This application is based upon and claims the benefit of priority from Japanese Patent Application No. 2021-115453, filed on Jul. 13, 2021, the entire contents of which are incorporated herein by reference.
The present disclosure relates to a pattern formation method and a photosensitive hard mask.
As the next-generation exposure technique for coping with the miniaturization of semiconductor devices, there has been studied a technique that makes use of EUV (extreme ultraviolet) having a very short wavelength of 13.5 nm. In the pattern formation using an EUV exposure apparatus, a chemically amplified resist is used as a photosensitive material. In addition, various proposals have been made to increase the sensitivity of the chemically amplified resist to EUV and shorten the exposure time (for example, Patent Document 1).
Patent Document 1: Japanese Laid-Open Patent Publication No. 2020-101593
According to one embodiment of the present disclosure, there is provided a pattern formation method, including: forming a photosensitive hard mask made of a transition metal oxide film on a surface of a substrate; exposing the photosensitive hard mask to EUV light in a desired pattern; causing a state change in an exposed region by heat generated during exposure; and selectively removing either a region where the state change has occurred or a region where the state change has not occurred.
The accompanying drawings, which are incorporated in and constitute a part of the specification, illustrate embodiments of the present disclosure, and together with the general description given above and the detailed description of the embodiments given below, serve to explain the principles of the present disclosure.
Hereinafter, embodiments will be described with reference to the accompanying drawings. In the following detailed description, numerous specific details are set forth in order to provide a thorough understanding of the present disclosure. However, it will be apparent to one of ordinary skill in the art that the present disclosure may be practiced without these specific details. In other instances, well-known methods, procedures, systems, and components have not been described in detail so as not to unnecessarily obscure aspects of the various embodiments.
First, a method of forming a pattern by performing EUV exposure and development on a photosensitive hard mask will be described.
First, a photosensitive hard mask 101 made of a transition metal oxide film is formed on the surface of a substrate 100 (step ST1 in
Examples of a transition metal oxide include tetravalent transition metal oxides such as HfO2 and ZrO2, and low-melting-point polyvalent oxides such as WOx, MoOx and VOx. The photosensitive hard mask 101 may be formed by a thin film formation technique, for example, physical vapor deposition (PVD) such as sputtering or the like, chemical vapor deposition (CVD), or atomic layer deposition (ALD). As the transition metal oxide constituting the photosensitive hard mask 101, a material whose state change occurs when irradiated with EUV light may be used. Examples of the state change include a phase transition (phase change) and a composition change.
Subsequently, the photosensitive hard mask 101, which is a transition metal oxide film, is exposed to an EUV light 102 in a desired pattern to form an exposed region 103 (step ST2 in
Subsequently, the heat generated by the exposure causes a state change in the exposed region 103, and the exposed region 103 is used as a state change region 104 (step ST3 in
Subsequently, in the photosensitive hard mask 101, either the state change region 104 or a non-state change region 105, which is not exposed and not subjected to state change, is selectively removed (step ST4 in
In an exposure process using a conventional chemically amplified resist, when irradiating EUV light, high-energy photons are incident into the resist, and electrons generated by excitation activate a photoacid generator (PAG), thereby allowing the process to proceed. At this time, the number of electrons generated is small and the sensitivity of the photosensitive material is low. Therefore, there are problems that the exposure time is long and the throughput is low. In order to overcome these problems, various proposals have been made to increase the sensitivity of the chemically amplified resist to EUV and shorten the exposure time. For example, there has been widely studied a technique for improving sensitivity such as a technique for increasing the number of electrons generated by excitation by photons by doping a chemically amplified resist with a metal element having a large absorption of EUV light. However, these effects are also limited. There is a demand for a photosensitive material that can fundamentally shorten the exposure time.
Therefore, in the present embodiment, a photosensitive hard mask made of a transition metal oxide film, which is an inorganic material, is used, and a photosensitive process utilizing a state change due to the heat generated when exposed to EUV light as described above is performed instead of the conventional exposure process using a chemical reaction.
EUV light has a wavelength close to X-rays among electromagnetic waves, and EUV light having a wavelength of 13.5 nm (13.5 nm light) used for exposure has a high energy of 91 eV. When the high-energy photons are incident on a film made of an inorganic material, it excites the valence electrons of constituent atoms, and the energy thereof is finally transferred to a crystal lattice to become heat. In the present embodiment, this heat is used to cause a local temperature rise in a transition metal oxide film, which is an inorganic material film, thereby causing a state change of a material.
In the exposure process by a chemical reaction using a chemically amplified resist, only a small portion of the energy of EUV light is used in the chemical reaction, and the remaining energy is dissipated as heat. On the other hand, in the present embodiment, almost all of the energy of EUV light, which has been dissipated as heat in the past, is used to cause a state change, thereby making the energy efficiency essentially high. Therefore, it is possible to shorten the exposure time.
In addition, the unit cell of the inorganic material is smaller than that of a general polymer photosensitive material. In the case of HfO2, the side length of the unit cell is about 0.5 nm. This makes it possible to suppress fluctuations in the pattern width due to the molecular size which is problematic in a chemically amplified resist. Fluctuations in the resulting pattern width may be suppressed. Further, the heat generated at the time of exposure spreads from the exposed region to the outside due to heat diffusion. However, moderate heat diffusion reduces the effect of statistical fluctuation of a pattern width.
Further, both the positive type and the negative type may be selected by either removing the exposed region whose state has been changed or removing the non-exposed region. Thus, the degree of freedom is high.
Next, the photosensitive hard mask will be described in detail.
As mentioned above, the photosensitive hard mask is composed of a transition metal oxide. Examples of the transition metal oxide may include tetravalent transition metal oxides such as HfO2 and ZrO2, which are widely used in the semiconductor field, and low-melting-point polyvalent metal oxides such as WOx, MoOx and VOx. The transition metal oxide has a small extinction length (length at which the light intensity is attenuated to 1/e) for the 13.5 nm light, which is the EUV light used for exposure. As shown in
Regarding the film thickness of the transition metal oxide film constituting the photosensitive hard mask, as shown in
Among the above transition metal oxides, the tetravalent transition metal oxides such as HfO2 and ZrO2 and the low-melting-point polyvalent oxides such as WOx, MoOx, and VOx have different characteristics.
In the case of HfO2 and ZrO2, which are tetravalent transition metal oxides, the melting point thereof is as high as about 2700 degrees C. Therefore, HfO2 and ZrO2 may not be melted by the exposure to the EUV light. However, HfO2 and ZrO2 undergo a phase transition at about 1000 degrees C. or lower. Thus, the phase transition is used.
For example, in the case of an HfO2 film, negative patterning may be performed as shown in
Positive patterning may be performed by selectively etching the crystalline phase in the exposed region.
When ZrO2 is used as the transition metal oxide, it becomes a crystalline phase (low temperature phase) in the as-deposition state. However, since ZrO2 has a high temperature phase, the exposed region is caused to undergo a phase transition to the high temperature phase by setting the heating temperature of the exposed region to be equal to or higher than the phase transition temperature to the high temperature phase. Then, one of them may be selectively removed according to the difference in etching rate between the low temperature phase and the high temperature phase.
In the case of WOx, MoOx and VOx, which are low-melting-point multivalent oxides, the melting point thereof is about 800 to 1,500 degrees C., which is lower than the melting point of HfO2 and ZrO2. In particular, the melting point of MoO3 as MoOx is as extremely low as 795 degrees C. MoO3 may be formed into a film by sputtering. By setting the substrate temperature during sputtering to room temperature, MoO3 has an amorphous phase in an as-deposition state. By setting the substrate temperature to 200 degrees C. or higher, MoO3 has a crystalline phase in an as-deposition state. As a result, negative patterning and positive patterning may be performed.
The negative patterning of the MoO3 film may be performed as shown in
The positive patterning of the MoO3 film may be performed as shown in
In the case of negative patterning, the MoO3 film having the amorphous phase is exposed to EUV light. As shown in
Further, if the non-phase transition region has an amorphous phase and the phase transition region has a crystalline phase, positive patterning may be performed by adjusting the etching method and changing the portion to be removed to the phase transition region having a crystalline phase. In the example in which the phase transition region has an amorphous phase and the non-phase transition region has a crystalline phase, negative patterning may be performed by adjusting the etching method and changing the portion to be removed to the non-phase transition region having a crystalline phase.
Although the MoO3 film has been described above by way of example, patterning may be similarly performed for the WO3 film as a WOx film and the VO3 film as a VOx film. However, since WO3 and VO3 have a higher melting point than MoO3, it is necessary to lengthen the irradiation time of EUV light at the time of melting.
Further, regarding WOx, MoOx and VOx, which are low-melting-point multivalent oxides, the state change at the time of exposure to EUV light is not limited to the phase transition described above, but may be a composition change. WOx, MoOx and VOx are oxides whose valences are changeable. Therefore, by using any of WOx, MoOx and VOx, for example, MoO3 as a photosensitive hard mask and forming, for example, a layer having a reducing action adjacent thereto, MoO3 in the exposed region may be reduced through the reaction with the adjacent layer having a reducing action by the heat generated during the exposure to EUV light, thereby causing a change in composition.
<Advantages of Patterning by EUV Exposure using Photosensitive Hard Mask>
Next, advantages of patterning by EUV exposure using a transition metal oxide film will be described in detail.
The first advantage is that the exposure time may be shortened.
The exposure time when exposing the transition metal oxide film to the EUV light may be easily calculated from the physical properties of a material and the like. The EUV light incident on the transition metal oxide film, which is an inorganic thin film, locally heats a volume determined by the extinction length in the film. HfO2, ZrO2, WO3, and MoO3 used as the transition metal oxide film have a heat capacity of about 1.2 to 2.4×106 J/m3K. Further, it is known that the heat load on a substrate (wafer) at the time of EUV exposure is about 3 W/cm2 (Laser Focus World, Aug. 29, 2019, “EUV lithography revised”). When patterning is performed using the phase transition caused by heat as described above, the temperature of the exposed region is raised to the temperature required for the phase transition. Since the temperature rise in the exposed region is determined by the power, the dose amount may be small and, therefore, the exposure time may be short. In a simple adiabatic calculation using the above parameters, it is possible to heat the transition metal oxide film to about 1000 degrees C., which is necessary for crystallizing the amorphous phase, in an EUV light exposure time of several milliseconds. The dose amount when the EUV light exposure time is 1 millisecond is 3 mJ/cm2 according to the calculation. This value is 1/20 or less of 70 mJ/cm2, which is the dose amount during EUV light exposure using a conventional chemically amplified resist. That is, by using the patterning method in which the photosensitive hard mask composed of the transition metal oxide film is exposed to the EUV light to cause a phase transition, the exposure time may be reduced to 1/20 of the exposure time in the case of using a conventional chemically amplified resist, and the throughput may be greatly improved.
The second advantage is that the pattern edge may be smoothed by thermal diffusion to reduce line edge roughness (LER).
In the transition metal oxide film, which is an inorganic thin film, when the film is locally heated by the exposure to EUV light, the high temperature region expands outside the exposed region due to heat diffusion caused by heat conduction in the film. However, materials such as HfO2 and ZrO2, which are transition metal oxides, have a thermal diffusivity of about 1×10−6 m2/sec. The temperature of the high temperature region expanded outside the exposed region is lower than the phase transition temperature, and does not affect the pattern shape. On the other hand, heat diffusion occurs sufficiently fast for the formation of nanometer-scale fine patterns. Due to this effect, the temperature of the exposed region and the high temperature region outside the exposed region becomes uniform. As a result, it may be expected to obtain the effect of smoothing the irregular shape (LER) of the pattern edge due to the inhomogeneous structure of the transition metal oxide film when the film is formed.
<Pattern Formation on Film to be etched>
Next, a method of forming a pattern on a film to be processed using the above-described photosensitive hard mask will be described.
First, a photosensitive hard mask 304 made of a transition metal oxide film is formed on a substrate 300 having a film to be processed (step ST11 in
Subsequently, EUV exposure and development are performed on the photosensitive hard mask 304 in the procedure of steps ST2 to ST4 described above to form a pattern (step ST12 in
Subsequently, the hard mask 303 is etched by using the patterned photosensitive hard mask 304 as a mask to transfer the pattern of the photosensitive hard mask 304 to the hard mask 303 (step ST13 in
Subsequently, the film 302 to be processed is etched by using the hard mask 303 to which the pattern is transferred is used as a mask, to form a pattern on the film 302 to be processed (step ST14 in
By using the photosensitive hard mask made of the transition metal oxide film for patterning the film to be processed in this way, it is possible to obtain not only the above-mentioned effects such as shortening the exposure time when forming the exposure pattern but also an effect of reducing the number of masks when patterning the film to be processed.
In the case of an organic material such as a conventional chemically amplified resist or the like, the etching resistance is low when the film to be processed is patterned by etching. Therefore, for example, as shown in
On the other hand, the photosensitive hard mask made of a transition metal oxide film has higher etching resistance than an organic material such as a conventional chemically amplified resist. Therefore, as described above, the pattern of the photosensitive hard mask may be directly transferred to the hard mask, and the film to be processed may be patterned by the transfer pattern of the hard mask.
Although the embodiments have been described above, the embodiments disclosed herein should be considered to be exemplary and not limitative in all respects. The above embodiments may be omitted, replaced, or modified in various forms without departing from the scope of the appended claims and their gist.
For example, in the above-described embodiments, there has been described the example in which HfO2, ZrO2, WOx, MoOx, or VOx is used as the transition metal oxide constituting the photosensitive hard mask. However, the present disclosure is not limited thereto, and other transition metal oxides may be used.
According to the present disclosure, it is possible to provide a pattern formation method capable of forming a pattern in a short time when performing EUV exposure, and a photosensitive hard mask.
Number | Date | Country | Kind |
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2021-115453 | Jul 2021 | JP | national |