KR20130095033A - Apparatus and method for treating substrate - Google Patents

Apparatus and method for treating substrate Download PDF

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KR20130095033A
KR20130095033A KR1020120016424A KR20120016424A KR20130095033A KR 20130095033 A KR20130095033 A KR 20130095033A KR 1020120016424 A KR1020120016424 A KR 1020120016424A KR 20120016424 A KR20120016424 A KR 20120016424A KR 20130095033 A KR20130095033 A KR 20130095033A
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South Korea
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gas
substrate
catalyst
purge
nitrogen
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KR1020120016424A
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Korean (ko)
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이기훈
조병철
한창희
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주식회사 원익아이피에스
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Publication of KR20130095033A publication Critical patent/KR20130095033A/en

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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
    • C23C16/44—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
    • 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
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
    • H01L21/283—Deposition of conductive or insulating materials for electrodes conducting electric current
    • H01L21/285—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation
    • H01L21/28506—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers
    • H01L21/28512—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers on semiconductor bodies comprising elements of Group IV of the Periodic System
    • H01L21/28556—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers on semiconductor bodies comprising elements of Group IV of the Periodic System by chemical means, e.g. CVD, LPCVD, PECVD, laser CVD
    • 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
    • H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
    • H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
    • H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
    • H01L21/76838—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the conductors
    • H01L21/76841—Barrier, adhesion or liner layers
    • H01L21/76843—Barrier, adhesion or liner layers formed in openings in a dielectric

Abstract

The present invention relates to a substrate processing apparatus and a substrate processing method, and more particularly, to a substrate processing apparatus and a substrate processing method for depositing a diffusion barrier film to suppress diffusion. An embodiment of the present invention provides a method of loading a substrate into a chamber, exposing the substrate to a catalyst gas, activating the catalyst gas, adsorbing activated catalyst active species to the substrate, Purging the substrate with a purge gas. In addition, before the substrate is treated with the catalyst gas or after the catalyst gas is discharged, the process of adsorbing the nitrogen-activated species generated by activating the nitrogen-containing gas on the surface of the substrate.

Figure P1020120016424

Description

Substrate processing apparatus and substrate processing method {Apparatus and Method for treating substrate}

The present invention relates to a substrate processing apparatus and a substrate processing method, and more particularly, to a substrate processing apparatus and a substrate processing method for depositing a diffusion barrier film to suppress diffusion.

As the integrated circuit density increases, the line width of the metal wiring decreases and the length increases, which causes malfunction of the device, and also causes spikes, electromigration, etc., resulting in inferior circuit reliability. It can also be thrown. As a way to solve this problem is to lower the resistance value of the metal wiring. In order to lower the resistance value and achieve high integration, a material having a low specific resistance is required as the wiring material. The use of materials with low resistivity as the wiring material shortens the RC delay time, reducing the signal delay caused by the connection, resulting in faster device operation.

For this reason, copper is used as a wiring material for semiconductor devices. The melting point of copper is 1080 ° C, which is higher than other metal materials (aluminum: 660 ° C, tungsten: 3400 ° C). (2.7μΩ㎝), because it is much lower than tungsten (5.6μΩ㎝), it is widely used as wiring material. However, copper has a very fast diffusion rate in silicon and oxide, so a diffusion barrier is necessary to prevent the diffusion of copper.

 As the diffusion barrier, a metal or nitride that does not react with copper at all is used, and the performance of the diffusion barrier for copper is better than that of a single element heat-resistant metal (refractory metal). In order to have the characteristics of the diffusion barrier and at the same time to play the role of the electrode, the specific resistance should be low, excellent thermal stability and excellent chemical stability.

Binary nitrides used as diffusion barriers in the past include tantalum nitride (TaN), titanium nitride (TiN), and tungsten nitride (WN) thin films. The resistivity of the tantalum nitride film or tungsten nitride film is the lowest, below 500 micro ohm centimeters.

In addition, due to the reduction in wiring width due to the high directivity, the thickness of the diffusion barrier layer must be thin, and the demand for step coverage is also increased, and there is a limit to using the physical vapor deposition method (PVD) currently applied in the industry. Therefore, the diffusion barrier film deposition method using monoatomic layer deposition (ALD) is the only deposition method to replace the physical vapor deposition method. However, the monoatomic layer deposition method is important in the nature of the deposition method and the reactivity with the incoming gas and vapor pressure, there is a limit in the selection of the incoming gas.

As described above, tungsten nitride film (WN) and tantalum nitride film (TaN) are regarded as the best diffusion barrier films, and when applied to the monolayer deposition method, the gas introduced therein is tungsten hexafluoride gas (WF 6 ) and tantalum. Pentafluoride gas (TaF 5 ), bis (tertbutylimide) bis (secondary methylamide) tungsten gas (BTBMW; bis (tert-butylimido) -bis- (dimethylamido) tungsten), hexakis (secondary methylamide ) Ditungsten gas (W 2 (NMe 2 ) 6 ; hexakis (dimethylamido) ditungsten)). Among them, BTBMW and W 2 (NMe 2 ) 6 are metal organic precursors in which tungsten (W) is combined with a carbon compound. When the thin film is deposited using such a metal organic precursor, the reactivity with the substrate is not good, so the incubation cycles are high, the deposition rate is slow, and the specific resistance is very high due to impurities such as carbon not reacted. . In addition, the price of the metal organic precursor itself is very high, it is necessary to configure an expensive reactor according to the stability and reactivity of the raw material gas, the process is complicated and difficult to apply to mass production.

In addition, when a diffusion barrier is deposited on the surface by monoatomic layer deposition using tungsten hexafluoride (WF 6 ) or tantalum pentafluoride gas (TaF 5 ) instead of a metal organic precursor, tungsten hexafluoride, a halide series, is deposited. If suntan or tantalum pentafluoride gas is used as a reactor, the monoatomic layer process itself is difficult. This is because the tungsten hexafluoride gas or tantalum pentafluoride gas which is not adsorbed on the oxide surface is removed by the purge gas injected after the tungsten hexafluoride gas or tantalum pentafluoride gas during the monolayer layer deposition process, so that the monolayer layer deposition itself does not occur.

Korean Patent Publication 10-2011-0020484

An object of the present invention is to form a diffusion barrier of the monoatomic layer to prevent diffusion on the surface of the substrate. In addition, the technical problem of the present invention is to deposit a diffusion barrier of the monoatomic layer on the surface of the substrate to prevent diffusion into the substrate. In addition, the technical problem of the present invention is to deposit a diffusion barrier film by the atomic layer deposition process on the surface of the substrate. In addition, the technical problem of the present invention is to easily deposit the diffusion barrier on the surface of the substrate.

An embodiment of the present invention provides a method of loading a substrate into a chamber, exposing the substrate to a catalyst gas, activating the catalyst gas, adsorbing activated catalyst active species to the substrate, Purging the substrate with a purge gas.

In addition, before the substrate is treated with the catalyst gas or after the catalyst gas is discharged, the process of adsorbing the nitrogen-activated species generated by activating the nitrogen-containing gas on the surface of the substrate.

In addition, the process of adsorbing nitrogen active species on the surface of the substrate, the process of exposing the substrate to a nitrogen-containing gas, activating the nitrogen-containing gas, adsorbing activated nitrogen active species to the substrate, And purging the substrate with a purge gas.

In addition, activating a catalyst gas may include generating a plasma in the catalyst gas inside or outside the chamber, and activating the nitrogen-containing gas may generate plasma in the nitrogen-containing gas inside or outside the chamber. It includes the process of making.

In addition, after the substrate is purged with a purge gas, a deposition film is deposited. The process of depositing the deposition film includes exposing the source gas to expose the substrate to the source gas, and unreacted source gas present on the substrate as the purge gas. A source gas purge process to purge, a reaction gas exposure process to expose the substrate to the reaction gas, a reaction gas purge process to purge the unreacted reaction gas present on the substrate with the purge gas, and the source gas exposure process , The source gas purge process, the reaction gas exposure process, and the reaction gas purge process are repeated.

In addition, a source gas exposure process, a source gas purge process, a reaction gas exposure process, and a reaction gas purge process are repeatedly performed until the desired thickness of the deposited film is formed, but from the second cycle, before the source gas exposure, the substrate is exposed to the catalyst gas. Then purge with purge gas.

In addition, the substrate processing apparatus according to the embodiment of the present invention includes a chamber having an internal space in which a substrate is located and including a catalyst gas inlet through which a catalyst gas for processing the substrate is introduced and a purge gas inlet through which purge gas is introduced; A substrate support on which the substrate is positioned in the interior space of the chamber, a gas injection unit for injecting the catalyst gas and the purge gas introduced through the catalyst gas inlet and the purge gas inlet into the surface of the substrate, and the interior space of the chamber And a control unit for controlling the gas supply unit and the plasma generating unit to generate a plasma to activate the catalyst gas, and to activate the catalyst gas and treat the substrate with the activated catalyst active species.

According to an embodiment of the present invention, a diffusion barrier film may be deposited on a surface of a substrate using an atomic layer deposition process. In addition, according to the embodiment of the present invention, it is possible to deposit without an intermediate layer between the substrate or the lower layer and the diffusion barrier. In addition, according to an embodiment of the present invention, by performing the surface treatment using a catalyst before the deposition of the diffusion barrier, it is possible to improve the deposition properties of the diffusion barrier. Therefore, the diffusion barrier can be easily deposited on the surface of the substrate.

1 is a perspective view illustrating a substrate processing apparatus 10 for depositing a diffusion barrier film according to an exemplary embodiment of the present invention.
2 is a flowchart illustrating a substrate processing process for depositing a diffusion barrier film according to an embodiment of the present invention.
3 is a time chart sequentially showing the appearance of gas injection and plasma for surface treatment and diffusion barrier film deposition according to an embodiment of the present invention.
4 is a diagram illustrating a process of depositing a diffusion barrier film on a substrate after surface treatment according to an embodiment of the present invention.
5 is a view showing a cross-sectional view of a multi-layered metal wiring window.
6 shows that when a tungsten nitride film was prepared by monoatomic deposition using tungsten hexafluoride gas (WF 3 ) and ammonia (NH 3 ) gas, no tungsten or tungsten nitride film was deposited on the oxide surface. Results and analysis of the aromatic element distribution as a result of the diffusion of tungsten into the silicon through the silicon and oxide interface.
FIG. 7 is a diagram illustrating a series of flowcharts for forming a single layer of tungsten nitride thin film using a monoatomic layer deposition method using plasma according to an embodiment of the present invention.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings. It will be apparent to those skilled in the art that the present invention may be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, It is provided to let you know. Wherein like reference numerals refer to like elements throughout.

1 is a perspective view illustrating a substrate processing apparatus 10 for depositing a diffusion barrier film according to an exemplary embodiment of the present invention.

An internal space 110 in which the deposition, etching, etc. are performed on the substrate is formed in the chamber 100. In addition, the chamber 100 is provided with a gate 101 through which the substrate enters and exits and an exhaust passage 102 for discharging gas in the chamber for loading / unloading the substrate. The exhaust passage 102 is connected to an external pump for discharging the gas supplied to the internal space of the chamber to the outside. In addition, the chamber 100 may include a reaction part having a predetermined space, including a substantially circular flat part and a side wall part extending upwardly from the planar part, and a lid positioned on the reaction part in a substantially circular shape to keep the chamber airtight. Can be. Of course, the reaction unit and the cover may be manufactured in various shapes other than a circular shape, for example, may be manufactured in a shape corresponding to the shape of the substrate. In addition, a catalyst gas inlet through which the catalyst gas for treating the substrate is introduced and a purge gas inlet through which the purge gas is introduced are formed in the chamber. The catalyst gas inlet and the purge gas inlet are supplied with the catalyst gas and the purge gas from the gas supply unit through pipes and valves, respectively.

The substrate support 200 is formed in a flat plate shape where a plurality of substrates are seated, and a plurality of substrates W are disposed radially on the substrate support 200. The substrate support 200 is coupled to the drive shaft and formed in the inner space of the chamber so as to be lifted and rotated. Therefore, when the process proceeds, the substrate support 200 rotates in parallel to the shower head 300. A plurality of seating portions (not shown) on which the substrate is mounted is formed on the upper surface of the substrate support 200. In addition, a heater (not shown) is mounted inside or outside the substrate support 200. The heater generates heat to a predetermined temperature to heat the substrate so that the diffusion barrier film by the vapor deposition source is easily deposited on the substrate.

A plurality of substrates W may be disposed on the substrate support 200 to form a radial shape, and each of the plurality of substrates is sequentially moved to an area where source gas, purge gas, and reactive gas are injected, and is exposed to each gas. The diffusion barrier film is deposited by the vapor deposition process.

The plasma generator 500 excites a source used for surface treatment, such as nitrogen (N 2 ) containing gas or a catalyst gas, into a plasma state to generate active species (radicals) having charges. The plasma generating unit 500 applies electric power to the shower head on the substrate of the reaction chamber 100 and grounds it to the substrate support, thereby capacitively coupling plasma (CCP) to excite the plasma using RF in the reaction space which is the deposition space of the substrate. ; Capacitively Coupled Plasma) can be driven. In the exemplary embodiment of the present invention, the capacitively coupled plasma (CCP) method is exemplified, but the present invention is not limited thereto and may be implemented by an inductively coupled plasma (ICP) method. In addition, as in the remote plasma generator, the gas may be remotely activated by the plasma to be supplied into the chamber.

The gas injection unit 300 is a device for injecting a gas, for example, a shower head, and is installed above the chamber internal space, that is, above the substrate support 200.

The gas injection unit is implemented in a structure of one gas injection zone or a plurality of gas injection zones.

When the gas injection unit is implemented in a structure having one gas injection zone, the gas is injected into the chamber in the order of catalyst gas (nitrogen-containing gas)-> source gas-> purge gas-> reactive gas-> purge gas A layer deposition process takes place.

Meanwhile, when the gas injection unit is implemented in a structure having a plurality of gas injection zones, the gas injection unit 300 injects a catalyst gas, an atomic layer deposit (ALD) source gas, a purge gas, and a reaction gas. It is implemented by a plurality of gas injection zones. When the gas injection unit is implemented as a shower head, a plurality of gas injection regions in a single unit may be formed by combining a plurality of gas injection regions in a lower portion (lower surface) of the top plate. That is, the shower head includes a top plate into which different gases are introduced, and a plurality of gas injection zones coupled to the bottom of the top plate to inject different gases. In addition, the central portion of the shower head includes a curtain gas injection zone in which a purge gas serving as a curtain gas is injected so that the gases injected from each gas injection zone are not mixed. The gas injection zones provided in the gas injection unit include gas injection zones for injecting catalyst gas-> source gas-> purge gas-> reactive gas-> purge gas. That is, a plurality of gas injection zones including a catalyst gas injection zone, a source gas injection zone, a purge gas injection zone, and a reaction gas injection zone is provided so that these gas injection zones are radially disposed along the circumference of the shower head which is a gas injection device. do. Therefore, gases are injected from each gas injection zone, the substrate support rotates, and the substrates placed on the substrate are sequentially exposed in the order of the catalyst gas-> source gas-> purge gas-> reaction gas-> purge gas. On the other hand, the gas injection unit may be rotated so that the gases are sequentially exposed to the substrate.

On the other hand, the source gas and the reaction gas is a gas used in the atomic layer deposition process (ALD) to deposit the diffusion barrier, the source gas is a tungsten hexafluoride gas (WF 6 ) or tantalum (Ta) containing tungsten (W) ) Tantalum pentafluoride gas (TaF 5 ) is used, and a nitrogen-containing gas such as ammonia gas (NH 4 ) containing nitrogen (N 2 ) is used as the reaction gas. The purge gas is a gas used to deposit and purge the remaining source gas and the reaction gas on the remaining substrate in the chamber, and an inert gas such as argon (Ar), nitrogen (N 2 ) or hydrogen (H 2 ) is purged gas. It can be used as.

The gas supply unit 400 is a means for supplying a purge gas for purging a space, a source gas for atomic layer deposition, and a reaction gas to the internal space of the chamber via the gas injection unit. Include. The gas supply unit is a catalyst gas such as diborane (B 2 H 6 ) or sealant (SiH 4 ), tungsten hexafluoride gas (WF 6 ) containing tungsten (W) or tantalum pentafluoride gas containing tantalum (Ta). (TaF 5) containing source gas, a nitrogen-containing nitrogen (N 2), such as gas, hydrogen (H 2) or nitrogen (N 2) or argon supplying a purge gas, such as (Ar) into the reservoir chamber interior to each do.

The control unit 600 performs a surface treatment for adsorbing the catalytically active species (catalyst radicals) generated by activation by the catalyst gas plasma in the internal space 110 of the chamber, and then through the atomic layer deposition process (ALD). The diffusion barrier film, which is a vapor deposition film, is deposited on the substrate surface or the like.

When the diffusion barrier layer is deposited on the surface of the substrate through the atomic layer deposition process using tungsten hexafluoride gas (WF 6 ) or tantalum pentafluoride gas (TaF 5 ) as a source gas, it is difficult to deposit a monoatomic layer. In order to solve this problem, the surface treatment is performed to adsorb the active species (radicals) by activating boron and / or nitrogen by plasma before the atomic layer deposition process of the diffusion barrier.

The control unit 600 adsorbs the catalytically active species (radicals) generated by plasma-activating the catalyst gas to the surface on which the diffusion barrier is to be formed. At this time, before or after the adsorption of the catalytically active species, the nitrogen-activated species which activated the nitrogen-containing gas is adsorbed. Adsorb onto the substrate surface. These nitrogen active species are provided activated within or outside the chamber.

In addition, the control unit 600 exposes the substrate by exposing the catalyst gas to the substrate before proceeding to the next atomic layer deposition process after the exposure of the source gas and the reaction gas and the purge discharge according to the atomic layer deposition process. Process. At this time, plasma is not generated when the substrate is exposed to the catalyst gas.

In addition, the controller 600 controls the plasma generation on / off of the plasma generator 500 according to the type of gas exposed to the substrate. That is, the plasma is generated when the substrate is exposed to the catalyst active species or the nitrogen active species, and the plasma is turned off when the substrate is exposed to the source gas and the reaction gas according to the atomic layer deposition process. In addition, when the catalyst gas is exposed to the substrate after the reaction gas purge discharge of the atomic layer deposition process, a control to turn off the plasma is performed.

2 is a flowchart illustrating a substrate treatment process for depositing a diffusion barrier film according to an embodiment of the present invention, Figure 3 is a sequence of gas injection and plasma application for the surface treatment and diffusion barrier film deposition according to an embodiment of the present invention 4 is a diagram illustrating a process of depositing a diffusion barrier on a substrate after surface treatment according to an embodiment of the present invention.

Conventionally, in order to deposit a diffusion barrier, a thin film is deposited using a metal organic precursor such as BTBMW and W 2 (NMe 2 ) 6 . However, when the deposition using the metal organic precursor, due to the poor reactivity with the substrate (incubation cycles), the deposition rate is slow, the specific resistance is very high due to impurities such as carbon not reacted. In addition, the price of the metal organic precursor itself is very high, and according to the stability and reactivity of the raw material gas, an expensive reactor must be configured, and the process is complicated and there is a problem that it is difficult to apply to mass production.

Therefore, a method of using tungsten hexafluoride gas (WF 6 ) as a tungsten source and a tantalum pentafluoride gas (TaF 5 ) as a tantalum source may be considered instead of metal organic precursors such as BTBMW and W 2 (NMe 2 ) 6 . However, when a halide-based tungsten hexafluoride gas (WF 6 ) or tantalum pentafluoride gas (TaF 5 ) is used as a reactor, the monoatomic layer process itself is difficult. The reason for this is shown in FIG. 5, which shows a cross-sectional view of the multi-layered metal interconnection window. The surface on which the diffusion barrier 12 is formed is mostly an interlayer insulating film 1, and most of the oxide is tungsten hexafluoride gas (WF 6 ). Alternatively, tungsten hexafluoride gas or tantalum penta is not adsorbed on the oxide surface by the purge gas injected after tungsten hexafluoride gas or tantalum pentafluoride gas during the monolayer deposition process because no tantalum pentafluoride gas (TaF 5 ) is adsorbed. By removing the fluorine gas, monoatomic layer deposition itself does not occur. In addition, the tungsten hexafluoride gas or tantalum pentafluoride gas adsorbed on the silicon surface has a problem in that a fluorine component of the tungsten hexafluoride gas or tantalum pentafluoride gas remains as a by-product and penetrates into the silicon and oxide interface to generate a defect. In Fig. 5 showing a cross-sectional and enlarged view of the multi-layered metal wiring, reference numeral 1 denotes an interlayer insulating film, reference numeral 2 denotes a p-type well, reference numeral 3 denotes a source / drain, reference numeral 4 denotes a silicon substrate, and 5 is a spacer, 6 is a capping layer of an interlayer insulating film, 7 is a gate insulating film, 8 is a gate, 9 is a thin trench isolation, 10 is a tungsten contact plug, and 11 is a A metal wiring window, reference numeral 12 denotes a diffusion barrier, reference numeral 13 denotes a copper seed layer, and reference numeral 14 denotes a copper wiring.

For reference, FIG. 6 shows that when a tungsten nitride film was manufactured by monoatomic deposition using tungsten hexafluoride gas (WF 3 ) and ammonia (NH 3 ) gas, no tungsten or tungsten nitride film was deposited on the oxide surface. Depth element distribution analysis using an Auger electron spectrometer showing the results (Fig. 6A) and the result of tungsten diffusion into the silicon through the silicon and oxide interface (Fig. 6B), deposited on an oxide substrate, which is a problem of the prior art. This shows a problem of not penetrating and penetrating deep into the substrate due to the fluoride element of the halide series. Therefore, in the conventional method, it is not possible to form a monoatomic layer metal-nitride film intended to be used as the diffusion barrier film 12 of copper through the metal wiring window 11 having various multilayer structures as shown in FIG. 5.

In order to solve this problem, an embodiment of the present invention, when depositing a copper diffusion barrier, a surface treatment process (or xylene) that boronizes or boronizes the surface on which the diffusion barrier is to be formed using a highly reactive boron. Surface treatment process using (SiH 4 ), followed by reaction with fluorine elements by hydrogen radicals of tungsten hexafluoride gas (WF 6 ) or tantalum pentafluoride gas (TaF 5 ) to tungsten (W) or tantalum (Ta). ) Only the elements contribute to the reaction.

In the following description, an example of depositing a diffusion barrier layer using tungsten hexafluoride gas (WF 6 ) or tantalum pentafluoride gas (TaF 5 ) in a trench of a substrate is described, but is not limited thereto. It will be apparent that the barrier film deposition can be made.

In detail, first, the substrate is loaded into the chamber as shown in Fig. 4A (S202 in Fig. 2). To this end, a substrate mounting means is used to move a substrate having a predetermined structure, for example, a trench, to a required position on a deposition process inside a chamber to seat the substrate. When the substrate is loaded into the chamber, the substrate is seated on the substrate support, and the substrate elevator is lifted upward to maintain the gap between the substrate support and the gas injection means at a predetermined interval.

The heater in the substrate support is used to maintain the substrate at a predetermined temperature, for example 200 ° C. to 400 ° C., and the pressure in the reaction chamber to maintain 10 [mTorr] to 30 [Torr].

In operation S204, a nitrogen-containing gas containing nitrogen for nitriding the surface on which the diffusion barrier film is to be deposited is exposed to the substrate. The nitrogen-containing gas may include ammonia (NH 4 ), nitrogen (N 2 ), nitrous oxide (NO 2 ), and the like. The nitrogen-containing gas is exposed in the range of 0.05 seconds to 5 seconds, preferably at 0.3 seconds.

As shown in FIG. 4 (b), the nitrogen-containing gas is exposed to the substrate and the nitrogen-containing gas is activated while the nitrogen-containing gas is exposed (S204). Ammonia (NH 4 ), which is a nitrogen-containing gas exposed to the substrate, is decomposed into nitrogen-activated species (nitrogen-reactive atoms) and hydrogen-activated species due to the simultaneously applied plasma, thereby making the reactive nitrogen species highly reactive to the surface of the substrate on which the diffusion barrier film is to be deposited. Nitrogen radicals are adsorbed and nitrided.

After exposure of the nitrogen-containing gas and simultaneous activation, a process of purging the nitrogen-containing gas and discharging it to the outside of the chamber using a purge gas such as hydrogen (H 2 ) or nitrogen (N 2 ) as shown in FIG. 4 (c). It has (S206).

After treating and purging the surface of the substrate on which the diffusion barrier film is to be deposited with the plasma-activated nitrogen-containing gas as described above, the substrate is exposed to the catalyst gas (S208). As the catalyst gas, highly reactive diborane (B 2 H 6 ) or xylene (SiH 4 ) may be used. In the following description, an example using diborane (B 2 H 6 ) as the catalyst gas will be described. The catalyst gas is exposed to the substrate within the range of 0.05 seconds to 5 seconds, preferably exposed to 0.2 seconds.

As shown in FIG. 4D, the plasma is simultaneously generated through the plasma generator while the catalyst gas is exposed to the substrate (S208). For example, diborane (B 2 H 6 ), which is a catalyst gas, is exposed to the substrate for 0.2 seconds and plasma is simultaneously applied to maintain 0.2 seconds. Diborane activated by plasma after being exposed to the substrate is decomposed into boron radicals and hydrogen radicals, and boron active species (boron radicals) are adsorbed onto the surface on which the diffusion barrier film is to be deposited. Diborane (B 2 H 6 ), which is a catalyst gas, is adsorbed on the surface of the substrate in the form of boron active species (boron radical) using plasma as an energy source.

After exposure of the catalyst gas and simultaneous adsorption of active species by plasma activation, the catalyst gas is purged using purge gas such as hydrogen (H 2 ) or nitrogen (N 2 ) as shown in FIG. It has a process of discharging to the outside of the chamber (S210). On the other hand, the above description has been given an example of the catalyst gas treatment after the nitriding treatment, on the contrary, the same result can be obtained even if the nitriding treatment after the catalyst gas treatment.

When the adsorption treatment of nitrogen active species and adsorption of boron active species as described above, the adsorbed nitrogen active species and some of the boron active species react to form boron nitride, and some are adsorbed as nitrogen active species and boron active species. do. Due to the surface treatment of nitriding treatment and adsorption treatment of boron active species as described above before forming the diffusion barrier, the metal is easily combined with the source gas and the reaction gas by the subsequent atomic layer deposition (ALD) process. Deposition of monoatomic layer of nitride film is easily followed. After the diffusion barrier in the form of a metal-nitride film of the monoatomic layer is formed, the components of the catalyst gas do not remain.

After the adsorption treatment of the nitrogen-activated species and the adsorption treatment of the boron-activated species is completed, an atomic layer deposition process (ALD) as shown in FIG. 4 (f) is performed on the surface of the adsorption treatment, as a result shown in FIG. 4 (g). A diffusion barrier film such as tungsten nitride film WN or tantalum nitride film TaN is deposited. After deposition of the diffusion barrier, a metal wiring such as copper (Cu) or tungsten (W) is deposited on the diffusion barrier as shown in FIG. The metallization is deposited by chemical vapor deposition (CVD).

The process of depositing the diffusion barrier film by the atomic layer deposition process (ALD) on the surface of the substrate surface-treated with nitrogen-containing gas and catalyst gas will be described in detail. First, the substrate is exposed to the source gas by injecting the source gas into the chamber (S214). The source gas may be tungsten hexafluoride gas (WF 6 ) or tantalum pentafluoride gas (TaF 5 ). Tungsten hexafluoride gas (WF 6 ) is used as the source gas when the diffusion barrier of the metal nitride film is formed of tungsten nitride, and tantalum pentafluoride gas (TaF) is used as the source gas when the diffusion barrier is formed of tantalum nitride. 5 ). The source gas is exposed to the substrate for a stabilization time in the range of 0.05 seconds to 5 seconds, preferably 2 seconds. The stabilization time refers to the time required for the source gas to be seated on the substrate.

After the source gas exposure has a source gas purge discharge process to purge the unreacted source gas by purging the purge gas after the stabilization time (S214). The purge gas may be nitrogen (N 2 ), hydrogen (H 2 ), argon (Ar) and the like.

After the source gas purge discharge, the substrate is exposed to the reaction gas (S216). The reaction gas may be a nitrogen-containing gas such as ammonia (NH 4 ), nitrogen (N 2 ), nitrous oxide (NO 2 ) and the like. The reaction gas is exposed to the substrate for a stabilization time within the range of 0.05 seconds to 5 seconds by exposure for the same time as the exposure time of the source gas, preferably 2 seconds.

Exposing the substrate to the reaction gas and purging the substrate with a purge gas after the stabilization time has elapsed reaction gas purge process to discharge the unreacted reaction gas (S218). In this case, a separate plasma is not generated when the source gas and the reactant gas are exposed.

It is determined whether or not the desired deposition film thickness is formed (S220), and ends when the desired deposition film thickness is deposited. For reference, when the source gas is used as tungsten hexafluoride gas (WF 6 ), the diffusion barrier is formed of tungsten nitride film (WN), when the source gas is used as tungsten hexafluoride gas (WF 6 ), the diffusion barrier is tantalum nitride film It is formed of (TaN).

On the other hand, if the desired deposited film thickness is not formed, the substrate is exposed to the catalyst gas (S222). At this time, as the catalyst gas, diborane (B 2 H 6 ) or xylene (SiH 4 ) may be used, and does not generate a separate plasma for activating the catalyst gas. After exposure of the catalyst gas, it is purged and discharged (S224).

The above processes are repeated in sequence until the desired deposited film thickness is formed (S212, S214, S216, S218, S220, S222, S224).

After all, after the nitrogen-activated species adsorption treatment and the boron-activated species adsorption treatment, which are catalysts, the source gas of tungsten hexafluoride gas (WF 6 ) or tantalum pentafluoride gas (TaF 5 ) is exposed, the source gas is exposed to the substrate. Is reacted with hydrogen radicals generated during the decomposition of nitrogen gas and diborane gas, which are exposed, and only tungsten element is easily separated and reacts with nitrogen-activated species or boron-activated species to deposit monoatomic layers of metal-nitride films containing boron. do.

That is, as described in the conventional problem, the problem that the adsorption reaction does not occur between tungsten hexafluoride gas (WF 6 ) or tantalum pentafluoride gas (TaF 5 ) generated in the monoatomic layer deposition process and tungsten hexafluoride gas or tantalum pentafluoride gas In order to prevent defects caused by nitrogen and boron active species, a highly reactive nitriding active species or boron active species is first adsorbed to the surface of the metal wiring window 11 of FIG. 5, followed by tungsten fluoride gas or tantalum pentafluoride gas. It is a method in which only tungsten or tantalum elements contribute to the reaction by allowing the decomposition of to react with the fluorine element by the generated hydrogen radicals even without applying plasma.

For reference, FIG. 7 illustrates an ammonia gas formed on a surface of a tungsten nitride thin film by using a tungsten hexafluoride gas and an ammonia gas in a monolayer layer deposition method using plasma as an embodiment of the present invention. Decomposition process, adsorption process and diborane gas are injected, and the plasma is decomposed into active species (radicals) and reacted with active species including nitrogen already adsorbed on the surface and tungsten hexafluoride gas is injected. This is a series of flow charts that react with the active species adsorbed on the surface to form a thin layer of tungsten nitride.

Although the present invention has been described with reference to the accompanying drawings and the preferred embodiments described above, the present invention is not limited thereto but is limited by the following claims. Accordingly, those skilled in the art will appreciate that various modifications and changes may be made thereto without departing from the spirit of the following claims.

10: substrate processing apparatus 100: chamber
200: substrate support 300: gas injection unit
400: gas supply unit 500: plasma generating unit
600:

Claims (14)

Loading the substrate into the chamber;
Exposing the substrate to a catalyst gas;
Activating the catalyst gas;
Adsorbing activated catalyst active species to the substrate;
Purging the substrate with a purge gas;
≪ / RTI > The method of claim 1, further comprising adsorbing the nitrogen-activated species generated by activating a nitrogen-containing gas to the surface of the substrate before exposing the substrate to the catalyst gas or purging the substrate with a purge gas. . The method of claim 2, wherein the process of adsorbing the nitrogen active species on the substrate surface comprises:
Exposing the substrate to a nitrogen containing gas;
Activating the nitrogen-containing gas;
Adsorbing activated nitrogen active species to the substrate;
Purging the substrate with a purge gas;
≪ / RTI > The substrate treating method of claim 2, wherein the activated catalyst gas and the nitrogen-containing gas are adsorbed onto the substrate within 0.05 seconds to 5 seconds, respectively. The method of claim 1, wherein the activating of the catalyst gas comprises generating a plasma in the catalyst gas inside or outside the chamber. The method of claim 3, wherein activating the nitrogen-containing gas includes generating a plasma in the nitrogen-containing gas inside or outside the chamber. The method of claim 1, wherein the substrate is exposed to the catalyst gas and the catalyst gas is activated. The method of claim 3, wherein the substrate is exposed to the nitrogen-containing gas and the nitrogen-containing gas is activated. The method of claim 1 or 2, wherein the deposition of the deposition film after purging the substrate with a purge gas, the process of depositing the deposition film,
A source gas exposure process of exposing the substrate to the source gas;
A source gas purge process of purging the unreacted source gas existing on the substrate with a purge gas;
A reaction gas exposure process of exposing the substrate to the reaction gas;
A reaction gas purge process of purging the unreacted reaction gas existing on the substrate with a purge gas;
Substrate treatment method for repeating the source gas exposure process, source gas purge process, reaction gas exposure process, reaction gas purge process. The method of claim 9, wherein the deposition film is repeatedly subjected to a source gas exposure process, a source gas purge process, a reaction gas exposure process, and a reaction gas purge process until the desired thickness is formed, but from the second cycle, before the source gas exposure, the substrate is removed. And purging with purge gas after exposure to the catalyst gas. The substrate treating method according to claim 1 or 2, wherein the catalyst gas is any one of diborane (B 2 H 6 ) and xylene (SiH 4 ). The method of claim 9, wherein the source gas is tungsten hexafluoride gas (WF 6 ) or tantalum pentafluoride gas (TaF 5 ), and the reaction gas is a nitrogen-containing gas. The substrate processing method according to claim 9, wherein the substrate is treated in an environment of a chamber internal pressure of 10 [mTorr] to 30 [Torr] and a substrate temperature of 200 ° C to 400 ° C. A chamber having an internal space in which a substrate is located and including a catalyst gas inlet through which a catalyst gas for processing the substrate is introduced and a purge gas inlet through which purge gas is introduced;
A substrate support on which the substrate is placed in the inner space of the chamber;
A gas injection unit spraying the catalyst gas and the purge gas introduced through the catalyst gas inlet and the purge gas inlet to the surface of the substrate;
A plasma generator for generating a plasma in an inner space of the chamber;
A controller activating the catalyst gas and treating the substrate with the activated catalyst active species;
Substrate processing apparatus comprising a.




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