CN103339688A - Transparent electrode substrate, method for producing same, photoelectric conversion device, method for producing same, and photoelectric conversion module - Google Patents
Transparent electrode substrate, method for producing same, photoelectric conversion device, method for producing same, and photoelectric conversion module Download PDFInfo
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- CN103339688A CN103339688A CN2011800659437A CN201180065943A CN103339688A CN 103339688 A CN103339688 A CN 103339688A CN 2011800659437 A CN2011800659437 A CN 2011800659437A CN 201180065943 A CN201180065943 A CN 201180065943A CN 103339688 A CN103339688 A CN 103339688A
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- 239000000758 substrate Substances 0.000 title claims abstract description 99
- 238000006243 chemical reaction Methods 0.000 title claims description 76
- 238000004519 manufacturing process Methods 0.000 title claims description 74
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 604
- 239000011787 zinc oxide Substances 0.000 claims abstract description 301
- 239000002019 doping agent Substances 0.000 claims abstract description 46
- 229910052782 aluminium Inorganic materials 0.000 claims description 156
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 156
- 238000000034 method Methods 0.000 claims description 104
- 239000004411 aluminium Substances 0.000 claims description 71
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- 230000031700 light absorption Effects 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 238000005229 chemical vapour deposition Methods 0.000 description 5
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- 238000013459 approach Methods 0.000 description 4
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- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
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- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
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- 240000007833 Dracaena angustifolia Species 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910000577 Silicon-germanium Inorganic materials 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
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- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- MRNHPUHPBOKKQT-UHFFFAOYSA-N indium;tin;hydrate Chemical compound O.[In].[Sn] MRNHPUHPBOKKQT-UHFFFAOYSA-N 0.000 description 1
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- 229910052703 rhodium Inorganic materials 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
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- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
Images
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0224—Electrodes
- H01L31/022466—Electrodes made of transparent conductive layers, e.g. TCO, ITO layers
- H01L31/022483—Electrodes made of transparent conductive layers, e.g. TCO, ITO layers composed of zinc oxide [ZnO]
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0236—Special surface textures
- H01L31/02366—Special surface textures of the substrate or of a layer on the substrate, e.g. textured ITO/glass substrate or superstrate, textured polymer layer on glass substrate
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
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- Condensed Matter Physics & Semiconductors (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Photovoltaic Devices (AREA)
- Non-Insulated Conductors (AREA)
- Manufacturing Of Electric Cables (AREA)
- Laminated Bodies (AREA)
- Physical Vapour Deposition (AREA)
Abstract
A transparent electrode substrate in which a transparent electrode formed from a zinc oxide-based thin film is formed on a translucent insulating substrate, the zinc oxide-based thin film containing zinc oxide as the main component and at least one type of dopant element. The zinc oxide-based thin film has an uneven surface and a dopant element concentration gradient in which the concentration of the dopant element continuously decreases from the side of the translucent insulating substrate to the surface of the zinc oxide-based thin film. The concentration of the dopant element in the zinc oxide-based thin film is 1.5 atom % to 3 atom % in a region from the translucent insulating substrate to 50 nm inward in the thickness direction and is 0.2 atom % to 1 atom % in a region from the surface of the zinc oxide-based thin film to 300 nm inward in the thickness direction.
Description
Technical field
The present invention relates to transparent electrode substrate and manufacture method thereof, photo-electric conversion device and manufacture method thereof, light-to-current inversion module.
Background technology
In photo-electric conversion device, transparency electrode is one of important factor.For the demanding photopermeability of transparency electrode and conductivity.Mainly be that photopermeability is influential to short-circuit current density (Jsc), conductivity is influential to fill factor, curve factor (FF).Particularly ought only use under the situation of transparency electrode as the electrode of sensitive surface side, the electric current that takes place in the light-to-current inversion layer has horizontal current path, so it is very important to improve conductivity.In addition, knownly concavo-convexly make light scattering prolong light path by arranging on the transparency electrode surface, Jsc increases, and light-to-current inversion efficient further improves.But the formation of concave-convex surface follows local film thickness to reduce, so reduce as the conductivity of electrode integral body.Though can seek to improve conductivity by high carrier concentrationization, free carrier absorb to increase thus, and the light transmission rate in near-infrared wavelength zone reduces, so can not avoid the reduction to the photoelectric conversion performance of the light of near-infrared wavelength.That is, as the performance that requires in the transparency electrode that is used for photo-electric conversion device, improving on the basis of light scattering effect by forming concave-convex surface, it is important taking into account photopermeability and conductivity.
In patent documentation 1, recorded and narrated following content, at the opposition side of the light entrance face of substrate, possess the nesa coating of the even doping with concaveconvex shape, concavo-convex by this and light incident is scattered, so the light restriction effect improves, and makes the photo-electric conversion device high efficiency.Relative therewith, in patent documentation 2, recorded and narrated the manufacture method of following transparency electrode, form zinc-oxide film in glass substrate, this zinc-oxide film with the boundary vicinity concentration of dopant height of substrate, have low CONCENTRATION DISTRIBUTION near surface.
Patent documentation:
Patent documentation 1: No. 3801342 communique of Japan Patent
Patent documentation 2: TOHKEMY 2001-189114 communique
But, forming under the big concavo-convex situation of diameter at electrode surface in order to improve light scattering effect, in the local attenuation of concavo-convex recess thickness, so the resistance of this part increases.In addition, the crystallinity on the thickness direction of Zinc oxide film near the part of substrate owing to be early growth period and step-down uprises by the growth progress in the part that approaches the surface.Forming by etching under the situation of concave-convex surface, residual near the part that the crystallinity of substrate is low, so can't avoid reduction as the carrier mobility of a film integral body.
Because above reason is by forming the concavo-convex resistance that increases at electrode surface.Relative therewith, in order to remedy the reduction amount of conductance, can consider to increase the doping of film integral body, increase the method for carrier concentration.But the concavo-convex size that is formed at the transparency electrode surface also depends on the impurity concentration of doping.As mentioned above, between the transmitance of conductance and near infrared wavelength region, exist the increase of carrier concentration to cause the relation that transmitance reduces.And then formed concavo-convex more big light scattering effect is more high, but increases doping content in order to improve conductance, thereby formed concavo-convex diameter diminishes, and light scattering effect reduces.That is, the optimum value of the doping content of seeing from the conductance aspect is different with the optimum value of seeing from concavo-convex formation aspect.Therefore, in the method for the carrier concentration that only increases nesa coating integral body, it is difficult addressing this problem.
In the manufacture method of the transparency electrode of patent documentation 1, though the scattering of light effect increases, the light-to-current inversion efficient of photo-electric conversion device improves, because concavo-convex formation and the part resistance of thickness attenuation increases, so increase as the resistance of electrode integral body.In the manufacture method of patent documentation 2, though can possess effects such as antireflection in transparency electrode, but only be conceived to because situation, conductance that the formation of concave-convex surface improves the scattering of light effect do not have to consider to remain on transmitance under the near-infrared wavelength, so in photo-electric conversion device, use the method that surpasses patent documentation 1 on this point.
Summary of the invention
The present invention proposes in view of the above problems, its purpose is to obtain a kind ofly to possess for the concave-convex surface that improves light scattering effect, transparent electrode substrate excellent on conductivity and the photopermeability and manufacture method thereof, on light-to-current inversion efficient excellent photo-electric conversion device and manufacture method thereof, light-to-current inversion module.
In order to address the above problem the realization purpose, it is the transparent electrode substrate that forms transparency electrode at the light transmission insulated substrate, this transparency electrode is by being that main component and the Zinc oxide film that comprises at least a above dopant element are formed with zinc oxide, this transparent electrode substrate is characterised in that: described Zinc oxide film possesses concaveconvex shape on the surface, have from described light transmission insulated substrate side direction and the face side concentration gradient of the described dopant element of minimizing continuously, the concentration of the described dopant element in described Zinc oxide film in the zone from described light transmission insulated substrate to thickness 50nm more than or equal to 1.5 atom % and smaller or equal to 3 atom %, from the surface to the zone of thickness 300nm more than or equal to 0.2 atom % and smaller or equal to 1 atom %.
According to the present invention, can access have high light scattering effect and on conductivity and photopermeability excellent transparency electrode, obtain by using this transparency electrode to improve the effect of the light-to-current inversion efficient of photo-electric conversion device.
Description of drawings
Fig. 1 is the profile that schematically shows the manufacture method of the manufacture method of transparency electrode of embodiments of the present invention 1 and photo-electric conversion device.
Fig. 2 is the performance plot that is illustrated in the relation of the concentration of the aluminium that mixes in the zinc-oxide film and the diameter by the formed concave-convex surface of etching.
Fig. 3 is the performance plot that is illustrated in the relation of the concentration of the aluminium that mixes in the zinc-oxide film and conductance.
Fig. 4 is the performance plot of relation that is illustrated in the transmitance of the concentration of the aluminium that mixes in the zinc-oxide film and near-infrared wavelength light.
Fig. 5 is that expression is apart from the performance plot of the relation of the distance of light transmission insulated substrate and the aluminum concentration in the film.
Fig. 6 is the profile that schematically shows the manufacture method of the manufacture method of transparency electrode of embodiments of the present invention 2 and photo-electric conversion device.
Fig. 7 is the profile that schematically shows the manufacture method of the manufacture method of transparency electrode of embodiments of the present invention 3 and photo-electric conversion device.
(symbol description)
1: the light transmission insulated substrate; 2: the aluminium film; 3: the Zinc oxide film; 4: the Zinc oxide film with aluminum concentration gradient continuous on thickness direction; 5: the Zinc oxide film with concave-convex surface and the aluminum concentration gradient on thickness direction; 6: the Zinc oxide film with concave-convex surface; 7: have that concave-convex surface distributes and the Zinc oxide film of continuous aluminum concentration gradient on thickness direction; 11: the light-to-current inversion layer; 12: back side transparency conducting layer; 13: the backplate layer.
Embodiment
Below describe the execution mode of transparent electrode substrate of the present invention and manufacture method thereof, photo-electric conversion device and manufacture method thereof, light-to-current inversion module with reference to the accompanying drawings in detail.And the present invention is not limited to following record, can change aptly in the scope that does not break away from purport of the present invention.In addition, in accompanying drawing shown below, for easy understanding, the engineer's scale of each parts is with actual different sometimes.Between each accompanying drawing too.
Fig. 1 is the profile that schematically shows the manufacture method of the manufacture method of transparency electrode of embodiments of the present invention 1 and photo-electric conversion device.At this, contain the dopant film as what formed by the material that contains dopant, be that example describes with aluminium (Al) film.At first, as Fig. 1 (a) be shown in sequential cascade aluminium film 2 on the light transmission insulated substrate 1, zinc oxide (ZnO) is film 3.Various insulated substrates with light transmission such as light transmission insulated substrate 1 use glass or transparent resin, plastics, quartz.
In Zinc oxide film 3, for example use Zinc oxide film.Zinc oxide is one of transparent conductive oxides (TCO:Transparent Conductive Oxide) that generally is used as transparent electrode material.And Zinc oxide film 3 is with the main component of zinc oxide as its composition, comprises as with respect to more than the aluminium of the dopant of zinc oxide, gallium (Ga), boron (B), nitrogen (N), phosphorus (P), fluorine impurity elements such as (F) at least a.At this moment, if adopt etched concave-convex surface to form step after considering, then preferred when the film processed of Zinc oxide film 3, doping will be after thermal diffusion from the surface of Zinc oxide film 3 to the aluminum concentration (containing ratio) the zone of thickness 300nm be adjusted to as the value that is suitable for concavo-convex formation more than or equal to the aluminium of 0.2 atom % smaller or equal to the concentration of 1 atom %.Fig. 2 is the performance plot that is illustrated in the aluminum concentration (atom %) that mixes in the Zinc oxide film and the relation by being etched in the formed concavo-convex diameter (μ m) of zinc oxide surface.Adopt concavo-convex size that etching forms because of etching condition, Zinc oxide film 3 create conditions that some changes, but under more than or equal to the aluminum concentration (containing ratio) of 0.2 atom % smaller or equal to 1 atom %, have concavo-convex size as shown in Figure 2 and become big trend.Thereby, be arranged in this scope by the aluminum concentration with the near surface place of the Zinc oxide film after the thermal diffusion, can improve light scattering effect, be increased in the Jsc in the photo-electric conversion device.Under situation big under the situation of aluminum concentration (containing ratio) the less than 0.2 atom % from the surface of Zinc oxide film to thickness 300nm zone after thermal diffusion and than 1 atom %, the size decreases of possible concave-convex surface can not fully obtain light scattering effect.Zinc oxide film 3 can be by being the various film-forming methods film processed of representative with sputtering method or electron beam method of piling, atomic layer method of piling, chemical meteorology deposition (CVD:Chemical Vapor Deposition) method, Metalorganic chemical vapor deposition (MOCVD:Metal Organic Chemical Vapor Deposition) method, sol-gel process, print process, spray-on process.
Aluminium film 2 is material membranes that dopant is provided to Zinc oxide film 3.At this, example as the film of being made up of the material that comprises the dopant that offers Zinc oxide film 3 uses aluminium film 2, but also can replace aluminium film 2 and use the film that is made of the material that comprises the element more than select at least a from the element that becomes dopant at above-mentioned zinc oxide.Aluminium film 2 can be by being the various film-forming methods film processed of representative with sputtering method, vapour deposition method.In addition, provide the material of dopant also to need the viewpoint of the anti-reflection effect that produces from the modulation by refractive index to go out to send selection.The aluminium of enumerating as an example, the oxide (Al of aluminium
2O
3) refractive index be 1.8, have glass (SiO
2) 1.45 and zinc oxide 2.0 between value.Therefore, by at the sequential cascade according to aluminium film 2, Zinc oxide film 3 on glass, the refractive index in these films after the thermal diffusion of explanation changes continuously later on, can improve anti-reflection effect.
Even using under aluminium film 2 situation of material membrane as the film of being formed by the material that comprises the dopant that offers Zinc oxide film 3 in addition, being that film 3 possesses sufficient transmitance and conductance at thermal diffusion rear oxidation zinc preferably also, is the material that its refractive index has the value between glass and the Zinc oxide film 3.
Then, make the aluminium of aluminium film 2 in Zinc oxide film 3, carry out thermal diffusion, make aluminium film 2 and Zinc oxide film 3 rotten for such having below the Zinc oxide film 4(of continuous aluminum concentration gradient at thickness direction shown in Fig. 1 (b), be called Zinc oxide film 4 sometimes simply).At this, the aluminum concentration gradient in the Zinc oxide film 4 a surperficial side from light transmission insulated substrate 1 side direction and is reduced continuously.That is, more near light transmission insulated substrate 1, aluminum concentration is more high.Be modulated at conductance on the thickness direction in the Zinc oxide film 4 by aluminum concentration being arranged continuous gradient, main current path is set near the boundary vicinity (the substrate-side border) of Zinc oxide film 4 and light transmission insulated substrate 1 in Zinc oxide film 4, thereby even also can realize high light transmission and conductance in the Zinc oxide film 4 after forming concave-convex surface.For example, in Zinc oxide film 4, the aluminum concentration (containing ratio) from the border of light transmission insulated substrate 1 and Zinc oxide film to the zone of thickness 50nm is preferably greater than from conductivity and the transmitance this point the near-infrared wavelength zone and equals 1.5 atom % smaller or equal to 3 atom %.In Zinc oxide film 4, by near the aluminum concentration light transmission insulated substrate 1 is arranged in this scope, can improve the conductivity of electrode integral body, be increased in the FF in the photo-electric conversion device.Fig. 3 is the performance plot of relation that is illustrated in the conductance (S/cm) of the aluminum concentration (atom %) that mixes in the Zinc oxide film and Zinc oxide film.In Zinc oxide film 4, under the situation of the aluminum concentration less than 1.5 atom % when from the border of light transmission insulated substrate 1 and Zinc oxide film 4 to the zone of thickness 50nm, can not obtain sufficient conductivity.In addition, in Zinc oxide film 4, saturated greater than conductivity under the situation of 3 atom % to the aluminum concentration the zone of thickness 50nm from the border of light transmission insulated substrate 1 and Zinc oxide film 4.In addition, Fig. 4 is the performance plot of relation of transmitance (%) that is illustrated in the light of the aluminum concentration (atom %) that mixes in the Zinc oxide film and near-infrared wavelength.In Fig. 4, the expression wavelength is the transmitance of the light of 1100nm.Under the situation of the aluminum concentration that in Zinc oxide film, mixes greater than 3 atom %, can not obtain the light transmission rate in the near infrared ray wavelength region may fully.
At this, even the formed Zinc oxide film of manufacture method of the transparency electrode in the past by the dopant that mixes equably on thickness direction (evenly doping zinc-oxide is film) thinks also that the average aluminum concentration in the relative film of aluminum concentration in the film has ± about 5% distribution.On the other hand, make by thermal diffusion aluminium in Zinc oxide film 3, spread aluminum concentration in the Zinc oxide film 4 of the execution mode 1 that forms be distributed near the light transmission insulated substrate 1 high, along with reducing near the surface of film.Therefore, the aluminum concentration that the aluminum concentration in Zinc oxide film 4 distributes and evenly doping zinc-oxide is film distributes and differs widely.The performance plot of the relation of the aluminum concentration (atom %) that Fig. 5 is expression in the distance of light transmission insulated substrate 1 and the film.In Fig. 5, distribute for the aluminum concentration of the thickness direction in Zinc oxide film 4 represent the situation (the solid line A among the figure) of execution mode 1 respectively, change to non-doping zinc-oxide film when the situation that Zinc oxide film 4 is changed to non-doping zinc-oxide film (the dotted line B among the figure), with Zinc oxide film 3 and make dopant be diffused into electrode surface situation (the single-point line C among the figure), increase the situation (the dotted line D among the figure) of the thickness of aluminium film 2.Under the situation of using non-doping zinc-oxide film (the dotted line B among the figure), low at the aluminum concentration of near surface, so the diameter of concave-convex surface diminishes, can not obtain sufficient light scattering effect.In that being changed into non-doping zinc-oxide film, Zinc oxide film 3 make dopant be diffused into (the single-point line C among the figure) under the situation of zinc-oxide film thin surface, can access fully big concave-convex surface, but near the doping substrate reduces, and the conductivity of the electrode integral body after the concavo-convex formation reduces.And, for the diameter of conductivity, concave-convex surface all is worth fully, under the situation of the film thickness that increases aluminium film 2 (the dotted line D among the figure), uprise at the aluminum concentration in the whole zone of electrode, so the transmitance of near infrared ray wavelength region may reduces significantly.
Namely, in the Zinc oxide film, in order to improve light scattering effect by concavo-convex formation and also to be worth fully for conductance and transmitance, the aluminium of the concentration that is suitable for concavo-convex formation of need mixing constantly at the film processed of Zinc oxide film improves conductance (the solid line A among the figure) near by diffusion aluminium only being diffused into substrate.For example, preferred aluminum concentration is the scope of 0.2 atom %～1 atom % on the surface from Zinc oxide film 4 from the viewpoint of concavo-convex formation to the zone of thickness 300nm in Zinc oxide film 4, is the scope of 1.5 atom %～3 atom % on the border from light transmission insulated substrate 1 and Zinc oxide film from the viewpoint of taking into account conductivity and permeability to the zone of thickness 50nm.
This thermal diffusion by the heat treatment behind aluminium film 2 and Zinc oxide film 3 stacked, follow the heating of the film processed of Zinc oxide film 3 to implement.Heat treatment temperature preferably in the stable on heating while of considering employed light transmission insulated substrate 1, is for example selected from 300 ℃～600 ℃ scope.Heat treatment temperature is being lower than under 300 ℃ the situation, and is might the aluminium diffusion insufficient.
In addition, heat treatment also can be in a vacuum or is being comprised in the scope of 0 volume %～10 volume % in the atmosphere of oxygen and carry out.The carrying out of thermal diffusion carries out speed control by temperature and time, and the carrying out of the more high thermal diffusion of temperature is more fast.That is, in order in the aluminum concentration on the thickness direction of Zinc oxide film 4 gradient to be set, need select thickness, thermal diffusion temperature, the time of aluminium film aptly.And then, promote crystallization by heat-treating in the low part of the crystallinity of Zinc oxide film 4, so degree of excursion improves, as a result of can seek the further raising of conductance.
In addition, the thickness of aluminium film 2 need be selected in the mode that near the aluminum concentration the light transmission insulated substrate 1 after the diffusion as mentioned above becomes the concentration that can take into account conductance and near-infrared wavelength transmitance.For example, from 0.1% to 20% of the thickness of the preferred Zinc oxide film 3 of the thickness of aluminium film 2 scope.The thickness of aluminium film 2 than 0.1% of the thickness of Zinc oxide film 3 thin situation under, the aluminium amount that is diffused into Zinc oxide film 3 is insufficient, conductivity that might Zinc oxide film 4 is insufficient.When the thickness of aluminium film 2 than 20% of the thickness of Zinc oxide film 3 thick situation under, the aluminium amount in the Zinc oxide film 3 of being diffused into is superfluous or diffusion is not enough, light transmission rate that might Zinc oxide film 4 reduces.
Then, etching is carried out on the surface of Zinc oxide film 4, shown in Fig. 1 (c), formation has concave-convex surface and below the Zinc oxide film 5(of the continuous aluminum concentration gradient on the thickness direction, is called Zinc oxide film 5 sometimes simply).Zinc oxide film 5 is nesa coatings, uses as the transparency electrode in the photo-electric conversion device.This etching can be that the various soups of representative carry out etching method, use reactive ion etching (the RIE:Reactive Ion Etching) method of methane gas etc. to wait to realize by adopting with hydrochloric acid.
At this moment, even the even doping zinc-oxide in the past is to make in the film under the long etched situation that the surface of light transmission insulated substrate 1 exposes, aluminum concentration on thickness direction has that the high part of aluminum concentration diminishes by the formed concavo-convex diameter of etching (size) in the Zinc oxide film 4 of gradient, so the concavo-convex degree of depth also diminishes, the film ratio is easier to residual.Therefore, in the Zinc oxide film 4 of present embodiment, even carry out under the long etched situation, be that film is compared the continuity that also keeps film easily with in the past even doping zinc-oxide.
In addition, when carrying out under the situation of thermal diffusion according to the sequential cascade of aluminium film 2, Zinc oxide film 3, electric current flows through centered by the zone that approaches the high light transmission insulated substrate 1 of aluminum concentration in Zinc oxide film 5.Therefore, obtain concave-convex surface even Zinc oxide film 5 forms by etching, also can keep high conductance.
In Zinc oxide film 5, centered by the zone near high light transmission insulated substrate 1, flow through electric current, so the phenomenon that the resistance of direction part increases in the recess place face of thickness attenuation in the formation of concave-convex surface is difficult to take place.In addition, in Zinc oxide film 5, be that film is compared with in the past even doping zinc-oxide, the conductance height in the zone that electric current flows through is so can reduce the light absorption of long wavelength side with reduced thickness.
In addition, has concave-convex surface at Zinc oxide film 5, so can obtain high light scattering effect.And then, be formed at by etching the Zinc oxide film concave-convex surface shape since the aluminum concentration in the Zinc oxide film and the temperature during film processed change, so be provided with in the etching of Zinc oxide film 4 of aluminum concentration gradient at thickness direction, modulation etching speed, concave-convex surface shape and in the past even doping zinc-oxide are that film is compared and become complicated.Therefore, the light scattering effect at Zinc oxide film 5 places further improves.
Below, use the Zinc oxide film of making by above-mentioned method 5 to make photo-electric conversion device.That is, be shown on the above-mentioned Zinc oxide film 5 order as Fig. 1 (d) and form light-to-current inversion layer 11, back side transparency conducting layer 12, backplate layer 13, form photo-electric conversion device.
Light-to-current inversion layer 11 is made up of the silicon based thin film semiconductor layer that for example has pin knot, the pin semiconductor junction of the p-type semiconductor layer parallel with the face direction of light transmission insulated substrate 1, i type semiconductor layer and n type semiconductor layer that has been included on the Zinc oxide film 5 sequential cascade.At this, the silicon based thin film semiconductor layer can be by being added with Si semiconductor, and perhaps at least a film of carbon (C), germanium (Ge), oxygen (O) or other elements constitutes.This light-to-current inversion layer 11 uses plasma CVD method or hot CVD method etc. and piles up formation.
In addition, in order to improve the junction characteristic of each layer in light-to-current inversion layer 11, between p-type semiconductor layer and the i type semiconductor layer, between i type semiconductor layer and n type semiconductor layer, can insert the centre of band gap of each knitting layer or the semiconductor layer with band gap of equal size.That is, between p-type semiconductor layer and i type semiconductor layer, also can insert non-monocrystalline silicon (Si) layer, the on-monocrystalline carborundum (Si of the middle big or small band gap of the band gap with p-type semiconductor layer and i type semiconductor layer
xC
1-x) layer, on-monocrystalline silica (Si
xO
1-x) layer, on-monocrystalline SiGe (Si
xGe
1-x) semiconductor layer such as layer grade.Equally, between i type semiconductor layer and n type semiconductor layer, also can insert the centre of band gap of i type semiconductor layer and n type semiconductor layer or the various semiconductor layers with band gap of equal size.
Back side transparency conducting layer 12 is for example by comprising zinc oxide, tin indium oxide (ITO), tin oxide (SnO
2), indium oxide (In
2O
3) at least a TCO constitute.In addition, back side transparency conducting layer 12 also can constitute by the transparent conductive oxides of having added the element of selecting more than a kind in these TCO from aluminium, gallium, boron etc. at least.Back side transparency conducting layer 12 waits to form by electron beam evaporation plating method, sputtering method, atomic layer method of piling, CVD method, low pressure chemical vapor deposition method, mocvd method, sol-gel process, print process, semar technique.
As mentioned above, in the manufacture method of the transparency electrode of execution mode 1, will as comprise provide to Zinc oxide film 3 dopant of dopant be the aluminium film 2 of material of aluminium atom and Zinc oxide film 3 according to this sequential cascade after, make the aluminium atom carry out thermal diffusion to Zinc oxide film 3.By this thermal diffusion, be formed on the Zinc oxide film 4 of the structure of the continuous concentration gradient that has the aluminium atom on the thickness direction.At this moment, conductance uprises near the light transmission insulated substrate 1 that aluminum concentration is high in Zinc oxide film 4.Then, form concave-convex surface by the surface of this Zinc oxide film 4 of etching at Zinc oxide film 4, form the Zinc oxide film 5 with concave-convex surface and the aluminum concentration gradient on thickness direction.At this moment, be the aluminum concentration of the near surface of film 4 by selective oxidation zinc aptly, strengthen the shape of the concave-convex surface that forms by etching, can obtain high light scattering effect.
In the manufacture method of the transparency electrode of execution mode 1, by make so the high zone of conductance be confined to light transmission insulated substrate 1 near, after the formation of concave-convex surface, also can keep the high zone of conductance, can realize high conductivity.
In addition, in Zinc oxide film 5, be that film is compared with in the past even doping zinc-oxide, the conductance height in the zone that electric current flows through.Thus, in the manufacture method of the transparency electrode of execution mode 1, can make the thickness attenuation of Zinc oxide film 5, can be reduced in the light absorption of the long wavelength side in the Zinc oxide film 5, can realize high photopermeability.
In addition, in the manufacture method of the transparency electrode of execution mode 1, in Zinc oxide film 4, the aluminum concentration that can be chosen near surface respectively is suitable for improving the value of the conductivity that value that the concave-convex surface of light scattering effect forms and near the aluminum concentration light transmission insulated substrate 1 be suitable for keeping high.That is, by near the modulation light transmission insulated substrate 1 and the doping content of near surface, can handle conductance that the doping content of the aluminium in Zinc oxide film 4 influences and the size of concave-convex surface independently.In addition, the concaveconvex shape on the surface of Zinc oxide film 5 is that film is compared with in the past even doping zinc-oxide, become more complicated, so can also obtain light scattering effect in Zinc oxide film 5 is compared the effect of further raising, brought by the index modulation that forms by the aluminum concentration gradient with uniform doping zinc-oxide film anti-reflection effect.
And, the method of the film of concentration of dopant continually varying method, stacked different concentration of dopant is compared, also can more easily be obtained above-mentioned effect.
Thereby, according to the manufacture method of the transparency electrode of execution mode 1, compare with transparency electrode in the past such as patent documentation 1 grade, can realize easily having high light scattering effect and having high conductivity and the transparency electrode of photopermeability.
In addition, manufacture method according to the photo-electric conversion device of execution mode 1, the Zinc oxide film 5 that possesses high conductivity and photopermeability that use is made by the manufacture method of the transparency electrode of execution mode 1 in transparency electrode is made photo-electric conversion device, so can realize the photo-electric conversion device of light-to-current inversion efficient excellence.
Execution mode 2
Fig. 6 is the profile that schematically shows the manufacture method of the manufacture method of transparency electrode of embodiments of the present invention 2 and photo-electric conversion device.The manufacture method of the transparency electrode of execution mode 2 is compared with the manufacture method of the transparency electrode of execution mode 1, carries out etching step this point difference in the front and back of thermal diffusion step both sides' the moment.Below for the additional identical symbol of the parts identical with execution mode 1.
The thermal history of having reported the film of the temperature during according to the film processed of the aluminum concentration in the Zinc oxide film shown in Figure 2 and Zinc oxide film of the shape of concave-convex surface on surface that is formed on the Zinc oxide film by etching, heat treatment etc. changes.In execution mode 2, by utilizing such phenomenon surperficial concaveconvex shape is arranged distribution, compare with execution mode 1, can obtain higher light scattering effect.
At first, shown in Fig. 6 (a), sequential cascade aluminium film 2, zinc oxide (ZnO) are film 3 on light transmission insulated substrate 1.And light transmission insulated substrate 1, aluminium film 2, Zinc oxide film 3 can be selected from the various materials of recording and narrating execution mode 1.At this moment, the aluminum concentration that preferably is doped to Zinc oxide film 3 is also lower for maximum concentration than the diameter of the concave-convex surface that forms by etching.In addition, aluminium is to the thermal diffusion of Zinc oxide film 3 in the film processed in order to be suppressed at, and the film processed of preferred Zinc oxide film 3 carries out under than 400 ℃ of low temperature.
Then, etching is carried out on the surface of Zinc oxide film 3, shown in Fig. 6 (b), formed the Zinc oxide film 6 with concave-convex surface.The concave-convex surface that form this moment is low at the aluminum concentration of the near surface of Zinc oxide film 3, and film temperature processed is also low, so formation has the smaller concavo-convex of 0.2 μ m left and right sides diameter easily.This etching can be selected from the whole bag of tricks of recording and narrating execution mode 1.
Then, make the aluminium of aluminium film 2 in Zinc oxide film 6, carry out thermal diffusion, make aluminium film 2 and Zinc oxide film 6 rotten Zinc oxide film 5 for the continuous gradient of the aluminum concentration with concave-convex surface and thickness direction shown in Fig. 6 (c).At this, the aluminum concentration gradient in Zinc oxide film 5 face side from light transmission insulated substrate 1 side direction and is reduced continuously.That is, more near light transmission insulated substrate 1, it is more high that aluminum concentration becomes.
Then, etching is appended on the surface of Zinc oxide film 5, shown in Fig. 6 (d), form the concave-convex surface that appends on the surface of Zinc oxide film 5.Thus, form in the shape of the concave-convex surface on the surface of Zinc oxide film 5 and to distribute, form have that concave-convex surface distributes and thickness direction on below the Zinc oxide film 7(of continuous aluminum concentration gradient, be called Zinc oxide film 7 sometimes simply).Zinc oxide film 7 is transparent and electrically conductive films, uses as the transparency electrode in photo-electric conversion device.
This appends etching and can select from the whole bag of tricks of recording and narrating execution mode 1.Compare with etched moment last time by appending concave-convex surface that etching forms, the aluminum concentration height at the near surface of Zinc oxide film 5 also carries out under high state at thermal history, surpasses the bigger concavo-convex of 1 μ m so form diameter easily.
At this moment, even doping zinc-oxide in the past is in the film, even make the surface of light transmission insulated substrate 1 expose under such long-time etched situation, have in the aluminum concentration on thickness direction in the Zinc oxide film 5 of gradient, its etching speed of part that aluminum concentration is high is slack-off, and is more residual than being easier to.Therefore, be that film is compared with in the past even doping zinc-oxide, keep the continuity of film easily.
In addition, at the sequential cascade of working as according to aluminium film 2, Zinc oxide film 3, carry out under the situation of thermal diffusion after forming Zinc oxide film 6 by etching, electric current flows through centered by the zone that approaches the high light transmission insulated substrate 1 of aluminum concentration in Zinc oxide film 7.Therefore, even Zinc oxide film 7 forms by appending the resultant concave-convex surface of etching, also can keep high conductance.
In Zinc oxide film 7, electric current flows through centered by near the zone of high light transmission insulated substrate 1, thus in the formation of concave-convex surface in the recess place face of thickness attenuation the local phenomenon that increases of the resistance of direction be difficult to take place.In addition, in zinc-oxide film 5, be that film is compared with in the past even doping zinc-oxide, the conductance height in the zone that electric current flows through so can make the thickness attenuation, can reduce the light absorption of long wavelength side.
In addition, has concave-convex surface at Zinc oxide film 7, so can obtain high light scattering effect.And then thickness direction is provided with in the etching of Zinc oxide film 5 of aluminum concentration gradient, the modulation etching speed, the concaveconvex shape on surface with in the past evenly doping zinc-oxide be that film is compared and become complicated.Therefore, the light scattering effect at Zinc oxide film 7 places further improves.
Then, use the Zinc oxide film of making by above-mentioned method 7 to make photo-electric conversion device.That is, shown in Fig. 6 (e), order forms light-to-current inversion layer 11, back side transparency conducting layer 12, backplate layer 13 on above-mentioned Zinc oxide film 7, forms photo-electric conversion device.Light-to-current inversion layer 11, back side transparency conducting layer 12, backplate layer 13 can be selected from the various materials of recording and narrating execution mode 1.
As mentioned above, in the manufacture method of the transparency electrode of execution mode 2, will as comprise provide to Zinc oxide film 3 alloy of dopant be the aluminium film 2, Zinc oxide film 3 of the material of aluminium atom according to this sequential cascade after, be that the surface of film 3 forms the Zinc oxide film 6 with concave-convex surface by etching oxidation zinc.Then, make the aluminium atom carry out thermal diffusion to Zinc oxide film 6.By this thermal diffusion, form the Zinc oxide film 5 of structure have concave-convex surface and to have the continuous concentration gradient of aluminium atom at thickness direction.At this moment, conductance uprises near the light transmission insulated substrate 1 that aluminum concentration is high in Zinc oxide film 5.And, by being appended etching, the surface of this Zinc oxide film 5 forms the concave-convex surface that appends at Zinc oxide film 5, and the shape that is formed on concave-convex surface has the Zinc oxide film 7 that distributes and have the aluminum concentration gradient on thickness direction.
In the manufacture method of the transparency electrode of execution mode 2, by make so the high zone of conductance be confined to light transmission insulated substrate 1 near, even after concave-convex surface forms, also can keep the high zone of conductance, can realize high conductivity.
In addition, in Zinc oxide film 7, be that film is compared with in the past even doping zinc-oxide, the conductance height in the zone that electric current flows through.Thus, in the manufacture method of the transparency electrode of execution mode 2, can make the thickness attenuation of Zinc oxide film 7, can be reduced in the light absorption of the long wavelength side in the Zinc oxide film 7, can realize high photopermeability.
And, in the manufacture method of the transparency electrode of execution mode 2, can form in the shape of the concave-convex surface of Zinc oxide film 7 and distribute, so be that film is compared with in the past even doping zinc-oxide, can access higher light scattering effect.
And, in the thermal diffusion of in the manufacture method of the transparency electrode of execution mode 2, using and the film processed at the Zinc oxide film concentration of dopant is changed continuously and compare, can more easily be implemented in the continuous dopant concentration gradient in the Zinc oxide film.
Thereby, according to the manufacture method of the transparency electrode of execution mode 2, compare with the transparency electrode in the past of patent documentation 1 grade, realize having high conductivity easily, the transparency electrode of high photopermeability and higher light scattering effect.
In addition, manufacture method according to the photo-electric conversion device of execution mode 2, the Zinc oxide film 7 that possesses high conductivity and photopermeability that use is made by the manufacture method of the transparency electrode of execution mode 2 in transparency electrode is made photo-electric conversion device, so can realize the photo-electric conversion device that light-to-current inversion efficient is more excellent.
Fig. 7 is the profile that schematically shows the manufacture method of the manufacture method of transparency electrode of embodiments of the present invention 3 and photo-electric conversion device.The manufacture method of the transparency electrode of execution mode 3 is compared with the manufacture method of the transparency electrode of execution mode 1, and is different by using mocvd method to omit on the etching step this point in the formation of Zinc oxide film.Below, for adding identical symbol with execution mode 1 identical parts.
At first, shown in Fig. 7 (a), after light transmission insulated substrate 1 forms aluminium film 2, by the stacked Zinc oxide film 6 that is provided with concave-convex surface of mocvd method.And light transmission insulated substrate 1, aluminium film 2, Zinc oxide film 6 can be selected from the various materials that execution mode 1 is recorded and narrated.In the formation of the Zinc oxide film 6 that is undertaken by mocvd method, by select piling up film forming conditions such as temperature, material quantity delivered aptly, do not implement the such etching step of execution mode 1, execution mode 2, just concave-convex surface can be set.Thus, do not need to be used to form the etching step of concave-convex surface.
Then, make the aluminium of aluminium film 2 in Zinc oxide film 6, carry out thermal diffusion, make aluminium film 2 and Zinc oxide film 6 rotten Zinc oxide films 5 for the continuous gradient of the aluminum concentration that shown in Fig. 7 (b), has concave-convex surface and thickness direction like that.Thus, form the Zinc oxide film 5 of the aluminum concentration gradient with concave-convex surface and thickness direction.At this, the aluminum concentration gradient in Zinc oxide film 5 face side from light transmission insulated substrate 1 side direction and is reduced continuously.That is, more become more high near light transmission insulated substrate 1 aluminum concentration.Zinc oxide film 5 is transparent and electrically conductive films, uses as the transparency electrode in photo-electric conversion device.
Like this, when carrying out under the situation of thermal diffusion according to the sequential cascade of aluminium film 2, Zinc oxide film 6, electric current flows through centered by the zone that approaches the high light transmission insulated substrate 1 of aluminum concentration in Zinc oxide film 5.Therefore, even forming concave-convex surface, Zinc oxide film 6 also can keep high conductance.
Electric current flows through centered by near the zone of light transmission insulated substrate 1 in Zinc oxide film 5, thus in the formation of concave-convex surface in the recess place of thickness attenuation face the local phenomenon that increases of the resistance of direction be difficult to take place.In addition, in Zinc oxide film 5, be that film is compared with in the past even doping zinc-oxide, the conductance height in the zone that electric current flows through so can make the thickness attenuation, can reduce the light absorption of long wavelength side.And then Zinc oxide film 5 has concave-convex surface, so can obtain high light scattering effect.And, as shown in Embodiment 2, also can append etching and concave-convex surface is set distributes.
Then, use the Zinc oxide film of making by said method 5 to make photo-electric conversion device.That is, shown in Fig. 7 (c), order forms light-to-current inversion layer 11, back side transparency conducting layer 12, backplate layer 13 on above-mentioned Zinc oxide film 5, forms photo-electric conversion device.Light-to-current inversion layer 11, back side transparency conducting layer 12, backplate layer 13 can be selected from the various materials of recording and narrating execution mode 1.
As mentioned above, in the manufacture method of the transparency electrode of execution mode 3, after the Zinc oxide film 6 that will to provide the dopant of dopant to Zinc oxide film 3 is the aluminium film 2 of the material of aluminium atom as comprising, is provided with concave-convex surface by mocvd method is according to this sequential cascade, thermal diffusion aluminium atom in the Zinc oxide film 6.By this thermal diffusion, be formed on the Zinc oxide film 5 of the structure of the continuous concentration gradient that has the aluminium atom on the thickness direction.At this moment, conductance uprises near the light transmission insulated substrate 1 that aluminum concentration is high in Zinc oxide film 5.
In the manufacture method of the transparency electrode of execution mode 3, be confined to even after the formation of concave-convex surface, also can keep the high zone of conductance near the light transmission insulated substrate 1 by making the high zone of conductance like this, can realize high conductivity.
In addition, in Zinc oxide film 5, be that film is compared with in the past even doping zinc-oxide, the conductance height in the zone that electric current flows through.Thus, in the manufacture method of the transparency electrode of execution mode 3, can make the thickness attenuation of Zinc oxide film 5, can be reduced in the light absorption of the long wavelength side in the Zinc oxide film 5, can realize high photopermeability.
In addition, Zinc oxide film 5 has concave-convex surface, so can realize high light scattering effect.
In addition, in the manufacture method of the transparency electrode of execution mode 3, do not implement etching step, can form the Zinc oxide film 6 with concave-convex surface by mocvd method.Thus, the etching step that is used to form concave-convex surface can be omitted, number of steps can be reduced.In addition, the even doping zinc-oxide that forms with mocvd method by in the past is that film is compared, not only conductivity, transmitance excellence, and can cut down the MO material of the processing danger of using as dopant in order by thermal diffusion dopant to be offered Zinc oxide film 5, the use amount of special material gas, can seek the raising of fail safe.
Then, in the thermal diffusion of using in the manufacture method of the transparency electrode of execution mode 3 and the film processed at the Zinc oxide film concentration of dopant being changed continuously compares, can be implemented in the continuous dopant concentration gradient in the Zinc oxide film easilier.
Thereby, according to the manufacture method of the transparency electrode of execution mode 3, compare with the transparency electrode in the past of patent documentation 1 grade, can easier realization have the transparency electrode of high conductivity, high photopermeability and high light scattering effect.
And, also can the heating by based on the formation of the Zinc oxide film 6 of mocvd method the time make the aluminium of aluminium film 2 in Zinc oxide film 6, carry out thermal diffusion.In this case, heat treatment step also no longer needs, further the reduction step number.
In addition, manufacture method according to the photo-electric conversion device of execution mode 3, the Zinc oxide film 5 that possesses high conductivity and photopermeability that use is made by the manufacture method of the transparency electrode of execution mode 1 in transparency electrode is made photo-electric conversion device, so can realize the photo-electric conversion device of light-to-current inversion efficient excellence.
Embodiment
Followingly specify the present invention according to embodiment, but the present invention only otherwise surmounting its purport is not limited to following embodiment.
In embodiment 1, transparency electrode and photoelectric conversion units have been made by the manufacture method of the transparency electrode in execution mode 1, recorded and narrated and the manufacture method of photo-electric conversion device.At first, prepare the glass substrate of thickness 5mm as the light transmission insulated substrate, thereon by high frequency (RF:Radio Frequency, radio frequency) sputtering method with the aluminium film, be doped with 1 * 10
21Cm
-3The basic zinc-oxide film of aluminium atom according to this sequential cascade, form the tectosome shown in Fig. 1 (a).At this moment, the thickness of aluminium film is made as 50nm, and the thickness of basic zinc-oxide film is made as 1 μ m.Substrate temperature during based on the film processed of the film separately of high frequency sputtering method is made as 200 ℃.
Then, in the nitrogen atmosphere of the pressure 100Pa of the oxygen that has added this 1 volume %, under 500 ℃, 1 hour condition, carry out the heat treatment of aluminium film and basic zinc-oxide film, make aluminium in basic zinc-oxide film, carry out thermal diffusion.Thus, make aluminium film and basic zinc-oxide film be changed to the structure shown in Fig. 1 (b) and form the zinc-oxide film that possesses continuous gradient in the aluminum concentration of thickness direction.Then, the etching of carrying out the surface of zinc-oxide film by the hydrochloric acid that concentration is diluted as 0.5 volume % forms the structure shown in Fig. 1 (c), obtains having the zinc-oxide film of the embodiment 1 of the aluminum concentration gradient on concave-convex surface and the thickness direction.
Then, measure sheet resistance (Ω/) and the transmitance of the light of wavelength 1100nm (%) of the zinc-oxide film of embodiment 1.Its result shown in the table 1.
[table 1]
Then, the zinc-oxide film of embodiment 1 is used as transparency electrode, order forms semiconductor optoelectronic transform layer, back side transparency conducting layer, backplate layer thereon, makes photoelectric conversion units.At first, as the semiconductor optoelectronic transform layer, by the p-type crystallite Si film of the stacked thickness 20nm of plasma CVD method, the i type crystallite Si film of thickness 3 μ m, the n type crystallite Si film of thickness 30nm.Then, as back side transparency conducting layer, mixed 2 * 10 by sputtering method with thickness 100nm formation
21Cm
-3About the aluminium atom as the zinc-oxide film of impurity.Then, by with the silver of sputtering method deposit thickness 500nm as the backplate layer, make the photoelectric conversion units of the embodiment 1 with the structure shown in Fig. 1 (d).
Then, as the characteristic of the photoelectric conversion units of embodiment 1, estimate light-to-current inversion efficient (η), short-circuit current density (Jsc), open end voltage (V), fill factor, curve factor (FF).Table 2 illustrates its result.
[table 2]
Embodiment 2
In embodiment 2, make transparency electrode and photoelectric conversion units by the manufacture method of the transparency electrode in execution mode 2, recorded and narrated and the manufacture method of photo-electric conversion device.At first, prepare the glass substrate of thickness 5mm as the light transmission insulated substrate, thereon with the high frequency sputtering method according to the aluminium film, be doped with 1 * 10
21Cm
-3The sequential cascade of basic zinc-oxide film of aluminium atom, form the structure shown in Fig. 6 (a).At this moment, the thickness of aluminium film is made as 50nm, and the thickness of basic zinc-oxide film is made as 1 μ m.Substrate temperature during based on the film processed of the film separately of high frequency sputtering method is made as 200 ℃.
Then, the etching of carrying out the surface of basic zinc-oxide film by the hydrochloric acid that concentration is diluted as 0.5 volume % forms the zinc-oxide film of the concave-convex surface shown in (b) that possesses Fig. 6.Then, in the nitrogen atmosphere of the pressure 100Pa of the oxygen that has added 1 volume %, the heat treatment of carrying out the aluminium film and possessing the zinc-oxide film of concave-convex surface under 500 ℃, 1 hour condition makes the aluminium atom carry out thermal diffusion in possessing the zinc-oxide film of concave-convex surface.Thus, aluminium film and the zinc-oxide film that possesses concave-convex surface are changed into the structure shown in Fig. 6 (c), form the zinc-oxide film with aluminum concentration gradient on concave-convex surface and the thickness direction.Then, the etching of appending of carrying out the surface of this zinc-oxide film by the hydrochloric acid that concentration is diluted as 0.5 volume % forms the structure shown in Fig. 6 (d), obtains distributing and having the zinc-oxide film of the embodiment 2 of the aluminum concentration gradient on thickness direction having in shape of concave-convex surface.
Then, the zinc-oxide film of embodiment 2 is used as transparency electrode, make the photoelectric conversion units of the embodiment 2 with the structure shown in Fig. 6 (e) similarly to Example 1.And, as the characteristic of the photoelectric conversion units of embodiment 2, estimate light-to-current inversion efficient (η), short-circuit current density (Jsc), open end voltage (V), fill factor, curve factor (FF).Table 2 illustrates its result.
In embodiment 3, make transparency electrode and photoelectric conversion units by the manufacture method of the transparency electrode in execution mode 3, recorded and narrated and the manufacture method of photo-electric conversion device.At first, as the glass substrate of light transmission insulated substrate preparation thickness 5mm, by behind high frequency (RF:Radio Frequency, radio frequency) the sputtering method formation aluminium film, be doped with 1 * 10 by mocvd method is stacked thereon
21Cm
-3The zinc-oxide film with concave-convex surface of aluminium atom, form the structure shown in Fig. 7 (a).At this moment, the thickness of aluminium film is made as 50nm, and the average thickness with zinc-oxide film of concave-convex surface is made as 1.5 μ m.Substrate temperature during the film processed of aluminium film is made as 200 ℃, and the substrate temperature when having the film processed of zinc-oxide film of concave-convex surface also is made as 200 ℃.
Then, in the nitrogen atmosphere of the pressure 100Pa of the oxygen that has added 1 volume %, the heat treatment of carrying out the aluminium film and possessing the zinc-oxide film of concave-convex surface under 500 ℃, 1 hour condition makes aluminium carry out thermal diffusion in possessing the zinc-oxide film of concave-convex surface.Thus, the zinc-oxide film that makes the aluminium film and have a concave-convex surface is changed to the structure shown in Fig. 7 (b), and obtains having the zinc-oxide film of the embodiment 3 of concave-convex surface and the aluminum concentration gradient on thickness direction.
Then, as the zinc-oxide film of transparency electrode use embodiment 3, make the photoelectric conversion units of the embodiment 3 with the structure shown in Fig. 7 (c) similarly to Example 1.And, as the characteristic of the photoelectric conversion units of embodiment 3, estimate light-to-current inversion efficient (η), short-circuit current density (Jsc), open end voltage (V), fill factor, curve factor (FF).Table 2 illustrates its result.
Comparative example
In comparative example, the manufacture method of the transparency electrode by in the past and the manufacture method of photo-electric conversion device are made transparency electrode and photoelectric conversion units.In the manufacture method of the transparency electrode of comparative example, only evenly different with embodiment 1～embodiment 3 on the adulterated al this point in film when the film processed of zinc-oxide film.In addition, in the manufacture method of the photo-electric conversion device of comparative example, have only as transparency electrode and use the zinc-oxide film this point of comparative example 1 different with embodiment 1～embodiment 3.
At first, prepare the glass substrate of thickness 5mm as the light transmission insulated substrate, form with the thickness of 1 μ m by sputtering method thereon and be doped with 2 * 10
21Cm
-3About the aluminium atom as the zinc-oxide film of impurity (evenly doping zinc-oxide film).
Then, carry out the surface etching of even doping zinc-oxide film by the hydrochloric acid that concentration is diluted as 0.5 volume %, obtain having the even doping zinc-oxide film of concave-convex surface comparative example 1.
In addition, except being doped with 8 * 10 forming with the thickness of 1 μ m by sputtering method
21Cm
-3About zinc-oxide film (the evenly doping zinc-oxide film) this point of aluminium atom beyond, similarly obtain the even doping zinc-oxide film of comparative example 2 with comparative example 1.
Then, measure sheet resistance (Ω/) and the transmitance of the light of wavelength 1100nm (%) of the even doping zinc-oxide film of comparative example 1 and comparative example 2.Table 1 illustrates its result.
Then, use the even doping zinc-oxide film of comparative example 1 as transparency electrode, make the photoelectric conversion units of comparative example 1 similarly to Example 1.And the characteristic of 1 photoelectric conversion units is estimated light-to-current inversion efficient (η), short-circuit current density (Jsc), open end voltage (V), fill factor, curve factor (FF) as a comparative example.Table 2 illustrates its result.
As shown in table 1, the sheet resistance of the zinc-oxide film of embodiment 1 is 5 Ω/, and the transmitance of the light of wavelength 1100nm is 81%.In addition, as shown in table 1, the sheet resistance of the even doping zinc-oxide film of comparative example 1 is 8 Ω/, and transmitance is 83%.In addition, the sheet resistance of the even doping zinc-oxide film of comparative example 2 is 4 Ω/, and transmitance is 64%.
Hence one can see that, and the zinc-oxide film of embodiment 1 is compared with the even doping zinc-oxide film of the comparative example of making of manufacture method in the past 1, the light transmission rate that shows low sheet resistance and almost do not have to change.Hence one can see that, realizes high conductivity and high photopermeability in the zinc-oxide film of embodiment 1.And the even doping zinc-oxide film of comparative example 1 is compared with the zinc-oxide film of embodiment 1, low sheet resistance is shown, but transmitance reduces significantly.
In addition, as shown in table 2, the light-to-current inversion efficient (η) of the photoelectric conversion units of embodiment 1 is 8.0%, and short-circuit current density (Jsc) is 21.0mA/cm
2, open end voltage (Voc) is 0.50V, fill factor, curve factor (FF) is 0.75.In addition, as shown in table 2, the light-to-current inversion efficient (η) of the photoelectric conversion units of comparative example 1 is 6.7%, and short-circuit current density (Jsc) is 18.3mA/cm
2, open end voltage (Voc) is 0.51V, fill factor, curve factor (FF) is 0.72.
Hence one can see that, use as transparency electrode embodiment 1 zinc-oxide film embodiment 1 photoelectric conversion units and the comparative example 1 of the even doping zinc-oxide film that uses comparative example 1 as transparency electrode photoelectric conversion units relatively, because fill factor, curve factor (FF) increases, light-to-current inversion efficient (η) improves.
In addition, as shown in table 2, the light-to-current inversion efficient (η) of the photoelectric conversion units of embodiment 2 is 7.8%, and short-circuit current density (Jsc) is 21.7mA/cm
2, open end voltage (Voc) is 0.50V, fill factor, curve factor (FF) is 0.72.Hence one can see that, use as transparency electrode embodiment 2 zinc-oxide film embodiment 2 photoelectric conversion units and the comparative example 1 of the even doping zinc-oxide film that uses comparative example 1 as transparency electrode photoelectric conversion units relatively, because short-circuit current density (Jsc) increases, light-to-current inversion efficient (η) improves.
In addition, as shown in table 2, the light-to-current inversion efficient (η) of the photoelectric conversion units of embodiment 3 is 8.0%, and short-circuit current density (Jsc) is 21.5mA/cm
2, open end voltage (Voc) is 0.50V, fill factor, curve factor (FF) is 0.74.Hence one can see that, use as transparency electrode embodiment 3 zinc-oxide film embodiment 3 photoelectric conversion units and the comparative example 1 of the even doping zinc-oxide film that uses comparative example 1 as transparency electrode photoelectric conversion units relatively, because short-circuit current density (Jsc) increases, light-to-current inversion efficient (η) improves.
And, by form a plurality of photo-electric conversion devices of the formation of explanation in the above-described embodiment that have at the light transmission insulated substrate, electricity is connected or is connected in parallel adjacent photo-electric conversion device each other, can realize the photoelectric conversion units of light-to-current inversion efficient excellence.In this case, being electrically connected a side the transparency electrode of adjacent photo-electric conversion device and the opposing party's backplate layer gets final product.
Utilizability on the industry
As mentioned above, transparent electrode substrate of the present invention is useful in the photo-electric conversion device of realizing light-to-current inversion efficient excellence.
Claims (10)
1. transparent electrode substrate, it is the transparent electrode substrate that forms transparency electrode at the light transmission insulated substrate, this transparency electrode is by being that main component and the Zinc oxide film that comprises at least a above dopant element are formed with zinc oxide, and this transparent electrode substrate is characterised in that:
Described Zinc oxide film possesses concaveconvex shape on the surface, has from described light transmission insulated substrate side direction the face side concentration gradient of the described dopant element of minimizing continuously,
The concentration of the described dopant element in described Zinc oxide film is more than or equal to 1.5 atom % and smaller or equal to 3 atom % in the zone from described light transmission insulated substrate to thickness 50nm, is being more than or equal to 0.2 atom % and smaller or equal to 1 atom % from the surface to the zone of thickness 300nm.
2. transparent electrode substrate according to claim 1 is characterized in that:
Described concaveconvex shape is that variform concaveconvex shape mixes.
3. photo-electric conversion device is characterized in that possessing:
Claim 1 or 2 described transparent electrode substrates;
Be formed on the light-to-current inversion layer on the described transparency electrode of described transparent electrode substrate; And
Be formed on the backplate layer on the described light-to-current inversion layer.
4. the manufacture method of a transparent electrode substrate, it is the manufacture method that forms the transparent electrode substrate of transparency electrode at the light transmission insulated substrate, this transparency electrode is made up of the Zinc oxide film that with zinc oxide is main component, and this manufacture method is characterised in that, comprises:
The 1st step, on described light transmission insulated substrate, form comprise at least a above dopant element at described Zinc oxide film contain the dopant film;
The 2nd step contains on the dopant film described, forms the basic Zinc oxide film contain at least a above dopant element at described Zinc oxide film;
The 3rd step, by from the described dopant film that contains to described basic Zinc oxide film diffusion dopant, form described Zinc oxide film, this Zinc oxide film has the concentration of the described dopant element of face side from described light transmission insulated substrate side direction to be reduced continuously, is more than or equal to 1.5 atom % and smaller or equal to 3 atom % in the zone from described light transmission insulated substrate to thickness 50nm, from the surface is being more than or equal to 0.2 atom % and smaller or equal to the concentration gradient of the dopant element of 1 atom % to the zone of thickness 300nm;
The 4th step forms concaveconvex shape on the surface of the described Zinc oxide film that has spread described dopant element.
5. the manufacture method of transparent electrode substrate according to claim 4 is characterized in that:
In described the 3rd step, make described dopant element diffusion by thermal diffusion.
6. according to the manufacture method of claim 4 or 5 described transparent electrode substrates, it is characterized in that:
Between described the 2nd step and described the 3rd step, have the 5th step that forms concaveconvex shape on the surface of described basic Zinc oxide film,
In described the 4th step, form partly and the difform concaveconvex shape of concaveconvex shape that in described the 5th step, forms.
7. according to the manufacture method of any described transparent electrode substrate of claim 4～6, it is characterized in that:
The described dopant film that contains is the aluminium film of 0.1%～20% film thickness with film thickness of described basic Zinc oxide film.
8. according to the manufacture method of claim 4,5, any described transparent electrode substrate of 7, it is characterized in that:
Replacement forms described concaveconvex shape in described the 4th step, in described the 2nd step, be formed on the surface and have the Zinc oxide film of concaveconvex shape as described basic Zinc oxide film.
9. the manufacture method of a photo-electric conversion device, this photo-electric conversion device possesses transparency electrode, light-to-current inversion layer and backplate layer in order on the light transmission insulated substrate, and this manufacture method is characterised in that, comprises:
The manufacture method of any described transparent electrode substrate by claim 4～8 forms the step of described transparency electrode at described light transmission insulated substrate;
On described transparency electrode, form the step of described light-to-current inversion layer and described backplate layer in order.
10. light-to-current inversion module is characterized in that:
Be electrically connected more than at least 2 of the described photo-electric conversion device of claim 3.
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| JP2011-014481 | 2011-01-26 | ||
| JP2011014481 | 2011-01-26 | ||
| PCT/JP2011/073844 WO2012101876A1 (en) | 2011-01-26 | 2011-10-17 | Transparent electrode substrate, method for producing same, photoelectric conversion device, method for producing same, and photoelectric conversion module |
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| JP (1) | JP5602251B2 (en) |
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| CN103794665A (en) * | 2014-03-04 | 2014-05-14 | 南开大学 | High-reflection and high-texture-degree composite structure back electrode and manufacturing method thereof |
| CN105874893A (en) * | 2014-12-09 | 2016-08-17 | 英特尔公司 | Microelectronic substrates having copper alloy conductive route structures |
| CN106531835A (en) * | 2016-10-31 | 2017-03-22 | 新奥光伏能源有限公司 | Silicon heterojunction solar cell and solar cell module |
| CN111566065A (en) * | 2018-01-15 | 2020-08-21 | 索尼公司 | Functional element, method for manufacturing functional element, and electronic device |
| CN112736148A (en) * | 2020-12-03 | 2021-04-30 | 圣晖莱南京能源科技有限公司 | Flexible CIGS thin-film battery with high photoelectric conversion efficiency |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104037244B (en) * | 2014-06-17 | 2016-01-13 | 辽宁工业大学 | A kind of crystal silicon solar batteries passivating material Al 2o 3znO thin film doped and the preparation method of concentration gradient |
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- 2011-10-17 JP JP2012554621A patent/JP5602251B2/en not_active Expired - Fee Related
- 2011-10-17 WO PCT/JP2011/073844 patent/WO2012101876A1/en active Application Filing
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| JP2000277763A (en) * | 1999-03-23 | 2000-10-06 | Sanyo Electric Co Ltd | Solar cell and fabrication thereof |
| US20050145972A1 (en) * | 2002-01-28 | 2005-07-07 | Susumu Fukuda | Tandem thin-film photoelectric transducer and its manufacturing method |
| JP2007234996A (en) * | 2006-03-02 | 2007-09-13 | Kaneka Corp | Method of manufacturing thin-film solar cell, and thin-film solar cell |
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| CN111566065B (en) * | 2018-01-15 | 2022-12-02 | 索尼公司 | Functional element, method for manufacturing functional element, and electronic device |
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| JPWO2012101876A1 (en) | 2014-06-30 |
| JP5602251B2 (en) | 2014-10-08 |
| CN103339688B (en) | 2015-12-02 |
| WO2012101876A1 (en) | 2012-08-02 |
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