JP2010258012A - Silicon film manufacturing apparatus, and electronic device manufacturing apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a silicon film manufacturing apparatus for generating doped silicon films efficiently. <P>SOLUTION: The apparatus includes: a silicon precursor generator 113 for generating a doped silicon precursor, where a dopant is coupled to a polymer of cyclopentasilane by supplying dopant gas while applying light having a first wavelength for radicalizing the dopant and light having a second wavelength for radicalizing cyclopentasilane to a cyclopentasilane solution; a coating apparatus 102 for coating a substrate with a solution including the doped silicon precursor; and a baking apparatus 125 for forming a doped silicon film on the substrate by baking the substrate coated with the doped silicon precursor. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a silicon film manufacturing apparatus, an electronic device manufacturing apparatus, and the like.

  As a method for manufacturing silicon for semiconductors, vacuum processes such as a pulling method such as CZ method and FZ method and a CVD (Chemical Vapor Deposition) method are known. These methods require a large-scale apparatus, and unnecessary portions of the silicon film are removed by photolithography, so that the raw material use efficiency is poor. In addition, when an impurity as a dopant is added to semiconductor silicon manufactured by the CZ method, the FZ method, or the like, a method of directly adding it to dissolved silicon is employed. Further, impurity diffusion such as a thermal diffusion method or an ion implantation method is performed on the silicon film formed by the CVD method. These methods require a large-scale dedicated apparatus, and a technique skilled in doping control is required.

  On the other hand, a method for forming a silicon film by applying a liquid semiconductor material (silicon precursor liquid) onto a substrate by a printing technique or the like and baking the substrate does not require a large-scale apparatus such as CVD. Further, since patterning can be performed by application of a liquid semiconductor material, photolithography is unnecessary, and the use efficiency of raw materials is good.

  Patent Document 1 discloses a method for forming a uniform phosphorus-doped silicon conductive film on a substrate by a coating method under normal pressure, and a method for producing a phosphorus atom-containing higher order silane compound therefor.

JP 2007-284439 A

  However, the P-type doped material used for generating the P-type doped silicon film is generally very stable in a solid or liquid state, and is high in temperature in order to be bonded to the silane compound polymer. Or a long-time reaction under high energy conditions is required. When the reaction is performed under such conditions, the silane compound volatilizes or becomes amorphous, so that a doped silicon film cannot be efficiently generated.

  One of the aspects according to the present invention is to obtain a silicon manufacturing apparatus that efficiently generates a doped silicon film.

  A silicon manufacturing apparatus according to the present invention includes a light irradiation unit that irradiates light to a solution containing a silane compound, and a gas supply unit that supplies a gas containing an element serving as a dopant to the solution containing the silane compound, and includes the silane compound. A solution containing a silicon precursor, a silicon precursor generation unit that generates a silicon precursor in which a dopant is bonded to a polymer of a silane compound by supplying a gas containing an element serving as a dopant while irradiating light to the solution, and a solution containing the silicon precursor The coating part which apply | coats to a board | substrate, and the baking part which forms a silicon | silicone on a board | substrate by baking a silicon precursor.

  According to the said structure, a dope silicon precursor can be produced | generated efficiently by activating the gas and silane compound containing the element used as a dopant by irradiation of light. Further, since it is not necessary to perform a long-time reaction under high temperature and high energy conditions, it is possible to prevent the silane compound from volatilizing or becoming amorphous. In addition, a large dedicated device is not required, and silicon can be formed efficiently by a simple method.

Further, it is desirable that the light irradiation unit irradiates light having a first wavelength for radicalizing an element serving as a dopant and light having a second wavelength for radicalizing a silane compound.
Thereby, the element used as a dopant and a silane compound can be activated reliably, and a dope silicon precursor can be produced | generated efficiently.

In addition, the gas supply unit desirably supplies a gas containing a compound of a Group 13 element that is a gas at normal temperature and pressure as a gas containing an element serving as a dopant.
Thereby, it is not necessary to carry out the reaction under high temperature and high pressure conditions, and volatilization and amorphization of the silane compound can be prevented.

Moreover, it is desirable that the silicon precursor generation part, the application part, and the baking part are arranged in an atmosphere containing an inert gas.
Thereby, since the liquid which is easy to deteriorate in air | atmosphere can be used without exposing to air | atmosphere, a quality silicon | silicone can be obtained. Further, since a liquid that reacts with a compound in the atmosphere can be used without being exposed to the atmosphere, silicon can be produced safely.

In addition, it is desirable to include a transport unit that moves the substrate from the coating unit to the baking unit.
Thereby, silicon can be manufactured efficiently.

In addition, it is desirable that the application unit apply a solution containing a silicon precursor to the substrate by an inkjet method.
Thereby, silicon can be patterned accurately by a simple method.

Moreover, it is desirable that the firing part can introduce an inert gas during firing.
Good quality silicon can be formed by injecting an inert gas during firing.

  An electronic device manufacturing apparatus according to the present invention includes a light irradiation unit that irradiates light to a solution containing a silane compound, and a gas supply unit that supplies a gas containing an element serving as a dopant to the solution containing the silane compound. A silicon precursor generation unit that generates a silicon precursor in which a dopant is bonded to a polymer of a silane compound by supplying a gas containing an element serving as a dopant while irradiating light to the solution including the substrate, and a silicon precursor A coating portion to be applied to the substrate, a firing portion for forming silicon on the substrate by firing the silicon precursor, and an electrode forming portion for forming an electrode on the silicon.

  This eliminates the need for a large-scale dedicated device, and allows an electronic device to be efficiently manufactured by a simple method. The electronic device is, for example, a solar cell or a thin film transistor (TFT).

It is sectional drawing which shows typically the structure which looked at the device manufacturing apparatus by embodiment of this invention from the horizontal direction. It is sectional drawing which shows typically the structure which looked at the device manufacturing apparatus by embodiment of this invention from the top. It is sectional drawing which shows typically the board | substrate conveyance mechanism of the device manufacturing apparatus by embodiment of this invention. It is sectional drawing which shows typically the internal structure of a silicon precursor production | generation apparatus. It is a figure which shows the example of the structure of a P-type dope silicon precursor polymer. It is sectional drawing which shows the internal structure of a coating device typically. It is a top view which shows typically the structure which looked at the coating film baking chamber from the top. It is sectional drawing which shows typically the manufacturing process of the PIN type silicon thin film solar cell which is an example of the electronic device by this invention. It is sectional drawing which shows typically the structure of the HIT type solar cell which is an example of the electronic device by this invention. It is sectional drawing which shows typically the structure of the pn junction type solar cell which is an example of the electronic device by this invention. It is sectional drawing which shows typically the manufacturing process of the thin-film transistor which is an example of the electronic device by this invention.

Hereinafter, embodiments of the present invention will be described with reference to the drawings.
Embodiment FIG. 1 is a cross-sectional view schematically showing a structure of a device manufacturing apparatus (silicon manufacturing apparatus, electronic device manufacturing apparatus) 10 according to an embodiment of the present invention viewed from the lateral direction. FIG. 2 is a cross-sectional view schematically showing the structure of the device manufacturing apparatus 10 according to the embodiment of the present invention as viewed from above.

  As shown in the figure, the device manufacturing apparatus 10 includes a glove box glove 101, a coating apparatus (application section) 102, an oxygen filter 103, an exhaust shutter 104, an exhaust port 105, a hot plate 106, a coating film baking chamber 107, an inert film. Gas inlet 108, gas flow meter 109, dry pump 110, vacuum line 111, transfer chamber 112, silicon precursor generator (silicon precursor generator) 113, ink line 114, i-type ink tank 115, p-type Ink tank 116, n-type ink tank 117, vapor deposition apparatus (electrode formation unit) 118, dopant gas supply line 119, gas chromatography 120, gel chromatography 121, sample inlet 122, transport robot arm (transport means) 123, Rubber glove 124, firing device (baking Parts) 125, standby area 126, and a silane compound tank 127.

First, an outline of the operation of the device manufacturing apparatus 10 will be described.
The device manufacturing apparatus 10 is an apparatus for manufacturing an electronic device by forming a silicon film, a doped silicon film, an electrode, or the like on a substrate. First, in the silicon precursor generator 113, a doped silicon precursor and a silicon precursor are generated. Specifically, ultraviolet rays are irradiated while supplying a dopant gas to the silane compound in the container. The silicon precursor generator 113 collects a small amount (100 to 500 μl) of the generated silicon precursor or doped silicon precursor, confirms polymerization by mass gas chromatography analysis, and then polymerizes silicon by gel permeation chromatography. Quantify the molecular weight of the precursor or doped silicon precursor. Here, when the result of insufficient polymerization is obtained, the container is removed by the robot arm. The silicon precursor or doped silicon precursor that has been confirmed to be polymerized is diluted with an organic solvent and sent to the ink tank 116 through the ink line 114. In the coating apparatus 102, a silicon precursor or a doped silicon precursor is applied on a substrate. Thereafter, the substrate is transferred to the coating film baking chamber 107 and baked to form a silicon film or a doped silicon film. Thereafter, the substrate is transported to the vapor deposition device 118 to form electrodes.

  The silicon precursor generation device 113, the coating device 102, the baking device 125, and the vapor deposition device 118 are sealed in the glove box 101, and the inside is maintained in an inert atmosphere. Specifically, the inside of the glove box 101 is filled with an inert gas such as nitrogen, helium, or argon, and is maintained at oxygen of 0.1 ppm or less and moisture of 0.1 ppm or less.

  FIG. 3 is a cross-sectional view schematically showing the substrate transport mechanism of the device manufacturing apparatus 10. The device manufacturing apparatus 10 can carry the substrate 600 together with the substrate holder 601 by placing the substrate 600 in the substrate holder 601. Since the substrate holder 601 is formed of a material having a high thermal conductivity and a heat-resistant temperature of 800 ° C. or higher, the substrate holder 601 can be baked as it is. Examples of such a material include quartz and SUS. Note that the substrate 600 may be removed from the substrate holder 601 only when firing in the firing apparatus 125.

  Inside the transfer chamber 112, the substrate holder 601 is supported by the support column 153. As a means for transferring the substrate holder 601 from the transfer chamber 112, for example, a transfer robot arm 123 or the like is used. The substrate holder 601 can be transferred between the transfer chamber 112, the coating apparatus 102, the baking apparatus 125, and the vapor deposition apparatus 118. Further, a standby area 126 for the substrate holder 601 is provided, and the substrate holder 601 can be temporarily retracted in accordance with the progress of the process.

  An alignment camera 151 that can move along the rail 154 is provided in the transfer chamber 112, and it can be confirmed whether the substrate 600 carried in from the outside of the apparatus is installed at an accurate position of the substrate holder 601. Further, the transfer chamber 112 is provided with an inert gas inlet 108 and an exhaust line 152, and the inside can be maintained in an inert atmosphere.

  The movement of the substrate 600 in the glove box 101 is basically performed by the transfer robot arm 123. However, if necessary, an operator can operate from the outside using the rubber glove 124.

[Silicon precursor generator]
Next, the silicon precursor generator 113 will be described in detail.
FIG. 4 is a cross-sectional view schematically showing the internal configuration of the silicon precursor generator 113. As shown in the figure, the silicon precursor generation device 113 collects the first optical fiber 201, the second optical fiber 202, the light leakage prevention enclosure 203, the quartz container 204, the belt conveyor 206, and the generated silicon precursor. Syringe 207, ink line 114, guide structure 211 for moving syringe 207, robot arm 212 for removing quartz container 204 containing defective products, dopant gas supply line (gas supply unit) 119, exhaust line 214 , An organic solvent injection line 215, a stirrer 216, a first light source (light irradiation unit) 217, a second light source (light irradiation unit) 218, a flow meter 219, and a silane compound injection line 220.

  A quartz container 204 is installed on the belt conveyor 206 and is rotated so that the quartz containers 204 enter the enclosure 203 one by one. Before entering the enclosure 203, the quartz container 204 is supplied with the silane compound from the silane compound tank 127 through the silane compound injection line 220. As the silane compound, for example, cyclopentasilane can be used. The injection amount of cyclopentasilane can be set to 10 ml, for example.

  The quartz container 204 contains a stir bar 216, and the belt conveyor 206 has a magnetic stirrer function for rotating the stir bar 216. For this reason, the solution in the quartz container 204 can be stirred.

Next, when the quartz container 204 enters the enclosure 203, the dopant gas is supplied to the cyclopentasilane solution 500 in the quartz container 204 through the dopant gas supply line 119. The dopant gas can be, for example, diborane (B ₂ H ₆ ) gas. The gas flow rate can be set, for example, to 0.005 ml / min using the flow meter 219.

  Simultaneously with the supply of the dopant gas, the cyclopentasilane solution 500 in the quartz container 204 is irradiated with light of the first wavelength from the first light source 217 through the first optical fiber 201. At the same time, light of the second wavelength is emitted from the second light source 218 through the second optical fiber 202.

The light with the first wavelength is light with a wavelength of 195 nm, and the light with a second wavelength is light with a wavelength of 400 nm. The intensity of the irradiation light is 1 mW / cm ² or more 6000mW / cm ² or less. Diborane gas becomes a boron radical when irradiated with ultraviolet rays of 195 nm or less. Cyclopentasilane becomes a silane radical when irradiated with ultraviolet rays of 200 to 450 nm and starts ring-opening polymerization. By reacting the generated silane radical and boron radical, boron is bonded to the silane polymer, and a P-type doped silicon precursor polymer (doped silicon precursor) is generated.

  Thus, simultaneously with the supply of the dopant gas and the start of light irradiation, the polymerization reaction of cyclopentasilane starts. At this time, by stirring the cyclopentasilane solution 500, the polymerization reaction can be made uniform in the solution.

  Note that when the dopant gas is supplied in a large amount with respect to the amount of cyclopentasilane, the irradiation intensity of light with a wavelength of 195 nm may be weak. This is because the probability that the energy of light is transmitted to the dopant (diborane) is high. On the other hand, when the amount of dopant gas is small relative to cyclopentasilane, the energy of light may be blocked by cyclopentasilane and not sufficiently transmitted to the dopant, so the irradiation intensity of light with a wavelength of 195 nm is It should be stronger.

  As for the supply amount of the dopant gas, since there is much unreacted cyclopentasilane for a while from the start of supply, the supply reaction of the silane polymer and boron is efficiently performed by increasing the supply amount of the dopant gas. It is desirable to do so. Further, at this stage, the reaction efficiency can be further enhanced by increasing the irradiation intensity of 195 nm light for activating the dopant gas and promoting the activation of the dopant gas. On the other hand, when the generation of the P-type doped silicon precursor polymer proceeds to some extent, the amount of activated cyclopentasilane is reduced, so it is desirable to reduce the supply amount of the dopant gas. The total supply amount of the dopant gas is such that the number of boron atoms contained in the dopant gas is 1 to 10 times the number of atoms required to react with the silicon atoms contained in the cyclopentasilane solution 500, A P-type doped silicon precursor can be efficiently generated without wasting raw materials. Thus, by controlling the supply amount of the dopant gas using the flow meter 219, the doped silicon precursor polymer can be efficiently purified.

  When irradiation with light of the first wavelength and the second wavelength and supply of the dopant gas are performed for about 30 minutes, almost all of the cyclopentasilane in the cyclopentasilane solution 500 is polymerized to form a P-type doped silicon precursor polymer. Become. The P-type doped silicon precursor polymer has a structure such as compounds 1001 to 1006 shown in FIG. In the figure, X and Y are integers, or X = 2n and Y = 2n (n is an integer). The amount of dopant in the P-type doped silicon precursor polymer is such that the number of dopant atoms (here, boron atoms) contained in the polymer is 0.0001% or more and 10% relative to the number of silicon atoms contained in the polymer. The following is desirable.

In addition, as a silane compound, you may use the polymer of other silicon compounds other than cyclopentasilane. As the silicon compound, a silicon compound represented by Si _n X _m can be used. Specific examples of the compound in which m = 2n + 2 include hydrogenated silanes such as trisilane, tetrasilane, pentasilane, hexasilane, and heptasilane, and those obtained by substituting some or all of these hydrogen atoms with halogen atoms. Specific examples of m = 2n include one ring system such as cyclotrisilane, cyclotetrasilane, the above-mentioned cyclopentasilane, silylcyclopentasilane, cyclohexasilane, silylcyclohexasilane, and cycloheptasilane. Silicon hydride compounds and hexachlorocyclotrisilane, trichlorocyclotrisilane, octachlorocyclotetrasilane, tetrachlorocyclotetrasilane, decachlorocyclopentasilane, pentane in which some or all of these hydrogen atoms are substituted with halogen atoms Chlorocyclopentasilane, dodecachlorocyclohexasilane, hexachlorocyclohexasilane, tetradecachlorocycloheptasilane, heptachlorocycloheptasilane, hexabromocyclotrisilane, tribromocyclotrisilane, Interbromocyclotrisilane, tetrabromocyclotrisilane, octabromocyclotetrasilane, tetrabromocyclotetrasilane, decabromocyclopentasilane, pentabromocyclopentasilane, dodecabromocyclohexasilane, hexabromocyclohexasilane, tetradeca Examples thereof include halogenated cyclic silicon compounds such as bromocycloheptasilane and heptabromocycloheptasilane. Specific examples of the compound in which m = 2n-2 include 1,1′-biscyclobutasilane, 1,1′-biscyclopentasilane, 1,1′-biscyclohexasilane, 1,1′-bis. Cycloheptasilane, 1,1′-cyclobutasilylcyclopentasilane, 1,1′-cyclobutasilylcyclohexasilane, 1,1′-cyclobutasilylcycloheptasilane, 1,1′-cyclopentasilylcyclohexasilane Lan, 1,1′-cyclopentasilylcycloheptasilane, 1,1′-cyclohexasilylcycloheptasilane, spiro [2,2] pentasilane, spiro [3,3] heptatasilane, spiro [4,4] nonasilane, Spiro [4,5] decasilane, spiro [4,6] undecasilane, spiro [5,5] undecasilane, spiro [5,6] dodecasilane, spiro [6 6] Silicon hydride compounds having two ring systems such as tridecasilane, and silicon compounds in which some or all of these hydrogen atoms are substituted with SiH ₃ groups or halogen atoms. Further, compounds in which m = n, silicon compounds in which some or all of these hydrogen atoms are partially substituted with SiH ₃ groups or halogen atoms, and silicon compounds represented by the general formula Si _a X _b Y _c May be used. These compounds can be used in combination of two or more. In the polymerization, in addition to the ultraviolet rays, heat or other energy rays may be used.

  In addition to diborane, a group 13 element compound can be used as the dopant gas. For example, boron compounds such as tetraborane, which is a boron compound, boron halide compounds such as boron trifluoride and boron trichloride, boron-containing hydrocarbons such as methylborane, aluminum halide compounds such as aluminum chloride, trimethylaluminum Aluminum-containing hydrocarbons such as gallium halides such as gallium chloride, gallium-containing hydrocarbons such as trimethylgallium, and indium-containing hydrocarbons such as trimethylindium can be used. In addition, a compound of a Group 13 element that is a gas at normal temperature and pressure can be used. Moreover, even if it is solid at normal temperature, what is necessary is just to be usable as gas by vaporizing.

  Moreover, the light irradiation method to the cyclopentasilane solution 500 is not limited to that shown in FIG. For example, the irradiation direction of light is not limited to the top of the quartz container 204 as shown in FIG. Light may be irradiated from the side of the quartz container 204 or may be irradiated from below the quartz container 204.

  Also. In FIG. 4, light is guided by the first optical fiber 201 and the second optical fiber 202, but the method is not limited as long as the cyclopentasilane solution 500 in the quartz container 204 is reliably irradiated with light. In FIG. 4, two light sources are used, but one or a plurality of light sources may be used as long as they can emit light having a wavelength of 195 nm or less and light having a wavelength of 200 to 450 nm.

  As the light source, high pressure mercury lamp, excimer lamp, dielectric barrier discharge excimer lamp, low pressure mercury lamp, medium pressure mercury lamp, high pressure mercury lamp, ultra high pressure mercury lamp, xenon lamp, xenon mercury lamp, deuterium lamp, Use UV-LED light source, rare gas halide excimer laser, rare gas excimer laser, nitrogen laser, fluorine laser, Nd: YAG triple harmonic, Nd: YAG quadruple harmonic, Ce: LiSAF laser, semiconductor laser, etc. it can.

The enclosure 203 is provided with an exhaust line 214, and it is desirable to remove silane and borane inside the enclosure 203 by a rotary pump or the like.
The volume of the quartz container 204 is desirably 100 ml to 10 ml, and the silane compound injected into the quartz container 204 is preferably 1 to 30% of the volume of the quartz container 204.

  When the quartz container 204 is unloaded from the enclosure 203, a small amount (100 to 500 μl) of the doped silicon precursor polymer is collected from the quartz container 204 using the syringe 207. After collection, the syringe 207 moves along the guide structure 211 and supplies the collected sample to the gas chromatography 120. As shown in FIG. 1, since the gas chromatography 120 is outside the glove box 101, the sample is supplied through the sample inlet 122.

  In the gas chromatography 120, the polymerization is confirmed by mass gas chromatography analysis. Further, in the gel chromatography 121, the molecular weight of the polymerized doped silicon precursor polymer is quantified by gel permeation chromatography. Here, when a result of insufficient polymerization is obtained, the quartz container 204 is removed by the robot arm 212. In the quartz container 204 that has been confirmed to be polymerized, an organic solvent is supplied from the organic solvent injection line 215 to the quartz container 204 to dilute the doped silicon precursor polymer, and the diluted solution passes through the ink line 114 to the p-type ink tank 116. Sent.

  After the dope silicon precursor solution is fed, the quartz container 204 that has been emptied is washed and then placed on the belt conveyor 206 again for reuse. Note that the cleaning is performed after taking the glove box 101 out. The cleaning is desirably performed with a basic solution for inactivating the residual silane compound, water cleaning, and organic solvent cleaning. You may perform stirring, ultrasonic cleaning, etc. in combination with these.

  Analytical means include mass gas chromatography, gel chromatography, particle size distribution analyzer, dynamic light scatterometer, static light scatterometer, viscometer, vapor pressure measurement, osmotic pressure measurement, boiling point increase measurement, etc. Those that perform molecular weight distribution measurement, those that perform synthesis confirmation such as infrared spectroscopy, visible / ultraviolet absorption spectrum measurement, and nuclear magnetic resonance measurement can be used.

In addition to the syringe 207, the means for collecting the sample for analysis is not limited as long as a small amount of solution can be weighed.
The timing for sampling the sample for analysis may be after polymerization as described above or after dilution with an organic solvent. Moreover, you may carry out at both timings.

Those determined to be insufficiently polymerized as a result of analysis may be discarded or may be returned to the polymerization reaction process.
Yes.
In addition, analyzers such as the gas chromatography 120 and the gel chromatography 121 may be provided outside the glove box 101 as shown in FIG. 1 so as to supply the sample solution via the sample inlet 122, It may be provided in the glove box 101 and supplied from the syringe 207.

The organic solvent for dissolving the doped silicon precursor polymer is not particularly limited as long as it dissolves toluene or a silicon compound. Specific examples include carbonization of n-hexane, n-heptane, n-octane, n-decane, dicyclopentane, cyclohexane, cyclooctane, benzene, toluene, xylene, durene, indene, tetrahydronaphthalene, decahydronaphthalene, squalane and the like. In addition to hydrogen 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 Ether solvents such as (2-methoxyethyl) ether and p-dioxane, and further propylene carbonate γ- butyrolactone, N- methyl-2-pyrrolidone, dimethylformamide, acetonitrile, dimethylsulfoxide, polar solvents such as chloroform. Moreover, it is a compound represented by Si _n X _m , and m = 2n + 2 (m is an integer of 3 or more). Specific examples are trisilane, tetrasilane, pentasilane and the like. Further, a cyclic silane compound represented by Si _n X _m and m = 2n (m is an integer of 3 or more) can be used. Specific examples include liquid lower silane compounds such as cyclotrisilane, cyclotetrasilane, and cyclopentasilane. Of these, hydrocarbon solvents and ether solvents are preferred in view of the solubility of the silicon compound and the modified silicon compound and the stability of the solution, and more preferred solvents include hydrocarbon solvents. These solvents can be used alone or in admixture of two or more. In particular, a hydrocarbon solvent has a high solubility of a silicon compound, and has an effect of suppressing residual silicon compound during heat treatment.

  As described above, light having a wavelength of 195 nm (first wavelength light) for radicalizing the dopant gas and light having a wavelength of 400 nm for radicalizing cyclopentasilane are added to the cyclopentasilane solution 500. By supplying the dopant gas while simultaneously irradiating the light of the second wavelength, the P-type doped silicon precursor can be efficiently generated while activating the dopant gas and cyclopentasilane by the light irradiation. . Further, since it is not necessary to perform a long-time reaction under high temperature and high energy conditions, it is possible to prevent cyclopentasilane from volatilizing or becoming amorphous.

  Note that a non-doped silicon precursor polymer can be generated by performing the same process without supplying the dopant gas. In this case, the produced non-doped silicon precursor polymer is diluted with an organic solvent and sent to the i-type ink tank 115 through the ink line 114. Similarly, an n-type doped silicon precursor polymer can be produced using an n-type dopant. In this case, the produced N-type doped silicon precursor polymer is diluted with an organic solvent and sent to the n-type ink tank 117 through the ink line 114.

[Coating equipment]
FIG. 6 is a cross-sectional view schematically showing the internal configuration of the coating apparatus 102. As shown in the figure, the coating apparatus 102 includes an inkjet head 403, a substrate holder 405, an alignment mark 406, an alignment camera 407, a substrate base 408, a suction port 409, and a substrate push-up bar 410.

  In the coating apparatus 102, the doped silicon precursor solution sent from the silicon precursor generation apparatus 113 to the p-type ink tank 116 through the ink line 114 is applied onto the substrate 600 to form a coating film 502. Application is performed by discharging the dope silicon precursor solution in the ink tank 116 onto the substrate 600 from the inkjet head 403. In addition to the ink jet method, the coating method includes a thermal jet method, a micro contact printing method, a contact printing method, a roll-to-roll method, an intaglio printing method, a patterning method by a printing technique such as a relief printing method, a spin coating method, A method such as a dipping method can be used.

  The coating apparatus 102 is provided with an alignment camera 407 so that the dope silicon precursor solution can be applied to a desired position on the substrate 600. For example, an alignment mark 406 is provided on the substrate holder 601, and the alignment mark 406 is provided. By confirming the position with the alignment camera 407, it can be applied to the correct position.

  Further, the substrate pedestal 408 of the coating apparatus 102 is provided with a substrate push-up bar 410 and has a function of floating the substrate 600 together with the substrate holder 601 from the substrate pedestal 408. As a result, the distance between the inkjet head 403 and the substrate 600 can be shortened, and more accurate coating can be performed. Examples of a mechanism for pushing up the substrate 600 include a motor type, a hydraulic type, and a pneumatic type. Further, the coating device 102 is provided with a suction port 409 of the vacuum line 111 of the dry pump 110.

[Baking equipment]
After applying the doped silicon precursor solution in the coating apparatus 102, the substrate 600 is baked at 300 ° C. or higher in the baking apparatus 125, thereby forming a P-type doped amorphous silicon film.

  As shown in FIG. 1, the coating apparatus 102 is covered with a coating film baking chamber 107 made of quartz, stainless steel or the like. FIG. 7 is a plan view schematically showing the structure of the inside of the coating film baking chamber 107 as viewed from above. An exhaust port 701 is provided on the bottom surface of the coating film baking chamber 107, and air in the coating film baking chamber 107 is sucked by a pump or the like and exhausted from the exhaust port 105 to the outside of the glove box 101. An exhaust shutter 104 is provided, and the exhaust shutter 104 is opened only during firing. Further, the inside of the coating film baking chamber 107 is connected to the dry pump 110 through the vacuum line 111, so that the inside of the coating film baking chamber 107 can be kept in a vacuum.

  Further, an inert gas can be supplied into the coating film baking chamber 107 through the inert gas inlet 108. The inert gas to be supplied is maintained at 10 ppb or less for both oxygen and moisture through the oxygen filter 103.

  A hot plate 106 is provided in the coating film baking chamber 107, and the substrate 600 is baked by heating with the hot plate 106. The substrate 600 can be heated together with the substrate holder 601. As the heating method, in addition to the resistance heating method using the hot plate 106, a heating method using light such as far infrared rays, infrared rays, and ultraviolet rays may be used.

  During the firing, it is desirable to supply the inert gas from the inert gas inlet 108 as described above. It is desirable to adjust the flow rate of the inert gas using a gas flow meter 109 and supply the inert gas in an amount of 0.1 to 1 times the volume of the coating film baking chamber 107 per minute. Thereby, a high-quality silicon film can be formed.

  The coating film baking chamber 107 is provided with a substrate push-up rod 702 and has a function of floating the substrate 600 together with the substrate holder 601. Examples of the push-up mechanism include a motor type, a hydraulic type, and a pneumatic type.

  As described above, the substrate 600 coated with the doped silicon precursor solution in the coating apparatus 102 is baked by the baking apparatus 125, whereby a doped silicon film is formed on the substrate 600. The P-type doped silicon precursor polymer has a very high sublimation temperature because boron is bonded to the silane polymer, and the silane compound and dopant do not volatilize even when baked at 300 ° C. A silicon film containing can be formed.

  Note that a non-doped silicon film can be formed by applying a non-doped silicon precursor solution to the substrate 600 in the coating apparatus 102 and baking in the baking apparatus 125 in the same manner as described above.

[Vapor deposition equipment]
In the vapor deposition apparatus 118, electrodes can be formed on the substrate 600 by a technique such as vapor deposition by resistance heating or ion beam vapor deposition. Further, the electrode may be formed by using a sputtering method, a CVD method, or the like. Specifically, a transparent electrode such as ITO, an extraction electrode such as Al, Ni, Cu, and Au, and an auxiliary electrode are formed.
The vapor deposition apparatus 118 is provided with a substrate push-up bar and has a function of floating the substrate 600 together with the substrate holder 601. Examples of the push-up mechanism include a motor type, a hydraulic type, and a pneumatic type.

  As described above, according to the present embodiment, the dopant gas and the silane compound are activated by light irradiation in the silicon precursor generation apparatus 113 to efficiently generate the doped silicon precursor and apply it. Since the doped silicon precursor is applied to the substrate 600 in the apparatus 102 and the substrate 600 is baked by the baking apparatus 125 to form the doped silicon film, the liquid material is used and the doped silicon film is efficiently doped by a simple method. A silicon film can be formed. Further, since it is not necessary to perform a long-time reaction under high temperature and high energy conditions, it is possible to prevent the silane compound from volatilizing or becoming amorphous.

  In addition, since a series of steps are performed in the glove box 101 controlled in an inert atmosphere, a silicon precursor that easily reacts with a compound in the atmosphere can be used without being exposed to the atmosphere, and a high-quality doped silicon film can be obtained. Can do. Moreover, a doped silicon film can be manufactured safely.

  Moreover, since the vapor deposition apparatus 118 is provided in the glove box 101 and an electrode can be formed, an electronic device can be efficiently manufactured in one apparatus.

  Note that an openable / closable shutter or the like may be provided between the coating apparatus 102 and the baking apparatus 125 and between the baking apparatus 125 and the vapor deposition apparatus 118. Thereby, each process can be implemented without being influenced by the adjacent apparatus inside each apparatus.

  Next, electronic devices that can be manufactured by the device manufacturing apparatus 10 according to the present embodiment will be described with some examples.

[PIN type silicon thin film solar cell]
FIG. 8 is a cross-sectional view schematically showing the manufacturing process of the PIN-type silicon thin film solar cell.
First, as shown in FIG. 8A, in the vapor deposition apparatus 118, a transparent electrode 332 is formed on a transparent substrate 331 by a sputtering method or the like.

  Next, as shown in FIG. 8B, the P-type doped silicon precursor solution generated by the silicon precursor generation device 113 is applied on the transparent electrode 332 in the coating device 102, and the baking device 125 is 300 ° C. By baking, a P-type doped silicon film 333 having a thickness of 30 nm is formed. The thickness of the P-type doped silicon film 333 is preferably 10 nm or more and 100 nm or less.

  Next, as shown in FIG. 8C, in the coating apparatus 102, a non-doped silicon precursor produced by applying ultraviolet light to cyclopentasilane on the P-type doped silicon film 333 by the silicon precursor production apparatus 113. A polymer dissolved in an organic solvent is applied and baked at 300 ° C. in a baking apparatus 125, whereby an I-type amorphous silicon film 334 having a thickness of 500 nm is formed. The thickness of the I-type amorphous silicon film 334 is preferably 200 nm or more and 1 μm or less.

  Next, as shown in FIG. 8D, the coating apparatus 102 is obtained by irradiating a mixture of yellow phosphorus and cyclopentasilane on the I-type amorphous silicon film 334 with ultraviolet light in the silicon precursor generation apparatus 113. An N-type amorphous silicon film 335 is formed by applying a solution obtained by dissolving the obtained N-type doped silicon precursor in an organic solvent and baking it at 300 ° C. in a baking apparatus 125. The thickness of the N-type amorphous silicon film 335 is preferably 10 nm or more and 100 nm or less.

  Finally, as shown in FIG. 8E, a PIN type silicon thin film solar cell is formed by forming an electrode 336 by depositing aluminum on the N type amorphous silicon film 335 by sputtering or the like in the vapor deposition apparatus 118. A battery is obtained.

[HIT solar cell]
FIG. 9 is a cross-sectional view schematically showing the structure of a HIT type solar cell. The manufacturing method of a HIT type solar cell will be described with reference to FIG.
First, in the coating apparatus 102, a non-doped silicon precursor polymer generated in the silicon precursor generation apparatus 113 is applied to the N-type silicon substrate 70 in an organic solvent by a spin coating method or the like. By baking at 300 ° C., an I-type amorphous silicon film 71 having a thickness of 7 nm is formed. The thickness of the I-type amorphous silicon film 71 is desirably 5 nm or more and 10 nm or less. It is desirable to use an N-type silicon substrate 70 having a texture structure with good light collection efficiency.

  Next, in the coating apparatus 102, the P-type doped silicon precursor solution generated in the silicon precursor generation apparatus 113 is applied on the I-type amorphous silicon film 71 by a spin coating method or the like, and in the baking apparatus 125, 300 ° C. By baking, a P-type doped silicon film 72 having a thickness of 30 nm is formed. The thickness of the P-type doped silicon film 72 is desirably 10 nm or more and 100 nm or less.

  Next, in the vapor deposition apparatus 118, the transparent electrode 73 is formed on the P-type doped silicon film 72 by sputtering or the like, and the auxiliary electrode 75 is formed on the transparent electrode 73 with aluminum. An aluminum electrode 74 is formed on the back surface of the N-type silicon substrate 70 by sputtering or the like. The auxiliary electrode 75 can be formed by a method such as vapor deposition, sputtering, CVD, electrode formation with a liquid material such as conductive tape or metal fine particles, electroless plating, or electrolytic plating.

[Pn junction solar cell]
FIG. 10 is a cross-sectional view schematically showing the structure of a pn junction solar cell. A method for manufacturing a pn junction solar cell will be described with reference to FIG.
First, in the coating apparatus 102, the P-type doped silicon precursor solution generated in the silicon precursor generation apparatus 113 is applied to the N-type silicon substrate 80 by a spin coating method or the like, and is baked at 300 ° C. in the baking apparatus 125. A P-type doped silicon film 81 having a thickness of 30 nm is formed. The thickness of the P-type doped silicon film 81 is preferably 10 nm or more and 100 nm or less. It is desirable to use an N-type silicon substrate 80 having a texture structure with good light collection efficiency.

  Next, in the vapor deposition apparatus 118, the transparent electrode 82 is formed on the P-type doped silicon film 81 by sputtering or the like, and the auxiliary electrode 84 is formed on the transparent electrode 82 with aluminum. An aluminum electrode 83 is formed on the back surface of the N-type silicon substrate 80 by sputtering or the like. The auxiliary electrode 84 can be formed by a method such as vapor deposition, sputtering, CVD, electrode formation with a liquid material such as conductive tape or metal fine particles, electroless plating, or electrolytic plating.

[Thin film transistor]
FIG. 11 is a cross-sectional view schematically showing the manufacturing process of the thin film transistor.
First, as shown in FIG. 11A, in the coating apparatus 102, the non-doped silicon precursor polymer produced by the silicon precursor production apparatus 113 was dissolved in an organic solvent on an insulating substrate 411 such as a glass substrate. Apply one in the desired shape. Next, the substrate is heated (baked) at 300 ° C. for 30 minutes in a baking apparatus 125, thereby forming an I-type silicon film 412 that is an intrinsic semiconductor. The I-type silicon film 412 may be an amorphous silicon film, but may be crystallized by irradiation with excimer laser light or heating at 700 ° C. or higher after firing to form a polycrystalline silicon film.

  Next, as shown in FIG. 11B, in the coating apparatus 102, the P-type doped silicon precursor solution generated by the silicon precursor generation apparatus 113 is applied to both ends on the I-type silicon film 412, and the baking apparatus 125. The P-type doped silicon film 413 is formed by baking at 300 ° C. in FIG.

  Next, as illustrated in FIG. 11C, a gate insulating film 414 is formed so as to cover the P-type doped silicon film 413 in the vapor deposition apparatus 118. Further, as shown in FIG. 11D, a gate electrode 415 is formed by depositing a conductive film such as tantalum (Ta) on the gate insulating film 414 in an evaporation apparatus 118 and patterning the conductive film.

  Next, as illustrated in FIG. 11E, an interlayer insulating film 416 is formed so as to cover the gate electrode 415. Further, as shown in FIG. 11F, a part of the interlayer insulating film 416 is removed to form a contact hole C1. Further, as shown in FIG. 11G, wiring (source electrode and drain electrode) M1 made of a conductive film such as aluminum Al is formed inside and above the contact hole C1. The wiring M1 can be formed by forming a conductive film using, for example, a sputtering method and then patterning the conductive film.

  The examples and application examples described through the above-described embodiments can be used in appropriate combination depending on the application, or can be used with modifications or improvements, and the present invention is limited to the description of the above-described embodiments. It is not a thing.

  DESCRIPTION OF SYMBOLS 10 Device manufacturing apparatus, 101 Glove box, 102 Coating apparatus, 103 Oxygen filter, 104 Exhaust shutter, 105 Exhaust port, 106 Hot plate, 107 Coating film baking chamber, 108 Inert gas inlet, 109 Gas flow meter, 110 Dry pump , 111 vacuum line, 112 transfer chamber, 113 silicon precursor generator, 114 ink line, 115 i-type ink tank, 116 p-type ink tank, 117 n-type ink tank, 118 vapor deposition apparatus, 119 dopant gas supply line , 120 Gas chromatography, 121 Gel chromatography, 122 Sample inlet, 123 Transfer robot arm, 124 Rubber glove, 125 Baking device, 126 Standby area, 127 Silane compound tank 151 alignment camera, 152 exhaust line, 153 strut, 154 rail, 201 first optical fiber, 202 second optical fiber, 203 enclosure, 204 quartz container, 206 belt conveyor, 207 syringe, 210 ink line, 211 guide structure, 212 robot Arm, 213 dopant gas supply line, 214 exhaust line, 215 organic solvent injection line, 216 stirrer, 217 first light source, 218 second light source, 219 flow meter, 220 silane compound injection line, 403 inkjet head, 405 substrate Holder, 406 Alignment Mark, 407 Alignment Camera, 408 Substrate Base, 409 Suction Port, 410 Substrate Push-up Bar, 500 Cyclopentasilane Solution, 502 Coating Film, 600 Substrate 601 Substrate holder, 701 Exhaust port, 702 Substrate push-up rod, 70 N-type silicon substrate, 71 I-type amorphous silicon film, 72 P-type doped silicon film, 73 Transparent electrode, 74 electrode, 75 Auxiliary electrode, 80 N-type silicon substrate, 81 P-type doped silicon film, 82 transparent electrode, 83 electrode, 84 auxiliary electrode, 331 transparent substrate, 332 transparent electrode, 333 P-type doped silicon film, 334 I-type amorphous silicon film, 335 N-type amorphous silicon film, 411 insulating property Substrate, 412 I-type silicon film, 413 P-type doped silicon film, 414 Gate insulating film, 415 Gate electrode, 416 Interlayer insulating film

Claims (8)

A light irradiation unit for irradiating light to a solution containing a silane compound, and a gas supply unit for supplying a gas containing an element serving as a dopant to the solution containing the silane compound, and irradiating the solution containing the silane compound with the light While supplying a gas containing the element to be the dopant, a silicon precursor generation unit that generates a silicon precursor in which the dopant is bonded to the polymer of the silane compound,
An application unit for applying a solution containing the silicon precursor to a substrate;
A silicon manufacturing apparatus comprising: a baking unit that forms silicon on the substrate by baking the silicon precursor.   The said light irradiation part irradiates the light of the 1st wavelength for radicalizing the element used as the said dopant, and the light of the 2nd wavelength for radicalizing the said silane compound, It is characterized by the above-mentioned. 2. The silicon manufacturing apparatus according to 1.   The said gas supply part supplies the gas containing the compound of the group 13 element which is gas at normal temperature normal pressure as gas containing the element used as the said dopant, The Claim 1 or Claim 2 characterized by the above-mentioned. Silicon manufacturing equipment.   4. The silicon production according to claim 1, wherein the silicon precursor generation unit, the coating unit, and the baking unit are arranged in an atmosphere containing an inert gas. 5. apparatus.   5. The silicon manufacturing apparatus according to claim 1, further comprising a conveying unit configured to move the substrate from the coating unit to the baking unit.   The silicon manufacturing apparatus according to claim 1, wherein the application unit applies a solution containing the silicon precursor to a substrate by an ink jet method.   The silicon manufacturing apparatus according to claim 1, wherein the baking unit can introduce an inert gas during baking. A light irradiation unit for irradiating light to a solution containing a silane compound, and a gas supply unit for supplying a gas containing an element serving as a dopant to the solution containing the silane compound, and irradiating the solution containing the silane compound with the light While supplying a gas containing the element to be the dopant, a silicon precursor generation unit that generates a silicon precursor in which the dopant is bonded to the polymer of the silane compound,
An application part for applying the silicon precursor to the substrate;
By firing the silicon precursor, a firing part for forming silicon on the substrate;
The electronic device manufacturing apparatus provided with the electrode formation part which forms an electrode in the said silicon | silicone.

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