TW201543698A - Method for producing thin-film solar cell, and thin-film solar cell - Google Patents
Method for producing thin-film solar cell, and thin-film solar cell Download PDFInfo
- Publication number
- TW201543698A TW201543698A TW104108480A TW104108480A TW201543698A TW 201543698 A TW201543698 A TW 201543698A TW 104108480 A TW104108480 A TW 104108480A TW 104108480 A TW104108480 A TW 104108480A TW 201543698 A TW201543698 A TW 201543698A
- Authority
- TW
- Taiwan
- Prior art keywords
- graphene
- layer
- solar cell
- substrate
- thin film
- Prior art date
Links
- 239000010409 thin film Substances 0.000 title claims abstract description 57
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 146
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 135
- 239000000758 substrate Substances 0.000 claims abstract description 72
- 239000004065 semiconductor Substances 0.000 claims abstract description 42
- 239000010408 film Substances 0.000 claims description 39
- 238000000034 method Methods 0.000 claims description 19
- 229910002804 graphite Inorganic materials 0.000 claims description 8
- 239000010439 graphite Substances 0.000 claims description 8
- 238000005229 chemical vapour deposition Methods 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 239000011888 foil Substances 0.000 claims description 4
- 229910052582 BN Inorganic materials 0.000 claims description 3
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 3
- 150000001336 alkenes Chemical class 0.000 claims description 3
- 150000004770 chalcogenides Chemical class 0.000 claims description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 claims description 2
- 238000013461 design Methods 0.000 abstract description 5
- 239000010410 layer Substances 0.000 description 156
- 239000011521 glass Substances 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 229910052732 germanium Inorganic materials 0.000 description 8
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 8
- 239000002070 nanowire Substances 0.000 description 8
- 238000005755 formation reaction Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 239000002356 single layer Substances 0.000 description 6
- 239000006059 cover glass Substances 0.000 description 5
- 239000003822 epoxy resin Substances 0.000 description 5
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 5
- 229920000647 polyepoxide Polymers 0.000 description 5
- 238000012546 transfer Methods 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 229910021417 amorphous silicon Inorganic materials 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- -1 polyethylene Polymers 0.000 description 4
- 239000004926 polymethyl methacrylate Substances 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 229910052715 tantalum Inorganic materials 0.000 description 4
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 4
- 238000002230 thermal chemical vapour deposition Methods 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000011889 copper foil Substances 0.000 description 3
- 239000004205 dimethyl polysiloxane Substances 0.000 description 3
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000005304 joining Methods 0.000 description 2
- CXQXSVUQTKDNFP-UHFFFAOYSA-N octamethyltrisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C CXQXSVUQTKDNFP-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000004987 plasma desorption mass spectroscopy Methods 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- SXPGQGNWEWPWQZ-UHFFFAOYSA-N 4-(triethoxymethyl)dodecan-1-amine Chemical compound NCCCC(C(OCC)(OCC)OCC)CCCCCCCC SXPGQGNWEWPWQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910004613 CdTe Inorganic materials 0.000 description 1
- 229910005543 GaSe Inorganic materials 0.000 description 1
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000003486 chemical etching Methods 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 239000005001 laminate film Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920002098 polyfluorene Polymers 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000002096 quantum dot Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- HUAUNKAZQWMVFY-UHFFFAOYSA-M sodium;oxocalcium;hydroxide Chemical compound [OH-].[Na+].[Ca]=O HUAUNKAZQWMVFY-UHFFFAOYSA-M 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 239000006200 vaporizer Substances 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/04—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of carbon-silicon compounds, carbon or silicon
-
- 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
-
- 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
- H01L31/042—PV modules or arrays of single PV cells
- H01L31/0445—PV modules or arrays of single PV cells including thin film solar cells, e.g. single thin film a-Si, CIS or CdTe solar cells
- H01L31/046—PV modules composed of a plurality of thin film solar cells deposited on the same substrate
-
- 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
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/1884—Manufacture of transparent electrodes, e.g. TCO, ITO
-
- 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
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/1892—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof methods involving the use of temporary, removable substrates
-
- 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
Abstract
Description
本發明是有關於一種薄膜太陽電池之製造方法及薄膜太陽電池。 The present invention relates to a method of manufacturing a thin film solar cell and a thin film solar cell.
矽系薄膜太陽電池可藉由將各電池連續成膜而輕易地多接合化(專利文獻1)，然而，在與其他薄膜太陽電池之接合時必須有剝下技術。雖然可使用氧化膜作為剝離層來剝下薄膜矽太陽電池(專利文獻2)，然而，剝離製程中所必須的穿孔等構造本身煩雜，且剝離後必須除去剝離層而形成新的電極層。 The bismuth-based thin film solar cell can be easily multi-bonded by continuously forming a film (Patent Document 1). However, it is necessary to have a peeling technique when joining with other thin film solar cells. Although a thin film tantalum solar cell can be peeled off using an oxide film as a peeling layer (Patent Document 2), the structure such as a perforation necessary for the peeling process itself is complicated, and after peeling, it is necessary to remove the peeling layer to form a new electrode layer.
化合物系薄膜太陽電池可自底層金屬電極層與吸收層之界面剝下(非專利文獻1)，然而，在多接合化時必須重新堆積電極層。 The compound-based thin film solar cell can be peeled off from the interface between the underlying metal electrode layer and the absorption layer (Non-Patent Document 1). However, it is necessary to re-deposit the electrode layer at the time of multi-bonding.
若使用氧化石墨烯來剝下，則剝下後必須除去絕緣性之氧化石墨烯層而形成新的電極層(非專利文獻2)。 When the graphene is used for the peeling, the insulating graphene oxide layer must be removed after the stripping to form a new electrode layer (Non-Patent Document 2).
[專利文獻1]日本專利公開公報特公昭63-48197號公報 [Patent Document 1] Japanese Patent Laid-Open Publication No. SHO 63-48197
[專利文獻2]特開平7-226528號公報 [Patent Document 2] Japanese Patent Publication No. 7-226528
[非專利文獻1]Jpn.J.Appl.Phys.49(2010)04DP06 [Non-Patent Document 1] Jpn. J. Appl. Phys. 49 (2010) 04DP06
[非專利文獻2]第60次應用物理學會春季學術演說會29p-PA9-17 [Non-Patent Document 2] The 60th Society of Applied Physics Spring Academic Lecture 29p-PA9-17
本發明乃藉由自基板表面直接或間接剝下業已形成於基板上的複數層石墨烯層且實質上不會損害其特性，製作無需支持基板之自立型薄膜太陽電池等半導體元件，藉此，可提升高效率之多接合薄膜太陽電池等之設計自由度。 According to the present invention, a plurality of layers of graphene layers which have been formed on a substrate are directly or indirectly peeled off from the surface of the substrate without substantially impairing the characteristics thereof, thereby producing a semiconductor element such as a self-supporting thin film solar cell which does not require a supporting substrate. It can improve the design freedom of high-efficiency multi-junction thin film solar cells.
為了解決上述課題，本發明乃提供以下發明。 In order to solve the above problems, the present invention provides the following invention.
(1)一種薄膜太陽電池之製造方法，其係製造包含有含石墨烯層之第1電極、半導體薄膜及第2電極之薄膜太陽電池，且其特徵在於藉由下述方法來製造含有半導體薄膜之自立型薄膜太陽電池，即：於基板上形成複數層石墨烯層；於該石墨烯層上形成半導體薄膜及第2電極；接著，自基板直接或間接剝下石墨烯層，並將所剝下的石墨烯層作成第1電極。 (1) A method of producing a thin film solar cell, which comprises producing a thin film solar cell including a first electrode including a graphene layer, a semiconductor thin film, and a second electrode, and characterized in that a semiconductor thin film is produced by the following method a self-supporting thin film solar cell, that is, forming a plurality of layers of graphene on a substrate; forming a semiconductor film and a second electrode on the graphene layer; and then directly or indirectly stripping the graphene layer from the substrate, and stripping The lower graphene layer was formed as the first electrode.
(2)如上述(1)之薄膜太陽電池之製造方法，其a)自該基板、b)於該石墨烯層間或c)自與該基板鄰接或設置於該石墨烯層間之剝離用犧牲層，剝下石墨烯層。 (2) The method for producing a thin film solar cell according to the above (1), wherein a) from the substrate, b) between the graphene layers, or c) a sacrificial layer for peeling from the substrate or between the graphene layers , peel off the graphene layer.
(3)如上述(1)或(2)之薄膜太陽電池之製造方法，其中複數層石墨烯層是將業已藉由化學蒸鍍法形成於觸媒金屬箔或板上之石墨烯層轉印於基板上而形成。 (3) The method for producing a thin film solar cell according to the above (1) or (2), wherein the plurality of graphene layers are transferred by a graphene layer which has been formed on a catalytic metal foil or a plate by a chemical vapor deposition method. Formed on the substrate.
(4)如上述(2)之薄膜太陽電池之製造方法，其中剝離用犧牲層為硫屬化物系層狀物質、氧化石墨烯或六方晶氮化硼。 (4) The method for producing a thin film solar cell according to the above (2), wherein the sacrificial layer for peeling is a chalcogenide layered material, graphene oxide or hexagonal boron nitride.
(5)一種薄膜太陽電池，其包含有：第1電極，其含有已自基板直接或間接剝下之石墨烯層；半導體薄膜；及第2電極。 (5) A thin film solar cell comprising: a first electrode comprising a graphene layer which has been directly or indirectly peeled off from a substrate; a semiconductor film; and a second electrode.
(6)一種薄膜太陽電池，其藉由如上述(1)或(2)之製造方法所製得。 (6) A thin film solar cell produced by the production method of the above (1) or (2).
若藉由本發明，則可提供以下方法，即：可將屬於原子級、平坦之層狀化合物且作成電極亦具有充分導電性之多層石墨烯，於石墨烯層間或石墨烯層-基板間等輕易地剝離，再者，將石墨烯直接活用作為電極，藉此，製作自立型薄膜太陽電池。 According to the present invention, it is possible to provide a multilayer graphene which is an atomic-grade, flat layered compound and which is also excellent in electrical conductivity, and is easily bridged between graphene layers or graphene layers-substrates. The ground was peeled off, and further, graphene was directly used as an electrode, whereby a self-standing thin film solar cell was produced.
舉例言之，為了自由地設計高效率之多接合太陽電池，適當的是剝下太陽電池而與其他電池構造或基板接合。利用多接合之高效率化必須考量各電池之分光感度特性與輸出特性之平衡而設計，然而，由於製程上之制約， 因此，被限制面多。故，可自基板剝離薄膜太陽電池並自立會對多接合太陽電池之設計帶來廣大之自由度。於本發明中，舉例言之，藉由使用多層石墨烯膜作為透明電極層，剝離後可直接作成自立型薄膜太陽電池來動作。由於剝下後的石墨烯層會構成電極，因此，亦可輕易地與例如藉由其他機構所製作的太陽電池連接，且可提升高效率之多接合薄膜太陽電池等之設計自由度。 For example, in order to freely design a highly efficient multi-junction solar cell, it is appropriate to strip the solar cell to bond with other cell structures or substrates. The efficiency of multi-joining must be designed in consideration of the balance between the spectral sensitivity characteristics and the output characteristics of each battery. However, due to process constraints, Therefore, there are many restrictions. Therefore, the peeling of the thin film solar cell from the substrate and self-standing can bring a great degree of freedom to the design of the multi-joint solar cell. In the present invention, by way of example, a multilayer graphene film is used as the transparent electrode layer, and after peeling, it can be directly operated as a self-standing thin film solar cell. Since the graphene layer after peeling constitutes an electrode, it can be easily connected to, for example, a solar cell fabricated by another mechanism, and the design freedom of a highly efficient bonded thin film solar cell or the like can be improved.
1‧‧‧基板 1‧‧‧Substrate
2‧‧‧石墨烯層 2‧‧‧graphene layer
3‧‧‧剝離用犧牲層 3‧‧‧Sacrificial layer for stripping
4‧‧‧p-a-SiC層 4‧‧‧p-a-SiC layer
5‧‧‧p-緩衝層 5‧‧‧p-buffer layer
6‧‧‧i-a-Si層 6‧‧‧i-a-Si layer
7‧‧‧n-mc-SiO層 7‧‧‧n-mc-SiO layer
8‧‧‧Ag層 8‧‧‧Ag layer
9‧‧‧Al層 9‧‧‧Al layer
10‧‧‧樹脂 10‧‧‧Resin
11‧‧‧蓋玻璃 11‧‧‧ Cover glass
12‧‧‧半導體元件 12‧‧‧Semiconductor components
圖1(a)~(c)乃使用多層石墨烯膜之薄膜太陽電池之剝下示意圖。 1(a) to (c) are schematic views showing the stripping of a thin film solar cell using a multilayer graphene film.
圖2(a)~(d)乃顯示剝下石墨烯層之態樣之示意圖。 2(a) to (d) are schematic views showing the state in which the graphene layer is peeled off.
圖3顯示所剝下的石墨烯表面之掃描型電子顯微鏡(SEM)相片(500倍)之一例。 Fig. 3 shows an example of a scanning electron microscope (SEM) photograph (500 times) of the surface of the stripped graphite.
圖4(a)~(c)顯示實施例1中所剝下的薄膜矽太陽電池之構造。 4(a) to (c) show the construction of the film tantalum solar cell stripped in Example 1.
圖5(a)、(b)顯示實施例1中剝下前後之太陽電池特性。 5(a) and 5(b) show solar cell characteristics before and after peeling in Example 1.
圖6乃實施例2中所塗佈的氧化石墨烯之SEM相片(150倍)。 Figure 6 is a SEM photograph (150 times) of graphene oxide coated in Example 2.
圖7乃實施例3中矽奈米線陣列之SEM相片(2萬倍)。 Figure 7 is a SEM photograph (20,000 times) of the nanowire array of Example 3.
本發明之薄膜太陽電池之製造方法乃包含有含石墨烯層之第1電極、半導體薄膜及第2電極之薄膜太陽電池之製造，其特徵在於藉由下述來製造含有半導體薄膜之 自立型薄膜太陽電池，即：於基板上形成複數層石墨烯層；於該石墨烯層上形成半導體薄膜及第2電極；接著，自基板直接或間接剝下石墨烯層，並將所剝下的石墨烯層作成第1電極。「複數層石墨烯層」乃指積層之石墨烯層。 The method for producing a thin film solar cell of the present invention includes the production of a thin film solar cell including a first electrode including a graphene layer, a semiconductor thin film, and a second electrode, and is characterized in that a semiconductor thin film is produced by the following a self-supporting thin film solar cell, that is, forming a plurality of layers of graphene on a substrate; forming a semiconductor film and a second electrode on the graphene layer; and then directly or indirectly stripping the graphene layer from the substrate and peeling off The graphene layer is formed as a first electrode. The "multilayer graphene layer" refers to a layered graphene layer.
石墨烯亦包括維持由6員環碳片所構成之石墨烯骨架而附加各種官能基之石墨烯衍生物，舉例言之，可列舉如：業已藉由含氧官能基修飾之氧化石墨烯(可藉由還原輕易地形成導電膜)。再者，為了增加載體濃度並提升導電性，石墨烯可含有摻雜物。 Graphene also includes a graphene derivative which maintains a graphene skeleton composed of a 6-membered ring carbon sheet and various functional groups. For example, graphene oxide which has been modified by an oxygen-containing functional group may be mentioned. The conductive film is easily formed by reduction). Further, in order to increase the concentration of the carrier and improve the conductivity, the graphene may contain a dopant.
自基板直接或間接剝下石墨烯層時，適當的是a)自基板、b)於石墨烯層間或c)自與基板鄰接或設置於石墨烯層間之剝離用犧牲層，剝下石墨烯層。剝離用犧牲層乃用以順利進行石墨烯層之剝下而設置，若於剝離用犧牲層與石墨烯層間剝下，則剝離用犧牲層會殘留於基板側而並非是含有石墨烯層之半導體元件側。a)乃相當於自基板直接剝下石墨烯層之情形，另一方面，b)或c)乃相當於自基板間接剝下之情形。 When the graphene layer is directly or indirectly peeled off from the substrate, it is appropriate to a) peel off the graphene layer from the substrate, b) between the graphene layers, or c) from the sacrificial layer for peeling between the substrate and the graphene layer. . The release sacrificial layer is provided for smooth stripping of the graphene layer. If the sacrificial layer is peeled off between the sacrificial layer and the graphene layer, the sacrificial layer for peeling remains on the substrate side instead of the semiconductor containing the graphene layer. Component side. a) is equivalent to the case where the graphene layer is directly peeled off from the substrate, and on the other hand, b) or c) corresponds to the case of indirect peeling from the substrate.
圖1乃b)於石墨烯層間自基板間接剝下石墨烯層之使用多層石墨烯膜之薄膜太陽電池之剝下示意圖。於圖1中，(a)表示於基板1上積層石墨烯膜而形成複數層石墨烯層2，(b)表示在進一步形成含有半導體膜之半導體元件(薄膜太陽電池之製作)後，於石墨烯層間剝下，其結果，(c)表示製作將石墨烯層作成電極之自立型薄膜太陽電池作為半導體元件12。 1 is a schematic view showing the stripping of a thin film solar cell using a multilayer graphene film in which a graphene layer is indirectly peeled off from a substrate between graphene layers. In FIG. 1, (a) shows that a graphene film is laminated on a substrate 1 to form a plurality of graphene layers 2, and (b) shows that after further forming a semiconductor element including a semiconductor film (manufacture of a thin film solar cell), graphite is formed. The olefin layer was peeled off, and as a result, (c) shows that a self-standing thin film solar cell in which a graphene layer was formed as an electrode was produced as the semiconductor element 12.
於圖2中，(a)~(c)乃顯示藉由上述a)、b)及c)之態樣自基板直接或間接剝下石墨烯層之態樣之示意圖(未圖示積層於石墨烯層上之層體)。於圖2中，1表示基板，2表示石墨烯層，3表示剝離用犧牲層。於(a)中，乃於基板1上積層第1~3之3層石墨烯層2，在進一步形成含有半導體膜之半導體元件(太陽電池)後(未圖示)，於基板1與第1石墨烯層2間進行剝下，且3層石墨烯層2會保持於半導體元件側(圖2(d))。在此，石墨烯層2乃自基板直接剝下。 In Fig. 2, (a) to (c) are schematic views showing a state in which the graphene layer is directly or indirectly peeled off from the substrate by the above-mentioned a), b) and c) (the layer is not shown in the graphite layer). a layer on the olefin layer). In Fig. 2, 1 denotes a substrate, 2 denotes a graphene layer, and 3 denotes a sacrificial layer for peeling. In (a), the first to third three-layer graphene layer 2 is laminated on the substrate 1, and after the semiconductor element (solar cell) including the semiconductor film is further formed (not shown), the substrate 1 and the first layer are formed. The graphene layer 2 is peeled off, and the three layers of the graphene layer 2 are held on the side of the semiconductor element (Fig. 2(d)). Here, the graphene layer 2 is directly peeled off from the substrate.
於(b)中，乃於基板1上積層第1~4之4層石墨烯層2，在進一步形成含有半導體膜之半導體元件後(未圖示)，於第1石墨烯層2與第2石墨烯層2間進行剝下，且第2~4之3層石墨烯層2會保持於半導體元件側(圖2(d))，第1石墨烯層2則與基板一同脫離。 In (b), four layers of the first to fourth graphene layers 2 are laminated on the substrate 1, and after further forming a semiconductor element including a semiconductor film (not shown), the first graphene layer 2 and the second layer are formed. The graphene layer 2 is peeled off, and the second to fourth three-layer graphene layers 2 are held on the semiconductor element side (Fig. 2 (d)), and the first graphene layer 2 is separated from the substrate.
於(c)之左圖中，乃於基板1上成膜剝離用犧牲層3，接著，積層第1~3之3層石墨烯層2，在進一步形成含有半導體膜之半導體元件後(未圖示)，於剝離用犧牲層3與第1石墨烯層2間進行剝下，且第1~3之3層石墨烯層2會保持於半導體元件側(圖2(d))，剝離用犧牲層3則與基板一同脫離。 In the left diagram of (c), the sacrificial layer 3 for film-peeling is formed on the substrate 1, and then the third-layer graphene layer 2 of the first to third layers is laminated, and after further forming the semiconductor element including the semiconductor film (not shown) The stripping sacrificial layer 3 and the first graphene layer 2 are peeled off, and the first to third three graphene layers 2 are held on the semiconductor element side (Fig. 2(d)), and the peeling is sacrificed. Layer 3 is then detached from the substrate.
於(c)之右圖中，乃於基板1上成膜第1石墨烯層2，接著，成膜剝離用犧牲層3，再者，積層第2~4之3層石墨烯層2，在進一步形成含有半導體膜之半導體元件後(未圖示)，於剝離用犧牲層3與第2石墨烯層2間進行剝下，且第2~4之3層石墨烯層2會保持於半導體元件側(圖2(d))，第1石墨烯層2及剝離用犧牲層3則與基板一同脫離。如以上，於上述(b)及(c) 中，石墨烯層2乃自基板間接剝下。 In the right diagram of (c), the first graphene layer 2 is formed on the substrate 1, and then the sacrificial layer 3 for film formation is formed, and further, the second to fourth layers of the graphene layer 2 are laminated. After the semiconductor element including the semiconductor film is further formed (not shown), the sacrificial layer 3 for peeling and the second graphene layer 2 are peeled off, and the second to fourth layers of the graphene layer 2 are held in the semiconductor element. On the side (Fig. 2(d)), the first graphene layer 2 and the sacrificial layer 3 for peeling are separated from the substrate. As above, in (b) and (c) above The graphene layer 2 is indirectly peeled off from the substrate.
以下可適當地使用作為上述剝離用犧牲層。 The sacrificial layer for peeling described above can be suitably used as follows.
(1)化學剝離石墨烯(藉由將石墨氧化後剝離成單層及數層之石墨烯片所製得之氧化石墨烯，或是插層於石墨而剝離成單層及數層之石墨烯片所製得之化學修飾石墨烯等化學方式所製作的石墨烯)；(2)SiC上之磊晶石墨烯(將單晶SiC基板加熱至1100℃以上而將SiC還原，並於最表面磊晶成長之石墨烯。視條件，亦可使數層之石墨烯成長，亦可於石墨烯上製作元件構造，且剝下後再度使石墨烯成長，藉此，將SiC基板再利用)；及(3)石墨烯以外之層狀物質(顯示絕緣性之h-BN(六方氮化硼)，或是MoS2或GaSe等硫屬化物系層狀物質等。製作法可列舉如：公知之塊材劈開法、成長法等。) (1) Chemically exfoliated graphene (graphene oxide obtained by oxidizing graphite and then stripping it into single-layer and several-layer graphene sheets, or intercalating into graphite to be stripped into single-layer and several-layer graphene Graphene produced by chemical modification of graphene prepared by the film) (2) Epitaxial graphene on SiC (heating the single crystal SiC substrate to 1100 ° C or higher to reduce SiC, and to the top surface Graphene grown by crystal growth. Depending on the conditions, it is also possible to grow several layers of graphene, or to fabricate a device structure on graphene, and then to grow graphene after stripping, thereby recycling the SiC substrate); (3) a layered substance other than graphene (having an insulating h-BN (hexagonal boron nitride) or a chalcogenide-based layered substance such as MoS 2 or GaSe, etc. The production method may be, for example, a well-known block. Material development, growth method, etc.)
基板可適當地使用鹼石灰、無鹼玻璃等玻璃、其他陶瓷、塑料等，塑料可列舉如：聚碳酸酯、聚苯乙烯、聚乙烯、聚丙烯、聚對苯二甲酸乙二酯、聚醯亞胺、聚丙烯酸酯等。厚度通常選自於50μm~5mm。 As the substrate, glass such as soda lime or alkali-free glass, other ceramics, plastics, or the like can be suitably used, and examples of the plastic include polycarbonate, polystyrene, polyethylene, polypropylene, polyethylene terephthalate, and polyfluorene. Imine, polyacrylate, and the like. The thickness is usually selected from 50 μm to 5 mm.
於基板上形成複數層石墨烯層時，可採用各種方法，舉例言之，可適當地採用以下方法，即：將以甲烷等烴類等含氧作為原料而藉由熱CVD(熱化學蒸鍍)法形成於金屬觸媒箔或板(銅箔、鎳板等)上之石墨烯單層轉印於基板上，並反覆轉印而形成複數層石墨烯層。即，熱CVD法乃藉由900~1000℃來實施，且能以大面積成膜，層數控制亦容易，但必須將業已形成於金屬觸媒箔或板上之石墨烯膜 轉印於所期望之基板。轉印法本身可利用常法，舉例言之，可適當地採用使用PMMA(聚甲基丙烯酸甲酯)之轉印法。轉印法亦可採用一次轉印複數層石墨烯層之方法。 When a plurality of graphene layers are formed on a substrate, various methods can be employed. For example, a method in which oxygen is used as a raw material such as a hydrocarbon such as methane by thermal CVD (thermochemical vapor deposition) can be suitably employed. The graphene monolayer formed on the metal catalyst foil or plate (copper foil, nickel plate, etc.) is transferred onto the substrate, and is repeatedly transferred to form a plurality of graphene layers. That is, the thermal CVD method is carried out at 900 to 1000 ° C, and it is possible to form a film in a large area, and the number of layers is also easily controlled, but it is necessary to form a graphene film which has been formed on a metal catalyst foil or a plate. Transfer to the desired substrate. The transfer method itself can be carried out by a usual method. For example, a transfer method using PMMA (polymethyl methacrylate) can be suitably employed. The transfer method may also employ a method of primarily transferring a plurality of layers of graphene layers.
舉例言之，亦可使用將氧化石墨烯溶液塗佈於基板而成膜並還原之溶液塗佈法等。 For example, a solution coating method in which a graphene oxide solution is applied to a substrate to form a film and is reduced can also be used.
複數層石墨烯層乃視目的而不同，通常為2~10層，適當的是剝下後3~4層作為導電膜而包含於半導體元件。 The plurality of layers of the graphene layer are different depending on the purpose, and are usually 2 to 10 layers. Suitably, 3 to 4 layers are peeled off and included as a conductive film in the semiconductor element.
所剝下的石墨烯層會構成透明導電膜(第1電極)，並視目的於其上積層形成半導體薄膜，接著，可形成第2電極。 The peeled graphene layer constitutes a transparent conductive film (first electrode), and a semiconductor thin film is formed by stacking thereon, and a second electrode can be formed.
剝下乃適合於形成第2電極後進行，然而，當半導體薄膜與相當於背面電極之導電性基板或膜可取得良好之接觸時，可於即將形成第2電極前進行。為了於預定位置均一地產生剝離，剝下乃施加拉伸應力、剪應力來實施。於該實施時，可適當地使用黏著片、保護片等。舉例言之，可塗佈環氧樹脂、PDMS(聚二甲基矽氧烷)等樹脂，並放上蓋玻璃或黏貼黏著片而用手或鑷子等器具適當地施加拉伸應力及剪應力，並均一地實施剝下。 The peeling is performed after forming the second electrode. However, when the semiconductor film and the conductive substrate or film corresponding to the back electrode are in good contact, the second electrode can be formed immediately before. In order to uniformly peel off at a predetermined position, peeling is performed by applying tensile stress and shear stress. At the time of this implementation, an adhesive sheet, a protective sheet, or the like can be suitably used. For example, an epoxy resin, a resin such as PDMS (polydimethyl siloxane) may be applied, and a cover glass or an adhesive sheet may be placed and a tensile stress and a shear stress may be appropriately applied by means of a hand or a tweezers, and Stripping is performed uniformly.
依此作成而自基板直接或間接剝下石墨烯層所製得之半導體元件屬於自立型。由於沒有基板，因此，可自由地黏貼於任何支持體，且多接合化亦容易。 The semiconductor element produced by directly or indirectly stripping the graphene layer from the substrate is a self-standing type. Since there is no substrate, it can be freely adhered to any support, and multi-bonding is also easy.
半導體元件可列舉如：太陽電池。特別適合的是包含有下述之薄膜太陽電池，即：第1電極，其含有自基板 直接或間接所剝下的石墨烯層；半導體薄膜；及第2電極。 The semiconductor element can be exemplified by a solar cell. Particularly suitable is a thin film solar cell comprising: a first electrode comprising a self-substrate a graphene layer directly or indirectly stripped; a semiconductor film; and a second electrode.
半導體薄膜並無特殊之限制，可列舉如：微晶矽、非晶矽等矽；及III-V族、CdTe系、CIGS系等化合物半導體等，亦可採用混合物系。於非晶矽之情形時，通常會氫化來使用(a-Si：H)，且適合使用於p層與n層將i層***其間之pin接合。舉例言之，具有於附加有透明導電膜(第1電極)之玻璃基板積層a-Si：H層(p層、i層、n層)、背面電極(第2電極)之構造。半導體薄膜可含有超晶格、量子點、奈米線等奈米構造。該等之成膜可利用常法。 The semiconductor thin film is not particularly limited, and examples thereof include germanium such as microcrystalline germanium and amorphous germanium, and compound semiconductors such as III-V, CdTe, and CIGS, and a mixture system. In the case of amorphous germanium, hydrogenation is usually used to use (a-Si:H), and it is suitable for pin bonding in which the p layer and the n layer intercalate the i layer. For example, a glass substrate having a transparent conductive film (first electrode) is laminated with a layer of a-Si:H layer (p layer, i layer, n layer) and a back electrode (second electrode). The semiconductor film may contain a nanostructure such as a superlattice, a quantum dot, or a nanowire. These film formations can be carried out by a conventional method.
於本發明中，薄膜太陽電池包括奈米線陣列型太陽電池。奈米線乃直徑1μm以下、長度為數μm以上之線狀構造體，且光捕捉效應大，並可藉由量子尺寸效應進行能帶隙控制。故，奈米線陣列型太陽電池被期待作為高效率之太陽電池。舉例言之，奈米線之材質可列舉如：矽、GaAs、ZnO等。 In the present invention, the thin film solar cell includes a nanowire array type solar cell. The nanowire is a linear structure having a diameter of 1 μm or less and a length of several μm or more, and has a large light trapping effect, and can perform band gap control by a quantum size effect. Therefore, the nanowire array type solar cell is expected to be a highly efficient solar cell. For example, the material of the nanowire can be exemplified by germanium, GaAs, ZnO, and the like.
於本發明中，自基板直接或間接所剝下的石墨烯層乃透明導電膜，且可適當地使用作為第1電極。舉例言之，於利用長波長紅外線之太陽電池等ITO(銦錫氧化物)不擅長之領域中，亦可適當地使用。相較於ITO，石墨烯乃片電阻同等且透光性更加良好，更具有於全波長領域中吸收小之優點。 In the present invention, the graphene layer which is directly or indirectly peeled off from the substrate is a transparent conductive film, and can be suitably used as the first electrode. For example, in the field where ITO (indium tin oxide) such as a solar cell using long-wavelength infrared rays is not good, it can be suitably used. Compared with ITO, graphene has the same resistance and better light transmittance, and has the advantage of small absorption in the whole wavelength field.
有關本發明之石墨烯層含有伴隨著剝離之缺損領域。圖3顯示所剝下的石墨烯表面之SEM相片(500倍)之一例。於所剝下的石墨烯表面，觀察到在剝下前未看見的數 μm~數十μm之***部，並作成伴隨著剝離之缺損領域。缺損領域之密度(頻度)乃依存於剝下條件等，然而，由於缺損領域之存在，石墨烯層之導電性會有若干降低，但由於片電阻可獲得100Ω/□以下，因此，雖然亦視用途而有所不同，但卻可充分供實用。 The graphene layer of the present invention contains a field of defects accompanying peeling. Figure 3 shows an example of a SEM photograph (500 times) of the surface of the stripped graphite. On the surface of the exfoliated graphene, the number not seen before peeling was observed. The ridges of μm to several tens of μm are formed in the field of defects accompanying peeling. The density (frequency) in the defect area depends on the stripping conditions, etc. However, the conductivity of the graphene layer is somewhat reduced due to the existence of the defect area, but since the sheet resistance can be 100 Ω/□ or less, it is also considered It varies depending on the application, but it is fully functional.
以下，藉由實施例更詳細說明本發明。 Hereinafter, the present invention will be described in more detail by way of examples.
於銅箔上使用甲烷與氫而藉由熱CVD(化學氣相沉積，Chemical Vapor Deposition)使單層石墨烯成長(科學324(2009)1312)。將厚度為0.7mm之「EAGLE-XG」玻璃(無鹼玻璃)基板藉由丙酮及乙醇溶液分別進行10分鐘超音波洗淨，在進行過吹氮後，進行UV-臭氧處理5分鐘，並將表面親水性化。使用PMMA(聚甲基丙烯酸甲酯，Poly(methyl methacrylate))，將成長的單層CVD石墨烯膜轉印於業經親水性化之玻璃基板上(Nano Lett.9(2009)4359)。藉由反覆轉印，堆積5層之CVD石墨烯膜。 Single-layer graphene is grown by thermal CVD (Chemical Vapor Deposition) using methane and hydrogen on copper foil (Science 324 (2009) 1312). The "EAGLE-XG" glass (alkali-free glass) substrate having a thickness of 0.7 mm was ultrasonically washed by acetone and ethanol solution for 10 minutes, and after nitrogen blowing, UV-ozone treatment was performed for 5 minutes, and The surface is hydrophilic. The grown single-layer CVD graphene film was transferred onto a hydrophilic glass substrate using PMMA (poly(methyl methacrylate)) (Nano Lett. 9 (2009) 4359). Five layers of CVD graphene film were deposited by reverse transfer.
其次，使非晶矽太陽電池堆積。將上述附加有石墨烯之玻璃基板投入電漿CVD裝置之試樣取入用反應管，並進行真空抽吸後，將基板朝p層形成用反應管搬送，並設置於業已設為200℃之基板支撐電極。使p層形成用之SiH4，單甲基矽烷(MMS)、H2及B2H6氣體流動，並將氣體壓力保持於70Pa。接著，將13.56MHz之高頻投入電極，並使p層堆積。然後，停止高頻及各氣體而作成真空抽吸，並朝i層 形成用反應管搬送，且使i層堆積。使i層形成用之SiH4及H2氣體流動，並將氣體壓力保持於50Pa。再者，將60MHz之高頻投入電極，並使i層堆積。然後，停止高頻及各氣體而作成真空抽吸，並朝n層形成用反應管搬送，且使種層及中間層堆積。在形成電池後，搬送至試樣取入用反應管，並藉由氮氣沖洗後，取出試樣。接著，使用真空蒸鍍器，將背面銀電極蒸鍍成500nm之厚度。 Second, the amorphous germanium solar cells are stacked. The glass substrate to which the graphene is added is placed in a sample-receiving reaction tube of a plasma CVD apparatus, and after vacuum suction, the substrate is transferred to a p-layer formation reaction tube, and the substrate is set to 200 ° C. The substrate supports the electrodes. The p layer was formed into SiH 4 , monomethyl decane (MMS), H 2 and B 2 H 6 gas, and the gas pressure was maintained at 70 Pa. Next, a high frequency of 13.56 MHz was applied to the electrodes, and the p layer was deposited. Then, the high frequency and each gas are stopped and vacuum suction is performed, and the reaction is carried out in the i-layer formation reaction tube, and the i layer is deposited. The SiH 4 and H 2 gases for forming the i layer were flowed, and the gas pressure was maintained at 50 Pa. Further, a high frequency of 60 MHz was applied to the electrodes, and the i layer was deposited. Then, the high frequency and each gas are stopped and vacuum suction is performed, and the n-layer formation reaction tube is transported, and the seed layer and the intermediate layer are deposited. After the battery was formed, it was transferred to a reaction tube for sample take-in, and after flushing with nitrogen, the sample was taken out. Next, the back surface silver electrode was vapor-deposited to a thickness of 500 nm using a vacuum vaporizer.
接著，塗佈環氧樹脂，並放上蓋玻璃而施加拉伸及剪應力，且於多層石墨烯層之第2層與第3層間剝下，並連同石墨烯導電膜一起剝離太陽電池(圖2之(b)態樣)。剝下後為了評價太陽電池特性，在業已預先固定銀線後塗佈環氧樹脂，並蓋上其他玻璃基板而硬化一晚後，剝下並確認太陽電池動作。 Next, the epoxy resin is applied, and the cover glass is placed to apply tensile and shear stress, and is peeled off between the second layer and the third layer of the multilayer graphene layer, and the solar cell is peeled off together with the graphene conductive film (Fig. 2 (b) aspect). After the peeling, in order to evaluate the characteristics of the solar cell, the epoxy resin was fixed in advance, and the epoxy resin was applied, and the other glass substrate was covered and hardened for one night, and then peeled off and the solar cell was operated.
圖4顯示所剝下的薄膜矽太陽電池之構造，圖5顯示剝下前後之太陽電池特性。於圖4中，首先，製作如(a)所示之薄膜矽太陽電池。層構造如下。 Figure 4 shows the construction of the stripped film tantalum solar cell, and Figure 5 shows the characteristics of the solar cell before and after stripping. In Fig. 4, first, a thin film tantalum solar cell as shown in (a) is produced. The layer is constructed as follows.
基板1(玻璃)/石墨烯層2(5層)/p-a-SiC(10nm)4/p-緩衝層5/i-a-Si(500nm)6/n-mc(微晶)-SiO(40nm)7/Ag8/Al9 Substrate 1 (glass) / graphene layer 2 (5 layers) / pa-SiC (10 nm) 4 / p - buffer layer 5 / ia - Si (500 nm) 6 / n - mc (microcrystalline) - SiO (40 nm) 7 /Ag8/Al9
於(b)中，在Ag/Al電極形成後(在此將p-a-SiC(10nm)4/p-緩衝層5/i-a-Si(500nm)6/n-mc-SiO(40nm)7作成「a-Si電池」)，塗佈環氧樹脂10，再者，為了能均一地剝下，放上蓋玻璃11。接著，藉由鑷子自蓋玻璃上施加拉伸及剪應力，並於石墨烯層2內(第2層與第3層間)剝下(c)。如圖5所示，剝下後的太陽電池特性有若干降低。 In (b), after the formation of the Ag/Al electrode (here, pa-SiC (10 nm) 4/p-buffer layer 5/ia-Si (500 nm) 6/n-mc-SiO (40 nm) 7 is made" The a-Si battery ") was coated with an epoxy resin 10, and in order to be uniformly peeled off, the cover glass 11 was placed. Next, tensile and shear stresses are applied from the cover glass by the tweezers, and (c) is peeled off in the graphene layer 2 (between the second layer and the third layer). As shown in Fig. 5, there is a slight decrease in the characteristics of the solar cell after peeling.
將EAGLE-XG玻璃基板藉由丙酮及乙醇溶液分別進行10分鐘超音波洗淨，在進行過吹氮後，進行UV-臭氧處理5分鐘，並將表面親水性化。浸漬於1wt%之APTES((3-胺丙基)三乙氧矽烷)溶液中15分鐘，並藉由超純水淋洗而吹氮後，藉由150℃焙燒30分鐘。於依此使表面帶胺基端之玻璃基板旋轉澆鑄約10wt%之氧化石墨烯分散液後，藉由150℃焙燒5分鐘。其次，使用PMMA，將業已於銅箔上使用甲烷與氫而進行熱CVD成長的單層CVD石墨烯膜轉印於氧化石墨烯層上。非晶矽太陽電池之製作步驟、剝下步驟乃與實施例1相同，然而，剝下乃於屬於剝離用犧牲層的氧化石墨烯與石墨烯間實施(圖2之(c)態樣)。 The EAGLE-XG glass substrate was ultrasonically washed by acetone and ethanol solution for 10 minutes, and after nitrogen blowing, UV-ozone treatment was performed for 5 minutes to hydrophilize the surface. The solution was immersed in a 1 wt% APTES ((3-aminopropyl) triethoxy decane) solution for 15 minutes, and after being blown with nitrogen by ultrapure water, it was baked at 150 ° C for 30 minutes. Thereafter, about 10% by weight of the graphene oxide dispersion was spin-cast on the glass substrate having the amine-terminated end surface, and then baked at 150 ° C for 5 minutes. Next, using a PMMA, a single-layer CVD graphene film which has been subjected to thermal CVD growth using methane and hydrogen on a copper foil is transferred onto the graphene oxide layer. The production step and the peeling step of the amorphous germanium solar cell were the same as in the first embodiment. However, the peeling was performed between the graphene oxide and the graphene which are the sacrificial layer for peeling (the aspect (c) of Fig. 2).
圖6顯示實施例2中所塗佈的氧化石墨烯之SEM相片(150倍)。 Fig. 6 shows a SEM photograph (150 times) of graphene oxide coated in Example 2.
於石墨烯積層膜上成膜非晶矽薄膜，並藉由金屬觸媒化學蝕刻(Metal-Assisted Chemical Etching)法，製作奈米線陣列(Adv.Mater.23(2011)285等)。混合使用作為樹脂之PDMS(聚(二甲基矽氧烷))之基劑與硬化劑，並攪拌5分鐘。將其旋轉澆鑄於試樣基板上，並以12小時自然乾燥後，藉由120℃焙燒15分鐘。於樹脂硬化後，使用保護片來剝離。剝下乃於屬於剝離用犧牲層的氧化石墨烯與石墨烯間實施(圖2之(c)態樣)。 An amorphous germanium film was formed on the graphene laminate film, and a nanowire array (Adv. Mater. 23 (2011) 285, etc.) was produced by a metal-catalyst chemical etching method. A base of PDMS (poly(dimethyloxane)) as a resin and a hardener were mixed and stirred for 5 minutes. This was spin-cast on a sample substrate, and dried naturally for 12 hours, followed by baking at 120 ° C for 15 minutes. After the resin is cured, a protective sheet is used for peeling. The stripping is carried out between graphene oxide and graphene which are sacrificial layers for peeling (Fig. 2 (c)).
圖7顯示所製得之矽奈米線陣列之SEM相片(2萬 倍)。 Figure 7 shows an SEM photograph of the prepared nanowire array (20,000) Double).
若藉由本發明，則可提供以下方法，即：可將屬於原子級、平坦之層狀化合物且作成電極亦具有充分導電性之多層石墨烯，於石墨烯層間或石墨烯層-基板間等輕易地剝離，再者，將石墨烯層直接活用作為電極，藉此，製作自立型薄膜太陽電池。 According to the present invention, it is possible to provide a multilayer graphene which is an atomic-grade, flat layered compound and which is also excellent in electrical conductivity, and is easily bridged between graphene layers or graphene layers-substrates. In addition, the graphene layer was directly used as an electrode, thereby producing a self-standing thin film solar cell.
1‧‧‧基板 1‧‧‧Substrate
2‧‧‧石墨烯層 2‧‧‧graphene layer
12‧‧‧半導體元件 12‧‧‧Semiconductor components
Claims (6)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014055402A JP2015179695A (en) | 2014-03-18 | 2014-03-18 | Manufacturing method of semiconductor device, semiconductor device, and transparent conductive film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| TW201543698A true TW201543698A (en) | 2015-11-16 |
Family
ID=54144588
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| TW104108480A TW201543698A (en) | 2014-03-18 | 2015-03-17 | Method for producing thin-film solar cell, and thin-film solar cell |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP2015179695A (en) |
| TW (1) | TW201543698A (en) |
| WO (1) | WO2015141620A1 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106952738B (en) * | 2017-03-09 | 2019-04-09 | 安徽大学 | A kind of electrode and the preparation method and application thereof with flexible self-supporting structure |
| WO2018225736A1 (en) * | 2017-06-07 | 2018-12-13 | 国立研究開発法人産業技術総合研究所 | Method for improving electrical conductivity of graphene sheet and electrode structure which uses graphene sheet having improved electrical conductivity |
| KR102068322B1 (en) * | 2018-04-03 | 2020-01-20 | 세종대학교산학협력단 | Epitaxy structure using graphene sacrificial layer and method for manufacturing the same |
| CN110061112B (en) * | 2019-02-28 | 2022-07-08 | 华灿光电(苏州）有限公司 | GaN-based light emitting diode epitaxial wafer and preparation method thereof |
| WO2023173171A1 (en) * | 2022-03-17 | 2023-09-21 | Commonwealth Scientific And Industrial Research Organisation | A transferrable photovoltaic device |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10164135B2 (en) * | 2009-08-07 | 2018-12-25 | Guardian Glass, LLC | Electronic device including graphene-based layer(s), and/or method or making the same |
| JP5742335B2 (en) * | 2011-03-18 | 2015-07-01 | 富士通株式会社 | Semiconductor device |
| JP5887947B2 (en) * | 2011-03-28 | 2016-03-16 | ソニー株式会社 | Transparent conductive film, heater, touch panel, solar cell, organic EL device, liquid crystal device, and electronic paper |
| JP5883571B2 (en) * | 2011-03-31 | 2016-03-15 | 三井金属鉱業株式会社 | Electrode foil and organic device |
| JP5961355B2 (en) * | 2011-08-31 | 2016-08-02 | 国立大学法人埼玉大学 | Photo-induced charge separation device, photovoltaic cell and method for producing the same |
-
2014
- 2014-03-18 JP JP2014055402A patent/JP2015179695A/en active Pending
-
2015
- 2015-03-16 WO PCT/JP2015/057688 patent/WO2015141620A1/en active Application Filing
- 2015-03-17 TW TW104108480A patent/TW201543698A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| JP2015179695A (en) | 2015-10-08 |
| WO2015141620A1 (en) | 2015-09-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Geng et al. | Recent advances in growth of novel 2D materials: beyond graphene and transition metal dichalcogenides | |
| Jiang et al. | Flexible electronics based on 2D transition metal dichalcogenides | |
| Lee et al. | Heterostructures based on inorganic and organic van der Waals systems | |
| CN104538526B (en) | Nitride LED epitaxial wafer structure based on copper substrate and manufacturing method thereof | |
| KR101698228B1 (en) | Large area deposition and doping of graphene, and products including the same | |
| KR101724773B1 (en) | Debonding and transfer techniques for hetero-epitaxially grown graphene, and products including the same | |
| RU2535235C2 (en) | Electronic device with graphene-based layer(s) and/or method of its manufacturing | |
| KR101724772B1 (en) | Large area deposition of graphene hetero-epitaxial growth, and products including the same | |
| CN102897750B (en) | PrPrearation method for graphene film | |
| TW201543698A (en) | Method for producing thin-film solar cell, and thin-film solar cell | |
| Seo et al. | Low dimensional freestanding semiconductors for flexible optoelectronics: materials, synthesis, process, and applications | |
| US9419158B2 (en) | Solar cell and method for manufacturing same | |
| JP2013502745A5 (en) | ||
| Jia et al. | Toward the commercialization of chemical vapor deposition graphene films | |
| Hong et al. | One-dimensional semiconductor nanostructures grown on two-dimensional nanomaterials for flexible device applications | |
| CN104576862B (en) | A kind of nitride LED vertical chip based on copper substrate and preparation method thereof | |
| KR20110064164A (en) | Method of forming graphene layer using chemical vapor deposition | |
| JP4949540B2 (en) | Solar cell and manufacturing method thereof | |
| CN110963484A (en) | Doping layer-assisted large-area high-quality graphene nondestructive transfer method | |
| KR20120095553A (en) | Electric device of using graphene, photovoltaic device of using the same and method of manufacturing the photovoltaic device using the same | |
| CN202217689U (en) | Photovoltaic device and photovoltaic converter panel comprising same | |
| US9935207B2 (en) | Tunneling diode using graphene-silicon quantum dot hybrid structure and method of manufacturing the same | |
| KR20130022438A (en) | The method of forming silicon carbide film comprising silicon nano-crystals | |
| KR101437280B1 (en) | Etching-free graphene growth method using conductive metal oxide | |
| KR20200040169A (en) | A method for epitaxial growth of single crystalline heterogeneous 2D materials and stacked structure |