KR20110117155A - Method and device for simultaneous micro structuring and passivation - Google Patents

Method and device for simultaneous micro structuring and passivation Download PDF

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Publication number
KR20110117155A
KR20110117155A KR1020117018922A KR20117018922A KR20110117155A KR 20110117155 A KR20110117155 A KR 20110117155A KR 1020117018922 A KR1020117018922 A KR 1020117018922A KR 20117018922 A KR20117018922 A KR 20117018922A KR 20110117155 A KR20110117155 A KR 20110117155A
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South Korea
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solid body
passivation
silicon
same time
microstructuring
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KR1020117018922A
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Korean (ko)
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쿠노 메이어
다니엘 크레이
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프라운호퍼 게젤샤프트 쭈르 푀르데룽 데어 안겐반텐 포르슝 에. 베.
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Publication of KR20110117155A publication Critical patent/KR20110117155A/en

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/02—Details
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    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K26/00—Working by laser beam, e.g. welding, cutting or boring
    • B23K26/0006—Working by laser beam, e.g. welding, cutting or boring taking account of the properties of the material involved
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    • B23K26/00—Working by laser beam, e.g. welding, cutting or boring
    • B23K26/02—Positioning or observing the workpiece, e.g. with respect to the point of impact; Aligning, aiming or focusing the laser beam
    • B23K26/06—Shaping the laser beam, e.g. by masks or multi-focusing
    • B23K26/062—Shaping the laser beam, e.g. by masks or multi-focusing by direct control of the laser beam
    • B23K26/0622—Shaping the laser beam, e.g. by masks or multi-focusing by direct control of the laser beam by shaping pulses
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    • B23K26/00—Working by laser beam, e.g. welding, cutting or boring
    • B23K26/14—Working by laser beam, e.g. welding, cutting or boring using a fluid stream, e.g. a jet of gas, in conjunction with the laser beam; Nozzles therefor
    • B23K26/144—Working by laser beam, e.g. welding, cutting or boring using a fluid stream, e.g. a jet of gas, in conjunction with the laser beam; Nozzles therefor the fluid stream containing particles, e.g. powder
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    • B23K26/00—Working by laser beam, e.g. welding, cutting or boring
    • B23K26/14—Working by laser beam, e.g. welding, cutting or boring using a fluid stream, e.g. a jet of gas, in conjunction with the laser beam; Nozzles therefor
    • B23K26/146—Working by laser beam, e.g. welding, cutting or boring using a fluid stream, e.g. a jet of gas, in conjunction with the laser beam; Nozzles therefor the fluid stream containing a liquid
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    • B23K26/00—Working by laser beam, e.g. welding, cutting or boring
    • B23K26/352—Working by laser beam, e.g. welding, cutting or boring for surface treatment
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    • B23K26/00—Working by laser beam, e.g. welding, cutting or boring
    • B23K26/352—Working by laser beam, e.g. welding, cutting or boring for surface treatment
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    • B23K26/00—Working by laser beam, e.g. welding, cutting or boring
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    • C03—GLASS; MINERAL OR SLAG WOOL
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    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
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    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
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    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
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    • C03C23/00—Other surface treatment of glass not in the form of fibres or filaments
    • C03C23/0005—Other surface treatment of glass not in the form of fibres or filaments by irradiation
    • C03C23/0025—Other surface treatment of glass not in the form of fibres or filaments by irradiation by a laser beam
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    • 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
    • H01L31/0216—Coatings
    • H01L31/02161—Coatings for devices characterised by at least one potential jump barrier or surface barrier
    • H01L31/02167—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells
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    • H01L31/02—Details
    • H01L31/0216—Coatings
    • H01L31/02161—Coatings for devices characterised by at least one potential jump barrier or surface barrier
    • H01L31/02167—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells
    • H01L31/02168—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells the coatings being antireflective or having enhancing optical properties for the 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
    • H01L31/02—Details
    • H01L31/0236—Special surface textures
    • H01L31/02363—Special surface textures of the semiconductor body itself, e.g. textured active layers
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    • B23K2101/36—Electric or electronic devices
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    • C03C2217/00—Coatings on glass
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Abstract

The present invention relates to a method for simultaneous microstructuring and passivation of a silicon-comprising solid body by a liquid jet-guided laser procedure. While the precursor for passivation of the solid body surface is included in the liquid jet, the solid body surface is locally heated by the laser beam. The invention likewise relates to an apparatus for simultaneous microstructuring and passivation. The method is particularly used for the production of solar cells.

Description

METHOD AND DEVICE FOR SIMULTANEOUS MICRO STRUCTURING AND PASSIVATION}

The present invention relates to a method for simultaneous microstructuring and passivation of a silicon-comprising solid body by a liquid jet-guided laser procedure. While the liquid jet includes a precursor for passivation of the solid body surface, the solid body surface is locally heated by the laser beam. The invention likewise relates to an apparatus for simultaneous microstructuring and passivation. The method is especially used for the production of solar cells.

Microstructuring of solid bodies is known in the art, in which a current laser process or an etching process is known together with a liquid jet-guided laser or the like. Thereafter, passivation of the previously structured surface takes place in a further step. For example, this can be brought about through PECVD deposition or thermal oxidation of SiNx in a furnace. In general, however, the preceding cleaning step is required here. As a result, the entire wafer must be processed and all elements already present on the wafer must be compatible with processing conditions such as temperature. As a result, after metallisation, no further oxidation can occur in the furnace.

It is an object of the present invention to eliminate the disadvantages known in the prior art and to provide a method for structuring and passivation, which allows for more efficient and more flexible process control.

This object is achieved by a method having the features of claim 1 and an apparatus having the features of claim 14. The other dependent claims reveal advantageous improvements.

According to the present invention, there is provided a method for microstructuring and passivation of a solid body comprising silicon at the same time, comprising a liquid comprising at least one precursor towards the solid body surface and for passivation of the solid body surface. A liquid jet is guided over the area of the solid body to be structured, the laser beam is combined with a liquid jet, so that the solid body surface is partially heated by the laser beam and consequently structured in at least the area. And as a result of the structuring the free surface bonds formed by the precursor are saturated and a passivation layer is formed in the structured region of the solid body surface.

The method according to the invention is based on a liquid jet combined with a laser beam, the laser beam being guided in a liquid jet, preferably having a diameter of ≦ 100 μm. The laser beam likewise hits the impact point of the liquid jet on the solid body surface and locally heats the solid body. In this way, the temperature required for melting in this region of the solid body surface and possible evaporation of the solid body are produced. When the carrier liquid of the liquid jet impinges on the molten solid body, after the carrier liquid is pyrolyzed and cooled, the component saturates the surface bonds of the solid body and also the closed layer ( closed layer).

As a result of the method according to the invention, short-pulsed laser radiation, preferably with a pulse of <15 μs, can be used to quickly resolidify the surface melt and thereby liquid-jet Since the melt can be avoided by the jet, crystal damage to the solid body during local microstructuring can be avoided.

In particular, if the carrier liquid essentially contains the chemical element hydrogen, oxygen, nitrogen or carbon, thermal decomposition of the element at the hot body surface can be used to saturate the free surface bonds and epitaxially grow the passivation layer. Can be.

Basically, a passivation layer formed of SiN x , SiO x or SiC x can be produced.

In order to produce the SiNx passivation layer, the precursor is preferably an ammonium salt, in particular ammonium nitrite, ammonium nitrate, ammonium hydroxide or ammonium chloride, nitrous alkali salts of organic acids, organic solvents or water-soluble solvents, in particular N 2 O of water, and mixtures thereof.

In order to produce a passivation layer forming the SiOx passivation layer, the precursor is preferably water, an inorganic acid, in particular nitric acid, hydrochloric acid, permonosulphuric acid, and also dilution thereof. Form, also selected from the group consisting of organic acids, in particular peracetic acid, trichloroacetic acid, formic acid, BHF with oxidant and mixtures thereof.

To produce a SiCx passivation layer, the precursor is preferably selected from the group consisting of formic acid, glycol, glycerin, polyethylene glycol and mixtures thereof.

Preferably, the substrate is selected from the group consisting of silicon, glass, silicon-comprising ceramics and their composite systems.

In addition, the liquid jet may preferably further have a cleaning media, such as hydrochloric acid, for cleaning additives, for example structured areas. This allows for an additional cleaning step in the process according to the invention without interrupting the process.

Preferably, a possible laminar liquid jet is used to carry out the method. The laser beam is then guided in a particularly effective way by total reflection in the liquid jet so that the liquid jet achieves its function as a light guide. The connection of the laser beam can be brought about through a window or the like of the nozzle unit, the window having a direction perpendicular to the jet direction of the liquid jet. Thereby the window can also be formed as a lens for focusing the laser beam. Alternatively or additionally, a lens, also independent of the window, may be used to focus or form the laser beam. Thereby the nozzle unit can be formed in a particularly simple embodiment of the invention so that the liquid can be supplied from one side or several sides in the radial direction with respect to the jet direction.

Useful types of lasers include:

Various solid lasers, in particular commercially used Nd-YAG lasers with wavelengths 1064 nm, 532 nm, 355 nm, 266 nm, and 213 nm wavelengths, diode lasers with <1000 nm wavelength, 514-458 nm Argon-ion laser and Excimer laser of wavelength (wavelength: 157-351 nm).

Since the energy induced by the laser in the surface layer is more and more concentrated on the surface, the quality of microstructuring tends to increase as the wavelength decreases, which decreases in the heat influence zone, and In this regard, there is a tendency to reduce the crystalline damage of the material, first of all in phosphorus-doped silicon, which is phosphorus under the passivation layer.

In this context, blue lasers and lasers in the near UV range (eg 355 nm) with pulse lengths in the femtosecond or nanosecond range prove to be particularly effective. In particular, with shortwave laser light, there is an option to directly generate electron-hole pairs of silicon that can be used in an electrochemical process during nickel deposition (photochemical activation). . Thus, in addition to the redox process of nickel ions with phosphorous acid described above, free electrons of silicon, for example generated by laser light, can contribute to the reduction of nickel directly on the surface. The generation of this electron-hole can be maintained permanently by permanent illumination of the sample at defined wavelengths (especially in near ultraviolet light with λ ≦ 355 nm) during the structuring process and The metal nucleus forming process may then be facilitated.

For this purpose, solar cell properties can be used to separate excess charge carriers through p-n junctions and to negatively charge the n-conducting surface.

Preferably, the diameter of the liquid jet is at most 500 μm, in particular at most 100 μm.

Following the passivation caused by the liquid jet, it is desirable to sinter the passivated area of the solid body surface. In particular, sintering while forming a gas is used for this purpose.

The method according to the invention is suitable here for the structuring of silicon solar cells, in particular for edge isolation of solar cells. First, the surface may be locally melted or removed by a laser beam contained in a liquid jet acting on the surface. Thereafter, a thin passivation layer can be created on the surface using a suitable carrier liquid in a liquid jet. By this passivation layer, the recombination activity is reduced on the one hand and the insulating layer is applied on the other hand. The latter may be advantageous, for example, in the case of cells in the case of back contacting cells or in the subsequent metallization step in the processing chain.

The apparatus implementing the method of the described type is configured to comprise a nozzle unit having a window for connecting a laser beam, a liquid supply and a nozzle opening, the nozzle unit being controlled, preferably automated, of the nozzle unit over the surface layer to be structured. It is held by a guide device for guidance. In addition, the device typically also includes a laser light source having a light exit surface disposed corresponding to the window and provided by one end of the light guide. Alternatively or in addition, the apparatus for carrying out the method according to the invention may comprise a nozzle for producing a liquid jet and a laser light source, the nozzle and the laser light source each being by one guide device or It is held by a general guide device for guiding the nozzle and the laser light source is kept in the same area of the surface layer to be structured.

The method according to the invention is not limited to the particular embodiments described herein and will be described in more detail with reference to the following examples.

Example 1

For the front-side severing of the emitter and for the continuous deposition of the thin SiN x passivation layer, an aqueous solution of ammonium nitrite with a concentration of 3 mol / l is used as the carrier liquid.

As the laser light source, an Nd: YAG laser having a wavelength of 1064 nm and a beam power of 76 watts is used. The rate of movement of the substrate relative to the liquid jet is 100 mm / s. The diameter of the jet is 80 μm.

Example 2

A second embodiment for front-side severing of the emitter and subsequent deposition of the SiNx thin film layer provides perfluorodecaline as a solvent for the nitrogen source. Nitrous oxide (Naughing gas) dissolved in the liquid at a concentration of 0.1 mol / l (N 2 0) serves as a nitrogen source. An Nd: YAG laser with a wavelength of 1064 nm and a beam power of 76 watts serves as a laser light source. The rate of movement of the substrate relative to the liquid jet is 200 mm / s. The jet diameter is 80 μm.

Example 3

In one embodiment for front-side severing of the emitter and subsequent deposition of the SiO x thin film layer, a dilute aqueous solution formed of hydrochloric acid and hydrogen peroxide (H 2 O 2 ) is provided as a jet medium. The concentration of hydrochloric acid is 0.01 mol / l, and the concentration of hydrogen peroxide is 0.1 mol / l.

A frequency-doubled Nd: YAG laser with a wavelength of 532 nm and beam power of 11 watts serves as a laser light source. The rate of movement of the substrate relative to the liquid jet is 100 mm / s. The jet diameter is 60 μm.

Claims (16)

At the same time a method for microstructuring and passivation of a silicon-comprising solid body,
A liquid jet directed towards the surface of the solid body and comprising at least one precursor for passivation of the solid body surface, over an area of the solid body to be structured,
A laser beam is coupled with the liquid jet, such that the solid body surface is locally heated by the laser beam and consequently structured in at least a region and by the precursor as a result of the structuring A method for microstructuring and passivation of a silicon-comprising solid body while at the same time a free surface bond formed is saturated and a passivation layer is formed in the structured region of the solid body surface. The method of claim 1,
The precursor is
Ammonium salts, in particular ammonium nitrite, ammonium nitrate, ammonium hydroxide or ammonium chloride,
-Alkali salts of nitrous acid,
Organic or water-soluble solvents, in particular N 2 O dissolved in water, and mixtures thereof
Is selected from a group consisting of
As a result a SiNx passivation layer is formed on the solid body surface while at the same time microstructure and passivation of a silicon-comprising solid body. The method according to claim 1 or 2,
The precursor is
-water,
Inorganic acids, in particular nitric acid, hydrochloric acid, permonosulphuric acid, also in diluted form thereof,
Organic acids, in particular peracetic acid, trichloroacetic acid, or formic acid,
BHF with oxidant and mixtures thereof
Is selected from a group consisting of
As a result a SiOx passivation layer is formed on the solid body surface while at the same time microstructure and passivation of a silicon-comprising solid body. 4. The method according to any one of claims 1 to 3,
The precursor is selected from the group consisting of formic acid, glycol, glycerin, polyethylene glycol and mixtures thereof, while at the same time microstructuring the silicon-containing solid body. And a method for passivation. The method according to any one of claims 1 to 4,
Wherein said substrate is selected from the group consisting of silicon, glass, silicon-comprising ceramics and composite systems thereof, while at the same time microstructure and passivation of a silicon-comprising solid body. The method according to any one of claims 1 to 5,
The liquid jet comprises a cleaning agent for cleaning the structured area, in particular HCl, while at the same time a method for microstructuring and passivation of a silicon-containing solid body. The method according to any one of claims 1 to 6,
Wherein said liquid jet is a laminar, while at the same time microstructure and passivation of a silicon-comprising solid body. The method according to any one of claims 1 to 7,
And said laser beam is guided by total reflection in said liquid jet, while at the same time for microstructuring and passivation of a silicon-comprising solid body. The method according to any one of claims 1 to 8,
A method for microstructuring and passivation of a silicon-comprising solid body, characterized in that the diameter of the liquid jet is at most 500 μm, in particular at most 100 μm. The method according to any one of claims 1 to 9,
Said liquid being supplied in a radial direction in the jet direction, while at the same time for microstructuring and passivation of a silicon-comprising solid body. The method according to any one of claims 1 to 10,
The laser beam is adapted to be activated in a temporal and / or spatial pulse form, in particular in a flat-top form, an M-profile or a rectangular pulse. Methods for Microstructuring and Passivation. The method according to any one of claims 1 to 11,
And sintering the passivated region of the solid body surface, while at the same time microstructure and passivation of the silicon-comprising solid body. The method according to any one of claims 1 to 12,
The structuring is at the same time silicon-containing, characterized in that it is the edge isolation of silicon solar cells, in particular rear-side-contacted solar cells or subsequently metallised solar cells. Method for microstructuring and passivation of solid bodies. The apparatus according to any one of claims 1 to 13, comprising a nozzle unit having a window connected to the laser beam, a laser light source, a liquid supply for a liquid comprising at least one precursor, and a nozzle opening facing the surface of the solid body. Device running method. The method of claim 14,
And the nozzle unit and the laser light source are connected to a guide device for controlled guidance of the nozzle unit on the surface to be structured. The method of claim 14,
The nozzle unit and the laser light source are in a stationary state, and the solid body is connected to a guide device for controlled guidance of the solid body relative to the nozzle unit and the laser light source.
KR1020117018922A 2009-01-16 2009-12-29 Method and device for simultaneous micro structuring and passivation KR20110117155A (en)

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