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WO2011009681A1 - Procédé de dépôt amélioré par plasma, dispositif à semi-conducteurs et dispositif de dépôt - Google Patents

Procédé de dépôt amélioré par plasma, dispositif à semi-conducteurs et dispositif de dépôt Download PDF

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Publication number
WO2011009681A1
WO2011009681A1 PCT/EP2010/058740 EP2010058740W WO2011009681A1 WO 2011009681 A1 WO2011009681 A1 WO 2011009681A1 EP 2010058740 W EP2010058740 W EP 2010058740W WO 2011009681 A1 WO2011009681 A1 WO 2011009681A1
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Prior art keywords
precursor
surface region
plasma enhanced
substrate
plasma
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English (en)
Inventor
Robert Seguin
Peter Engelhart
Bernd Hintze
Wilhelmus Mathijs Marie Kessels
Gijs Dingemans
Mauritius Cornelius Maria Van De Sanden
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Q Cells SE
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Q Cells SE
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    • 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
    • C23C16/45523—Pulsed gas flow or change of composition over time
    • 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
    • C23C16/45523—Pulsed gas flow or change of composition over time
    • C23C16/45525—Atomic layer deposition [ALD]
    • C23C16/45527—Atomic layer deposition [ALD] characterized by the ALD cycle, e.g. different flows or temperatures during half-reactions, unusual pulsing sequence, use of precursor mixtures or auxiliary reactants or activations
    • C23C16/45536—Use of plasma, radiation or electromagnetic fields
    • 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
    • C23C16/50—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 using electric discharges
    • C23C16/515—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 using electric discharges using pulsed discharges
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F71/00—Manufacture or treatment of devices covered by this subclass
    • H10F71/129—Passivating
    • 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

  • Plasma enhanced deposition method plasma enhanced deposition method, semiconductor device, and deposition device
  • the invention relates to a plasma enhanced deposition method, a
  • the efficiency of solar cells can be reduced significantly due to the
  • One possibility for surface passivation consists of applying a dielectric passivation onto the solar cell surface.
  • a dielectric passivation onto the solar cell surface.
  • Such a layer may for example be formed out of SiO2, SiNx, A12O3 or SiC.
  • aluminum oxide (A12O3) has proven itself as a promising candidate for the application in industrially produced solar cells.
  • To its positive properties belongs, besides a good passivation effect due to a very high negative surface charge density, also a high stability, for example against a subsequent temperature treatment in form of a so called firing step, which is necessary for burning in metallic electrodes of the solar cell using screen printing paste for industrial production.
  • a method for time and cost effective deposition of material layers is the plasma enhanced chemical vapor deposition (PECVD).
  • PECVD plasma enhanced chemical vapor deposition
  • precursors are continuously introduced into a reaction chamber, in which a substrate is placed.
  • the precursors react with each other under the influence of a plasma discharge in the gas phase and on the surface of the substrate, such that eventually a material layer in form of a thin layer is deposited on the substrate surface.
  • this deposition method takes place continuously, and the reaction is supported by the energy of the plasma, very high deposition rates and therefore also high layer growth rates are achievable.
  • the material layers produced in this way do not meet the high quality requirements in particular for A12O3 passivation layers, which is why PECVD processes are usually not utilized therefor.
  • ALD atomic layer deposition
  • TMA trimethylaluminum
  • the chemical reaction takes place not already in the gas phase as well, but exclusively on the surface of the substrate. Furthermore, the chemical reaction in the ALD process takes place in two sub-reactions on the substrate surface. Only when such a separation is possible, the ALD process, having a strict separation of the precursors in the gas phase, may work.
  • the plasma enhanced ALD one reactant is activated by the plasma energy, such that the surface reaction also takes place, whereby in each deposition cycle a monolayer of the material layer is made, just as during not plasma enhanced, thermal ALD processes.
  • the material layer deposited in this way is very homogeneous. Furthermore, its layer thickness is almost digitally adjustable by way of the number of cycles, and its passivation properties are very good also at solar cell level, especially when compared to material layers produced with a PECVD process.
  • the ALD process is, however, inherently a very slow deposition process, because the material layer is deposited monolayer after monolayer. The economic feasibility of this technology for industrial production is therefore questionable, despite the very good layer properties.
  • a further deposition method is suggested in WO 2005104634 A2 and utilized in an embodiment described therein for the deposition of an A12O3 layer. It also relates to a plasma enhanced deposition process, which in the embodiment disclosed therein takes place in a self limiting process similar to the ALD process, and can therefore also obtain very slow layer growth rates.
  • one of the precursors namely the precursor consisting of a metal or semiconductor compound, is introduced into the reaction chamber continuously and reacts in the gas phase with a further precursor, which may for example be oxygen, which is activated by the plasma discharge.
  • a further precursor which may for example be oxygen
  • the invention is based on the idea that a gas phase reaction leads to an accelerated layer deposition, compared to a layer deposition process solely based on a self limiting chemical reaction on the substrate surface.
  • the surrounding space may be a reaction space relevant to the material layer deposition onto the surface region, as will be explained in the following.
  • the second precursor activated by plasma discharge may either also be varied in its concentration in the surrounding space in a pulse shape, or it may be added thereto continuously.
  • the chemical deposition reaction is the entirety of sub-reactions, which begin in the gas phase, whereby they take place at least partially in the surrounding space of the substrate surface, and end in the solid phase in form of the material layer on the substrate surface.
  • the deposition reaction may possible also comprise chemical reactions on the substrate surface, for example a conditioning of the substrate surface by plasma activated reactants.
  • the participation of the two precursors in the chemical deposition reaction means that also other precursors may participate therein, preferably however, only the first and the second precursor participate therein.
  • the surface region may be substantially the entire substrate surface.
  • the surrounding space above the surface region is the space, which surrounds the surface region adjacently inside the reaction chamber, and in which reaction products form due to gas phase reactions, which as part of the entire deposition reaction lead to the deposition of the solid thin layer on the surface region.
  • the surrounding space is the space region relevant to the deposition onto the corresponding surface region.
  • pulse shaped concentration variation as well as any pulse shaped progress of temporally changing variables and parameters, relate not only to the case of a substantially rectangular progression, but also includes temporally repeating pulse shaped variations. Since strictly rectangular progressions are physically not possible, the slopes of such pulses inevitably have a more or less steep progression.
  • the pulse shaped variation of the concentration of a precursor in the surrounding space may for example be achieve by way of a pulse shaped streaming of the precursor into the surrounding space.
  • a material layer produced in this manner can also have further advantages besides the already mentioned time and cost efficient production, for example a better layer quality.
  • a passivation layer produced with this method to some extent provides for a better passivation quality for a wafer solar cell, than passivation layers produced by ALD processes, which leads to a lower surface recombination rate on the solar cell surface passivated in this way, and therefore to solar cells with a higher efficiency.
  • concentration relates in all the herein described precursors and reactants in general on an amount of substance or a particle number per volume.
  • the second precursor for example, molecular oxygen may be used.
  • other substances or substance compounds that may be activated by plasma are thinkable. This includes substances and substance compounds, which are also active without a plasma discharge, which activity level is, however, raised by plasma discharge.
  • the deposition device at least comprising a reaction chamber, a transport device, a plurality of introduction units, such as introduction nozzles, a control device, and a plasma discharge device, is preferably designed as an inline device. It can therefore be integrated into a solar cell production line.
  • the transport device which is controlled by the control device, the substrate is moved along the substrate movement direction through the reaction chamber from a start section to an end section, being preferably an entrance and an exit of the reaction chamber, respectively.
  • the previously described embodiments of the plasma enhanced deposition method may also be performed with simpler deposition devices.
  • the pulse-shaped variation of the precursor concentration in the surrounding space above the surface region may be achieved exclusively by way of a time-dependent actuation of a single or multiple introduction units.
  • a movement or transportation of the substrate by way of a transport device could then be omitted.
  • the plasma discharge device which produces the plasma discharge for activation of the second precursor, can use a method of energy supply suitable therefor.
  • an actuation by a high frequency voltage or by high-frequency currents is preferred for this purpose, although a plasma generation by way of supplying an electromagnetic wave is also possible.
  • the concentration of the first precursor in the surrounding space above the surface region is reduced in a pulse shape, such that the deposition of the material layer is substantially prevented.
  • the concentration of the first precursor is reduced such that, for example, it falls below a concentration threshold value necessary for maintaining the chemical deposition reaction.
  • the concentration is reduced to zero, such that there is substantially no precursor presence in the surrounding space anymore.
  • the second precursor is activated for the chemical gas phase reaction with the first precursor by the plasma discharge.
  • the second precursor functions as a reactant for the chemical gas phase reaction with the first precursor.
  • a third precursor is introduced in vapor form into the reaction chamber.
  • This third precursor can also be activated for the chemical gas phase reaction with the first precursor by a plasma discharge, for example generated by the plasma discharge device or by a further plasma discharge device independent thereon.
  • a plasma discharge for example generated by the plasma discharge device or by a further plasma discharge device independent thereon.
  • a substance or a component is used, which is reactive even without the help of a plasma discharge.
  • water (H2O) or ozone (03) may be used instead of molecular oxygen (02).
  • the second and / or the third precursor are introduced such that their concentration in the surrounding space above the surface region is varied in a pulse shape.
  • the varying of the concentration of the second and / or the third precursor in this as well as in the following embodiment may additionally or solely be controlled with the help of a movement of the substrate in the reaction chamber.
  • the second and the third precursor are introduced such that their concentration in the surrounding space above the surface region is varied alternately in a pulse shape.
  • the second and the third precursor are present in a temporally alternating sequence, whereby the respective other precursor is present in the surrounding space preferably only as a residue or substantially not at all.
  • the surrounding space is freed from the respective other precursor, for example by way of flushing the first precursor or a substantially inert gas through the surrounding space.
  • the second precursor is introduced such that its concentration in the surrounding space above the surface region is substantially constant. With a second precursor such constantly present, the reactivity may be controlled by temporally varying the activation of the second precursor by way of controlling the plasma discharge.
  • the plasma discharge for activating the second precursor is confined to a plasma region, having a distance to the surface region of the substrate. It is therefore an indirect plasma, which does not extend to the surface of the substrate. This way, one may accomplish that while the activation of the second precursor for the chemical reaction with the first precursor takes place, the surface region of the substrate is not under the direct influence of the utilized plasma discharge.
  • the plasma discharge utilized for the activation of the second precursor may extend to the surface region of the substrate. In this case, one speaks of a direct plasma.
  • the plasma discharge is controlled such that the surface region is at least temporarily conditioned.
  • the conditioning of the surface region relates to an interaction between particles of the substrate surface and the plasma positioned above it, for influencing physical and / or chemical properties of the produced material layer.
  • Such a conditioning of the surface region takes place preferably before each pulse-shaped appearance of the first precursor in the surrounding space.
  • an indirect plasma may be continued to be utilized for the activation of the second precursor, the plasma having a distance to the surface region of the substrate, while for the conditioning of the surface region in-between the pulses of the second precursor it may be switched to a direct plasma.
  • the same direct plasma may be used for the activation of the second precursor, and simultaneously for the conditioning of the surface region.
  • an inert gas is introduced into the reaction chamber such that it reaches the surrounding space above the surface region continuously or in a pulse-shape.
  • the surrounding space is flushed by the inert gas in a pulsed manner to free it from the precursors present there.
  • the inert gas may be just a buffer or carrier gas, utilized for controlling the progression of the chemical gas phase reaction, or for measured application of one or multiple of the precursors.
  • the first precursor comprises a metal or semiconductor compound, preferably trimethylaluminum (Al(CH3)3) or aluminum chloride (AIC13).
  • organometallic precursors suitable for the thin layer deposition
  • organometallic precursors may be utilized, in particular organometallic precursors.
  • TMMA trimethylamine alane
  • Al(C5H7O2)n aluminum acetylacetonate
  • oxygen (02) or nitrous oxide (N20) may be considered.
  • a wafer solar cell is provided as substrate, and as material layer a passivation layer for surface passivation of the solar cell is produced.
  • the introduction of the second and / or the third precursor and / or the movement of the substrate is performed such that the concentration of the second and / or the third precursor in a surrounding space above the surface region is varied in a pulse shape.
  • the pulse-shaped concentration variation of the second and / or the third precursor in the surrounding space above the surface region is preferably controlled solely by way of controlling the introduction of the respective precursor into the reaction chamber, or solely by way of movement of the substrate through a spatially varying concentration profile inside the reaction chamber.
  • the pulse-shaped variation of the concentration of the first precursor in the surrounding space above the surface region takes place with a pulse duration of between about 0.5 seconds to about 2 seconds, preferably with a pulse duration of about 1 second.
  • a pulse duration of between about 0.5 seconds to about 2 seconds preferably with a pulse duration of about 1 second.
  • These values may be achieved with a purely temporal control of the introduction unit by way of introducing the first precursor in a pulse shape with a pulse duration of about 5 milliseconds to about 50 milliseconds, preferably with a pulse duration of about 20 milliseconds.
  • These values may thus for example be valve opening times.
  • AU pulse duration values may for example be measured as full width at half maximum.
  • the pulse-shaped variation of the concentration of the first precursor in the surrounding space above the surface region takes place with a pulse spacing of between about 0.1 seconds and about 5 seconds, preferably with a pulse spacing of about 3.5 seconds. These are preferably the spacings between two pulse peak values.
  • the pulse durations and the pulse spacings optimal for the material layer production may among others be dependent on the reactor geometry, but also on valve switching times of the introduction unit. The previously mentioned values apply in particular but not solely for single wafer reactor chambers, which are comparatively small. In production-scale deposition devices having large volume reaction chambers, both the pulse durations and the pulse spacings may be chosen to be significantly longer.
  • a material sub-layer of the material layer with a layer thickness of between about 1 angstrom and about 50 angstrom is produced, preferably between about 2 angstrom and about 5 angstrom, more preferred with a layer thickness of about 3.5 angstrom.
  • the plasma discharge is placed in front of and behind at least one of the introduction units when viewed in the direction of the substrate movement direction.
  • the plasma discharge may spatially be positioned above the introduction unit, thus on a side of the introduction unit facing away from the substrate. In such a case, it is an indirect plasma, which has no direct influence in form of a conditioning of the solar cell surface.
  • the plasma discharge device produces a plasma discharge space, which spans or encompasses a plurality of introduction units.
  • the introduction units are placed inside the plasma discharge space.
  • the plasma discharge device comprises a plurality of plasma discharge units, which when viewed along the substrate transport direction each comprise plasma discharge spaces separated from each other.
  • the plasma discharge spaces can each have different plasma parameters.
  • a further reason for greater flexibility for example compared to a PEALD deposition device designed as an inline device, is that in PEALD deposition devices the layer thickness of the deposited material layer is set, once the device length (and therefore also the number of deposition cycles) is determined during the device conception.
  • there is the possibility to deposit material layers of different thickness by way of variation of process parameters (for example TMA amount or plasma intensity).
  • material layers made of A12O3 with very good layer qualities may be deposited, when the precursors are chosen appropriately:
  • AIxOyNz aluminum oxynitride or aluminum nitride, whereby as the precursor aluminum precursors as well as N2, H2, NH3, N2O and / or 02 may be utilized.
  • Such material layers may for example be utilized for anti-reflective and / or passivation applications.
  • TiO2 whereby as precursor titanium tetrachloride (TiCW), tetraisopropyl titanate (TIPT, Ti(OC3H7)4) and / or tetraethoxy titanate (TEOT, Ti(C2H5)4 ) may be utilized.
  • TiO2 material layers are suitable for example as anti- reflective coating.
  • Tantalum oxide (Ta2O5) whereby as precursor tantalum pentaethoxide (Ta(OC2H5)5 or Ta(OCH3)5) may be utilized. Tantalum oxide material layers are suitable for example as corrosion protection layers.
  • SiO2 whereby as precursor tetraethoxysilane (TEOS, Si(OC2H5)4),
  • HMDSO hexamethyldisiloxane
  • TMDSO tetramethyldisiloxane
  • SiO2 material layers are suitable for various purposes, such as for example surface passivation.
  • SiN whereby as precursor hexamethyldisilazane (HMDSN) and / or
  • HMCTSZN hexamethylcyclotrisilazane
  • Layer systems of different materials may be deposited by for example changing the precursors and / or their combinations in a deposition process taking place continuously.
  • layer systems which comprise A12O3 material layers and AIxOyNz material layers.
  • a layer comprising A12O3 material layers and TiO2 material layers may be mentioned.
  • Fig. 1 shows a schematic cross section view of a deposition device
  • Fig. 2a and 2b show time diagrams for known PEALD deposition methods
  • Fig. 3 a time diagram for a known PECVD deposition method
  • Fig. 5 an arrangement for an inline deposition method according to one embodiment
  • Fig. 6 an arrangement for an inline deposition method according to a further embodiment.
  • Fig. 1 shows an arrangement of a substrate 3 in a reaction chamber 1 of the deposition device 10 in a schematic cross section view.
  • the substrate 3 is positioned on a substrate holder 2, with the help of which the substrate 3 may for example be heated up or cooled down for an optimal deposition
  • a first precursor 7 and a second precursor 8 are in a vapor mixture in the reaction chamber 1.
  • the material layer 5 is deposited on the surface region 4 of the substrate 3.
  • spatial region in the reaction chamber 1 shall be regarded as a surrounding space 6 above the surface region 4, where the precursors present in the spatial region and the processes taking place in it, in particular chemical gas phase reactions, have a direct influence on the surface region 4 lying underneath.
  • the processes and precursors in the surrounding space 6 as well as their temporal succession are significant for the deposition and, if applicable, for the conditioning of the material layer 5 of the surface region 4 by way of a plasma, which is not shown herein.
  • the deposition device 10 comprises further an introduction unit 9, for example furnished as an injection nozzle.
  • introduction unit for example furnished as an injection nozzle.
  • the introduction unit the first precursor 7 and the second precursor 8 and, if applicable, further precursors, reactants and / or inert substances are introduced into the reaction chamber 1.
  • further introduction units 9 may be provided for, through each of which different substances may be introduced into the reaction chamber 1.
  • introduction unit 9 for the introduction of the various gases into the reaction chamber as well as the energy supply to that plasma discharge are visualized by way of timing diagrams.
  • the following figures show the temporal actuation of the introduction units 9, the diagrams shown therein may also be schematic depictions of the
  • the first (topmost) line shows a temporal introduction unit actuation 11 for the introduction of an inert gas
  • the second line shows a temporal introduction unit actuation 12 for the first precursor 7
  • the third line shows a temporal introduction unit actuation 13 for the second precursor 8
  • the fourth line shows the temporal high frequency actuation 14 for plasma generation.
  • each actuation takes place digitally.
  • the actuation is either activated or deactivated.
  • a deposition comprises in general a multitude of deposition cycles, in order to obtain a sufficient layer thickness.
  • the time diagrams depicted herein would continue periodically.
  • the corresponding introduction unit will introduce the corresponding gas or the corresponding precursor with a predetermined pressure, while the high frequency source is turned on for plasma generation in the active state.
  • each actuation will have a rise and a fall time, which may be more or less short, depending on the design of the mechanical or electronic components utilized herein.
  • Fig. 2a, 2b and 3 depict the situation for the known prior art. While the Fig. 2a and 2b relate to two different plasma enhanced atomic layer deposition methods (PEALD methods), a time diagram for a plasma enhanced chemical vapor deposition method (PECVD method) is shown in Fig. 3.
  • PEALD methods plasma enhanced atomic layer deposition methods
  • Fig. 3 a time diagram for a plasma enhanced chemical vapor deposition method (PECVD method) is shown in Fig. 3.
  • PEALD methods plasma enhanced atomic layer deposition methods
  • PECVD method plasma enhanced chemical vapor deposition method
  • the two precursors 7 and 8 are introduced into the reaction chamber 1 in continuous alternation, whereby a plasma is ignited in the second precursor by way of the high frequency actuation 14, which activates it for a chemical reaction.
  • the reaction chamber 1 is flushed by an inert gas, which is indicated by the corresponding introduction unit actuation 11. This takes place in order for the two precursors 7 and 8 not to be present in gas phase
  • the timing diagram shown in Fig. 2b differs from the one in Fig. 2a only by that the second precursor is introduced continuously into the reaction chamber 1. Because the high frequency actuation 14 for the plasma generation continues to take place in a pulse shape, the plasma generation and therefore the activation of the second precursor 8 takes place in a pulse shape as well. In this case, it is substantially not harmful that the two precursors 7 and 8 are temporarily inside the reaction chamber 1 simultaneously, since a chemical gas phase reaction cannot take place in this case either.
  • Fig. 3 shows the corresponding temporary progress in the PECVD process. As initially described, this is a continuous deposition process, whereby the actuations 12 and 13 of introduction units 9 for the two precursors 7 and 8 and also the high frequency actuation 14 take place simultaneously and
  • the first precursor 7 and a second precursor 8 activated by plasma discharge coexist inside the reaction chamber 1.
  • Fig. 4a to 4i show in diagram form the temporal progress of the actuations 11 , 12, 13 for the introduction units 9 for introducing of the inert gas, the first precursor 7, and the second precursor 8, as well as for the high frequency actuation 14 in exemplary embodiments of a plasma enhanced deposition process. While in the cases shown in Fig. 4a to 4c the actuation 13 for the introduction of the second precursor 8 is activated continuously, and therefore the concentration of the second precursor 8 in the surrounding space 6 above the surface region 4 is or is held constant, supplying the second precursor 8 in the embodiments according to Fig. 4d to 4f takes place in a pulse shape. In all embodiments, however, the introduction of the first precursor 7 is taking place solely in a pulse shape.
  • the pulse duration for the actuation 12 is substantially shorter that the pulse spacing between two pulses, although these two parameters appear to be of the same length at least in the Fig. 4a to 4c.
  • the pulse duration is shorter than the pulse spacing by about two orders of magnitude.
  • a feeding-in of the first precursor 7 and a feeding-in of the inert gas take place alternately, whereby the feeding-in of the second precursor 8 and its activation by way of plasma discharge takes place continuously.
  • the inert gas is introduced continuously, while in the embodiment according to Fig. 4c it is avoided altogether. In the latter case, the continuously introduced second precursor takes over the purging function.
  • the first precursor 7 and the inert gas are introduced alternately, like in the case according to Fig. 4a.
  • the second precursor 8 is introduced substantially
  • a pulse-shaped high frequency actuation 14 differs by that the pulse-shaped introduction of the first precursor 7 takes place with half the repetition frequency compared to the pulse-shaped introduction of the second precursor 8. Furthermore, the embodiments according to Fig. 4d and 4e differ by way of a differing high frequency actuation 14 for the plasma generation, which is pulse-shaped in the former case and substantially continuously in the latter case.
  • Fig. 4a to 4f comprise each the same four lines, which is why in the further figures the reference numerals are omitted.
  • a further temporal actuation is depicted in the Fig. 4g, 4h, and 4i by way of an additional line.
  • It relates to a temporal introduction actuation 15 for the introduction of a third precursor.
  • It temporarily replaces the second precursor 8 in the chemical gas phase reaction with the first precursor 7.
  • the second precursor 8 has to be first activated by way of the plasma discharge for the chemical reaction with the first precursor 7
  • the third precursor is preferably active on its own and does not need a plasma therefor. This may for example be ozone or water, which may replace the molecular oxygen as the second precursor 8.
  • the introduction of the second precursor 8 takes place in alternation with the introduction of the third precursor.
  • the high frequency actuation 14 corresponds to the introduction unit actuation 13 for the second precursor 8, and takes place preferably substantially synchronous to it.
  • the flushing or purging of the surrounding space 6 above the surface region 4 or of the entire reaction chamber 1 takes place in a temporal spacing or a time window between the alternating introduction of the second and the third precursor.
  • Fig. 4a to 4i differ in a frequency, with which the introduction unit actuation 12 for the first precursor 7 takes place. While the introduction unit actuation 12 according to Fig. 4h takes place
  • TMA trimethylaluminum
  • 02 molecular oxygen
  • the inert gas argon (Ar) is well suitable.
  • a very long charge carrier lifetime and therefore a good surface passivation is achieved in this case for example by way of a continuous plasma discharge, with a pulse duration of the introduction of TMA of about 20 milliseconds and a time interval between introduction pulses of the TMA or a pulse spacing of about 3.5 seconds (s).
  • the temperature of the substrate 3 should in this case be about 200 0 C, while the 02 gas is introduced with a gas flow of about 50 standard cubic centimetre per minute (seem), and the Ar gas with a gas flow of about 20 seem.
  • the plasma frequency that is the frequency of the high frequency actuation for the plasma discharge, is preferably 13.56 MHz, whereby the plasma has a plasma power of about 150 Watts.
  • the pressure in the reaction chamber 1 should preferably have a value of about 150 millitorr.
  • the material layer thickness per deposition cycle, or per pulse of the first precursor may be adjusted by way of the amount of the first precursor introduced per deposition cycle.
  • a suitable material layer with a layer thickness of at least 5 nanometres is deposited.
  • the layer thickness is preferably well above this value. If the material layer additionally or exclusively takes over the function of a backside mirror of the solar cell, a layer thickness of about 100
  • nanometres or more are advantageous.
  • Fig. 5 shows a schematic cross section view of an arrangement inside a reaction chamber 1 according to an inline embodiment of the deposition device 10.
  • the deposition device 10 comprises multiple introduction units 9 distributed side by side equidistantly along a substrate movement direction 22. They are
  • a substrate 3 is positioned, which is moved by a transport device (also not shown) along a substrate movement direction 22, preferably with a constant transport speed.
  • a schematic and, in comparison to the dimensions of the substrate 3, extremely expanded depiction of the material layer 5 is shown, in order to illustrate its growth along the substrate movement direction 22.
  • the horizontal and vertical auxiliary dashed lines drawn in Fig. 5 make it clear that the material layer 5 is composed of material sub-layers 51 , each of which are generated due to the first precursor 7 introduced by a corresponding introduction unit 9.
  • the layer thickness of the material layer 5 grows substantially in steps along the substrate movement direction 22.
  • a material sub-layer 51 would correspond to the deposition result after a deposition cycle.
  • the Fig. 6 shows an arrangement in a reaction chamber 1 according to a further embodiment of the deposition device 10.
  • multiple substrates 3 are arranged consecutively on a substrate holder 2.
  • the substrates 6 are moved through the reaction chamber 1 along the transport direction 22 by a transport device not shown in Fig. 6.
  • the substrate holder 2 may be a transport belt, which is moved by spools positioned outside of the reaction chamber 1.
  • an introduction unit 9 is positioned, with which help the first precursor 7 (dashed arrows) and the second precursor 8 (solid arrows) are introduced in the direction of the substrate 3, alternately along the transport direction 22.
  • An energy source 25 shown in Fig. 6 may both serve for supplying the introduction unit 9 as well as for supplying the plasma discharge device for the generation of the plasma discharge in the plasma discharge spaces 21 , which are positioned along the transport direction 22. Therefore, the substrates 3, while moving along the transport direction 22, traverse alternately regions, in which exclusively the first precursor 7 is present, and plasma discharge spaces 21 , wherein the second precursor 8 is present.
  • the plasma discharge spaces 21 distributed along the substrate transport direction 22 can be generated by one or by multiple plasma discharge units.

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

Abstract

L'invention concerne un procédé de dépôt amélioré par plasma d'une couche de matériau (5), un dispositif à semi-conducteurs et un dispositif de dépôt. Au cours du dépôt amélioré par plasma de la couche de matériau (5), un premier précurseur (7) et un second précurseur (8) sont introduits en phase vapeur dans une chambre de réaction (1) et participent à une réaction chimique de dépôt par l'intermédiaire de laquelle la couche de matériau (5) est déposée sur une zone de surface (4) d'un substrat (3) placé à l'intérieur de la chambre de réaction (1). Pendant ce dépôt, l'introduction (12) du premier précurseur (7) et/ou un déplacement (22) du substrat (3) sont réalisés d'une manière telle que la concentration du premier précurseur (7) dans un espace voisin (6) au-dessus de la zone de surface (4) est modifiée selon une forme pulsatile. Dans l'espace voisin (6), il se produit au moins partiellement une réaction chimique en phase gazeuse du premier précurseur (7) à un réactif. De plus, pendant ce dépôt, le second précurseur (8) est activé en vue d'une réaction chimique avec le premier précurseur (7) au moyen d'une décharge de plasma.
PCT/EP2010/058740 2009-07-24 2010-06-21 Procédé de dépôt amélioré par plasma, dispositif à semi-conducteurs et dispositif de dépôt Ceased WO2011009681A1 (fr)

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DE102009026249A DE102009026249B4 (de) 2009-07-24 2009-07-24 Plasma unterstütztes Abscheideverfahren, Halbleitervorrichtung und Abscheidevorrichtung
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR3056992A1 (fr) * 2016-10-04 2018-04-06 Kobus Sas Procede d'injection d'especes chimiques en phase gazeuse sous forme pulsee avec plasma
US10597778B2 (en) 2014-12-22 2020-03-24 Picosun Oy ALD method and apparatus including a photon source
EP4365964A4 (fr) * 2021-10-19 2024-10-23 Tongwei Solar (Meishan) Co., Ltd. Procédé de préparation de cellule solaire double face de type n

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040082171A1 (en) * 2002-09-17 2004-04-29 Shin Cheol Ho ALD apparatus and ALD method for manufacturing semiconductor device
US20060134345A1 (en) * 2004-12-20 2006-06-22 Micron Technology, Inc. Systems and methods for depositing material onto microfeature workpieces
WO2007145513A1 (fr) * 2006-06-16 2007-12-21 Fujifilm Manufacturing Europe B.V. Procédé et appareil pour la déposition d'une couche atomique utilisant un plasma à décharge luminescente à pression atmosphérique
US20090165715A1 (en) * 2007-12-27 2009-07-02 Oh Jae-Eung Vapor deposition reactor

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5242530A (en) * 1991-08-05 1993-09-07 International Business Machines Corporation Pulsed gas plasma-enhanced chemical vapor deposition of silicon
US6511539B1 (en) * 1999-09-08 2003-01-28 Asm America, Inc. Apparatus and method for growth of a thin film
US20040224504A1 (en) * 2000-06-23 2004-11-11 Gadgil Prasad N. Apparatus and method for plasma enhanced monolayer processing
US7081271B2 (en) * 2001-12-07 2006-07-25 Applied Materials, Inc. Cyclical deposition of refractory metal silicon nitride
US20050221021A1 (en) * 2004-03-31 2005-10-06 Tokyo Electron Limited Method and system for performing atomic layer deposition
DE102005003336B3 (de) * 2005-01-25 2006-07-13 Bte Bedampfungstechnik Gmbh Verfahren zur Bildung einer dünnen Schicht auf einer Substratoberfläche
CA2670809A1 (fr) * 2007-02-27 2008-09-04 Sixtron Advanced Materials, Inc. Procede de formation d'un film sur un substrat
US7713868B2 (en) * 2007-03-30 2010-05-11 Tokyo Electron Limited Strained metal nitride films and method of forming
WO2009042713A1 (fr) * 2007-09-28 2009-04-02 Applied Materials, Inc. Dépôt en phase vapeur de matériaux à base de tungstène
DE102008028537B4 (de) * 2008-06-16 2012-11-29 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Verfahren zum Abscheiden einer Kratzschutzbeschichtung auf einem Kunststoffsubstrat

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040082171A1 (en) * 2002-09-17 2004-04-29 Shin Cheol Ho ALD apparatus and ALD method for manufacturing semiconductor device
US20060134345A1 (en) * 2004-12-20 2006-06-22 Micron Technology, Inc. Systems and methods for depositing material onto microfeature workpieces
WO2007145513A1 (fr) * 2006-06-16 2007-12-21 Fujifilm Manufacturing Europe B.V. Procédé et appareil pour la déposition d'une couche atomique utilisant un plasma à décharge luminescente à pression atmosphérique
US20090165715A1 (en) * 2007-12-27 2009-07-02 Oh Jae-Eung Vapor deposition reactor

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10597778B2 (en) 2014-12-22 2020-03-24 Picosun Oy ALD method and apparatus including a photon source
FR3056992A1 (fr) * 2016-10-04 2018-04-06 Kobus Sas Procede d'injection d'especes chimiques en phase gazeuse sous forme pulsee avec plasma
WO2018065321A1 (fr) * 2016-10-04 2018-04-12 Kobus Sas Procede d'injection d'especes chimiques en phase gazeuse sous forme pulsee avec plasma
EP4365964A4 (fr) * 2021-10-19 2024-10-23 Tongwei Solar (Meishan) Co., Ltd. Procédé de préparation de cellule solaire double face de type n

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