WO2013147202A1 - 半導体積層体及びその製造方法、半導体デバイスの製造方法、半導体デバイス、ドーパント組成物、ドーパント注入層、並びにドープ層の形成方法 - Google Patents
半導体積層体及びその製造方法、半導体デバイスの製造方法、半導体デバイス、ドーパント組成物、ドーパント注入層、並びにドープ層の形成方法 Download PDFInfo
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- WO2013147202A1 WO2013147202A1 PCT/JP2013/059629 JP2013059629W WO2013147202A1 WO 2013147202 A1 WO2013147202 A1 WO 2013147202A1 JP 2013059629 W JP2013059629 W JP 2013059629W WO 2013147202 A1 WO2013147202 A1 WO 2013147202A1
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Definitions
- the first present invention relates to a semiconductor laminate and a method for manufacturing the same.
- the second aspect of the present invention relates to a method for manufacturing a semiconductor device.
- the second aspect of the present invention also relates to a semiconductor device that can be obtained by using the method of the second aspect of the present invention for manufacturing a semiconductor device.
- the third aspect of the present invention relates to a method for forming a dopant composition, a dopant injection layer, and a dope layer.
- the third aspect of the present invention also relates to a method of manufacturing a semiconductor device using the method of the third aspect of the present invention for forming a doped layer.
- TFTs thin film transistors
- solar cells one or more silicon layers stacked on a substrate such as a silicon substrate are used.
- an amorphous silicon layer is deposited on a base material, and the amorphous silicon layer is crystallized with a laser or the like to form a polysilicon layer.
- the silicon crystal may grow abnormally and a convex portion may be formed on the surface of the polysilicon layer.
- a semiconductor stacked body is manufactured by performing light irradiation (A15) on an amorphous silicon layer (A30) (FIG. 3A)
- the resulting silicon layer is a flat portion. It has a projection (A30b) protruding from (A30a). This is because, when the amorphous silicon layer is melted and solidified while forming crystals, solidification occurs at the final stage at the grain boundary triple point, and during the solidification at the grain boundary triple point, the convex portion (A30b ) Occurs.
- Such convex portions on the surface may cause an interlayer short circuit or an interlayer leakage when an insulating layer is deposited thereon, and may cause a contact failure when an electrode is formed thereon. It is preferable to remove. Therefore, in order to obtain such a flat surface by removing such protrusions, it has been proposed to perform etching with acid, polishing, and the like (Patent Documents 1 and 2).
- Patent Documents 3 to 5 a method has been developed in which a silicon particle dispersion containing silicon particles is applied to a substrate, and the applied dispersion is dried and heated to form a silicon layer in which silicon particles are sintered.
- Second Invention In the manufacture of certain semiconductor devices, such as solar cells, in particular back contact solar cells and PERL solar cells (Passive Emitter, Rear Locally Diffused Cell), a dopant such as phosphorus or boron is selected for the semiconductor layer or substrate. Injecting into a region, a doped layer is formed only in a selected region.
- a dopant such as phosphorus or boron
- p-type and n-type doped layers and respective electrodes in contact with these doped layers are formed in selected regions on the back side.
- the back contact solar cell (B40) has a semiconductor substrate (B45) made of an n-type (or p-type or intrinsic) semiconductor, and this semiconductor substrate (B45).
- a passivation layer (B46) is disposed on the light receiving surface side, and backside electrodes (B42, B44) and a passivation layer (B48) are disposed on the backside of the semiconductor substrate (B45).
- a doped layer in which a region in contact with the electrodes (B42, B44) on the back surface side of the semiconductor substrate (B45) is selectively highly doped to n-type or p-type.
- Contact layers) (B45b) are alternately arranged.
- the other part is an intrinsic semiconductor region, a region doped with p or n at a low concentration, or a region where a pn junction is formed, and an electromotive force is generated when the region is irradiated with light.
- the electromotive force generated in this way is taken out by the n-type electrode (B42) and the p-type electrode (B44) through the n-type doped layer (B45a) and the p-type doped layer (B45b), respectively.
- the back contact solar cell (B40) by providing a doped layer (B45a, B45b) doped with p or n at a high concentration, the loss of electromotive force due to contact resistance is kept low, and the electric power generated by light (100) Can be taken out efficiently.
- the back contact solar cell is usually formed on the back surface with the doped layer and electrode formed on the light receiving surface side, the substantial light receiving area can be increased, thereby improving the solar cell conversion efficiency. Can be made.
- p-type or n-type doped layers and selected electrodes in contact with these doped layers are formed in selected regions on the back side.
- the PERL solar cell (B50) has a semiconductor substrate (B55) made of an n-type (or p-type or intrinsic) semiconductor, and the semiconductor substrate (B55)
- the light receiving surface side electrode (B52) and the passivation layer (B56) are disposed on the light receiving surface side, and the back surface side electrode (B54) and the passivation layer (B58) are disposed on the back surface side of the semiconductor substrate (B55).
- the light receiving surface side has a doped layer (B55c) which is highly doped n-type.
- Electromotive force is generated by irradiating light (B100) to an intrinsic semiconductor region, a region doped with p or n at a low concentration, or a region where a pn junction is formed.
- the electromotive force generated in this way is taken out by the p-type electrode (B54) and the n-type electrode through the p-type doped layer (B55a) and the n-type doped layer, respectively.
- the passivation layer formed on the back surface can suppress recombination on the back surface of the substrate and improve the solar cell conversion efficiency.
- a doped layer is formed in a selected region of a semiconductor layer or a substrate, and an electrode is formed on the doped layer in the selected region.
- a diffusion mask layer (B72) is formed on the semiconductor substrate (B65) (FIGS. 13A and 13B), and the diffusion mask layer (B72) is selected.
- a hole (B72a) is opened in the exposed region to expose the semiconductor substrate (B65) (FIG. 13 (c)).
- a doping gas such as phosphorus oxychloride (POCl 3 ), coating type doping
- a doped layer (B65a) is formed in a selected region of the semiconductor substrate by a dopant injection layer (B74) formed of an agent or the like (FIG. 13D), and a diffusion mask layer (B72) and a dopant injection layer (B74) ) Is removed (FIG. 13 (e)), and a passivation layer (B68) is formed on the semiconductor substrate (B65) having the doped layer (B65a) (FIG. 13 (f)), corresponding to the doped layer (B65a).
- a doping gas such as phosphorus oxychloride (POCl 3 ), coating type doping
- POCl 3 phosphorus oxychloride
- a hole (B68a) is formed in a selected region of the passivation layer (B68) to expose the semiconductor substrate (B65), and an electrode (B62) is formed through the hole (B68a). Electrical contact is formed between the doped layer (B65a) and the electrode (B62) in the region.
- Patent Documents 6 and 7 In order to make holes in the diffusion mask layer and the passivation layer, photolithography, laser, and the like have been used (Patent Documents 6 and 7).
- a dispersion containing doped silicon particles is applied to form a dispersion layer, the dispersion layer is dried and fired, the substrate is doped, and then Thus, it has also been proposed to remove a layer derived from silicon particles (Patent Document 8).
- ⁇ 3rd invention In the production of a semiconductor device such as a solar cell, when a doped layer is formed on a semiconductor substrate, a dopant composition containing a dopant is applied to the semiconductor substrate, and the semiconductor substrate is heated in a furnace. The dopant has been diffused in the semiconductor substrate.
- heating with a furnace requires a high temperature treatment for a long time, and there is a problem that it is costly. Therefore, in recent years, a technique for diffusing a dopant from a dopant composition into a semiconductor substrate by irradiating a laser has been actively developed.
- Patent Document 9 states that heating by an electric furnace or laser irradiation can be used to diffuse a dopant using a dopant composition containing a silicon compound such as silicon oxide.
- the light absorption layer containing carbon is formed on a transparent base material, this light absorption layer is stuck to a dopant composition layer, and absorption of a laser beam is carried out. Propose to improve.
- a silicon nitride layer for passivation and antireflection is formed on a dopant composition layer, and a dopant is injected into a semiconductor substrate by irradiating a laser from the silicon nitride film. Propose to do.
- JP-A-2-163935 Japanese Patent Laid-Open No. 2006-261681 US Patent No. 7,704,866 JP 2010-519731 Special table 2010-514585 Special table 2006-80450 gazette JP 2005-150609 Gazette US Pat. No. 7,923,368 JP 2012-019162 A JP 2010-3834 A
- the silicon layer obtained by sintering the silicon particles as described above also preferably has a flat surface as described above. However, such a silicon layer generally has a relatively large convex portion on the surface. Yes. Specifically, as shown in FIG. 4, when a semiconductor laminate is manufactured by irradiating light to a single silicon particle layer (A40) (FIG. 4 (a)), the resulting silicon layer is formed by sintering particles. It has comparatively small particles (A40a) and comparatively large particles (A40b) generated by the sizing, and the relatively large particles (A40b) among them have large irregularities on the surface. Moreover, the obtained silicon layer may not have sufficient continuity due to the occurrence of portions where the sintered particles are not in contact with each other.
- a semiconductor laminate in which a highly continuous silicon layer is formed on a substrate with less surface irregularities and a method for producing such a semiconductor laminate.
- Second Invention As described above, in the manufacture of certain semiconductor devices such as back contact solar cells and PERL solar cells, a doped layer is formed in selected regions.
- the second aspect of the present invention provides a method for manufacturing a semiconductor device that does not have the above-described problems.
- the second aspect of the present invention provides a semiconductor device obtained by the method of the second aspect of the present invention.
- Patent Documents 9 and 10 discuss the use of a dopant compound containing a silicon compound such as silicon oxide or carbon.
- the dopant composition of Patent Document 9 since the dopant composition containing a silicon compound such as silicon oxide does not absorb light but only the substrate absorbs light, the substrate is damaged by laser irradiation. It can happen.
- carbon used in the light absorption layer may diffuse into the base material during laser irradiation and become an undesirable impurity.
- Non-Patent Document 1 has a problem in that it requires a CVD method using a high vacuum in order to form a silicon nitride layer for passivation and antireflection, which is costly.
- the third aspect of the present invention provides a dopant composition that does not have the above problems.
- the third aspect of the present invention is a doped layer that can be obtained using the dopant composition of the third aspect of the present invention, a method for forming a doped layer using the dopant composition of the third aspect of the present invention, and the third aspect of the present invention.
- a method for manufacturing a semiconductor device using the method for forming a doped layer is provided.
- ⁇ A1> (a) A step of applying a silicon particle dispersion containing a dispersion medium and silicon particles dispersed in the dispersion medium on a substrate to form a silicon particle dispersion layer, (B) drying the silicon particle dispersion layer to form an unsintered silicon particle layer; (C) a step of laminating a light-transmitting layer on the unsintered silicon particle layer; and (d) irradiating the unsintered silicon particle layer with light through the light-transmitting layer and Sintering the silicon particles constituting the particle layer, thereby forming a sintered silicon particle layer;
- the manufacturing method of the semiconductor laminated body which has a base material and the sintered silicon particle layer on a base material including these.
- ⁇ A2> Step (d) The method according to ⁇ A1>, wherein the light transmissive layer is maintained after light irradiation.
- ⁇ A3> Step (d) The method according to ⁇ A1>, wherein the light transmissive layer is removed by light irradiation.
- ⁇ A4> The method according to any one of ⁇ A1> to ⁇ A3>, wherein the light-transmitting layer contains any one of an organic compound, an inorganic compound, and an organic-inorganic hybrid compound.
- ⁇ A5> The method according to any one of ⁇ A1> to ⁇ A4>, wherein the light-transmitting layer contains a silicon compound.
- ⁇ A6> The method according to any one of ⁇ A1> to ⁇ A5>, wherein the light transmissive layer contains a compound having a silicon oxide or a siloxane bond.
- ⁇ A7> The method according to any one of ⁇ A1> to ⁇ A6>, wherein the light-transmitting layer is formed of spin-on glass.
- ⁇ A8> The method according to any one of ⁇ A1> to ⁇ A7>, wherein the light transmissive layer is formed by a liquid phase method.
- ⁇ A9> The method according to any one of ⁇ A1> to ⁇ A8> above, wherein the light-transmitting layer has a volume resistivity of 10 12 ⁇ ⁇ cm or more.
- ⁇ A10> The method according to any one of ⁇ A1> to ⁇ A9>, wherein the light transmissive layer has a thickness of 50 to 1,000 nm.
- ⁇ A11> The method according to any one of ⁇ A1> to ⁇ A10>, wherein the sintered silicon particle layer has a thickness of 50 to 500 nm.
- ⁇ A12> The method according to any one of ⁇ A1> to ⁇ A11>, wherein the light irradiation is performed using a laser.
- ⁇ A13> The method according to ⁇ A12>, wherein the laser has a wavelength of 600 nm or less.
- ⁇ A14> The method according to any one of ⁇ A1> to ⁇ A13>, wherein the light irradiation is performed in a non-oxidizing atmosphere.
- ⁇ A15> The method according to any one of ⁇ A1> to ⁇ A13>, wherein the light irradiation is performed in an air atmosphere.
- ⁇ A16> A semiconductor laminate having a base material and a sintered silicon particle layer on the base material, produced by the method according to any one of ⁇ A1> to ⁇ A15> above.
- ⁇ A17> A semiconductor device comprising the semiconductor laminate according to ⁇ A16> above.
- ⁇ A18> After manufacturing a semiconductor laminate having a substrate and a sintered silicon particle layer on the substrate by the method described in ⁇ A2> above, a part of the light transmissive layer is removed from the semiconductor laminate. Removing, forming an opening reaching the sintered silicon particle layer, and providing a source electrode and a drain electrode in the opening, and forming a gate electrode on the light transmissive layer, Manufacturing method of gate top contact type thin film transistor.
- ⁇ A19> A top-gate / top-contact thin film transistor manufactured by the method described in ⁇ A18> above.
- ⁇ A20> (a) base material, (B) an unsintered silicon particle layer made of silicon particles laminated on the substrate; (C) a light transmissive layer laminated on the green silicon particle layer, An unsintered silicon laminate.
- ⁇ A21> (a) base material, (B) a sintered silicon particle layer made of silicon particles laminated on the substrate; (C) a light-transmitting layer laminated on the sintered silicon particle layer, A semiconductor laminate.
- ⁇ A22> (a) glass substrate, (B) a sintered silicon particle layer made of silicon particles directly laminated on the glass substrate, and having an arithmetic average roughness of 100 nm or less, A semiconductor laminate.
- a semiconductor device manufacturing method including forming a first doped layer in a first region of a semiconductor layer or a substrate by the following steps: Providing a laminate having the following (i) and (ii): (i) first and / or second passivation layers disposed on the semiconductor layer or substrate, and (ii) first A dopant injection layer disposed in a region corresponding to the first region on the upper side of the passivation layer and on the lower side of the second passivation layer, comprising a first particle, the first particle A first dopant injection layer consisting essentially of the same element as the semiconductor layer or substrate and doped with a p-type or n-type dopant, and the first dopant injection layer of the stack
- the first region is doped with the p-type or n-type dopant to form the first doped layer, and the first doped layer is irradiated with light.
- a region corresponding to the dopant implantation layer in the first implantation layer and the passivation layer is at least partially removed.
- the method according to ⁇ B1> including the following steps: Depositing the first passivation layer on the semiconductor layer or substrate; Applying a first dispersion containing first particles to a region of the first passivation layer corresponding to the first region, wherein the first particles are the semiconductor Consisting essentially of the same element as the layer or substrate and doped with a p-type or n-type dopant, The applied first dispersion is dried to form the first dopant injection layer, and the first dopant injection layer is irradiated with light to thereby change the first region into the p-type.
- the first doped layer is formed by doping with an n-type dopant, and the region corresponding to the first dopant implanted layer in the first dopant implanted layer and the first passivation layer.
- the method according to ⁇ B1> which comprises the following steps: Applying a first dispersion containing first particles to the first region, wherein the first particles consist essentially of the same element as the semiconductor layer or substrate; And doped with a p-type or n-type dopant, Drying the applied first dispersion to form the first dopant injection layer; Depositing the second passivation layer on the semiconductor layer or substrate and the first dopant implantation layer; and a region of the second passivation layer corresponding to the first dopant implantation layer.
- the first region is doped with the p-type or n-type dopant to form the first doped layer, the first dopant injection layer, and the first A region corresponding to the first dopant implantation layer in the two passivation layers is at least partially removed;
- ⁇ B4> The method according to ⁇ B1>, including the following steps: Depositing the first passivation layer on the semiconductor layer or substrate; Applying a first dispersion containing first particles to a region of the first passivation layer corresponding to the first region, wherein the first particles are the semiconductor Consisting essentially of the same element as the layer or substrate and doped with a p-type or n-type dopant, Drying the applied first dispersion to form the first dopant injection layer; Depositing a second passivation layer on the first passivation layer and the first dopant implantation layer; and in a region of the second passivation layer corresponding to the first dopant implantation layer.
- the first region is doped with the p-type or n-type dopant by light irradiation to form the first doped layer, the first dopant injection layer, and the first And at least partially removing a region of the second passivation layer corresponding to the first dopant implantation layer.
- ⁇ B5> The method according to any one of ⁇ B1> to ⁇ B4>, further including a step of forming an electrode through the passivation layer so as to be in contact with the first doped layer.
- ⁇ B6> Any one of the items ⁇ B1> to ⁇ B5>, wherein the concentration of the dopant is 1 ⁇ 10 17 atoms / cm 3 or more at a depth of 0.1 ⁇ m from the surface of the first region.
- the method described in 1. ⁇ B7> The method according to any one of ⁇ B1> to ⁇ B6>, wherein the passivation layer has a layer thickness of 1 to 200 nm.
- the passivation layer is formed of a material selected from the group consisting of SiN, SiO 2 , Al 2 O 3 , and combinations thereof.
- the method described in 1. ⁇ B9> The method according to any one of ⁇ B1> to ⁇ B8>, wherein the semiconductor layer or substrate is a semiconductor layer or substrate of silicon, germanium, or a combination thereof.
- ⁇ B10> The method according to any one of ⁇ B1> to ⁇ B9>, wherein the dispersion is applied by a printing method.
- ⁇ B11> The method according to any one of ⁇ B1> to ⁇ B10>, wherein the average primary particle diameter of the particles is 100 nm or less.
- ⁇ B12> The method according to any one of the above items ⁇ B1> to ⁇ B11>, further comprising forming a second doped layer in the second region of the semiconductor layer or the base material by the following step: Simultaneously with application of the first dispersion, between application and drying of the first dispersion, between drying of the first dispersion and removal of the first dopant implantation layer, or with the first Applying a second dispersion containing second particles to a second region of the semiconductor layer or substrate after removal of one dopant implantation layer, wherein the second particles are , Consisting essentially of the same element as the semiconductor layer or substrate, and doped with a different type of dopant than the dopant of the first particle, Simultaneously with the drying of the first dispersion or separately from the drying of the first dispersion, the applied second dispersion is dried to form a second dopant injection layer; and By irradiating the second dopant injection layer simultaneously with the light irradiation
- a passivation layer is laminated on the semiconductor substrate or layer, In the first region of the semiconductor substrate or layer, the passivation layer is at least partially removed, the first particles are sintered to the semiconductor substrate or layer, and the first particles are And the first electrode reaching the first region is formed through the passivation layer,
- the first particle is essentially composed of the same element as the semiconductor layer or the substrate, and is doped with a p-type or n-type dopant, and the concentration of the dopant is the surface of the first region. 1 ⁇ 10 17 atoms / cm 3 or more at a depth of 0.1 ⁇ m to 0.1 ⁇ m, Semiconductor device.
- the passivation layer is at least partially removed, second particles are sintered in the semiconductor substrate or layer, and the second A second electrode reaching the second region is formed through the particles and through the passivation layer,
- the second particle is essentially composed of the same element as the semiconductor layer or substrate, and is doped with a different type of dopant from the dopant of the first particle, and the concentration of the dopant is 1 ⁇ 10 17 atoms / cm 3 or more at a depth of 0.1 ⁇ m from the surface of the second region,
- ⁇ B17> The semiconductor device according to ⁇ B15> or ⁇ B16>, which is a solar cell.
- ⁇ C1> solvent A light-absorbing particle composed of a dopant compound having a dopant element, and a material having at least one peak absorption wavelength in the range of 100 to 1000 nm, Containing a dopant composition.
- ⁇ C4> The composition according to any one of ⁇ C1> to ⁇ C3>, wherein a peak at the peak absorption wavelength is a maximum peak in a range of 200 to 2500 nm.
- ⁇ C5> The composition according to any one of ⁇ C1> to ⁇ C4>, wherein the light-absorbing particles substantially contain no dopant.
- ⁇ C6> The composition according to any one of ⁇ C1> to ⁇ C4>, wherein the light absorbing particles are doped with a dopant.
- ⁇ C7> a light-absorbing particle composed of a dopant compound having a dopant element, and a material having at least one peak absorption wavelength in the range of 100 to 1000 nm, Containing a dopant injection layer.
- Dopant injection layer having the following layers stacked on each other: A dopant compound-containing layer containing a dopant compound having a dopant element, and a light-absorbing particle-containing layer containing light-absorbing particles composed of a material having a peak absorption wavelength in the range of 100 to 1000 nm.
- ⁇ C9> The dopant injection layer according to ⁇ C8>, wherein the dopant compound-containing layer is laminated on the light-absorbing particle-containing layer.
- ⁇ C10> The dopant injection layer according to ⁇ C8>, wherein the light absorbing particle-containing layer is laminated on the dopant compound-containing layer.
- ⁇ C11> Any one of the items ⁇ C8> to ⁇ C10>, wherein the dopant compound-containing layer further contains light-absorbing particles made of a material having a peak absorption wavelength in the range of 100 to 1000 nm.
- ⁇ C12> The dopant injection layer according to any one of ⁇ C8> to ⁇ C11>, wherein the light-absorbing particle-containing layer further contains a dopant compound having a dopant element.
- ⁇ C13> The dopant injection layer according to any one of ⁇ C7> to ⁇ C12>, which is laminated on a semiconductor substrate.
- ⁇ C14> The dopant injection layer according to ⁇ C13>, wherein the light-absorbing particles are composed of the same element as that of the semiconductor substrate.
- ⁇ C15> A method for forming a doped layer, comprising irradiating the dopant injection layer according to the above ⁇ C13> or ⁇ C14> with light to diffuse the dopant element into the semiconductor substrate.
- ⁇ C16> The method according to ⁇ C15>, wherein the light-absorbing particles have an absorptance of 0.1 times or more of the absorptivity at the peak absorption wavelength at the main wavelength of the irradiated light.
- ⁇ C17> The method according to ⁇ C15> or ⁇ C16>, wherein the irradiated light is laser light.
- ⁇ C18> A method for producing a semiconductor device, comprising forming a doped layer by the method according to any one of ⁇ C15> to ⁇ C17> above.
- ⁇ C19> The method according to ⁇ C18>, wherein the semiconductor device is a solar cell.
- ⁇ C20> A semiconductor device manufactured by the method according to ⁇ C18> or ⁇ C19>.
- the sintered silicon particle layer on the substrate may have a relatively flat and highly continuous surface without an additional step of removing surface irregularities. it can.
- the sintered silicon particle layer can have a relatively flat and highly continuous surface, and therefore, when the insulating layer, the electrode, and the like are deposited thereon, it is good. A semiconductor device having characteristics can be obtained.
- a doped layer (also referred to as a “diffusion layer”) is formed in a selected region in a relatively small number of steps, and the passivation layer in a region corresponding to the doped layer is at least partially formed. Can be removed. Therefore, according to the second method of the present invention, it is possible to manufacture a semiconductor device having a doped layer only in a selected region, for example, a solar cell, particularly a back contact solar cell and a PERL solar cell, with relatively few steps. it can.
- the dopant injection layer can be easily formed by coating, and the obtained dopant injection layer is effectively doped with light such as a green laser (wavelength of 532 nm). Can be diffused into the substrate.
- the dopant composition of the third aspect of the present invention when using light-absorbing particles composed of the same element as the semiconductor substrate, the light-absorbing particles should not contain undesirable impurities. Therefore, it can suppress that such an undesirable impurity diffuses with a dopant.
- FIG. 1 is a view for explaining a first method of the present invention for manufacturing a semiconductor stacked body.
- FIG. 2 is a view for explaining a method of manufacturing a top gate / top contact type TFT using the semiconductor stacked body obtained by the method of the first aspect of the present invention for manufacturing a semiconductor stacked body.
- FIG. 3 is a diagram for explaining a method of manufacturing a semiconductor stacked body by irradiating an amorphous silicon layer with light.
- FIG. 4 is a view for explaining a method of manufacturing a semiconductor laminate by irradiating a single unsintered silicon particle layer with light.
- FIGS. 5A to 5D are cross-sectional FE-SEM photographs of the semiconductor stacked bodies obtained in Examples A1-1 to A1-4, respectively.
- FIG. 8 is a diagram for explaining a first embodiment of the second method of the present invention for forming a doped layer on a part of a substrate.
- FIG. 9 is a diagram for explaining a second embodiment of the second method of the present invention for forming a doped layer on a part of a substrate.
- FIG. 10 is a diagram for explaining a third embodiment of the second method of the present invention for forming a doped layer on a part of a substrate.
- FIG. 11 is a diagram for explaining an example of the back contact solar cell.
- FIG. 12 is a diagram for explaining an example of a PERL solar cell.
- FIG. 13 is a diagram for explaining a conventional method for forming a dope layer on a part of a substrate.
- FIG. 14 is a diagram showing a dynamic secondary ion mass spectrometry (Dynamic SIMS) result of the base material produced in Example B1.
- FIG. 15 is a view showing a field emission scanning electron microscope (FE-SEM) photograph of a cross section of the base material produced in Example B1.
- FIG. 16 is a diagram showing a dynamic secondary ion mass spectrometry (Dynamic SIMS) result of the base material produced in Example B2.
- FIG. 17 conceptually shows the light absorption by the dopant injection layer of the third aspect of the present invention (FIGS. 17A, 17C and 17D) and the light absorption by the dopant injection layer of the prior art (FIG. 17B).
- FIG. 17 is a diagram showing the light transmittance of the dopant injection layer used in Examples C1-1 to C1-3 and Comparative Example C1.
- FIG. 19 is a diagram showing the light transmittance of the dopant injection layer used in Example C2.
- FIG. 20 is a diagram showing the light transmittance of the dopant injection layer used in Example C3.
- the first inventive method for producing a semiconductor laminate having a substrate and a sintered silicon particle layer on the substrate comprises the following steps (a) to (d): (A) a step of applying a silicon particle dispersion containing silicon particles dispersed in a dispersion medium and a dispersion medium on a substrate to form a silicon particle dispersion layer; (B) drying the silicon particle dispersion layer to form a green silicon particle layer; (C) a step of laminating a light transmissive layer on the green silicon particle layer; and Sintering silicon particles to form a sintered silicon particle layer.
- step (a) of the first method of the present invention first, a silicon particle dispersion containing a dispersion medium and silicon particles dispersed in the dispersion medium is applied onto the substrate (A10), A silicon particle dispersion layer (A1) is formed (see FIG. 1A).
- the silicon particles contained in the silicon particle dispersion are not limited as long as the objects and effects of the first aspect of the present invention are not impaired as long as they are particles made of silicon.
- silicon particles for example, silicon particles as disclosed in Patent Documents 4 and 5 can be used.
- examples of the silicon particles include silicon particles obtained by a laser pyrolysis method, particularly a laser pyrolysis method using a CO 2 laser.
- the particles of the dispersion have a relatively small particle size in order to melt and sinter the particles by light irradiation to form a semiconductor laminate having a flat surface.
- the average primary particle diameter of the particles may be 1 nm or more, 3 nm or more, 5 nm or more, 10 nm or more, or 15 nm or more.
- the average primary particle diameter of the particles may be 100 nm or less, 40 nm or less, 30 nm or less, 20 nm or less, or 10 nm or less.
- the average primary particle diameter of the particles is an image taken by observation with a scanning electron microscope (SEM: Scanning Electron Microscope), a transmission electron microscope (TEM: Transmission Electron Microscope), or the like.
- the number average primary particle diameter can be obtained by directly measuring the particle diameter based on the above and analyzing the particle group having the aggregate number of 100 or more.
- the silicon particles may be doped with a p-type or n-type dopant.
- the p-type or n-type dopant is, for example, boron (B), aluminum (Al), gallium (Ga), indium (In), titanium (Ti), phosphorus (P), arsenic (As), antimony (Sb), or It is selected from the group consisting of those combinations.
- the degree to which the silicon particles are doped is determined depending on the desired concentration of the dopant in the sintered silicon particle layer as the dopant injection layer and the substrate. be able to.
- the particles have a dopant of 1 ⁇ 10 18 atoms / cm 3 or more, 1 ⁇ 10 19 atoms / cm 3 or more, 1 ⁇ 10 20 atoms / cm 3 or more, 5 ⁇ 10 20 atoms / cm 3 or more. More than or 1 ⁇ 10 21 atoms / cm 3 can be included.
- the dispersion medium of the dispersion is not limited as long as the purpose and effect of the first invention are not impaired, and therefore, for example, an organic solvent that does not react with the silicon particles used in the first invention can be used.
- the dispersion medium is a non-aqueous solvent such as alcohol, alkane, alkene, alkyne, ketone, ether, ester, aromatic compound, or nitrogen-containing ring compound, particularly isopropyl alcohol (IPA), N-methyl-2. - May be pyrrolidone (NMP), terpineol and the like.
- glycol (dihydric alcohol) like ethylene glycol can also be used as alcohol.
- the dispersion medium is preferably a dehydrated solvent in order to suppress oxidation of the particles used in the first invention.
- the base material used in the method of the first invention is not limited as long as the object and effect of the first invention are not impaired. Therefore, for example, a silicon substrate, a glass substrate, a polymer substrate, or the like can be used as the substrate. According to the first aspect of the present invention, it is difficult to obtain a sintered silicon particle layer having a flat and highly continuous surface, particularly on a glass substrate, having a relatively flat and highly continuous surface. A sintered silicon particle layer can be obtained.
- the thickness of the silicon particle dispersion layer obtained in the step (a) can be arbitrarily determined according to the thickness of the sintered silicon particle layer desired to be finally obtained.
- step (b) of the first method of the present invention the silicon particle dispersion layer 1 is dried to form an unsintered silicon particle layer (A2) (see FIG. 1B).
- the unconsolidated silicon particle layer may be a single layer or a plurality of layers may be laminated.
- the unsintered silicon particle layer of the step (b) includes an unsintered silicon particle layer containing a p-type dopant, an unsintered silicon particle layer substantially free of a dopant, and an unsintered silicon particle layer containing an n-type dopant.
- a sintered silicon particle layer having a pin structure can be obtained at a time by sintering the laminated body.
- This drying is not particularly limited as long as the dispersion medium can be substantially removed from the dispersion.
- a substrate having the dispersion is placed on a hot plate and placed in a heated atmosphere. And so on.
- the drying temperature can be selected so as not to deteriorate the particles of the substrate and the dispersion.
- the drying temperature is 50 ° C. or higher, 70 ° C. or higher, 90 ° C. or higher, and 100 ° C. or lower, 150 ° C. or lower, 200 ° C. Or below 250 ° C.
- the light transmissive layer (A3) is laminated on the unsintered silicon particle layer (A2) (see FIG. 1C).
- the light-transmitting layer is an arbitrary layer that enables the green silicon particle layer to be irradiated with light through the light-transmitting layer in the light irradiation in the step (d).
- the light-transmitting layer has a transmittance for the light irradiated in the step (d), that is, a ratio of the luminous flux of the transmitted light to the incident light is 80% or more, 85% or more, 90% or more, 95% or more, It is a layer that is 98% or more, or 99% or more.
- the light-transmitting layer is a layer having a total light transmittance measured in accordance with JIS K7361-1 having these values.
- Properties such as the material and thickness of the light-transmitting layer are not limited as long as the object and effect of the first aspect of the present invention are not impaired, and the transmittance with respect to the light irradiated in step (d), sintering. This can be determined based on the ability to planarize the silicon particle layer and the properties of this layer that are desired to remain in the resulting semiconductor stack.
- the material of such a light transmissive layer may be any of an organic compound, an inorganic compound, or an organic-inorganic hybrid compound, and in particular, may be a silicon compound.
- a silicon compound include silicon oxide, silicon nitride, and a compound having a siloxane bond.
- any method such as a gas phase method and a liquid phase method can be used.
- a gas phase method include chemical vapor deposition (CVD) and physical vapor deposition (PVD).
- vapor phase method include chemical vapor deposition (CVD) and physical vapor deposition (PVD).
- PVD physical vapor deposition
- the liquid phase method include a solution method.
- the light transmissive layer may be a so-called spin-on-glass (SOG) layer.
- SOG spin-on-glass
- an organosilicon compound is mixed with a solvent to form a spin-on-glass solution, this solution is applied to the substrate, such as by spin coating, and then The organosilicon compound is dehydrated and condensed by heating.
- organosilicon compound that can be used in forming the spin-on-glass layer include alkoxysilane, silanol, siloxane, and silicate.
- the material of the light transmissive layer is, for example, 10 10 ⁇ ⁇ cm or more, 10 11 ⁇ ⁇ cm or more, 10 12 ⁇ ⁇ cm or more, 10 13 ⁇ ⁇ cm or more, or 10 14 ⁇ ⁇ cm or more. Can have. It is preferable for the material of the light transmissive layer to have a large volume resistivity in order to use this layer as an insulating layer when the light transmissive layer is maintained after light irradiation in the step (d). Sometimes.
- the thickness of the light transmissive layer is, for example, 50 nm or more, 100 nm or more, 200 nm or more, or 300 nm or more, and can be 1,000 nm or less, 900 nm or less, 800 nm or less, or 700 nm or less.
- step (d) of the method of the first invention the unsintered silicon particle layer (A2) is irradiated with light (A15) through the light transmissive layer (A3) to the unsintered silicon particle layer (A2). Is sintered, thereby forming a sintered silicon particle layer (A5) (see FIGS. 1 (d), (d1), and (d2)).
- the light transmissive layer is a layer that essentially transmits the irradiated light. Therefore, when the green silicon particle layer is irradiated with light through the light transmissive layer, the light transmissive layer transmits a substantial portion of the irradiated light, thereby reaching the green silicon particle layer, Silicon particles can be sintered.
- the fact that the light transmissive layer is maintained after the light irradiation in the step (d) is that a semiconductor device is manufactured using the sintered silicon particle layer as the semiconductor layer and the light transmissive layer as the insulating layer. It may be preferable in some cases. However, even if the light transmissive layer is maintained after the light irradiation in the step (d), the light transmissive layer is partially or completely removed to expose the sintered silicon particle layer. It can also be made.
- a semiconductor laminate having a base material and a sintered silicon particle layer on the base material is manufactured by the method of the first invention. Thereafter, a part of the light transmissive layer is removed from the semiconductor stacked body to form an opening (A7) reaching the sintered silicon particle layer, and the source electrode S and the drain electrode D are formed in the opening (A7). And a gate electrode G is formed on the light-transmitting layer, whereby a top-gate / top-contact thin film transistor can be manufactured (see FIG. 2 (d1-1)).
- the semiconductor laminate having the base material and the sintered silicon particle layer on the base material by the method of the first invention is used.
- an electrode is formed on the light transmissive layer, and the sintered silicon particle layer is reached by heating so that the electrode penetrates the light transmissive layer, ie by using the so-called fire-through technique.
- An electrode can be formed. Such a configuration can be used in a solar cell.
- the light-transmitting layer is removed by light irradiation in the step (d) in order to eliminate the subsequent step of removing the light-transmitting layer. Also, if the light transmissive layer has been removed by light irradiation in step (d), another layer can optionally be laminated to the sintered silicon particle layer.
- the sintered silicon particle layer obtained after the light irradiation in the step (d) can have any thickness depending on the intended use, for example, 50 nm or more, 100 nm or more, or 200 nm or more, The film thickness may be 1,000 nm or less, 800 nm or less, 500 nm or less, or 300 nm or less.
- arbitrary light can be used if formation of the above sintered silicon particle layers can be achieved.
- laser light having a single wavelength, particularly laser light having a wavelength of 800 nm or less, 700 nm or less, 600 nm or less, 500 nm or less, or 400 nm or less and having a wavelength of 300 nm or more can be used.
- the light irradiation to the unsintered silicon particle layer can also be performed using a flash lamp that irradiates light in a wavelength range of a specific band (for example, 200 to 1100 nm) at a time, such as a xenon flash lamp.
- a flash lamp that irradiates light in a wavelength range of a specific band (for example, 200 to 1100 nm) at a time, such as a xenon flash lamp.
- light such as pulsed light and light that is continuously oscillated can be arbitrarily used.
- the number of pulsed light irradiations is, for example, 1 or more, 2 or more, 5 or more, or 10 or more, and 300 or less, 200 Times or less, or 150 times or less.
- the irradiation energy of the pulsed light for example, 15mJ / (cm 2 ⁇ shot ) above, 50mJ / (cm 2 ⁇ shot ) above, 100mJ / (cm 2 ⁇ shot ) above, 200mJ / (cm 2 ⁇ shot ) 300 mJ / (cm 2 ⁇ shot) or more, 350 mJ / (cm 2 ⁇ shot) or more, 400 mJ / (cm 2 ⁇ shot) or more, 500 mJ / (cm 2 ⁇ shot) or more, 600 mJ / (cm 2 ⁇ shot) As mentioned above, it can be set to 700 mJ / (cm 2 ⁇ shot) or more.
- the irradiation energy 5000mJ / (cm 2 ⁇ shot ) or less, 4000mJ / (cm 2 ⁇ shot ) or less, 3000mJ / (cm 2 ⁇ shot ) or less, 2,000mJ / (cm 2 ⁇ shot ) or less, 1 , 500mJ / (cm 2 ⁇ shot ) or less, 1,000mJ / (cm 2 ⁇ shot ) or less, 800mJ / (cm 2 ⁇ shot ) or less, or 600mJ / (cm 2 ⁇ shot) can be below.
- the irradiation time of the pulsed light can be set to, for example, 200 nanoseconds / shot or less, 100 nanoseconds / shot or less, or 50 nanoseconds / shot or less.
- the optimum conditions such as irradiation energy and number of irradiations depend on the wavelength of light irradiation used, the characteristics of the particles, etc., and those skilled in the art can optimally carry out experiments by referring to the present specification. Can be obtained.
- the light irradiation for sintering the dispersion particles is preferably performed in a non-oxidizing atmosphere, for example, an atmosphere composed of hydrogen, a rare gas, nitrogen, and a combination thereof, in order to prevent the dispersion particles from being oxidized.
- a non-oxidizing atmosphere for example, an atmosphere composed of hydrogen, a rare gas, nitrogen, and a combination thereof.
- Light irradiation can also be performed in an oxidizing atmosphere.
- argon, helium, and neon can be mentioned especially.
- the atmosphere containing hydrogen has a reducing action of the dispersion particles, and may be preferable for reducing the oxidized surface portion to form a continuous layer.
- the oxygen content of the atmosphere can be 1% by volume or less, 0.5% by volume or less, 0.1% by volume or less, or 0.01% by volume or less.
- the semiconductor laminate of the first invention has a substrate and a sintered silicon particle layer on the substrate, and is produced by the method of the first invention.
- the semiconductor laminate of the first aspect of the present invention includes, for example, (a) a base material, (b) a sintered silicon particle layer made of silicon particles laminated on the base material, and (c) a sintered silicon particle layer. It has a light-transmitting layer laminated thereon.
- the semiconductor laminate of the first invention is, for example, a sintered silicon particle layer made of (a) a glass substrate and (b) silicon particles directly laminated on the glass substrate.
- the sintered silicon particle layer has an arithmetic average roughness of 100 nm or less, 90 nm or less, 80 nm or less, 70 nm or less, 60 nm or less, 50 nm or less, or 40 nm or less.
- the unsintered silicon laminate of the first present invention can be irradiated with light.
- the unsintered silicon laminated body according to the first aspect of the present invention includes: (a) a base material; and (b) a non-sintered silicon particle layer made of silicon particles stacked on the base material. (C) having a light transmissive layer laminated on the green silicon particle layer.
- the semiconductor device of the first aspect of the present invention has the semiconductor multilayer body of the first aspect of the present invention.
- the semiconductor device of the first aspect of the present invention is a field effect transistor such as a top gate / top contact type thin film transistor or a solar cell
- the silicon layer has a highly continuous silicon layer with less surface irregularities.
- stable characteristics can be provided when an insulating layer, an electrode, or the like is deposited thereon.
- a second inventive method of manufacturing a semiconductor device includes forming a first doped layer in a first region of a semiconductor layer or substrate by the following steps.
- the method of the second aspect of the present invention first provides a laminate having the following (i) and (ii): (i) the first and / or the first disposed on the semiconductor layer or the substrate. And (ii) a first dopant injection layer disposed in a region corresponding to the first region above the first passivation layer and below the second passivation layer.
- the dopant injection layer consists of first particles, and the first particles consist essentially of the same elements as the semiconductor layer or substrate and are doped with a p-type or n-type dopant. Has been.
- the first region is doped with a p-type or n-type dopant by irradiating light to a region corresponding to the dopant injection layer of the stacked body.
- a doped layer is formed, and at least a portion of the first dopant implantation layer and the passivation layer corresponding to the first dopant implantation layer is removed.
- the dopant concentration is set to 1 ⁇ 10 17 atoms / cm 3 or more at a depth of 0.1 ⁇ m from the surface of the first region, 1 ⁇ 10 18 atoms / cm 3 or more, 1 ⁇ 10 19 atoms / cm 3 or more can be set to 1 ⁇ 10 20 atoms / cm 3 or more.
- the semiconductor device manufactured by the method of the second aspect of the present invention may be a solar cell or a thin layer transistor. Moreover, this solar cell may be a back contact solar cell or a RERL solar cell, and the first region may be on the back side of the semiconductor layer or the substrate.
- the first aspect of the second inventive method comprises the following steps: Depositing a first passivation layer on a semiconductor layer or substrate; Applying a first dispersion containing first particles to a region corresponding to the first region of the first passivation layer, wherein the first particles are a semiconductor layer or a substrate; Consisting essentially of the same element and doped with a p-type or n-type dopant, The applied first dispersion is dried to form a first dopant injection layer, and by irradiating the first dopant injection layer with light, the first region is formed with a p-type or n-type dopant. Doping to form a first doped layer and at least partially removing a region corresponding to the first dopant implanted layer in the first dopant implanted layer and the first passivation layer. .
- the passivation layer (B15) is formed on the semiconductor substrate (B15).
- B18) is deposited (FIGS. 8A and 8B), and the first dispersion containing the first particles is applied to the region corresponding to the first region of the first passivation layer (B18). Then, the dispersion is dried to form a first dopant injection layer (B2) (FIG. 8C), and the first dopant injection layer (B2) is irradiated with light (B5) to obtain the first dopant injection layer (B2).
- the region to be removed is at least partially removed (FIG. 8 (d)) and, optionally, in contact with the first doped layer (B15a), an electrode (B12) is formed through the passivation layer (B18). (FIG. 8 (e)).
- the first dispersion is applied simultaneously with the application of the first dispersion. Between the drying of the first dispersion and the removal of the first dopant implantation layer, or after the removal of the first dopant implantation layer, into the second region of the semiconductor layer or substrate. A second dispersion containing the second particles is applied.
- the applied second dispersion is dried to form a second dopant injection layer, and the first dopant injection.
- the second region of the semiconductor layer or the substrate is changed to p.
- Doping with a n-type or n-type dopant to form a second doped layer and corresponding to the second dopant implanted layer of the second dopant implanted layer and the first and / or second passivation layer The region to be removed is at least partially removed.
- the particles doped with the p-type dopant and the n-type dopant are doped. It is also possible to sinter the particles together by light irradiation or to dry them together and to sinter by light irradiation. Such a process may be beneficial to shorten the manufacturing process. In this case, applying the dispersion using a printing method such as inkjet printing or screen printing without using photolithography may be particularly beneficial to shorten the manufacturing process.
- the second book for each of the n-type doped layer and the p-type doped layer is used. It is also possible to repeat the method of the invention.
- the second particles are essentially composed of the same element as the semiconductor layer or the substrate, and are doped with a different type of dopant from the dopant of the first particles.
- the description of the present specification relating to the first doped layer can be referred to, and in particular, for the manufacturing method of the second dopant implanted layer, the doping concentration, etc., the present application relating to the first dopant implanted layer. The description in the specification can be referred to.
- the second aspect of the second inventive method comprises the following steps: Applying a first dispersion containing first particles to the first region, wherein the first particles consist essentially of the same elements as the semiconductor layer or substrate and are p-type Or doped with an n-type dopant, Drying the applied first dispersion to form a first dopant injection layer; Depositing a second passivation layer on the semiconductor layer or the substrate and the first dopant implantation layer, and irradiating the region of the second passivation layer corresponding to the first dopant implantation layer with light irradiation; By performing, the first region is doped with a p-type or n-type dopant to form a first doped layer, and the first of the first dopant implanted layer and the second passivation layer. Removing at least part of the region corresponding to the dopant implantation layer.
- the first region of the semiconductor substrate (B25) First, a first dispersion containing first particles is applied, and the dispersion is dried to form a first dopant injection layer (B2) (FIGS. 9A and 9B).
- a second passivation layer (B28) is deposited on the first dopant implantation layer (B2) (FIG. 9C) and corresponds to the first dopant implantation layer (B2) of the second passivation layer (B28).
- the first region of the semiconductor substrate is doped with a p-type or n-type dopant to form a first doped layer (B25a) by performing light irradiation (B5) on the region to be formed, and the first region Dopant injection layer (B2) and second passivation layer B28), the region corresponding to the first dopant implantation layer (B2) is at least partially removed (FIG. 9 (d)) and optionally in contact with the first doped layer (B25a) Thus, an electrode (B22) is formed through the second passivation layer (B28) (FIG. 9E).
- the second dispersion is used as described in the first aspect. Can be used to dope the second region of the semiconductor substrate with a p-type or n-type dopant.
- the third aspect of the second inventive method comprises the following steps: Depositing a first passivation layer on a semiconductor layer or substrate; Applying a first dispersion containing first particles to a region corresponding to the first region of the first passivation layer, wherein the first particles are a semiconductor layer or a substrate; Consisting essentially of the same element and doped with a p-type or n-type dopant, Drying the applied first dispersion to form a first dopant injection layer; Depositing a second passivation layer on the first passivation layer and the first dopant implantation layer, and irradiating a region of the second passivation layer corresponding to the first dopant implantation layer with light irradiation; A first region doped with a p-type or n-type dopant to form a first doped layer, a first dopant implanted layer, and a first and second passivation layer, , At least partially removing the region corresponding to the first
- the first passivation layer (B38a) is deposited (FIGS. 10A and 10B), and the first passivation layer (B38a) contains first particles in a region corresponding to the first region.
- the first dispersion is applied, and the dispersion is dried to form a first dopant injection layer (B2) (FIG. 10C), the first passivation layer (B38a) and the first dopant injection.
- a second passivation layer (B38b) is deposited on the layer (2) (FIG.
- the first region of the semiconductor substrate is doped with the p-type or n-type dopant to form the first doped layer (B35a), the first dopant injection layer (B2), and the first And in the second passivation layer (B38a, B38b) the region corresponding to the first doped layer (B35a) is at least partially removed (FIG. 10 (e)), and optionally the first An electrode (B32) is formed through the first and second passivation layers (B38a, B38b) so as to be in contact with the doped layer (B35a) (FIG. 10 (f)).
- the second dispersion is used as described in the first aspect. Can be used to dope the second region of the semiconductor substrate with a p-type or n-type dopant.
- any semiconductor layer or substrate made of a semiconductor element can be used.
- silicon, germanium, or a combination thereof can be used as the semiconductor element.
- examples of the semiconductor layer or the substrate include a silicon wafer, a gallium wafer, an amorphous silicon layer, an amorphous gallium layer, a crystalline silicon layer, and a crystalline gallium layer.
- the semiconductor layer or the substrate may be pre-doped to a concentration lower than that of the particles by the same dopant element as the particles contained in the dispersion.
- the semiconductor layer or the base material may be doped in whole or in part.
- the passivation layer that can be used in the method of the second invention can have any thickness that can function as a passivation layer, for example, 1 nm or more, 5 nm or more, 10 nm or more, 30 nm or more, 50 nm or more. It may be.
- the thickness can be 300 nm or less, 200 nm or less, 100 nm or less, 50 nm or less, 30 nm or less, 20 nm or less, or 10 nm or less. If this thickness is too thin, the properties as a passivation layer may be inferior, and if this thickness is too thick, it may not be removed by light irradiation.
- the passivation layer is the first passivation layer, i.e., depositing a dopant injection layer on the passivation layer and doping the first region with the dopant by light irradiation, the first When forming the doped layer and removing the region corresponding to the dopant injection layer and the dopant injection layer of the passivation layer, if the thickness of the passivation layer is too thick, the dopant may not be sufficiently injected into the semiconductor layer or substrate. May be.
- the passivation layer may be formed of any material that can function as a passivation layer, such as silicon nitride (SiN), silicon oxide (SiO 2 ), aluminum oxide (Al 2 O 3 ), and combinations thereof. It may be made of a material selected from the group consisting of:
- the application of the dispersion in the method of the second invention for manufacturing a semiconductor device is not particularly limited as long as the dispersion can be applied with a desired thickness and uniformity.
- an inkjet printing method, a spin coating method, Or, it can be performed by a screen printing method or the like, and particularly using a printing method such as ink jet printing or screen printing is particularly useful for applying the dispersion to a specific region and shortening the manufacturing process.
- a printing method such as ink jet printing or screen printing is particularly useful for applying the dispersion to a specific region and shortening the manufacturing process.
- the thickness of the dopant injection layer obtained when the dispersion layer is dried is 10 nm or more, 30 nm or more, 50 nm or more, 100 nm or more, or 200 nm or more, and is 2000 nm or less, 1000 nm or less, 500 nm. Or less than 300 nm.
- the thickness of the dopant implantation layer may be the degree of doping of the doped layer in the obtained semiconductor device, the thickness of the doped implantation layer that can be removed by a laser, or remaining on the semiconductor substrate or layer. The thickness can be determined in consideration of the thickness of the doped implantation layer to be formed. However, the thickness of the dopant injection layer is not particularly limited as long as the effect of the second aspect of the present invention can be obtained.
- the dispersion medium of the dispersion is not limited as long as it does not impair the object and effect of the second invention. Therefore, for example, an organic solvent that does not react with the particles used in the second invention can be used.
- this dispersion medium may be the dispersion medium mentioned in relation to the first present invention such as isopropyl alcohol (IPA).
- Dispersion particles As long as the particles of the dispersion are particles made of the same element as the semiconductor layer or the base material and doped with a p-type or n-type dopant, the dispersion particles are limited as long as the object and effect of the second aspect of the present invention are not impaired. It is not a thing.
- silicon particles or germanium particles as shown in Patent Documents 4 and 5 can be used.
- examples of the silicon particles or germanium particles include silicon particles or germanium particles obtained by a laser pyrolysis method, particularly a laser pyrolysis method using a CO 2 laser.
- the particles of the dispersion In order to inject the dopant from the particles by light irradiation, it may be preferable that the particles of the dispersion have a relatively low crystallinity of the particles and / or a relatively small particle size of the particles.
- the average primary particle diameter of the particles may be 1 nm or more, 3 nm or more, 5 nm or more, 10 nm or more, or 15 nm or more.
- the average primary particle diameter of the particles may be 100 nm or less, 50 nm or less, 40 nm or less, 30 nm or less, 20 nm or less, or 10 nm or less.
- the average primary particle diameter of the particles can be determined as described in relation to the first aspect of the present invention.
- the average primary particle size of the silicon particles was measured by TEM observation and image analysis at a magnification of 100,000 times.
- the average primary particle diameter and dispersion of the silicon particle dispersion were calculated based on a set of 500 or more n.
- the dopant that is doped with the particles of the dispersion may be either a p-type or an n-type dopant, for example, selected from the dopants mentioned in connection with the first invention.
- the degree to which the particles of the dispersion are doped can be determined depending on the dopant injection layer and the desired dopant concentration in the semiconductor layer or substrate. Specifically, for example, the dopant concentration mentioned in connection with the first aspect of the present invention may be used.
- the dopant concentration may be, for example, 1 ⁇ 10 22 atoms / cm 3 or less, or 1 ⁇ 10 21 atoms / cm 3 or less.
- the drying in the method of the second present invention for producing a semiconductor device is not particularly limited as long as the dispersion medium can be substantially removed from the dispersion.
- a substrate having the dispersion is treated with a hot plate. It can be carried out by placing it on top or in a heated atmosphere.
- the drying temperature can be selected so as not to deteriorate the particles of the base material and the dispersion, for example, 50 ° C. or higher, 70 ° C. or higher, 90 ° C. or higher, and 100 ° C. or lower, 200 ° C. or lower, 300 ° C.
- it can be selected to be 400 ° C. or lower, 500 ° C. or lower, 600 ° C. or lower, 700 ° C. or lower, or 800 ° C. or lower.
- the light irradiation in the second inventive method of manufacturing a semiconductor device diffuses the p-type or n-type dopant contained in the dopant implantation layer into a selected region of the semiconductor layer or substrate, and the first dopant implantation.
- the layer and any of the first and / or second passivation layers corresponding to the first dopant implantation layer may be any light irradiation that can at least partially be removed.
- “at least partially removed” means that at least part of the dopant injection layer and the first and / or second passivation layer is removed. Therefore, it is necessary not only to remove these layers to such an extent that electrodes can be formed on the doped layer as they are, but also to further remove the remaining layers such as a dopant injection layer by further processing such as etching and cleaning. Including cases.
- the dopant injection layer and the passivation layer, and the surface portion of the semiconductor layer or base material under them are quickly cooled by heat transfer to the main body portion of the semiconductor layer or base material. Is done. Therefore, in the second method of the present invention, the first region is doped with a p-type or n-type dopant to form a doped layer without exposing the semiconductor layer or the body portion of the substrate to high heat. Can do.
- arbitrary light can be used as long as doping of a specific region of the semiconductor layer or the substrate can be achieved as described above.
- laser light having a single wavelength or the like can be used as described in connection with the first aspect of the present invention. It is effective to perform irradiation using light having a wavelength that is absorbed by Si.
- the irradiation energy of light is too small, desired dopant implantation and removal of the dopant implantation layer and the passivation layer may not be achieved. Moreover, when the irradiation energy of light is too large, the semiconductor layer or the substrate may be damaged. Note that the optimum conditions such as irradiation energy and number of irradiations depend on the wavelength of light irradiation used, the characteristics of the particles, etc., and those skilled in the art can optimally carry out experiments by referring to the present specification. Can be obtained.
- the light irradiation for sintering the dispersion particles is performed in a non-oxidizing atmosphere, for example, an atmosphere including hydrogen, a rare gas, nitrogen, and a combination thereof. preferable.
- a specific irradiation atmosphere the description relating to the first aspect of the present invention can be referred to.
- the atmosphere containing hydrogen has a reducing action of the dispersion particles, and may be preferable for reducing the oxidized surface portion to form a continuous layer.
- the passivation layer is laminated on the semiconductor substrate or layer, and the passivation layer is at least partially removed in the first region of the semiconductor substrate or layer, and the semiconductor substrate A first electrode is formed in the material or layer, and the first electrode reaching the first region is formed through the first particle and through the passivation layer. Consisting essentially of the same element as the semiconductor layer or substrate and doped with a p-type or n-type dopant, and the concentration of the dopant is 1 ⁇ at a depth of 0.1 ⁇ m from the surface of the first region 10 17 atoms / cm 3 or more.
- the passivation layer is at least partially removed in the second region of the semiconductor substrate or layer, and the second particle is formed on the semiconductor substrate or layer.
- a second electrode reaching the second region is formed through the second particle and through the passivation layer, and the second particle is the same as the semiconductor layer or the substrate. It consists essentially of elements and is doped with a different type of dopant than the dopant of the first particles, and the concentration of the dopant is 1 ⁇ 10 17 at a depth of 0.1 ⁇ m from the surface of the second region. atoms / cm 3 or more.
- Such a semiconductor device is, for example, a solar cell or a thin layer transistor.
- the manufacturing method of the semiconductor device of the second invention is not particularly limited, but can be obtained by, for example, the method of the second invention.
- the description relating to the method of the second aspect of the present invention for manufacturing a semiconductor device can be referred to.
- the dopant composition of the third aspect of the present invention contains light absorbing particles composed of a solvent, a dopant compound having a dopant element, and a material having at least one peak absorption wavelength in the range of 100 to 1000 nm.
- a green laser (wavelength: 532 nm)
- the light-absorbing particles in the dopant injection layer (C22) are heated by absorbing at least part of the irradiated light (C10), and optionally the semiconductor underneath
- the substrate (C30) absorbs the remainder of the light (C10a) and is heated, thereby promoting the diffusion of the dopant from the dopant injection layer (C22) to the semiconductor substrate (C30).
- the conventional dopant composition does not contain light absorbing particles, and thus the resulting dopant injection layer (C23) also does not contain light absorbing particles. Therefore, in the prior art, as shown in FIG. 17B, when the light (C10) is irradiated, the light is transmitted through the conventional dopant injection layer (C23), and the semiconductor substrate (C30 underneath) ) Only absorbs light and is heated, and the heat of the semiconductor substrate (C30) is transferred to the conventional dopant injection layer (C23) to heat the dopant injection layer (C23), thereby heating the dopant injection layer (C23). ) To the semiconductor substrate (C30) is promoted.
- the dopant injection layer does not contain light absorbing particles, light passes through the dopant injection layer and is absorbed only by the underlying semiconductor substrate, thereby causing defects in the semiconductor substrate due to light irradiation. There is a possibility that the semiconductor substrate is deteriorated due to generation of heat or heat.
- the dopant composition of 3rd this invention such a problem can be suppressed because a dopant injection layer absorbs at least one part of the irradiated light.
- solvent will not be restrict
- grains used by a dopant composition can be used.
- this solvent may be a solvent such as isopropyl alcohol (IPA) mentioned as the dispersion medium in the present invention.
- IPA isopropyl alcohol
- the material constituting the light-absorbing particles used in the dopant composition of the third aspect of the present invention has at least one peak absorption wavelength in the range of 100 to 1000 nm, such as 200 to 1000 nm, 200 to 800 nm, or 200 to 600 nm.
- the peak at the peak absorption wavelength may be the maximum peak in the range of 100 to 2500 nm or 200 to 2500 nm.
- the light absorbing particles are made of, for example, a metal or metalloid element, particularly silicon, germanium, or a combination thereof.
- the metal or metalloid element generally has an absorption peak in the visible light region, and therefore can be used as light absorbing particles in the third dopant composition of the present invention.
- silicon has an absorption peak in the range of 200 nm to 400 nm.
- a metal oxide such as silicon oxide usually does not have an absorption peak in the visible light region, and therefore cannot be used as a light-absorbing particle.
- metal oxide particles that have at least one peak absorption wavelength in the range of 100 to 1000 nm can be used as the light-absorbing particles of the third aspect of the present invention.
- These light-absorbing particles in particular silicon particles or germanium particles, can be obtained, for example, by laser pyrolysis, in particular by laser pyrolysis using a CO 2 laser.
- the light absorbing particles are composed of, for example, the same element as that of the semiconductor substrate doped with the dopant composition of the third aspect of the present invention.
- the light absorbing particles may be composed of silicon, germanium, or a combination thereof.
- the light-absorbing particles may contain no dopant or may be doped with a dopant.
- substantially free of dopant means that the element to be doped is not intentionally added, and thus is not intentionally contained. This means that a trace amount of dopant may be contained.
- the light absorbing particles When the light absorbing particles are doped with a dopant, they may be doped with either a p-type or n-type dopant. This dopant is selected, for example, from the dopants mentioned for the first invention.
- the degree to which the light absorbing particles are doped can be determined depending on the concentration of the dopant compound contained in the dopant composition, the desired dopant concentration in the semiconductor substrate, and the like.
- the dopant concentration of the light-absorbing particles may be the dopant concentration mentioned in connection with the first aspect of the present invention.
- the light-absorbing particles can have an average primary particle diameter of, for example, 1 nm or more, 3 nm or more, 5 nm or more, 10 nm or more, or 15 nm or more.
- the light absorbing particles can have an average primary particle diameter of, for example, 100 nm or less, 50 nm or less, 40 nm or less, 30 nm or less, 20 nm or less, or 10 nm or less.
- a relatively small particle diameter of the light-absorbing particles may be preferable in order to uniformly heat the dopant injection layer containing the light-absorbing particles by light irradiation.
- the content of the light-absorbing particles in the dopant composition of the third aspect of the present invention can be determined in consideration of the absorbance of the light-absorbing particles with respect to the wavelength and the handleability of the dopant composition.
- the dopant composition of the third aspect of the present invention contains, for example, 0.1% by mass or more, 0.5% by mass or more, 1.0% by mass or more, 2% by mass or more, or 3% by mass or more of light absorbing particles. It may be.
- the dopant compound used in the dopant composition of the third invention has a dopant element.
- the dopant element may be either p-type or n-type. This dopant element may be those shown above for the light absorbing particles, such as boron (B), phosphorus (P), and the like.
- the specific dopant compound may be any compound that can inject the dopant element into the semiconductor substrate when heated in the dopant injection layer, and a compound generally used for this purpose can be used.
- Examples of the dopant compound having an n-type dopant include phosphate esters such as P 2 O 5 , dibutyl phosphate, tributyl phosphate, monoethyl phosphate, diethyl phosphate, triethyl phosphate, monopropyl phosphate, and dipropyl phosphate. , mention may be made of Bi 2 O 3, Sb (OCH 2 CH 3) 3, SbCl 3, H 3 AsO 4, As (OC 4 H 9) 3. Examples of the dopant compound having a p-type dopant include B 2 O 3 , Al 2 O 3 , and gallium trichloride.
- the concentration of the dopant compound in the dopant composition of the third invention and the ratio of the light-absorbing particles to the dopant compound can be determined in consideration of the doping depth of the desired doped layer, the doping concentration, and the like.
- the dopant composition of the third aspect of the present invention may contain any other component such as a binder resin, a surfactant, and a thickener as other components.
- a binder resin for example, ethyl cellulose may be used from the viewpoints of thixotropy and dispersibility of silicon particles.
- the first dopant injection layer of the third aspect of the invention contains a light-absorbing particle composed of a dopant compound having a dopant element and a material having at least one peak absorption wavelength in the range of 100 to 1000 nm. .
- the dopant injection layer of the third aspect of the present invention from the dopant injection layer (C22) as described above with reference to FIG. 17A regarding the dopant composition of the third aspect of the present invention. Diffusion of the dopant into the semiconductor substrate (C30) can be promoted.
- the second dopant injection layer of the third invention has the following layers laminated together: A dopant compound-containing layer containing a dopant compound having a dopant element, and a light-absorbing particle-containing layer containing light-absorbing particles composed of a material having a peak absorption wavelength in the range of 100 to 1000 nm.
- the dopant compound-containing layer may further contain light-absorbing particles composed of a material having a peak absorption wavelength in the range of 100 to 1000 nm.
- the light absorbing particle-containing layer may further contain a dopant compound having a dopant element. That is, in the second dopant injection layer of the third aspect of the present invention, either or both of the dopant compound-containing layer and the light absorbing particle-containing layer may be the dopant composition of the third aspect of the present invention.
- light (C10) such as a green laser (wavelength 532 nm) is irradiated.
- the light-absorbing particles in the light-absorbing particle-containing layer (C26) are heated by absorbing at least part of the irradiated light (C10), and optionally the underlying semiconductor substrate (C30)
- the remainder (C10a) of the light transmitted through the dopant compound-containing layer (C24) is absorbed and heated, whereby the diffusion of the dopant from the dopant injection layer (C24, C26) to the semiconductor substrate (C30) can be promoted.
- the dopant injection layer of the third aspect of the present invention may be laminated on a semiconductor substrate.
- the semiconductor substrate may be any semiconductor substrate that is intended to implant a dopant to form a dopant injection layer.
- the semiconductor substrate may be composed of, for example, silicon, germanium, or a combination thereof. Accordingly, examples of the semiconductor substrate include a silicon wafer, a germanium wafer, an amorphous silicon layer, an amorphous germanium layer, a crystalline silicon layer, and a crystalline germanium layer.
- the first dopant injection layer of the third invention can be formed by applying the dopant composition of the third invention to a semiconductor substrate in any manner, for example, ink jet, spin coating, or screen printing.
- the process can be particularly beneficial to shorten the manufacturing process, especially by using a printing method such as ink jet printing or screen printing.
- the dopant composition can be applied by a printing method to form a dopant injection layer having a pattern.
- the 2nd dopant injection layer of 3rd this invention is a dopant compound containing composition containing the solvent and the dopant compound instead of the dopant composition of 3rd this invention, and a solvent and light absorption particle
- the light-absorbing particle-containing composition containing can be applied to a semiconductor substrate.
- the thickness of the obtained dopant injection layer is preferably set to a thickness that allows the dopant element to be favorably injected from the dopant injection layer into the semiconductor substrate by light irradiation.
- the thickness can be 50 nm or more, 100 nm or more, or 200 nm or more, and can be 5000 nm or less, 4000 nm or less, and 3000 nm or less.
- the dopant injection layer can optionally be dried by a drying process. This drying can be performed in any manner that can substantially remove the solvent from the dopant injection layer, for example by placing the substrate having the dopant injection layer on a hot plate, in a heated atmosphere. It can be carried out.
- the drying temperature in this drying can be selected so as not to deteriorate the semiconductor substrate and the dopant injection layer, for example, 50 ° C. or higher, 70 ° C. or higher, 90 ° C. or higher, and 100 ° C. or lower, 150 ° C. or lower. , 200 ° C. or lower, or 250 ° C. or lower.
- a third inventive method of forming a doped layer includes irradiating the dopant injection layer of the third inventive light with light to diffuse the dopant element into the semiconductor substrate.
- the dopant injection layer (C22, C22, C24) is used. Diffusion of the dopant into the semiconductor substrate (30) can be promoted.
- the light-absorbing particles may have an absorbance of 0.05 times or more, or 0.1 times or more of the absorbance at the peak absorption wavelength at the main wavelength of the irradiated light. It is preferable for efficiently absorbing the irradiated light and converting it into heat.
- the light irradiation may be any light irradiation that can diffuse the dopant contained in the dopant injection layer into selected regions of the semiconductor substrate.
- any light can be used as long as the dopant can be diffused as described above.
- laser light having a single wavelength or the like can be used as described in connection with the first aspect of the present invention.
- the number of times of irradiation with pulsed light is, for example, 1 or more, 2 or more, 5 or more, or 10 times. It is above, and it can be 100 times or less, 80 times or less, or 50 times or less.
- the irradiation energy of the pulsed light for example, 15mJ / (cm 2 ⁇ shot ) above, 50mJ / (cm 2 ⁇ shot ) above, 100mJ / (cm 2 ⁇ shot ) above, 150 mJ / (cm 2 ⁇ shot) above, comprising at 200mJ / (cm 2 ⁇ shot) or 300mJ / (cm 2 ⁇ shot) above, 1,000mJ / (cm 2 ⁇ shot ) or less, to 800mJ / (cm 2 ⁇ shot) or less .
- the irradiation time of the pulsed light can be set to, for example, 200 nanoseconds / shot or less, 100 nanoseconds / shot or less, or 50 nanoseconds / shot or less.
- the number of irradiation times of the pulsed light is, for example, 1 or more, 5 or more, 10 or more, 25 Times or more, or 50 times or more, and can be 300 times or less, 200 times or less, or 100 times or less.
- the irradiation energy of the pulsed light for example, 100mJ / (cm 2 ⁇ shot ) above, 300mJ / (cm 2 ⁇ shot ) above, 500mJ / (cm 2 ⁇ shot ) above, 900 mJ / (cm 2 ⁇ shot) above, 1000mJ / (cm 2 ⁇ shot ) or more, or 1300 mJ / (a in cm 2 ⁇ shot) above, 5000mJ / (cm 2 ⁇ shot ) or less, to 4000mJ / (cm 2 ⁇ shot) or less .
- the irradiation time of the pulsed light is, for example, 50 nanoseconds / shot or more, 100 nanoseconds / shot or more, or 150 nanoseconds / shot or more, and 300 nanoseconds / shot or less, 200 nanoseconds. / Shot or less, or 180 nanoseconds / shot or less.
- the dopant injection layer breaks down, under the dopant injection layer. There is a possibility of deterioration of the characteristics of the semiconductor substrate. Moreover, when the irradiation energy per time is too small, there is a possibility that dopant diffusion to the semiconductor substrate does not occur sufficiently. Even when dopant diffusion into the semiconductor substrate occurs, if the energy is too low, the number of irradiations required to obtain the required accumulated energy increases, and the processing time is long. There is a possibility.
- Optimum conditions such as irradiation energy and the number of irradiations depend on the wavelength of light irradiation used, the characteristics of the light-absorbing particles, etc., and those skilled in the art can optimally carry out experiments by referring to the present specification. Can be obtained.
- the light irradiation can be performed in the atmosphere.
- a non-oxidizing atmosphere such as hydrogen, a rare gas, nitrogen, or a combination thereof depending on the material.
- the rare gas include argon, helium, and neon.
- the oxygen content of the atmosphere can be 1% by volume or less, 0.5% by volume or less, 0.1% by volume or less, or 0.01% by volume or less.
- a third inventive method of manufacturing a semiconductor device includes forming a doped layer by the third inventive method.
- a solar cell can be mentioned as such a semiconductor device manufactured by the method of the third aspect of the present invention.
- the semiconductor device of the third invention is manufactured by the method of the third invention for manufacturing a semiconductor device.
- the third aspect of the present invention is not limited to the above-described embodiment, and various modifications such as design changes can be added based on the knowledge of those skilled in the art, and such modifications are added. Embodiments are also included in the scope of the third invention. A new embodiment generated by the combination of the above-described embodiment and the following modified example has the effects of the combined embodiment and modified example.
- Example A1-1> the laminated body which has a structure shown in FIG.1 (d1) was obtained. That is, in Example A1, the laminated body by which the sintered silicon particle layer and the light transmissive layer were laminated
- Silicon particles were produced by a laser pyrolysis (LP) method using a CO 2 laser using SiH 4 gas as a raw material.
- the obtained silicon particles had an average primary particle size of about 7 nm.
- the silicon particles were ultrasonically dispersed in isopropyl alcohol (IPA) to obtain a silicon particle dispersion having a solid content concentration of 3% by mass.
- IPA isopropyl alcohol
- the average primary particle size of the silicon particles was calculated based on a set of 500 or more by performing image analysis at a magnification of 100,000 times by TEM observation.
- the silicon particle dispersion was applied to the substrate by dropping several drops of the silicon particle dispersion onto the substrate and spin coating at 500 rpm for 5 seconds and 4,000 rpm for 10 seconds.
- the substrate coated with the silicon particle dispersion is dried on a hot plate at 70 ° C. to remove isopropyl alcohol as a dispersion medium in the silicon particle dispersion, whereby silicon particles (average primary particle diameter of about An unsintered silicon particle layer (film thickness: 300 nm) including 7 nm) was formed.
- MSQ methylsilsesquioxane film, which is a compound having optical transparency, was formed on a substrate coated with an unsintered silicon particle layer.
- this MSQ membrane is obtained by using a solution in which MSQ is dissolved in propylene glycol monomethyl ether acetate (PGMEA) (solid content concentration: 30% by mass, manufactured by Honeywell, trade name PTS R-6) as unsintered silicon. A few drops are dropped on the substrate coated with the particle layer, spin-coated at 500 rpm for 5 seconds, and further at 3,200 rpm for 20 seconds, and then on a hot plate in an atmosphere of N 2 at 80 ° C. for 5 minutes. And dried by heating in a furnace at 400 ° C. for 60 minutes. The film thickness of the obtained MSQ film was 700 nm.
- the obtained laminate had a structure as shown in FIG.
- a YVO 4 laser (wavelength) is applied to the laminate obtained by laminating the light transmissive layer on the unsintered silicon particle layer using a laser light irradiation apparatus (trade name Osprey 355-2-0, manufactured by Quantronix). 355 nm) to sinter silicon particles in the unsintered silicon particle layer to produce a sintered silicon particle layer.
- the laser irradiation conditions were irradiation energy of 50 mJ / (cm 2 ⁇ shot), 20 shots, and laser irradiation was performed in an atmosphere containing nitrogen (N 2 ) and hydrogen (H 2 ) of 3.5%. .
- Examples A1-2 to A1-4 In Examples A1-2 to A1-4, the laser irradiation energy was changed to 100 mJ / (cm 2 ⁇ shot), 200 mJ / (cm 2 ⁇ shot), and 300 mJ / (cm 2 ⁇ shot), respectively.
- a sintered silicon particle layer was produced in the same manner as in Example A1-1.
- Example A1-2 the sintered silicon particle layer (A5) and the light transmissive layer (A3) are laminated on the structure shown in FIG. 1 (d1), that is, on the base material (A10). Had a configuration.
- the laminates obtained in Examples A1-3 and 1-4 had the configuration shown in FIG. 1 (d2), that is, only the sintered silicon particle layer (A5) was laminated on the base material (A10). Had a configuration.
- Example A1-2 to A1-4 were evaluated by observing the cross section of the silicon layer in the same manner as in Example A1-1. FE-SEM photographs of the laminates obtained in Examples A1-2 to A1-4 are shown in FIGS. 5 (b) to 5 (d), respectively. Table 1 shows the crystallinity of the sintered silicon particle layer by Raman spectroscopic analysis.
- Example A1-1 was used except that a light-transmitting layer (see below) composed mainly of silicon oxide obtained from a silanol solution was used as the light-transmitting layer. In the same manner as above, a sintered silicon particle layer was produced.
- the laser irradiation energy was 100 mJ / (cm 2 ⁇ shot), 200 mJ / (cm 2 ⁇ shot), 300 mJ / (cm 2 ⁇ shot), and 400 mJ / (respectively). cm 2 ⁇ shot).
- the laminates obtained in Examples A2-1 and A2-2 had the structure shown in FIG. 1 (d1), that is, the sintered silicon particle layer (A5) and the light transmissive layer (A3) on the base material (A10). ) Are stacked.
- the laminates obtained in Examples A2-3 and A2-4 were obtained by laminating only the sintered silicon particle layer (A5) on the structure shown in FIG. 1 (d2), that is, on the base material (A10). Had a configuration.
- Example A2-1 to A2-4 were evaluated by observing the cross section of the silicon layer in the same manner as in Example A1-1. FE-SEM photographs of the laminates obtained in Examples A2-1 to A2-4 are shown in FIGS. 6 (a) to 6 (d), respectively. In addition, Table 1 shows the crystallinity by Raman spectroscopic analysis.
- the light transmissive layer mainly composed of silicon oxide used in Examples A2-1 to A2-4 was made of unsintered silicon using a silanol solution (OCD Type-7 12000-T (manufactured by Tokyo Ohka Kogyo)). It formed on the base material with which the particle layer was apply
- this coating type insulating film used as the light transmissive layer has an ultraviolet ray and visible ray transmittance of 99% or more.
- this coating type insulating film is prepared by dropping a few drops of the above solution onto a substrate coated with an unsintered silicon particle layer, spin coating at 5,000 rpm for 15 seconds, It was obtained by heating and drying on a plate at 80 ° C. for 1 minute, 150 ° C. for 2 minutes, and further in a tube furnace under a nitrogen (N 2 ) atmosphere at 400 ° C. for 30 minutes.
- the film thickness obtained is 400 nm.
- Comparative Examples A1 to A4 sintered silicon particle layers were produced in the same manner as in Example A1-1 except that the light transmissive layer was not used.
- Comparative Example A1 ⁇ A4 respectively laser irradiation energy, 100mJ / (cm 2 ⁇ shot ), 200mJ / (cm 2 ⁇ shot), 300mJ / (cm 2 ⁇ shot), and 400mJ / (cm 2 ⁇ shot )
- the laminates obtained in Comparative Examples A1 to A4 have the configuration shown in FIG. 1 (d2), that is, the configuration in which only the sintered silicon particle layer (A5) is laminated on the base material (A10). It was.
- Examples A3-1 to A3-5 silicon particles having an average primary particle diameter of about 20 nm were used, the thickness of the light transmissive layer was changed, and a laser beam irradiation apparatus (Quantronix) was used as the light irradiation.
- Sintered silicon particle layers were produced in the same manner as in Examples A2-1 to A2-4 except that a green laser (wavelength: 532 nm) was used under the trade name Osprey 532-8-0 manufactured by the company.
- the laser irradiation energy was 1000mJ / (cm 2 ⁇ shot) ⁇ 1800mJ / (cm 2 ⁇ shot).
- the light-transmitting layers of Examples A3-1 to A3-5 are such that the spin coating conditions of the silanol solution dropped on the unsintered silicon particle layer are 20 seconds at 4000 rpm. It was fabricated in the same manner as in Examples A2-1 to A2-4 except that the film thickness was 300 nm.
- the laminates obtained in Examples A3-1 to 3-3 had the structure shown in FIG. 1 (d1), that is, the sintered silicon particle layer (A5) and the light transmissive layer (A3) on the base material (A10). ) Are stacked.
- the laminates obtained in Examples A3-4 and A3-5 have the configuration shown in FIG. 1 (d2), that is, only the sintered silicon particle layer (A5) is laminated on the base material (A10). Had a configuration.
- Examples A4-1 to A4-5 sintered silicon particle layers were produced in the same manner as in Examples A3-1 to 3-5, except that the thickness of the light transmissive layer was changed.
- the light-transmitting layers of Examples A4-1 to A4-5 are such that the spin coating condition of the silanol solution dropped on the unsintered silicon particle layer is 20 seconds at 2000 rpm. It was fabricated in the same manner as in Examples A3-1 to A3-5 except that the film thickness was 400 nm.
- the laminates obtained in Examples A4-1 to A4-3 had the structure shown in FIG. 1 (d1), that is, the sintered silicon particle layer (A5) and the light transmissive layer (A3) on the base material (A10). ) Are stacked.
- the laminates obtained in Examples A4-4 and A4-5 have the configuration shown in FIG. 1 (d2), that is, only the sintered silicon particle layer (A5) is laminated on the base material (A10). Had a configuration.
- Examples A5-1 to A5-5 In Examples A5-1 to A5-5, sintered silicon particle layers were produced in the same manner as in Examples A3-1 to A3-5, except that the thickness of the light transmissive layer was changed.
- the light-transmitting layers of Examples A5-1 to A5-5 have a spin coating condition of the silanol solution dropped on the unsintered silicon particle layer at 1000 rpm for 20 seconds. It was fabricated in the same manner as in Examples A3-1 to A3-5 except that the film thickness was 650 nm.
- the laminates obtained in Examples A5-1 to A5-4 had the structure shown in FIG. 1 (d1), that is, the sintered silicon particle layer (A5) and the light transmissive layer (A3) on the base material (A10). ) Are stacked.
- the laminate obtained in Example A5-5 has the configuration shown in FIG. 1 (d2), that is, the configuration in which only the sintered silicon particle layer (A5) is stacked on the base material (A10). It was.
- FIGS. 5 (c) and (d) for Examples A1-3 and A1-4 and the examples shown in FIGS. 6 (c) and (d) for Examples A2-3 and A2-4.
- the silicon particle layer is compared with the sintered silicon particle layer of the comparative example shown in FIGS. 7A to 7D for the comparative examples A1 to A4, the flatness of the surface is obtained in the sintered silicon particle layer of the example. And it is understood that the continuity is significantly improved. Also, it can be seen from Table 1 that the crystallinity of the sintered silicon particle layers of the examples of Examples A1-4 and A2-3 is significantly improved.
- Example B1> (Preparation of phosphorus (P) doped silicon particles) Silicon particles were produced by a laser pyrolysis (LP) method using a carbon dioxide (CO 2 ) laser using monosilane (SiH 4 ) gas as a raw material. At this time, phosphine (PH 3 ) gas was introduced together with SiH 4 gas to obtain phosphorus-doped silicon particles.
- LP laser pyrolysis
- CO 2 carbon dioxide
- phosphine (PH 3 ) gas was introduced together with SiH 4 gas to obtain phosphorus-doped silicon particles.
- the dopink concentration of the obtained phosphorus-doped silicon particles was 1 ⁇ 10 21 atoms / cm 3 .
- the obtained phosphorus-doped silicon particles had an average primary particle size of 20.5 nm.
- the average primary particle size of the silicon particles was calculated based on a set of 500 or more by performing image analysis at a magnification of 100,000 times by TEM observation.
- phosphorus-doped silicon particles obtained as described above were ultrasonically dispersed in isopropyl alcohol (IPA) to obtain a silicon particle dispersion having a solid content concentration of 2% by mass.
- IPA isopropyl alcohol
- the silicon particle dispersion was applied to the silicon substrate with a line width of 200 ⁇ m by an ink jet printer (Dimatix).
- the substrate coated with the silicon particle dispersion is dried on a hot plate at 80 ° C. to remove isopropyl alcohol, which is a dispersion medium in the silicon particle dispersion, and thereby a dopant injection layer containing silicon particles ( A layer thickness of 200 nm) was formed.
- a silicon nitride (SiN) layer having a thickness of 50 nm was formed as a passivation layer (second passivation layer) by plasma-enhanced chemical vapor deposition (PE-CVD) on the substrate on which the dopant injection layer was formed.
- PE-CVD plasma-enhanced chemical vapor deposition
- a green laser (wavelength of 532 nm) is irradiated to the laminate having the passivation layer on the dopant injection layer using a laser beam irradiation apparatus (trade name Osprey 532-8-0-2, manufactured by Quantronix). Then, the dopant was injected into the substrate, and the passivation layer and the dopant injection layer were ablated.
- the laser irradiation conditions were an irradiation energy of 700 mJ / (cm 2 ⁇ shot), 20 shots, and laser irradiation was performed in a nitrogen (N 2 ) atmosphere.
- Dynamic SIMS dynamic secondary ion mass spectrometry
- the measurement conditions are primary ion species O 2 + , primary acceleration voltage: 3.0 kV, and detection region 30 ⁇ m ⁇ .
- the result of Dynamic SIMS is shown in FIG. From this observation result, it is understood that the substrate is doped.
- FIG. 14 the evaluation results before laser irradiation are also shown for reference.
- FIG. 15A shows the observation result of the dopant injection layer before laser irradiation
- FIG. 15B shows the observation result of the dopant injection layer after laser irradiation.
- the passivation layer (SiN layer) laminated on the dopant injection layer was ablated by laser irradiation, and only a part of the silicon particle layer constituting the dopant injection layer was present on the substrate surface. It was confirmed that
- Example B2> (Creation of silicon particles) Phosphorous doped silicon particles were obtained in the same manner as Example B1. The obtained phosphorus-doped silicon particles had an average primary particle size of about 7.4 nm.
- a silicon particle dispersion was applied with a line width of 200 ⁇ m on a silicon substrate on which a passivation layer was laminated by an ink jet printer (Dimatix).
- the base material coated with the silicon particle dispersion was dried in the same manner as in Example B1 to form a silicon particle layer (layer thickness 200 nm).
- Example B3> (Preparation of boron (B) doped silicon particles) Silicon particles were produced by laser pyrolysis using a carbon dioxide (CO 2 ) laser using monosilane (SiH 4 ) gas as a raw material. At this time, diborane (B 2 H 6 ) gas was introduced together with monosilane gas to obtain boron-doped silicon particles.
- the dopink concentration of the obtained boron-doped silicon particles was 1 ⁇ 10 21 atoms / cm 3 .
- the obtained boron-doped silicon particles had an average primary particle size of about 19.7 nm.
- the average primary particle size of the silicon particles was calculated based on a set of 500 or more by performing image analysis at a magnification of 100,000 times by TEM observation.
- a silicon particle dispersion was applied with a line width of 200 ⁇ m on a silicon substrate on which a passivation layer was laminated by an ink jet printer (Dimatix).
- the base material coated with the silicon particle dispersion was dried in the same manner as in Example B1 to form a silicon particle layer (layer thickness 200 nm).
- the passivation layer (SiN layer) laminated on the dopant injection layer was ablated by laser irradiation, and only a part of the silicon particle layer constituting the dopant injection layer was present on the substrate surface. It was confirmed.
- Example B4> (Creation of silicon particles) Boron-doped silicon particles were obtained in the same manner as Example B3. The obtained boron-doped silicon particles had an average primary particle size of about 20.9 nm.
- a silicon particle dispersion was applied with a line width of 200 ⁇ m on a silicon substrate on which a passivation layer was laminated by an ink jet printer (Dimatix).
- the base material coated with the silicon particle dispersion was dried in the same manner as in Example B1 to form a silicon particle layer (layer thickness 200 nm).
- Example B5> (Creation of silicon particles) Phosphorous doped silicon particles were obtained in the same manner as Example B1. The obtained phosphorus-doped silicon particles had an average primary particle size of about 7.2 nm.
- the silicon particle dispersion was applied to the silicon substrate with a line width of 200 ⁇ m by screen printing.
- the substrate coated with the silicon particle dispersion is dried on a hot plate at 200 ° C. to remove propylene glycol, which is a dispersion medium in the silicon particle dispersion, and thereby a silicon particle layer (layer thickness: 200 nm). Formed.
- a silicon nitride (SiN) layer having a thickness of 50 nm was formed as a passivation layer (first passivation layer) on the substrate having the silicon particle layer in the same manner as in Example B1.
- Example C1-1 (Preparation of base material) The silicon substrate was ultrasonically cleaned in acetone and isopropyl alcohol for 5 minutes each. Thereafter, it was immersed in a 5% ammonium fluoride solution for 10 minutes and washed with pure water.
- Dopant composition A dopant compound-containing solution (manufactured by Filmtronics, P8545SF) and a silicon particle dispersion (solid content: 5% by mass) were mixed at a weight ratio of 1: 1 to obtain a dopant composition.
- Formation of dopant injection layer A few drops of the adjusted dopant composition were dropped on the substrate, and the dopant composition was applied to the substrate by spin coating at 500 rpm for 5 seconds and 4000 rpm for 10 seconds to form a dopant injection layer. .
- the substrate having the dopant injection layer is irradiated with a green laser (wavelength: 532 nm) using a laser beam irradiation apparatus (trade name: Osprey 532-8-0-2 manufactured by Quantronix), and the substrate is doped with the dopant. Injected.
- the laser irradiation conditions were an irradiation energy of 700 mJ / (cm 2 ⁇ shot), 20 shots, and laser irradiation was performed in a nitrogen (N 2 ) atmosphere.
- Example C1-2 As in Example C1-1, except that a dopant compound-containing solution (manufactured by Filmtronics, P8545SF) as a dopant composition and a silicon particle dispersion (solid content 5 mass%) were mixed at a weight ratio of 3: 1, A dopant injection layer was formed, and the dopant injection layer was irradiated with laser.
- a dopant compound-containing solution manufactured by Filmtronics, P8545SF
- solid content 5 mass% solid content 5 mass%
- Example C1-3 As in Example C1-1, except that a dopant compound-containing solution (manufactured by Filmtronics, P8545SF) as a dopant composition and a silicon particle dispersion (solid content 5 mass%) were mixed at a weight ratio of 1: 3, A dopant injection layer was formed, and the dopant injection layer was irradiated with laser.
- a dopant compound-containing solution manufactured by Filmtronics, P8545SF
- solid content 5 mass% solid content 5 mass%
- Comparative Example C1 The dopant injection layer was irradiated with laser in the same manner as in Example C1-1 except that a single dopant compound-containing solution (P85545SF, manufactured by Filmtronics) was used as the dopant composition.
- a single dopant compound-containing solution P85545SF, manufactured by Filmtronics
- Example C2 (Dopant composition)
- a dopant compound-containing solution (Filmtronics, P85545SF) and a silicon particle dispersion (solid content 5 mass%) were used without mixing.
- a dopant compound-containing solution (Filmtronics, P85545SF) is dropped on the substrate, and the dopant composition is applied to the substrate by spin coating at 500 rpm for 5 seconds and 4000 rpm for 10 seconds, A dopant compound-containing layer was formed.
- a silicon particle dispersion (solid content: 5% by mass) was further coated on the dopant compound-containing layer to form a light-absorbing particle-containing layer, thereby obtaining a laminate having the following constitution: (Base material) / light absorbing particle-containing layer / dopant compound-containing layer
- Example C3 (Formation of dopant injection layer) By reversing the stacking order from Example C2 and forming a dopant compound-containing layer on the light-absorbing particle-containing layer, a laminate having the following constitution was obtained: (Base material) / dopant compound-containing layer / light-absorbing particle-containing layer
- a dopant injection layer was formed as in the above Examples and Comparative Examples except that a glass substrate was used as a base material, and a spectrophotometer (Spectrophotometer, U-4000, manufactured by Hitachi) The transmittance measurement was performed.
- the results for Examples C1-1 to C1-3 and Comparative Example C1 are shown in FIG. 18, the results for Example C2 are shown in FIG. 19, and the results for Example C3 are shown in FIG.
- the dopant injection layers of Examples C1-1 to C1-3 containing silicon particles have a peak absorption wavelength in the range of 200 nm to 300 nm, thereby causing light irradiation. It is understood that it has a significant absorptance with respect to light having a wavelength of 532 nm used for the purpose. On the other hand, it is understood that the dopant injection layer of Comparative Example C1 containing no silicon particles does not substantially absorb light having a wavelength of 532 nm used for light irradiation.
- the light-absorbing particle-containing layer and the dopant compound-containing layer are laminated, it has a peak absorption wavelength in the range of 200 nm to 300 nm, thereby allowing light irradiation. It is understood that it has a significant absorptance with respect to light having a wavelength of 532 nm used for the purpose.
- Example C1-1 The surface dopant concentration of Example C1-1 was 5 ⁇ 10 19 atoms / cm 3 , and the surface dopant concentration of Comparative Example C1-1 was 2 ⁇ 10 19 atoms / cm 3 . According to this, the dopant injection layer of Example C1-1 containing silicon particles absorbed light having a wavelength of 532 nm used for light irradiation, and thus efficient diffusion of the dopant occurred. It is understood.
- Example C1-1 36 ⁇ / ⁇
- Example C1-2 35 ⁇ / ⁇
- Example C1-3 22 ⁇ / ⁇
- Comparative Example C1 78 ⁇ / ⁇
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Abstract
Description
薄膜トランジスタ(TFT)及び太陽電池のような半導体デバイスの製造においては、シリコン基材等の基材上に積層された1又は複数のシリコン層を用いている。
ある種の半導体デバイス、例えば太陽電池、特にバックコンタクト太陽電池及びPERL太陽電池(Passivated Emitter, Rear Locally diffused cell)の製造においては、リン又はホウ素のようなドーパントを半導体層又は基材の選択された領域に注入して、選択された領域にのみドープ層を形成することが行われている。
従来、太陽電池のような半導体デバイスの製造において、半導体基材にドープ層を形成する場合、ドーパントを含有するドーパント組成物を半導体基材に塗布し、この半導体基材を、炉で加熱することによって、半導体基材中にドーパントを拡散させることが行われてきた。しかしながら、炉による加熱は、長時間の高温処理が必要であり、コストがかかるという課題があった。そこで、近年、レーザーを照射することによってドーパント組成物から半導体基材中にドーパントを拡散させる技術の開発が盛んに行われている。
上記のようなシリコン粒子を焼結させて得たシリコン層も、上記のように平坦な表面を有することが好ましいが、このようなシリコン層は一般に、表面に比較的大きな凸部を有している。具体的には、図4に示すように、単独のシリコン粒子層(A40)に光照射を行って半導体積層体を製造する場合(図4(a))、得られるシリコン層は、粒子の焼結によって生じる比較的小さい粒子(A40a)と比較的大きい粒子(A40b)とを有しており、これらのうちの比較的大きい粒子(A40b)によって表面が大きい凹凸を有している。また、得られるシリコン層は、焼結した粒子同士が互いに接触していない部分が生じることにより、連続性が十分でない場合がある。
上記のように、バックコンタクト太陽電池及びPERL太陽電池のようなある種の半導体デバイスの製造においては、選択された領域にドープ層を形成することが行われている。
上記のように、例えば特許文献9及び10では、酸化ケイ素等のケイ素化合物又はカーボンを含有するドーパント組成物の使用が検討されている。
(b)上記シリコン粒子分散体層を乾燥して、未焼結シリコン粒子層を形成する工程、
(c)上記未焼結シリコン粒子層上に光透過性層を積層する工程、及び
(d)上記光透過性層を通して上記未焼結シリコン粒子層に光を照射して、上記未焼結シリコン粒子層を構成する上記シリコン粒子を焼結させ、それによって焼結シリコン粒子層を形成する工程、
を含む、基材及び基材上の焼結シリコン粒子層を有する半導体積層体の製造方法。
〈A2〉工程(d)光照射の後で、上記光透過性層が維持されている、上記〈A1〉項に記載の方法。
〈A3〉工程(d)光照射によって、上記光透過性層が除去される、上記〈A1〉項に記載の方法。
〈A4〉上記光透過性層が、有機化合物、無機化合物又は有機無機ハイブリッド化合物のいずれかを含む、上記〈A1〉~〈A3〉項のいずれかに記載の方法。
〈A5〉上記光透過性層が、ケイ素化合物を含む、上記〈A1〉~〈A4〉項のいずれかに記載の方法。
〈A6〉上記光透過性層が、酸化ケイ素又はシロキサン結合を有する化合物を含む、上記〈A1〉~〈A5〉項のいずれかに記載の方法。
〈A7〉上記光透過性層が、スピン・オン・ガラスにより形成される、上記〈A1〉~〈A6〉項のいずれかに記載の方法。
〈A8〉上記光透過性層が、液相法により形成される、上記〈A1〉~〈A7〉項のいずれかに記載の方法。
〈A9〉上記光透過性層が、1012Ω・cm以上の体積抵抗率を有する、上記〈A1〉~〈A8〉項のいずれかに記載の方法。
〈A10〉上記光透過性層が、50~1,000nmの膜厚を有する、上記〈A1〉~〈A9〉項のいずれかに記載の方法。
〈A11〉上記焼結シリコン粒子層が、50~500nmの膜厚を有する、上記〈A1〉~〈A10〉項のいずれかに記載の方法。
〈A12〉上記光照射を、レーザーを用いて行う、上記〈A1〉~〈A11〉項のいずれかに記載の方法。
〈A13〉上記レーザーの波長が600nm以下である、上記〈A12〉項に記載の方法。
〈A14〉上記光照射を非酸化性雰囲気下で行う、上記〈A1〉~〈A13〉項のいずれかに記載の方法。
〈A15〉上記光照射を大気雰囲気下で行う、上記〈A1〉~〈A13〉項のいずれかに記載の方法。
〈A16〉上記〈A1〉~〈A15〉項のいずれかに記載の方法で製造される、基材及び基材上の焼結シリコン粒子層を有する半導体積層体。
〈A17〉上記〈A16〉項に記載の半導体積層体を含む、半導体デバイス。
〈A18〉上記〈A2〉項に記載の方法で基材及び基材上の焼結シリコン粒子層を有する半導体積層体を製造した後で、上記半導体積層体から上記光透過性層の一部を除去して、上記焼結シリコン粒子層に達する開口部を形成し、そして上記開口部にソース電極及びドレイン電極を提供し、かつ上記光透過性層上にゲート電極を形成することを含む、トップゲート・トップコンタクト型薄膜トランジスタの製造方法。
〈A19〉上記〈A18〉項に記載の方法で製造される、トップゲート・トップコンタクト型薄膜トランジスタ。
〈A20〉(a)基材、
(b)上記基材上に積層されているシリコン粒子から作られている未焼結シリコン粒子層、
(c)上記未焼結シリコン粒子層上に積層されている光透過性層、
を有する、未焼結シリコン積層体。
〈A21〉(a)基材、
(b)上記基材上に積層されているシリコン粒子から作られている焼結シリコン粒子層、
(c)上記焼結シリコン粒子層上に積層されている光透過性層、
を有する、半導体積層体。
〈A22〉(a)ガラス基材、
(b)上記ガラス基材上に直接に積層されているシリコン粒子から作られている焼結シリコン粒子層であって、算術平均粗さが100nm以下である焼結シリコン粒子層、
を有する、半導体積層体。
下記の(i)及び(ii)を有する積層体を提供すること:(i)上記半導体層又は基材上に配置されている第1及び/又は第2のパッシベーション層、並びに(ii)第1のパッシベーション層の上側であって第2のパッシベーション層の下側において上記第1の領域に対応する領域に配置されているドーパント注入層であって、第1の粒子からなり、上記第1の粒子が、上記半導体層又は基材と同一の元素から本質的になり、かつp型又はn型ドーパントによってドープされている、第1のドーパント注入層、並びに
上記積層体の上記第1のドーパント注入層に対応する領域に光照射を行うことによって、上記第1の領域を、上記p型又はn型ドーパントによってドープして、上記第1のドープ層を形成すると共に、上記第1のドーパント注入層、及び上記パッシベーション層のうちの、上記ドーパント注入層に対応する領域を、少なくとも部分的に除去すること。
〈B2〉下記の工程を含む、上記〈B1〉項に記載の方法:
上記半導体層又は基材上に、上記第1のパッシベーション層を堆積させること、
上記第1のパッシベーション層のうちの、上記第1の領域に対応する領域に、第1の粒子を含有する第1の分散体を適用すること、ここで、上記第1の粒子は、上記半導体層又は基材と同一の元素から本質的になり、かつp型又はn型ドーパントによってドープされている、
適用した上記第1の分散体を乾燥して、上記第1のドーパント注入層とすること、並びに
上記第1のドーパント注入層に光照射を行うことによって、上記第1の領域を、上記p型又はn型ドーパントによってドープして、上記第1のドープ層を形成すると共に、上記第1のドーパント注入層、及び上記第1のパッシベーション層のうちの、上記第1のドーパント注入層に対応する領域を、少なくとも部分的に除去すること。
〈B3〉下記の工程を含む、上記〈B1〉項に記載の方法:
上記第1の領域に、第1の粒子を含有する第1の分散体を適用すること、ここで、上記第1の粒子は、上記半導体層又は基材と同一の元素から本質的になり、かつp型又はn型ドーパントによってドープされている、
適用した上記第1の分散体を乾燥して、上記第1のドーパント注入層とすること、
上記半導体層又は基材及び上記第1のドーパント注入層上に、上記第2のパッシベーション層を堆積させること、並びに
上記第2のパッシベーション層のうちの、上記第1のドーパント注入層に対応する領域に、光照射を行うことによって、上記第1の領域を、上記p型又はn型ドーパントによってドープして、上記第1のドープ層を形成すると共に、上記第1のドーパント注入層、及び上記第2のパッシベーション層のうちの、上記第1のドーパント注入層に対応する領域を、少なくとも部分的に除去すること。
〈B4〉下記の工程を含む、上記〈B1〉項に記載の方法:
上記半導体層又は基材上に、上記第1のパッシベーション層を堆積させること、
上記第1のパッシベーション層のうちの、上記第1の領域に対応する領域に、第1の粒子を含有する第1の分散体を適用すること、ここで、上記第1の粒子は、上記半導体層又は基材と同一の元素から本質的になり、かつp型又はn型ドーパントによってドープされている、
適用した上記第1の分散体を乾燥して、上記第1のドーパント注入層とすること、
上記第1のパッシベーション層及び上記第1のドーパント注入層上に、第2のパッシベーション層を堆積させること、並びに
上記第2のパッシベーション層のうちの、上記第1のドーパント注入層に対応する領域に、光照射を行うことによって、上記第1の領域を、上記p型又はn型ドーパントによってドープして、上記第1のドープ層を形成すると共に、上記第1のドーパント注入層、並びに上記第1及び第2のパッシベーション層のうちの、上記第1のドーパント注入層に対応する領域を、少なくとも部分的に除去すること。
〈B5〉上記第1のドープ層に接触するように、上記パッシベーション層を通して電極を形成する工程を更に含む、上記〈B1〉~〈B4〉項のいずれか一項に記載の方法。
〈B6〉上記ドーパントの濃度が、上記第1の領域の表面から0.1μmの深さにおいて1×1017atoms/cm3以上である、上記〈B1〉~〈B5〉項のいずれか一項に記載の方法。
〈B7〉上記パッシベーション層が、1~200nmの層厚を有する、上記〈B1〉~〈B6〉項のいずれか一項に記載の方法。
〈B8〉上記パッシベーション層が、SiN、SiO2、Al2O3、及びそれらの組合せからなる群より選択される材料で形成されている、上記〈B1〉~〈B7〉項のいずれか一項に記載の方法。
〈B9〉上記半導体層又は基材が、シリコン、ゲルマニウム又はそれらの組合せの半導体層又は基材である、上記〈B1〉~〈B8〉項のいずれか一項に記載の方法。
〈B10〉上記分散体の適用を印刷法によって行う、上記〈B1〉~〈B9〉項のいずれか一項に記載の方法。
〈B11〉上記粒子の平均一次粒子径が100nm以下である、上記〈B1〉~〈B10〉項のいずれか一項に記載の方法。
〈B12〉下記の工程によって半導体層又は基材の第2の領域に第2のドープ層を形成することを更に含む、上記〈B1〉~〈B11〉項のいずれか一項に記載の方法:
上記第1の分散体の適用と同時に、上記第1の分散体の適用と乾燥の間に、上記第1の分散体の乾燥と上記第1のドーパント注入層の除去の間に、又は上記第1のドーパント注入層の除去の後で、上記半導体層又は基材の第2の領域に、第2の粒子を含有する第2の分散体を適用すること、ここで、上記第2の粒子は、上記半導体層又は基材と同一の元素から本質的になり、かつ上記第1の粒子のドーパントとは異なる型のドーパントによってドープされている、
上記第1の分散体の乾燥と同時に、又は上記第1の分散体の乾燥とは別に、適用した上記第2の分散体を乾燥して、第2のドーパント注入層とすること、及び
上記第1のドーパント注入層への光照射と同時に、又は上記第1のドーパント注入層への光照射とは別に、上記第2のドーパント注入層に光照射を行うことによって、上記第2の領域を、上記p型又はn型ドーパントによってドープして、上記第2のドープ層を形成すると共に、上記第2のドーパント注入層、及び上記第1及び/又は第2のパッシベーション層のうちの、上記第2のドーパント注入層に対応する領域を、少なくとも部分的に除去すること。
〈B13〉上記第2のドープ層に接触するように、上記パッシベーション層を通して電極を形成する工程を更に含む、上記〈B12〉項に記載の方法。
〈B14〉上記半導体デバイスが太陽電池である、上記〈B12〉又は〈B13〉項に記載の方法。
〈B15〉半導体基材又は層上にパッシベーション層が積層されており、
上記半導体基材又は層の第1の領域において、上記パッシベーション層が少なくとも部分的に除去されて、上記半導体基材又は層に第1の粒子が焼結されており、かつ上記第1の粒子を介し、かつ上記パッシベーション層を通して、上記第1の領域に達する第1の電極が形成されており、
上記第1の粒子が、上記半導体層又は基材と同一の元素から本質的になり、かつp型又はn型ドーパントによってドープされており、かつ
上記ドーパントの濃度が、上記第1の領域の表面から0.1μmの深さにおいて1×1017atoms/cm3以上である、
半導体デバイス。
〈B16〉上記半導体基材又は層の第2の領域において、上記パッシベーション層が少なくとも部分的に除去されて、上記半導体基材又は層に第2の粒子が焼結されており、かつ上記第2の粒子を介し、かつ上記パッシベーション層を通して、上記第2の領域に達する第2の電極が形成されており、
上記第2の粒子が、上記半導体層又は基材と同一の元素から本質的になり、かつ上記第1の粒子のドーパントとは異なる型のドーパントによってドープされており、かつ
上記ドーパントの濃度が、上記第2の領域の表面から0.1μmの深さにおいて1×1017atoms/cm3以上である、
上記〈B15〉項に記載の半導体デバイス。
〈B17〉太陽電池である、上記〈B15〉又は〈B16〉項に記載の半導体デバイス。
ドーパント元素を有するドーパント化合物、及び
100~1000nmの範囲に少なくとも1つのピーク吸収波長を有する材料で構成されている光吸収粒子、
を含有している、ドーパント組成物。
〈C2〉上記光吸収粒子が、ケイ素、ゲルマニウム又はそれらの組合せで構成されている、上記〈C1〉に記載の組成物。
〈C3〉上記光吸収粒子が、100nm以下の平均一次粒子径を有する、上記〈C1〉又は〈C2〉に記載の組成物。
〈C4〉上記ピーク吸収波長におけるピークが、200~2500nmの範囲における最大ピークである、上記〈C1〉~〈C3〉項のいずれか一項に記載の組成物。
〈C5〉上記光吸収粒子が、ドーパントを実質的に含有していない、上記〈C1〉~〈C4〉項のいずれか一項に記載の組成物。
〈C6〉上記光吸収粒子が、ドーパントによってドープされている、上記〈C1〉~〈C4〉項のいずれか一項に記載の組成物。
〈C7〉ドーパント元素を有するドーパント化合物、及び
100~1000nmの範囲に少なくとも1つのピーク吸収波長を有する材料で構成されている光吸収粒子、
を含有している、ドーパント注入層。
〈C8〉互いに積層されている下記の層を有する、ドーパント注入層:
ドーパント元素を有するドーパント化合物を含有しているドーパント化合物含有層、及び
100~1000nmの範囲にピーク吸収波長を有する材料で構成されている光吸収粒子を含有している光吸収粒子含有層。
〈C9〉上記光吸収粒子含有層上に、上記ドーパント化合物含有層が積層されている、上記〈C8〉項に記載のドーパント注入層。
〈C10〉上記ドーパント化合物含有層上に、上記光吸収粒子含有層が積層されている、上記〈C8〉項に記載のドーパント注入層。
〈C11〉上記ドーパント化合物含有層が、100~1000nmの範囲にピーク吸収波長を有する材料で構成されている光吸収粒子を更に含有している、上記〈C8〉~〈C10〉項のいずれか一項に記載のドーパント注入層。
〈C12〉上記光吸収粒子含有層が、ドーパント元素を有するドーパント化合物を更に含有している、上記〈C8〉~〈C11〉項のいずれか一項に記載のドーパント注入層。
〈C13〉半導体基材上に積層されている、上記〈C7〉~〈C12〉項のいずれか一項に記載のドーパント注入層。
〈C14〉上記光吸収粒子が、上記半導体基材と同一の元素で構成されている、上記〈C13〉項に記載のドーパント注入層。
〈C15〉上記〈C13〉又は〈C14〉項に記載の上記ドーパント注入層に光を照射して、上記ドーパント元素を上記半導体基材中に拡散させることを含む、ドープ層の形成方法。
〈C16〉上記光吸収粒子が、照射される上記光の主波長において、上記ピーク吸収波長における吸光率の0.1倍以上の吸光率を有する、上記〈C15〉項に記載の方法。
〈C17〉照射される上記光が、レーザー光である、上記〈C15〉又は〈C16〉項に記載の方法。
〈C18〉上記〈C15〉~〈C17〉項のいずれか一項に記載の方法によってドープ層を形成することを含む、半導体デバイスの製造方法。
〈C19〉上記半導体デバイスが、太陽電池である、上記〈C18〉項に記載の方法。
〈C20〉上記〈C18〉又は〈C19〉項に記載の方法によって製造される、半導体デバイス。
《半導体積層体の製造方法》
基材及び基材上の焼結シリコン粒子層を有する半導体積層体を製造する第1の本発明の方法は、下記の工程(a)~(d)を含む:
(a)分散媒及び分散媒中に分散しているシリコン粒子を含有するシリコン粒子分散体を、基材上に塗布して、シリコン粒子分散体層を形成する工程、
(b)シリコン粒子分散体層を乾燥して、未焼結シリコン粒子層を形成する工程、
(c)未焼結シリコン粒子層上に光透過性層を積層する工程、及び
(d)光透過性層を通して未焼結シリコン粒子層に光を照射して、未焼結シリコン粒子層を構成するシリコン粒子を焼結させ、それによって焼結シリコン粒子層を形成する工程。
第1の本発明の方法の工程(a)では、始めに、分散媒及び分散媒中に分散しているシリコン粒子を含有するシリコン粒子分散体を、基材(A10)上に塗布して、シリコン粒子分散体層(A1)を形成する(図1(a)を参照)。
シリコン粒子分散体に含まれるシリコン粒子は、シリコンからなる粒子であれば、第1の本発明の目的及び効果を損なわない限り制限されるものではない。このようなシリコン粒子としては、例えば特許文献4及び5で示されるようなシリコン粒子を用いることができる。具体的には、このシリコン粒子としては、レーザー熱分解法、特にCO2レーザーを用いたレーザー熱分解法によって得られたシリコン粒子を挙げることができる。
分散体の分散媒は、第1の本発明の目的及び効果を損なわない限り制限されるものではなく、したがって例えば第1の本発明で用いるシリコン粒子と反応しない有機溶媒を用いることができる。具体的にはこの分散媒は、非水系溶媒、例えばアルコール、アルカン、アルケン、アルキン、ケトン、エーテル、エステル、芳香族化合物、又は含窒素環化合物、特にイソプロピルアルコール(IPA)、N-メチル-2-ピロリドン(NMP)、テルピネオール等であってよい。また、アルコールとしては、エチレングリコールのようなグリコール(2価アルコール)を用いることもできる。なお、分散媒は、第1の本発明で用いる粒子の酸化を抑制するために、脱水溶媒であることが好ましい。
第1の本発明の方法で用いられる基材は、第1の本発明の目的及び効果を損なわない限り制限されるものではない。したがって例えば、基材としてはシリコン基材、ガラス基材、ポリマー基材などを用いることができる。第1の本発明によれば、平坦かつ連続性の高い表面を有する焼結シリコン粒子層を得ることが難しい基材、特にガラス基材上においても、比較的平坦かつ連続性の高い表面を有する焼結シリコン粒子層を得ることができる。
工程(a)において得るシリコン粒子分散体層の厚さは、最終的に得ることが望まれる焼結シリコン粒子層の厚さに応じて任意に決定することができる。
第1の本発明の方法の工程(b)では、シリコン粒子分散体層1を乾燥して、未焼結シリコン粒子層(A2)を形成する(図1(b)を参照)。
この乾燥は、分散体から分散媒を実質的に除去することができる方法であれば特に限定されず、例えば分散体を有する基材を、ホットプレート上に配置して行うこと、加熱雰囲気に配置して行うこと等ができる。
第1の本発明の方法の工程(c)では、未焼結シリコン粒子層(A2)上に光透過性層(A3)を積層する(図1(c)を参照)。
第1の本発明の方法の工程(d)では、光透過性層(A3)を通して未焼結シリコン粒子層(A2)に光(A15)を照射して、未焼結シリコン粒子層(A2)を構成するシリコン粒子を焼結させ、それによって焼結シリコン粒子層(A5)を形成する(図1(d)、(d1)、及び(d2)を参照)。
ここで照射される光としては、上記のような焼結シリコン粒子層の形成を達成できれば任意の光を用いることができる。
例えば、照射される光としては、単一波長からなるレーザー光、特に波長800nm以下、700nm以下、600nm以下、500nm以下又は400nm以下であって、300nm以上の波長を有するレーザー光を用いることができる。また、未焼結シリコン粒子層への光照射は、特定の帯域の波長範囲(例えば200~1100nm)の光を一度に照射するフラッシュランプ、例えばキセノンフラッシュランプを用いて行うこともできる。また、上記のような焼結シリコン粒子層の形成を達成できれば、パルス状の光、連続発振される光などの光を任意に用いることができる。
分散体粒子を焼結するための光照射は、非酸化性雰囲気、例えば水素、希ガス、窒素、及びそれらの組合せからなる雰囲気において行うことが、分散体粒子の酸化を防ぐために好ましい。ただし、第1の本発明の方法では、未焼結シリコン粒子層上に光透過性層が積層されており、それによって未焼結シリコン粒子層が雰囲気から隔離されているので、大気雰囲気のような酸化雰囲気において光照射を行うこともできる。なお、希ガスとしては、特にアルゴン、ヘリウム、及びネオンを挙げることができる。なお、雰囲気が水素を含有することは、分散体粒子の還元作用があり、酸化された表面部分を還元して、連続層を形成するために好ましいことがある。また、非酸化性雰囲気とするために、雰囲気の酸素含有率は、1体積%以下、0.5体積%以下、0.1体積%以下、又は0.01体積%以下とすることができる。
第1の本発明の半導体積層体は、基材及び基材上の焼結シリコン粒子層を有し、かつ第1の本発明の方法によって製造される。
また、第1の本発明の半導体デバイスは、第1の本発明の半導体積層体を有する。第1の本発明の半導体デバイスが、トップゲート・トップコンタクト型薄膜トランジスタのような電界効果トランジスタ又は太陽電池である場合、表面の凹凸が少なく、連続性の高いシリコン層を有することによって、このシリコン層上に、絶縁層、電極等を堆積させたときに、安定な特性を提供できる。
《半導体デバイスの製造方法》
半導体デバイスを製造する第2の本発明の方法は、下記の工程によって、半導体層又は基材の第1の領域に第1のドープ層を形成することを含む。
第2の本発明の方法の第1の態様は、下記の工程を含む:
半導体層又は基材上に、第1のパッシベーション層を堆積させること、
第1のパッシベーション層のうちの、第1の領域に対応する領域に、第1の粒子を含有する第1の分散体を適用すること、ここで、第1の粒子は、半導体層又は基材と同一の元素から本質的になり、かつp型又はn型ドーパントによってドープされている、
適用した第1の分散体を乾燥して、第1のドーパント注入層とすること、並びに
第1のドーパント注入層に光照射を行うことによって、第1の領域を、p型又はn型ドーパントによってドープして、第1のドープ層を形成すると共に、第1のドーパント注入層、及び第1のパッシベーション層のうちの、第1のドーパント注入層に対応する領域を、少なくとも部分的に除去すること。
第2の本発明の方法の第2の態様は、下記の工程を含む:
第1の領域に、第1の粒子を含有する第1の分散体を適用すること、ここで、第1の粒子は、半導体層又は基材と同一の元素から本質的になり、かつp型又はn型ドーパントによってドープされている、
適用した第1の分散体を乾燥して、第1のドーパント注入層とすること、
半導体層又は基材及び第1のドーパント注入層上に、第2のパッシベーション層を堆積させること、並びに
第2のパッシベーション層のうちの、第1のドーパント注入層に対応する領域に、光照射を行うことによって、第1の領域を、p型又はn型ドーパントによってドープして、第1のドープ層を形成すると共に、第1のドーパント注入層、及び第2のパッシベーション層のうちの、第1のドーパント注入層に対応する領域を、少なくとも部分的に除去すること。
第2の本発明の方法の第3の態様は、下記の工程を含む:
半導体層又は基材上に、第1のパッシベーション層を堆積させること、
第1のパッシベーション層のうちの、第1の領域に対応する領域に、第1の粒子を含有する第1の分散体を適用すること、ここで、第1の粒子は、半導体層又は基材と同一の元素から本質的になり、かつp型又はn型ドーパントによってドープされている、
適用した第1の分散体を乾燥して、第1のドーパント注入層とすること、
第1のパッシベーション層及び第1のドーパント注入層上に、第2のパッシベーション層を堆積させること、並びに
第2のパッシベーション層のうちの、第1のドーパント注入層に対応する領域に、光照射を行うことによって、第1の領域を、p型又はn型ドーパントによってドープして、第1のドープ層を形成すると共に、第1のドーパント注入層、並びに第1及び第2のパッシベーション層のうちの、第1のドーパント注入層に対応する領域を、少なくとも部分的に除去すること。
第2の本発明で使用できる半導体層又は基材としては、半導体元素からなる任意の半導体層又は基材を用いることができる。ここで、半導体元素としては、シリコン、ゲルマニウム又はそれらの組合せを用いることができる。したがって、半導体層又は基材としては、シリコンウェハー、ガリウムウェハー、アモルファスシリコン層、アモルファスガリウム層、結晶質シリコン層、結晶質ガリウム層を挙げることができる。
第2の本発明の方法において用いることができるパッシベーション層は、パッシベーション層として機能させることができる任意の厚さを有することができ、例えば1nm以上、5nm以上、10nm以上、30nm以上、50nm以上であってよい。またこの厚さは、300nm以下、200nm以下、100nm以下、50nm以下、30nm以下、20nm以下、又は10nm以下であるように行うことができる。この厚さが薄すぎる場合、パッシベーション層としての性質に劣る可能性があり、またこの厚さが厚すぎる場合、光照射によって除去できないことがある。また、特に、パッシベーション層が、第1のパッシベーション層である場合、すなわちそのパッシベーション層の上にドーパント注入層を堆積させ、そして光照射によって第1の領域を、ドーパントによってドープして、第1のドープ層を形成すると共に、ドーパント注入層及びパッシベーション層のドーパント注入層に対応する領域を除去する場合、パッシベーション層の厚さが厚すぎると、半導体層又は基材へのドーパントの注入が不充分になることがある。
半導体デバイスを製造する第2の本発明の方法における分散体の適用は、分散体を所望の厚さ及び均一性で塗布できる方法であれば特に限定されず、例えばインクジェット印刷法、スピンコーティング法、又はスクリーン印刷法等によって行うことができ、特にインクジェット印刷やスクリーン印刷のような印刷法を用いて行うことが、特定の領域に分散体を適用し、かつ製造工程を短くするために特に有益なことがある。
分散体の分散媒は、第2の本発明の目的及び効果を損なわない限り制限されるものではなく、したがって例えば第2の本発明で用いる粒子と反応しない有機溶媒を用いることができる。具体的にはこの分散媒は、イソプロピルアルコール(IPA)等の第1の本発明に関して挙げた分散媒であってよい。
分散体の粒子は、半導体層又は基材と同一の元素からなりかつp型又はn型ドーパントによってドープされている粒子であれば、第2の本発明の目的及び効果を損なわない限り制限されるものではない。このような粒子としては、例えば特許文献4及び5で示されるようなシリコン粒子又はゲルマニウム粒子を用いることができる。具体的には、このシリコン粒子又はゲルマニウム粒子としては、レーザー熱分解法、特にCO2レーザーを用いたレーザー熱分解法によって得られたシリコン粒子又はゲルマニウム粒子を挙げることができる。
半導体デバイスを製造する第2の本発明の方法における乾燥は、分散体から分散媒を実質的に除去することができる方法であれば特に限定されず、例えば分散体を有する基材を、ホットプレート上に配置して行うこと、加熱雰囲気に配置して行うこと等ができる。
半導体デバイスを製造する第2の本発明の方法における光照射は、ドーパント注入層に含まれるp型又はn型ドーパントを半導体層又は基材の選択された領域に拡散させると共に、第1のドーパント注入層、並びに第1及び/又は第2のパッシベーション層のうちの、第1のドーパント注入層に対応する領域を、少なくとも部分的に除去することができる任意の光照射であってよい。なお、第2の本発明に関して、「少なくとも部分的に除去」は、ドーパント注入層、並びに第1及び/又は第2のパッシベーション層の少なくとも一部が除去されることを意味しており、この除去によって、そのままドープ層上に電極を形成できる程度までこれらの層が除去される場合だけでなく、エッチング、洗浄のような更なる処理によって残存するドーパント注入層等の層をさらに除去する必要がある場合を含む。
ここで照射される光としては、上記のようにして半導体層又は基材の特定の領域のドーピング等を達成できれば任意の光を用いることができる。照射される光としては、第1の本発明に関して説明したように、単一波長からなるレーザー光等を用いることができる。なお、Siに吸収される波長の光を用いて照射を行うことが有効である。
分散体粒子を焼結するための光照射は、非酸化性雰囲気、例えば水素、希ガス、窒素、及びそれらの組合せからなる雰囲気において行うことが、半導体デバイスの特性に与える影響を小さくするために好ましい。具体的な照射雰囲気については、第1の本発明に関する記載を参照することができる。なお、雰囲気が水素を含有することは、分散体粒子の還元作用があり、酸化された表面部分を還元して、連続層を形成するために好ましいことがある。
第2の本発明の半導体デバイスでは、半導体基材又は層上にパッシベーション層が積層されており、半導体基材又は層の第1の領域において、パッシベーション層が少なくとも部分的に除去されて、半導体基材又は層に第1の粒子が焼結されており、かつ第1の粒子を介し、かつパッシベーション層を通して、第1の領域に達する第1の電極が形成されており、第1の粒子が、半導体層又は基材と同一の元素から本質的になり、かつp型又はn型ドーパントによってドープされており、かつドーパントの濃度が、第1の領域の表面から0.1μmの深さにおいて1×1017atoms/cm3以上である。
《ドーパント組成物》
第3の本発明のドーパント組成物は、溶媒、ドーパント元素を有するドーパント化合物、及び100~1000nmの範囲に少なくとも1つのピーク吸収波長を有する材料で構成されている光吸収粒子を含有している。
溶媒は、第3の本発明の目的及び効果を損なわない限り制限されるものではなく、したがって例えばドーパント組成物で用いる粒子と反応しない有機溶媒を用いることができる。具体的にはこの溶媒は、本発明に関して分散媒として挙げたイソプロピルアルコール(IPA)等の溶媒であってよい。
第3の本発明のドーパント組成物において用いられる光吸収粒子を構成する材料は、100~1000nm、例えば200~1000nm、200~800nm、又は200~600nmの範囲に少なくとも1つのピーク吸収波長を有する。ここで、このピーク吸収波長におけるピークは、100~2500nm又は200~2500nmの範囲における最大ピークであってよい。
第3の本発明のドーパント組成物において使用されるドーパント化合物は、ドーパント元素を有する。
第3の本発明のドーパント組成物は、その他の成分として、バインダー樹脂、界面活性剤、増粘剤等の任意の他の成分を含有していてもよい。バインダー樹脂としては、例えば、チクソ性やシリコン粒子の分散性等の観点からエチルセルロースを用いてもよい。
〈第1のドーパント注入層〉
第3の本発明の第1のドーパント注入層は、ドーパント元素を有するドーパント化合物、及び100~1000nmの範囲に少なくとも1つのピーク吸収波長を有する材料で構成されている光吸収粒子を含有している。
第3の本発明の第2のドーパント注入層は、互いに積層されている下記の層を有する:
ドーパント元素を有するドーパント化合物を含有しているドーパント化合物含有層、及び
100~1000nmの範囲にピーク吸収波長を有する材料で構成されている光吸収粒子を含有している光吸収粒子含有層。
第3の本発明のドーパント注入層は、半導体基材上に積層されていてよい。この場合、半導体基材は、ドーパントを注入してドーパント注入層を形成することを意図される任意の半導体基材であってよい。
第3の本発明の第1のドーパント注入層は、任意の様式で、第3の本発明のドーパント組成物を半導体基材に適用して形成でき、例えばインクジェット法、スピンコーティング法、又はスクリーン印刷法等によって形成でき、特にインクジェット印刷やスクリーン印刷のような印刷法を用いて形成することが、処理は製造工程を短くするために特に有益なことがある。例えば、ドーパント組成物を印刷法によって適用して、パターンを有するドーパント注入層を形成できる。
ドープ層を形成する第3の本発明の方法は、第3の本発明のドーパント注入層に光を照射して、ドーパント元素を半導体基材中に拡散させることを含む。
光照射は、ドーパント注入層に含まれるドーパントを半導体基材の選択された領域に拡散させることができる任意の光照射であってよい。
光照射は、大気下で行うことができる。ただし、材料に応じて非酸化性雰囲気、例えば水素、希ガス、窒素、及びそれらの組合せからなる雰囲気において行うことが、光吸収粒子の酸化を防ぐために好ましい。ここで、希ガスとしては、特にアルゴン、ヘリウム、及びネオンを挙げることができる。また、非酸化性雰囲気とするために、雰囲気の酸素含有率は、1体積%以下、0.5体積%以下、0.1体積%以下、又は0.01体積%以下とできる。
半導体デバイスを製造する第3の本発明の方法は、第3の本発明の方法によってドープ層を形成することを含む。このような第3の本発明の方法によって製造される半導体デバイスとしては、太陽電池を挙げることができる。また、第3の本発明の半導体デバイスは、半導体デバイスを製造する第3の本発明の方法によって製造される。
第3の本発明は、上述の実施の形態に限定されるものではなく、当業者の知識に基づいて各種の設計変更などの変形を加えることも可能であり、そのような変形が加えられた実施形態も第3の本発明の範囲に含まれるものである。上述の実施の形態と以下の変形例との組合せによって生じる新たな実施の形態は、組み合わされる実施の形態及び変形例それぞれの効果をあわせもつ。
〈実施例A1-1〉
実施例A1では、図1(d1)に示す構成を有する積層体を得た。すなわち、実施例A1では、基材上に、焼結シリコン粒子層及び光透過性層が積層されている積層体を得た。
シリコン粒子は、SiH4ガスを原料として、CO2レーザーを用いたレーザー熱分解(LP:Laser Pyrolysis)法により作製した。得られたシリコン粒子は、平均一次粒子径が約7nmであった。このシリコン粒子を、イソプロピルアルコール(IPA)中に超音波分散させて、固形分濃度3質量%のシリコン粒子分散体を得た。
ガラス基材を、アセトン及びイソプロピルアルコール中で各5分間ずつ、超音波洗浄した。
シリコン粒子分散体を基材上に数滴滴下し、500rpmで5秒間にわたって、そして4,000rpmで10秒間にわたって、スピンコートすることにより、基材にシリコン粒子分散体を塗布した。
シリコン粒子分散体が塗布された基材を、70℃のホットプレート上で乾燥させることによって、シリコン粒子分散体中の分散媒であるイソプロピルアルコールを除去し、それによってシリコン粒子(平均一次粒子径約7nm)を含む未焼結シリコン粒子層(膜厚300nm)を形成した。
未焼結シリコン粒子層が塗布された基材上に、光透過性を有する化合物であるMSQ(メチルシルセスキオキサン)膜を形成した。具体的には、このMSQ膜は、プロピレングリコールモノメチルエーテルアセテート(PGMEA)中にMSQが溶解した溶液(固形分濃度30質量%、Honeywell社製、商品名PTS R―6)を、未焼結シリコン粒子層が塗布された基材上に数滴滴下し、500rpmで5秒間にわたって、更に3,200rpmで20秒間にわたってスピンコートした後、N2の雰囲気下のホットプレート上において、80℃で5分間にわたって、更にファーネス中において400℃で60分間にわたって加熱して乾燥させることによって得た。得られたMSQ膜の膜厚は700nmであった。得られた積層体は、図1(c)で示すような構成を有していた。
次に、未焼結シリコン粒子層上に光透過性層を積層した積層体に対して、レーザー光照射装置(Quantronix社製、商品名Osprey 355-2-0)を用いてYVO4レーザー(波長355nm)を照射して、未焼結シリコン粒子層中のシリコン粒子を焼結して、焼結シリコン粒子層を作製した。レーザー照射条件は、照射エネルギー50mJ/(cm2・shot)、ショット数20回であり、レーザー照射は、窒素(N2)に水素(H2)を3.5%含んだ雰囲気中で行った。
作製された積層体の断面観察評価を、試料傾斜角度20°及び100,000倍の倍率で、FE-SEM(電界放射型走査電子顕微鏡)(S-5200型、日立ハイテクノロジーズ製)によって行った。FE-SEMの観察結果を図5(a)に示す。図5(a)で示されるように、この積層体は、基材(A52)上に、焼結シリコン粒子層(A54)及び光透過性層(A56)が積層された構成を有していた。すなわち、実施例A1-1で得られた積層体は、図1(d1)に示す構成を有していた。
実施例A1-2~A1-4ではそれぞれ、レーザー照射エネルギーを、100mJ/(cm2・shot)、200mJ/(cm2・shot)、及び300mJ/(cm2・shot)にしたこと以外は実施例A1-1と同様にして、焼結シリコン粒子層を作製した。
実施例A2-1~A2-4では、光透過性層として、シラノール溶液から得られた酸化ケイ素を主成分とする光透過性層(下記参照)を用いたことを以外は実施例A1-1と同様にして、焼結シリコン粒子層を作製した。なお、実施例A2-1~A2-4では、レーザー照射エネルギーをそれぞれ、100mJ/(cm2・shot)、200mJ/(cm2・shot)、300mJ/(cm2・shot)、及び400mJ/(cm2・shot)にした。
実施例A2-1~A2-4において用いた酸化ケイ素を主成分とする光透過性層は、シラノール溶液(OCD Type-7 12000―T(東京応化工業製))を用いて、未焼結シリコン粒子層が塗布された基材上に形成した。なお、光透過性層として用いたこの塗布型絶縁膜は、紫外光線及び可視光線透過率が99%以上である。
比較例A1~A4では、光透過性層を用いなかったことを以外は実施例A1-1と同様にして、焼結シリコン粒子層を作製した。なお、比較例A1~A4では、レーザー照射エネルギーをそれぞれ、100mJ/(cm2・shot)、200mJ/(cm2・shot)、300mJ/(cm2・shot)、及び400mJ/(cm2・shot)にした。
実施例A3-1~A3-5では、シリコン粒子として平均一次粒子径が約20nmであるものを用いたこと、光透過性層の膜厚を変更したこと、光照射としてレーザー光照射装置(Quantronix社製、商品名Osprey 532-8-0)によりグリーンレーザー(波長532nm)を用いたこと以外は実施例A2-1~A2-4と同様にして、焼結シリコン粒子層を作製した。なお、実施例A3-1~A3-3では、下記の表2に示すように、レーザー照射エネルギーを、1000mJ/(cm2・shot)~1800mJ/(cm2・shot)にした。
実施例A4-1~A4-5では、光透過性層の膜厚を変更したこと以外は実施例A3-1~3-5と同様にして、焼結シリコン粒子層を作製した。
実施例A5-1~A5-5では、光透過性層の膜厚を変更したこと以外は実施例A3-1~A3-5と同様にして、焼結シリコン粒子層を作製した。
実施例A1-1~A2-4、及び比較例A1~4の評価結果を、製造条件と併せて、下記の表1に示し、かつ実施例A3-1~A5-5の評価結果を、製造条件と併せて、下記の表2に示す。なお、積層体の粗さは、JIS B 0601(1994)に従って触針段差計(アルバック社製のDEKTAK)により求めた算術平均粗さ(Ra)であり、基準長さを1000μmとして求めた。粗さの測定は、レーザーを照射された箇所の中心部不均について行った。
〈実施例B1〉
(リン(P)ドープシリコン粒子の作成)
シリコン粒子は、モノシラン(SiH4)ガスを原料として、二酸化炭素(CO2)レーザーを用いたレーザー熱分解(LP:Laser Pyrolysis)法により作製した。このとき、SiH4ガスと共にホスフィン(PH3)ガスを導入して、リンドープシリコン粒子を得た。
上記のようにして得たリンドープシリコン粒子を、イソプロピルアルコール(IPA)中に超音波分散させて、固形分濃度2質量%のシリコン粒子分散体を得た。
シリコン基材を、アセトン及びイソプロピルアルコール中で各5分間ずつ超音波洗浄し、5%フッ化アンモニウム溶液中で10分間にわたって酸化層除去を行い、そして純水で洗浄した。
インクジェットプリンター(Dimatix)により、シリコン粒子分散体を200μmの線幅でシリコン基材に塗布した。
シリコン粒子分散体が塗布された基材を、80℃のホットプレート上で乾燥させることによって、シリコン粒子分散体中の分散媒であるイソプロピルアルコールを除去し、それによってシリコン粒子を含むドーパント注入層(層厚200nm)を形成した。
ドーパント注入層が形成された基材上に、プラズマ促進化学気相堆積(PE-CVD)によって、層厚50nmの窒化シリコン(SiN)層を、パッシベーション層(第2のパッシベーション層)として形成した。
次に、ドーパント注入層上にパッシベーション層を有する積層体に対して、レーザー光照射装置(Quantronix社製、商品名Osprey 532-8-0-2)を用いてグリーンレーザー(波長532nm)を照射して、基板中へのドーパントの注入、並びにパッシベーション層及びドーパント注入層のアブレーションを行った。
作製された基材のDynamic SIMS(動的二次イオン質量分析)を、CAMECA IMS-7fを用いて行った。測定条件は一次イオン種O2 +、一次加速電圧:3.0kV、検出領域30μmΦである。Dynamic SIMSの結果を図14に示す。この観察結果からは、基材がドープされていることが理解される。なお、この図14では、参考までに、レーザー照射を行う前の評価結果も示している。
作製された基材の断面を、FE-SEM(電界放射型走査電子顕微鏡)(日立ハイテクノロジーズ製、S5200型)を用いて試料傾斜角度20°及び倍率100,000倍で観察した結果を、図15に示す。ここで、図15(a)は、レーザー照射前のドーパント注入層についての観察結果であり、また図15(b)は、レーザー照射後のドーパント注入層についての観察結果である。
(シリコン粒子の作成)
実施例B1と同様にして、リンドープシリコン粒子を得た。得られたリンドープシリコン粒子は、平均一次粒子径が約7.4nmであった。
実施例B1と同様にして、固形分濃度2質量%のシリコン粒子分散体を得た。
実施例B1と同様にして、シリコン基板を洗浄した。
洗浄したシリコン基板上に、実施例B1と同様にして、層厚50nmの窒化シリコン(SiN)層をパッシベーション層(第1のパッシベーション層)として形成した。
パッシベーション層を積層したシリコン基板上に、インクジェットプリンター(Dimatix)により、シリコン粒子分散体を200μmの線幅で塗布した。
シリコン粒子分散体が塗布された基材を、実施例B1と同様にして乾燥させて、シリコン粒子層(層厚200nm)を形成した。
次に、パッシベーション層上にシリコン粒子層を有する積層体に対して、実施例B1と同様にして、グリーンレーザーを照射して、パッシベーション層及びシリコン粒子層のアブレーションを行った。
実施例B1と同様にして、SIMS測定を行った。この結果を図16に示す。この観察結果からは、基材がドープされていることが理解される。
SEM分析より、実施例B1と同様に、基板表面にはドーパント注入層を構成していたシリコン粒子層の一部のみが存在していることが確認された。
(ボロン(B)ドープシリコン粒子の作成)
シリコン粒子は、モノシラン(SiH4)ガスを原料として、二酸化炭素(CO2)レーザーを用いたレーザー熱分解法により作製した。このとき、モノシランガスと共にジボラン(B2H6)ガスを導入して、ボロンドープシリコン粒子を得た。
実施例B1と同様にして、固形分濃度2質量%のシリコン粒子分散体を得た。
実施例B1と同様にして、シリコン基板を洗浄した。
洗浄したシリコン基板上に、実施例B1と同様にして、層厚50nmの窒化シリコン(SiN)層をパッシベーション層(第1のパッシベーション層)として形成した。
パッシベーション層を積層したシリコン基板上に、インクジェットプリンター(Dimatix)により、シリコン粒子分散体を200μmの線幅で塗布した。
シリコン粒子分散体が塗布された基材を、実施例B1と同様にして乾燥させて、シリコン粒子層(層厚200nm)を形成した。
次に、パッシベーション層上にシリコン粒子層を有する積層体に対して、実施例B1と同様にして、グリーンレーザーを照射して、パッシベーション層及びシリコン粒子層のアブレーションを行った。
SIMS分析より、実施例B1と同様に基材がドープされていることを確認した。
SEM分析より、ドーパント注入層上に積層されたパッシベーション層(SiN層)は、レーザー照射によりアブレーションし、基板表面にはドーパント注入層を構成していたシリコン粒子層の一部のみが存在していることを確認した。
(シリコン粒子の作成)
実施例B3と同様にして、ボロンドープシリコン粒子を得た。得られたボロンドープシリコン粒子は、平均一次粒子径が約20.9nmであった。
実施例B1と同様にして、固形分濃度2質量%のシリコン粒子分散体を得た。
実施例B1と同様にして、シリコン基板を洗浄した。
洗浄したシリコン基板上に、実施例B1と同様にして、層厚50nmの窒化シリコン(SiN)層をパッシベーション層(第1のパッシベーション層)として形成した。
パッシベーション層を積層したシリコン基板上に、インクジェットプリンター(Dimatix)により、シリコン粒子分散体を200μmの線幅で塗布した。
シリコン粒子分散体が塗布された基材を、実施例B1と同様にして乾燥させて、シリコン粒子層(層厚200nm)を形成した。
次に、パッシベーション層上にシリコン粒子層を有する積層体に対して、実施例B1と同様にして、グリーンレーザーを照射して、パッシベーション層及びシリコン粒子層のアブレーションを行った。
SIMS分析より、実施例B2と同様に基材がドープされていることを確認した。
SEM分析により、基板表面にはドーパント注入層を構成していたシリコン粒子層の一部のみが存在していることを確認した。
(シリコン粒子の作成)
実施例B1と同様にして、リンドープシリコン粒子を得た。得られたリンドープシリコン粒子は、平均一次粒子径が約7.2nmであった。
上記のようにして得たシリコン粒子を、プロピレングリコール(PG)中に超音波分散させて、固形分濃度5質量%のシリコン粒子分散体を得た。
実施例B1と同様にして、シリコン基板を洗浄した。
スクリーンプリントによって、シリコン粒子分散体を200μmの線幅でシリコン基材に塗布した。
シリコン粒子分散体が塗布された基材を、200℃のホットプレート上で乾燥させることによって、シリコン粒子分散体中の分散媒であるプロピレングリコールを除去し、それによってシリコン粒子層(層厚200nm)を形成した。
シリコン粒子層を有する基材上に、実施例B1と同様にして、層厚50nmの窒化シリコン(SiN)層を、パッシベーション層(第1のパッシベーション層)として形成した。
次に、シリコン粒子層上にパッシベーション層を有する積層体に対して、実施例B1と同様にして、グリーンレーザーを照射して、シリコン粒子層及びパッシベーション層のアブレーションを行った。
SIMS分析より、実施例B1と同様に基材がドープされていることを確認した。
SEM分析より、ドーパント注入層上に積層されたパッシベーション層(SiN層)は、レーザー照射により除去されていること、基板表面にはドーパント注入層を構成していたシリコン粒子層の一部のみが存在していることを確認した。
以下、第3の本発明の実施例を説明するが、これら実施例は、第3の本発明を好適に説明するための例示に過ぎず、なんら第3の本発明を限定するものではない。
(基材の準備)
ケイ素基材を、アセトン及びイソプロピルアルコール中で各5分間ずつ、超音波洗浄した。その後、5%フッ化アンモニウム溶液に10分間浸漬し、純水にて洗浄を行った。
ドーパント化合物含有溶液(Filmtronics社製、P8545SF)、及びシリコン粒子分散体(固体分5質量%)を重量比1:1で混合して、ドーパント組成物を得た。
調整したドーパント組成物を基材上に数滴滴下し、500rpmで5秒間にわたって、そして4000rpmで10秒間にわたって、スピンコートすることにより、基材にドーパント組成物を塗布し、ドーパント注入層を形成した。
次に、ドーパント注入層を有する基材に、レーザー光照射装置(Quantronix社製、商品名Osprey 532-8-0-2)を用いてグリーンレーザー(波長532nm)を照射して、基材にドーパントを注入した。レーザー照射条件は、照射エネルギー700mJ/(cm2・shot)、ショット数20回であり、レーザー照射は、窒素(N2)雰囲気中で行った。
ドーパント組成物としてドーパント化合物含有溶液(Filmtronics社製、P8545SF)、及びシリコン粒子分散体(固体分5質量%)を重量比3:1で混合した以外は実施例C1-1でのようにして、ドーパント注入層を形成し、そしてドーパント注入層にレーザー照射を行った。
ドーパント組成物としてドーパント化合物含有溶液(Filmtronics社製、P8545SF)、及びシリコン粒子分散体(固体分5質量%)を重量比1:3で混合した以外は実施例C1-1でのようにして、ドーパント注入層を形成し、そしてドーパント注入層にレーザー照射を行った。
ドーパント組成物として単独のドーパント化合物含有溶液(Filmtronics社製、P8545SF)を用いた以外は実施例C1-1でのようにして、ドーパント注入層にレーザー照射を行った。
(ドーパント組成物)
ドーパント化合物含有溶液(Filmtronics社製、P8545SF)、及びシリコン粒子分散体(固体分5質量%)を混合せずに、それぞれ用いた。
ドーパント化合物含有溶液(Filmtronics社製、P8545SF)を基材上に数滴滴下し、500rpmで5秒間にわたって、そして4000rpmで10秒間にわたって、スピンコートすることにより、基材にドーパント組成物を塗布し、ドーパント化合物含有層を形成した。
(基材)/光吸収粒子含有層/ドーパント化合物含有層
(ドーパント注入層の形成)
実施例C2と積層順を逆にして、光吸収粒子含有層上にドーパント化合物含有層を形成することによって、下記の構成の積層体を得た:
(基材)/ドーパント化合物含有層/光吸収粒子含有層
レーザー照射後の実施例C1-1~C1-3及び比較例C1の基材の表面の状態を確認した。実施例C1-1~C1-3では、レーザー照射後の基材にクラック等の損傷は観察されなかった。これに対して、比較例C1では、レーザー照射後の基材にクラックが観察された。
参考までに、基材としてガラス基板を用いた以外は上記の実施例及び比較例でのようにしてドーパント注入層を形成して、分光光度計(Spectrophotometer、U-4000、日立製)にて、透過率測定を行った。実施例C1-1~C1-3及び比較例C1についての結果を図18に、実施例C2についての結果を図19に、実施例C3についての結果を図20に示す。
実施例C1-1及び比較例C1の基材のDynamic SIMS分析(動的二次イオン質量分析)を、CAMECA IMS-7fを用いて行った。測定条件は一次イオン種O2 +、一次加速電圧:3.0kV、検出領域30μmΦであった。
実施例C1-1~C1-3及び比較例C1の基材の表面抵抗率を、抵抗率計(MCP-T360、三菱化学製)にて測定した。
実施例C1-1: 36Ω/□
実施例C1-2: 35Ω/□
実施例C1-3: 22Ω/□
比較例C1: 78Ω/□
A2 未焼結シリコン粒子層
A3 光透過性層
A5 焼結シリコン粒子層
A7 開口部
A10 基材
A15 照射される光
A30 アモルファスシリコン層
A40 シリコン粒子層
S ソース電極
G ゲート電極
D ドレイン電極
B2 ドーパント注入層
B5 レーザー光
B12、B22、B32、B42、B44、B52、B54 電極
B15、B25、B35、B45、B55、B65 半導体層又は基材
B15a、B25a、B35a、B45a、B45b、B55a、B65a 第1又は第2の領域のドープ層
B18、B28、B38a、B38b、B46、B48、B56、B58、B68 パッシベーション層
B40 バックコンタクト太陽電池
B50 PERL太陽電池
B45c、B55c ドープ層
B68a パッシベーション層の孔
B72 拡散マスク層
B72a 拡散マスク層の孔
B74 ガラス質ドーパント注入層
B100 太陽電池に入射する光
C10 照射される光
C22 第3の本発明のドーパント注入層
C23 従来のドーパント注入層
C24 第3の本発明のドーパント化合物含有層
C26 第3の本発明の光吸収粒子含有層
C30 半導体基材
Claims (59)
- (a)分散媒及び前記分散媒中に分散しているシリコン粒子を含有するシリコン粒子分散体を、基材上に塗布して、シリコン粒子分散体層を形成する工程、
(b)前記シリコン粒子分散体層を乾燥して、未焼結シリコン粒子層を形成する工程、
(c)前記未焼結シリコン粒子層上に光透過性層を積層する工程、及び
(d)前記光透過性層を通して前記未焼結シリコン粒子層に光を照射して、前記未焼結シリコン粒子層を構成する前記シリコン粒子を焼結させ、それによって焼結シリコン粒子層を形成する工程、
を含む、基材及び基材上の焼結シリコン粒子層を有する半導体積層体の製造方法。 - 工程(d)光照射の後で、前記光透過性層が維持されている、請求項1に記載の方法。
- 工程(d)光照射によって、前記光透過性層が除去される、請求項1に記載の方法。
- 前記光透過性層が、有機化合物、無機化合物又は有機無機ハイブリッド化合物のいずれかを含む、請求項1~3のいずれかに記載の方法。
- 前記光透過性層が、ケイ素化合物を含む、請求項1~4のいずれかに記載の方法。
- 前記光透過性層が、酸化ケイ素又はシロキサン結合を有する化合物を含む、請求項1~5のいずれかに記載の方法。
- 前記光透過性層が、スピン・オン・ガラスにより形成される、請求項1~6のいずれかに記載の方法。
- 前記光透過性層が、液相法により形成される、請求項1~7のいずれかに記載の方法。
- 前記光透過性層が、1012Ω・cm以上の体積抵抗率を有する、請求項1~8のいずれかに記載の方法。
- 前記光透過性層が、50~1,000nmの膜厚を有する、請求項1~9のいずれかに記載の方法。
- 前記焼結シリコン粒子層が、50~500nmの膜厚を有する、請求項1~10のいずれかに記載の方法。
- 前記光照射を、レーザーを用いて行う、請求項1~11のいずれかに記載の方法。
- 前記レーザーの波長が600nm以下である、請求項12に記載の方法。
- 前記光照射を非酸化性雰囲気下で行う、請求項1~13のいずれかに記載の方法。
- 前記光照射を大気雰囲気下で行う、請求項1~13のいずれかに記載の方法。
- 請求項1~15のいずれかに記載の方法で製造される、基材及び基材上の焼結シリコン粒子層を有する半導体積層体。
- 請求項16に記載の半導体積層体を含む、半導体デバイス。
- 請求項2に記載の方法で基材及び基材上の焼結シリコン粒子層を有する半導体積層体を製造した後で、前記半導体積層体から前記光透過性層の一部を除去して、前記焼結シリコン粒子層に達する開口部を形成し、そして前記開口部にソース電極及びドレイン電極を提供し、かつ前記光透過性層上にゲート電極を形成することを含む、トップゲート・トップコンタクト型薄膜トランジスタの製造方法。
- 請求項18に記載の方法で製造される、トップゲート・トップコンタクト型薄膜トランジスタ。
- (a)基材、
(b)前記基材上に積層されているシリコン粒子から作られている未焼結シリコン粒子層、
(c)前記未焼結シリコン粒子層上に積層されている光透過性層、
を有する、未焼結シリコン積層体。 - (a)基材、
(b)前記基材上に積層されているシリコン粒子から作られている焼結シリコン粒子層、
(c)前記焼結シリコン粒子層上に積層されている光透過性層、
を有する、半導体積層体。 - (a)ガラス基材、
(b)前記ガラス基材上に直接に積層されているシリコン粒子から作られている焼結シリコン粒子層であって、算術平均粗さが100nm以下である焼結シリコン粒子層、
を有する、半導体積層体。 - 下記の工程によって半導体層又は基材の第1の領域に第1のドープ層を形成することを含む、半導体デバイスの製造方法:
下記の(i)及び(ii)を有する積層体を提供すること:(i)前記半導体層又は基材上に配置されている第1及び/又は第2のパッシベーション層、並びに(ii)第1のパッシベーション層の上側であって第2のパッシベーション層の下側において前記第1の領域に対応する領域に配置されているドーパント注入層であって、第1の粒子からなり、前記第1の粒子が、前記半導体層又は基材と同一の元素から本質的になり、かつp型又はn型ドーパントによってドープされている、第1のドーパント注入層、並びに
前記積層体の前記第1のドーパント注入層に対応する領域に光照射を行うことによって、前記第1の領域を、前記p型又はn型ドーパントによってドープして、前記第1のドープ層を形成すると共に、前記第1のドーパント注入層、及び前記パッシベーション層のうちの、前記ドーパント注入層に対応する領域を、少なくとも部分的に除去すること。 - 下記の工程を含む、請求項23に記載の方法:
前記半導体層又は基材上に、前記第1のパッシベーション層を堆積させること、
前記第1のパッシベーション層のうちの、前記第1の領域に対応する領域に、第1の粒子を含有する第1の分散体を適用すること、ここで、前記第1の粒子は、前記半導体層又は基材と同一の元素から本質的になり、かつp型又はn型ドーパントによってドープされている、
適用した前記第1の分散体を乾燥して、前記第1のドーパント注入層とすること、並びに
前記第1のドーパント注入層に光照射を行うことによって、前記第1の領域を、前記p型又はn型ドーパントによってドープして、前記第1のドープ層を形成すると共に、前記第1のドーパント注入層、及び前記第1のパッシベーション層のうちの、前記第1のドーパント注入層に対応する領域を、少なくとも部分的に除去すること。 - 下記の工程を含む、請求項23に記載の方法:
前記第1の領域に、第1の粒子を含有する第1の分散体を適用すること、ここで、前記第1の粒子は、前記半導体層又は基材と同一の元素から本質的になり、かつp型又はn型ドーパントによってドープされている、
適用した前記第1の分散体を乾燥して、前記第1のドーパント注入層とすること、
前記半導体層又は基材及び前記第1のドーパント注入層上に、前記第2のパッシベーション層を堆積させること、並びに
前記第2のパッシベーション層のうちの、前記第1のドーパント注入層に対応する領域に、光照射を行うことによって、前記第1の領域を、前記p型又はn型ドーパントによってドープして、前記第1のドープ層を形成すると共に、前記第1のドーパント注入層、及び前記第2のパッシベーション層のうちの、前記第1のドーパント注入層に対応する領域を、少なくとも部分的に除去すること。 - 下記の工程を含む、請求項23に記載の方法:
前記半導体層又は基材上に、前記第1のパッシベーション層を堆積させること、
前記第1のパッシベーション層のうちの、前記第1の領域に対応する領域に、第1の粒子を含有する第1の分散体を適用すること、ここで、前記第1の粒子は、前記半導体層又は基材と同一の元素から本質的になり、かつp型又はn型ドーパントによってドープされている、
適用した前記第1の分散体を乾燥して、前記第1のドーパント注入層とすること、
前記第1のパッシベーション層及び前記第1のドーパント注入層上に、第2のパッシベーション層を堆積させること、並びに
前記第2のパッシベーション層のうちの、前記第1のドーパント注入層に対応する領域に、光照射を行うことによって、前記第1の領域を、前記p型又はn型ドーパントによってドープして、前記第1のドープ層を形成すると共に、前記第1のドーパント注入層、並びに前記第1及び第2のパッシベーション層のうちの、前記第1のドーパント注入層に対応する領域を、少なくとも部分的に除去すること。 - 前記第1のドープ層に接触するように、前記パッシベーション層を通して電極を形成する工程を更に含む、請求項23~26のいずれか一項に記載の方法。
- 前記ドーパントの濃度が、前記第1の領域の表面から0.1μmの深さにおいて1×1017atoms/cm3以上である、請求項23~27のいずれか一項に記載の方法。
- 前記パッシベーション層が、1~200nmの層厚を有する、請求項23~28のいずれか一項に記載の方法。
- 前記パッシベーション層が、SiN、SiO2、Al2O3、及びそれらの組合せからなる群より選択される材料で形成されている、請求項23~29のいずれか一項に記載の方法。
- 前記半導体層又は基材が、シリコン、ゲルマニウム又はそれらの組合せの半導体層又は基材である、請求項23~30のいずれか一項に記載の方法。
- 前記分散体の適用を印刷法によって行う、請求項23~31のいずれか一項に記載の方法。
- 前記粒子の平均一次粒子径が100nm以下である、請求項23~32のいずれか一項に記載の方法。
- 下記の工程によって半導体層又は基材の第2の領域に第2のドープ層を形成することを更に含む、請求項23~33のいずれか一項に記載の方法:
前記第1の分散体の適用と同時に、前記第1の分散体の適用と乾燥の間に、前記第1の分散体の乾燥と前記第1のドーパント注入層の除去の間に、又は前記第1のドーパント注入層の除去の後で、前記半導体層又は基材の第2の領域に、第2の粒子を含有する第2の分散体を適用すること、ここで、前記第2の粒子は、前記半導体層又は基材と同一の元素から本質的になり、かつ前記第1の粒子のドーパントとは異なる型のドーパントによってドープされている、
前記第1の分散体の乾燥と同時に、又は前記第1の分散体の乾燥とは別に、適用した前記第2の分散体を乾燥して、第2のドーパント注入層とすること、及び
前記第1のドーパント注入層への光照射と同時に、又は前記第1のドーパント注入層への光照射とは別に、前記第2のドーパント注入層に光照射を行うことによって、前記第2の領域を、前記p型又はn型ドーパントによってドープして、前記第2のドープ層を形成すると共に、前記第2のドーパント注入層、及び前記第1及び/又は第2のパッシベーション層のうちの、前記第2のドーパント注入層に対応する領域を、少なくとも部分的に除去すること。 - 前記第2のドープ層に接触するように、前記パッシベーション層を通して電極を形成する工程を更に含む、請求項34に記載の方法。
- 前記半導体デバイスが太陽電池である、請求項34又は35に記載の方法。
- 半導体基材又は層上にパッシベーション層が積層されており、
前記半導体基材又は層の第1の領域において、前記パッシベーション層が少なくとも部分的に除去されて、前記半導体基材又は層に第1の粒子が焼結されており、かつ前記第1の粒子を介し、かつ前記パッシベーション層を通して、前記第1の領域に達する第1の電極が形成されており、
前記第1の粒子が、前記半導体層又は基材と同一の元素から本質的になり、かつp型又はn型ドーパントによってドープされており、かつ
前記ドーパントの濃度が、前記第1の領域の表面から0.1μmの深さにおいて1×1017atoms/cm3以上である、
半導体デバイス。 - 前記半導体基材又は層の第2の領域において、前記パッシベーション層が少なくとも部分的に除去されて、前記半導体基材又は層に第2の粒子が焼結されており、かつ前記第2の粒子を介し、かつ前記パッシベーション層を通して、前記第2の領域に達する第2の電極が形成されており、
前記第2の粒子が、前記半導体層又は基材と同一の元素から本質的になり、かつ前記第1の粒子のドーパントとは異なる型のドーパントによってドープされており、かつ
前記ドーパントの濃度が、前記第2の領域の表面から0.1μmの深さにおいて1×1017atoms/cm3以上である、
請求項37に記載の半導体デバイス。 - 太陽電池である、請求項37又は38に記載の半導体デバイス。
- 溶媒、
ドーパント元素を有するドーパント化合物、及び
100~1000nmの範囲に少なくとも1つのピーク吸収波長を有する材料で構成されている光吸収粒子、
を含有している、ドーパント組成物。 - 前記光吸収粒子が、ケイ素、ゲルマニウム又はそれらの組合せで構成されている、請求項40に記載の組成物。
- 前記光吸収粒子が、100nm以下の平均一次粒子径を有する、請求項40又は41に記載の組成物。
- 前記ピーク吸収波長におけるピークが、200~2500nmの範囲における最大ピークである、請求項40~42のいずれか一項に記載の組成物。
- 前記光吸収粒子が、ドーパントを実質的に含有していない、請求項40~43のいずれか一項に記載の組成物。
- 前記光吸収粒子が、ドーパントによってドープされている、請求項40~44のいずれか一項に記載の組成物。
- ドーパント元素を有するドーパント化合物、及び
100~1000nmの範囲に少なくとも1つのピーク吸収波長を有する材料で構成されている光吸収粒子、
を含有している、ドーパント注入層。 - 互いに積層されている下記の層を有する、ドーパント注入層:
ドーパント元素を有するドーパント化合物を含有しているドーパント化合物含有層、及び
100~1000nmの範囲にピーク吸収波長を有する材料で構成されている光吸収粒子を含有している光吸収粒子含有層。 - 前記光吸収粒子含有層上に、前記ドーパント化合物含有層が積層されている、請求項47に記載のドーパント注入層。
- 前記ドーパント化合物含有層上に、前記光吸収粒子含有層が積層されている、請求項47に記載のドーパント注入層。
- 前記ドーパント化合物含有層が、100~1000nmの範囲にピーク吸収波長を有する材料で構成されている光吸収粒子を更に含有している、請求項47~49のいずれか一項に記載のドーパント注入層。
- 前記光吸収粒子含有層が、ドーパント元素を有するドーパント化合物を更に含有している、請求項47~50のいずれか一項に記載のドーパント注入層。
- 半導体基材上に積層されている、請求項46~51のいずれか一項に記載のドーパント注入層。
- 前記光吸収粒子が、前記半導体基材と同一の元素で構成されている、請求項52に記載のドーパント注入層。
- 請求項52又は53に記載の前記ドーパント注入層に光を照射して、前記ドーパント元素を前記半導体基材中に拡散させることを含む、ドープ層の形成方法。
- 前記光吸収粒子が、照射される前記光の主波長において、前記ピーク吸収波長における吸光率の0.1倍以上の吸光率を有する、請求項54に記載の方法。
- 照射される前記光が、レーザー光である、請求項54又は55に記載の方法。
- 請求項54~56のいずれか一項に記載の方法によってドープ層を形成することを含む、半導体デバイスの製造方法。
- 前記半導体デバイスが、太陽電池である、請求項57に記載の方法。
- 請求項57又は58に記載の方法によって製造される、半導体デバイス。
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Also Published As
Publication number | Publication date |
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HK1204142A1 (en) | 2015-11-06 |
CN104205293A (zh) | 2014-12-10 |
US20150053263A1 (en) | 2015-02-26 |
CN104205293B (zh) | 2017-09-12 |
EP2833391A4 (en) | 2015-04-22 |
CN107039532B (zh) | 2020-08-25 |
CN106887384A (zh) | 2017-06-23 |
CN106887384B (zh) | 2018-12-14 |
TWI556440B (zh) | 2016-11-01 |
EP2833391A1 (en) | 2015-02-04 |
JPWO2013147202A1 (ja) | 2015-12-14 |
CN107039532A (zh) | 2017-08-11 |
KR20140142690A (ko) | 2014-12-12 |
JP5818972B2 (ja) | 2015-11-18 |
TW201405815A (zh) | 2014-02-01 |
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