10,615,287 B2
9 10
and found that the characteristics of the transistor, such as an a small leak current and hysteresis, and large electron
on /off ratio , saturation current at a pinch -off state , and mobility . Since a gate insulator formation process and a
switching speed , further increase . channel layer formation process can be performed at room
In a film transistor formed by using the transparent temperature , not only a stagger- structure TFT but also an
semi-insulating amorphous oxide thin film as the channel 5 inverse -stagger structure TFT may be formed .
layer, when an electron mobility is more than 1 cm²/V.sec , A TFT is a device having three terminals , namely, a gate
preferably more than 5 cm ? /V.sec, and an electron carrier terminal , source terminal and drain terminal. In the TFT, a
concentration to less than 1x1018/cm °, preferably , less than semiconductor thin film formed on an insulating substrate
1x1016/ cm ", the current between the drain and source ter such as ceramic , glass, or plastic substrate is used as a
minals in the off time (gate voltage is not applied ) can be 10 channel layer for migrating electrons and holes there
reduced to less than 10 micro ampere , preferably , less than through . The current flowing through the channel layer is
0.1 micro ampere. Further, in this case (of using the afore controlled by applying a voltage to the gate terminal, thereby
mentioned thin film ), when an electron mobility is more than switching the current between the source terminal and the
1 cm ?/V.sec , preferably more than 5 cm ? /V.sec, the satura drain terminal. Since the TFT has such a switching function ,
tion currentafter the pinch off can be increased to more than 15 it is an active device .
10 micro ampere. In short, an on /off ratio can be increased As described above, the second invention is directed to
to more than 1x104. improvement of a composition in the film thickness direc
In a TFT, a high voltage is applied to a gate terminal in a tion of the transparent film , which serves as the active layer
pinch off state , with the result that electrons are present at a of a field effect transistor (FET), when the FET is formed
high density in the channel. Therefore, according to the 20 using the transparent film .
present invention , the saturation current can be increased by To explain more specifically, when a pulse laser deposi
the extent corresponding to an increase of electron mobility . tion method is used , a composition is changed in the
As a result , almost all characteristics of the transistor, such film -thickness direction by varying oxygen partial pressure
as an on /off ratio , saturation current, and switching rate, are in the film thickness direction , varying oscillation power of
increased and improved . Note that, in a general compound , 25 a pulse laser or an oscillation frequency, or varying the
when the number of electrons increases , collision between distance between a target and a substrate in the film thick
electrons takes place , with the result that the electron mobil ness direction . On the other hand , when a sputter deposition
ity decreases. method is used , a composition is changed in the film
The amorphous oxide according to the present invention thickness direction by additionally sputtering a target, such
can be used in a staggered (top gate) structure TFT in which 30 as In2O3 or ZnO . For example ,when a film is formed under
the gate insulator and the gate terminal are sequentially an oxygen atmosphere, the amount of oxygen contained in
formed in this order on the semiconductor channel layer and the film increases as the distance between a target and a
in an inverse staggered (bottom gate ) structure TFT in which substrate increases . Furthermore , when a Zno target is
the gate insulator and the semiconductor channel layer are added during film formation time, the amount of Zn
sequentially formed in this order on the gate terminal. 35 increases in the film formed after the addition of the Zn
< Film Composition > target.
In a transparent amorphous oxide thin film whose crys
talline portion has a composition represented by InGaOz Third Embodiment: Amorphous Oxide Containing
( ZnO ) m (m is a natural number of less than 6 ), when the an Additive (s )
value m is less than 6 , the amorphous state can be stably 40
maintained to a temperature as high as 800° C. or more . An amorphous oxide according to this embodiment is
However, as the value m increases , in other words, the ratio characterized in that the amorphous oxide contains at least
of ZnO to InGaOz increases ( that is, the composition of the one or plurality of types of elements selected from the group
film becomes closer to ZnO ), the film comes to be easily
crystallized
consisting of Li, Na, Mn, Ni, Pd, Cu , Cd , C , N , P, Ti, Zr, V ,
45 Ru, Ge, Sn , and F are contained as an additive . Introduction
For this reason , it is preferable that the value m is less than of an additive into an amorphous oxide is attained by
6 when the amorphous film is used as the channel layer of introducing the additive in a gas for use in a film formation
an amorphous TFT. apparatus or in the film formation apparatus , or in a target
A thin film transistor employing the transparent film material that is used in the apparatus . As a matter of course,
mentioned above preferably uses a gate insulator formed of 50 after a film is formed from an amorphous oxide without an
a mixed crystal compound containing one type of compound additive , the additive may be introduced into the film as is
selected from the group consisting of Al2O3, Y2O3 and HfO2 described later in Examples .
or a mixed crystal compound containing at least two types The electron carrier concentration of the amorphos oxide
of compounds selected from the group consisting of A1,03, is preferably less than 1018/cm3.
Y2O3 and HfO2 When a defect ( deficiency ) is present in the 55 An amorphous oxide according to the present invention
interface between the gate insulating thin film and the may include a transparent amorphous oxide comprising
channel layer thin film , the electron mobility decreases and In — Ga - Zn- and whose composition in a crystalline
hysteresis as a transistor characteristic, takes place . Further state is represented by InGaOz(ZnO )m (m is a natural num
more , if the types of gate insulators differs, leak current ber of less than 6 ) and include an oxide comprising In
greatly varies. For this reason , it is necessary to select a 60 Ga - Zn - Mg and whose composition in a crystalline
suitable gate insulator for the channel layer. If an A1203 film state is represented by InGaO (Zn , Mg, 0 ), (m is a natural
is used as the gate insulator ), the leak current can be number of less than 6 , 0 < xsl). To these oxides, further at
reduced . If an Y203 film is used, the hysteresis can be least one type or plurality of types of elements selected from
reduced . If an HfO , film having a high dielectric constant is the group consisting ofLi, Na, Mn,Ni, Pd, Cu , Cd , C , N , and
used , the electron mobility can be increased . Furthermore, if 65 P are introduced as an additive .
a mixed crystal of these compounds is used (as a gate In this manner, the electron carrier concentration can be
insulator), leak current, it is possible to form a TFT having reduced . Even though the electron carrier concentration is
 US 10,615,287 B2
11 12
significantly reduced, it is possible to prevent the electron because it can maintain good contact with the electrodes . In
carrier mobility from decreasing, rendering the control of other words, the impurity concentration of this portion
electron carrier concentration easy. As a result , when the preferably low . Such a constitution can be attained by
transparent amorphous oxide film is employed as the chan bringing the channel layer 2 into contact with a solution
nel layer of a TFT, the resultant TFT panel has a uniform 5 containing impurities after the drain electrode 5 and the
characteristic even though the panel has a large area . source electrode 6 are formed and before a gate insulting
When Li, Na, Mn, Ni, Pd , Cu, Cd, C , N , and P , are used film 3 is formed . In this manner, the impurities can be
as an impurity (additive ), these impurities can substitute for diffused with the drain electrode 5 and the source electrode
any one of In , Ga, Zn , O and serve as an acceptor and may 6 used as a mask .
decrease the electron carrier density , although the details of 10 In FIG . 5 , the portion of the channel layer 2 especially in
the mechanism are unknown. In a general oxide semicon
ductor, since the oxygen concentration cannot be appropri contact with the substrate is not easily placed under the
ately controlled , a large number of oxygen deficiencies are Therefore, the
control of gate electrode 4 for electron carrier density.
it is helpful if the electron carrier density of the
produced . Furthermore, mostly in the case where deficiency
are produced in the grain boundary due to a polycrystalline 15 portion is previously suppressed low , in order to increase the
state , the electron carrier density cannot be controlled well of on/off ratio . Then , it is effective to increase the concentration
even if impurities are introduced . In this respect , a trans impurities particularly at the interface facing the sub
parent amorphous oxide film according to the present inven strate . Such a constitution can be attained by controlling the
tion has a few oxygen deficiencies and no grain boundary concentration of a gas such as CH4, NO and PHz to be
due to the amorphous state . Hence, it is considered that 20 introduced into the atmosphere, in such a manner that the
impurities effectively work as the acceptor. When a thin film gas is started to supply at an excessive concentration and
is formed by increasing oxygen partial pressure in order to gradually reduced in concentration . Alternatively, in the case
reduce the electron carrier density , the skeleton of atomic of an impurity such as Na previously contained in a sub
bonding changes, increasing the tail state of the conduction strate, such a constitution can be attained by diffusing Na by
band . If electrons are trapped by the tail state , the electron 25 heating the substrate at an appropriate temperature .
carrier mobility may substantially decrease . However, the As an additive , at least one type or a plurality of types of
addition of Li, Na, Mn, Ni, Pd , Cu , Cd , C , N , and P , makes elements selected from the group consisting of Ti, Zr, V, Ru ,
it possible to control the carrier density while maintaining Ge, Sn, and F may be introduced into an amorphous oxide .
oxygen partial pressure within an appropriate range . There In this case , it is expected that the electron mobility can be
fore, the electron carrier mobility is conceivably less 30 increased to 1 cm ?N.sec or more, and further to 5 cm ?N.sec
affected . Thus, when the present invention is compared to or more while keeping an electron carrier concentration of
the case where the electron carrier concentration and the less than 1x1018 / cm2. Even if the electron field - effectmobil
electron carrier mobility are controlled only by controlling ity in ases, the electron carrier concentration rarely
oxygen partial pressure , the in -plain uniformity of charac increases in accordance therewith . Hence, when the trans
teristics of an oxide film can be easily enhanced even though 35 parent amorphous oxide film is used as the channel layer, it
a large substrate is used . is possible to obtain a TFT having a high on /off ratio and a
The additive may be selected from the group consisting of large saturation current during the pinch off time as well as
Ti, Zr, V, Ru , Ge, Sn and F as mentioned below . a high switching speed . Furthermore , it is easy to enhance
Note that the concentration of impurities required for the in -plane uniformity of oxide-film characteristics even if
obtaining a desired effect (in a amorphous film ) is about 0.1 40 a large substrate is used , compared to the case where the
to 3 atomic % , which is higher than that in a crystalline film electron carrier concentration and the electron carrier mobil
formed of Si or the like . This is considered because the ity are controlled only by adjusting oxygen partial pressure .
probability that impurity atoms enter effective sites for Although details of the mechanism are unknown, when an
controlling valence electrons is lower in the amorphous state oxide is formed by increasing the partial oxygen pressure ,
than on the crystalline state. Most generally, a desired 45 the tail state density of a portion under a conduction band
impurity is introduced into the target by an impurity intro increases, with the result that the mobility may decrease .
duction method . In the case of impurities such as C , N , and However, impurities such as Ti, Zr, V , Ru , Ge, Sn , and F ,
P, they can be introduced into a film by introducing a gas conceivably act on the skeleton of atomic bonding, thereby
such as CH4, NO and PHz together with oxygen to the reducing the tail state, with the result that the electron carrier
atmosphere . When a metallic element is introduced as an 50 mobility can be enhanced while maintaining the electron
impurity , after a transparent amorphous oxide film is carrier density.
formed , the film is brought into contact with a solution or These impurities mentioned above are preferably used in
paste containing the metallic -element ion . Furthermore , a concentration within the range of about 0.1 to 3 atomic %
when a substrate such as a glass having a high heat resis or 0.01 to 1 atomic % . The term “ atomic % ” is a ratio of the
tance is used , these metallic elements are previously con- 55 atomic number of a constitutional element contained in an
tained in the substrate and then , the substrate is heated oxide. Note that when it is difficult to measure the amount
during or after the film formation , thereby diffusing the of oxygen , the aforementioned ranges may be defined by a
metallic elements into a transparent amorphous oxide film . ratio of the atomic numbers of constitutional elements
As a Na source , for example , soda glass can be used since except for oxygen . Most generally , a desired impurity is
it contains 10 to 20 atomic % of Na . 60 introduced into the target by a method of introducing an
FIG . 5 shows a typical structure of a TFT device . In the impurity . In the case of an impurity of F, it can be introduced
TFT device , the portion that can effectively reduce the into a film by introducing a gas such as SF6, SiF4, or CLF :
electron carrier density is that of a channel layer 2 sand together with oxygen to the atmosphere. When a metallic
wiched between a drain electrode 5 and a source electrode element is introduced as the impurity , after a transparent
6. In contrast, it is advantageous that the portion of the 65 amorphous oxide film is formed , the film is brought into
channel layer 2 in contact with the drain electrode 5 and the contact with a solution or paste containing the metallic
source electrode 6 has a high electron carrier density . This is element ion .
 US 10,615,287 B2
13 14
FIG . 5 shows a typical structure of a TFT device . In the In the present specification , the description “ less than
TFT device , the portion in which especially high electron 1018 /cm3» means preferably less than 1x1018/cm and
mobility is required , is that of the channel layer 2 in contact more preferably less than 1.0x1018 /cms
with the gate insulator 3. Then , it is effective that the The electron carrier concentration can be measured by
impurity concentration of the present invention is increased 5 measurement of a Hall Effect.
particularly in the interface in contact with the gate insula The amorphous oxide in the present invention is an oxide
tion film 3. Such a constitution can be attained by introduc which exhibits a halo pattern and no characteristic diffrac
ing a gas such as SF6, SiF4, and CLFz into an atmosphere tion line in an X -ray diffraction spectrometry.
during the channel layer formation timewhile increasing the 10 In the amorphous oxide of the present invention , the lower
concentration of the gas ( starting from a lower level). limit of the electron carrier concentration is, for example ,
In the present invention , it is basically important that 1x1012/cm3, but is not limited insofar as it is applicable as
atomic bonding structure can be appropriately formed by a channel layer of a TFT.
controlling the amount of oxygen ( oxygen defect amount). Accordingly, in the present invention, the electron carrier
In the aforementioned description, the amountof oxygen 15 concentration is adjusted by controlling the material, com
in a transparent oxide film is controlled by forming a film in position ratio , production conditions, and so forth of the
an atmosphere containing a predetermined amount of oxy amorphous oxide as in the Examples described later to be in
gen . It is also preferable that after an oxide film is formed , the range , for instance , from 1x1012 /cm² to 1x1018 / cm3,
it is treated in an atmosphere containing oxygen , thereby preferably from 1x1013/cm²to 1x1017/ cm ",more preferably
controlling (decreasing or increasing ) the oxygen defect 20 from 1x1015/cm2 to 1x1016/cm ”.
amount. The amorphous oxide , other than the InZnGa oxides, can
To effectively control the oxygen defect amount, a film is be selected suitably from In oxides, In , Znj-x oxides
treated in an atmosphere containing oxygen set at a tem (0.2sxsl), In Sn1-x oxides (0.8sxsl ), and In , (Zn , Sn ) 1-x
perature from 0 to 300 ° C. (both inclusive ), preferably from oxides (0.15sxsl). The In (Zn,Sn )1-x oxide can also be
25 to 250 ° C.(both inclusive ), further preferable 100 to 200 ° 25 represented by In (Zn, Sni-y) 1-4 (Osxsl).
C. (both inclusive). When the In oxide contains neither Zn nor Sn , the In can
As a matter of course , not only film formation but also be partly substituted by Ga: In ,Gal-x oxide (Osxsl).
treatment after the film formation may be performed in an An amorphous oxide of an electron carrier concentration
atmosphere containing oxygen . Furthermore , as long as a 30 of 1x1018 /cm² which is prepared by the inventors of the
predetermined electron carrier concentration (less than present invention is described below in detail.
1x1018 /cm ) is obtained , a film may be formed without One group of the aforementioned oxides are characteris
controlling oxygen partial pressure and thereafter the film tically constituted of In - Ga - Zn - O , represented by
may be treated in an atmosphere containing oxygen . InGaOz(ZnO )m (m : a natural number of less than 6 ) in a
In the present invention , the lowermost electron carrier 35 crystal state , and containing electron carriers at a concen
concentration varies depending upon the use of the obtained tration of less than 1x1018 /cm3.
oxide film , more specifically , the type of device, circuit, and The other group of the aforementioned oxides are char
apparatus; however, for example, 1x1014 /cm3 or more is acteristically constituted of InGa - Zn - MgO, repre
preferable . sented by InGaOz(Zn - Mg, 0 )m (m : a natural number of less
Now , amorphous oxides applicable to Embodiments 1 to 40 than 6 , and 0 < x :1) in a crystal state, and containing electron
3 will be described in detail below . To the amorphous oxides carriers at a concentration of less than 1x1018 /cm3.
or the manufacturing methods thereof, the following condi The film constituted of such an oxide is preferably
tions are added . In the invention according to the first designed to exhibit preferably an electron mobility ofhigher
embodiment, light irradiation is added to the manufacturing than 1 cm ? /V.sec .
conditions. In the invention according to the second embodi- 45 By use of the above film as the channel layer, a TFT can
ment, means for changing a film composition are used as be prepared which is normally -off with a gate current of less
described in Examples . In the invention according to the than 0.1 microampere in a transistor off -state , having an
third embodiment, in addition to the film formation condi on -off ratio of higher than 1x10 ',being transparent to visible
tions , a gas and a target for adding impurities are used or, light and flexible .
after the film formation , a predetermined method for adding 50 In the above film , the electron mobility increases with the
impurities to amorphous oxide shown below may be increase of the conduction electrons. The substrate for
employed . forming the transparent film includes glass plates , plastic
(Amorphous Oxide ) plates, and plastic films.
The active layer employed in the above Embodiments 1 to In using the above amorphous oxide film as the channel
3 of the invention is explained below . 55 layer, at least one of layers constituted of Al2O3, Y203 or
The electron carrier concentration in the amorphous oxide HfO 2 : or a mixed crystal compound thereof is useful as the
in the present invention is a value measured at a room gate insulator.
temperature. The room temperature is a temperature in the In a preferred embodiment, the film is formed in an
range from 0 ° C. to about 40 ° C., for example, 25 ° C. The oxygen gas -containing atmosphere without intentional addi
electron carrier concentration in the amorphous oxide in the 60 tion of an impurity for increasing the electric resistance to
present invention need not be less than 1018/cmº throughout the amorphous oxide.
the entire range from 0 to 40 ° C. For example, the electron The inventors of the present invention found that the
carrier concentration of less than 1x1018/cm at a tempera amorphous thin films of semi- insulating oxides have char
ture of 25 ° C. is acceptable . At a lower electron carrier acteristics that the electron mobility therein increases with
concentration , not more than 1x1017/cm ", or not more than 65 increase in number of conduction electrons, and further
1x1016/cm ", a normally -off TFT can be produced at a high found that a TFT prepared by use of the film is improved in
yield . transistor characteristics such as the on -off ratio , the satu
 US 10,615,287 B2
15 16
ration current in a pinch -off state, and the switching rate . manometer ); 719 , a PG (Pirani gage ); 720, a BG (baratron
Thus a normally -off type TFT can be produced by use of the gage ); and 721 , a growth chamber.
amorphous oxide . An In - Ga - Zn O type amorphous oxide semiconduc
By use of the amorphous oxide thin film as the channel tor thin film was deposited on an SiO2 glass substrate
layer of a film transistor, the electron mobility can be made 5 (Corning Co.: 1737 ) by a pulse laser vapor deposition
higher than 1 cm²/V -sec, preferably higher than 5 cm²/ employing a KrF excimer laser. As the pretreatment before
V.sec . The current between the drain terminal and the source the deposition , the substrate was washed ultrasonically for
terminal at an off -state (no gate voltage applied ) can be defatting with acetone, ethanol, and ultrapure water each for
controlled to be less than 10 microamperes, preferably less five minutes , and dried in the air at 100° C.
than more than 0.1 microamperes at the carrier concentration 10 The polycrystalline target was an InGaOz(ZnO )4 sintered
of lower than 1x1018 /cm ", preferably lower than 1x1016 / compact (size : 20 mm diameter, 5 mm thick ), which had
cm °. Further by use of this thin film , the saturation current been prepared by wet-mixing In2O3, Ga ,03, and ZnO (each
after pinch -off can be raised to 10 microamperes ormore and 4N reagent) as the source material (solvent: ethanol), cal
the on -off ratio can be raised to be higher than 1x103 for the cining the mixture ( 1000 ° C., 2 hours ), dry -crushing it, and
electron mobility higher than 1 cm ?/V -sec , preferably higher 15 sintering it ( 1550 ° C., 2 hours). The target had an electro
than 5 cm ? /V.sec . conductivity of 90 S /cm .
In a pinch -off state of the TFT, a high voltage is being The film formation was conducted by controlling the final
applied to the gate terminal, and electrons are existing in a vacuum of the growth chamber to be 2x10- Pa, and the
high density in the channel. Therefore, according to the oxygen partial pressure during the growth to be 6.5 Pa . The
present invention , the saturation current can be increased in 20 oxygen partial pressure in growth chamber 721 was 6.5 Pa,
correspondence with the increase of the electron mobility. and the substrate temperature was 25 ° C. The distance
Thereby , the transistor characteristics can be improved , such between target 708 and film -holding substrate 707 was 30
as increase of the on -off ratio , increase of the saturation mm , the power introduced through introduction window 716
current, and increase of the switching rate . In contrast , in a was in the range of 1.5-3 mJ/cm²/pulse . The pulse width was
usual compound, the increase of electrons decreases the 25 20 nsec , the repeating frequency was 10 Hz, and the irra
electron mobility owing to collision between electrons. diation spot size was 1x1 mm square . Under the above
The structure of the aforementioned TFT may be a stagger conditions , the film was formed at a rate of 7 nm /min .
(top gate) structure in which a gate insulator and a gate The resulting thin film was examined by small angle
terminal are successively formed on a semiconductor chan X - ray scattering method (SAXS) ( thin film method, inci
nel layer, or a reversed stagger (bottom gate ) structure in 30 dence angle : 0.5° ): no clear diffraction peak was observed .
which a gate insulator and a semiconductor channel layer Thus the obtained In Ga - Zn- type thin film was
successively on a gate terminal. judged to be amorphous . From X -ray reflectivity and its
(First Process for Film Formation: PLD Process ) pattern analysis, the mean square roughness (Rrms) was
The amorphous oxide thin film having the composition found to be about 0.5 nm , and the film thickness to be about
InGaO3(ZnO )m (m : a natural number of less than 6 ) in a 35 120 nm . From fluorescence X -ray spectrometric analysis
crystal state is stable up to a high temperature of 800 ° C. or (XRF ) , the metal composition of the film was found to be
higher when m is less than 6 , whereas with increase of m , In :Ga:Zn = 0.98 : 1.02 :4 . The electric conductivity was less
namely with increase of the ratio of ZnO to InGaOz near to than about 1x10-2 S /cm . The electron carrier concentration
the composition of ZnO , the oxide tends to crystallize . was estimated to be notmore than 1x10-16/ cm². The elec
Therefore, the value m of the oxide is preferably less than 6 40 light
tron mobility was estimated to be about 5 cm /V.sec. From
absorption spectrum analysis , the optical band gap
for use as the channel layer of the amorphous TFT.
The film formation is conducted preferably by a gas phase energy breadth of the resulting amorphous thin film was
film formation process by use of a target of a polycrystalline estimated to be about 3 eV .
sintered compact having a composition InGaOz(ZnO ) m . Of The above results show that the obtained In - Ga
the gas phase film formation processes , sputtering, and pulse 45 Zn O type thin film is a transparent flat thin film having an
laser vapor deposition are suitable. The sputtering is par amorphous phase of a composition near to a crystalline
ticularly suitable for the mass -production . InGao , (ZnO ) ,having less oxygen defect, and having lower
However, in formation of the amorphous film under usual electric conductivity.
conditions, oxygen defect can occur, so that the electron The above film formation is explained specifically by
carrier concentration of less than 1x1018 /cm² and electric 50 reference to FIG . 1. FIG . 1 shows dependency of the
conductivity of less the 10 S /cm cannot be achieved . With electron carrier concentration in the formed transparent
such a film , a normally -off transistor cannot be constituted . amorphous oxide thin film on the oxygen partial pressure for
The inventors of the present invention produced an In the film of a composition of InGaO3(ZnO )m (m : an integer
Ga - Zn - O film by a pulse laser vapor deposition by use of less than 6 ) in an assumed crystalline state under the same
the apparatus shown in FIG . 7 . 55 film formation conditions as in the above Example .
The film -forming was carried out by using such a PLD By formation of the film in an atmosphere having an
film -forming apparatus as shown in FIG . 7 . oxygen partial pressure ofhigher than 4.5 Pa under the same
In FIG . 7 , the numerals indicate the followings : 701, an conditions as in the above Example , the electron carrier
RP (rotary pump); 702, a TMP ( turbo molecular pump); 703, concentration could be lowered to less than 1x1018/cm3 as
a preliminary chamber; 704 , an electron gun for RHEED ; 60 shown in FIG . 1. In this film formation , the substrate was
705 , a substrate holding means for rotating and vertically kept nearly at room temperature without intentional heating.
moving the substrate; 706 , a laser- introducing window ; 707, For use of a flexible plastic film as the substrate , the
a substrate ; 708 , a target ; 709 , a radical source ; 710, a gas substrate temperature is kept preferably at a temperature
inlet; 711, a target-holding means for rotating and vertically lower than 100 ° C.
moving the target; 712 , a by -pass line; 713 , a main line; 714 , 65 The higher oxygen partial pressure enables decrease of
a TMP ( turbo molecular pump ); 715 , an RP (rotary pump ); the electron carrier concentration. For instance , as shown in
716 , a titanium getter pump; 717 , a shutter; 718 , an IG (ion FIG . 1, the thin InGaOz( ZnO )4 film formed at the substrate
 US 10,615,287 B2
17 18
temperature of 25 ° C. and the oxygen partial pressure of 5 electron carriers at a lower concentration to achieve higher
Pa had a lower electron carrier concentration of 1x1016/ cm3. electric resistance and exhibiting a higher electron mobility.
In the obtained thin film , the electron mobility was higher The above amorphous oxide has excellent characteristics
than 1 cm ? /V.sec as shown in FIG . 2. However, the film that the electron mobility increases with the increase of the
deposited by the pulse laser vapor deposition at an oxygen 5 electron carrier concentration , and exhibits degenerate con
partial pressure of higher than 6.5 Pa as in this Example has duction . In this Example, the thin film was formed on a glass
a rough surface, being not suitable for a channel layer of the substrate . However, a plastic plate or film is useful as the
substrate since the film formation can be conducted at room
TFT.
Accordingly, a normally -off type transistor can be con temperature . Further, the amorphous oxide obtained in this
structed by using a transparent thin amorphous oxide rep 10 Example , absorbs visible light only little to give transparent
resented by InGaOz(ZnO )m (m : a number less than 6 ) in a flexible TFT.
crystal state formed at an oxygen partial pressure of higher (SP ProcessProcess
( Second
))
for Film Formation : Sputtering Process
than 4.5 Pa, preferably higher than 5 Pa, but lower than 6.5
Pa by a pulse laser vapor deposition method in the above 15 an Film formation by a high - frequency SP process by use of
argon gas as the atmosphere gas is explained below .
Example . The above obtained thin film exhibited an electron The SP process was conducted by use of the apparatus
mobility higher than 1 cm ?/V , and the on -off ratio could be shown in FIG . 8. In FIG . 8 , the numerals indicates the
made higher than 1x103. followings: 807 , a substrate for film formation ; 808 , a target;
As described above, in formation of an InGaZn oxide film 805 , a substrate -holding means equipped with a cooling
by a PLD method under the conditions shown in this 20 mechanism ; 814 , a turbo molecular pump ; 815 , a rotary
Example , the oxygen partial pressure is controlled in the pump ; 817, a shutter; 818 , an ion manometer; 819 , a Pirani
range preferably from 4.5 Pa to 6.5 Pa. gage ; 821, a growth chamber; and 830 , a gate valve .
For achieving the electron carrier concentration of Substrate 807 for film formation was an SiO2 glass
1x1018/cm ”, the oxygen partial pressure conditions, the substrate ( Corning Co .: 1737 ) which had been washed
constitution of the film formation apparatus , the kind and 25 ultrasonically for defatting with acetone, ethanol, and ultra
composition of the film - forming material should be con pure water respectively for 5 minutes, and dried at 100° C.
trolled . in the air.
Next, a top - gate type MISFET element as shown in FIG . The target was a polycrystalline sintered compact having
5 was produced by forming an amorphous oxide with the a composition of InGaO3(ZnO )4 (size : 20 nm diameter , 5
aforementioned apparatus at an oxygen partial pressure of 30 mm thick ), which had been prepared by wet -mixing In203,
6.5 Pa. Specifically , on glass substrate 1, a semi- insulating Ga203, and ZnO ( each 4N reagent) as the source material
amorphous InGaOz(ZnO )4 film of 120 nm thick was formed (solvent: ethanol), calcining the mixture ( 1000 ° C., 2 hours),
for use for channel layer 2 by the above method of formation dry -crushing it, and sintering (1550 ° C., 2 hours). Target 808
of amorphous thin Ga - Ga - Zn film . Further thereon had an electro conductivity of 90 S / cm , being semi-insulat
an InGao , (ZnO ) , film having a higher electro conductivity 35 ing .
and a gold film were laminated respectively in a thickness of The final vacuum degree of growth chamber 821 was
30 nm by pulse laser deposition at an oxygen partial pressure 1x10-4 Pa. During the growth , the total pressure of the
of lower than 1 Pa in the chamber. Then drain terminal 5 and oxygen and argon gas was kept constant within the range of
source terminal 6 were formed by photolithography and a 4 to 0.1x10-1 Pa. The partial pressure ratio of argon to
lift-offmethod . Finally, a Y203 film for gate insulator 3 was 40 oxygen was changed in the range of the oxygen partial
formed by an electron beam vapor deposition method ( thick pressure from 1x10-3 to 2x10-1 Pa.
ness: 90 nm , relative dielectric constant: about 15 , leak The substrate temperature was room temperature . The
current density : 1x10-3 A /cmº at application of 0.5 MV/cm ). distance between target 808 and substrate 807 for film
Thereon , a gold film was formed , and gate terminal 4 was formation was 30 mm .
formed by photolithography and lifting -off. 45 The inputted electric power was RF 180 W , and the film
Evaluation of Characteristics of MISFET Element forming rate was 10 nm /min .
FIG . 6 shows current-voltage characteristics of the MIS The resulting thin film was examined by small angle
FET element measured at room temperature . The channel is X -ray scattering method (SAXS ) ( thin film method, inci
understood to be an n - type semiconductor from the increase dence angle : 0.5°): no clear diffraction peak was observed .
of the drain current IDs with the increase of the drain voltage 50 Thus the obtained In — Ga - Zn- type thin film was
Vps. This is consistent with the fact that an amorphous judged to be amorphous. From X -ray reflectivity and its
In Ga - Zn- type semiconductor is of an n -type . The pattern analysis, the mean square roughness (Rrms) was
Ids becomes saturated (pinched off ) at VDs =6V, which is found to be about 0.5 nm , and the film thickness to be about
typical behavior of a semiconductor transistor. From exami 120 nm . From fluorescence X -ray spectrometric analysis
nation of the gain characteristics, the threshold value of the 55 (XRF ), the metal composition of the film was found to be
gate voltage V DS under application of VDs =4V was found to In :Ga:Zn = 0.98 : 1.02 :4 .
be about -0.5 V. A current flow of IDs = 1.0x10-5 A was The films were formed at various oxygen partial pressure
caused at VG= 10V. This corresponds to carrier induction by of the atmosphere, and the resulting amorphous oxide films
gate bias in the In— Ga - Zn- type amorphous semicon were measured for electric conductivity . FIG . 3 shows the
ductor thin film . 60 result.
The on -off ratio of the transistor was higher than 1x103. As shown in FIG . 3 , the electric conductivity can be
From the output characteristics, the field effect mobility was lowered to less than 10 S /cm by conducting the film forma
calculated to be about 7 cm ? (Vs) -7. Irradiation of visible tion in an atmosphere having an oxygen partial pressure
light did not change the transistor characteristics of the higher then 3x10-2 Pa. The electron carrier number could be
produced element according to the samemeasurement. 65 decreased by increase of the oxygen partial pressure .
According to the present invention , a thin film transistor As shown in FIG . 3, for instance, the thin InGaO3(Zn04
can be produced which has a channel layer containing film formed at the substrate temperature of 25 ° C. and the
 US 10,615,287 B2
19 20
oxygen partial pressure or 1x10- Pa had a lower electric esis, and exhibiting a higher electron mobility. Since the gate
conductivity of about 1x10-10 S / cm . Further , the thin insulator forming process and the channel layer forming
InGaOz(ZnO )4 film formed at the oxygen partial pressure or process can be conducted at room temperature , the TFT can
1x10- Pa had an excessively high electric resistance, hav be formed in a stagger constitution or in a reversed stagger
ing the electric conductivity not measurable . With this film , 5 constitution .
although the electron mobility was not measurable , the The TFT thus formed is a three-terminal element having
electron mobility was estimated to be about 1 cm²/V.sec by a gate terminal, a source terminal, and a drain terminal. This
extrapolation from the values of the films of high electron TFT is formed by forming a semiconductor thin film on a
carrier concentration . insulating substrate of a ceramics, glass, or plastics as a
Thus, a normally -off transistor having the on -off ratio of 10 channel layer for transport of electrons or holes, and serves
higher than 1x102 could be obtained by use of a transparent as an active element having a function of controlling the
thin amorphous oxide film constituted of In — Ga - ZnO current flowing
represented in a crystal state by InGaOz (ZnO )m (m : a natural a voltage to thethrough the channel layer by application of
number of less than 6 ) produced by sputtering vapor depo between the source terminal and, and
gate terminal switching the current
sition in an argon atmosphere containing oxygen at a partial 15 In the present invention , it is important terminal
the drain .
that an intended
pressure of higher than 3x10-2 Pa, preferably higher than electron carrier concentration is achieved by controlling the
5x10-1 Pa.
In use of the apparatus and the material employed in this amount of the oxygen defect.
Example, the film formation by sputtering is conducted in In the above description, the amount of the oxygen in the
the oxygen partial pressure ranging from 3x10-2 Pa to 20 amorphous oxide film is controlled by controlling the oxy
5x10- Pa. Incidentally , in the thin film produced by pulse gen concentration in the film - forming atmosphere . Other
laser vapor deposition or sputtering, the electron mobility wise the oxygen defect quantity can be controlled (decreased
increases with increase in number of the conductive elec or increase ) by post-treatment of the oxide film in an
trons . oxygen - containing atmosphere as a preferred embodiment.
As described above, by controlling the oxygen partial 25 For effective control of the oxygen defect quantity , the
pressure , the oxygen defect can be decreased , and thereby temperature of the oxygen -containing atmosphere is con
the electron carrier concentration can be decreased . In the trolled in the range from 0 ° C. to 300 ° C., preferably from
amorphous thin film , the electron mobility can be high , since 25 ° C. to 250 ° C., more preferably from 100 ° C. to 200 ° C.
no grain interface exists essentially in the amorphous state Naturally , a film may be formed in an oxygen -containing
differently from polycrystalline state . 30 atmosphere and further post-treated in an oxygen -containing
Incidentally , the substitution of the glass substrate by a atmosphere. Otherwise the film is formed without control of
200 um - thick polyethylene terephthalate (PET) film did not the oxygen partial pressure and post - treatment is conducted
change the properties of the amorphous oxide film of in an oxygen -containing atmosphere , insofar as the intended
InGaOz(ZnO ) 4 formed thereon . electron carrier concentration (less than 1x1018/ cm ) can be
A high -resistance amorphous film InGaOz( Zn1- Mg, 0 )m 35 achieved .
(m : an natural number less than 6 ; 0 < x :1 ) can be obtained by The lower limit of the electron carrier concentration in the
using , as the target , polycrystalline InGaOz (Zn , Mg, 0 ) present invention is , for example , 1x1024 /cm % depending
even at an oxygen partial pressure less than 1 Pa . For on the kind of the element, circuit, or device employing the
instance , with a target in which 80 atom % ofZn is replaced produced oxide film .
by Mg, the electron carrier concentration lower than 1x1016/ 40 (Broader Range of Materials )
cm (resistance: about 1x10-2 S /cm ) can be achieved by pulse After investigation on other materials for the system , it
laser deposition in an atmosphere containing oxygen at a was found that an amorphous oxide composed of at least one
partial pressure of 0.8 Pa . In such a film , the electron oxide of the elements of Zn , In , and Sn is useful for an
mobility is lower than that of the Mg- free film , but the amorphous oxide film of a low carrier concentration and
decrease is slight: the electron mobility is about 5 cm ?N.sec 45 high electron mobility .
at room temperature, being higher by about one digit than This amorphous oxide film was found to have a specific
that of amorphous silicon . When the filmsare formed under property that increase in number of conductive electrons
the same conditions, increase of the Mg content decreases therein increases the electron mobility. Using this film , a
both the electric conductivity and the electron mobility. normally -off type TFT can be produced which is excellent in
Therefore , the content of the Mg ranges preferably from 50 transistor properties such as the on -off ratio , the saturation
20 % to 85 % (0.2 < x <0.85 ). current in the pinch -off state, and the switching rate .
In the thin film transistor employing the above amorphous In the present invention , an oxide having any one of the
oxide film , the gate insulator contains preferably a mixed characteristics of (a ) to (h ) below are useful:
crystal compound containing two or more of Al2O3, Y203, ( a ) An amorphous oxide which has an electron carrier
HfO2, and compounds thereof. 55 concentration less than 1x1018/cm²;
The presence of a defect at the interface between the (b ) An amorphous oxide in which the electron mobility
gate - insulating thin film and the channel layer thin film becomes increased with increase of the electron carrier
lowers the electron mobility and causes hysteresis of the concentration ;
transistor characteristics. Moreover, the current leakage ( The room temperature signifies a temperature in the range
depends greatly on the kind of the gate insulator. Therefore 60 from about 0 ° C. to about 40 ° C. The term “ amorphous
the gate insulator should be selected to be suitable for the compound ” signifies a compound which shows a halo pat
channel layer. The current leakage can be decreased by use tern only without showing a characteristic diffraction pattern
of an Al2O3 film , the hysteresis can be made smaller by use in X -ray diffraction spectrum . The electron mobility signi
of a Y203 film , and the electron mobility can be increased by fies the one measured by the Hall effect.)
use ofan HfO , film having a high dielectric constant. By use 65 (c ) An amorphous oxide mentioned in the above items (a ) or
of the mixed crystal of the above compounds, TFT can be (b ), in which the electron mobility at room temperature is
formed which causes smaller current leakage , less hyster higher than 0.1 cm ?/V.sec ;
 US 10,615,287 B2
21 22
(d ) An amorphous oxide mentioned , in any of the items (b ) of an A1203 film , the hysteresis can be made smaller by use
to (c ), which shows degenerate conduction ; ( The term of a Y203 film , and the electron mobility can be increased by
“ degenerate conduction ” signifies the state in which the use of an HfO , film having a high dielectric constant. By use
thermal activation energy in temperature dependency of the of the mixed crystal of the above compounds, TFT can be
electric resistance is not higher than 30 meV.) 5 formed which causes smaller current leakage, less hyster
( e) An amorphous oxide, mentioned in any of the above item esis , and exhibiting a higher electron mobility . Since the gate
(a ) to (d ), which contains at least one of the elements of Zn , insulator- forming process and the channel layer-forming
In , and Sn as the constituting element; process can be conducted at room temperature , the TFT can
(f) An amorphous oxide film composed of the amorphous be formed in a stagger constitution or in a reversed stagger
oxidementioned the above item (e ), and additionally at least 10 constitution .
one of the elements of The In Oz oxide film can be formed through a gas -phase
Group -2 elements M2 having an atomic number lower than process, and addition of moisture in a partial pressure of
Zn (Mg, and Ca), about 0.1 Pa to the film -forming atmosphere makes the
Group -3 elements M3 having an atomic number lower than formed film amorphous.
In (B , Al, Ga, and Y ), 15 ZnO and SnO2 respectively cannot readily be formed in
Group -4 elements M4 having an atomic number lower than an amorphous film state . For formation of the ZnO film in
Sn (Si, Ge, and Zr), an amorphous state , In2O3 is added in an amountof 20 atom
Group - 5 elements M5 (V , Nb, and Ta ), and Lu , and W to % . For formation of the SnO2 film in an amorphous state ,
lower the electron carrier concentration ; In2O3 is added in an amount of 90 atom % . In formation of
(g ) An amorphous oxide film , mentioned in any of the above 20 Sn - In O type amorphous film , gaseous nitrogen is intro
items (a ) to (f), constituted of a single compound having a duced in a partial pressure of about 0.1 Pa in the film
composition of In1-xM3,03 (Zn1-M2,0 )m (Osxsl; Osysl; formation atmosphere .
m : 0 or a natural number of less than 6 ) in a crystal state, or To the above amorphous film , may be added an element
a mixture of the compounds different in number m , an capable of forming a complex oxide , selected from Group- 2
example of M3 being Ga, and an example ofM2 being Mg; 25 elements M2 having an atomic number lower than Zn (Mg,
and and Ca), Group -3 elements M3 having an atomic number
(h ) An amorphous oxide film ,mentioned in any ofthe above lower than In (B , Al, Ga, and Y ), Group - 4 elements M4
items (a ) to (g ) formed on a plastic substrate or an plastic having an atomic number lower than Sn (Si, Ge, and Zr ),
film . Group-5 elements M5 (V , Nb, and Ta ), and Lu, and W. The
The present invention also provides a field -effect transis- 30 addition of the above element stabilizes the amorphous film
tor employing the above mentioned amorphous oxide or at room temperature , and broadens the composition range
amorphous oxide film as the channel layer. for amorphous film formation .
A field -effect transistor is prepared which is employs an In particular, addition of B , Si, or Ge tending to form a
amorphous oxide film having an electron carrier concentra covalent bond is effective for amorphous phase stabilization.
tion of less than 1x1018/cm but more than 1x1015/cm as 35 Addition of a complex oxide constituted of ions having
the channel layer, and having a source terminal and a drain largely different ion radiuses is effective for amorphous
terminal, and a gate terminal with interposition of a gate phase stabilization . For instance, in an In — Zn – O system ,
insulator. When a voltage of about 5 V is applied between for formation of a film stable at room temperature , In should
the source and drain terminals without application of gate be contained more than about 20 atom % . However, addition
voltage, the electric current between the source and drain 40 of Mg in an amount equivalent to In enables formation of
terminals is about 1x10-7 amperes. stable amorphous film in the composition range of In of not
The electron mobility in the oxide crystal becomes larger less than about 15 atom % .
with increase of the overlap of the s -orbitals of the metal In a gas -phase film formation , an amorphous oxide film of
ions. In an oxide crystal of Zn , In , or Sn having a higher the electron carrier concentration ranging from 1x1015/cm3
atomic number, the electron mobility is in the range from 0.1 45 to 1x1018 /cm² can be obtained by controlling the film
to 200 cm ? N.sec . forming atmosphere.
In an oxide , oxygen and metal ions are bonded by ionic An amorphous oxide film can be suitably formed by a
bonds without orientation of the chemical bonds , having a vapor phase process such as a pulse laser vapor deposition
random structure. Therefore in the oxide in an amorphous process (PLD process), a sputtering process (SP process ),
state, the electron mobility can be comparable to that in a 50 and an electron -beam vapor deposition . Of the vapor phase
crystal state . processes, the PLD process is suitable in view of ease of
On the other hand , substitution of the Zn , In , or Sn with material composition control , whereas the SP process is
an element of a lower atomic number decreases the electron suitable in view of the mass production . However, the
mobility . Thereby the electron mobility in the amorphous film -forming process is not limited thereto .
oxide of the present invention ranges from about 0.01 to 20 55 (Formation of InZn Ga o Type Amorphous Oxide
cm ? /V.sec . Film by PLD Process )
In the transistor having a channel layer constituted of the An In - Zn Ga O type amorphous oxide was depos
above oxide, the gate insulator is preferably formed from ited on a glass substrate (Corning Co .: 1737 ) by a PLD
Al2O3, Y203, HfO2, or a mixed crystal compound contain process employing a KrF excimer laser with a polycrystal
ing two or more thereof. 60 sintered compact as the target having a composition of
The presence of a defect at the interface between the InGaO ( ZnO ) or InGaO (ZnO ) 4
gate-insulating thin film and the thin channel layer film The apparatus shown in FIG . 7 was employed which is
lowers the electron mobility and causes hysteresis of the mentioned before , and the film formation conditions were
transistor characteristics. Moreover, the current leakage the same as mentioned before for the apparatus.
depends greatly on the kind of the gate insulator. Therefore 65 The substrate temperature was 25 ° C.
the gate insulator should be selected to be suitable for the The resulting two thin films were examined by small
channel layer. The current leakage can be decreased by use angle X -ray scattering method (SAXS) (thin film method ,
 US 10,615,287 B2
23 24
incidence angle: 0.5 °): no clear diffraction peak was A film of InGaOz( Zn1--Mg 04(0 < x : 1) was formed on a
observed , which shows that the obtained In - Ga - Zn glass substrate by a PLD process with an InGaOz(Znj.
type thin films produced with two different targets were both xMg O )4 target (0 < x : 1). The apparatus employed was the
amorphous . one shown in FIG . 7 .
From X -ray reflectivity of the In — Zn — Ga— type 5 An SiO2 glass substrate (Corning Co .: 1737) was used as
amorphous oxide film of the glass substrate and its pattern the substrate . As the pretreatment, the substrate was washed
analysis, the mean square roughnesses (Rrms) of the thin ultrasonically for defatting with acetone, ethanol, and ultra
films were found to be about 0.5 nm , and the film thick pure water each for five minutes, and dried in the air at 100 °
nesses to be about 120 nm . From fluorescence X -ray spec 10 C. The target was a sintered compact of InGaOz (Zn )
trometric analysis (XRF), the film obtained with the targetof xMg 04 (x = 1-0 ) (size: 20 mm diameter, 5 mm thick ).
the polycrystalline sintered compact of InGaOz( ZnO ) was The target was prepared by wet-mixing source materials
found to contain the metals at a composition ratio In :Ga: In203, Ga2O3, and ZnO (each 4N reagent) ( solvent: etha
Zn = 1.1: 1.1 :0.9 , whereas the film obtained with the target of nol), calcining the mixture ( 1000 ° C., 2 hours ), dry -crushing
the polycrystalline sintered compact of InGaOz (ZnO )4 was 15 it , and sintering it (1550 ° C., 2 hours). The final pressure in
found to contain the metals at a composition ratio In :Ga: the growth chamber was 2x10- Pa . The oxygen partial
Zn = 0.98 : 1.02 : 4 . pressure during the growth was controlled at 0.8 Pa. The
Amorphous oxide films were formed at various oxygen substrate temperature was room temperature (25º C.). The
partial pressure of the film - forming atmosphere with the distance between the target and the substrate for film for
target having the composition of InGaOz(Zn04. The 20 mation was 30 mm . The KrF excimer laser was irradiated at
formed amorphous oxide films were measured for the elec a power of 1.5 mJ/cm²/pulse with the pulse width of 20 nsec ,
tron carrier concentration . FIG . 1 shows the results. By the repeating frequency of 10 Hz, and the irradiation spot
formation of the film in an atmosphere having an oxygen size of 1x1 mm square . The film -forming rate was 7 nm /min .
partial pressure of higher than 4.2 Pa , the electron carrier The oxygen partial pressure in the film - forming atmosphere
concentration could be lowered to less than 1x1018 /cm² as 25 was 0.8 Pa . The substrate temperature was 25 ° C.
shown in FIG . 1. In this film formation, the substrate was The resulting thin film was examined by small angle
kept nearly at room temperature without intentional heating. X -ray scattering method (SAXS ) (thin film method, inci
At the oxygen partial pressure of lower than 6.5 Pa , the dence angle: 0.5 °): no clear diffraction peak was observed .
surfaces of the obtained amorphous oxide films were flat. Thus the obtained In Ga - Zn - Mg O type thin film was
At the oxygen partial pressure of 5 Pa, in the amorphous 30 amorphous. The resulting film had a flat surface.
film formed with the InGaOz(ZnO )4 target, the electron By using targets of different x -values (different Mg con
carrier concentration was 1x1016/cm , the electro conduc tent), InZn Ga Mg / type amorphous oxide films
tivity was 1x10-2 S /cm , and the electron mobility therein were formed the oxygen partial pressure of 0.8 Pa in a
was estimated to be about 5 cm ? NV.sec. From the analysis of film - forming atmosphere to investigate the dependency of
the light absorption spectrum , the optical band gap energy 35 the conductivity, the electron carrier concentration , and the
breadth of the formed amorphous oxide film was estimated electron mobility on the x -value .
to be about 3 eV . FIGS. 4A , 4B , and 4C show the results. At the x values
The higher oxygen partial pressure further lowered the higher than 0.4 , in the amorphous oxide films formed by the
electron carrier concentration . As shown in FIG . 1, in the PLD process at the oxygen partial pressure of 0.8 Pa in the
In - Zn - Ga- type amorphous oxide film formed at a 40 atmosphere , the electron carrier concentration was
substrate temperature of 25 ° C. at an oxygen partial pressure decreased to be less than 1x1018/cm3. In the amorphous film
of 6 Pa , the electron carrier concentration was lowered to of x value higher than 0.4 , the electron mobility was higher
8x10ls / cm² (electroconductivity : about 8x10-3 S/cm ). The than 1 cm ? /V .
electron mobility in the film was estimated to be 1 cm N.sec As shown in FIGS . 4A , 4B , and 4C , the electron carrier
or more.However,by the PLD process, at the oxygen partial 45 concentration less than 1x1016/cm could be achieved in the
pressure of 6.5 Pa or higher, the deposited film has a rough film prepared by a pulse laser deposition process with the
surface ,being not suitable for use as the channel layer of the target in which 80 atom % of Zn is replaced by Mg and at
TFT. the oxygen partial pressure of 0.8 Pa (electric resistance :
The In - Zn Ga O type amorphous oxide films were about 1x10-2 S.cm ). In such a film , the electron mobility is
formed at various oxygen partial pressures in the film- 50 decreased in comparison with the Mg- free film , but the
forming atmosphere with the target constituted of a poly decrease is slight. The electron mobility in the films is about
crystalline sintered compact having the composition of 5 cm²/V.sec, which is higher by about one digit than that of
InGaOz( ZnO )4. The resulting films were examined for the amorphous silicon . Under the same film formation condi
relation between the electron carrier concentration and the tions, both the electric conductivity and the electron mobil
electron mobility . FIG . 2 shows the results . Corresponding 55 ity in the film decrease with increase of the Mg content.
to the increase of the electron carrier concentration from Therefore , the Mg content in the film is preferably more than
1x1016 /cm² to 1x102° /cm², the electron mobility increased 20 atom % and less than 85 atom % (0.2 < x < 0.85 ), more
from about 3 cmPNV sec to about 11 cm’N.sec . The same preferably 0.5 < x < 0.85.
tendency was observed with the amorphous oxide films The amorphous film of InGaO2(Zn - Mg 04 (0 < x :1 )
obtained with the polycrystalline sintered InGaO3(ZnO ) 60 formed on a 200 um -thick polyethylene terephthalate (PET )
target. film in place of the glass substrate had similar characteris
The InZn Ga type amorphous oxide film which tics.
was formed on a 200 um -thick polyethylene terephthalate ( Formation of In2O3 Amorphous Oxide Film by PLD Pro
(PET) film in place of the glass substrate had similar cess )
characteristics. 65 An In203 film was formed on a 200 um -thick PET film by
( Formation of In - Zn Ga Mg 0 Type Amorphous use of a target constituted of In2O3 polycrystalline sintered
Oxide Film by PLD Process ) compact by a PLD process employing a KrF excimer laser.
 US 10,615,287 B2
25 26
The apparatus used is shown in FIG . 7. The substrate for In the obtained In - Sn- type amorphous oxide film ,
the film formation was an SiO2 glass substrate (Corning Co .: the electron carrier concentration was 8x1017 /cm , and the
1737 ) electron mobility was about 5 cm ? NV.sec . The film thickness
As the pretreatment before the deposition , the substrate was 100 nm .
was washed ultrasonically for defatting with acetone, etha- 5 (Formation of In Ga- Type Amorphous Oxide Film
nol, and ultrapure water each for five minutes , and dried in by PLD Process )
the air at 100 ° C. The substrate for the film was an SiO2 glass substrate
The target was an In2O3 sintered compact ( size: 20 mm ( Corning As the
Co .: 1737) .
pretreatment before the deposition , the substrate
diameter, 5 mm thick ), which had been prepared by calcin
ing the source material In2O3 (4N reagent) (1000 ° C., 2 10 nol was, washed ultrasonically
water eachfor fordefatting with acetone , ethain
hours), dry -crushing it , and sintering it ( 1550° C., 2 hours ). the airandatultrapure
100 ° C.
five minutes , and dried
The final vacuum of the growth chamber was 2x10m Pa,
the oxygen partial pressure during the growth was 5 Pa, and (Ga_03), (x = 0-1was
The target
) (
a sintered compact of (In2O3) 1-x
size : 20 mm diameter, 5 mm thick ). For
the substrate temperature was 25 ° C. 15 instance , at x = 0.1 , the target is a polycrystalline sintered
The water vapor partial pressure was 0.1 Pa , and oxygen compact of ( In ...G..1202 .
radicals were generated by the oxygen radical-generating This target was prepared by wet-mixing the source mate
assembly by application of 200 W. rials In 0 , Ga. , (4N reagents) ( solvent: ethanol), calcin
The distance between the target and the film -holding ing the mixture ( 1000 ° C., 2 hours), dry - crushing it, and
substrate was 40 mm , the power of the Krf excimer laser was 20 sintering it ( 1550 ° C., 2 hours ).
0.5 mJ/ cm²/pulse , the pulse width was 20 nsec, the repeating The final pressure of the growth chamber was 2x10- Pa .
frequency was 10 Hz, and the irradiation spot size was 1x1 The oxygen partial pressure during the growth was 1 Pa.
mm square . The substrate was at room temperature . The distance
The film - forming rate was of 3 nm /min . between the target and the film -holding substrate was 30
The resulting thin film was examined by small angle 25 mm . The power of the Krf excimer laser was 1.5 mJ/cm²/
X -ray scattering method (SAXS ) ( thin film method , inci pulse. The pulse width was 20 nsec . The repeating frequency
dence angle : 0.5 °): no clear diffraction peak was observed , was 10 Hz. The irradiation spot size was 1x1 mm square.
which shows that the obtained In— type oxide film was The film -forming rate was of 6 nm /min .
amorphous . The film thickness was 80 nm . The substrate temperature was 25 ° C. The oxygen pres
In the obtained In - O type amorphous oxide film , the 30 angle
sure wasX -ray1 Pascattering
. The resulting film was examined by small
method (SAXS ) ( thin film method ,
electron carrier concentration was 5x1017/cm ", and the incidence angle : 0.5 ° ): no clear diffraction peak was
electron mobility was about 7 cm ? /V.sec . detected , which shows that the obtained In Ga O type
(Formation of In - Sn- Type Amorphous Oxide Film oxide film is amorphous. The film thickness was 120 nm .
by PLD Process ) 35 In the obtained In — Ga— type amorphous oxide film ,
An In - Sn- type oxide film was formed on a 200 the electron carrier concentration was 8x1016 /cm², and the
um -thick PET film by use of a target constituted of poly electron mobility was about 1 cm²/V.sec .
crystalline sintered compact of (In ... Sno.1 )03.1 by a PLD (Preparation of TFT Element Having In - Zn Ga
process employing a KrF excimer laser . The apparatus used Type Amorphous Oxide Film (Glass Substrate ))
is shown in FIG . 7 . 40 A top gate type TFT element shown in FIG . 5 was
The substrate for the film formation was an SiO2 glass prepared .
substrate (Corning Co .: 1737). Firstly , an In — Ga - Zn- type amorphous oxide film
As the pretreatment before the deposition , the substrate was prepared on glass substrate 1 by the aforementioned
was washed ultrasonically for defatting with acetone , etha PLS apparatus with a target constituted of a polycrystalline
nol, and ultrapure water each for five minutes, and dried in 45 sintered compact having a composition of InGaOz (ZnO )4 at
the air at 100 ° C. an oxygen partial pressure of 5 Pa. The formed In Ga
The target was an In203 SnO , sintered compact (size : Zn- film had a thickness of 120 nm , and was used as
20 mm diameter, 5 mm thick ), which had been prepared by channel layer 2 .
wet-mixing the source materials In2O3 SnO2 (4N reagents ) Further thereon , another InGaZn type amor
(solvent: ethanol), calcining the mixture (1000 ° C., 2 hours), 50 layer
phouswere
film having
laminated , each in 30 nm thick , byandthea PLD
a higher electro conductivity gold
dry -crushing it , and sintering it (1550° C., 2 hours).
The substrate was kept at room temperature . The oxygen method at the oxygen partial pressure of lower than 1 Pa in
partial pressure was 5 Pa . The nitrogen partial pressure was 6thewere chamber. Therefrom drain terminal 5 and source terminal
0.1 Pa . Oxygen radicals were generated by the oxygen 55 Finallyformed , a
by photolithography and a lift-off method .
Y203 film as gate insulator 3 was formed by
radical-generating assembly by application of 200 W. electron beam vapor deposition (thickness: 90 nm , relative
The distance between the target and the film -holding dielectric constant: about 15 , leakage current density : 1x103
substrate was 30 mm , the power of the Krf excimer laser was A /cm² under application of 0.5 MV/cm ). Further thereon , a
1.5 mJ/ cm²/pulse , the pulse width was 20 nsec , the repeating gold film was formed and therefrom gate terminal 4 was
frequency
mm square .
was 10 Hz, and the irradiation spot size was 1xl 60 formed by photolithography and a lift-off method . The
channel length was 50 um , and the channel width was 200
The film -forming rate was of 6 nm /min . um .
The resulting thin film was examined by small angle Evaluation of Characteristics of TFT Element
X -ray scattering method (SAXS) (thin film method, inci FIG . 6 shows current- voltage characteristics of the TFT
dence angle: 0.5 °): no clear diffraction peak was detected , 65 element at room temperature . Drain current IDs increased
which shows that the obtained In Sn O type oxide film is with increase of drain voltage Vos, which shows that the
amorphous. channel is of an n - type conduction .
 US 10,615,287 B2
27 28
This is consistent with the fact that an amorphous In The TFT employing the A1203 film as the gate insulator
Ga - Zn- type semiconductor is of an n -type. The IDs has also transistor characteristics similar to that shown in
become saturated (pinched off ) at VDs =6V, which is typical FIG . 6. A current flow of lds = 1.0x10-8 A was caused at
behavior of a semiconductor transistor. From examination of VG GEO V , and a current flow of Ids=5.0x10-6 A was caused
the gain characteristics, the threshold value of the gate 5 at VG - 10 V. The on -off ratio of the transistor was higher than
voltage VGs under application of VDs =4V was found to be 1x102. From the output characteristics, the field effect
about -0.5 V. A current flow of Ips = 1.0x10-5 A was cased mobility was calculated to be about 2 cm²(Vs)-l in the
at VG= 10V. This corresponds to carrier induction by a gate saturation region.
bias in the In - GaZn O type amorphous semiconductor The TFT employing the HfO , film as the gate insulator
thin film as the insulator. 10 has also transistor characteristics similar to that shown in
The on -off ratio of the transistor was higher than 1x103. FIG . 6. A current flow of Ips = 1x10-8 Awas caused at VG = 0
From the output characteristics, the field effectmobility was V , and a current flow of Ips= 1.0x10-6 A was caused at
calculated to be about 7 cm ? (Vs )- ' in the saturation region . VG= 10 V. The on -off ratio of the transistor was higher than
Irradiation of visible light did not change the transistor 1x102. From the output characteristics, the field effect
characteristics of the produced element according to the 15 mobility was calculated to be about 10 cm ’(Vs)-! in the
same measurement. saturation region.
The amorphous oxide of the electron carrier concentration (Preparation of TFT Element Employing In 03 Amor
lower than 1x1018 /cm² is useful as a channel layer of a TFT . phous Oxide Film by PLD Process )
The electron carrier concentration is more preferably less A top gate type TFT element shown in FIG . 5 was
than 1x101 /cm , still more preferably less than 1x1016 /cm². 20 prepared.
(Preparation of TFT Element Having In — Zn — Ga Firstly, an In203 type amorphous oxide film was formed
Type Amorphous Oxide Film ( Amorphous Substrate )) on polyethylene terephthalate ( PET) film 1 by the PLD
A top gate type TFT element shown in FIG . 5 was method as channel layer 2 in a thickness of 80 nm .
prepared . Further thereon , another In2O3 amorphous film having a
Firstly , an In— Ga - Zn- type amorphous oxide film 25 higher electro conductivity and a gold layer were laminated ,
was prepared on polyethylene terephthalate (PET) film 1 by each in 30 nm thick , by the PLD method at the oxygen
the aforementioned PLS apparatus with a target constituted partial pressure of lower than 1 Pa in the chamber, and at the
of a polycrystalline sintered compact having a composition voltage application of zero volt to the oxygen radical gen
of InGaOz(ZnO ) at an oxygen partial pressure of 5 Pa in the erating assembly. Therefrom drain terminal 5 and source
atmosphere. The formed film had a thickness of 120 nm , and 30 terminal 6 were formed by photolithography and a lift-off
was used as channel layer 2 . method .
Further thereon , another In Ga - Zn - 0 type amor Finally, a Y203 film as gate insulator 3 was formed by an
phous film having a higher electro conductivity and a gold electron beam vapor deposition method. Further thereon , a
layer were laminated , each in 30 nm thick , by the PLD gold film was formed and therefrom gate terminal 4 was
method at the oxygen partial pressure of lower than 1 Pa in 35 formed by photolithography and a lift -off method .
the chamber. Therefrom drain terminal5 and source terminal Evaluation of Characteristics of TFT Element
6 were formed by photolithography and a lift -off method . The TFT elements formed on a PET film was examined
Finally , gate insulator 3 was formed by an electron beam for current-voltage characteristics at room temperature .
vapor deposition method . Further thereon, a gold film was Drain current Ids increased with increase of drain voltage
formed and therefrom gate terminal 4 was formed by 40 V ,DS, which shows that the channel is an n -type conductor.
photolithography and a lift -off method . The channel length This is consistent with the fact that an amorphous In O
was 50 um , and the channel width was 200 um . Three TFTs type amorphous oxide film is an n type conductor. The IDs
of the above structure were prepared by using respectively become saturated (pinched off ) at about VDs =6 V , which is
one of the three kinds of gate insulators: Y203 (140 nm typicalbehavior of a transistor. A current flow of lps = 2x10-8
thick ), Al2O3 (130 um thick ), and HfO2 (140 um thick ). 45 Awas caused at VG-0 V, and a current flow of Ips= 2.0x10-6
Evaluation of Characteristics of TFT Element A was caused at VG = 10 V. This corresponds to electron
The TFT elements formed on a PET film had current carrier induction by gate bias in the insulator, the In— type
voltage characteristics similar to that shown in FIG . 6 at amorphous oxide film .
room temperature . Drain current Ips increased with increase The on -off ratio of the transistor was about 1x102 . From
of drain voltage VDs, which shows that the channel is of an 50 the output characteristics, the field effect mobility was
n -type conduction . This is consistent with the fact that an calculated to be about 1x10 cm (Vs)-! in the saturation
amorphous In — Ga - Zn- type semiconductor is of an n region . The TFT element formed on a glass substrate had
type . The Ids become saturated (pinched off) at VDs= 6V , similar characteristics.
which is typical behavior of a semiconductor transistor. A The elements formed on the PET film were curved in a
current flow of Ips = 1.0x10-8 Awas caused at V60 V , and 55 curvature radius of 30 mm , and in this state, transistor
a current flow of lps = 2.0x10-5 A was caused at V6 = 10 V. characteristics were measured . No change was observed in
This corresponds to carrier induction by gate bias in the the transistor characteristics .
insulator, the InGa - Zn O type amorphous semicon (Preparation of TFT Element Employing In - Sn
ductor oxide film . Type Amorphous Oxide Film by PLD Process)
The on -off ratio of the transistor was higher than 1x10 %. 60 A top gate type TFT element shown in FIG . 5 was
From the output characteristics, the field effectmobility was prepared .
calculated to be about 7 cm ?(Vs)-1 in the saturation region . Firstly, an In - Sn- type amorphous oxide film was
The elements formed on the PET film were curved at a formed in a thickness of 100 nm as channel layer 2 on
curvature radius of 30 mm , and in this state, transistor polyethylene terephthalate (PET) film 1 by the PLD method.
characteristics were measured . However the no change was 65 Further thereon , another In Sn O amorphous film hav
observed in the transistor characteristics. Irradiation of vis ing a higher electro conductivity and a gold layer were
ible light did not change the transistor characteristics . laminated , each in 30 nm thick , by the PLD method at the
 US 10,615,287 B2
29 30
oxygen partial pressure lower than 1 Pa in the chamber, and calculated to be about 0.8 cm (Vs)-1 in the saturation range.
at voltage application of zero volt to the oxygen radical The TFT element formed on a glass substrate had similar
generating assembly. Therefrom drain terminal 5 and source characteristics .
terminal 6 were formed by photolithography and a lift-off The elements formed on the PET film were curved at a
method . 5 curvature radius of 30 mm , and in this state , transistor
Finally, a Y203 film as gate insulator 3 was formed by an characteristics were measured . No change was caused
electron beam vapor deposition method . Further thereon , a thereby in the transistor characteristics .
gold film was formed and therefrom gate terminal 4 was The amorphous oxide of the electron carrier concentration
formed by photolithography and a lift-off method . of lower than 1x1018/cm² is useful as the channel layer of
Evaluation of Characteristics of TFT Element 10 the TFT. The electron carrier concentration is more prefer
The TFT elements formed on a PET film was examined ably not higher than 1x1017/cm ", still more preferably not
for current- voltage characteristics at room temperature . higher Now
than 1x1016/cm3.
, Examples of the present invention will be
Drain current Ids increased with increase of drain voltage
Vps which shows that the channel is an n -type conductor. 15 explained .
This is consistent with the fact that an amorphous In Example 1: Preparation of an Amorphous
Sn— type amorphous oxide film is an n type conductor. In - Ga - Zn- Thin Film Containing
The Ids became saturated (pinched off ) at about VDs =6 V, Microcrystals
which is typical behavior of a transistor. A current flow of
IDs= 5x10-8 A was caused at V60 V , and a current flow of 20 A film is prepared by using the apparatus shown in FIG .
IDs = 5.0x10-5 Awas caused at VG = 10 V. This correspondsto 7. A pulse laser deposition method using KrF excimer laser
electron carrier induction by the gate bias in the insulator, is performed with a polycrystalline sintered body having a
the In - Sn- type amorphous oxide film . composition of InGaOz(ZnO )4 as a target . On a glass sub
The on - off ratio of the transistor was about 1x103. From strate ( 1737 , manufactured by Corning Incorporated ), an
the output characteristics, the field effect mobility was 25 InGa - Zn based amorphous oxide semiconductor
calculated to be about 5 cm (Vs)-1 in the saturation range. thin film containing microcrystals is deposited . In the film
The TFT element formed on a glass substrate had similar formation step , a substrate surface is irradiated with a
characteristics . halogen lamp (20 mW /cm ?). The presence or absence of
The elements formed on the PET film were curved at a microcrystals is confirmed under TEM ( transmission elec
curvature radius of 30 mm , and in this state, transistor 30 tron microscope ) observation of a film section .
characteristics were measured . No change was caused < Preparation of MISFET (Metal Insulator Semiconductor
thereby in the transistor characteristics. Field Effect Transistor) Device>
(Preparation of TFT Element Employing In Ga A top - gate type MISFET device shown in FIG . 5 is
Type Amorphous Oxide Film by PLD Process) manufactured . First, a semi- insulating amorphous InGaOz
A top gate type TFT element shown in FIG . 5 was 35 (ZnO )4 film of 30 nm in thickness containing microcrystals
prepared . and serving as a channel layer (2 ) is formed on the glass
Firstly , an In — Ga— type amorphous oxide film was substrate ( 1 ) in accordance with the aforementioned method
formed in a thickness of 120 nm as channel layer 2 on for preparing an amorphous In — Ga - Zn— thin film con
polyethylene terephthalate (PET) film 1 by the PLD method taining microcrystals . Further on the resultant construct,
shown in Example 6 . 40 InGaOz( ZnO )4 film and a gold film large in electric con
Further thereon , another In - Ga - O amorphous film hav ductivity , each having 30 nm thickness , are stacked by a
ing a higher conductivity and a gold layer were laminated , pulse laser deposition method while setting the oxygen
each in 30 nm thick , by the PLD method at the oxygen partial pressure of a chamber at less than 1 Pa. Then , a drain
partial pressure of lower than 1 Pa in the chamber, and at the terminal (5 ) and a source terminal (6 ) are formed by a
voltage application of zero volt to the oxygen radical- 45 photolithographic method and a lift -off method . Finally, an
generating assembly. Therefrom drain terminal 5 and source Y203 film serving as a gate insulator (3) is formed by an
terminal 6 were formed by photolithography and a lift-off electron beam deposition method (the obtained film has a
method . thickness of 90 to 110 nm , a specific dielectric constant of
Finally, a Y202 film as gate insulator 3 was formed by an about 15 , leak current density of 1x103 A /cm² when a
electron beam vapor deposition method . Further thereon , a 50 current of 0.5 MV/cm is applied ). Thereafter, a gold film is
gold film was formed and therefrom gate terminal 4 was formed on the resultant construct, and then , a gate terminal
formed by photolithography and a lift -off method . (4 ) is formed by a photolithographic method and a lift -off
Evaluation of Characteristics of TFT Element method . In this manner, the field effect transistor is formed .
The TFT elements formed on a PET film was examined The on /off ratio of the transistor exceeds 1x104. When the
for current-voltage characteristics at room temperature. 55 field effectmobility is calculated based on power character
Drain current Ids increased with increase of drain voltage istics, an electron field -effect mobility of about 7.5 cm ?
VDs, which shows that the channel is an n -type conductor. (Vs)-1 was obtained in a saturation field . The device thus
This is consistent with the fact that an amorphous In manufactured was irradiated with visible light and subjected
Ga— type amorphous oxide film is an n type conductor. to the same measurement. As a result, any change in the
The Ids became saturated (pinched off) at about VDs= 6 V, 60 characteristics of a transistor was not observed .
which is typical behavior of a transistor. A current flow of Furthermore, in the aforementioned Example for manu
IDs = 1x10-8 A was caused at VG = 0 V, and a current flow of facturing an In - Ga - Zn - O thin film containing microc
IDs= 1.0x10-6 A was caused at VG= 10 V. This corresponds to rystals, effective results are obtained when the substrate is
electron carrier induction by the gate bias in the insulator, irradiated with lighthaving a power density of0.3 mW /cm²
the In — Ga O type amorphous oxide film . 65 to 100mW /cm². As a result, the on /off ratio of the transistor
The on - off ratio of the transistor was about 1x102. From can be increased and large electron field -effect mobility can
the output characteristics , the field effect mobility was be obtained . For this reason , light irradiation is preferable .
 US 10,615,287 B2
31 32
Although it varies depending upon the amount of microc An In — Ga - Zn- based amorphous oxide semicon
rystals in an amorphous oxide film , the presence of micro ductor thin film containing nitrogen as an impurity (simply
crystals is generally confirmed if a peak is detected by X -ray referred to as “ In — Ga - Zn - O (N )'') is deposited on a glass
diffraction. substrate of the same type as above by a pulse laser
Example 2: Preparation of an Amorphous 5 deposition method using KrF excimer laser with an InGaOz
In Ga - Zn- Thin Film Having a ( ZnO )4 polycrystalline sintered body used as a target. Note
Compositional Distribution in the Film Thickness that the oxygen partial pressure within a chamber is set at,
Direction for example , 4 Pa, the nitrogen partialpressure is set at 1 Pa ,
and the temperature of a substrate is set at 25° C. The
An In Ga - Zn 0 based amorphous oxide semicon- 10 iscompositional ratio ofoxygen and nitrogen of the thin film
preferably about 50 : 1, as analyzed by a secondary ion
ductor thin film having a compositional distribution in the mass spectrum (SIMS) .
film thickness direction is deposited on a glass substrate
( 1737 , manufactured by Corning Incorporated ) by a pulse Example 5 : Preparation of Amorphous
laser deposition method using KrF excimer laser with a In — Ga - ZnO( Ti) Thin Film
polycrystalline sintered body having a composition of 15
InGaOz(ZnO )4 as a target. The film is deposited in a cham An In — Ga - Zn - 0 based amorphous oxide semicon
ber having inner oxygen partial pressure within a predeter
ductor
mined range while increasing the distance between the target manufactured thin film is deposited on a glass substrate (1737,
and the substrate up to 5 mm . As the distance increases, the by Corning Incorporated ) by a pulse laser
amount of oxygen incorporated into the formed film 20 deposition method usingKrF excimer laser with a polycrys
talline sintered body having a composition of InGaOz(ZnO )
increases. Note that the temperature of the substrate is set at used as a target. The resultant In Ga - Zn – O based thin
25 ° C.
In the Example 2 ( for forming a thin film having a film is soaked in an aqueous solution of titanium trichloride
compositional distribution in the film thickness direction ), a kept at 80º C. Thereafter, the film is taken up and annealed
composition may be changed by varying oxygen partial 25 anat 300 ° C. in the air. In this manner, Ti can be introduced as
impurity in the amorphous oxide . As the Ti concentration
pressure in the film thickness direction , or alternatively , by of the
changing an oscillation power or oscillation frequency of a SIMS,thin the
film is analyzed from the surface to the bottom by
Ti concentration of the outermost surface is about
pulse laser. In this manner, leak current can be reduced or the
on /off ratio of a transistor can be increased , as well as 30 0.5An % and gradually decreases toward the bottom .
amorphous oxide according to the present invention is
electron field -effect mobility can be increased .
applicable to the channel layer of a transistor. Such a
Example 3 : Preparation of an Amorphous transistor can be used as switching devices for LCDs and
In - Ga - Zn- Thin Film Having a organic EL displays . Alternatively, the amorphous oxide
Compositional Distribution in the Film Thickness may be applied on a flexible material such as a plastic film
Direction 35 to form a semiconductor thin film . Such a semiconductor
thin film can be widely used as panels of flexible displays ,
The film is formed by a sputtering method using argon IC This cards and ID tags.
application claims priority from Japanese Patent
gas. As targets , (1) a polycrystalline sintered body having a
composition of InGaOz(ZnO )4 and ( 2) a zinc oxide sintered Application No. 2004-326687 filed on Nov. 10 , 2004,which
body are prepared . Then , an amorphous In Ga - Zn- 40 is hereby incorporated by reference herein .
thin film having a compositional distribution in the film
thickness direction is deposited on a glass substrate (1737, What is claimed is :
manufactured by Corning Incorporated ). The film is formed 1. An article with a field effect transistor comprising:
by the sputtering method in an atmosphere having a prede a substrate ; and
termined oxygen partial pressure, first by using target ( 1 ), 45 a field effect transistor disposed on the substrate ,
subsequently by using target (1 ) and target (2 ), simultane wherein the field effect transistor comprises an active
ously . In this manner, the amorphous In — Ga — ZnO thin layer comprising an amorphous oxide and a gate elec
film having a compositional distribution in the film thickness trode formed so as to face the active layer through a
direction can be prepared . Note that the temperature of the gate insulator,
substrate is set at 25 ° C. 50 wherein the amorphous oxide comprises an oxide com
The In — Ga - Zn - 0 thin film having a compositional prising In — Ga Zn- or In Ga - Zn Mg0,
distribution in the film thickness direction may be prepared and
by the following manner. The composition is distributed in wherein the amorphous oxide comprises one type of
the film thickness direction by sputtering an In2O3 target element or a plurality of elements selected from the
simultaneously or separately , or changing oxygen partial 55 group consisting of Li, Na,Mn, Ni, Pd, Cu, C , N , P , Ti,
pressure in the film thickness direction , or alternatively, Ru and F.
changing power supply in the film thickness direction for 2. The article according to claim 1, wherein the amor
each target in a sputtering step . Particularly, in the amor phous oxide exhibits a halo pattern and no characteristic
phous thin film near a gate insulator, electron field -effect diffraction line in an X -ray diffraction spectrometry .
mobility is expected to increase as the amount of In203 or 60 3. The article according to claim 2 , wherein the amor
ZnO increases. phous oxide has an electron carrier concentration of less
than 1018 /cm at a temperature of 25 ° C.
Example 4 : Preparation of Amorphous 4. The article according to claim 3, wherein the amor
In Ga - Zn O (N ) Thin Film phous oxide is obtained by using a target having a compo
65 Sition InGaOz (ZnO )m or InGaOz(Zn - MgxO )m in a crystal
A method of preparing an amorphous oxide containing line state where m is a natural number of less than 6 and x
nitrogen (N ) as an additive will be explained . is greater than 0 and not greater than 1.
 US 10,615,287 B2
33 34
5. An article with a field effect transistor comprising: 17. A display apparatus with a field effect transistor
a substrate ; and comprising:
a field effect transistor disposed on the substrate, a substrate; and
wherein the field effect transistor comprises an active a field effect transistor disposed on the substrate,
layer comprising an amorphous oxide and a gate elec- 5 wherein the field effect transistor comprises an active
trode formed so as to face the active layer through a layer comprising an amorphous oxide and a gate elec
gate insulator, and trode formed so as to face the active layer through a
wherein the amorphous oxide comprises an oxide com gate insulator, and
prising InGaZn 0 or In Ga - Zn - Mg 0 , wherein the amorphous oxide comprises an oxide com
and 10
prising In GaZn 0 or In GaZnMg 0 ,
wherein the amorphous oxide comprises one type of and
element or a plurality of elements selected from the wherein the amorphous oxide comprises at least one
group consisting of Li, Na,Mn, Ni, Pd , Cu, C , N , P, TI, element selected from the group consisting of Li, Na,
Ru and F at a concentration within the range of 0.1 to Mn, Ni, Pd , Cu , C , N , P , Ti, Ru, and F at a concentration
3 atomic % . 15
6. The article according to claim 5 , wherein the amor within the range of 0.1 to 3 atomic % .
phous oxide exhibits a halo pattern and no characteristic the amorphous18. The display apparatus according to claim 17 , wherein
diffraction line in an X -ray diffraction spectrometry . oxide exhibits a halo pattern and no charac
7. The article according to claim 6 , wherein the amor teristic diffraction line in an X -ray diffraction spectrometry.
phous oxide has an electron carrier concentration of less 20 the19. The display apparatus according to claim 18 , wherein
amorphous oxide has an electron carrier concentration of
than 1018/ cm at a temperature of 25 ° C.
8. The article according to claim 7 , wherein the amor less20.thanThe1018 /cm2 at a temperature of 25 ° C.
display apparatus according to claim 19 , wherein
phous oxide is obtained by using a target having a compo the amorphous oxide is obtained by using a target having a
sition InGaOz (ZnO )mor InGaO2( Zn ,Mg,Om in a crystal
line state where m is a natural number of less than 6 and x 25 crystalline
compositionstateInGaOz(ZnO )m or InGaOz(Zn -Mg,0 )m in a
where m a natural number of less than 6
is greater than 0 and not greater than 1 . and x is greater than 0 and not greater than 1 .
9. A display apparatus with a field effect transistor com 21. The display apparatus according to claim 17 ,wherein
prising :
a substrate ; and the display apparatus includes the field effect transistor as
a field effect transistor disposed on the substrate , 30 switching device.
wherein the field effect transistor comprises an active 22. The display apparatus according to claim 21, wherein
layer comprising an amorphous oxide and a gate elec the display is an organic EL display.
trode formed so as to face the active layer through a 23. The display apparatus according to claim 22 , wherein
gate insulator, the display is a flexible display .
wherein the amorphous oxide comprises an oxide com- 35 24. The display apparatus according to claim 21, wherein
prising InGaZn 0 or In Ga - Zn - Mg 0 , the display is an LCD .
and 25. An article with a field effect transistor comprising :
wherein the amorphous oxide comprises at least one a substrate ; and
element selected from the group consisting of Li, Na, a field effect transistor disposed on the substrate,
Mn, Ni, Pd , Cu , C , N , P, Ti, Ru, and F. 40 wherein the field effect transistor comprises an active
10. The display apparatus according to claim 9 , wherein layer comprising an amorphous oxide and a gate elec
the amorphous oxide exhibits a halo pattern and no charac trode formed so as to face the active layer through a
teristic diffraction line in an X -ray diffraction spectrometry. gate insulator, and
11. The display apparatus according to claim 10, wherein wherein the amorphous oxide comprises at least In , Ga
the amorphous oxide has an electron carrier concentration of 45 and Zn or at least In , Ga, Zn and Mg, and further
less than 1018 / cm² at a temperature of 25 ° C. comprises one type of element or a plurality of ele
12. The display apparatus according to claim 11 , wherein ments selected from the group consisting ofLi, Na, Mn ,
the amorphous oxide is obtained by using a target having a Ni, Pd, Cu , C , N , P , Ti, Ru and F.
composition InGaO , (ZnO )m or InGao ,(Zn - Mg, 0 )m in a 26. The article according to claim 25 , wherein the amor
crystalline state where m is a natural number of less than 6 50 phous oxide exhibits a halo pattern and no characteristic
and x is greater than 0 and not greater than 1. diffraction line in an X -ray diffraction spectrometry .
13. The display apparatus according to claim 9 , wherein 27. The article according to claim 25 , wherein the amor
the display apparatus includes the field effect transistor as phous oxide has an electron carrier concentration of less
switching device . than 1018 /cm3 at a temperature of 25 ° C.
14. The display apparatus according to claim 13 , wherein 55 28. The article according to claim 25 , wherein the amor
the display is an organic EL display. phous oxide is obtained by using a target having a compo
15. The display apparatus according to claim 14 , wherein sition InGaOz (ZnO )m or InGaOz (Zn1- Mg,Om in a crystal
the display is a flexible display. line state where m is a natural number of less than 6 and x
16. The display apparatus according to claim 13, wherein is greater than 0 and not greater than 1.
the display is an LCD .