CN111599878A - Monocrystalline cuprous oxide nano generator based on crystal face junction and manufacturing method thereof - Google Patents
Monocrystalline cuprous oxide nano generator based on crystal face junction and manufacturing method thereof Download PDFInfo
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- CN111599878A CN111599878A CN201910982833.5A CN201910982833A CN111599878A CN 111599878 A CN111599878 A CN 111599878A CN 201910982833 A CN201910982833 A CN 201910982833A CN 111599878 A CN111599878 A CN 111599878A
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- 239000013078 crystal Substances 0.000 title claims abstract description 61
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 title claims abstract description 53
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 229940112669 cuprous oxide Drugs 0.000 title claims abstract description 48
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 8
- 239000000758 substrate Substances 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims description 9
- 239000011521 glass Substances 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- 239000004020 conductor Substances 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 238000000861 blow drying Methods 0.000 claims description 3
- 238000004070 electrodeposition Methods 0.000 claims description 3
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 3
- 239000002985 plastic film Substances 0.000 claims description 3
- 229920006255 plastic film Polymers 0.000 claims description 3
- 239000010453 quartz Substances 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 238000005240 physical vapour deposition Methods 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims 1
- 239000003292 glue Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 7
- 239000004065 semiconductor Substances 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000010248 power generation Methods 0.000 abstract description 2
- 239000010949 copper Substances 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 229910000365 copper sulfate Inorganic materials 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- CYDQOEWLBCCFJZ-UHFFFAOYSA-N 4-(4-fluorophenyl)oxane-4-carboxylic acid Chemical compound C=1C=C(F)C=CC=1C1(C(=O)O)CCOCC1 CYDQOEWLBCCFJZ-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- DZGCGKFAPXFTNM-UHFFFAOYSA-N ethanol;hydron;chloride Chemical compound Cl.CCO DZGCGKFAPXFTNM-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000003760 hair shine Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000001540 sodium lactate Substances 0.000 description 1
- 229940005581 sodium lactate Drugs 0.000 description 1
- 235000011088 sodium lactate Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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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
- H01L31/0248—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 characterised by their semiconductor bodies
- H01L31/0256—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 characterised by their semiconductor bodies characterised by the material
- H01L31/0264—Inorganic materials
- H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
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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
- H01L31/022408—Electrodes for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/022425—Electrodes for devices characterised by at least one potential jump barrier or surface barrier for solar cells
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- H01L31/036—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 characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes
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Abstract
The invention relates to the technical field of wiener energy, in particular to a single crystal cuprous oxide nano generator based on a crystal face junction and a manufacturing method thereof, which can be applied to the fields of semiconductors, photovoltaic power generation and thermoelectric conversion and comprises a transparent substrate, a bottom electrode layer, a single crystal cuprous oxide layer and a top electrode layer, wherein the single crystal cuprous oxide layer is obtained by directional growth, the contact part of the single crystal cuprous oxide layer and the bottom electrode layer is a {111} crystal face, and the contact part of the single crystal cuprous oxide layer and the top electrode layer is a {100} crystal face. Due to the difference of crystal plane energy band structures, electrons and holes in the cuprous oxide single crystal are spontaneously separated and respectively flow to the {100} crystal plane and the {111} crystal plane, so that the bottom electrode and the top electrode respectively become a cathode and an anode of the battery. The invention can be used as a photoelectric conversion element and a thermoelectric conversion element, and has the advantages and characteristics of simple structure, low production cost, economy, environmental protection and the like.
Description
Technical Field
The invention relates to the technical field of wiener energy, in particular to a monocrystalline cuprous oxide nano generator based on crystal face junctions and a manufacturing method thereof, which can be applied to the fields of semiconductors, photovoltaic power generation and thermoelectric conversion.
Background
Solar cells are devices that directly convert light energy into electrical energy. Solar cells currently under development and in commercial use rely primarily on p-n junctions. Sunlight shines on the semiconductor p-n junction, forming new hole-electron pairs. Under the action of the p-n junction electric field, holes flow from the n area to the p area, electrons flow from the p area to the n area, and current is formed after the electrons are connected with an external circuit.
Cuprous oxide (Cu)2O) is a direct band gap semiconductor material, and has the characteristics of rich raw materials, simple preparation, low price, environmental friendliness and the like. The forbidden band width is related to the preparation condition of the film, generally 1.7-2.1 eV, and the theoretical photoelectric conversion efficiency of the solar cell can exceed 20%.
Cu of the present disclosure2O solar cells, which typically require the formation of heterojunctions to assist carrier separation, such as p-Cu2O/n-ZnO (zinc oxide) not only has complex structure, high requirement on manufacturing process and higher cost, but also has high interface defect density of the heterojunction battery, thereby causing larger interface composite current and having low actual generating efficiency.
Although Cu has been reported to be disclosed2O homojunction solar cell, p-Cu2O/n-Cu2O (CN 102376783A), but at present, there is still a lack of theoretical basis and detection analysis, and the conversion efficiency is still low.
Disclosure of Invention
The first purpose of the invention is to develop a carrier separation structure different from the traditional p-n junction, and provide a brand-new 'crystal face junction' carrier separation structure.
The second purpose of the invention is to provide a preparation method of a monocrystalline cuprous oxide nanometer generator based on crystal face junctions.
In order to realize the first purpose, the technical scheme of the invention is as follows: a monocrystal cuprous oxide nanometer generator based on crystal face junction has the following battery structure: and growing a bottom electrode layer, a single crystal cuprous oxide layer and a top electrode layer in sequence by taking the transparent substrate as a substrate.
A monocrystalline cuprous oxide nanometer generator based on crystal face junctions comprises a transparent substrate layer, wherein a bottom electrode layer is arranged on the transparent substrate layer, a monocrystalline cuprous oxide layer is arranged on the bottom electrode layer, and a top electrode layer is arranged on the monocrystalline cuprous oxide layer.
In the technical scheme, the transparent substrate layer is made of glass, quartz or plastic film materials; the bottom electrode layer is a transparent conductive layer and is an ITO layer or an FTO layer; the top electrode layer is made of a conductor material and comprises a metal or conductive organic matter, an inorganic matter or an oxide film; the single crystal cuprous oxide layer is obtained by oriented growth, and the contact part with the bottom electrode layer is a {111} crystal plane (A), and the contact part with the top electrode layer is a {100} crystal plane (B).
In order to realize the purpose of the second invention, the adopted technical scheme is as follows: a manufacturing method of a crystal face junction-based single crystal cuprous oxide nanometer generator comprises the following steps: cleaning of the transparent substrate and preparation of the bottom electrode layer: cleaning and blow-drying the transparent substrate, and growing a bottom electrode layer by using a magnetron sputtering method; preparing single crystal cuprous oxide: growing a cuprous oxide single crystal film by using an electrodeposition method; preparing a top electrode layer: and covering a conductor layer on the crystal face of the cuprous oxide {100} by adopting a physical vapor deposition method.
According to the invention, Cu2O grown by electrodeposition is a {111} crystal plane on one side of the bottom electrode layer and a {100} crystal plane on one side of the top electrode layer, and natural energy difference is formed due to the fact that energy band structures between the two crystal planes are inconsistent, so that electrons generated in Cu2O spontaneously flow to the {111} crystal plane, and holes flow to the {100} crystal plane, and thus, the separation of carriers is achieved. When the external circuit is connected, the bottom electrode layer is used as a negative electrode (anode), the top electrode layer is used as a positive electrode (cathode), and electric energy is transmitted outwards.
The invention has the beneficial effects that: the invention adopts the dissimilarity among different crystal faces to realize the automatic separation of current carriers, thereby outputting electric energy outwards. The invention has novel principle, simple structure and low cost.
Drawings
Fig. 1 is a schematic structural view of the present invention.
In the figure, 1-the transparent substrate layer, 2-the bottom electrode layer, 3-the monocrystalline cuprous oxide layer, 4-the top electrode layer.
Detailed Description
For the purpose of enhancing the understanding of the present invention, the present invention will be described in further detail with reference to the accompanying drawings and examples, which are provided for the purpose of illustration only and are not intended to limit the scope of the present invention.
Example (b): as shown in fig. 1, a single crystal cuprous oxide nanometer generator based on crystal face junction comprises a transparent substrate layer 1, a bottom electrode layer 2 is arranged on the transparent substrate layer 1, a single crystal cuprous oxide layer 3 is arranged on the bottom electrode layer 2, a top electrode layer 4 is arranged on the single crystal cuprous oxide layer 3, the upper surface of the single crystal cuprous oxide layer 3 is in a zigzag shape, and the top electrode layer 4 is arranged on the surface of a nanometer cube on the upper surface of the single crystal cuprous oxide.
In the present embodiment, the transparent substrate layer 1 is made of a material of glass, quartz or plastic film; the bottom electrode layer 2 is a transparent conducting layer which is an ITO layer or an FTO layer; the top electrode layer 4 is made of a conductor material including a metal or conductive organic, inorganic or oxide film; the single-crystal cuprous oxide layer 3 is obtained by directional growth, and the contact portion with the bottom electrode layer 2 is the {111} crystal plane (A), and the contact portion with the top electrode layer 4 is the {100} crystal plane (B).
In the above examples, the transparent substrate layer was made of Corning glass and had a thickness of 1.1 mm. Sequentially adopting cleaning powder, deionized water, isopropanol, ethanol hydrochloric acid and acetone to carry out ultrasonic cleaning on the substrate for 10min, removing organic and inorganic impurities on the surface, and finally blowing the substrate by using nitrogen for standby. And growing an FTO transparent conductive layer on the transparent substrate by adopting a radio frequency magnetron sputtering method, wherein the thickness of the FTO transparent conductive layer is 300 nm. Dissolving 1.2g of anhydrous copper sulfate in 40mL of deionized water, and magnetically stirring until the anhydrous copper sulfate is fully dissolved to obtain a clear and transparent light blue solution. 10mL of sodium lactate was added and stirred magnetically to give a clear and transparent dark blue solution. A1M NaOH solution was gradually added dropwise until the pH was 12. And (3) taking the conductive glass as a negative electrode and the metal platinum electrode as a positive electrode, applying a constant voltage of 2V to deposit cuprous oxide on the surface of the conductive glass, and cutting off the power supply until the thickness of the film grows to 3000 nm. And taking out the cuprous oxide single crystal electrode, repeatedly washing with deionized water, and blow-drying with nitrogen. And (4) shielding the exposed FTO area by using a mask plate, and evaporating a layer of copper electrode on the {100} surface of the cuprous oxide single crystal, wherein the thickness of the copper electrode is 100 nm.
The working principle of the embodiment is as follows: and respectively connecting the conductive glass end and the aluminum electrode of the obtained nano generator with the anode and the cathode of a desk multimeter. In the dark (20 ℃ C.), an open-circuit voltage of 34.5mV and a short-circuit current of 14.3. mu.A/cm were measured2. Under standard lighting conditions (AM1.5, 100 mW/cm)2At 20 ℃ C, the open-circuit voltage was 0.887V and the short-circuit current density was 3.38mA/cm2The fill factor was 74% and the photoelectric conversion efficiency was 2.2%.
Furthermore, the nanogenerator can spontaneously convert thermal energy into electrical energy. Under the dark state of 200 ℃, the open circuit voltage of the single crystal cuprous oxide nano generator can reach 1.41V, and the short circuit current density reaches 8.03mA/cm2。
The foregoing illustrates and describes the principles, general features, and advantages of the present invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (8)
1. The monocrystalline cuprous oxide nano generator based on crystal face junctions is characterized by comprising a transparent substrate layer, wherein a bottom electrode layer is arranged on the transparent substrate layer, a monocrystalline cuprous oxide layer is arranged on the bottom electrode layer, a top electrode layer is arranged on the monocrystalline cuprous oxide layer, the upper surface of the monocrystalline cuprous oxide layer is a nano cube completely exposing {100} crystal faces, and the top electrode layer is arranged on the nano cube on the upper surface of the monocrystalline cuprous oxide layer.
2. The monocrystalline cuprous oxide nanogenerator based on crystal face junction of claim 1, wherein the transparent substrate layer is made of glass, quartz or plastic film material.
3. The monocrystalline cuprous oxide nanogenerator based on crystal plane junctions of claim 1, wherein said bottom electrode layer is a transparent conductive layer.
4. The monocrystalline cuprous oxide nanogenerator based on crystal plane junctions of claim 3, wherein the transparent conductive layer is an ITO layer or an FTO layer.
5. The monocrystalline cuprous oxide nanogenerator based on crystalline surface junction of claim 1, wherein said top electrode layer is made of conductive material.
6. The monocrystalline cuprous oxide nanogenerator based on crystalline surface junction of claim 5, wherein the conductor material is a metal or conductive organic, inorganic or oxide film.
7. The single-crystal cuprous oxide nanometer generator based on crystal plane junction as claimed in any of claims 1-6, wherein said single-crystal cuprous oxide layer is obtained by directional growth, and its contact part with bottom electrode layer is {111} crystal plane (A) and its contact part with top electrode layer is {100} crystal plane (B).
8. The manufacturing method of the crystal face junction-based single crystal cuprous oxide nanometer generator as claimed in claim 7, characterized by comprising the following steps: the method comprises the following steps: cleaning of the transparent substrate and preparation of the bottom electrode layer: cleaning and blow-drying the transparent substrate, and growing a bottom electrode layer by using a magnetron sputtering method; step two: preparing single crystal cuprous oxide: growing a cuprous oxide single crystal film by using an electrodeposition method; step three: preparing a top electrode layer: and covering a conductor layer on the crystal face of the cuprous oxide {100} by adopting a physical vapor deposition method, a glue homogenizing method and a blade coating method.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103117322A (en) * | 2013-02-01 | 2013-05-22 | 中国科学技术大学 | Photovoltaic device based on polar/nonpolar heterojunctions and production method thereof |
| JP2015079881A (en) * | 2013-10-17 | 2015-04-23 | 独立行政法人産業技術総合研究所 | Structure of semiconductor device having p-type semiconductor layer composed of cuprous oxide film, and manufacturing method thereof |
| CN108773852A (en) * | 2018-05-28 | 2018-11-09 | 济南大学 | A kind of preparation method of crystal face hetero-junctions rutile crystal type titanium dioxide optical catalyst and production hydrogen application |
| CN109056057A (en) * | 2018-07-19 | 2018-12-21 | 复旦大学 | A kind of preparation method of large size single crystal gallium oxide nanometer sheet |
-
2019
- 2019-10-16 CN CN201910982833.5A patent/CN111599878B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103117322A (en) * | 2013-02-01 | 2013-05-22 | 中国科学技术大学 | Photovoltaic device based on polar/nonpolar heterojunctions and production method thereof |
| JP2015079881A (en) * | 2013-10-17 | 2015-04-23 | 独立行政法人産業技術総合研究所 | Structure of semiconductor device having p-type semiconductor layer composed of cuprous oxide film, and manufacturing method thereof |
| CN108773852A (en) * | 2018-05-28 | 2018-11-09 | 济南大学 | A kind of preparation method of crystal face hetero-junctions rutile crystal type titanium dioxide optical catalyst and production hydrogen application |
| CN109056057A (en) * | 2018-07-19 | 2018-12-21 | 复旦大学 | A kind of preparation method of large size single crystal gallium oxide nanometer sheet |
Non-Patent Citations (1)
| Title |
|---|
| FAIZ ARITH 等: "low cost electro-deposition of cuprous oxide p-n homo-junction solar cell", 《ADVANCED MATERIALS RESEARCH》 * |
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