JP2002237453A - Manufacturing method of crystalline semiconductor film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To solve the problem that a large amount of a catalyst element solution is disposed in treatment and hence the amount of a used solution has a problem since spin drying is made after the catalyst element solution is filled on the substrate in the addition process of the catalyst element solution by a spin treatment method that is one portion of the manufacturing process of a crystalline semiconductor film containing silicon, and to solve the problem that a spin-treating device becomes expensive since it becomes more difficult to secure treatment uniformity as the substrate becomes larger in the spin- treating device. SOLUTION: When a roll treatment method (Fig. 2 (A)), a sheet-type dip treatment method (Fig. 2 (B)), or a spray (or shower type) treatment method (Fig. 2 (C)) is used as a means for solving problematical points that the spin treatment method has, any one of the treatment methods is effective for reducing the amount of usage of the catalyst element solution since the catalyst element solution is not filled on the substrate. Also, since no spin treatment means are used, the device price can be restrained within a certain range.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thin film transistor using a crystalline semiconductor film containing silicon.
The present invention relates to a method for manufacturing a semiconductor device such as a ransistor (hereinafter abbreviated as TFT), and particularly to a method for manufacturing a crystalline semiconductor film containing silicon.

[0002]

2. Description of the Related Art In recent years, T has been used on insulating substrates such as glass substrates.
The technology of forming a semiconductor circuit by forming an FT is rapidly advancing, and an electro-optical device such as an active matrix liquid crystal display device is manufactured using this technology. The active matrix type liquid crystal display device is a monolithic type liquid crystal display device provided with a pixel matrix circuit and a driver circuit on the same substrate. In addition, using the above technology, the development of a system-on-panel incorporating a logic circuit such as a gamma correction circuit, a memory circuit, and a clock generation circuit has been advanced.

Since such driver circuits and logic circuits need to operate at high speed, it is inappropriate to apply an amorphous silicon film to a semiconductor layer which is an active layer of a TFT.
At present, TFTs using a polycrystalline silicon film as a semiconductor layer are becoming mainstream. In addition, for a substrate on which a TFT is formed, it is required to use a glass substrate that is inexpensive in cost, and a low-temperature process that can be applied to a glass substrate is being actively developed.

As a low-temperature process technology, a technology for forming a crystalline silicon film on a glass substrate has been developed. A technology for adding a catalytic element has been disclosed. The technique described in the publication is to add a catalytic element for promoting crystallization to an amorphous silicon film by a spin treatment method, perform heat treatment, and crystallize the amorphous silicon film. With this crystallization technique, the crystallization temperature of the amorphous silicon film can be reduced by about 50 to 100 ° C., and the time required for crystallization is also reduced by 1/5 to 1 /
It has become possible to reduce it to 10. As a result, a crystalline silicon film can be formed over a large area even on a glass substrate having low heat resistance. It has been experimentally confirmed that the crystalline silicon film obtained by the above low-temperature process has excellent crystallinity.

[0005] The crystallization technique of an amorphous silicon film using the technique of adding a catalyst element by the spin treatment method described above is based on a solution containing a catalyst element on the amorphous silicon film (hereinafter abbreviated as a catalyst element solution). Is added by a spin treatment method, a predetermined amount of a catalyst element is adsorbed on the surface of the amorphous silicon film, and then heat treatment is performed to form a crystalline silicon film. I have. The concentration of the catalyst element in the solution can be strictly controlled in advance. If the solution is in contact with the surface of the amorphous silicon film, the amount of the catalyst element introduced into the amorphous silicon film depends on the concentration of the catalyst element in the solution. Since the catalyst element adsorbed on the surface of the amorphous silicon film contributes to crystallization, the catalyst element can be introduced at a minimum necessary concentration. For the reliability and electrical stability of the semiconductor device, it is necessary to minimize the amount of the catalytic element in the crystallized crystalline silicon film.
In the case of adding a catalytic element by a spin treatment method, crystallization can be performed with a minimum necessary amount by precisely controlling the amount of the catalytic element added, which is advantageous in terms of reliability and electrical stability of a semiconductor device. is there.

[0006]

According to the above-mentioned technique for adding a catalyst element by the spin treatment method, a larger amount of a catalyst element solution than the actual addition amount is dropped on the substrate surface, so that the solution is added on the substrate, and the substrate is added. By spinning at high speed, the dropped catalyst element solution is shaken off, and a desired amount of the catalyst element is added to the substrate surface. The spin treatment method has an advantage that a strictly controlled amount of the catalyst element can be easily added by adjusting the concentration of the catalyst element in the catalyst element solution and the spin rate of the substrate.

However, in the case of the spin treatment method, since the catalyst element solution is loaded on the substrate and then spin-dried, the amount of the catalyst element solution added to the substrate surface is only a part of the dropped catalyst element solution. However, there is a drawback in terms of use efficiency that most of the catalyst element solutions are discarded during processing. on the other hand,
In the manufacture of active matrix type liquid crystal display devices and the like, since improvement in productivity and cost reduction are required, the size of substrates is rapidly increasing. For example, 60
A substrate having a size of 0 mm × 720 mm or 680 mm × 880 mm has been employed, but recently a substrate having a size of about 1 m square has been studied. With such an increase in the size of the substrate, a drawback in the use efficiency of the catalyst element solution in the spin treatment method is considered to be a major problem in production cost.

In the spin processing apparatus, it is necessary to finely adjust the acceleration at the time of spinning the substrate in order to secure the processing uniformity. It's getting more and more difficult. Under such circumstances, in the case of the spin processing method, there is a concern that the cost of the apparatus becomes high in order to ensure both processing uniformity and increase the size of the substrate.

[0009] It is an object of the present invention to solve the above-mentioned problems of the prior art. More specifically, it is an object of the present invention to solve the problem of the efficiency of using a catalyst element solution in a spin treatment method. Another object of the present invention is to solve the problem of the apparatus cost in the spin processing method.

[0010]

The above problem in the spin processing method is an essential problem of the spin processing method, and it is considered that it is difficult to solve it by simply improving the spin processing method. Here, a solution by a roll-type processing method, a dip-type processing method, and a spray-type processing method was studied, and the details of each processing method will be described below.

[Roll Type Processing Method] In the alignment film coating step which is a manufacturing step of a liquid crystal display device, a roll coating apparatus has been conventionally used, and it is known that only a necessary area can be coated with a minimum required coating amount. Have been. Therefore, by applying a roll-type processing apparatus to the addition step of the catalyst element solution,
We thought that the above problem could be solved. In the lateral growth method of an amorphous semiconductor film containing silicon, a partial region of the amorphous semiconductor film is selectively formed through an opening region formed in a mask insulating film on the amorphous semiconductor film. It is necessary to introduce a catalyst element solution. In this case, it is sufficient to add the catalyst element solution only to the opening region of the mask insulating film, and a roll type processing apparatus that can selectively add only the necessary region is excellent in reducing the amount of the catalyst element solution used. Thought. Under the above-mentioned background, as a means for solving the above-mentioned problem, a treatment for adding a catalyst element solution by a roll treatment method was studied.

FIG. 11 is a schematic view (side view) of a roll type processing apparatus. As shown in this figure, the roll-type processing apparatus includes a catalyst element solution adding section 801 and a substrate drying section 802.
Is divided into two parts. Catalyst element solution addition section 801
Has a dispense unit 8 for supplying a catalyst element solution
03 and a doctor blade 8 for uniformly spreading the catalyst element solution
04, an anilox roll 805 for controlling the amount of the catalyst element solution, a printing roll 806 capable of attaching a letterpress portion,
A drive stage 807 for fixing the substrate is provided.
The substrate drying unit 802 is provided with an air knife nozzle 808 for blowing air blow, a drive stage 809 for fixing the substrate, and a drain tank 810 for draining the catalyst element solution blown off by air blow. Then, the roll type processing apparatus is connected to the dispensing unit 80.
The catalyst element solution dropped from 3 onto the anilox roll 805 is uniformly attached by a doctor blade 804,
Further, the catalyst element solution is uniformly adhered onto the printing roll 806, and the printing roll 806 is rotated and brought into contact with the substrate 811 by rotating the printing roll 806 to add the catalyst element solution to the substrate 811 one by one, and thereafter, a substrate transport unit (not shown) Transports the substrate 811 to the drive stage 809 of the adjacent substrate drying unit 802 by the air knife nozzle 80 installed above.
It is configured to dry by air blow from step 8. Note that a hot plate method may be applied to the drying unit of the substrate drying unit 802 (see FIG. 11).

In the above configuration, it is assumed that a letterpress portion is not provided on the print roll 806 and a letterpress portion (not shown) is provided on the print roll 806. When the printing roll 806 without the letterpress portion is applied, the catalyst element solution adhering to the entire surface of the printing roll 806 can be uniformly added to the entire surface of the substrate. It is suitable for a vertical growth method in which a catalytic element is added to the entire surface of the substrate. On the other hand, when the printing roll 806 provided with a relief portion (not shown) is applied, only the catalyst element solution attached to the relief portion can be selectively and uniformly added to a partial region on the substrate. It has become. In this case, from the viewpoint of reducing the amount of the catalyst element solution used, the method is suitable for the lateral growth method in which a catalytic element is selectively introduced, but is not limited to the lateral growth method. It is also suitable for growing. Incidentally, in the lateral growth method, a printing roll 80 having no letterpress portion is not provided.
6 may be applied and the catalyst element solution may be added to the entire surface of the mask insulating film on the amorphous semiconductor film. However, since it is disadvantageous in reducing the amount of the catalyst element solution used, a letterpress portion is provided. It is preferable to apply the print roll 806 (see FIG. 11).

By the way, the surface of the anilox roll 805 and the printing roll 806 is generally made of a metal material having fine grooves (irregularities). There is a disadvantage that only the additive solution can be processed. In addition, the above-described drawback is of course present in the case where no relief portion is provided on the printing roll 806. However, even when the relief portion is provided in a partial area on the printing roll 806, the relief portion is generally formed of plastic. Has been
Since the plastic has no water absorption, it has the same disadvantage (see FIG. 11).

Therefore, when the conventional roll coating apparatus applied in the alignment film coating step is applied to the step of adding the catalyst element solution, it is necessary to give the catalyst element solution some viscosity. Viscosity of 1 cp to 50 c
p, preferably in the range of 5 cp to 30 cp. The viscosity of the catalyst element solution can be adjusted by preparing an organic compound having viscosity, for example, an organic compound having a medium to high molecular weight. Here, when a catalyst element solution whose viscosity has been adjusted by preparing a viscous organic compound is added, it is necessary to remove the organic compound adhering to the substrate, and the thermal crystallization which is a subsequent step is performed. Before processing, a substrate cleaning step is required.

The above viscosity adjustment of the catalyst element solution is made to cope with the fact that the surface of the printing roll is rigid and has no water absorption.
6 can be dealt with by modifying it, and the method is described below.

The catalyst element solution is a solution in which a catalyst element that promotes crystallization of an amorphous semiconductor film containing silicon is dissolved, and a metal element such as Ni or Co element is applied as the catalyst element. Normally, as a catalyst element solution, nickel acetate dissolved in pure water at a concentration of 1 ppm to 200 ppm
In many cases, an i aqueous solution is used, and the viscosity of the Ni aqueous solution is very low, equivalent to that of pure water. Therefore, the Ni aqueous solution cannot be applied to the roll type processing apparatus as it is. For this reason, it is necessary to remodel the roll type processing apparatus so that an ultra-low viscosity solution such as an aqueous Ni solution can be added. . When a water-absorbing sheet is mounted on the surfaces of the anilox roll 805 and the printing roll 806, the Ni aqueous solution penetrates into the water-absorbing sheet on the surface of the printing roll 806, and the water-absorbing sheet rotates while the substrate 8 is rotated.
By contacting the surface of the substrate 11, it can be considered that it can be uniformly added to the surface of the substrate 811. Further, instead of the water-absorbent sheet, a sheet material such as velvet whose surface is finely raised may be attached. In this case, it is considered that the catalyst element solution permeates into minute gaps of the raised portion due to the surface tension of the catalyst element solution, and the catalyst element solution is uniformly added to the surface of the substrate 811. In the case of the printing roll 806 having a relief portion, the relief portion is formed from the water-absorbent sheet or the sheet material whose surface portion is finely brushed, and the like. It is thought that the solution can be used.

Therefore, regardless of the viscosity of the catalyst element solution,
It is considered that a roll type processing apparatus can be applied.
That is, when the viscosity of the catalyst element solution is in the range of 1 cp to 50 cp, preferably 5 cp to 30 cp, it is possible to apply a conventional roll processing apparatus (roll coating apparatus), Even in the case of a solution, a roll-type processing apparatus can be applied by modifying the surface of the anilox roll 805 and the printing roll 806 such as mounting a water-absorbing sheet.

The roll processing method is similar to the spin processing method.
Since there is no need to pour the Ni aqueous solution on the substrate, it is advantageous in reducing the amount of the Ni aqueous solution used. In addition, since it is not necessary to provide a substrate spin unit including a spin motor and a spin speed adjusting mechanism, it is considered that the apparatus is advantageous in terms of apparatus cost even when the substrate is enlarged.

[Dip processing method] As a means for solving the problem of the spin processing method, a dip processing method can be considered. In the case of the dip treatment method, the catalyst element solution is added to the substrate by immersing the substrate in the catalyst element solution. The dip processing method will be described below.

As the dip type processing method, a batch type in which a plurality of substrates accommodated in a carrier is immersed in a processing liquid or a single-wafer type method in which substrates are sequentially processed one by one can be considered. In the case of a large-sized substrate, the drying mechanism becomes large in the batch method, and there are many difficult problems such as measures against vibration of the drying mechanism. Therefore, a single-wafer dip processing method was studied here.

FIG. 12 is a schematic (side view) of a single-wafer dip processing apparatus. As shown in this figure, the single-wafer type dipping type processing apparatus includes a catalyst element solution immersion section 901.
And a substrate drying unit 902. The catalyst element solution immersion section 901 is provided with a processing tank 904 filled with the catalyst element solution 903 and a substrate holding arm 905 that holds the substrate 909 and immerses the substrate 909 in the catalyst element solution 903 in the processing tank 904. . The substrate drying unit 90
2 is an air knife nozzle 9 for blowing air blow
06, a drive stage 907 for fixing the substrate 909,
A drain tank 908 for draining the catalyst element solution blown off by air blow is provided. Then, the dip-type processing apparatus performs a dipping process on the substrate 909 one by one in the catalyst element solution 903 in the processing tank 904 for a predetermined time, and thereafter, the substrate drying unit 902 of the adjacent substrate drying unit 902 by a substrate transport unit (not shown). The substrate 909 is transferred to the drive stage 907, and the air knife nozzle 906 installed on the side
It is configured to dry by air blow from the air.
Here, the substrate 909 in the catalyst element solution immersion section 901 and the substrate drying section 902 of the dip type processing apparatus has a substrate surface perpendicular to gravity to prevent bending of the substrate 909 due to gravity and to save space in the apparatus. Although it is configured to face in the direction, the substrate surface may be configured to face in a direction parallel to gravity. Note that a hot plate method may be applied to the drying unit of the substrate drying unit 902 (see FIG. 12).

When a substrate is processed by a dip processing method,
Since a plurality of substrates are sequentially immersed in the processing liquid in the processing bath 904 one by one, if the processing liquid involves any chemical reaction, the processing liquid is deteriorated, and the processing liquid varies from one substrate to another. There is. However, in the case of the catalyst element solution 903, since the processing solution only adheres to the substrate and there is no chemical reaction of the processing solution, no processing variation for each substrate can occur in principle. In addition, in the case of the dip treatment method, since only the catalyst element solution attached to the substrate 909 is dried, there is no problem in the use efficiency of the catalyst element solution as in the spin treatment method. Also, unlike the spin processing method, there is no need to provide a substrate spin means including a spin motor and a spin speed adjusting mechanism, so that even if the substrate becomes larger, the apparatus price can be kept within a certain range. It is. Therefore, it is considered that the problem of the prior art that the spin processing method has can be solved by introducing the single-wafer dip processing method in the step of adding the catalyst element.

[Spray processing method] As a solution to the problem of the spin processing method, a spray processing method can be considered. In the case of the spray treatment method, a fine mist-like catalyst element solution is attached to a substrate to add the catalyst element solution to the substrate. The spray processing method is described below.

FIG. 13 is a schematic view (side view) of a spray type processing apparatus. As shown in this figure, the spray-type processing apparatus includes a catalyst element solution adding section 1001 and a substrate drying section 101.
02 is divided into two parts. The catalyst element solution adding section 1001 includes a processing stage 1003 for fixing the substrate.
And a spray nozzle 1005 for spraying a mist-like catalyst element solution 1004 and a drain tank 1006 for discharging the catalyst element solution. The substrate drying unit 10
02, an air knife nozzle 1007 for blowing air blow, a drive stage 1008 for fixing the substrate,
A drain tank 1009 for draining the catalyst element solution blown off by air blow is provided. Then, the spray type processing apparatus transports the substrate 1010 to the processing stage 1003 by a substrate transport unit (not shown), and the spray nozzle arranged right beside the substrate on the substrate 1010 fixed to the processing stage 1003. A mist-like catalyst element solution 1004 is sprayed for a predetermined time from 1005,
Thereafter, the substrate 1 is moved to the drive stage 1008 of the adjacent substrate drying unit 1002 by a substrate transport unit (not shown).
010 is conveyed and dried by air blow from an air knife nozzle 1007 installed on the lateral side. Here, the substrate 1010 in the catalyst element solution adding section 1001 and the substrate drying section 1002 of the spray type processing apparatus has a horizontal substrate surface in order to prevent the substrate 1010 from bending due to gravity and to save space in the apparatus. Although the configuration is such that the substrate surface is oriented in a direction perpendicular to gravity, the substrate surface may be configured so as to be oriented parallel to gravity. Note that the air knife method is suitable for the drying means of the substrate drying unit 1002, and the hot plate method is considered to be unsuitable.

In the case of the spray treatment method, since the mist-like catalyst element solution 1004 is sprayed on the substrate 1010, the amount of addition can be arbitrarily adjusted while being added substantially uniformly to the substrate 1010. That is, the mist-like catalyst element can be sprayed until the catalyst element solution uniformly adheres to the substrate surface, or the spray can be performed so that the adhesion region and the non-adhesion region are present in spots. Even when the adhesion region and the non-adhesion region are present in the spots, it is considered that the catalyst element can be added substantially uniformly because the adhesion region is dried while moving in the drying step using an air knife. For this reason, it is considered that the catalyst element solution can be uniformly added on the substrate with a considerably small addition amount of the catalyst element solution.

Here, a spray method was examined as a method for uniformly adding a small amount of the catalyst element solution onto the substrate, but there is no particular problem in the shower method. In the case of the shower type, in a device configuration in which the substrate surface faces sideways, the catalyst element solution ejected from a shower nozzle (not shown)
Since there is a problem that it is difficult to uniformly add the catalyst element solution due to gravity flowing downward in a state of being attached to the surface of the substrate 10, the apparatus configuration in which the substrate surface faces upward is more preferable. In this case, the amount of the catalyst element solution added may be increased as compared with the spray method, but it is considered that the catalyst element solution can be added considerably less as compared with the conventional spin treatment method.

In the spray type or the shower type, the catalyst element solution is added from the spray nozzle 1005 or the shower nozzle (not shown) onto the substrate 1010. A certain amount of the catalyst element solution adhered to the drain tank 1006 flows. In this case, recover the catalyst element solution,
By using the system for reuse, it is possible to further reduce the amount of the catalyst element solution used.

As described above, the spray (or shower) treatment method allows the catalyst element solution to be substantially uniformly added to the substrate while reducing the amount of the catalyst element solution used. In addition, since there is no need to provide a substrate spin means including a spin motor and a spin speed adjustment mechanism,
It is considered that even if the size of the substrate increases, the device price can be kept within a certain range. Therefore, it is considered that the problem of the prior art that the spin treatment method has can be solved by introducing a spray treatment method (or a shower treatment method) into the catalyst element addition step.

As described above, the roll processing method, the single-wafer processing dip processing method, and the spray (or shower) processing method were examined as means for solving the problems of the prior art that the spin processing method has. As a result, it is considered that any of the processing methods can solve the problem.

[Details of Catalyst Element Solution] Next, the catalyst element solution used in each of the above-mentioned addition treatment methods (roll treatment method, single-wafer dipping treatment method, spray treatment or shower treatment treatment). Describe. The catalyst element and its solution used in the conventional spin treatment method have already been disclosed in Japanese Patent Application Laid-Open No. Hei 7-2111636. For each of the above-mentioned addition treatment methods (roll treatment method, single-wafer treatment dipping treatment method, spray treatment or shower treatment treatment method), basically the same catalyst element and its solution as in the spin treatment method can be used. Therefore, it is specifically described below.

As the catalyst element solution, an aqueous solution or an organic solvent can be used, and polar solvents such as pure water, alcohols, acids, and ammonia are preferable from the viewpoint of solubility of the catalyst element. Further, as the solvent containing the catalytic element, benzene, toluene, xylene, carbon tetrachloride, chloroform, ether, trichloroethylene, chlorofluorocarbon, and the like, which are nonpolar organic solvents, can also be used. As the state of the catalyst element in the solution, there are a case where it is dissolved as a compound and a case where it is dissolved as a single element.

When a Ni element is used as a catalyst element, it is usually introduced into a solution as a Ni compound. Representative Ni compounds include nickel bromide, nickel acetate, nickel oxalate, nickel carbonate, nickel chloride,
Examples include nickel iodide, nickel nitrate, nickel sulfate, nickel formate, nickel acetyl acetate, 2-ethylhexane nickel, nickel 4-cyclohexylbutyrate, nickel oxide, nickel hydroxide and the like. In the case of dissolving in a solution not as a Ni compound but as a Ni element alone, a method of dissolving in an acid is preferable. The Ni element in the solution is usually preferably in a completely dissolved state, but may be in an emulsion state in which the Ni element is uniformly dispersed.

As a catalyst element other than the Ni element, F
e, Co, Ru, Rh, Pd, Os, Ir, Pt, C
Metals such as u and Au are also applicable. As a method of applying the catalyst element, a method of dissolving a single catalyst element in a solution is generally used, but a plurality of types of catalyst elements may be mixed and used. These catalyst elements may be dissolved in a solution in the form of a compound as in the case of the Ni element, or there is no particular problem even if the catalyst element alone is dissolved in acids. Representative compounds of the above catalyst elements are described below. In the case of Fe element: ferrous bromide, ferric bromide, ferric acetate
Iron, ferrous chloride, ferric fluoride, ferric nitrate, ferrous phosphate, ferric phosphate, etc. For Co element: cobalt bromide, cobalt acetate, cobalt chloride, cobalt fluoride, nitric acid , Cobalt, etc. Ru element: ruthenium chloride, etc. Rh element: rhodium chloride, etc. Pd element: palladium chloride, etc. Os element: osmium chloride, etc. Ir element: 3 iridium chloride, iridium chloride, etc. Pt element In the case of: cupric platinum chloride, etc. In the case of Cu element: cupric acetate, cupric chloride, cupric nitrate, etc. In the case of Au element: gold trichloride, gold chloride, sodium tetrachloroaurate, etc.

[Method for Producing Crystalline Semiconductor Film] Next, the above-mentioned respective addition treatments (roll treatment, dipping treatment, spray treatment or shower treatment treatment) are added to the step of adding a catalytic element for promoting crystallization. In the case where ()) is applied, a method for manufacturing a crystalline semiconductor film containing silicon will be described. Note that there are a so-called vertical growth method and a lateral growth method in a method for manufacturing a crystalline semiconductor film containing silicon. Therefore, each of the growth methods will be described.

(1) In the case of the vertical growth method In the vertical growth method in which a catalytic element is uniformly added to the entire surface of an amorphous semiconductor film containing silicon and then thermally crystallized, each of the above-described addition treatment methods (roll type) The following describes the case where a processing method, a dip type processing method, a spray type or a shower type processing method) is applied. The vertical growth method is a crystal growth method in which a catalyst element is added uniformly over the entire surface of an amorphous semiconductor film containing silicon and then thermally crystallized. There is a feature that crystal growth proceeds in a direction (a direction perpendicular to the substrate surface). For this reason, in this specification, it is called a vertical growth method. First step: An amorphous semiconductor film containing silicon is deposited on an insulating substrate such as a glass substrate. Second step: A catalytic element for promoting crystallization is applied to the entire surface of the amorphous semiconductor film by a roll processing method (dip processing method,
(Spray or shower treatment).
When a viscous catalyst element solution is added in the roll treatment method, an additional washing step is required to remove organic compounds. Third step: a crystalline semiconductor film containing silicon is formed by heat-treating the amorphous semiconductor film (vertical growth method).

When the catalyst element is added by the roll-type processing method, the catalyst element is added not to the entire surface of the substrate but to a partial region of the substrate by applying a printing roll provided with a relief. A method of selectively crystallizing only the amorphous semiconductor film containing silicon corresponding to the region by the vertical growth method is considered. In this case, the crystalline semiconductor film is formed by the vertical growth method only in the region where the catalytic element is added.
In the boundary region between the added region and the non-added region, a crystallization region is formed by the lateral growth method due to the lateral diffusion of the catalytic element from the added region. Regions need to be excluded. Hereinafter, main steps for manufacturing a crystalline semiconductor film containing silicon will be described.

First step: An amorphous semiconductor film containing silicon is deposited on an insulating substrate such as a glass substrate. Second step: A catalytic element for promoting crystallization is added to a partial region of the amorphous semiconductor film by a roll processing method. Note that a printing roll provided with a letterpress portion is used as a printing roll in the roll processing method. Third step: by heat-treating the amorphous semiconductor film, a crystalline semiconductor film containing silicon (vertical growth method) is formed in a region to which a catalytic element is added, and a polycrystalline semiconductor film containing ordinary silicon is formed in a non-added region. A crystalline semiconductor film is formed. (2) In the case of the lateral growth method In the lateral growth method in which a catalytic element is selectively added to a partial region of an amorphous semiconductor film containing silicon and then thermally crystallized, each of the above-described addition processing methods (roll The following describes the case in which a formula treatment method, a dip treatment method, a spray treatment or a shower treatment method) is applied. The lateral growth method is a crystal growth method in which a catalyst element is added to a partial region of an amorphous semiconductor film containing silicon through an opening of a mask insulating film and then thermally crystallized. Is characterized in that crystallization proceeds in a lateral direction (a direction parallel to the substrate surface) by thermally diffusing into a peripheral region with the base point as a base point. For this reason, in this specification, it is called a lateral growth method. First step: An amorphous semiconductor film containing silicon is deposited on an insulating substrate such as a glass substrate. Second step: depositing a mask insulating film on the amorphous semiconductor film and forming an opening region in the mask insulating film. Third step: An opening is formed in the amorphous semiconductor film by adding a catalyst element for promoting crystallization to the mask insulating film by a roll processing method (dip processing method, spray processing or shower processing method). The catalytic element is selectively introduced through the region. In the roll-type processing method, it is more preferable to use a printing roll provided with a relief in order to reduce the amount of the catalyst element solution used. In addition, when a viscous catalyst element solution is added in the roll-type treatment method, an additional washing step is required to remove organic compounds. Fourth step: a crystalline semiconductor film containing silicon is formed by heat-treating the amorphous semiconductor film (lateral growth method).

In the present specification, since the technical term of a crystalline semiconductor film is used instead of a polycrystalline semiconductor film,
The crystalline semiconductor film will be described. The reason that the term “crystalline” is used instead of polycrystalline is because, as compared with a normal polycrystalline semiconductor film, the crystal grains are oriented in substantially the same direction, and have characteristics such as high field-effect mobility. This is to distinguish it from a normal polycrystalline semiconductor film.

[0040]

[Embodiment 1] In this embodiment,
A method for forming a crystalline silicon film by a vertical growth method in which a catalytic element is added to the entire surface of the amorphous silicon film will be specifically described with reference to FIGS. Here, in the step of adding the catalyst element solution, application examples of a roll type processing method, a single-wafer type dipping type processing method, and a spray type processing method will be described with reference to FIG.
FIGS. 1A to 1F are cross-sectional views of a substrate showing a step of forming a crystalline silicon film by a vertical growth method.
FIG. 2C specifically illustrates each processing method (roll processing method, single-wafer dipping processing method, and spray processing method) in the step of adding the catalyst element solution shown in FIG. 1D. It is the schematic diagram (side view) shown.

First, low pressure CVD or plasma CVD
The amorphous silicon film 10 on the glass substrate 101
2 is deposited to a thickness of 10 to 150 nm. In this embodiment, an amorphous silicon film 102 of 100 nm is deposited by a plasma CVD method. At the time of deposition, the surface of the amorphous silicon film 102 is contaminated with an extremely thin natural oxide film 103 due to the influence of oxygen in the air mixed into the processing atmosphere (see FIG. 1A).

Next, the substrate is washed with diluted hydrofluoric acid for a predetermined time by a single wafer processing method. By the treatment, the natural oxide film 103 contaminating the surface of the amorphous silicon film 102 is removed, and the substrate is dried with an air knife or the like after performing a water washing treatment (see FIG. 1B). ).

Next, the amorphous silicon film 102 is oxidized by performing ozone water treatment for a predetermined time by a single wafer processing method. By the oxidation treatment, the amorphous silicon film 10
Then, a clean ultra-thin silicon oxide film 104 is formed on the substrate 2, and the substrate is subsequently dried with an air knife or the like. The ultra-thin silicon oxide film 104 may be formed by treating with a hydrogen peroxide solution, or may be formed by generating ozone by ultraviolet (UV) irradiation in an oxygen atmosphere. Absent. The formation of the ultra-thin silicon oxide film 104 has an effect of improving wettability to the amorphous silicon film 102 and uniformly attaching the Ni element when a Ni aqueous solution as a catalyst element solution is added later. (See FIG. 1C).

Next, a Ni aqueous solution, which is a catalytic element solution having a crystallization promoting effect, is added to the entire surface of the amorphous silicon film 102 (strictly, an extremely thin silicon oxide film 104). In this embodiment, a nickel acetate salt, which is a Ni compound, is dissolved in pure water, and a Ni aqueous solution adjusted to a concentration of 10 ppm in terms of weight is added by the roll treatment method shown in FIG. D), FIG. 2 (A)).

As shown in this figure, the roll-type processing method uses the anilox roll 20 from the dispensing unit 201.
The Ni aqueous solution dropped onto the printing roll 204 is uniformly adhered by the doctor blade 203, and the Ni aqueous solution is evenly applied onto the printing roll 204 having no letterpress portion. By bringing the substrate into contact with a substrate (consisting of a glass substrate 101, an amorphous silicon film 102, and an extremely thin silicon oxide film 104) fixed on a substrate 205, a Ni aqueous solution 206 is added onto the substrate, and then the substrate The processing is performed in such a procedure that the substrate is transported to an adjacent drying unit (not shown) by a transport unit (not shown) and the substrate is dried by a drying means such as an air knife and a hot plate. By this processing,
A uniform Ni-containing layer 105 is formed on the surface of the ultra-thin silicon oxide film 104 formed on the amorphous silicon film 102. In this case, since an ultra-low viscosity Ni aqueous solution is used as the catalyst element solution, the anilox roll 2 is used.
A water-absorbing sheet (not shown) capable of absorbing a Ni aqueous solution is attached to the surfaces of the print roll 02 and the printing roll 204.
Further, the print roll 204 having no letterpress portion was used (see FIGS. 1D, 1E, and 2A).

In addition, in the step of adding the Ni aqueous solution as the catalyst element solution, the Ni aqueous solution can be added by a single-wafer dip processing method shown in FIG. 2B.
In this case, the Ni aqueous solution 2 filled in the processing tank 207
08, the substrate (consisting of the glass substrate 101, the amorphous silicon film 102, and the ultra-thin silicon oxide film 104) held by the substrate holding arm 209 is immersed for a predetermined time. The processing is performed in such a procedure that the substrate is lifted, transported to an adjacent drying unit (not shown), and the substrate is dried by a drying means such as an air knife or a hot plate. With this process, a uniform Ni-containing layer 105 is formed on the surface of the ultra-thin silicon oxide film 104 formed on the amorphous silicon film 102. The dip type processing method is configured so that the substrate surface is oriented in a direction parallel to the gravity. (See FIG. 1D, FIG. 1E, and FIG. 2B).

In addition, in the step of adding the Ni aqueous solution as the catalyst element solution, the Ni aqueous solution can be added by a spray treatment method shown in FIG. 2 (C). In this case, a spray nozzle 211 disposed directly above a substrate (comprised of a glass substrate 101, an amorphous silicon film 102, and an ultra-thin silicon oxide film 104) fixed to a processing stage 210 forms a mist-like structure. Is sprayed for a predetermined period of time and then transferred to an adjacent drying unit (not shown) by a substrate transfer unit (not shown), and the substrate is dried by an air knife (hot plate is inappropriate). Processing is performed in a procedure. By this processing,
A uniform Ni-containing layer 105 is formed on the surface of the ultra-thin silicon oxide film 104 formed on the amorphous silicon film 102. The spray processing method is configured so that the substrate surface is oriented in a direction parallel to the gravity. However, in order to prevent the substrate from bending due to gravity and to save space in the apparatus, the substrate surface is perpendicular to the gravity. You may be comprised so that it may turn. Also,
In this embodiment, the spray processing method is described, but a similar processing method can be a shower processing method. In this case, a Ni aqueous solution is supplied from a shower nozzle instead of the spray nozzle 211. (Figure 1
(D), FIG. 1 (E) and FIG. 2 (C)).

As described above, in the step of adding the Ni aqueous solution, which is a catalyst element solution, any of a roll type processing method, a single-wafer type dipping type processing method, and a spray type (or shower type) processing method is used. Even if the method is used, the amorphous silicon film 10
It is possible to form a uniform Ni-containing layer 105, which is an adsorption layer of Ni element, on the surface of the ultra-thin silicon oxide film 104 formed on the substrate 2. Also, in any of the processing methods, unlike the spin processing method, the Ni aqueous solution is not deposited on the substrate, which is effective in reducing the usage amount of the Ni aqueous solution. Further, since it is not necessary to provide a substrate spin means including a spin motor and a spin speed adjusting mechanism, it is considered that the apparatus price can be kept within a certain range even if the size of the substrate increases.

The above-described step of removing the natural oxide film 103 → the step of oxidizing the amorphous silicon film 102 → the step of adding the catalyst element solution may be continuously performed by a dedicated continuous processing apparatus. In this case, in addition to reducing the usage of the Ni aqueous solution,
It is also advantageous in terms of productivity.

Next, the amorphous silicon film 102 is heat-treated in a nitrogen atmosphere using a dedicated heat treatment furnace. The heat treatment is performed by the action of a catalytic element that promotes crystallization.
Crystallization can be achieved by performing heat treatment in the temperature range of 0 to 750 ° C. However, if the heat treatment temperature is low, the treatment time must be extended, and there is a general property that production efficiency is reduced. In addition, heat treatment at 600 ° C. or higher causes a problem of heat resistance of a glass substrate used as a substrate. Therefore, when a glass substrate is used, it is appropriate that the temperature of the heat treatment step is in the range of 450 to 600 ° C.
In addition, in the actual heat treatment, suitable heat treatment conditions are different depending on the method of depositing the amorphous silicon film 102. For example, when deposition is performed by a low pressure CVD method, a heat treatment of about 600 ° C. for about 12 hours is preferable. It has been found that a heat treatment at about 550 ° C. for about 4 hours is sufficient for the deposition by the plasma CVD method. In this embodiment, since the amorphous silicon film 102 having a thickness of 100 nm is deposited by the plasma CVD method, the crystalline silicon film 106 is formed by performing a heat treatment at 550 ° C. for 4 hours ( FIG. 1 (F)).

[Embodiment 2] In this embodiment, a roll-type processing method equipped with a printing roll provided with a letterpress portion is applied to the step of adding a catalyst element, and only a partial region of the amorphous silicon film is lengthened. A specific example in which a crystalline silicon film is formed by a growth method and a normal polycrystalline silicon film is formed in other regions will be described with reference to FIG. 3A to 3C are a cross-sectional view and a plan view of a substrate illustrating a step of manufacturing a crystalline silicon film.
Incidentally, the step of adding the catalyst element solution by the roll-type treatment method,
See FIG. 2A of the first embodiment.

Deposition of the amorphous silicon film 302 on the glass substrate 301 (depositing a film thickness of 100 nm by plasma CVD), removal of the natural oxide film (not shown), and The process of forming the ultra-thin silicon oxide film 303 is basically the same as that of the first embodiment, and a detailed description thereof will be omitted. By the following roll processing method,
The step of adding the catalyst element solution will be described.

In a specific region of the amorphous silicon film 302 (strictly, an extremely thin silicon oxide film 303), a Ni aqueous solution 3 as a catalyst element solution having a crystallization promoting action is selectively applied.
04 (concentration: 10 ppm in terms of weight) is added by the roll treatment method shown in FIG. In the roll-type processing method, a print roll 204 provided with a relief (not shown) was used. This is because the use of the printing roll 204 provided with a letterpress portion (not shown) allows the Ni aqueous solution to be selectively added to a specific region on the substrate. The right view of FIG. 3A is a plan view of the substrate showing the step of adding the Ni aqueous solution, and shows the Ni aqueous solution added region 305 and the non-added regions 306 and 307. 3A is a cross-sectional view of the substrate taken along a dashed line in a plan view of the substrate. Addition area 30
5), an Ni aqueous solution 304 is selectively added (see FIGS. 3A and 2A).

Next, the substrate is heated on a hot plate (7
0 to 100 ° C.) to obtain an aqueous Ni solution 304
Is dried. When the Ni aqueous solution 304 has dried,
The containing layer 308 is formed. In the drying step, a hot plate method is adopted instead of the air knife method. In the case of the air knife method,
This is because the Ni aqueous solution 304 is blown off by air blowing, so that the Ni aqueous solution 304 is re-adhered to the non-added regions 306 and 307, which may cause the adverse effect of adding the Ni element (see FIG. 3B). .

Next, the amorphous silicon film 302 is heat-treated in a nitrogen atmosphere using a dedicated heat treatment furnace. In this embodiment, since the amorphous silicon film 302 having a thickness of 100 nm is deposited by the plasma CVD method as in the first embodiment, the heat treatment is performed at 550 ° C. for 4 hours. By the heat treatment, a crystalline silicon film 309 is formed in the Ni element added region 305 by the vertical growth method. On the other hand, in the non-added regions 306 and 307, since the Ni element does not basically exist, it is considered that crystallization hardly progresses. Note that, in the actual manufacturing process, in order to improve the crystallinity of the crystalline silicon film 309 in the added region 305, the polycrystalline amorphous silicon film 310 in the non-added regions 306 and 307 is further polycrystallized. Therefore, a laser irradiation step is added (see FIG. 3C).

As described above, the Ni aqueous solution can be selectively added to a specific region on the substrate by the roll processing method including the printing roll 204 provided with the relief portion. When this manufacturing method is applied to a manufacturing process of a liquid crystal display device, a process in which a Ni element is added only to a driver portion which is a peripheral circuit without adding a Ni element to a pixel portion is assumed. The reason is that when a TFT is manufactured using a crystalline silicon film obtained by using a Ni element as a catalytic element, the TFT has good field-effect mobility, but has a disadvantage that the off-current increases. In this case, good field-effect mobility is not required, and a lower off-state current is preferable. Also, in one driver TFT, the field effect mobility is a more important TFT characteristic than the off current characteristic.

[Embodiment 3] In this embodiment, a method for forming a crystalline silicon film by a lateral growth method using a catalytic element will be specifically described with reference to FIG. 4 (A) to 4
(F) is a sectional view showing a step of manufacturing a crystalline silicon film by a lateral growth method. The step of adding the catalyst element solution shown in FIG. 4 (D) is basically the same as each processing method shown in FIG. .

First, low pressure CVD or plasma CVD
The amorphous silicon film 40 on the glass substrate 401
2 is deposited to a thickness of 10 to 150 nm. In this embodiment, an amorphous silicon film 402 having a thickness of 100 nm is deposited by a plasma CVD method. At the time of deposition, the surface of the amorphous silicon film 402 is contaminated with an extremely thin natural oxide film 403 due to the influence of oxygen in the air mixed in the processing atmosphere (see FIG. 4A).

Next, a film thickness of 70
Mask insulating film 4 made of a silicon oxide film having a thickness of 200 nm
04 is deposited. In this embodiment, a mask insulating film 404 having a thickness of 120 nm is deposited by the plasma CVD method.
Then, an opening region 405 is formed in a partial region of the mask insulating film 404 by a normal photolithography process and an etching process (wet etching is generally performed). The opening region 405 is a region for selectively introducing a catalytic element (Ni element is applied in this embodiment), and the bottom of the opening region 405 is in a state where the amorphous silicon film 402 is exposed (FIG. 4). (B)).

Next, by oxidizing the substrate, an extremely thin silicon oxide film 40 of about 3 to 10 nm is formed on the exposed area of the amorphous silicon
6 is formed. In the present embodiment, the film is formed by an ozone water treatment for a predetermined time. However, the film may be formed by a treatment with a hydrogen peroxide solution, or may be formed by ultraviolet (UV) irradiation in an oxygen atmosphere. Ozone may be generated to form a film. The formation of the ultra-thin silicon oxide film 406 in the opening region 405 improves the wettability to the amorphous silicon film 402 when a Ni aqueous solution as a catalyst element solution is added later, and (See FIG. 4C).

Next, to the mask insulating film 404 having the opening region 405, a Ni aqueous solution as a catalyst element solution having a crystallization promoting action is added. Specifically, nickel acetate, which is a Ni compound, is dissolved in pure water, and the weight is reduced to 10 p.
The Ni aqueous solution adjusted to a pm concentration is added by each of the addition methods shown in FIG. 2 (roll processing method, single-wafer dipping processing method, spray processing or shower processing method). In any treatment method, like the spin treatment method,
Since the Ni aqueous solution is not deposited on the substrate, it is effective to reduce the amount of the Ni aqueous solution used. Further, since it is not necessary to provide a substrate spin means including a spin motor and a spin speed adjusting mechanism, it is considered that the apparatus price can be kept within a certain range even if the size of the substrate increases.
By the way, in the case of the lateral growth method of the present embodiment, the opening region 40
5, the Ni element is selectively introduced through
The Ni aqueous solution 407 may be selectively added only to the opening region 405. In this case, the roll-type processing method including the printing roll having the relief portion described in the second embodiment is applied, and the usage amount of the catalyst element solution can be further reduced (FIG. 4D, FIG. A) (B) (C).

The Ni-containing layer 408 is formed by adding by each of the addition processing methods (roll type processing method, single-wafer type dipping type processing method, spray type or shower type processing method) and then drying with an air knife or the like. Film. FIG. 4 (E)
N is selectively applied only to the opening region 405 by the roll processing method.
FIG. 4 shows a Ni-containing layer 408 when an i aqueous solution 407 is added (see FIG. 4E).

The process of oxidizing the amorphous silicon film 402 in the opening region 405 and the process of adding the Ni aqueous solution may be performed continuously. In this case, it is advantageous in terms of productivity if a processing device equipped with each processing unit and capable of continuous processing is applied.

Next, the amorphous silicon film 402 is heat-treated in a nitrogen atmosphere using a dedicated heat treatment furnace. The heat treatment is performed by the action of a catalytic element that promotes crystallization.
Crystallization can be achieved by performing heat treatment in the temperature range of 0 to 750 ° C. However, if the heat treatment temperature is low, the treatment time must be extended, and there is a general property that production efficiency is reduced. In addition, heat treatment at 600 ° C. or higher causes a problem of heat resistance of a glass substrate used as a substrate. Therefore, when a glass substrate is used, it is appropriate that the temperature of the heat treatment step is in the range of 450 to 600 ° C.
In this embodiment, the temperature is 570 ° C.-14
By performing the heat treatment for a long time, the amorphous silicon film 40
2 was crystallized, and a crystalline silicon film 409 was formed. At this time, since the Ni element is selectively introduced through the opening region 405, the Ni element diffuses into the peripheral region with the opening region 405 as a base point, and the crystallization of the amorphous silicon film 402 is performed during the diffusion process. Proceeds in a lateral direction (a direction parallel to the substrate surface) (see FIG. 4F).

[0065]

[Embodiment 1] This embodiment is an example in which a method for manufacturing a crystalline silicon film by a vertical growth method using a catalytic element is applied to a manufacturing process of a liquid crystal display device. 1
0 is specifically described. 5 to 9 are cross-sectional views showing a manufacturing process of the liquid crystal display device. FIG. 10 shows a pretreatment process of adding a catalytic element solution shown in FIG. Oxidation process of porous silicon film) → N
It is the schematic (plan view) which shows the example of the manufacturing apparatus which can perform the addition process of i aqueous solution-> dehydrogenation process continuously. FIG. 2 is a schematic view (side view) specifically showing each processing method (roll processing method, single-wafer dipping processing method, spray processing method) in the step of adding a catalyst element solution. .

First, the plasma C is placed on the glass substrate 501.
By a VD method, a first-layer silicon oxynitride film 502a having a different composition ratio is deposited to a thickness of 50 nm and a second-layer silicon oxynitride film 502b is deposited to a thickness of 100 nm to form a base film 502. The glass substrate 501 used here
Examples thereof include quartz glass, barium borosilicate glass, and aluminoborosilicate glass. Next, a plasma CV is formed on the base film 502 (502a and 502b).
An amorphous silicon film 503a is deposited to a thickness of 55 nm by the D method. At the time of deposition, the surface of the amorphous silicon film 503a is contaminated with an extremely thin natural oxide film (not shown) due to the influence of oxygen in the air mixed in the processing atmosphere.
In this embodiment, the amorphous silicon film 503a is deposited by the plasma CVD method, but may be deposited by the low pressure CVD method (see FIG. 5A).

In depositing the amorphous silicon film 503a, there is a possibility that carbon, oxygen and nitrogen existing in the air are mixed. It has been empirically known that the incorporation of these impurity gases causes deterioration of the TFT characteristics finally obtained. Therefore, the inventors of the present invention believe that the incorporation of the impurity gas acts as a factor inhibiting crystallization. Is aware. Therefore, it is preferable to thoroughly remove the impurity gas. Specifically, the concentration range is 5 × 10 ¹⁷ atoms / cm ³ or less for carbon and nitrogen, and 1 × 10 ¹⁷ atoms / cm ³ or less for oxygen. ^It is preferable that the concentration be ¹⁸ atoms / cm ³ or less (see FIG. 5A).

Next, using a continuous processing apparatus shown in FIG. 10, a pretreatment step of adding a catalyst element solution (a step of diluting hydrofluoric acid of an amorphous silicon film → a step of oxidizing an amorphous silicon film)
→ Addition step of catalyst element solution (Ni aqueous solution) → Continuously perform dehydrogenation step. The specific processing is as follows. For the configuration of the continuous processing apparatus, see the following description (FIG. 5).
(A), FIG. 5 (B), FIG. 10).

First, the substrate is washed with diluted hydrofluoric acid for a predetermined time. By this treatment, a natural oxide film (not shown) contaminating the surface of the amorphous silicon film 503a is removed, followed by washing with water, and then drying the substrate.
After that, the amorphous silicon film 503a is oxidized by performing ozone water treatment for a predetermined time. By the oxidation treatment, a clean ultrathin silicon oxide film (not shown) is formed on the amorphous silicon film 503a, and the substrate is subsequently dried. Further, an extremely thin silicon oxide film (not shown) may be formed by processing with a hydrogen peroxide solution. still,
The formation of the ultra-thin silicon oxide film (not shown) improves the wettability to the amorphous silicon film 503a and uniformly attaches the Ni element when a Ni aqueous solution as a catalyst element solution is added later. (See FIG. 5A).

Next, Ni, which is a catalytic element solution having a crystallization promoting action, is formed on the entire surface of the amorphous silicon film 503a.
Add the aqueous solution. Specifically, a nickel acetate salt, which is a Ni compound, is dissolved in pure water, and a Ni aqueous solution adjusted to a concentration of 10 ppm in terms of weight is added to each of the addition treatment methods shown in FIG. (Dip treatment, spray treatment or shower treatment). In any of the processing methods, as in the spin processing method, N
Since the i aqueous solution is not liquid-filled, it is effective in reducing the usage amount of the Ni aqueous solution. In addition, since it is not necessary to provide a substrate spin unit including a spin motor and a spin speed adjusting mechanism, it is considered that the apparatus price can be kept within a certain range even if the size of the substrate increases (see FIG. A)
reference).

Next, in order to control the amount of hydrogen contained in the amorphous silicon film 503a to 5 atom% or less, the substrate is heat-treated at 450 ° C. for 1 hour in a nitrogen atmosphere. The dehydrogenation of the contained hydrogen is performed.
The processing up to this point is performed by the continuous processing apparatus shown in FIG. 10 (see FIGS. 5B and 10).

Next, after the above-described continuous processing step is completed, the amorphous silicon film 503a is crystallized by performing a heat treatment in an electric furnace at 550 ° C. for 4 hours. The film 503b is formed. afterwards,
Laser irradiation is performed on the crystalline silicon film 503b in order to improve the crystallinity of the obtained crystalline silicon film 503b. By the laser irradiation, the crystalline silicon film 50
The crystallinity of 3b is greatly improved. In this embodiment, a pulse oscillation type KrF excimer laser (wavelength: 248 nm)
Has been applied. This excimer laser not only improves the crystallinity of the crystalline silicon film 503b, but also has the effect of improving the gettering efficiency by the gettering source because the Ni element is in a state where it is very easy to move (FIG. 5).
(B)).

Next, the crystalline silicon film 503 is formed by ordinary photolithography and dry etching.
By patterning b, semiconductor layers 504 to 508 to be the channel region and the source / drain region of the TFT are formed. After the formation of the semiconductor layers 504 to 508, the V
Impurity element (boron or phosphorus) to control th
(See FIG. 6A).

Next, a gate insulating film 509 made of a 100-nm-thick silicon oxynitride film is deposited by a plasma CVD method so as to cover the semiconductor layers 504 to 508.
Note that when depositing the gate insulating film 509, the semiconductor layers 504 to 504 are formed.
Since the surface of 508 is contaminated with a natural oxide film (not shown), it is removed by dilute hydrofluoric acid treatment. After that, a conductive film serving as a gate electrode material is deposited over the gate insulating film 509 by a sputtering method or a CVD method. As the gate electrode material applied here, a heat-resistant material that can withstand a heat treatment temperature for gettering (about 550 to 650 ° C.) that also serves as activation of an impurity element later is preferable. Examples of the heat resistant material include Ta (tantalum), Mo (molybdenum),
Ti (titanium), W (tungsten), Cr (chromium)
And a metal silicide which is a compound of silicon and a high melting point metal, and polycrystalline silicon having n-type or p-type conductivity. In this embodiment,
A gate electrode film 510 made of a W film having a thickness of 400 nm was deposited by a sputtering method (see FIG. 6B).

On the substrate having the above structure, gate electrodes 517 to 520, a storage capacitor electrode 521, and an electrode 522 functioning as a source wiring are formed by performing a photolithography process for forming a gate electrode and a dry etching process. After dry etching, the gate electrodes 517 to 52
The resist patterns 511 to 514, which are dry etching masks, are left on the substrate 0, and the storage capacitor electrodes 5 are similarly formed.
A resist pattern 515 is left on the resist pattern 515 and a resist pattern 516 is left on the electrode 522 functioning as a source wiring. Note that with the dry etching, the gate insulating film 509 made of the underlying silicon oxynitride film is deformed into a shape of the gate insulating film 523 due to the film thickness reduction (FIG. 7).
(A)).

Next, in a state where the resist patterns 511 to 516 are left, the gate electrodes 517 to 520 and the storage capacitor electrode 521 are used as masks to form the first
The low-concentration ion implantation of the n-type impurity, which is the ion implantation process, is performed. The conditions for the ion implantation are as follows.
The treatment is performed using an element at an acceleration voltage of 60 to 100 keV and an ion implantation amount of 3 × 10 ^{12 to} 3 × 10 ¹³ ions / cm ² . By this first ion implantation process, low-concentration impurity regions (n-regions) 529 to 533 of n-type impurities are formed in the semiconductor layers 504 to 508 corresponding to the outside of the gate electrodes 517 to 520 and the storage capacitor electrode 521. Is done. At the same time, immediately below the gate electrodes 517 to 520, T
Substantially intrinsic region 52 functioning as a channel of FT
4 to 527 are formed. In addition, the storage capacitor electrode 521
Since the region is not a TFT formation region but a storage capacitance 605 formation region, an intrinsic region 528 functioning as one side of a capacitance formation electrode is formed in the semiconductor layer 508 directly below the semiconductor layer 508 (FIG. 7A )reference).

Since the technical term of ion implantation is used in the first ion implantation process, the definition of ion implantation will be clarified. In general, when implanting impurity ions separated by mass, the term is referred to as ion implantation, and when implanting impurity ions not separated by mass, a technical term of ion doping is used. Both the ion implantation and the ion doping are the same in that the impurity ions are electrically accelerated and implanted, and in the present specification, there is not much sense in distinguishing between the two, regardless of the presence or absence of mass separation. The technique of electrically accelerating and implanting impurity ions is called ion implantation in a broad sense.

Next, the resist pattern 511 to 516 used as a dry etching mask is removed by washing the substrate with a dedicated stripper. After the removal, the n-channel TFTs 601 and 60 in the drive circuit 606 are removed.
3 and the pixel TFT 604 in the pixel area 607 are LDD
In order to form a structure, the gate electrodes 517,
A resist pattern 53 for forming an n + region serving as a mask for the second ion implantation process so as to cover 519 to 520
4 to 536 are formed. Then, high-concentration ion implantation of n-type impurities, which is a second ion implantation process, is performed. As the ion implantation conditions, an element P which is an n-type impurity is used, the acceleration voltage is 60 to 100 keV, and the ion implantation amount is 1.7.
The treatment is performed under ion implantation conditions of × 10 ¹⁵ ions / cm ² . By the ion implantation, the resist patterns 534 to 5
Semiconductor layers 504, 506-5 corresponding to the outer region
In 07, a high-concentration impurity region (n + region) 53 of an n-type impurity is provided.
7, 539 to 540 are formed. With the formation of the high-concentration impurity regions (n + regions) 537, 539 to 540,
Low-concentration impurity regions (n-regions) 529, 5 already formed
31 to 532 are high-concentration impurity regions (n + regions) 53
7, 539 to 540 and a low concentration impurity region (n-region) 5
42 to 544, and a source region and a drain region having an LDD structure are formed (see FIG. 7B).

At this time, in the region other than the LDD structure forming region, the region of the p-channel TFT 602 of the driving circuit 606 and the region of the storage capacitor 605 of the pixel region 607,
Since ions are respectively implanted using the gate electrode 518 and the storage capacitor electrode 521 as masks, a high-concentration impurity region (n + region) 538 of an n-type impurity is formed in the semiconductor layer 505 corresponding to the outer region of the gate electrode 518. Capacitor electrode 52
A high-concentration impurity region (n + region) 541 of an n-type impurity is also formed in the semiconductor layer 508 corresponding to the outer region of the first region (see FIG. 7B).

Next, the semiconductor layer 50 corresponding to the p-channel type TFT 602 is subjected to a normal photolithography process.
Pattern 545-547 having an opening in the region of semiconductor layer 508 corresponding to region 5 and storage capacitor 605
To form Then, the resist patterns 545-5
Using the ion implantation apparatus 47 as a mask, a high-concentration ion implantation of p-type impurities, which is a third ion implantation process, is performed. By the ion implantation process, the p-channel TFT 6
02 is formed on the semiconductor layer 505 corresponding to the gate electrode 518.
Is used as a mask to ion-implant a B element as a p-type impurity. As a result, a high-concentration impurity region (p + region) 548 having a p-type conductivity is formed in the semiconductor layer 505 corresponding to the region outside the gate electrode 518. The P element, which is an n-type impurity, has already been ion-implanted into the high-concentration impurity region (p + region) 548, but the ion implantation amount of the B element is set to 2.5 × 10 ¹⁵ atoms / cm ² . High concentration impurity region (p + region) 5 having p-type conductivity and functioning as a source / drain region because ions are implanted at a high concentration.
48 are formed. Also in the formation region of the storage capacitor 605, a high-concentration impurity region (p + region) 549 having a p-type conductivity is formed in the semiconductor layer 508 corresponding to the region outside the storage capacitor electrode 521. (FIG. 8 (A)
reference).

Next, the resist patterns 545 to 54
After removing 7, a first interlayer insulating film 550 made of a 150-nm-thick silicon oxynitride film is deposited by a plasma CVD method. Then, in order to thermally activate the impurity elements (P element and B element) injected into the semiconductor layers 504 to 508,
In an electric furnace, heat treatment is performed at 600 ° C. for 12 hours.
The heat treatment is performed for thermal activation of the impurity element, and is present in the substantially intrinsic regions 524 to 527 functioning as channel regions and the intrinsic region 528 functioning as one side of the capacitor forming electrode. It also has the purpose of gettering the Ni element by the impurity element. still,
The thermal activation treatment may be performed before the deposition of the first interlayer insulating film 550. However, when the heat resistance of a wiring material such as a gate electrode is weak, it is better to perform the thermal activation treatment after the deposition of the first interlayer insulating film 550. preferable. Thereafter, in order to terminate dangling bonds in the semiconductor layers 504 to 508, hydrogenation treatment is performed at 410 ° C. for 1 hour in a nitrogen atmosphere containing 3% of hydrogen (FIG. 8B).
reference).

Next, a second interlayer insulating film 551 made of an acrylic resin film having a thickness of 1.6 μm is formed on the first interlayer insulating film 550. Thereafter, a contact hole is formed by a normal photolithography process and a dry etching process so as to penetrate the second interlayer insulating film 551, the first interlayer insulating film 550, and the gate insulating film 523 as a lower layer film. . At this time, the contact hole is formed so as to be connected to the electrode 522 functioning as a source wiring and the high-concentration impurity regions 537, 539 to 540, and 548 to 549 (see FIG. 9A).

Next, conductive metal wirings 552 to 557 are formed so as to be electrically connected to the high-concentration impurity regions 537, 539, and 548 of the driver circuit 606. Further, the connection electrodes 558 and 560 to 561 in the pixel region 607 and the gate wiring 559 are formed using the same conductive material. In this embodiment,
Metal wirings 552-557, connection electrodes 558, 560-5
61 and the gate wiring 559 as a constituent material.
A laminated film of a Ti film having a thickness of 500 nm and an Al—Ti alloy film having a thickness of 500 nm is applied. The connection electrode 558 is formed so as to electrically connect the impurity region 540 and the electrode 522 functioning as a source wiring. Connection electrode 56
0 is formed so as to be electrically connected to the impurity region 540 of the pixel TFT 604, and the connection electrode 561 is formed so as to be electrically connected to the impurity region 549 of the storage capacitor 605. The gate wiring 559 is a pixel TFT.
604 are formed so as to electrically connect the plurality of gate electrodes 520. Then, the I-layer having a thickness of 80 to 120 nm is formed.
After depositing a transparent conductive film such as TO (Indium-Ti-Oxide), by photolithography and etching,
The pixel electrode 562 is formed. The pixel electrode 562 is electrically connected to the impurity region 540 which is a source / drain region of the pixel TFT 604 via the connection electrode 560, and is also electrically connected to the impurity region 549 of the storage capacitor 605 via the connection electrode 561. (Fig. 9
(B)).

Hereafter, the configuration of the continuous processing apparatus will be described with reference to FIGS. FIG. 10 is a schematic view (plan view) of a manufacturing apparatus capable of continuous processing of the above steps.
The manufacturing apparatus includes a loader-side carrier 702 capable of storing a plurality of processing substrates 701 (usually, storing about 20 substrates).
And a plurality of processing units 703 to 7 for processing the substrate
09, 712, buffers 710-711 for temporarily storing the substrate being processed and transferred to an adjacent unit, and an unloader-side carrier 7 for storing the processed substrate 714.
15 and a substrate transport unit (not shown) for transporting the substrate, and the processing substrate 701 stored in the loader-side carrier 702 is moved by the substrate transport unit (not shown) by an arrow in the figure. The sheets are sequentially conveyed one by one in the direction indicated by (→) and processed by the processing units 703 to 709 and 712. The processing unit includes an oxide film removing unit 703 for removing a natural oxide film (not shown) on the surface of the amorphous silicon film 503a;
A washing unit 704 for washing the surface of the substrate after removing the natural oxide film, a drying unit 705 for drying the surface of the substrate after washing, and an oxidation unit 706 for oxidizing the surface of the amorphous silicon film 503a. A drying unit 707 for drying the substrate after the oxidation treatment, and an amorphous silicon film 5
03a (strictly, an ultra-thin silicon oxide film: not shown), an addition unit 708 for adding a Ni aqueous solution as a catalyst element solution, and a drying unit for drying the substrate after the Ni aqueous solution is added. It comprises a drying unit 709 and a dehydrogenation unit 712 for dehydrogenating hydrogen contained in the amorphous silicon film 503a (see FIG. 10).

First, the processing unit applied to the pretreatment step of adding the catalyst element solution (the step of diluting hydrofluoric acid of the amorphous silicon film → the step of oxidizing the amorphous silicon film) will be described in detail. The oxide film removing unit 703 is a processing unit for removing a natural oxide film (not shown) existing on the surface of the amorphous silicon film 503a, and a shower nozzle (not shown) installed above the processing unit. ) Is processed by supplying diluted hydrofluoric acid onto the substrate. The water washing unit 704 is a processing unit for washing dilute hydrofluoric acid adhering to the substrate surface with water, and pure water is supplied onto the substrate from a shower nozzle (not shown) provided above the unit. As a result, a washing process is performed. Drying unit 70
Reference numeral 5 denotes a processing unit for drying the substrate after washing with water, which uses an air knife method. Oxidation unit 706
Is a processing unit for oxidizing the surface of the amorphous silicon film 503a, and is configured to be oxidized with ozone water or hydrogen peroxide by a dipping method. The drying unit 707 is a processing unit for drying the substrate after being oxidized with ozone water or hydrogen peroxide water, and uses an air knife method (see FIG. 10).

Here, a processing unit applied to the step of adding the Ni aqueous solution will be described in detail. The addition unit 708 is a processing unit for adding a catalyst element solution to the surface of the amorphous silicon film 503a (strictly, an ultra-thin silicon oxide film: not shown). Dissolve in pure water, 10ppm by weight
The Ni aqueous solution adjusted to the concentration of is used as the catalyst element solution. The addition unit 708 is provided with any one of the addition mechanisms shown in FIG. 2 (roll processing method, single-wafer dipping processing method, spray processing method), and has a high efficiency. The structure is such that a Ni aqueous solution is added to the substrate. The drying unit 709 is Ni
An air knife system is used in a processing unit for drying the substrate after the addition of the aqueous solution (see FIGS. 2 and 10).

Here, the processing unit applied to the dehydrogenation step will be described in detail. The dehydrogenation unit 712 removes hydrogen contained in the amorphous silicon film 503a by 5 at.
In a processing unit that performs a dehydrogenation process in order to control the temperature to om% or less, the substrate is continuously transferred onto eight hot plates 713 controlled at 450 ° C. in a nitrogen atmosphere. Conventionally, the dehydrogenation process was performed at 450 ° C in an electric furnace.
Since the processing is performed under the processing condition of 1 hour, the eight hot plates 713 are also used in the dehydrogenation unit 712.
Accordingly, the processing is performed for about one hour in total per substrate (one-eighth processing time for each hot plate 713). In this embodiment, the hot plate 713
Although only the heat treatment is performed by using only the hot plate 7 in order to improve the heat treatment efficiency.
A configuration may be adopted in which a halogen lamp for lamp annealing is additionally provided above 13. In order to improve the heat treatment efficiency, a horizontal electric heating furnace provided with a substrate transfer unit may be provided, and the heat treatment may be performed by passing the substrates one by one through the electric heating furnace. In this case, it is considered that not only the dehydrogenation step but also the thermal crystallization step can be performed by appropriately adjusting the heat treatment temperature and the treatment time (see FIG. 10).

As shown in this embodiment, an n-channel TFT having an LDD structure and a p-channel TFT having a single drain structure are used.
In the manufacturing process of an active matrix type liquid crystal display device having an FT, a process for adding a catalyst element solution is performed by using a dedicated continuous processing device (a process of diluting hydrofluoric acid for an amorphous silicon film → amorphous silicon film). (A step of oxidizing a porous silicon film) → a step of adding a catalyst element solution (aqueous Ni solution) → a step of dehydrogenation. In the unit for adding the catalyst element solution of the continuous treatment apparatus, a treatment unit of a roll treatment method, a single-wafer treatment dipping treatment method, or a spray treatment method (also a shower treatment method) is installed. Unlike the conventional spin treatment method, the catalyst element solution is not filled on the substrate, which is effective for reducing the amount of the catalyst element solution used. Further, since it is not necessary to provide a substrate spin means including a spin motor and a spin speed adjusting mechanism in the addition unit, the apparatus is advantageous in terms of the apparatus cost even when the substrate is enlarged. By processing the above series of processing steps by the continuous processing apparatus, the following unique effects can be obtained.

Since the above series of processing steps can be continuously processed by the continuous processing apparatus, the tact time is shortened, which is effective for improving the productivity. Further, in the continuous processing apparatus, since the substrate is transported in one axis direction, the uniformity of the entire substrate can be obtained only by securing the uniformity in the lateral direction (the direction perpendicular to the transport direction). Can be easily secured, which is advantageous in terms of securing uniformity. Further, by adding a horizontal electric heating furnace to the continuous processing apparatus, continuous processing up to the thermal crystallization step of the amorphous silicon film can be performed continuously, so that it is possible to further improve productivity.

Embodiment 2 The present invention relates to a method for manufacturing a crystalline semiconductor film containing silicon, and can be applied to the manufacture of various active matrix type liquid crystal display devices. Therefore, the present invention is applicable to the manufacture of electronic devices incorporating active matrix type liquid crystal display devices in various fields. Here, specific examples of the electronic devices will be described with reference to FIGS. The electronic devices include a video camera, a digital camera, a projector (rear or front type), a head mounted display (goggle type display), a game machine, a personal computer, and a portable information terminal (mobile computer, mobile phone, electronic book, etc.). ) And the like.

FIG. 14A shows a personal computer including a main body 2001, a video input unit 2002, a display device 2003, and a keyboard 2004. The present invention can be applied to the display device 2003 and other circuits.

FIG. 14B shows a video camera, which includes a main body 2101, a display device 2102, an audio input unit 2103, an operation switch 2104, a battery 2105, and an image receiving unit 21.
06. The present invention can be applied to the display device 2102 and other circuits.

FIG. 14C shows a mobile computer (mobile computer), which comprises a main body 2201, a camera section 2202, an image receiving section 2203, operation switches 2204, and a display device 2205. Display device 220 of the present invention
5 and other circuits.

FIG. 14D shows a goggle type display, which comprises a main body 2301, a display device 2302, and an arm 23.
03. The present invention can be applied to the display device 2302 and other circuits.

FIG. 14E shows a player used for a recording medium (hereinafter, abbreviated as a recording medium) on which a program is recorded.
403, a recording medium 2404, and operation switches 2405. This device uses DVD and C as recording media.
D or the like is used and can be used for music appreciation, games, or the Internet. The present invention can be applied to the display device 2402 and other circuits.

FIG. 14F shows a mobile phone, which includes a display panel 2501, an operation panel 2502, and a connection portion 2503.
, Display unit 2504, audio output unit 2505, and operation keys 25
06, a power switch 2507, an audio input unit 2508, and an antenna 2509. The display panel 2501 and the operation panel 2502 are connected by a connection portion 2503. The surface of display panel 2501 on which display portion 2504 is installed and operation keys 2506 of operation panel 2502
Can be arbitrarily changed at the connection portion 2503. Display unit 250 of the present invention
4 can be applied.

FIG. 15A shows a front type projector, which comprises a light source optical system and display device 2601 and a screen 2602. The present invention can be applied to the display device 2601 and other circuits.

FIG. 15B shows a rear type projector, which comprises a main body 2701, a light source optical system, a display device 2702, mirrors 2703 to 2704, and a screen 2705. The present invention can be applied to the display device 2702 and other circuits.

FIG. 15C is a diagram showing an example of the structure of the light source optical system and display device 2601 of FIG. 15A and the light source optical system and display device 2702 of FIG. is there. Light source optical system and display device 2601, 2702
Are light source optical system 2801 and mirrors 2802, 2804-
2806, dichroic mirror 2803, and optical system 28
07, a display device 2808, a phase difference plate 2809, and a projection optical system 2810. The projection optical system 2810 includes a plurality of optical lenses provided with a projection lens. This configuration is called a three-plate type because three display devices 2808 are used. In the optical path indicated by the arrow in the figure, the practitioner may appropriately provide an optical lens and a film having a polarizing function, a film for adjusting a phase difference, an IR film, or the like.

FIG. 15D is a diagram showing an example of the structure of the light source optical system 2801 in FIG. 15C. In this embodiment, the light source optical system 2801 includes a reflector 2811, a light source 2812, and a lens array 281.
3, 2814, polarization conversion element 2815, and condenser lens 28
16. Note that the light source optical system shown in the figure is an example, and is not limited to this configuration. For example, the practitioner may appropriately provide an optical lens and a film having a polarizing function, a film for adjusting a phase difference, an IR film, or the like in the light source optical system.

FIG. 16A shows an example of a single-plate type. The light source optical system and the display device shown in FIG.
Light source optical system 2901, display device 2902, and projection optical system 2
903 and a phase difference plate 2904. Projection optical system 2
Reference numeral 903 includes a plurality of optical lenses including a projection lens. The light source optical system and the display device shown in FIG.
5A and the light source optical system and display device 26 shown in FIG.
01, 2702. Further, the light source optical system 290
1 may use the light source optical system shown in FIG. Note that the display device 2902 is provided with a color filter (not shown) to color the displayed image.

The light source optical system and the display device shown in FIG. 16B are an application example of FIG. 16A, and display is performed by using an RGB rotating color filter disk 2905 instead of providing a color filter. The video is colorized.
The light source optical system and the display device shown in FIG.
And the light source optical system and display device 2601, 2 shown in FIG.
702.

The light source optical system and the display device shown in FIG. 16C are called a color filterless single plate type. In this method, a microlens array 2915 is provided on a display device 2916, and a dichroic mirror (green) 2
A display image is colored using 912, a dichroic mirror (red) 2913, and a dichroic mirror (blue) 2914. The projection optical system 2917 includes a plurality of optical lenses provided with a projection lens. 15A and 15B can be applied to the light source optical system and the display devices 2601 and 702 shown in FIGS. As the light source optical system 2911, an optical system using a coupling lens and a collimator lens in addition to the light source may be used.

As described above, the method for manufacturing a crystalline semiconductor film of the present invention has an extremely wide range of application, and the present invention is applicable to the manufacture of electronic equipment incorporating active matrix type liquid crystal display devices in various fields. It is possible.

[0105]

The present invention relates to a method for manufacturing a crystalline semiconductor film containing silicon, and more particularly to a method for adding a catalyst element solution instead of a spin treatment method, and has the following effects. In the case of the roll processing method, the single-wafer processing dip processing method and the spray (shower) processing method, which are addition methods of the catalyst element solution instead of the spin processing method, the substrate is treated on the substrate like the conventional spin processing method. This is effective in reducing the amount of the catalyst element solution to be used because the catalyst element solution is not filled in the first step. Further, in the case of a roll processing method including a printing roll having a relief portion, the catalyst element solution can be selectively added to a specific region of the amorphous silicon film, which is effective in further reducing the amount of the catalyst element solution used. It is. In addition, in the manufacturing apparatus of each of the above-described processing methods, it is not necessary to provide a substrate spin unit including a spin motor and a spin speed adjusting mechanism, so that the apparatus is advantageous in terms of the apparatus cost even for a large-sized substrate. .

Further, in a continuous processing apparatus, a pretreatment step of adding a catalyst element solution (a dilute hydrofluoric acid treatment step of an amorphous silicon film →
The following specific effects can be obtained by continuously processing the step of oxidizing the amorphous silicon film) → the step of adding the catalyst element solution → the step of dehydrogenation. Since the series of processing steps can be continuously processed by the continuous processing apparatus, the tact time is shortened, which is effective in improving productivity. Further, in the continuous processing apparatus, since the substrate is transported in one axis direction, the uniformity of the entire substrate can be obtained only by securing the uniformity in the lateral direction (the direction perpendicular to the transport direction). Is easy to secure,
This is advantageous in securing uniformity. Further, by adding a horizontal electric heating furnace to the continuous processing apparatus, continuous processing up to the thermal crystallization step of the amorphous silicon film can be performed continuously, so that productivity can be further improved.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view showing a step of forming a crystalline silicon film (in the case of a vertical growth method).

FIG. 2 is a schematic view (side view) showing a roll-type processing method, a dip-type processing method, and a spray-type processing method.

FIGS. 3A and 3B are a cross-sectional view and a plan view of a substrate, respectively, illustrating a step of manufacturing a crystalline silicon film (when only a specific region is vertically grown).

FIG. 4 is a cross-sectional view showing a step of forming a crystalline silicon film (in the case of a lateral growth method).

FIG. 5 is a sectional view showing a manufacturing process of the active matrix type liquid crystal display device.

FIG. 6 is a sectional view showing a manufacturing process of the active matrix liquid crystal display device.

FIG. 7 is a sectional view illustrating a manufacturing process of the active matrix liquid crystal display device.

FIG. 8 is a sectional view showing a manufacturing process of the active matrix liquid crystal display device.

FIG. 9 is a cross-sectional view illustrating a manufacturing process of the active matrix liquid crystal display device.

FIG. 10 is a schematic diagram (plan view) of a continuous processing apparatus.

FIG. 11 is a schematic view (side view) of a roll type processing apparatus.

FIG. 12 is a schematic diagram (side view) of a single-wafer dip processing apparatus.

FIG. 13 is a schematic view (side view) of a spray processing apparatus.

FIG. 14 is a schematic view of an example of an electronic apparatus incorporating a liquid crystal display device.

FIG. 15 is a schematic view showing an example of an electronic apparatus incorporating a liquid crystal display device.

FIG. 16 is a schematic view showing an example of an electronic apparatus incorporating a liquid crystal display device.

[Explanation of symbols]

101: Glass substrate 102: Amorphous silicon film 103: Natural oxide film 104: Silicon oxide film 105: Ni-containing layer 106: Crystalline silicon film 201: Dispense unit 202: Anilox roll 203: Doctor blade 204: Printing roll 205: Driving stage 206: Ni aqueous solution 207: Processing bath 208: Ni aqueous solution 209: Substrate holding arm 210: Processing stage 211: Spray nozzle 212: Mist-shaped Ni aqueous solution 301: Glass substrate 302: Amorphous silicon film 303: Silicon oxide film 304: Ni aqueous solution 305: Addition region 306: Non-addition region 307: Non-addition region 308: Ni-containing layer 309: Crystalline silicon film 310: Amorphous silicon film 401: Glass substrate 402: Amorphous silicon film 403: Natural Oxide film 404: Mask insulating film (silicon oxide film) 405: Open area 406: Silicon oxide film 407: Ni aqueous solution 408: Ni-containing layer 409: crystalline Silicon film 501: glass substrate 502: base film 502a: first layer of silicon oxynitride film 502b: second layer of silicon oxynitride film 503a: amorphous silicon film 503b: crystalline silicon film 504 to 508: semiconductor Layer 509: Gate insulating film (silicon oxynitride film) 510: Gate electrode film (W film) 511 to 516: Resist pattern (for forming gate electrode and other electrodes) 517 to 520: Gate electrode 521: Electrode for storage capacitor 522 : Electrode (functions as source wiring) 523: Gate insulating film (after gate electrode dry etching) 524 to 527: Substantially intrinsic region (functions as channel region) 528: Intrinsic region (functions as one side of capacitance forming electrode) 529-533: Low-concentration impurity region of n-type impurity (n-region) 534-536: Resist pattern (for forming n + region) 537-541: High-concentration impurity region of n-type impurity (n + region) 542-544: Low-concentration impurity region of n-type impurity (n-region) 545 to 547: resist pattern (for forming p + region) 548: high-concentration impurity region of p-conductivity type (p + region) (functions as source / drain region) 549: p-conductivity 550: first interlayer insulating film (silicon oxynitride film) 551: second interlayer insulating film (acrylic resin film) 552 to 557 : Metal wiring (laminated film of Ti film and Al-Ti alloy film) 558: connection electrode 559: gate wiring 560 to 561: connection electrode 562: pixel electrode (ITO film) 601: n-channel TFT 602: p-channel TFT 603: n-channel TFT 604: pixel TFT 605: storage capacitor 606: drive circuit 607: pixel area 701: processing substrate 702: loader side carrier 703: oxide film removing unit 704: washing unit 705: drying unit 7 06: Oxidation unit 707: Drying unit 708: Addition unit 709: Drying unit 710: Buffer 711: Buffer 712: Dehydrogenation unit 713: Hot plate 714: Treated substrate 715: Unloader side carrier 801: Catalyst element solution addition section 802: Substrate drying section 803: Dispensing unit 804: Doctor blade 805: Anilox roll 806: Printing roll 807: Driving stage 808: Air knife nozzle 809: Driving stage 810: Drain tank 811: Substrate 901: Catalyst element solution immersing section 902: Substrate drying section 903: Catalyst element solution 904: Processing tank 905: Substrate holding arm 906: Air knife nozzle 907: Driving stage 908: Drain tank 909: Substrate 1001: Catalyst element solution adding section 1002: Substrate drying section 1003: Processing stage 1004 : Mist-like catalyst element solution 1005: Spray nozzle 1006: Drain tank 1007: Aerna Funozuru 1008: drive stage 1009: drain tank 1010: board

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Takuya Matsuo 22-22 Nagaikecho, Abeno-ku, Osaka City, Osaka Inside Sharp Corporation (72) Inventor Naoki Makita 22-22 Nagaikecho, Abeno-ku, Osaka City, Osaka (72) Inventor Hiromi Sakamoto 22-22, Nagaike-cho, Abeno-ku, Osaka City, Osaka F-term (reference) 5F052 AA02 AA11 BB07 CA10 DA02 DB02 DB03 EA15 FA06 FA19 JA01 5F110 BB02 BB04 CC02 DD02 DD03 DD15 DD17 EE04 EE05 EE09 EE28 EE44 EE45 FF04 FF12 FF30 GG02 GG13 GG24 GG25 GG32.

Claims (10)

[Claims] 1. A first step of depositing an amorphous semiconductor film containing silicon on an insulating substrate, and a roll treatment of a catalyst element for promoting crystallization in a partial region of the amorphous semiconductor film. A method for manufacturing a crystalline semiconductor film, comprising: a second step of adding a crystalline semiconductor film by a thermal method; and a third step of forming a crystalline semiconductor film in a region where a catalytic element is added by heat-treating the amorphous semiconductor film. 2. A first step of depositing an amorphous semiconductor film containing silicon on an insulating substrate, and a second step of adding a catalytic element for promoting crystallization to the entire surface of the amorphous semiconductor film. And a third step of forming a crystalline semiconductor film by heat-treating the amorphous semiconductor film, wherein the second step is a roll-type processing method. A method for producing a crystalline semiconductor film, characterized by adding a catalytic element according to (1). 3. A first step of depositing an amorphous semiconductor film containing silicon on an insulating substrate and a second step of adding a catalytic element for promoting crystallization to the entire surface of the amorphous semiconductor film. And a third step of forming a crystalline semiconductor film by heat-treating the amorphous semiconductor film. A method for producing a crystalline semiconductor film, characterized by adding a catalytic element according to (1). 4. A first step of depositing an amorphous semiconductor film containing silicon on an insulating substrate, and a second step of adding a catalytic element for promoting crystallization to the entire surface of the amorphous semiconductor film. And a third step of forming a crystalline semiconductor film by heat-treating the amorphous semiconductor film. A method for producing a crystalline semiconductor film, characterized by adding a catalytic element according to (1). 5. A first step of depositing an amorphous semiconductor film containing silicon on an insulating substrate, and a second step of adding a catalytic element for promoting crystallization to the entire surface of the amorphous semiconductor film. And a third step of forming a crystalline semiconductor film by heat-treating the amorphous semiconductor film, wherein the second step is a shower processing method. A method for producing a crystalline semiconductor film, characterized by adding a catalytic element according to (1). 6. A first step of depositing an amorphous semiconductor film containing silicon on an insulating substrate, and a step of depositing a mask insulating film on the amorphous semiconductor film and forming a part of the mask insulating film. A second step of forming an opening region in the region, a third step of adding a catalytic element for promoting crystallization to the mask insulating film,
And a fourth step of forming a crystalline semiconductor film by heat-treating the amorphous semiconductor film. A method for manufacturing a crystalline semiconductor film, characterized by adding an element. 7. A first step of depositing an amorphous semiconductor film containing silicon on an insulating substrate, and depositing a mask insulating film on the amorphous semiconductor film, and forming a part of the mask insulating film. A second step of forming an opening region in the region, a third step of adding a catalytic element for promoting crystallization to the mask insulating film,
And a fourth step of forming a crystalline semiconductor film by heat-treating the amorphous semiconductor film. A method for manufacturing a crystalline semiconductor film, characterized by adding an element. 8. A first step of depositing an amorphous semiconductor film containing silicon on an insulating substrate, and depositing a mask insulating film on the amorphous semiconductor film, and forming a part of the mask insulating film. A second step of forming an opening region in the region, a third step of adding a catalytic element for promoting crystallization to the mask insulating film,
And a fourth step of forming a crystalline semiconductor film by heat-treating the amorphous semiconductor film. A method for manufacturing a crystalline semiconductor film, characterized by adding an element. 9. A first step of depositing an amorphous semiconductor film containing silicon on an insulating substrate, and depositing a mask insulating film on the amorphous semiconductor film, and forming a part of the mask insulating film. A second step of forming an opening region in the region, a third step of adding a catalytic element for promoting crystallization to the mask insulating film,
And a fourth step of forming a crystalline semiconductor film by heat-treating the amorphous semiconductor film. A method for manufacturing a crystalline semiconductor film, characterized by adding an element. 10. The method according to claim 1, wherein the catalyst element is Fe, Co, Ni, Ru, Rh, Pd, Os, I
A method for manufacturing a crystalline semiconductor film, characterized by adding using a solution containing one or more kinds of elements selected from r, Pt, Cu, and Au.