EP2612362A2 - Procédé de gravure par voie humide d'une couche de semiconducteur à dopage élevé - Google Patents

Procédé de gravure par voie humide d'une couche de semiconducteur à dopage élevé

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Publication number
EP2612362A2
EP2612362A2 EP11754360.3A EP11754360A EP2612362A2 EP 2612362 A2 EP2612362 A2 EP 2612362A2 EP 11754360 A EP11754360 A EP 11754360A EP 2612362 A2 EP2612362 A2 EP 2612362A2
Authority
EP
European Patent Office
Prior art keywords
emitter
etching solution
etching
alkaline
organic
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP11754360.3A
Other languages
German (de)
English (en)
Inventor
Berthold Schum
Knut Vaas
Agata Lachowicz
Norman Hermert
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
Original Assignee
Schott Solar AG
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Filing date
Publication date
Application filed by Schott Solar AG filed Critical Schott Solar AG
Publication of EP2612362A2 publication Critical patent/EP2612362A2/fr
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • H01L31/0236—Special surface textures
    • H01L31/02363—Special surface textures of the semiconductor body itself, e.g. textured active layers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K13/00—Etching, surface-brightening or pickling compositions
    • C09K13/04—Etching, surface-brightening or pickling compositions containing an inorganic acid
    • C09K13/08—Etching, surface-brightening or pickling compositions containing an inorganic acid containing a fluorine compound
    • 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
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
    • H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
    • H01L21/30604—Chemical etching
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/02—Details
    • H01L31/0224—Electrodes
    • H01L31/022408—Electrodes for devices characterised by at least one potential jump barrier or surface barrier
    • H01L31/022425—Electrodes for devices characterised by at least one potential jump barrier or surface barrier for solar cells
    • 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
    • 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
    • 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
    • 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
    • H01L31/186—Particular post-treatment for the devices, e.g. annealing, impurity gettering, short-circuit elimination, recrystallisation
    • 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 method for wet-chemical etching of a silicon layer in an alkaline etching solution, wherein the silicon layer is surface area of an emitter of a solar cell.
  • the quality of an emitter is one of the decisive factors for the efficiency of a solar cell.
  • the emitter depth, the dopant profile, surface concentration of the dopant and the emitter layer resistance must be precisely adjusted to achieve optimum cell properties.
  • the emitter properties are influenced by the diffusion parameters temperature and time as well as by the type of dopant. In the context of economically applicable industrial processes, however, not all properties are arbitrary and independently adjustable.
  • homogeneously doped mono- or multicrystalline silicon wafers of the p-type generally with boron basic doping, are used as starting material.
  • the concentration of the dopant is of the order of 10 16 atoms / cm 3 .
  • the emitter is generated by diffusing phosphorus.
  • the phosphorus surface concentration may be in the range of 10 19 to more than 10 21 atoms / cm 3, the maximum concentration of the electrically active phosphorus atoms and the solubility of the phosphor in silicon (approx * 10 20 atoms / cm 3) are exceeded.
  • the phosphorus is then present in an inactive form and forms recombination centers for the charge carrier pairs produced (so-called "dead layer").
  • the metal contacts of the front side are predominantly produced by means of silver thick film pastes by screen printing with subsequent sintering.
  • a high phosphorus surface concentration is advantageous, on the other hand, such a high surface concentration of the dopant causes, as mentioned, an increased recombination of the charge carrier pairs generated by light absorption.
  • An improvement of the emitter surface can be achieved by etching back the near-surface highly doped layers. The surface recombination of the charge carriers generated is thereby reduced.
  • the phosphorus silicate glass formed from silicon oxide and the oxide of the dopant is removed in dilute hydrofluoric acid.
  • alkaline cleaning solutions based on ammonia or alkylammonium hydroxides and hydrogen peroxide are used. Solutions of this type were originally developed for semiconductor cleaning, known as "SC-1", part of the RCA purification sequence.
  • the RCA cleaning standard includes the treatment in the SC-1 solution consisting of ammonia or ammonia derivatives and hydrogen peroxide, rinsing and treatment in a dilute solution of hydrochloric acid with hydrogen peroxide (known as "SC-2")
  • SC-2 hydrochloric acid with hydrogen peroxide
  • Ammonia and hydrochloric acid are usually in the concentration range of 3 to 10 weight percent used, hydrogen peroxide - concentration is usually about 1 percent by weight.
  • the applied temperatures are in the range 60 ° C to 85 ° C, the contact times about 10 minutes. Such conditions can only be realized in batch plants.
  • the change in the emitter layer resistance is an easily accessible measure with which the strength of the emitter etch back and reduction of the surface concentration of the dopant can be approximately estimated.
  • the mass removal by the etching solution is very small (on the order of 1 mg for 156 ⁇ 156 mm large wafers) and corresponds to the removal of only a very thin emitter layer of less than 10 nm.
  • Standard emitters have a sheet resistance in the range of 50 to 70 ohms / sq after diffusion. By treatment in dilute hydrofluoric acid and subsequent treatment in the RCA sequence, ie 10 minutes SC-1 solution, rinsing and 10 minutes SC-2 solution, the sheet resistance is raised by 5 to 10 ohms / sq. Emitter etch back occurs primarily in the alkaline SC-1 solution.
  • the sheet resistance is increased only by about 1 - 2 Ohm / sq.
  • TMAH tetramethylammonium hydroxide
  • surfactants acetic acid
  • complexing agents fluoride and peroxide
  • the emitter can be strongly etched back, i. the increase of the emitter layer resistance is, for example, 20 ohms / sq and more at short contact time and low temperature, for example 60 s to 15 ° C.
  • the etch rate of this solution is too high for a controlled moderate etch back of a flat emitter.
  • the remaining surface doping would be too low to form a low resistance contact with screen printed silver paste.
  • This solution can be used to make a selective emitter. In this type of emitter, portions under the metal contacts have a low sheet resistance and a high surface concentration of the dopant and a high sheet resistance between the metal contacts.
  • emitter etchback As a further possibility of emitter etchback, a repeated sequence of chemical oxidation, for example with nitric acid, and removal of the silicon oxide formed in dilute hydrofluoric acid is described.
  • the etchback of the emitter in this way is very slow and requires multiple process solutions.
  • the disadvantage of the available alkaline solutions for emitter etch back is too low an etch rate. For a favorable, uniform and moderate etching back of the emitter and increasing the sheet resistance in the range between 5 and 15 ohms / sq long contact times and high temperatures are necessary.
  • Typical alkaline emitter etch solutions are based on ammonia or ammonia derivatives and hydrogen peroxide.
  • SCI solution of RCA purification developed for semiconductor production
  • the alkyl and hydroxyalkyl derivatives of ammonia have the advantage of a lower vapor pressure and thus a lower emission problem compared to ammonia.
  • Other components such as complexing agents, surfactants and stabilizers can also be used (see, for example, WO-A-2006/039090).
  • EP-A-1 843 389 discloses a sequence of repeated chemical oxidation followed by dilute HF to remove the silica to remove the uppermost highly doped emitter layers.
  • chemical oxidation are indicated: ozone, ozone / H 2 0, 0 3 / H 2 0 / HF, H 2 0 2 , HN0 3 , H 2 S0 4 , NH 4 OH at a temperature between 20 ° C to 90 ° C.
  • This method is intended to offer the advantage of better controllability of the generated emitter profile / phosphorus surface concentration against oxidation during diffusion. Due to the chemical oxidation under the specified conditions, however, only an approximately 1 nm thick oxide layer is produced.
  • EP-A-EP 0 731 495 describes aqueous HF solutions with ozone (and surfactant for improving ozone solubility) or hydrogen peroxide as cleaning solutions for semiconductors in the context of a modified RCA purification sequence.
  • WO-A-2009/013307 discloses the production of a selective emitter via the back-etching of an emitter diffused by conventional methods in regions between the metal contacts. The areas below the metal contacts are protected by a previously applied etch barrier. For the etching back, a mixture of nitric and hydrofluoric acid is used in the first step for the controlled production of a porous silicon layer. The etch progress is readily apparent as the porous silicon appears in different colors depending on the layer thickness. In the second step, the porous silicon is oxidized wet-chemically. As the oxidizing agent HN0 3 and H 2 SO 4 are given. Subsequently, the removal of the S1O 2 in dilute HF.
  • a disadvantage of the mixed acid used is that the formation of a homogeneous porous Si layer is technically difficult to control, so that, as a result of inhomogeneous etchbacks, there is a strong scattering of the emitter layer resistance values over the wafer surface.
  • the present invention has for its object to provide a method of the type mentioned in such a way that the disadvantages of the prior art are avoided.
  • a homogeneous etching back of the surface area of the emitter should be made possible.
  • process times and parameters are to be used which do not lead to a negative influence on the production process of a solar cell in a process line.
  • Dodants such as phosphorus surface concentrations should also be precisely adjusted.
  • the blue sensitivity in solar cells should be improved.
  • the invention essentially provides that an oxidant onsffenschreib alkaline etching solution is used with at least one organic moderator for isotropic etching back of the emitter in its surface region having a dodant concentration of at least 10 18 atoms / cm 3 , in particular of at least 10 19 atoms / cm 3 .
  • the etching solution used is one in which the alkaline component is in the concentration range between 1 g / L (0.1 wt%) to 50 g / L (5 wt%).
  • the concentration range of the alkaline component is between 2 g / L (0.2 wt%) and 15 g / L (1.5 wt%).
  • etching solution one should be used whose organic moderator in the concentration range between 0.1 g / L (0.01 wt%) to 5 g / L (0.5 wt%), in particular in the range between 0.2 g / L (0.02 wt%) and 1 g / L (0.1 wt%). Furthermore, it is provided in particular that the contact time between etching solution and the surface area between 10 sec and 80 sec, preferably between 15 sec and 60 sec, the temperature of the etching solution preferably in the range between 35 ° C and 65 ° C, in particular between 45 ° C and 60 ° C.
  • the surface area of the emitter having surface homogeneous doping is isotropically etched back with at least a dodant concentration of more than 10 18 atoms / cm 3 , whereby the topography of the previously textured surface is retained.
  • a consistent thick surface layer of the emitter is thus removed. It is provided in particular that is removed by the choice of the contact time and the temperature and the concentration ranges of the alkaline component and the organic moderator less than 10 nm, in particular between 3 nm and 7 nm, preferably in the range of about 5 nm.
  • the teaching of the invention avoids anisotropic etching without changing the topography of the surface, so that even fragile structures protruding from the surface are retained.
  • a method for a microscopically homogeneous, wet-chemical isotropic deep etching of a near-surface highly doped emitter zone is achieved while retaining the topography details of the surface with a dodant surface.
  • DE-A-10 2007 058 829 discloses a texturing and cleaning medium for surface treatment of wafers.
  • Anisotropic etching is proposed to produce surface roughness to minimize light reflections.
  • the alkaline solutions used are only suitable for texturing monocrystalline silicon, resulting in pyramids.
  • Suitable etching media are KOH, NaOH, THAH or other inorganic etching media.
  • Aliphatic and aromatic carboxylic acids, aminocarboxylic acids, polyalcohols, EDTA, polyethylene sorbitan monolaurate, catechol alkyl-substituted are provided as additives.
  • the concentration of the etching medium is between 4 and 15 wt% and that of the additives between 1 and 20 wt%.
  • the contact times are 10 to 30 minutes at a temperature of more than 80 ° C provided.
  • the etched silicon layer is in the range between 5 and 10 ⁇ .
  • the subject of DE-A-10 2008 052 660 is a method for producing a solar cell with a two-stage doping. It is intended to produce a selective emitter with the aid of an inorganic mask.
  • the mask is prepared by applying a paste containing Si0 2 glass, followed by melting. For re-etching HF-HNO 3 is used. The mask is partially or completely etched away with it. To remove the porous silicon formed by the etching, an alkaline etching solution is used. The function of the alkaline etching solution is based on the selective etching of the porous silicon layer, which is previously built up in an upstream acidic etching step. With the related measures, an isotropic re-etching in the range of 5 nm is unmanageable.
  • Anisotropic etching by means of z. B. KOH with isopropanol to produce a three-dimensional structure is described in GB-A-2,209,245. In this case, higher-doped regions are selectively removed.
  • a multi-stage process for the generation of lateral etching steps in the surface is described by creating a highly boron-doped surface resistant to the anisotropically acting etching medium.
  • a 40 nm thick substrate is thinned to 10 nm according to US-A-2004/0259324.
  • the etching medium used is an alkaline etching medium which contains quaternary ammonium hydroxides, substituted amines, in particular TMAH, at a concentration of between 10 wt% and 45 wt%.
  • the etching rate at 25 ° C amounts to 7.5 nm / min.
  • Possible further additives in the etching solution are anionic, cationic and neutral surfactants, oxidizing agents in the form of peroxide or persulfate or, alternatively, reducing agents. It is also possible to use acids such as silica for the pH change.
  • the described method is directed specifically to a substantial thinness of the existing substrate made of silicon, wherein etching etch depths are to be achieved which, due to the etch rate alone, do not lead to a re-etching depth that can be reproducibly set for highly doped emitters.
  • Etching solutions for undoped silicon, highly doped silicon and silicon nitride are known from US-A-2005/0065050. It is intended by the etching solution as high as possible ⁇ tzselektdite, i. different etching rates for the corresponding substrates can be achieved.
  • Possible additives have the properties water-soluble, non-volatile, non-flammable, ethylene glycol being preferably stated.
  • the etching method is aimed at the expression of a high selectivity of the etching rate of different dopant concentrations in the silicon or at interfaces to adjacent layers such as SiN or SiOx.
  • the etching solution consists of a strong base such as TMAH, NaOH or KOH, an etch moderator, oxidizers such as persulfates and wetting agents.
  • the contact time between the etching solution and the polysilicon thin film to be planarized is between 0.5 minutes and 10 minutes at a temperature between 40.degree. C. and 80.degree.
  • Etchings are to be etched in the order of between 80 nm and 100 nm.
  • Corresponding etching solutions are not suitable to use controllably highly doped surface regions of an emitter, in particular at a re-etching depth of ⁇ 5 nm.
  • etching medium are KOH, NaOH TMAH in the concentration range of about 8 wt%.
  • aromatic alcohols and ethers, also substituted, novolacs, polyvinyl alcohol As additives it is also possible to use aromatic alcohols and ethers, also substituted, novolacs, polyvinyl alcohol. The etch rate ranges from a few nanometers to a few micrometers per minute, with a temperature range between 45 ° C and 104 ° C being selected.
  • Suitable etching media are hydroxides, alkanolamines.
  • concentration range when using KOH is given as an example with 6 wt%.
  • Suitable additives are alkoxylated glycols or glycol alkyl ethers such as triethylene glycol, diethylene glycol monomethyl ether.
  • chlorides and silicates are provided.
  • the ⁇ tzabtrag amounts to 10 ⁇ at temperatures between 80 ° C and 100 ° C.
  • the mixtures described are used for the anisotropic texturing of a Si surface.
  • the invention relates to an alkaline etching solution with at least one organic ⁇ tzmoderator.
  • This solution allows for optimal etchback of the emitter within short contact times since the etch rate for silicon is higher than that of alkaline solutions containing hydrogen peroxide as etch moderating component.
  • Another advantage of the solution according to the invention is that porous silicon, which can arise in previous process steps, is removed.
  • organic moderators surface-active substances (surfactants) can be used, which inhibit the etching attack of the liquor. Since surfactant molecules contain a hydrophobic and a hydrophilic group, both H-terminated (hydrophobic) and oxidized (hydrophilic) substrate surfaces are protected.
  • the advantage of the organic moderators over hydrogen peroxide is that the silicon surface is not completely “blocked.” Moderate and even silicon dissolution is still possible Hydrogen peroxide oxidizes the silicon surface, and the etch rate of silica in an alkaline solution is extremely low Even at very low concentrations, above 0.1% by weight, lower concentrations do not interfere and may also be present in the etching solutions according to the invention.
  • the solution according to the invention contains an alkaline component and at least one organic etching moderator.
  • complexing agents and buffer substances can be used as further constituents.
  • alkaline component at least one of LiOH, NaOH, KOH, ammonium hydroxide, quaternary ammonium hydroxides, organic bases and organic amines is used.
  • Quaternary ammonium hydroxides include tetraalkylammonium hydroxides and substituted tetraalkylammonium hydroxides with hydroxy- and alkoxy-substituted alkyl radicals, for example tetraalkylammonium hydroxide, trimethyl-2-hydroxyethylammonium hydroxide (choline), triethyl- (ethoxypropyl) ammonium hydroxide.
  • Organic bases examples include pyrimidine and guanidine.
  • Organic amines include alkylamines, polyalkyleneamines, alkanolamines, cyclic N-substituted amines and derivatives with substituted alkyl radicals.
  • alkylamines are mono-, di-, triethylamine, dodecyldimethylamine, for polyalkyleneamines diethylenetriamine, for alkanolamines mono-, di-, triethanolamine, 2- (2-aminoethoxy) ethanol.
  • cyclic N-substituted amines are such as N-methylpyrrolidine, N-methylpiperidine and N-ethylpyrrolidone.
  • anionic surfactants such as alkyl sulphates and their salts, alkylcarboxylic acids and their salts, alkyl and alkylbenzene sulphonic acids and their salts, orthophosphates mono- and diesters, fluorinated carboxylic acids, fluorinated sulphonic acids,
  • nonionic surfactants such as polyalkylene glycol ethers (for example fatty alcohol ethoxylates, fatty alcohol propoxylates), alkyl polyglucosides, sucrose esters, sorbitan fatty acid esters, N-methylglucamides, alkylphenol ethoxylates or alkylphenol propoxylates, alkanolamides, alkynediols, substituted alkynols, ethoxylated alkynediols, fluorinated alkylalkoxylates,
  • polyalkylene glycol ethers for example fatty alcohol ethoxylates, fatty alcohol propoxylates
  • alkyl polyglucosides sucrose esters
  • sorbitan fatty acid esters N-methylglucamides
  • alkylphenol ethoxylates or alkylphenol propoxylates alkanolamides
  • alkynediols substituted alkynols
  • amphoteric surfactants such as alkylbetaines, amidoalkylbetaines, alkylsulfobetaines, amidoalkylsulfobetaines, alkylamioxides, alkylamidoalkylamine oxides, fluorinated amphoteric alkyl compounds,
  • cationic surfactants such as amine ethoxylates, dialkyldimethylammonium salts, alkylbenzyldimethylammonium salts.
  • anionic surfactants are: sodium dodecyl hydrogen sulfate, sulfosuccinic acid diester, sodium dodecyl benzene sulfonate, ammonium lauryl sulfate, 2-ethyl hexanol phosphoric acid ester, perfluorooctane sulfonate.
  • nonionic surfactants are: tetraethylene glycol octyl ether, lauryl myristyl polyglycol ether, octyl phenol ethoxylates, sodium acearostearic acid ester,
  • amphoteric surfactants are: cocoamidopropylbetaine, dodecyldimethylamine oxide, octyliminodipropionate, N-dodecyl-N, N-dimethylammoniumpropanesulfonate.
  • cationic surfactants are: oleylbis (2-hydroxyethyl) methylammonium chloride, dioctyldimethylammonium chloride, cocobenzyldimethylammonium chloride.
  • the emitter etch solution may also contain:
  • Complexing agent for silicic acid (reaction product), such as. O-dihydroxybenzene and other hydroxyphenols, as well as aromatic ethers, chelating agents for metal cations: amines such as EDTA, DTPA, di- and tricarboxylic acids, hydroxycarboxylic acids (eg citric acid, tartaric acid), polyalcohols e.g. Glycerin, sorbitol and other sugars and sugar alcohols, phosphonic acids and polyphosphates,
  • reaction product such as. O-dihydroxybenzene and other hydroxyphenols, as well as aromatic ethers, chelating agents for metal cations: amines such as EDTA, DTPA, di- and tricarboxylic acids, hydroxycarboxylic acids (eg citric acid, tartaric acid), polyalcohols e.g. Glycerin, sorbitol and other sugars and sugar alcohols, phosphonic acids and polyphosphates,
  • Buffer substances such as ammonium acetate, potassium hydrogen phthalate
  • Peroxides such as hydrogen peroxide in very low concentrations ( ⁇ 0.1 wt.% (Wt%)).
  • the invention is characterized by the use of one of the above-described etching solutions for etching back the emitter, wherein after etching back of the emitter on the surface of the crystalline solar cell at least selectively a metal layer by chemical or galvanic deposition of a nickel / silver or nickel / copper Layer or applied by physical vapor deposition.
  • a metal layer by chemical or galvanic deposition of a nickel / silver or nickel / copper Layer or applied by physical vapor deposition.
  • vapor deposition in particular a titanium / palladium / S layer is applied.
  • Field of application of the invention is the production of solar cells made of silicon. Therefore, the invention is also characterized by a solar cell whose emitter is etched back with measures which have been explained above.
  • the etching effect of a hydrogen peroxide-containing alkaline solution on the emitter of a solar cell was compared with the etching effect of a surfactant-containing solution.
  • the hydrogen peroxide-containing solution contained 1 to 6 weight percent sodium hydroxide solution and about 2 weight percent hydrogen peroxide.
  • the temperature was in the range of 49 ° C to 55 ° C.
  • the surfactant-containing solution contained 1.2 percent by weight of NaOH and 0.1 percent by weight of sodium dodecylbenzenesulfonate.
  • the temperature of the solution was constantly 53 ° C.
  • Multicrystalline wafers after diffusion and after chemical edge isolation including dissolution of phosphorus silicate glass in dilute hydrofluoric acid were etched in the alkaline solutions.
  • the contact cells and the resulting increase in emitter layer resistance are summarized in Tables 1 and 2.
  • Multicrystalline wafers after diffusion were etched after chemical edge isolation including dissolution of phosphosilicate glass in dilute hydrofluoric acid in a hydrogen peroxide-containing or surfactant-containing solution.
  • the wafers were then coated with a silicon nitride antireflection coating in standard production processes and metallized by screen printing.
  • the electrical values of the cells as well as the emitter layer resistance directly in front of a nitride coating are shown in Table 3.
  • etching effect of the inventive solution from Examples 1 and 2 was compared with the etching effect of a cleaning solution consisting of 1 weight percent tetramethyl ammonium hydroxide (TM AH) and 1 weight percent hydrogen peroxide.
  • TM AH tetramethyl ammonium hydroxide
  • Multicrystalline wafers were used after diffusion and chemical edge isolation including dissolution of phosphosilicate glass in dilute hydrofluoric acid. After treatment in the emitter etch solutions, further standard production processes were carried out.
  • Multicrystalline wafers after diffusion with an emitter layer resistance of 48 ohms / sq were first applied in dilute hydrofluoric acid for 2 Treated, rinsed and then etched for 2 minutes at 50 ° C in a solution of the following composition:
  • 1,2-dihydroxybenzene (catechol), 0.1% w.
  • the measured sheet resistance after treatment in the etching solution averaged 53 ohms / sq.
  • Tetramethylammonium hydroxide 1 w%
  • Diethylenetriaminepentaacetic acid 0.05% by weight.
  • the sheet resistance was on average 56 ohms / sq.

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Abstract

L'invention concerne un procédé de gravure par voie humide d'une couche de silicium dans une solution de gravure alcaline, la couche de silicium étant une zone superficielle d'un émetteur de cellule solaire. Afin de réaliser une gravure en retrait homogène de la zone superficielle de l'émetteur, on utilise une solution de gravure alcaline sans agent oxydant avec au moins un ralentisseur organique pour la gravure en retrait isotrope de l'émetteur sur sa zone superficielle, l'émetteur présentant une concentration de dopant d'au moins 1018 atomes/cm3.
EP11754360.3A 2010-09-03 2011-09-02 Procédé de gravure par voie humide d'une couche de semiconducteur à dopage élevé Withdrawn EP2612362A2 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE102010037311 2010-09-03
DE102011050903A DE102011050903A1 (de) 2010-09-03 2011-06-07 Verfahren zum nasschemischen Ätzen einer hochdotierten Halbleitrschicht
PCT/EP2011/065222 WO2012028723A2 (fr) 2010-09-03 2011-09-02 Procédé de gravure par voie humide d'une couche de semiconducteur à dopage élevé

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EP2612362A2 true EP2612362A2 (fr) 2013-07-10

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EP11760429.8A Withdrawn EP2612365A2 (fr) 2010-09-03 2011-09-02 Procédé de gravure en retrait par voie humide d'un émetteur de cellule solaire
EP11754360.3A Withdrawn EP2612362A2 (fr) 2010-09-03 2011-09-02 Procédé de gravure par voie humide d'une couche de semiconducteur à dopage élevé

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EP11760429.8A Withdrawn EP2612365A2 (fr) 2010-09-03 2011-09-02 Procédé de gravure en retrait par voie humide d'un émetteur de cellule solaire

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US (2) US20130228220A1 (fr)
EP (2) EP2612365A2 (fr)
JP (1) JP2013536992A (fr)
KR (1) KR20140014065A (fr)
CN (2) CN103403875B (fr)
DE (2) DE102011050136A1 (fr)
WO (2) WO2012028728A2 (fr)

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CN103403875B (zh) 2017-07-25
WO2012028728A2 (fr) 2012-03-08
WO2012028728A3 (fr) 2012-10-11
WO2012028723A2 (fr) 2012-03-08
DE102011050903A8 (de) 2012-05-16
CN103403875A (zh) 2013-11-20
US20130255772A1 (en) 2013-10-03
DE102011050903A1 (de) 2012-03-08
US9583652B2 (en) 2017-02-28
US20130228220A1 (en) 2013-09-05
JP2013536992A (ja) 2013-09-26
WO2012028723A3 (fr) 2012-10-18
DE102011050136A1 (de) 2012-03-08
KR20140014065A (ko) 2014-02-05
CN103314448A (zh) 2013-09-18
EP2612365A2 (fr) 2013-07-10

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