JP2007165524A - Semiconductor device, manufacturing method thereof, electronic equipment, and manufacturing method thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a technology for forming an impurity-doped silicon film of low resistance, through thermal process of relatively low temperature. <P>SOLUTION: A solution containing a high-order silane composition, catalyst, and dopant element, for example cyclopentasilane, is irradiated with ultraviolet ray. Thereafter, the solution is diluted with toluene (solvent) to obtain a liquid (solution 1 of high-order silane composition). The solution is mixed with a dopant element containing compound (for example yellow phosphorus) and catalyst (nickel chloride) to obtain a solution A for application. The solution is applied on a substrate to form a coating film 13 and is heated (baked) at, for example, 300-600°C to form an impurity-doped silicon film 13a. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a method for manufacturing a semiconductor device, and more particularly to a method for forming a film of a semiconductor device having an impurity-doped silicon film.

  An impurity-doped silicon film (impurity silicon film, n-type silicon film, p-type silicon film, impurity semiconductor layer) is widely used in semiconductor devices such as solar cells and thin film transistors (TFTs). Such an impurity-doped silicon film can be formed by CVD (chemical vapor deposition), sputtering, or ion implantation, but there is a problem that a large apparatus is required.

  Therefore, for example, Patent Document 1 (Japanese Patent Laid-Open No. 2003-313299) below discloses a technique for forming a polycrystalline silicon film by applying a high-order silane composition to a substrate and performing laser treatment. Also disclosed is a technique for forming a p-type or n-type silicon film by adding a dopant to a higher order silane composition.

  Also, in Patent Document 2 below (Japanese Patent Laid-Open No. 11-214311), a solid high-order silane doped with Group 3 or Group 5 atoms is applied and heated to form a doped a-Si film. Technology is disclosed.

  On the other hand, in the crystallization of an amorphous silicon film, a technique for forming a coating of a catalyst material such as nickel on or under the film and performing crystallization at a low temperature is disclosed in Patent Document 3 (Japanese Patent Laid-Open No. 6-244103) and 4 below. (Japanese Patent Laid-Open No. 6-296020).

In addition, regarding a catalyst such as nickel, a silicon film is formed by applying a mixture of a solution of a higher order silane and a catalyst onto a substrate and thermally decomposing it in the following Patent Document 5 (JP-A-10-321536), A technique using nickel or the like as a catalyst is disclosed.
JP 2003-313299 A JP-A-11-214311 JP-A-6-244103 JP-A-6-296020 Japanese Patent Laid-Open No. 10-321536

  However, when the impurity-doped silicon film is formed by the technique of Patent Document 1, a low-resistance impurity-doped silicon film cannot be obtained unless a heat treatment such as laser processing is performed. In other words, the heat treatment at a low temperature of about 400 ° C., for example, increases the resistance of the impurity-doped silicon film and cannot be used as each part (for example, an electrode or a wiring) constituting the semiconductor device. In addition, it is possible to reduce the resistance by heat treatment exceeding 600 ° C. or laser irradiation, but there is a problem that the lower layer film is damaged by the high temperature treatment, and when a laser apparatus is used. There are problems such as high cost and reduced throughput. In the technique disclosed in Patent Document 2, a low-resistance impurity-doped silicon film cannot be obtained by low-temperature heat treatment.

  In addition, as disclosed in Patent Documents 3 to 5, the silicon film has been studied for crystallization at a low temperature using a catalyst, but the impurity-doped silicon film has not been studied. .

  An object of the present invention is to provide a technique for forming a low-resistance impurity-doped silicon film by heat treatment at a relatively low temperature.

  (1) A method for manufacturing a semiconductor device of the present invention includes a step of applying a solution containing a higher order silane composition, a catalyst and a dopant element on a substrate to form a coating film, heating the coating film, And a step of forming a doped silicon film.

  According to such a method, the resistance of the impurity-doped silicon film can be reduced even by heat treatment at a relatively low temperature.

  The high-order silane composition contains a high-order silane compound obtained by photopolymerizing a liquid silane compound having photopolymerizability by irradiating ultraviolet light.

  Before the step of forming the coating film, a step of forming the higher order silane composition containing the higher order silane compound formed by irradiating light to the liquid silane compound having photopolymerization property and photopolymerization; Mixing the compound containing the dopant element with the higher silane composition and the catalyst to form the solution.

  Before the step of forming the coating film, a liquid silane compound having photopolymerizability is mixed with the compound containing the dopant element and the catalyst to form a silane composition, and the silane composition Forming a solution containing the higher order silane composition formed by irradiating the material with light and photopolymerizing.

  The catalyst includes a metal or a metal compound.

  The catalyst contains nickel or a nickel compound.

  The catalyst includes nickel nanoparticles.

    The dopant element includes phosphorus or boron.

  The dopant element is phosphorus, and the solution contains yellow phosphorus.

  (2) A method for manufacturing an electronic device according to the present invention includes any one of the above-described methods for manufacturing a semiconductor device.

  (3) A semiconductor device according to the present invention is an impurity-doped silicon film obtained by firing a coating film containing a higher order silane, a nickel catalyst and a dopant element, and the impurity-doped silicon film containing a nickel element in the film. Have.

  (4) An electronic apparatus of the present invention includes a semiconductor device manufactured by any one of the above-described semiconductor device manufacturing methods or the semiconductor device. Here, the “electronic device” refers to a general device having a certain function provided with the semiconductor device according to the present invention, and includes, for example, an electro-optical device and a memory. Although there is no particular limitation on the configuration, for example, an IC card, a mobile phone, a video camera, a personal computer, a head-mounted display, a rear-type or front-type projector, a fax machine with a display function, a digital camera finder, a portable TV, Examples include PDAs, electronic notebooks, electronic bulletin boards, and advertising displays. The “electro-optical device” includes a display device such as a liquid crystal device, an organic EL device, and an electrophoretic display device including the semiconductor device according to the present invention, and a light emitting device. In addition, the “semiconductor device” includes a structure in which an impurity-doped silicon film is used, such as a switching element such as a transistor or a photoelectric conversion element such as a solar cell, and a plurality of these are formed on a substrate. Also means.

Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. In addition, the same or related code | symbol is attached | subjected to what has the same function, and the repeated description is abbreviate | omitted.
<Method for forming impurity-doped silicon film>
A method for forming the impurity-doped silicon film will be described. FIG. 1 is a process cross-sectional view illustrating a method for forming an impurity-doped silicon film.

  As shown in FIG. 1A, a liquid material 1 is spin-coated on a glass substrate (substrate, quartz substrate, transparent substrate, insulating substrate) 10 to form a coating film 13. Next, after volatilizing the solvent in the liquid material (after the drying step), as shown in FIG. 1B, the coating film 13 is heated (baked) to form the impurity-doped silicon film 13a.

  The liquid material 1 is a liquid obtained by mixing (adding) a dopant element-containing compound and a catalyst to a solution of a higher order silane composition.

  A solution of a higher order silane composition refers to a solution containing a silane compound (a silane composition) that is irradiated with light such as ultraviolet light (UV) to polymerize at least a portion of the silane compound to form a higher order silane compound. The solution containing the higher silane compound. Even a solution in which a higher order silane compound is dissolved in a solvent, or a solution in which a higher order silane compound is dissolved in a liquid silane compound may be used.

  Hereinafter, detailed examples will be described with reference to the drawings. 2 to 4 are tables showing the resistivity and crystallization ratio of the impurity-doped silicon films of Examples 1 to 3. FIG. FIG. 5 is a chart showing the resistivity and crystallization rate of an impurity-doped silicon film for comparison.

Example 1
A liquid obtained by irradiating 10 g of cyclopentasilane with 405 nm ultraviolet light at an intensity of 100 mW / cm ² for 10 minutes while stirring, diluting it with toluene (solvent) to a concentration of 10%, and filtering through a 0.2 μm membrane filter. A dopant element-containing compound and a catalyst were mixed in (High-Order Silane Composition Solution 1) to obtain a coating solution A.

Yellow phosphorus or decaborane was used as the dopant element-containing compound, and nickel chloride (NiCl ₂ ) was used as the catalyst. 10 mg of the dopant element-containing compound (yellow phosphorus or decaborane) and 1 mg of nickel chloride (NiCl ₂ ) were mixed in Solution 1 of the higher order silane composition. The heating temperature was appropriately set between 300 ° C. and 600 ° C., and the heating time was 1 hour.

  (1) First, the case where yellow phosphorus is used as the dopant element-containing compound (1-1 to 1-4 in FIG. 2) will be described.

  As shown in FIG. 2, the resistivity and crystallization rate of the impurity-doped silicon film 13a formed under such processing conditions were a resistivity of 0.005 to 0.5 Ωcm and a crystallization rate of 0 to 90%.

As shown in 4-1 to 4-4 in FIG. 5 (comparative example), when the dopant element-containing compound is yellow phosphorus, the heating temperature is about 300 ° C. as compared with the case where the catalyst is not added with nickel chloride. Also, a good numerical value with a resistivity of 0.5 Ωcm (> 10 ^{5 in the} comparative example) could be obtained. In particular, the resistivity is greatly improved even at 400 to 500 ° C. (400 ° C .: 10 → 0.05 Ωcm, 500 ° C .: 0.1 → 0.01 Ωcm), and the impurity-doped silicon film has low resistance even at relatively low temperature processing. Could get. In addition, 4-5-4-8 of FIG. 5 is a result at the time of not mixing yellow phosphorus. When yellow phosphorus was not mixed, the crystallization ratio (0 → 5%, 5 → 30%) was higher at 400 to 500 ° C. than the case of mixing, but the resistivity was very high. However, even if the crystallization is insufficient, if the resistivity is small, that is, if the ratio of the activated dopants (that is, at positions replacing Si atoms) is sufficiently large, it can be put into practical use. It is.

  When nickel chloride was added together with yellow phosphorus, the resistivity (0.03 Ωcm → 0.005 Ωcm) decreased and the crystallization rate (50 → 90%) increased even at 600 ° C.

  As described above, in this embodiment, a dopant and a catalyst (nickel chloride) are added to the solution of the higher order silane composition to form a low resistance impurity-doped silicon film even at a low temperature of 600 ° C. or lower. it can.

  (2) Next, the case where decaborane is used as the dopant element-containing compound (1-5 to 1-8 in FIG. 2) will be described.

  In this case, the resistivity and crystallization rate of the impurity-doped silicon film 13a were 0.008 to 1 Ωcm, and 0 to 85% crystallization rate, as shown in FIG.

  For example, even when the heating temperature is about 300 ° C., a favorable numerical value with a resistivity of 1 Ωcm could be obtained. In particular, a low resistance impurity-doped silicon film having a resistivity of 0.1 Ωcm and 0.02 Ωcm could be obtained even at 400 to 500 ° C. Moreover, the crystallization rate in 400-500 degreeC was 3% and 25%, respectively. Furthermore, a low resistance impurity-doped silicon film having a resistivity of 0.008 Ωcm was obtained even at 600 ° C. The crystallization rate was 85%.

  As described above, in this embodiment, a dopant and a catalyst (nickel chloride) are added to the solution of the higher order silane composition to form a low resistance impurity-doped silicon film even at a low temperature of 600 ° C. or lower. it can.

(Example 2)
In Example 1, the minimum resistivity (0.005 Ωcm) could be obtained in Nos. 1-4. Therefore, the same experiment was performed by appropriately changing the added catalyst among the conditions of 1-4.

  The resistivity and crystallization rate of the impurity-doped silicon film 13a formed under such processing conditions are 0.007 to 0.01 Ωcm, 85 to 95%, as indicated by 2-1 to 2-4 in FIG. The crystallization rate was.

More specifically, when 1 mg of Co ₂ (CO) ₈ was added as a catalyst, the resistivity was 0.007 Ωcm, and the crystallization rate was 85%. When 1 mg of PdCl ₂ was added as a catalyst, the resistivity was 0.008 Ωcm and the crystallization rate was 85%. In addition, when 20 ml of a toluene dispersion (5 wt% concentration) of nickel (Ni) nanoparticles was added, the resistivity was 0.003 Ωcm and the crystallization rate was 95%. In addition, when 20 ml of a toluene dispersion of silver nanoparticles (5 wt% concentration) was added, the resistivity was 0.01 Ωcm, and the crystallization rate was 85%. The average particle size of the nanoparticles was 10 nm for both.

  As described above, an impurity-doped silicon film having a low resistance can be obtained when any catalyst is used. In particular, it has been found that the resistivity when Ni nanoparticles are used as a catalyst is low, and it is suitable as a catalyst.

(Example 3)
In this example, an experiment was performed using a solution obtained by adding a dopant element-containing compound to a silane compound and then irradiating it with ultraviolet light for photopolymerization.

Specifically, 10 mg of a dopant element-containing compound (yellow phosphorus or decaborane) was dissolved in 10 g of cyclopentasilane, and irradiated with 405 nm ultraviolet light at an intensity of 100 mW / cm ² for 60 minutes while stirring. This was diluted with toluene (solvent) to a concentration of 10%, and the catalyst was mixed with a liquid (solution 2 of a higher silane composition) filtered through a 0.2 μm membrane filter to obtain a coating solution B.

Nickel chloride (NiCl ₂ ) was used as the catalyst, and 1 mg was mixed with the solution 2 of the higher order silane composition. The heating temperature was appropriately set between 300 ° C. and 600 ° C., and the heating time was 1 hour.

  (1) First, the case where yellow phosphorus is used as the dopant element-containing compound (3-1 to 3-4 in FIG. 4) will be described.

  As shown in FIG. 4, the resistivity and crystallization rate of the impurity-doped silicon film 13a formed under such processing conditions are a resistivity of 0.003 to 0.3 Ωcm and a crystallization rate of 0 to 90%. Compared with Example 1 (1-1 to 1-4 in FIG. 2), the resistivity is smaller.

  (2) Next, the case where decaborane is used as the dopant element-containing compound (3-5 to 3-8 in FIG. 4) will be described.

  Also in this case, the resistivity and crystallization rate of the impurity-doped silicon film 13a are 0.005 to 0.5 Ωcm resistivity and 0 to 85% crystallization rate as shown in FIG. Compared to 1 (1-5 to 1-8 in FIG. 2), the resistivity is smaller.

  Thus, it has been found that an impurity-doped silicon film having a lower resistance can be obtained by performing photopolymerization after previously mixing a dopant element-containing compound with a silane compound. This is because the dopant atoms are taken into the polymer (higher order silane composition) in the form of replacing the Si atoms in advance, so that the dopant atoms easily enter the substitution position in the film by heating (firing) ( That is, it is considered that it is easily activated).

  In addition, it is considered that a solution obtained by adding a dopant element-containing compound and a catalyst to a silane compound and then performing photopolymerization by irradiation with ultraviolet light may be used.

<Description of silane compounds and solvents>
In Examples 1 to 3 above, cyclopentasilane was used as the silane compound, but the silane compound is not particularly limited as long as it has photopolymerizability such that it can be polymerized by UV irradiation. For example, the general formula Si _n A silane compound or the like represented by X _m (where n represents an integer of 3 or more, and m represents an independent integer of 4 or more, and X represents a substituent such as a hydrogen atom and / or a halogen atom). Can be mentioned.

As such a silane compound, a cyclic silane compound represented by the general formula Si _n X _2n (wherein n represents an integer of 3 or more and X represents a hydrogen atom and / or a halogen atom), In addition to a silane compound having two or more cyclic structures represented by the general formula Si _n X _2n-2 (wherein n represents an integer of 4 or more and X represents a hydrogen atom and / or a halogen atom), All of the photopolymerizable silane compounds to which the photopolymerization process by irradiation with ultraviolet light according to the present invention can be applied, such as silicon hydride having at least one cyclic structure in the molecule and a halogen substitution product thereof.

Specific examples of such silane compounds include cyclotrisilane, cyclotetrasilane, cyclopentasilane, cyclohexasilane, cycloheptasilane, and the like as those having one cyclic structure. 1, 1'-bicyclobutasilane, 1, 1'-bicyclopentasilane, 1, 1'-bicyclohexasilane, 1, 1'-bicycloheptasilane, 1, 1'-cyclobuta Silylcyclopentasilane, 1,1′-cyclobutasilylcyclohexasilane, 1,1′-cyclobutasilylcycloheptasilane, 1,1′-cyclopentasilylcyclohexasilane, 1,1′-cyclopentasilylcyclo Heptasilane, 1,1′-cyclohexasilylcycloheptasilane, spiro [2,2] pentasilane, spiro [3,3] Tatasilane, spiro [4,4] nonasilane, spiro [4,5] decasilane, spiro [4,6] undecasilane, spiro [5,5] undecasilane, spiro [5,6] undecasilane, spiro [6,6] tridecasilane, etc. In addition, silane compounds in which hydrogen atoms of these skeletons are partially substituted with SiH ₃ groups or halogen atoms can be exemplified. These may be used in combination of two or more.

Of these, a silane compound having a cyclic structure in at least one position in the molecule is preferably used as a raw material because it has extremely high reactivity with light and photopolymerization can be performed efficiently. Among them, Si _n X _2n such as cyclotetrasilane, cyclopentasilane, cyclohexasilane, cycloheptasilane (wherein, n represents an integer of 3 or more, X is a hydrogen atom and / or fluorine atom, chlorine atom, bromine) In addition to the above reasons, a silane compound represented by the formula (1) represents a halogen atom such as an atom or an iodine atom.

  As the silane compound, the silane compound having the above-mentioned cyclic structure is preferable. However, as long as the photopolymerization process by irradiation with ultraviolet light according to the present invention is not inhibited, n-pentasilane, n-hexasilane, A silane compound such as n-heptasilane, a modified silane compound modified with a boron atom and / or a phosphorus atom, or the like may be used in combination.

  The solvent for forming the silane compound solution is not particularly limited as long as it dissolves the silane compound and does not react with the compound, but usually has a vapor pressure of 0.001 to 200 mmHg at room temperature. Is used. When the vapor pressure is higher than 200 mmHg, when a coating film is formed by coating, the solvent evaporates first and it becomes difficult to form a good coating film. On the other hand, when the vapor pressure is lower than 0.001 mmHg, similarly, when forming a coating film by coating, drying is slow and the solvent tends to remain in the coating film of the silicon compound, and heat and / or light treatment in the subsequent process It is difficult to obtain a good quality silicon film later. Further, it is preferable to use a solvent having a boiling point at normal pressure of room temperature or higher and lower than 250 ° C. to 300 ° C. which is the decomposition point of the higher order silane compound. By using a solvent lower than the decomposition point of the higher order silane compound, it is possible to selectively remove only the solvent by heating without decomposing the higher order silane compound after coating, thus preventing the solvent from remaining in the silicon film. And a film with better quality can be obtained.

  In Examples 1 to 3, toluene was used as the solvent. Specific examples of the solvent used in the silane compound solution include n-hexane, n-heptane, n-octane, n-decane, and dicyclopentane. , Benzene, toluene, xylene, durene, indene, tetrahydronaphthalene, decahydronaphthalene, squalane and other hydrocarbon solvents, dipropyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol methyl ethyl ether, diethylene glycol dimethyl ether, Diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, tetrahydrofuran, tetrahydropyran, 1,2-dimethoxyethane, bis (2-methoxyethyl) ether, p Ether solvents such as dioxane, propylene carbonate, .gamma.-butyrolactone, N- methyl-2-pyrrolidone, dimethyl formamide, may be mentioned acetonitrile, polar solvent such as dimethyl sulfoxide. Of these, hydrocarbon solvents and ether solvents are preferred in view of the solubility of the silane compound and the stability of the solution, and more preferred solvents are hydrocarbon solvents. These solvents can be used singly or as a mixture of two or more.

  As a solution coating method, a spin coating method, a roll coating method, a curtain coating method, a dip coating method, a spray method, a droplet discharge method, or the like can be used. The application is generally performed at a temperature above room temperature. If the temperature is lower than room temperature, the solubility of the higher order silane compound may decrease and partly precipitate. Since the silane compound, higher order silane compound and higher order silane composition in the present invention react with water and oxygen to be modified, it is preferable that the series of steps is in a state in which water and oxygen are not present. Therefore, the atmosphere during the series of steps is preferably performed in an inert gas such as nitrogen, helium, or argon. Furthermore, what mixed reducing gas, such as hydrogen, as needed is preferable. Further, it is desirable to use a solvent or additive from which water or oxygen has been removed.

  In the present invention, the droplet discharge method is a method of forming a desired pattern including an object to be discharged by discharging droplets to a desired region, and is sometimes called an ink jet method. However, in this case, the liquid droplets to be ejected are not so-called ink used for printed matter, but a liquid containing a material substance constituting the device, and this material substance functions as, for example, a conductive substance or an insulating substance constituting the device. It contains a possible substance. Furthermore, the droplet discharge is not limited to spraying at the time of discharge, but also includes a case where each droplet of liquid is discharged so as to be continuous.

  In addition to yellow phosphorus or decaborane, as a dopant element-containing compound, a substance containing a Group 3B element of the periodic table or a substance containing a Group 5B element of the periodic table may be added as a dopant source.

<Application example of impurity-doped silicon film to semiconductor device>
An application example of the impurity-doped silicon film described above in detail to a semiconductor device will be described. Here, application to a thin film transistor (TFT) will be described as an example of a semiconductor device. The TFT is widely used as a switching element or a drive circuit of a device using a liquid crystal or an electroluminescence (EL) element.

  6 and 7 are process cross-sectional views illustrating a method for manufacturing a semiconductor device (TFT) according to the present embodiment. Hereinafter, a method for manufacturing a semiconductor device (TFT) will be described in detail with reference to the drawings. In addition, the same or related code | symbol is attached | subjected to what has the same function, and the repeated description is abbreviate | omitted.

  As shown in FIG. 6A, for example, a silicon oxide film is formed on the glass substrate 10 as the base protective film 11. This silicon oxide film is formed by using, for example, a plasma CVD method using TEOS (tetraethyl orthosilicate, tetraethoxysilane), oxygen gas, or the like as a source gas.

  Next, a metal film, for example, is formed as a conductive film (conductor film, conductive film, conductive layer) 12 on the base protective film 11. The conductive film 12 serves as a source / drain lead wiring. Here, for example, Mo (molybdenum) is deposited by a sputtering method. In addition to Mo, a metal material such as Cu (copper) may be used, or ITO (indium tin oxide film) may be used. Also, the deposition method is not limited to the sputtering method, but may be formed by other PVD (physical vapor deposition) methods such as a vapor deposition method and a CVD method.

  Next, an impurity-doped silicon film 13a is formed on the conductive film 12. At this time, the above-described coating solution (a solution obtained by mixing a dopant element-containing compound and a catalyst with a solution of a higher order silane composition). Is applied on the conductive film 12 and heated (400 ° C.) to form the impurity-doped silicon film 13a.

  Next, as shown in FIG. 6B, by exposing and developing (photolithography) a not-shown photoresist film (hereinafter simply referred to as “resist film”) on the impurity-doped silicon film 13a, a source and a drain are formed. The conductive film 12 and the impurity-doped silicon film 13a are etched using the resist film as a mask, leaving only on the electrode formation region. This impurity-doped silicon film 13a becomes a source / drain region.

  Next, the resist film is removed, and an amorphous silicon film, for example, is deposited as the semiconductor film 16 on the impurity-doped silicon film 13a (source and drain regions) by the CVD method as shown in FIG. 7A. The substrate temperature at that time is 350 ° C. or lower.

  Next, the semiconductor film 16 is patterned into a desired shape by etching using a resist film (not shown) as a mask. As a result, the semiconductor film 16 is separated for each element.

  Next, as shown in FIG. 7B, a silicon oxide film, for example, is formed as a gate insulating film 17 on the semiconductor film 16 by a plasma CVD method (substrate temperature 350 ° C.), and then a conductive film 18 is formed thereon. For example, a Ta (tantalum) film is deposited by sputtering. Next, the conductive film 18 is patterned into a desired shape, and the gate electrode G is formed.

  Through the above steps, a staggered TFT is almost completed.

  Thus, by using the above-described method for forming an impurity-doped silicon film, a low-resistance source / drain electrode (impurity-doped silicon film 13a) can be formed even by heating at 400 ° C.

  Note that here, a so-called top gate type (forward stagger type) TFT is illustrated, but the above-described impurity-doped silicon film may be used for an inverted stagger type TFT.

  In particular, it is suitable for use in a transistor of a type in which a silicon layer (16) serving as a channel is formed in a separate process from the impurity doped silicon film (source / drain region) 13a. This is because it is not necessary to consider the remaining catalyst when a silicon layer to be a channel is separately formed.

  Here, for example, an amorphous silicon film is formed as the semiconductor film 16 by the CVD method, but the silicon film (16) may be formed by applying a solution of a non-doped higher order silane composition and heating (firing). In this case, it is considered that a catalyst in the lower impurity-doped silicon film (source / drain region) 13a contributes and a silicon film having good characteristics can be obtained even at low temperature baking.

  Although the case where the impurity-doped silicon film 13a is used for the source and drain regions of the transistor has been described here, the present invention is not limited to such a part, and the present invention can be widely applied to a part using the impurity-doped silicon film.

  Further, the present invention is not limited to TFTs and can be widely applied to semiconductor devices using impurity-doped silicon films such as solar cells.

  FIG. 8 shows a configuration example of a solar cell. As shown in the figure, the solar cell has a laminated structure of a plus electrode 81, a p-type silicon film 82, a non-doped silicon film 83, an n-type silicon film 84, an antireflection film 85, and a minus electrode 86. The plus electrode 81 and the minus electrode 85 are made of a conductive film such as metal or ITO. The film thicknesses of the p-type silicon film 82, the non-doped silicon film 83, and the n-type silicon film 84 are, for example, about 500 nm, 3 μm, and 500 nm, respectively. The impurity-doped silicon film of the present invention can be used for the p-type silicon film 82 and the n-type silicon film 83.

  Thus, according to the present invention, the resistance of the impurity-doped silicon film can be reduced, and the characteristics of the semiconductor device can be improved.

<Description of electro-optical device and electronic device>
Next, an electro-optical device and an electronic apparatus in which the above-described TFT is used will be described.

  Such a TFT is used, for example, in a liquid crystal panel which is a display unit of an electro-optical device (display device) or an electronic device. FIG. 9 illustrates an example of an electronic device using the electro-optical device. FIG. 9A shows an application example to a mobile phone, and FIG. 9B shows an application example to a video camera. FIG. 9C shows an application example to a television (TV), and FIG. 9D shows an application example to a roll-up television.

  As shown in FIG. 9A, the cellular phone 530 includes an antenna portion 531, an audio output portion 532, an audio input portion 533, an operation portion 534, and an electro-optical device (display portion) 500. The electro-optical device (TFT) of the present invention can be used for this electro-optical device.

  As shown in FIG. 9B, the video camera 540 includes an image receiving unit 541, an operation unit 542, an audio input unit 543, and an electro-optical device (display unit) 500. The electro-optical device of the present invention can be used for this electro-optical device.

  As shown in FIG. 9C, the television 550 includes an electro-optical device (display unit) 500. The electro-optical device of the present invention can be used for this electro-optical device. The electro-optical device of the present invention can also be used for a monitor device (electro-optical device) used in a personal computer or the like.

  As shown in FIG. 9D, the roll-up television 560 includes an electro-optical device (display unit) 500. The electro-optical device of the present invention can be used for this electro-optical device.

  The electro-optical device is not limited to a display device for the purpose of display as described above, and may be used for a light-emitting device for light emission.

  In addition to the above, the electronic apparatus having the electro-optical device includes a fax machine with a display function, a digital camera finder, a portable TV, an electronic notebook, an electric bulletin board, a display for advertisements, and the like.

  In addition, the semiconductor device having the impurity-doped silicon film of the present invention such as a solar cell as well as the above-described TFT is widely used in various electronic devices.

Process cross-sectional view showing a method for forming an impurity-doped silicon film Chart showing resistivity and crystallization ratio of impurity-doped silicon film of Example 1 Chart showing resistivity and crystallization ratio of impurity-doped silicon film of Example 2 Chart showing resistivity and crystallization ratio of impurity-doped silicon film of Example 3 Chart showing resistivity and crystallization rate of impurity-doped silicon film for comparison Process sectional drawing which shows the manufacturing method of the semiconductor device (TFT) of this Embodiment Process sectional drawing which shows the manufacturing method of the semiconductor device (TFT) of this Embodiment The figure which shows the structural example of the solar cell of this Embodiment. FIG. 6 is a diagram illustrating an example of an electronic apparatus using an electro-optical device.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 ... Glass substrate 11 ... Base protective film 12 ... Conductive film 13 ... Coating film, 13a ... Impurity doped silicon film 16 ... Semiconductor film 17 ... Gate insulating film 18 ... Conductive film 81 ... Positive electrode 82 ... P-type silicon film 83 ... Non-doped silicon film 84 ... n-type silicon film 85 ... antireflection film 86 ... negative electrode 500 ... electro-optical device 530 ... mobile phone 531 ... antenna part 532 ... audio output part 533 ... audio input part 534 ... operation part 540 ... video camera 541 ... Image receiving unit 542 ... Operation unit 543 ... Audio input unit 550 ... Television 560 ... Roll-up television G ... Gate electrode

Claims (12)

Applying a solution containing a higher order silane composition, a catalyst and a dopant element on a substrate to form a coating film;
Heating the coating film to form an impurity-doped silicon film;
A method for manufacturing a semiconductor device, comprising:   2. The semiconductor according to claim 1, wherein the high-order silane composition contains a high-order silane compound obtained by photopolymerizing a liquid silane compound having photopolymerization properties by irradiating ultraviolet light. Device manufacturing method.   Before the step of forming the coating film, a step of forming the higher order silane composition containing a higher order silane compound formed by photopolymerization by irradiating light to a liquid silane compound having photopolymerizability; The method of manufacturing a semiconductor device according to claim 1, further comprising: mixing the compound containing the dopant element with the high-order silane composition and the catalyst to form the solution. Before the step of forming the coating film, a step of mixing the compound containing the dopant element with the liquid silane compound having photopolymerizability and the catalyst to form a silane composition;
The method of manufacturing a semiconductor device according to claim 1, further comprising: forming the solution containing the higher order silane composition formed by irradiating the silane composition with light and photopolymerizing.   The method for manufacturing a semiconductor device according to claim 1, wherein the catalyst includes a metal or a metal compound.   The method for manufacturing a semiconductor device according to claim 1, wherein the catalyst contains nickel or a nickel compound.   The method for manufacturing a semiconductor device according to claim 1, wherein the catalyst includes nickel nanoparticles.   The method for manufacturing a semiconductor device according to claim 1, wherein the dopant element includes phosphorus or boron.   The method for manufacturing a semiconductor device according to claim 1, wherein the dopant element is phosphorus, and the solution contains yellow phosphorus. A method of manufacturing an electronic apparatus having a semiconductor device,
A method for manufacturing an electronic device, comprising the method for manufacturing a semiconductor device according to claim 1.   A semiconductor device comprising an impurity-doped silicon film obtained by firing a coating film containing a higher order silane, a nickel catalyst and a dopant element, wherein the film has an impurity-doped silicon film containing a nickel element. An electronic apparatus comprising the semiconductor device according to claim 11.

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