JP2010183011A - Method of manufacturing doped silicon film, method of manufacturing doped silicon precursor, and device manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method of manufacturing a doped silicon film by which much doping material is left in the doped silicon film. <P>SOLUTION: The method of manufacturing the doped silicon film 110 includes a step of applying a liquid material 108 to form a coating film 109, and a step of thermally treating the coating film 109. The liquid material 108 contains a silicon precursor composition matter, which is acquired by irradiating a solution containing a silane compound 11 and a dopant compound 12 with a first light emitted from a first light source 111 and a second light emitted from a second light source 112 having a wavelength different from that of the first light. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a technology related to devices such as a photoelectric conversion device, an integrated circuit, and a thin film transistor, for example, and more specifically, a method for manufacturing a doped silicon film in which a liquid silicon precursor is mixed and baked, and doped silicon The present invention relates to a precursor manufacturing method and a device manufacturing method.

  Conventionally, doped silicon films have been used in photoelectric conversion devices, integrated circuits, thin film transistors, and the like. This doped silicon film employs CVD (Chemical Vapor Deposition) as a method for forming amorphous silicon or a photolithography method as a method for forming a polysilicon film. However, these methods require devices such as a high-vacuum and high-energy device and an exposure / development device, which are high in cost and use efficiency of materials (for example, Patent Document 1).

  Therefore, using a mixed liquid material of a silicon precursor, a compound containing a silicon precursor and a Group 3B element of the periodic table, or a compound containing a Group 5B element of the periodic table, it is applied only to a desired region and fired (solidified). Thus, a technique for forming a silicon film or a doped silicon film has attracted attention. For example, Patent Documents 2 and 3 disclose a technique for forming all or part of a thin film such as a silicon film using a liquid material, and a technique for forming a doped silicon film using a liquid material.

JP 2000-31116 A International Publication WO00 / 59040 Pamphlet JP 2003-318191 A

  However, when forming a doped silicon film using these liquid materials, the loss rate of the doped material in the formation process is high, so that more doped material than the amount of the doped material desired to remain in the film is mixed with the silicon precursor. There was a need to do. Therefore, the use efficiency of the dope material was low.

  SUMMARY An advantage of some aspects of the invention is to solve at least a part of the problems described above, and the invention can be implemented as the following forms or application examples.

  Application Example 1 A method for producing a doped silicon film according to this application example includes a step of applying a liquid material to form a coating film, and a step of heat-treating the coating film, wherein the liquid material is silane. A silicon precursor composition obtained by irradiating a solution containing a compound and a dopant compound with the first light and the second light having a wavelength different from that of the first light is included.

  Application Example 2 In the method for manufacturing a doped silicon film, the dopant compound includes a periodic table group 3B element or a periodic table group 5B element, and the dopant compound and the silicon precursor are combined or mixed. It is preferable that it contains.

  [Application Example 3] The method for producing a doped silicon precursor described in this application example is the first in a solution in which a silicon precursor and a dopant compound containing a Group 3B element of the periodic table or a Group 5B element of the periodic table are mixed. And a step of irradiating the second light and the second precursor to bond or mix the silicon precursor and the dopant compound.

  Application Example 4 In the method for manufacturing a doped silicon precursor, the wavelength of the first light is in the range of 300 nm to 600 nm, and the wavelength of the second light is in the range of less than 300 nm and 120 nm or more. It is preferable that

  According to the above application example, a large amount of the element to be doped can remain in the formed silicon film. Moreover, it can be set as the dope silicon precursor with improved film forming property and material utilization efficiency.

  Moreover, according to the said application example, a dopant compound can be efficiently couple | bonded or mixed with the dope silicon precursor obtained by light irradiation.

  Moreover, according to the said application example, the raw material and / or waste material of the dopant compound used for manufacture can be reduced.

  Application Example 5 A device manufacturing method according to this application example includes a step of forming a first electrode on a substrate, a step of forming a first conductivity type silicon film on the first electrode, and the first conductivity type. Forming a second conductive silicon film on the silicon film; and forming a second electrode on the second conductive silicon film; and forming the first conductive silicon film, A step of applying a first liquid material on the first electrode to form a first coating film; and a step of heat-treating or light-treating the first coating film, wherein the first liquid material is a first material. A first silicon precursor composition obtained by irradiating a solution containing a silane compound and a first dopant compound with a first light and a second light having a wavelength different from that of the first light, It is characterized by.

  Application Example 6 According to the device manufacturing method described in the application example described above, the step of forming the second conductivity type silicon film is performed by applying a second liquid material on the first conductivity type silicon film. A step of forming a second coating film, and a step of heat-treating or phototreating the second coating film, wherein the second liquid material includes a first silane compound and a second dopant compound in a first solution. It is preferable that it contains the 2nd silicon precursor composition obtained by irradiating light, 3rd light from which said 1st light and a wavelength differ.

  Application Example 7 According to the device manufacturing method described in the application example, an intrinsic silicon film is formed between the step of forming the first conductivity type silicon film and the step of forming the second conductivity type silicon film. A step of forming the intrinsic silicon film, the step of forming a third coating film by applying a third liquid material on the first conductivity type silicon film, and a step of heat-treating the third coating film. Or a step of performing an optical treatment, wherein the third liquid material contains a third silane compound, and the second conductivity type silicon film is formed on the intrinsic silicon film. preferable.

  Application Example 8 According to the device manufacturing method described in the application example, it is preferable that the first to third silane compounds are cyclopentasilane.

  Application Example 9 According to the device manufacturing method described in the application example, the first conductive silicon film is a P-type silicon film, and the first dopant compound includes a Group 3B element in the periodic table. It is preferable that the wavelength of the second light is in the range of less than 300 nm and 120 nm or more.

  Application Example 10 According to the device manufacturing method described in the application example, the first conductive silicon film is an N-type silicon film, and the first dopant compound includes a Group 5B element of the periodic table. It is preferable that the wavelength of the second light is in the range of less than 300 nm and 120 nm or more.

Process drawing which shows the manufacturing process of a dope silicon precursor. Process drawing which shows the process of forming dope silicon film. The front sectional view which shows the outline of the light irradiation method to the liquid mixture of a silicon precursor and a dopant compound. Process drawing which shows the manufacturing process of a PIN structure solar cell. Process drawing which shows the manufacturing process of a thin-film transistor. Sectional drawing which shows an example of the cross-section of a HIT type solar cell. Sectional drawing which shows an example of the cross-sectional structure of a PN junction solar cell. The figure which shows the compound used with the mixed solution concerning this embodiment. FIG. 3 is an exemplary diagram of a boron-doped silicon precursor polymer. Shows a silicon hydride compound and a silicon compound obtained by substituting partially SiH ₃ or a halogen group some or all of these hydrogen atoms having a polycyclic. The illustration of the boron dope material used by this embodiment.

  DESCRIPTION OF EXEMPLARY EMBODIMENTS Hereinafter, exemplary embodiments of the invention will be described with reference to the drawings. Note that the drawings to be used are appropriately enlarged or reduced so that the part to be described can be recognized.

(First embodiment)
FIG. 1 shows a process for producing a boron-doped silicon precursor polymer 14. All subsequent steps are operated in a glove box maintained at an oxygen concentration of 10 ppm or less and a moisture dew point of −65 ° C. or less.

  First, as a silane compound in glass container 100, 1 g of cyclopentasilane of compound 11 which is a silicon precursor monomer shown in FIG. 8 and 0.01 g of decaborane of compound 12 which is a boron-doped material shown in FIG. Are mixed to obtain a mixed solution 103.

Next, the glass container 100 containing the mixed solution 103 is placed on an aluminum table 105, and light having a wavelength of 405 nm is emitted from the excimer lamp 111 of 100 mW / cm ² as the first light source through the first optical fiber 104. The mixed solution 103 is irradiated with light having a wavelength of 254 nm from a 50 mW / cm ² xenon mercury lamp 112 as a second light source via the second optical fiber 106. The mixed solution 103 is shielded by the wall portion 105a of the table 105 so that light other than light of a predetermined wavelength is not irradiated. The first optical fiber 104 and the second optical fiber 106 are inserted into the through holes in the wall portion of the base 105 and are arranged so that the mixed solution 103 can be irradiated with light.

  At this time, when the mixed solution 103 is irradiated with ultraviolet light having a wavelength of 405 nm, a photo-ring-opening reaction occurs in cyclopentasilane and silane radicals are generated. The molecular weight of the silane compound is increased by bonding of the silane radicals. In addition, dehydrogenation occurs from decaborane by irradiation with ultraviolet light having a wavelength of 254 nm, and decaborane radicals are generated. By simultaneously irradiating these ultraviolet rays, a silane radical and a decaborane radical are combined to form a Si-B bond. As a result, a boron-doped silicon precursor polymer 14 containing boron and borohydride somewhere in the hydrogenated silane polymers of compounds 1001 to 1004 as shown in FIG. 9 is produced. Note that X and Y in the chemical formula shown in FIG. 9 are integers.

  When this boron-doped silicon precursor polymer 14 is compared with the mixed solution 103, the dopant compound does not volatilize even when the temperature exceeds the sublimation temperature of the dopant compound and reaches 300 ° C. where the silane compound is heat-treated. More dopant compounds can be retained in the silicon film to be formed.

  Next, as shown in FIGS. 2A to 2C, a boron-doped silicon precursor solution 108 as an example of a liquid material obtained by dissolving the boron-doped silicon precursor polymer 14 in an organic solvent, The ink is ejected from the inkjet head 106 and applied onto the substrate 107 to form a coating film 109. In this example, an inkjet method is used as a coating method. When this coating film 109 is baked (heat treatment) at 300 ° C., a boron-doped amorphous silicon film 110 as a doped silicon film is formed.

As the silicon precursor monomer used in the present embodiment, a known monomer may be used as long as it is a silicon compound represented by the general formula Si _n X _m . Examples of the compound in which m = 2n + 2 include hydrogenated silanes such as pentasilane, and compounds obtained by substituting some or all of these hydrogen atoms with halogen atoms. Specific examples of m = 2n include a silicon hydride compound having one ring system such as cyclopentasilane and a halogenated cyclic silicon compound in which some or all of these hydrogen atoms are substituted with halogen atoms. Specific examples of the compound in which m = 2n-2 include two compounds such as 1,1′-biscyclopentasilane, 1,1,1′-cyclobutasilylcyclopentasilane, spiro [2,2] pentasilane, and the like. And silicon compounds obtained by substituting some or all of these hydrogen atoms with SiH ₃ groups or halogen groups. Specific examples of the compound in which m = n include a silicon hydride compound having a polycyclic system such as compound 1 to compound 5 of the formula shown in FIG. 10 and a part or all of these hydrogen atoms. Examples thereof include silicon compounds substituted with SiH ₃ or a halogen group. These compounds can be used in combination of two or more.

An example of the boron-doped material used in this embodiment is shown in FIG. Examples thereof include borohydride compounds such as monoborane, diborane, tetraborane, pentaborane, hexaborane, and decaborane, and those in which some or all of these hydrogen atoms are partially substituted with SiH ₃ or halogen atoms. For example, the compound 6 to the compound 10 boron-modified silane compound represented by the formula shown in FIG.

  The mixing ratio between the silicon precursor monomer and the boron-doped material is such that the boron atom contained in the compound of the boron-doped material is within the range of 5% or less and 0.001% or more with respect to the silicon atom contained in the silicon precursor monomer. .

  An organic solvent can be used as a solvent for the mixed solution of cyclopentasilane and decaborane. The solvent to be used is not particularly limited as long as it dissolves the silicon compound and does not react with the solute, but in addition to hydrocarbon solvents such as toluene, xylene, cyclohexylbenzene, ethers such as ethylene glycol dimethyl ether, and γ -Polar solvents such as butyl lactone. Of these, hydrocarbon solvents and ether solvents are preferred in view of the solubility of the silicon compound and the stability of the solution, and more preferred solvents include hydrocarbon solvents. These solvents can be used alone or as a mixture of two or more. In particular, the hydrocarbon system is preferable from the viewpoint of improving the solubility of the silicon compound and suppressing the remaining of the silicon compound and the doping element during heat treatment and light treatment described later.

  The two types of ultraviolet irradiation methods in the present embodiment are not limited to those shown in FIG. 1, but can be modified as shown in FIGS. As shown in FIG. 3A, the first light source 201 and the second light source 202, which are two types of light sources, are installed side by side on the upper portion of the box 203, and the mixed solution 103 in the glass container 100 disposed in the box 203 has two. There is a method of irradiating various kinds of ultraviolet rays. Further, as shown in FIG. 3B, the lower portion of the box 203 is formed of a transparent member 204 such as a quartz glass plate, and one of the first light source 201 and the second light source 202 is placed on the upper portion of the box 203. There is a method in which the other is disposed under the transparent member 204 for irradiation. In this example, the first light source 201 is disposed above the box 203 and the second light source 202 is disposed below the transparent member 204. Further, as shown in FIG. 3C, the first light source 201 and the second light source 201 and the second light source 201 and the second light source can be provided so that light can be transmitted through the side surface of the box 203, for example. A method of arranging the light source 202 and irradiating from the lateral direction can be used.

  Further, the box 203 used in the present embodiment desirably has a condensing function and a structure in which the reflected light is again irradiated to the solution in order to improve the light irradiation efficiency. The material of the box 203 is preferably a metal such as SUS (stainless steel) that is not deteriorated by ultraviolet rays.

  In this embodiment, by using two or more types of light sources and adjusting the power of light of each wavelength, the polymerization rate of the silicon precursor compound and the polymerization rate of dopan are adjusted, and the efficiency of the polymerized silicon precursor is improved. The dopant compound can be bonded well. The irradiation timings of two or more types of light sources are preferably irradiated at the same time in order to simultaneously generate dopant compound radicals and silicon precursor radicals. However, when the radical lifetime of the dopant compound is sufficiently long, the irradiation timings of two or more light sources can be shifted in a pulse manner.

  The combination of the first light source and the second light source used in the present embodiment is not limited to the above-described xenon mercury lamp and excimer lamp, and xenon lamp, xenon mercury lamp, xenon flash lamp, deuterium lamp, hollow cathode lamp, tungsten A combination capable of irradiating the above-described two kinds of ultraviolet rays can be selected from light irradiation devices such as a lamp, an LED light source, an arc light source, an ultrahigh pressure UV lamp, a high pressure UV lamp, a low pressure UV lamp, and an excimer lamp. In addition, a laser light source that oscillates pulsed laser light can be used. Further, an irradiation apparatus that allows the mixed solution 103 to absorb multiphotons using a long-wavelength ultrashort pulse laser beam in the near-infrared and infrared regions can be used.

  Further, the light output from the light irradiation device can be used as light having a narrow wavelength by using a light that blocks a specific wavelength such as a band pass filter.

  In addition to the inkjet method, the coating film forming method in the present embodiment uses a liquid phase method such as a dispenser method, a spin coat method, a drop cast method, a roll coat method, a curtain coat method, a spray method, an intaglio printing method, and a relief printing method. It can be used as appropriate.

  For the firing method in the present embodiment, a heat treatment apparatus such as an oven, a baking furnace, an annealing furnace, or a hot plate can be used as appropriate.

  In this embodiment, an example is shown in which a boron-doped amorphous silicon film is formed by performing a heat treatment on the coating film, but in addition to the heat treatment, a light irradiation treatment using a halogen lamp, a UV lamp, a laser beam, or the like as a light source is performed only or simultaneously. Can be used.

(Second Embodiment)
As a silicon precursor monomer, 1 g of cyclopentasilane of Compound 11 and 0.01 mg of yellow phosphorus dissolved as a phosphorus dope material are used as a mixed solution. This mixed solution is irradiated with ultraviolet rays of 405 nm, 100 mW / cm ² and ultraviolet rays of 254 nm, 50 mW / cm ² to simultaneously cause photoopening polymerization of cyclopentasilane and decomposition of yellow phosphorus, thereby obtaining a phosphorus-doped silicon precursor polymer. The ultraviolet irradiation method uses the same method as in the first embodiment. A phosphorus-doped silicon precursor liquid material, which is an example of a liquid material dissolved in an organic solvent, is applied onto a substrate by an inkjet method to form a coating film. When the coating film is baked (heat treatment) at 300 ° C., a phosphorus-doped amorphous silicon film as a doped silicon film is formed.

Examples of the phosphorus-doped material described in the second embodiment include phosphorus allotropes such as yellow phosphorus and red phosphorus, phosphorus hydride compounds such as phosphine, diphosphine and triphosphine, and part or all of these hydrogen atoms. Those substituted with SiH ₃ or a halogen atom can be used. For example, although the compounds 6 to 10 exemplified in the first embodiment are boron-modified silane compounds, compounds obtained by substituting these borons with phosphorus can be cited as phosphorus-doped materials.

  The mixing ratio of the silicon precursor monomer and the phosphorus-doped material may be set such that the phosphorus atoms contained in the phosphorus-doped material are within a range of 5 percent or less and 0.001 percent or more with respect to the silicon atoms contained in the silicon precursor monomer. preferable.

  According to the first embodiment and the second embodiment described above, the following effects can be obtained.

  A large amount of boron atoms or phosphorus atoms can be left in the silicon film, and P-type and N-type silicon films having high electrical conductivity can be formed.

  By selecting a wavelength suitable for polymerization of the silane precursor and a wavelength suitable for decomposing the dope material and bonding with the silane compound, a modified silicon precursor having excellent film forming properties can be provided.

(Third embodiment)
In the present embodiment, an example of a process for manufacturing a PIN structure solar cell 330 as an example of a device will be described with reference to FIGS.

  A PIN structure solar cell 330 is shown in FIG. The PIN structure solar cell 330 is a device in which a lower electrode 332, a P-type semiconductor layer 333, an intrinsic semiconductor layer 334, an N-type semiconductor layer 335, and an upper electrode 336 are stacked in this order on a substrate 331. The P-type semiconductor layer 333 is formed using the boron-doped silicon film described in the first embodiment, and the N-type semiconductor layer 335 is formed using the phosphorus-doped silicon film described in the second embodiment. It is. The P-type semiconductor layer 333, the intrinsic semiconductor layer 334, and the N-type semiconductor layer 335 are formed by a liquid phase method.

  First, as shown in FIG. 4A, the lower electrode 332 (first electrode) is formed on the substrate 331. The lower electrode 332 is formed of aluminum having a film thickness of about 200 nm, for example, by sputtering. Then, as shown in FIG. 4B, the boron-doped silicon precursor solution 108 (first liquid material) described in the first embodiment is applied onto the lower battery 332 by a spin coating method, and a coating film (first Coating film) is formed. This coating film is baked at 300 ° C. for 30 minutes in an oven furnace to obtain a P-type semiconductor layer 333 which is a boron-doped amorphous silicon film (first conductivity type silicon film). At this time, the film thickness of the boron-doped amorphous silicon film is 20 nm.

Next, as shown in FIG. 4C, a solution containing the silicon precursor polymer (third liquid material) is applied onto the P-type semiconductor layer 333 by spin coating, and a coating film (third coating film) is formed. Then, this coating film is baked at 300 ° C. for 30 minutes in an oven furnace to obtain an intrinsic semiconductor layer 334 (intrinsic silicon film) which is amorphous silicon. This solution is a silicon precursor polymer obtained by irradiating a silicon precursor monomer with ultraviolet rays of 405 nm and 10 mW / cm ² and diluted with 10 weight percent in toluene. At this time, the film thickness of the amorphous silicon film is 500 nm.

  Next, as shown in FIG. 4D, the phosphorus-doped silicon precursor polymer solution described in the second embodiment is applied onto the intrinsic semiconductor layer 334 by spin coating to form a coating film (second coating film). Then, this coating film is baked (heat treatment) at 300 ° C. for 30 minutes in an oven furnace to obtain an N-type semiconductor layer 335 which is a phosphorus-doped amorphous silicon film (second conductivity type silicon film). The film thickness of the phosphorus-doped amorphous silicon film at this time is 20 nm. Next, as shown in FIG. 4E, an ITO (indium tin oxide) film having a thickness of 150 nm is formed on the N-type semiconductor layer 335 as an upper electrode 336 (second electrode) by sputtering. The PIN structure solar cell 330 is formed by the above process.

  In this embodiment, quartz glass is used as the substrate 331. However, alkali-free glass, common glass, plastic substrate, plastic film substrate, metallic conductive substrate, or the like is used instead of quartz glass depending on the subsequent process. You can also.

  In this embodiment, the light collecting function can be added to the substrate 331 by performing physical processing or chemical processing. Examples of physical methods include sand blasting, plasma etching, and laser processing. Examples of chemical methods include wet etching with acid / alkali, CMP (chemical mechanical polishing), and the like.

  In this embodiment, the P-type semiconductor layer 333, the intrinsic semiconductor layer 334, and the N-type semiconductor layer 335 are formed in this order from the substrate 331 side, but the N-type semiconductor layer 335, the intrinsic semiconductor layer 334, and the P-type semiconductor layer 333 are formed in this order. You can also. Further, the lower electrode 332 and the upper electrode 336 can form a transparent electrode on one side or both sides.

  In this embodiment, the intrinsic semiconductor layer 334 is formed with a thickness (film thickness) of 500 nm, but can also be formed in a range of 100 nm to 1 μm using amorphous silicon.

  In this embodiment, the intrinsic semiconductor layer 334 can be provided with unevenness for relaxing stress on the substrate 331 in order to prevent generation of cracks during firing and cooling.

  In this embodiment, the P-type semiconductor layer 333 and the N-type semiconductor layer 335 are formed with a thickness of 20 nm, but may be formed within a range of 1 nm to 50 nm.

  In this embodiment, ITO is used for the transparent electrode, but other conductive films such as IZO (indium / zinc / oxide), FTO (fluorine-doped tin oxide), and other thin films such as thin films can be used. Can be used if present.

  In the present embodiment, the upper electrode 336 and the lower electrode 332 are both formed of a liquid material, so that all layers constituting the device can be formed of a liquid material. Examples of the liquid material at this time include a silver fine particle dispersion solution, an ITO fine particle dispersion solution, a gold fine particle dispersion solution, a copper fine particle dispersion solution, and a nickel fine particle dispersion solution.

(Fourth embodiment)
In the present embodiment, an example of a process of manufacturing a thin film transistor as an example of a device using both the first embodiment and the second embodiment, or one of the doped silicon precursor polymer solutions is shown in FIG. This will be described with reference to a) to (g). Note that the thin film transistor 420 illustrated in FIG. 5G has a stacked structure of an insulating substrate 411, a silicon film 412, a doped silicon film 413, a gate insulating film 414, and a gate electrode 415. The gate electrode 415 includes an interlayer insulating film. The doped silicon film 413 covered with the film 416 and located on both sides of the gate electrode 415 is connected to the wiring (source electrode and drain electrode) M1 through the contact hole C1 on the upper side.

  First, as shown in FIG. 5A, a silicon precursor polymer solution similar to that described in the third embodiment is applied in a desired shape on an insulating substrate 411 such as a glass substrate. Next, the silicon film 412 which is an intrinsic semiconductor is formed by heating (baking) at 300 ° C. for 30 minutes. The silicon film 412 may be an amorphous silicon film, or may be a polycrystalline silicon film that is crystallized by irradiation with excimer laser light or heating at 700 ° C. or higher after firing.

  Next, as shown in FIG. 5B, a doped silicon precursor polymer similar to that described in the first embodiment or the second embodiment is applied and fired on both ends of the silicon film 412, and the doped silicon film 413 is formed. Form.

  Next, as shown in FIG. 5C, a gate insulating film 414 is formed so as to cover the doped silicon film 413. As shown in FIG. 5D, a gate electrode 415 is formed by depositing and patterning a conductive film such as tantalum (Ta) on the gate insulating film 414. Thereafter, as shown in FIG. 5E, an interlayer insulating film 416 is formed so as to cover the gate electrode 415, and as shown in FIG. 5F, a part of the interlayer insulating film 416 is removed to make contact. A hole C1 is formed, and as shown in FIG. 5G, a 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. Through the above process, the thin film transistor 420 is formed.

  In this embodiment, the interlayer insulating film 416 may be formed in the same manner as the gate insulating film 414. The gate insulating film 414 and the interlayer insulating film 416 can be formed by baking at 200 ° C. in a nitrogen atmosphere and further heating to 200 ° C. or higher in the air.

  The wiring M1 may be formed by forming a conductive film using a sputtering method or the like and then patterning the conductive film. Alternatively, a dispersion liquid in which conductive fine particles are dispersed may be used in forming the conductive film. When the conductive film is formed by the liquid phase method, all the constituent films of the device can be formed by the liquid phase method.

  As described above, by using the method for forming a doped silicon film disclosed in the first to fourth embodiments, the disappearance amount of the doped material can be reduced. Therefore, it is possible to reduce the amount of the dope material used, and the effect of reducing waste can be obtained. In addition, since a device can be manufactured from a liquid material, an effect of eliminating a large vacuum apparatus or an etching apparatus that requires high energy can be obtained.

  Various modifications other than the above embodiment are conceivable. Hereinafter, a modification will be described.

(Modification 1)
In addition to the PIN type solar cell described in the third embodiment, the present invention is applied to the HIT type solar cell 60 shown in FIG. 6, the photoelectric conversion device 70 using the PN junction shown in FIG. It is possible.
The HIT solar cell 60 shown in FIG. 6 includes an I-type semiconductor layer 63 formed on the upper surface of the single crystal N-type semiconductor substrate 64, a P-type semiconductor layer 62 formed on the upper surface of the I-type semiconductor layer 63, and P The transparent electrode 61 formed on the upper surface of the type semiconductor layer 62 and the metal electrode 65 formed on the lower surface of the single crystal N-type semiconductor substrate 64 are included.
7 includes a P-type semiconductor layer 72 formed on the upper surface of a single-crystal N-type semiconductor substrate 73, a transparent electrode 71 formed on the upper surface of the P-type semiconductor layer 72, and a single-crystal N-type semiconductor device. And a metal electrode 74 formed on the lower surface of the semiconductor substrate 73.
Note that in FIGS. 6 and 7, the HIT type solar cell and the photoelectric conversion device using a PN junction are N-type substrates, but the substrate is P-type and the semiconductor layer to be formed is N-type. good.

  DESCRIPTION OF SYMBOLS 11 ... Compound (cyclopentasilane), 12 ... Compound (decaborane), 60 ... HIT type solar cell, 61 ... Transparent electrode, 62 ... P type semiconductor layer, 63 ... I type semiconductor layer, 64, Single crystal N type semiconductor substrate , 65, metal electrode, 70 ... photoelectric conversion device, 71 ... transparent electrode, 72 ... P-type semiconductor layer, 73 ... single crystal N-type semiconductor substrate, 74 ... metal electrode, 100 ... glass container, 103 ... mixed solution, 104 ... Optical fiber, 105 ... stand, 106 ... inkjet head, 107 ... substrate, 108 ... boron-doped silicon precursor solution, 109 ... coating film, 110 ... boron-doped silicon film, 111, 201 ... excimer lamp as a first light source, 112, 202: Xenon mercury lamp as a second light source, 203 ... Box, 204 ... Quartz glass plate, 330 ... PIN structure solar cell, 3 DESCRIPTION OF SYMBOLS 1 ... Substrate, 332 ... Lower electrode, 333 ... P type semiconductor layer, 334 ... I type semiconductor layer, 335 ... N type semiconductor layer, 336 ... Upper electrode, 411 ... Insulating substrate, 412 ... Silicon film, 413 ... P type / N-type doped silicon film, 414... Gate insulating film, 415... Gate electrode, 416 .. interlayer insulating film, 420... Thin film transistor, C1.

Claims (10)

Forming a coating film by applying a liquid material;
Heat-treating the coating film,
The liquid material includes a silicon precursor composition obtained by irradiating a solution containing a silane compound and a dopant compound with first light and the first light and second light having a different wavelength.
A method for producing a doped silicon film. In the manufacturing method of the dope silicon film according to claim 1,
The dopant compound includes a group 3B element or a group 5B element of the periodic table, and includes a substance in which the dopant compound and the silicon precursor composition are combined or mixed. Method. A solution obtained by mixing a silicon precursor composition and a dopant compound containing a Group 3B element of the periodic table or a Group 5B element of the periodic table is irradiated with first light and second light, and the silicon precursor and the above Combining or mixing with a dopant compound,
A method for producing a doped silicon precursor. In the manufacturing method of the dope silicon precursor according to claim 3,
The wavelength of the first light is a wavelength in the range of 300 nm or more and 600 nm or less, and the wavelength of the second light is a wavelength in the range of less than 300 nm and 120 nm or more,
A method for producing a doped silicon precursor. Forming a first electrode on a substrate;
Forming a first conductivity type silicon film on the first electrode;
Forming a second conductivity type silicon film on the first conductivity type silicon film;
Forming a second electrode on the second conductivity type silicon film,
Forming the first conductive silicon film includes applying a first liquid material on the first electrode to form a first coating film; and heat-treating or light-treating the first coating film. And the first liquid material is obtained by irradiating a solution containing the first silane compound and the first dopant compound with the first light and the second light having a different wavelength from the first light. A first silicon precursor composition to be produced,
A device manufacturing method characterized by the above. In the manufacturing method of the device according to claim 5,
The step of forming the second conductivity type silicon film includes a step of applying a second liquid material on the first conductivity type silicon film to form a second coating film, and a heat treatment or light treatment of the second coating film. And irradiating a solution containing the second silane compound and the second dopant compound in the second liquid material with the first light and the third light having a wavelength different from that of the first light. A second silicon precursor composition obtained by
A device manufacturing method characterized by the above. In the manufacturing method of the device of Claim 5 or 6,
Forming an intrinsic silicon film between the step of forming the first conductivity type silicon film and the step of forming the second conductivity type silicon film;
Forming the intrinsic silicon film includes applying a third liquid material on the first conductive silicon film to form a third coating film; and heat-treating or light-treating the third coating film. And the third liquid material contains a third silane compound,
The second conductivity type silicon film is formed on the intrinsic silicon film;
A device manufacturing method characterized by the above. In the manufacturing method of the device according to any one of claims 5 to 7,
The first to third silane compounds are cyclopentasilane;
A device manufacturing method characterized by the above. In the manufacturing method of the device according to any one of claims 5 to 8,
The first conductive silicon film is a P-type silicon film, the first dopant compound is a dopant compound containing a Group 3B element of the periodic table, and the wavelength of the second light is less than 300 nm and a wavelength in the range of 120 nm or more. Is,
A device manufacturing method characterized by the above. In the manufacturing method of the device according to any one of claims 5 to 8,
The first conductive silicon film is an N-type silicon film, the first dopant compound is a dopant compound containing a Group 5B element of the periodic table, and the wavelength of the second light is less than 300 nm and a wavelength in the range of 120 nm or more. Is,
A device manufacturing method characterized by the above.

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