EP3701559A1 - Procédé et dispositif de dépôt continu en phase gazeuse de silicium sur des substrats - Google Patents

Procédé et dispositif de dépôt continu en phase gazeuse de silicium sur des substrats

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Publication number
EP3701559A1
EP3701559A1 EP18793404.7A EP18793404A EP3701559A1 EP 3701559 A1 EP3701559 A1 EP 3701559A1 EP 18793404 A EP18793404 A EP 18793404A EP 3701559 A1 EP3701559 A1 EP 3701559A1
Authority
EP
European Patent Office
Prior art keywords
silicon
reaction chamber
precursor compound
based intermediate
gas
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.)
Pending
Application number
EP18793404.7A
Other languages
German (de)
English (en)
Inventor
Stefan Reber
Kai SCHILLINGER
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.)
Nexwafe GmbH
Original Assignee
Nexwafe GmbH
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 Nexwafe GmbH filed Critical Nexwafe GmbH
Publication of EP3701559A1 publication Critical patent/EP3701559A1/fr
Pending legal-status Critical Current

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02612—Formation types
    • H01L21/02617—Deposition types
    • H01L21/0262—Reduction or decomposition of gaseous compounds, e.g. CVD
    • 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
    • C23C16/24—Deposition of silicon only
    • 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
    • C23C16/45593—Recirculation of reactive gases
    • 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
    • C23C16/52—Controlling or regulating the coating process
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02518—Deposited layers
    • H01L21/02521—Materials
    • H01L21/02524—Group 14 semiconducting materials
    • H01L21/02532—Silicon, silicon germanium, germanium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
    • H01L21/67005—Apparatus not specifically provided for elsewhere
    • H01L21/67011—Apparatus for manufacture or treatment
    • H01L21/67017—Apparatus for fluid treatment

Definitions

  • a substrate is placed in a reaction chamber and heated to 700 ° C to 1400 ° C. Subsequently, a silicon precursor compound is introduced into the reaction chamber, which thermally decomposes in the reaction chamber, whereby solid silicon is deposited on the substrate. Possible by-products of this chemical reaction as well as the excess of the silicon precursor compound are derived from the reaction chamber.
  • polycrystalline and monocrystalline silicon layers can be produced by the chemical vapor deposition by chemical vapor deposition on crystalline substrates.
  • the silicon precursor compound u u Silanes and chlorosilanes, wherein the use of silanes is disadvantageous because of their autoignition in contact with atmospheric oxygen and the tendency to gas phase nucleation.
  • chlorosilanes the silicon deposition reaction is carried out on the substrate in the presence of hydrogen as the process gas and proceeds according to the simplified reaction equation:
  • the present invention is therefore based on the object of specifying a method and a device for the vapor deposition of silicon on substrates, whereby the formation of parasitic deposits prevented o- which can at least be reduced and the throughput can be increased over the method known from the prior art.
  • the invention relates to a method for continuous vapor deposition of silicon on substrates according to the preamble of claim 1. Furthermore, the invention relates to a device for continuous vapor deposition of silicon on substrates according to the preamble of patent claim 12.
  • the method according to the invention for the continuous vapor deposition of silicon on substrates has the following method steps:
  • a method step (a) at least one substrate is introduced into a reaction chamber.
  • a process gas and at least one gaseous silicon precursor compound are introduced into the reaction chamber.
  • a gaseous mixture of at least one silicon-based intermediate product is formed in coexistence with the gaseous silicon precursor compound and the process gas in the reaction chamber.
  • a silicon layer is formed by vapor deposition of silicon from the silicon precursor compound and / or the silicon-based intermediate product on the substrate.
  • an excess of the gaseous mixture is removed from the reaction chamber.
  • the silicon precursor compound is present in excess or in the same amount as the silicon-based intermediate in the gas inflow of the reaction chamber.
  • the substrate is formed of polycrystalline or monocrystalline silicon, ceramic, glass and / or their composites or layer systems.
  • the invention is not limited to this, because there are, for example, polymer-containing substrates or other semiconductor materials such. As silicon carbide or other compound semiconductors conceivable.
  • the invention is based on the recognition that the deposition of silicon is not only temperature-dependent, but also depends on the molar composition of the gaseous mixture, which consists of the at least one silicon-based intermediate, the silicon precursor compound and composed of the process gas.
  • Applicant's investigations have shown that the choice of a suitable molar ratio of the silicon-based intermediate and the silicon precursor compound inhibits or completely inhibits the deposition of silicon. This finding is based on the fact that a chemical vapor deposition of silicon from Siliziu m precursor compounds and / or silicon-based intermediates tends to run as an equilibrium reaction, which is temperature and concentration-dependent.
  • the parasitic deposition can be largely prevented.
  • the parasitic deposition can even be completely prevented.
  • Such a molar ratio can be controlled by controlled introduction of the silicon precursor compound and recycling of at least one of the constituents of the excess of the gaseous mixture selected from the precursor silicon compound, the silicon-based intermediate and / or the process gas into the gas feed to the reaction chamber become .
  • the deposition rate of solid silicon on substrates during chemical vapor deposition also depends on the composition of the gas stream introduced into the reaction chamber.
  • the stated molar ratio refers to one of the silicon precursor compounds.
  • the molar ratio preferably refers to the higher chlorosilane in relation to the silicon-based intermediate.
  • step (f) Due to the formation of the gaseous mixture of at least one silicon-based intermediate product, the silicon precursor compound and the process gas in the reaction chamber in process step (c) and the subsequent silicon deposition in process step (d) is the composition of the derivative excess of the gaseous mixture n inaccurate predictable. Therefore, in a first advantageous embodiment of the method in step (f), a determination of the molar ratio of the silicon-based intermediate product and the silicon precursor compound in excess of the gaseous mixture by a measuring unit.
  • this measuring unit is designed directly for determining the molar ratio or for determining an equivalent size, in particular the concentration and / or the amount and / or the volume or mass flow of one and / or more silicon-based intermediates, from which the molar ratio of the silicon-based intermediate and the silicon precursor compound in excess of the gaseous mixture can be derived.
  • the measuring unit may also serve to directly determine the molar ratio of the silicon-based intermediate and the silicon precursor compound in excess of the gaseous mixture.
  • the measuring unit can serve for the online determination of the relevant molar ratio or the concentration of one and / or more silicon-based intermediates.
  • the measuring unit may only be used intermittently to determine the relevant molar ratio or the concentration of one or more silicon-based intermediates, for example at the beginning of the chemical vapor deposition and / or after certain time intervals.
  • the invention is not limited thereto.
  • the molar ratio, determined by the measuring unit, of the silicon-based intermediate product to the silicon precursor compound is forwarded to a control unit, which control unit controls the introduction of the silicon precursor compound such that the molar ratio of the silicon-based intermediate product to the silicon precursor compound has a value of 0.2: 0.8 to 0, 5: 0.5, preferably 0.3: 0.7 to 0.5: 0.5, particularly preferably 0.5: 0.5 having in the process gas.
  • the forwarding of the molar ratio determined by the measuring unit can be carried out automatically, in particular by data line or wirelessly, or manually by a user who reads the result of the measuring unit and transmits this information to the control unit. Subsequent introduction of the silicon precursor compound by the control unit may also be automatic or manual by the user. H it is within the scope of the invention that the control unit is designed as Du rchpound controller. However, the invention is not limited thereto.
  • the automatic control however, it has significant advantages in terms of process reliability and reduced labor costs.
  • an advantageous embodiment of the method according to the invention provides that the excess of the gaseous mixture in step (f) is freed of impurities.
  • the method may, in a preferred embodiment in step (f), provide a recovery unit which minimizes the excess of the gaseous mixture partially separated. Such a recovery unit thereby enables not only the recycling of a desired constituent of the excess of the gaseous mixture, but also the separation of unwanted by-products of the silicon deposition.
  • the silicon-based intermediate and / or the silicon precursor compound and / or the process gas is recycled into the reaction chamber.
  • the silicon precursor compound is a chlorosilane, preferably silicon tetrachloride and / or trichlorosilane.
  • the deposition rate of silicon can preferably be optimized by introducing not only one but also a plurality of silicon precursor compounds into the deposition chamber in process step (b). If several silicon precursor compounds are introduced into the reaction chamber, the silicon precursor compounds are preferably silicon tetrachloride and trichlorosilane.
  • chlorosilanes are significantly cheaper and less dangerous to handle, because they show ia. no auto-ignition in the presence of atmospheric oxygen.
  • the use of chlorosilanes allows a significantly higher deposition rate to achieve a high layer quality compared to said silanes, whereby the throughput of silicon-coated substrates is significantly increased.
  • the deposition rate is significantly lower.
  • Applicant's investigations have shown that the use of silicon tetrachloride in the presence of trichlorosilane leads to an optimized deposition rate while avoiding parasitic deposits. Since silicon tetrachloride is thermally stable at a temperature of 1,600 ° C. and the silicon deposition proceeds at lower temperatures only in the presence of hydrogen, a further advantageous embodiment provides that the process gas is hydrogen.
  • the silicon-based intermediate is a chlorosilane, preferably trichlorosilane.
  • process step (b) advantageously several silicon precursor compounds can be introduced into the reaction chamber, the silicon precursor compounds preferably being silicon tetrachloride and trichlorosilane. It should be noted that in this case trichlorosilane is introduced into the reaction chamber as a silicon precursor compound and can also be recycled as an intermediate in process step (f) into the reaction chamber.
  • an advantageous embodiment of the method provides that a total amount of silicon-based precursor compound and silicon-based intermediate product in step (c) in a molar ratio of 1 to 1 0 mol%, preferably 2 to 7 mol%, particularly preferably 3 to 6 mol%, is present in the process gas.
  • a further advantageous embodiment of the method provides that the formation of a silicon layer by chemical vapor deposition of silicon from the on silicon precursor compound and / or the silicon-based intermediate on the substrate at a pressure of 0.8 bar to 1, 2 bar takes place in the reaction chamber. It is therefore within the scope of the invention that the inventive method is carried out at approximately atmospheric pressure. This results in a timely Tensive transfer of the reaction chamber into vacuum avoided, whereby the throughput of silicon-coated substrates can be significantly increased.
  • the substrate in the reaction chamber in a further advantageous embodiment of the method according to the invention at a temperature of 700 ° C to 1400 ° C, preferably at 1 000 ° C to 1 300 ° C. , more preferably heated to 1 1 00 ° C to 1200 ° C.
  • heating the substrate to a certain temperature makes it possible to set the deposition rate of silicon on the substrate in a targeted manner.
  • the substrate not only the substrate, but also the reaction chamber and / or arranged on the reaction chamber gas lines are heated.
  • the substrate and / or the reaction chamber and / or the gas lines can each be heated to different temperatures. H hereby an optimal gas supply to the reaction chamber and a gas return is possible.
  • a further aspect of the present invention is an apparatus for continuous vapor deposition of silicon on substrates, in particular for carrying out a method according to one of claims 1 to 11, comprising: a reaction chamber, which reaction chamber comprises at least one inlet opening and one at least one outlet opening for substrates, a transport device for transporting the substrates from the inlet opening to the outlet opening through the reaction chamber, at least two gas inlets for supplying a gas into the reaction chamber, at least one gas outlet for removing the gas from the reaction chamber, at least two fluid supply lines, preferably gas supply lines, which fluid supply lines are connected to two of the gas inlets of the reaction chamber.
  • the gas inlets serve to supply the process gas, the silicon-based intermediate and / or the silicon precursor compound to the reaction chamber.
  • the device according to the invention has at least one control unit and that a circulation line is arranged between the gas outlet and the gas inlet of the reaction chamber, which circulation line is connected to the fluid supply line and to the gas outlet of the reaction chamber, the device comprising at least one measuring unit for determining a molar ratio of the silicon-based intermediate product and the silicon precursor compound and / or a size equivalent thereto, and wherein the control unit and the measuring unit are designed to cooperate such that a flow of the supply lines through the control unit due to a signal transmitted from the measuring unit to the control unit Is controllable or controllable.
  • the measuring unit for determining the concentration and / or the amount and / or the volume or mass flow of one and / or more silicon-based intermediates is formed, from which the molar ratio of the silicon-based intermediate and the Siliziu m precursor compound in excess of the gaseous mixture can be derived.
  • the measuring unit may also serve to directly determine the molar ratio of the silicon-based intermediate and the silicon precursor compound in excess of the gaseous mixture.
  • the measuring unit is designed for the online determination of the relevant molar ratio or the concentration of one or more silicon-based intermediates.
  • the measuring unit may only be used intermittently to determine the relevant molar ratio or the concentration of one or more silicon-based intermediates, for example at the beginning of the chemical vapor deposition and / or after certain time intervals.
  • the invention is not limited thereto.
  • the automatic control has considerable advantages in terms of process reliability and a reduced workload.
  • Such a device enables the continuous transport of substrates into the reaction chamber, wherein the substrates are transported by means of the transport device from the inlet opening of the reaction chamber to the outlet opening.
  • the gas inlets of the devices according to the invention serve for introducing the process gas, the silicon dioxide precursor compound and for recycled components of the excess of the gaseous precursor compounds after their discharge from the reaction chamber.
  • a first preferred embodiment of the device according to the invention is that the measuring unit is arranged on the circulation line.
  • the measuring unit is integrated either in the circulation line or disposed on the circulation line. If the measuring unit is integrated into the circulation line, the determination of the molar ratio of the silicon-based intermediate product and the silicon precursor compound takes place online. This measurement can be done continuously or at user-preset time intervals. If the measuring unit is arranged on the circulation line, the measurement of the molar ratio of the silicon-based intermediate and the Siliziu m precursor compound either by automatically feeding a sample or after sampling by the user, which is the sample of the excess of the gaseous mixture of the measuring unit feeds manually.
  • the invention is not limited thereto.
  • a further preferred embodiment of the device according to the invention provides that the measuring unit is designed as a spectrometer or as a mass flow meter, for example as Coriolis mass flow meter, or as a volume flow meter.
  • At least one of the fluid supply lines has an evaporator, which evaporator is based on silicon precursor compound and / or silicon converted intermediate into the gaseous state.
  • a further preferred embodiment of the device according to the invention is that the circulation line comprises a recovery unit, which recovery unit for separating the excess of the gaseous mixture discharged from the reaction chamber and recovery the silicon precursor compound and / or the silicon-based intermediate product and / or the process gas is used.
  • this recovery unit is designed as a distillative separation apparatus and / or dry absorber or adsorber.
  • dry absorber or -adsorbers of hydrogen chloride formed during the chemical vapor deposition of solid silicon and / or the Siliziu m precursor compound in the return of the excess of the gaseous mixture can be separated.
  • the circulation line preferably has a plurality of sub-lines between the recuperation unit and the fluid supply line, which sub-lines separate Returning the process gas, serve the silicon-based intermediate product and / or the silicon precursor compound, each sub-line having a separate measuring unit for determining the mass flow and / or volume flow of the process gas, the silicon-based intermediate product and / or the silicon precursor compound.
  • the process gas and / or the silicon-based intermediate and / or the silicon precursor compound are removed from the device after their separation.
  • the gas scrubber and / or the distillative separation apparatus may have a gas outlet connected to a gas discharge line.
  • the invention is not limited thereto, since such a gas outlet with gas discharge line can also be arranged on the circulation line in the region of the measuring unit.
  • FIG. 1 shows a schematic illustration of a first exemplary embodiment of a device according to the invention for continuous gas-phase deposition of silicon on substrates
  • Figure 2 is a schematic representation of a second embodiment of a device according to the invention for the continuous gas phase deposition of silicon on substrates and
  • Figure 3 is a schematic representation of a third embodiment of a device according to the invention for the continuous gas phase senabscheidung of silicon on substrates.
  • FIG. 1 shows a first exemplary embodiment of a device 1 according to the invention for the continuous vapor deposition of silicon on substrates.
  • This device 1 has a reaction chamber 2, a measuring unit 3, a control unit 4, a circulation line 5, a scrubber 6 and a recovery unit 7.
  • the reaction chamber 2 has an inlet opening 8, via which substrates to be coated can be introduced into the reaction chamber 2. Furthermore, an outlet opening 9 is located on the side of the reaction chamber 2 opposite the inlet opening 8, via which outlet opening 9 silicon-coated substrates can be led out of the reaction chamber 2.
  • the transport of the substrates into and out of the reaction chamber 2 takes place by means of a transport device 10. As indicated in FIG. 1 by an arrow, the transport device 10 has a transport direction of the substrates from the inlet opening 8 to the outlet opening 9.
  • the transport device 1 0 may be formed as a conveyor belt. Alternatively, the transport device 1 0 may also have a plurality of transport rollers, or be designed as a slide rail transport. As shown in FIG.
  • the reaction chamber 2 has a temperature of 1100 ° C.
  • two gas inlets 1 1, 12 are arranged on the reaction chamber 2 in the region of the inlet opening 8, via which the gaseous Siliziu m precursor compound and the process gas can be introduced separately into the reaction chamber.
  • highly pure hydrogen is used as the process gas.
  • the gas inlets 1 1, 12 are each connected to a fluid supply line 1 3, 14, via which the silicon precursor compound and the process gas to the gas inlets 1 1, 12 can be supplied.
  • silicon tetrachloride is used as the silicon precursor compound. Since silicon tetrachloride has a boiling point of 57.6 ° C. and is therefore liquid at room temperature, an evaporator 15 is arranged on the fluid supply line 1 3. By means of the evaporator 1 5 liquid silicon tetrachloride is converted into the gaseous state of matter before it is introduced into the reaction chamber 2.
  • the reaction chamber 2 After the substrates have been coated with silicon, the excess of the gas mixture from the excess silicon precursor compound, the silicon-based intermediate product and the process gas can be removed from the reaction chamber 2, the reaction chamber 2 has a gas outlet 16 in the region of the outlet opening 9 , The gas outlet 1 6 is connected to the circulation line 5, which for the return of at least one of the components of the excess of the gaseous mixture selected from the Siliziu m precursor compound, the silicon-based intermediate and / or the process gas, in the reaction chamber 2 is used. Furthermore, the circulation line 5 is connected to the fluid supply line 1 3.
  • the gas scrubber 6, the recovery unit 7 and the measuring unit 3 are arranged on the circulation line 5, which are connected to each other via the continuous circulation line 5 and from the side of the gas outlet 1 6 to the side of the fluid supply line 1 third
  • the gas scrubber 6 serves to concentrate the discharged excess of the gaseous mixture from the reaction chamber, by bringing the discharged gaseous excess into contact with a scrubbing liquid in the gas scrubber 6, as a result of which usable constituents of the excess can be taken up in the scrubbing liquid.
  • the passing components may be solid, liquid or gaseous substances.
  • a washing liquid for example, chlorosilane can be used.
  • the purified excess of the gaseous mixture can be passed via the circulation line 5 in the recovery unit 7.
  • the recovery unit 7 is designed as a distillative separation apparatus. It serves to separate the silicon precursor compound and / or the silicon-based intermediate from the process gas. In addition, the recovery unit 7 allows the separation of unwanted by-products of the chemical vapor deposition from the circulation line. 5
  • the measuring unit 3 is arranged on the circulation line 5.
  • the measuring unit 3 is designed as an infrared spectrometer which measures a concentration of the silicon-based intermediate and the silicon precursor compound in the gas flow of the circulation line 5 and thereby determines the molar ratio of the silicon-based intermediate and the silicon precursor compound.
  • the measuring unit 3 can also be designed as a Coriolis mass flowmeter.
  • the invention is not limited thereto.
  • a control unit 4 is arranged on the fluid supply line 1 3, which control unit may be designed, for example, as a gas flow regulator.
  • the control unit 4 also serves to control the molar ratio of the silicon-based intermediate to the silicon precursor compound in the reaction chamber 2 upon introduction.
  • the control unit 4 is connected to the measuring unit 3.
  • a molar ratio determined by the measuring unit 3 from the silicon-based intermediate product to the silicon precursor compound in the excess of the gaseous mixture in the circulation line 5 is forwarded to the control unit 4.
  • U m is a desired molar ratio of the silicon-based intermediate to the silicon precursor compound of 0.2: 0.8 to 0.5: 0.5, preferably 0.3: 0.7 to 0.5: 0.5, particularly preferably 0.5: 0.5 in the process gas in the reaction chamber 2, controls the control unit 4 based on the determined by the measuring unit 3 molar ratio of the silicon-based intermediate to the silicon precursor compound in the excess of the gaseous mixture in the Circulation line 5, the amount of supplied silicon precursor compound via the fluid supply line 1 3 and the gas inlet 12 into the reaction chamber.
  • control unit 4 and the measuring unit 3 are electrically conductively connected to each other, whereby the measured values of the measuring unit 3 are automatically transmitted to the control unit 4.
  • a user of the device 1 reads the molar ratio determined by the measuring unit 3 and transmits it manually to the control unit 4.
  • FIG. 2 shows a second exemplary embodiment of a device 1 according to the invention for the continuous vapor deposition of silicon on substrates.
  • the device 1 has a construction largely identical to the embodiment described in FIG. 1, for which reason further details are not to be considered initially.
  • control unit 4 In order to regulate the feed of the silicon precursor compound and the process gas into the reaction chamber 2, the control unit 4 is arranged on the fluid supply line 1 3, 14. On the one hand, the control unit 4 serves to increase the molar ratio of the silicon-based intermediate product to the silicon. To control u m precursor compound in the reaction chamber 2 at m initiation and on the other hand, a total amount of the silicon precursor compound and the silicon-based intermediate in step (c) in a molar ratio of 1 to 1 mol%, preferably 2 to 7 mol %, more preferably 3 to 6 mol%, in the process gas to adjust. Also in this embodiment, the control unit 4 is connected to the measuring unit 3.
  • the gas scrubber has a gas outlet 1 7 with a discharge line 18, via which the excess process gas is removed.
  • the invention is not limited thereto.
  • the distillative separation apparatus can also have a gas outlet with a discharge line.
  • FIG. 3 shows a third exemplary embodiment of a device 1 according to the invention for the continuous vapor deposition of silicon on substrates. Also, this device 1 has a structure largely identical to the embodiment described in Figure 1, which is why, for the time being, no further details are to be considered.
  • the circulation line 5 is split after the recovery unit 7 into three separately guided partial lines 51, 52, 53 for the process gas, the silicon-based intermediate and the silicon precursor compound. It is within the scope of the invention that more than three separately guided sub-lines of the recovery unit are connected downstream, in particular, to separately recycle other gases, such as hydrogen chloride.
  • the respective mass or volume flows are determined with separate measuring units 31, 32, 33, which are arranged on the partial lines 51, 52, 53 after the recovery unit 7. From this, the molar ratio of the silicon-based intermediate to the silicon precursor compound can be derived.
  • the recovered process gas is then supplied to the fluid feed line 14, the silicon-based intermediate product and the silicon precursor compound to the fluid supply line 13.

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  • Chemical Vapour Deposition (AREA)
  • Silicon Compounds (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)

Abstract

L'invention concerne un procédé de dépôt continu en phase vapeur de silicium sur des substrats. Le procédé comprend les étapes suivantes : a) introduire au moins un substrat dans une chambre de réaction (2) ; b) introduire un gaz de traitement et au moins un composé précurseur de silicium gazeux dans la chambre de réaction (2) ; c) former un mélange gazeux à partir d'au moins un produit intermédiaire à base de silicium en coexistence avec le composé précurseur de silicium gazeux et le gaz de traitement dans la chambre de réaction (2) ; d) former une couche de silicium par dépôt en phase vapeur de silicium à partir du composé précurseur de silicium gazeux et/ou du produit intermédiaire à base de silicium sur le substrat; e) éliminer un excès du mélange gazeux de la chambre de réaction (2); caractérisé en ce que le procédé comprend en outre une étape (f) dans laquelle l'un au moins des constituants de l'excès de mélange gazeux, choisi parmi le composé précurseur de silicium , le produit intermédiaire à base de silicium et/ou le gaz de traitement est ramené dans la chambre de réaction (2). Dans le procédé, l'introduction du composé précurseur de silicium gazeux dans la chambre de réaction (2) est régulée de sorte que le rapport molaire du produit intermédiaire à base de silicium au composé précurseur de silicium soit compris entre 0,2:0,8 et 0,5:0,5, de préférence 0,3:0,7 à 0,5:0,5, de manière particulièrement préférée soit de 0,5:0,5 dans le gaz de traitement.
EP18793404.7A 2017-10-27 2018-10-25 Procédé et dispositif de dépôt continu en phase gazeuse de silicium sur des substrats Pending EP3701559A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102017125232.0A DE102017125232A1 (de) 2017-10-27 2017-10-27 Verfahren und Vorrichtung zur kontinuierlichen Gasphasenabscheidung von Silizium auf Substraten
PCT/EP2018/079228 WO2019081618A1 (fr) 2017-10-27 2018-10-25 Procédé et dispositif de dépôt continu en phase gazeuse de silicium sur des substrats

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EP3701559A1 true EP3701559A1 (fr) 2020-09-02

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US (1) US11862462B2 (fr)
EP (1) EP3701559A1 (fr)
JP (1) JP2021501261A (fr)
CN (1) CN111279456A (fr)
DE (1) DE102017125232A1 (fr)
WO (1) WO2019081618A1 (fr)

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JPS5964516A (ja) * 1982-10-01 1984-04-12 Fuji Electric Corp Res & Dev Ltd アモルフアスシリコン膜生成方法
JPH07277720A (ja) * 1994-03-31 1995-10-24 Sumitomo Sitix Corp 多結晶シリコンの製造における塩化水素ガス分析方法
US7033561B2 (en) * 2001-06-08 2006-04-25 Dow Corning Corporation Process for preparation of polycrystalline silicon
JP2004071970A (ja) * 2002-08-08 2004-03-04 Shin Etsu Chem Co Ltd 太陽電池用シリコン基板の製造方法およびその製造システム
DE102005045582B3 (de) * 2005-09-23 2007-03-29 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Vorrichtung und Verfahren zur kontinuierlichen Gasphasenabscheidung unter Atmosphärendruck und deren Verwendung
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US11862462B2 (en) 2024-01-02
CN111279456A (zh) 2020-06-12
US20210202237A1 (en) 2021-07-01
WO2019081618A1 (fr) 2019-05-02
DE102017125232A1 (de) 2019-05-02
JP2021501261A (ja) 2021-01-14

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