JP6524614B2 - Mask blanks, mask blanks with negative resist film, phase shift mask, and method of manufacturing patterned body using the same - Google Patents

Description

  The present invention relates to a mask blank used for manufacturing a semiconductor device, a phase shift mask, and a method for manufacturing a patterned body using the same, and more specifically, a high NA exposure apparatus using ArF excimer laser exposure light with a wavelength of 193 nm. Mask blanks, negative resists capable of improving transfer characteristics in ArF excimer laser exposure light irradiation and cleaning resistance in photolithography when transferring a mask pattern to a wafer using the mask pattern The present invention relates to a film-formed mask blank, a phase shift mask, and a method of manufacturing a patterned body using the same.

  As a resolution improvement measure in a phase shift mask used in photolithography, a halftone phase shift mask is known which is configured of a portion transmitting light and a portion transmitting light semi-transparently. Then, as a representative example of such a halftone phase shift mask, a halftone phase shift mask having a light transmittance of 6% in which a MoSi film is used as a light semitransmissive film is known.

  Then, in the halftone phase shift mask, when the pitch of the wiring formed on the wafer becomes fine, as a light transflective film constituting a portion which transmits light semi-transparently, as a characteristic when transferring the wiring to the wafer, There is a need for lower EMF and OPC biases and higher exposure latitude and focus latitude (EL-DOF) characteristics.

  Also, in the case of a halftone phase shift mask, the light intensity at the interfered portion becomes zero due to the light interference of the pattern boundary due to the phase effect, and the contrast of the transferred image can be improved, but it is high by 15% or more In the case of light transmittance, it is expected that this phase effect will be more pronounced and the contrast of the transferred image can be further improved.

  In the halftone phase shift mask, the light transmissivity of the light transflective film is adjusted by including metal in the light transflective film in order to make the light transmittance of the light transmissive film within the target range. (Patent Documents 1, 2, 3 and 4).

  However, in a conventional halftone phase shift mask composed of a metal-containing light semitransparent film, ArF excimer laser exposure light irradiation resistance and cleaning resistance due to the light semitransparent film containing metal. Problems are known to occur. For example, Mo is often used as the metal contained in the light transflective film, as described in the examples of Patent Documents 1 and 2. When Mo is used, moisture is generated by the humidity atmosphere as a result of long-time irradiation of ArF excimer laser exposure light to Mo, and the MoSi film is oxidized by the moisture generated, silicon (Si) The problem of laser irradiation resistance is known to be caused by the phenomenon that the pattern dimension changes due to the growth of the oxide film. Further, in this case, there is also known a problem of cleaning resistance in which such a phenomenon similarly occurs in the cleaning process of the halftone phase shift mask.

  On the other hand, when it is intended to construct a halftone phase shift mask from a metal-free semitransparent film in order to avoid such problems of ArF excimer laser exposure light irradiation resistance and cleaning resistance, the light semitransmission The light transmittance of the portion where the film is formed will be too high (Patent Documents 5 and 6).

  As a result, for example, in Patent Document 5, since the light transmittance is too large only with the phase adjustment film (light semi-transmissive film) containing no metal, the phase adjustment film (light semi-transmissive film) containing no metal is used. It is necessary to construct a halftone phase shift mask by laminating a light transmittance adjusting film containing another metal.

Unexamined-Japanese-Patent No. 2003-322948 JP, 2009-217282, A JP, 2005-284213, A Unexamined-Japanese-Patent No. 2010-9038 Japanese Patent Laid-Open No. 2002-351049 JP, 2008-310091, A

  The present invention has been made in view of the above-described circumstances, and its main object is to make transfer characteristics excellent in photolithography and to increase ArF excimer laser exposure light irradiation resistance and cleaning resistance.

In order to solve the above problems, in the present invention, a mask blank is used to manufacture a halftone phase shift mask to which ArF excimer laser exposure light is applied, and it is a transparent substrate, and the above transparent substrate. A layer formed of Si _x O _1-x-y N _y (where x and y satisfy 0 <x <1, 0 <y <1, and 0 <x + y <1), and Si _z N _{And a} light semi-transmissive film configured by laminating layers formed of _1-z (z satisfies 0 <z <1) in random order, and the light semi-transmissive film includes ArF excimer laser exposure light. The present invention provides mask blanks characterized in that the light transmittance at a wavelength of 3 is in the range of 3% to 40%, and the film thickness is in the range of 50 nm to 70 nm.

According to the present invention, in the mask blank, the light transflective film is formed by laminating, in particular, a layer composed of the above Si _x O _{1 -x-y} N _y and a layer composed of the above Si _z N _1-z. As compared with the light transflective film of Si _z N _1-z alone or the light transflective film of Si _x O _1-x-y N _y alone, The feasible range is broadened. For this reason, using the phase shift mask formed from the above-mentioned mask blanks, the light intensity is made zero by interference of light due to the phase effect at the boundary of the pattern, and the contrast of the transferred image is improved to manufacture the pattern formed body. In this case, the phase effect can be made more remarkable by making the light semitransparent film have high light transmittance. Furthermore, since the above-mentioned light semi-transmissive film does not contain metal, even when irradiated with ArF excimer laser exposure light for a long time, the oxide film of silicon (Si) does not grow, and the pattern dimension (Critical Dimension) It can be prevented from changing. Similarly, also in the step of cleaning the phase shift mask, it is possible to prevent the pattern dimension from changing. Therefore, in photolithography, transfer characteristics can be made excellent, and ArF excimer laser exposure light irradiation resistance and cleaning resistance can be made high.

In the above invention, the light transflective film includes the layer made of the above Si _z N _1-z and the layer made of the above Si _x O _1-x-y N _{y in} this order from the above-mentioned transparent substrate side Preferably, they are laminated. The _Si z _{N 1-z} (z satisfies the 0 <z <1), the above _{Si x O 1-x-y} N y (x and y, 0 <x <1,0 <y <1 , And 0 <x + y <1), since the etching selectivity with the material such as SiO ₂ constituting the transparent substrate is higher, the layer made of the above Si _z N _1-z is on the transparent substrate It is because it becomes easier to etch the said light semipermeable membrane, if it is directly laminated | stacked on this.

  In the above invention, it is preferable that the light transflective film be formed directly on the transparent substrate. By not having the etching barrier layer between the transparent substrate and the light transflective film, the etching process does not become complicated because etching process does not need to be performed multiple times, and etching of the etching barrier layer is difficult. This is because it is possible to prevent deterioration of the shape of the light transflective film and the transparent substrate or deterioration of the uniformity of the shape of the light transflective film.

  In the above invention, the optical density (OD value) at the wavelength of ArF excimer laser exposure light formed on the light transflective film is a desired optical density (OD value) in combination with the light transflective film. It is preferable to further have a light shielding film adjusted to Thereby, by further having the light shielding film, when there is a light semi-transmissive film pattern having a large area, an effect of avoiding the problem that the transferred image becomes unclear due to the exposure light which transmits such a pattern is obtained. It is because it can obtain more notably.

  In the above invention, the light shielding film is formed on the light transflective film, and includes a single layer including a light absorbing layer having an etching barrier function to the light transflective film and a light absorbing function to ArF excimer laser exposure light. It is preferable to have a structure. This is because it is possible to obtain a phase shift mask having the necessary functions in fewer steps.

  In the above invention, the light shielding film is formed on the light semitransparent film, and has a light absorbing layer having an etching barrier function to the light semitransparent film and a light absorbing function to ArF excimer laser exposure light; It is preferable to have a two-layer structure including a hard mask layer formed on the absorption layer and having an etching mask function to the light absorption layer. Thereby, a pattern formed by etching the hard mask layer can be used instead of the resist pattern when the light absorption layer is etched. As a result, the fine pattern of the light shielding film can be easily formed.

  In the above invention, the light shielding film is formed on the light semitransparent film, and is formed on the etching barrier layer having an etching barrier function to the light semitransparent film, and the etching barrier layer; It is preferable to have a three-layer structure including a light absorbing layer having a light absorbing function to exposure light and a hard mask layer formed on the light absorbing layer and having an etching mask function to the light absorbing layer. Thereby, a pattern formed by etching the hard mask layer can be used instead of the resist pattern when the light absorption layer is etched. As a result, the fine pattern of the light shielding film can be easily formed. Then, the range of selection of the material of the layer having a light absorbing function with respect to ArF excimer laser exposure light is broadened, and the film thickness of the light shielding film can be made thinner. In addition, since the light absorbing layer and the etching barrier layer can be etched with different reactive etching gases, damage to the light transflective film occurs when the light absorbing layer is etched. It is because it can have an etching barrier function with respect to the above-mentioned light transflective film which suitably prevents that.

  Further, in the above invention, it is preferable that the light absorption layer is made of silicon (Si) alone. This is because damage to the light absorption layer can be prevented when the hard mask layer is etched. In addition, since silicon (Si) alone has a high extinction coefficient, the thickness of the light shielding film can be made thinner by forming the light absorption layer from silicon (Si) alone.

  In the above invention, the light shielding film is adjusted so that the optical density (OD value) at the wavelength of ArF excimer laser exposure light becomes 3.0 or more in combination with the light semitransparent film. preferable. This is because it is possible to obtain the required light shielding property for the desired part at the time of exposure.

  Further, in the present invention, there is provided a negative resist film provided mask blank comprising the above mask blank and a negative resist film formed on the mask blank.

  According to the present invention, a negative phase shift mask to be described later can be manufactured in a shorter time.

Further, in the present invention, it is a halftone phase shift mask to which ArF excimer laser exposure light is applied, which is formed on a transparent substrate and the above-mentioned transparent substrate, and Si _x O _1-x N _y ( a layer in which x and y satisfy 0 <x <1, 0 <y <1, and 0 <x + y <1), and Si _z N _1−z (z satisfies 0 <z <1 And a light transflective film pattern formed by laminating layers in an irregular order, and the light transflective film pattern has a light transmittance of 3% to 40% at the wavelength of ArF excimer laser exposure light. Provided is a phase shift mask which is characterized in that the film thickness is in the range of 50 nm to 70 nm.

  According to the present invention, in the case of producing a pattern-formed body by using the above-mentioned phase shift mask and making light intensity zero by interference of light due to phase effect at the boundary of a pattern to improve the contrast of a transferred image. The phase effect can be made more remarkable by making the light transflective film pattern to have high light transmittance. In addition, since the light semi-transmissive film pattern does not contain a metal, the oxide film of silicon (Si) does not grow even when irradiated with ArF excimer laser exposure light for a long time, and the pattern dimension changes. Can be prevented. Similarly, also in the step of cleaning the phase shift mask, it is possible to prevent the pattern dimension from changing. Therefore, in photolithography, transfer characteristics can be made excellent, and ArF excimer laser exposure light irradiation resistance and cleaning resistance can be made high.

Further, in the above invention, in the light transflective film pattern, the layer made of the above Si _z N _1-z and the layer made of the above Si _x O _1-x-y N _y are in this order from the transparent substrate side Preferably, they are laminated. The _Si z _{N 1-z} (z satisfies the 0 <z <1), the above _{Si x O 1-x-y} N y (x and y, 0 <x <1,0 <y <1 , And 0 <x + y <1), since the etching selectivity with the material such as SiO ₂ constituting the transparent substrate is higher, the layer made of the above Si _z N _1-z is on the transparent substrate It is because it becomes easier to etch the said light semipermeable membrane, if it is directly laminated | stacked on this.

  In the above invention, it is preferable that the light transflective film pattern be formed directly on the transparent substrate. Since the etching barrier layer is not provided between the transparent substrate and the light transflective film pattern, the etching process does not become complicated because etching process does not need to be performed multiple times, and etching of the etching barrier layer is difficult. Because of this, it is possible to prevent the shape of the light transflective film and the transparent substrate from being deteriorated and the uniformity of the shape of the light transflective film from being deteriorated.

  In the above invention, the optical density (OD value) at the wavelength of ArF excimer laser exposure light formed on the light transflective film pattern is a desired optical density (OD value) in combination with the light transflective film pattern. It is preferable to further have a light shielding film pattern adjusted to be. Thereby, by further having the light shielding film pattern, in the case where there is a light transflective film pattern having a large area, an effect of avoiding the problem that the transferred image becomes unclear due to the exposure light which transmits such a pattern Can be obtained more remarkably.

  In the above invention, the light shielding film pattern is formed on the light semitransparent film pattern, and has a light absorbing layer pattern having an etching barrier function to the light semitransparent film pattern and a light absorbing function to ArF excimer laser exposure light. It is preferable to have a single layer structure containing Thus, in the light shielding film having the two-layer structure described above, the light shielding film pattern is formed by using the pattern formed by etching the hard mask layer instead of the resist pattern when the light absorption layer is etched. It is because it can be formed. As a result, it is because it becomes easy to form the fine pattern of the said light shielding film pattern.

  In the above invention, the light shielding film pattern is formed on the light semitransparent film pattern, and is formed on the etching barrier layer pattern having an etching barrier function to the light semitransparent film and the etching barrier layer pattern. It is preferable to have a two-layer structure including a light absorption layer pattern having a light absorption function to ArF excimer laser exposure light. Thus, in the light shielding film having the three-layer structure described above, the light shielding film pattern is formed by using the pattern formed by etching the hard mask layer instead of the resist pattern when the light absorption layer is etched. It is because it can be formed. As a result, it is because it becomes easy to form the fine pattern of the said light shielding film pattern. Then, the range of selection of the material of the layer having a light absorbing function with respect to ArF excimer laser exposure light is broadened, and the film thickness of the light shielding film pattern can be made thinner. In addition, since the light absorbing layer pattern and the etching barrier layer pattern can be respectively etched by different reactive etching gases, the light transmitting film is damaged when the light absorbing layer is etched. It is because it can have an etching barrier function to the above-mentioned light semipermeable membrane which suitably prevents being given.

  Further, in the above invention, it is preferable that the light absorption layer pattern is made of silicon (Si) alone. This is because damage to the light absorption layer can be prevented when the hard mask layer is etched. In addition, since silicon (Si) alone has a high extinction coefficient, the thickness of the light shielding film can be made thinner by forming the light absorption layer from silicon (Si) alone.

  In the above invention, the light shielding film pattern is adjusted so that the optical density (OD value) at the wavelength of ArF excimer laser exposure light is 3.0 or more in combination with the light semitransparent film pattern. Is preferred. This is because the light shielding property required for the desired part can be obtained at the time of exposure.

  Further, in the present invention, a method for producing a patterned body using a phase shift mask formed from the above mask blanks, comprising the step of forming a resist pattern by negative tone development using the above phase shift mask The present invention provides a method for producing a patterned product, characterized in that

  According to the present invention, the light transflective film has a light transmittance at the wavelength of ArF excimer laser exposure light in the range of 3% to 40%, and the range in which the light transmittance can be realized becomes wider than before. . Therefore, in negative tone development, it is possible to further increase the phase effect at the edge of the light shielding portion in a portion corresponding to a minute pattern such as a contact hole. Thus, it is possible to transfer a fine pattern such as a contact hole to the wafer more easily than in the prior art by negative tone development.

  In the present invention, in the photolithography, the transfer characteristic is made excellent, and the resistance to irradiation of ArF excimer laser exposure light and the resistance to cleaning can be enhanced.

It is a schematic sectional drawing which shows an example of the mask blank of this invention. It is a schematic sectional drawing which shows the other example of the mask blank of this invention. It is a schematic sectional drawing which shows the other example of the mask blank of this invention. It is a schematic sectional drawing which shows the other example of the mask blank of this invention. It is a schematic sectional drawing which shows the other example of the mask blank of this invention. It is a schematic sectional drawing which shows an example of the mask blank with a negative resist film of this invention. It is a schematic sectional drawing which shows an example of the phase shift mask of this invention. It is a schematic process drawing which shows an example of the manufacturing method of the pattern formation body using the phase shift mask of this invention. It is a figure showing the graph showing the result of simulation of the OPC bias value corresponding to light transmittance. It is the figure which showed the graph which represented the relationship of the focus latitude at the time of pattern transfer of HOLE pitch 180 nm in a phase shift mask, and exposure latitude by the result of simulation. It is the figure which showed the graph which represented the relationship of the focus latitude at the time of pattern transfer of HOLE pitch 240 nm in a phase shift mask, and exposure latitude with the result of simulation. It is the figure which showed the graph which represented the relationship of the focus latitude at the time of pattern transfer of HOLE pitch 300 nm in a phase shift mask, and exposure latitude by the result of simulation. It is the figure which showed the graph which represented the contrast of the wafer transfer space optical image calculated supposing the phase shift mask which is 6%-38% in light transmittance of a light semipermeable membrane. It is the figure which showed the graph showing OPC bias which was calculated supposing the phase shift mask which is 6%-38% in the light transmittance of a semitransparent film.

  Hereafter, the mask blanks of this invention, the mask blanks with a negative resist film, the phase shift mask, and the manufacturing method of the pattern formation body using the same are demonstrated in detail.

A. Mask Blanks The mask blanks of the present invention are mask blanks used for producing a halftone phase shift mask to which ArF excimer laser exposure light is applied, and are formed on a transparent substrate and the above transparent substrate, A layer consisting of Si _x O _1-x-y N _y (where x and y satisfy 0 <x <1, 0 <y <1, and 0 <x + y <1), and Si _z N _1-z (where z has a light semi-transmissive film configured by laminating layers formed by 0 <z <1 in random order, and the light semi-transmissive film is a light at the wavelength of ArF excimer laser exposure light The transmittance is in the range of 3% to 40%, and the film thickness is in the range of 50 nm to 70 nm.

FIG. 1 is a schematic cross-sectional view showing an example of the mask blank of the present invention. The mask blanks 100 shown in FIG. 1 are mask blanks used to manufacture a halftone phase shift mask to which ArF excimer laser exposure light is applied. The mask blanks 100 shown in FIG. 1 are formed on a transparent substrate 101 and a transparent substrate 101, and Si _x O _1-x-y N _y (where x and y are 0 <x <1, 0 <y <1. , and 0 <x + y <layer 102a made from 1 to satisfy), and _Si z _{N 1-z} (z is, 0 <z <satisfying 1) layer 102b is laminated configured light transflective consisting And a membrane 102. The light transflective film 102 has a light transmittance at the wavelength of ArF excimer laser exposure light in the range of 3% to 40%, and a film thickness in the range of 50 nm to 70 nm.

  In the mask blank of the present invention, the light transflective film realizes a wide range of light transmittance of 3% to 40% as the light transmittance at the wavelength of ArF excimer laser exposure light. Therefore, using the phase shift mask formed from the mask blank of the present invention, the light intensity is made zero by the interference of light due to the phase effect at the boundary of the pattern, and the contrast of the transferred image is improved. In the case of manufacturing, the phase effect can be made more remarkable by making the light semi-transmissive film to have high light transmittance. In addition, since the above-mentioned light semi-transmissive film does not contain metal, the oxide film of silicon (Si) does not grow even if it is irradiated with ArF excimer laser exposure light for a long time, and the pattern dimension changes. It can be prevented. Similarly, also in the step of cleaning the phase shift mask, it is possible to prevent the pattern dimension from changing. Therefore, according to the present invention, in photolithography, transfer characteristics can be made excellent, and ArF excimer laser exposure light irradiation resistance and cleaning resistance can be made high.

  Moreover, the said light semipermeable film implement | achieves the film thickness of the wide range of 50 nm-70 nm. For this reason, the thickness of the light semitransmissive film can be made smaller than that of the conventional light semitransmissive film, so that it becomes easy to form a semitransmissive film pattern by etching. And since the time required for the etching may be short, as described later, even if the etching barrier layer for preventing damage to the transparent substrate is not provided between the transparent substrate and the light transflective film, When forming a light semi-transmissive film pattern by etching, damage to the transparent substrate can be sufficiently avoided.

Furthermore, since the layer consisting of the single Si _x O _1-x-y N _y contains oxygen as compared to the layer consisting of the single Si _z N _1-z alone, the light transmittance tends to be high. Although it is excellent in some aspects, it is inferior in that the film thickness becomes large because the extinction coefficient and the refractive index decrease. The layer consisting of the single Si _z N _1-z alone has a smaller film thickness because the extinction coefficient and the refractive index are larger than the layer consisting of the single Si _x O _1-x-y N _y alone. Although they are excellent, they are inferior in that the light transmittance is low. For this reason, in the mask blank of the present invention, the light semipermeable film is particularly a light semitransparent film made of the above Si _z N _1-z alone or a light half made of the Si _x O _1-x-y N _y alone. The achievable range of the film thickness and the light transmittance becomes wider as compared with the transmission film.

  Hereinafter, the mask blanks of the present invention will be described separately for the members of the mask blanks and the configurations of the mask blanks.

1. First, the members of the mask blank of the present invention will be described. The mask blank of the present invention has at least a transparent substrate and a light semitransparent film.

(1) semi-transmission film in semi-transmission film present invention is formed on a transparent substrate to be described _{later, Si x O 1-x-} y N y (x and y, 0 <x <1,0 <y Layers comprising <1 and 0 <x + y <1), and layers comprising _{SizN1 -z} (z is satisfying 0 <z <1) are stacked in random order The light transmittance at the wavelength of ArF excimer laser exposure light is in the range of 3% to 40%, and the film thickness is in the range of 50 nm to 70 nm.

_{(A) Si x O 1-} x-y N Si in the layer present invention consisting of _{y x O 1-x-y} N y (x and y, 0 <x <1, 0 <y <1, and 0 < The layer consisting of x + y <1 is not particularly limited, but the composition ratio x of the above Si and the composition ratio y of the above N are 0.1 ≦ x ≦ 0.6, 0.05 ≦ Those satisfying y ≦ 0.6 and 0.15 ≦ x + y ≦ 0.9 are preferable, and in particular, 0.25 ≦ x ≦ 0.55, 0.1 ≦ y ≦ 0.5, and 0.25 ≦ Those satisfying x + y ≦ 0.6 are preferable, and those satisfying 0.35 ≦ x ≦ 0.45, 0.2 ≦ y ≦ 0.5, and 0.3 ≦ x + y ≦ 0.6 are particularly preferable. .

x, y, and x + y is, when each smaller than the above range, the Si x _{O 1-x-y} consisting of N _y layer of the light transmittance does not become sufficiently high, the light semi-transmitting film as a whole The reason is that the light transmittance does not increase. Also, x, y, and x + y is, as each larger than the above range, the _{Si x O 1-x-y} N above for extinction coefficient and refractive index of _y consists of a layer becomes too small _Si x _{O 1} the thickness of the layer comprising the _-x-y N _y becomes too thick, the light semi-transmitting film as a whole, because the film thickness does not become thin. In addition, when x is smaller than the above range and y is larger than the above range, the structure of the film may be unstable.

Further, adjustment of the composition ratio x of Si, the composition ratio 1-xy of O, and the composition ratio y of N mentioned above is carried out by the conventionally known film forming method such as sputtering as described later. in the case of forming a layer composed of _{x O 1-x-y N} y, apparatus used, can be done by selecting the materials used, the film formation conditions or the like as appropriate. For example, as described in the examples to be described later, a layer composed of the above Si _x O _1-x-y N _y is formed by sputtering on the above-mentioned transparent substrate using a parallel plate type DC magnetron sputtering apparatus. In this case, the target, the distance between the target and the transparent substrate (TS distance), the gas flow ratio, the gas pressure, the input power (power), and the like can be selected as appropriate. In addition, the film thickness of the layer made of Si _x O _1-x-y N _y and the layer made of Si _z N _1-z described later can be adjusted by controlling the processing time of the sputtering or the like. It can.

The layer made of Si _x O _1-x-y N _y is not particularly limited, but the extinction coefficient is 0 in order to obtain high light transmittance at the wavelength of ArF excimer laser exposure light. .2 is preferably in the range of 2 to 0.8, more preferably in the range of 0.2 to 0.4, and particularly preferably in the range of 0.2 to 0.3 .

If the above range is not _satisfied , the extinction coefficient of the layer consisting of Si _x O _1-x-y N _y is too small, so the light transmittance of the layer consisting of Si _x O _1-x-y N _y is high. Because the light transflective film as a whole is too high in light transmittance to become too high. If the above range is exceeded, the extinction coefficient of the layer consisting of Si _x O _1-x-y N _y is too large, so the light transmittance of the layer consisting of Si _x O _1-x-y N _y is This is because the light transflective film does not have a high light transmittance as a whole because it becomes too low.

Moreover, adjustment of the value of the extinction coefficient of the layer consisting of the Si _x O _1-x-y N _y is made by the composition ratio x of the Si, the composition ratio 1-x-y of the O, and the composition of the N It can be done by adjusting the ratio y.

The extinction coefficient of the layer made of Si _x O _{1 -x-y} N _y can be measured and calculated using an ellipsometer VUV-VASE manufactured by J.A.

Furthermore, the layer made of the above Si _x O _1-x-y N _y is not particularly limited, but the desired antiphase effect is obtained within the range of an appropriate film thickness at the wavelength of ArF excimer laser exposure light. The refractive index at the wavelength of ArF excimer laser exposure light is preferably in the range of 1.5 to 2.5, and more preferably in the range of 2.3 to 2.5. And in the range of 2.4 to 2.5 are preferable. If the above range is not _satisfied , the refractive index of the layer consisting of Si _x O _1-x-y N _y is too small, so the film thickness of the layer consisting of Si _x O _1-x-y N _y becomes too thick. This is because the light semitransmissive film does not have a thin film thickness as a whole.

The adjustment of the value of the _{Si x O 1-x-y} consisting of _{N y} the refractive index of the layer, the composition ratio of the composition ratio of Si x, the O composition ratio 1-x-y, and the N It can be done by adjusting y.

The refractive index of the layer made of Si _x O _{1 -x-y} N _y can be measured and calculated using an ellipsometer VUV-VASE manufactured by J.A. Moreover, the measurement of the said refractive index can be performed by the method of calculating using the simulation from the reflectance curve measured by the spectrophotometer.

Further, adjustment of the light transmittance of the layer made of Si _x O _1-x-y N _{y at} the wavelength of ArF excimer laser exposure light is performed by adjusting the composition ratio x of Si and the composition ratio 1-x of O above. It can carry out by adjusting the film thickness of the layer which consists of _y and the said composition ratio y of N, and said Si _x O _1-xy N _y .

_(B) Si _{z Si} in _N layers present invention consisting of _{1-z z N 1-z} (z is, 0 <z <satisfying 1) layer is composed of, but are not particularly limited, ArF excimer In order to obtain high light transmittance at the wavelength of laser exposure light, it is preferable that the composition ratio z of Si satisfies 0.35 ≦ z ≦ 0.6, and in particular, 0.35 ≦ z ≦ 0.55. In particular, those satisfying 0.35 ≦ z ≦ 0.50 are preferable.

If z is smaller than the above range, the film structure of the layer made of Si _z N _1-z is chemically unstable. In addition, if z is larger than the above range, the light transmittance of the layer made of Si _z N _1-z becomes too small to obtain a desired phase effect.

The adjustment of the composition ratio z of Si and the composition ratio 1-z of N is, as in the case of the layer composed of Si _x O _1-x-y N _y , the conventional method such as sputtering as described later. by a known film deposition method, in the case of forming a layer composed of the Si _{z N 1-z,} apparatus used, can be done by selecting the materials used, the film formation conditions or the like as appropriate. For example, as described in the examples to be described later, it is composed of the above Si _z N _1-z on a layer composed of the above _- mentioned Si _x O _1-x-y N _y using a parallel plate type DC magnetron sputtering apparatus. In the case where the layer is formed by sputtering, the target, the distance between the target and the layer consisting of Si _x O _1-x-y N _y (TS distance), gas flow ratio, gas pressure, input power (power), etc. It can do by selecting as appropriate. The thickness of the layer composed of the Si _{z N 1-z} by controlling the like processing time such as the sputtering, can be adjusted.

The layer made of Si _z N _1-z is not particularly limited, but in order to obtain high light transmittance at the wavelength of ArF excimer laser exposure light, extinction at the wavelength of ArF excimer laser exposure light The coefficient is preferably in the range of 0.2 to 0.45, and more preferably in the range of 0.2 to 0.4, and particularly preferably in the range of 0.2 to 0.35 Some are preferred.

If the above range is not satisfied, the extinction coefficient of the layer made of Si _z N _1-z is too small, and the light transmittance of the layer made of Si _z N _1-z becomes too high. This is because the light transmission rate of the transmission film as a whole is too high. For this reason, the light shielding property of the light semi-transparent film is lowered more than necessary, and the light shielding effect of the light shielding portion of the phase shift mask formed from the mask blank of the present invention becomes insufficient. The reason is that Further, if the above range is not satisfied, the extinction coefficient and the refractive index of the layer made of Si _z N _1-z become too small, so it is necessary to obtain a predetermined retardation at the wavelength of ArF excimer laser exposure light. This is because the film thickness is increased. If the above range is exceeded, the extinction coefficient of the layer made of Si _z N _1-z is too large, and the light transmittance of the layer made of Si _z N _1-z becomes too low. This is because the semitransparent film does not have a high light transmittance as a whole, and a desired phase shift effect at the wavelength of ArF excimer laser exposure light can not be obtained.

The adjustment of the Si z _N the extinction coefficient value of a layer consisting of _1-z can be carried out by adjusting the composition ratio 1-z of the composition ratio z, and said N of said Si.

The extinction coefficient of the layer made of Si _z N _1-z can be measured and calculated using an ellipsometer VUV-VASE manufactured by JA Woollam.

Furthermore, the layer made of Si _z N _1-z is not particularly limited, but in order to obtain a desired antiphase effect within the range of an appropriate film thickness at the wavelength of ArF excimer laser exposure light, ArF The refractive index at the wavelength of the excimer laser exposure light is preferably in the range of 2.3 to 2.7, and more preferably in the range of 2.5 to 2.7, particularly 2.6 Those which are within the range of-2.7 are preferred. If the above range is not satisfied, the refractive index of the layer made of Si _z N _1-z is too small, so the film thickness for obtaining the desired retardation of the layer made of Si _z N _1-z becomes too thick. This is because the light semitransmissive film does not have a thin film thickness as a whole.

The adjustment of the value of the refractive index of the layer composed of the Si z _{N 1-z} can be carried out by adjusting the composition ratio 1-z of the composition ratio z, and said N of said Si.

Further, it is possible to the refractive index of the layer composed of the _{Si z N 1-z} is measured by J. JA Woollam Co. ellipsometer VUV-VASE, calculated. Moreover, the measurement of the said refractive index can be performed by the method of calculating using the simulation from the reflectance curve measured by the spectrophotometer.

Further, the adjustment of the light transmittance of the layer made of Si _z N _{1-z at} the wavelength of ArF excimer laser exposure light is the composition ratio z of Si and the composition ratio 1-z of N, and the Si the thickness of the layer consisting _{z N 1-z} can be done by adjusting the.

(C) Light semi-transmissive film The light semi-transmissive film in the present invention is not particularly limited as far as the light transmittance is such that the light transmittance is in the range of 3% to 40%. Among them, those in which the light transmittance is in the range of 18% to 40% are preferable, and those in which the light transmittance is in the range of 20% to 40% are particularly preferable. If the above range is not satisfied, the desired phase shift effect at the wavelength of ArF excimer laser exposure light can not be obtained. If the above range is exceeded, the light shielding property of the light transflective film is lowered more than necessary. This is because the light shielding effect of the light shielding portion of the phase shift mask formed from the mask blanks of the above becomes insufficient, which causes a problem in the transfer characteristics of the desired pattern.

  In addition, the light transmittance of the light transflective film, ArF excimer laser exposure light having a wavelength of 193 nm passing only the transparent substrate, and the laser exposure light passing the transparent substrate and the light transflective film The phase difference and the like can be measured by using a phase shift amount measuring machine (manufactured by Lasertec Corporation, MPM 193) and the like.

  Further, the light semi-transmissive film is not particularly limited as far as the film thickness is in the range of 50 nm to 70 nm, but the film thickness of the light semi-transmissive film is particularly set forth above. Is preferably in the range of 50 nm to 60 nm, and particularly preferably in the range of 50 nm to 55 nm. As a result, since it is thinner than the thickness of the conventional light transflective film, it becomes easy to form the light transflective film pattern by etching. And, since the time required for the etching can be shortened, even if the etching barrier layer for preventing damage to the transparent substrate is not provided between the transparent substrate and the light semitransparent film, the light semitransparent by the etching This is because damage to the transparent substrate can be sufficiently avoided when forming the film pattern. In addition, when the film thickness of the light semitransparent film is thinner, generation of defects such as pattern collapse can be suppressed in a light semitransparent film pattern to be described later formed from the light semitransparent film, or This is because it is easy to process the above-mentioned light semipermeable film and correct the light semitransparent film pattern.

The light semi-transmissive film is formed by stacking the layer made of the above Si _x O _{1 -x-y} N _y and the layer made of the above Si _z N _{1-z in} random order, and the light semi-transmissive film It is not particularly limited as long as the light transmittance and the film thickness of the light semi-transmissive film are in the above ranges, respectively. As the above-mentioned light semi-transmissive film, for example, other than the one having a two-layer structure in which a layer composed of the above Si _x O _{1 -x-y} N _y and a layer composed of the above Si _z N _1-z are laminated in random order. And the layer having the above three layers of Si _x O _1-x-y N _y , and the layer having a three or more layer structure in which the layers consisting of the above-mentioned Si _z N _1-z are laminated in random order and the like. .

Then, the light semi-transmissive film is, if one intends layer composed of the _{Si x O 1-x-y} N y, and a layer made of the _{Si z N 1-z} is formed by laminating the above-mentioned The order in which the layer composed of Si _x O _{1 -x-y} N _y and the layer composed of the above Si _z N _1-z are laminated on the transparent substrate described later is not particularly limited, and the above Si _x Even in the order in which the layer made of O _{1 -x-y} N _y and the layer made of Si _z N _1-z are laminated in this order from the transparent substrate side, the layer made of Si _z N _1-z , and a layer composed of the _{Si x O 1-x-y} N y is the even order are stacked from the transparent substrate side in this order, may be either. However, a layer made of the _{Si z N 1-z,} and a layer made of the _{Si x O 1-x-y} N y is the order to be stacked in this order from the transparent substrate side is preferred. The _Si z _{N 1-z} (z satisfies the 0 <z <1), the above _{Si x O 1-x-y} N y (x and y, 0 <x <1,0 <y <1 , And 0 <x + y <1), since the etching selectivity with the material such as SiO ₂ constituting the transparent substrate is higher, the layer made of the above Si _z N _1-z is on the transparent substrate It is because it becomes easier to etch the said light semipermeable membrane, if it is directly laminated | stacked on this.

  Further, the light transflective film is not particularly limited, but ArF excimer laser exposure light having a wavelength of 193 nm passing only through the transparent substrate, and the laser exposure passing through the transparent substrate and the light transflective film The phase difference with light is preferably in the range of 160 ° to 200 °, more preferably in the range of 170 ° to 190 °, and particularly preferably in the range of 177 °. When forming a phase shift mask by etching the light semi-transmissive film from the mask blank of the present invention, even if the transparent substrate is etched to form a dug portion in the portion where the light semi-transmissive film is etched, In the phase shift mask, the phase difference between ArF excimer laser exposure light of 193 nm having a wavelength of 193 nm which passes through the transmission region in which the dug portion is formed and the laser which passes through the semi-transmissive region where the light semi-transmissive film remains. It is because it can be made into °. This is because a halftone phase shift mask can be manufactured.

(2) Transparent Substrate The transparent substrate in the present invention is not particularly limited, and examples thereof include optically polished synthetic quartz glass which transmits exposure light with high transmittance, fluorite, calcium fluoride and the like. Among them, synthetic quartz glass, which is frequently used and stable in quality and has a high transmittance to exposure light of short wavelength, is preferable.

(3) Light Shielding Film As the mask blank of the present invention, the film configuration, the material, the optical density (OD value) at the wavelength of ArF excimer laser exposure light, etc. The optical density (OD value) at the wavelength of ArF excimer laser exposure light, which is formed on the light transflective film, is a desired optical density (OD value) in combination with the light transflective film. It is preferable to further have a light shielding film adjusted to

FIG. 2 is a schematic cross-sectional view showing another example of the mask blank of the present invention. The mask blanks 100 shown in FIG. 2 are formed on the transparent substrate 101 and the transparent substrate 101, and Si _x O _1-x-y N _y (where x and y are 0 <x <1, 0 <y <1). , and 0 <x + y <layer 102a made from 1 to satisfy), and _Si z _{N 1-z} (z is, 0 <z <satisfying 1) layer 102b is laminated configured light transflective consisting Single-layer structure formed on the film 102 and the light transflective film 102 such that the optical density (OD value) at the wavelength of ArF excimer laser exposure light is 3.0 or more in combination with the light transflective film 102 The light shielding film 103 of The light shielding film 103 has all the functions of a reflection preventing function, a light absorbing function to ArF excimer laser exposure light, and an etching barrier function to the light semitransparent film. Specifically, the light absorbing layer included in the light shielding film 103 has an etching barrier function and a light absorbing function to the light semi-transmissive film 102. Further, in the phase shift mask formed from the mask blank of the present invention In the light shielding area of the outer frame, a reflection preventing function is required, but the outermost surface of the light absorption layer included in the light shielding film 103 remains in the light shielding area as a light shielding film, and has the reflection preventing function.

  In the phase shift mask formed from mask blanks, when there is a light semi-transmissive film pattern having a large area, there is a possibility that the problem of blurring of the transferred image may be caused by the exposure light which transmits such a pattern. . Then, in the phase shift mass, by forming a light shielding film pattern on the light semitransparent film pattern having a large area, such problems are eliminated by shielding unnecessary exposure light that transmits such a pattern. I am trying to do it. And, as in the case of the mask blank of the present invention, when the light transmittance of the light transflective film is in the range of 3% to 40% and can be a particularly large value than 6% of the general light transmittance. Will cause the above-mentioned problems more prominently. Therefore, according to the present invention, the effect of avoiding such a problem can be more significantly obtained by further including the light shielding portion.

  The light shielding film is formed on the light semitransparent film, and the optical density (OD value) at the wavelength of ArF excimer laser exposure light becomes a desired optical density (OD value) in combination with the light semitransparent film. It is not particularly limited as long as it is adjusted and has a light absorbing function of absorbing exposure light. As the light shielding film, a reflection preventing function for preventing multiple reflection between the phase shift mask and the lens when transferring the mask pattern to the wafer, and damage to the light semitransparent film when etching the light shielding film It is preferable to have an etching barrier function to the above-mentioned light semi-permeable film which suitably prevents Among them, one having a conductive function to prevent charging by an electron beam at the time of drawing is preferable.

  In the mask blank of the present invention, as in the mask blank 100 shown in FIG. 2, the light shielding film is formed on the light semitransparent film, and has an etching barrier function to the light semitransparent film and ArF excimer laser exposure light. It is preferable to have a single layer structure including a light absorbing layer having a light absorbing function to This is because a mask having the necessary functions can be obtained with fewer steps.

  When the light shielding film has a single-layer structure as in the mask blanks 100 shown in FIG. 2, the material of the light shielding film is not particularly limited, but Cr, Ta, W, Mo, etc. may be used. It can be mentioned. Among them, Cr and the like are preferable. Since the type of reactive etching gas used when etching the light shielding film is different from the reactive etching gas used when etching the light semitransparent film, the light shielding film has the etching barrier function described above. It is because it can be expected.

  Moreover, when the said light shielding film has the said single layer structure, the thickness of the said light shielding film changes with kinds of the material, Although it does not specifically limit, It is in the range of 30 nm-80 nm. Is preferred. In order to obtain a film thickness such that the optical density (OD value) at the wavelength of Ar-F excimer laser exposure light is 3.0 or more in combination with the light semitransparent film, the material of the light shielding film is any case It is because the said film thickness is needed.

  The optical density (OD value) of the light shielding film combined with the light transflective film can be calculated and measured using MCPD3000 manufactured by Otsuka Electronics Co., Ltd. and the reflectance of the light shielding film MCPD7000 manufactured by Otsuka Electronics Co., Ltd.

  FIG. 3 is a schematic cross-sectional view showing another example of the mask blank of the present invention. The mask blank 100 shown in FIG. 3 is a two-layer structure including a light absorbing layer 103a in which the light shielding film 103 is formed on the light transflective film 102 and a hard mask layer 103b formed on the light absorbing layer 103a. It has a structure. The light absorption layer 103 a has both a light absorption function for ArF excimer laser exposure light and an etching barrier function for the light transflective film 102. In addition, the hard mask layer 103 b has an etching barrier function to the light absorption layer 103 a.

  In the mask blank of the present invention, as in the mask blank 100 shown in FIG. 3, the light shielding film is formed on the light semitransparent film, and the etching barrier function and the ArF excimer laser exposure to the light semitransparent film described above It is preferable to have a two-layer structure including a light absorbing layer having a light absorbing function to light and a hard mask layer formed on the light absorbing layer and having an etching mask function to the light absorbing layer described above. Thus, the pattern formed by etching the hard mask layer can be used instead of the resist pattern when the light absorption layer is etched, so that the resist film thickness can be reduced. This is because the fine pattern of the light shielding film can be easily formed.

  More specifically, when the light shielding film has a single layer structure as in the mask blanks 100 shown in FIG. 2, since the light shielding film of the single layer structure is thick, the light shielding film is formed with a thick resist pattern. The light shielding film pattern is formed by etching. For this reason, it is difficult to form a fine pattern of the light shielding film from the relationship of the aspect ratio of the resist pattern. On the other hand, when the light shielding film has a two-layer structure as shown in FIG. 3 as in the mask blanks 100 shown in FIG. 3, the hard mask layer is thinner than the light shielding film of the single layer structure. The hard mask layer pattern can be formed by etching the hard mask layer with a resist pattern thinner than that used for etching the light shielding film of the single layer structure. And the pattern can be used instead of the resist pattern at the time of etching the said light absorption layer. Thus, the resist film thickness required to form the light shielding film pattern can be reduced. Thereby, the fine pattern of the light shielding film can be formed more easily than the light shielding film of the single layer structure.

When the light shielding film has the two-layer structure, the hard mask layer is not particularly limited, but may have the above-described conductive function. In addition, when the light shielding film has the two-layer structure, the material of the hard mask layer is not particularly limited as long as it has an etching mask function to the light absorption layer described above, but Si SiN, SiON, SiO, SiO ₂ , MoSi, Cr, CrO, CrON and the like can be mentioned. Among them, Si, SiN, SiON, SiO ₂ , MoSi and the like are preferable. When a material containing Cr is used as the material of the light absorption layer, the type of reactive etching gas used when etching the light absorption layer is different from the reactive etching gas used when etching the hard mask layer This is because the light absorption layer can be prevented from being damaged when the hard mask layer is etched.

  When the light shielding film has the above-described two-layer structure, the material of the light absorption layer is particularly a material having the above-described etching barrier function for the light semitransparent film and the light absorption function for ArF excimer laser exposure light. Although not limited, Cr, CrN, CrON, CrO, Si, SiO, SiON, MoSi and the like can be mentioned. Among them, Cr is preferred. Since the type of reactive etching gas used when etching the light absorption layer is different from the reactive etching gas used when etching the hard mask layer, the light absorption when the hard mask layer is etched It is because it can prevent that a layer is damaged. In addition, since Cr has a high extinction coefficient, the optical density (OD value) at the wavelength of ArF excimer laser exposure light is combined with the light semi-transmissive film to obtain a desired optical density ( It is because it can adjust to OD value.

  Moreover, when the said light shielding film has the said 2 layer structure, the thickness of the said hard mask layer changes with kinds of the material, Although it does not specifically limit, Within 2 nm-10 nm Among them, it is preferable to be in the range of 2 nm to 7 nm, particularly in the range of 2 nm to 5 nm. This is because the thinner the film thickness, the more accurate the processing. Moreover, when the said light shielding film has the said 2 layer structure, the thickness of the said light absorption layer changes with kinds of the material, Although it does not specifically limit, Within the range of 30 nm-80 nm Among them, it is preferable to be in the range of 30 nm to 70 nm, particularly in the range of 30 nm to 50 nm. This is because the optical density (OD value) of the light shielding film at the wavelength of ArF excimer laser exposure light can be easily made 3.0 or more in combination with the light semitransparent film, and the light shielding film can be easily etched.

  FIG. 4 is a schematic cross-sectional view showing another example of the mask blank of the present invention. The mask blanks 100 shown in FIG. 4 have an etching barrier layer 103c in which the light shielding film 103 is formed on the light transflective film 102, a light absorbing layer 103a formed on the etching barrier layer 103c, and a light absorbing layer 103a. And a hard mask layer 103b formed thereover. The etching barrier layer 103c has an etching barrier function to the light transflective film 102, the light absorbing layer 103a has a light absorbing function to ArF excimer laser exposure light, and the hard mask layer 103b has an etching barrier to the light absorbing layer 103a. It has a function.

  FIG. 5 is a schematic cross-sectional view showing another example of the mask blank of the present invention. In the mask blanks 100 shown in FIG. 5, an etching barrier layer 103c in which the light shielding film 103 is formed on the light transflective film 102, a light absorbing layer 103a formed on the etching barrier layer 103c, and a light absorbing layer 103a. And a hard mask layer 103b formed thereover. The etching barrier layer 103c has an etching barrier function to the light transflective film 102, the light absorbing layer 103a has a light absorbing function to ArF excimer laser exposure light, and the hard mask layer 103b has an etching barrier to the light absorbing layer 103a. It has a function.

  In the mask blank of the present invention, as in the mask blanks 100 shown in FIGS. 4 and 5, the light shielding film is formed on the light semitransparent film and has an etching barrier function to the light semitransparent film described above. An etching barrier layer, a light absorbing layer formed on the etching barrier layer and having a light absorbing function to the above-described ArF excimer laser exposure light, and an etching mask function formed on the light absorbing layer and the light absorbing layer described above It is preferable to have a three-layer structure including a hard mask layer having Thus, the pattern formed by etching the hard mask layer can be used in place of the resist pattern when the light absorption layer is etched, as in the case where the light shielding film has the two-layer structure. It is. As a result, the fine pattern of the light shielding film can be easily formed.

In the mask blank of the present invention, the light shielding film preferably has the three-layer structure. As a layer having a light absorption function with respect to the ArF excimer laser exposure _{light, Si x O 1-x-} y N y (x and y, 0 <x <1, 0 <y <1, and 0 <satisfying x + y <1 Can be etched with a highly reactive etching gas with a light transflective film configured by laminating a layer consisting of (a) and a layer consisting of Si.sub.z _{N.sub.1 -z} (z satisfies 0 <z <1). It is because the light absorption layer which consists of these materials can be used. Thereby, the range of selection of the material of the layer having a light absorbing function with respect to ArF excimer laser exposure light is broadened, and the film thickness of the light shielding film can be made thinner. In addition, the layer having a light absorbing function for ArF excimer laser exposure light and the layer having an etching barrier function for the light transflective film may be respectively used as the light absorbing layer and the etching barrier layer made of different materials. It is because it can. As a result, the light absorption layer and the etching barrier layer can be etched with different etching gases, so that the light transflective film is damaged when the light absorption layer is etched. It is because it can be made to have an etching barrier function to the above-mentioned light semipermeable membrane which prevents suitably.

For example, in the mask blank 100 shown in FIG. 4, Si _x O _1-x-y N _y (where x and y are 0 <x <1, 0) as a layer having a light absorbing function to ArF excimer laser exposure light. <y <1, and 0 <x + y <satisfying 1) consisting of a layer, and _Si z _{N 1-z} (z is, 0 <z <1 light composed layer consisting satisfactory) is laminated It is possible to use the light absorption layer 103 a made of MoSi, which is a material that can be etched by the etching gas having high reactivity with the semi-transmissive film. In addition, a layer having a light absorbing function for ArF excimer laser exposure light and a layer having an etching barrier function for the above light semitransparent film can be respectively formed as a light absorbing layer 103a made of MoSi and an etching barrier layer 103c made of Cr. . Thus, the light absorption layer 103a and the etching barrier layer 103c can be etched with different fluorine-based gas and chlorine-based gas, respectively. Therefore, the etching barrier layer 103c may be used as one having an etching barrier function to the above-mentioned light semi-transmissive film which suitably prevents the light semi-transmissive film 102 from being damaged when the light absorption layer 103a is etched. it can.

Further, in the mask blank 100 shown in FIG. 5, Si _x O _1-x-y N _y (where x and y are 0 <x <1, 0) as a layer having a light absorbing function to ArF excimer laser exposure light. <y <1, and 0 <x + y <satisfying 1) consisting of a layer, and _Si z _{N 1-z} (z is, 0 <z <1 light composed layer consisting satisfactory) is laminated It is possible to use the light absorption layer 103a made of Si which is a material that can be etched by the etching gas having high reactivity with the semi-transmissive film. In addition, a layer having a light absorbing function for ArF excimer laser exposure light and a layer having an etching barrier function for the above-mentioned light transflective film can be respectively used as a light absorbing layer 103a made of Si and an etching barrier layer 103c made of Cr. . Thus, the light absorption layer 103a and the etching barrier layer 103c can be etched with different fluorine-based gas and chlorine-based gas, respectively. Therefore, the etching barrier layer 103c can be used as a layer having an etching barrier function which suitably prevents the light semitransparent film 102 from being damaged when the light absorption layer 103a is etched.

  When the light shielding film has the three-layer structure, the hard mask layer is not particularly limited, but may have the above-described conductive function. Further, when the light shielding film has the three-layer structure, the material of the hard mask layer is not particularly limited as long as it has an etching mask function to the light absorption layer described above, but Cr And CrN, CrON, CrO, SiN, SiON, SiO and the like. Among them, those containing Cr as the main component are preferable. Since the type of reactive etching gas used when etching the light absorption layer is different from the reactive etching gas used when etching the hard mask layer, the light absorption when the hard mask layer is etched It is because it can prevent that a layer is damaged.

  When the light shielding film has the three-layer structure, the material of the light absorbing layer is not particularly limited as long as it has the above-described light absorbing function, but metals such as MoSi and A material containing silicon (Si) or a metal such as W or Ta or a simple substance of silicon (Si) can be mentioned. Among them, silicon (Si) is particularly preferable. Since the type of reactive etching gas used when etching the light absorption layer is different from the reactive etching gas used when etching the hard mask layer, the light absorption when the hard mask layer is etched It is because it can prevent that a layer is damaged. In addition, since silicon (Si) alone has a high extinction coefficient, the thickness of the light shielding film can be made thinner by forming the light absorption layer from silicon (Si) alone.

  Further, when the light shielding film has the three-layer structure, the material of the etching barrier layer is not particularly limited as long as it has the above-mentioned etching barrier function, but Cr, CrN, CrON , CrO and the like. Since the type of reactive etching gas used when etching the etching barrier layer is different from the reactive etching gas used when etching the light absorbing layer, the etching barrier when etching the light absorbing layer It is because it can prevent that a layer is damaged. For example, when etching the light absorption layer with a fluorine-based gas, the etching barrier layer can be prevented from being damaged, and the etching barrier layer can be etched with a chlorine-based gas.

  When the light shielding film has the three-layer structure, the thickness of the hard mask layer is different depending on the type of the material and is not particularly limited, but it is in the range of 2 nm to 10 nm. Among them, it is preferable to be in the range of 2 nm to 7 nm, particularly in the range of 2 nm to 5 nm. This is because the film thickness is the minimum required film thickness for the etching mask function for the light absorption layer, and the film thickness can make it easy to form the fine pattern of the light shielding film by thinning the resist film thickness. .

  Moreover, when the said light shielding film has the said 3 layer structure, the thickness of the said light absorption layer changes with kinds of the material, Although it does not specifically limit, Within 20 nm-70 nm Among them, it is preferable to be in the range of 20 nm to 60 nm, particularly in the range of 30 nm to 50 nm. This is because the optical density (OD value) of the light shielding film at the wavelength of ArF excimer laser exposure light can be easily made 3.0 or more in combination with the light semitransparent film, and the light shielding film can be easily etched. Further, when the light absorption layer is composed of Si alone, Si has a high extinction coefficient as compared with the case where it is composed of MoSi, so the thickness of the light shielding film can be thinner.

  Furthermore, when the light shielding film has the three-layer structure, the thickness of the etching barrier layer is different depending on the type of the material, and is not particularly limited, but it is within the range of 2 nm to 6 nm. And particularly preferably in the range of 2 nm to 4 nm. This is because the thickness of the etching barrier layer is sufficient to have the etching barrier function described above.

  Furthermore, the light shielding film is not particularly limited, but the optical density (OD value) at the wavelength of ArF excimer laser exposure light was adjusted to 3.0 or more in combination with the light semitransparent film. Is preferred. This is because it is possible to obtain the required light shielding property for the desired part at the time of exposure.

(4) Other members The mask blank of the present invention is not particularly limited as long as it has the above-mentioned semipermeable membrane and transparent substrate, and other necessary members can be appropriately added.

2. Next, the configuration of the mask blank of the present invention will be described. In the mask blank of the present invention, the light semi-transmissive film is formed on the transparent substrate. Hereinafter, the structure and manufacturing method of mask blanks of this invention are demonstrated.

(1) Configuration of Mask Blanks Although the mask blanks are not particularly limited, it is preferable that the light transflective film is formed directly on the transparent substrate.

As in the case of the light semi-transmissive film in the present invention, the refractive index of the light semi-transmissive film having a large light transmittance tends to be small. Therefore, in the halftone phase shift mask, in order to realize an appropriate phase shift, a phase difference of 180 ° is made between the portion where such a light transflective film is formed and the portion through which the exposure light passes. To form the film, it was necessary to increase the thickness of the light semipermeable film (Patent Documents 1 and 2). When the thickness of the light transflective film is increased, the etching barrier layer may be formed on the transparent substrate so as not to damage the transparent substrate when the light transflective film is etched (patented) References 1 and 2). As the etching barrier layer, a layer which is not etched by an etching species (for example, CF ₄ , SF ₆ , CHF ₃ gas or the like) of the light semitransparent film is formed in order to increase the etching selectivity with the light semitransparent film. However, in the case of forming such an etching barrier layer, for example, in Patent Document 1, a Ta-Hf film is formed and etching is performed using a Cl-based gas, as described in the example. In addition, there is a problem that etching becomes complicated, and etching with a Cl-based gas is difficult, and shape and dimensional uniformity in the mask surface deteriorate. Further, Patent Document 2 also describes a structure in which the etching barrier layer is made of Zr and Hf, but similarly, the etching process has to be performed a plurality of times, and there is a similar problem due to the difficulty in etching.

  However, according to the present invention, since the light transflective film is thinner than the thickness of the conventional light transflective film, it becomes easy to form a semitransparent film pattern by etching. As a result, the time required for etching can be shortened, so that even if the etching barrier layer is not provided between the transparent substrate and the light transflective film, the transparent film pattern can be formed by etching. Damage to the substrate can be sufficiently avoided. Therefore, in the mask blank, the light transflective film is formed directly on the transparent substrate. Thus, as described above, since it is not necessary to form the etching barrier layer, it is not necessary to perform the etching process multiple times, so the etching process is not complicated and etching of the etching barrier layer is difficult. This is because it is possible to prevent deterioration of the shape of the light transflective film and the transparent substrate or deterioration of the uniformity of the shape of the light transflective film.

(2) Method of Producing Mask Blanks The method of producing mask blanks of the present invention is not particularly limited as long as it is a method by which desired mask blanks can be obtained. In an example of the method for producing a mask blank of the present invention, first, the above-mentioned transparent substrate is prepared. Next, the light transflective film is formed on the transparent substrate by a conventionally known film forming method such as a sputtering method. Next, the light shielding film is formed on the light transflective film by a conventionally known film forming method such as a sputtering method. When the light shielding film has the two-layer structure, the light absorbing layer is formed on the light semitransparent film by a conventionally known film forming method such as sputtering, and then the sputtering method or the like is formed on the light absorbing layer. The hard mask layer is formed by the conventionally known film forming method. When the light shielding film has the three-layer structure, the etching barrier layer is formed on the light transflective film by a conventionally known film forming method such as a sputtering method, and the sputtering method or the like is formed on the etching barrier layer. After the light absorbing layer is formed by the conventionally known film forming method, the hard mask layer is formed on the light absorbing layer by the conventionally known film forming method such as the sputtering method. Thereby, the mask blank of the present invention is obtained.

B. Negative Resist Film Mask Blanks Next, the negative resist film mask blanks of the present invention will be described. The negative resist film with mask blank of the present invention is characterized by having the above-mentioned mask blank and a negative resist film formed on the mask blank.

  FIG. 6 is a schematic cross-sectional view showing an example of the mask blank with negative resist film of the present invention. The negative resist film with mask blank 110 shown in FIG. 6 is a negative resist film with mask blank used to manufacture a halftone phase shift mask to which ArF excimer laser exposure light is applied. The negative resist film with mask blank 110 includes the mask blank 100 described above and the negative resist film 111 formed on the mask blank 100.

  In the case where a fine pattern such as contact holes or lines is transferred to a wafer using a halftone phase shift mask having a light transflective film as described in the item “D. In addition, negative tone development can easily avoid the side lobe phenomenon and transfer a fine pattern such as contact holes or lines to the wafer.

  When a fine pattern such as a contact hole or line is transferred to a wafer by negative tone development, a half-tone phase shift mask is used to transfer a light beam corresponding to the fine pattern such as a contact hole or line. It is necessary to form a convex fine pattern composed of a permeable membrane.

  According to the present invention, the light semi-transmissive film is etched using the pattern of the negative resist film to form a convex fine pattern composed of the light semi-transmissive film, whereby a negative type described later can be obtained. Phase shift mask can be manufactured. For this reason, when manufacturing a negative phase shift mask to be described later, the range exposed to light in the negative resist film of the mask blank with negative resist film has a convex fine pattern composed of the light semitransparent film. It corresponds to a very narrow range. Therefore, a negative phase shift mask to be described later can be manufactured in a shorter time.

  The negative resist film with mask blank of the present invention has the above-described mask blank and a negative resist film formed on the mask blank. About the mask blanks in the present invention, since it is the same as the contents described in the above-mentioned "A. mask blanks", the description here is omitted.

  On the other hand, the negative resist composition used to form the negative resist film in the present invention is not particularly limited. For example, SEBN 1637, SEBN 1702 and SEBN 2014 manufactured by Shin-Etsu Chemical Co., Ltd., and Sumitomo Chemical NEB-22 etc. made by Corporation can be mentioned. Among them, SEBN 2014 manufactured by Shin-Etsu Chemical Co., Ltd. is preferable. It is because it is suitable for forming a fine pattern.

  Moreover, the film thickness of the said negative resist film is although it does not specifically limit, It is preferable to exist in the range of 50 nm-150 nm. Among them, the range of 80 nm to 100 nm is preferable. This is because when forming a pattern on a mask, a minute pattern can be formed while having a sufficient etching barrier function.

  Furthermore, the method for forming the negative resist film is not particularly limited, and examples thereof include spin coating and the like.

C. Phase Shift Mask Next, the phase shift mask of the present invention will be described. The phase shift mask of the present invention is a halftone type phase shift mask to which ArF excimer laser exposure light is applied, and is formed on a transparent substrate and the above-mentioned transparent substrate, and is formed of Si _x O _{1 -x-y} N _y (x and y, 0 <x <1,0 <y <1, and 0 <x + y <1 and satisfies) a layer consisting of, and _Si z _{N 1-z} (z is, 0 <z <satisfying 1 And a light transflective film pattern formed by stacking layers formed of different layers in a random order, and the light transflective film pattern has a light transmittance of 3% to 40% at the wavelength of ArF excimer laser exposure light. And the film thickness is in the range of 50 nm to 70 nm.

FIG. 7 is a schematic cross-sectional view showing an example of the phase shift mask of the present invention. The phase shift mask 200 shown in FIG. 7 is a halftone phase shift mask to which ArF excimer laser exposure light is applied. The phase shift mask 200 shown in FIG. 7 is formed on a transparent substrate 201 and a transparent substrate 201, and Si _x O _1-x-y N _y (where x and y are 0 <x <1, 0 <y < 1, and 0 <x + y <layer 202a made from 1 to satisfy), and _Si z _{N 1-z} (z is, 0 <z <satisfying 1) layer 202b is laminated configured light semi consisting And a permeable membrane pattern 202. The light transflective film pattern 202 has a light transmittance at the wavelength of ArF excimer laser exposure light in the range of 3% to 40%, and a film thickness in the range of 50 nm to 70 nm.

  In the phase shift mask of the present invention, the light transflective film pattern realizes a wide range of light transmittance of 3% to 40% as the light transmittance at the wavelength of ArF excimer laser exposure light. Therefore, in the case of producing a pattern-formed body by using the phase shift mask of the present invention and making the light intensity zero at the pattern boundaries by light interference due to the phase effect to improve the contrast of the transferred image. The phase effect can be made more remarkable by making the semi-transmissive film pattern have high light transmittance. In addition, since the light semi-transmissive film pattern does not contain a metal, the oxide film of silicon (Si) does not grow even when irradiated with ArF excimer laser exposure light for a long time, and the pattern dimension changes. Can be prevented. Similarly, also in the step of cleaning the phase shift mask, it is possible to prevent the pattern dimension from changing. Therefore, according to the present invention, in photolithography, transfer characteristics can be made excellent, and ArF excimer laser exposure light irradiation resistance and cleaning resistance can be made high.

  Moreover, the said light semipermeable membrane pattern implement | achieves the film thickness of the wide range of 50 nm-70 nm. Therefore, the film thickness can be made smaller than that of the conventional light semi-transmissive film pattern, so that it becomes easy to form the semi-transmissive film pattern by etching. Then, since the time required for the etching may be short, as described later, even if the etching barrier layer for preventing damage to the transparent substrate is not provided between the transparent substrate and the light transflective film pattern. This is because damage to the transparent substrate can be sufficiently avoided when forming the semipermeable film pattern by etching.

Furthermore, since the layer consisting of the single Si _x O _1-x-y N _y contains oxygen as compared to the layer consisting of the single Si _z N _1-z alone, the light transmittance tends to be high. Although it is excellent in some aspects, it is inferior in that the film thickness becomes large because the extinction coefficient and the refractive index decrease. The layer consisting of the single Si _z N _1-z alone has a smaller film thickness because the extinction coefficient and the refractive index are larger than the layer consisting of the single Si _x O _1-x-y N _y alone. Although they are excellent, they are inferior in that the light transmittance is low. Therefore, in the phase shift mask of the present invention, the light transflective film pattern is, in particular, a light transflective film pattern consisting of the above Si _z N _1-z alone or the above Si _x O _1-x-y N _y alone. As compared with the light semi-transmissive film pattern made of the above, the feasible range of the film thickness and the light transmittance becomes wider.

  Hereinafter, the phase shift mask of the present invention will be described separately for the members of the phase shift mask and the configuration of the phase shift mask.

1. First, a member of the phase shift mask of the present invention will be described. The phase shift mask of the present invention comprises at least a transparent substrate and a light semitransmissive film pattern.

(1) Light semi-transmissive film pattern The light semi-transmissive film pattern in the present invention is formed on a transparent substrate to be described later, and Si _x O _1-xy N _y (where x and y are 0 <x <1, 0) A layer comprising a layer comprising <y <1 and 0 <x + y <1) and a layer comprising _{SizN1 -z} (z is satisfying 0 <z <1) It is.

  The configuration of the light semitransmissive film pattern in the present invention is the same as that described in the above “A. mask blanks 1. members of mask blanks (1) light semitransmissive film” except that the pattern is formed in a pattern. The configuration is the same as that of the light semitransmissive film in the invention. Therefore, the description here is omitted.

(2) Transparent substrate The configuration of the transparent substrate in the present invention is the same as the configuration of the transparent substrate in the present invention described in the section of “A. Mask blanks 1. members of mask blanks (2) transparent substrate”. Therefore, the description here is omitted.

(3) Light-shielding film pattern As the phase shift mask of the present invention, if it has the above-mentioned transparent substrate and a light-semitransmissive film pattern, particularly the film configuration, material, optical density (OD value at the wavelength of ArF excimer laser exposure light Such as, but not limited to, the optical density (OD value) at the wavelength of ArF excimer laser exposure light formed on the above light transflective film pattern and combined with the above light transflective film pattern is the desired optical It is preferable to further have a light shielding film pattern adjusted to have a concentration (OD value).

  The light shielding film pattern is preferably formed on the light transflective film pattern and has a single layer structure including a light absorbing layer pattern having an etching barrier function and a light absorbing function to the light transflective film. Thus, in the light shielding film having the two-layer structure described above, the light shielding film pattern is formed by using the pattern formed by etching the hard mask layer instead of the resist pattern when the light absorption layer is etched. It is because it can be formed. As a result, it is because it becomes easy to form the fine pattern of the said light shielding film pattern.

  The light shielding film pattern is formed on the light semitransparent film pattern, and is formed on the etching barrier layer pattern having an etching barrier function to the light semitransparent film, and the light etching function. And a light absorbing layer pattern having a two-layer structure. Thus, in the light shielding film having the three-layer structure described above, the light shielding film pattern is formed by using the pattern formed by etching the hard mask layer instead of the resist pattern when the light absorption layer is etched. It is because it can be formed. As a result, it is because it becomes easy to form the fine pattern of the said light shielding film pattern. Then, the range of selection of the material of the layer having a light absorbing function is broadened, and the film thickness of the light shielding film pattern can be made thinner. In addition, since the light absorbing layer pattern and the etching barrier layer pattern can be respectively etched by different reactive etching gases, the light transmitting film is damaged when the light absorbing layer is etched. It is because it can be made to have an etching barrier function which suitably prevents being given.

  The configuration of the light shielding film pattern in the present invention is the same as that described in the above "A. mask blanks 1. members of mask blanks (3) light shielding film" except for the points described above and the point that the pattern is formed. It is the same as the configuration of the light shielding film in the invention. Therefore, the description here is omitted.

(4) Other members The phase shift mask of the present invention is not particularly limited as long as it has the above-mentioned semipermeable film pattern and transparent substrate, and other necessary members can be appropriately added. .

  The other members in the present invention are the same as the other members in the present invention described in the section “A. Mask blanks 1. members of mask blanks (4) other members”. Therefore, the description here is omitted.

2. Next, the configuration of the phase shift mask of the present invention will be described. In the phase shift mask of the present invention, the light transflective film pattern is formed on the transparent substrate. Hereinafter, the structure and manufacturing method of the phase shift mask of this invention are demonstrated.

Configuration of phase shift mask The configuration of the phase shift mask of the present invention is the same as the configuration of the mask blank of the present invention described in the above "A. Mask blanks 2. Configuration of mask blanks (1) Configuration of mask blanks". is there. Therefore, the description here is omitted.

(2) Method of Manufacturing Phase Shift Mask The method of manufacturing a phase shift mask of the present invention is not particularly limited as long as it can obtain a desired phase shift mask. In an example of a method of manufacturing a phase shift mask, first, a mask blank having the above-mentioned light shielding film is prepared as a mask blank of the present invention. Next, an electron beam resist is coated on the light shielding film, pattern exposure is performed by an electron beam drawing apparatus, and development is performed using a developer dedicated to the resist to form a resist pattern having a desired shape. Next, the light shielding film is dry etched using a desired gas with a dry etching apparatus using the resist pattern of the desired shape as a mask, to process the light shielding film into the shape of a light semitransparent film pattern described later. Next, using the light shielding film processed into the shape of a light transmitting film pattern described later as a mask, the light transmitting film is dry etched to form a light transmitting film pattern. Next, an electron beam resist is coated on the light shielding film processed into the shape of the light semitransparent film pattern, pattern exposure is performed by an electron beam drawing apparatus, and development is performed by a resist solution dedicated to resist, and a resist pattern of a desired shape Form Next, the light shielding film processed into the shape of the light semitransparent film pattern is dry etched using a desired gas with a dry etching apparatus using the resist pattern of the desired shape as a mask, to form a light shielding film pattern. Thereby, the phase shift mask of the present invention is obtained.

D. Next, a method of manufacturing a patterned body of the present invention will be described. The method for producing a patterned body according to the present invention is a method for producing a patterned body using a phase shift mask formed from the mask blank according to the present invention, wherein a resist pattern is formed by negative tone development using the phase shift mask. And the step of forming

  FIG. 8 is a schematic process view showing an example of a method for producing a patterned body using the phase shift mask of the present invention. In the method for producing a patterned body using the phase shift mask according to the present invention, first, a positive resist composition is applied directly on the substrate to be processed 301 or via the intermediate intervening layer 302 to form a resist film 303 (see FIG. 8 (a). Next, the resist film 303 is exposed using the phase shift mask 200 having the transparent substrate 201 and the light transflective film pattern 202 formed from the mask blank of the present invention (FIG. 8 (b)). Next, the exposed resist film 303 is developed with an organic solvent to form a resist pattern 403 in which the unexposed portion 303a of the resist film 303 is dissolved and removed (FIG. 8C). Thereby, using the phase shift mask 200, a resist pattern 403 is formed by negative tone development.

  For example, in the case of transferring a contact hole to a wafer by using a halftone phase shift mask having a light transflective film by positive tone development, the edge of the contact hole is sharpened by phase effect can do. However, as the distance from the contact hole edge increases, the phase effect decreases. For this reason, even in the part where the exposure light is to be blocked in the light semi-transmissive film, the exposure light is transmitted, which may cause a side lobe phenomenon in which the resist film other than the part where the contact hole is formed is exposed. Then, as a method of preventing such a side lobe phenomenon, there is a method of providing a light shielding film on the light transflective film so that the exposure light is not transmitted in a portion where the exposure light is to be shielded. However, in this method, in order to prevent the side lobe phenomenon while maintaining the phase effect at the edge of the contact hole, it is necessary to dispose the light shielding film at a predetermined distance from the edge of the contact hole. Specifically, after performing the optical proximity correction (OPC processing), it is necessary to arrange the light shielding film at an accurate position based on a certain rule. For this reason, complicated data processing has to be performed, and it has been difficult to manufacture a halftone phase shift mask.

  On the other hand, when a contact hole is transferred to a wafer, for example, by using a halftone phase shift mask having a light transflective film by negative tone development, the resist composition of a portion to which exposure light is irradiated Things become difficult to dissolve. Therefore, in the halftone phase shift mask, the portion corresponding to the contact hole is a light shielding portion that shields the exposure light formed of the light semitransparent film. And, the size of the light shielding portion is only several tens nm in size on the wafer. Therefore, even if the exposure light passes through the light shielding portion in the portion corresponding to the contact hole, the exposure light interferes and cancels out due to the phase effect at the edge, and the intensity of the exposure light becomes zero. Therefore, the resist composition in the portion where the exposure light is to be blocked by the light blocking portion is not exposed. Therefore, it is possible to easily manufacture a halftone phase shift mask capable of transferring the contact holes to the wafer while easily avoiding the side lobe phenomenon as described above.

  According to the present invention, the light transflective film has a light transmittance in the range of 3% to 40%, and the range in which the light transmittance can be realized becomes wider than before. Therefore, in negative tone development, it is possible to further increase the phase effect at the edge of the light shielding portion in a portion corresponding to a minute pattern such as a contact hole. Thus, it is possible to transfer a fine pattern such as a contact hole to the wafer more easily than in the prior art by negative tone development.

  In the present invention, the resist composition used to form a resist pattern is not particularly limited as long as the resist pattern can be formed by negative tone development. The resist composition used to form a resist pattern may be either a positive resist composition or a negative resist composition, but a positive resist composition is preferred. This is because the positive resist composition has higher resolution than the negative resist composition.

  The positive resist composition is not particularly limited, and examples thereof include TOK 6063 manufactured by Tokyo Ohka Kogyo Co., Ltd.

  Furthermore, when using a positive resist composition, the exposed portion is reacted with the organic solvent by developing the positive resist composition with an organic solvent to reduce its dissolution rate, and the unexposed portion is dissolved and removed. Form a resist pattern.

  The present invention is not limited to the above embodiment. The above embodiment is an exemplification, and it has substantially the same configuration as the technical idea described in the claims of the present invention, and any one having the same function and effect can be used. It is included in the technical scope of the invention.

  Hereinafter, the present invention will be more specifically described using examples and comparative examples.

Example 1
First 6 inches angles optically polished, on 0.25 inches thick transparent synthetic quartz substrate (transparent substrate), using a parallel plate type DC magnetron sputtering apparatus, constituting the light semi-transmitting film Si _z N _1- The composition ratio of Si _z N _1-z is desired by using silicon (Si) as the target and adjusting the nitrogen gas inflow conditions with a layer consisting of _z (z satisfies 0 <z <1) The film is formed by sputtering under the film forming conditions such that the ratio of

Next, using a parallel plate type DC magnetron sputtering apparatus on a layer made of Si _z N _1-z , Si _x O _1-x-y N _y (where x and y are 0) constituting a light semitransparent film The layer consisting of <x <1, 0 <y <1, and 0 <x + y <1 is treated with silicon (Si) as a target by adjusting the inflow conditions of nitrogen gas and oxygen gas. A film is formed by sputtering under film forming conditions such that the composition ratio of _x O _1-x-y N _y is a desired ratio.

The composition ratio of the layer formed of Si _z N _1-z and the layer formed of Si _x O _1-x-y N _y is an X-ray photoelectron spectrometer (XPS: Xray Photoelectron Spectroscopy, ULVAC-PHI, Inc. It can be determined from the spectrum analysis of photoelectron binding energy of Al2p using Quantum 2000).

Thus, the layer composed of Si _z N _1-z and the layer composed of Si _x O _1-x-y N _y are laminated in this order from the transparent substrate side (Qz side), and the Qz side layer is Si a layer consisting of _z N _1-z, a semi-transmission film is a layer vacuum side layer is made of _{Si x O 1-x-y} N y, the light transmittance at the wavelength of the Ar-F excimer laser exposure light It is possible to obtain a semitransparent film having a ratio of 30.2% and a total film thickness of 59 nm.

  Next, a light shielding film is formed on the light semitransparent film by sputtering using a parallel plate type DC magnetron sputtering apparatus. Thereby, mask blanks can be produced. By using Cr as a target and adjusting the film forming conditions, a light shielding film of a desired composition is formed. As a result, it is possible to obtain a light shielding film in which the optical density (OD value) at the wavelength of Ar-F excimer laser exposure light is adjusted to a desired optical density (OD value) in combination with the light transflective film.

  Next, an electron beam resist is coated on the light shielding film, pattern exposure is performed by an electron beam drawing apparatus, and development is performed using a developer exclusively used for the resist to form a resist pattern having a desired shape. Next, the light shielding film is dry etched using a chlorine-based gas by a dry etching apparatus using the resist pattern of the desired shape as a mask, and the light shielding film is processed into the shape of a light semitransparent film pattern described later.

  Next, using the light-shielding film processed into the shape of the light-semitransmissive film pattern described later as a mask, the light-semitransmissive film is dry-etched using a fluorine-based gas by a dry etching apparatus to form the light-semitransmissive film pattern Do. Next, an electron beam resist is applied on the light shielding film processed into the shape of the light semitransparent film pattern, pattern exposure is performed by an electron beam drawing apparatus, and development is performed with a resist solution dedicated to resist, thereby forming a resist pattern of a desired shape. Form. Next, the light shielding film processed into the shape of the semipermeable film pattern is dry etched using a chlorine-based gas by a dry etching apparatus using the resist pattern of the desired shape as a mask, to form a light shielding film pattern. Thereby, a phase shift mask can be produced.

Example 2
First, in the same manner as in Example 1, a semitransparent film is formed. Thus, a layer made of Si _z N _1-z and a layer made of Si _x O _1-x-y N _y are laminated in this order from the transparent substrate side (Qz side), and the Qz side layer is made of Si _z A light transflective film which is a layer consisting of N _1-z and whose vacuum side layer is a layer consisting of Si _x O _1-x-y N _y , the light transmittance at the wavelength of Ar-F excimer laser exposure light Is 35.7%, and a total thickness of 60 nm can be obtained.

  Next, as in the first embodiment, a light shielding film is formed on the light semitransparent film by sputtering. Thereby, mask blanks can be produced. Next, as in the first embodiment, a light semi-transmissive film pattern and a light shielding film pattern are formed. Thereby, a phase shift mask can be produced.

[Example 3]
First, in the same manner as in Example 1, a semitransparent film is formed. Thus, a layer made of Si _z N _1-z and a layer made of Si _x O _1-x-y N _y are laminated in this order from the transparent substrate side (Qz side), and the Qz side layer is made of Si _z A light transflective film which is a layer consisting of N _1-z and whose vacuum side layer is a layer consisting of Si _x O _1-x-y N _y , the light transmittance at the wavelength of Ar-F excimer laser exposure light Is 35.2%, and a total thickness of 60 nm can be obtained.

  Next, as in the first embodiment, a light shielding film is formed on the light semitransparent film by sputtering. Thereby, mask blanks can be produced. Next, as in the first embodiment, a light semi-transmissive film pattern and a light shielding film pattern are formed. Thereby, a phase shift mask can be produced.

Example 4
First, in the same manner as in Example 1, a semitransparent film is formed. Thus, a layer made of Si _z N _1-z and a layer made of Si _x O _1-x-y N _y are laminated in this order from the transparent substrate side (Qz side), and the Qz side layer is made of Si _z A light transflective film which is a layer consisting of N _1-z and whose vacuum side layer is a layer consisting of Si _x O _1-x-y N _y , the light transmittance at the wavelength of Ar-F excimer laser exposure light Is 5.4%, and a total thickness of 60 nm can be obtained.

  Next, as in the first embodiment, a light shielding film is formed on the light semitransparent film by sputtering. Thereby, mask blanks can be produced. Next, as in the first embodiment, a light semi-transmissive film pattern and a light shielding film pattern are formed. Thereby, a phase shift mask can be produced.

[Example 5]
First, in the same manner as in Example 1, a semitransparent film is formed. Thus, a layer made of Si _z N _1-z and a layer made of Si _x O _1-x-y N _y are laminated in this order from the transparent substrate side (Qz side), and the Qz side layer is made of Si _z A light transflective film which is a layer consisting of N _1-z and whose vacuum side layer is a layer consisting of Si _x O _1-x-y N _y , the light transmittance at the wavelength of Ar-F excimer laser exposure light Is 5.3%, and a total thickness of 60 nm can be obtained.

  Next, as in the first embodiment, a light shielding film is formed on the light semitransparent film by sputtering. Thereby, mask blanks can be produced. Next, as in the first embodiment, a light semi-transmissive film pattern and a light shielding film pattern are formed. Thereby, a phase shift mask can be produced.

[Example 6]
First, in the same manner as in Example 1, a semitransparent film is formed. Thus, a layer made of Si _z N _1-z and a layer made of Si _x O _1-x-y N _y are laminated in this order from the transparent substrate side (Qz side), and the Qz side layer is made of Si _z A light transflective film which is a layer consisting of N _1-z and whose vacuum side layer is a layer consisting of Si _x O _1-x-y N _y , the light transmittance at the wavelength of Ar-F excimer laser exposure light Is 35.7%, and a total thickness of 57 nm can be obtained.

  Next, as in the first embodiment, a light shielding film is formed on the light semitransparent film by sputtering. Thereby, mask blanks can be produced. Next, as in the first embodiment, a light semi-transmissive film pattern and a light shielding film pattern are formed. Thereby, a phase shift mask can be produced.

[Example 7]
First, in the same manner as in Example 1, a semitransparent film is formed. Thus, a layer made of Si _z N _1-z and a layer made of Si _x O _1-x-y N _y are laminated in this order from the transparent substrate side (Qz side), and the Qz side layer is made of Si _z A light transflective film which is a layer consisting of N _1-z and whose vacuum side layer is a layer consisting of Si _x O _1-x-y N _y , the light transmittance at the wavelength of Ar-F excimer laser exposure light Is 3.8%, and a total thickness of 67 nm can be obtained.

  Next, as in the first embodiment, a light shielding film is formed on the light semitransparent film by sputtering. Thereby, mask blanks can be produced. Next, as in the first embodiment, a light semi-transmissive film pattern and a light shielding film pattern are formed. Thereby, a phase shift mask can be produced.

[Example 8]
First, in the same manner as in Example 1, a semitransparent film is formed. Thus, a layer composed of Si _x O _1-x-y N _y and a layer composed of Si _z N _1-z are stacked in this order from the transparent substrate side (Qz side), and the Qz side layer is Si _x A light transflective film which is a layer consisting of O _{1 -x-y} N _y and the vacuum side layer is a layer consisting of _Siz N _1-z , and the light transmittance at the wavelength of Ar-F excimer laser exposure light Is 32.5%, and a total thickness of 58 nm can be obtained.

  Next, as in the first embodiment, a light shielding film is formed on the light semitransparent film by sputtering. Thereby, mask blanks can be produced. Next, as in the first embodiment, a light semi-transmissive film pattern and a light shielding film pattern are formed. Thereby, a phase shift mask can be produced.

[Example 9]
First, in the same manner as in Example 1, a semitransparent film is formed. Thus, a layer composed of Si _x O _1-x-y N _y and a layer composed of Si _z N _1-z are stacked in this order from the transparent substrate side (Qz side), and the Qz side layer is Si _x A light transflective film which is a layer consisting of O _{1 -x-y} N _y and the vacuum side layer is a layer consisting of _Siz N _1-z , and the light transmittance at the wavelength of Ar-F excimer laser exposure light Is 3.7%, and a total thickness of 67 nm can be obtained.

  Next, as in the first embodiment, a light shielding film is formed on the light semitransparent film by sputtering. Thereby, mask blanks can be produced. Next, as in the first embodiment, a light semi-transmissive film pattern and a light shielding film pattern are formed. Thereby, a phase shift mask can be produced.

[Example 10]
First, in the same manner as in Example 1, a semitransparent film is formed. Thus, a layer made of Si _z N _1-z and a layer made of Si _x O _1-x-y N _y are laminated in this order from the transparent substrate side (Qz side), and the Qz side layer is made of Si _z A light transflective film which is a layer consisting of N _1-z and whose vacuum side layer is a layer consisting of Si _x O _1-x-y N _y , the light transmittance at the wavelength of Ar-F excimer laser exposure light Is 36.4%, and a total thickness of 53 nm can be obtained.

  Next, as in the first embodiment, a light shielding film is formed on the light semitransparent film by sputtering. Thereby, mask blanks can be produced. Next, as in the first embodiment, a light semi-transmissive film pattern and a light shielding film pattern are formed. Thereby, a phase shift mask can be produced.

[Example 11]
First, in the same manner as in Example 1, a semitransparent film is formed. Thus, a layer made of Si _z N _1-z and a layer made of Si _x O _1-x-y N _y are laminated in this order from the transparent substrate side (Qz side), and the Qz side layer is made of Si _z A light transflective film which is a layer consisting of N _1-z and whose vacuum side layer is a layer consisting of Si _x O _1-x-y N _y , the light transmittance at the wavelength of Ar-F excimer laser exposure light Is 3.3%, and a total thickness of 70 nm can be obtained.

  Next, as in the first embodiment, a light shielding film is formed on the light semitransparent film by sputtering. Thereby, mask blanks can be produced. Next, as in the first embodiment, a light semi-transmissive film pattern and a light shielding film pattern are formed. Thereby, a phase shift mask can be produced.

[Example 12]
First, in the same manner as in Example 1, a semitransparent film is formed. Thus, a layer composed of Si _x O _1-x-y N _y and a layer composed of Si _z N _1-z are stacked in this order from the transparent substrate side (Qz side), and the Qz side layer is Si _x A light transflective film which is a layer consisting of O _{1 -x-y} N _y and the vacuum side layer is a layer consisting of _Siz N _1-z , and the light transmittance at the wavelength of Ar-F excimer laser exposure light Is 33%, and a total thickness of 56 nm can be obtained.

  Next, as in the first embodiment, a light shielding film is formed on the light semitransparent film by sputtering. Thereby, mask blanks can be produced. Next, as in the first embodiment, a light semi-transmissive film pattern and a light shielding film pattern are formed. Thereby, a phase shift mask can be produced.

[Example 13]
First, in the same manner as in Example 1, a semitransparent film is formed. Thus, a layer composed of Si _x O _1-x-y N _y and a layer composed of Si _z N _1-z are stacked in this order from the transparent substrate side (Qz side), and the Qz side layer is Si _x A light transflective film which is a layer consisting of O _{1 -x-y} N _y and the vacuum side layer is a layer consisting of _Siz N _1-z , and the light transmittance at the wavelength of Ar-F excimer laser exposure light Is 3.2%, and a total thickness of 70 nm can be obtained.

  Next, as in the first embodiment, a light shielding film is formed on the light semitransparent film by sputtering. Thereby, mask blanks can be produced. Next, as in the first embodiment, a light semi-transmissive film pattern and a light shielding film pattern are formed. Thereby, a phase shift mask can be produced.

Comparative Example 1
First, on a transparent synthetic quartz substrate (transparent substrate) of 6 inch square and 0.25 inch thickness optically polished, using a parallel plate type DC magnetron sputtering device, a light transflective film, Mo, silicon as a target By adjusting the gas inflow conditions using (Si), a film is formed by sputtering under film forming conditions such that the composition ratio becomes a desired ratio.

  As a result, it is possible to obtain a light transflective film having a light transmittance of 6% at the wavelength of Ar-F excimer laser exposure light and a film thickness of 68 nm.

  Next, as in the first embodiment, a light shielding film is formed on the light semitransparent film by sputtering. Thereby, mask blanks can be produced. Next, as in the first embodiment, a light semi-transmissive film pattern and a light shielding film pattern are formed. Thereby, a phase shift mask can be produced.

  In Examples 1 to 13 above, it is assumed that the light shielding film is a film of a single Cr-based film, but as shown in FIGS. 3 and 4, the light shielding film is a plurality of films such as two or three layers. In some cases, the same phase shift mask as described above can be produced by appropriately selecting the etching gas, etching conditions, and the like so as to etch the respective films.

[Evaluation 1]
The phase shift masks of Examples 1 to 13 and Comparative Example 1 can be manufactured. In this case, the materials, compositions, etc. of the layers constituting the light transflective film of the phase shift mask are appropriately selected, and the refractive index (n) and extinction coefficient (k The light transflective films of Examples 1 to 13 which are constituted by laminating a layer consisting of Si _z N _1-z and a layer consisting of Si _x O _1-x-y N _y , shown in Table 1 below. The light transflective film of Comparative Example 1 having the refractive index (n) and the extinction coefficient (k) is formed. Table 1 below shows the Qz-side layer and the vacuum-side layer in the light transflective films of Examples 1 to 13.

In addition, the film thickness of the layer composed of Si _z N _1-z and the layer composed of Si _x O _1-x-y N _y constituting the light semi-transmissive film of Example 1 and the light semi-transmissive film of Comparative Example 1 The film thickness is assumed to be the film thickness (d) shown in Table 1 below. The film thickness (d) shown in Table 1 below is a half of the transparent substrate in which the light semitransparent film remains with ArF excimer laser exposure light having a wavelength of 193 nm which passes through the transparent region from which the light semitransparent film is removed. To obtain a desired phase difference between the ArF excimer laser exposure light passing through the transmission region, and to obtain a desired light transmittance of the light semitransmissive film of Example 1 and the light semitransmissive film of Comparative Example 1 To the selected film thickness. In Table 1 below, for Examples 1 to 13 and Comparative Example 1, ArF excimer laser exposure light having a wavelength of 193 nm passing through the transmission area and ArF excimer laser exposure light passing through the semi-transmission area are used. The phase differences obtained between are indicated.

  Furthermore, from the refractive index (n) and the extinction coefficient (k) shown in Table 1 below, and the film thickness (d) of each layer constituting the light semipermeable film, the light semitransparent films of Examples 1 to 13 and The results of calculation of the light transmittance (trans) of the light semipermeable film of Comparative Example 1 are shown in Table 1 below. When the maximum value (max EL) of the exposure latitude and the maximum value (max DoF) of the focus latitude of the phase shift mask of Comparative Example 1 are calculated, the maximum value (max EL) of the exposure margin is 7.69%. The maximum focus latitude (max DoF) is 0.047 μm. The light transmittance (trans), the maximum exposure latitude (max EL), and the maximum focus latitude (max DoF) are calculated using the EM-Suite made by Panoramic according to the following simulation evaluation conditions. It is determined by

<Simulation evaluation conditions>
・ NA: 1.35
Sigma: c-quad 0.95 / 0.80-30 deg
・ Polarization: X / Y
Target: 60 nm HOLE (NTD)
・ Pitch: 180, 240, 300 nm

[Evaluation 2]
FIG. 9 is a graph showing the simulation result of the OPC bias value corresponding to the light transmittance. FIG. 9 is a graph in which the horizontal axis represents the light transmittance of the light transflective film, and the vertical axis represents the OPC bias value, for the phase shift masks of 180 nm, 240 nm, and 300 nm, respectively.

  From FIG. 9, in the illumination system suitable for 1x node, the OPC bias value of the phase shift mask in which the light transmittance of the light semi-transmissive film is 30%, the phase shift in which the light transmittance of the light semi-transmissive film is 6% It can be seen that it is smaller than the mask. In addition, it can be seen that the higher the light transmittance of the light transflective film, the smaller the OPC bias value. From these facts, the OPC bias value of the phase shift mask in which the light transmittance of the light transflective film of Example 1 is 30.2%, and the light transmittance of the light transflective film of Comparative Example 1 is 6%. It is presumed that it is smaller than the phase shift mask.

[Evaluation 3]
FIGS. 10-1 to 10-3 are graphs showing the relationship between the focus margin and the exposure margin at the time of pattern transfer in the phase shift mask, as a result of simulation. In FIG. 10-1 to FIG. 10-3, the horizontal axis represents the focus latitude (DoF: Depth of Focus), and the vertical axis represents the exposure latitude (for the HOLE pitch of 180 nm, 240 nm, and 300 nm), respectively. The graph shows EL: Exposure Latitude. Further, in FIGS. 10-1 to 10-3, phase shift masks in which the light transmittance of the light semitransmissive film is 3%, 6%, 15%, 20%, 25%, 30%, and 38%. , Showed a graph. Furthermore, Table 2 shows EL (%) when DoF is 0 nm, and Table 3 shows DoF (nm) when EL is 10%.

  From FIG. 10-1, Table 2 and Table 3, when the pitch is 180 nm, the EL in the case of Do nm of 0 nm has a calculation result of light transmittance of 30% and a calculation result of light transmittance of 6%. It is understood that the DoF in the case where the EL is 10% is about 37% larger than the calculation result of the light transmittance of 30% is about 37% larger than the calculation result of the light transmittance of 6%. Further, from FIG. 10B, Table 2 and Table 3, even in the case where the pitch is 240 nm, the EL in the case where DoF is 0 nm has a light transmittance of 6% in the calculation result of the light transmittance of 30%. It can be seen that the calculation result of the light transmittance of 30% is 31% larger than the calculation result of the light transmittance of 6%, which is 42% larger than the calculation result and the EL is 10%. Further, from FIG. 10-3, Table 2, and Table 3, even when the pitch is 300 nm, the EL in the case of Do nm of 0 nm has a light transmittance of 6% in the calculation result of the light transmittance of 30%. It can be seen that the calculation result of the light transmittance of 30% is 40% larger than the calculation result of the light transmittance of 6%, which is 42% larger than the calculation result and the EL is 10%.

  Therefore, it can be seen that the calculation result of the light transmittance of 30% is higher in both DoF and EL than the calculation result of the light transmittance of 6%. It can also be seen that the higher the light transmittance of the light transflective film, the higher both DoF and EL. From these facts, both DoF and EL of the phase shift mask in which the light transmissivity of the light transflective film of Example 1 is 30.2%, the light transmittance of the light transflective film of Comparative Example 1 is 6%. It is surmised that it is higher than the phase shift mask.

[Evaluation 4]
FIG. 11 is a graph showing the contrast of a wafer transfer space optical image, calculated on the assumption of a phase shift mask in which the light transmittance of the light semitransparent film is 6% to 38%. In FIG. 11, the horizontal axis represents the pitch of the pattern formed on the wafer, and the vertical axis represents the image contrast. In FIG. 11, the wafer transfer space is calculated assuming a phase shift mask in which the light transmittance of the light semitransmissive film is 3%, 6%, 15%, 20%, 25%, 30%, and 38%. The graph which showed the contrast of the optical image was shown.

  It can be seen from FIG. 11 that at each of the pitches of the patterns formed on the wafer, the calculation result of the light transmittance of 30% is larger in image contrast than the calculation result of the light transmittance of 6%. In addition, it can be seen that, at each of the pitches of the patterns formed on the wafer, the image shift is greater as the phase shift mask has a higher light transmittance of the light transflective film. That is, since the image contrast is large, it is shown that the amount of change in the dimension of the pattern formed on the wafer may be small (EL is large) even if the amount of exposure changes (the slice level changes in the aerial image). There is. From these facts, in each of the pitches of the pattern formed on the wafer, the phase shift mask in which the light transmittance of the light semitransmissive film of Example 1 is 30.2% is the light transmissivity of Comparative Example 1. It is presumed that the image contrast is larger than that of a phase shift mask in which the light transmittance of the film is 6%.

[Evaluation 5]
FIG. 12 is a graph showing an OPC bias calculated on the assumption of a phase shift mask in which the light transmittance of the light semi-transmissive film is 6% to 38%. In FIG. 12, the horizontal axis represents the pitch of the pattern formed on the wafer, and the vertical axis represents the pattern dimension (CD) of the phase shift mask with the OPC bias. In FIG. 12, the OPC bias is calculated on the assumption of phase shift masks in which the light transmittance of the light semi-transmissive film is 3%, 6%, 15%, 20%, 25%, 30%, and 38%. The graph is shown.

  From FIG. 12, it can be seen that, in each of the pitches of the patterns formed on the wafer, as the phase shift mask with the higher light transmittance of the light transflective film, the pattern dimension of the mask with the OPC bias becomes smaller. In particular, in each of the pitches of the pattern formed on the wafer, the phase shift mask in which the light transmittance of the light semi-transmissive film is 6% in the case of the phase shift mask in which the light transmittance of the light semi-transmissive film is 30%. It can be seen that the pattern size of the mask with the OPC bias is smaller than that. In other words, it is shown that since the smaller OPC bias allows a finer pattern to be formed on the wafer, the degree of freedom in designing the pattern to be formed on the wafer is increased. Further, from these facts, in each of the pitches of the patterns formed on the wafer, the phase shift mask having the light transmissivity of 30.2% of the light semitransmissive film of Example 1 is the light of Comparative Example 1 It is surmised that the pattern dimension of the mask with the OPC bias is smaller than that of the phase shift mask in which the light transmittance of the semi-transmissive film is 6%.

100 ... mask blanks, 101 ... transparent substrate, 102 ... light transflective film, 102a ... a layer formed of Si _x O _{1 -x-y} N _y 102b ... Si _z N _1- layer consisting of _z , 103 ... light shielding film, 110 ... mask blanks with negative resist film, 200 ... phase shift mask, 201 ... transparent substrate, 202 ... light semitransparent film pattern

Claims (19)

A mask blank used to manufacture a halftone phase shift mask to which ArF excimer laser exposure light is applied,
A transparent substrate, is formed on the transparent _{substrate, Si x O 1-x-} y N y (x and y, 0 <x <1,0 <y <1, and 0 satisfies <x + y <1) Tona is, the range in der Ru layer having a refractive index at the wavelength of ArF excimer laser exposure light 2.4 to 2.5, and _Si z _{N 1-z} (z satisfies the 0 <z <1) Tona is, anda light semi-transmissive film composed of a layer refractive index is Ru der range of 2.5 to 2.7 is stacked in random order at the wavelength of ArF excimer laser exposure light,
The light transflective film is characterized in that the light transmittance at the wavelength of ArF excimer laser exposure light is in the range of 5.3% to 36.4% , and the film thickness is in the range of 50 nm to 60 nm. Mask blanks. The light transflective film is configured by layering the layer made of Si _z N _1-z and the layer made of Si _x O _1-x-y N _{y in} this order from the transparent substrate side. The mask blank according to claim 1, characterized in that   The mask blank according to claim 1, wherein the light transflective film is formed directly on the transparent substrate.   A light shielding film which is formed on the light semitransparent film and adjusted so that the optical density (OD value) at the wavelength of ArF excimer laser exposure light becomes a desired optical density (OD value) in combination with the light semitransparent film The mask blank according to any one of claims 1 to 3, further comprising:   The light shielding film is formed on the light transflective film, and has a single layer structure including a light absorbing layer having an etching barrier function to the light transflective film and a light absorbing function to ArF excimer laser exposure light. The mask blanks according to claim 4.   The light shielding film is formed on the light transflective film, and is formed on a light absorbing layer having an etching barrier function to the light transflective film and a light absorbing function to ArF excimer laser exposure light, and the light absorbing layer. 5. The mask blank according to claim 4, having a two-layer structure including a hard mask layer having an etching mask function for the light absorption layer.   The light shielding film is formed on the light semitransparent film, an etching barrier layer having an etching barrier function to the light semitransparent film, and the light shielding film formed on the etching barrier layer and having a light absorbing function for ArF excimer laser exposure light 5. The mask blank according to claim 4, having a three-layer structure including a light absorbing layer having the above-mentioned structure and a hard mask layer formed on the light absorbing layer and having an etching mask function to the light absorbing layer. .   The mask blank according to claim 7, wherein the light absorption layer is made of silicon (Si) alone.   5. The light shielding film according to claim 4, wherein an optical density (OD value) at a wavelength of ArF excimer laser exposure light is adjusted to 3.0 or more in combination with the light semitransparent film. A mask blank according to any of the preceding claims.   A mask blank with negative resist film comprising: the mask blank according to any one of claims 1 to 9; and a negative resist film formed on the mask blank. A halftone phase shift mask to which ArF excimer laser exposure light is applied,
A transparent substrate, is formed on the transparent _{substrate, Si x O 1-x-} y N y (x and y, 0 <x <1,0 <y <1, and 0 satisfies <x + y <1) Tona is, the layer refractive index n Ru der range of 2.4 to 2.5, and _Si z _{n 1-z} (z is 0 <satisfies z <1) Tona is, the refractive index n but has a configured light semi-transmitting film pattern range der Ru layer of 2.5 to 2.7 is stacked in random order,
The light transflective film pattern is characterized in that the light transmittance at the wavelength of ArF excimer laser exposure light is in the range of 5.3% to 36.4% , and the film thickness is in the range of 50 nm to 60 nm. Phase shift mask. The light semi-transmitting film pattern is constituted the layers of _{Si z N 1-z,} and a layer composed of the _{Si x O 1-x-y} N y is, are laminated in this order from the transparent substrate side The phase shift mask according to claim 11, characterized in that:   The phase shift mask of claim 11, wherein the light transflective film pattern is formed directly on the transparent substrate.   The optical density (OD value) at the wavelength of ArF excimer laser exposure light is adjusted to a desired optical density (OD value) in combination with the optical semitransparent film pattern, which is formed on the optical semitransparent film pattern. The phase shift mask according to any one of claims 11 to 13, further comprising a light shielding film pattern.   The light blocking film pattern is formed on the light transflective film pattern, and has a single layer structure including a light absorbing layer pattern having an etching barrier function to the light transflective film pattern and a light absorbing function to ArF excimer laser exposure light. The phase shift mask according to claim 14, characterized in that:   The light blocking film pattern is formed on the light transflective film pattern, an etching barrier layer pattern having an etching barrier function to the light transflective film pattern, and the etching barrier layer pattern, and ArF excimer laser exposure light The phase shift mask according to claim 14, having a two-layer structure including a light absorption layer pattern having a light absorption function with respect to.   The phase shift mask of claim 16, wherein the light absorption layer pattern is made of silicon (Si) alone.   The light shielding film pattern is adjusted such that an optical density (OD value) at a wavelength of ArF excimer laser exposure light is 3.0 or more in combination with the light semitransparent film pattern. The phase shift mask according to any one of claims 14 to 17. A method for producing a patterned body using a phase shift mask formed from mask blanks according to any one of claims 1 to 9,
A method for producing a patterned product, comprising the step of forming a resist pattern by negative tone development using the phase shift mask.