KR100300808B1 - Crystalline Semiconductor Manufacturing Method - Google Patents

Abstract

The method for producing a crystalline silicon film having excellent crystalline properties is characterized by the addition of a catalytic metal for accelerating the crystallization of the amorphous silicon film. Since the catalytic element is adsorbed on the surface of the amorphous silicon film by using steam or gas, the crystal element can be crystallized at low temperature for a short time by using the catalytic element at the time of heat crystallization. In particular, by controlling the partial pressure, a crystalline silicon film excellent in uniformity can be obtained when the adsorption state becomes monomolecular layer adsorption having a coverage of 1.

Description

Crystalline Semiconductor Manufacturing Method

[Background of invention]

The present invention relates to a method for producing a crystalline silicon semiconductor film such as a polycrystalline silicon film, a single crystal silicon film, and a microcrystalline silicon film. Crystalline silicon films produced using the present invention are used in various semiconductor devices.

Thin film transistors (hereinafter referred to as TFTs) using thin film semiconductors are known, which are formed using thin film semiconductors, especially silicon semiconductor films formed on substrates. TFTs are used in various types of integrated circuits. In particular, they have attracted attention as switching elements provided for each pixel of the active matrix liquid crystal display, or as driving elements formed on the peripheral circuit portion.

As the silicon film used for the TFT, it is easy to use an amorphous silicon film. However, there is a problem that its electrical characteristics are much inferior to that of the single crystal semiconductor used for semiconductor integrated circuits. Therefore, its use has been limited only to switching elements such as active matrix circuits. The characteristics of the TFT can be improved by using a crystalline silicon thin film. Crystalline silicon other than monocrystalline silicon is called polycrystalline silicon, polysilicon, microcrystalline silicon, and the like. Such a crystalline silicon film can be crystallized and obtained by first forming an amorphous silicon film and then heating (heat annealing). This method is called a solid phase growth method because the amorphous state changes to a crystalline state while maintaining a solid state.

However, the solid phase growth of silicon requires a heating temperature of about 600 ° C. and a time of about 10 minutes. Therefore, there exists a problem that it is difficult to use a cheap glass substrate as a board | substrate. For example, Corning 7059 glass used for active liquid crystal devices has a glass strain point of 593 ° C., resulting in difficulty when considering the expansion of the substrate area in performing thermal annealing at around 600 ° C. FIG.

According to the inventor (s) study to solve this problem, when a small amount of an element such as nickel or palladium, or lead is deposited on the surface of the amorphous film and then the film is heated, the crystallization is at 550 ° C. and about 4 hours. It can be realized that the processing time of can be realized.

A small amount of element (catalyst element for accelerating crystallization) can be introduced by depositing a catalytic element or a coating film of the compound by sputtering. However, if the element is present in a semiconductor in large quantities, the reliability and electrical safety of the device using such a semiconductor is impaired, which is not preferable. If the film is formed by sputtering, it is difficult to precisely control the amount, that is, the thickness. It is also more difficult to obtain a film with a uniform thickness on the substrate. Therefore, the characteristics of the semiconductor devices thus obtained are not uniform.

Moreover, when the film is formed by sputtering, the amorphous silicon film is significantly damaged by the impact of sputtering, so the characteristics of the semiconductor devices obtained as described above are naturally unsatisfactory.

Instead of sputtering, there is also a method of forming a coating film by means such as spin coating. However, the spin coating method has a difficulty in obtaining a uniform coating film. For example, in a rectangular board | substrate like a liquid crystal display, a solution collects easily at the edge, and film thickness is not uniform. Moreover, when the solvent is dried to produce a coating film of the catalytic element compound, due to uneven drying or generation of crystal nuclei, the film thickness becomes uneven, resulting in uneven characteristics of the semiconductor devices.

In manufacturing a crystalline thin film silicon semiconductor by heat treatment at a lower temperature than in the case of a conventional solid phase growth method using a catalytic element, the object of the present invention is to (1) control the trace of the catalytic element And (2) satisfy the requirements for allowing the introduction of the catalytic element uniformly. Moreover, the objective of this invention is to improve productivity when (3) a catalytic element is introduce | transduced.

In order to achieve the above objects, according to the present invention, vapor or gas having a catalytic element is adsorbed directly or indirectly on the surface of the amorphous silicon film, and low temperature crystallization is performed using the adsorbed catalytic element.

The above configuration of the present invention has the following basic features.

(a) The concentration of the catalytic element in the amorphous silicon film is determined by the amount of catalytic element adsorbed on the surface. The amount of adsorbed catalytic element on the surface is set based on the ratio between the adsorption rate of the catalytic element to the surface and the separation rate from the surface. If the substrate temperature and the total pressure are constant, the amount can be determined solely (by partial pressure in the present invention) by the chemical potential of the vapor or gas containing the catalytic element in the vapor state.

(b) During the adsorption step onto the surface, an extremely uniform coating film is formed on the surface. By controlling the partial pressure of the vapor or gas containing the catalytic element, three types of adsorption layers, that is, a complete monomolecular adsorption layer (coating ratio = 1), a monomolecular adsorption layer having a coverage of less than 1, and a plurality of molecules It is possible to form a multilayer adsorbent layer consisting of layers. In particular, in the region of the complete monomolecular adsorbent layer, a wide flat region is obtained in relation to the time change and the small partial pressure change, so that the control characteristics are very high.

(c) Since only the adsorption phenomenon is used, a film containing a catalytic element can be formed at a significantly lower energy, and the amorphous silicon film is not damaged at all compared with other sputtering or evaporation methods.

1a to 1e show the adsorption steps of the monoatomic layer according to the present invention.

2 shows the apparatus used in the adsorption steps of monolayers.

3 shows the apparatus used in the adsorption steps of monolayers.

4a to 4c show the adsorption steps of the monoatomic layer according to the present invention.

5a to 5e show the steps of the crystal growth method according to the invention.

6a to 6e show the steps of the crystal growth method according to the invention.

7A to 7F show steps in the case of applying the present invention to TFT fabrication steps.

8A to 8F show steps in the case of applying the present invention to TFT fabrication steps.

9 shows a model of the adsorption process of the invention.

10 shows an apparatus used for the adsorption steps of a monolayer according to the invention.

<Description of the symbols for the main parts of the drawings>

11: substrate 12, 302, 402: silicon oxide film

13, 23, 53, 303, 403: amorphous silicon film 21, 51, 401: glass substrate

22: silicon oxide film 54: organic metal

101, 201, 600: chamber 202: light source

204 Heater 308 Gate electrode

601, 604: evaporator

In the present invention, many compounds can be used to add catalytic elements, which is one feature of the present invention. For example, when a group of water soluble salts are selected, they are dissolved in pure water and then bubbled by a carrier gas such as argon and thus transported into the chamber. The vapor pressure can be controlled by the temperature of the solvent and the flow rate of the carrier gas. Similar methods can also be used for compounds that are soluble in organic solvents.

When using some of the volatile salts and a group of organometals, they have a low melting point and themselves have some vapor pressure, so the amount (partial pressure) of catalytic elements introduced into the chamber is controlled by controlling the heating temperature of the compounds. Can be. As an example of such an organic metal material, when nickel is used as the catalytic element, biscyclofetadianinickel, that is, Ni (C ₅ H ₂ ) ₂ (hereinafter referred to as BCP nickel or BCP salt), bismethylcyclopentadienyl Nickel, ie Ni (CH ₃ C ₅ H ₄ ) ₂ (hereinafter referred to as BMCP nickel or BMCP salts), bis- (2, 2, 6, 6-tetramethyl-3, 5-haptanediono-nickel, ie Ni (C ₁₁ H ₁₉ O ₂ ) ₂ ) may be used.

The melting point of BCP nickel is 173 to 174 ° C and the vapor pressures at 90 ° C and 130 ° C are 0.4 Torr and 0.6 Torr, respectively. BMCP nickel has a melting point of 34 ° C. and vapor pressures of 90 ° C. and 130 ° C. are 1.6 Torr and 15 Torr, respectively.

The coating film obtained by adsorption of these organic metals may be deposited directly on the amorphous silicon film in the region where the catalytic element is to be introduced. However, the surface of the amorphous silicon film is very active and easily oxidized. Therefore, there is a problem that the surface state or the adsorption state tends to be uneven. In this case, on the contrary, a thin oxide film of about 100 GPa is first formed on the surface of the amorphous silicon film, and then a coating film is deposited on the oxide film. This method is not limited to only organic metals. When the catalytic element is introduced by the bubbles of the dissolving agent, this method is also effective in obtaining a uniform coating film having a small contact angle on the surface.

By selectively depositing a coating film of a catalytic element or a compound thereof, crystal growth may be selectively performed. For example, a mask film is selectively formed, and only in certain portions, to actually expose the surface of the amorphous silicon film. The thickness required for the mask film depends on the material of the mask film. In the case of silicon oxide, a thickness of about 500 GPa is sufficient. In some cases, it may be thinner. The quality of the membrane is more important than the thickness of the membrane. Since the step coverage in the catalyst addition method using the adsorption phenomenon of the present invention is at the level of monomolecules, care must be taken so that the catalyst does not easily reach inside due to the presence of pinholes and the like. Therefore, attention is required to quality. Next, according to the present invention, by depositing a coating film containing the catalytic element, the catalytic element is introduced into specific portions of the amorphous silicon film.

In this case, crystal growth can proceed from the region where the coating film is deposited to a direction parallel to the surface of the silicon film and toward the region where the coating film of the catalytic element or the compound is not introduced. The region in which crystal growth is performed in a direction parallel to the surface of the silicon film will be referred to herein as a transverse crystal growth region.

In this transverse crystal growth region, it was confirmed that the concentration of the catalytic element is low. It is effective to use a crystalline silicon film as an active layer region of a semiconductor device. However, in general, it is more preferable that the concentration of the catalytic element in the active layer region is low. Therefore, in forming the device, it is useful to form the active layer region of the semiconductor device using the lateral crystal growth region. However, the conventional method of adding the catalytic element has the drawback that the photolithography step must be performed prior to the selective deposition of the coating film containing the catalytic element, which makes the process complicated. However, when organometallic compounds containing catalytic elements are used, these materials are easily decomposed by ultraviolet light. Therefore, the ultraviolet light is irradiated only to the portion that will remain intact after the formation of the monomolecular adsorbent layer, thereby decomposing such a material, and the undecomposed organometallic compound is then purified by the organic solvent, making it easy to make a similar structure. It becomes possible.

However, using any of the above methods, since the thermal crystallization step is performed before the next photolithography step (generally forming protrusions), problems such as shrinkage of the substrate can easily occur. Therefore, this problem should be taken into account in selecting transverse crystal growth.

The present invention is generally realized by the following steps.

(1) The substrate is placed in a chamber, and the temperature of the substrate is controlled to a predetermined value.

(2) A vapor or gas containing a catalytic element for accelerating the crystallization of the amorphous silicon film is introduced into the chamber and allowed to adsorb on the surface of the amorphous silicon film.

(3) If necessary, the catalytic element adsorbed on the surface of the amorphous silicon film is decomposed by heat or light so that a coating film of the catalyst element or the compound thereof is formed on the substrate surface.

(4) The amorphous silicon film is heat treated to thereby crystallize.

Among these steps, step (2) will be described with reference to FIG. The figure shows an example in which a silicon oxide film is formed on a glass substrate, an amorphous silicon film is formed on it, and a sample in which the surface of the amorphous silicon film is oxidized by about 10 mV by UV / ozone to improve the contact angle. The model of FIG. 9 is taken from the relationship between partial pressure and catalyst metal concentration after SPC. The unit ML of the vertical axis is a single layer, that is, a unit is a monolayer. The raw material is placed in a chamber of normal pressure or reduced pressure, and then a vapor or gas containing a catalytic metal is supplied. When the partial pressure of vapor or gas is low, these molecules are partially adsorbed on the surface of the sample to obtain state (A). This corresponds to a monomolecular adsorbent layer having a coverage of less than one. As shown in Fig. 9, this state is sensitive to the change in the partial pressure of steam or gas. Therefore, this state is difficult to reliably control.

In addition, when the partial pressure is increased, region (B) is obtained, in which the compound comprising the catalytic metal is uniformly adsorbed on the front surface of the sample. This region corresponds to a complete monomolecular adsorbent layer (coating ratio = 1), which is generally called an ALE window. Of course, adsorption in all cases is not as shown in FIG. In this case, the above adsorption easily occurs by oxidizing the surface of the sample by about 10 mW with UV / ozone to improve the contact angle. That is, compared to the case where the next molecules are adsorbed on the once adsorbed molecules, it is more advantageous in terms of energy that the molecules are adsorbed on the oxide film formed by UV / ozone. Thus, region B can be obtained over a relatively wide region. In addition, in order to increase the adsorption of such a monolayer, the movement on the surface of the molecule is inevitable. Therefore, a certain temperature is required.

However, only by the partial pressure control and the temperature control described above, there are cases where the ALE window hardly exists. In this case, it is necessary to consider creating a state in which only the monoatomic layer can be adsorbed by greatly increasing the flow rate of the raw material gas. The monomolecular adsorbed layer thus obtained is basically a constant saturated region, and thus is insensitive to changes in partial pressure, film growth (adsorption) time, and the like. Thus, there is an advantage that can take a large margin.

If the partial pressure is further increased, the saturation characteristic is broken, and then the molecules begin to adsorb to the molecules that have already been adsorbed (state C). In the model of FIG. 9, when the partial pressure is further increased, the figure appears to have a flat area D with a coverage of 2 again. However, this figure is absolutely based on the model, and in the second layer and the subsequent layers, it appears that a fine flat region as shown in FIG. 9 cannot be obtained. This is because the energy difference between the case of uniform adsorption and the case of adsorption with vertical piling is small. Thus, the process margin is still large when region B is used instead of region D. FIG. If it is necessary to deposit thicker (i.e., the amount of addition of the catalytic element is to be increased), it is preferable to repeat the formation of the region (B) several times through the decomposition step of the adsorbed compound such as the heating step. Step (3) may also be used for this purpose.

The atmosphere in the adsorption and decomposition step may be reduced pressure or atmospheric pressure. In the case of reduced pressure, an apparatus having a structure such as LPCVD may be used. In the case of atmospheric pressure, an apparatus such as in APCVD (atmospheric pressure CVD) may be used. However, they are determined by temperature and raw materials. It may be appropriate if an area is used where the adsorption and re-separation are nearly balanced resulting in a wide ALE window. However, using a pressure reducing device is not preferable in terms of yield and cost. It is desirable to select raw materials and temperatures so that a wide ALE window can be taken in the region close to atmospheric pressure.

It is also useful to react the catalytic element deposited during or after step (3) with amorphous silicon at the interface to form a reaction product. If the product has been previously formed, it may be easier to carry out the crystallization in the next thermal crystallization step. Although the reason is not clear, it is believed that these products act as crystallization nuclei.

With regard to step (4), after taking the substrate out of the chamber, heat treatment can be performed in another annealing apparatus. However, it may be performed continuously in the same chamber.

After step (4), irradiation of strong light, such as laser light, can crystallize the parts that have not been completely crystallized by solid phase growth. Thus, crystalline silicon with better properties can be obtained. As for the laser used, various kinds of excimer lasers are easily used.

In the present invention, the most significant effect can be obtained when nickel is used as the catalytic element. As a kind of other catalytic elements that can be used, Pd, Pt, Cu, Ag, Au, In, Sn, P, As, Sb may be preferably used. In addition, one or a plurality of kinds of elements selected from the group VIII, the elements IIIb, IVb, and the Vb may be used.

Example 1

In this embodiment, a crystalline silicon film is formed on the entire surface of the glass substrate. Referring to Fig. 1, the steps from introduction of the catalytic element (nickel is used in this example) to crystallization are described. In this example, Corning 7059 glass was used as the substrate. Its size is 100mmX100mm.

First, the silicon oxide film 12 was formed on the substrate 11 by the sputtering method or the plasma CVD method. The thickness of the silicon oxide film 12 was 1000-5000 kPa, for example 2000 kPa.

Next, an amorphous silicon film 13 having a thickness of 100 to 1500 mW was formed by the plasma CVD method or the LPCVD method. Here, an amorphous silicon film 13 having a thickness of 500 kHz was formed by the plasma CVD method (Fig. 1A).

Hydrofluoric acid treatment was then performed to remove contaminants and native oxide films, and the substrate was placed in a chamber 201 as shown in FIG. Here, the chamber 201 will be briefly described. The chamber 201 is connected to a tube for introduction of gas from the outside and a tube for exhaust. The former has two lines. The first line is a line for introducing organic nickel gas / vapor, and the second line is a line for carrier gas. In the first line, the organic nickel gas / vapor generated from the evaporator (eg BMCP nickel) is carried by a suitable gas (eg hydrogen). At this time, in order to prevent the organic nickel from solidifying in the pipe, the pipe should be maintained at a suitable temperature, preferably at a temperature above the evaporator temperature.

From the first gas line, organic nickel gas / vapor can be obtained. It is difficult to control the concentration in the required amount. That is, the vapor pressure is determined by the temperature of the evaporator, and the concentration is significantly changed by a slight temperature difference. Then, from the second gas line, a carrier gas (eg argon) is introduced to dilute the organic nickel gas / vapor. This dilution is also used to control the flow rate.

In this way, organic nickel gas or vapor is introduced into the chamber 201. A substrate temperature control mechanism 204 controlled by a Peltier element is disposed in the chamber, and the substrate is placed thereon. The substrate is heated to the temperature at which the ALE window is the largest depending on the material. In this embodiment, the substrate need not be heated, but the substrate temperature was controlled to be 25 ° C. in order to control the amount of adsorption.

Of course, it is desirable to maintain the entire chamber at a temperature at which organic nickel does not solidify.

A method of depositing a nickel film using the chamber of this structure will be described. First, the substrate is placed and the interior of the chamber is evacuated to a suitable pressure. Since this step does not require very high vacuum, exhaust of 1 to 500 mTorr is sufficient. Next, in order to control a board | substrate to 25 degreeC, an electric current is sent to the board | substrate temperature control mechanism 204.

In this state, the valve V12 is opened, and argon flows so that the inside of the chamber becomes a predetermined pressure. The flow rate of argon was 1 SLM and the reaction pressure was 1 × 10 5 Pa in this example. Next, after confirming that the stable state is established at a predetermined pressure and temperature, an organic metal containing a catalytic metal element is introduced. In this example, BMCP nickel was used and the flow rate was 100 sccm. The valve V11 is opened at the same time as the inflow of the argon carrier gas, so that the organometallic gas collides on the surface and is adsorbed on the surface of the amorphous silicon film. Under the conditions of this example, the partial pressure of BMCP nickel was about 3 × 10 ³ Pa, so that monomolecular adsorption could be obtained (FIG. 1B).

Simultaneously with the collision of the organic metal gas, light irradiation from the light source 202 is performed on the surface of the amorphous silicon film on which the organic metal molecules containing the catalytic metal element are adsorbed (FIG. 1C). The light source may be a laser or other light source such as a xenon lamp, a halogen lamp, or a low and high pressure mercury lamp. This only encourages the decomposition of the organic metal on the surface of the amorphous silicon film, so that the light intensity does not necessarily have to be high. The importance of this light irradiation is demonstrated.

When the organic nickel metal gas is adsorbed on the amorphous silicon film surface, the chamber is in equilibrium, where the substrate temperature is 25 ° C. Then upon thermal crystallization, the equilibrium is broken and almost all of the organic nickel metal gas is re-separated and leaks into the gaseous state. This is a problem caused because the BMCP nickel used in this example is a material having low melting point and high vapor pressure. The problem does not occur if a soluble salt is used and is transported and adsorbed by the foam. Thus, this embodiment requires a step of performing light irradiation (especially ultraviolet irradiation) immediately after adsorption to decompose the adsorbed molecules so that they turn into compounds having low volatilization properties. Note that if the vapor or gas containing the catalytic metal continues to flow after light irradiation, the adsorption step of the second layer proceeds, so it is necessary to stop the gas flow at the same time as the light irradiation.

In this embodiment, a xenon lamp was used as the light source, which lamp was made in synchronism with the stop of the gas collision using the shutter 203. At this time, almost every single layer of Ni could be adsorbed in every sequence of gas collision and light irradiation. In this way, a nickel compound film 14 is formed on the surface of the substrate (FIG. 1D).

Thereafter, the solid phase growth phase proceeds. Solid state growth may be performed in the same chamber in which the nickel compound film 14 was deposited. However, in general, the yield is considerably low (due to the sheet feeding type), and it is suitable to be taken out and performed in a diffusion furnace or the like. In this embodiment, another vertical furnace is used. The gas in the chamber is completely replaced by a gas that is harmless to the human body. The chamber is then opened to the atmosphere where the substrate is taken out. The subsequent solid growth stage is similar to the conventional case.

In solid phase growth, the substrate is arranged to heat to 500-650 ° C. For example, when a Corning 7059 substrate is used, it is heated to 500 ° C. In the state where the substrate is kept as it is, solid phase growth proceeds. When a Corning 1737 substrate is used as the substrate, it is possible to raise the temperature further to allow crystallization at about 600 ° C. In this way, even when the temperature is raised, compared with the conventional case in which the catalyst metal is added, since crystal growth is performed in a very short time, about 24 hours in the conventional method is reduced to about 2 hours, which is a satisfactory advantage. This can be obtained. In this way, the crystallized silicon film 15 could be obtained. As described above, even if the heat treatment can be performed at a temperature of about 450 ° C., if the temperature is low, a long heating time is required, which lowers the productivity. In addition, when heated to about 650 ° C., a problem of heat resistance of the glass substrate used as the substrate appears. Therefore, the thermal annealing temperature should be determined in consideration of the productivity of the substrate and the thermal resistance (FIG. 1E).

As in this example, when monomolecular layer adsorption with a coverage of about 1 was used, it was found that the particle size in the obtained crystalline silicon film was uniform. A secco etch was performed and the particle size was measured in the particle size evaluation mode of AFM (made by Seiko Instruments SPI-3000). The average particle size was about 0.5 μm and the standard deviation (sigma) was about 0.1 μm. On the other hand, when evaluating the film | membrane using the area | region A with a coverage less than 1, the average particle size was about 0.6 micrometers and the standard deviation (sigma) was about 0.5 micrometers. In other words, it was quite uneven. Further, in the region C of the monolayer adsorbed region, the average particle size was about 0.3 μm and the standard deviation (sigma) was about 0.3 μm. That is still uneven. Therefore, it became clear that the adsorption of the monomolecular layer of coverage 1 is important. In general, as a weak point of a TFT using a polycrystalline silicon film, the grain count across the channel is significantly different for each device, thus exemplifying a phenomenon in which non-uniformity of device characteristics is caused directly. On the other hand, when monomolecular adsorption with a coverage of 1 is used in accordance with the present invention, the number of these grain boundaries can be even, and thus the uniformity of the TFTs is greatly improved.

Example 2

In this embodiment, hydrogen is used as the carrier gas when the monomolecular layer of nickel is formed on the amorphous silicon film 13 of the first embodiment.

In this embodiment, a method of depositing a nickel film will be described. First, as shown in Fig. 2, the substrate is placed, and the interior of the chamber is evacuated to a suitable pressure. Very high vacuum is not necessary at this stage, so an exhaust of 1 to 500 mTorr is sufficient. Next, an electric current flows to the substrate temperature control mechanism 204, and the substrate is heated to 350 ° C.

In this state, the valve V12 is opened to flow hydrogen gas so that the inside of the chamber is at a predetermined pressure. The flow rate of hydrogen was 3 SLM and the reaction pressure was 1 × 10 ⁴ Pa in this example. Next, after confirming that the stable state is established at a predetermined pressure and temperature, an organic metal containing a catalytic metal element is introduced. In this example, BMCP nickel was used and the flow rate was 100 sccm. Simultaneously with the introduction of the hydrogen carrier gas, the valve V11 was opened for 1 second to allow the organometallic gas to hit the surface and adsorb onto the surface of the amorphous silicon film (FIG. 1B).

Simultaneously with the collision of the organic metal gas, light irradiation from the light source 202 is performed on the surface of the amorphous silicon film to which the organic metal molecules are adsorbed (FIG. 1C).

In this embodiment, a xenon lamp was used as the light source, and light irradiation was performed in synchronism with the gas collision using the shutter 203. At this time, almost every single molecule layer of Ni could be adsorbed for each sequence of gas collision and light irradiation. It was found that when almost the same conditions as those described above were used and BMCP nickel was used as the organic metal, the nickel layer formed in one sequence did not become a complete monoatomic layer. This seems to be the result of the coverage being less than 1 because of the large solid obstacle. In this way, a nickel compound film 14 is formed on the substrate surface (FIG. 1D).

Subsequently, similarly to Embodiment 1, solid growth of the amorphous silicon film 13 may be performed.

Example 3

In this embodiment, a raw material similar to Example 1 is used, selective light irradiation is performed, and nickel is added only to the portion where light irradiation is performed. Referring to Fig. 3, the steps from introduction of the catalytic element (nickel is used in this example) to crystallization are described. Also in this example, Corning 1737 glass was used as the substrate. Its size is 100mm × 100mm.

The steps from the formation of the amorphous silicon film 13 on the substrate 11 to the introduction into the chamber 101 after removal of the native oxide film are similar to those in the first embodiment. Therefore, description thereof is omitted. Next, the part where selective light irradiation is performed is described with reference to FIG. After the substrate 11 is placed in the chamber 101, in an operation similar to that of Example 1, organic nickel gas is introduced. When introducing the organic nickel gas to reach the adsorption equilibrium, the argon gas laser 105 irradiates the substrate surface. Since the argon gas laser is a CW laser, irradiation was performed by pulse irradiation using the shutter 106. Then only the carrier gas flowed for about 100 seconds, so the organic nickel gas was removed from the atmosphere in the chamber. Next, gas collision and light irradiation were performed again. Since this sequence was repeated about 10 times, it was possible to form a nickel layer having a thickness of monoatomic layer thickness x sequence number of times. In contrast to Example 1, the film formation was repeated several times to sufficiently perform the transverse growth. In the part where light irradiation is not performed, since decomposition of organic nickel on the surface hardly occurs, the monomolecular layer does not pile and the monomolecular layer remains as it is. Because it doesn't get higher). Finally, while only the carrier gas was flowing, since the substrate temperature was raised, the remaining monomolecular adsorbent layer was completely re-separated so that the nickel compound was deposited only on the portion where light irradiation was performed.

The substrate temperature control mechanism 104 is disposed in the chamber and the sample 107 is placed thereon. This structure is the same as in Example 1. Of course, it is preferable that the entire chamber is maintained at a temperature at which organic nickel does not solidify.

Subsequently, solid phase growth proceeds. In this embodiment, since the substrate temperature is significantly different from the substrate temperature required for thermal crystallization, it is not advantageous to perform the steps in the same chamber in terms of yield. At this time, a method of taking out the substrate to the outside and performing a solid phase growth step is adopted. In this case, the substrate temperature control mechanism 104 is turned off, the substrate is cooled, the inside is cleaned with nitrogen, and the chamber is opened in the air to take out the substrate. The next solid growth was almost similar to Example 1, but in order to perform lateral growth in this example, the temperature was brought to 600 ° C. higher than Example 1 (possibly because Corning 1737 glass is used). , The time was 4 hours.

Thus, elliptic crystallization only occurred in the region where light irradiation was performed, and a lateral growth region of about 100 mu m was observed around the region. Crystallization was hardly observed in other areas, confirming that nickel could be added selectively.

Also in this embodiment, hydrogen can be used as the carrier gas. In this case, the argon laser 105 irradiates the substrate surface in synchronization with the introduction of the organic nickel gas. Only hydrogen then flows for about 10 seconds, and then gas collisions and light irradiation are performed again.

Since this sequence is repeated about 10 times, it is possible to accurately form a nickel layer having a thickness of monolayer thickness x sequence number of times.

Example 4

In this embodiment, after nickel is formed on the amorphous silicon film surface by the method shown in Examples 1 or 2, nickel silicide is successively formed on the surface, and then thermal crystallization is performed.

Since the steps up to decomposition and deposition of the organic nickel by the xenon lamp are the same as those in Example 3, description thereof will be omitted.

Then, in order to purify the gas remaining inside, the valve V is opened to completely exhaust the organic nickel, followed by purging with nitrogen. Subsequently, the temperature of the heater (substrate temperature control mechanism) 204 is raised to a temperature of 450 ° C. or higher in a state where nitrogen is flowed. Then, nickel silicide is formed from nickel adsorbed as monoatomic layer and amorphous silicon.

Comparing the film in which silicide was formed above by the above step with that in which silicide was not formed as in Example 3, it was found by electron microscopy that the nucleation density in thermal crystallization was increased by silicide formation.

Example 5

In this embodiment, using a raw material and a method different from those of Example 1 or 2, a crystalline silicon film is formed on the entire glass substrate. Referring to Fig. 4, the steps from the introduction of the catalytic element (nickel is used in this example) to the crystallization will be described. In this example, Corning 7059 glass was used as the substrate. Its size is 100mm × 100mm.

First, a silicon oxide film 12 was formed on the substrate 11 by the sputtering method or the plasma CVD method. The thickness of the silicon oxide film 12 was 1000-5000 kPa, for example 2000 kPa.

Next, an amorphous silicon film 13 having a thickness of 100 to 1500 mW was formed by the plasma CVD method or the LPCVD method (Fig. 4A). In this embodiment, an amorphous silicon film 13 having a thickness of 500 kHz was formed by the plasma CVD method.

Hydrofluoric acid treatment was then performed to remove contaminants and native oxide films, and the substrate was placed in chamber 600 as shown in FIG. Here, the chamber 600 will be described briefly. The chamber 600 is connected to a tube for introduction of gas from the outside and a tube for exhaust. The former is formed of three lines. The first line is a purification line. Nitrogen, argon, etc. are used as a gas. The second line is a line for introducing nickel vapor. Solvent 602 comprising dissolved nickel salt is placed in an evaporator 601 maintained at a constant temperature and bubbles the carrier gas so that the nickel salt flows into chamber 600. The third line is a line for introducing water vapor. By controlling the partial sum of the second line and the third line, the concentration of the adsorbed nickel compound can be finely controlled. The third line may be omitted in some cases. Although not shown, the chamber is configured to maintain the pipe at a suitable temperature (about 100 ° C.) to prevent water vapor from solidifying in the pipe.

This embodiment is similar to Embodiment 1 and the like in that the substrate temperature control mechanism 607 controlled by the Peltier element is disposed in the chamber 600. The substrate 605 is disposed thereon. The substrate is heated to the temperature at which the ALE window is widest. Also in this embodiment, although the substrate need not be heated, the substrate temperature was controlled to be 50 ° C. to control the amount of adsorption.

Of course, the entire chamber is preferably maintained at a temperature that prevents water vapor from solidifying.

A method of depositing a nickel film using the chamber 600 of this structure will be described. First, the substrate 605 is disposed. The interior of chamber 600 is then evacuated to a suitable pressure. Since this step does not require very high vacuum, an exhaust of 1 to 500 mTorr is sufficient. Next, in order to control a board | substrate at 50 degreeC, an electric current is sent to the board | substrate temperature control mechanism 607.

In this state, argon flows through the line 606 so that the inside of the chamber is at a predetermined pressure. The argon flow rate was 1 SLM and the reaction pressure was 1 × 10 ⁵ Pa. Next, after confirming that the stable state is established at a predetermined pressure and temperature, steam containing nickel salt is introduced. In this embodiment, nickel nitrate (6N) was used and steam was introduced using a solvent 602 containing 1000 ppm of dissolved salts. In addition, the temperature of the evaporators 601 and 604 and the flow rate of the carrier gas were adjusted, and the adsorption was performed under a condition in which the ratio between the partial pressure of the water vapor containing nickel and the partial pressure of the water vapor containing no nickel was 1: 1. . From subsequent SIMS analysis, it was found that this condition was in a region having a coverage of less than one. If the partial pressure of the water vapor containing nickel further increases, it is possible to form a state in which the coverage is 1 (Fig. 4B).

In Example 1, there was a light irradiation step which could in some respects be called a fixing step. However, this step is not necessary because the inorganic salt used in this example is a non-volatile material having a high melting point.

Thereafter, solid phase growth proceeds. Subsequent solid growth conditions and the like are similar to those in Example 1, and thus description thereof will be omitted (FIG. 4C).

Example 6

In the manufacturing method of Example 1 or 2, a silicon oxide film having a thickness of 1200 kPa is selectively provided, nickel is selectively introduced using this silicon oxide film as a mask, and the solid phase is subjected to lateral crystallization according to this embodiment. Growth is carried out. 5 schematically shows the manufacturing steps of this embodiment. First, a silicon oxide film 22 having a thickness of 1000 to 5000 GPa was formed on a glass substrate (Corning 7059, 10 cm ² ) 21. In addition, an amorphous silicon film 23 having a thickness of 500 to 1000 GPa was formed by a plasma CVD method or a reduced pressure CVD method. Furthermore, in this embodiment, the silicon oxide film 24 was formed by the sputtering method as a mask film having a thickness of about 1200 mW in this embodiment. From the experiments of the inventors, it was confirmed that even in the case where the thickness of the silicon oxide film 24 was 500 kPa, a margin in the film thickness was further provided in this embodiment to prevent the nickel from flowing into unexpected portions due to the presence of pinholes or the like. (FIG. 5A).

Then, by normal photolithography patterning, the silicon oxide film 24 is patterned in a desired pattern to form a window 25 for introducing nickel. The substrate thus treated was placed in the chamber 101 as in Example 1, and a nickel compound film 26 having a suitable thickness was deposited using organic nickel gas (FIG. 5B).

Subsequently, crystallization of the amorphous silicon film 23 was performed by heat treatment at 550 ° C. for 8 hours (in a nitrogen atmosphere). At this time, crystallization first started at the portion 27 where the nickel compound film 26 was in intimate contact with the amorphous silicon film 23.

Subsequently, crystallization proceeded to the periphery as shown by the arrows in the figure, and crystallization was also performed on the region 28 covered with the mask film 24 (FIG. 5D).

In this manner, crystallization of the amorphous silicon film 23 was performed. As shown in Fig. 5E, when lateral crystallization was performed as in this example, three regions having different characteristics were obtained approximately. The first region is a region indicated by reference numeral 27 in FIG. 5E and is a region in which the nickel compound film 26 is in intimate contact with the amorphous silicon film 23. This region is crystallized in the first step of the thermal annealing step. This area will be referred to as the vertical growth area. In this region, the concentration of nickel is relatively high, and the crystallization directions are inconsistent. Therefore, the crystallinity of silicon is not very good, so the etching ratio to hydrofluoric acid or other acid is relatively high.

The second region is a region in which transverse crystallization is performed as a portion indicated by reference numeral 28 in FIG. 5E. This region will be referred to as the lateral growth region. Since the crystallization direction is uniform in this region and the concentration of nickel is relatively low, the region can be used well for use in the device. The third region is an amorphous region where transverse crystallization does not proceed.

Example 7

In this example, the selective crystallization growth method shown in Example 3 is applied to Example 6. This is the most remarkable difference from Example 6 in that it is not necessary to form a mask made of a silicon oxide film. 6 schematically shows the manufacturing steps of this embodiment. First, a silicon oxide film 52 having a thickness of 1000 to 5000 GPa was formed on a glass substrate (corning glass 7059, 10 cm ² ) 51. In addition, an amorphous silicon film 53 having a thickness of 500 to 1000 GPa was formed by a plasma CVD method or a reduced pressure CVD method (FIG. 5A).

The substrate is placed in a chamber having a structure substantially the same as that used in Example 1, and according to Example 1, the organic metal 54 containing the catalytic metal element (nickel is used in this embodiment) is amorphous silicon. Adsorbed on the membrane surface (soft adsorption without decomposition) (FIG. 6B). Next, at the same time, light irradiation is performed only in the region where nickel addition is required (Fig. 6C). This is done as follows.

A window is provided over the substrate installed in the chamber. The window is designed so that a reticle in which a predetermined pattern is formed can be placed. Next, laser irradiation is performed from the upper portion of this window, so that light irradiation is performed only on the area without a mask on the reticle. Since the distance between the reticle and the substrate is longer than a normal pattern gap, the formed pattern becomes very blurred unless a coherent light source is used. Therefore, a laser is used. Of course, in order to improve this patterning accuracy, the distance between the reticle and the substrate and the window should be made small. However, since the substrate is in a heated state, it is impossible to compare this gap with a stepper or the like. Therefore, this method can be said to be suitable for forming a relatively large pattern. Therefore, it is possible to form the monoatomic layer or the nickel film of the compound only in the region to which light is irradiated. Of course, as in Example 3, it is important that the sequence is repeated several times to adjust the amount of nickel added (Fig. 6D).

The amorphous silicon film 53 was crystallized by heat treatment at 550 ° C. for 8 hours (in a nitrogen atmosphere). At this time, crystallization first started in the region 56 in which the nickel compound film 55 is in intimate contact with the amorphous silicon film 53 (FIG. 6D).

Crystallization then proceeded to the periphery shown by the arrows in the figure. Thus, crystallization by lateral growth was also performed in the region 57 where no nickel was deposited (FIG. 6E).

In this way, crystallization of the amorphous silicon film 53 was performed. As shown in Fig. 6E, when transverse crystallization is performed as in this example, three main regions having different characteristics are obtained. The first region, which is indicated by reference numeral 56 in FIG. 6E, is a region in which the nickel compound film 55 comes into close contact with the amorphous silicon film 53. This region is crystallized in the first step of the thermal annealing step. In this region, the concentration of nickel is relatively high, and the crystallization direction is not uniform. Therefore, the crystallinity of silicon is not very good, so the etching ratio to hydrofluoric acid or other acid is relatively high.

The second region is a region denoted by reference numeral 57 in FIG. 6E and in which lateral crystallization is performed. This region will be referred to as the lateral growth region. In this region, the crystallization direction is uniform, and the concentration of nickel is relatively low, and this region is preferably used for the device. The third region is a region in which no transverse crystallization is performed.

Example 8

In this embodiment, using the crystalline silicon film formed by the method of the present invention, a thin film transistor (TFT) is formed. 7 schematically shows the manufacturing steps of this embodiment. First, a silicon oxide film 302 having a thickness of 2000 GPa as a base layer was formed on the glass substrate 301. This silicon oxide film 302 was provided to prevent diffusion of impurities from the glass substrate. Then, an amorphous silicon film 303 having a thickness of 500 kPa was formed by a method similar to that of the first embodiment (Fig. 7A).

Then, similarly to Example 4, the nickel nitrate film 304 of the monomolecular layer was adsorbed onto the surface of the amorphous silicon film 303 by a method similar to that of Example 4 (FIG. 7B).

Then, by thermal annealing at a temperature of 550 ° C. for 4 hours, the amorphous silicon film 303 was crystallized to form the crystalline silicon film 305. This silicon film was irradiated with KrF excimer laser light (wavelength 248 nm) to further improve crystallization. The energy density of the laser is preferably 300 to 400 mJ / cm ² . In this way, in addition to crystallization by solid phase growth, laser light irradiation was performed to further improve crystallinity. This is because, as also described in Example 5, the crystallization direction is not uniform at the portion where the nickel compound comes into contact with the amorphous silicon film, and in this example, the crystal obtained by the addition of nickel is a needle crystal, This is because a region is formed in which sufficient crystallization is not performed only by the solid phase growth method. In particular, many amorphous residues were observed at the crystal grain boundaries. Then, it is desirable to completely crystallize these amorphous elements at the crystal grain boundaries by performing laser irradiation (FIG. 7C).

Next, the crystallized silicon film was patterned to form the protrusion region 306. This protrusion region 306 constitutes an active layer of the TFT. Subsequently, a silicon oxide film 307 having a thickness of 200 to 1500 mW, in this embodiment, 1000 mW was deposited by the plasma CVD method. This silicon oxide film 307 also functions as a gate insulating film (Fig. 7D).

Care should be taken in the formation of the silicon oxide film 307. Here, TEOS was a raw material, which was decomposed and deposited with oxygen by the RF plasma CVD method at a substrate temperature of 150 to 600 ° C, preferably 300 to 450 ° C. The ratio of the pressure of TEOS and the pressure of oxygen was 1: 1 to 1: 3, the pressure was 0.05 to 0.5 Torr, and the RF power was 100 to 250 W. Alternatively, the film was formed from the raw material of TEOS with ozone gas by a low pressure CVD method or an atmospheric pressure CVD method at a substrate temperature of 350 to 600 ° C., preferably 400 to 550 ° C. After formation of the film, the annealing treatment may be performed at 400 to 600 ° C. for 30 to 60 minutes in an atmosphere of oxygen or ozone.

Subsequently, a polycrystalline silicon film having a thickness of 2000 kPa to 1 μm and doped with phosphorus was formed by a low pressure CVD method, which was patterned to form a gate electrode 308. Thereafter, by the ion doping method (also referred to as plasma doping method), impurities (phosphorus) were implanted into the projection silicon film of the TFT using the gate electrode as a mask in a self-aligning manner. Phosphine (PH ₃ ) was used as the doping gas. The dose was 1 × 10 ¹⁴ to 4 × 10 ¹⁵ cm ^-2 . In this way, N-type impurity (phosphorus) regions 309 and 310 were formed (FIG. 7E).

Then, as the interlayer insulator 311, a silicon oxide film having a thickness of 3000 to 8000 kPa was formed by the plasma CVD method of the TEOS raw material with oxygen, or the low pressure CVD method or the atmospheric pressure CVD method with the ozone. Substrate temperature was 250-450 degreeC, for example 350 degreeC. After film growth, the silicon oxide film may be mechanically polished, or may be planarized by a reetching method, in order to obtain flatness of the surface. The interlayer insulator 311 was etched to form contact holes in the source / drain of the TFT, and the wirings / electrodes 312 and 313 of chromium or titanium nitride were formed.

Finally, annealing with hydrogen was performed at a temperature of 300 to 400 ° C. for 0.1 to 2 hours to complete the hydrogenation of the silicon. In this way, the TFT is completed. At the same time, by forming many TFTs and arranging them in a matrix, an integrated circuit for use in an active matrix liquid crystal display device or the like can be formed (Fig. 7F).

Example 9

This embodiment relates to a TFT manufacturing step. 8 schematically shows the manufacturing steps of this embodiment. First, a silicon oxide film 402 having a thickness of 2000 GPa was formed on the glass substrate 401 as a base layer, and an amorphous silicon film 403 having a thickness of 500 GPa was also formed thereon. The window 405 was selectively opened in the mask film 404 (FIG. 8A).

In a similar manner to Example 4, a nickel nitrate film 406 was formed. In order to perform the adsorption more easily, an oxide thin film was previously formed on the surface of the amorphous silicon film by ozone treatment (not shown) (Fig. 8B).

Thereafter, thermal annealing was performed at 550 ° C. for 8 hours, so that the amorphous silicon film 403 crystallized in the transverse direction shown by the arrows in the figure to form the vertical growth region 403 and the transverse growth region 409. . The region not crystallized at this stage remains as amorphous region 410 (FIG. 8C).

As in this embodiment, in the lateral crystallization, the crystallinity of the lateral growth region 409 is excellent. Therefore, even if the crystallinity is not improved by irradiation of laser light or the like as in Example 6, since a TFT can be formed, irradiation of laser light was not performed in this embodiment. However, when laser light irradiation is performed, a TFT with better characteristics can be obtained.

Next, the crystallized silicon film was patterned to form the projection region 411. This projection region 411 constitutes an active layer of the TFT. As can be seen from the figure, the protrusion region 411 includes a vertical growth region 408, a lateral growth region 409, and an amorphous region 410. In this embodiment, the lateral growth region 409 was formed in the channel region of the TFT. This is because the channel region is an important region that determines the characteristics of the TFT.

Thereafter, a silicon oxide film 412 was deposited. This silicon oxide film 412 also functions as a gate insulating film. Subsequently, an aluminum film having a thickness of 2000 kPa to 1 µm was formed by the sputtering method. This film was patterned to form a gate electrode 413. Aluminum may be doped with 0.15 to 0.2 wt% scandium (Sc). Subsequently, the substrate was precipitated in an ethylene glycol solubilizer of tartaric acid of 1-3% and ph = 7, and anodization was performed using the anode of platinum and the anode of the gate electrode of this aluminum. Anodic oxidation was first carried out in such a way that the voltage was first raised to 220V at a constant current, in which state it was maintained for 1 hour and the oxidation was completed. In this embodiment, in the constant current state, the rate of rise of the voltage is suitably 2 to 5 V / min. Thus, anodized oxide 414 having a thickness of 1500 to 3500 mV, for example 2000 mV, was formed on the side and top surfaces of the gate electrode 413 (FIG. 8D).

Then, by the ion doping method (also referred to as plasma doping method), impurities (phosphorus) were implanted into the projection silicon film of each TFTs in a self-matching manner using the gate electrode as a mask. Phosphine (PH3) was used as the doping gas. The dose was 1 * 10 <^14> -4 * 10 <^15> cm <^-2> . Since the anodic oxide 414 is present in this doping step, the impurity regions 415 and 416 and the gate electrode do not overlap each other but are separated. That is, they are in the so-called offset state.

Thereafter, irradiation with a KrF excimer laser (wavelength 248 nm, pulse width 20 nsec) was performed to improve the crystallinity of the portion where the crystallinity is reduced by the influx of impurities. The energy density of the laser was 150 to 400 mJ / cm 2, preferably 200 to 250 mJ / cm 2. In this way, N-type impurity regions (phosphorus) 414 and 416 were formed. The sheet resistance of these areas was 200-800 kPa / square. By the step of laser irradiation, the amorphous region 410 in the projection region 411 was also crystallized (FIG. 8E).

Thereafter, a silicon oxide film 417 having a thickness of 5000 kPa was deposited on the entire surface. Subsequently, the silicon oxide film 417 is etched by a buffered hydrofluoric acid solubilizer to form contact holes in the source / drain of the TFT to form the wiring / electrodes 418 and 419 of the polylayer film of titanium nitride and aluminum. In the etching step of the contact hole, among the protrusion regions, since the vertical growth region 408 has a higher etching ratio than the lateral growth region 409 and the amorphous region 410, the deeply etched region 420 as shown in the figure. ) Was formed. As is apparent from this, if the entire contact hole is included in the vertical growth region, there is a strong risk of contact defects, and it is preferable that the contact hole is designed to extend into an area other than the vertical growth region. In this way, TFT was completed (FIG. 8F).

As described above, as a method of introducing a catalytic element for accelerating the crystallization of an amorphous silicon film, vapor or gas containing the catalytic element is used, which are adsorbed on the amorphous silicon film directly or through a very thin oxide film. Therefore, the concentration of the catalytic element is finely controlled, and uniform addition thereof can be performed, so that the uniformity of crystallization can be improved. In particular, in the adsorption step, by using monomolecular layer adsorption, in particular, uniformity, controllability, and regeneration characteristics can be improved. Therefore, it is possible to provide an electric device using a crystalline silicon film and having high reliability.

Claims (32)

In the crystalline semiconductor manufacturing method, a material containing a catalytic element for accelerating crystallization of a silicon film in a continuous monolayer having a coverage of 1 on the surface of an amorphous silicon film by using vapor or gas of an organic material containing a catalyst element. Adsorbing; And crystallizing the amorphous silicon film by heat treatment using the catalytic element. The crystalline semiconductor manufacturing method according to claim 1, wherein the surface of the amorphous silicon film is completely covered with one monolayer in the monolayer having the coverage 1. In the crystalline semiconductor manufacturing method, a material containing a catalytic element is adsorbed on the surface of an amorphous silicon film to accelerate the crystallization of the silicon film in a continuous multi-molecular layer by using a vapor or a gas of an organic material containing a catalytic element. Doing; And crystallizing the amorphous silicon film by heat treatment using the catalytic element. 4. The method of claim 3, wherein in the multi-molecular layer having a coverage of at least 1, the surface of the amorphous silicon film is completely covered with at least one monomolecular layer, and adsorbed molecules are present on the monomolecular layer. 12. A method of manufacturing a crystalline semiconductor, comprising: disposing a substrate having an amorphous silicon film in a chamber; Introducing a vapor or gas of an organic material comprising at least one catalytic element into the chamber to accelerate crystallization of the amorphous silicon film; Adsorbing said introduced vapor or gas of said organic material in a continuous monolayer having a coverage of 1 on the surface of said amorphous silicon film; And crystallizing the amorphous silicon film by heat treatment using the catalytic element. 10. A method of manufacturing a crystalline semiconductor, comprising: disposing a substrate having an amorphous silicon film in a chamber; Generating a vapor or gas of an organic material containing at least one catalytic element in an evaporator to accelerate crystallization of the amorphous silicon film; Introducing the generated vapor or gas of the organic material into the chamber; Adsorbing the introduced gas or vapor of the organic material in the continuous monolayer having a coverage of 1 on the surface of the amorphous silicon film; And crystallizing the amorphous silicon film by heat treatment using the catalytic element. 10. A method of manufacturing a crystalline semiconductor, comprising: disposing a substrate having an amorphous silicon film in a chamber; Introducing a vapor or gas of an organic material containing a catalytic element into the chamber to accelerate the crystallization of the amorphous silicon film; Adsorbing the introduced gas or vapor of the organic material in the continuous monolayer having a coverage of 1 on the surface of the amorphous silicon film; Irradiating light simultaneously with the adsorption step to decompose molecules of the adsorbed vapor or gas to deposit a coating film of the catalyst element or the compound of the catalyst element on the surface of the amorphous silicon film; And crystallizing the amorphous silicon film by heat treatment using the catalytic element. 12. A method of manufacturing a crystalline semiconductor, comprising: disposing a substrate having an amorphous silicon film in a chamber; Introducing a vapor or gas of an organic material containing a catalytic element into the chamber to accelerate crystallization of the amorphous silicon film; Adsorbing the introduced gas or vapor of the organic material in the continuous monolayer having a coverage of 1 on the surface of the amorphous silicon film; Depositing a coating film of the catalyst element or the compound of the catalyst element on the surface of the amorphous silicon film by decomposing molecules of the adsorbed vapor or gas by heating simultaneously with the adsorption step; And crystallizing the amorphous silicon film by heat treatment using the catalytic element. 12. A method of manufacturing a crystalline semiconductor, comprising: disposing a substrate having an amorphous silicon film in a chamber; Introducing a vapor or gas of an organic material comprising at least one catalytic element into the chamber to accelerate crystallization of the amorphous silicon film; Adsorbing the introduced vapor or gas of the organic material in a continuous multi-molecular layer on the surface of the amorphous silicon film; And crystallizing the amorphous silicon film by heat treatment using the catalytic element. 10. A method of manufacturing a crystalline semiconductor, comprising: disposing a substrate having an amorphous silicon film in a chamber; Generating a vapor or gas of an organic material containing at least one catalytic element in an evaporator to accelerate crystallization of the amorphous silicon film; Introducing the generated vapor or gas of the organic material into the chamber; Adsorbing the introduced gas or vapor of the organic material in a continuous multi-molecular layer on the surface of the amorphous silicon film; And crystallizing the amorphous silicon film by heat treatment using the catalytic element. 12. A method of manufacturing a crystalline semiconductor, comprising: disposing a substrate having an amorphous silicon film in a chamber; Introducing a vapor or gas of an organic material containing a catalytic element into the chamber to accelerate crystallization of the amorphous silicon film; Adsorbing the introduced gas or vapor of the organic material in a continuous multi-molecular layer on the surface of the amorphous silicon film; Depositing a coating film of the catalyst element or the compound of the catalyst element on the surface of the amorphous silicon film by decomposing molecules of the adsorbed vapor or gas by light irradiation simultaneously with the adsorption step; And crystallizing the amorphous silicon film by heat treatment using the catalytic element. 12. A method of manufacturing a crystalline semiconductor, comprising: disposing a substrate having an amorphous silicon film in a chamber; Introducing a vapor or gas of an organic material containing a catalytic element into the chamber to accelerate crystallization of the amorphous silicon film; Adsorbing the introduced gas or vapor of the organic material in a continuous multi-molecular layer on the surface of the amorphous silicon film; Depositing a coating film of the catalytic element or a compound of the catalytic element on the surface of the amorphous silicon film by decomposing molecules of the adsorbed vapor or gas by heating simultaneously with the adsorption step; And crystallizing the amorphous silicon film by heat treatment using the catalytic element. The method of claim 5, wherein the catalytic element is Ni, Pd, Pt, Cu, Ag, Au, In, Sn, P, As, or Sb. The method of claim 5, wherein the catalytic element is selected from VIII group elements, IIIb, IVb, and Vb elements. The method of claim 6, wherein the catalytic element is Ni, Pd, Pt, Cu, Ag, Au, In, Sn, P, As, or Sb. The method of claim 6, wherein the catalytic element is selected from VIII group elements, IIIb, IVb, and Vb elements. The method of claim 7, wherein the catalytic element is Ni, Pd, Pt, Cu, Ag, Au, In, Sn, P, As, or Sb. 8. The method of claim 7, wherein the catalytic element is selected from VIII group elements, IIIb, IVb, and Vb elements. The method of claim 8, wherein the catalytic element is Ni, Pd, Pt, Cu, Ag, Au, In, Sn, P, As, or Sb. The method of claim 8, wherein the catalytic element is selected from VIII group elements, IIIb, IVb, and Vb elements. The method of claim 9, wherein the catalytic element is Ni, Pd, Pt, Cu, Ag, Au, In, Sn, P, As, or Sb. 10. The method of claim 9, wherein the catalytic element is selected from VIII group elements, IIIb, IVb, and Vb elements. The method of claim 10, wherein the catalytic element is Ni, Pd, Pt, Cu, Ag, Au, In, Sn, P, As, or Sb. The method of claim 10, wherein the catalytic element is selected from VIII group elements, IIIb, IVb, and Vb elements. The method of claim 11, wherein the catalytic element is Ni, Pd, Pt, Cu, Ag, Au, In, Sn, P, As, or Sb. 12. The method of claim 11 wherein the catalytic element is selected from VIII group elements, IIIb, IVb, and Vb elements. The method of claim 12, wherein the catalytic element is Ni, Pd, Pt, Cu, Ag, Au, In, Sn, P, As, or Sb. The method of claim 12, wherein the catalytic element is selected from VIII group elements, IIIb, IVb, and Vb elements. The method of claim 1, wherein the catalytic element is Ni, Pd, Pt, Cu, Ag, Au, In, Sn, P, As, or Sb. The method of claim 1, wherein the catalytic element is selected from VIII group elements, IIIb, IVb, and Vb elements. The method of claim 3, wherein the catalytic element is Ni, Pd, Pt, Cu, Ag, Au, In, Sn, P, As, or Sb. The method of claim 3, wherein the catalytic element is selected from VIII group elements, IIIb, IVb, and Vb elements.