U.S. patent application number 17/725012 was filed with the patent office on 2022-08-04 for method of manufacturing metal oxide film and display device including metal oxide film.
The applicant listed for this patent is Samsung Display Co., Ltd.. Invention is credited to Myung Soo HUH, Sung Chul KIM, Woo Jin KIM, Dong Kyun KO, Keun Hee PARK, Cheol Lae ROH.
Application Number | 20220246708 17/725012 |
Document ID | / |
Family ID | 1000006284877 |
Filed Date | 2022-08-04 |
United States Patent
Application |
20220246708 |
Kind Code |
A1 |
HUH; Myung Soo ; et
al. |
August 4, 2022 |
METHOD OF MANUFACTURING METAL OXIDE FILM AND DISPLAY DEVICE
INCLUDING METAL OXIDE FILM
Abstract
A method of manufacturing a metal oxide film includes injecting
a reaction gas and metal precursors into a chamber, forming a first
metal precursor film on a substrate in a plasma OFF state, forming
a first sub-metal oxide film by oxidizing the first metal precursor
film in a plasma ON state, and forming a second metal precursor
film on the first sub-metal oxide film in the plasma OFF state,
where the metal oxide film has an amorphous phase, a thickness of
about 20 nanometer (nm) to about 130 nm, and a dielectric constant
of about 10 to about 50.
Inventors: |
HUH; Myung Soo; (Suwon-si,
KR) ; KO; Dong Kyun; (Hwaseong-si, KR) ; KIM;
Sung Chul; (Seongnam-si, KR) ; KIM; Woo Jin;
(Hwaseong-si, KR) ; ROH; Cheol Lae; (Seongnam-si,
KR) ; PARK; Keun Hee; (Seoul, KR) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Samsung Display Co., Ltd. |
Yongin-si |
|
KR |
|
|
Family ID: |
1000006284877 |
Appl. No.: |
17/725012 |
Filed: |
April 20, 2022 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
16132031 |
Sep 14, 2018 |
11362162 |
|
|
17725012 |
|
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
H01L 21/0228 20130101;
H01L 27/3265 20130101; H01L 21/02274 20130101; H01L 2227/323
20130101; H01L 21/02252 20130101; H01L 51/5206 20130101; H01L
21/02189 20130101; H01L 27/1225 20130101; H01L 28/60 20130101; H01L
21/02244 20130101; H01L 27/1255 20130101; H01L 2251/303 20130101;
H01L 21/02186 20130101; H01L 21/02205 20130101; H01L 21/02181
20130101; H01L 27/1248 20130101; H01L 27/1214 20130101 |
International
Class: |
H01L 27/32 20060101
H01L027/32; H01L 21/02 20060101 H01L021/02; H01L 49/02 20060101
H01L049/02; H01L 51/52 20060101 H01L051/52; H01L 27/12 20060101
H01L027/12 |
Foreign Application Data
Date |
Code |
Application Number |
Oct 13, 2017 |
KR |
10-2017-0133462 |
Claims
1. A display device comprising: a substrate; and a metal oxide film
disposed on the substrate, wherein the metal oxide film has an
amorphous phase, a thickness of about 20 nanometers to about 130
nanometers, and a dielectric constant of about 10 to about 50.
2. The display device of claim 1, further comprising a first
electrode and a second electrode disposed with the metal oxide film
interposed between the first electrode and the second electrode,
wherein the first electrode, the second electrode, and the metal
oxide film constitute a capacitor.
3. The display device of claim 2, wherein the thickness of the
metal oxide film is about 90 nanometers to about 130
nanometers.
4. The display device of claim 2, further comprising an insulating
film disposed between the second electrode and the metal oxide
film.
5. The display device of claim 4, wherein the insulating film
comprises at least one of silicon oxide, silicon nitride, and
silicon oxynitride.
6. The display device of claim 5, wherein the thickness of the
metal oxide film is about 60 nanometers to about 80 nanometers.
7. The display device of claim 6, wherein a thickness of the
insulating film is about 30 nanometers to about 50 nanometers.
8. The display device of claim 1, wherein the metal oxide film
comprises at least one of zirconium oxide, hafnium oxide, and
titanium oxide.
9. The display device of claim 1, further comprising: a transparent
electrode disposed on the metal oxide film; an organic light
emitting layer disposed on the transparent electrode; and a common
electrode disposed on the organic light emitting layer.
10. An apparatus for manufacturing a metal oxide film, the
apparatus comprising: a chamber; a susceptor which is disposed
inside the chamber and configured to support a substrate; a shower
head which faces the susceptor; and a power supply unit which
supplies radio frequency power to the shower head, wherein a plasma
ON state in which electric power is supplied to the shower head and
a plasma OFF state in which no electric power is supplied to the
shower head are defined and alternate with each other, wherein a
plasma region is provided between the shower head and the susceptor
in the plasma ON state.
11. The apparatus of claim 10, wherein a time interval of the
plasma ON state and a time interval of the plasma OFF state are
equal.
12. The apparatus of claim 10, wherein a pressure inside the
chamber is about 0.1 torr to about 10 torr, and a temperature
inside the chamber is about 100 degrees Celsius to about 400
degrees Celsius.
Description
[0001] This application is a divisional of U.S. patent application
Ser. No. 16/132,031, filed on Sep. 14, 2018, which claims priority
to Korean Patent Application No. 10-2017-0133462, filed on Oct. 13,
2017, and all the benefits accruing therefrom under 35 U.S.C.
.sctn. 119, the content of which in its entirety is herein
incorporated by reference.
BACKGROUND
1. Field
[0002] Exemplary embodiments of the invention relate to a method of
manufacturing a metal oxide film and a display device including a
metal oxide film.
2. Description of the Related Art
[0003] With a development of multimedia, display devices are
becoming increasingly important. Accordingly, various types of the
display devices such as a liquid crystal display and an organic
light emitting display are being used.
[0004] Among these display devices, the liquid crystal display is
one of the most widely used types of flat panel displays. The
liquid crystal display generally includes a pair of substrates
respectively having field generating electrodes, such as pixel
electrodes and a common electrode, and a liquid crystal layer
interposed between the pair of substrates. In the liquid crystal
display, voltages are respectively applied to the field generating
electrodes to generate an electric field in the liquid crystal
layer. The electric field determines orientations of liquid crystal
molecules in the liquid crystal layer and controls polarization of
incident light. Accordingly, an image is displayed on the liquid
crystal display.
[0005] In addition, the organic light emitting display displays
images using an organic light emitting diode that generates light
through recombination of electrons and holes. The organic light
emitting display has various advantages such as fast response
speed, high luminance, wide viewing angle, and low power
consumption.
[0006] In order to manufacture such display devices, a chemical
vapor deposition ("CVD") method is being widely used.
SUMMARY
[0007] Exemplary embodiments of the invention provide a method of
manufacturing a high dielectric constant metal oxide film having a
predetermined thickness or more.
[0008] Exemplary embodiments of the invention also provide a method
of manufacturing an amorphous metal oxide film.
[0009] Exemplary embodiments of the invention also provide a
display device including an amorphous metal oxide film having a
high dielectric constant.
[0010] However, exemplary embodiments of the invention are not
restricted to the one set forth herein. The above and other
exemplary embodiments of the invention will become more apparent to
one of ordinary skill in the art to which the invention pertains by
referencing the detailed description of the invention given
below.
[0011] According to an exemplary embodiment of the invention, there
is provided a method of manufacturing a metal oxide film. The
method includes injecting a reaction gas and metal precursors into
a chamber, forming a first metal precursor film on a substrate in a
plasma OFF state, forming a first sub-metal oxide film by oxidizing
the first metal precursor film in a plasma ON state, and forming a
second metal precursor film on the first sub-metal oxide film in
the plasma OFF state, where the metal oxide film provided has an
amorphous phase, a thickness of about 20 nanometers (nm) to about
130 nm, and a dielectric constant of about 10 to about 50.
[0012] In an exemplary embodiment, the metal precursors may include
at least one of zirconium-based, hafnium-based, and titanium-based
materials.
[0013] In an exemplary embodiment, the metal precursors may include
at least one of Zr(N(CH3)2(C2H5))3, Zr(N(CH3)C2H5)4, Zr(OC(CH3)3)4,
Ti(N(CH3)2(C2H5)), Hf(N(CH3)3(C2H5))3, Hf(N(CH3)C2H5))4, and
Hf(OC(CH3)3)4.
[0014] In an exemplary embodiment, the metal oxide film may include
at least one of zirconium oxide, hafnium oxide, and titanium
oxide.
[0015] in an exemplary embodiment, the method may further include
forming a second sub-metal oxide film by oxidizing the second metal
precursor film in the plasma ON state.
[0016] In an exemplary embodiment, the forming the first sub-metal
oxide film by oxidizing the first metal precursor film in the
plasma ON state and the forming the second metal precursor film on
the first sub-metal oxide film in the plasma OFF state may be
performed one or more times.
[0017] In an exemplary embodiment, a pressure inside the chamber
may be about 0.1 torr to about 10 torr.
[0018] In an exemplary embodiment, a temperature inside the chamber
may be about 100 degrees Celsius (.degree. C.) to about 400.degree.
C.
[0019] In an exemplary embodiment, the injecting the reaction gas
and the metal precursors into the chamber may include injecting a
carrier gas together with the metal precursors.
[0020] In an exemplary embodiment, a time interval of the plasma ON
state and a time interval of the plasma OFF state may be equal.
[0021] In an exemplary embodiment, a ratio of a time interval of
the plasma ON state and a time interval of the plasma OFF state may
be one of 1:2, 1:3, 1:4, and 1:5.
[0022] According to another exemplary embodiment of the invention,
there is provided a display device including a substrate, and a
metal oxide film disposed on the substrate, where the metal oxide
film has an amorphous phase, a thickness of about 20 nm to about
130 nm, and a dielectric constant of about 10 to about 50.
[0023] In an exemplary embodiment, the display device may further
include a first electrode and a second electrode disposed with the
metal oxide film interposed between the first electrode and the
second electrode, where the first electrode, the second electrode,
and the metal oxide film may constitute a capacitor.
[0024] In an exemplary embodiment, the thickness of the metal oxide
film may be about 90 nm to about 130 nm.
[0025] In an exemplary embodiment, the display device may further
include an insulating film disposed between the second electrode
and the metal oxide film.
[0026] In an exemplary embodiment, the insulating film may include
at least one of silicon oxide, silicon nitride, and silicon
oxynitride.
[0027] In an exemplary embodiment, the thickness of the metal oxide
film may be about 60 nm to about 80 nm.
[0028] In an exemplary embodiment, a thickness of the insulating
film may be about 30 nm to about 50 nm.
[0029] In an exemplary embodiment, the metal oxide film may include
at least one of zirconium oxide, hafnium oxide, and titanium
oxide.
[0030] The display device may further include a transparent
electrode disposed on the metal oxide film, an organic light
emitting layer disposed on the transparent electrode, and a common
electrode disposed on the organic light emitting layer.
BRIEF DESCRIPTION OF THE DRAWINGS
[0031] These and/or other exemplary embodiments will become
apparent and more readily appreciated from the following
description of the exemplary embodiments, taken in conjunction with
the accompanying drawings, in which:
[0032] FIG. 1 is a conceptual diagram of an exemplary embodiment of
an apparatus for manufacturing a metal oxide film, the apparatus
designed to perform a method of manufacturing a metal oxide
film;
[0033] FIG. 2 is a flowchart illustrating an exemplary embodiment
of a method of manufacturing a metal oxide film;
[0034] FIG. 3 is a cross-sectional view illustrating an exemplary
embodiment of the method of manufacturing a metal oxide film;
[0035] FIG. 4 is a cross-sectional view illustrating an exemplary
embodiment of the method of manufacturing a metal oxide film;
[0036] FIG. 5 is a cross-sectional view illustrating an exemplary
embodiment of the method of manufacturing a metal oxide film;
[0037] FIG. 6 is a graph illustrating an exemplary embodiment of
the method of manufacturing a metal oxide film;
[0038] FIGS. 7(a) and 7(b) show an exemplary embodiment of
transmission electron microscope ("TEM") photographs of the
resultant structure of the method of manufacturing a metal oxide
film and a conventional structure of a conventional method of
manufacturing a metal oxide film;
[0039] FIG. 8 illustrates the results of X-ray diffraction ("XRD")
analysis of the resultant structure of the exemplary embodiment and
a thin film provided using an atomic layer deposition ("ALD")
method;
[0040] FIG. 9 is a cross-sectional view of an exemplary embodiment
of a display device;
[0041] FIG. 10 is a cross-sectional view of an exemplary embodiment
of a display device;
[0042] FIG. 11 is a cross-sectional view of the display device
according to the exemplary embodiment of FIG. 10;
[0043] FIG. 12 is a cross-sectional view of an exemplary embodiment
a display device; and
[0044] FIG. 13 is a partial cross-sectional view of an exemplary
embodiment of a display device.
DETAILED DESCRIPTION
[0045] The advantages and features of the invention and methods for
achieving the advantages and features will be apparent by referring
to the exemplary embodiments to be described in detail with
reference to the accompanying drawings. However, the invention is
not limited to the exemplary embodiments disclosed hereinafter, but
can be implemented in diverse forms. The matters defined in the
description, such as the detailed construction and elements, are
nothing but specific details provided to assist those of ordinary
skill in the art in a comprehensive understanding of the invention,
and the invention is only defined within the scope of the appended
claims.
[0046] Where an element is described as being related to another
element such as being "on" another element or "located on" a
different layer or a layer, includes both a case where an element
is located directly on another element or a layer and a case where
an element is located on another element via another layer or still
another element. In contrast, where an element is described as
being is related to another element such as being "directly on"
another element or "located directly on" a different layer or a
layer, indicates a case where an element is located on another
element or a layer with no intervening element or layer
therebetween. In the entire description of the invention, the same
drawing reference numerals are used for the same elements across
various drawing figures.
[0047] Although the terms "first, second, and so forth" are used to
describe diverse constituent elements, such constituent elements
are not limited by the terms. The terms are used only to
discriminate a constituent element from other constituent elements.
Accordingly, in the following description, a first constituent
element may be a second constituent element.
[0048] The terminology used herein is for the purpose of describing
particular embodiments only and is not intended to be limiting. As
used herein, the singular forms "a," "an," and "the" are intended
to include the plural forms, including "at least one," unless the
content clearly indicates otherwise. "At least one" is not to be
construed as limiting "a" or "an." "Or" means "and/or." As used
herein, the term "and/or" includes any and all combinations of one
or more of the associated listed items. It will be further
understood that the terms "comprises" and/or "comprising," or
"includes" and/or "including" when used in this specification,
specify the presence of stated features, regions, integers, steps,
operations, elements, and/or components, but do not preclude the
presence or addition of one or more other features, regions,
integers, steps, operations, elements, components, and/or groups
thereof.
[0049] Furthermore, relative terms, such as "lower" or "bottom" and
"upper" or "top," may be used herein to describe one element's
relationship to another element as illustrated in the drawing
figures. It will be understood that relative terms are intended to
encompass different orientations of the device in addition to the
orientation depicted in the drawing figures. For example, if the
device in one of the drawing figures is turned over, elements
described as being on the "lower" side of other elements would then
be oriented on "upper" sides of the other elements. The exemplary
term "lower," can therefore, encompasses both an orientation of
"lower" and "upper," depending on the particular orientation of the
figure. Similarly, if the device in one of the figures is turned
over, elements described as "below" or "beneath" other elements
would then be oriented "above" the other elements. The exemplary
terms "below" or "beneath" can, therefore, encompass both an
orientation of above and below.
[0050] "About" or "approximately" as used herein is inclusive of
the stated value and means within an acceptable range of deviation
for the particular value as determined by one of ordinary skill in
the art, considering the measurement in question and the error
associated with measurement of the particular quantity (i.e., the
limitations of the measurement system). For example, "about" can
mean within one or more standard deviations, or within .+-.30%,
20%, 10% or 5% of the stated value.
[0051] Unless otherwise defined, all terms (including technical and
scientific terms) used herein have the same meaning as commonly
understood by one of ordinary skill in the art to which this
invention belongs. It will be further understood that terms, such
as those defined in commonly used dictionaries, should be
interpreted as having a meaning that is consistent with their
meaning in the context of the relevant art and the invention, and
will not be interpreted in an idealized or overly formal sense
unless expressly so defined herein.
[0052] Exemplary embodiments are described herein with reference to
cross section illustrations that are schematic illustrations of
idealized embodiments. As such, variations from the shapes of the
illustrations as a result, for example, of manufacturing techniques
and/or tolerances, are to be expected. Thus, embodiments described
herein should not be construed as limited to the particular shapes
of regions as illustrated herein but are to include deviations in
shapes that result, for example, from manufacturing. For example, a
region illustrated or described as flat may, typically, have rough
and/or nonlinear features. Moreover, sharp angles that are
illustrated may be rounded. Thus, the regions illustrated in the
drawing figures are schematic in nature and their shapes are not
intended to illustrate the precise shape of a region and are not
intended to limit the scope of the claims.
[0053] Hereinafter, embodiments of the invention will be described
with reference to the attached drawings.
[0054] FIG. 1 is a conceptual diagram of an apparatus for
manufacturing a metal oxide film, the apparatus designed to perform
a method of manufacturing a metal oxide film according to an
exemplary embodiment.
[0055] Referring to FIG. 1, the apparatus for manufacturing a metal
oxide film may include a chamber CH, a susceptor 300, a shower head
SH, a power supply unit 124, an inlet 100, and an outlet (not
shown).
[0056] The chamber CH may define an internal space desired for a
process. A plurality of elements to be described later may be
disposed in the internal space of the chamber CH. The chamber CH
may be maintained at atmospheric pressure or in a vacuum depending
on a process step. In addition, the internal space of the chamber
CH may be connected to the outside air or may be sealed depending
on a process step.
[0057] The susceptor 300 may be disposed in a lower part of the
space inside the chamber CH. The susceptor 300 may support a
substrate S to be processed.
[0058] In an exemplary embodiment, the substrate S may be an
insulating substrate used in a display device.
[0059] Although not illustrated in the drawing, in an exemplary
embodiment, the susceptor 300 may be connected to a driving unit
for moving the substrate S up and down. Accordingly, the substrate
S placed on the susceptor 300 may be moved up or down as needed in
the space inside the chamber CH.
[0060] Although not illustrated in the drawing, the susceptor 300
may be connected to a temperature control unit for changing the
temperature of the substrate S. Accordingly, the temperature of the
substrate S may be adjusted according to process conditions. The
shower head SH may be placed to face the susceptor 300. The shower
head SH may include a plurality of nozzles to evenly distribute a
gas supplied through the inlet 100. That is, the gas supplied
through the inlet 100 may be evenly distributed into the chamber CH
via the shower head SH.
[0061] The shower head SH may be connected to the power supply unit
124. In an exemplary embodiment, the power supply unit 124 may
supply radio frequency ("RF") power to the shower head SH, for
example.
[0062] The susceptor 300 may be placed to face the shower head SH.
As will be described in detail later, in an exemplary embodiment,
the shower head SH may function as a top electrode, and the
susceptor 300 may function as a bottom electrode. Thus, when
electric power is supplied to the shower head SH, a plasma region
PL may be provided between the shower head SH and the susceptor
300. In the plasma region PL, a reaction gas to be described later
may be excited into a plasma state. This will be described in
detail later.
[0063] A method of manufacturing a metal oxide film according to an
exemplary embodiment will now be described with reference to FIGS.
2 through 5.
[0064] FIG. 2 is a flowchart illustrating a method of manufacturing
a metal oxide film according to an exemplary embodiment. FIGS. 3
through 5 are cross-sectional views illustrating the method of
manufacturing a metal oxide film according to the exemplary
embodiment.
[0065] Referring to FIG. 2 along with FIGS. 1 and 3 to 5, the
method of manufacturing a metal oxide film according to the
exemplary embodiment may include injecting a reaction gas and metal
precursors into a chamber CH (operation S1), forming a first metal
precursor Film 501 on a substrate S (operation S2), forming a first
sub-metal oxide film 502 by oxidizing the first metal precursor
film 501 (operation S3), and forming a second metal precursor film
503 on the first sub-metal oxide film 502 (operation S4).
[0066] First, the injecting of the reaction gas and the metal
precursors into the chamber CH may be performed. In an exemplary
embodiment, the reaction gas and the metal precursors may be
simultaneously provided into the chamber CH. In an exemplary
embodiment, the reaction gas and the metal precursors may be
sequentially provided into the chamber CH.
[0067] In an exemplary embodiment, the injecting of the reaction
gas and the metal precursors may be continuous throughout the
entire process. In other words, the reaction gas and the metal
precursors may be continuously supplied during the process.
[0068] In an exemplary embodiment, the injecting of the reaction
gas and the metal precursors may be discontinuous. In this case,
the reaction gas and the metal precursors may be supplied into the
chamber CH periodically or non-periodically.
[0069] In an exemplary embodiment, the reaction gas may be nitrous
oxide (N2O) and/or oxygen (O2). In either case, the reaction gas
may generate oxygen anions in the plasma state to be described
below.
[0070] In an exemplary embodiment, the metal precursors may include
at least one of zirconium (Zr)-based, hafnium (HF)-based, and
titanium (Ti)-based materials, for example.
[0071] More specifically, the metal precursors may include at least
one of Zr(N(CH3)2(C2H5))3, Zr(N(CH3)C2H5)4, Zr(OC(CH3)3)4,
Ti(N(CH3)2(C2H5)), Hf(N(CH3)3(C2H5))3, Hf(N(CH3)C2H5))4, and
Hf(OC(CH3)3)4, for example.
[0072] In an exemplary embodiment, a carrier gas may be further
injected together with the reaction gas and the metal
precursors.
[0073] The carrier gas may be a gas that moves the metal precursors
without intervening in a reaction.
[0074] In an exemplary embodiment, the carrier gas may be an inert
gas. In an exemplary embodiment, the carrier gas may he argon (Ar)
gas, for example.
[0075] Next, referring to FIG. 3, the forming of the first metal
precursor film 501 on the substrate S may be performed.
[0076] For ease of description, some terms will be defined. The
term "plasma ON state," as used herein, refers to a state in which
a plasma region PL is provided between a shower head SH and a
susceptor 300 because electric power is supplied to the shower head
SH. The term "plasma OFF state," as used herein, refers to a state
in which the plasma region PL is not provided between the shower
head SH and the susceptor 300 because no electric power is supplied
to the shower head SH.
[0077] The forming the first metal precursor film 501 on the
substrate S may be performed in the plasma OFF state. That is, in
this state, the reaction gas and the metal precursors may not react
with each other.
[0078] In the plasma OFF state, a plurality of metal precursors 700
may be adsorbed on the substrate S. The metal precursors 700 may
form the first metal precursor film 501 on the substrate S. In an
exemplary embodiment, the provided first metal precursor film 501
may be a monolayer, for example.
[0079] Next, referring to FIG. 4, the forming of the first
sub-metal oxide film 502 by oxidizing the first metal precursor
film 501 (operation S3) may be performed.
[0080] The forming of the first sub-metal oxide film 502 by
oxidizing the first metal precursor film 501 (operation S3) may be
performed in the plasma ON state. In the plasma ON state, the
reaction gas may become a plasma state. Accordingly, the reaction
gas may generate oxygen anions.
[0081] Referring to FIG. 4, the reaction gas 800 in the plasma
state may be bonded to the metal precursors 700 that form the first
sub-metal oxide film 502. In other words, the first metal precursor
film 501 may be oxidized by the reaction gas 800. In an exemplary
embodiment, since the metal precursors 700 are at least one of
Zr-based, HF-based and Ti-based materials, the first sub-metal
oxide film 502 thus provided may include at least one of zirconium
oxide (ZrO2), hafnium oxide (HfO2), and titanium oxide (TiO2), for
example.
[0082] Next, referring to FIG. 5, the forming of the second metal
precursor film 503 on the first sub-metal oxide film 502 (operation
S4) may be performed. The forming of the second metal precursor
film 503 on the first sub-metal oxide film 502 may be performed in
the plasma OFF state.
[0083] A repulsive force between homogeneous particles is generated
between the first metal precursor film 501 (refer to FIG. 3) before
being oxidized and the metal precursors 700. Therefore, the metal
precursors 700 are not adsorbed on the first metal precursor film
501. When the first metal precursor film 501 is oxidized to the
first sub-metal oxide film 502, the repulsive force between the
first sub-metal oxide film 502 and the metal precursors 700 is
weakened. Therefore, the metal precursors 700 may be adsorbed on
the first sub-metal oxide film 502. Accordingly, the second metal
precursor film 503 including the metal precursors 700 may be
disposed on the first sub-metal oxide film 502. Like the fist metal
precursor film 501 described above, the second metal precursor film
503 may be a monolayer.
[0084] The method of manufacturing a high dielectric constant (k)
metal oxide film according to the exemplary embodiment may further
include forming a second sub-metal oxide film by oxidizing the
second metal precursor film 503.
[0085] Specifically, in the plasma ON state after the formation of
the second metal precursor film 503, the reaction gas 800 in the
plasma state may be bonded to the second metal precursor film 503
to form the second sub-metal oxide film. The second sub-metal oxide
film may be substantially the same as the first sub-metal oxide
film 502.
[0086] The above process may be repeatedly performed one or more
times until a film of a desired thickness is obtained.
[0087] After a thin film is grown to a desired thickness, the
substrate S may be taken out of the chamber CH (operation S5).
[0088] The method of manufacturing a metal oxide film according to
the exemplary embodiment may be performed under the condition that
the plasma ON state and the plasma OFF state are repeated
periodically or non-periodically.
[0089] FIG. 6 is a graph illustrating the method of manufacturing a
metal oxide film according to the exemplary embodiment.
[0090] In an exemplary embodiment, the method of manufacturing a
metal oxide film may start in the plasma OFF state.
[0091] Referring to FIG. 6 along with FIGS. 1 to 5, first, a first
period 1p which is the plasma OFF state may proceed. The forming of
the first metal precursor film 501 on the substrate S (operation
S2) may be performed in the first period 1p.
[0092] Then, a second period 2p which is the plasma ON state may
proceed. The forming of the first sub-metal oxide film 502 by
oxidizing the first metal precursor film 501 may be performed in
the second period 2p.
[0093] Then, a third period 3p which is the plasma OFF state may
proceed. The forming of the second metal precursor film 503 on the
first sub-metal oxide film 502 (operation S4) may be performed in
the third period 3p.
[0094] Then, a fourth period 4p which is the plasma ON state may
proceed. In the fourth period 4p, the second metal precursor film
503 disposed on the first sub-metal oxide film 502 may be oxidized
to a second sub-metal oxide film (not illustrated).
[0095] The above process may be generalized as follows. The method
of manufacturing a high-k metal oxide film according to the
exemplary embodiment may include the plasma ON state of an n.sup.th
period and the plasma OFF state of an (n+1).sup.th period.
[0096] In addition, the n.sup.th period and the (n+1).sup.th period
may alternate with each other.
[0097] In an exemplary embodiment, the time interval of the
n.sup.th period may be about 0.1 seconds to about 10 seconds, so
that the metal precursors may be sufficiently adsorbed.
[0098] In FIG. 6, the intervals of the nth period and the
(n+1).sup.th period are equal to each other. However, embodiments
are not limited to this case. That is, in an exemplary embodiment,
a ratio of the time intervals of the n.sup.th period and the
(n+1).sup.th period may be one of 1:2, 1:3, 1:4, and 1:5, for
example.
[0099] In an exemplary embodiment, the time intervals of the
n.sup.th period and the (n+1).sup.th period may be irregular. That
is, the time intervals of the n.sup.th period and the (n+1).sup.th
period may be changed depending on the condition or purpose of the
process.
[0100] The method of manufacturing a metal oxide film according to
the exemplary embodiment may be terminated after the plasma ON
state. That is, the last deposited film may be a metal oxide film
including oxidized metal precursors.
[0101] A conventional atomic layer deposition ("ALD") method
includes a purging time. Thus, a lot of time is desired to form a
thin film having a large area with a thickness equal to or greater
than about 20 nanometers (nm), for example. The method of
manufacturing a high-k metal oxide film according to the exemplary
embodiment may omit the purging process by simultaneously supplying
the reaction gas and the metal precursors. Thus, a thin film having
a thickness equal to or greater than about 20 nm may be provided
within a short time.
[0102] In addition, the resultant structure of the manufacturing
method may have the following characteristics.
[0103] In an exemplary embodiment, the thickness of a metal oxide
film provided as a result of the above manufacturing method may be
about 20 nm to about 130 nm, for example.
[0104] The metal oxide film provided as a result of the
manufacturing method may have high permittivity. In an exemplary
embodiment, the metal oxide film may have a dielectric constant (k)
of about 10 to about 50, for example.
[0105] Since the broken bond charge of oxygen anions generated by
the reaction gas is discontinuous, the resultant structure grown by
the above process may have an amorphous phase. This will now be
described in detail with reference to FIGS. 7(a), 7(b) and 8.
[0106] FIGS. 7(a) and 7(b) show transmission electron microscope
("TEM") photographs of the resultant structure of the method of
manufacturing a metal oxide film according to the exemplary
embodiment and a conventional structure of a conventional method of
manufacturing a metal oxide film.
[0107] FIG. 7 (a) shows a diffraction pattern of the resultant
structure according to an exemplary embodiment, and FIG. 7(b) shows
a diffraction pattern of a thin film provided using a conventional
ALD method.
[0108] Referring to FIG. 7(a), the diffraction pattern has a ring
shape. This phenomenon occurs when particles of a thin film scatter
light in all directions, that is, when the particles are amorphous.
This shows that the resultant structure of the exemplary embodiment
has an amorphous phase.
[0109] Referring to FIG. 7(b), the diffraction pattern includes a
plurality of dots. This phenomenon occurs when particles of a thin
film scatter light in a specific direction, that is, when the
particles are crystalline. With the conventional ALD method, a
crystalline metal oxide film is provided.
[0110] FIG. 8 is a graph comparing the resultant structures of the
method of manufacturing a high-k metal oxide film according to the
exemplary embodiment and the conventional ALD method.
[0111] FIG. 8 illustrates the results of X-ray diffraction ("XRD")
analysis of the resultant structure of the exemplary embodiment and
a thin film provided using the ALD method.
[0112] Here, graph (a) represents the resultant structure of the
exemplary embodiment, and graph (b) represents the thin film
provided using the conventional method.
[0113] When a thin film having a crystal structure is subjected to
XRD analysis, at least one peak is observed.
[0114] Referring to the analysis result of graph (a), a peak which
is a proof of the crystal structure is not detected. That is, it
may be seen that the resultant structure of the exemplary
embodiment has an amorphous structure.
[0115] Graph (b) includes one or more peaks 11, 12, 13 and 14. That
is, it may be seen that the metal oxide film provided using the
conventional ALD method has a crystalline structure.
[0116] The method of manufacturing a high-k metal oxide film
according to the exemplary embodiment may be performed under the
following process conditions.
[0117] In an exemplary embodiment, the chamber CH may be maintained
in a vacuum, and the pressure of the chamber CH may be adjusted
between about 0.1 torr and about 10 torr, for example.
[0118] In an exemplary embodiment, the temperature inside the
chamber CH may be adjusted between about 100 degrees Celsius
(.degree. C.) and about 400.degree. C., for example.
[0119] A display device including a metal oxide film according to
an exemplary embodiment will now be described. The display device
including the metal oxide film according to the exemplary
embodiment may be manufactured using the method of manufacturing a
metal oxide film according to the above-described embodiment.
[0120] FIG. 9 is a cross-sectional view of a display device
according to an exemplary embodiment.
[0121] Referring to FIG. 9, the display device according to the
exemplary embodiment includes a substrate S and a metal oxide film
220 disposed on the substrate S.
[0122] In an exemplary embodiment, the metal oxide film 220 may be
a thin film provided using the method of manufacturing a metal
oxide film according to the exemplary embodiment.
[0123] In an exemplary embodiment, the metal oxide film 220 may
have a first thickness t1. In an exemplary embodiment, the first
thickness t1 may be about 20 nm to about 130 nm, for example.
[0124] In an exemplary embodiment, the metal oxide film 220 may
have an amorphous phase over the entire area.
[0125] In an exemplary embodiment, the metal oxide film 220 may be
a high-k metal oxide film. Thus, the dielectric constant (k) of the
metal oxide film 220 may be about 10 to about 50.
[0126] FIGS. 10 and 11 are cross-sectional views of a display
device according to an exemplary embodiment.
[0127] Referring to FIGS. 10 and 11, the display device according
to the exemplary embodiment may include at least one capacitor Cst
including a first electrode E1, a second electrode E2, and a metal
oxide film (not illustrated) disposed between the first electrode
E1 and the second electrode E2. In an exemplary embodiment, the
capacitor Cst included in the display device may be a storage
capacitor.
[0128] In an exemplary embodiment, the display device may be an
organic light emitting display.
[0129] In this case, a buffer layer BU may be disposed on a
substrate S. The buffer layer BU may prevent the penetration of
moisture and oxygen from the outside through the substrate S. In
addition, the buffer layer BU may planarize the surface of the
substrate S. In an exemplary embodiment, the buffer layer BU may
include at least one of a silicon nitride (SiNx) film, a silicon
oxide (SiO.sub.2) film, and a silicon oxynitride (SiOxNy) film, for
example. In another exemplary embodiment, the buffer layer BU may
be omitted depending on the type of the substrate S or process
conditions.
[0130] A semiconductor layer including a semiconductor pattern ACT
may be disposed on the buffer layer BU. The semiconductor layer
will be described based on the semiconductor pattern ACT. In an
exemplary embodiment, the semiconductor pattern ACT may include a
combination of at least one of polycrystalline silicon,
monocrystalline silicon, low temperature polycrystalline silicon,
amorphous silicon, and an oxide semiconductor, for example. The
semiconductor pattern ACT may include, in an exemplary embodiment,
a channel region not doped with an impurity and source and drain
regions ACTb and ACTc doped with an impurity. The source region
ACTb is located on a side of the channel region ACTa and is
electrically connected to a source electrode SE to he described
later. The drain region ACTc is located on the other side of the
channel region ACTa and is electrically connected to a drain
electrode DE to be described later.
[0131] A gate insulating film GI may be disposed on the
semiconductor layer including the semiconductor pattern ACT. The
gate insulating film GI may be a gate insulating layer in an
exemplary embodiment. In an exemplary embodiment, the gate
insulating film GI may include any at least one of inorganic
insulating materials such as silicon oxide (SiOx) and silicon
nitride (SiNx) and organic insulating materials such as
benzocyclobutene ("BCB"), acrylic materials and polyimide, for
example.
[0132] A gate conductor including a gate electrode GE may be
disposed on the gate insulating film GI. The gate electrode GE may
extend from a scan line (not illustrated) and overlap the
semiconductor pattern ACT. In an exemplary embodiment, the gate
conductor may include at least one of aluminum (Al)-based metal
including aluminum alloys, silver (Ag)-based metal including silver
alloys, copper (Cu)-based metal including copper alloys, molybdenum
(Mo)-based metal including molybdenum alloys, chromium (Cr),
titanium (Ti), and tantalum (Ta), for example.
[0133] A first insulating film ILD1 may be disposed on the gate
conductor including the gate electrode GE. The first insulating
film ILD1 may be a high-k metal oxide film. That is, the first
insulating film ILD1 may have an amorphous phase, and the
dielectric constant (k) of the first insulating film ILD1 may be
about 10 to about 50, for example. In an exemplary embodiment, the
thickness of the first insulating film ILD1 may be about 20 nm to
about 130 nm, for example.
[0134] In an exemplary embodiment, the first insulating film ILD1
may include at least one of zirconium oxide (ZrO2), hafnium oxide
(HfO2), and titanium oxide (TiO2), for example.
[0135] A data conductor including the source electrode SE and the
drain electrode DE may be disposed on the first insulating film
ILD1. The data conductor may include the source electrode SE and
the drain electrode DE. The source electrode SE and the drain
electrode DE are disposed on the first insulating film ILD1 to be
spaced apart from each other. The data conductor may include at
least one of a metal, an alloy, a metal nitride, a conductive metal
oxide, and a transparent conductive material. In an exemplary
embodiment, the data conductor may have a monolayer structure or a
multilayer structure including at least one of nickel (Ni), cobalt
(Co), titanium (Ti), silver (Ag), copper (Cu), molybdenum (Mo),
aluminum (Al), beryllium (Be), niobium (Nb), gold (Au), iron (Fe),
selenium (Se), and tantalum (Ta). In an exemplary embodiment, the
source electrode SE and the drain electrode DE may include an alloy
of at least one of the above metals and at least one of titanium
(Ti), zirconium (Zr), tungsten (W), tantalum (Ta), niobium (Nb),
platinum (Pt), hafnium (Hf), oxygen (O) and nitrogen (N), for
example.
[0136] The semiconductor pattern ACT, the gate electrode GE, the
source electrode SE and the drain electrode DE described above
constitute a second switching element TR2. In FIG. 10, the second
switching element TR2 is illustrated as a top gate type. However,
the second switching element TR2 is not limited to the top gate
type. That is, in another exemplary embodiment, the second
switching element TR2 may be provided as a bottom gate type.
[0137] A second insulating film ILD2 may be disposed on the data
conductor. The second insulating film ILD2 may remove steps,
thereby increasing the luminous efficiency of a pixel electrode 250
and an organic light emitting layer 270 which will be described
later. The second insulating, film ILD2 may include an organic
material in an exemplary embodiment. In an exemplary embodiment,
the second insulating film ILD2 may include at least one of
polyimide, polyacryl, and polysiloxane, for example. In an
exemplary embodiment, the second insulating film ILD2 may include
an inorganic material or a composite of an inorganic material and
an organic material. A first contact hole CNT1 may be defined in
the second insulating film ILD2 to expose at least a part of the
drain electrode DE.
[0138] The pixel electrode 250 may be disposed on the second
insulating film ILD2. The pixel electrode 250 may be electrically
connected to the drain electrode DE exposed by the first contact
hole CNT1. That is, the pixel electrode 250 may be an anode which
is a hole injection electrode. When provided as an anode, the pixel
electrode 250 may include a material having a high work function in
order to facilitate hole injection. In addition, the pixel
electrode 250 may be a reflective electrode, a transflective
electrode, or a transmissive electrode. The pixel electrode 250 may
include a reflective material in an exemplary embodiment. In an
exemplary embodiment, the reflective material may include at least
one of silver (Ag), magnesium (Mg), chromium (Cr), gold (Au),
platinum (Pt), nickel (Ni), copper (Cu), tungsten (W), aluminum
(Al), aluminum-lithium (Al--Li), magnesium-indium (Mg--In), and
magnesium-silver (Mg--Ag), for example.
[0139] The pixel electrode 250 may be provided as a monolayer in an
exemplary embodiment. In an alternative exemplary embodiment, the
pixel electrode 250 may be provided as a multilayer in which two or
more materials are stacked.
[0140] When provided as a multilayer, the pixel electrode 250 may
include, in an exemplary embodiment, a reflective film and a
transparent or translucent electrode disposed on the reflective
film. In an exemplary embodiment, the pixel electrode 250 may
include a reflective film and a transparent or translucent
electrode disposed under the reflective film. In an exemplary
embodiment, the pixel electrode 250 may have a three-layer
structure of ITO/Ag/ITO, for example.
[0141] Here, the transparent or translucent electrode may include
at least one of indium tin oxide ("ITO"), indium zinc oxide
("IZO"), zinc oxide (ZnO), indium oxide (In.sub.2O.sub.3), indium
gallium oxide ("IGO") and aluminum zinc oxide ("AZO"), for
example.
[0142] A pixel defining layer PDL may be disposed on the pixel
electrode 250. An opening that at least partially exposes the pixel
electrode 250 is defined in the pixel defining layer PDL. The pixel
defining layer PDL may include an organic material or an inorganic
material. In an exemplary embodiment, the pixel defining layer PDL
may include a material such as photoresist, polyimide resin,
acrylic resin, a silicon compound, or polyacrylic resin, for
example.
[0143] The organic light emitting layer 270 may he disposed on the
pixel electrode 250 and the pixel defining layer PDL. More
specifically, the organic light emitting layer 270 may be disposed
on an area of the pixel electrode 250 which is exposed through the
opening of the pixel defining layer PDL. In an exemplary
embodiment, the organic light emitting layer 270 may at least
partially cover sidewalls of the pixel defining layer PDL.
[0144] In an exemplary embodiment, the organic light emitting layer
270 may emit light of one of red, blue and green colors, for
example. In an exemplary embodiment, the organic light emitting
layer 270 may emit white light or emit light of one of cyan,
magenta and yellow colors, for example. When the organic light
emitting layer 270 emits white light, it may include a white light
emitting material or may have a stack of a red light emitting
layer, a green light emitting layer and a blue light emitting
layer.
[0145] A common electrode 280 may be disposed on the organic light
emitting layer 270 and the pixel defining layer PDL. In an
exemplary embodiment, the common electrode 280 may be disposed on
the entire surface of the organic light emitting layer 270 and the
pixel defining layer 260. The common electrode 280 may be a cathode
in an exemplary embodiment. In an exemplary embodiment, the common
electrode 280 may include at least one of Li. Ca, Lif/Ca, LiF/Al,
Al, Ag, and Mg, for example. In addition, the common electrode 280
may include a material having a low work function. The common
electrode 280 may be, in an exemplary embodiment, a transparent or
translucent electrode including at least one of ITO, IZO, zinc
oxide (ZnO), indium oxide (In.sub.2O.sub.3), IGO, and AZO, for
example.
[0146] The pixel electrode 250, the organic light emitting layer
270 and the common electrode 280 described above may constitute an
organic light emitting diode OLED. However, the organic light
emitting diode OLED is not limited to this configuration and may be
a multilayer structure further including a hole injection layer
("HIL"), a hole transport layer ("HTL"), an electron transport
layer ("ETL"), and an electron injection layer ("EIL").
[0147] A counter substrate 290 may be placed to face the substrate
S. The counter substrate 290 may be bonded to the substrate S by a
sealing member. The counter substrate 290 may be a transparent
insulating substrate in an exemplary embodiment. When the counter
substrate 290 is a transparent insulating substrate, the
transparent insulating substrate may be a glass substrate, a quartz
substrate, a transparent resin substrate, or the like, for
example.
[0148] In an exemplary embodiment, an encapsulation film (not
illustrated), instead of the counter substrate 290, may be disposed
on the common electrode 280. The encapsulation film may include at
least one inorganic film and/or at least one organic film.
[0149] Referring to FIG. 11, the first electrode E1 and the second
electrode E2 may be disposed with the first insulating film ILD1
interposed between them.
[0150] In an exemplary embodiment, the first electrode E1, the
second electrode E2, and the first insulating layer ILD1 may
constitute the storage capacitor Cst. That is, the first insulating
film ILD1 may be a dielectric of the storage capacitor Cst.
[0151] In an exemplary embodiment, the first electrode E1 may be
disposed in the same layer as the gate electrode GE, and the second
electrode E2 may be disposed in the same layer as the source
electrode SE or the drain electrode DE. When elements are "disposed
in the same layer," it may mean that the elements are formed
simultaneously in the same process and thus including the same
material.
[0152] In an exemplary embodiment, the thickness of the first
insulating film ILD1 may be about 100 nm to about 110 nm, for
example.
[0153] A metal oxide film according to embodiments has a very small
leakage current. Therefore, the metal oxide film may be used to
realize a capacitor having excellent electrical
characteristics.
[0154] FIG. 12 is a cross-sectional view of a display device
according to an exemplary embodiment.
[0155] FIG. 12 is different from FIG. 11 in that a first electrode
E1 and the second electrode E2 are disposed with a third insulating
film ILD3 interposed between them.
[0156] In an exemplary embodiment, the first electrode E1, the
second electrode E2, and the third insulating film ILD3 may
constitute a program capacitor Cpr. That is, the third insulating
film ILD3 may be a dielectric of the program capacitor Cpr.
[0157] In this case, the third insulating film ILD3 may be a high-k
metal oxide film. That is, the third insulating film ILD3 may have
an amorphous phase and may have a dielectric constant (k) of about
10 to about 50, for example. In an exemplary embodiment, the
thickness of the third insulating film ILD3 may be about 90 nm to
about 130 nm, for example.
[0158] In an exemplary embodiment, the third insulating film ILD3
may include at least one of zirconium oxide (ZrO2), hafnium oxide
(HfO2), and titanium oxide (TiO2), for example.
[0159] FIG. 13 is a partial cross-sectional view of a display
device according to an exemplary embodiment.
[0160] Referring to FIG. 13, a first insulating layer ILD1_1 may be
a laminate of a first sub-film 511 and a second sub-film 512.
[0161] In an exemplary embodiment, the first sub-film 511 may be a
metal oxide film. In this case, the first sub-film 511 may have an
amorphous phase. In an exemplary embodiment, the dielectric
constant (k) of the first sub-film 511 may be about 10 to about 50,
for example.
[0162] In an exemplary embodiment, the first sub-film 511 may
include at least one of zirconium oxide (ZrO2), hafnium oxide
(HfO2), and titanium oxide (TiO2), for example.
[0163] In an exemplary embodiment, the thickness d1 of the first
sub-film 511 may be about 60 nm to about 80 nm, for example.
[0164] The second sub-film 512 may be disposed on the first
sub-film 511. In an exemplary embodiment, the second sub-film 512
may include at least one of a silicon nitride (SiNx) film, a
silicon oxide (SiO.sub.2) film, and a silicon oxynitride (SiOxNy)
film, for example.
[0165] In an exemplary embodiment, the thickness d2 of the second
sub-film 512 may be about 30 nm to about 50 nm, for example.
[0166] As described above, the first insulating film ILD1_1 may be
a dielectric of a capacitor. When the dielectric of the capacitor
is a laminate of a metal oxide film and a silicon-including
insulating film, its electrical characteristics may be stably
maintained.
[0167] In FIG. 13, the first insulating film ILD1_1 includes the
first sub-film 511 and the second sub-film 512. However,
embodiments are not limited to this case.
[0168] In an exemplary embodiment, the third insulating film ILD3
of FIG. 12 may have the structure described in FIG. 13.
[0169] According to embodiments, the resistance of a display device
may be measured in real time during a process.
[0170] However, the effects of the exemplary embodiments are not
restricted to the one set forth herein. The above and other effects
of the exemplary embodiments will become more apparent to one of
daily skill in the art to which the exemplary embodiments pertain
by referencing the claims.
[0171] While the invention has been particularly illustrated and
described with reference to exemplary embodiments thereof, it will
be understood by those of ordinary skill in the art that various
changes in form and detail may be made therein without departing
from the spirit and scope of the invention as defined by the
following claims. The exemplary embodiments should be considered in
a descriptive sense only and not for purposes of limitation.
* * * * *