WO2012175331A1 - Procédé d'usinage de substrats et dispositif correspondant - Google Patents

Procédé d'usinage de substrats et dispositif correspondant Download PDF

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Publication number
WO2012175331A1
WO2012175331A1 PCT/EP2012/060580 EP2012060580W WO2012175331A1 WO 2012175331 A1 WO2012175331 A1 WO 2012175331A1 EP 2012060580 W EP2012060580 W EP 2012060580W WO 2012175331 A1 WO2012175331 A1 WO 2012175331A1
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WO
WIPO (PCT)
Prior art keywords
substrate
injector
substrates
gases
precursor
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.)
Ceased
Application number
PCT/EP2012/060580
Other languages
German (de)
English (en)
Inventor
Christian Schmid
Dirk Habermann
Chuck Attema
Tom Stewart
Kenneth Provancha
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.)
Gebrueder Schmid GmbH and Co
Original Assignee
Gebrueder Schmid GmbH and Co
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Gebrueder Schmid GmbH and Co filed Critical Gebrueder Schmid GmbH and Co
Publication of WO2012175331A1 publication Critical patent/WO2012175331A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C23C16/45595—Atmospheric CVD gas inlets with no enclosed reaction chamber
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/40—Oxides
    • C23C16/403—Oxides of aluminium, magnesium or beryllium
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C23C16/45514—Mixing in close vicinity to the substrate

Definitions

  • the invention relates to a method for processing substrates, in particular of silicon wafers for solar cell production, and to an apparatus for carrying out this method.
  • EP 503 382 A1 it is known, by means of a multi-channel injector to bring various gases on a silicon substrate or bring it to this to treat the surface or edit.
  • the process is a so-called APCVD process, ie a CVD process, which can be carried out without vacuum under atmospheric pressure.
  • the invention is based on the object to provide an aforementioned method and an aforementioned device with which problems of the prior art can be avoided and in particular processed reliably and with very high throughput substrates or their surfaces can be treated.
  • an Al 2 O 3 passivation layer is applied to a named substrate by an APCVD process.
  • the precursor and the oxidizing agent are at least partially separated spatially or temporally from one another by nitrogen or another suitable separating gas.
  • a silicon wafer is advantageously used or processed and coated for solar cell production.
  • the gases, at least the precursor on the one hand and the oxidizing agent on the other hand are introduced separately from one another to the substrate. Only shortly before hitting the substrate or on its surface or even just at this impact, the two gases are mixed together.
  • this is done so that first the oxidizing agent impinges on the substrate or on its surface and immediately after the precursor is introduced or is applied, then also again the oxidizing agent and thus by the mixture on the surface of the passivation layer on the Substrate is formed.
  • the precursor and the oxidizing agent may mix at least partially with each other at the last moment prior to impinging on the substrate and then impinge on the substrate in this mixed state, at which time the mixing need not necessarily be complete or even.
  • the introduction by means of nitrogen, in particular as a kind of separation between precursor on the one hand and oxidizing agent on the other hand, has the purpose to prevent too early mixing of the two gases and thus a premature reaction, in particular special directly after the exit from the respective channels of an injector or the like, with which the gases are brought to the substrate.
  • each gas in the said injector, which is known per se from the aforementioned prior art in a similar form and which has a plurality of channels, it is advantageous for each gas to have its own channel with its own channel inlet and separate channel outlet. As a result, it is very easy to adjust both the amount of the respective gas to be led to the substrate and to determine the mixing ratio via parameters such as pressure or flow rate. In the process, these parameters can be varied correspondingly both on the one hand to the precursor and on the other hand in the case of the oxidizing agent and in the case of release agents, in particular in the form of nitrogen.
  • the separate bringing the gases by means of their own channels in the injector just serves to prevent the precursor undesirably comes prematurely together with oxygen either from the ambient air or from the oxidizing agent, resulting in precipitation of the aluminum content in powder form and thus to an obvious undesirable result including negative contamination of the substrates.
  • the channels of the injector should be relatively close to each other, at least at the channel exits, and this can also be changed by different geometry or design.
  • the gases are led to just before the substrate surface separated from each other, preferably up to a distance of less than 5mm.
  • the gases, in particular by means of the above-mentioned injector are guided to about 2 mm in front of the substrate surface or the injector reaches as far as the substrate surface.
  • the nitrogen and / or the aforementioned oxidizing agent are brought in larger quantity or with more channels with the injector to the substrate as the precursor.
  • this makes it possible to increase the separation effect between the precursor and the oxidant.
  • location or time of mixing of precursor and oxidant it is possible by a particularly strong addition of the oxidizing agent, in case of mixing only on impact of the gases on the substrate surface while still sufficient amount of oxidizing agent to introduce the precursor so that on the Substrate surface gives the desired passivation layer.
  • a low negative pressure This can be, for example, up to 0.8 bar.
  • another gas stream of nitrogen may be provided outside the gas stream of the oxidizing agent as a separation from the ambient air or the atmospheric oxygen. This makes it possible, inter alia, to keep atmospheric oxygen as far as possible from the precursor or from the impact and mixing area on the substrate, which can also be regarded as a mixing zone. This enables a well-defined reaction or separation and construction of the passivation layer.
  • the method can also be carried out under atmospheric pressure. Then, under certain circumstances, another gas stream of nitrogen outside the gas stream of the oxidizing agent may be provided as a separation from the ambient air or the atmospheric oxygen.
  • a process temperature may advantageously be in the usual range, preferably at 100 ° C to 400 ° C. Particularly advantageous may be a process temperature at 200 ° C to 300 ° C.
  • the substrates are preferably transported continuously during the coating. Thus, both a uniform coating is possible and ensures a high throughput of substrates to be coated.
  • the injector is advantageous fixed.
  • the substrates are preferably coated in an inline process or an entire system can be designed as an inline system, in particular also with regard to a transport of the substrates.
  • the substrates are transported along a horizontal path, in particular lying, advantageously on an aforementioned inline system.
  • the gas streams or the injector are aligned perpendicular to the transport path, which applies to the gas streams in particular with respect to their impact on the substrate.
  • the gases are brought from above to the substrates or the injector is arranged above the substrate. It can be provided that several injectors are provided one behind the other during the passage path of the substrates or a plurality of gas streams at least of the precursor are directed to the substrate or impinge on this. In this case, of course, that in turn surrounds each gas stream of precursor surrounded by a gas stream of nitrogen from the injector and impinging on the substrate for separation of the oxidant until just before hitting the substrate or directly to hitting the substrate, as before has been described.
  • a mixing zone is formed.
  • This mixing zone is advantageously limited at least in the direction away from the injector by the substrate or the surface, but may also extend 1 mm or 2 mm over the substrate surface.
  • the deposition of the precursor on the substrate or by the Al 2 O 3 reached passivation then takes place in this mixing zone or gas mixture region.
  • a channel in the injector or the gas guide is not a single substantially round channel, but has an extension transverse to the direction of passage of the substrates.
  • the channel exits may then have the form of slot nozzles or be slit-like with the corresponding slot width.
  • the oxidizing agent may be dissolved in the form of H 2 O in an atmosphere of nitrogen or O 2 .
  • Fig. 1 is a side view of an inventive device for carrying out the method with an injector with multiple channels and
  • Fig. 2 is a plan view of a device according to FIG. 1 for
  • Fig. 1 is shown for a device according to the invention, which has an injector 1 1, as it is known in the art per se from the basic principle.
  • the injector 11 has a main body 12 in which a plurality of channels 13a to 13e extend in the vertical direction.
  • the channels 13a to 13e have gas connections or fluid connections, which are not shown in more detail above, which are not shown here for the sake of simplicity, but are clear and understandable to a person skilled in the art.
  • a gas mixing zone 15 is formed for the gases emerging from the channels 13a to 13e at channel exits 14a to 14e. This will be explained in more detail below.
  • the injector 1 1 substrates 17 pass, which are to be processed, this being silicon wafer for solar cell production, which should be provided with an Al 2 0 3 passivation layer on a substrate top 18.
  • the substrates 17 run on a Roller conveyor 20 under the injector 1 1 and its channel outputs 14a to 14e and past the gas mixing zone 15.
  • the distance of the injector 1 1 or its underside or the channel exits 14a to 14e to the substrate upper side 18, which is indicated by d may advantageously be less than 5 mm. It is particularly advantageous about 2mm, so it is relatively low.
  • the injector 1 1 projects laterally beyond the substrates 17.
  • the channels 13a to 13e are formed as slots or as longitudinal slots at least with respect to the lower channel exits 14a to 14e shown in FIG. These longitudinal slots likewise project laterally beyond the substrates 17, so that it becomes clear that fumigation on the one hand and coating as a result on the other hand take place simultaneously and substantially uniformly over the entire width of the substrates 17. This also means that the gas mixing zone 15 extends over the full width of the substrates 17, which is also important for a uniformity of the passivation or coating with a passivation layer seen across the width of the substrates 17.
  • an Al-metalorganic precursor is introduced at the channel entrance for the channel 13c, preferably as so-called TMA or trimethyl aluminum.
  • TMA trimethyl aluminum
  • suitable precursors are trialkylaluminum, triethylaluminum and aluminum 2,4-pentaerytionates.
  • nitrogen is introduced as a kind of separating agent or as a separator and discharged at the corresponding channel exits 14b and 14d in the gas mixing zone 15th
  • an oxidizing agent in the form of H 2 0 is introduced at their channel entrances, which enters the gas mixing zone 15 at the respective channel exits 14a and 14e.
  • This H 2 O can be dissolved in an atmosphere of N 2 , alternatively in an atmosphere of 0 2 .
  • the preferred process temperature is about 200 ° C to 300 ° C.
  • the precursor thus hits the upper side of the substrate 18, so to speak in the middle region below the injector 11.
  • the precursor encounters oxidizing agent, which has already been applied by the movement of the substrate 17 shortly before and is still located on the substrate upper side 18.
  • a first contact or a first mixing of the precursor with the oxidizing agent takes place and thus a first incipient build-up of the passivation layer.
  • the precursor is protected to the left and to the right by the separator nitrogen during the bridging of the distance d from the direct contact with the oxidant flowing laterally therefrom, so that no oxidation of the precursor takes place quasi in the middle of the air. This would have the consequence that only white powder is precipitated from the precursor and no more desired reaction takes place on the substrate top 18.
  • the above-described mixing of the precursor with the oxidant present on the substrate 17 takes place on the substrate surface 18 and is therefore desirable.
  • the now secondarily applied gases swirl, as it were, and through the gas layer of the separator, the oxidizing agent can further oxidize the precursor on the substrate top side 18. This then results in the reaction on the substrate top side 18 and continues to build up the Al 2 O 3 passivation layer on the substrate top side 18.
  • the channel output 14c for the precursor that, for improved shielding, the channel outputs 14b and 14d of the separator are pulled even further to the side for better shielding of the precursor. Under certain circumstances, they may even be arcuately closed and thus in the plan view of FIG. 2, the middle channel output 14c actually fully enclose.
  • the substrates 17 are advantageously carried out continuously under the injector 11. In this case, their distance from each other can also be considerably less than shown, for example just so much that it is ensured that the opposite edges of the substrates 17 do not abut one another due to the risk of breakage.
  • the outflow of gases from the injector 1 1 can take place continuously, whereby it can also be achieved that, as it were, stable and balanced or leveled conditions prevail in the gas mixing zone 15 and optimum deposition of passivation layers on the substrate top side 18 can be achieved.
  • the method according to the invention is particularly preferably used for p-type and n-type crystalline solar cells.

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Vapour Deposition (AREA)

Abstract

L'invention concerne un procédé et un dispositif d'usinage de tranches de silicium pour la production de cellules solaires, selon lequel une couche de passivation Al2O3 est appliquée sur un substrat par un procédé APCVD. Cette application est effectuée dans une atmosphère gazeuse d'un précurseur organo-métallique d'aluminium, d'un agent oxydant contenant H2O, et de N2. Les gaz sont amenés séparément jusqu'au substrat et se mélangent seulement lorsqu'ils rencontrent le substrat ou juste avant, une première couche se formant par application sur le substrat de l'agent oxydant avant le précurseur puis une nouvelle fois juste après.
PCT/EP2012/060580 2011-06-20 2012-06-05 Procédé d'usinage de substrats et dispositif correspondant Ceased WO2012175331A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102011077833.0 2011-06-20
DE201110077833 DE102011077833A1 (de) 2011-06-20 2011-06-20 Verfahren zur Bearbeitung von Substraten und Vorrichtung dazu

Publications (1)

Publication Number Publication Date
WO2012175331A1 true WO2012175331A1 (fr) 2012-12-27

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DE (1) DE102011077833A1 (fr)
TW (1) TW201308489A (fr)
WO (1) WO2012175331A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN118480868A (zh) * 2024-07-12 2024-08-13 上海钧乾智造科技有限公司 一种用于电池片切面钝化镀膜的喷淋结构、装置及工作方法

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102011080202A1 (de) 2011-08-01 2013-02-07 Gebr. Schmid Gmbh Vorrichtung und Verfahren zur Herstellung von dünnen Schichten
CN107623052B (zh) * 2017-09-01 2023-12-05 常州比太科技有限公司 一种太阳能电池片钝化用Al2O3镀膜系统和方法

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0503382A1 (fr) 1991-03-13 1992-09-16 Watkins-Johnson Company Méthode et dispositif pour le dépôt de films très conducteur et transparent d'oxyde d'indium dopée au étain et fluor par APCVD
US5304398A (en) * 1993-06-03 1994-04-19 Watkins Johnson Company Chemical vapor deposition of silicon dioxide using hexamethyldisilazane
US5545436A (en) * 1993-11-12 1996-08-13 Sony Corporation CVD method and apparatus for making silicon oxide films
WO1999004059A1 (fr) * 1997-07-14 1999-01-28 Silicon Valley Group Thermal Systems, Llc Injecteur monobloc et chambre pour formation de depots
US5944900A (en) * 1997-02-13 1999-08-31 Watkins Johnson Company Protective gas shield for chemical vapor deposition apparatus
US20030226502A1 (en) * 2002-06-11 2003-12-11 Taiwan Semiconductor Manufacturing Co., Ltd. Chemical vapor deposition (CVD) method and calibration apparatus providing enhanced uniformity
WO2007126585A2 (fr) * 2006-03-29 2007-11-08 Eastman Kodak Company Procédé de dépôt de couche atomique
WO2007126582A2 (fr) * 2006-03-29 2007-11-08 Eastman Kodak Company Appareil de dépôt de couche atomique
US20090053482A1 (en) * 2007-08-25 2009-02-26 Julie Baker Method of reducing image fade
WO2009042052A2 (fr) * 2007-09-26 2009-04-02 Eastman Kodak Company Procédé de formation de couches d'encapsulation de films minces
US7887884B2 (en) * 2005-09-20 2011-02-15 Semiconductor Manufacturing International (Shanghai) Corporation Method for atomic layer deposition of materials using an atmospheric pressure for semiconductor devices

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Publication number Priority date Publication date Assignee Title
NL2003836C2 (en) * 2009-11-19 2011-05-23 Levitech B V Floating wafer track with lateral stabilization mechanism.

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0503382A1 (fr) 1991-03-13 1992-09-16 Watkins-Johnson Company Méthode et dispositif pour le dépôt de films très conducteur et transparent d'oxyde d'indium dopée au étain et fluor par APCVD
US5304398A (en) * 1993-06-03 1994-04-19 Watkins Johnson Company Chemical vapor deposition of silicon dioxide using hexamethyldisilazane
US5545436A (en) * 1993-11-12 1996-08-13 Sony Corporation CVD method and apparatus for making silicon oxide films
US5944900A (en) * 1997-02-13 1999-08-31 Watkins Johnson Company Protective gas shield for chemical vapor deposition apparatus
WO1999004059A1 (fr) * 1997-07-14 1999-01-28 Silicon Valley Group Thermal Systems, Llc Injecteur monobloc et chambre pour formation de depots
US20030226502A1 (en) * 2002-06-11 2003-12-11 Taiwan Semiconductor Manufacturing Co., Ltd. Chemical vapor deposition (CVD) method and calibration apparatus providing enhanced uniformity
US7887884B2 (en) * 2005-09-20 2011-02-15 Semiconductor Manufacturing International (Shanghai) Corporation Method for atomic layer deposition of materials using an atmospheric pressure for semiconductor devices
WO2007126585A2 (fr) * 2006-03-29 2007-11-08 Eastman Kodak Company Procédé de dépôt de couche atomique
WO2007126582A2 (fr) * 2006-03-29 2007-11-08 Eastman Kodak Company Appareil de dépôt de couche atomique
US20090053482A1 (en) * 2007-08-25 2009-02-26 Julie Baker Method of reducing image fade
WO2009042052A2 (fr) * 2007-09-26 2009-04-02 Eastman Kodak Company Procédé de formation de couches d'encapsulation de films minces

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN118480868A (zh) * 2024-07-12 2024-08-13 上海钧乾智造科技有限公司 一种用于电池片切面钝化镀膜的喷淋结构、装置及工作方法

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DE102011077833A1 (de) 2012-12-20
TW201308489A (zh) 2013-02-16

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