WO2019205230A1 - Dispositif hybride permettant de réaliser une production d'hydrogène solaire au moyen d'une dissociation d'eau et son procédé de fabrication - Google Patents

Dispositif hybride permettant de réaliser une production d'hydrogène solaire au moyen d'une dissociation d'eau et son procédé de fabrication Download PDF

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WO2019205230A1
WO2019205230A1 PCT/CN2018/089532 CN2018089532W WO2019205230A1 WO 2019205230 A1 WO2019205230 A1 WO 2019205230A1 CN 2018089532 W CN2018089532 W CN 2018089532W WO 2019205230 A1 WO2019205230 A1 WO 2019205230A1
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layer
sinx
type silicon
ingan
intermediate layer
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PCT/CN2018/089532
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English (en)
Chinese (zh)
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内策尔理查德
周国富
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华南师范大学
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Publication of WO2019205230A1 publication Critical patent/WO2019205230A1/fr

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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
    • H01L31/04—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 adapted as photovoltaic [PV] conversion devices
    • H01L31/06—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 adapted as photovoltaic [PV] conversion devices characterised by potential barriers
    • H01L31/068—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 adapted as photovoltaic [PV] conversion devices characterised by potential barriers the potential barriers being only of the PN homojunction type, e.g. bulk silicon PN homojunction solar cells or thin film polycrystalline silicon PN homojunction solar cells
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • C25B1/04—Hydrogen or oxygen by electrolysis of water
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/50—Processes
    • C25B1/55—Photoelectrolysis
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • 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
    • Y02E10/547—Monocrystalline silicon PV cells
    • 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
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

Definitions

  • the present invention relates to the field of renewable energy, and in particular to the field of solar water hydrolysis to hydrogen production, and more particularly to a mixing device for producing hydrogen by solar energy by hydrolysis and a method for manufacturing the same.
  • a promising candidate is solar energy.
  • One possibility for solar energy regeneration is to use photovoltaic cells to convert solar energy directly into electrical energy.
  • one problem in this case is the storage of energy to cope with different energy harvests (day, night, weather) and different demand supplies.
  • Another method is to use solar energy to decompose water into hydrogen and oxygen; the hydrogen thus produced can be stored and used if necessary by direct combustion or by combining with oxygen in a fuel cell to generate energy.
  • the advantage of this method is that hydrogen storage is easier than electrical storage; and the combination of hydrogen and oxygen produces water, so it is completely safe and environmentally friendly.
  • the two main ways of solar hydrogen production are based on (i) a wide band gap metal oxide or a III-V semiconductor used as a photoelectrode for direct photoelectrochemical hydrolysis; and (ii) a photovoltaic cell for assisting catalytic water electrolysis. .
  • the efficiency of electrodes currently used for direct photoelectrochemical hydrolysis is less than 2%; in addition, an applied voltage is required to drive the hydrolysis away reaction, thereby reducing the net energy balance and utility of the system.
  • ⁇ is the conversion efficiency of solar energy into hydrogen energy
  • j is the photocurrent density (mA/cm 2 );
  • P is the incident light power density (mW/cm 2 ).
  • the quantum dots of InN must be grown on the c-surface of the hexagonal wurtzite crystalline InGaN layer, which is also the preferred fastest growing surface since the c-surface has the highest surface energy in all other surfaces.
  • This is due to the imprinted epitaxial relationship achieved by direct growth of InGaN on the Si exposed on the surface of the crystal (111).
  • the most common commercial Si photovoltaic cells are n-type on and fabricated on a p-type Si substrate exposed (100) surface.
  • the present invention provides a mixing device that integrates a photoanode with a commercial silicon photovoltaic cell.
  • the present invention relates to a hybrid device for monolithically integrating a photoanode with a commercial silicon photovoltaic cell comprising a p-type silicon layer and an n-type silicon layer, wherein the p-type silicon layer and n
  • the silicon-type layers each have a main exposed surface corresponding to a (100) crystal plane of the silicon crystal
  • the photoanode includes a SiNx intermediate layer formed on the (100) crystal plane of the p-type silicon layer, and epitaxially grown on the SiNx intermediate layer a faceted InGaN layer, and InN quantum dots formed on the exposed surface of the InGaN layer.
  • the ratio of height/diameter of the InN quantum dots is less than 0.25
  • the InGaN layer is continuous on the silicon surface and has a thickness of between 10 and 100 nm.
  • the InGaN layer has a thickness of between 50 and 60 nm.
  • the InN quantum dots have a thickness of less than 5 nm and a diameter of between 20 and 30 nm.
  • the thickness of the InN quantum dots is between 3 and 4 nm.
  • the SiNx intermediate layer has a thickness of between 1 and 4 nm.
  • the SiNx intermediate layer has a thickness of 2 nm.
  • the invention relates to a method of manufacturing the mixing device of the first aspect, comprising the steps of:
  • a commercial silicon photovoltaic cell comprising a p-type silicon layer and an n-type silicon layer, wherein both the p-type silicon layer and the n-type silicon layer have a main exposed surface corresponding to the (100) crystal plane of the silicon crystal;
  • the p-type silicon layer of the silicon photovoltaic cell is thinned prior to performing step b).
  • the thinning is accomplished by mechanical milling.
  • step b) is performed by supplying a flow of reactive nitrogen.
  • the flow of reactive nitrogen is provided by a radio frequency reactive nitrogen plasma source or by insertion of ammonia in an epitaxial growth chamber.
  • the SiNx intermediate layer is grown under conditions of a nitrogen flow rate of 0.5-10 sccm, a radio frequency power of 100-500 W, a nitriding temperature of 600-900 ° C, and an active nitrogen supply time of between 1 and 20 minutes.
  • the SiNx intermediate layer is grown under conditions of a nitrogen flow rate of 1 sccm, a radio frequency power of 250-350 W, a nitriding temperature of 800 ° C, and an active nitrogen supply time of between 5 and 10 minutes.
  • the InGaN layer and the InN quantum dots are generated by molecular beam epitaxy or metal organic vapor phase epitaxy.
  • the key to the present invention is to fabricate an improved hybrid cell by reducing the conditions of the epitaxial relationship to facilitate the use of a preferred c-plane growth surface by introducing a SiNx intermediate layer.
  • the invention has the beneficial effects that the present invention can directly epitaxially grow c-plane InGaN on the (100) surface of Si by introducing a SiNx intermediate layer between the Si (100) surface and InGaN, thereby realizing photoanode and commercial silicon.
  • the mixing device is capable of decomposing water into hydrogen and oxygen when irradiated with visible light or ultraviolet light, and the solar hydrogen production efficiency is 20% or more.
  • Figure 1 shows the different stages of manufacture of the mixing device of the present invention.
  • the dimensions of the different portions are not to scale, and the thickness of the SiNx layer, the film thickness of InGaN, and the size of the quantum dots of InN present on the InGaN film are particularly enlarged for clarity.
  • the invention relates to a mixing device for monolithically integrating a photoanode with a commercial silicon photovoltaic cell.
  • the photoanode is an InGaN film formed on a photovoltaic cell on which an InN quantum dot is formed; specifically, the InGaN film is in surface contact with the positively doped silicon (p-Si) of the photovoltaic cell.
  • the InGaN film is continuous on the silicon surface and has a thickness of between 10 and 100 nm, preferably between 50 and 60 nm.
  • the morphology of the InGaN film can be flat and modulated in the form of nanosheets or nanowalls.
  • InN quantum dots are discontinuous structures generated on the surface of InGaN.
  • the ratio of height/diameter of these InN quantum dots is less than 0.25, the thickness is below 5 nm, preferably between 3 and 4 nm, and the diameter is between 20 and 30 nm; since usually InN quantum dots are not completely circular, so-called “ “Diameter” refers to the length of the long axis of the point.
  • the quantum dots must expose the crystal c-plane of the InN crystal; this condition is by growing quantum dots onto the InGaN film, and the InGaN film It is also exposed by the corresponding c-plane of its crystal structure.
  • the preferred thickness of the SiNx layer is 1-4 nm, which reduces, but does not eliminate, the conditions of the epitaxial relationship, allowing the InGaN film to grow along the preferred c-direction of the exposed c-plane surface while maintaining the in-plane crystal ordering, the c-plane surface and all other surfaces It has the highest surface energy and chemical activity. So far, the SiNx intermediate layer has only been used to improve the growth of the c-plane InGaN layer on the Si (111) surface having the correct epitaxial relationship.
  • these previously described intermediate layers are SiNx/Si (111) intermediate layers, and the SiNx/Si (100) intermediate layer of the present invention changes the Si (100) surface. Crystal properties to allow c-plane InGaN growth.
  • the invention relates to a method for manufacturing the above described mixing device.
  • an InGaN layer is first grown on the silicon photovoltaic cell thus treated, and finally an InN quantum dot is formed on the layer to fabricate a hybrid device. This process will be described with reference to FIG. 1.
  • FIG. 1 schematically shows a standard silicon photovoltaic cell 10.
  • the standard cell typically includes two silicon layers, one being a positively doped silicon (p-type Si) layer 11 and the other being a negatively doped silicon (n-type Si) layer 12.
  • both layers have a primary (exposed) surface corresponding to the (100) crystal plane of the silicon crystal.
  • it is necessary to grow an InGaN film in the c direction of the exposed c-plane surface, which is incompatible with the (100) surface of Si, and it is necessary to grow an InGaN film on the p-type side of the photovoltaic cell. .
  • the first step of the method of the present invention is to modify the crystal characteristics of the (100) surface of Si to reduce the conditions of the epitaxial relationship, so that the InGaN film grows in the preferred c direction, and the c direction is the preferred growth direction because in all other crystals.
  • the surface energy of the c-plane of InGaN in the surface is the highest.
  • the p-type (100) surface of the photovoltaic cell is exposed to a flow rate of reactive nitrogen prior to growth of the InGaN film, forming a SiNx layer 13 of B) in Figure 1, having a thickness of 1-4 nm, preferably 2 nm. .
  • This process is called surface nitridation.
  • the reactive nitrogen flow rate may preferably be by a radio frequency nitrogen plasma source or by introduction of ammonia for growing InGaN with a nitrogen flow rate of 0.5-10 sccm (standard cubic centimeters per Minutes), preferably about 1 sccm, RF power is 100-500 W, preferably 250-350 W.
  • the nitriding is carried out at a high temperature of 600 to 900 ° C, preferably about 800 ° C.
  • the time for supplying the active nitrogen is between 1 and 20 minutes, preferably between 5 and 10 minutes. The result is shown in B) of Fig. 1.
  • Thinning can be done by mechanical grinding.
  • the InGaN layer 14 (C in Fig. 1) is formed on the surface of the SiNx intermediate layer (C in Fig. 1)).
  • preferred epitaxial growth techniques are molecular beam epitaxy and metal organic vapor phase epitaxy.
  • InN quantum dots 15 are grown on the InGaN layer, thereby obtaining the mixing device 16 of the present invention.

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  • Chemical & Material Sciences (AREA)
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  • Organic Chemistry (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
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  • Condensed Matter Physics & Semiconductors (AREA)
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Abstract

La présente invention porte sur un dispositif hybride permettant d'intégrer de manière monolithique une photoanode ayant une cellule photovoltaïque au silicium commercial (10), et sur son procédé de fabrication, la cellule photovoltaïque au silicium commercial du dispositif comprenant une couche de silicium de type p (11) ayant une surface exposée principale qui correspond à une surface de cristal (100) d'un cristal de silicium, et une couche de silicium de type n (12), la photoanode de cette dernière comprenant une couche intermédiaire de SiNx (13) produite sur une surface de cristal (100) de la couche de silicium de type p, une couche d'InGaN de surface c (14) qui est développée de manière épitaxiale sur la couche intermédiaire, et des points quantiques d'InN (15) produits sur une surface exposée de la couche d'InGaN. Le dispositif hybride peut diviser l'eau en hydrogène et en oxygène lorsqu'il est éclairé par une lumière visible.
PCT/CN2018/089532 2018-04-23 2018-06-01 Dispositif hybride permettant de réaliser une production d'hydrogène solaire au moyen d'une dissociation d'eau et son procédé de fabrication WO2019205230A1 (fr)

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CN201810366607.X 2018-04-23
CN201810366607.XA CN108630777B (zh) 2018-04-23 2018-04-23 通过水解离进行太阳能制氢的混合装置及其制造方法

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CN111912886B (zh) * 2019-05-08 2022-01-11 华南师范大学 外延片及其制造方法以及电化学传感器

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101589474A (zh) * 2006-12-29 2009-11-25 桑迪奥德公司 活性区域带有具有能量阱的纳米结构的太阳能电池
CN102693902A (zh) * 2011-03-25 2012-09-26 索泰克公司 实现至少部分松弛的应变材料的岛状物的方法
CN104584240A (zh) * 2012-09-24 2015-04-29 Imec非营利协会 制造硅光伏电池的方法

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CN103531656B (zh) * 2013-09-05 2016-01-20 西南科技大学 太阳能电池单晶硅片绒面的制备方法
JP2015230985A (ja) * 2014-06-05 2015-12-21 三菱電機株式会社 太陽電池セルおよびその製造方法、太陽電池パネル

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101589474A (zh) * 2006-12-29 2009-11-25 桑迪奥德公司 活性区域带有具有能量阱的纳米结构的太阳能电池
CN102693902A (zh) * 2011-03-25 2012-09-26 索泰克公司 实现至少部分松弛的应变材料的岛状物的方法
CN104584240A (zh) * 2012-09-24 2015-04-29 Imec非营利协会 制造硅光伏电池的方法

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