KR100276047B1 - Resist pattern forming method and thin film forming method - Google Patents

Abstract

A method for discovering the best condition of an antireflective film when forming a resist pattern in exposure under a single wavelength, a method of forming an antireflection film thereby, a method of forming a resist pattern using a novel antireflection film, and a thin film forming method that can be used for these To provide.

The best condition of the antireflection film is determined by the following means, and an antireflection film is formed. Further, by this means, an appropriate antireflection film is found and used for resist pattern formation. (I) Preparation of contours of the amount of absorbed light using the optical conditions of the antireflection film as a parameter for photoresist of any film thickness, (II) Operation similar to (I) in which a plurality of resist film thicknesses were obtained, and (III) each trace obtained Determination of the optical conditions of the antireflection film by finding a common region of the absorbed light amount with respect to the antireflection film, (IV) the change of the antireflection film conditions, and the determination of the optical conditions of the antireflection film subjected to the above operation, The best optical conditions such as the type of anti-reflection film, film thickness, and the like are found.

Description

Resist pattern formation method and thin film formation method

1 is a flowchart showing the configuration of an optimal condition determination method according to the present invention.

2 is a diagram showing standing wave effects.

FIG. 3 is a diagram showing a trajectory (contour of absorbed light amount) of the amount of absorbed light in the resist film when n _arl and k _arl are changed by fixing the film thickness of the antireflection film ARL to a certain resist film thickness.

4, 5, and 6 show trajectories (contours) for different resist film thicknesses.

7 shows standing wave effects to be solved.

Fig. 8 is a diagram showing the trajectory (contour of absorbed light amount) of the amount of absorbed light in the resist film with respect to the change in n _arl and k _arl with respect to the resist film thickness of 985 nm at the film thickness of the antireflection film at 30 nm.

Fig. 9 shows the trajectory (contour) for the resist film thickness of 1000 nm.

Fig. 10 shows the trajectory (contour) for the resist film thickness 1017.5 nm.

Fig. 11 shows the trajectory (contour) for the resist film thickness 1035 nm.

12 and 13 show standing wave effects under optimum conditions (Example 1).

Fig. 14 shows the relationship between the film thickness of the antireflection film and n as optical conditions.

Fig. 15 is a diagram showing the relationship between the film thickness of the antireflection film and k as optical conditions.

16 is an n and k chart for finding an optimal antireflection film material.

Fig. 17 is a diagram showing the antireflection effect of SiC (film thickness of 5 Onm) on W-Si in comparison with the case of comparison.

FIG. 18 is a diagram illustrating a problem of the prior art, showing the interference of light in the resist film.

19, 20 and 21 illustrate the problems of the prior art, showing the standing wave effect.

22 is a view for explaining the problems of the prior art, showing the effect of the step.

23, 24 and 25 show the influence of standing wave effects.

Fig. 26 is a graph showing the relationship between variation in absorbed light quantity and variation in pattern dimension.

FIG. 27 is a partial sectional view showing the structure of Example 7. FIG.

28 is a partial sectional view showing the structure of Example 14;

29 is a view showing a standing wave effect.

Fig. 30 is a diagram showing the trajectory (contour of absorption amount) of the change in absorption amount of the resist film with respect to the change in n _arl and k _arl with respect to the resist film thickness 982 nm in the case of the film thickness of the antireflection film at 30 nm.

Fig. 31 is a diagram showing the trajectory (contour line) for the resist film thickness of 1000 nm.

32 is a view showing the trajectory (contour line) for the resist film thickness of 1018 nm.

33 is a view showing the trajectory (contour) for the resist film thickness 1035 nm.

34 and 35 show standing wave effects in optimal conditions.

36 shows the relationship between the film thickness of the antireflection film and k as optical conditions.

Fig. 37 is a graph showing the deposition condition dependence of n and k values of the SiC film.

FIG. 38 shows the antireflection effect of SiC (film thickness of 20 nm) on Al, Al-Si, and Al-Si-Cu in comparison with the case of comparison.

Fig. 39 shows the antireflection effect of SiO (film thickness of 30 nm) on Al, Al-Si, and Al-Si-Cu in comparison with the case of comparison.

40 is a partial sectional view showing the structure of Example 34;

41 shows standing wave effects.

42 shows the antireflection effect of the SiC film (25 nm) on a silicon substrate in comparison with the case of comparison.

Fig. 43 is a diagram showing the antireflection effect of the SiO film (30 nm) on a silicon substrate in comparison with the case of comparison.

44 is a sectional view showing the structure of Example 43;

45 is a view showing the operation of SiO film formation by CVD.

FIG. 46 shows the antireflection effect of SiO (24 nm) on W-Si.

47 is a sectional view showing the structure of Example 53;

48 is a view showing the operation of Si _x O _y N _z film formation by CVD.

FIG. 49 shows the antireflection effect of Si _x O _y N _z (25 nm) on W-Si.

50 is a sectional view showing the structure of Example 65;

FIG. 51 shows Si _x O _y N _z and Si _x N _y optical constant characteristics; FIG.

FIG. 52 is a view showing standing wave effects under optimum conditions in Example 65; FIG.

53 is a sectional view showing the structure of Example 77;

54 is a diagram showing the antireflection effect of a Si _x O _y N _z film and a Si _x N _y film (32 nm) on Si.

55 is a diagram showing the antireflection effect of a Si _x O _y N _z film and a Si _x N _y film (100 nm) on Si.

56 shows Si _x O _y N _z and Si _x N _y optical constant characteristics.

FIG. 57 shows the antireflection effect of a Si _x O _y N _z film and a Si _x N _y film (33 nm) on a Si-based material. FIG.

FIG. 58 is an explanatory diagram of Example 9O and illustrates a relationship between a SiH ₄ / N ₂ O flow rate ratio and n, k values of SiO _x N _y formed; FIG.

FIG. 59 is an explanatory diagram of Example 90 and illustrates a relationship between a SiH ₄ / N ₂ O flow rate ratio and a Si, O, N, and H amount (RBS) in SiO _x N _y formed. FIG.

60 is an absorption spectrum diagram of the IR of the film formed in Example 90. FIG.

61 shows SiH ₄ / N ₂ O flow rate ratio range generally used.

62 to 66 show the antireflection effect in Example 90;

67 and 68 are explanatory views of the operation of the ninetieth embodiment.

* Explanation of symbols for main parts of the drawings

I to V condition determination means for antireflection film

ARL: Antireflection Film PR: Photoresist

S: Substrate

The present invention relates to a resist pattern forming method and a thin film forming method using a novel antireflection film. In particular, when the photoresist on the anti-reflection film formed on the material is exposed by a single wavelength to form a resist pattern, the reflection which determines the optical conditions such as the film thickness of the anti-reflection film and refractive index conditions such as the refractive index and the absorption refractive index A method for determining a protective film, a method for forming a reflective anti-reflective film using the method, a method for forming a resist pattern using a novel anti-reflective film, and a thin film forming method applicable to the formation of such an anti-reflective film. The present invention is, for example, in the case of setting an anti-reflection film formed to prevent the influence of standing wave effects when using photolithography technology when manufacturing an electronic material (semiconductor device, etc.), Moreover, it can use suitably for the case of resist pattern formation using the anti-reflective film at the time of using the photolithography technique.

For example, in the photolithography technique, the stepper (projection exposure machine) of the present stage uses KrF excimer laser light (248 nm) as a light source, and mounts the lens of about 0.37-0.42 NA (for example, Nikon NSR 1505 EX1, Canon FPA 4500). Using these steppers, research and development of design rule devices in the sub-half micron (0.5 µm or less) region has been studied.

Stepper uses a single wavelength of light for the exposure light source. It is widely known that when exposing at a single wavelength, a phenomenon called a standing wave effect occurs. The cause of standing waves is caused by light interference in the resist film. That is, as shown in Fig. 18, the incident light P and the reflected light R from the interface between the resist PR and the substrate S cause interference in the film of the resist RR.

As a result, as shown in FIG. 19, the amount of light absorbed by the resist (vertical axis) changes depending on the thickness of the resist film (horizontal axis). In the present specification, the amount of light absorbed by the resist refers to the amount of light absorbed by the resist itself except for surface reflection and, when present, absorption of the metal, amount of light emitted from the resist, and the like. This amount of absorbed light becomes energy for photoreacting the resist.

The degree of change in absorbed light amount also varies depending on the type of material substrate, as understood from the comparison between FIG. 20 and FIG. In FIG. 19, FIG. 20, and FIG. 21, all resists use XP8843 (Siprey), The material is Si, Al-Si, W-Si, respectively. That is, the degree of change in the amount of absorbed light is determined by the complex amplitude reflectance (R) in consideration of the multiple interferences determined according to the optical constants (n, k) of the material (substrate) and the optical constants (n, k) of the resist. ((R) denotes a vector amount having a real part and an imaginary part).

In the real device, as shown in FIG. 22, unevenness is always present on the substrate surface. For example, iron portions In such as poly Si are present. Therefore, when the resist PR is applied, the resist film thickness is different at the upper and lower portions of the step. That is, the resist film thickness dPR2 on the cut In is smaller than the resist film thickness dPR1 other than that. It is as described above that the standing wave effect differs depending on the thickness of the resist film, and therefore, the change in the amount of light absorbed by the resist also varies depending on the standing wave effect. As a result, the dimensions of the resist pattern obtained after exposure and development become different at the top and the bottom of the step.

The influence of the standing wave effect on the pattern dimension becomes more remarkable as the pattern becomes finer when the steppers of the same wavelength and the same opening are used. 23 to 25, Nikon NSR 1505 EX1 (used exposure light: lambda = 248 nm, KrF excimer, NA = O.42) was used as a resist, and the chemically amplified type of XP8843 (Siffray Microelectronics Co., Ltd.) was used as a resist. The effect of the standing wave effect in the case of using a resist or a polyvinylphenol-based resist containing a photoacid generator is shown for each pattern size. Obviously, the finer the pattern becomes, the more the standing wave effect becomes remarkable (see also the nonuniformity of the critical dimension shift CDShif of 0.5 占 퐉, 0.4 占 퐉, and 0.35 占 퐉 line-and-space pattern indicated by o in the figure).

This tendency is a phenomenon commonly seen with any kind of resist.

The dimensional accuracy of the resist pattern in the grape lithography step in manufacturing a device such as a semiconductor device is generally ± 5%. Although it is thought that the total furnace can be practical even if it exceeds + 5%, considering that nonuniformity due to focus or other factors also occurs, it is preferable to keep the pattern accuracy within this exposure ± 5%. In order to achieve the dimensional accuracy of +/- 5%, reduction of standing wave effects is essential.

FIG. 26 shows the dimensional variation (vertical axis) of the resist pattern with respect to the variation (horizontal axis) of the absorbed light amount in the resist film. From Fig. 26, it can be seen that, for example, in producing a 0.35 mu m rule device, the variation in the amount of absorbed light in the resist film is required to be in the range of 6% or less.

In order to meet the above-mentioned demand, the examination of the anti-reflective technology in each area is energetically performed now. However, even if the material of the material or the resist to be used is determined, it is not always easy to determine what the conditions of the antireflection film can be obtained in that case.

For example, in the pattern formation of a gate structure (for example, a W-Si film) in which an antireflection film is indispensable, the antireflection film having a variation in the amount of absorbed light in the resist film, for example, within a range of 6% or less What kind of condition is not decided. Naturally, no effective antireflection film material has been found on such W-Si.

As for the structure using this W-Si material as a gate, pattern formation is currently performed by the multilayer resist method or the die addition resist or the like. Therefore, it is considered necessary to establish an antireflection technology on W-Si as soon as possible.

In such a case, if any single wavelength is used as the exposure light source, and there is a means for determining the comprehensive conditions and specific conditions for the antireflection film for performing stable micropattern formation on any material (substrate), yes For example, it can be found what kind of antireflection film should be formed on W-Si as described above. However, such a technique has not been proposed yet.

This invention is made | formed in view of the said situation, When forming a resist pattern on arbitrary raw materials (substrate) using the light of arbitrary single wavelength as an exposure light source, even if the resist pattern is fine, it is a favorable stable resist An object of the present invention is to provide a method for determining an antireflection film that can determine a condition of an antireflection film used therein so that a pattern can be formed.

Another object of the present invention is to provide a method of forming an antireflection film under such conditions.

In addition, a novel antireflection film has been developed to provide a resist pattern forming method using such an antireflection film.

The invention of claim 1 of the present application achieves the above object, and a Si _x O _y N _z film having a refractive index n = 2.4 ± 0.6 and an absorption refractive index k = O.7 ± 0.2 as an antireflection film on a metal material. Or a resist pattern forming method characterized by using a Si _x N _y film, by which the above object is achieved.

The invention of claim 2 of the present application is a resist pattern forming method according to claim 1, wherein the metal-based material is made of a high melting point metal silicide, and the above object is achieved by this configuration.

The invention of claim 3 of the present application is to form a resist pattern by forming a Si _x O _y N _z film as an antireflection film on a metal material, wherein the resist pattern forming method achieves the above object by this configuration. will be.

The invention according to claim 4 of the present application is a method of forming a resist pattern according to claim 3, wherein the metal material is an aluminum material, and the above object is achieved by this configuration.

The invention of claim 5 of the present application is a resist pattern forming method, wherein a resist pattern is formed by forming a Si _x O _y N _z or Si _x N _y film as an antireflection film on a silicon-based material material. To achieve the above object.

The invention according to claim 6 of the present application is a resist pattern forming method according to claim 5, wherein the silicon-based material is any one of single crystal silicon, polycrystalline silicon, amorphous silicon, and doped polysilicon. To achieve.

The invention, as shown in Figure 1,

(I) The contour of the absorbed light quantity is determined for the photoresist of any film thickness arbitrarily determined by the optical conditions of the antireflection film (e.g., refractive index condition, reflection refractive index n, absorption refractive index k, etc.) Obtained by plotting Fig. 1 (I)),

(II) A plurality of resist film thicknesses were taken to obtain a contour of the hop light receiving amount as in (I) above, thereby obtaining a trace of the change in absorbed light amount with respect to the change in resist film thickness (FIG. 1 (II)),

(III) For each contour line obtained in the above-mentioned (II), a common area of the absorption amount is found, and the optical conditions of the antireflection film under the conditions specified in (I) are initially determined by optical conditions such as refractive index, which are manifested by this common area. Conditions (refractive index, etc.) (Fig. 1 (III)),

(IV) The optical conditions (refractive index, etc.) of the antireflection film are determined by changing the antireflection film conditions and performing the same operation as described above (Fig. 1 (IV)),

(V) According to the above (IV), the best optical conditions such as the best refractive index of the antireflection film under certain antireflection film conditions are found (Fig. 1 (V)).

With the above configuration, it is possible to obtain an optimum antireflection film condition, and to select a material suitable for such a condition, that is, satisfying or to some extent the condition, thereby forming an effective antireflection film.

For example, the refractive indices n and k at specific wavelengths (exposure wavelengths) are obtained by means of a spectroscopic ellipsoidal polarimeter, and a substance having such refractive indices n and k is found in existing materials to prevent antireflection materials. Or a material having such conditions can be synthesized to provide an antireflective material.

Next, a description will be given of a method for determining the comprehensive conditions of the antireflection film using the present invention with reference to the drawings.

(1) The resist film thickness between the maximum value and the minimum value of the standing wave effect is given by λ / 4n when the refractive index of the resist is n _PR and the exposure wavelength is λ (see Fig. 2).

(2) Assuming an antireflection film ARL between the resist and the substrate, the film thickness is d _arl and the optical constants are n _arl and k _arl .

(3) When attention is paid to the film thickness of any one point (for example, the film thickness at which the standing wave effect is maximized) in Fig. 2, the film thickness d _arl of the antireflection film is fixed and n _arl and k _arl are changed. The amount of absorbed light of the resist film at that point changes. The contour of the changing trajectory, i.e., the amount of absorbed light, is obtained as shown in FIG. The above corresponds to the means (I) of the present invention.

(4) Repeating (3) at four intervals of λ / 8n _PR on the basis of the different resist film thickness d _PR and the film thickness at which the standing wave effect is maximum or minimum, the fourth corresponding to FIG. Figs. 6 to 6 are obtained (Figs. 3 to 6 define the antireflection film thickness at 20 nm and the resist film thicknesses at 985 nm, 1000 nm, 1018 nm and 1035 nm, respectively). This corresponds to means (II).

(5) The common areas of the graphs of Figs. 3 to 6 show areas where the amount of absorbed light in the resist film does not change even if the resist film thickness changes due to the film thickness of the antireflection film. That is, the common area is the area with the highest antireflection effect that minimizes standing wave effects. Thus, this common area is found. The common area can be found by, for example, simply overlapping the drawings (graphs) and taking the common area (of course, by searching for the common area on a computer). This corresponds to means (III).

⑥ Change the film thickness d of the anti-reflection film continuously and repeat ③ ④ ⑤. For example, suppose that operation was carried out to d = 20 nm until 5), d is changed and the above is repeated. Thereby, the conditions for the film thickness d _arb optical constants n _arl and k _arl of the antireflection film which minimize the standing wave effect can be specified. This corresponds to means (IV).

(7) The kind of film which satisfies the conditions (film thickness, optical constant) which should be satisfied of the specific antireflection film in (6) is found by measuring the optical constant of each film type in exposure light. This corresponds to means (V).

This method can be applied in principle to all kinds of wavelengths and materials (substrates). Further, according to the conditions obtained in the above (7), the antireflection film of the best condition can be formed by the substance having the condition (corresponding to (VI) in FIG. 1).

By using the technique of the present invention, it is possible to facilitate the design of the antireflection film, which is an influential means for performing stable micropattern formation on any material (substrate) by using a stepper having any single wavelength as a light source. do.

The present invention can be used for discovering the conditions of an organic or inorganic film for forming an antireflection film used for forming a stable resist pattern on a W-Si film using a KrF excimer laser. In that case, the substance which has n and k conditions shown to FIG. 14, FIG. 15 demonstrated later can be used. At this time, it is preferable to use the organic or inorganic film | membrane whose tolerance range for each n, k value of FIG. 14, FIG. 15 is ± 0.2 with respect to n and ± 0.05 with respect to k. As such an antireflection film, it is preferable to use SiC having n = 3.16 ± 0.2 and k = 0.24 ± 0.05 at a film thickness of 50 ± 10 nm. SiC constituting the antireflection film can be formed by sputtering and CVD. In addition, this SiC can be etched by RIE in which CF ₄ , CHF ₃ , C ₂ F ₆ , C ₃ F ₈ , SF ₆ , and NF ₃ -based gases are etchant, and Ar is added to increase the ionicity.

In addition, the present invention has been achieved by performing a task of finding a substance having the conditions obtained above using the above technique, and knows that SiC (silicon carbide) is suitable for high melting point metal silicides, especially W-Si phases. The present invention has been completed.

In addition, the present invention can be suitably used in the case of forming a stable resist pattern on the W-Si film by using a KrF excimer laser, in which case Si = 50 n ± 3.16 ± 0.2, k = 0.24 ± 0.05 It is preferable to use it with a film thickness of 1 Onm. SiC constituting the antireflection film can be formed by sputtering or CVD. In addition, this SiC can be etched by RIE in which CF ₄ , CHF ₃ , C ₂ F ₆ , C ₃ F ₈ , SF ₆ , and NF ₃ -based gases are etchant, and Ar is added to increase the ionicity.

Moreover, this invention is applied when it uses as a raw material metal materials, such as a high melting-point metal compound.

In addition, when the resist is formed on the antireflection film to form a resist pattern, the present invention has been carried out to find a substance having the condition according to the conditions obtained by the above method. Knowing that SiC (silicon carbide) and SiO (silicon oxide) are suitable on Al-based metal materials such as -Si, Al-Si-Cu, and Cu-based metal materials such as Cu, and also found by the above method. Knowing that an organic or inorganic material is appropriate, the present invention has been completed.

In addition, the present invention can be suitably used when a stable resist pattern is formed on an Al-based metal material such as Al, Al-Si, Al-Si-Cu, or Cu-based metal material such as Cu using a KrF excimer laser. have. In this case, for example, on an Al-based metal material, SiO having n = 1.83 ± 0.2 and k = 0.75 ± 0.2 is preferably used as a film thickness of 30 ± 10 nm as an antireflection film. Alternatively, it is preferable to use SiC having n = 2.3 ± 0.2 and k = 0.8 ± 0.2 with a film thickness of 20 ± 10 nm. Alternatively, the organic or inorganic material in the range of the refractive index of the antireflection film obtained in the above method (V), the best curve on the film thickness, and the curve value ± 0.2 for n, and the curve value ± 0.15 for k. It is preferable to use. SiO constituting the antireflection film can be formed by CVD and thermal oxidation. SiC can be formed by sputtering and CVD. Etching of these antireflective coatings is performed by RIE having an ionicity of CF ₄ , CHF ₃ , C ₂ F ₆ , C ₃ F ₈ , SF ₆ , and HF ₃ -based gases, and by adding Ar and O ₂ . Can be.

In addition, this invention uses the invention, when using inorganic materials, such as a silicone type material as a raw material.

In addition, the present invention was carried out to find a substance having the conditions according to the conditions obtained by the above method. As a result, it was found that SiC (silicon carbide) or SiO was appropriate for silicon-based materials, particularly silicon substrates, and completed the present invention. will be.

In addition, the present invention can be suitably used when a stable resist pattern is formed on a silicon substrate using a KrF excimer laser. In this case, it is preferable to use SiC having n = 2.3 ± 0.2 and k = 0.65 ± 0.2 as the antireflection film at a film thickness of 25 nm ± 10 nm. Alternatively, SiO having n = 2.1 ± 0.2 and k = 0.7 ± 0.2 is preferably used at a film thickness of 30 ± 10 nm. SiO constituting the antireflection film can be formed by, for example, CVD or thermal oxidation. SiC can be formed by, for example, sputtering or CVD. Etching of these antireflection films was performed by using CF ₄ , CHF ₃ , C ₂ F ₆ , C ₃ H ₈ , SF ₆ , and NF ₃ -based gases as an etchant, and adding Ar and O ₂ or Ar or O ₂ to increase the ionicity. It can etch by RIE.

The invention of Claims 1 and 2 has completed the present invention by knowing that a Si _x O _y N _z film and a Si _x N _y film are suitable on a metal material material such as a high melting point metal silicide according to the conditions obtained by the above method.

The present invention can be suitably used when a stable resist pattern is formed on a W-Si film by using a KrF excimer laser. In this case, an anti-reflection film, it is preferable to use a film thickness of 30 ± 10nm of the Si0 _x n = 2.4 ± 0.6, k = 0.7 ± 0.2. In addition, this SiO _x can be formed into a film by the CVD method. In addition, SiO _x may be etched by RIE enhanced _{CHF 3, C 4 F 8,} CHF 3, a Trojan etchant S ₂ F ₂ based gas and the ionic.

In addition, the inventions of Claims 3 and 4 have completed the present invention, knowing that a Si _x O _y N _y film is suitable on a metal material such as an Al-based material.

In addition, the inventions of claims 5 and 6 have completed the present invention, knowing that a Si _x O _y N _y film and a Si _x N _y film are suitable on a silicon-based material.

Next, the Example of this invention is described concretely. However, as a matter of course, the present invention is not limited by the following examples.

Example 1

This embodiment applies the present invention to the determination of conditions (film thickness, optical constant) to be satisfied of an antireflection film for forming a stable pattern on a W-Si film using KrF excimography. This embodiment is provided with the following steps (1) to (6).

(1) Standing wave effect when XP8843 resist (Spray Microelectronics Co., Ltd.) was applied on a W-Si film in the absence of an antireflection film, and was exposed and developed with KrF excimer laser light having a wavelength of 248 nm. Is shown in FIG. In Fig. 7, the standing wave effect is about ± 20%.

(2) In FIG. 7, the maximum value of the standing wave effect is, for example, when the resist film thickness is 985 nm. Focusing on the resist film thickness of 985 nm and setting the film thickness of the antireflective film to 30 nm, the eighth change in the amount of absorbed light in the resist film (contour of absorbed light quantity) relative to the change in the optical constants n _arl and k _arl of the antireflective film Shown in the figure.

(3) The results of the above (2) being repeated for each of the resist film thicknesses of 1000 nm, 1017.5 nm, and 1035 nm are shown in FIGS. 9, 10, and 11, respectively.

(4) As a result of obtaining the common area shown in FIGS.

n _arl = 4.9, k _arl = 0.1

Alternatively, n _arl = 2.15 and k _arl = 0.67 were obtained.

That is, the condition to be satisfied of the optimum antireflection film when the film thickness of the antireflection film is 30 nm is

n _arl = 4.9, k _arl = 0.1

Or n _arl = 2.15 and k _arl = 0.67.

When the standing wave effect was obtained using these conditions, the results shown in Figs. 12 and 13 were obtained. In FIG. 12 and FIG. 13, the standing wave effect was very small and in any case was about +/- 1%. Compared with the case without the antireflection film, the standing wave effect was reduced to about 1/20.

(5) The pieces of (2) to (4) above are cases where the thickness of the antireflection film is set to 30 nm. However, the steps (2) to (4) are repeated with respect to the film thickness (ARL film thickness) of other different antireflection films. In this case, the optimum condition of the antireflection film in accordance with the film thickness of the antireflection film is obtained. The obtained result is shown in FIG. 14 and FIG.

(6) Spectroscopic ellipsometer (SOPRA, "Moss System") and handbook ("Handbook of Optical Constants of Solids", ED) Palik, Academy Press, '85). As a result, the n and k charts shown in FIG. 16 were obtained. On this chart, substances having corresponding n and k are shown. It was found from FIG. 16 that 50 nm of SiC (silicon carbide) completely satisfies the conditions of FIG. 14 and FIG. 15. 17 shows the standing wave effect when SiC is a 50-nm-thick W-Si antireflection film and when no antireflection film is used. The standing wave effect is ± 1% when SiC 50nm is used as the antireflection film (figure with ARL in the drawing), and the standing wave effect is 1/20 compared with the case where no antireflection film is used (graph without ARL in the drawing). It was reduced to an extent.

Example 2

In this embodiment, an SiC film having n = 3.16 ± 0.2 and k = 0.24 ± 0.1 shown in Example 1 was formed by the following method to form an antireflection film.

That is, in this embodiment, the thermal CVD method is used, and as the source gas,

SiCl ₄ + C ₃ H ₈ + H ₂

Or SiHCl ₃ + C ₃ H ₈ + H ₂

Or SiH ₄ + C ₃ H ₈ + H ₂

Or SiH ₄ + C ₂ H ₄ + H ₂

Or SiH ₄ + C ₃ H ₈ + H ₂

Or, SiCl ₃ + CH ₃ + H ₂

Or SiH ₄ + C ₃ H ₈ + H ₂

Or SiH ₄ + C ₃ H ₈ + H ₂

The film was formed under a pressure of 0.01 to 10,000 Pa at a temperature of 100 ° C to 1500 ° C using a gas of. As a result, a SiC film having a desired antireflection effect was obtained.

Example 3

In this embodiment, a SiC film was formed as follows to obtain an antireflection film.

That is, in this embodiment, the film was formed by using a plasma CVD method using a photochemical reaction of a Si ₂ H ₆ + Si (CH ₃ ) H ₃ + C ₂ H ₂ mixed gas.

Example 4

In this embodiment, a SiC film was formed as follows to obtain an antireflection film.

Using the ECR plasma method, the ECR plasma method using a microwave (2.45GHz), it was formed by using SiH ₄ + CH ₄ + H ₂ mixed gas.

Example 5

In this embodiment, a SiC film was formed as follows to obtain an antireflection film. That is, it formed into a film by the sputtering method which made SiC the target using the sputtering method.

Example 6

In this embodiment, the SiC film was patterned by etching to form an antireflection film.

Here, the etching of the SiC film is performed by a reactive ion etching method in which CF ₄ , CHF ₃ , C ₂ F ₆ , C ₃ F ₈ , SF ₆ , and NF ₃ -based gases are etchant, and Ar is added to increase the ionicity. It was etched and the antireflection film of the desired pattern was obtained.

Example 7

This embodiment is an example in which the present invention uses SiC as an antireflection film to form a stable pattern on a W-Si film using KrF excimography.

In the resist pattern forming method of this embodiment, as shown in FIG. 27, an antireflection film ARL is formed by silicon carbide on a W-Si material, which is a high melting point metal silicide G, and a photoresist PR is formed on the antireflection film ARL. The resist pattern is formed.

In this embodiment, in particular, when a material layer to be gated by W-Si is formed on a substrate 1 such as a Si semiconductor substrate and patterned by a photolithography process and an etching process using photoresist PR, a gate structure is obtained. The present invention is applied using SiC as an antireflection film ARL.

First, as an antireflection film to be used on W-Si, a description will be given of a procedure for selecting SiC and a method for determining the conditions to be satisfied of the SiC.

The following procedures (1) to (6) were performed.

(1) XP8843 resist (Spray Microelectronics Co., Ltd.) was apply | coated on W-Si film | membrane in the absence of an anti-reflective film, and it exposed and developed by KrF excimer laser light of wavelength 248nm. The standing wave effect at this time is shown in FIG. In Fig. 7, the standing wave effect is about ± 20%.

(2) In FIG. 7, the maximum value of the standing wave effect is, for example, when the resist film thickness is 985 nm. When the thickness of the resist film is set to 985 nm and the thickness of the anti-reflection film is 30 nm, the change in the amount of absorbed light in the resist film with respect to the change of the optical constants n _arl and k _arl of the anti-reflection film is shown in FIG.

(3) The results of the above (2) being repeated for each of the resist film thicknesses of 1000 nm, 1017.5 nm, and 1035 nm are shown in FIGS. 9, 10, and 11, respectively.

(4) As a result of determining the common area shown in FIGS. 8 to 11, n _arl = 4.9, k _arl = 0.1 or n _arl = 2.15 and k _arl = 0.67.

That is, the conditions to satisfy the optimum antireflection film when the film thickness of the antireflection film is 30 nm are n _arl = 4.9 k _arl = 0.1 or n _arl = 2.15 and k _arl = 0.67.

When the standing wave effect was obtained using these conditions, the results shown in Figs. 12 and 13 were obtained. In FIG. 12 and FIG. 13, the standing wave effect was very small and in any case was about +/- 1%. Compared with the case without the antireflection film, the standing wave effect was reduced to about 1/20.

(5) The above operations (2) to (4) are performed when the thickness of the antireflection film is set to 30 nm, but the figures (2) to (4) are repeated with respect to the film thickness (ARL film thickness) of other different antireflection films. In this case, the optimum conditions of the antireflection film corresponding to the film thickness of the antireflection film are obtained. The obtained result is shown in FIG. 14 and FIG.

(6) Spectroscopic ellipsometer (SOPRA, "Moss System") and handbook ("Handbook of Optical Constants of Solids", ED) Palik, Academy Press, '85). As a result, the n and k charts shown in FIG. 16 were obtained. On this chart, substances having corresponding n and k are shown. It was found from FIG. 16 that 50 nm of SiC (silicon carbide) completely satisfies the conditions of FIG. 14 and FIG. 15. 17 shows the standing wave effect when SiC is a 50-nm-thick W-Si antireflection film and when no antireflection film is used.

The standing wave effect is ± 1% when SiC 5Onm is used as the antireflection film (Graph with ARL in the drawing), and the standing wave effect is 1/20 compared with the case where no antireflection film is used (Graph without ARL in the drawing). It was reduced to an extent.

Example 8

In this embodiment, an SiC film having n = 3.16 ± 0.2 and k = 0.24 ± 0.1 shown in Example 1 was formed by the following method to form an antireflection film as shown in FIG.

That is, in this embodiment, the thermal CVD method is used, and as the source gas,

SiCl ₄ + C ₃ H ₈ + H ₂

Or SiHCl ₃ + C ₃ H ₈ + H ₂

Or SiH ₄ + C ₃ H ₈ + H ₂

Or SiH ₄ + C ₂ H ₄ + H ₂

Or SiH ₄ + C ₃ H ₈ + H ₂

Or, SiCl ₃ + CH ₃ + H ₂

Or SiH ₄ + C ₃ H ₈ + H ₂

Or SiH ₄ + C ₃ H ₈ + H ₂

The film was formed under a pressure of 0.01 to 10,000 Pa at a temperature of 100 ° C to 1500 ° C using a gas of. As a result, a SiC film having a desired antireflection effect was obtained.

Example 9

In this embodiment, a SiC film was formed as follows to obtain an antireflection film.

That is, in this embodiment, the film was formed by using a plasma CVD method using a photochemical reaction of a Si ₂ H ₆ + Si (CH ₃ ) H ₃ + C ₂ H ₂ mixed gas.

Example 10

In this embodiment, a SiC film was formed as follows to obtain an antireflection film.

Using the ECR plasma method, the ECR plasma method using a microwave (2.45GHz), it was formed by using SiH ₄ + CH ₄ + H ₂ mixed gas.

Example 11

In the present Example, the film was formed using the SiH ₄ + C ₂ H ₄ gas using the ECR plasma CVD method and the plasma method using microwave 2.45 GHz.

Example 12

In this embodiment, a SiC film was formed as follows to obtain an antireflection film.

It formed into a film by the sputtering method which made SiC the target using the sputtering method.

Example 13

In this embodiment, the SiC film was patterned by etching to form an antireflection film.

Here, the etching of the SiC film is performed by using CF ₄ , CHF ₃ , C ₂ F ₆ , C ₃ F ₈ , SF ₆ or NF ₃ -based gas (also referred to as a mixed gas system) as an etchant, and adding Ar to improve ionicity. Etching was performed by the reactive ion etching method to obtain an antireflection film having a desired pattern.

Example 14

This embodiment is an example in which SiC is used as an antireflection film to form a stable pattern on Al, Al-Si, and Al-Si-Cu films, which are Al-based materials, using KrF excimography.

In the resist pattern forming method of this embodiment, as shown in FIG. 28, an antireflection film ARL is formed by silicon carbide on Al, Al-Si, Al-Si-Cu, which is an Al-based metal wiring material? The photoresist PR is formed on the substrate to form a resist pattern.

In this embodiment, in particular, a material layer, which is wired by Al, Al-Si, Al-Si-Cu, is formed on a substrate S, such as a Si semiconductor substrate, and patterned by a photolithography process and an etching process using photoresist PR. When the wiring structure is obtained, the present invention is applied using SiC as the antireflection film ARL. As Al-Si, in addition to the 1-wt% Si-containing Al-Si alloy which is generally used, it can use suitably also about what is less or more than this Si. As Al-Si-Cu, for example, Si may be around 1 wt%, and Cu may be preferably applied to about 0.1 to 2 wt%, but is not limited thereto. Typically, Al-Si-Cu alloys of Si 1 wt% and Cu 0.5 wt% are used.

First, as an antireflection film used on Al, Al-Si, and Al-Si-Cu, which are Al-based metals, a method of selecting SiC in this embodiment and a method of determining the conditions to be satisfied of SiC will be described. The following procedures (1) to (6) were performed.

(1) XP8843 resist (Spray Microelectronics Co., Ltd.) was apply | coated on Al, Al-Si, Al-Si-Cu film | membrane in the absence of an anti-reflective film, and it exposed and developed by KrF excimer laser light of wavelength 248nm. The standing wave effect at this time is shown in FIG. In Fig. 29, the standing wave effect is about ± 29.6%.

(2) In FIG. 29, the maximum value of the standing wave effect is, for example, when the resist film thickness is 982 nm. Focusing on the resist film thickness of 982 nm and setting the film thickness of the antireflection film to 30 nm, the change in the amount of absorbed light in the resist film (contour of absorbed light quantity) relative to the change of the optical constants n _arl and k _arl of the antireflection film is thirtieth. Shown in the figure.

(3) The results of repeating the above (2) for each of the resist film thicknesses of 1000 nm, 1018 nm, and 1035 nm are shown in FIGS. 31, 32, and 33, respectively.

(4) As a result of determining the common area shown in FIGS. 30 to 33, n _arl = 4.8, k _arl = 0.45, or n _arl = 2.0 and k _arl = 0.8.

That is, the conditions to satisfy the optimum antireflection film when the film thickness of the antireflection film is 30 nm are n _arl = 4.8, k _arl = 0.45 or n _arl = 2.0 and k _arl = 0.8.

When the standing wave effects were obtained using these conditions, the results shown in the "optimal conditions" in Figs. 34 and 35 were obtained. 34 and 35, the standing wave effect was very small, as apparent from the contrast with "no antireflection film", and in all cases was about ± 1% or less. Compared with the case without the antireflection film, the standing wave effect was reduced to about 1/30.

(5) The above operations (2) to (4) are performed when the thickness of the antireflection film is set to 30 nm. However, with respect to the film thickness (ARL film thickness) of other different antireflection films, (2) to (4) When repeated, the optimum condition of the antireflection film corresponding to the film thickness of the antireflection film is obtained. The obtained result is shown in FIG. 14 and FIG.

(6) Spectral ellipsometer (SOPRA, "Moss System") and handbook ("Handbook of Optical Constants of Sdids", ED) Palik, Academy Press, '85). As a result, the n and k charts shown in FIG. 16 were obtained. On this chart, substances having corresponding n and k are shown. It was found from FIG. 16 that 20 nm of SiC (silicon carbide) completely satisfied the conditions of FIG. 14 and FIG. 38 shows the standing wave effect when SiC is used as an antireflection film on Al, Al-Si, Al-Si-Cu phases with a thickness of 20 nm and when no antireflection film is used. The standing wave effect is ± 2.2% (1.4%) when SiC 20nm is used as the antireflection film (Fig. 38 with ARL), and the standing wave effect is compared with the case where no antireflection film is used (graph without ARL in the drawing). Is reduced to about 1/15. 37 shows the dependence of the film forming conditions on n and k values of the SiC film.

Example 15

In this embodiment, an SiC film having n = 2.3 ± 0.2 and k = 0.8 ± 0.2 shown in Example 1 was formed by the following method to form an antireflection film as shown in FIG.

That is, in this embodiment, the thermal CVD method is used, and as the source gas,

SiCl ₄ + C ₃ H ₈ + H ₂

Or, SiHCl ₃ + C ₃ H ₈ + H ₂

Or SiH ₄ + C ₃ H ₈ + H ₂

Or SiH ₄ + C ₂ H ₄ + H ₂

Or SiH ₄ + C ₃ H ₈ + H ₂

Or, SiCl ₃ + CH ₃ + H ₂

Or SiH ₄ + C ₃ H ₈ + H ₂

Or SiH ₄ + C ₃ H ₈ + H ₂

The film was formed at a temperature of 100 DEG C to 1500 DEG C, generally at a pressure of preferably from 0.1 to 100 Pa, more preferably from 100 to 100 Pa. As a result, a SiC film having a desired antireflection effect was obtained.

Example 16

In this embodiment, a SiC film was formed as follows to obtain an antireflection film.

That is, in this embodiment, the film was formed by using a plasma CVD method using a photochemical reaction of a Si ₂ H ₆ + Si (CH ₃ ) H ₃ + C ₂ H ₂ mixed gas.

Example 17

In this embodiment, a SiC film was formed as follows to obtain an antireflection film.

Mixing SiH ₄ + C ₂ H ₄ , or SiH ₄ + C ₂ H ₄ + H ₂ , or SiH ₄ + CH ₄ + H ₂ by ECR plasma CVD using an ECR plasma method and using microwave (2.45 GHz) The film was formed using gas.

Example 18

In this embodiment, a SiC film was formed as follows to obtain an antireflection film. That is, it formed into a film by the sputtering method which made SiC the target using the sputtering method.

Example 19

In this embodiment, the SiC film was patterned by etching to form an antireflection film.

Here, the etching of the SiC film is performed by using CF ₄ , CHF ₃ , C ₂ F ₆ , C ₃ F ₈ , SF _6, or NF ₃ -based gas (also referred to as a mixed gas system) as an etchant, and adding Ar to improve ionicity. It was made to etch by the reactive ion etching method, and the antireflection film of the desired pattern was obtained.

Example 20

This embodiment uses Si0 as an antireflection film to form a stable pattern on Al, Al-Si, Al-Si-Cu films using KrF excimography.

In the resist pattern forming method of this embodiment, as shown in FIG. 28, an antireflection film ARL is formed of silicon oxide SiO on Al, Al-Si, Al-Si-Cu, which is an Al-based metal wiring material? The photoresist PR is formed on the ARL to form a resist pattern.

In this embodiment, in particular, a material layer to be interconnected by Al, Al-Si, Al-Si-Cu is formed on a substrate S such as a Si semiconductor substrate, and patterned by a photolithography process and an etching process using photoresist PR. In order to obtain the wiring structure, the present invention is applied using SiO as the antireflection film ARL.

First, as an antireflection film used on Al, Al-Si, and Al-Si-Cu which are Al-based metals, a procedure of selecting SiO in this embodiment and a method of determining the conditions to be satisfied of SiC will be described. As in Example 14, the following procedures (1) to (6) were performed.

(1) XP8843 resist (Spray Microelectronics Co., Ltd.) was apply | coated on Al, Al-Si, Al-Si-Cu film | membrane in the absence of an anti-reflective film, and it exposed and developed by KrF excimer laser light of wavelength 248nm. . The standing wave effect at this time is shown in FIG. In Fig. 29, the standing wave effect is about ± 29.6%.

(2) In FIG. 29, the maximum value of the standing wave effect is, for example, when the resist film thickness is 982 nm. When the resist film thickness is focused at 982 nm and the film thickness of the antireflection film is 30 nm, the change in the amount of absorbed light in the resist film with respect to the change in the optical constants n _arl and k _arl of the antireflection film is shown in FIG. 30.

(3) The results of repeating the above (2) for each of the resist film thicknesses of 1000 nm, 1018 nm, and 1035 nm are shown in FIGS. 31, 32, and 33, respectively.

(4) As a result of determining the common area shown in FIGS. 30 to 33, n _arl = 4.8, k _arl = 0.45, or n _arl = 2.0 and k _arl = 0.8.

That is, the conditions to satisfy the optimum antireflection film when the film thickness of the antireflection film is 30 nm are n _arl = 4.8, k _arl = 0.45 or n _arl = 2.0 and k _arl = 0.8.

The result of the standing wave effect obtained using this condition is the result shown in FIG. 34 and FIG. 35 as described in Example 14. FIG. 34 and 35, the standing wave effect was very small and in all cases was about ± 1% or less. Compared with the case without the antireflection film, the standing wave effect was reduced to about 1/30.

(5) The above operations (2) to (4) are performed when the thickness of the antireflection film is set to 30 nm, but the figures (2) to (4) are repeated with respect to the film thickness (ARL film thickness) of other different antireflection films. In this case, the optimum conditions of the antireflection film corresponding to the film thickness of the antireflection film are obtained. The obtained result is shown in FIG. 14 and FIG.

(6) Spectroscopic ellipsometer (SOPRA, "Moss System") and handbook ("Handbook of Optical Constants of Solids", ED) Palik, Academy Press, '85). As a result, the n and k charts shown in FIG. 16 were obtained. On this chart, substances having corresponding n and k are shown. From Fig. 16, it was found that 30 nm of Si0 (silicon oxide) completely satisfied the conditions of Figs. FIG. 39 shows the standing wave effect when Si0 is used as an antireflection film on Al, Al-Si, Al-Si-Cu with a thickness of 30 nm and when no antireflection film is used. The standing wave effect is ± 2.2% (1.4%) when Si0 30nm is used as the antireflection film (graph with Si0 in the drawing), and the standing wave effect is compared with the case where no antireflection film is used (graph without SiO in the drawing). Is reduced to about 1/20.

Example 21

In this embodiment, an SiO film having n = 1.83 ± 0.2 and k = 0.75 ± 0.2 shown in Example 20 was formed by the following method to form an antireflection film as shown in FIG.

That is, in this embodiment, film formation was carried out under a pressure of 0.01 Pa to 10 Pa at a temperature of room temperature to 500 ° C. using a mixed gas of SiH ₄ + O ₂ + N ₂ . As a result, an SiO film having a desired antireflection effect was obtained.

Example 22

In this embodiment, the Si0 film was patterned by etching to form an antireflection film.

Here, the etching of the SiO film is performed by using CF ₄ , CHF ₃ , C ₂ F ₆ , C ₃ F ₈ , SF ₆ or NF ₃ -based gas (also referred to as a mixed gas system) as an etchant, and adding Ar to increase ionicity. It was made to etch by the reactive ion etching method, and the antireflection film of the desired pattern was obtained.

Example 23

In this embodiment, an organic / inorganic material suitable for forming a stable pattern on Al, Al-Si, and Al-Si-Cu films is obtained by using KrF excimer lithography.

In the resist pattern forming method of this embodiment, as shown in FIG. 28, an antireflection film ARL is formed on Al, Al-Si, Al-Si-Cu, which is an Al-based metal wiring material, and a photoresist is formed on the antireflection film ARL. When forming a resist pattern by forming PR, an appropriate material is selected to form an antireflection film.

In this embodiment, in particular, a material layer to be interconnected by Al, Al-Si, Al-Si-Cu is formed on a substrate S such as a Si semiconductor substrate, and patterned by a photolithography process and an etching process using photoresist PR. In order to obtain the wiring structure, antireflection film design was performed.

(1) XP8843 resist (Spray Microelectronics Co., Ltd.) was apply | coated on Al, Al-Si, Al-Si-Cu film | membrane in the absence of an anti-reflective film, and it exposed and developed by KrF excimer laser light of wavelength 248nm. The standing wave effect at this time is shown in FIG. In Fig. 29, the standing wave effect is about ± 29.6%.

(2) In FIG. 29, the maximum value of the standing wave effect is, for example, when the resist film thickness is 982 nm. When the resist film thickness is focused at 982 nm and the film thickness of the antireflection film is 30 nm, the change in the amount of absorbed light in the resist film with respect to the change in the optical constants n _arl and k _arl of the antireflection film is shown in FIG. 30.

(3) The results of repeating the above (2) for each of the resist film thicknesses of 1000 nm, 1018 nm, and 1035 nm are shown in FIGS. 31, 32, and 33, respectively.

(4) As a result of determining the common area shown in FIGS. 30 to 33, n _arl = 4.8, k _arl = 0.45, or n _arl = 2.0 and k _arl = 0.8.

That is, the conditions to satisfy the optimum antireflection film when the film thickness of the antireflection film is 30 nm are n _arl = 4.8, k _arl = 0.45 or n _arl = 2.0 and k _arl = 0.8.

When the standing wave effects were obtained using these conditions, the results shown in FIGS. 34 and 35 were obtained. 34 and 35, the standing wave effect shown by "the most recent condition" was very small, and in any case was about ± 1% or less. Compared with the case without the antireflection film, the standing wave effect was reduced to about 1/30.

(5) The above operations (2) to (4) are performed when the thickness of the antireflection film is set to 30 nm, but the figures (2) to (4) are repeated with respect to the film thickness (ARL film thickness) of other different antireflection films. In this case, the optimum conditions of the antireflection film corresponding to the film thickness of the antireflection film are obtained. The obtained result is shown in FIG. 14 and FIG.

If the organic or inorganic materials are used to satisfy the optical characteristics of the curves in Figs. 14 and 36 or in the range of ± 0.2 for the curve and ± 0.15 for the k, the standing wave effect is ± It becomes 3% or less. Thus, such an organic or inorganic material was obtained, thereby forming an antireflection film. Compared with the case where no antireflection film was used, the standing wave effect was reduced to about 1/10.

[Examples 24 to 33]

In this embodiment, in Examples 14 to 23, instead of Al-based metal materials such as Al, Al-Si, and Al-Si-Cu, Cu, which is a Cu-based metal material, is used to form Cu wiring. In this manner, as in each of the above examples, an antireflection film (an antireflection film made of an organic or inorganic material obtained by the same method as in Example 23 when SiC, Si0, or Cu is a material) was formed to perform resist patterning.

As a result, standing wave effects were reduced as in each of the above examples, and good patterning was performed.

Example 34

This embodiment is an example in which the present invention uses SiC as an antireflection film to form a stable pattern on a Si substrate using KrF excimography.

In the resist pattern forming method of this embodiment, as shown in FIG. 40, an antireflection film ARL is formed on silicon substrate S made of silicon based material by silicon carbide, and a photoresist PR is formed on the antireflection film ARL to form a resist pattern. It was made to form.

First, a procedure for selecting SiC as an antireflection film and a method of determining the conditions to be satisfied of the SiC will be described. The following procedure was performed.

(1) XP8843 resist (Spray Microelectronics Co., Ltd.) was apply | coated on Si board | substrate in the state without an anti-reflective film, and it exposed and developed by KrF excimer laser light of wavelength 248nm. The standing wave effect at this time is shown in FIG. In Fig. 41, the standing wave effect is about ± 20%.

(2) In FIG. 41, the maximum value of the standing wave effect is, for example, when the resist film thickness is 985 nm. Focusing on the resist film thickness of 985 nm and setting the film thickness of the antireflection film to 30 nm, the change in the amount of absorbed light in the resist film with respect to the change of the optical constants n _arl and k _arl of the antireflection film is determined.

(3) A plurality of different resist film thicknesses were taken, and (2) was repeated for each of them.

(4) The results are shown and their common areas are obtained. Such an operation is obtained for various antireflection film thicknesses, thereby obtaining the optimum values (n values, k values) of optical characteristics for a certain film thickness.

Using the above method, the optimum condition of the antireflection film was obtained. Based on these results, the standing wave effect was greatly reduced by using SiC having n = 2.3 and k = 0.65 as the antireflection film at a film thickness of 25 nm.

Fig. 42 shows a comparison between the case where SiC 25 nm is used as the antireflection film (graph with SiC) and when the antireflection film is not used (graph without SiC). When SiC 25 nm is used, the standing wave effect is reduced to ± 1% or less. The standing wave effect without using SiC is ± 23%. Therefore, by using SiC as an antireflection film of Si phase, the standing wave effect is reduced to 1/23 or less.

Example 35

This embodiment also obtained the same silicon oxide (SiO) as the antireflection film using the same method as the above embodiment. That is, in this embodiment, by using SiO having n = 2.1 and k = 0.7 as the antireflection film at a film thickness of 30 nm, the standing wave effect was greatly reduced.

Fig. 43 shows a comparison between the case where SiO 30 nm is used as the antireflection film (graph with SiO) and when the antireflection film is not used (graph without SiO). In case of using Si0 30nm, the standing wave effect is about ± 1%. The standing wave effect when Si0 30nm is not used as an antireflection film is ± 23%. Therefore, by using Si0 as an antireflection film of Si phase, the spot wave effect is reduced to about 1/23.

Example 36

In this embodiment, an SiC film having n = 2.3 ± 0.2 and k = 0.65 ± 0.2 shown in Example 34 was formed by the following method to form an antireflection film as shown in FIG.

That is, in this embodiment, the thermal CVD method is used, and as the source gas,

SiCl ₄ + C ₃ H ₈ + H ₂

Or SiHCl ₃ + C ₃ H ₈ + H ₂

Or SiH ₄ + C ₃ H ₈ + H ₂

Or SiH ₄ + C ₂ H ₄ + H ₂

Or SiH ₄ + C ₃ H ₈ + H ₂

Or, SiCl ₃ + CH ₃ + H ₂

Or SiH ₄ + C ₃ H ₈ + H ₂

Or SiH ₄ + C ₃ H ₈ + H ₂

The film was formed at a temperature of 100 ° C. to 1500 ° C. under a pressure of preferably 0.1 to 100 Pa, more preferably 100 to 100 Pa. As a result, a SiC film having a desired antireflection effect was obtained.

Example 37

In this embodiment, a SiC film was formed as follows to obtain an antireflection film.

That is, in this embodiment, the film was formed by using a plasma CVD method using a photochemical reaction of a Si ₂ H ₆ + Si (CH ₃ ) H ₃ + C ₂ H ₂ mixed gas.

Example 38

In this embodiment, a SiC film was formed as follows to obtain an antireflection film.

Mixing SiH ₄ + C ₂ H ₄ , or SiH ₄ + C ₂ H ₄ + H ₂ , or SiH ₄ + CH ₄ + H ₂ by ECR plasma CVD using an ECR plasma method and using microwave (2.45 GHz) The film was formed using gas.

Example 39

In this embodiment, a SiC film was formed as follows to obtain an antireflection film. That is, it formed into a film by the sputtering method which made SiC target using the sputtering method.

Example 40

In this embodiment, the SiC film was patterned by etching to form an antireflection film.

Here, the etching of the SiC film is performed by using CF ₄ , CHF ₃ , C ₂ F ₆ , C ₃ F ₈ , SF ₆ or NF ₃ -based gas (also referred to as a mixed gas system) as an etchant, and adding Ar to improve ionicity. It was made to etch by the reactive ion etching method, and the antireflection film of the desired pattern was obtained.

Example 41

In this embodiment, an SiO film having n = 2.1 ± 0.2 and k = 0.7 ± 0.2 shown in Example 35 was formed by the following method to form an antireflection film as shown in FIG. 40 and described in FIG. .

That is, film formation was carried out using a mixed gas of SiH ₄ + O ₂ + N ₂ under a pressure of 0.1 Pa to 1 OPa at a temperature of normal temperature to 50,000 캜. As a result, an SiO film having a desired antireflection effect was obtained.

Example 42

The SiC film and the Si0 film of each of the above-described examples were formed on a single crystal silicon material, a polycrystalline silicon material, and an amorphous silicon material to form an antireflection film. As a result, a desired antireflection effect was obtained, and good pattern formation could be realized.

Example 43

This embodiment is an example in which the present invention uses SiO _x as an antireflection film to form a stable pattern on a W-Si film using KrF excimography.

In the resist pattern forming method of this embodiment, as shown in FIG. 44, an antireflection film ARL is formed on SiO 2 _by W _x Si, a high melting point metal silicide, and a photoresist PR is formed on the antireflection film ARL. It was set as the structure which forms a pattern.

In this embodiment, in particular, when a material layer to be gated by W-Si is formed on a substrate 1 such as a Si semiconductor substrate and patterned by a photolithography process and an etching process using photoresist PR, a gate structure is obtained. Is applied to the present invention using SiO _x as the antireflection film ARL.

First, as an anti-reflection coating used on W-Si, it will be described a method of determining conditions to be satisfied in the selection procedure for the SiO _x and the SiO _x. The following procedures (1) to (6) were performed.

(1) XP8843 resist (Spray Microelectronics Co., Ltd.) was apply | coated on W-Si in the absence of an anti-reflective film, and it exposed and developed by KrF excimer laser light of wavelength 248nm. The standing wave effect at this time is shown in FIG. In Fig. 7, the standing wave effect is ± 20%.

(2) In FIG. 7, the maximum value of the standing wave effect is, for example, when the resist film thickness is 985 nm. Focusing on the resist film thickness of 985 nm and setting the film thickness of the antireflection film to 30 nm, the contour of the amount of absorbed light in the resist film with respect to the change of the optical constants n _arl and k _arl of the antireflection film is shown in FIG.

(3) The results of the above (2) being repeated for each of the resist film thicknesses of 1000 nm, 1017.5 nm, and 1035 nm are shown in FIGS. 9, 10, and 11, respectively.

(4) As a result of determining the common area shown in FIGS. 8 to 11, n _arl = 4.9, k _arl = 0.1 or n _arl = 2.15 and k _arl = 0.67.

That is, the conditions to satisfy the optimum antireflection film when the film thickness of the antireflection film is 30 nm are n _arl = 4.9, k _arl = 0.1 or n _arl = 2.15, k _arl = 0.67.

When the standing wave effect was obtained using these conditions, the results shown in Figs. 12 and 13 were obtained. In FIG. 12 and FIG. 13, the standing wave effect was very small and in any case was about 1% or less. Compared with the case without the antireflection film, the standing wave effect was reduced to about 1/20.

(5) The above operations (2) to (4) are performed when the thickness of the antireflection film is set to 30 nm. However, with respect to the film thickness (ARL film thickness) of other different antireflection films, (2) to (4) When repeated, the optimum condition of the antireflection film corresponding to the film thickness of the antireflection film is obtained. The obtained result is shown in FIG. 14 and FIG.

(6) The presence or absence of a film species satisfying the conditions to be satisfied of the antireflection film obtained in the above (5) was investigated using a spectroscopic ellipsoid (SOPRA). As a result, it was found that the optical constant showed the change shown in FIG. 45 corresponding to the film formation conditions when the SiO _x film was formed by the CVD method. The region indicated by o in FIG. 45 satisfies the conditions of FIG. 14 and FIG. That is, FIG. 46 shows the standing wave effect when the SiO _x film is 25 nm thick as an anti-reflection film on W-Si and when no anti-reflection film is used. In the case where the SiO _x film was 25 nm, the standing wave effect was about ± 1.8%, and the standing wave effect was reduced to about 1/12 compared with the case where no antireflection film was used.

Example 44

In this example, an SiO _x film having n = 2.4 ± 0.6 and k = 0.7 ± 0.2 shown in Example 43 was formed by the following method to form an antireflection film as shown in FIG.

That is, in this embodiment, the film was formed using a microwave (2.45 GHz) using a parallel plate plasma CVD method and using a SiH ₄ + O ₂ mixed gas.

Example 45

In this embodiment, a Si0 _x film having n = 2.4 ± 0.6 and k = 0.7 ± 0.2 shown in Example 43 was formed by the following method to form an antireflection film having an antireflection function as shown in FIG. .

That is, in this embodiment, the film was formed using a microwave (2.45 GHz) using a parallel plate plasma CVD method, using a SiH ₄ + O ₂ mixed gas, and using Ar as a buffer gas.

Example 46

In this embodiment, a Si0 _x film having n = 2.4 ± 0.6 and k = 0.7 ± 0.2 shown in Example 43 was formed by the following method to form an antireflection film as shown in FIG.

That is, in this embodiment, the film was formed using a microwave (2.45 GHz) using an ECR plasma CVD method and using a SiH ₄ + O ₂ mixed gas.

Example 47

In this embodiment, a Si0 _x film having n = 2.4 ± 0.6 and k = 0.7 ± 0.2 shown in Example 43 was formed by the following method to form an antireflection film having an antireflection function as shown in FIG. .

That is, in this embodiment, the film was formed using microwave (2.45 GHz), SiH ₄ + O ₂ mixed gas, and Ar as the buffer gas using the ECR plasma CVD method.

Example 48

In this example, an SiO _x film having n = 2.4 ± 0.6 and k = 0.7 ± 0.2 shown in Example 43 was formed by the following method to form an antireflection film having an antireflection function as shown in FIG. .

In other words, in this embodiment, the film was formed using a microwave (2.45 GHz) and a SiH ₄ + O ₂ mixed gas using a bias ECR plasma CVD method.

Example 49

In this embodiment, a Si0 _x film having n = 2.4 ± 0.6 and k = 0.7 ± 0.2 shown in Example 43 was formed by the following method to form an antireflection film having an antireflection function as shown in FIG. .

That is, in this embodiment, the film was formed using a microwave (2.45 GHz) using a bias ECR plasma CVD method, using a SiH ₄ + O ₂ mixed gas, and using Ar as a buffer gas.

Example 50

In this example, the material was etched using a SiO _x film having n = 2.4 ± 0.6 and k = 0.7 ± 0.2 shown in Example 43 as a resist pattern as a mask by the following method.

That is, the etching of the SiO _x film is performed by using a gas system of CHF ₃ (50 to 10 OSCCM) + O ₂ ( ₃ to 20 SCCM), and applying reactive power of about 100 to 100 OW under a pressure of about 2 Pa to increase ionicity. The desired pattern was etched by etching.

Example 51

In this example, the Si0 _x film having n = 2.4 ± 0.6 and k = 0.7 ± 0.2 shown in Example 43 was etched using the resist pattern as a mask by the following method.

That is, the etching of the SiO _x film is performed by using a gas system of C ₄ F ₈ (30 to 70 SCCM) + CHF ₃ (10 to 30 SCCM) and applying a power of about 100 to 1000 W at a pressure of about 2 Pa to increase ionicity. The desired pattern was etched by etching by the active etching method.

Example 52

In this example, the material was etched using a SiO _x film having n = 2.4 ± 0.6 and k = 0.7 ± 0.2 shown in Example 43 as a resist pattern as a mask by the following method.

In other words, the etching of the SiO _x film is performed by using a reactive gas etching method of S ₂ F ₂ (5 to 30 SCCM), applying a power of about 100 to 100 OW under a pressure of about 2 Pa, and increasing the ionicity. The desired pattern was etched.

Example 53

This embodiment is an example in which the Si _x O _y N _z and Si _x N _y films are used as the antireflection film to form a stable pattern on the W-Si film by using KrF excimography.

In the resist pattern forming method of this embodiment, as shown in FIG. 47, an antireflection film ARL is formed on a W-Si material, which is a high melting point metal silicide, by Si _x O _y N _z and Si _x N _y . The photoresist PR is formed on the substrate to form a resist pattern.

In this embodiment, in particular, a material layer to be gated by W-Si is formed on a substrate 1 such as a Si semiconductor substrate, and patterned by a photolithography process and an etching process using photoresist PR to obtain a gate structure. In this case, Si _x O _y N _z and Si _x N _y are used as the antireflection film ARL.

First, the procedure for selecting Si _x O _y N _z and Si _x N _y as an anti-reflection film used on the W-Si, and a method of determining the conditions for satisfying the Si _x O _y N _z and Si _x N _y will be described. do. The following procedures (1) to (6) were performed.

(1) XP8843 resist (Spray Microelectronics Co., Ltd.) was apply | coated on W-S in the state without an anti-reflective film, and it exposed and developed by KrF excimer laser light of wavelength 248nm. The standing wave effect at this time is shown in FIG. In Fig. 7, the standing wave effect is about ± 20%.

(2) In FIG. 7, the maximum value of the standing wave effect is, for example, when the resist film thickness is 985 nm. Focusing on the resist film thickness of 985 nm and setting the film thickness of the antireflection film to 30 nm, the contour of the amount of absorbed light in the resist film with respect to the change of the optical constants n _arl and k _arl of the antireflection film is shown in FIG. 8.

(3) The results of the above (2) being repeated for the resist film thicknesses of 1000 nm, 1017.5 nm, and 1035 nm are shown in FIGS. 9, 10, and 11, respectively.

(4) As a result of obtaining the common area shown in FIGS.

n _arl = 4.9, k _arl = 0.1

Alternatively, n _arl = 2.15 and k _arl = 0.67 were obtained.

That is, the conditions to be satisfied of the optimum anti-reflection film when the film thickness of the anti-reflection film is 30 nm are n _arl = 4.9, k _arl = 0.1 or n _arl = 2.15, k _arl = 0.67.

When the standing wave effect was obtained using these conditions, the results shown in Figs. 12 and 13 were obtained. In FIG. 12 and FIG. 13, the standing wave effect was very small and in all cases was about 1% or less. Compared with the case without the antireflection film, the standing wave effect was reduced to about 1/20.

(5) The above operations (2) to (4) are performed when the thickness of the antireflection film is set to 30 nm, but the figures (2) to (4) are repeated with respect to the film thickness (ARL film thickness) of other different antireflection films. In this case, the optimum conditions of the antireflection film corresponding to the film thickness of the antireflection film are obtained. The obtained result is shown in FIG. 14 and FIG.

(6) The presence or absence of a film species satisfying the conditions to be satisfied of the antireflection film obtained in the above (5) was investigated using a spectroscopic ellipsometer (SOPRA).

As a result, it was found that the optical constant showed the change shown in FIG. 48 in accordance with the film forming conditions when the Si _x O _y N _z and Si _x N _y films were formed by the CVD method. The region indicated by o in FIG. 48 satisfies the conditions of FIG. 14 and FIG. That is, FIG. 49 shows the standing wave effect in the case where the Si _x O _y N _z and Si _x N _y films 25 nm in thickness are used as anti-reflection films on W-Si and when anti-reflection films are not used. In the case where the Si _x O _y N _z and Si _x N _y films were 25 nm, the standing wave effect was about ± 1.8%, and the standing wave effect was reduced to about 1/12 compared with the case where no antireflection film was used.

Example 54

In this embodiment, a Si _x O _y N _z film having n = 2.4 ± 0.6 and k = 0.7 ± 0.2 shown in Example 53 is formed by the following method to form an antireflection film as shown in FIG. It was.

In other words, in the present embodiment, a mixed gas of SiH ₄ + O ₂ + N ₂ or SiH ₄ is used by using microwave (2.45 GHz) using a parallel plasma CVD method, an ECR plasma CVD method, or a bias ECR plasma CVD method. + N ₂ O was deposited by using a mixed gas.

Example 55

In this example, a Si _x O _y N _z film having n = 2.4 ± 0.6 and k = 0.7 ± 0.2 shown in Example 53 was formed by the following method to form an antireflection film as shown in FIG.

In other words, in this embodiment, a mixed gas of SiH ₄ + O ₂ + N ₂ or SiH is used, using microwave (2.45 GHz), using a parallel plate plasma CVD method, an ECR plasma CVD method, and a bias ECR plasma CVD method. using ₄ + N ₂ O gas mixture and, as a buffer gas was formed by using Ar.

Example 56

In this example, a Si _x O _y N _z film having n = 2.4 ± 0.6 and k = 0.7 ± 0.2 shown in Example 53 was formed by the following method to form an antireflection film as shown in FIG.

That is, in this embodiment, film formation is performed using a mixed gas of SiH ₄ + O ₂ + N ₂ or a mixed gas of SiH ₄ + N ₂ O using a parallel plate plasma CVD method, an ECR plasma CVD method, or a bias ECRCVD method. It was.

Example 57

In this example, a Si _x O _y N _z film having n = 2.4 ± 0.6 and k = 0.7 ± 0.2 shown in Example 53 was formed by the following method to form an antireflection film as shown in FIG.

That is, in this embodiment, a mixed gas of SiH ₄ + O ₂ + N ₂ or a mixed gas of SiH ₄ + N ₂ O is used by using a parallel plate plasma CVD method, an ECR plasma CVD method, or a bias ECR plasma CVD method. The film was formed using Ar as a buffer gas.

Example 58

In this example, a Si _x N _y film having n = 2.4 ± 0.6 and k = 0.7 ± 0.2 shown in Example 53 was formed by the following method to form an antireflection film as shown in FIG.

In other words, in this embodiment, microwave (2.45 GHz) is used, using a parallel plate plasma CVD method, an ECR plasma CVD method or a bias ECR plasma CVD method, and a SiH ₄ + NH ₃ mixed gas or a SiH ₂ Cl ₂ + It was formed by using the NH ₃ gas mixture.

Example 59

In this example, a Si _x N _y film having n = 2.4 ± 0.6 and k = 0.7 ± 0.2 shown in Example 53 was formed by the following method to form an antireflection film as shown in FIG.

That is, in the present embodiment, microwaves (2.45 GHz) are used using a parallel plate plasma CVD method, an ECR plasma CVD method, or a bias ECR plasma CVD method, and a SiH ₄ + O ₂ mixed gas or SiH ₂ Cl ₂ + The film was formed by using an NH ₃ mixed gas and using Ar as a buffer gas.

Example 60

In this example, a Si _x N _y film having n = 2.4 ± 0.6 and k = 0.7 ± 0.2 shown in Example 53 was formed by the following method to form an antireflection film as shown in FIG.

That is, in this embodiment, the film was formed using a parallel plate plasma CVD method, an ECR plasma CVD method, or a bias ECR plasma CVD method, using a SiH ₄ + NH ₃ mixed gas or a SiH ₂ Cl ₂ + NH ₃ mixed gas. .

Example 61

In this example, a Si _x N _y film having n = 2.4 ± 0.6 and k = 0.7 ± 0.2 shown in Example 53 was formed by the following method to form an antireflection film as shown in FIG.

That is, in this embodiment, a parallel plate plasma CVD method, an ECR plasma CVD method, or a bias ECR plasma CVD method is used, and a SiH ₄ + O ₂ mixed gas or a SiH ₂ Cl ₂ + NH ₃ mixed gas is used, and a buffer is used. It formed into a film using Ar as a gas.

Example 62

In this example, the material was etched using a Si _x O _y N _z and Si _x N _y film having n = 2.4 ± 0.6, k = 0.7 ± 0.2 shown in Example 53 as a resist pattern as a mask by the following method. .

That is, the etching of the Si _x O _y N _z and Si _x N _y films uses a gas system of CHF ₃ (50 to 10 OSCCM) + O ₂ ( ₃ to 20 SCCM), and the power is about 100 to 100 OW under a pressure of about 2 Pa. Was added to etch by the reactive etching method of increasing the ionicity, and the desired pattern was etched.

Example 63

In this embodiment, the Si _x O _y N _z and Si _x N _y films of n = 2.4 ± 0.6, k = 0.7 ± 0.2 shown in Example 53 were etched using the resist pattern as a mask by the following method. .

That is, the etching of the Si _x O _y N _z and Si _x N _y films is performed using a gas system of C ₄ F ₈ (30 to 70 SCCM) + CHF ₃ (10 to 30 SCCM), and is about 100 to 100 OW under a pressure of about 2 Pa. The desired pattern was etched by applying the reactive power to the etching by the reactive etching method of increasing the ionicity.

Example 64

In this example, the material was etched using a Si _x N _y film having n = 2.4 ± 0.6 and k = 0.7 ± 0.2 shown in Example 53 as a resist pattern as a mask by the following method.

That is, the etching of the Si _x O _y N _z and Si _x N _y films is performed using a gas system of S ₂ F ₂ (5 to 30 SCCM), and the ionicity is increased by applying a power of about 100 to 100 OW under a pressure of about 2 Pa. The desired pattern was etched by etching by the reactive etching method.

Example 65

This embodiment uses the KrF excimer morphography as an anti-reflection film to form a stable resist pattern on Al, Al-Si, Al-Si-Cu materials, and silicon oxide films such as SiO ₂ on the materials. _It is an example using xO _y N _z and Si _x N _y films.

In the resist pattern forming method of this embodiment, as shown in FIG. 50, the antireflection film ARL is formed by Si _x O _y N _z and Si _x N _y on Al, Al-Si, Al-Si-Cu materials, which are metal wiring materials. A photoresist PR is formed on the antireflection film ARL or a silicon oxide film such as SiO ₂ is formed on the antireflection film ARL, and then a photoresist PR is formed to form a resist pattern. In this embodiment, in particular, a material layer to be interconnected by Al, Al-Si, Al-Si-Cu is formed on a substrate such as a Si semiconductor substrate, or a silicon oxide film such as SiO ₂ is formed on the material layer. In the case of patterning the photolithography step and the etching step using the photoresist PR to obtain a wiring structure, Si _x O _y N _z and Si _x N _y are applied to the present invention as the antireflection film ARL.

Firstly, satisfying of Al, Al-Si, Al-Si-Cu as an anti-reflection coating used on the material procedure selected an Si _x O _y N _z, Si _x N _y and the Si _x O _y N _z, Si _x N _y Explain how to determine the conditions to be met. The following procedures (1) to (6) were performed.

(1) XP8843 resist (Spray Microelectronics Co., Ltd.) was applied onto Al, Al-Si, and Al-Si-Cu substrates in the absence of an antireflection film, and exposed and developed with KrF excimer laser light having a wavelength of 248 nm. . The standing wave effect at this time is shown in FIG. In Fig. 20, the standing wave effect is about ± 29.6%.

(2) In FIG. 20, the maximum value of the standing wave effect is, for example, when the resist film thickness is 982 nm. Focusing on the resist film thickness of 982 nm and setting the film thickness of the antireflection film to 30 nm, the contour of the amount of absorbed light in the resist film with respect to the change of the optical constants n _arl and k _arl of the antireflection film is shown in FIG. 30.

(3) The results of repeating the above (2) for each of the resist film thicknesses of 1000 nm, 1018 nm, and 1035 nm are shown in FIGS. 31, 32, and 33, respectively.

(4) As a result of determining the common area shown in FIGS. 30 to 33, n _arl = 4.8, k _arl = 0.45, or n _arl = 2.0 and k _arl = 0.8.

That is, the conditions to satisfy the optimum antireflection film when the film thickness of the antireflection film is 30 nm are n _arl = 4.8, k _arl = 0.45 or n _arl = 2.0 and k _arl = 0.8.

When the standing wave effects were obtained using these conditions, the results shown in FIGS. 34 and 35 were obtained. 34 and 35, the standing wave effect was very small, and in either case, the range was about 1% or less. Compared to the case without the antireflection film, the standing wave effect was reduced to about 1 / 60th.

(5) The above operations (2) to (4) are performed when the thickness of the antireflection film is set to 30 nm, but the figures (2) to (4) are repeated with respect to the film thickness (ARL film thickness) of other different antireflection films. In this case, the optimum conditions of the antireflection film corresponding to the film thickness of the antireflection film are obtained. The obtained result is shown in FIG. 14 and FIG.

(6) The presence or absence of a film species satisfying the conditions to be satisfied of the antireflection film obtained in the above (5) was investigated using a spectroscopic ellipsometer (SOPRA). As a result, it was found that the optical constant showed the change shown in FIG. 51 in accordance with the film forming conditions when the Si _x O _y N _z and Si _x N _y films were formed by the CVD method. The region indicated by ○ in Fig. 51 satisfies the conditions in Figs. 14 and 36. That is, the Si _x O _y N _z and Si _x N _y films are 25 nm thick and are reflected on Al, Al-Si and Al-Si-Cu materials. 52 shows the standing wave effect when the protective film is used and when the anti-reflective film is not used. In the case where the Si _x O _y N _z and Si _x N _y films were 25 nm, the standing wave effect was about ± 0.5%, and the standing wave effect was reduced to about 1/60 compared with the case where no antireflection film was used.

Example 66

In this embodiment, the curved value or n in the figure (FIGS. 14 and 36) showing the relationship between the antireflection film shown in Example 65 and the optical characteristics to be satisfied of the optimum antireflection film is shown in FIG. Regarding the values ± 0.3 and k, a Si _x O _y N _z film in the range of the curve value ± 0.3 was formed by the following method to form an antireflection film as shown in FIG.

That is, in the present embodiment, a mixed gas of SiH ₄ + O ₂ + N ₂ or SiH is used, using microwave (2.45 GHz) using a parallel plate plasma CVD method, an ECR plasma CVD method or a bias ECR plasma CVD method. ₄ + N ₂ O was deposited by using a mixed gas.

Example 67

In this embodiment, the curved values in the figures (FIGS. 14 and 36) showing the relationship between the antireflection film shown in Example 65 and the optical characteristics to be satisfied of the optimum antireflection film, or n, are curved. Recommend the phase values ± 0.3 and k, the Si _x O _y N _z film in the range of the curve value ± 0.3 was formed by the following method to form an antireflection film as shown in FIG.

In other words, in this embodiment, a mixed gas of SiH ₄ + NO ₂ + N ₂ or SiH is used, using microwave (2.45 GHz), using a parallel plate plasma CVD method, an ECR plasma CVD method, and a bias ECR plasma CVD method. using ₄ + N ₂ O gas mixture and, as a buffer gas was formed by using Ar.

Example 68

In this embodiment, the curved values in the figures (FIGS. 14 and 136) showing the relationship between the antireflection film thickness shown in Example 65 and the optical characteristics to be satisfied of the optimum antireflection film, or n, Regarding the curve value ± 0.3 and k, a Si _x 0 _y N _z film in the range of the curve value ± 0.3 was formed by the following method to form an antireflection film as shown in FIG.

That is, in this embodiment, the film was formed by using a parallel plate plasma CVD method, an ECRCVD method or a bias ECRCVD method using a mixed gas of SiH ₄ + O ₂ + N ₂ or a SiH ₄ + N ₂ O mixed gas.

Example 69

In the present embodiment, the curve values in the figures (FIGS. 14 and 36) showing the relationship between the antireflection film thickness shown in Example 65 and the optical characteristics to be satisfied of the optimum antireflection film, or n, Regarding the curve value ± 0.3 and k, a Si _x O _y N _z film in the range of the curve value ± 0.3 was formed by the following method to form an antireflection film as shown in FIG.

That is, in the present embodiment, a parallel gas plasma CVD method, an ECR plasma CVD method, or a bias ECR plasma CVD method is used, and a mixed gas of SiH ₄ + O ₂ + N ₂ or a SiH ₄ + N ₂ O mixed gas is used. The film was formed using Ar as the buffer gas.

Example 70

In the present embodiment, the curve values in the figures (FIGS. 14 and 36) showing the relationship between the antireflection film thickness shown in Example 65 and the optical characteristics to be satisfied of the optimum antireflection film, or n, Regarding the curve value ± 0.3 and k, a Si _x 0 _y N _z film in the range of the curve value ± 0.3 was formed by the following method to form an antireflection film as shown in FIG.

That is, in this embodiment, microwaves (2.45 GHz) are used, using a parallel plate plasma CVD method, an ECR plasma CVD method, or a bias ECR plasma CVD method, and a SiH ₄ + NH ₃ mixed gas or SiH ₂ Cl ₂ + It was formed by using the NH ₃ gas mixture.

Example 71

In the present embodiment, the curve values in the figures (FIGS. 14 and 36) showing the relationship between the antireflection film thickness shown in Example 65 and the optical characteristics to be satisfied of the optimum antireflection film, or n, Regarding the curve value ± 0.3 and k, a Si _x 0 _y N _z film in the range of the curve value ± 0.3 was formed by the following method to form an antireflection film as shown in FIG.

In other words, in the present embodiment, microwave (2.45 GHz) is used using a parallel plate plasma CVD method, an ECR plasma CVD method or a bias ECR plasma CVD method, and a SiH ₄ + O ₂ mixed gas or a SiH ₂ HCl ₂ + The film was formed using NH ₃ mixed gas and Ar as the buffer gas.

Example 72

In the present embodiment, the curve values in the figures (FIGS. 14 and 36) showing the relationship between the antireflection film thickness shown in Example 65 and the optical characteristics to be satisfied of the optimum antireflection film, or n, Regarding the curve value ± 0.3 and k, a Si _x N _y film in the range of the curve value ± 0.3 was formed by the following method to form an antireflection film as shown in FIG.

That is, in this embodiment, the film was formed using a parallel plate plasma CVD method, an ECR plasma CVD method, or a bias ECR plasma CVD method, using a SiH ₄ + NH ₃ mixed gas or a SiH ₂ Cl ₂ + NH ₃ mixed gas. .

Example 73

In the present embodiment, the curve values in the figures (FIGS. 14 and 36) showing the relationship between the antireflection film thickness shown in Example 65 and the optical characteristics to be satisfied of the optimum antireflection film, or n, Regarding the curve value ± 0.3 and k, a Si _x N _y film in the range of the curve value ± 0.3 was formed by the following method to form an antireflection film as shown in FIG.

That is, in this embodiment, a parallel plate plasma CVD method, an ECR plasma CVD method, or a bias ECR plasma CVD method is used, and a SiH ₄ + O ₂ mixed gas or a SiH ₂ Cl ₂ + NH ₃ mixed gas is used, and a buffer is used. It formed into a film using Ar as a gas.

Example 74

In the present embodiment, the curve values in the figures (FIGS. 14 and 36) showing the relationship between the antireflection film thickness shown in Example 65 and the optical characteristics to be satisfied of the optimum antireflection film, or n, Regarding the values of the curves ± 0.3 and k, the material was etched using the Si _x O _y N _z and Si _x N _y films within the range of the curve values ± 0.3 and Si _x Ny as a mask using a resist pattern as follows.

In other words, the etching of the Si _x O _y N _z and Si _x N _y films is performed using a gas system of CHF ₃ (50-100 SCCM) + O ₂ (3-20 SCCM), and about 100 to 100 OW under a pressure of about 2 Pa. Was added to etch by the reactive etching method of increasing the ionicity, and the desired pattern was etched.

Example 75

In the present embodiment, the curved values in the figures (FIGS. 14 and 36) showing the relationship between the antireflection film thickness shown in Example 65 and the optical characteristics to be satisfied of the optimum antireflection film, or n, Regarding the curve values ± 0.3 and k, the material was etched using the Si _x O _y N _z and Si _x N _y films within the range of the curve value ± 0.3 and Si _x N _y as a mask by the following method.

That is, the etching of the Si _x O _y N _z and Si _x N _y films is performed using a gas system of C ₄ F ₈ (30 to 70 SCCM) + CHF ₃ (10 to 30 SCCM), and is about 100 to 100 OW under a pressure of about 2 Pa. The desired pattern was etched by applying reactive power to etch by reactive etching with increased ionicity.

Example 76

In the present embodiment, the curve values in the figures (FIGS. 14 and 36) showing the relationship between the antireflection film thickness shown in FIG. 65 and the optical characteristics to be satisfied of the optimum antireflection film, or n, Regarding the curve values ± 0.3 and k, the material was etched using the Si _x O _y N _z and Si _x N _y films within the range of the curve value ± 0.3 and Si _x N _y as a mask by the following method.

That is, the etching of the Si _x O _y N _z and Si _x N _y films is performed using a gas system of S ₂ F ₂ (5 to 30 SCCM), and the ionicity is increased by applying a power of about 100 to 100 OW under a pressure of about 2 Pa. The desired pattern was etched by etching by the reactive etching method.

Example 77

In this embodiment, a KrF excimer laser is used to form a stable resist pattern on a silicon substrate such as monocrystalline silicon, polycrystalline silicon, amorphous silicon, doped polysilicon, and the like on a silicon oxide film such as SiO ₂ . According to the present invention, it is preferable to use an organic or inorganic film of n = 1.8 to 2.6, k = 0.1 to 0.8, in particular a Si _x O _y Nz, Si _x N _y film, having a film thickness of 20 to 150 nm as an antireflection film. Found and constructed.

When Si _x O _y N _z and Si _x N _y films are used as antireflection films, they can be formed by various CVD methods. In addition, this Si _x O _y N _z and Si _x N _y can be etched by RIE with high ionicity using CHF ₃ , C ₄ F ₈ , CHF ₃ , and S ₂ F ₂ -based gas as an etchant.

In other words, this embodiment uses the KrF excimer morphography and uses Si _x O _y as an anti-reflection film to form a stable resist pattern on a silicon substrate such as single crystal silicon and a silicon oxide film such as SiO ₂ on this material. It is an example using N _z and Si _x N _y films.

In the resist pattern forming method of this embodiment, as shown in FIG. 53, an antireflection film ARL is formed on a silicon substrate such as single crystal silicon by Si _x O _y N _z and Si _x N _y , and the photoresist is formed on the antireflection film ARL. After the resist PR is formed or a silicon oxide film such as SiO ₂ is formed on the antireflection film, the photoresist PR is formed to form a resist pattern.

In this embodiment, in particular, a silicon oxide film such as SiO ₂ is formed on a silicon substrate such as single crystal silicon or on this material layer, and the Si _x O as an antireflection film ARL is formed when the silicon oxide film is patterned by a photolithography process and an etching process using photoresist PR. _It applies to this invention using _y N _z and Si _x N _y .

Firstly, an inorganic or organic film having n = 1.8 to 2.6, k = 0.1 to 0.8 and a film thickness of 20 to 150 nm as an antireflection film used on a silicon substrate such as single crystal silicon or on a material, in particular, Si _x O _y N _z , The procedure for selecting the Si _x N _y film and the method of determining the conditions to be satisfied will be described. The following procedures (1) to (6) were performed.

(1) An XP8843 resist (Spray Microelectronics Co., Ltd.) was applied onto a Si substrate in the absence of an antireflection film, and exposed and developed with an exposure apparatus using KrF excimer laser light having a wavelength of 248 nm as a light source. The standing wave effect at this time is shown in FIG. In Fig. 41, the standing wave effect is about ± 20%.

(2) In FIG. 2, the maximum value of the standing wave effect is, for example, when the resist film thickness is 985 nm. Focusing on the resist film thickness of 985 nm and setting the film thickness of the antireflection film to 30 nm, the change in the amount of absorbed light in the resist film with respect to the change of the optical constants n _arl and k _arl of the antireflection film is determined.

(3) A plurality of different resist film thicknesses were taken, and (2) was repeated for each of them.

(4) The results are shown and their common areas are obtained. Such an operation is obtained for various antireflection films, thereby obtaining an optimum value (n value, k value) of an optical constant for a certain film thickness. For example, the optical conditions to be satisfied of the optimum antireflection film when the film thickness of the antireflection film is 32 nm are n _arl = 2.0 and k _arl = 0.55.

The optical conditions to be satisfied of the optimum antireflection film when the film thickness of the antireflection film is 100 nm are n _arl = 1.9 and k _arl = 0.35.

When the standing wave effects were obtained using the above two conditions, the results shown in Figs. 54 and 55 were obtained. 54 and 55, the standing wave effect shown by the optimum value was very small, and in either case, the range was about 1% or less. Compared with the case without the antireflection film, the standing wave effect was reduced to about 1/20 or less.

(5) The above operations (2) to (4) are performed when the thickness of the antireflective film is set to 32 nm and 100 nm, but the film thickness (ARL film thickness) of other different antireflective films is also (2) to (4). When repeated, the optimum condition of the antireflection film corresponding to the film thickness of the antireflection film is obtained.

(6) The conditions to be satisfied of the antireflection film obtained in the above (5) were examined by using a spectroscopic ellipsometer (SOPRA Co., Ltd.). As a result, it was found that the optical constant showed the change shown in FIG. 56 corresponding to the film formation conditions when the Si _x O _y N _z and Si _x N _y films were formed by the CVD method. A region indicated by ○ in Fig. 56 satisfies the condition (4) described above. 54 and 55 show the results of determining the standing wave effect under the condition indicated by ○ in FIG. In either case, by using the Si _x O _y N _z and Si _x N _y films as antireflection films, the standing wave effect is about ± 1.0% or less, and the standing wave effect is about 1/20 as compared with the case where no antireflection film is used. Reduced.

Example 78

This example uses the method shown in Example 77, in particular, a photolithography process using photoresist PR on a silicon oxide film such as SiO ₂ on a silicon-based substrate such as polycrystalline silicon, amorphous silicon, doped polysilicon or the like or a material layer thereof. ARL as an anti-reflection film in the case of patterning by an etching process to a configuration using the _{Si x O y N z, Si} x N y.

First, as an antireflection film used on silicon-based substrates such as polycrystalline silicon, amorphous silicon, doped polysilicon, etc. using the same method as in Example 77, n = 1.8 to 2.6, k = 0.1 to 0.8, and a film thickness of 20 to 150 nm. The procedure for selecting an inorganic or organic film, in particular, a Si _x O _y N _z , Si _x N _y film and the conditions to be satisfied will be described.

(1) Using the same technique as in Example 77, for example, the optical conditions to be satisfied of the optimum antireflection film when the film thickness of the antireflection film is 33 nm are n _arl = 2.01 and k _arl = 0.62. When the standing wave effect was obtained using these conditions, the result shown in FIG. 57 was obtained. In Fig. 57, the standing wave effect was very small and in any case was about ± 1% or less. Compared with the case without the antireflection film, the standing wave effect was reduced to about 1/20.

(2) The above operation is a case where the thickness of the antireflection film is set to 33 nm. However, if the above-described steps are repeated with respect to the film thickness (ARL film thickness) of the other antireflection film, the reflection corresponding to the film thickness of the antireflection film is repeated. The optimum condition of the prevention film is obtained.

(3) The conditions for satisfying the antireflection film obtained as described above are as follows. The optical constant change (Fig. 57) corresponding to the film forming conditions when the Si _x O _y N _z and Si _x N _y films are formed by the CVD method is used. Corresponds to the area indicated by. That is, when the Si _x O _y N _z and Si _x N _y films are 33 nm thick, the standing wave effect is reduced when the antireflection film is used on a silicon substrate such as polycrystalline silicon, amorphous silicon, doped polysilicon, or the like. It is shown at 57 degrees. In the case where the Si _x O _y N _z and Si _x N _y films were set to 33 nm, the standing wave effect was about ± 1.0% or less, and the standing wave effect was reduced to about 1/20 or less compared with the case where no antireflection film was used.

Example 79

In this embodiment, the Si _x O _y N _z films shown in Examples 77 and 78 were formed by the following method to form an antireflection film as shown in FIG.

That is, in the present embodiment, a mixed gas of SiH ₄ + O ₂ + N ₂ or SiH is used, using microwave (2.45 GHz) using a parallel plate plasma CVD method, an ECR plasma CVD method or a bias ECR plasma CVD method. ₄ + N ₂ O was deposited by using a mixed gas.

Example 80

In this embodiment, the Si _x O _y N _z films shown in Examples 77 and 78 were formed by the following method to form an antireflection film as shown in FIG.

In other words, in this embodiment, a mixed gas of SiH ₄ + O ₂ + N ₂ or SiH is used, using microwave (2.45 GHz), using a parallel plate plasma CVD method, an ECR plasma CVD method, and a bias ECR plasma CVD method. using ₄ + N ₂ O gas mixture and, as a buffer gas was formed by using Ar.

Example 81

In this embodiment, the Si _x O _y N _z films shown in Examples 77 and 78 were formed by the following method to form an antireflection film as shown in FIG.

That is, in this embodiment, the film was formed by using a parallel plate plasma CVD method, an ECRCVD method or a bias ECRCVD method using a mixed gas of SiH ₄ + O ₂ + N ₂ or a SiH ₄ + N ₂ O mixed gas.

Example 82

In this embodiment, the Si _x O _y N _z films shown in Examples 77 and 78 were formed by the following method to form an antireflection film as shown in FIG.

That is, in the present embodiment, a parallel gas plasma CVD method, an ECR plasma CVD method, or a bias ECR plasma CVD method is used, and a mixed gas of SiH ₄ + O ₂ + N ₂ or a SiH ₄ + N ₂ O mixed gas is used. The film was formed using Ar as the buffer gas.

Example 83

In this example, the Si _x N _Y films shown in Examples 77 and 78 were formed by the following method to form an antireflection film as shown in FIG.

In other words, in this embodiment, microwave (2.45 GHz) is used, using a parallel plate plasma CVD method, an ECR plasma CVD method or a bias ECR plasma CVD method, and a SiH ₄ + NH ₃ mixed gas or a SiH ₂ Cl ₂ + It was formed by using the NH ₃ mixed gas.

Example 84

In this example, the Si _x N _Y films shown in Examples 77 and 78 were formed by the following method to form an antireflection film as shown in FIG.

That is, in the present embodiment, microwaves (2.45 GHz) are used using a parallel plate plasma CVD method, an ECR plasma CVD method, or a bias ECR plasma CVD method, and a SiH ₄ + O ₂ mixed gas or SiH ₂ Cl ₂ + The film was formed by using an NH ₃ mixed gas and using Ar as a buffer gas.

Example 85

In this example, the Si _x N _Y films shown in Examples 77 and 78 were formed by the following method to form an antireflection film as shown in FIG.

That is, in this embodiment, the film was formed using a parallel plate plasma CVD method, an ECR plasma CVD method, or a bias ECR plasma CVD method, using a SiH ₄ + NH ₃ mixed gas or a SiH ₂ Cl ₂ + NH ₃ mixed gas. .

Example 86

In this example, the Si _x N _Y films shown in Examples 77 and 78 were formed by the following method to form an antireflection film as shown in FIG.

That is, in this embodiment, a parallel plate plasma CVD method, an ECR plasma CVD method, or a bias ECR plasma CVD method is used, and a SiH ₄ + O ₂ mixed gas or a SiH ₂ Cl ₂ + NH ₃ mixed gas is used, and a buffer is used. It formed into a film using Ar as a gas.

Example 87

In this embodiment, the Si _x O _y N _z and Si _x N _y films shown in Examples 77 and 78 were etched using the resist pattern as a mask by the following method.

That is, etching of Si _x O _y N _z and Si _x N _y films is performed using a gas system of CHF ₃ (50 to 10 OSCCM) + O ₂ (3 to 20 SCCM), and the power is about 100 to 100 OW under a pressure of about 2 Pa. Was added to etch by the reactive etching method of increasing the ionicity, and the desired pattern was etched.

Example 88

In this embodiment, the Si _x O _y N _z and Si _x N _y films shown in Examples 77 and 78 were etched using the resist pattern as a mask by the following method.

That is, the etching of the Si _x O _y N _z and Si _x N _y films is performed using a gas system of C ₄ F ₈ (30 to 70 SCCM) + CHF ₃ (10 to 30 SCCM), and is about 100 to 100 OW under a pressure of about 2 Pa. The desired pattern was etched by applying the reactive power to the etching by the reactive etching method of increasing the ionicity.

Example 89

In this embodiment, the Si _x O _y N _z and Si _x N _y films shown in Examples 77 and 78 were etched using the resist pattern as a mask by the following method.

That is, the etching of the Si _x O _y N _z and Si _x N _y films is performed using a gas system of S ₂ F ₂ (5 to ₃ OSCCM), applying a power of about 100 to 100 OW under a pressure of about 2 Pa to increase ionicity. The desired pattern was etched by etching by the reactive etching method.

Example 90

In the present Example, when SiO _x N _y film was formed by using SiH ₄ and N ₂ O mixed gas, it was confirmed that the formed film contained hydrogen.

That is, Fig. 58 shows the relationship between the SiH ₄ / N ₂ O flow rate ratio in the film formation in this embodiment, and the n and k values of the formed SiO _x N _y film, and Fig. 59 also shows SiH ₄ / N _2. The relationship between the O flow rate ratio and the amount (atom%) of each element of Si, O, N, and H in the formed SiO _x N _y is shown, and fluctuates by the SiH ₄ / N ₂ O flow rate ratio as understood from FIG. However, it is understood that the SiO _x N _y film formed contains H, and in fact, an SiO _x N _y H _z elemental film is formed.

Qualitatively, as shown in the infrared absorption spectrum diagram (particularly the FTIR diagram) shown in FIG. 60, the peaks derived from the Si-O and Si-N bonds in any flow rate ratio are shown. In addition, peaks derived from NH and Si-H bonds exist.

The existence of such hydrogen is unknown, but it may be considered to some extent that it contributes to the antireflection function. When hydrogen is used as a source gas, hydrogen is generally considered to be contained in the film in some form, and particularly, the content of hydrogen is remarkable in plasma usable film means such as plasma CVD.

In the present embodiment, as the material the material a refractory metal silicide of WSi, also SiO ₂ addition of WSi and the metal material of Al-1wt% Si the various film the SiH ₄ / N ₂ O gas mixture to an anti-reflection film having a thickness in the The film was formed using and the SiH ₄ / N ₂ O flow rate ratio giving optimum k value and n value for i-ray or excimer laser light was obtained from Fig. 58, and x, y of SiO _x N _y H _z obtained by and z values were examined, and were as shown in Table 1 below.

TABLE 1

Lines were shown where the flow rate ratios respectively correspond to the above 1 to 4 in FIG.

As the anti-reflection film for the WSi from this embodiment in a range of wavelength 150nm~450nm, SiO _x N _y; When H _z is used, x is preferably in the range of 0.30 to 0.80, y is in the range of 0.10 to 0.30, and z is zero, i.e. it does not need to contain hydrogen, but in the case of hydrogen, z is 0.20 to 0.60 It can be seen that it is desirable to be in the range.

Further, in the range of 150~450nm wavelength as the anti-reflection film for the _{Al-Si, SiO x N y} ; When H _z is used, x is preferably in the range of 0.30 to 0.70, y is in the range of 0.05 to 0.30, and z is zero, i.e. it does not need to contain hydrogen, but in the case of hydrogen, z is 0.1 to 0.5 It is understood that the range is preferable.

In addition, the general flow ratio used for the deposition of the SiO _x N _y film is SiH ₄ / N ₂ O in the range of 0.2 to 2.0, as shown in FIG.

Although the antireflection effect (resistance wave reduction effect) in the case of using the antireflection film obtained in the present embodiment was simulated, it is shown in Figs. 62 (WSO phase with SiO ₂ added) and 63 (Al-Si phase). From both figures, it can be seen that the standing wave effect is almost lost in the case of ARL, which is the case of the antireflection film, of the anti-reflection film.

In fact, FIG. 64 shows the anti-reflection effect of the 0.44 mu m line and space pattern on the WSi with respect to the i-line lithography. Also from this figure, the effect of the antireflection film in the present embodiment can be understood.

Again, the simulation results are shown in Figs. 65 (WSi phase, i-line, absorbance) and 66 degrees (WSi phase, i-line, reflectance). The n and k values of the antireflection film described in this drawing were formed to a thickness of 30 nm, and measured using the n and k values of the photoresist described in this drawing. In both cases of reflection and absorption, excellent antireflection effect was obtained.

67 and 68 show the relationship between the resist thickness and the critical dimension. All were tested using KrF excimer laser light on WSi. FIG. 67 shows a case of a 30 탆 line and space pattern, and FIG. 68 shows a case of a 0.35 탆 line and space pattern. In either case, a chemically amplified positive resist was used as the resist.

Example 91

As described above, as the antireflection film in the excimer laser light, for example, in the case of the high melting point metal silicide phase, materials around n of about 2.4 and k about 0.7 are suitable, and SiO _x , SiN _x , and SiO _x N are suitable. _y is effective as an antireflection film. In addition, by changing the composition ratio (x, y) of these films to form SiO _x , SiN _x , and SiO _x N _y having n and k having these antireflection film effects, it is thought that the n and k of the film can be changed. It is not necessarily easy to form a film having these desired n and k by controlling the composition ratio with good controllability.

In this embodiment, in order to form a film having desired n and k as the antireflection film, an antireflection film is formed using as a source gas of a material containing at least Si element and a material containing at least 0 element. For example, when the gas composition ratio is used as a parameter for controlling the composition ratio _{x in the} SiO _x film, x becomes smaller as the ratio of source gas containing Si element is higher, thereby changing the composition of the film. As a result, the optical constants (n, k) can be controlled.

In this embodiment, SiH ₄ is used as the material containing at least Si, N ₂ O is used as the material containing at least O, and the optical constant of the film is controlled by using the gas flow rate ratio of SiH ₄ and N ₂ O as parameters. A film with the desired antireflection effect was formed. The optical constant of the film when the gas flow rate ratio of SiH ₄ to N ₂ O is changed by using the parallel plate plasma CVD apparatus is changed as shown in FIG. For example, the following conditions may be used as one of film forming conditions suitable for excimography.

SiH ₄ = 50 sccm

N ₂ O = 5 Osccm

RF power = 190 W

Pressure = 332.5 Pa (2.5torr)

Substrate Temperature = 400 ℃

Interelectrode Distance = 1cm

Here, the method of controlling the optical constant of the film mainly using the gas flow rate as a parameter has been described, but the optical constant of the film can be controlled even if the film formation pressure, RF power, and substrate temperature are used as parameters.

Example 92

This embodiment is a method of forming an antireflection film using at least an organic compound containing Si element as a raw material. When the organic compound is used as a raw material, the coverage of the antireflection film in the stepped portion is improved, that is, the film thickness difference between the antireflection film in the flat portion and the stepped vertical portion is reduced, thereby improving the uniformity of the antireflection effect in the semiconductor device chip. do.

Therefore, since the present embodiment uses an organic compound having excellent step coverage (coverage of the stepped portion) as the raw material gas, it can be said to be particularly effective in devices having a strict step. As the organic compound, for example, TEOS or OMCTS (Si ₄ O (CH ₃ ) ₈ ; Si / O ratio = 1) or HMDS (Si ₂ O (CH ₃ ) ₆ ; Si / O ratio = 2) can be used. have. In this embodiment, a parallel plate plasma CVD apparatus was used under the following film forming conditions.

OMCTS = 50 sccm

RF power = 190 W

Pressure = 332.5 Pa (2.5torr)

Substrate Temperature = 400 ℃

Interelectrode Distance = 1cm

Example 93

In Example 92, when it is desired to form a film having a high Si ratio, SiH ₄ or the like may be added as the Si source containing no O or N. Film formation conditions in the case of using a parallel plate plasma CVD apparatus are as follows.

OMCTS = 50 sccm

SiH ₄ = 5 sccm

RF power = 190 W

Pressure = 332.5 Pa (2.5torr)

Substrate Temperature = 400 ℃

Interelectrode Distance = 1cm

As described above, according to the invention of the present application, when a resist pattern is formed on an arbitrary material (substrate) using light of any single wavelength as an exposure light source, even if the resist pattern is fine, a stable resist is satisfactory. The conditions of the antireflection film to be used therein can be determined so that a pattern can be formed. In addition, according to the invention of the present application, an antireflection film under such conditions can be formed. Further, according to the invention of the present application, a novel antireflection film can be developed, and a resist pattern forming method using the antireflection film can be provided. In addition, according to the present invention, it is possible to provide a thin film forming method that can be suitably used for the formation of such an antireflection film.

Claims (14)

A resist pattern forming method comprising a Si _x O _y N _z film or a Si _x N _y film having a reflection refractive index n = 2.4 ± 0.6 and an absorption refractive index k = 0.7 ± 0.2 as an antireflection film on a metal material. The method of claim 1, wherein the metal-based material is made of a high melting point metal silicide. A Si _x O _y N _z or Si _x N _y film is formed as an antireflection film on the silicon material to form a resist pattern, and the silicon material is any one of monocrystalline silicon, polycrystalline silicon, amorphous silicon, and doped polysilicon. Resist pattern forming method, characterized in that. (Gangjung) A resist pattern forming method for forming at least one antireflection film made of silicon carbide containing hydrogen, and forming a resist pattern by forming a photoresist on the antireflection film. SiO _x N _y H _z (where x is 0.30 to 0.80, y is 0.10 to 0.30, and z is 0 to 0.60) as the antireflection film in the range of 150 to 450 nm on the high melting point metal silicide material. A film is formed, and a photoresist is formed on the antireflection film to form a resist pattern. SiO _x N _y H _z (where x is 0.30 to 0.80, y is 0.10 to 0.30, and z is 0.20 to 0.60) as the antireflection film in the range of 150 to 450 nm on the high melting point metal silicide material. A film is formed, and a photoresist is formed on the antireflection film to form a resist pattern. 7. The method of forming a resist pattern according to claim 5 or 6, wherein the high melting point metal silicide is tungsten silicide. SiO _x N _y H _z (where x is 0.30 to 0.70, y is 0.05 to 0.30, and z is 0 to 0.50) as an antireflection film in the wavelength range of 150 to 450 nm on the metal material. And a photoresist is formed on the anti-reflection film to form a resist pattern. SiO _x N _y Hz (where x is 0.30 to 0.70, y is 0.05 to 0.30, and z is 0.1 to 0.50) as an antireflection film in the wavelength range of 150 to 450 nm on the metal material. And a photoresist is formed on the antireflection film to form a resist pattern. The method of forming a resist pattern according to claim 8 or 9, wherein the metal material is an aluminum-based material. The method of claim 10, wherein the aluminum-based material is an aluminum-silicon alloy. In the method of forming a thin film by vapor phase growth using at least a substance containing a silicon element and an oxygen element as a source gas, the content ratio of the silicon element and the oxygen element contained in the source gas is Thin film formation method, characterized in that the range. The method of claim 2, wherein the source gas contains at least a hydrogen element. In the thin film formation method by vapor deposition using SiH ₄ and N ₂ O as source gases, the flow rate of the SiH ₄ and N ₂ O gas, Thin film formation method, characterized in that the range.