WO2002037576A2 - Dispositif a semi-conducteur et son procede de production - Google Patents

Dispositif a semi-conducteur et son procede de production Download PDF

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Publication number
WO2002037576A2
WO2002037576A2 PCT/EP2001/012372 EP0112372W WO0237576A2 WO 2002037576 A2 WO2002037576 A2 WO 2002037576A2 EP 0112372 W EP0112372 W EP 0112372W WO 0237576 A2 WO0237576 A2 WO 0237576A2
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WIPO (PCT)
Prior art keywords
semiconductor
layer
semiconductor device
carrier
insulation layer
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PCT/EP2001/012372
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German (de)
English (en)
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WO2002037576A3 (fr
Inventor
Steffen Jäger
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Futech Gmbh
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Priority to EP01993027A priority Critical patent/EP1362379A2/fr
Priority to AU2002219062A priority patent/AU2002219062A1/en
Publication of WO2002037576A2 publication Critical patent/WO2002037576A2/fr
Publication of WO2002037576A3 publication Critical patent/WO2002037576A3/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
    • H01L31/1804—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof comprising only elements of Group IV of the Periodic Table
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
    • H01L27/14—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components 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
    • H01L27/142—Energy conversion 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
    • H01L31/0248—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
    • H01L31/0352—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 shape or by the shapes, relative sizes or disposition of the semiconductor regions
    • H01L31/035272—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 shape or by the shapes, relative sizes or disposition of the semiconductor regions characterised by at least one potential jump barrier or surface barrier
    • H01L31/035281—Shape of the body
    • 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
    • H01L31/048—Encapsulation of modules
    • 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
    • H01L31/054—Optical elements directly associated or integrated with the PV cell, e.g. light-reflecting means or light-concentrating means
    • H01L31/0547—Optical elements directly associated or integrated with the PV cell, e.g. light-reflecting means or light-concentrating means comprising light concentrating means of the reflecting type, e.g. parabolic mirrors, concentrators using total internal reflection
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/52—PV systems with concentrators
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/547—Monocrystalline silicon PV cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the invention relates to a semiconductor device with the features of the preamble of claim 1, in particular a photovoltaic semiconductor device, such as. B. a solar cell device, and methods for their production.
  • Photovoltaics is one of the most important and most promising options for using renewable energy sources.
  • the high production costs of photovoltaic systems (especially solar cells, module production, integration) continue to make it difficult for a broad and consequent breakthrough of this technology.
  • the current focus of international research and development is consequently in the search for new ways to reduce costs.
  • the solar cells are mainly made from planar single-crystal or polycrystalline silicon wafers.
  • the conventional p / n semiconductor structure is preferred for silicon.
  • silicon solar cells only dimensions of up to approx. 15 x 15 cm 2 are technologically possible today.
  • a high use of material thicknesses of greater than approx. 300 ⁇ m is necessary.
  • Further disadvantages can be seen in the complex and cost-intensive further processing of the solar cells into solar modules and the low flexibility in terms of shapes and sizes. Further systems for solar cells are described in US4691076, US4992138 and US5028546.
  • the silicon balls are housed in flexible aluminum foils that are insulated from one another and that simultaneously represent the electrical contacts for the p- and n-doping regions.
  • the semiconductor balls must be positioned and fixed in advance in prefabricated recesses, which are usually made by perforating.
  • complex structuring and chemical etching processes for the partial removal of the oppositely doped outer shell of the silicon balls are required to produce the necessary electrical contact surfaces.
  • US4173494 and US4614835 the process from US4691076 is expanded to embedding in a glass matrix.
  • a possible Interconnection to large-area arrays is proposed in ÜS 07320.
  • US5419782 and US5468304 describe modifications of the solar cell array for better utilization of the incident radiation.
  • the solution proposed in US5419782 provides for, by appropriate combinations of layers with different optical properties (refractive index) to be applied to the front of the arrays, to direct the light falling into the spaces between the silicon particles directly onto the silicon balls the layers have to be deposited completely symmetrically and in a defined thickness on the surfaces of the silicon balls. This can hardly be realized in industrial mass production or only with great effort.
  • US5468304 the spaces between the balls are concave with a transparent material to improve the optical performance In combination with a flat reflection layer to be realized in this area, the incoming light is then reflected laterally onto the individual silicon cells.
  • the proposed solar cells and the corresponding manufacturing processes have a number of disadvantages.
  • p or n type certain conductivity type
  • n or p type oppositely doped shell
  • the semiconductor particles have to be introduced into predetermined perforated carriers in an orderly manner. This results in the highest demands on the accuracy of the geometry and the dimensions of the particles, which can only be implemented in industrial practice with a high level of process engineering and thus financial expense.
  • a particular disadvantage is that the known processes can only be applied to particles larger than 0.5 mm due to the complicated process steps. Due to the large dimensions of the particles, the methods described are in practice essentially limited to silicon (indirect semiconductor). In the case of direct semiconductors, which have a very high absorption, thicknesses of only a few ⁇ m (approx. 1 to 50 ⁇ m) are sufficient to absorb the entire solar spectrum almost completely. With these small geometric dimensions, the proposed methods fail.
  • Patents EP0940860 and EP0866506 describe a spherical semiconductor component.
  • the complete production is dealt with independently of individual semiconductor components, ie including the two required electrodes.
  • the semiconductor balls are produced as follows: a semiconductor layer is applied as a shell to a spherical silicon core in order to produce the p / n transition. Very large ball diameters of> 1 mm are also used here. For reasons of possible cost reduction, lower quality material (metallurgical silicon) is used for the core. A thermal melting process creates a monocrystalline or polycrystalline structure in the preserved semiconducting shell.
  • a coating consisting of two transparent layers (SiO x , SiN x ) is applied in order to carry out an optical adjustment (reflection, scattering of the incident light). Furthermore, windows have to be etched through the reflection layer in order to then be able to apply the p-type semiconductor layer.
  • a diffusion mask with a diameter of approximately 500 ⁇ m has to be produced and a further etching process has to be carried out. In the following, the semiconductor layer must be doped.
  • An oxidic passivation layer is then applied. Removing the layers again creates openings for the subsequent attachment of the contacts (metallization).
  • the proposed semiconductor components in accordance with EP0940860 and EP0866506 are produced by very complex and complex process steps. Several structuring and etching steps as well as additional high-temperature process steps are also necessary, so that a transfer to cost-effective mass production is not possible.
  • a further disadvantage is that the semiconductors have to be spherical in principle in order to carry out the methods. The methods described are based to a large extent on today's semiconductor industry on planar wafers (dimensions of up to 8 "). It is unsolved here whether the transfer of semiconductor technology to individual, individual semiconductor balls can be realized from an economic point of view. The semiconductor balls have to be used in the many necessary process steps (see e.g.
  • the second option is to apply the semiconductor particles in one layer to a perforated conductive carrier and then to coat them with an insulating material. In this case, however, it is necessary to cover the areas on the semiconductor balls provided for the subsequent electrical contacting, or to subsequently remove the insulator layer there.
  • the implementation of this method also places high demands on the uniformity of the semiconductor particles in terms of size and shape. This method cannot be applied to small, irregularly shaped semiconductor particles. For example, conventional thin-film deposition processes could be used for coating. In these, however, disadvantageous shadowing effects occur on the semiconductor particles. A deposited insulation layer becomes inhomogeneous. Isolation cannot be reliably provided.
  • thermal oxidation of aluminum electrodes would result in a number of disadvantages.
  • a high temperature is required for thermal oxidation.
  • Other components such as, in particular, the semiconductor particles can be adversely affected by the effect of the heating.
  • aluminum oxide layers can only be produced with a limited thickness by thermal oxidation.
  • a first oxide covering limits the reactivity of the metallic electrode layer, which in turn can only be compensated for by elevated temperatures.
  • the layer properties during thermal oxidation can only be influenced to a limited extent. After all, thermal oxide layers are brittle and unstable under mechanical loads. Cracks can occur. The functionality and service life of the insulator layer and thus of the entire semiconductor device are thereby limited.
  • Oxygen can diffuse deep into the silicon and form electronically active traps. Charge carriers generated by radiation are captured on the traps. Recombination occurs so that the efficiency of the solar cell is reduced.
  • a third possibility consists in introducing the semiconductor particles into two conductive metal foils (representing the two electrodes) and then filling the interspace with an insulating material at great technological expense (cf. US5086003). It is unclear to what extent such a method can be applied to large areas. On the other hand, the particle size and shape also have to meet high accuracy requirements.
  • the most important requirements to be placed on such an insulator layer can be summarized as follows: (a) good electrical insulation of the layer, (b) high optical transparency, if possible into the UV range, and with a low reflectivity, ( c) high chemical, thermal and light stability, (d) possibility of selective deposition / conversion, (e) the deposition must also be possible in shaded areas or in cavities and corners etc., (f) any layer thicknesses must be able to be produced , (g) their properties (density, porosity etc.) must be able to be defined and controlled in a wide range and in a simple manner, (h) a corresponding scientific and technological know-how as well as the manufacturing techniques should be available, (i ) the production must be inexpensively transferable to large areas, (j) the production must be compatible with the materials used and those based on process steps used in semiconductor technology, etc. This entire complex of requirements cannot be met by the previously known processes.
  • the object of the invention is to provide an improved semiconductor device with which the disadvantages of conventional
  • the basic idea of the invention is, in particular, a generic semiconductor device with a layer structure consisting of a carrier layer which has an electrically conductive carrier material, an insulation layer which is formed by electrically insulating insulation material, is arranged on the carrier layer and contains semiconductor particles, and a cover layer which has at least one electrically conductive cover material and is arranged on the insulation layer, each semiconductor particle touching both the support layer and the cover layer, to further develop in such a way that the insulation material is formed by at least one metal oxide compound which at least partially contains an oxide of the support material.
  • the semiconductor particles are advantageously firmly embedded in the insulation layer, the above-mentioned requirements for the insulation layer being met.
  • insulation layer consist in particular in that it is mechanically firmly connected to the carrier layer.
  • the formation of the insulation layer from an oxide of the carrier material can cause the insulation layer on the carrier layer growing are formed so that the semiconductor • particles are embedded.
  • the insulation layer can be formed over the entire area on the carrier layer.
  • the object of the present invention is in particular to provide inexpensive, efficient semiconductor components which can be produced over a large area on rigid or flexible substrate carriers with a simple structure. Furthermore, the invention includes the processes required for their manufacture and the processes for further processing, for. B. solar modules, large-area detectors or sensors, electrochemical components, etc. a.
  • the invention is not restricted to the use of the semiconductor device as a solar cell arrangement. Rather, other areas of application of the proposed semiconductor components are also part of the invention.
  • the object of the invention is also to provide a semiconductor component in which very small semiconductor particles are applied in a disordered manner and in any form on electrochemically or in a similar manner oxidizable carrier materials.
  • the semiconductor components can be produced with a very low use of materials and costs.
  • the necessary protective and insulation layer is formed directly from the carrier material and is preferably carried out by an electrochemical oxidation or similar processes. It is also an object of the invention to produce the semiconductor component arrangements without complicated structuring, masking and chemical etching processes.
  • An insulation layer formed by electrochemical oxidation, in particular on aluminum carrier material has a number of features which, in accordance with the findings first discovered by the inventor, interact particularly advantageously in the construction of photovoltaic semiconductor devices. These features relate in particular to the layer structure and composition, the achievable layer thicknesses, the optical properties of the insulation layer, electrical and mechanical properties.
  • Electrochemical oxide layers are characterized by a porosity which is advantageous both for the layer formation and for the mechanical properties of the insulation layer.
  • Porosity means that the layer structure contains fine pores, the size of which is given by the material and the process parameters in the electrochemical conversion.
  • the porosity enables the electrochemical bath to come into contact with the carrier material even with increasing layer thickness.
  • Thicker layers can be set than, for example, with thermal oxidation.
  • oxide layer thicknesses are set in the range from 5 nm to 15 ⁇ m, preferably 200 nm to 15 ⁇ m.
  • the considerably enlarged compared to thermal oxide layers, for example Layer thicknesses have the additional advantage of increased dielectric strength of the insulation layer.
  • the porosity provides flexibility of the insulation layer. Cracks are also avoided during bending, which results in increased flexural strength. The reliability and life of the semiconductor device is increased.
  • the porosity of the electrochemically produced insulation layer also makes it possible to set a low refractive index, which, for example in the case of aluminum oxide, can be reduced to values equal to or below 1.5. As a result, the incident light is reflected less strongly. The efficiency of the solar cell increases.
  • the porosity of the electrochemically produced oxide layer also opens up the possibility of incorporating additional functional substances into the insulation layer, such as e.g. B. particles to increase light scattering in the insulation layer between the semiconductor particles. The result is' increased efficiency according to the invention semiconductor devices.
  • electrochemically produced oxide layers are distinguished by improved adhesion to the carrier material and also advantageously increased wettability of the layer surface. This is of particular advantage when implementing further process steps, such as B. the deposition of additional layers on the insulation layer.
  • electrochemical conversion is a low temperature process.
  • thermal oxidation the diffusion of oxygen into silicon is practically reduced to a negligible level. Foreign substances that could reduce the efficiency of the photovoltaic semiconductor device are avoided.
  • An insulation layer provided according to the invention contains a (metal) hydroxide of the carrier material.
  • a (metal) hydroxide of the carrier material For example, when using aluminum as the carrier and electrode material, the inventor has found an unexpected advantage resulting from the chemical composition of the insulation layer.
  • the electrochemical conversion of aluminum creates an insulation layer that essentially consists of Aluminum oxide and also parts of aluminum hydroxide (AI (OH) 3 ).
  • the aluminum hydroxide content can be varied depending on the process conditions. The inventor found that the aluminum hydroxide content in the insulation layer results in an increase in the efficiency of the photovoltaic device in the% range.
  • a further advantage of the invention is that various measures make it possible to optimize the efficiency of the semiconductor component.
  • a further advantage is that a semiconductor device is given increased mechanical stability of the particle fixation by the layer structure according to the invention, in particular by the insulation layer according to the invention.
  • the conversion of the carrier material has shown that the process can be designed so that part of the oxide grows directly out of the substrate. This conversion process can now be designed so that this part can account for up to approximately two thirds of the total thickness of the oxide layer. This improves the necessary mechanical interlocking of the semiconductor particles on the carrier material.
  • Another object of the invention is that when using photovoltaically active semiconductor particles, highly efficient and long-term stable components for converting radiation into other forms of energy (electricity, chemical energy) or also electronic states can be constructed.
  • the invention also relates to a method for producing the semiconductor device mentioned, which is distinguished in particular by the fact that the insulation layer is formed in whole or in part by an electrochemical conversion of the carrier material. Further advantages and details of the invention will become apparent from the following description of the accompanying drawings. Show it:
  • Figures la-g a schematic overview of the steps of a method according to the invention for producing a semiconductor device
  • Figures 4a-d schematic sectional views of a semiconductor device according to the invention.
  • Figures 5a-g a schematic overview of the use of optical microswitches in a semiconductor device according to the invention.
  • FIGS. 1 a to g The method according to the invention for producing the semiconductor device or semiconductor component arrangement is shown schematically in FIGS. 1 a to g.
  • the starting point corresponds to Fig. La forms a semiconductor material which is in the form of small semiconductor particles (1).
  • the particles do not necessarily have to have a spherical or spherical shape. Rather, it has been shown that, for. B. to optimize the area coverage can be advantageous to use arbitrarily shaped particles. In the experiments, he has give ⁇ that it is not necessary also to use particles of almost equal size.
  • Such a semiconductor particle represents the basic element of the semiconductor component.
  • the material silicon, its connections, heterostructures etc. are used as examples to describe the invention. A transfer to other materials is given and is part of the invention.
  • p-doped crystalline or polycrystalline silicon particles (1) The following is an example of p-doped crystalline or polycrystalline silicon particles (1).
  • intrinsic or n-doped semiconductor materials or also semiconductor particles known from the prior art can also be used.
  • Particularly high-purity semiconductor materials, such as those used in microelectronics, are preferably to be used in order to obtain high-quality semiconductor properties of the particles.
  • the use of the semiconductor particles according to the invention has the advantage over the planar semiconductor components used today that, due to the curved surfaces, the light can penetrate almost equally regardless of the direction of incidence. Due to the irregularly shaped particles, part of the light that has penetrated can be totally reflected within the semiconductor particles, as a result of which the optical losses can be further reduced.
  • Aluminum was preferably used as the metallic base or carrier layer (2) with good electrical and thermal conductivity.
  • Aluminum is available inexpensively and in almost any processing shape and size. supply. However, other materials that can be converted by electrochemical oxidation or similar processes (e.g. Ti) can also be used.
  • For the metallic carrier layer (2) in FIG. 1 a aluminum foil with a thickness of approximately 5 ⁇ m to approximately 1 mm was used, depending on the embodiment of the semiconductor component and the intended area of application. The purest possible material is preferably used. This prevents electronically active defects from occurring due to the carrier material — as a result of additional impurities in the semiconductor or at the semiconductor-metal transition — which could lead to a reduction in the efficiency of the semiconductor components.
  • Commercial aluminum with an alloy portion of silicon to adjust the mechanical film properties could be used.
  • the metallic carrier material also acts as a reflector for the light that has passed through the intermediate region and the semiconductor particles. This means that the incident light can be used more effectively.
  • Such carrier layers with thicknesses between about 0.2 microns and 100 microns can be by various known coating methods such.
  • B. vacuum-based coating processes sputtering, thermal evaporation, plasma-assisted or thermal vapor deposition processes or the like), chemical or electrochemical processes, etc., generate.
  • An advantage of such layers compared to film material can be seen above all in the fact that the thin layers can be deposited on almost any substrate materials and shapes with the highest degree of purity.
  • the carrier materials should be subjected to a further cleaning by the known wet-chemical or “dry” plasma-assisted methods or combinations of both before use.
  • a mechanically and electrically strong bond between the semiconductor particles (1) and the carrier material (2) is produced. It is preferably ensured that the semiconductor particles penetrate into the carrier material. The depth of penetration to be selected depends on semiconductor-physical, geometric and application-oriented factors and must therefore be adapted to the specific application. Furthermore, the semiconductor particles are preferably applied to the carrier in one layer. As a result, each semiconductor particle can optimally act as a single semiconductor component.
  • the composite can be produced by mechanical pressing - preferably at temperatures between 350 ° C. and approx. 600 ° C., preferably in the vicinity of the eutectic point of 577 ° C.
  • the contact pressure to be selected as well as the contact time depend on. a. on the selected temperature.
  • the temperature processes heatating, tempering, cooling, etc. are precisely controlled.
  • the supply of the energy required for heating can be done by known techniques such as. B. by spectrally adapted radiant heaters, ultrasound, laser exposure, conventional heating processes (convective processes, current heating) or similar processes.
  • the oxide layer which is only a few nanometers thick and forms immediately on the aluminum surface in the presence of oxygen, is removed.
  • Known methods such as wet chemical pickling or etching, “dry” plasma etching processes, etc. can be used for the implementation.
  • Semiconductor particles are applied to the carrier under an inert gas atmosphere which preferably contains reducing constituents (for example a mixture of argon and / or nitrogen with hydrogen or the like) or in vacuo.
  • a mixing region (3) forms under the favorable influence of the temperature and / or the pressure (see FIG. 1c). This is particularly important to ensure good ohmic contact in addition to mechanical adhesion.
  • a further p-doping of the p-silicon particles is also used.
  • the diffusion of the trivalent aluminum atoms into the p-doped silicon particle is set by the process parameters in such a way that a defined increase in the acceptor concentration (p + doping) takes place in the mixing area (3). It can thus be achieved that the electrical recombination losses at the pp + semiconductor-metal interface (back surface field), e.g. B. in favor of a higher efficiency, can be significantly reduced.
  • FIG. 1d shows the formation of the protective and insulation layer (4) on the conductive carrier material (2).
  • the layer (4) is necessary, on the one hand, to enable protection of the back contact (3) and, on the other hand, to electrically isolate the contacts of the semiconductor particles.
  • the protective and insulator layer is produced according to the invention by selective conversion of the carrier material, preferably by an electrochemical oxidation or a similar process. It is crucial that the selective process - ie only on the metallic carrier surface and not on the semiconductor particle - creates a sufficiently dense and well electrically insulating layer. Since the Protective and insulator layer almost grows out of the substrate, no complex masking, etching or other lithographic processes are required.
  • the insulation layer has a thickness of at least 5 nm, preferably with a view to a high dielectric strength of at least 200 nm.
  • the anodic oxidation of aluminum in acidic media has been researched for a long time and is now used industrially on a large scale.
  • the thickness of the aluminum oxide layer, its microstructure (density, porosity), the mechanical and electrical insulating properties, the stability towards chemical reagents etc. can be defined in a wide range.
  • the specific parameters are to be adapted to the respective combination of particle type (semiconductor material, size, etc.) and carrier material by means of experiments to be carried out beforehand.
  • the properties can be further modified by known aftertreatment processes.
  • the thickness of the protective and insulation layer can easily be set in the range from a few nanometers to a few micrometers. It has been shown that thicknesses of the aluminum oxide layer of ⁇ approx. 15 ⁇ m are sufficient. It is particularly advantageous that the acid solution can get into any area at the carrier substrate-semiconductor particle interface (also in shaded areas, in corners and cavities) and is able to build up the insulating oxide layer precisely at these critical locations for other processes. Only in this way is it possible according to the invention to use semiconductor particles of almost any size and shape. Electrical short circuits between the electrodes, as they occur in the other methods, can be almost completely avoided by the invention.
  • the insulator layer For optimal use of the entire spectral range of the incident radiation, it is necessary to choose the insulator layer so that, if possible, no additional optical absorption and reflection losses occur.
  • a non-absorbent material with a band gap greater than 3.1 eV is sufficient for the insulator layer.
  • the lowest possible refractive index (n ⁇ 1.7) of the isolator leads to a better optical adaptation of the overall system and thus brings about a reduction in reflection losses.
  • Material-specific treatment processes known per se from the semiconductor industry e.g. cleaning, etching processes, conditioning processes, etc.
  • cleaning, etching processes, conditioning processes, etc. can be used to heal, remove or neutralize defects in the semiconductor material or at its interfaces.
  • corresponding doping atoms are introduced or diffused in on the upper side of the Si semiconductor particle (1).
  • V-valued donor atoms e.g. B. P, As, Sb - used.
  • p-doping III-valued acceptor elements such as B. boron, Al, Ga etc. used.
  • the elements phosphorus or boron or aluminum are preferably used as donors or acceptors.
  • the inversion of p-type into n-type silicon z. B. by thermal activation of oxygen installed on interstitial sites is also possible.
  • other doping methods and semiconductor structures known from the prior art can also be used and are part of the invention as special designs.
  • the doping methods known from semiconductor technology vacuum-based methods, plasma-assisted or thermal vapor deposition, implantation, wet-chemical methods, etc. are used to introduce the dopants. It has proven to be advantageous to support the diffusion processes by partially heating the Si particle surface.
  • a phosphorus-doped amorphous hydrogenated silicon layer (a-Si: H (P)) of up to approximately 500 nm in thickness was applied to the p-doped silicon particle.
  • a-Si: H (P) a phosphorus-doped amorphous hydrogenated silicon layer
  • PECVD plasma-assisted chemical vapor deposition
  • semiconductor components could be coated by coating semiconductor particles consisting of I-III-VI semiconductor compounds (e.g. Cu (In, Ga) selenide or sulfide) with n-conducting II-VI compounds (e.g. (Zn , Cd) S) are produced, which are particularly important for solar applications.
  • I-III-VI semiconductor compounds e.g. Cu (In, Ga) selenide or sulfide
  • n-conducting II-VI compounds e.g. (Zn , Cd) S
  • a conductive layer (6) is advantageously applied for the electrical contacting of the front side of the semiconductor arrangement in FIG. 1 f facing sunlight.
  • the thickness of the layer was chosen so that, if possible, only a low surface resistance of ⁇ 10 ohms / sqr. is present.
  • Particularly transparent conductive materials have been used Oxides (TCO; e.g. Sn-doped In 2 0 3 (ITO), F- or Sb-doped Sn0 2 , Al- or Ga-doped ZnO or mixtures etc.) with layer thicknesses> 50 nm or very thin semitransparent layers of metals or metal mixtures or combinations of both have been found to be suitable.
  • the transparent conductive oxide layers have the advantage over the semitransparent metallic layers (layer thicknesses of only a few nanometers) that they have a significantly higher light transmission in the relevant spectral range of greater than approx. 300 nm.
  • These transparent conductive oxide layers have good chemical and mechanical stability and can be known, z. B. reproducibly apply vacuum-based, wet chemical or similar coating processes. A particularly inexpensive and at the same time high-quality large-area coating was obtained using the DC or MF magnetron sputtering process.
  • conductive materials known from the prior art such as, for. B. conductive polymers, nanocomposites, etc. with or without fillers.
  • thicker transparent conductive layers which in a simple manner by wet chemical processes (eg., Sol-gel method) ⁇ he follows, it can be done a certain smoothing of the surface out.
  • thin metal grid structures are applied to the front of the component, similar to the method known from solar cell wafer production. This can further reduce ohmic losses.
  • the conductor tracks partially shade the semiconductor components and thus less light is available for the generation of the charge carriers.
  • Fig. Lg the application of a further layer (7) is shown, which is selected depending on the application and function. Various examples are given below.
  • the transparent conductive oxide layer (6) has a refractive index of approximately 2.0 at 550 nm.
  • the TCO layer can itself be used as an anti-reflective coating as a monolayer (6).
  • the reflection on the Si semiconductor particles can be reduced to a few percent by the deposition of the corresponding ⁇ / 4 TCO layer with a thickness of approximately 70 nm.
  • the TCO layer thickness is too small to allow a sufficiently low resistance of the front contact.
  • An additional combination with e.g. B. a thin metal grid would be necessary in this case.
  • the interference layer system is to be made in such a way that the TCO layer is a high and / or medium refractive index Material and with a thickness of at least ⁇ / 2 or a multiple thereof is inserted (see. DE19624838).
  • the layer system is to be adapted to the respective overall system in accordance with the theory of thin-film optics.
  • the methods known from the prior art can be used to produce the interference layer system.
  • the magnetron sputtering methods and the plasma-assisted CVD methods have proven to be particularly advantageous. Precisely because of the complicated surface topography (see differently shaped particles), the coating must be as three-dimensional as possible and with a high layer thickness uniformity, which is possible with the CVD method.
  • the layer (7) generally consists of a light-stable and transparent plastic, polymer or alternatively of glass-like substances.
  • the layer is, for example, as a film or as a cover plate, such as. B. EVA or PVB, laminated.
  • the layer (7) can also be applied as a multilayer system, in which a first sub-layer optical functions, for. B. reflection reduction, and a second sub-layer takes over the protective function.
  • the layer (7) can have, for example, a structuring for reducing a directed reflection from its surface.
  • the surface appears matt.
  • the efficiency of the semiconductor device is advantageously independent of the radiation angle.
  • the layer (7) also increases the long-term stability and functional reliability. Sometimes it is of interest for some applications (e.g. in architectural facade design, with curved glass laminates, in space travel, etc.) to keep surfaces as smooth as possible and / or to provide the surfaces with additional protective functions. In other application fields, special demands are placed on the color impression. These requirements are met in further embodiments according to the invention by the front application of additional functional layers and materials known from the prior art.
  • the outermost layer is provided with hydrophobic or hydrophilic surface properties.
  • hydrophobic or hydrophilic surface properties With such layers, the wettability of water, oils, etc. can be varied within a wide range.
  • “easy-to-clean or almost self-cleaning" surfaces can be designed with this.
  • the hydrophobic materials have become particularly important. For this purpose, a number of polymers, oils, etc. are known from the prior art.
  • the hybrid materials or nanocomposites based on Si compounds, produced by the sol-gel process are particularly suitable for the semiconductor system according to the invention and have the light and long-term stability required in the applications. It has proven to be particularly advantageous that the microstructured surface morphology impressed by the particles in the ⁇ m range significantly reduces the adhesion of dirt particles, so that “almost self-cleaning surface ". Due to the low refractive index of approx. 1.5 at 550 nm, these coatings significantly reduced the reflection.
  • the porosity of the layer (4-1) can be adjusted so that the incident light can be scattered.
  • the light incident almost vertically into the interspaces in this embodiment can now be optimally used, as shown in FIG. 2b.
  • a positive side effect is that the refractive index of the partial layer (4-1) can be reduced in a targeted manner due to the porosity (to approx. 1.45 to 1.52 at 550 nm). In this way, the reflection losses when the light enters the A1 2 0 3 layer can be further minimized.
  • the version shown has proven to be a particularly suitable process from an economic and procedural point of view and to avoid additional parasitic impurities.
  • Combinations of the insulator layer (4) with overlying, at least partially transparent organic, inorganic and / or hybrid materials can also be used.
  • additional materials (8) were introduced as scattering centers in the porous partial layer (4-1).
  • the additional scattering centers could, on the one hand, be trapped by microparticles of a few ⁇ m thickness that were as non-absorbent as possible
  • the interface between the insulator layer (4) and the metal base (2) was roughened in a targeted manner in order to produce a diffuse reflection there. This could be implemented through a suitable process control directly during the selective conversion of the aluminum.
  • Some of the semiconductor particles to be used for solar applications have a lower spectral sensitivity in the blue-violet wavelength range (approx. ⁇ 450 nm).
  • One approach to using this spectral range more effectively is spectral sensitization, e.g. B. by the adsorption of suitable organic materials, etc.
  • the porous alumina matrix (4-1 in Fig. 2c) made it easy to pass through such materials introduce the known methods. This situation is shown schematically as an example in FIG. 2c.
  • the light (S6) that falls directly into the spaces between the semiconductor particles or is reflected into this area (S7) is absorbed by the fluorescent materials (9) and then re-emitted in all directions.
  • these substances should preferably be inserted into layers above the semiconductor particles due to the low fluorescence efficiency.
  • the carrier material ' (4) is completely oxidized between the semiconductor particles.
  • the area of the ohmic contact (3) is not chemically converted and the necessary electrical contact (10) also remains.
  • the semiconductor arrangement according to the invention can additionally be illuminated from behind (cf. FIG. 3a). It is advantageous to have a transparent one for the layer or the support or a part thereof (11) conductive material (similar to 6) to make a good electrical connection between the semiconductor particles.
  • the semiconductor arrangement can be designed in such a way that a certain light transmittance remains (cf. FIG. 3b). As a result, the efficiency of the semiconductor arrangement is reduced compared to an almost 100% occupancy density. However, there are applications in which this disadvantage is accepted in favor of the translucency.
  • a possible field of application is e.g. B. in semi-transparent insulating glazing or facade parts of buildings, in vehicles, etc.
  • Such insulating glazing unit consists in the simplest case (see. Fig. 3c-l) of at least two glasses 12a-b, which are spatially separated from one another by spacers (14) and with an additional edge seal are protected against external influences.
  • Now z. For example, if the semiconductor arrangement (13) according to the invention is applied to the side of the pane 12a facing away from the light, a certain amount of sun protection can be achieved with simultaneous light transmission and power generation. The light transmittance or the sun protection can be adjusted in a wide range as required by the occupancy density of the semiconductor particles (15) (cf. detail illustration in FIGS.
  • the small size of the semiconductor particles has a particularly advantageous effect. With average “microscopic" particle dimensions of only approx. ⁇ 100 ⁇ m, the semiconductor elements can almost no longer be resolved with the naked eye, so that a very uniform visual impression is produced on the "macroscopic scale".
  • z. B. coated glasses, safety glasses, etc. can also be combined with thermal insulation, color, statics, security, etc.
  • the semiconductor arrangement according to the invention can contain other junction types, such as metal-semiconductor junctions (Schottky type), heterojunctions, metal-insulator junctions and also an MIS structure.
  • junction types such as metal-semiconductor junctions (Schottky type), heterojunctions, metal-insulator junctions and also an MIS structure.
  • the simultaneous combination of several semiconductor arrangements is also possible.
  • the known materials and manufacturing processes can be used to produce these designs.
  • the possible uses of the invention also exist in large-area arrangements for light sensors, for displays, for light-emitting elements, for components in which a latent image is generated, etc.
  • a particular advantage of the invention lies in its use in electrochemical cells. If catalytically active substances are applied to the reducing electrode of the semiconductor arrangement, the semiconductor arrangement according to the invention can be used for the photocatalytic dissociation of electrolytes. It is known that for the production of gaseous hydrogen z. B. Ru, Ir, Ni, Pt or similar materials or Pd, Rh or similar materials for photoreduction from C0 to CH 4 are suitable. These catalytic systems can be produced on the basis of the invention. The gases obtained from the electrolyte dissociation are then collected, stored or otherwise used for energy generation. The metallic catalyst layers are to be applied as a semi-permeable layer (layer thicknesses ⁇ approx. 80 nm) in order to make optimal use of the incident light. The voltages required for the respective electrolyte are realized by the arrangement or electrical connection of the semiconductor elements.
  • a photocatalytically active n-semiconductor layer (for example titanium dioxide or the like) is applied to the reducing electrode by known methods.
  • the semiconductor arrangement itself ultimately acts as a bias for the targeted shifting of the oxidation potential in the photocatalysis of water. Since only the spectral range ⁇ 400 nm is absorbed due to the relatively large band gap of the Ti0 2 (approx. 3.0 eV), the Ti0 2 must also be sensitized to the longer-wavelength spectral range by suitable substances.
  • FIG. 4a schematically shows the lateral section through the semiconductor device according to the invention.
  • the semiconductor structure is now completely pierced at predetermined points, which can be done by mechanical drilling, punching, laser ablation or similar processes.
  • the diameter of the holes (16) in Fig. 4b should be as small as possible (a few hundred ⁇ m).
  • Prefabricated insulated conductor pins (17) are introduced into the holes and a firm electrical connection to the conductive layer (6) is produced on the front.
  • the series connection is then made via the conductor bridges (18).
  • the dimensions of the electrical lines can be made very small and thus almost invisible to the human eye.
  • the entire process can be carried out fully automatically with minimal material expenditure, high throughput and low costs at the same time.
  • the arrays are electrically separated from one another by mechanical or laser processing, etc., as shown in FIG. 4b.
  • the separation points (19) can, for. B. with a insulating and adhesive material at the same time to guarantee safe electrical insulation even under mechanical stress.
  • the production is carried out in such a way that different types of semiconductor components (n- and p-material, cf. 20-1 and 20-2 in FIG. 4c) are applied alternately to defined areas.
  • an integrated circuit can be implemented.
  • “have only the electrodes are interrupted alternately up and down 21-1 21-2, as shown in Fig. 4d is clear.
  • the methods already mentioned can be used, the methods already mentioned.
  • the photovoltaic semiconductor device according to the invention which is produced in particular with the electrochemically formed insulation layer between the carrier material and the counterelectrode, also has a number of advantages which are important for the practical implementation of solar cells and their use under the most varied lighting conditions. This is explained below by way of example with reference to FIGS. 5a-5f.
  • a fundamental problem for all solar modules made up of individual cells is always shadowing. These are local areas on a solar module that at least temporarily no or only very little light can fall on. In the case of solar cells that are electrically connected in series, the shading of just a single cell can lead to failure of the entire module. The solar cells, which are exposed to little or no light, have a current-limiting effect and thus lead to considerable energy losses. Often this can result in energy losses of up to 10% and more in photovoltaic systems be connected. In addition, the so-called hot spot effect can occur when individual cells are completely covered. The cells can sometimes be completely destroyed by overheating.
  • a basic device is proposed by means of which these or similar problems can be avoided.
  • the solution provides for the individual cells and / or cell arrangements to be assigned special optical switches.
  • the use of such switches in cells or arrays with the lowest possible electrical powers is particularly advantageous because (a) the switching elements can then be designed as microswitches, (b) they can then also be integrated directly on the cells and (c) the optical losses are minimized can be.
  • These conditions exist in particular in the photovoltaic semiconductor devices produced according to the invention, so that the principles explained below are preferably applied to them.
  • the improved optical properties and the increased breakdown voltage of the insulation layer provided according to the invention are also utilized.
  • FIGS. 5a-c show an example of an application of such integrated optical microswitches.
  • the exemplary module consists of a total of 24 cells or semiconductor component arrays that are electrically insulated from one another.
  • a uniform semiconductor type is used as a basis, so that the interconnection principle demonstrated in FIG. 4b is used.
  • the sequence of the series connection is marked with ascending numbers.
  • the electrical energy generated is then tapped via the contacts (22).
  • the electrical connection of the neighboring cells via the conductive carrier layer or via the electrically conductive front is shown schematically by 23-1 or 23-2.
  • the microswitches are small passive optical switching elements that can reversibly maintain or interrupt an electrical connection depending on the light radiation. It is particularly advantageous that the microswitches can be integrated directly on the cells are so that the shadowing can be detected locally and at the same time.
  • the variant was selected in which the electrical connection of the cells to be short-circuited is electrically interrupted during the light irradiation.
  • the basic principle for the circuit state (“switch position” (26)) without or with incidence of light is shown schematically in FIGS. 5d-1 and 5d-2.
  • a very simple way of applying the microswitch consists in that the elements are on applied to the front of the cells by means of bonding, gluing, coating or similar processes (see (27) in FIG. 5d). It is also important to ensure that the microswitches have a low overall height (if possible ⁇ approx. 300 ⁇ m), So that they do not interfere with the further processing of the modules, etc.
  • the dimensions of the contact areas, the cable cross-sections, the limit switching point, etc. must be designed for the respective specific application.
  • FIGS. 5e-1 and 5e-2 show an arrangement in which, in the “dark phase”, the two conductors (28) and (29) are in contact with one another.
  • the contact (28) is designed as a bimetal 5e-2
  • heating (28) causes the bimetal or the like to bend so that the conductive connection is broken
  • the window (30) is to be designed to be translucent or partially translucent, in another example 5f
  • a gas volume (31) eg air
  • the upper side of the chamber is designed as a light-permeable conductive membrane (32), on the opposite side a light absorber material (33).
  • optically active materials can also be used as microswitches.
  • Such materials and connections have the advantage that their application is technologically very simple and inexpensive.
  • the materials are substances that change their electrical conductivity depending on the incident light - as suddenly as possible. This can be done either directly through the direct action of light (e.g. direct generation of charge carriers) or through secondary effects caused by the light (e.g. heating, changing the solubility in substance mixtures, the chemical structure, changing the orientation of conductive particles in matrices, agglomeration or formation of conductive phases, etc.).
  • materials which consist of at least two components, at least one of which is conductive on its own. Up to a critical temperature, which is set via the composition, the material is not considered to be mixed, at least two-phase system and has a high conductivity in this example. The effect of light and the associated increase in temperature result in a spontaneous chemical reaction of the components near the critical temperature. The resulting reaction product has a high resistance and causes the desired electrical insulation between the cells. When the temperature is reduced below the critical value, the initial state is reached again. With a suitable combination of materials, this variant can also be operated in the opposite way, or can be combined or modified as desired.
  • the microswitches are integrated directly between the different polarities of the respective cells (see FIG. 5d), the voltages that arise on the cells when light is incident can also be used for switching.
  • microswitch technology described is preferably implemented with the semiconductor devices according to the invention, but according to the invention can also be used advantageously in conventional solar cells known per se.

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Abstract

La présente invention concerne un dispositif à semi-conducteur comprenant une structure stratifiée, constituée d'une couche de support (2), qui présente un matériau de support électroconducteur, d'une couche d'isolation (4), qui est constituée de matériau d'isolation électroisolant, est pourvue sur la couche de support (2) et contient des particules de semi-conducteur (1), et d'une couche de protection (6), qui présente au moins un matériau de protection électroconducteur et est pourvue sur la couche d'isolation (4). Chaque particule de semi-conducteur (1) touche aussi bien la couche de support (2) que la couche de protection (6) et forme au moins une jonction p-n (3, 5). Le matériau d'isolation est constitué d'au moins un composé à base d'oxyde métallique qui renferme au moins partiellement un oxyde du matériau de support. La présente invention concerne également des procédés de production dudit dispositif à semi-conducteur.
PCT/EP2001/012372 2000-10-25 2001-10-25 Dispositif a semi-conducteur et son procede de production WO2002037576A2 (fr)

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AU2002219062A AU2002219062A1 (en) 2000-10-25 2001-10-25 Semiconductor device and method for producing the same

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KR101976673B1 (ko) * 2017-12-19 2019-05-10 한국에너지기술연구원 실리콘 태양전지

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EP1521308A1 (fr) * 2003-10-02 2005-04-06 Scheuten Glasgroep Composant semiconducteur sphérique ou granulaire utilisé pour des cellules solaires et son procédé de fabrication; procédé de fabrication d'une cellule solaire avec ce composant semiconducteur et cellule solaire
EP1521309A1 (fr) * 2003-10-02 2005-04-06 Scheuten Glasgroep Connexion en série de cellules solaires comprenant des corps semiconducteurs intégrés, méthode de fabrication et module photovoltaique avec connexion en série
DE102004055186B4 (de) * 2004-11-16 2012-07-19 Beck Energy Gmbh Photovoltaikmodul mit Submodulen
DE102007061977A1 (de) 2007-12-21 2009-06-25 Futech Gmbh Verfahren zur Herstellung von Halbleiterpartikeln, insbesondere aus Silizium

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US8597971B2 (en) 2005-02-18 2013-12-03 Clean Venture 21 Corporation Method for producing photovoltaic device and photovoltaic device
KR101976673B1 (ko) * 2017-12-19 2019-05-10 한국에너지기술연구원 실리콘 태양전지

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