JP5178996B2 - Reflective photomask blank, reflective photomask, and pattern transfer method using the same - Google Patents

Description

  The present invention relates to a reflective photomass used for a semiconductor device using a photolithographic method using light having a wavelength of extreme ultraviolet light, that is, EUV (Extreme Ultraviolet) light, a reflective photomask blank used therefor, and the same The present invention relates to a pattern transfer method.

  With the recent high integration in semiconductor elements, the miniaturization of patterns transferred by photolithography is accelerating. Since the resolution limit of the pattern is proportional to the exposure wavelength, exposure apparatuses using short-wavelength light sources such as mercury lamps (wavelength 365 nm) and excimer lasers (wavelengths 248 nm and 193 nm) have been developed so far. .

  However, in order to form a pattern of 100 nm or less which is smaller than such a wavelength, it is necessary to make full use of techniques such as a phase shift method and proximity effect correction. Has been increasing.

Development of lithography technology using F ₂ laser light (wavelength 157 nm), which is an excimer laser with a shorter wavelength, is also in progress, but resolution of about 70 nm is the limit. In addition, in order to resolve a pattern smaller than such a wavelength, it is necessary to apply a stronger super-resolution technique.

Therefore, in recent years, lithography technology using EUV light having a wavelength of 10 to 15 nm, which is one digit or more shorter than that of an F ₂ laser, as a light source has been developed, and a wavelength near 13.5 nm is the most promising candidate because of the characteristics of the reflective multilayer film. It has become.

  In the EUV wavelength region, the refractive index of most substances is slightly smaller than 1 (0.9 to 1.01), and the light absorption is very high. For this reason, in EUV lithography, the refractive optical system conventionally used cannot be used, but becomes a reflection optical system. Similarly, since a conventional transmission type mask cannot be used for the photomask, it is necessary to use a reflection type mask. As described above, in the EUV lithography method, the optical system and the mask used for the exposure are significantly different from the conventional exposure technique.

  In this reflective photomask for EUV lithography, a mirror (reflecting mirror) having a high reflectivity at the EUV wavelength is provided on a flat substrate made of a material having a very low coefficient of thermal expansion, and further on the EUV light. On the other hand, a light absorption layer made of a highly absorptive substance is formed by patterning according to a desired exposure pattern.

  A mirror (reflecting mirror) for EUV light is composed of a multilayer reflective film in which materials having a large refractive index difference are combined. In the reflection type photomask, the exposure pattern is transferred by the contrast of the EUV light reflectance between the absorption area where the multilayer reflection film surface is covered with the light absorption layer pattern and the reflection area where there is no light absorption layer and the multilayer reflection film surface is exposed. Do it. In some cases, a layer called a buffer layer is provided between the multilayer reflective film and the light absorption layer in order to prevent the multilayer reflective film from being damaged due to pattern defect correction or other processes, thereby reducing the reflectance. Many.

In general, the pattern formed on the light absorption layer is inspected by making DUV (far ultraviolet) light having a wavelength of about 190 to 260 nm incident on the mask surface, detecting the reflected light, and examining the pattern shape based on the contrast of reflectance. Is done.

  Specifically, a portion where the buffer layer provided immediately below the light absorption layer as a protective layer of the multilayer reflection film is exposed to the surface becomes a reflection region, and due to the reflection contrast with the absorption region consisting of the patterned light absorption layer surface, A first stage inspection is first performed to determine whether the light absorbing layer is patterned as designed. There, the portion of the light absorbing layer that should be etched is not etched but remains on the buffer layer (black defect), and the portion of the light absorbing layer that should remain on the buffer layer without being etched is etched away. Detecting the spot (white defect). As a material for the buffer layer, the light absorption layer has high resistance to dry etching, high resistance in the correction process, and damage to the light absorption layer when removing unnecessary buffer layers after inspection and correction. A small amount is required (see, for example, Patent Document 1).

  After correcting the defects detected in the first stage inspection, the buffer layer is further removed to expose the surface of the multilayer film immediately below the buffer layer, and then the second stage for the pattern formed in the light absorption layer. The final inspection of the eye is performed. This inspection is performed by examining the pattern shape based on the reflection contrast between the absorption region composed of the light absorption layer surface and the reflection region composed of the multilayer reflective film surface.

  If the buffer layer is sufficiently transparent at the exposure wavelength, the buffer layer may not be removed. Further, instead of completely removing the buffer layer, a part of the buffer layer may be removed to leave only a film thickness that does not significantly impair the reflectance of the multilayer film. Such a layer functions as a so-called capping layer that protects the surface of the multilayer film in various subsequent processes. Further, a capping layer can be separately provided between the buffer layer and the reflective multilayer film.

  In the following description, the surface of the reflective multilayer film can be appropriately read as the remaining buffer layer surface or capping layer surface.

  In the inspection of the pattern of the light absorption layer by the DUV inspection light in the first stage and the second stage described above, the surface of the buffer layer from which the light absorption layer has been removed and the light absorption layer remain without being removed. The DUV light reflection contrast between the surface of the multilayer reflective film from which the light absorption layer and the buffer layer are removed and the surface of the light absorption layer is used. Therefore, in order to obtain high inspection accuracy, the DUV inspection is performed on the buffer layer surface and the light absorption layer surface in the first stage inspection, and on the multilayer reflective film surface and the light absorption layer surface in the second stage inspection. It is desirable that the difference in reflectance at wavelengths is large.

  In response to such a demand, a multilayer absorption layer in which a chromium or tantalum oxide or nitride is provided on a light absorption layer as in the case of a conventionally used transmission type low reflection chromium mask blank. (For example, refer to Patent Document 2).

  In order to reduce the reflectance using a multilayer film, the interference effect of multiple reflections on the upper and lower surfaces of the film is used. The higher the transparency at the wavelength of the inspection light, the greater this effect. By setting the film thickness to an appropriate thickness, a film having a lower reflectance can be obtained.

  In the case of metals such as chromium and tantalum, the transparency is low in the ultraviolet region used in inspection, and the transparency tends to improve as oxidation and nitridation progress. Therefore, the film with more advanced oxidation and nitridation can reduce the reflectance, and the contrast with the high reflection region from which the absorption layer is removed can be increased.

  However, as nitridation and oxidation progress in chromium and tantalum, the absorption of EUV light tends to decrease. For this reason, it is necessary to increase the thickness of the absorption layer in order to make the reflection contrast sufficiently large with respect to EUV light. The exposure optical system in EUV lithography is composed of a reflection optical system as described above. For this reason, the light is incident on the mask at an incident angle of 5 to 6 degrees rather than perpendicularly. For example, if the X axis is the direction parallel to the incident surface within the mask substrate surface and the Y axis is perpendicular to the X axis within the mask substrate surface, the aerial image of the pattern symmetric with respect to the center line in the Y axis direction is asymmetric. Or a dimensional difference in the XY direction is pointed out. Such a phenomenon becomes more remarkable as the thickness of the absorption pattern, that is, the thickness of the absorption layer increases. For this reason, it is desired that the thickness of the light absorption layer be as thin as possible.

  In addition, as the oxidation and nitridation of the metal progresses, the conductivity decreases and becomes an insulator. In general, a mask pattern is formed by an electron beam lithography technique. If a thick insulating layer is present under the resist in the electron beam exposure process, the pattern position accuracy is lowered due to charge-up, and the pattern shape is distorted. In order to avoid such a problem, it is necessary to perform pattern drawing after further forming an organic conductive film on the resist.

  In recent years, chemically amplified resists are widely used as resists in processes that require high resolution, and chemically amplified resists for electron beam exposure for photomask manufacturing are also used. In general, chemically amplified resists can change the solubility in a developing solution by a deprotection reaction or a crosslinking reaction by using an acid generated from a photoacid generator in an exposed region as a catalyst. When the base material to which the resist is applied is a material containing nitrogen, a problem has been pointed out that the acid generated in the exposed region in the resist is deactivated. Due to this phenomenon, in the case of a positive type resist, the pattern has a shape with a tail in the vicinity of the interface with the base material, and in the case of a negative type resist, on the contrary, the shape has an undercut near the interface with the base material. End up. Therefore, when nitrogen is contained for the purpose of improving characteristics such as reflectance, there is a problem that the resolution performance is deteriorated in forming a resist pattern.

Known documents are described below.
JP-A-7-333829 JP 2004-39884 A

  To solve such a problem, there has been a method for solving the problem by making the light absorption layer a multilayer structure in which the concentration of tantalum is changed. That is, in a reflective photomask blank comprising a substrate, a multilayer reflective film provided on the substrate, and a light absorption layer provided on the multilayer reflective film, the light absorption layer includes a plurality of layers containing tantalum. Thus, a reflective photomask blank is obtained in which the content of tantalum contained in the layer closer to the multilayer reflective film is higher than the tantalum content of the layer formed by subsequent lamination. The layer containing tantalum may contain silicon in addition to tantalum. A layer containing a metal other than tantalum as a main component may be provided between the multilayer reflective film and the layer containing tantalum. Zirconium can be used as a metal other than tantalum. Alternatively, the layer containing a metal other than tantalum as a main component may contain silicon. A reflection type photomax created using such a reflection type photomask blank is used.

Thus, the light absorption layer used in the reflective photomask blank and the reflective photomask is composed of a plurality of layers containing tantalum, and the tantalum content of the layer close to the multilayer reflective film is formed thereon. By contrast, the contrast of the reflective area is good not only when exposed to EUV light but also when inspected with DUV light, and the inspection accuracy of the reflective photomask and its pattern transfer accuracy are good. It becomes. In addition, by providing a layer containing a metal other than tantalum as a main component between the light absorption layer and the multilayer reflection film, the multilayer reflection film is prevented from being damaged during patterning of the light absorption layer, and the surface of the reflection region Variations in reflection contrast due to oxidation can be suppressed.

  However, a light absorption film having a low tantalum content near the surface layer of the light absorption layer has lower conductivity than a film having a high tantalum content. For this reason, when pattern exposure is performed with an electron beam to pattern a film with increased transparency, the pattern position and shape may be distorted by charge-up. Such a problem has not been solved.

  The present invention solves the above-described problems. A good contrast is obtained with respect to a reflection region at the time of exposure with EUV light and at the time of inspection with DUV light, and there is no charge-up due to pattern exposure with an electron beam. It is an object of the present invention to provide a reflective photomask blank, a reflective photomask using the same, and a pattern transfer method using the same.

This invention is made | formed in view of the subject which concerns, The reflective photomask blank of this invention Claim 1 is,
A substrate, a multilayer reflection film provided on the substrate, and a light absorption layer provided on the multilayer reflection film, the light absorption layer comprising a plurality of layers containing tantalum, the layer closer to the multilayer reflection film In the reflection type photomask blank in which the content of tantalum contained in is higher than the tantalum content of the layer formed by subsequent lamination,
A layer containing a metal other than tantalum as a main component is further laminated on a plurality of layers containing tantalum, and the metal other than tantalum is titanium, and titanium and silicon are formed as a sputtering target. It is characterized by that.

According to the present invention, the light absorption layer used in the reflective photomask blank and the reflective photomask is composed of a plurality of layers containing tantalum, and the tantalum content of the layer close to the multilayer reflective film is on it. By being higher than the formed layer, it is possible to obtain a good contrast with respect to the reflective area not only during exposure with EUV light but also during inspection with DUV light. A reflective photomask blank without charge-up due to pattern exposure with an electron beam by further laminating a layer containing a metal other than tantalum as a main component on a plurality of layers containing tantalum, and A reflective photomask using the same can be obtained.
.

  Moreover, according to the pattern transfer method of the present invention, it is possible to perform pattern exposure with high accuracy for a resist formed on a sample substrate for a long period of time, and as a result, it is possible to manufacture patterns of electronic devices and the like with a high yield. I can do it.

  The reflective photomask blank of the present invention comprises a substrate, a multilayer reflective film provided on the substrate, and a light absorbing layer provided on the multilayer reflective film, the light absorbing layer comprising a plurality of layers containing tantalum. Thus, it is premised on a reflective photomask blank in which the content of tantalum contained in the layer closer to the multilayer reflective film is higher than the tantalum content of a layer formed by subsequent lamination. A reflective photomask blank is obtained by further laminating a layer containing a metal other than tantalum as a main component on the plurality of layers containing tantalum.

  The reflection type photomask blank is a product before being processed into a reflection type photomask, and the light absorption layer is not subjected to pattern processing according to the transferred exposure pattern.

  FIG. 1 is an explanatory view showing the structure of an example of a reflective photomask blank according to the present invention in cross section, and FIG. 2 is an explanatory view showing the structure of an example of a reflective photomask according to the present invention in cross section.

  As shown in FIG. 1, the reflective photomask blank 10 of this example is an etching that is a layer including a multilayer reflective film 2, a capping layer 3, two-layer light absorption films 4, 5, and a metal other than tantalum on a substrate 1. The mask layer 6 is sequentially laminated. Although the multilayer reflective film 2 is multilayered, it is simply shown as a single layer.

  The reflection type photomask of the present invention has a configuration in which the light absorption films 4 and 5 of the reflection type photomask blank are patterned and the etching mask layer 6 is removed.

  As shown in FIG. 2, the reflective photomask 20 of the present invention is provided with patterned light absorption layers 4 a and 5 a instead of the light absorption films 4 and 5. A portion where the capping layer 5 is partially removed and a portion of the capping layer is exposed constitutes the reflection region B, and the surfaces of the light absorption layers 4a and 5a remaining without being removed constitute the absorption region A.

  The method for producing a reflective photomask blank of the present invention is an example of a method for obtaining the reflective photomask using the reflective photomask blank, and is an etching mask layer of the reflective photomask blank. A resist layer is formed thereon, exposed and developed to partially remove the resist layer in accordance with a predetermined pattern to expose the surface of the etching mask layer, and the light absorbing layer through the etching mask layer A pattern processing step.

  3 to 4 are sectional views for explaining an example of the manufacturing process of the reflective photomask blank and the reflective photomask of the present invention.

As the substrate, a material having a small thermal expansion coefficient and good flatness and a small surface roughness is preferable. For example, as shown in FIG. 3A, the surface is cleaned by flatly polishing SiO ₂ —TiO ₂ glass. A glass substrate 1 is prepared.

  Next, approximately 40 cycles of molybdenum 2.8 nm and silicon 4.2 nm are alternately laminated on the substrate 1 by DC magnetron sputtering, and as shown in FIG. 3B, for EUV light having a wavelength of 13 to 14 nm. Thus, the multilayer reflective film 2 having the maximum reflectance can be produced. Although the multilayer reflective film 2 is a multilayer film, it is shown as a single layer in the drawing.

  Thereafter, as shown in FIG. 3C, a capping layer 3 such as zirconium silicide can be formed to a thickness of, for example, 5 to 10 nm by DC magnetron sputtering.

  Further, as shown in FIG. 3D, a first light absorption film 4 made of tantalum and silicon and a second light absorption film 5 made of tantalum silicon, oxygen, and nitrogen are formed on the capping layer 3 to 50 to 100 nm, respectively. The film can be formed by DC magnetron sputtering to a thickness of 20 to 60 nm.

  An etching mask layer 6 made of, for example, niobium silicide can be formed on the light absorption film 5 as shown in FIG. In this way, the reflective photomask blank of this example can be created.

  Thereafter, the etching mask layer 6 can be patterned by, for example, an electron beam lithography technique.

  First, as shown in FIG. 3F, an electron beam exposure resist coating solution is applied on the etching mask layer 6 and baked to form an electron beam exposure resist layer 7.

  Next, a desired pattern is drawn on the resist layer 7 by an electron beam drawing apparatus, and developed with, for example, a 2.38 wt% tetramethylammonium hydroxide aqueous solution, and the etching mask layer 6 is formed as shown in FIG. A resist pattern 7a for etching can be formed.

  Next, by performing dry etching in an atmosphere containing chlorine, a pattern 6a of the etching mask layer 6 can be formed as shown in FIG.

Next, dry etching is performed using, for example, a gas containing C ₂ F ₆ gas in an atmosphere containing fluorine, and the light absorption film pattern 5a corresponding to the resist pattern 7a and the etching mask pattern 6a is shown in FIG. Can be formed. Although FIG. 4 (i) shows the resist pattern 7a, it may disappear during the etching for forming the absorption film pattern 5a, and the etching mask pattern 6a only needs to remain sufficiently.

  Next, the resist pattern 7a is removed by, for example, plasma ashing using oxygen gas, and the etching mask pattern 6a is removed by etching in an atmosphere containing, for example, chlorine gas, thereby obtaining an absorption film pattern 5a as shown in FIG. And part of the light absorption layer 4 is exposed on the surface.

  In this state, whether or not the absorption film pattern is normally formed can be inspected with far ultraviolet light, and defects can be corrected as necessary. Moreover, you may provide a washing | cleaning process suitably before and after an inspection and correction.

Further, by performing dry etching in an atmosphere containing chlorine using the absorption film pattern 5a as an etching mask, a reflective mask having the two-layer absorption patterns 4a and 5a as shown in FIG. 4K is obtained. The capping layer 3 functions as an etching stop layer when forming the absorption film pattern 4a.

  As the multilayer reflective film used in the present invention, a film in which materials having different refractive indexes are laminated in multiple layers in order to obtain a high reflectance at a wavelength in the EUV region can be used. In order to obtain a high reflectance, it is desirable that the refractive index changes sharply at the interface between the layers. When EUV light having a wavelength near 13.5 nm is used, a multilayer film in which molybdenum and silicon are alternately stacked can be used. The uppermost layer of the multilayer film can have a higher reflectance with molybdenum having a larger refractive index difference from vacuum, but the uppermost layer is often made of silicon because the oxide film formed on the molybdenum surface is unstable. The uppermost layer is called a capping layer from the viewpoint of protecting the multilayer film. The capping layer may be made of a material other than silicon that is stable against surface oxidation, and its extinction coefficient is small so as not to impair the reflection of the multilayer film, and the refractive index is as far as possible from 1 for the above reasons. It is preferable.

  The light absorption layer according to the present invention has at least two light absorption films.

  The light absorption film used here refers to a film that is patterned on a mask and forms a low light intensity region of a pattern transferred in an exposure process. As the light absorbing film, a material having a high ability to absorb light having an EUV wavelength can be used. The absorption capacity is determined by the extinction coefficient at the wavelength of light used for exposure.

  In the present invention, the light absorption film used is composed of a plurality of layers containing tantalum, and the tantalum content of the layer close to the multilayer reflective film is higher than the tantalum content of the absorption layer formed thereon.

  When a single tantalum film is formed by sputtering, crystal grains are likely to grow and the change with time of stress increases, so that it tends to be difficult to form a film with low stress. Further, if the particles are rough, the roughness of the pattern edge (Line Edge Roughness) increases, which causes the transfer performance to deteriorate.

  For example, when sputtering is performed using tantalum and silicon as targets, if the silicon content is 5% or more, the crystal structure of tantalum is not seen and the film becomes amorphous. Under these conditions, a low-stress film can be obtained by appropriately selecting the sputtering current value and the gas flow rate. If the amount of silicon is excessive, the density of the film is lowered and the high absorption effect by tantalum is impaired. Therefore, it is preferable that the light absorption film containing tantalum as a main component has a relatively high tantalum content.

  Reflection of the film having a high tantalum content when a defect inspection apparatus using far ultraviolet light is used to inspect whether a pattern is normally formed after etching away a part of the light absorption film. The rate is generally in the range of 40-60%. On the other hand, the reflectance of the portion where the surface of the multilayer reflective film is exposed by removing a part of the light absorbing film is also in the range of 40 to 60%. Therefore, it becomes difficult to perform pattern defect inspection of a light absorption film having a high tantalum content with far ultraviolet light.

  As a method for solving such a problem, there are a method using a film material containing nitrogen or oxygen, and a method of providing an antireflection layer on the light absorption film. The antireflection layer utilizes the interference effect of reflection on the upper and lower surfaces of the layer, and is required to be a material having a relatively high transparency at the wavelength of light used.

When patterning a material having a high tantalum content, dry etching using a gas containing chlorine can be used. A material whose tantalum content is 90% or more is IC
When using P (inductively coupled plasma) type dry etching equipment to form a pattern using a typical resist for electron beam exposure using a polyhydroxystyrene base polymer as an etching mask, the etching selectivity to the resist Is about 0.5 to 0.7, which is not necessarily good, but it is possible to form a required pattern by appropriately setting the etching bias of the element dimensions.

  However, when a film with a high degree of oxidation is etched using chlorine gas for the purpose of improving the contrast of the inspection light, the etching rate is greatly reduced and the selectivity with respect to the resist is less than 0.1. End up. For this reason, it is extremely difficult to etch a film having a light absorption film mainly composed of tantalum so that the reflectance with respect to the DUV inspection light is lowered by using only chlorine-based plasma.

Such a material mainly composed of tantalum that has been oxidized can be etched using a fluorine-based gas. For example, when a film having an oxygen content of 40-60% is etched using C ₂ F ₆ as an etching gas, the selectivity with respect to the resist is about 0.7.

  In the reflection type photomask blank having a single light absorption layer proposed so far, a correction buffer layer is typically provided between the light absorption layer and the multilayer reflection film. A combination in which the light absorption layer and the buffer layer have a high selectivity with respect to dry etching is preferably used.

  For example, one is a material with a high etching rate for a chlorine-based etching gas and a small etching rate for a fluorine-based etching gas, and the other is a material with a low etching rate for a chlorine-based etching gas, and a fluorine-based etching gas. Typically, a material with a high etch rate relative to the gas is selected.

Here, the chlorine-based etching gas refers to, for example, chlorine (Cl ₂ ), boron trichloride (BCl ₃ ), hydrogen chloride (HCl), and the like. The fluorine-based etching gas refers to, for example, perfluoroethane (C ₂ F ₆ ) Gases such as sulfur hexafluoride (SF ₆ ) and nitrogen trifluoride (NF ₃ ).

  A buffer layer for correction can be further provided on the two-layer absorption film. However, the etching mask is peeled off at the stage of etching the absorption film to inspect and correct the upper absorption film pattern. If the pattern processing can be performed, it is not necessary to provide a correction buffer layer in addition to the two-layer absorption film.

  When attention is paid to the reflection contrast when pattern inspection is performed using a defect inspection apparatus using far ultraviolet light, as already described, the reflectance in the far ultraviolet region of a layer containing 90% or more of tantalum is an absorption film. The difference between the reflectance of the surface of the multilayer reflective film or the capping layer by etching is small. In other words, if the film-forming conditions of the second absorption layer with a high oxygen content and a low tantalum content are appropriately selected and the reflection contrast is increased with respect to the first absorption layer, The first absorption layer is removed by etching, and the reflection contrast with the exposed portion of the surface of the multilayer film or the capping layer is advantageously increased.

In the photomask blank of the present invention, a layer mainly containing a metal other than tantalum can be further provided on the plurality of absorption films. This layer becomes an etching mask together with the resist when part of the absorption film is removed by etching. Hereinafter, this layer is referred to as an etching mask layer. The light absorption film having a low tantalum content can be suitably etched with a fluorine-based gas. Accordingly, it is desirable that the etching mask layer can be easily etched with a chlorine-based etching gas and has high resistance to a fluorine-based etching gas.

  In addition, the light absorption film having a low tantalum content has lower conductivity than a film having a high tantalum content. For this reason, when pattern exposure is performed with an electron beam to pattern a film with increased transparency, the pattern position and shape may be distorted by charge-up. Therefore, a material having a high metal content and high conductivity can be suitably used as the material for the etching mask layer.

  Furthermore, as the etching mask layer, a material containing no nitrogen can be suitably used. This also makes it possible to further improve the film characteristics by incorporating nitrogen into the light absorption layer having a low tantalum content.

  Specific examples of the material for the etching mask layer that satisfies the above requirements include a material containing one or more metals selected from niobium, titanium, aluminum, and chromium. When sputtering is performed with a single metal, crystal grains are likely to grow. Therefore, a film containing the above metals or further containing silicon can be suitably used.

  If a light element such as titanium or aluminum is used as a main component, it is also possible to reduce the influence on the pattern dimension variation due to backscattering of electrons during electron beam drawing.

  In the reflective photomask blank of the present invention, a film containing a metal other than tantalum as a main component can be further provided between the multilayer reflective film and the light absorbing film. This layer is just above the multilayer reflective film, and is called a capping layer because it prevents a change in reflectance due to damage to the multilayer reflective film. In the present invention, the light absorbing layer having a high tantalum content immediately above the capping layer is etched using a chlorine-based etching gas. Therefore, the capping layer in the present invention can be preferably made of a material selected from materials having high resistance to dry etching using a chlorine-based gas.

  Further, as is apparent from FIG. 2, the capping layer becomes the uppermost layer of the reflective region when the reflective photomask is finally formed. For this reason, a material for the capping layer having a small extinction coefficient at the EUV exposure wavelength and a refractive index having a large difference from the refractive index of vacuum, that is, 1 can be preferably used.

  Specifically, a material containing one or more metals selected from ruthenium, zirconium, and yttrium can be preferably used. In particular, by using a material containing zirconium and silicon, a film that is stable against chemical substances such as a cleaning liquid can be obtained.

  In the pattern transfer method using the photomask according to the present invention, for example, first, a photoresist layer is provided on a substrate on which a layer to be processed is formed, and then the extreme ultraviolet rays reflected through the photomask according to the present invention are selectively selected. Irradiate.

  Next, unnecessary portions of the photoresist layer in the development process are removed, and a pattern of the resist layer is formed on the substrate. Then, the layer to be processed is processed using the pattern of the resist layer as a mask. In this method, a pattern faithful to the photomask pattern is transferred onto the substrate by removing the pattern.

  The following examples illustrate the present invention in more detail.

  A manufacturing process of the reflective photomask of Example 1 will be described with reference to FIGS.

  As the substrate 1, a synthetic quartz glass substrate having a size of 6 inches × 6 inches × 0.25 inches was prepared as shown in FIG.

  As shown in FIG. 3B, a Mo layer having a film thickness of 2.8 nm in an argon atmosphere using a DC magnetron sputtering apparatus alternately on a substrate 1 and a film thickness of 2.8 nm, and 4.2 nm. A multilayer reflection film 2 having a thickness of 280 nm was formed by laminating 40 periods each having an Si layer having a thickness of 280 nm. The uppermost layer of the multilayer reflective film 2 was silicon. The reflectance of the multilayer reflective film 2 at a wavelength of 257 nm was 63%.

  Next, as shown in FIG. 3C, a sputtering target having a zirconium / silicon atomic ratio of 1: 2 is used on the multilayer reflective film 2 to form a capping layer 3 made of zirconium silicide with a thickness of 7 nm. A film was formed.

  Next, as shown in FIG. 3D, a tantalum and silicon sputtering target is used in an argon gas atmosphere, and a power ratio of 6: 1 is formed by DC magnetron sputtering to a thickness of 80 nm. The light absorption film 4 is formed, and then the second absorption is performed by reactive DC sputtering using a sputtering target of tantalum and silicon, with a power ratio of 1: 3, and a flow ratio of argon and oxygen of 7: 1. The film 5 was formed to a thickness of 28 nm. When each absorption film was analyzed by X-ray photoelectron spectroscopy and the composition of the film was examined, the tantalum content of the first light absorption film was 94%, and the tantalum content of the second light absorption film was 30%. %Met. The reflectance at a wavelength of 257 nm of the surface on which the second light absorption film was formed was 5%.

  Further, using niobium and silicon as a sputtering target, a power ratio of 1: 2, and an etching mask layer 6 having a thickness of 30 nm is formed by DC magnetron sputtering under an argon gas atmosphere, as shown in FIG. A reflective mask blank for EUV light was obtained.

  The mask blank is spin-coated with an electron beam resist FEP171 (manufactured by FUJIFILM Electronics Materials Co., Ltd.) to a thickness of 300 nm, and baked at 110 ° C. for 10 minutes on a hot plate, as shown in FIG. A resist layer 7 was formed.

Next, a pattern was drawn with a dose of 10 μC / cm ² using an electron beam drawing apparatus. The blank after drawing was baked on a hot plate at 110 ° C. for 10 minutes, developed with a 2.38 wt% tetramethylammonium hydroxide aqueous solution for 90 seconds, rinsed with pure water, spin-dried, and dried as shown in FIG. A resist pattern 7a as shown in FIG.

  Subsequently, using an ICP etching apparatus, an etching mask pattern 6a for patterning the absorption film is obtained as shown in FIG. 3 (h) through the resist pattern 7a using chlorine gas and helium gas. It was.

  Under these etching conditions, the etching rate of the etching mask layer 6 was 230 nm / min, the etching rate of the resist film was 85 nm / min, and the selectivity was 2.7, which was a sufficiently large value.

Next, using the ICP etching apparatus, the pattern 5a of the second light absorption layer was obtained in an atmosphere in which C ₂ F ₆ gas and helium gas were mixed at 1: 7. Under these etching conditions, the etching rate of the etching mask layer 6 was 9 nm / min, the etching rate of the second absorption film was 13 nm / min, and the etching selectivity with respect to the etching mask was a sufficiently large value. On the other hand, the etching rate of the resist material under these etching conditions was 22 nm / min. For this reason, the effect of improving the selectivity by the etching mask layer is twice or more, which is very large.

  Next, the resist pattern 7a was removed by oxygen plasma, and then the etching mask layer made of niobium and silicon was removed in a plasma atmosphere in which chlorine gas and helium gas were mixed. Since the etching rate of the etching mask layer is very high at 230 nm / min and is removed in about 8 seconds, the exposed portion of the first absorption layer remains with a sufficient film thickness.

  In this state, the reflectance at 257 nm of the absorption region where the second absorption layer having a low tantalum content remains is 3.0%, and the reflectance at 257 nm of the reflection region where the first absorption layer having a high tantalum content remains is It was 54.2%. Therefore, the reflection contrast was 90%, and the pattern shape could be confirmed with sufficient contrast.

The reflection contrast here is (reflectance of the high reflectance part−reflectance of the low reflectance part) / (reflectance of the high reflectance part + reflectance of the low reflectance part) × 100.
It is a value calculated by.

  After confirming the pattern, the first absorption film was etched again by plasma with a mixed gas of chlorine gas and helium gas, and the reflective mask 20 was obtained.

  Under these etching conditions, the etching rate of the second absorption layer having a low tantalum content was 4 nm / min, and the etching rate of the first absorption layer having a high tantalum content was 42 nm / min. Since the film thickness of the first absorption layer is 80 nm, the amount of decrease in the film thickness of the second absorption layer was as small as about 9 nm even if overetching of about 20% was performed.

  In this state, the reflectivity at a wavelength of 257 nm of the remaining portion of the second absorption layer having a low tantalum content was 3.4%, and the reflectivity at 257 nm of the capping layer made of zirconium and silicon was 55.0%. It was. Therefore, the reflection contrast was 88%, which was a value that could sufficiently inspect pattern defects.

  The reflective photomask for EUV light according to the present invention can be suitably used for forming a fine pattern using a resist for EUV light in a manufacturing process of a semiconductor element, a semiconductor device, an electronic circuit device or the like.

Explanatory drawing which shows the structure of an example of the reflective photomask blank concerning this invention in a cross section Explanatory drawing which shows the structure of an example of the reflective photomask concerning this invention in a cross section Partial explanatory drawing which shows an example of the manufacturing process of the reflective photomask of this invention in a cross section Partial explanatory drawing which shows an example of the manufacturing process of the reflective photomask of this invention in a cross section

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Substrate, 2 ... Multilayer reflective film, 3 ... Capping layer, 4, 5 ... Light absorption film, 4a, 5a ... Light absorption layer, 6 ... Etching mask layer, 6a ... Etching mask pattern, 7 ... Resist layer, 7a ... Resist pattern

Claims (1)

A substrate, a multilayer reflection film provided on the substrate, and a light absorption layer provided on the multilayer reflection film, the light absorption layer comprising a plurality of layers containing tantalum, the layer closer to the multilayer reflection film In the reflection type photomask blank in which the content of tantalum contained in is higher than the tantalum content of the layer formed by subsequent lamination,
A layer containing a metal other than tantalum as a main component is further laminated on a plurality of layers containing tantalum, and the metal other than tantalum is titanium, and titanium and silicon are formed as a sputtering target. A reflective photomask blank characterized by that.

Images