Etching Method

Abstract

A continuous or cyclic etching method is disclosed for etching a metal carbide on a metal nitride. 2 and H 2 and providing a plasma generated from a gas mixture containing fluorine, chlorine, bromine, and iodine, to at least a portion of the surface of the metal carbide to modify the surface of the metal carbide, and removing the modified surface on the metal carbide by ion bombardment or heating.

Description

[Technical field]

[0001] The present invention relates to an etching method. [Background technology]

[0002] Advanced fabrication of three-dimensional structures in semiconductor devices requires the selective removal of one or more types of material without removing any of the other materials that were not damaged during fabrication. This can be achieved using controlled isotropic etching techniques, as well as multiple metal gate materials made from titanium-containing compounds.

[0003] Work function metal gates can be used in multi-layer stack structures in FinFETs. Among these metal gates, the ternary compound TiAlC has good control of threshold voltage and thermal resistance with respect to semiconductor manufacturing processes for n-type FinFETs. The fabrication of FinFETs is achieved by etching the TiAlC film without removing any of the non-target materials that are exposed in the surrounding area or appear under the TiAlC film, e.g., TiN metal gate in the case of p-type FinFETs. Selectivity of TiAlC is required over metal compounds, insulators, and semiconductors, such as TiN, TaN, HfO2, and Si.

[0004] Prior to the present invention, wet etching using H2O2 mixtures was applied. Although the TiAlC film can be removed by wet etching with selected chemicals, the wet etching has a low etching rate and poor selectivity, which leads to damage to other exposed materials due to the long processing time.

[0005] In the related art, etching of titanium carbide, which may contain aluminum, using a wet peroxide mixture is disclosed in US2015 / 0132953A1, which uses a liquid mixture of ammonia, peroxide, and water at 25°C to obtain maximum selectivity of TiC over TiN, with an etch rate of TiC of 8.6 nm / min.

[0006] Controllable and highly selective removal methods are required to fabricate next-generation FinFETs in the semiconductor industry. To increase the selectivity of the etch rate of TiAlC films, dry etching and plasma etching techniques are feasible. In the related art, dry etching of the ternary material TiAlC has been developed by near-atmospheric pressure plasma. This is disclosed in PCT / JP2021 / 038955. This method relies on treatment with high density radicals generated in an Ar / liquid vapor plasma, such as NH4OH vapor, H2O vapor, or a vapor mixture of NH4OH, H2O2, and H2O. Ions and charged particles have very short lifetimes, and thus far, the substrate surface has not been bombarded with ions. Thus, isotropic etching can be obtained in conditions where the emission of NH and H atoms is observed. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] US2015 / 0132953A1 Summary of the Invention [Problem to be solved by the invention]

[0008] There is a strong demand for stacks of thin metal layers for the next generation of fin-type nanosheet field effect transistors. A stack structure is required in which a TiAlC film is on a TiN film. In this case, both anisotropic and isotropic etching is required. For anisotropic etching, the key challenge is to suppress lateral etching at the sidewalls to the non-targeted films. Metal-containing films are typically etched by using plasmas of halogen-containing gas mixtures. However, halogen mixtures produce lateral etching features. For this reason, plasmas of non-halogen mixtures are required. For isotropic etching, it is important to suppress damage caused in the underlying layers. [Means for solving the problem]

[0009] The present inventors have developed a new dry etching method using a plasma of a non-halogen mixture to anisotropically and isotropically etch metal carbides without removing any metal nitrides.

[0010] Plasma is a source of ions, radicals, etc. Ions or charged particles may reach the substrate surface. At low pressures below 1000 Pa, ions or charged particles may impinge on the surface in certain cases when bias power is applied. Low pressure plasmas below 100 Pa are more preferred.

[0011] Here, both continuous and cyclic etching techniques are applied. In the case of atomic layer etching, cyclic etching can be processed in a self-limiting manner to selectively remove a film relative to other films. In the present invention, ion bombardment or heating is required to obtain anisotropic or isotropic etching.

[0012] First, surface modification may be controlled by treating the surface with the above ions and radicals as excited species, and photons. The modification layer consists of metal compounds containing nitrogen, carbon, and hydrogen.

[0013] This application discloses the best example of selectively removing metal carbides on metal nitrides by adding a small amount of oxygen (less than 10%) to the mixture of N2 and H2 gases to process the plasma etching process. The etching mechanism can be explained by the selective removal of volatile products containing NH and CN on the metal carbides and the selective inhibition via nitridation on the metal nitrides. The bias power that controls the ion bombardment energy towards the surface must be set within the range below the threshold at which the ion-enhanced removal of the metal nitrides begins. Effect of the Invention

[0014] The effects of the representative configuration of the present invention disclosed herein are as follows: According to the embodiments of the present invention, it is possible to provide a technique for dry etching titanium aluminum carbide films with high surface reactions, with ion or heating induced removal of the surface modification layer, in a continuous or cycle etching manner. High selectivity etching of titanium aluminum carbide over titanium nitride and other materials can be obtained by different surface reactions under high energy ion bombardment or heating. The lateral etching at the sidewalls of non-target materials can be suppressed without using halogens such as fluorine, chlorine, bromine. Non-halogen based chemistry N2, H2, and O2 mixtures can be used at temperatures above 50°C or 20°C. The method can be applied to anisotropic or isotropic selective etching of other metal carbides over metal nitrides. [Brief description of the drawings]

[0015] [Figure 1] FIG. 1 illustrates an example of a capacitively coupled plasma (CCP) etching system design. [Diagram 2] FIG. 1 is a diagram showing an outline of a procedure for a continuous etching method for a titanium aluminum carbide film. [Diagram 3] FIG. 13 shows the change in TiAlC film thickness during an etching process with pure N2 at 4 Pa ​​and a flow rate of 150 sccm. [Figure 4]FIG. 13 shows the change in TiAlC film thickness during the etching process of a mixture of N2 and H2 at 4 Pa ​​with flow rates of 75 sccm and 75 sccm, respectively. [Diagram 5] FIG. 13 shows the change in TiAlC film thickness during an etching process with pure H2 at 4 Pa ​​and a flow rate of 100 sccm. [Figure 6] FIG. 1 shows the dependence of the etch rate and selectivity (TiAlC / TiN) of TiAlC and TiN as a function of the fraction of H2 in a mixture of H2 and N2 gases at a pressure of 4 Pa, a bias power of 200 W, and a substrate temperature of 20° C. [Figure 7] FIG. 1 shows the dependence of the etch rate and selectivity (TiAlC / TiN) of TiAlC and TiN as a function of the fraction of H2 in a mixture of H2 and N2 gases at a pressure of 2 Pa, a bias power of 200 W, and a substrate temperature of 20° C. [Figure 8] FIG. 13 is a list of cross-sectional scanning electron microscope images of TiAlC and TiN films before and after plasma etching under various mixture conditions at a pressure of 4 Pa ​​and a treatment time of 10 min. [Figure 9] FIG. 1 shows emission spectra and photographic images of plasma obtained with various mixtures of N2 and H2 at a pressure of 4 Pa. [Figure 10] FIG. 13 shows the dependence of the intensity ratio of the Balmer lines of NH at 336.3 nm, the second positive band of N2 at 337.2 nm, and H atoms at 656.3 nm and 486.1 nm. [Figure 11] FIG. 1 shows narrow scans of the core regions Al 2p, C 1s, Ti 2p, and N 1s in X-ray photoelectron spectra obtained on the surface of a TiAlC film before and after 5 min of treatment with a mixture of H2 and N2 at flow rates of 50 and 50 sccm, respectively, bias power of 200 W, and pressure of 2 Pa. [Figure 12]FIG. 1 shows narrow scans of the core regions Ti 2p and N 1s in X-ray photoelectron spectra obtained on the surface of a TiN film before and after 5 min of treatment with a mixture of H2 and N2 at flow rates of 50 and 50 sccm, respectively, bias power of 200 W, and pressure of 2 Pa. [Figure 13] FIG. 1 shows an outline of element ratios and peak compositions versus chemical shifts in XPS analysis under representative conditions. [Figure 14] FIG. 11 is a cross-sectional view showing selective plasma etching of TiAlC using N2 / H2 plasma. [Figure 15] FIG. 13 shows the dependence of TiAlC and TiN etch rates on the substrate temperature range −20 to 50° C., with plasma flow rates of N2 and H2 mixture of 100 and 50 sccm, respectively, bias power of 200 W applied, and pressure of 4 Pa. [Figure 16] FIG. 13 shows the dependence of TiAlC and TiN etch rates on the bias power range 25-200 W, with plasma flow rates of N2 and H2 mixtures of 50 and 50 sccm, respectively, excitation VHF power of 300 W applied, and operating pressure of 2 Pa. [Figure 17] FIG. 13 is a graph showing the dependence of TiN sputtering rate on √Vpp for Vpp in the range of 900 to 1300 Vpp when the flow rate of Ar plasma at a pressure of 1 Pa is 50 sccm. [Figure 18] 1 shows narrow scans of the core region N 1s in X-ray photoelectron spectra obtained on the surfaces of TiAlC and TiN films before and after treatment with a mixture of H2 and N2 at flow rates of 50 and 50 sccm, respectively, for various bias powers of 25, 50, 100, and 200 W, pressure of 2 Pa, and substrate temperature of 20° C., with the treatment time of the sample using a bias power of 200 W being 5 minutes and the treatment time of the others being 20 minutes. [Figure 19] FIG. 1 shows an outline of element ratios and peak compositions versus chemical shifts in XPS analysis under representative conditions. [Figure 20]FIG. 1 shows the dependence of the etch rate of TiAlC, and for reference, the dependence of the etch rate of TiN, as a function of the fraction of O2 in a mixture of O2 and N2 gases at a pressure of 2 Pa, a bias power of 200 W, and a substrate temperature of 20° C. [Figure 21] FIG. 1 shows the dependence of the etch rate of TiAlC, and for reference, of the etch rate of TiN, as a function of the fraction of N2 in a mixture of H2 and N2 gases with 10% O2 addition, at a pressure of 2 Pa, a bias power of 200 W, and a substrate temperature of 20° C. [Figure 22] FIG. 1 shows the etch rate contours of TiAlC and TiN as a function of the fractions of N2, O2, and H2 in a mixture of H2, O2, and N2 gases at a pressure of 2 Pa, a bias power of 200 W, and a substrate temperature of 20° C. [Diagram 23] FIG. 11 is a cross-sectional view showing the inhibition of etching of TiN in N2 / H2 / O2 plasma. [Figure 24] FIG. 1 shows the emission spectra of plasmas obtained with various mixtures of N2, O2, and H2 at a pressure of 2 Pa. [Diagram 25] FIG. 1 shows the emission spectra of plasmas obtained with various mixtures of N2, O2, and H2 at a pressure of 2 Pa. [Figure 26] 1 is a schematic cross-sectional view showing an apparatus for isotropic etching according to one embodiment of the present invention. [Figure 27] FIG. 2 is a diagram showing, from the top to the bottom, an example of temporal variations in parameters in isotropic atomic layer etching according to an embodiment of the present invention, including process gas flow rate, high frequency power source power, infrared lamp power, rear He flow rate, and wafer surface temperature, in that order. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0016] The present inventors have attempted to etch titanium aluminum carbide films using non-halogen gas mixtures, resulting in the following findings: (1) The surface of TiAlC was successfully modified by treatment with non-halogen gas mixtures. (2) Desorption of volatile products can be obtained by ion bombardment of appropriate incident energy or by heating. (3) TiN etching was successfully suppressed by adding a small amount of O2 to the plasma of N2 and H2 mixture, which resulted in highly selective removal of TiAlC film on TiN film. (4) The incident energy of the ions should be set below the threshold for the ion-enhanced removal process of TiAlC and TiN films. The relatively high etching rate of TiAlC improves the selectivity of TiAlC over TiN. (5) The substrate temperature should be set to 50° C. or higher than 20° C. because nonselective desorption reduces the selectivity for removing TiAlC on TiN.

[0017] <Process Example 1> A best example of the present invention will be described with reference to Figures 1 to 13. An example is described for the design of an isotropic plasma etching process for titanium aluminum carbide films on titanium nitride films on silicon wafers, as well as selective plasma chemistry for high selectivity removal of metal carbides (TiAlC, TiC, AlC) on metal nitrides (TiAlN, TiN, AlN).

[0018] FIG. 1 shows an example of a design for a capacitively coupled plasma (CCP) etching system 300. The spectroscopic ellipsometer 350 includes a system for in-situ observation of a surface (sample 341) of a wafer 340 disposed on a lower electrode 301. The upper electrode 311 is connected to a very high frequency (VHF) power source 313 (100 MHz) through a matching circuit 312. The lower electrode 301 is connected to a medium frequency (MF) power source 303 (2 MHz) through another matching circuit 302. Here, the example describes the application of the invention to a CCP etching system, but the invention is also applicable to other etching systems, including inductively coupled plasma (ICP) etching systems and electron cyclotron resonance (ECR) plasma etching systems.

[0019] FIG. 2 shows a schematic diagram of the steps in the method for sequentially etching a titanium aluminum carbide film according to the present embodiment. A wafer is to be processed in a chamber having a system for generating a capacitively coupled plasma. The wafer is placed on the lower electrode 301 of the chamber (S01). The temperature of the wafer is then set by circulating a cooling liquid (S02). A gas mixture of N2 and H2 is then introduced into the chamber from the gas inlet through the upper electrode 311 (S03). A plasma is then generated by applying VHF power and bias power (S04). Unless otherwise noted, an excitation VHF power of 300 W is used. Hydrogen- and nitrogen-containing ions and radicals can modify the metal carbide to form metal-nitrogen-hydrocarbon bonds. Energy-controlled ion bombardment can desorb only the metal-containing hydrocarbon layer while leaving the metal-containing and nitrogen-containing layers intact. The cycle of surface modification and metal-containing volatiles removal can selectively etch only the metal carbide with respect to the metal nitride. If the amount of etching is sufficient, the wafer is removed from the chamber (S05, S06).

[0020] Figure 3 shows the evolution of TiAlC film thickness during the etching process in pure N2 with a flow rate of 150 sccm at 4 Pa, measured in situ using ellipsometry. The modification of the top film is monitored simultaneously. A bias power of 200 W is applied and the substrate temperature is 20 °C.

[0021] Figure 4 shows the evolution of TiAlC film thickness during the etching process in a mixture of N2 and H2 with flow rates of 75 sccm and 75 sccm, respectively, at 4 Pa, measured in situ using ellipsometry. The modification of the top film is monitored simultaneously. A bias power of 200 W is applied and the substrate temperature is 20 °C.

[0022] Figure 5 shows the evolution of TiAlC film thickness during the etching process in pure H2 with a flow rate of 100 sccm at 4 Pa, measured in situ using ellipsometry. The modification of the top film is monitored simultaneously. A bias power of 200 W is applied and the substrate temperature is 20 °C.

[0023] As can be seen in FIG. 4, the etch rate of TiAlC is evident in N2 and H2 mixture plasma compared to the pure N2 or pure H2 cases (FIGS. 3 and 5).

[0024] Figure 6 shows the dependence of the etch rate of TiAlC as a function of the fraction of H2 in a mixture of H2 and N2 gases at a pressure of 4 Pa, a bias power of 200 W, and a substrate temperature of 20°C. For reference, the dependence of the etch rate of TiN is also shown. The selectivity is expressed by taking the ratio of the etch rate of TiAlC to the etch rate of TiN.

[0025] Figure 7 shows the dependence of the etch rate as a function of the fraction of H2 in a mixture of H2 and N2 gases at a pressure of 2 Pa, a bias power of 200 W, and a substrate temperature of 20°C. For reference, the dependence of the etch rate of TiN is also shown. The selectivity is expressed by taking the ratio of the etch rate of TiAlC to the etch rate of TiN.

[0026] FIG. 8 is a list of cross-sectional scanning electron microscope images of TiAlC and TiN films before and after plasma etching under various mixture conditions at a pressure of 4 Pa ​​and a treatment time of 10 min.

[0027] FIG. 9 shows the emission spectra and photographic images of plasma obtained with various mixtures of N2 and H2 at a pressure of 4 Pa.

[0028] Figure 10 shows the dependence of the intensity ratio of the NH at 336.3 nm, the second positive band of N2 at 337.2 nm, and the H atom Balmer lines at 656.3 nm and 486.1 nm. It is clear that the emission of NH is stronger when plasma is generated with H2 mixed with N2. The strongest NH emission was observed for mixtures of H2 and N2 with flow rates of 50 and 100 sccm.

[0029] FIG. 11 shows narrow scans of the core regions Al 2p, C 1s, Ti 2p, and N 1s in X-ray photoelectron spectra obtained on the surface of a TiAlC film before and after treatment with a mixture of H2 and N2 at flow rates of 50 and 50 sccm, bias power of 200 W, pressure of 2 Pa for 5 min.

[0030] FIG. 12 shows narrow scans of the core regions Ti 2p and N 1s in X-ray photoelectron spectra obtained on the surface of a TiN film before and after treatment with a mixture of H2 and N2 at flow rates of 50 and 50 sccm, bias power of 200 W, pressure of 2 Pa for 5 min.

[0031] For TiAlC films, the chemical shifts of TiN and AlN appear after the plasma etching process, which indicates the nitridation of the TiAlC film. There are more than two components in the N 1s. Two components can be assigned to AlN and TiN, and the remaining part is identified as the chemical shift due to hydrogen and carbon bonds, which indicates NH and CN bonds.

[0032] For the TiN film, the chemical shift of TiN appears before and after the plasma etching process. The peak features remain almost unchanged after the plasma etching process.

[0033] FIG. 13 is a diagram showing an outline of element ratios and peak compositions versus chemical shifts in XPS analysis under typical conditions.

[0034] The etching mechanism is as follows: N-H bonds can be formed in the carbides. In this configuration, the hydrocarbon group is bonded to the metal element. Ti and Al are placed at the center by the coordination of the hydrocarbon group through the bridging nitrogen. These metal-organic complexes can be desorbed by forming volatile products. This is the case for Al(C x H y ) z , Ti-(N(C x H y ) z ), and Ti-(CN) x This indicates the possibility of the generation of volatile products such as. A cross-sectional view of selective plasma etching of TiAlC is shown in FIG.

[0035] Here, this example describes the application of the invention to anisotropic etching, but the invention is also applicable to isotropic etching by using heating instead of ion bombardment.

[0036] <Process Example 2> A second embodiment will now be described with reference to FIG.

[0037] An example is described for the development of dry plasma etching of titanium aluminum carbide films on titanium nitride films on silicon wafers.

[0038] Figure 15 shows the dependence of the etch rates of TiAlC and TiN on the substrate temperature range of -20 to 50 °C. The flow rates of the plasma of the mixture of N2 and H2 are 100 and 50 sccm, respectively. A bias power of 200 W is applied and the pressure is 4 Pa.

[0039] In this setup, the etch rate and selectivity of TiAlC films over TiN films increases as the substrate temperature increases above 20°C.

[0040] <Process Example 3> The third embodiment will be described with reference to FIGS.

[0041] An example is described for the development of dry plasma etching of titanium aluminum carbide films on titanium nitride films on silicon wafers.

[0042] FIG. 16 shows the dependence of the etch rates of TiAlC and TiN on the bias power range of 25W-200W. The flow rates of the plasma of the mixture of N2 and H2 are 50 and 50sccm, respectively. An excitation VHF power of 300W is applied, and the working pressure is 2Pa. The bias power is converted to the square root of the peak-to-peak voltage, √Vpp. At the same bias power, the larger the √Vpp, the faster the TiAlC etch rate is than the TiN etch rate. This trend is fitted by linearly correlating the etch rate with √Vpp. It can be seen that the crossover value (threshold) for the etch rate zero is lower for TiAlC etch rate than for TiN etch rate. When the bias power is lower than the threshold, it may be possible to remove the TiAlC film on the TiN film with high selectivity.

[0043] FIG. 17 shows the dependence of TiN sputtering rate on √Vpp for Vpp in the range of 900-1300 Vpp. The flow rate of Ar plasma at 1 Pa pressure is 50 sccm. The trend is fitted by linearly correlating TiN sputtering rate with √Vpp. It can be seen that the crossover value (threshold) for zero sputtering rate is almost the same at √Vpp of 25 for TiN etch rate in plasma of H2 and N2 mixture. However, the trend of TiAlC does not follow that of physical sputtering. In other words, the physical sputtering rate fails to follow the results of the present invention obtained with plasma of N2 and H2 mixture and application of low bias power. This means that N2 and H2 chemistry plays an important role for the selective etching of TiAlC over TiN.

[0044] Figure 18 shows narrow scans of the core region N 1s in X-ray photoelectron spectra obtained on the surfaces of TiAlC and TiN films before and after a mixture of H2 and N2 at flow rates of 50 and 50 sccm with various bias powers of 25, 50, 100, and 200 W, pressure of 2 Pa, substrate temperature of 20°C. The treatment time of the sample using the bias power of 200 W is 5 min, and the treatment time of the others is 20 min.

[0045] For the TiN film, before plasma etching, there are two components of chemical shift in the N 1s region. One is assigned to bulk TiN and the other to the native oxide of the TiN film, which indicates TiON. At a binding energy of about 402 eV, a small feature is observed, especially for the low bias powers of 25 W and 50 W. This is identified as NO binding.

[0046] In the case of TiAlC films, nitrogen is certainly not present before plasma etching. As this pristine TiAlC film is etched, obvious peaks appear in the N 1s XPS spectrum. Similarly, in TiN films, there are components of TiN and AlN, as well as native oxides TiON and AlON. Above 50 W bias power, these peaks are almost unchanged regardless of the bias power. For low bias powers of 25 W and 50 W, the peak component at high binding energy of about 402 eV becomes stronger. The observed modification of the TiAlC surface leads to the formation of volatile products in the plasma of N2 and H2 mixtures. Bonds Al-C, Ti(Al)-N, NH, and CN were found in the samples after plasma treatment, which is consistent with the formation of methyl (Al-CH3), methylamine (Ti(Al)-NH n -CH 3-n This is evidence of the formation of volatile products having chemical bonds, including volatile compounds. These bond components should be controlled to obtain volatile products.

[0047] FIG. 19 is a diagram showing an outline of element ratios and peak compositions versus chemical shifts in XPS analysis under representative conditions.

[0048] <Process Example 4> The fourth embodiment will be described with reference to FIGS.

[0049] An example is described for the development of dry plasma etching of titanium aluminum carbide films on titanium nitride films on silicon wafers.

[0050] 20 shows the dependence of the etch rate of TiAlC as a function of the fraction of O2 in a mixture of O2 and N2 gases at a pressure of 2 Pa, a bias power of 200 W, and a substrate temperature of 20° C. For reference, the dependence of the etch rate of TiN is also shown.

[0051] 21 shows the dependence of the etch rate of TiAlC as a function of the fraction of N2 in a mixture of H2 and N2 gases with 10% O2 addition at a pressure of 2 Pa, a bias power of 200 W, and a substrate temperature of 20° C. For reference, the dependence of the etch rate of TiN is also shown.

[0052] FIG. 22 shows the etch rate contours of TiAlC and TiN as a function of the fractions of N2, O2, and H2 in a mixture of H2, O2, and N2 gases at a pressure of 2 Pa, a bias power of 200 W, and a substrate temperature of 20° C.

[0053] For TiAlC films, two maxima appear: one for the plasma of O2 and N2 mixture, and another for the plasma of N2 and H2 mixture. For the N2 and H2 mixture, adding less than 10% O2 gives an etch rate nearly the same as TiAlC. Further addition of O2 significantly reduces the TiAlC etch rate, but the etch rate remains relatively fast.

[0054] For TiN films, the maximum etch rate occurs for pure N2 in this mixture among O2, H2, and N2. With the addition of O2, surface oxidation significantly suppresses the etching off of TiN films.

[0055] To obtain the etch selectivity of TiAlC over TiN and high etch rate of TiAlC film, a mixture of H2 and N2 with H2 fraction ranging from 25% to 75% is the best example, and O2 should be added to the H2 and N2 mixture with O2 fraction less than 10%.

[0056] According to the etching results of the present invention, the surface modification of TiAlC and TiN films respectively can be controlled by the plasma etching chemistry, i.e., by controlling the gas mixture ratio. Plasma generates various kinds of ions and radicals. Mainly, the surface modification of NH and CN components can assist the removal of TiAlC film. This modified layer can form volatile products, forming bonds with hydrocarbon groups and nitrogen bridges to coordinate Ti and Al at the center. A small amount of oxidation in both films can help inhibit the etching of TiN film by the formation of TiON. A cross-sectional view of the inhibition of etching of TiN in N2 / H2 / O2 plasma is shown in Figure 23.

[0057] <Process Example 5> Figures 24 and 25 show the emission spectra of plasmas obtained with various mixtures of N2, O2, and H2 at a pressure of 2 Pa. For 100% N2, the second positive band of N2 is clearly observed around 337, 357, and 380 nm, and the first positive band of N2 is clearly observed around 600-800 nm. For 100% H2, the Balmer lines of H atoms are clearly observed at 656.3 nm and 486.1 nm. For 100% O2, O atom emission is seen at 777 and 844 nm. For N2 and H2 mixtures, NH emission can be observed, but in this setup, the overlap of N2 emission interferes with the observation of the NH band. For N2 and O2 mixtures, NO emission can be observed around 245 nm in the ultraviolet light range. For H2 and O2 mixtures, strong OH emission is clearly observed around 310 nm, as well as the Balmer lines of H. In a mixture of N2, H2, and 10% O2, all the emissions from NO and H atoms overlap. Thus, emission spectrum observations can be used to monitor the conditions of how the gases are mixed. In addition, when O2 is fixed at 10%, the balance of N2 and H2 is changed. The spectral intensities of H atoms (656 nm), N2 (337 nm), OH (310 nm), and NO (245 nm) show how these gases mix in the plasma.

[0058] <Process Example 6> One embodiment will be described with reference to Figures 26 to 27. This embodiment corresponds to an example in which a plasma generated from a mixture of N2 and H2 is used to selectively and isotropically etch a TiAlC film on a TiN film by using infrared heating in a plasma processing apparatus for 300 mm wafers.

[0059] A plasma processing apparatus for performing etching of a film containing titanium aluminum carbide as described above will now be described. Fig. 26 is a cross-sectional view showing a schematic configuration of a plasma processing apparatus 100.

[0060] The processing chamber 1 is composed of a base chamber 11, and a wafer stage 4 (hereinafter referred to as stage 4) on which a wafer 2 as a sample to be processed is placed is disposed in the processing chamber 1. The plasma source includes a quartz chamber 12, an ICP coil 34, and a high-frequency power source 20, and is disposed in a container 60 disposed above the base chamber 11. In this example, an inductively coupled plasma (ICP) discharge method is used for the plasma source. The high-frequency power source 20 for generating the plasma is connected to the ICP coil 34 outside the cylindrical quartz chamber 12 via a matching unit 22. A frequency band of several tens of MHz, such as 13.56 MHz, is used as the frequency of the high-frequency power.

[0061] The upper plate 6 is disposed in the upper portion of the quartz chamber 12. The shower plate 5 is disposed in the upper plate 6. The gas diffusion plate 17 is disposed below the upper plate 6. The process gas is introduced into the process chamber 1 from the outer periphery of the gas diffusion plate 17.

[0062] The supply flow rate of the process gas is adjusted by a mass flow controller 50 arranged for each type of gas in the process gas. Figure 26 shows an example in which N2 and H2 are used as the process gas. However, the types of gases in the process gas are not limited thereto.

[0063] The vacuum exhaust pipe 16 is connected to a pump 15 to reduce the pressure in the lower part of the processing chamber 1. The pump 15 is composed of, for example, a turbomolecular pump, a mechanical booster pump, or a dry pump. A pressure adjustment mechanism 14 is disposed upstream of the pump 15 to adjust the pressure in the discharge region 3 in the processing chamber 1 or the quartz chamber 12. The pressure adjustment mechanism 14, the pump 15, and the vacuum exhaust pipe 16 are collectively referred to as an exhaust mechanism. The stage 4 includes an O-ring 81 that implements a vacuum seal between the stage 4 and the bottom surface of the base chamber 11.

[0064] An infrared (IR) lamp unit for heating the wafer 2 is disposed between the stage 4 and the quartz chamber 12 that constitutes the ICP plasma source. The IR lamp unit mainly includes an IR lamp 62, a reflecting plate 63 that reflects IR light, and an IR light transmitting window 74. A circular (round) lamp is used as the IR lamp 62. The light (electromagnetic wave) emitted from the IR lamp 62 is light (referred to as IR light in this specification) that mainly includes light from visible light to light in the infrared light region. In this example, the IR lamp 62 includes three rounds of IR lamps 62-1, 62-2, and 62-3. However, the IR lamp 62 may include two or four rounds of IR lamps. A reflecting plate 63 that reflects the IR light downward (toward the arrangement direction of the wafer 2) is disposed above the IR lamp 62.

[0065] The IR lamp power source 64 is connected to the IR lamp 62. The high frequency cutoff filter 25 is disposed between the IR lamp power source 64 and the IR lamp 62. The high frequency cutoff filter 25 prevents noise of the high frequency power that generates the plasma generated by the high frequency power source 20 from flowing into the IR lamp power source 64. The IR lamp power source 64 has a function of independently controlling the power supplied to each of the IR lamps 62-1, 62-2, and 62-3, and therefore can adjust the radial distribution of the heating amount of the wafer 2.

[0066] In this example, the gas supplied into the quartz chamber 12 flows into the processing chamber 1, so that the gas flow passage 75 is formed in the center of the IR lamp unit. The gas flow passage 75 includes a slit plate (ion shielding plate) 78 that shields ions and electrons in the plasma generated inside the quartz chamber 12 and sends only neutral gas or neutral radicals to irradiate the wafer 2. The slit plate 78 includes a plurality of holes.

[0067] On the other hand, coolant channels 39 are formed in the stage 4 to cool the stage 4, and a coolant is supplied and circulated by a cooling device 38. In order to fix the wafer 2 to the stage 4 by electrostatic attraction, electrodes 30 for electrostatic attraction, which are plate-shaped electrode plates, are embedded in the stage 4. DC power supplies 31 for electrostatic attraction are respectively connected to the electrodes 30 for electrostatic attraction.

[0068] To efficiently cool the wafer 2, He gas (cooling gas) can be supplied between the stage 4 and the back surface of the wafer 2 placed on the stage 4. The front surface of the stage 4 (the surface on which the wafer is placed) is coated with a resin such as polyimide to prevent damage to the back surface of the wafer 2 even when the electrode 30 for electrostatic attraction is operated to perform heating and cooling while electrostatically attracting the wafer 2. A thermocouple 70 for measuring the temperature of the stage 4 is disposed inside the stage 4 and connected to a thermocouple thermometer 71.

[0069] The optical fibers 92-1 and 92-2 are disposed at three locations for measuring the temperature of the wafer 2, i.e., a location near the center of the wafer 2 placed on the stage 4, a location near the middle of the wafer 2 in the radial direction, and a location near the outer periphery of the wafer 2. The optical fiber 92-1 guides IR light from an external IR light source 93 to the rear surface of the wafer 2, thereby irradiating the rear surface of the wafer 2 with the IR light. On the other hand, the optical fiber 92-2 collects IR light that is transmitted through or reflected on the wafer 2 out of the IR light emitted by the optical fiber 92-1, and sends the transmitted or reflected IR light to a spectrometer 96.

[0070] That is, the external IR light generated by the external IR light source 93 is sent to the optical path switch 94 which turns the optical path on and off. The external IR light is then split into multiple (three in this case) lights by the optical distributor 95, and various positions on the back surface of the wafer 2 are irradiated with the multiple IR lights via the three optical fibers 92-1. The IR light absorbed or reflected by the wafer 2 is sent to the spectrometer 96 by the optical fiber 92-2, and the wavelength-dependent data of the spectral intensity is obtained by the detector 97. The wavelength-dependent data of the spectral intensity obtained by the detector 97 is sent to the arithmetic unit 41 of the control unit 40 to calculate the absorption wavelength, and the temperature of the wafer 2 can be determined based on the absorption wavelength. The optical multiplexer 98 is disposed in the middle part of the optical fiber 92-2, so that it is possible to switch the light to be spectroscopically measured at the measurement points of the center of the wafer, the middle of the wafer, and the outer periphery of the wafer. Therefore, the arithmetic unit 41 can determine the temperatures of the center of the wafer, the middle of the wafer, and the outer periphery of the wafer.

[0071] The control unit 40 controls each mechanism constituting the plasma processing apparatus 100. Specifically, the control unit 40 controls the high frequency power source 20, and controls the on / off of the high frequency power supply to the ICP coil 34. The gas supply unit 51 is controlled to adjust the type and flow rate of gas supplied from each of the mass flow controllers 50-1 to 50-4 to the inside of the quartz chamber 12. When the etching gas is supplied, the control unit 40 operates the pump 15 and controls the pressure adjustment mechanism 14 to adjust the pressure inside the processing chamber 1 to a desired pressure.

[0072] While activating the DC power supply unit 31 for electrostatic attraction to electrostatically attract the wafer 2 to the stage 4 and activating the mass flow controller 50-4 for supplying He gas between the wafer 2 and the stage 4, the control unit 40 controls the IR lamp power source 64 and the cooling device 38 based on the temperature of the stage 4 measured by the thermocouple thermometer 71 and information on the temperature distribution of the wafer 2 determined by the arithmetic unit 41 so that the temperature of the wafer 2 falls within a predetermined temperature range. The information on the temperature distribution of the wafer 2 is determined based on information on the spectral intensity near the center portion of the wafer 2, near the middle portion of the wafer 2 in the radial direction, and near the outer periphery of the wafer 2 measured by the detector 97.

[0073] FIG. 27 is a time chart of one cycle when isotropic atomic layer etching of a TiAlC film is performed by the plasma processing apparatus 100.

[0074] First, a wafer 2 having a TiAlC film to be etched formed thereon is transferred into the processing chamber 1 through a transfer port (not shown) provided in the processing chamber 1 and placed on the stage 4. The control unit 40 activates the DC power supply unit 31 to electrostatically adsorb the wafer 2 and fix it to the stage 4, and controls the gas supply unit 51 to supply He gas for wafer cooling between the rear surface of the wafer 2 and the stage 4 from the mass flow controller 50-4 corresponding to He gas, so that the pressure 230 of the He gas between the rear surface of the wafer 2 and the stage 4 is set to a predetermined pressure 231 and the wafer temperature 240 is set to a temperature 241. In this example, the wafer temperature 241 is 20° C.

[0075] Subsequently, the control unit 40 adjusts the flow rate of the gas, which is a mixture of N2H2 and is the reactive gas supplied into the processing chamber 1 by the mass flow controllers 50-2 and 50-3, and adjusts the opening degree of the pressure adjustment mechanism 14 so that the pressure inside the processing chamber 1 and the pressure inside the quartz chamber 12 are set to the target pressure. In this state, the control unit 40 turns on the high frequency power source 20 to apply the discharge power 211, thereby starting the plasma discharge inside the quartz chamber 12 and generating the plasma 10 inside the quartz chamber 12. At this time, the temperature of the wafer 2 is maintained at 20° C., so that the power 220 applied to the IR lamp 62 is zero (power 221).

[0076] In this state, a part of the mixture of N2 and H2 is ionized and dissociated in the plasma 10. The neutral gas and neutral radicals that are not ionized in the region where the plasma 10 is generated pass through the slit plate 78, so that the wafer 2 is irradiated with the neutral gas and neutral radicals containing NH. The radicals are adsorbed on the surface of the wafer 2 and react with the TiAlC film to form Al(C x H y ) z , Ti-(N(C x H y ) z ), and Ti-(CN) x Due to the effect of the slit plate 78, the ions generated in the plasma 10 hardly enter the wafer 2. Therefore, the surface reaction of the TiAlC film mainly proceeds isotropically by radicals, and the surface reaction layer is generated on the surface of the TiAlC film. The thickness of the generated surface reaction layer increases depending on the plasma treatment time using the gas mixture and the plasma treatment temperature. However, after 15 seconds at the temperature in this case, the amount of the surface reaction layer becomes saturated. Therefore, the time of the plasma treatment using the gas phase is set to 15 seconds.

[0077] After the plasma processing time required to form the surface reaction has elapsed, the control unit 40 turns off the high frequency power source 20 (discharge power 212) and stops the plasma discharge. The gas remaining in the processing chamber 1 is exhausted by the exhaust mechanism. The supply of He gas to the backside of the wafer is stopped, and the valve 52 is opened to set the pressure at the backside of the wafer 2 equal to the pressure in the processing chamber 1. The He gas at the backside of the wafer is removed, thereby setting the He gas pressure 230 at the backside of the wafer to pressure 232. This is the first step.

[0078] Subsequently, the control unit 40 turns on the output of the IR lamp power source 64 to turn on the IR lamp 62 (power 222). The IR light emitted from the IR lamp 62 passes through the IR light transmission window 74 and heats the wafer 2. Thus, the temperature of the wafer increases as shown as wafer temperature 242. The wafer temperature 240 reaches 200° C. 25 seconds after the start of the temperature increase when the second step ends. In this example, the wafer temperature to be reached is set to 200° C.

[0079] When the wafer temperature 240 reaches 200° C. (wafer temperature 243), the control unit 40 reduces the output of the IR lamp power source 64 to power 223, thereby keeping the wafer 2 temperature constant at temperature 243 for a certain period of time. The pressure is set to 5 Pa. x H y ) z , Ti-(N(C x H y ) z ), and Ti-(CN) x The surface reaction layer consisting of is volatile at high temperatures and is removed, thereby reducing the thickness of the TiAlC film. Since the entire surface reaction layer is removed, the etching is stopped and the surface of the TiAlC layer is exposed.

[0080] In the second step and this step (third step), the wafer 2 is heated by the electromagnetic waves from the IR lamps 62, so that the surface of the wafer to be heated can be efficiently warmed. For example, even if there is a temperature difference of about 180° C., the heating can be completed quickly. Although it is described that the wafer 2 is heated in a state where the wafer 2 is placed on the stage 4, the wafer 2 may be lifted from the stage 4 by using a lift pin or the like, and IR light (electromagnetic waves) may be irradiated in a state where the wafer 2 is not in thermal contact with the stage 4. Therefore, it is possible to prevent heat transfer from the wafer 2 to the stage 4, and therefore the temperature of the wafer 2 can be raised to a desired temperature in a shorter time. In this case, the temperature of the wafer 2 may be measured using light emitted from the IR lamps 62, transmitted through the wafer 2, and reaching the optical fiber 92-2. The power ratio of the IR lamps 62-1, 62-2, and 62-3 may be controlled based on the radial temperature distribution on the surface of the wafer 2.

[0081] Then, the control unit 40 turns off the output of the IR lamp power source 64 (power 224) to stop heating the wafer 2. The gas remaining in the processing chamber 1 is quickly exhausted by the exhaust mechanism. Thus, the third step is completed.

[0082] Next, the control unit 40 controls the mass flow controller 50-1 for supplying Ar gas and the mass flow controller 50-4 for supplying He gas to supply Ar gas into the processing chamber 1 and He gas between the back surface of the wafer 2 and the stage 4, whereby the pressure 230 of the He gas between the back surface of the wafer 2 and the stage 4 is set to a predetermined pressure 233, and cooling of the wafer 2 is started (temperature 244). The wafer temperature is cooled down to 20° C., and the time required for cooling is 30 seconds. Thus, the fourth step is completed.

[0083] Thus, in this embodiment, the surface reaction process in the first step and the sublimation removal process in the third step proceed isotropically, so that the thickness of the TiAlC film is reduced from the initial thickness of the film. The cycle including the first to fourth steps is repeated 10 times in this example, whereby the entire TiAlC film is etched. Also, the surface of the TiN underlayer is exposed. Since the heating step is low-damage, the damage caused to the TiN underlayer is negligible. [Explanation of symbols]

[0084] 1: Processing chamber, 2: Wafer, 3: Discharge area, 4: Wafer stage, 5: Shower plate, 6: Upper plate, 11: Base chamber, 12: Quartz chamber, 14: Pressure adjustment mechanism, 15: Pump, 16: Vacuum exhaust pipe, 17: Gas diffusion plate, 20 High frequency power source, 22: Matching unit, 25: High frequency cutoff filter, 30: Electrode, 31: DC power supply, 34: ICP coil, 38: Cooling device, 39: Coolant flow path, 40: Control unit, 41: Calculation unit, 50: Mass flow controller, 51: Gas supply unit, 60: Container, 62: IR lamp, 63: Reflection plate, 64: IR lamp power source, 70: Thermocouple, 71: Thermocouple thermometer, 74: IR light transmission window, 75: Gas flow path, 78: Slit plate (ion shielding plate), 81: O-ring, 92 : Optical fiber, 93: External IR light source, 94: Optical path switch, 95: Optical distributor, 96: Spectrometer, 97: Detector, 98: Optical combiner, 100: Plasma processing device, 200: Gas flow, 210: RF power, 220: IR lamp power, 230: He pressure, 240: Wafer temperature, 300: Capacitively coupled plasma (CCP) etching system, 301: Lower electrode, 302: Matching circuit, 303: MF power supply, 311: Upper electrode, 312: Matching circuit, 313: VHF power supply, 340: Wafer, 341: Sample, 350: Spectroscopic ellipsometer.

Claims

1. N ２ and H ２ 1. A continuous etching method for etching metal carbide on a metal nitride, comprising the steps of: supplying a plasma generated from a gas mixture containing fluorine, chlorine, bromine, and iodine to at least a portion of a surface of a metal carbide to modify the surface of the metal carbide; and removing the modified surface on the metal carbide by ion bombardment.

2. N ２ and H ２ 1. A cyclic etching method for etching metal carbide on a metal nitride, comprising one or more cycles of modifying a surface of a metal carbide by supplying a plasma generated from a gas mixture containing fluorine, chlorine, bromine, and iodine to at least a portion of the surface of the metal carbide, the plasma being generated from the gas mixture containing fluorine, chlorine, bromine, and iodine, and removing the modified surface from the surface of the metal carbide by ion bombardment.

3. N ２ and H ２ 1. A cyclic etching method for etching metal carbide on a metal nitride, comprising one or more cycles of modifying a surface of a metal carbide by supplying a plasma generated from a gas mixture containing fluorine, chlorine, bromine, and iodine to at least a portion of the surface of the metal carbide, the plasma being generated from the gas mixture containing fluorine, chlorine, bromine, and iodine, and removing the modified surface from the surface of the metal carbide by heating.

4. The etching method of claim 1, 2, or 3, wherein the metal carbide is titanium aluminum carbide.

5. The etching method of claim 1, 2, or 3, wherein the metal nitride is titanium nitride.

6. The gas mixture is O ２ The etching method according to claim 1 , 2 or 3 , comprising:

7. O in the gas mixture ２ The etching method according to claim 6 , wherein the flow rate ratio of

8. 4. The etching method of claim 1, 2, or 3, wherein the modified surface comprises CH, CN, and NH.

9. The etching method according to claim 1 , 2 or 3 , wherein the plasma pressure is less than 1000 Pa.

10. 4. The etching method according to claim 1, 2 or 3, wherein the temperature of the metal carbide is greater than 20°C.

11. 4. The etching method of claim 3, wherein the heating is performed by irradiating with infrared light from a lamp.

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