WO2012146397A1 - Procédé pour former une couche sur un substrat - Google Patents

Procédé pour former une couche sur un substrat Download PDF

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Publication number
WO2012146397A1
WO2012146397A1 PCT/EP2012/001861 EP2012001861W WO2012146397A1 WO 2012146397 A1 WO2012146397 A1 WO 2012146397A1 EP 2012001861 W EP2012001861 W EP 2012001861W WO 2012146397 A1 WO2012146397 A1 WO 2012146397A1
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WO
WIPO (PCT)
Prior art keywords
plasma
substrate
semiconductor substrate
layer
process chamber
Prior art date
Application number
PCT/EP2012/001861
Other languages
German (de)
English (en)
Inventor
Jürgen NIESS
Alexander Gschwandtner
Wilhelm Kegel
Wilfried Lerch
Original Assignee
Hq-Dielectrics Gmbh
Centrotherm Thermal Solutions Gmbh & Co. Kg
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
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Application filed by Hq-Dielectrics Gmbh, Centrotherm Thermal Solutions Gmbh & Co. Kg filed Critical Hq-Dielectrics Gmbh
Publication of WO2012146397A1 publication Critical patent/WO2012146397A1/fr

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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
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
    • H01L21/02227—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a process other than a deposition process
    • H01L21/0223—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a process other than a deposition process formation by oxidation, e.g. oxidation of the substrate
    • H01L21/02233—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a process other than a deposition process formation by oxidation, e.g. oxidation of the substrate of the semiconductor substrate or a semiconductor layer
    • H01L21/02236—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a process other than a deposition process formation by oxidation, e.g. oxidation of the substrate of the semiconductor substrate or a semiconductor layer group IV semiconductor
    • H01L21/02238—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a process other than a deposition process formation by oxidation, e.g. oxidation of the substrate of the semiconductor substrate or a semiconductor layer group IV semiconductor silicon in uncombined form, i.e. pure silicon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
    • H01J37/32—Gas-filled discharge tubes
    • H01J37/32009—Arrangements for generation of plasma specially adapted for examination or treatment of objects, e.g. plasma sources
    • H01J37/32192—Microwave generated discharge
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
    • H01J37/32—Gas-filled discharge tubes
    • H01J37/32431—Constructional details of the reactor
    • H01J37/32715—Workpiece holder
    • H01J37/32724—Temperature
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
    • H01J37/32—Gas-filled discharge tubes
    • H01J37/32431—Constructional details of the reactor
    • H01J37/32733—Means for moving the material to be treated
    • 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
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
    • H01L21/02227—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a process other than a deposition process
    • H01L21/02252—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a process other than a deposition process formation by plasma treatment, e.g. plasma oxidation of the substrate

Definitions

  • the present invention relates to a method for forming a layer on a substrate, in particular on a semiconductor substrate.
  • dielectric or other layers on a substrate For the formation of dielectric or other layers on a substrate, different methods are known.
  • An example of such a method is the formation of thermal oxide layers on semiconductor substrates in so-called ovens or rapid heating systems (RTP systems).
  • RTP systems rapid heating systems
  • a disadvantage of such a thermal oxidation can be, inter alia, the temperatures used in which the oxidation is carried out, since these can affect the underlying structures. Therefore, such systems always strive to reduce the thermal budget of the treatment, for example, by particularly rapid heating and / or cooling of the substrate, but only partially succeed.
  • the layer formation can be influenced, in particular in the case of thermal oxidation, by the orientation of the semiconductor crystal, which is the case, for example, with multicrystalline silicon substrates uneven layer thicknesses and the expression of undesirable structure formation can lead.
  • a plasma treatment of substrates for forming dielectric layers is also known.
  • US Patent 7,381,595 B2 discloses low temperature plasma oxidation of a silicon semiconductor using a high density plasma.
  • the plasma source hereinafter collectively referred to as a plasma electrode
  • the plasma electrode is formed by two plate-shaped opposing electrodes.
  • the substrates are received between the two plate-shaped opposing electrodes and themselves form part of the one electrode.
  • the temperatures used in plasma oxidation significantly reduce the thermal budget over thermal oxidation, and can thereby improve the associated disadvantages.
  • a similar plasma electrode which is formed from two opposing plate-shaped electrodes and in which a substrate to be treated is arranged between the electrodes, results from US Pat. No. 6,037,017 A.
  • the distance between the electrodes can be set as a function of different process parameters .
  • Further plasma electrodes of this type are known from US2007 / 0026540 A1, US Pat. No. 5,492,735 and US Pat. No. 5,281,557.
  • rod-shaped microwave plasma electrode in which an inner conductor is completely surrounded in a first portion of an outer conductor. Adjacent to this sub-area is followed by a sub-area, in which the outer conductor provides an opening which widens to a free end. In the area of the widening opening, microwave power is used to generate a Plasmas decoupled.
  • Another rod-shaped plasma electrode with inner conductor, outer conductor and a coupling structure is known for example from DE 197 22 272.
  • Such rod-shaped plasma electrodes may be disposed opposite to a substrate to be treated, and the substrate is not disposed between the plasma-generating electrodes. With such plasma electrodes, improved processing results can be achieved.
  • a method for forming a layer on a substrate in particular for forming thin dielectric layers on a semiconductor substrate, which overcomes at least one of the above disadvantages.
  • a method for forming a layer on a substrate according to claim 1 is provided for this purpose. Further embodiments of the invention will become apparent from the dependent claims. More specifically, in the method of forming the layer on the substrate, heating the substrate to a predetermined process temperature above 500 ° C, a process gas is brought into contact with the semiconductor substrate and a plasma is generated from the process gas adjacent to at least one surface of the semiconductor substrate.
  • a layer formation is initiated by the locally acting electric field (anodic oxidation). Due to the additionally high temperature of the substrate in combination with the process gas, the layer formation is supported. In particular, the interface between the substrate and the layer is positively influenced by the high temperature and the structural sensitivity is suppressed by the locally acting electric field.
  • the substrate is heated to a process temperature between 600 ° C and 900 ° C, and more preferably about 700 ° C.
  • This temperature range is well below normal temperature ranges for thermal layering processes, which are typically, for example, for oxide layers in RTP systems (rapid heating systems) above 900 ° C and usually even over 1000 ° C.
  • the combination of a high-temperature process in the range between 600 ° C and 900 ° C with the use of a plasma can be achieved in similar periods comparable layer thicknesses, which in particular have a more homogeneous structure, while the thermal budget for the layer formation can be reduced.
  • the plasma is generated at least at one time while the semiconductor substrate is heated to the process temperature and in contact with the process gas to directly assist the actual growth process.
  • the plasma it is also possible to use the plasma only in the event of subsequent annealing or else in addition to a previous use in order to subsequently influence the layer properties and the homogeneity of the layer.
  • the plasma is generated by means of microwaves, which are particularly suitable for providing a high electron concentration in the vicinity of the substrate surface whose electric field on the one hand can accelerate the oxidation rate and at the same time can have a "self-healing effect".
  • the plasma can preferably be generated by means of a microwave electrode having inner and outer conductors which is microwaved on one side, wherein the outer conductor forms a coupling-out opening widening to a free end of the electrode.
  • a microwave electrode which is described for example in WO 2010/015385, is particularly suitable for limiting the plasma to the region of the substrate and at the same time providing a high energy density.
  • a distance between the microwave electrode and the semiconductor substrate is changed during the layer formation or a subsequent thermal annealing process in order to influence the ratio between electrons and radicals in the region of the semiconductor surface.
  • a high electron concentration in the region of the substrate surface is present, which has a self-aligning effect independent of the electrochemical potential of the substrate orientation in the film formation and in particular allows a uniform (conformal) layer growth.
  • the electron concentration decreases and there are primarily radicals on the surface, which support another growth mechanism that is not self-healing.
  • the plasma is positioned to the semiconductor substrate during at least a portion of the layer formation or of a thermal annealing process such that primarily an anodic reaction takes place between the process gas and the semiconductor.
  • An anodic reaction (E-field driven) occurs when the reaction is primarily assisted by the electron concentration at the substrate surface and an E-field causes some drift of the reactive species to the reactant, as opposed to a concentration-related diffusion motion in thermal processes.
  • a larger local electric field is formed, which in turn leads to a stronger layer growth. This results in a self-alignment with regard to the layer thickness, which is independent of the orientation of the underlying substrate.
  • the interface between the layer and the underlying substrate becomes atomically homogeneous.
  • the substrate is a silicon substrate and the process gas is an oxygen-containing Gas for generating an oxide layer.
  • the method is also applicable to the formation of other layers, such as nitride, nitroxide, carbide, graphene, Al 2 O 3, Ta 2 O 5 and Nb 2 O 5 layers or other depositable or growable amorphous or crystalline Layers particularly suitable.
  • FIG. 1 shows a schematic sectional view through an apparatus for carrying out the method according to the invention
  • FIG. 2 shows a schematic sectional view through an alternative device for carrying out the method according to the invention
  • Figures 3a and 3b are schematic representations showing different interaction between a plasma and a substrate as a function of the distance between the plasma electrode and the substrate.
  • Figures 4a and 4b are schematic diagrams illustrating different correlations between a plasma and a substrate in response to an electrical bias of a grid interposed between the plasma electrode and the substrate;
  • FIG. 5 shows a temperature heating power and microwave power profile of an exemplary microwave based plasma oxidation at elevated wafer temperature in accordance with the invention
  • FIG. 6 is a graph showing a temperature dependence of a resulting SiO 2 layer thickness and sensitivity of an exemplary microwave-based plasma oxidation
  • FIG. and Fig. 7 is a graph showing a comparison of grown Si0 2 layer thicknesses by means of microwave-based plasma oxidation and by means of thermal dry oxidation (RTO).
  • RTO thermal dry oxidation
  • the device 1 has a vacuum housing 3, which is only indicated in outline, and which defines an elongate process chamber of the flow-through type 4.
  • the device 1 further comprises a transport mechanism 6, a plasma unit 8, and a heating unit 10.
  • a cooling unit may also be provided which forms a temperature control unit together with the heating unit.
  • the substrate may be at least partially surrounded by a protective element, not shown, which is in the same plane as the substrate in order to avoid edge effects in the coating and to virtually increase the physical surface of the substrate.
  • the protective element should preferably have the same or at least similar physical property as the substrate.
  • the vacuum housing 3 has suitable, not shown locks for loading and unloading of the substrates 2 in the process chamber 4.
  • the process chamber 4 is limited, inter alia, by an upper wall 12 and a lower wall 14.
  • the top wall 12, for example, is constructed of aluminum and treated so as to avoid metal contamination or particles in the process chamber.
  • the upper wall 12 has an oblique portion which is angled relative to the lower wall 14 and a portion substantially parallel to the lower wall, as can be clearly seen in FIG.
  • the inclined wall portion is arranged so that the process chamber from left to right - as will be explained in more detail below from an input end to an output end - tapers.
  • the straight area then joins this oblique area.
  • the lower wall 14 extends in a straight line and is constructed, for example, of quartz glass in order to be able to conduct electromagnetic radiation, as will be explained in more detail below.
  • a vacuum pump 16 is provided, via which the process chamber 4 can be pumped out.
  • the pump can also be provided at a different location and it can also be provided several.
  • a pyrometer 18 is provided for a temperature measurement of the substrate 2. Instead of a pyrometer but also another temperature measuring device may be provided at another location of the process chamber or directly on the substrate 2, for example, also from above the temperature of the substrate measure 2. It can also be provided more temperature measuring devices.
  • the process chamber 4 also has at least one gas supply, not shown, via which a process gas can be introduced into the process chamber 4.
  • the transport unit 6 consists essentially of an endless conveyor belt 20, which is circumferentially guided over a plurality of deflection and / or transport rollers 22.
  • the normal direction of rotation for a treatment of the substrate 2 is in the clockwise direction, but it is also possible to move the conveyor belt in a counterclockwise direction circumferentially.
  • an overhead Transporttrum the conveyor belt 20 is arranged such that it extends straight through the process chamber 4 therethrough.
  • the return of the conveyor belt 20 takes place outside the process chamber 4 in order to be able to carry out, for example, cooling and / or cleaning processes on the conveyor belt 20 there.
  • the conveyor belt 20 consists of a material substantially transparent to electromagnetic radiation, such as quartz glass.
  • the conveyor belt 20 should be arranged as completely as possible within the vacuum range, but may also be at least partially outside the vacuum range in a suitable arrangement.
  • the transport unit 6, for example also have a different transport mechanism, such as transport rollers or a magnetic guide.
  • the transport unit 6 can optionally be moved up and down as a whole, as indicated by the double arrow A. This makes it possible, the transport unit 6 and in particular its Transporttrum closer to the upper wall 12 or the lower wall 14 to place, as will be explained in more detail below.
  • the plasma unit 8 is further arranged.
  • the plasma unit 8 consists of a plurality of plasma electrodes 24.
  • the plasma electrodes are preferably designed as rod-shaped microwave applicators having an inner conductor and an outer conductor.
  • the outer conductor is designed so that it allows outcoupling of the microwaves from the intermediate region between the inner and outer conductors in order to form a plasma outside this region, which surrounds, for example, the rod-shaped plasma electrode in the radial direction.
  • the microwave applicators are preferably constructed in particular in such a way that microwave radiation can emerge essentially vertically downwards, that is to say in the direction of the lower wall 14.
  • one or more plasma ignition devices may be provided.
  • the respective plasma electrodes have in common that the Do not place substrates between the conductors / electrodes of the plasma electrode.
  • the structure of the plasma electrodes can be chosen so that the burning plasma is limited in its extent and does not come into contact with walls of the process chamber. This could otherwise result in undesirable reactive species that could lead to metal contamination on the substrate.
  • a corresponding impurity can also be avoided, provided that a critical bombardment energy of 14 eV is not exceeded by species emerging from the plasma.
  • the rod-shaped plasma electrodes 24 each extend perpendicular to the plane of the drawing across the process chamber 4. From left to right, i. from an input end to an output end of the process chamber 4, the plasma electrodes are each equally spaced from the contour of the top wall 12 following. As a result, the plasma electrode 24 closest to the input end of the process chamber 4 is furthest away from the transport strand of the conveyor belt 20. Towards the center of the process chamber, the plasma electrodes 24 are then arranged closer and closer to the conveyor belt 20, and from the middle they are then arranged in each case at the same distance from the conveyor belt. As a result, the distance between the substrate 2 and the plasma electrodes 24 lying directly above it changes during the movement through the process chamber 24.
  • the heating unit 10 consists of a multiplicity of radiation sources 30 which emit electromagnetic radiation for heating the substrate 2 in the direction of the process chamber 4.
  • halogen and / or arc lamps 31 can be used, as they are commonly used, for example, in high-speed heating systems.
  • the lamps 31 may optionally be housed in quartz tubes 32 to provide isolation from process gases and / or vacuum ratios in the range of Provide process chamber 4. This may be particularly useful if the radiation sources are received directly within the process chamber 4. That is not on the lower wall 14 are separated from this.
  • heating lamps can also be arranged above the transport unit 6, for example also between the plasma electrodes 24.
  • the heating unit 10 is designed such that it accommodates substrates 2 accommodated in the process chamber 4 at temperatures above 500.degree.
  • FIG. 2 shows a schematic sectional view of an alternative device 1 for applying layers on a substrate 2 according to an alternative embodiment.
  • the same reference numerals will be used as before, if the same or similar elements are described.
  • the device 1 again has a housing, which is shown only very schematically at 3.
  • the housing 3 is in turn filled out as a vacuum housing, and can be pumped off via a vacuum unit, no longer shown, to vacuum pressure.
  • a process chamber 4 is defined.
  • the device 1 further has a substrate support unit 6, a plasma unit 8 and a heating unit 10.
  • the support unit 6 has a substrate support 40, which is rotatably supported by a shaft 42 within the process chamber 4, as shown by the arrow B.
  • the shaft 42 is connected for this purpose with a rotary unit, not shown.
  • the shaft 42 and thus the pad 40 is movable up and down, as shown by the double arrow C.
  • the support level of the support 40 within the process chamber 4 can be adjusted upwards or downwards, as will be explained in more detail below.
  • the plasma unit 8 again consists of a plurality of plasma electrodes 24, which may be of the same type as before described.
  • the plasma electrodes may be slidably supported individually within the process chamber 4 via respective guides 46, as indicated by the double-headed arrow D.
  • the up and down mobility of the support unit 6 could be omitted, but it can also be provided in addition.
  • this makes it possible in combination with the rotation of a substrate 2 by the support unit 6, for example, in an edge region of the substrates 2 to provide larger or smaller distances compared to a central region thereof.
  • a protective device may be provided which surrounds the substrate 2 at least partially in its plane in order to avoid edge effects.
  • the protective device may be arranged with respect to the rotation static or rotatable.
  • the substrate 2 and / or the plasma electrodes 24 it is also possible to provide a grid of electrically conductive material between the plasma electrodes 24 and the substrate 2. This can then be applied, for example via a corresponding control unit with different electrical biases. Both a distance adjustment between the plasma electrode 24 and the substrate 2 as well as the application of a different grating to the above-described grating can influence the interaction between the plasma and the substrate, as will be explained in more detail below. Likewise, the substrate may additionally be electrically biased, thereby further enhancing the anodic effect.
  • the heating unit 10 in turn consists of a plurality of radiation sources 30, which may be arranged parallel or perpendicular to the plasma electrodes 24.
  • the radiation sources each comprise a lamp, such as an arc or halogen lamp, that of a quartz tube 32 is surrounded.
  • the radiation of the radiation sources 30 is able to heat the substrate 2 directly when the support 40 for the radiation of the radiation source 30 is substantially transparent.
  • the support 40 could be constructed, for example, of quartz.
  • the device 1 preferably has at least one temperature measuring unit in order to determine the temperature of the substrate 2.
  • the determined temperature can be forwarded to a control unit, not shown, which can then regulate the heating unit 10 according to a temperature specification accordingly to obtain a predetermined temperature of the substrate, as is known in the art.
  • the substrate 2 is in each case a silicon semiconductor wafer.
  • a silicon oxide layer is to be formed as a dielectric layer during the process described below.
  • the method is also suitable for the formation of other layers.
  • a suitable process gas for example, pure oxygen or an oxygen-hydrogen mixture or mixed with N 2 or NH 3 is introduced into the process chamber 4, in which there is a negative pressure. Subsequently, in each case a plasma of the process gas is generated in the region of the plasma electrodes 24.
  • the substrate 2 is conveyed via the conveyor belt 20 from left to right through the process chamber passed, while below the respective plasma electrodes 24 a corresponding plasma burns.
  • the substrate 2 is heated during the transport via the heating unit 10 to a temperature of over 500 ° C, for example to a temperature in the range of 700 ° C.
  • the substrate already has an elevated temperature when it enters the process chamber 4 and the heating unit 10 only keeps this temperature.
  • the left-lying plasma electrodes 24, that is to say inlet plasma electrodes 24, are further away from the substrate 2 than the plasma electrodes 24 on the right, ie in the exit region of the process chamber 4, as it is conveyed through the process chamber.
  • the distance of the plasma electrodes from the substrate surface changes. This results in different growth mechanisms for layer growth. These are caused by different interactions between plasma and substrate, as will be explained in more detail below with reference to FIGS. 3a and 3b.
  • Figures 3a and 3b show different correlations between a plasma and a substrate as a function of a distance between a rod-shaped plasma electrode 300 and a substrate 320.
  • the rod-shaped plasma electrode 300 is of the type described in WO 2010/015385 A, and which have an inner conductor 304 and an outer conductor 306.
  • the outer conductor 306 does not completely surround the inner conductor 304. Rather, the outer conductor 306 provides an opening that enlarges to a free end thereof that faces the substrate 320.
  • 3 a and 3 b each show a cross section in this coupling-out region of the microwave electrode 300.
  • the plasma electrode 300 is surrounded in each case by a cladding tube 308, such as a quartz tube, which is substantially transparent to microwave radiation. With a corresponding activation of the plasma electrode 300 a plasma surrounding the cladding tube 308 is generated, which consists of electrons 310, radicals 312 and ions 314.
  • FIGS. 3 a and 3 b each show a section of a substrate 320, which consists for example of an Si base substrate 322 with a dielectric layer 324 of, for example, SiO x N y , where x and y can vary as desired.
  • a substrate 320 which consists for example of an Si base substrate 322 with a dielectric layer 324 of, for example, SiO x N y , where x and y can vary as desired.
  • positive Si ions are indicated.
  • the plasma electrode is arranged at a distance from the surface of the substrate 320.
  • the plasma in this arrangement is positioned with respect to the substrate such that there is a significant excess of electrons 310 to ions 314 and even more to radicals 312 adjacent to the surface of the substrate. This results in a process gas-dependent anodic oxidation of the substrate surface.
  • Such anodic oxidation is self-adjusting, because where smaller layer thicknesses are formed a larger electric field is formed. This in turn accelerates layer growth locally.
  • any geometric shapes and layer structures (3D structures) can be homogeneously oxidized or any other layers can be deposited or grown.
  • the self-adjusting effect of the anodization leads to a homogeneous breakdown resistance of the grown layer over the substrate, since the oxide grows until the electric field has decayed to a constant value over the layer thickness, so that no significant electrical current can flow through the layer.
  • the potential difference is constant given by the electron density at the surface of the dielectric layer 324.
  • the oxide growth is also largely independent of the orientation of the underlying material and the interface between oxide and silicon is homogenized.
  • the term anodic is intended to mean that the oxidation / nitridation reaction, etc., is primarily driven by electrons / ions or by the resulting electric field.
  • the plasma electrode is arranged at a greater distance D 2 from the surface of the substrate 320.
  • the plasma is arranged with respect to the substrate such that essentially only the radicals 312 adjacent to the surface of the substrate occur. This results in a process gas-dependent radical oxidation of the substrate surface.
  • a radical a reaction is described which is driven primarily by radicals generated in the plasma.
  • the distance between the substrate 2 and the plasma electrode 24 in the input region is selected, for example, in the range of 8 to 15 cm (preferably about 10 cm) to first achieve radical oxidation.
  • the distance is, for example, 2 mm to 5 cm (preferably about 2 cm) in order to provide anodic oxidation.
  • the distance is reduced as the substrate 2 moves through the process chamber 4 to about the middle of the process chamber, and then remains substantially constant until the exit. This may, for example, correlate with the temperature of the substrate, the input of the process chamber 4 may be at ⁇ 500 ° C, and then when the substrate reaches the constant pitch region, for example at 500 ° C or above.
  • the distance between the substrate 2 and the plasma electrode 24 can also be changed via a lifting movement of the conveyor belt 20.
  • different gas compositions and / or different pressures can be set in the region of the respective plasmas below the plasma electrodes 24, which can of course overlap one another.
  • the plasmas can also be separated from each other by suitable separating elements, such as glass plates.
  • the substrate during the Movement through the process chamber 4 through heated differently, so that it has, for example in the entrance area a lower temperature than in the exit area or vice versa.
  • the substrate can be maintained at a constant temperature or heated continuously. If there is excessive heating by the plasma, even cooling could be provided. This can further influence the growth processes.
  • the substrate 2 is arranged on the support unit 6 and is heated by the heating unit 10, while a plasma burns in the area of the respective plasma electrodes 24.
  • the substrate is optionally rotated to homogenize the layer formation.
  • the distance between the substrate 2 and the plasma electrode is changed during the layer growth.
  • the distance is reduced from a large initial distance in the range of, for example, 8 to 15 cm to a small distance in the range of, for example, 2 mm to 5 cm.
  • the distance is varied within a range of 10 to 2 cm. This in turn can be done in correlation with the heating of the substrate via the heating units.
  • process parameters relating to the plasmas such as the power of the plasma electrodes 24, the process gas pressure, a gas inflow as well as a gas composition within the process chamber 4.
  • the growth process can be influenced alternatively to the distance adjustment or in addition thereto via a grid made of an electrically conductive material.
  • a change between a primary anodic oxidation / nitridation and a primary radical oxidation / nitridation at a constant distance between the plasma electrode and the substrate is possible.
  • FIGS. 4a and 4b show similar representations to FIGS. 3a and 3b.
  • a respective plasma electrode 300 with inner conductor 304 and outer conductor 306 and a substrate 320 from a base substrate 322 with a dielectric layer 324 are shown.
  • FIGS. 4a and 4b show similar representations to FIGS. 3a and 3b.
  • FIGS. 4a and 4b Surrounding the plasma electrode 300 is a respective plasma of electrons 310, radicals 312 and ions 314. At 326, positive ions are again shown. Furthermore, a grid 330 made of electrically conductive material is shown between the plasma electrode 300 and the substrate 320, which can be acted on by a control unit, not shown, with different electrical bias voltages. When the grid is floating, it does not substantially affect the plasma and results in the situation shown in Fig. 3a, which results in anodic oxidation. On the other hand, when the grid is applied with a positive voltage or grounded, the situation shown in FIG.
  • the distance of the grid 330 to the surface of the substrate 320 can optionally also be adjusted.
  • the plasma can be operated preferably pulsed during the process.
  • the process described above is particularly suitable for forming an oxide layer as a dielectric layer, but may, as mentioned, also form other dielectric layers, such as a nitride layer or an oxynitride layer.
  • Suitable process gases for this purpose are, for example, O 2 , N 2 , NH 3, NF 3 , H 2 O, D 2 O, Ar, N 2 O, H 2 , D 2 , silane or dichlorosilane or trichlorosilane or dichloroethylene, GeH 4 , boranes (US Pat. BH 3 B 2 H 6 ), arsine (ASH 3 ), phosphine (PH 3 CF 4 ), triMethylAluminum ((CH 3 ) 3 Al), SF 6 or carbon-containing other gases or mixtures thereof or the various precursors for the production of HF. or Zr-containing dielectric layers.
  • the gas composition and / or the pressure of the process gas can be adjusted during the process.
  • the plasma electrodes 24 and the lamps 31 can each be controlled individually and independently of each other. In particular, it is possible to control their performance by means of mathematical functions, such as, for example, a linear function, an exponential function, a quadratic function or other functions.
  • the plasma electrodes 24 or the arc lamps / halogen lamps 31 can be set as groups or completely independently of each other, if this is predetermined by a corresponding process.
  • a purely thermal treatment of a substrate take place, in which the substrate is brought to a predetermined temperature via the heating unit, as it for example, a post oxidation anneal is the case.
  • the transport unit may return the substrate to the substrate after the application of the oxide layer while the plasma is switched off by the process chamber.
  • different gases can be introduced into the process chamber.
  • the substrate would remain in the process chamber beyond the oxidation for a predetermined process duration and be heated by the heating unit.
  • FIG. 5 are exemplary profiles for heating power, wafer temperature and microwave power for plasma generation of a microwave-based plasma oxidation according to the invention at wafer temperatures between 600 ° C and 900 ° C shown.
  • the substrate is first heated to the desired process temperature and then ignited the plasma using the microwave. After switching off the plasma, the temperature is lowered again.
  • Fig. 6 is a graph showing a temperature dependency of a resulting SiO 2 film thickness and sensitivity of the microwave-based plasma oxidation. The results were determined for a plasma burning time of 80 seconds.
  • FIG. 6 shows that the highest SiO 2 growth rates can be achieved in the temperature range> 600 ° C. with the plasma parameters (not specified). In particular, between 700 ° C and 900 ° C, while a further increase in temperature at these parameters no longer has a significant impact on the growth rate, as can be read at the excessive temperatures again decreasing sensitivity curve.
  • FIG. 7 is a graph showing a comparison of grown SiO 2 layer thicknesses by microwave based plasma oxidation and by thermal dry oxidation (RTO).
  • the grown SiO 2 layer thicknesses shown in FIG. 7 during plasma oxidation are comparable to those of purely thermal processes at temperatures higher by about 400-600 ° C.
  • the flattening of the plasma layer thickness curve toward higher temperatures indicates a gradual transition of growth into a predominantly thermally driven mode.
  • the arrangement described above may also be used for cleaning the substrate surface prior to a growth process. With the arrangement contaminations or an undefined layer (eg native SiO 2 ) could be removed from the surface. Then, without breaking a vacuum, a defined layer could be grown by the given process gas.
  • cleaning gases one can imagine a reducing gas of pure hydrogen or an arbitrary with noble gases (such as He, Ar, etc.) diluted hydrogen atmosphere or a pure noble gas atmosphere. In a second process step after replacement of the reducing atmosphere, the growth process described above is possible.
  • the cleaning effect could also be affected by the distance between the plasma electrode and the substrate and / or the electrical bias on the grid (if any).

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Abstract

L'invention porte sur un procédé pour former une couche sur un substrat de semi-produit, suivant lequel le substrat de semi-produit est chauffé à une température de processus prédéterminée supérieure à 500°C, un gaz de processus est projeté sur une surface du substrat de semi-produit et un plasma est produit au voisinage d'au moins une surface du substrat de semi-produit.
PCT/EP2012/001861 2011-04-29 2012-04-30 Procédé pour former une couche sur un substrat WO2012146397A1 (fr)

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DE102011100024A DE102011100024A1 (de) 2011-04-29 2011-04-29 Verfahren zum ausbilden einer schicht auf einem substrat
DE102011100024.4 2011-04-29

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WO2012146397A1 true WO2012146397A1 (fr) 2012-11-01

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DE102011113751B4 (de) 2011-09-19 2016-09-01 Hq-Dielectrics Gmbh Verfahren zum stetigen oder sequentiellen abscheiden einer dielektrischen schicht aus der gasphase auf einem substrat
DE102013010408A1 (de) 2013-06-21 2014-12-24 Hq-Dielectrics Gmbh Verfahren und vorrichtung zum detektieren einer plasmazündung
DE102013014147B4 (de) 2013-08-23 2017-02-16 Centrotherm Photovoltaics Ag Verfahren und vorrichtung zum detektieren einer plasmazündung

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US5281557A (en) 1990-08-02 1994-01-25 At&T Bell Laboratories Soluble oxides for integrated circuit fabrication formed by the incomplete dissociation of the precursor gas
US5492735A (en) 1993-08-31 1996-02-20 Sony Corporation Process for plasma deposition
DE19722272A1 (de) 1997-05-28 1998-12-03 Leybold Systems Gmbh Vorrichtung zur Erzeugung von Plasma
US6037017A (en) 1994-04-26 2000-03-14 Kabushiki Kaisha Toshiba Method for formation of multilayer film
US20060003603A1 (en) * 2004-06-30 2006-01-05 Cannon Kabushiki Kaisha Method and apparatus for processing
US20070026540A1 (en) 2005-03-15 2007-02-01 Nooten Sebastian E V Method of forming non-conformal layers
EP1840950A1 (fr) * 2005-01-07 2007-10-03 Tokyo Electron Limited Procede de traitement au plasma
US7381595B2 (en) 2004-03-15 2008-06-03 Sharp Laboratories Of America, Inc. High-density plasma oxidation for enhanced gate oxide performance
WO2010015385A1 (fr) 2008-08-07 2010-02-11 Gschwandtner, Alexander Dispositif et procédé pour générer des couches diélectriques dans un plasma micro-ondes

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GB8507601D0 (en) * 1985-03-23 1985-05-01 Standard Telephones Cables Ltd Integrated circuits
DE69807006T2 (de) * 1997-05-22 2003-01-02 Canon Kk Plasmabehandlungsvorrichtung mit einem mit ringförmigem Wellenleiter versehenen Mikrowellenauftragsgerät und Behandlungsverfahren
US7517751B2 (en) * 2001-12-18 2009-04-14 Tokyo Electron Limited Substrate treating method
JP2007258585A (ja) * 2006-03-24 2007-10-04 Tokyo Electron Ltd 基板載置機構および基板処理装置

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5281557A (en) 1990-08-02 1994-01-25 At&T Bell Laboratories Soluble oxides for integrated circuit fabrication formed by the incomplete dissociation of the precursor gas
US5492735A (en) 1993-08-31 1996-02-20 Sony Corporation Process for plasma deposition
US6037017A (en) 1994-04-26 2000-03-14 Kabushiki Kaisha Toshiba Method for formation of multilayer film
DE19722272A1 (de) 1997-05-28 1998-12-03 Leybold Systems Gmbh Vorrichtung zur Erzeugung von Plasma
US7381595B2 (en) 2004-03-15 2008-06-03 Sharp Laboratories Of America, Inc. High-density plasma oxidation for enhanced gate oxide performance
US20060003603A1 (en) * 2004-06-30 2006-01-05 Cannon Kabushiki Kaisha Method and apparatus for processing
EP1840950A1 (fr) * 2005-01-07 2007-10-03 Tokyo Electron Limited Procede de traitement au plasma
US20070026540A1 (en) 2005-03-15 2007-02-01 Nooten Sebastian E V Method of forming non-conformal layers
WO2010015385A1 (fr) 2008-08-07 2010-02-11 Gschwandtner, Alexander Dispositif et procédé pour générer des couches diélectriques dans un plasma micro-ondes

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