U.S. patent number RE38,266 [Application Number 09/838,216] was granted by the patent office on 2003-10-07 for method for fabricating semiconductor thin film.
This patent grant is currently assigned to Semiconductor Energy Laboratory Co., Ltd.. Invention is credited to Akiharu Miyanaga, Hisashi Ohtani, Satoshi Teramoto, Shunpei Yamazaki.
United States Patent |
RE38,266 |
Yamazaki , et al. |
October 7, 2003 |
**Please see images for:
( Certificate of Correction ) ** |
Method for fabricating semiconductor thin film
Abstract
An object of the present invention is to provide a technology of
reducing a nickel element in the silicon film which is crystallized
by using nickel. An extremely small amount of nickel is introduced
into an amorphous silicon film which is formed on the glass
substrate. Then this amorphous silicon film is crystallized by
heating. At this time, the nickel element remains in the
crystallized silicon film. Then an amorphous silicon film is formed
on the surface of the silicon film crystallized with the action of
nickel. Then the amorphous silicon film is further heat treated. By
carrying out this heat treatment, the nickel element is dispersed
from the crystallized silicon film into the amorphous silicon film
with the result that the nickel density in the crystallized silicon
film is lowered.
Inventors: |
Yamazaki; Shunpei (Tokyo,
JP), Ohtani; Hisashi (Kanagawa, JP),
Miyanaga; Akiharu (Kanagawa, JP), Teramoto;
Satoshi (Kanagawa, JP) |
Assignee: |
Semiconductor Energy Laboratory
Co., Ltd. (JP)
|
Family
ID: |
17329557 |
Appl.
No.: |
09/838,216 |
Filed: |
April 20, 2001 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
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536977 |
Sep 29, 1995 |
5789284 |
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Reissue of: |
115838 |
Jul 15, 1998 |
06071766 |
Jun 6, 2000 |
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Foreign Application Priority Data
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Sep 29, 1994 [JP] |
|
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6-259117 |
|
Current U.S.
Class: |
438/151; 438/156;
438/162; 438/166 |
Current CPC
Class: |
H01L
21/2022 (20130101); H01L 29/78675 (20130101); C03C
17/3482 (20130101); H01L 21/02532 (20130101); H01L
21/02672 (20130101); C03C 2218/153 (20130101); C03C
2218/152 (20130101) |
Current International
Class: |
H01L
29/786 (20060101); H01L 21/20 (20060101); H01L
29/66 (20060101); H01L 21/02 (20060101); H01L
021/00 (); H01L 021/44 () |
Field of
Search: |
;438/162,166,151,156,486,487 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
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03-229415 |
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Oct 1991 |
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JP |
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6333824 |
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Dec 1994 |
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JP |
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06-333824 |
|
Dec 1994 |
|
JP |
|
6333825 |
|
Dec 1994 |
|
JP |
|
Other References
Dvurechenskii.A, Transport Phenomena in Amorphous Silicon Doped by
Ion Implantation of 3D Metals, pp. 635-640Phys. Stat. Sol. No date.
.
Hayzelden.C, In Situ Transmission Electron Microscopy Studies of
Silicide-Mediated Crystallization of Amorphous Silicon, vol.60/pp.
225-227Appl. Phys. Lett. No date. .
Hempel. T, Needle-Like Crystallization of NI Doped Amorphous
Silicon Thin Films, vol. 85/pp. 921-924Solid State Communications
No date. .
Kakkad.R, Crystallized SI Films by Low-Temerature Rapid Thermal
Annealing of Amorphous Silicon, vol. 65/pp. 2069-2072J. Appl. Phys.
No date. .
Kakkad.R, Low Temperature Selective Crystallization of Amorphous
Silicon, vol. 115/pp. 66-68Journal of Non-Crystalline Solids No
date. .
Liu.G, Selective Area Crystallization of Amorphous Silicon Films by
Low-Temperature Rapid Thermal Annealing, vol. 55/pp. 660-662Appl.
Phys. Lett. No date. .
Liu.G, Polycrystalline Silicone Thin Film Transistors on Corning
7059 Glass Substrates Using Short Time, vol. 62/pp. 2554-2556Appl.
Phys. Lett. No date..
|
Primary Examiner: Lebentritt; Michael S.
Attorney, Agent or Firm: Nixon Peabody LLP Costellia;
Jeffrey L.
Parent Case Text
This application is a Division of application Ser. No. 08/536,977,
filed Sep. 29, 1995 now U.S. Pat No. 5,789,284.
Claims
What is claimed is:
1. A method for fabricating a semiconductor thin film comprising
the steps of: providing an amorphous silicon film with a metal
element which promotes crystallization of said semiconductor film;
crystallizing said amorphous silicon film by heat treatment to
obtain a crystalline semiconductor film; forming a silicon nitride
film in contact with said crystalline semiconductor film; forming a
metal element diffusion film comprising a semiconductor in contact
with said silicon nitride film; diffusing said metal element into
said metal element diffusion film; and removing said metal element
diffusion film into which said metal element has been diffused,
using said silicon nitride film as an etching stopper.
2. A method for fabricating a semiconductor thin film comprising
the steps of: providing an amorphous silicon film with a metal
element which promotes crystallization of said silicon film;
obtaining a crystalline silicon film by crystallizing said
amorphous silicon film by heat treatment; forming a silicon nitride
film in contact with said crystalline silicon film; forming an
amorphous semiconductor film in contact with said silicon nitride
film; dispersing by heat treatment the metal element in said
crystalline silicon film into the smorphous semiconductor film
formed in contact with said silicon nitride film; and removing the
semiconductor film formed in contact with said silicon nitride film
by using said silicon nitride film as an etching stopper.
3. The method of claim 2 wherein said amorphous semiconductor film
comprises silicon.
4. A method for fabricating a semiconductor thin film comprising
the steps of: providing an amorphous silicon film with a metal
element which promotes crystallization of said silicon film;
obtaining a crystalline silicon film by crystallizing said
amorphous silicon film by heat treatment; forming a silicon nitride
film in contact with said crystalline silicon film; forming an
amorphous semiconductor film in contact with said silicon nitride
film; crystallizing by heat treatment the amorphous semiconductor
film which is formed in contact with said silicon nitride film; and
removing the semiconductor film which is formed in contact with
said silicon nitride film by using said silicon nitride film as an
etching stopper.
5. The method of claim 4 wherein said amorphous semiconductor film
comprises silicon.
6. A method for fabricating a semiconductor thin film comprising
the steps of: providing an amorphous semiconductor film with a
metal element which promotes crystallization of said semiconductor
film; obtaining said amorphous semiconductor film by heat treatment
to obtain a crystalline semiconductor film; forming a silicon
nitride film in contact with said semiconductor film; forming a
metal element diffusion film comprising a semiconductor in contact
with said silicon nitride film; diffusing said metal element into
said metal element diffusing film; and removing said metal element
diffusion film into which said metal element has been diffused.
.Iadd.
7. A method for fabricating a semiconductor device comprising the
steps of: providing an amorphous semiconductor film with a metal
element which promotes crystallization of said semiconductor film;
crystallizing said amorphous semiconductor film to obtain a
crystalline semiconductor film; forming an etching stopper film on
said crystalline semiconductor film; forming a metal element
diffusion film comprising a semiconductor on said etching stopper
film; diffusing said metal element into said metal element
diffusion film from said crystalline semiconductor film; and
removing said metal element diffusion film after diffusing said
metal element thereto..Iaddend..Iadd.
8. The method according to claim 7 wherein said metal element is
selected from the group consisting of Fe, Co, Ni, Ru, Rh, Pd, Os,
Ir, Pt, Cu and Au..Iaddend..Iadd.
9. A method for fabricating a semiconductor device comprising the
steps of: providing an amorphous semiconductor film with a metal
element which promotes crystallization of said semiconductor film;
crystallizing said amorphous semiconductor film to obtain a
crystalline semiconductor film; forming an etching stopper film on
said crystalline semiconductor film; forming a metal element
diffusion film comprising silicon on said etching stopper film;
diffusing said metal element into said metal element diffusion film
from said crystalline semiconductor film; and removing said metal
element diffusion film after diffusing said metal
element..Iaddend..Iadd.
10. The method according to claim 9 wherein said metal element
diffusion film comprises amorphous silicon..Iaddend..Iadd.
11. The method according to claim 9 wherein said metal element
diffusion film comprises polycrystalline
silicon..Iaddend..Iadd.
12. The method according to claim 9 wherein said metal element
diffusion film comprises amorphous Si.sub.x Ge.sub.1-x
(0<x<1)..Iaddend..Iadd.
13. The method according to claim 9 wherein said metal element is
selected from the group consisting of Fe, Co, Ni, Ru, Rh, Pd, Os,
Ir, Pt, Cu and Au..Iaddend..Iadd.
14. A method for fabricating a semiconductor device comprising the
steps of: providing an amorphous semiconductor film with a metal
element which promotes crystallization of said semiconductor film;
crystallizing said amorphous semiconductor film to obtain a
crystalline semiconductor film; forming an etching stopper film on
said crystalline semiconductor film; forming a gettering film
comprising silicon by sputtering on said etching stopper film;
diffusing said metal element into said gettering film from said
crystalline semiconductor film; and removing said gettering film
after diffusing said metal element..Iaddend..Iadd.
15. The method according to claim 14 wherein said etching stopper
film comprises silicon oxide..Iaddend..Iadd.
16. The method according to claim 14 wherein said etching stopper
film comprises silicon nitride..Iaddend..Iadd.
17. The method according to claim 14 wherein said gettering film
comprises amorphous silicon..Iaddend..Iadd.
18. The method according to claim 14 wherein said gettering film
comprises polycrystalline silicon..Iaddend..Iadd.
19. The method according to claim 14 wherein said gettering film
comprises amorphous Si.sub.x Ge.sub.1-x
(0<x<1)..Iaddend..Iadd.
20. The method according to claim 14 wherein said metal element is
selected from the group consisting of Fe, Co, Ni, Ru, Rh, Pd, Os,
Ir, Pt, Cu and Au..Iaddend..Iadd.
21. A method for fabricating a semiconductor device comprising the
steps of: providing an amorphous semiconductor film with a metal
element which promotes crystallization of said semiconductor film;
crystallizing said amorphous semiconductor film to obtain a
crystalline semiconductor film; forming an etching stopper film on
said crystalline semiconductor film; forming a gettering film
comprising silicon on said etching stopper film; diffusing said
metal element into said gettering film from said crystalline
semiconductor film; and removing said gettering film after
diffusing said metal element, wherein said gettering film is so
formed that a defect density in the gettering film is higher than a
density of said metal element in the crystalline semiconductor
film..Iaddend..Iadd.
22. The method according to claim 21 wherein said etching stopper
film comprises silicon oxide..Iaddend..Iadd.
23. The method according to claim 21 wherein said etching stopper
film comprises silicon nitride..Iaddend..Iadd.
24. The method according to claim 21 wherein said gettering film
comprises amorphous silicon..Iaddend..Iadd.
25. The method according to claim 21 wherein said gettering film
comprises polycrystalline silicon..Iaddend..Iadd.
26. The method according to claim 21 wherein said gettering film
comprises amorphous Si.sub.x Ge.sub.1-x
(0<x<1)..Iaddend..Iadd.
27. The method according to claim 21 wherein said metal element is
selected from the group consisting of Fe, Co, Ni, Ru, Rh, Pd, Os,
Ir, Pt, Cu and Au..Iaddend..Iadd.
28. A method for fabricating a semiconductor device comprising the
steps of: providing an amorphous semiconductor film with a metal
element which promotes crystallization of said semiconductor film;
crystallizing said amorphous semiconductor film to obtain a
crystalline semiconductor film; forming an oxide film on the
crystalline semiconductor film by oxidizing a surface of said
crystalline semiconductor film; forming a gettering film comprising
silicon on said oxide film; diffusing said metal element into said
gettering film from said crystalline semiconductor film; and
removing said gettering film after diffusing said metal
element..Iaddend..Iadd.
29. The method according to claim 28 wherein said gettering film
comprises amorphous silicon..Iaddend..Iadd.
30. The method according to claim 28 wherein said gettering film
comprises polycrystalline silicon..Iaddend..Iadd.
31. The method according to claim 28 wherein said gettering film
comprises amorphous Si.sub.x Ge.sub.1-x
(0<x<1)..Iaddend..Iadd.
32. The method according to claim 28 wherein said metal element is
selected from the group consisting of Fe, Co, Ni, Ru, Rh, Pd, Os,
Ir, Pt, Cu and Au..Iaddend..Iadd.
33. A method for fabricating a semiconductor device comprising the
steps of: providing an amorphous semiconductor film with a metal
element which promotes crystallization of said semiconductor film;
crystallizing said amorphous semiconductor film to obtain a
crystalline semiconductor film; forming an oxide film on the
crystalline semiconductor film by oxidizing a surface of said
crystalline semiconductor film; forming a gettering film comprising
silicon by sputtering on said oxide film; and diffusing said metal
element into said gettering film from said crystalline
semiconductor film; and removing said gettering film after
diffusing said metal element..Iaddend..Iadd.
34. The method according to claim 33 wherein said gettering film
comprises amorphous silicon..Iaddend..Iadd.
35. The method according to claim 33 wherein said gettering film
comprises polycrystalline silicon..Iaddend..Iadd.
36. The method according to claim 33 wherein said gettering film
comprises amorphous Si.sub.x Ge.sub.1-x
(0<x<1)..Iaddend..Iadd.
37. The method according to claim 33 wherein said metal element is
selected from the group consisting of Fe, Co, Ni, Ru, Rh, Pd, Os,
Ir, Pt, Cu and Au..Iaddend..Iadd.
38. A method for fabricating a semiconductor device comprising the
steps of: providing an amorphous semiconductor film with a metal
element which promotes crystallization of said semiconductor film;
crystallizing said amorphous semiconductor film to obtain a
crystalline semiconductor film; forming an oxide film on the
crystalline semiconductor film by oxidizing a surface of said
crystalline semiconductor film; forming a gettering film comprising
silicon on said oxide film; diffusing said metal element into said
gettering film from said crystalline semiconductor film; and
removing said gettering film after diffusing said metal element,
wherein said gettering film is so formed that a defect density in
the gettering film is higher than a density of said metal element
in the crystalline semiconductor film..Iaddend..Iadd.
39. The method according to claim 38 wherein said gettering film
comprises amorphous silicon..Iaddend..Iadd.
40. The method according to claim 38 wherein said gettering film
comprises polycrystalline silicon..Iaddend..Iadd.
41. The method according to claim 38 wherein said gettering film
comprises amorphous Si.sub.x Ge.sub.1-x
(0<x<1)..Iaddend..Iadd.
42. The method according to claim 38 wherein said metal element is
selected from the group consisting of Fe, Co, Ni, Ru, Rh, Pd, Os,
Ir, Pt, Cu and Au..Iaddend.
Description
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a method for forming a silicon
semiconductor thin film which has a crystallinity and is formed on
a substrate having an insulation surface of a glass substrate or
the like.
2. Description of the Related Art
In recent years, attention is paid on a technology for constructing
a thin film transistor by using a silicon thin film which is formed
on a glass substrate. This thin film transistor is primarily used
in an active matrix type liquid crystal electro-optical device and
other thin film integrated circuits. The liquid crystal
electro-optical device changes optical characteristics of a liquid
crystal thereby displaying an image by charging a liquid crystal
into a pair of glass substrates and applying an electric field.
In particular, the active matrix type liquid crystal display device
using a thin film transistor is characterized in that the thin film
transistor is arranged in each pixel, an electric charge held in a
pixel electrode is controlled by using the thin film transistor as
a switch. Since the active matrix type liquid crystal display
device is capable of displaying a fine image at a high speed, the
device can be used in displays for various electronic apparatuses
(for example, a portable word processor, and a portable computer or
the like).
As a thin film transistor used in the active matrix type liquid
crystal display device, an amorphous silicon thin film is commonly
used. However, the thin film transistor using the amorphous silicon
thin film has the following problems. (1) The liquid crystal thin
film transistor has low characteristics and cannot display a higher
quality image. (2) The liquid crystal thin film transistor cannot
constitute a peripheral circuit for driving a thin film transistor
arranged on a pixel.
The aforementioned second problem can be considered by dividing the
problem into the following two aspects. One aspect of the problem
is that since a P-channel type thin film transistor cannot be used
for practical purposes with the thin film transistor using an
amorphous silicon thin film, a CMOS circuit cannot be constituted.
Another aspect of the problem is that since the thin film
transistor using an amorphous silicon thin film cannot be operated
at a high speed, and a large current cannot flow in the thin film
transistor, a peripheral driving circuit cannot be assembled.
Means for solving the aforementioned problems include a technology
for forming a thin film transistor by using a crystalline silicon
thin film. The methods for obtaining a crystalline thin film
include a method for heat treating an amorphous silicon film and a
method for irradiating the amorphous silicon thin film with laser
light.
SUMMARY OF THE INVENTION
However, a method for crystallizing am amorphous silicon film by
heat treatment in the prior art has the following problem.
In the case where a thin film transistor is constituted which is
used in a liquid crystal electro-optical apparatus, it is demanded
that the thin film transistor is formed on a translucent substrate.
Examples of the translucent substrate include a quartz substrate
and a glass substrate. However, the quartz substrate is expensive
and cannot be used in the liquid crystal electro-optical device
which has a large technological problem of a cost reduction.
Consequently, the glass substrate is commonly used. However, it has
a problem of a low heat resistance.
Generally, as the glass substrate used in the liquid crystal
electro-optical device, Corning 7059 glass substrate is used. The
strain point of this glass substrate is 593.degree. C. When the
substrate is heat treated at this temperature or more, the
shrinkage or the deformation of the substrate becomes conspicuous.
In recent years, the liquid crystal electro-optical device tends to
have a larger area and the shrinkage and the deformation of the
substrate must be suppressed as much as possible.
However, it has been proved in the experiment that a temperature of
600.degree. C. or more is required to crystallize the amorphous
silicon film by heating. It is also made clear that tens of hours
are required for heating. A large area glass substrate cannot be
subjected to such high temperature and long hour heating at
all.
Further, a technology of crystallizing the amorphous silicon film
by laser light irradiation is also known. However, it is difficult
as a practical problem to irradiate uniformly a large area with
laser light and to irradiate the area while keeping a definite
level of irradiation power.
An object of the present invention is to solve the aforementioned
problems and to provide a technology of transforming the amorphous
silicon film into a crystalline silicon film by heat treatment at
an extremely low temperature.
In particular, an object of the invention is to provide a
crystalline silicon thin film which is capable of constituting a
thin film transistor with a high performance characteristics.
In accordance with a major aspect of the present invention, there
is provided a method for fabricating a semiconductor thin film
comprising the steps of:
introducing into an amorphous silicon film a metal element which
promotes the crystallization of silicon;
obtaining a crystalline silicon film by crystallizing the
aforementioned amorphous silicon film by heat treatment;
forming a metal element diffusion film on said crystalline silicon
film;
diffusing the aforementioned metal element into the aforementioned
metal element diffusion film; and
removing the metal element diffusion film into which the metal
element has been diffused.
In the aforementioned structure, examples of the amorphous silicon
film include a film which is formed by the plasma CVD or by the low
pressure thermal CVD on a glass substrate or on a glass substrate
on which an insulating film is formed.
Further, examples of the metal element which promotes the
crystallization of the aforementioned silicon include one or more
kinds of elements selected from Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt,
Cu and Au. Among these metal elements, the most effective metal
element is nickel (Ni).
Methods for introducing the metal element which promotes the
crystallization of the aforementioned silicon include a method for
providing these metal layers or a layer including the metal on the
surface of the amorphous silicon film. Specifically, the methods
include a method for forming a metal element layer or a layer
including a metal element by the CVD, the sputtering process, vapor
deposition or the like, and a method for coating a solution
containing a metal element on the amorphous silicon film. In
particular, since the latter method using the latter solution
enables easily controlling a density of the metal element, the
latter method is more favorable than the former method. In
addition, since the metal element can be held uniformly in contact
with the surface of the amorphous silicon film in the latter
method, the latter method is very favorable in this respect, too.
For reference, when the aforementioned CVD and the sputtering
process, vapor deposition or the like is used, it is difficult to
form an extremely thin uniform film. Consequently, there is a
problem in that the metal element is non-uniformly present on the
amorphous silicon film, and the metal element is liable to be
deviated at the time of the crystal growth.
To crystallize by heating the silicon film to which the metal
element promoting the crystallization of silicon is introduced, the
silicon film may be heated at a temperature of 450.degree. C. or
more. The upper limit of this heating temperature is limited by the
heat-resistant temperature of the glass substrate used as the
substrate. In the case of the glass substrate, the heat resistant
temperature can be regarded as the strain point of glass. When
materials such as quartz substrate or the like which can endure a
temperature of 1000.degree. C. or more, the heating temperature in
heating can be heightened in accordance with the heat insulating
temperature.
As one example of heat treatment, it is appropriate to set the
temperature to about 550.degree. C. from the viewpoint of the heat
resistance and the productivity of the glass substrate.
An amorphous silicon film used as the metal element diffusion film
and formed on crystalline silicon film crystallized as a result of
heat treatment may be formed by the general CVD process. For
example, the same method as used for forming the crystalline
silicon film by introducing the metal element into the amorphous
silicon starting film and crystallizing the amorphous silicon
starting film by heating is used.
However, more preferably, the film may be of the quality such that
a defect density is high and the metal element can be easily
trapped. This is because the metal element in the crystalline
silicon film can be easily dispersed in the metal element diffusion
film comprising silicon.
The defect density can be set to a high level by using such means
as forming the film only of silane without using. hydrogen in
accordance with the plasma CVD, using the sputtering method, or
lowering the temperature at which the film is formed in accordance
with the plasma CVD.
It is more advantageous to increase the thickness of this amorphous
silicon film with respect to the thickness of the crystalline
silicon film. This is because when the amorphous silicon film is
thicker than the crystalline silicon film, the volume ratio with
respect to the crystalline silicon film can be increased, and more
metal elements can be dispersed in the amorphous silicon film.
A polycrystalline silicon film and an amorphous Si.sub.x Gi.sub.1-x
film (0<x<1) can be used as the metal element diffusion film.
The polycrystalline silicon film can be formed by low pressure CVD.
The amorphous Si.sub.x Ge.sub.1-x film can be formed by plasma CVD
using silane (SiH.sub.4) and germane (GeH.sub.4) as a raw material
gas.
The step of diffusing (absorbing) the metal element in the
crystalline silicon film is carried out by heat treatment. Since
the metal element in the crystalline silicon film is diffused into
the metal element diffusion film by the heat treatment, the metal
element concentration is lowered in the crystalline silicon
film.
Next, the metal element diffusion film into which the metal element
has been diffused is removed. This removal can be a selective
etching of the metal element diffusion film by forming an oxide
film as an etching stopper on the silicon film to be
crystallized.
Concrete constitution of this method is described using FIG. 1.
First, a crystalline silicon film 105 is formed on a glass
substrate 101 using nickel as a metal element which promotes
crystallization of silicon. Reference numeral 102 designates a base
silicon oxide film. Heat treatment is used for the crystallization.
(FIG. 1(B))
Next as shown in FIG. 1(C), an oxide film 106 is formed, and an
amorphous silicon film 107 is formed as the metal element diffusion
film and heat treated.
This heat treatment can be classified into two methods; one method
is the one which is carried out at a temperature (generally,
450.degree. C. or less) at which the amorphous silicon film is not
crystallized while the other method is one which is carried out at
a temperature (generally, 450.degree. C. or more, and preferably
500.degree. C. or more) at which the amorphous silicon film is
crystallized.
When the heat treatment is carried out at a temperature at which
the amorphous silicon film 107 provided on the crystalline silicon
film 105 is not crystallized, the temperature of the heat treatment
is 400.degree. C. to 450.degree. C. and the heating duration is 5
minutes to 10 hours. The metal element in the amorphous silicon
film is gradually absorbed into the amorphous silicon film 107 by
this heat treatment. Consequently, when the heat treatment is
carried out over a long period, the density of the metal element in
the crystalline silicon film 105 can be gradually decreased.
By removing the amorphous silicon film 107 using the oxide film 106
as an etching stopper, a crystalline silicon film 108 containing a
metal element at a low concentration therein as compared with the
metal element concentration in the amorphous silicon film 107 can
be obtained. (FIG. 1(D)) This is because the silicon atom is
present in the amorphous silicon film 107 in the state that the
silicon atom is liable to be connected with the metal element (in
the amorphous state, a large quantity of unpaired bonds are
present). Further, this action can be conspicuously obtained when
the defect density is artificially increased in the amorphous
silicon film 107.
In the meantime, when the amorphous silicon film is heated at a
temperature at which the crystallization of the amorphous silicon
film 107 provided on the crystalline silicon film 105 proceeds, the
dispersion of the metal element is ostensibly suspended in the
state in which the amorphous silicon 107 is crystallized. Then when
the average value of the density of the metal element in the
crystalline silicon film 105 and the density of the metal element
in the silicon film 107 for absorbing the metal element
(crystallized in heat treatment) become approximately equal to each
other, the dispersion of the metal element is ostensibly
suspended.
However, it has been made clear that the metal element is locally
concentrated in the crystalline silicon film 105. This method
becomes effective for suppressing this phenomenon. Therefore, this
is a method which is intended to produce a state in which no
concentration of the metal element exists in the silicon film to be
used in the fabrication of the device by using the phenomenon that
the metal element is concentrated on the tip part of the crystal
growth to dispel the tip of the crystal growth to the silicon film
to be removed later.
Then, heat treatment is carried out at the temperature at which the
amorphous silicon film 107 is crystallized to crystallize the
amorphous silicon film 107. At this occasion, the crystal growth
proceeds from a surface at which the silicon film 107 contacts
the-oxide film 106 to the exposed surface thereof. Then, at the
same time with this crystal growth, a portion where the metal
element is concentrated moves in the silicon film 107. As a
consequence, a portion where a nickel element is concentrated is
dispelled from the silicon film 105 so that the nickel element
exists in the silicon film 107 (particularly on the surface
thereof). Then, a crystalline silicon film 108 free from an area
where the nickel element is deviated can be obtained by removing
the silicon film 107 using the oxide film 106 as an etching stopper
(FIG. 1(D)).
An amorphous silicon film is formed on the surface of the
crystalline silicon film crystallized with the action of metal
which promotes the crystallization, followed by heat treatment to
disperse the metal element into the amorphous silicon film. In this
manner, the metal element in the crystalline silicon film can be
virtually sucked out thereby making it possible to obtain a
crystalline silicon film having a low density of metal element and
having a crystallinity.
In addition, since all these steps can be carried out at a
temperature such as 550.degree. C. or less which the glass
substrate can endure, the steps are extremely useful in the
formation of a crystalline thin film silicon semiconductor used for
constructing a thin film transistor used in a liquid crystal
electro-optical device using, for example, a glass substrate.
To facilitate the removal of the silicon film for the absorption of
the metal element, it is effective to form an oxide film on the
crystalline silicon film. Since the oxide film has a selectivity
with respect to an etchant (for example, hydradine and ClF.sub.3),
the oxide film can serve as an etching stopper.
Further, on a surface of the crystalline silicon film (first
silicon film) crystallized with the action of the metal promoting
the crystallization, an amorphous silicon film (second silicon
film) is formed. Thereafter, heat treatment is carried out to
crystallize the second layer amorphous silicon film with the result
that the concentrated portion of the metal element which is present
in the first silicon film can be dispelled into the second silicon
film thereby suppressing the deviation of the metal element in the
first silicon film.
BRIEF DESCRIPTION OF THE DRAWINGS
FIGS. 1(A) to 1(D) are views showing a step of fabricating a
crystalline silicon film.
FIG. 2 is a view showing a density distribution of a nickel
element.
FIG. 3 is a view showing a density distribution of the nickel
element.
FIG. 4 is a view showing a density distribution of the nickel
element.
FIGS. 5(A) to 5(D) are views showing a step of fabricating a thin
film transistor.
FIGS. 6(A) to 6(D) are views showing a step of fabricating a
crystalline silicon film.
FIGS. 7(A) to 7(C) are views showing a step of fabricating a thin
film transistor.
FIGS. 8(A) to 8(C) are views showing a step of fabricating a
crystalline silicon film.
FIGS. 9(A) to 9(C) are views showing a step of fabricating a
crystalline silicon film.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Embodiment 1
Embodiment 1 relates to a technology of dispersing a nickel element
into an amorphous silicon film from a crystalline silicon film
(allowing the amorphous silicon film to such the nickel element) to
lower a density of the nickel element in the crystalline silicon
film as a consequence, by forming an amorphous silicon film,
introducing into the amorphous silicon film a metal film which
promotes the crystallization of silicon film, forming an amorphous
silicon film on a crystallized silicon film (crystalline silicon
film) via an oxide film (silicon oxide film), followed by
performing heat treatment again.
FIG. 1 shows a step of fabricating a crystalline silicon film
described in this embodiment. In the beginning, on Corning 7059
glass substrate 101 (having a strain point of 593.degree. C.), a
silicon oxide film 102 is formed to a thickness of 3000 .ANG. as a
base film. The silicon oxide film 102 is intended to prevent
impurities and alkaline ions from being dispersed into the
semiconductor thin film from the glass substrate 101. Then, the
amorphous silicon film 103 is formed to a thickness of 600 .ANG. by
the plasma CVD and the low pressure thermal CVD. Then, a nickel
acetate solution which is adjusted to a predetermined nickel
density is dripped on the amorphous silicon film 103 to form a
water film 104. Then, the spinner 100 is used for spin coating to
produce a state in which the nickel element is held in contact with
the surface of the amorphous silicon film 103 (FIG. 1(A)).
Subsequently, the amorphous silicon film 103 is crystallized by
heat treatment to obtain a crystalline silicon film 105. The heat
treatment can be carried out at a heating temperature of
450.degree. C. or more, or preferably, 500.degree. C. or more.
However, in consideration of heat resistance of the glass substrate
101, preferably, the temperature is set to a strain point of the
glass substrate 101 or less. Incidentally, when the heat treatment
is carried out at a temperature of 500.degree. C. or less, the heat
treatment requires tens of hours or more. Thus, the method is not
practical.
The density of nickel in this crystalline silicon film 105 is
required to be set to 1.times.10.sub.16 atom cm.sup.-3 to
5.times.10.sup.19 atom cm.sup.-3 if possible. Consequently, it is
necessary to adjust the nickel density in the crystalline silicon
film 105 thus obtained to the aforementioned range at the step
shown in FIG. 1(A). Incidentally, the nickel density is defined as
a minimum value measured by using the SIMS (secondary ion mass
spectrometer).
When the crystalline silicon film 105 is obtained, a silicon oxide
film 106 is formed on the surface of the film 105. The thickness of
the silicon oxide film 106 may be set to about tens of .ANG. to
about 100 .ANG.. Such a thin film is formed because the nickel
element in the crystalline silicon film is required to move via the
silicon oxide film 106. Here, an extremely thin silicon oxide film
106 is formed by the UV light irradiation in the air. Even when
this thin silicon oxide film 106 is as thick as a natural oxide
film, it has been made clear that the thin film 106 serves as an
etching stopper in the subsequent step of etching of the amorphous
silicon film (denoted by 107). Thus the thin film 106 may be as
thick as the aforementioned thickness. Here, the silicon oxide film
106 is formed by using the UV oxidation process, but the silicon
oxide film may be formed by the thermal oxidation process.
This silicon oxide film 106 serves as an etching stopper in the
later etching step, and the silicon oxide film 106 can be used as
long as it provides a selectivity with respect to the crystalline
silicon film 105. For example, in the place of the silicon oxide
film 106, an extremely thin silicon nitride film can be used.
Subsequently, the amorphous silicon film 107 is formed to a
thickness of 600 .ANG. by the plasma CVD and low pressure CVD.
FIG. 2 shows a density distribution of the nickel element in the
direction of the film thickness by using SIMS (secondary ion mass
spectrometer). What is shown in FIG. 2 is a distribution of the
nickel element in the depth direction from the surface of the
amorphous silicon film 107. As apparent in FIG. 2, it is made clear
that the nickel element in the amorphous silicon film 107 is less
than the measurement limit (here, in this case, 1.times.10.sub.17
atom cm.sup.-3), and a maximum of about 5.times.10.sub.18 atom
cm.sup.-3 of the nickel element is present in the crystalline
silicon film 105.
Then the nickel element in the crystalline silicon film 105 is
dispersed in the amorphous silicon film 107 via an oxide film 106
by heat treatment. This step can be understood as a step of sucking
out the nickel element in the crystalline silicon film 105 (FIG.
1(C)).
This step of heat treatment is carried out at a temperature of from
400 to 450.degree. C. at which the amorphous silicon film 107 is
not crystallized. In this embodiment, the heat treatment is carried
out at 450.degree. C. for two hours. When this heat treatment is
carried out, the nickel element in the crystalline silicon film 105
is dispersed in the amorphous silicon film 107 thereby making it
possible to lower the density of the nickel element in the
crystalline silicon film 105.
Generally, when the thickness of the amorphous silicon film 107 is
set to not less than the thickness of the crystalline silicon film
105, the density of the nickel element in the crystalline silicon
film 105 can be set to a half or less by carrying out the
aforementioned heat treatment.
FIG. 3 shows a density distribution of the nickel element in the
film thickness direction in a state in which the heat treatment is
carried out for two hours. Data shown in FIG. 3 is made with the
same measurement method as data shown in FIG. 2.
As is apparent in FIG. 3, nickel is dispersed in the amorphous
silicon film 107. However, it can be seen in FIG. 3 that the
density of nickel is somewhat higher in the crystalline silicon
film 105. From FIG. 3, it can be understood that the nickel element
in the crystalline film 105 is absorbed in the amorphous silicon
film 107 at the step of heat treatment shown in FIG. 1(C).
FIG. 4 shows a density distribution of nickel in four hour heat
treatment at 450.degree. C. when two hour heat treatment is further
carried out at 450.degree. C. after data shown in FIG. 3 is
obtained. (Finally, four hour treatment is carried out at
450.degree. C.) As is apparent in a comparison between FIGS. 3 and
4, it can be seen that the nickel element in the crystalline
silicon film 105 is gradually sucked into the amorphous silicon
film 107. It is considered that a large amount of unpaired bonds
and a large number of silicon atoms to which nickel can be easily
bonded exist in the amorphous silicon film 107. Further, the nickel
density in the crystalline silicon film 105 can be gradually
lowered by carrying out a long hour heat treatment. Such an action
is a feature that cannot be observed when the amorphous silicon
film 107 is crystallized.
Then, the amorphous silicon film 107 is removed by etching. Here,
as an etchant of the amorphous silicon film 107, hydradine (N.sub.2
H.sub.6) is used. When hydradine is used as an etchant, the
amorphous silicon film 107 has a faster etching rate than the
crystalline silicon film 105. Further, in the present embodiment,
an oxide silicon film 106 which cannot be etched with hydradine
(the etching rate is extremely low, and in a relative viewpoint, it
can be regarded that etching cannot be performed) is formed on the
crystalline silicon film as an etching stopper. Therefore, only the
amorphous silicon film 107 which has sucked out nickel can be
selectively removed. Incidentally, dry etching may be used for
etching the amorphous silicon film 107.
Subsequently, the silicon oxide film 106 is removed with buffer
acid and fluorine nitride to obtain a crystalline silicon film 108
in which the density of the contained nickel element as shown in
FIG. 1(D) can be lowered. The density of the nickel element in this
crystalline silicon film 108 is, for example, about
3.times.10.sup.18 atom cm.sup.-3. As apparent in the comparison
with FIG. 2, this value means that the density of the nickel
element can be lowered to a half (a half or less in average).
In this embodiment, the thickness of the amorphous silicon film 107
which is formed on the crystalline silicon film 105 is set to the
same thickness as the thickness of the crystalline silicon film
105. However, the density of the nickel element which is contained
in the crystalline silicon film 108 which is finally obtained can
be further lowered by increasing the thickness of the amorphous
silicon film 107. That is, a larger amount of the nickel element
can be sucked out into the amorphous silicon film 107 by increasing
the volume of the amorphous silicon film 107 compared with the
volume of the crystalline silicon film 105.
With the adoption of the structure of this embodiment, the density
of nickel in the crystalline silicon film 108 thus obtained can be
set to 5.times.10.sub.18 a tom cm.sup.-3 or less.
Embodiment 2
Embodiment 2 is characterized in that the step of heat treatment in
the fabrication process in embodiment 1 is carried out by setting
the conditions as follows; heating temperature is 550.degree. C.,
and heating duration is four hours. When the heat treatment step
shown in FIG. 1(C) is carried out at 550.degree. C. for four hours,
the amorphous silicon film denoted by 107 is crystallized with the
action of the nickel element which is dispersed from the
crystalline silicon film 105.
At this time, the crystalline advances in a direction of heading
from the crystalline silicon film 105 to the amorphous silicon film
107 via the oxide film 106. As described above, the metal element
which promotes the crystallization of silicon tends to be
concentrated at the tip portion of the crystal growth.
Consequently, an area where the nickel element is concentrated
exist in the crystallized silicon film 107 (which is transformed
into a crystalline film at this stage). Then naturally the density
of nickel in the crystalline silicon film is decreased.
Further, the nickel element deviated area which is present on the
surface of the crystalline silicon film 105 moves together with the
tip portion of the crystal growth along with the advancement of the
progress of the crystallization of the amorphous silicon film 107.
That is, the nickel element deviated area will be present in the
silicon film 107 (which is here designated as a crystallized state)
after the termination of the crystallization. Consequently, the
nickel element deviated area on the surface of the crystalline
silicon film 105 can be eliminated.
In the case where the amorphous silicon film 107 has been
crystallized in this manner, it is feared whether or not this
crystallized silicon film can be selectively removed. Since the
silicon oxide film 106 is formed which serves as an etching
stopper, only the silicon film denoted by 107 (crystallized in this
case crystallized) can be selectively removed. In other words, when
etching is carried out using hydradine and ClF.sub.3 gas, the
etching rate of oxide film denoted by reference numeral 106 is
extremely small compared with the etching rate of the silicon film
denoted by reference numeral 107. Thus the etching is suspended
when the etching of the silicon film 107 is ended.
When the structure shown in embodiment 2 is adopted, the heat
treatment step shown in FIG. 1(C) can be performed under the same
condition as the heat treatment as FIG. 1(B).
Embodiment 3
Embodiment 3 shows an example of fabricating a thin film transistor
by using the crystalline silicon film which is obtained by the
method for fabricating the silicon film shown in embodiments 1 and
2. Referring to FIG, 5, there is shown a method for fabricating the
thin film transistor. In the beginning, a crystalline silicon film
503 is formed on the glass substrate 501 on which a base film 502
is formed by using a method shown in embodiments 1 and 2. (FIG.
5(A)) Subsequently, the crystalline silicon film 503 thus obtained
is patterned to form an active layer of the thin film transistor as
shown by reference numeral 504. Then a silicon oxide film 505 is
formed to a thickness of 1000 .ANG. which functions as a gate
insulating film by the plasma CVD and the low pressure thermal CVD.
(FIG. 5(B))
Then an aluminum film containing scandium is formed to a thickness
of 6000 .ANG. followed by patterning the film to form a gate
electrode denoted by reference numeral 506. Further, in the
electrolyte, anodic oxidation is carried out by using the gate
electrode 506 as an anode to form an oxide layer 507. The thickness
of the oxide layer 507 is set to 2000 .ANG.. It is possible to form
an offset gate area to a thickness of this oxide layer 507 at the
subsequent step (FIG. 5(C)).
Then, impurity ions are doped into the active layer 504. Here,
phosphorus ions are doped as an impurity ion. At this step,
phosphorus ions are doped into an area denoted by reference
numerals 508 and 511. The area denoted by reference numerals 508
and 511 constitute a source area and a drain area. Further, an area
denoted by reference numeral 509 constitutes an offset area.
Further, the area denoted by reference numeral 510 constitutes a
channel-formation area.
After the completion of the impurity ion doping, the silicon film
is irradiated with laser light to activate the doped ions and to
anneal the source and drain areas 508 and 511 that has been damaged
at the time of ion doping. (FIG. 5(C)) Subsequently, a silicon
oxide film 512 is formed as an interlayer insulating film and then
a contact hole is formed to form a source electrode 513 and a drain
electrode 514 by using aluminum. Further, a thin film transistor is
completed by heat treatment in the hydrogen atmosphere of
350.degree. C. (FIG. 5(D)).
Embodiment 4
Embodiment 4 relates to a technology for obtaining a crystalline
silicon film which has crystal grown in a direction parallel to the
substrate and then lowering the density of nickel in this
crystalline silicon film by selectively introducing nickel which is
a metal element that promotes the crystallization of silicon.
In the beginning, a silicon oxide film is formed to have a
thickness of 3000 .ANG. as a base film on the glass substrate 601
by the sputtering method. Subsequently, the amorphous silicon film
603 is formed to have a thickness of 500 .ANG. by the plasma CVD or
the low pressure thermal CVD.
Subsequently, the amorphous silicon film is irradiated with UV
light in the atmosphere of oxygen to form an extremely thin oxide
film (not shown) on the surface of the amorphous silicon film 603.
This oxide film is intended to improve the moisture characteristics
of the solution at the subsequent step of coating the solution.
Then, a resist is used to form a mask 604. The area 605 exposed by
the resist mask 604 has a slit-like configuration with a
longitudinal direction from the surface side of the paper shown in
FIG. 6(A) to the rear surface of FIG. 6(A).
Then, a nickel acetate solution containing a predetermined density
of nickel is dripped to form a water film 606.
Further, a spinner 600 is used for spin coating to produce a state
in which the nickel element is held in contact with the surface of
the amorphous silicon film 603 via an oxide film (not shown) in an
area denoted by reference numeral 605.
Then, the resist mask 604 is removed. Then the amorphous silicon
film 603 is heat treated to be crystallized. Here, in the area
designated by reference numeral 605, the nickel element is
dispersed from a state in which the nickel element is held in
contact with the amorphous silicon film 603 via the oxide film (not
shown) into the amorphous silicon film via the oxide film (not
shown). Then, as denoted by an arrow 607, the crystal growth
proceeds in a direction parallel to the substrate. This crystal
growth advances in a column-like or a needle-like configuration. In
embodiment 4, since the area denoted by reference numeral 605 has a
slit-like configuration with a longitudinal direction from the
surface of the paper shown in FIG. 6(A) to the rear surface of FIG.
6(A). The crystal growth as shown by the arrow 607 advances
approximately in one direction. This crystal growth can be carried
out over tens of .mu.m to 100 .mu.m or more. (FIG. 6(B))
In this manner, the crystalline silicon film 608 is obtained as
shown in FIG. 6(C). Then, the oxide film 609 is formed to have a
thickness of 50 .ANG. by the thermal oxidization method. Moreover,
an amorphous silicon film 610 having a thickness of 1000 .ANG. is
formed by the plasma CVD or the low pressure thermal CVD.
Then, the heat treatment is carried out at 450.degree. C. for two
hours, and causes the nickel element in the crystalline silicon
film 608 to be dispersed in the amorphous silicon film 610 via an
oxide film 609. The amorphous silicon film 610 is etched with
ClF.sub.3 gas, and then the oxide film 609 is removed with buffer
fluoric acid. Thus the crystalline silicon film 611 having a
lowered nickel density as shown in FIG. 6(D) can be obtained. This
crystalline silicon film 611 is characterized in that the
crystalline silicon film 611 has an area which is crystal grown in
a direction parallel to the substrate as denoted by reference
numeral 607 and, further, the nickel density is low.
An experiment has made clear that somewhat large amount of nickel
which is introduced into the area shown by reference numeral 605
can have a longer distance of crystal growth in a direction
parallel to the substrate (which is referred to a longitudinal
direction growth). However, in the meantime, a larger amount of the
introduced nickel element can be a factor of heightening the nickel
element concentration in the silicon film. Therefore the large
amount of introduced nickel is not favorable. This is because when
the nickel density in the film is increased (5.times.10.sup.19 atom
cm.sup.-3 or more in the experiment), a problem becomes apparent in
that the characteristic of the silicon film is deteriorated or the
operation of thin film transistors becomes unstable and the
deterioration of characteristic becomes drastic.
However, as shown in Embodiment 4, the present invention can meet
the following two demands at the same time by removing the nickel
element after the completion of crystallization; a demand that the
distance of crystal growth in the longitudinal direction be
prolonged in the horizontal direction, and a demand that the nickel
density (density of metal element) in the obtained crystalline
silicon film 611 be lowered as much as possible.
Embodiment 5
Embodiment 5 shows an example in which a crystalline silicon film
obtained in embodiment 4 is used to constitute a thin film
transistor. FIG. 7 shows a fabrication step in embodiment 5. In the
beginning, a crystalline silicon film as shown by reference numeral
611 in FIG. 6(D) has an area which has crystal grown in a direction
parallel to the substrate.
Subsequently, as shown in FIG. 7(A), an active layer 703 of the
thin film transistor is formed by patterning the crystalline
silicon film. In FIG. 7(A), reference numeral 701 denotes a glass
substrate while reference numeral 702 denotes a silicon oxide film
as the base film.
Here, it is important that the beginning and the end of the crystal
growth in the crystal growth shown in FIG. 6(B) do not exist in the
active layer 703. This is because a high density of nickel is
contained in the beginning and the end of the crystal growth.
Further, a silicon oxide film 704 is formed which functions as a
gate insulating film to a thickness of 1000 .ANG. by the plasma
CVD. FIG. 7(A))
Subsequently, a film which primarily comprises aluminum is formed
followed by patterning the film to form a gate electrode 705. Then,
an oxide layer 706 is formed by anodic oxidation in the electrolyte
using the gate electrode 705 as an anode. An offset gate area can
be formed by the impurity ion doping to a thickness of the oxide
layer 706 at the subsequent step of impurity ion doping. (FIG.
7(B)).
Then, as an impurity ion, phosphorus ions are doped. At this step,
a source area 707 and a drain area 710 are formed. Further, an
offset gate area 708 and a channel formation area 709 are formed.
After the impurity ion doping is completed, the source and the
drain areas 707 and 710 are formed by irradiating a laser light or
an intense light to activate the source and the drain areas 707 and
710.
Then, the silicon oxide film 711 which constitutes an interlayer
insulating film is formed to a thickness of 6000 .ANG. by plasma
CVD. Then, after a contact hole is formed, the source electrode 712
and the drain electrode 713 are formed. Thus, a thin film
transistor is completed.
Embodiment 6
Embodiment 6 is characterized in that heat treatment is carried out
again after the step of fabricating the crystalline silicon film
according to embodiment 1 shown in FIG. 1. When heat treatment is
carried out at step shown in FIG. 1(C), nickel (metal element) in
the crystalline silicon film 105 is gradually absorbed into the
amorphous silicon film 107 as shown in FIG. 4. At this time, the
density of nickel in the vicinity of the surface of the crystalline
silicon film 105 becomes higher than the nickel density in the
vicinity of the interface of the silicon oxide film 102 on the
lower surface of the crystalline silicon film 105. This means that
nickel in the crystalline silicon film 105 is sucked out into the
amorphous silicon film 107 with the result that nickel element is
deviated to the surface side of the crystalline silicon film
105.
Consequently, in the case wherein a thin film transistor is
fabricated by using a crystalline silicon film 108 which is formed
on a glass plate 101 as shown in FIG. 1(D), carriers are to be
conducted on the surface of the crystalline silicon film 108. It is
not preferable that a high density of nickel exists in an area
where carriers are conducted.
Then, in embodiment 6, after a state shown in FIG. 1(D) is
obtained, heat treatment is conducted so that nickel is dispersed
again in the crystalline silicon film 108. In the heat treatment
discussed here, nickel may be dispersed. Therefore, the temperature
may be set to 400.degree. C. or more. Further, the upper limit of
the temperature is limited by the heat resistance of the glass
substrate 101. Consequently, the heating temperature used in
embodiment 6 is 400.degree. C. or more, and the temperature may be
less than the strain point of the glass substrate.
Details of embodiment 6 will be explained in detail by using FIG.
8. In the beginning, after passing through the fabrication step
shown in FIG. 1, a state shown in FIG. 1(D) will be obtained. The
state in FIG. 1(D) is described in FIG. 8(A). FIG. 8(A) shows a
layer 802 (on the surface side) in which nickel is segregated and a
high density of nickel is contained, and a layer 801 in which
nickel is contained with a density lower than that of the layer
side denoted by reference numeral 802. These layers 801 and 802
constitute a crystalline silicon film 108 (see FIG. 1(D)) formed on
the glass substrate 101 via a base film 102.
In a state shown in FIG. 8(A), the crystalline silicon film is heat
treated. Here the film is subjected to two hour heat treatment at
500.degree. C. Consequently, the nickel element in an area denoted
by reference numeral 802 is dispersed into an area denoted by
reference numeral 801 where the nickel element is present at a low
density. In this manner, this area 802 can be in a state in which
no segregation of nickel is present. Then, the crystalline silicon
film 803 can be obtained where the nickel density on the surface
can be lowered. (FIG. 8(C))
Embodiment 7
Embodiment 7 is an example in which laser light is irradiated in
place of heat treatment at the step of crystallization in the
structure shown in embodiment 1. The step of fabricating embodiment
7 is shown in FIG. 9. In the case of Embodiment 7, a layer denoted
by reference number 802 comprising a crystalline silicon film where
nickel is present at a high density in the surface of the
crystalline silicon film, and a layer 801 comprising a crystalline
silicon film in which the nickel element is present at a low
density are obtained. (FIG. 9(A))
Next, a laser light is irradiated to disperse the nickel element
from the layer 802 to the layer 801. (FIG. 9(B)) Then, a
crystalline silicon film 901 is obtained which has a state in which
nickel is uniformly dispersed in the film. (FIG. 9(C))
Embodiment 8
Embodiment 8 is characterized in that an amorphous silicon film 107
shown in FIG. 1(C) is formed in a state in which the defect density
is artificially high at the step shown in embodiment 1. At step
shown in embodiment 1, the crystalline silicon film 105 contains an
average of about 3.times.10.sup.18 atom cm.sup.-3 of the nickel
element as shown in FIG. 2. Then, embodiment 7 is characterized by
heightening the removing capabilities of the nickel element by
setting the defect density in the amorphous silicon film 107 at
least to a level more than the aforementioned density of the nickel
element.
The defect density in the amorphous silicon film 107 can be
estimated by measuring the spin density. In addition, to
artificially form defects, the sputtering method, plasma CVD at low
temperature may be used. Otherwise the plasma CVD or low pressure
thermal CVD using only silane and disilane may be used without
using hydrogen for neutralizing unpaired bonds.
When the defect density of the amorphous silicon film 17 is set to
a high level, the removing capabilities of nickel element can be
further enlarged. Then the effect shown in FIGS. 3 and 4 can be
made large.
Embodiment 9
In this embodiment, a polycrystalline silicon film is used as a
nickel element diffusion film for absorbing nickel element
thereinto.
A process for fabricating a crystalline silicon film in accordance
with this embodiment is described with reference to FIG. 1. First,
a silicon oxide film 102 is formed as a base film to a thickness of
3000 .ANG. on Corning 7059 glass substrate 101 (having a strain
point 593.degree. C.).
Next, an amorphous silicon film 103 is formed to a thickness of 600
.ANG. by plasma CVD or low pressure thermal CVD. Nickel acetate
solution adjusted to a prescribed nickel concentration is dripped
on the amorphous silicon film 103 and is spin-coated by spinner 100
to form an aqueous film 104. In this way, nickel is provided in
contact with a surface of the amorphous silicon film 103. (FIG.
1(A))
Next, the amorphous silicon film 103 is crystallized by heat
treatment to obtain a crystalline silicon film 105. Temperature of
the heat treatment is 550.degree. C. and the duration of the heat
treatment is 4 hours. (FIG. 1(B))
A silicon oxide film 106 is formed to a thickness of several tens
.ANG. to 100 .ANG. on a surface of the obtained crystalline silicon
film 105 by a UV light irradiation in air
Next, a polycrystalline silicon film 107 is formed to a thickness
of 600 .ANG. by low pressure thermal CVD. It is not necessary to
form the polycrystalline silicon film 107 with a film quality
required for an active layer of a semiconductor. The actual film
has a high defect density. It is preferred that this defect density
is higher than defect density of the crystalline silicon film
105.
Next, nickel element contained in the crystalline silicon film 105
is diffused into the polycrystalline silicon film 107 through the
oxide film 106 by heat treatment. (FIG. 1(C)).
The lower limit of the heating temperature of this heat treatment
is defined as a temperature at which nickel can diffuse and the
lower limit is 400.degree. C. or higher. The upper limit is defined
as a strain point of the glass substrate 101. Nickel element
contained in the crystalline silicon film 105 diffuses into the
polycrystalline silicon film 107 by this heat treatment to enable
the nickel element concentration in the crystalline silicon film
105 to decrease.
Generally, by forming the polycrystalline silicon film 107 to a
thickness more than that of the crystalline silicon film 105,
nickel concentration in the crystalline silicon film 105 can be
lowered to half or less by the heat treatment.
Then, the amorphous silicon film 107 is removed by etching.
Hydradine (N.sub.2 H.sub.6) or ClF.sub.3 gas can be used. Since the
etching rate of the silicon oxide is extremely low and the silicon
oxide film 106 serves as an etching stopper, only the
polycrystalline silicon film 107 which has absorbed nickel can
selectively be removed.
Next, the silicon oxide film 106 is removed by buffered
hydrofluoric acid and fluorine nitrate to obtain a crystalline
silicon film 108 in a low nickel element concentration therein, as
shown in FIG. 1(D).
Embodiment 10
An amorphous Si.sub.x Fe.sub.1-x film (0<x<1) is used as a
nickel element diffusion film for absorbing nickel element therein
in this embodiment.
A process for fabricating a crystalline silicon film according to
this embodiment is described with reference to FIG. 1. First, a
silicon oxide film 102 is formed as a base film to a thickness of
3000 .ANG. on Corning 7059 glass substrate 101 having a strain
point of 593.degree. C.
Next, an amorphous silicon film 103 is formed to a thickness of 600
.ANG. by plasma CVD or low pressure thermal CVD. A nickel acetate
solution adjusted to a prescribed nickel concentration is dripped
on the amorphous silicon film 103, and spin-coated by spinner 100
to form an aqueous film 104. In this way, nickel element is
provided in contact with a surface of the amorphous silicon film.
(FIG. 1(A))
Next, the amorphous silicon film 103 is crystallized by heat
treatment to obtain a crystalline silicon film 105. The heating
temperature is 550.degree. C. and the heating duration is 4 hours.
(FIG. 1(B)).
A silicon oxide film 106 is formed to a thickness of several tens A
to 100 .ANG. on a surface of the obtained crystalline silicon film
105 by a UV light irradiation in air.
Next, an amorphous Si.sub.x Ge.sub.1-x film 107 is formed to a
thickness of 600 .ANG. by plasma CVD using a silane (SiH.sub.4) and
germane (GeH.sub.4) as a raw material gas. In order to obtain the
amorphous Si.sub.x Ge.sub.1-x film 107 at a high defect density,
low temperature is used as the substrate temperature during the
film formation and the raw material gas is used without being
diluted with hydrogen.
Next, nickel element contained in the crystalline silicon film 105
is diffused into the amorphous Si.sub.x Ge.sub.1-x film 107 through
the oxide film 106 by heat treatment. (FIG. 1(C)).
The lower limit of the heating temperature of this heat treatment
is defined as a temperature at which nickel can be diffused. The
lower limit is 400.degree. C. or higher. The upper limit is defined
as a strain point of the glass substrate 101. The nickel element
contained in the crystalline silicon film 105 is diffused into the
amorphous Si.sub.x Ge.sub.1-x film 107 to lower nickel element
concentration in the crystalline silicon film 105.
The Si.sub.x Ge.sub.1-x film 107 is removed by etching. In order to
use the silicon oxide film 106 as an etching stopper, an etching
solution or etching gas having a high etching selectivity between
the Si.sub.x Ge.sub.1-x film 107 and the silicon oxide film 106 is
used. In this way, only the Si.sub.x Ge.sub.1-x film 107 which has
absorbed nickel can be selectively removed.
Next, the silicon oxide film 106 is removed by buffered
hydrofluoric acid or fluorine nitrate to obtain a crystalline
silicon film 108 with a low nickel element concentration, as shown
in FIG. 1(D).
As described above, in accordance with the present invention, by
the function of the metal element, the crystalline silicon film can
be fabricated at a low temperature such as about 550.degree. C. or
less which is lower than the prior art. Consequently, the
crystalline silicon film using a glass substrate can be
obtained.
Further, a crystalline silicon film having a low density of metal
element can be obtained by dispersing the metal element into the
amorphous silicon film from the crystalline silicon film
crystallized with the action of the metal element. Consequently, a
device free from the bad influence of the metal element, for
example, a thin film transistor can be obtained by using a
crystalline silicon film.
Further, the crystalline silicon film free from the deviation of
the metal element can be obtained by dispelling to a second silicon
film a portion where the metal element in the silicon film
crystallized by the action of the metal element is deviated. In
this manner, a device free from the bad influence of the metal
element can be obtained.
* * * * *