Classifications

• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
  • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
  • H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
  • H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
  • H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
  • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
  • C23C14/34—Sputtering
  • C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
  • C23C14/02—Pretreatment of the material to be coated
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
  • C23C14/02—Pretreatment of the material to be coated
  • C23C14/024—Deposition of sublayers, e.g. to promote adhesion of the coating
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
  • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
  • C23C14/08—Oxides
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
  • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
  • C23C14/08—Oxides
  • C23C14/086—Oxides of zinc, germanium, cadmium, indium, tin, thallium or bismuth
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
  • C23C14/58—After-treatment
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
  • C23C14/58—After-treatment
  • C23C14/5873—Removal of material
• • 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
  • H01L31/02016—Circuit arrangements of general character for the devices
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
  • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
  • H01L31/02—Details
  • H01L31/0224—Electrodes
  • H01L31/022466—Electrodes made of transparent conductive layers, e.g. TCO, ITO layers
  • H01L31/022483—Electrodes made of transparent conductive layers, e.g. TCO, ITO layers composed of zinc oxide [ZnO]
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
  • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
  • H01L31/18—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
• • 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

Definitions

• the present invention relates to a method of coating a substrate with aluminum-doped zinc oxide.
• TCO layers must have low transparent resistances with a high transparency in the visible spectral range (400 to 800 nm) nm) for amorphous silicon solar cells (a-Si: H) and up to 1100 nm for microcrystalline silicon solar cells
• sputtering for the production of TCO layers in particular so-called sputtering (synonymously also referred to as sputtering) can be used.
• sputtering When atomizing, atoms become one
• Solid-body target by bombardment with high-energy noble gas ions dissolved out and thereby transferred to the gas phase.
• Near the solid-state target from which the atoms are extracted is a
• Substrate provided on which the atoms can condense, so that they form a layer on the surface of the substrate.
• ZnO aluminum-doped zinc oxide
• the ZnO: Al layers produced with the aid of sputtering processes are generally relatively smooth. This means that their roughness is only a few nanometers.
• wet-chemical etching step these layers can be roughened so that crater-like structures having a relatively broad spectrum of structural sizes are formed (see: J. Müller, G. Schöpe, O. Kluth, B. Rech, V. Sittinger, B. Szyszka, R Geyer, P. Lechner, H. Schade, M. Ruske, G. Dittmar, H.-P.
• RMS roughness can be increased to about 200 nm.
• Such surface-textured layers have very good light-scattering properties and, in particular with the aid of high-frequency magnetron sputtering methods (in short:
• ZnO nucleation layer can be applied. It explicitly deals with the production of so-called “nanorods” (nanorods) .
• the ZnO layer is used in this document, the orientation and
• the surface structures which can be produced by the wet-chemical etching are mainly determined by the process parameters temperature and deposition pressure and by the selected
• Another important parameter is the doping of the solid-state target with aluminum.
• it is possible, depending on the doping concentration and temperature, to find an optimum "coating window" for layers produced by RF magnetron sputtering methods, which have an optimized optical waveguide structure after the wet-chemical etching step see M. Berginski, B. Rech, J. Hüpkes, H. Stiebig, M. Wuttig: "Design of ZnO: AI Films with Optimized Surface Texture for Silicon Thin-film Solar Cells” in: SPIE 6197 (2006), pp. 61970Y 1-10, M. Berginski, J. Hüpkes, M. Schulte, G. Schöpe, H. Stiebig, B. Rech: "The effect of front ZnO: AI surface texture and optical
• microcrystalline silicon c-Si: H
• tandem cells a-Si: H / c-Si: H
• an average roughness of about 100 nm to about 200 nm is achieved.
• the texture etching of ZnO Al layer systems exploits the anisotropy of the etch rate of crystalline ZnO layers to convert conventionally smooth deposited layers with a columnar growth (lateral dimension about 50 to 100 nm) into a rough interface whose lateral Dimensions with optimized process conditions in the ⁇ range.
• texture etching it is mainly of interest that the usually difficult production of large crystallites is avoided.
• the method is based on etching the ZnO: Al layers in dilute acid (for example, 0.5% HCl). The etching takes place anisotropically, so that the O-terminated, deposited in c-axis orientation crystallites an order of magnitude faster than the corresponding
• MF sputtering Medium frequency sputtering
• the desired etch morphology can be set by the process control (see Szyszka, B.: “Magnetron sputtering of ZnO films”).
• Operation in metallic mode at high substrate temperature can be achieved when excess zinc desorbs from the surface due to the high vapor pressure.
• High substrate temperatures are generally advantageous in this context.
• rough, fissured structures with a small lateral dimension result.
• the etching images show deep holes. It can be assumed that O-terminated crystallites were etched here at a high etch rate, whereas the etching attack over the flanks of the surrounding grains apparently does not occur.
• thermodynamically favorable segregation of aluminum at the grain boundaries which leads to the formation of an etch-resistant A ⁇ Oß enrichment there.
• Oxygen partial pressure results in flat structures, indicating a uniform Zn termination. Furthermore, it turns out that a repeated overflow in front of a cathode is necessary in order to suppress the throughput of defects.
• Substrate temperature, neutral particle energies, ion energies), ion current measurements in the production of aluminum-doped zinc oxide show the different ion energy contribution depending on
• Plasma excitation In order to achieve an etching structure suitable for solar cells, it is therefore important to influence the layer growth in such a way that a predominantly Zn-terminated surface with little O-terminated crystallites is present.
• Zinc oxide thin films are produced laser-based by laser plasma deposition.
• Rotational coating can be produced.
• the present invention is based on the object to provide a method for coating a substrate with aluminum-doped zinc oxide available, by means of which ZnO: Al layers with improved layer properties, high process reliability and high deposition rate can be generated.
• An inventive method for coating a substrate with aluminum-doped zinc oxide comprises the steps
• the nucleation layer which contains zinc oxide or doped, in particular aluminum-doped, zinc oxide, by sputtering a
• the doped zinc oxide may in principle have any dopants.
• In addition to aluminum are here
• This nucleation layer provides optimized conditions for the cover layer, which also contains aluminum-doped zinc oxide, can continue to grow quasi-epitaxially on the nucleation layer.
• cover layer which also contains aluminum-doped zinc oxide, can continue to grow quasi-epitaxially on the nucleation layer.
• glass, plastic, metals or ceramics can be used as substrate materials. Wet chemical etching of the
• the nucleation layer may advantageously have a thickness which is ⁇ 300 nm.
• the nucleation layer serves primarily to positively influence the electrical properties of the later-growing layer, which contains ZnO: Al, as well as its etching behavior.
• the nucleation layer can be used in particular on amorphous substrates such as glass. Since it is furthermore a polycrystalline layer and not a monocrystalline layer, there is no epitaxy but only quasi-epitaxy.
• the nucleation layer is produced with a thickness between 5 nm and 30 nm on the substrate. It has surprisingly been found that even relatively thin nucleation layers (in particular about 5 to about 30 nm thick nucleation layers) are sufficient to increase the quasi-epitaxial growth of the cover layer on the nucleation layer.
• the nucleation layer passes through
• Dopings is generated, which in particular maintains the lattice structure or at least almost maintained (and thus only slightly changed). It could be determined that such a nucleation layer produced by high-frequency magnetron sputtering during the subsequent deposition of the ZnO: Al layer, which is advantageous for
• the covering layer has an improved light-guiding trap structure. This is characterized in particular by the fact that the crater width predominantly in the area of the incident
• Producing the nucleation layer is a ceramic solid-state target is used, the ZnO and has a content of Al2O3, which is greater than 0 wt.% And less than 1 wt.%, And by
• High-frequency magnetron sputtering at a temperature T> 300 ° C is atomized.
• the content of Al 2 O 3 greater than 0% by weight and less than 1% by weight
• it was possible to determine an optimized "coating window" for the sputtering of the ceramic solid-state target for the production of the Nucleation layer can be obtained.
• a ceramic solid-state target is used to produce the nucleation, the ZnO and a content of Al2O3 between 1 and 2 wt.% Has and by high-frequency magnetron sputtering at a temperature T ⁇ 300 ° C is atomized. It has been found that by setting the content of Al 2 O 3 between 1 and 2% by weight at a temperature T ⁇ 300 ° C., a further optimized "coating window" for sputtering of the ceramic solid-state target for producing the nucleation layer can be obtained.
• Improving nucleation layer is one in particular
• the deposition rate, with the nucleation layer is applied to the substrate is less than 20 nm m / min.
• Deposition rate be adjusted so that it is less than 20 nm m / min, so that the nucleation layer has a corresponding nature, so that the cover layer quasi-epitaxially on the
• Nucleation layer can continue to grow.
• the covering layer further growing on the nucleation layer by sputtering a ceramic solid-state target containing ZnO and a content of Al2O 3, by DC magnetron sputtering or
• DC pulse magnetron sputtering is generated.
• DC magnetron sputtering or DC pulse magnetron sputtering of a ceramic solid state target allows rapid growth of the capping layer on the nucleation layer.
• these sputtering processes are very robust from the process engineering point of view.
• the covering layer which continues to grow on the nucleation layer is produced by sputtering a metallic solid-state target, which
• Zn aluminum-doped zinc oxide
• DC magnetron sputtering or medium frequency magnetron sputtering are examples of DC magnetron sputtering or medium frequency magnetron sputtering.
• the cover layer which continues to grow on the nucleation layer can be alternatively also by
• LP-CVD Low pressure CVD
• PECVD atmospheric plasma enhanced chemical vapor deposition
• the deposition rate of the total layer can advantageously be greatly increased, since the slowly grown nucleation layer the
• Nucleation layer was deposited in each case a cover layer of ZnO: Al by DC magnetron sputtering, wherein the total thickness was about 1 ⁇ . All layers deposited in this manner were etched with 0.5% hydrochloric acid (HCl).
• HCl hydrochloric acid
• Nucleation layer have similar ⁇ tzmorphologien. All SEM images showed a similar etch structure with crater widths of about 1 ⁇ . The etch structures are comparable to the cover layers, which are produced purely by means of RF magnetron sputtering.
• the growth of the layer subsequently produced by DC magnetron sputtering can thus be sustainably influenced.
• the nucleation layer initially applied to the substrate evidently provides a quasi-epitaxial growth of the further growing ZnO: Al layer.
• ZnO: Al layers have excellent resistivity between 286 and 338 ohmcm. This is also due to the quasi-epitaxial growth of the ZnO: Al layer on the
• DC layer shows much smaller structure sizes of the etching trenches.
• High-frequency magnetron sputtering nucleation-provided substrates clearly marked etching craters, wherein the layers have somewhat flatter structures at the same etching depth compared to the non-atmospheric samples. These structures can be optimized by adjusting the etching time.
• samples with a nucleation layer without vacuum fracture showed, independent of the thickness of the nucleation layer, a mean roughness of the cover layers (on average -150 nm), the
• High-frequency magnetron sputtering generated layer (Sample No. 1).
• the AFM images as in the SEM images, the lateral extent of each crater can be seen.
• a morphology optimized for the application should scatter as much of the red and near infrared light as possible into large angles.
• High frequency magnetron sputter deposition can be obtained.

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• 2009
  • 2009-12-23 DE DE102009060547A patent/DE102009060547A1/de not_active Withdrawn
• 2010
  • 2010-12-23 US US13/519,030 patent/US20130203211A1/en not_active Abandoned
  • 2010-12-23 EP EP10798099A patent/EP2516692A1/de not_active Withdrawn
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  • 2010-12-23 WO PCT/EP2010/070655 patent/WO2011076921A1/de active Application Filing
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