JPH09139502A - Semiconductor device and its manufacture - Google Patents

Abstract

PROBLEM TO BE SOLVED: To realize a semiconductor device of high performance by forming a crystalline silicon film of high qualty, on a plastic substrate of light weight and low cost. SOLUTION: An active region composed of a crystalline silicon film 103i is formed on a plastic substrate 101. The crystalline silicon film 103i is formed by the crystal growth of an amorphous silicon film whose hydrogen concentration is 5×10<20> atoms/cm<3> or lower by energy beam irradiation. The crystalline silicon film 103i is formed on the plastic substrate 101, interposing an insulating silicon compound film 102.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is suitable for use in, for example, an active matrix type liquid crystal display device, a contact type image sensor, a thin film integrated circuit, etc., and is particularly effective when a thin film transistor is used, and a method for manufacturing the same. More specifically, the present invention relates to a semiconductor device having a crystalline silicon film provided on a substrate made of a polymer material as an active region and a method for manufacturing the semiconductor device.

[0002]

2. Description of the Related Art In recent years, in order to achieve high resolution of the above-mentioned liquid crystal display device or high-speed resolution of the above-mentioned contact type image sensor or the like, an insulating film such as glass or an insulating film is used. Attempts have been made to form high performance semiconductor devices on top. On the other hand, in these fields, there are demands for weight reduction of products, improvement of productivity, flexibility for curved surface processing and cost reduction.

In order to meet the above requirements, polymer materials,
In particular, it is conceivable to employ a general-purpose plastic film such as polycarbonate or polyester film as the substrate. Unlike the glass substrate, the substrate made of these plastic films contains almost no impurities such as metals such as sodium and barium and arsenic in the material. Therefore, contamination or the like due to impurities does not occur, and a semiconductor device having stable characteristics can be realized. Furthermore, since the substrates made of these plastic films have resistance to hydrofluoric acid, they have great process advantages as compared with glass substrates.

Examples of semiconductor elements used in these semiconductor devices include thin film transistors (TFTs).
A thin film silicon semiconductor is generally used for the active region of the TFT. The thin film silicon semiconductor is roughly classified into two types, that is, an amorphous silicon (a-Si) semiconductor and a crystalline silicon semiconductor.

The former amorphous silicon semiconductor is most commonly used because it has a low production temperature, can be produced relatively easily by a vapor phase method, and has a high mass productivity. But,
The amorphous silicon semiconductor is inferior in physical properties such as conductivity to the latter silicon semiconductor having crystallinity. Therefore, in the future, in order to obtain higher speed characteristics, establishment of the latter method for manufacturing a semiconductor device made of a silicon semiconductor having crystallinity has been strongly demanded. As crystalline silicon semiconductors, polycrystalline silicon, microcrystalline silicon and the like are known.

As a conventional technique for forming a crystalline silicon film on a plastic substrate, Japanese Patent Laid-Open Nos. 5-315361, 5-315362, and 5-3 are known.
There is 26402 publication.

In Japanese Unexamined Patent Publication (Kokai) No. 5-315361, an a-Si film is formed on a plastic substrate, and an oxide insulating film such as a SiO ₂ film or a Ta ₂ O ₅ film is further formed on the a-Si film. Is irradiated to crystallization of the a-Si film. In Japanese Patent Laid-Open No. 5-315362,
The thermal conductivity (K) and the laser transmittance (T) for crystallization are K ≧ 0.03 (cal / cm · s) on the a-Si film.
.Degree. C.) and a film made of a ceramic insulating material satisfying the conditions of T.gtoreq.80% are formed, and then the a-Si film is crystallized by laser annealing. Also, Japanese Unexamined Patent Publication No.
In JP-A-326402, a thermal barrier layer made of ceramic or a porous material is provided on a plastic substrate, an a-Si film is formed thereon, and the a-Si film is irradiated with laser light to be crystallized. .

[0008]

As described above, the plastic substrate has a great merit, and since it can be molded into an arbitrary shape at a low temperature, the processing cost is low, the weight is light, and it is hard to break. It has various advantages. However, due to its low heat resistance, it has not been put to practical use at present. For example, general-purpose plastics do not have heat resistance of 200 ° C. or higher (operating temperature range). Therefore, further lowering of the semiconductor device manufacturing process is desired. Also, when plastic is heated, low molecular weight substances called oligomers are released. This oligomer opens pinholes in the film formed on the plastic, deteriorates the film quality, and adheres the film to the substrate. It reduces the power. The higher the heating temperature is, the larger the amount of released oligomers becomes. Therefore, in order to reduce the amount of oligomers, it is most effective to reduce the process temperature.

The above-mentioned JP-A-5-315361, JP-A-5-315362 and JP-A-5-3264.
All of the techniques disclosed in No. 02 are devised so as to prevent thermal damage to the plastic substrate under the a-Si film during laser irradiation when crystallizing the a-Si film. However, these techniques have some problems in terms of practical use.

In Japanese Patent Laid-Open No. 5-315361, an a-Si film is directly formed on a plastic substrate and laser annealing is performed. At that time, the insulating film is provided on the a-Si film, and the thickness of the a-Si film is set to 5 times or more of the absorption depth of laser light of 10 nm to 100 nm, thereby preventing thermal damage to the plastic substrate. However, according to an experiment conducted by the inventors of the present application, in the a-Si film having a thickness of 200 nm or less, the melting region reaches the lower portion almost at the same time as the surface is melted. Therefore, it is described in JP-A-5-315361. As described above, it was very difficult to melt and crystallize only the surface of the a-Si film. This is because the melting depth of the a-Si film is greatly related not only to the absorption depth of laser light, but also to the irradiation laser energy, the heat conduction of the a-Si film, and the latent heat generated during the solidification process. is there. In order to prevent the underlying plastic substrate from being damaged by this technique, aS
Although it is necessary to increase the thickness of the i film to at least 200 nm or more, the leakage current becomes a serious problem for a semiconductor device. Further, the insulating film provided on the upper layer actually only serves as an antireflection film for the laser light. Therefore, according to the experiments conducted by the inventors of the present application, it is possible to use this method without damaging the plastic substrate.
It is considered virtually impossible to crystallize the -Si film.

Japanese Unexamined Patent Publication No. 5-315362 is basically the same technique as Japanese Unexamined Patent Publication No. 5-315361 except that the material of the insulating film is different, and has the same problem. Therefore, even if this method is used, it is virtually impossible to crystallize the a-Si film without damaging the plastic substrate.

Compared to these techniques, Japanese Patent Laid-Open No. 5-326
The technique disclosed in Japanese Patent Publication No. 402 is provided with a thermal barrier layer on a plastic substrate and an a-S formed on the thermal barrier layer.
The i film is crystallized by laser annealing, and its effect is very large. As this thermal barrier layer, Al ₂
O ₃ -CrO ₃ system, MgO-NiO based, porous material such as a ceramic or SiO ₂ or the like _{(2MgO 2 · 2Al 2 O 3} · 5SiO 2) have been used. However, since many of these materials contain a metal element, the influence of contamination or the like on the semiconductor film cannot be ignored, and a semiconductor device having stable characteristics cannot be obtained. In addition, the merit of using a metal-free plastic substrate is reduced.

Further, the above-mentioned JP-A-5-315361, JP-A-5-315362 and JP-A-5-3.
A major problem common to all the techniques of Japanese Patent No. 26402 is the problem of the a-Si film itself. In these techniques, the a-Si film is formed by using ECR plasma C using silane (SiH ₄ ) gas or disilane (Si ₂ H ₆ ) gas as a material.
The VD method or the photo CVD method is used. According to these methods, the a-Si film can be formed at room temperature, which is certainly advantageous in terms of lowering the temperature. However, the a-Si film produced by these methods is S that is a material gas.
Since iH ₄ gas and Si ₂ H ₆ gas are decomposed and processed at a low temperature, hydrogen is contained in the film at a very high concentration of 1 × 10 ²¹ atoms / cm ³ or more. In the case of an a-Si TFT or the like which directly uses the a-Si film as an active region, a certain high concentration of hydrogen content is necessary to terminate the dangling bonds. However, when the a-Si film is crystallized and the crystalline silicon film is used as the active region, the following problems occur.

That is, when a large amount of hydrogen is present in the a-Si film, bumping of hydrogen occurs in the subsequent crystallization process, and film peeling of the a-Si film occurs in a pinhole shape.
FIG. 5 shows a typical example of a-Si film peeling by hydrogen bumping. In order to prevent this, in the crystalline silicon film formed on the glass substrate, after the a-Si film is formed by the plasma CVD method, a heat treatment is performed at a temperature of 400 ° C. to 500 ° C. for several hours to slowly dehydrate the film. The crystallization is performed and then the crystallization process is performed. However, since the bond energy of Si—H is about 400 ° C., dehydrogenation requires heat treatment at a minimum of 400 ° C., which cannot be performed when a plastic substrate is used. Therefore,
When a plastic substrate is used, if crystallization is attempted so as not to cause film peeling of the a-Si film, a-Si
The laser power necessary for crystallizing the film cannot be irradiated, and the crystallinity of the obtained crystalline silicon film becomes poor. Therefore, with the conventional technology, it has been impossible to realize a high-performance semiconductor element such as an active matrix for liquid crystal display or a thin film integrated circuit on a plastic substrate.

The present invention has been made to solve such problems of the prior art, and a high-quality crystalline silicon film can be formed without damaging a plastic substrate having low heat resistance. An object of the present invention is to provide a semiconductor device and a manufacturing method thereof.

[0016]

According to the present invention, there is provided a semiconductor device comprising:
A semiconductor device in which an active region made of a crystalline silicon film is formed on a substrate made of a polymer material, wherein the active region is formed by crystal growth of an amorphous silicon film by energy beam irradiation. Therefore, the hydrogen concentration in the amorphous silicon film is 5 × 10 ²⁰ atoms / cm ³ or less, which achieves the above object.

The semiconductor device of the present invention is a semiconductor device in which an active region made of a crystalline silicon film is formed on a substrate made of a polymer material, and the active region is made amorphous by irradiation with an energy beam. The silicon oxide film is formed by crystal growth, and the active region is formed on the substrate with an insulating silicon compound film having a thickness of 300 nm or more interposed therebetween, thereby achieving the above object. .

The insulating silicon compound film is preferably a silicon oxide film or a silicon nitride film.

According to the method of manufacturing a semiconductor device of the present invention, the hydrogen concentration in the film is 5 × 10 ²⁰ a on a substrate made of a polymer material.
a step of forming an amorphous silicon film having a dose of toms / cm ³ or less, a step of irradiating the amorphous silicon film with an energy beam to crystallize it to form a crystalline silicon film, and using the crystalline silicon film And forming an active region of the semiconductor device, whereby the above object is achieved.

The method of manufacturing a semiconductor device of the present invention comprises a step of forming an insulating silicon compound film having a thickness of 300 nm or more on a substrate made of a polymer material, and an amorphous silicon compound film on the insulating silicon compound film. A step of forming a silicon film, a step of irradiating the amorphous silicon film with an energy beam to crystallize it to form a crystalline silicon film, and a step of forming an active region of a semiconductor device using the crystalline silicon film The above object is achieved thereby.

The amorphous silicon film has a substrate heating temperature of 10
It is preferably formed by a low temperature sputtering method at 0 ° C. or lower or a vacuum evaporation method.

The insulating silicon film is an ECR plasma C
It is desirable to form by a VD method, a photo CVD method or a low temperature sputtering method at a substrate heating temperature of 100 ° C. or less.

The energy beam has a wavelength of 500.
It is desirable to use laser light of nm or less.

Hereinafter, the operation of the present invention will be described.

The inventors of the present invention, on a plastic substrate,
As a result of conducting daily experiments aiming to form a high-performance semiconductor device that constitutes an active matrix for liquid crystal display or a thin film integrated circuit, a high-quality crystalline silicon film was obtained without causing thermal damage to the plastic substrate. It was found that there are the following two major points in order to form them.

(1) The first point is to set the hydrogen concentration in the a-Si film to 5 × 10 ²⁰ atoms / cm ³ or less. The hydrogen concentration in the a-Si film was set to 5 × 10 ²⁰ at
By setting it to be oms / cm ³ or less, peeling of the a-Si film due to bumping of hydrogen, which has been a problem in the past, does not occur when the a-Si film is irradiated with a laser. Therefore, a-S
It becomes possible to apply a sufficient laser power for crystallization of the i film.

As a method for producing such an a-Si film having a low hydrogen concentration at a low temperature, a low temperature sputtering method at 100 ° C. or lower or a vacuum evaporation method is particularly effective. In these methods, the source material does not contain hydrogen, and the hydrogen concentration can be made extremely low even when the film is formed at a low temperature.

In the crystallization of the a-Si film, an energy beam can be used in general, but laser light is preferably used, and particularly laser light having a wavelength of 500 nm or less is desirable. In this wavelength range, since sufficient absorption occurs in silicon, only the silicon film can be annealed without damaging the substrate.

(2) The second point is that an insulating silicon compound film having a thickness of 300 nm or more is formed on a plastic substrate, and a crystalline silicon film is formed thereon. When the a-Si film is crystallized by laser irradiation,
The a-Si film is heated to its melting point of about 1200 ° C. or higher, but the insulating silicon compound film has a thickness of 300 n.
If it is at least m, the plastic substrate will not be thermally damaged even if it is irradiated with a laser having an energy of 250 mJ / cm ² or more, which is necessary for providing good crystallinity.

The insulating silicon compound film is preferably a silicon oxide film or a silicon nitride film. This is because these films do not contain a metal element that greatly affects the semiconductor.

As a method for forming such an insulating silicon compound film on a plastic substrate, ECR (Ele
ctron Cyclotron Resonance
e) It is desirable to use a low temperature CVD method such as a plasma CVD method, a photo CVD method using ultraviolet light, or a low temperature sputtering method at a substrate heating temperature of 100 ° C. or lower. This is because these methods allow film formation at a substrate temperature ranging from room temperature to 100 ° C.

[0032]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described below.

In the present invention, an amorphous silicon film having a hydrogen concentration in the film of 5 × 10 ²⁰ atoms / cm ³ or less is formed on a plastic substrate, and this is irradiated with an energy beam to be crystallized. , A crystalline silicon film.

According to the experiments conducted by the inventors of the present application, the film peeling of the a-Si film has a correlation between the hydrogen concentration in the film and the laser power for irradiation.

FIG. 1 shows the relationship between the hydrogen concentration in the a-Si film and the laser irradiation energy at the boundary value at which film peeling of the a-Si film occurs. In FIG. 1, the vertical axis is a-S
The i-film shows the hydrogen concentration, and the horizontal axis shows the irradiated laser energy. Region A is a region where film peeling has occurred, region B is a region where film peeling has not occurred, and curved lines are boundary lines of the respective regions. According to another experiment conducted by the inventors of the present application, laser irradiation with an energy of 250 mJ / cm ² or more is necessary in order to sufficiently crystallize the a-Si film to have good crystallinity. Is known.

From the above, by setting the hydrogen concentration in the film of the a-Si film to 5 × 10 ²⁰ atoms / cm ³ or less, it is possible to irradiate the laser with energy of 250 mJ / cm ² or more. is there. Therefore, film peeling due to bumping of hydrogen does not occur, and a crystalline silicon film having good crystallinity can be obtained.

As a method for forming such an a-Si film having a low hydrogen concentration at a low temperature, a low temperature sputtering method at 100 ° C. or lower or a vacuum evaporation method is desirable. These methods are PVD methods using a silicon material as a source, and unlike a general CVD method, the source material does not contain hydrogen. Therefore, even if the film is formed at a low temperature that does not damage the plastic substrate, the hydrogen concentration can be made extremely low.

Even when the a-Si film manufactured by these methods was irradiated with laser light, no film peeling due to bumping of hydrogen was observed. Especially, laser energy 400mJ /
At cm ² or more, no matter what a-Si film is used, the film itself is vaporized and film skipping occurs, but no film peeling due to hydrogen bumping was observed until reaching such a high energy range.

Further, in the present invention, an insulating silicon compound film having a thickness of 300 nm or more is formed on a plastic substrate, and the amorphous silicon film formed thereon is irradiated with an energy beam to be crystallized and crystallized. Silicon film.

When the a-Si film is crystallized by laser irradiation, the a-Si film is heated up to its melting point of about 1200 ° C. or higher. Therefore, it is important to prevent heat from flowing into the plastic substrate. It will be a point. With respect to this point, the inventors of the present application have conducted experiments to find that if the insulating silicon compound film has a thickness of 300 nm or more, even if a laser having an energy required to obtain good crystallinity is irradiated, It has been found that thermal damage can be prevented.

FIG. 2 shows the relationship between the film thickness of the insulating silicon compound film formed under the a-Si film and the substrate damage during laser crystallization. Polycarbonate is used as the substrate material, an insulating silicon compound film / a-Si film is deposited on it, and after actually irradiating laser light, the presence or absence of thermal damage is confirmed by examining the white turbidity and warpage of the substrate. did.
This experiment was conducted for each film using a silicon oxide film and a silicon nitride film as the insulating silicon compound film, and FIG. 2 shows data when the silicon oxide film was used. In FIG. 2, the vertical axis represents the thickness of the silicon oxide film,
The horizontal axis represents the laser energy applied to the a-Si film. Further, the region A is a region where no thermal damage is observed on the polycarbonate substrate, the region B is a region where the substrate is confirmed to be thermally damaged, and the curves are the boundary lines of each.
Further, as described above, in order to sufficiently crystallize the a-Si film to have good crystallinity, 250 mJ / cm ²
Laser irradiation with the above energy is required.

From the above, if the thickness of the silicon oxide film is 300 nm or more, the polycarbonate substrate will not be thermally damaged even if the laser is irradiated with energy of 250 mJ / cm ² . Therefore, a crystalline silicon film having good crystallinity can be obtained without causing thermal damage to the plastic substrate. However, in order to increase the laser power in order to further improve the crystallinity of the silicon film, it is necessary to increase the thickness of the insulating silicon compound film accordingly. Further, the same results were obtained for the silicon nitride film as for the silicon oxide film.

It is desirable to use a silicon oxide film or a silicon nitride film as the insulating silicon compound film. Since these films do not contain a metal element that greatly affects the semiconductor, contamination by them does not occur, and a semiconductor device having stable characteristics and excellent reliability can be manufactured. In particular, the silicon nitride film has a melting point of about 1900.
It is higher than the a-Si film at ℃, and the wettability when the a-Si film is melted and turned into a liquid is relatively good. Therefore, it is under the a-Si film crystallized by laser irradiation. It is very suitable as an insulating film to be formed.

As a method for forming such an insulating silicon compound film on a plastic substrate, low temperature CVD such as ECR plasma CVD method or photo CVD method using ultraviolet light is used.
It is desirable to use a low temperature sputtering method in which the substrate heating temperature is 100 ° C. or lower. By these methods, the substrate temperature can be formed in the range of room temperature to 100 ° C.
It is possible to obtain a high-quality insulating silicon compound film without damaging the plastic substrate.

The hydrogen concentration in the film is set to 5 × 10 ²⁰ atoms
When an a-Si film having a thickness of / cm ³ or less is formed on an insulating silicon compound film having a thickness of 300 nm or more and is irradiated with an energy beam, both effects described above can be realized at the same time.

In the present invention, the entire energy beam can be used for crystallization of the a-Si film.
It is desirable to use a laser beam, especially a wavelength of 500n
It is desirable to use laser light of m or less. In this wavelength range, since sufficient absorption occurs in silicon, only the silicon film can be annealed without damaging the substrate. The lasers used at present are pulse oscillation lasers such as XeCl excimer lasers having a wavelength of 308 nm, KrF excimer lasers having a wavelength of 248 nm, and A lasers having a wavelength of 488 nm which is a continuous oscillation laser.
r gas laser etc. are mentioned.

As the plastic substrate, in addition to the polycarbonate substrate, a substrate made of polyester, acrylic or the like can be used.

The semiconductor device of the present invention includes an active matrix type substrate for liquid crystal display, a contact image sensor, a thermal head having a built-in driver, an optical writing element having a built-in driver and a display element having an organic EL as a light emitting element. It can be applied to thin film integrated circuits in general. By applying the present invention, it becomes possible to fabricate these elements on a plastic substrate, and it is possible to reduce the weight, reduce the cost, improve the impact resistance, etc., and increase the speed,
Higher performance such as higher resolution can be realized. Furthermore, the present invention is not limited to MOS transistors, but can be widely applied to semiconductor processes and semiconductor devices in general, including bipolar transistors and static induction transistors using crystalline semiconductors as element materials.

A more specific embodiment of the present invention will be described below with reference to the drawings.

(Embodiment 1) In Embodiment 1, a case where the present invention is applied to an N-channel TFT on a polycarbonate substrate will be described.

This TFT can be used as a driver circuit of an active matrix type liquid crystal display device or a switching element of a pixel. Needless to say, the present invention can be applied not only to liquid crystal display devices but also to so-called thin film integrated circuits.

FIG. 3E shows a sectional view of the TFT of the first embodiment. This TFT is provided on the insulating substrate 101.
A silicon oxide film 102 having a thickness of 400 nm is provided as an insulating silicon compound film. On top of that, a crystalline silicon film 103i formed by crystallizing an a-Si film having a hydrogen concentration of about 2 × 10 ¹⁹ atoms / cm ³ by energy beam irradiation is formed in an island shape. The crystalline silicon film 103i, which is the active region of the TFT, is composed of the channel region 108 and the source / drain regions 109 and 110, and the gate electrode is formed thereon so as to face the channel region 108 with the gate insulating film 105 interposed therebetween. 106 are formed. The oxide layer 1 so as to cover the surface of the gate electrode 106.
07 is formed, and the interlayer insulating film 112 is further formed thereon. The electrodes / wirings 113 and 114 of the TFT are formed on the interlayer insulating film 112.
The source / drain regions 109 and 110 are electrically connected to each other in the contact hole portion formed in 2.

This TFT can be manufactured as follows in accordance with the manufacturing steps of FIGS. 3 (A) → (E).

First, as shown in FIG. 3A, the surface of the polycarbonate substrate 101 is washed with about 1% low-concentration hydrofluoric acid, and a silicon oxide film 102 having a thickness of 400 nm is formed by a sputtering method. The film forming conditions at this time are
Substrate temperature is room temperature, quartz target is the source,
The film formation was performed in an Ar / O ₂ mixed gas atmosphere.

Next, the a-Si film 10 having a thickness of 20 to 100 nm, for example, 30 nm is similarly formed by the sputtering method.
Form 3 The film forming conditions at this time were such that the substrate temperature was room temperature, the silicon target was used as a source, and the film was formed in an Ar gas atmosphere. The silicon oxide film 102 and the amorphous silicon film 103 were continuously formed in the same apparatus without breaking the vacuum. If the film thickness of the a-Si film 103 is thick, the heat capacity at the time of laser irradiation increases and the thermal damage to the substrate also increases. Therefore, a
The film thickness of the -Si film may be set to the minimum value within a range where the process margin and the TFT characteristics are good. The hydrogen concentration in the film of the a-Si film 103 produced by this method was measured by secondary ion mass spectrometry (SIMS), and was 2 × 1.
It was about 0 ¹⁹ atoms / cm ³ .

Subsequently, as shown in FIG. 3A, the laser beam 104 is irradiated from above the substrate to obtain aS.
The i film 103 is crystallized. The laser light 104 at this time is XeCl which is a laser with a wavelength of 500 nm or less.
Excimer laser (wavelength 308 nm, pulse width 40 ns
ec) was used. The irradiation condition of the laser light is that the substrate temperature is set to a room temperature state at the time of irradiation and the energy density is 250 to 350.
mJ / cm ^2, for example, 270mJ / cm ^2, and 20 shots per location. Thereby, the a-Si film 10
3 becomes a crystalline silicon film having good crystallinity in the process of being heated above its melting point, melting and solidifying.
At this time, the heat flow into the polycarbonate substrate 101 is a
Since the silicon oxide film 102 having a thickness of 400 nm formed under the -Si film 103 shuts out or is relaxed, no thermal damage was observed on the polycarbonate substrate 101.

After that, as shown in FIG. 3B, unnecessary portions of the crystalline silicon film are removed to perform element isolation, and the active regions of the TFT (channel region 108, source / drain regions 109 and 110) are later formed. An island-shaped crystalline silicon film 103i is formed.

Next, as shown in FIG. 3C, a thickness of 20 to 70 is formed so as to cover the crystalline silicon film 103i which will be the active region.
A silicon oxide film having a thickness of 150 nm, for example 100 nm, is formed as the gate insulating film 105. In this embodiment, the gate insulating film 105 is formed by the sputtering method. The film forming conditions at this time are that the substrate temperature is room temperature to 100 ° C., for example, 8
Arranged at 0 ° C. using silicon oxide as a target.
/ O ₂ gas = 0 to 0.5, for example, film formation was performed in an atmosphere of 0.1 or less.

Then, a thickness of 4 is obtained by the sputtering method.
A film of aluminum having a thickness of 00 to 800 nm, for example 600 nm, is formed and patterned to form the gate electrode 106.

Further, the surface of the gate electrode 106 is anodized to form an oxide layer 107 on the surface. Here, anodic oxidation is performed in an ethylene glycol solution containing tartaric acid in an amount of 1 to 5%, the voltage is initially raised to 220 V with a constant current, and the state is maintained for 1 hour to finish,
An oxide layer 107 having a thickness of 200 nm was formed. Since the thickness of the oxide layer 107 becomes the length of the offset gate region in the subsequent ion doping process, the length of the offset gate region can be determined in this anodic oxidation process.

Next, as shown in FIG. 3D, after removing the gate insulating film 105 other than the region covered by the gate electrode 106 and the oxide layer 107 around the gate electrode 106, the gate is formed by an ion doping method. Impurities (phosphorus) are implanted into the active region using the electrode 106 and the oxide layer 107 covering the surface thereof as a mask. Phosphine (PH ₃ ) is used as the doping gas, and the acceleration voltage is 2 to 15 kV, for example, 7
The kV and dose amount are set to 1 × 10 ¹⁵ to 8 × 10 ¹⁵ cm ⁻² , for example, 2 × 10 ¹⁵ cm ⁻² . As a result, the regions 109 and 110 into which the impurities are implanted will later become the source / drain regions of the TFT, and the gate electrode 106 and the oxide layer 10 will be formed.
The region 108 masked by 7 and not implanted with impurities is
It will later become the channel region of the TFT.

Subsequently, the laser beam 111 is irradiated to anneal to activate the ion-implanted impurities. As the laser beam 111 at this time, a XeCl excimer laser (wavelength 308 nm, pulse width 40 nsec) was used. The irradiation condition of the laser light is an energy density of 150.
~ 350 mJ / cm ² , preferably 200-250 mJ
Irradiation was performed for 4 shots at 1 spot / cm ² . N-type impurity (phosphorus) regions 109 and 1 thus formed
The sheet resistance of No. 10 was 200 to 800 Ω / □.

After that, as shown in FIG.
A silicon oxide film or a silicon nitride film having a thickness of about 00 nm is formed as the interlayer insulating film 112. In this embodiment, the optical CV
A silicon oxide film was formed by the D method. The film forming conditions were such that the substrate temperature was 75 ° C. and the chamber internal pressure was 1.00 Torr, and the SiH ₄ gas and the N ₂ O gas were decomposed by ultraviolet light to form a film. Further, when a silicon nitride film formed by similarly photodecomposing SiH ₄ gas and NH ₃ gas as source gases is used, hydrogen atoms are supplied to the interface of the active region / gate insulating film, and TFT characteristics Has the effect of reducing the dangling bonds that deteriorate the

Next, a contact hole is formed in the interlayer insulating film 112 to form a two-layer film of a metal material, for example, titanium nitride and aluminum, so that the electrodes of the TFT
The wirings 113 and 114 are formed. When the titanium nitride film is formed in this way, it can be used as a barrier film to prevent aluminum from diffusing into the semiconductor layer.

Finally, annealing is performed at a substrate temperature of 100 ° C. for about 30 minutes in a hydrogen plasma atmosphere, and then, as shown in FIG.
The TFT shown in is completed.

When the TFT of the first embodiment is used as a switching element for pixel electrodes, the electrodes 113 and 11 are used.
One of the four is ITO (Indium Tin Oxid)
e) and the like are connected to a pixel electrode made of a transparent conductive film, and a signal is input from the other electrode. When this TFT is used in a thin film integrated circuit, a contact hole may be formed also on the gate electrode 106 and necessary wiring may be provided.

The N-type TFT thus manufactured has a field effect mobility of 40 to 50 cm ² / Vs and a threshold voltage of 2 to 3.
It showed a good characteristic of V. Further, thermal damage did not occur on the polycarbonate substrate, and no film peeling of the crystalline silicon film was observed.

(Embodiment 2) In Embodiment 2, a case will be described in which the present invention is applied to a CMOS structure circuit in which an N-channel TFT and a P-channel TFT are formed in a complementary type on a polycarbonate substrate. This CMOS structure circuit can be used for a peripheral drive circuit of an active matrix type liquid crystal display device and a general thin film integrated circuit.

FIG. 4E shows a sectional view of the CMOS structure circuit of the second embodiment.

This CMOS structure circuit has an insulating substrate 20.
450 nm thick as an insulating silicon compound film on 1
A silicon nitride film 202 is provided. On top of that, the hydrogen concentration in the film is about 2 × 10 ¹⁹ atoms / cm ³
The crystalline silicon films 203n and 203p obtained by crystallizing the -Si film by energy beam irradiation are formed in an island shape. Crystalline silicon film 203 which is an active region of N-type TFT
n comprises a channel region 208n and source / drain regions 209n and 210n, on which a gate electrode 206n is formed so as to face the channel region 208n with a gate insulating film 205 interposed therebetween. P-type TF
The crystalline silicon film 203p which is the active region of T has a channel region 208p and source / drain regions 209p,
The gate electrode 206p is formed on the gate electrode 206p so as to face the channel region 208p with the gate insulating film 305 interposed therebetween. Interlayer insulation film 2 on it
12 is formed on the TFT electrode wiring 213,
214 and 215 are formed and electrically connected to the source / drain regions 209n, 210n, 209p, and 210p in the contact hole portion formed in the interlayer insulating film 212.

This CMOS structure circuit is shown in FIG.
It can be manufactured as follows according to the manufacturing process of (E).

First, as shown in FIG. 4A, the surface of the polycarbonate substrate 201 is washed with low concentration hydrofluoric acid of about 1%, and a silicon nitride film 202 having a thickness of 450 nm is formed by a sputtering method. The film forming conditions at this time are
Reactive sputtering was performed in a nitrogen gas atmosphere with the substrate temperature set to room temperature and a silicon target as a source. The silicon nitride film formed by this method has a better composition than that formed by a general low temperature CVD method, and Si ₃ N ₄ having an almost ideal ratio can be obtained. Further, the hydrogen concentration in the film becomes extremely low as compared with the low temperature CVD method.

Next, the a-Si film 20 having a thickness of 20 to 100 nm, for example, 50 nm is similarly formed by the sputtering method.
Form 3 The film forming conditions at this time were such that the substrate temperature was room temperature, the silicon target was used as a source, and the film was formed in an Ar gas atmosphere. Further, the silicon oxide film 202 and the amorphous silicon film 203 were continuously formed in the same apparatus.

Then, as shown in FIG. 4A, by irradiating the laser beam 204 from above the substrate, aS
The i film 203 is crystallized. The laser beam 204 at this time is, as in the first embodiment, a XeCl excimer laser (wavelength 308n, which is a laser having a wavelength of 500 nm or less.
m, pulse width 40 nsec) was used. The irradiation conditions of the laser light are such that the substrate temperature is set to a room temperature state at the time of irradiation and the energy density is 250 to 350 mJ / cm ² , for example, 300 mJ.
Irradiation was performed at 20 shots / cm ² per site. As a result, the a-Si film 203 becomes a crystalline silicon film having good crystallinity in the process of being heated to its melting point or higher, melting and solidifying. At this time, the heat inflow to the polycarbonate substrate 201 is shut out or mitigated by the silicon nitride film 202 having a thickness of 450 nm formed under the a-Si film 203, so that the polycarbonate substrate 201 is not thermally damaged. I couldn't see it.

After that, as shown in FIG. 4B, unnecessary portions of the crystalline silicon film are removed to perform element isolation, and the active regions (channel regions 208n and 208n) of the TFT are later formed.
p, source / drain regions 209n, 210n, 209
p, 210p), an island-shaped crystalline silicon film 203n,
203p is formed.

Next, as shown in FIG. 4C, a crystalline silicon film 203n which becomes an active region of the N-channel TFT is formed.
Then, a 100 nm-thick silicon oxide film is formed as the gate insulating film 205 so as to cover the crystalline silicon film 203p which becomes the active region of the P-channel TFT. In this embodiment, the silicon oxide film is formed by the photo CVD method. The film forming conditions are: substrate temperature 75 ° C., chamber internal pressure 1.00T
Under a reduced pressure of orr, SiH ₄ gas and N ₂ O gas were decomposed by an ultraviolet lamp to form a film.

Subsequently, an aluminum film (containing silicon of 0.1 to 2%) having a thickness of 400 to 800 nm, for example, 500 nm is formed at room temperature by a sputtering method, and this is patterned to form gate electrodes 206n and 206p. To form.

Next, as shown in FIG. 4D, the gate insulating film 20 is formed using the gate electrodes 206n and 206p as masks.
After removing 5, the impurities (phosphorus and boron) are implanted into the active regions 203n and 203p by an ion doping method. Phosphine (P
H ₃₎ and diborane (B ₂ H _6), in the former case 2~15kV the acceleration voltage, for example, and 7 kV, the acceleration voltage in the latter case is 2 to 10 kV, for example, 5 kV, the dose is 1 × 10 ^{15 ~8} × 10 ¹⁵ cm ^-2, for example, phosphorous 2
× 10 ¹⁵ cm ^-2 , and boron is 5 × 10 ¹⁵ cm ^-2 . As a result, the regions 208n and 208p masked by the gate electrodes 206n and 206p and into which impurities are not implanted will later become channel regions of the N-channel TFT and the P-channel TFT. In addition, at the time of doping, each element is selectively doped by covering a region where doping is unnecessary with a photoresist. As a result, N-type impurity regions 209n and 210n and P-type impurity regions 209p and 210p are formed, and an N-channel type TFT (NTFT) and a P-channel type TFT (PT) are formed.
FT) can be formed.

Subsequently, the laser beam 211 is irradiated to anneal to activate the ion-implanted impurities. As the laser beam 111 at this time, a XeCl excimer laser (wavelength 308 nm, pulse width 40 nsec) was used. The laser beam irradiation conditions are energy density 280
Irradiation with 4 shots per spot was performed at mJ / cm ² .

After that, as shown in FIG.
A silicon oxide film having a thickness of about 00 nm is formed as the interlayer insulating film 212. In the present embodiment, SiH ₄ is formed by the photo CVD method.
A gas and N ₂ O gas were decomposed to form a silicon oxide film.

Next, contact holes are formed in the interlayer insulating film 212 and a two-layer film of a metal material such as titanium nitride and aluminum is formed to form electrodes / wirings 213, 214, 215 of the TFT.

Finally, in a hydrogen plasma atmosphere, 100
After annealing at ℃ for 30 minutes, TF shown in Fig. 4 (E)
Complete T.

In the CMOS structure circuit thus manufactured, the field effect mobility is 5 for the N-channel TFT.
0-70 cm ² / Vs, P-channel TFT 30-
High as 40 cm ² / Vs and threshold voltage of N-channel type T
2-3V for FT, -5 to -6V for P-channel TFT
And good characteristics. Further, thermal damage did not occur on the polycarbonate substrate, and no film peeling of the crystalline silicon film was observed.

(Third Embodiment) In the third embodiment, a silicon oxide film is used as the insulating silicon compound film 102 by photo CVD.
The case where the a-Si film 103 is formed by the vacuum evaporation method and the a-Si film 103 is formed by the vacuum evaporation method will be described.

First, the surface of the polycarbonate substrate 101 is washed with low-concentration hydrofluoric acid of about 1%, and a silicon oxide film 102 having a thickness of 400 nm, for example, is formed by the photo-CVD method. The equipment used in this process is US; TYSTA
This is a photo-CVD apparatus using a strong UV lamp called PVD1000 manufactured by R, and a high-quality silicon oxide film excellent in pressure resistance can be obtained at a substrate temperature of 75 ° C. SiH ₄ gas and N ₂ O gas were used as the source gas, and the reaction was performed under a reduced pressure of 1.00 Torr in the chamber. The film forming rate at this time is 120 angstrom / min. Met.

Next, a thickness of 20 to 10 is formed by a vacuum evaporation method.
The 0-nm, for example, 30-nm a-Si film 103 is formed. The substrate temperature was room temperature, and high-purity silicon tablets were used as a vapor deposition source to perform vacuum vapor deposition by a resistance heating method. In the present embodiment, the resistance heating method is used for the convenience of the apparatus, but it is actually preferable to use the EB (electron beam) evaporation method in terms of efficiency. By this method, the hydrogen concentration in the film of the a-Si film 103 produced by this method was measured by secondary ion mass spectrometry (SIMS).
It was about 5 × 10 ¹⁹ atoms / cm ³ .

Subsequently, as shown in FIG. 3 (A), by irradiating the laser beam 104 from above the substrate, a-S
The i film 103 is crystallized. The laser light 104 at this time is XeCl which is a laser with a wavelength of 500 nm or less.
Excimer laser (wavelength 308 nm, pulse width 40 ns
ec) was used. The irradiation condition of the laser light is that the substrate temperature is set to a room temperature state at the time of irradiation and the energy density is 250 to 350.
mJ / cm ^2, for example, 270mJ / cm ^2, and 20 shots per location. Thereby, the a-Si film 10
3 becomes a crystalline silicon film having good crystallinity in the process of being heated above its melting point, melting and solidifying.
At this time, the heat flow into the polycarbonate substrate 101 is a
Since the silicon oxide film 102 having a thickness of 400 nm formed under the -Si film 103 shuts out or is relaxed, no thermal damage was observed on the polycarbonate substrate 101.

After that, the TFT is completed in the same manner as in the first embodiment. The N-type TFT manufactured in this manner has almost the same performance as that of the first embodiment.

[0089]

As is apparent from the above description, according to the present invention, it is possible to prevent the plastic substrate from being thermally damaged when the a-Si film is crystallized, and
-Peeling off of the Si film can be prevented. Therefore, a good crystalline silicon film can be formed on a plastic substrate, and a high-performance semiconductor device can be manufactured using a plastic substrate which is inexpensive, lightweight, and excellent in impact resistance. . As a result, it is possible to provide a lightweight, high-performance liquid crystal display device, an image sensor, and the like at a low price.

In particular, when the present invention is applied to a liquid crystal display device, the switching characteristics required for the pixel switching TFTs of the active matrix substrate are improved and the high performance required for the TFTs forming the peripheral drive circuit section. Higher integration and higher integration can be satisfied. Therefore, it is possible to realize a driver monolithic active matrix substrate in which the active matrix portion and the peripheral drive circuit portion are formed on the same substrate, and the module can be made compact, high performance and low cost.

[Brief description of the drawings]

FIG. 1 is a graph showing a relationship between a hydrogen concentration in an a-Si film and a laser irradiation energy at a boundary value at which film peeling of the a-Si film occurs.

FIG. 2 is a graph showing the relationship between the film thickness of an insulating silicon compound film formed under an a-Si film and substrate damage during laser crystallization.

3A to 3E are cross-sectional views showing a manufacturing process of the TFT of the first embodiment.

4A to 4E are cross-sectional views showing the manufacturing process of the CMOS structure circuit of the second embodiment.

FIG. 5 is a schematic view showing a typical example of a-Si film peeling by hydrogen bumping.

[Explanation of symbols]

101, 201 plastic substrate 102, 202 insulating silicon compound film 103, 203 a-Si film 103i, 203n, 203p crystalline silicon film 104, 204, 111, 211 laser light 105, 205 gate insulating film 106, 206n, 206p gate Electrode 107 Anodized layer 108, 208n, 208p Channel region 109, 110, 209n, 209p, 210n, 21
0p source / drain region 112,212 interlayer insulating film 113, 114, 213, 214, 215 electrode / wiring

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical display location H01L 29/78 627G

Claims (8)

[Claims] 1. A semiconductor device in which an active region made of a crystalline silicon film is formed on a substrate made of a polymer material, the active region being formed by crystallizing an amorphous silicon film by energy beam irradiation. A semiconductor device, which is grown and has a hydrogen concentration of 5 × 10 ²⁰ atoms / cm ³ or less in the amorphous silicon film. 2. A semiconductor device in which an active region made of a crystalline silicon film is formed on a substrate made of a polymer material, the active region being formed by crystallizing an amorphous silicon film by energy beam irradiation. A semiconductor device which is formed by growing the active region and is formed on the substrate with an insulating silicon compound film having a thickness of 300 nm or more interposed therebetween. 3. The semiconductor device according to claim 2, wherein the insulating silicon compound film is a silicon oxide film or a silicon nitride film. 4. A step of forming an amorphous silicon film having a hydrogen concentration in the film of 5 × 10 ²⁰ atoms / cm ³ or less on a substrate made of a polymer material, and an energy beam applied to the amorphous silicon film. A method of manufacturing a semiconductor device, comprising: a step of irradiating and crystallizing to obtain a crystalline silicon film; and a step of forming an active region of the semiconductor device by using the crystalline silicon film. 5. A substrate having a thickness of 30 on a substrate made of a polymer material.
A step of forming an insulating silicon compound film having a thickness of 0 nm or more, a step of forming an amorphous silicon film on the insulating silicon compound film, and irradiating the amorphous silicon film with an energy beam to crystallize, A method of manufacturing a semiconductor device, comprising: a step of forming a crystalline silicon film; and a step of forming an active region of a semiconductor device using the crystalline silicon film. 6. The amorphous silicon film has a substrate heating temperature of 1.
The semiconductor device according to claim 4, which is formed by a low temperature sputtering method at a temperature of 00 ° C. or lower or a vacuum evaporation method. 7. The semiconductor device according to claim 5, wherein the insulating silicon film is formed by an ECR plasma CVD method, a photo CVD method, or a low temperature sputtering method at a substrate heating temperature of 100 ° C. or lower. 8. The wavelength of the energy beam is 50.
The method for manufacturing a semiconductor device according to claim 4, wherein laser light having a wavelength of 0 nm or less is used.