JP2023002460A - Etching method and plasma processing apparatus - Google Patents

Abstract

To provide an etching method and a plasma processing apparatus that are capable of increasing the etching selection ratio.SOLUTION: An etching method includes the steps of: preparing a substrate, which includes a first region containing silicon and nitrogen and a second region containing silicon and oxygen; and etching the second region while forming a tungsten-containing protective layer on the first region, by exposing the first and second regions to plasma generated from a processing gas containing carbon, fluorine, and tungsten.SELECTED DRAWING: Figure 3

Description

An exemplary embodiment of the present disclosure relates to an etching method and a plasma processing apparatus.

US Pat. No. 5,300,003 discloses a method of selectively etching a first region made of silicon oxide with respect to a second region made of silicon nitride by plasma treatment of a substrate. The second region has a recess. The first region is provided so as to fill the recess and cover the second region. The first region is etched with a plasma generated from a process gas containing fluorocarbons.

JP 2016-157793 A

The present disclosure provides an etching method and plasma processing apparatus capable of improving etching selectivity.

In one exemplary embodiment, the etching method comprises providing a substrate, the substrate comprising a first region comprising silicon and nitrogen and a second region comprising silicon and oxygen; and etching the second region while forming a tungsten-containing protective layer over the first region by exposing the first region and the second region to a plasma generated from a process gas containing fluorine and tungsten. and

According to one exemplary embodiment, an etching method and plasma processing apparatus capable of improving etching selectivity are provided.

FIG. 1 is a schematic diagram of a plasma processing apparatus according to one exemplary embodiment. FIG. 2 is a schematic diagram of a plasma processing apparatus according to one exemplary embodiment. FIG. 3 is a flowchart of an etching method according to one exemplary embodiment. FIG. 4 is a partially enlarged cross-sectional view of an example substrate to which the method of FIG. 3 can be applied. FIG. 5 is a cross-sectional view showing one step of an etching method according to one exemplary embodiment. FIG. 6 is a partially enlarged cross-sectional view of an example substrate obtained by performing an etching method according to one exemplary embodiment. FIG. 7 is an example of a timing chart showing temporal changes in the RF power applied to the electrodes in the main body and the RF power applied to the counter electrode. FIG. 8 is a partially enlarged cross-sectional view of an example substrate to which the method of FIG. 3 can be applied. FIG. 9 is a partially enlarged cross-sectional view of an example substrate obtained by performing an etching method according to one exemplary embodiment. FIG. 10 is a diagram showing an example of the etching process. FIG. 11 shows TEM images of the cross section of the substrate obtained by performing the etching method in the first experiment and the second experiment. FIG. 12 is a diagram showing an example of a cross section of the substrate obtained by executing the etching method in the third experiment and the fourth experiment.

Various exemplary embodiments are described below.

In one exemplary embodiment, the etching method comprises providing a substrate, the substrate comprising a first region comprising silicon and nitrogen and a second region comprising silicon and oxygen; and etching the second region while forming a tungsten-containing protective layer over the first region by exposing the first region and the second region to a plasma generated from a process gas containing fluorine and tungsten. and

According to the above etching method, the etching selectivity of the second region to the first region can be improved. Moreover, according to the above etching method, since the tungsten-containing protective layer is formed on the first region, the shoulder portion of the first region can be particularly protected. As a result, it becomes difficult for the shoulder portion to be inclined, so that a large area of the flat portion on the upper surface of the first region can be secured.

In the etching step, the tungsten-containing protective layer may remain on the first region after the second region is removed.

The process gas may include a carbon- and fluorine-containing gas and a tungsten-containing gas.

The tungsten-containing gas may comprise tungsten hexafluoride gas.

The gas containing carbon and fluorine may include a fluorocarbon gas.

The process gas may contain oxygen. In this case, it becomes difficult to form the carbon-containing film on the first region.

The first region may have a recess, and the second region may be embedded within the recess. In this case, the recess can be formed by etching the second region.

The etching step may be performed in a self-aligned contact step.

In the step of etching, high-frequency power and bias power are supplied to a plasma processing apparatus in order to generate the plasma, and the step of etching comprises: (a) using the high-frequency power as a first power and the bias power as a first power; (b) setting the RF power to a third power lower than the first power, and (c) setting the high-frequency power to the third power and setting the bias power to a fourth power higher than the second power; and Etching two regions.

A cycle including the above (a) to (c) may be repeated two or more times.

In one exemplary embodiment, an etching method includes providing a substrate including silicon nitride having an exposed top surface and silicon oxide having an exposed top surface; forming a tungsten nitride-containing passivation layer on the silicon nitride by exposing it to a plasma generated from a process gas containing tungsten hexafluoride gas; and etching the silicon oxide preferentially relative to the silicon nitride by exposure to a plasma generated from a process gas containing tungsten fluoride gas.

The process gas may include a fluorocarbon gas.

In one exemplary embodiment, a plasma processing apparatus is a chamber and a substrate support for supporting a substrate within the chamber, the substrate comprising a first region containing silicon and nitrogen, and a first region containing silicon and oxygen. a gas supply configured to supply a process gas comprising carbon, fluorine and tungsten into the chamber; and generating a plasma from the process gas within the chamber. and a controller configured to: expose the first region and the second region to the plasma to form a tungsten-containing protective layer on the first region; The gas supply unit and the plasma generation unit are controlled such that the second region is etched while forming a

Various exemplary embodiments are described in detail below with reference to the drawings. In addition, suppose that the same code|symbol is attached|subjected to the part which is the same or equivalent in each drawing.

1 and 2 are schematic diagrams of a plasma processing apparatus according to one exemplary embodiment.

In one embodiment, a plasma processing system includes a plasma processing apparatus 1 and a controller 2 . The plasma processing apparatus 1 includes a plasma processing chamber 10 , a substrate support section 11 and a plasma generation section 12 . Plasma processing chamber 10 has a plasma processing space. The plasma processing chamber 10 also has at least one gas inlet for supplying at least one process gas to the plasma processing space and at least one gas outlet for exhausting gas from the plasma processing space. The gas supply port is connected to a gas supply section 20, which will be described later, and the gas discharge port is connected to an exhaust system 40, which will be described later. The substrate support 11 is arranged in the plasma processing space and has a substrate support surface for supporting the substrate.

The plasma generator 12 is configured to generate plasma from at least one processing gas supplied within the plasma processing space. The plasma formed in the plasma processing space includes capacitively coupled plasma (CCP), inductively coupled plasma (ICP), ECR plasma (Electron-Cyclotron-resonance plasma), helicon wave excited plasma (HWP), Alternatively, surface wave plasma (SWP) or the like may be used. Also, various types of plasma generators may be used, including AC (Alternating Current) plasma generators and DC (Direct Current) plasma generators. In one embodiment, the AC signal (AC power) used in the AC plasma generator has a frequency within the range of 100 kHz to 10 GHz. Accordingly, AC signals include RF (Radio Frequency) signals and microwave signals. In one embodiment, the RF signal has a frequency within the range of 200 kHz-150 MHz.

Controller 2 processes computer-executable instructions that cause plasma processing apparatus 1 to perform the various steps described in this disclosure. Controller 2 may be configured to control elements of plasma processing apparatus 1 to perform the various processes described herein. In one embodiment, part or all of the controller 2 may be included in the plasma processing apparatus 1 . The control unit 2 may include, for example, a computer 2a. The computer 2a may include, for example, a processing unit (CPU: Central Processing Unit) 2a1, a storage unit 2a2, and a communication interface 2a3. Processing unit 2a1 can be configured to perform various control operations based on programs stored in storage unit 2a2. The storage unit 2a2 may include RAM (Random Access Memory), ROM (Read Only Memory), HDD (Hard Disk Drive), SSD (Solid State Drive), or a combination thereof. The communication interface 2a3 may communicate with the plasma processing apparatus 1 via a communication line such as a LAN (Local Area Network).

A configuration example of the plasma processing system will be described below.
The plasma processing system includes a capacitively-coupled plasma processing apparatus 1 and a controller 2 . The capacitively coupled plasma processing apparatus 1 includes a plasma processing chamber 10, a gas supply section 20, a power supply 30 and an exhaust system 40. As shown in FIG. Further, the plasma processing apparatus 1 includes a substrate support section 11 and a gas introduction section. The gas introduction is configured to introduce at least one process gas into the plasma processing chamber 10 . The gas introduction section includes a showerhead 13 . A substrate support 11 is positioned within the plasma processing chamber 10 . The showerhead 13 is arranged above the substrate support 11 . In one embodiment, showerhead 13 forms at least a portion of the ceiling of plasma processing chamber 10 . The plasma processing chamber 10 has a plasma processing space 10 s defined by a showerhead 13 , side walls 10 a of the plasma processing chamber 10 and a substrate support 11 . The plasma processing chamber 10 has at least one gas supply port for supplying at least one processing gas to the plasma processing space 10s and at least one gas exhaust port for exhausting gas from the plasma processing space. Side wall 10a is grounded. The showerhead 13 and substrate support 11 are electrically insulated from the plasma processing chamber 10 housing.

The substrate support portion 11 includes a body portion 111 and a ring assembly 112 . The body portion 111 has a central region (substrate support surface) 111 a for supporting the substrate (wafer) W and an annular region (ring support surface) 111 b for supporting the ring assembly 112 . The annular region 111b of the body portion 111 surrounds the central region 111a of the body portion 111 in plan view. The substrate W is arranged on the central region 111 a of the main body 111 , and the ring assembly 112 is arranged on the annular region 111 b of the main body 111 so as to surround the substrate W on the central region 111 a of the main body 111 . In one embodiment, body portion 111 includes a base and an electrostatic chuck. Body portion 111 includes a conductive member. The conductive member of main body 111 functions as an electrode. An electrostatic chuck is arranged on the base. The upper surface of the electrostatic chuck has a substrate support surface 111a. Ring assembly 112 includes one or more annular members. At least one of the one or more annular members is an edge ring. Also, although not shown, the substrate supporter 11 may include a temperature control module configured to control at least one of the electrostatic chuck, the ring assembly 112, and the substrate to a target temperature. The temperature control module may include heaters, heat transfer media, flow paths, or combinations thereof. A heat transfer fluid, such as brine or gas, flows through the channel. Further, the substrate support section 11 may include a heat transfer gas supply section configured to supply a heat transfer gas between the back surface of the substrate W and the substrate support surface 111a.

The showerhead 13 is configured to introduce at least one processing gas from the gas supply 20 into the plasma processing space 10s. The showerhead 13 has at least one gas supply port 13a, at least one gas diffusion chamber 13b, and multiple gas introduction ports 13c. The processing gas supplied to the gas supply port 13a passes through the gas diffusion chamber 13b and is introduced into the plasma processing space 10s through a plurality of gas introduction ports 13c. Showerhead 13 also includes a conductive member. The conductive member of the showerhead 13 faces the substrate supporting portion 11 and functions as an electrode (hereinafter sometimes referred to as a counter electrode). In addition to the showerhead 13, the gas introduction part may include one or more side gas injectors (SGI: Side Gas Injectors) attached to one or more openings formed in the side wall 10a.

Gas supply 20 may include at least one gas source 21 and at least one flow controller 22 . In one embodiment, gas supply 20 is configured to supply at least one process gas from respective gas sources 21 through respective flow controllers 22 to showerhead 13 . Each flow controller 22 may include, for example, a mass flow controller or a pressure controlled flow controller. Additionally, gas supply 20 may include one or more flow modulation devices that modulate or pulse the flow of at least one process gas.

Power supply 30 includes an RF power supply 31 coupled to plasma processing chamber 10 via at least one impedance match circuit. RF power supply 31 is configured to supply at least one RF signal (RF power), such as a source RF signal and a bias RF signal, to conductive members of substrate support 11 and/or conductive members of showerhead 13 . be done. Thereby, plasma is formed from at least one processing gas supplied to the plasma processing space 10s. Accordingly, RF power source 31 may function as at least part of a plasma generator configured to generate a plasma from one or more process gases in plasma processing chamber 10 . Further, by supplying the bias RF signal to the conductive member of the substrate supporting portion 11, a bias potential is generated in the substrate W, and ion components in the formed plasma can be drawn into the substrate W. FIG.

In one embodiment, the RF power supply 31 includes a first RF generator 31a and a second RF generator 31b. The first RF generator 31a is coupled to the conductive member of the substrate support 11 and/or the conductive member of the showerhead 13 via at least one impedance matching circuit to provide a source RF signal for plasma generation (source RF electrical power). In one embodiment, the source RF signal has a frequency within the range of 13 MHz to 150 MHz. In one embodiment, the first RF generator 31a may be configured to generate multiple source RF signals having different frequencies. The generated one or more source RF signals are provided to conductive members of the substrate support 11 and/or conductive members of the showerhead 13 . The second RF generator 31b is coupled to the conductive member of the substrate support 11 via at least one impedance matching circuit and configured to generate a bias RF signal (bias RF power). In one embodiment, the bias RF signal has a lower frequency than the source RF signal. In one embodiment, the bias RF signal has a frequency within the range of 400 kHz to 13.56 MHz. In one embodiment, the second RF generator 31b may be configured to generate multiple bias RF signals having different frequencies. One or more bias RF signals generated are provided to the conductive members of the substrate support 11 . Also, in various embodiments, at least one of the source RF signal and the bias RF signal may be pulsed.

Power supply 30 may also include a DC power supply 32 coupled to plasma processing chamber 10 . The DC power supply 32 includes a first DC generator 32a and a second DC generator 32b. In one embodiment, the first DC generator 32a is connected to a conductive member of the substrate support 11 and configured to generate the first DC signal. The generated first bias DC signal is applied to the conductive members of substrate support 11 . In one embodiment, the first DC signal may be applied to other electrodes, such as electrodes in an electrostatic chuck. In one embodiment, the second DC generator 32b is connected to the conductive member of the showerhead 13 and configured to generate the second DC signal. The generated second DC signal is applied to the conductive members of showerhead 13 . In various embodiments, at least one of the first and second DC signals may be pulsed. Note that the first and second DC generators 32a and 32b may be provided in addition to the RF power supply 31, and the first DC generator 32a may be provided instead of the second RF generator 31b. good.

The exhaust system 40 may be connected to a gas outlet 10e provided at the bottom of the plasma processing chamber 10, for example. Exhaust system 40 may include a pressure regulating valve and a vacuum pump. The pressure regulating valve regulates the pressure in the plasma processing space 10s. Vacuum pumps may include turbomolecular pumps, dry pumps, or combinations thereof.

FIG. 3 is a flowchart of an etching method according to one exemplary embodiment. An etching method MT (hereinafter referred to as "method MT") shown in FIG. 3 can be performed by the plasma processing apparatus 1 of the above embodiment. The method MT may be applied to the substrate W.

FIG. 4 is a partially enlarged cross-sectional view of an example substrate to which the method of FIG. 3 can be applied. As shown in FIG. 4, in one embodiment the substrate W includes a first region R1 and a second region R2. The first region R1 may have at least one recess R1a. The first region R1 may have a plurality of recesses R1a. Each recess R1a may be a recess for forming a contact hole. The second region R2 may be embedded in the recess R1a. The second region R2 may be provided to cover the first region R1.

The first region R1 contains silicon. The first region R1 may contain at least one of nitrogen and carbon. The first region R1 may include silicon nitride (SiN _x ). The first region R1 may include silicon carbide (SiC). The first region R1 may include silicon carbonitride (SiCN). The first region R1 may contain silicon. The first region R1 may be, for example, a region formed by CVD or the like, or may be a region obtained by nitriding or carbonizing silicon. The first region R1 may include a first portion including silicon nitride (SiN _x ) and a second portion including silicon carbide (SiC). In this case, the first portion has the recess R1a.

The second region R2 contains silicon and oxygen. The second region R2 may include silicon oxide ( _SiOx ). The second region R2 may be, for example, a region formed by CVD or the like, or may be a region obtained by oxidizing silicon. The second region R2 may have a recess R2a. The recess R2a has a width larger than that of the recess R1a.

The substrate W may include an underlying region UR and at least one raised region RA provided on the underlying region UR. The base region UR and at least one raised region RA are covered by the first region R1. The underlying region UR may contain silicon. A plurality of raised areas RA are positioned on the base area UR. A recess R1a of the first region R1 is positioned between the plurality of raised regions RA. Each raised area RA may form a gate area of a transistor.

The substrate W may include a mask MK. A mask MK is provided on the second region R2. The mask MK may contain metal or silicon. The mask MK may have an opening OP. The opening OP corresponds to the recess R2a of the second region R2.

The method MT will be described below with reference to FIGS. 3 to 6, taking as an example the case where the method MT is applied to the substrate W using the plasma processing apparatus 1 of the above embodiment. FIG. 5 is a cross-sectional view showing one step of an etching method according to one exemplary embodiment. FIG. 6 is a partially enlarged cross-sectional view of an example substrate obtained by performing an etching method according to one exemplary embodiment. When the plasma processing apparatus 1 is used, the method MT can be performed in the plasma processing apparatus 1 by controlling each unit of the plasma processing apparatus 1 by the control unit 2 . In method MT, as shown in FIG. 2, a substrate W on a substrate supporter 11 (substrate supporter) placed in a plasma processing chamber 10 is processed.

As shown in FIG. 3, the method MT includes steps ST1 and ST2. Step ST1 and step ST2 may be performed in sequence.

In step ST1, a substrate W shown in FIG. 4 is prepared. A substrate W may be supported by a substrate support 11 within the plasma processing chamber 10 . Substrate W may have the shape shown in FIG. 4 as a result of plasma etching, or it may have the shape shown in FIG. In step ST1, the top surface of the first region R1 and the top surface of the second region R2 may be exposed. That is, in step ST1, the upper surface of silicon nitride and the upper surface of silicon oxide may be exposed.

In step ST2, as shown in FIG. 5, the second region R2 is etched by exposing the first region R1 and the second region R2 to plasma generated from a process gas containing carbon, fluorine and tungsten. A mask MK is used in the etching. Etching may be performed as follows. First, the gas supply unit 20 supplies a processing gas containing carbon, fluorine, and tungsten into the plasma processing chamber 10 . Next, plasma is generated from the processing gas in the plasma processing chamber 10 by the plasma generator 12 . The control unit 2 exposes the first region R1 and the second region R2 to plasma, thereby forming a tungsten-containing protective layer on the first region R1 and etching the second region R2 while the gas supply unit 20 and the plasma generator 12 are controlled.

The process gas may include a carbon- and fluorine-containing gas and a tungsten-containing gas. The carbon and fluorine containing gas may comprise at least one of a fluorocarbon gas and a hydrofluorocarbon gas. The fluorocarbon _{( CxFy} ) gas may include at least one of _CF4 gas, _C3F8 gas _{, C4F8 gas} , and _{C4F6 gas} . A _CxFy gas containing a relatively large amount of F, such as a _C4F8 gas, may be used instead of an oxygen _- containing gas ₍ eg, _O2 gas) as a gas for controlling carbon deposition. For example, a mixed gas of C ₄ F ₆ gas and C ₄ F ₈ gas may be used instead of the mixed gas of C ₄ F ₆ gas and oxygen-containing gas. The hydrofluorocarbon _{( CxHyFz} ) gas may include at _least one of _CH2F2 gas _{, CHF3} gas and _CH3F gas.

A tungsten-containing gas may include a tungsten halide gas. The tungsten halide gas may include at least one of tungsten hexafluoride (WF ₆ ) gas, tungsten hexabromide (WBr ₆ ) gas, tungsten hexachloride (WCl ₆ ) gas, and WF ₅ Cl gas. The tungsten-containing gas may include hexacarbonyl tungsten (W(CO) ₆ ) gas.

The process gas may or may not contain oxygen. The process gas may contain an oxygen-containing gas. The oxygen-containing gas may include at least one of _O2 gas, CO gas, and _CO2 gas. The process gas may include noble gases such as argon, for example.

In step ST2, the temperature of the substrate supporting portion 11 may be 100° C. or higher, 120° C. or higher, 130° C. or higher, may exceed 130° C., or may be 140° C. or higher. It may be 150° C. or higher. Also, the temperature of the substrate supporting portion 11 may be 250° C. or lower, or may be 200° C. or lower.

In step ST2, the pressure inside the plasma processing chamber 10 may be 1 mTorr (0.13 Pa) or higher, or may be 10 mTorr (1.3 Pa) or higher. Also, the pressure in the plasma processing chamber 10 may be 50 mTorr (6.7 Pa) or less, or may be 30 mTorr (4.0 Pa) or less.

In step ST2, as shown in FIG. 5, a tungsten-containing film DP (tungsten-containing protective layer) can be formed on the first region R1. The tungsten-containing film DP can particularly protect the shoulder portion SH in the recess R1a of the first region R1. As a result, the shoulder portion SH becomes less likely to incline, so that a large area of the flat portion on the upper surface of the first region R1 can be ensured. The tungsten-containing film DP may contain nitrogen. The tungsten-containing film DP may contain tungsten nitride (WN _x ). A carbon-containing film may be formed on the tungsten-containing film DP. The carbon-containing film may contain fluorine. Etching of the first region R1 is suppressed by the tungsten-containing film DP and the carbon-containing film. The second region R2 is etched because it is not covered with the tungsten-containing film DP. By etching the second region R2, a contact hole HL is formed as shown in FIG. Contact hole HL corresponds to recess R1a of first region R1. Thus, step ST2 may be performed in a self-aligned contact (SAC) step. After the second region R2 in the recess R1a is removed, the tungsten-containing film DP remains on the first region R1. The tungsten-containing film DP can be removed by cleaning after step ST2.

According to the method MT, the etching selectivity of the second region R2 with respect to the first region R1 can be improved. For example, the selection ratio of the second region R2 containing silicon oxide (SiO _x ) to the first region R1 containing silicon nitride (SiN _x ) can be 5 or more. Although not bound by theory, the reason is considered as follows. The second region R2 containing silicon oxide is etched by active species containing fluorine in the plasma. For example, _{WFx reacts} with _SiOx to produce _WOx or _WOxFy . This causes the _SiOx to be etched. On the other hand, active species containing tungsten in the plasma react with the silicon nitride of the first region R1 to deposit tungsten nitride on the upper surface of the first region R1. Alternatively, active species containing tungsten in the plasma react with the silicon nitride of the first region R1 to modify at least part of the upper surface of the first region R1, and the modified portion contains tungsten nitride. For example, when _WFx reacts with _SiNx , _WNx and _SiFx are produced. WN _x may be contained in the deposited layer on the upper surface of the first region R1, or may be contained in the layer modified on the upper surface of the first region R1. Thereby, a tungsten-containing film DP containing tungsten nitride is formed on the first region R1. The tungsten-containing film DP is preferentially deposited on the upper surface of the first region R1, or the silicon nitride on the upper surface of the first region R1, where active species containing tungsten in the plasma are incident with relatively high energy. is modified. Etching of the first region R1 is suppressed by the tungsten-containing film DP. As a result, the etching selectivity of the second region R2 with respect to the first region R1 is improved.

Furthermore, according to the method MT, the tungsten-containing film DP functions as an etching mask, so there is no need to form a thick carbon-containing film on the tungsten-containing film DP. A thick carbon-containing film can cause clogging of contact holes. Therefore, in the method MT, blocking of the contact hole HL by the carbon-containing film is suppressed.

When the processing gas contains oxygen, it becomes difficult to form a carbon-containing film on the first region R1. Therefore, blocking of the contact hole HL by the carbon-containing film is suppressed. On the other hand, when the processing gas contains oxygen, the surface of the first region R1 is oxidized to form silicon oxide on the surface of the first region R1. As a result, the surface of the first region R1 is etched. If the processing gas does not contain oxygen, such etching of the first region R1 is suppressed. As a result, the etching selectivity of the second region R2 with respect to the first region R1 is further improved.

FIG. 7 is an example of a timing chart showing temporal changes in the bias power applied to the electrodes in the body part 111 of the substrate support part 11 and the RF power applied to the counter electrode. This timing chart relates to step ST2 in method MT. In step ST2, bias power may be applied to the electrodes in the body portion 111 . The bias power may be, for example, RF power LF. The following description is an example of power used for a 300 millimeter diameter substrate. The RF power LF may be 10 W or more and 300 W or less, 30 W or more and 200 W or less, or 50 W or more and 100 W or less. The frequency of the RF power LF may be greater than or equal to 100 kHz and less than or equal to 40.68 MHz. When the RF power LF is small, etching of the first region R1 by ions in the plasma is suppressed. In step ST2, RF power HF may be applied to the counter electrode. The RF power HF may be 50 W or more and 1000 W or less, 80 W or more and 800 W or less, or 100 W or more and 500 W or less. The frequency of the RF power HF may be greater than or equal to 27 MHz and less than or equal to 100 MHz. RF power LF and RF power HF may be applied periodically with period CY. Incidentally, the bias power may be supplied to the conductive member of the substrate supporting portion 11 . RF power HF may also be supplied to an antenna that includes one or more coils.

The ion energy of the plasma may be 50 eV or more and 700 eV or less, 100 eV or more and 600 eV or less, or 120 eV or more and 500 eV or less. When the ion energy increases, the thickness of the tungsten-containing film DP can be increased. Note that the ion energy of the present disclosure may be the average ion energy incident on the upper surface of the substrate, or may be expressed as a distribution of the ion energy incident on the upper surface of the substrate.

A cycle CY can include a first period PA, a second period PB and a third period PC. In the first period PA, RF power LF is maintained at low power L1 (second power, eg, less than 100 W) and RF power HF is maintained at high power H2 (first power, eg, greater than 100 W). During the first period PA, deposition of the tungsten-containing film DP and the carbon-containing film is promoted. During the second period PB, the RF power LF is maintained at the low power L1 and the RF power HF is maintained at the low power L2 (third power, eg, less than 200 W). Low power L2 is less than high power H2 and greater than low power L1. During the third period PC, the RF power LF is maintained at the high power H1 (fourth power, eg, greater than 50 W) and the RF power HF is maintained at the low power L2. The high power H1 is greater than the low power L1 and less than the high power H2. During the third period PC, the etching of the second region R2 is promoted. The second period PB is a transition period from the first period PA to the third period PC. In step ST2, one cycle corresponding to the period CY including the first period PA, the second period PB and the third period PC may be repeated twice or more.

The ratio of the first period PA in the cycle CY is smaller than the ratio of the third period PC in the cycle CY. The ratio of the first period PA in the cycle CY may be 10% or more, or may be less than 50%. When the first period PA occupies a large proportion, the etching selectivity of the second region R2 to the first region R1 becomes large. If the proportion of the first period PA is small, blocking of the contact hole HL is suppressed. The ratio of the third period PC in the cycle CY may be 50% or more. When the proportion of the third period PC is large, the etching selectivity of the second region R2 to the first region R1 becomes large. A frequency that defines the period CY may be 1 kHz or more and 1 MHz or less. The time length of cycle CY is the reciprocal of the frequency that defines cycle CY.

FIG. 8 is a partially enlarged cross-sectional view of an example substrate to which the method of FIG. 3 can be applied. As shown in FIG. 8, in one embodiment the substrate W includes a first region R1 and a second region R2. The substrate W may include an underlying region UR. The first region R1 may be provided on the second region R2. The second region R2 may be provided on the underlying region UR. Each of the first region R1, the second region R2 and the underlying region UR may be a film. The first region R1 may function as a mask. The first region R1 may have at least one opening OP1. The first region R1 may have multiple openings OP1. Each opening OP1 may be an opening for forming a contact hole. The dimension of the opening OP1 may be 200 nm or less. The dimension of the opening OP1 may be 15 nm or more. The first region R1 contains silicon and nitrogen. The first region R1 may not contain nitrogen. The second region R2 contains silicon and oxygen. The underlying region UR may contain silicon and nitrogen. The underlying region UR may contain silicon nitride (SiN _x ).

FIG. 9 is a partially enlarged cross-sectional view of an example substrate obtained by performing an etching method according to one exemplary embodiment. When the method MT is applied to the substrate W of FIG. 8, a recess RS corresponding to the opening OP1 is formed in the second region R2, as shown in FIG. The recess RS may be a contact hole. The bottom of the recess RS may reach the underlying region UR. In step ST2, a tungsten-containing film DP can be formed on the first region R1, as shown in FIG.

According to the method MT, the etching selectivity of the second region R2 with respect to the first region R1 can be improved. In addition, since the flow rate of the gas containing carbon and fluorine can be reduced in step ST2, deposition of a carbon-containing film on the side wall of the recess RS can be suppressed. Therefore, the side wall of the recess RS can be made nearly vertical. Furthermore, since the etching rate in step ST2 can be increased, the etching time can be shortened, for example, by about half.

FIG. 10 is a diagram showing an example of the etching process. In the method MT, the step ST2 of etching may include a first step ST21 and a second step ST22. The first step ST21 and the second step ST22 can be performed in order. The etching step ST2 may further include a third step ST23 between the first step ST21 and the second step ST22.

In one exemplary embodiment, in the first step ST21, bias power (fifth power) is supplied to the plasma processing apparatus 1 to form a tungsten-containing film DP (first tungsten-containing deposit) on the first region R1. ) may be formed (see FIG. 5). The thickness of the tungsten-containing film DP may be 2 nm or more and 5 nm or less. The bias power may be RF power LF applied to electrodes in the body portion 111 of the substrate support portion 11 . The following description is an example of power used for a 300 millimeter diameter substrate. The RF power LF may be 50W or more, or 300W or more. When the RF power LF is increased, the ion energy of the plasma increases, so the thickness of the tungsten-containing film DP can be increased. The RF power LF may be 500W or less, or may be 800W or less. When the RF power LF is reduced, the reduction amount (etching amount) of the first region R1 can be reduced. In the first step ST21, the plasma processing apparatus 1 may not be supplied with the RF power HF applied to the counter electrode. Other process conditions (kind of processing gas, flow rate ratio of each gas, processing time, temperature, pressure, etc.) in the first step ST21 may be the same as those in the above-described step ST2. The processing gas in the first step ST21 may contain oxygen, carbon, fluorine and tungsten. The second region R2 may be etched in the first step ST21.

In the third step ST23, the tungsten-containing film DP may be exposed to plasma generated from a processing gas containing hydrogen-containing gas (hydrogen plasma processing). The processing gas containing hydrogen-containing gas may be different from the processing gas in the first step ST21. The hydrogen _- containing gas may include at _least one of H2 gas, _SiH4 gas and CH4 gas. The processing gas of the third step ST23 may further contain a noble gas such as argon. The time of the third step ST23 may be 5 seconds or more and 15 seconds or less. When the time of the third step ST23 is long, the amount of decrease in the first region R1 due to hydrogen radicals is large.

In the second step ST22, by supplying high-frequency power and bias power to the plasma processing apparatus 1, a further tungsten-containing film DP (second tungsten-containing deposit) is formed on the tungsten-containing film DP, while the second region is R2 may be etched. The high frequency power may be RF power HF applied to the counter electrode. The bias power (sixth power) in the second step ST22 may be lower than the bias power (fifth power) in the first step ST21. When the bias power varies in each step, the bias power in each step may be the average value of the bias power. The process conditions in the second step ST22 may be the same as the process conditions in the above-described step ST2. The processing gas in the second step ST22 may contain oxygen, carbon, fluorine and tungsten.

In another exemplary embodiment, in the first step ST21, the processing gas contains a hydrogen-containing gas to form a tungsten-containing film DP (first tungsten-containing deposit) on the first region R1. good. An example of the hydrogen-containing gas may be the same as the example of the hydrogen-containing gas in the third step ST23. An example of the gas contained in the processing gas may be the same as the example of the gas contained in the processing gas in step ST2 described above. Other process conditions (flow ratio of each gas, processing time, temperature, pressure, applied power, etc.) in the first step ST21 may be the same as the process conditions in the above-described step ST2. The processing gas in the first step ST21 may contain hydrogen, carbon, fluorine and tungsten. The second region R2 may be etched in the first step ST21.

In the second step ST22, the second region R2 may be etched while forming an additional tungsten-containing film DP (second tungsten-containing deposit) by including an oxygen-containing gas in the processing gas. The process conditions (kind of processing gas, flow rate ratio of each gas, processing time, temperature, pressure, applied power, etc.) in the second step ST22 may be the same as those in the above-described step ST2. The processing gas in the second step ST22 may contain oxygen, carbon, fluorine and tungsten.

Typically, an opening having relatively small dimensions makes it difficult for the tungsten-containing active species to be transported into the opening, which can reduce the thickness of the tungsten-containing film. In contrast, according to the method MT including the first step ST21, the tungsten-containing film DP having high film thickness uniformity can be formed regardless of the dimension of the opening OP of the mask MK (the width of the recess R2a). Therefore, the etching selectivity of the second region R2 with respect to the first region R1 can be improved in both the opening OP having a relatively large dimension and the opening OP having a relatively small dimension. Furthermore, according to the method MT including the first step ST21, the thickness of the tungsten-containing film DP can be increased. When the processing gas contains hydrogen-containing gas in the first step ST21, the thickness of the tungsten-containing film DP can be increased without increasing the RF power LF in the first step ST21. It is presumed that this is because the tungsten reduced by the hydrogen-containing gas is deposited by CVD.

When performing the third step ST23, or when the processing gas contains a hydrogen-containing gas in the first step ST21, the composition ratio of tungsten in the tungsten-containing film DP can be increased. It is presumed that this is because tungsten oxide is reduced by hydrogen to produce metallic tungsten.

After the first step ST21, the second region R2 may be etched using a processing gas containing no tungsten-containing gas without performing the second step ST22.

While various exemplary embodiments have been described above, various additions, omissions, substitutions, and modifications may be made without being limited to the exemplary embodiments described above. Also, elements from different embodiments can be combined to form other embodiments.

For example, the object to which the process ST2 of the method MT is applied is not limited to the self-aligned contact (SAC) process. Process ST2 may be applied to other processes in which a high etching selectivity is desired.

Also, for example, a molybdenum-containing gas may be used instead of, or in addition to, a tungsten-containing gas. Molybdenum-containing gases may include molybdenum halide gases. The molybdenum halide gas may include at least one of molybdenum hexafluoride (MoF ₆ ) gas and molybdenum hexachloride (MoCl ₆ ) gas.

Various experiments conducted for evaluation of the method MT are described below. The experiments described below do not limit the present disclosure.

(first experiment)
In a first experiment, a substrate W including a first region R1 containing silicon nitride (SiN _x ) and a second region R2 containing silicon oxide (SiO _x ) was prepared. After that, the process ST2 was performed on the substrate W using the plasma processing apparatus 1 . In step ST2, the processing gas is a mixed gas of fluorocarbon gas, oxygen gas, and tungsten hexafluoride gas (WF ₆ ). Further, the flow ratio of tungsten hexafluoride gas (WF ₆ ) is higher than that of fluorocarbon gas and higher than that of oxygen gas.

(Second experiment)
In the second experiment, the same method as in the first experiment was performed except that tungsten hexafluoride gas (WF ₆ ) was removed from the process gas in step ST2.

(Experimental result)
Cross-sectional TEM images of the substrate W on which the method was performed in the first and second experiments were observed. FIG. 11(a) is a diagram showing a TEM image of a cross section of the substrate obtained by performing the etching method in the first experiment. FIG. 11(b) is a diagram showing a TEM image of a cross section of the substrate obtained by performing the etching method in the second experiment. In (a) of FIG. 11, the film DP (black portion in the figure) formed on the first region R1 was confirmed. From the TEM-EDX results, it was confirmed that the portion corresponding to the film DP in FIG. 11(a) contained tungsten. On the other hand, in FIG. 11(b), no tungsten-containing film was confirmed on the first region R1. Furthermore, in (a) of FIG. 11, the bottom of the recess (the upper surface of the second region R2) formed by etching is flat. On the other hand, in FIG. 11(b), the bottom of the recess (the upper surface of the second region R2) formed by etching is inclined. Therefore, in the first experiment, it can be seen that the bottom of the recess can be processed into a desired shape by etching.

(Third experiment)
In the third experiment, the second region R2 including silicon oxide (SiO _x ), the first region R1 including silicon nitride (SiN _x ), and the underlying region UR including silicon nitride (SiN _x ) are shown in FIG. was prepared. After that, the process ST2 was performed on the substrate W using the plasma processing apparatus 1 . Thereby, the recess RS was formed in the second region R2. In step ST2, the processing gas is a mixed gas of fluorocarbon gas, oxygen gas, tungsten hexafluoride gas (WF ₆ ), and argon gas. Further, the flow ratio of tungsten hexafluoride gas (WF ₆ ) is higher than that of fluorocarbon gas and higher than that of oxygen gas. In step ST2, RF power HF and RF power LF shown in FIG. 7 were applied.

(Fourth experiment)
In the fourth experiment, in step ST2, tungsten hexafluoride gas (WF ₆ ) was removed from the processing gas, and the RF power HF and RF power LF in step ST2 were kept constant. executed. That is, in step ST2, the processing gas is a mixed gas of fluorocarbon gas, oxygen gas and argon gas.

(cross section)
Cross-sectional TEM images of the substrate W on which the method was performed in the third and fourth experiments were observed. FIGS. 12(a) and 12(b) are diagrams showing examples of cross sections of the substrate obtained by performing the etching method in the third experiment. FIG. 12(a) shows a cross section in a region where dense patterns are formed. FIG. 12(b) shows a cross section in a region where an isolated pattern is formed. In (a) and (b) of FIG. 12, the tungsten-containing film DP and the carbon-containing film CDP formed on the first region R1 were confirmed. The carbon-containing film CDP is formed to cover the tungsten-containing film DP. Only a very thin carbon-containing film CDP could be confirmed on the side wall of the recess RS formed in the second region R2.

(c) and (d) of FIG. 12 are diagrams showing examples of cross sections of the substrate obtained by performing the etching method in the fourth experiment. FIG. 12(c) shows a cross section in a region where dense patterns are formed. (d) of FIG. 12 shows a cross section in a region where an isolated pattern is formed. In (c) and (d) of FIG. 12, the tungsten-containing film DP was not confirmed on the first region R1, and the carbon-containing film CDP was confirmed. Also, a carbon-containing film CDP was confirmed on the side wall of the recess RS formed in the second region R2.

In (a) of FIG. 12, the value obtained by subtracting the dimension of the top surface of the second region R2 from the dimension of the bottom surface of the second region R2 was 4.0 nm. In (c) of FIG. 12, the value obtained by subtracting the dimension of the top surface of the second region R2 from the dimension of the bottom surface of the second region R2 was 5.1 nm. In FIG. 12(b), the value obtained by subtracting the dimension of the top surface of the second region R2 from the dimension of the bottom surface of the second region R2 was 8.5 nm. In (d) of FIG. 12, the value obtained by subtracting the dimension of the top surface of the second region R2 from the dimension of the bottom surface of the second region R2 was 12.4 nm. Therefore, in the third experiment, the side wall of the recess RS was closer to vertical than in the fourth experiment. This is probably because in the fourth experiment, the carbon-containing film CDP formed on the side wall of the recess RS makes it difficult for the etching to progress linearly.

(Etching selectivity)
By measuring the etching amount of the first region R1 and the etching amount of the second region R2, the etching selectivity of the second region R2 to the first region R1 was calculated. In the third experiment, the etching selectivity in the region (a) of FIG. 12 was 3.7. In the fourth experiment, the etching selectivity in the region (c) of FIG. 12 was 2.7. In the third experiment, the etching selectivity in the region (b) of FIG. 12 was 4.5. In the fourth experiment, the etching selectivity in the region (d) of FIG. 12 was 4.2. Therefore, it was found that the etching selectivity could be improved in the third experiment as compared with the fourth experiment. This is probably because the tungsten-containing film DP makes it difficult to etch the first region R1 in the third experiment.

(Fifth experiment)
In the fifth experiment, a substrate W having the structure shown in FIG. 4 was prepared. The substrate W includes a first region R1 comprising silicon nitride (SiN _x ) and a second region R2 comprising silicon oxide (SiO _x ). The substrate W has an opening OP having a relatively large dimension (hereinafter referred to as a long pattern) and an opening OP having a relatively small dimension (hereinafter referred to as a short pattern). After that, the substrate W was subjected to the first step ST21 and the second step ST22 using the plasma processing apparatus 1 (see FIG. 10).

In the first step ST21, a slit having a depth of about 20 nm was formed in the recess R1a by etching the second region R2 while forming the tungsten-containing film DP on the first region R1 (see FIG. 5). . _In the first step ST21, the processing gas is a mixed gas of fluorocarbon gas, oxygen ( _O2 ) gas, argon gas, and tungsten hexafluoride gas (WF6). Further, the flow ratio of tungsten hexafluoride gas (WF ₆ ) is higher than that of fluorocarbon gas and higher than that of oxygen gas. The RF power HF supplied to the plasma processing apparatus 1 is 0W. The RF power LF supplied to the plasma processing apparatus 1 is 400W. Therefore, the ion energy of the plasma is relatively large.

In the second step ST22, while forming the tungsten-containing film DP on the first region R1, the second region R2 was etched to form a slit having a depth of about 70 nm in the recess R1a. In the second step ST22, the processing gas is a mixed gas of fluorocarbon gas, oxygen gas, argon gas and tungsten hexafluoride gas (WF ₆ ). Further, the flow ratio of tungsten hexafluoride gas (WF ₆ ) is higher than that of fluorocarbon gas and higher than that of oxygen gas. The RF power HF and the RF power LF are supplied to the plasma processing apparatus 1 according to the timing chart of FIG. In the first period PA, the high power H2 is 800W and the low power L1 is 50W. In the third period PC, the low power L2 is 0W and the high power H1 is 100W. Therefore, the average value of the RF power LF in the second step ST22 is lower than the RF power LF in the first step ST21.

(6th experiment)
In the sixth experiment, the same substrate W as in the fifth experiment was prepared. After that, the process ST2 was performed on the substrate W using the plasma processing apparatus 1 . Process ST2 includes an etching process and a deposition process. The etching and deposition steps are performed in sequence.

In the etching process, the tungsten-containing film DP was formed on the first region R1, and the second region R2 was etched to form a slit having a depth of about 20 nm in the recess R1a (see FIG. 5). The process conditions of the etching step are the same as the process conditions (BSL conditions) of the second step ST22 of the fifth experiment.

In the deposition step, a slit having a depth of about 70 nm was formed in the recess R1a by etching the second region R2 while forming a deposited film on the tungsten-containing film DP. The deposition process includes the etching process and the carbon-containing film deposition process of the sixth experiment. In the carbon-containing film deposition process, the processing gas is a mixed gas of carbon monoxide (CO) gas and argon gas. The RF power HF supplied to the plasma processing apparatus 1 is 800W. The RF power LF supplied to the plasma processing apparatus 1 is 0W.

(Experimental result)
A cross-sectional TEM image of the substrate W etched in the fifth and sixth experiments was observed. In the fifth experiment, in the long pattern, the reduction amount (etching amount) of the first region R1 after the first step ST21 was 4.9 nm, and the reduction amount of the first region R1 after the second step ST22 was 7.3 nm. Met. Therefore, the amount of decrease in the first region R1 was increased by 2.4 nm due to the second step ST22.

On the other hand, in the sixth experiment, in the long pattern, the amount of decrease in the first region R1 after the etching process was 2.8 nm, and the amount of decrease in the first area R1 after the deposition process was 3.8 nm. Therefore, the amount of decrease in the first region R1 increased by 1.0 nm due to the deposition process.

In the fifth experiment, in the short pattern, the amount of decrease in the first region R1 after the first step ST21 was 6.7 nm, and the amount of decrease in the first region R1 after the second step ST22 was 10.2 nm. Therefore, the amount of decrease in the first region R1 was increased by 3.5 nm due to the second step ST22.

On the other hand, in the sixth experiment, in the short pattern, the amount of decrease in the first region R1 after the etching step was 4.3 nm, and the amount of decrease in the first region R1 after the deposition step was 10.4 nm. Therefore, the amount of decrease in the first region R1 increased by 6.1 nm due to the deposition process. Therefore, in the fifth experiment, compared to the sixth experiment, in the short pattern, the increase in the amount of decrease in the first region R1 by the second step ST22 can be made smaller. In the fifth experiment, it is presumed that the thick tungsten-containing film DP can be formed in the short pattern because the plasma ion energy in the first step ST21 is high.

In the fifth experiment, after the second step ST22, the width of the slit in the short pattern (the width of the recess R1a) was 12.8 nm, and the width of the slit in the long pattern was 9.4 nm. Therefore, the difference LtS between the width of the slit in the short pattern and the width of the slit in the long pattern is 3.4 nm.

On the other hand, in the sixth experiment, after the second step ST22, the width of the slit in the short pattern was 13.8 nm, and the width of the slit in the long pattern was 8.7 nm. Therefore, the difference LtS between the width of the slit in the short pattern and the width of the slit in the long pattern is 5.1 nm. Therefore, in the fifth experiment, the difference LtS can be made smaller than in the sixth experiment.

(Seventh experiment)
In the seventh experiment, the same substrate W as in the fifth experiment was prepared. After that, the substrate W was subjected to the first step ST21 using the plasma processing apparatus 1 (see FIG. 10). In the fifth experiment, the processing gas in the first step ST21 contained oxygen gas, while in the seventh experiment, the processing gas in the first step ST21 contained hydrogen (H ₂ ) gas.

In the first step ST21, a slit having a depth of about 20 nm was formed in the recess R1a by etching the second region R2 while forming the tungsten-containing film DP on the first region R1 (see FIG. 5). . In the first step ST21, the processing gas is a mixed gas of fluorocarbon gas, hydrogen gas, argon gas, and tungsten hexafluoride gas (WF ₆ ). Further, the flow ratio of tungsten hexafluoride gas (WF ₆ ) is higher than that of fluorocarbon gas and lower than that of hydrogen gas. The RF power HF supplied to the plasma processing apparatus 1 is 200W. The RF power LF supplied to the plasma processing apparatus 1 is 100W.

(Experimental result)
A cross-sectional TEM image of the substrate W on which etching was performed in the seventh experiment was observed. In the seventh experiment, in the long pattern, the amount of decrease in the first region R1 after the first step ST21 was 2.7 nm, and the amount of decrease in the first region R1 after the first step ST21 in the fifth experiment (4. 9 nm).

In the fifth experiment, the thickness of the tungsten-containing film DP formed over the first region R1 after the first step ST21 was 4.3 nm. In the seventh experiment, the thickness of the tungsten-containing film DP formed over the first region R1 after the first step ST21 was 4.9 nm. Therefore, in the seventh experiment, the thickness of the tungsten-containing film DP is larger than in the fifth experiment.

For the substrate W subjected to the first step ST21 in the fifth and seventh experiments, the tungsten-containing film DP formed on the first region R1 was analyzed by X-ray photoelectron spectroscopy (XPS). In the fifth experiment, the composition ratio of tungsten was 2.4 atom %. In the seventh experiment, the composition ratio of tungsten was 5.0 atom %. Therefore, in the seventh experiment, the composition ratio of tungsten in the tungsten-containing film DP is larger than in the fifth experiment. It is presumed that this is because _WO3 is reduced by hydrogen to form metallic tungsten.

(8th experiment)
In the eighth experiment, the same substrate W as in the fifth experiment was prepared. After that, the substrate W was subjected to the first step ST21 and the second step ST22 using the plasma processing apparatus 1 (see FIG. 10). The process conditions of the first step ST21 of the eighth experiment are the same as the process conditions of the first step ST21 of the seventh experiment. The process conditions of the second step ST22 of the eighth experiment are the same as the process conditions (BSL conditions) of the second step ST22 of the fifth experiment.

(Experimental result)
A cross-sectional TEM image of the substrate W on which etching was performed in the eighth experiment was observed. In the long pattern, the amount of decrease in the first region R1 after the second step ST22 in the eighth experiment is 3.9 nm, and the amount of decrease (3.8 nm) in the first region R1 after the deposition step in the sixth experiment. were equivalent. In the short pattern, the amount of decrease in the first region R1 after the second step ST22 in the eighth experiment was 9.5 nm, and the amount of decrease (10.4 nm) in the first region R1 after the deposition step in the sixth experiment were equivalent.

In the eighth experiment, after the second step ST22, the width of the slit in the short pattern (the width of the recess R1a) was 12.6 nm, and the width of the slit in the long pattern was 8.3 nm. Therefore, the difference LtS between the width of the slit in the short pattern and the width of the slit in the long pattern is 4.3 nm. Therefore, in the eighth experiment, the difference LtS can be made smaller than in the sixth experiment.

In the eighth experiment, the process time of the eighth experiment is shorter than that of the sixth experiment because the deposition step is not performed as in the sixth experiment.

(9th experiment)
In the ninth experiment, the same substrate W as in the fifth experiment was prepared. Thereafter, the substrate W was subjected to the first step ST21, the third step ST23, and the second step ST22 using the plasma processing apparatus 1 in the same manner as in the fifth experiment except that the third step ST23 was performed (Fig. 10).

In the third step ST23, a process (hydrogen plasma process) of exposing the tungsten-containing film DP to plasma generated from hydrogen gas was performed. The RF power HF supplied to the plasma processing apparatus 1 is 300W. The RF power LF supplied to the plasma processing apparatus 1 is 0W. The processing time of the third step ST23 is 5 seconds.

(Experimental result)
A cross-sectional TEM image of the substrate W on which etching was performed in the ninth experiment was observed. In the ninth experiment, in the long pattern, the amount of decrease in the first region R1 after the first step ST21 was 4.9 nm, and the amount of decrease in the first region R1 after the second step ST22 was 6.3 nm. Therefore, the amount of decrease in the first region R1 was increased by 1.4 nm due to the second step ST22.

In the ninth experiment, in the short pattern, the amount of decrease in the first region R1 after the first step ST21 was 6.7 nm, and the amount of decrease in the first region R1 after the second step ST22 was 9.4 nm. Therefore, the amount of decrease in the first region R1 was increased by 2.7 nm due to the second step ST22. In the ninth experiment, compared to the fifth experiment, in the short pattern, the increase in the amount of decrease in the first region R1 by the second step ST22 can be made smaller.

In the ninth experiment, after the second step ST22, the width of the slit in the short pattern (the width of the recess R1a) was 12.7 nm, and the width of the slit in the long pattern was 9.8 nm. Therefore, the difference LtS between the width of the slit in the short pattern and the width of the slit in the long pattern is 2.9 nm.

In the ninth experiment, the thickness of the tungsten-containing film DP formed over the first region R1 was about 5.6 nm after the third step ST23. Therefore, in the ninth experiment, the thickness of the tungsten-containing film DP is larger than in the fifth experiment.

For the substrate W subjected to the first step ST21 and the third step ST23 in the ninth experiment, the tungsten-containing film DP formed on the first region R1 was analyzed by X-ray photoelectron spectroscopy (XPS). In the ninth experiment, the composition ratio of tungsten was 12.5 atom %. Therefore, in the ninth experiment, the composition ratio of tungsten in the tungsten-containing film DP is higher than in the fifth experiment. It is presumed that this is because _WO3 is reduced by hydrogen to form metallic tungsten.

(Appendix 1)
providing a substrate, the substrate comprising a first region comprising silicon and nitrogen and a second region comprising silicon and oxygen;
Etching the second region while forming a tungsten-containing protective layer over the first region by exposing the first region and the second region to a plasma generated from a process gas containing carbon, fluorine and tungsten. and
A method of etching, comprising:
(Appendix 2)
2. The etching method of Claim 1, wherein in the step of etching, the tungsten-containing protective layer remains on the first region after the second region is removed.
(Appendix 3)
3. The etching method according to appendix 1 or 2, wherein the process gas includes a carbon- and fluorine-containing gas and a tungsten-containing gas.
(Appendix 4)
4. The etching method of Claim 3, wherein the tungsten-containing gas comprises a tungsten hexafluoride gas.
(Appendix 5)
5. The etching method according to appendix 3 or 4, wherein the gas containing carbon and fluorine includes a fluorocarbon gas.
(Appendix 6)
6. The etching method of any one of Appendixes 1-5, wherein the process gas comprises oxygen.
(Appendix 7)
7. The etching method according to any one of Appendices 1 to 6, wherein the first region has a recess, and the second region is embedded in the recess.
(Appendix 8)
8. The etching method according to appendix 7, wherein the step of etching is performed in a self-aligned contact step.
(Appendix 9)
In the etching step, high-frequency power and bias power are supplied to a plasma processing apparatus in order to generate the plasma,
The etching step includes
(a) using the high frequency power as a first power and the bias power as a second power to preferentially deposit a tungsten-containing deposit on the first region;
(b) transitioning the high frequency power to a third power lower than the first power and the bias power to the second power;
(c) etching the second region by setting the high-frequency power to the third power and the bias power to a fourth power higher than the second power;
The etching method according to any one of Appendices 1 to 8, comprising
(Appendix 10)
The etching method according to Appendix 9, wherein the cycle including (a) to (c) is repeated two or more times.
(Appendix 11)
providing a substrate comprising silicon nitride with an exposed top surface and silicon oxide with an exposed top surface;
forming a tungsten nitride-containing protective layer on the silicon nitride by exposing the silicon oxide and the silicon nitride to a plasma generated from a process gas comprising tungsten hexafluoride gas;
preferentially etching the silicon oxide relative to the silicon nitride by exposing the silicon oxide and the silicon nitride to a plasma generated from a process gas comprising tungsten hexafluoride gas;
A method of etching, comprising:
(Appendix 12)
12. The etching method of Claim 11, wherein the process gas comprises a fluorocarbon gas.
(Appendix 13)
a chamber;
a substrate support for supporting a substrate within the chamber, the substrate including a first region comprising silicon and nitrogen and a second region comprising silicon and oxygen;
a gas supply configured to supply a process gas containing carbon, fluorine and tungsten into the chamber;
a plasma generator configured to generate a plasma from the process gas within the chamber;
a control unit;
with
The control unit exposes the first region and the second region to the plasma to form a tungsten-containing protective layer on the first region while the second region is etched. A plasma processing apparatus configured to control a supply section and the plasma generation section.
(Appendix 14)
providing a substrate, the substrate comprising a first region comprising silicon and a second region comprising silicon and oxygen;
Etching the second region while forming a tungsten-containing protective layer over the first region by exposing the first region and the second region to a plasma generated from a process gas containing carbon, fluorine and tungsten. and
including
The etching step includes a first step and a second step,
forming a first tungsten-containing deposit on the first region by supplying bias power to the plasma processing apparatus in the first step, wherein the bias power is a fifth power;
In the second step, high-frequency power and bias power are supplied to the plasma processing apparatus to form a second tungsten-containing deposit on the first tungsten-containing deposit while etching the second region; The etching method, wherein the bias power in the second step is a sixth power lower than the fifth power.
(Appendix 15)
The etching step includes a third step between the first step and the second step,
Clause 15. The etching method of Clause 14, wherein the third step exposes the first tungsten-containing deposit to a plasma generated from a process gas comprising a hydrogen-containing gas.
(Appendix 16)
providing a substrate, the substrate comprising a first region comprising silicon and a second region comprising silicon and oxygen;
Etching the second region while forming a tungsten-containing protective layer over the first region by exposing the first region and the second region to a plasma generated from a process gas containing carbon, fluorine and tungsten. and
including
The etching step includes a first step and a second step,
In the first step, the process gas includes a hydrogen-containing gas to form a first tungsten-containing deposit on the first region;
In the second step, the etching method includes etching the second region while forming a second tungsten-containing deposit on the first tungsten-containing deposit by the process gas containing an oxygen-containing gas.

From the foregoing description, it will be appreciated that various embodiments of the present disclosure have been set forth herein for purposes of illustration, and that various changes may be made without departing from the scope and spirit of the present disclosure. Will. Therefore, the various embodiments disclosed herein are not intended to be limiting, with a true scope and spirit being indicated by the following claims.

DESCRIPTION OF SYMBOLS 1... Plasma processing apparatus 2... Control part 10... Plasma process chamber 11... Substrate support part 12... Plasma generation part 20... Gas supply part DP... Tungsten containing film (tungsten containing protective layer) R1... 1st 1 area, R2... second area, W... substrate.

Claims (13)

providing a substrate, the substrate comprising a first region comprising silicon and nitrogen and a second region comprising silicon and oxygen;
Etching the second region while forming a tungsten-containing protective layer over the first region by exposing the first region and the second region to a plasma generated from a process gas containing carbon, fluorine and tungsten. and
A method of etching, comprising: 2. The etching method of claim 1, wherein in the step of etching, the tungsten-containing protective layer remains on the first regions after the second regions are removed. 3. The etching method according to claim 1, wherein said processing gas comprises a gas containing carbon and fluorine and a gas containing tungsten. 4. The etching method of claim 3, wherein the tungsten-containing gas comprises tungsten hexafluoride gas. 4. The etching method of claim 3, wherein the gas containing carbon and fluorine comprises a fluorocarbon gas. 3. The etching method of claim 1 or 2, wherein the process gas contains oxygen. 3. The etching method according to claim 1, wherein said first region has a recess, and said second region is embedded in said recess. 8. The etching method according to claim 7, wherein said etching step is performed in a self-aligned contact step. In the etching step, high-frequency power and bias power are supplied to a plasma processing apparatus in order to generate the plasma,
The etching step includes
(a) using the high frequency power as a first power and the bias power as a second power to preferentially deposit a tungsten-containing deposit on the first region;
(b) transitioning the high frequency power to a third power lower than the first power and the bias power to the second power;
(c) etching the second region by setting the high-frequency power to the third power and the bias power to a fourth power higher than the second power;
The etching method according to claim 1 or 2, comprising: 10. The etching method according to claim 9, wherein the cycle including (a) to (c) is repeated two or more times. providing a substrate comprising silicon nitride with an exposed top surface and silicon oxide with an exposed top surface;
forming a tungsten nitride-containing protective layer on the silicon nitride by exposing the silicon oxide and the silicon nitride to a plasma generated from a process gas comprising tungsten hexafluoride gas;
preferentially etching the silicon oxide relative to the silicon nitride by exposing the silicon oxide and the silicon nitride to a plasma generated from a process gas comprising tungsten hexafluoride gas;
A method of etching, comprising: 12. The etching method of claim 11, wherein said process gas comprises a fluorocarbon gas. a chamber;
a substrate support for supporting a substrate within the chamber, the substrate including a first region comprising silicon and nitrogen and a second region comprising silicon and oxygen;
a gas supply configured to supply a process gas containing carbon, fluorine and tungsten into the chamber;
a plasma generator configured to generate a plasma from the process gas within the chamber;
a control unit;
with
The control unit exposes the first region and the second region to the plasma to form a tungsten-containing protective layer on the first region while the second region is etched. A plasma processing apparatus configured to control a supply section and the plasma generation section.

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