JP3309095B2 - Dry developing method and semiconductor device manufacturing method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a dry developing method used in a lithography step or the like in manufacturing a semiconductor element or the like and a method for manufacturing a semiconductor device using the dry developing method.

[0002]

2. Description of the Related Art Lithography for forming an etching mask on a substrate in the manufacture of a semiconductor device is an important pattern forming process which is performed not only in processing semiconductors but also dielectrics and metals. Conventionally, in lithography, a wet development method in which a substrate on which a resist film is deposited is immersed in a developing solution after exposure, and an exposed or unexposed portion is dissolved to form a positive or negative resist pattern, respectively, has been widely used. I have. However, with the miniaturization of processing dimensions, it is becoming an important problem to reduce the deterioration of the resist pattern shape due to the penetration of a developer. In addition, an increase in the number of steps accompanying the increase in the number of resist layers has also become a problem.

One solution to this problem is to dry the resist development process. Dry development removes the resist film using the energy of the exposure light itself, heat, plasma, etc., and since it does not use a developing solution, it has the potential to improve the resolution and further simplifies the process. It has the potential to improve throughput and reduce process and equipment costs.

[0004] As resist materials for dry development, see International Conference on Polymers for Microelectronics (1993) Proceedings, pp. 302-305.
(The International Symposium on Polymers for Micro
electronics, pp 302-305 (1993)). Among them, polymethacrylate containing silicon in the side chain has high self-developability and oxygen-reactive ion etching resistance, and is a particularly promising material.

On the other hand, a silicon-containing material has recently attracted attention as an upper layer resist material of a multilayer resist film used in a usual wet developing method. In particular, polysilane, silicon-containing polymethacrylate and polyolefin have been actively studied as positive resist materials because they have photosensitivity and oxygen-reactive ion etching resistance. For details, see, for example, Chemical Reviews, Vol. 89, (1989), pp. 1359-14.
Page 10 (Chemical Reviews, 198)
9, vol. 89, pp1359-1410), Journal of Electrochemical Society 132
Vol., (1985) pp. 1178 to 1182 (J.
Electrochem. Soc. vol. 132, p
pp. 1178-1182 (1985)). These materials also have a self-developing property of decomposing and evaporating only by exposure.

[0006]

In the above-mentioned conventional resist made of polymethacrylate containing silicon in the side chain, the residue after exposure is removed by dry etching using a halide gas. Since the etching rate of the remaining resist film in the exposed part is lower than the etching rate in the unexposed part, there is a problem that the pattern shape is deteriorated. This will be described with reference to FIG. In FIG. 1, 1 is a silicon substrate, 2 is a lower resist film having a thickness of 1 μm made of novolak resin formed by spin coating, and 3 is an upper resist film having a thickness of 0.2 μm, and is trimethylsilylmethyl methacrylate represented by the following formula 1. -Containing resist film composed of a copolymer of styrene and methyl methacrylate, 5 is a fragment of a silicon-containing resist material that has been decomposed and evaporated by soft X-ray exposure, and 8 is a resist in an unexposed portion during reactive ion etching using SF _6. The fragment 9 generated by etching the film is a fragment generated by etching the remaining resist film of the exposed portion during reactive ion etching using SF ₆ .

[0007]

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[0008] A soft X-ray 4 having a wavelength of 13 nm and an intensity of 20 mW / cm ² having a 0.1 μm line and space pattern on the surface of the resist film is irradiated to the two-layer resist shown in FIG. . Then, as shown in FIG. 1 (b), the polymer decomposes and evaporates in the exposed area, the film thickness is reduced to 0.1 μm by self-development, and the pattern having a height of 0.1 μm is formed on the upper resist film containing silicon. 6 is formed (FIG. 1C). Next, as shown in FIG. 1 (d), when reactive ion etching is performed using SF ₆ gas, the remaining resist film in the exposed portion is removed. Therefore, when the remaining resist film 7 in the exposed portion is completely removed, the height of the unexposed portion, that is, the pattern 10 of the upper resist film is reduced to about 0.03 μm (FIG. 1 ( e)).

The cause is considered as follows. The ester bond of the acrylate moiety is cut by irradiation with ionizing radiation, and is converted into CO or CO ₂ and evaporated, whereby the terminal portion of the side chain bonded to the ester moiety is also evaporated. As a result, the silicon content of the exposed portion is reduced, and the reactive ion etching using SF ₆ gas is less likely to be etched than the unexposed portion having a relatively high silicon content. For this reason, the height of the pattern formed on the silicon-containing resist film decreases when the remaining resist film in the exposed portion is removed.

When the oxygen-reactive ion etching is performed using the thus obtained silicon-containing upper resist film pattern 10 as a mask, the thickness of the silicon-containing resist film becomes smaller than that of the lower resist film 2. Because of the insufficientness, the aspect ratio of the pattern 11 of the obtained lower resist film becomes small as shown in FIG.

A first object of the present invention is to provide a dry developing method which does not cause shape deterioration when removing a residual resist film of a resist pattern formed by self-development. A second object of the present invention is to provide a method for manufacturing a semiconductor device using such a dry developing method.

[0012]

In order to achieve the first object, a dry developing method of the present invention comprises forming at least one lower resist film made of a resist material on a substrate, and forming the lower resist film on the lower resist film. First, an upper resist film made of a silicon-containing resist material containing a copolymer of an acrylic monomer and a silylated olefin is formed, and a desired portion of the upper resist film is irradiated with ionizing radiation to reduce the thickness of an exposed portion. Then, the remaining film of the upper resist film in the exposed portion is removed by dry etching using a gas containing halogen or a halide, so that the upper resist film has a desired pattern. Further, after these steps, it is preferable to perform reactive ion etching using oxygen gas to transfer the desired pattern to the lower resist film.

Further, in order to achieve the first object,
In the dry development method of the present invention, a resist film made of a silicon-containing resist material containing a copolymer of an acrylic monomer and a silylated olefin is formed on a substrate having a surface of carbon, and a desired portion of the resist film is formed. To reduce the thickness of the exposed portion of the resist film by removing the remaining film of the exposed portion by dry etching using a gas containing a halogen or a halide so that the resist film has a desired pattern. It was made. Also in this case, it is preferable that, after these steps, reactive ion etching using oxygen gas is performed to transfer the desired pattern to carbon on the substrate surface.

In any of the dry development methods, from the viewpoint of obtaining a high etching rate as a gas containing a halogen or a halide and securing safety, chlorine, bromine, hydrogen bromide, sulfur hexafluoride, tetrafluoride, etc. It is preferable to use a gas of sulfur fluoride, hydrocarbon trifluoride, or carbon tetrafluoride.

The composition ratio of the copolymer of the acrylic monomer and the silylated olefin is 0.5 ≦ k, where k is the molar ratio of the silylated olefin to the acrylic monomer.
≦ 3, preferably 0.5 ≦ k ≦ 0.9
More preferably, it is within the range. When k is 0.5 or more, good self-developability can be ensured.
Is 3 or less, high etching resistance is achieved, and k is equal to 0.
This is because if it is 9 or less, it has higher etching resistance.

As the acrylic monomer, at least one monomer selected from the group consisting of acrylate, methacrylate and ethacrylate can be used. However, using methacrylate or ethacrylate allows a resist film having a uniform film thickness to be formed. It is preferred.
Further, it is preferable to use an alkyl acrylate as the acrylate because high sensitivity can be obtained. Also,
As the alkyl acrylate, methyl acrylate or ethyl acrylate is preferable because it exhibits high self-developability.

Further, the silylated olefin is preferably an olefin having a trimethylsilyl group, a trimethylsilylmethyl group, a pentamethyldisilyl group or a pentamethyldisilylmethyl group because of exhibiting high self-developability. Further, when the silylated olefin is silylated styrene, the silicon content in the exposed area is increased, which is preferable. Examples of such a copolymer include a copolymer of methyl methacrylate and trimethylsilylmethylstyrene represented by the following formula 2.

[0018]

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[0019] Mochiiruko a copolymer of sulfone and silane
Can also be. Is in such a copolymer, a trimethylsilyl group, trimethylsilylmethyl group, and styrene having a pentamethyl silyl group or pentamethyl silyl methyl group, it is preferable to use a copolymer of sulfonated. Examples of such a copolymer include polytrimethylsilylstyrene sulfone represented by the following formula 3.

[0020]

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Further, in order to achieve the second object, a method of manufacturing a semiconductor device according to the present invention, wherein any one of the above dry development methods is used for at least a part of a method of manufacturing a semiconductor element. It is.

[0022]

When a resist film containing, for example, a copolymer of acrylate and silylated olefin is formed directly on a substrate or via a lower resist film made of an arbitrary resist material laminated on one or more layers, and then irradiated with ionizing radiation, Breakage of the polymer backbone and side chains occurs. The CO—O bond in the acrylate portion evaporates as carbon monoxide or carbon dioxide, and therefore, the terminal portion of the acrylate side chain also evaporates, contributing to a reduction in the resist film thickness, that is, self-developing. However, since the atoms forming the olefin portion or the bonded atoms are not easily scattered, the silyl groups present at the side chain terminal of the olefin portion do not evaporate and remain in the resist film. Therefore, after self-development, the silicon content in the remaining resist film in the exposed portion becomes higher than that in the unexposed portion.

Subsequently, if dry etching is performed using a halogen or a halide, radicals or ions generated from the halogen or the halide react with silicon atoms in particular to generate a volatile substance. Therefore, the remaining resist film in the exposed portion having a high silicon content is etched faster than the unexposed portion. As a result, it is possible to prevent the pattern shape from being deteriorated when the remaining resist film in the exposed portion is removed. Similar effects can be obtained when a copolymer of sulfone and silane is used. In this case, the sulfonyl group is decomposed and evaporated by irradiation with ionizing radiation. Therefore, the silicon content in the remaining resist film becomes higher than the unexposed portion.

[0024]

【Example】

<Embodiment 1> A first embodiment of the present invention will be described below with reference to the drawings. FIG. 2 is an explanatory view showing the steps of the dry developing method of the present embodiment. In FIG.
Reference numeral 1 denotes a silicon substrate, 2 denotes a lower resist film made of novolak resin formed by spin coating and has a thickness of 1 μm, and 4 denotes a wavelength of 13 nm having a line and space pattern of 0.1 μm on the resist film surface and an intensity of 20 mW / cm.
² is soft X-ray, 12 is 0.2 μm thick made of polytrimethylsilylstyrene sulfone represented by the structural formula of the above formula 3.
13 is a fragment of a silicon-containing resist material that has been decomposed and evaporated by soft X-ray exposure, 14 is a pattern formed on the upper resist film by self-development,
15 remaining resist film exposed portion, 16 fragment resist film occurs etched unexposed portion during the reactive ion etching using SF _6, 17 is the exposed portion at the time of reactive ion etching using SF ₆ Fragments generated by etching the remaining resist film, 18 is the pattern of the formed upper resist film, 19 is the pattern transferred to the lower resist film, and 20 is the remaining upper resist film.

First, a lower resist film was formed on the silicon substrate 1 by spin coating and baked at 200 ° C. for 20 minutes. Further, an upper resist film containing silicon was formed thereon by spin coating, and baked at 80 ° C. for 20 minutes. As a result, a two-layer resist film as shown in FIG. 2A was formed. Next, exposure is performed for 5 seconds using soft X-rays 4 in a vacuum chamber evacuated to a pressure of 1 × 10 ⁻² Pa or less (FIG. 2B), and the resist film thickness of the exposed portion is reduced to 0.1 μm. I let it. As a result, as shown in FIG. 2C, a pattern 14 having a height of 0.1 μm was formed.

Subsequently, SF ₆ gas was introduced and 0.27 P
The reactive ion etching was performed for 1 minute while maintaining the gas pressure of a. Both exposed and unexposed portions generate volatile substances by reaction with plasma and ions, and fragments 16 and 1
7 (FIG. 2D), but the etching rate of the exposed portion is higher than that of FIG.
As shown in (e), while the remaining resist film 15 in the exposed portion was removed, the difference in the resist film thickness between the exposed portion and the unexposed portion became large, and a pattern 18 having a height of 0.15 μm was formed.

Subsequently, after the vacuum chamber was evacuated to a pressure of 1 × 10 ⁻² Pa or less, oxygen gas was introduced and 1.3 Pa
When the oxygen-reactive ion etching was performed while maintaining the above gas pressure, the pattern 18 of the upper resist film had a height sufficient to process a novolak resin film having a thickness of 1 μm. As a result, the pattern 18 is transferred to the lower resist film, and the pattern 19 of the lower resist film having an aspect ratio of 10 is transferred.
was gotten.

The upper resist film was changed to polytrimethylsilylstyrene sulfone, and (1) a copolymer of methyl acrylate and trimethylsilylstyrene,
(2) a copolymer of ethyl acrylate and trimethylsilylstyrene, (3) a copolymer of methylacrylate and trimethylsilylmethylstyrene, (4) a copolymer of methylacrylate and pentamethyldisilylstyrene,
(5) a copolymer of methyl acrylate and pentamethyldisilylmethylstyrene, (6) a copolymer of methylmethacrylate and trimethylsilylstyrene, (7) a copolymer of methylmethacrylate and trimethylsilylmethylstyrene, (8) methylmethacrylate. A copolymer of pentamethyldisilylstyrene, (9) a copolymer of methylmethacrylate and pentamethyldisilylmethylstyrene,
(10) a copolymer of ethyl methacrylate and pentamethyldisilylstyrene, (11) a copolymer of methylethacrylate and trimethylsilylstyrene, (12) a copolymer of ethylethacrylate and trimethylsilylmethylstyrene, (13) A copolymer of ethyl ethacrylate and pentamethyldisilylmethylstyrene, (14) a copolymer of ethylethacrylate and pentamethyldisilylstyrene, (15) a copolymer of trimethylsilylmethylstyrene and sulfone, (16) Using a copolymer of pentamethyldisilylmethylstyrene and sulfone and (17) a copolymer of pentamethyldisilylmethylstyrene and sulfone, patterns were formed in the same manner. In either case,
A pattern of a lower resist film substantially free from shape deterioration as described above was obtained. Further, Cl ₂ , Br ₂ , HB is used instead of SF ₆ as a gas used for reactive ion etching.
Almost the same results were obtained using r, SF ₄ , CHF ₃ , and CF ₄ .

When the substrate is made of carbon graphite or amorphous carbon, it is not necessary to use a lower resist film, and an upper resist film is formed directly on the substrate, self-developed by exposure, and subsequently, the remaining resist film is formed. Was removed, and oxygen-reactive ion etching was performed using the formed pattern of the resist film containing silicon as an etching mask to process the substrate.

<Embodiment 2> A second embodiment of the present invention will be described below with reference to the drawings. FIG. 3 is a conceptual diagram of an apparatus for performing the dry developing method of the present embodiment.
In FIG. 3, 21, 22, 23, 24 and 25 are gate valves, 26 is a vacuum chamber for plasma polymerization, 27 is a vacuum chamber for photoexcited chemical vapor deposition, 28 is a vacuum chamber for exposure, and 29 is a vacuum chamber for reactive ion etching. , 3
0, 31, 32, 33 are turbo molecular pumps, 34, 3
5, 36, 37 and 38 are vacuum valves, 39 is a high-frequency voltage application electrode / substrate stage, 40 and 41 are substrate stages, 42 is a high-frequency voltage application electrode / substrate stage, 4
Reference numerals 3 and 44 denote a high-frequency voltage application device, 45 denotes a counter electrode,
Is an ultraviolet irradiation device, and 47 is 2
0.1 μm line and space soft X-ray flux of 0 mW / cm ² , 48 and 49 are methyl methacrylate gas, 50 is trimethylsilylmethylstyrene gas, 51
Is sulfur hexafluoride, 52 is oxygen, 53 is a silicon substrate, 5
4 is a polymethyl methacrylate film deposited on a silicon substrate, 55 is an upper resist film made of a copolymer of methyl methacrylate and trimethylsilylmethylstyrene deposited on the polymethyl methacrylate film, and 56 is formed on the upper resist film. 0.1 μm line and
The space pattern 57 is a 0.1 μm line and space pattern transferred to the polymethyl methacrylate film.

First, the gate valve 21 was opened, and the silicon substrate 53 was mounted on the high-frequency voltage application electrode / substrate stage 39. The gate valve 21 is closed, and the vacuum chamber 26 for plasma polymerization is
After evacuating to a pressure of 0 ^-4 Pa or less, the vacuum valve 34 is opened, and methyl methacrylate gas 48 is introduced, and 1.3 P
a, while maintaining the pressure of FIG.
When operated under the conditions of 56 MHz and 10 W, the substrate 5
A polymethyl methacrylate film 54 was deposited on No. 3.

Next, the vacuum chamber 26 for plasma polymerization and the vacuum chamber 27 for photoexcited chemical vapor deposition are evacuated by the turbo molecular pumps 30 and 31 to a pressure of 1 × 10 ⁻² Pa or less. Substrate 5
3 was moved into the vacuum chamber 27 for photoexcited chemical vapor deposition, the gate valve 22 was closed, and the silicon substrate 53 was mounted on the substrate stage 40. Further, the vacuum valves 35 and 36 are opened, and a methyl methacrylate gas 49 and a trimethylsilylmethylstyrene gas 50 are introduced.
6 is activated, and the vacuum ultraviolet light having a wavelength of
The entire surface of the substrate was irradiated at an intensity of mW / cm ² for 10 minutes. As a result, an upper resist film 55 made of a copolymer of methyl methacrylate and trimethylsilylmethylstyrene was deposited on the polymethyl methacrylate film 54.

Next, after the vacuum chamber 27 for photo-excited chemical vapor deposition and the vacuum chamber for exposure 28 are evacuated to a pressure of 1 × 10 ⁻² Pa or less by the turbo molecular pumps 31 and 32, the gate valve 23 is opened, and the silicon substrate is opened. The substrate 53 was moved into the exposure vacuum chamber 28, the gate valve 23 was closed, and the silicon substrate 53 was mounted on the substrate stage 41.
After that, when exposure was performed for 5 seconds using the soft X-ray flux 47, the upper resist film 55 in the exposed portion was decomposed and evaporated, and the resist was evaporated.
A 1 μm line and space pattern 56 was formed.

Next, after the vacuum chamber 28 for exposure and the vacuum chamber 29 for reactive ion etching are evacuated to a pressure of 1 × 10 ⁻² Pa or less by the turbo molecular pumps 32 and 33, the gate valve 24 is opened and the silicon Substrate 5
3 was moved into the vacuum chamber 29 for reactive ion etching, the gate valve 24 was closed, and the silicon substrate 53 was mounted on the electrode / substrate stage 42 for applying a high-frequency voltage. Thereafter, the vacuum valve 37 was opened, sulfur hexafluoride 51 was introduced, the high-frequency voltage applying device 44 was operated while maintaining the pressure at 0.27 Pa, and reactive ion etching with sulfur hexafluoride was performed. Of the exposed portion was removed. Further, the vacuum valve 37 is closed, and the vacuum chamber 29 for reactive ion etching is evacuated to a pressure of 1 × 10 ⁻² Pa or less by the turbo molecular pump 33. Then, the vacuum valve 38 is opened to introduce oxygen 52, and the pressure is reduced. When the high-frequency voltage applying device 44 was operated at 1.3 Pa to perform oxygen reactive ion etching, the pattern 56 was transferred to the polymethyl methacrylate film, and the 0.1 μm line and space pattern having a high aspect ratio was obtained. 57 were formed. In this embodiment, the first embodiment
The throughput was further improved as compared with the case of.

Also, in this embodiment, as in the first embodiment, an upper resist film is formed directly on the substrate without forming a lower resist film using a carbon substrate, and self-development by exposure is performed. The remaining resist film was removed, and oxygen-reactive ion etching was performed using the formed resist film pattern containing silicon as an etching mask to process the substrate. Although the upper resist film was formed by chemical vapor deposition, almost the same effect was obtained by plasma polymerization or vapor deposition polymerization.

<Embodiment 3> FIG. 4 is a sectional view of a semiconductor device for explaining a third embodiment of the present invention. A method for manufacturing the semiconductor device will be described. First, an element isolation region 102 is formed on a P-type Si single crystal substrate 101 by a LOCOS method (selective oxidation method of silicon).
An 8 nm SiO ₂ film 103 serving as a gate insulating film 103 was formed by the wet oxidation method described above. Subsequently, the gate electrode 104 is formed by low pressure chemical vapor deposition (LP-CVD) 200.
A phosphorus-doped polycrystalline Si film and a SiO ₂ film 105 are sequentially formed. The formation of the phosphorus-doped polycrystalline Si film is performed using Si
The test was performed at a temperature of 580 ° C. using H ₄ gas and PH ₃ gas.

Next, a 1 μm-thick lower resist film made of a novolak resin is formed on the SiO ₂ film 105 by a spin coating method, and a lower resist film made of a copolymer of trimethylsilylmethylstyrene and methyl methacrylate is further formed thereon. An upper resist film having a thickness of 0.2 μm was formed by a spin coating method. Thereafter, soft X-rays having a wavelength of 13 nm and an intensity of 500 mJ / cm ² are irradiated through a mask, and subsequently, reactive ion etching is performed at a gas pressure of 0.27 Pa using SF ₆ gas to form a pattern on the upper resist film. did. Further, using this as a mask, a gas pressure of 1.3 Pa
Then, oxygen-reactive ion etching was performed to transfer the pattern to the lower resist film. Using this as a mask, reactive ion etching was performed using CHF ₃ gas under the conditions of a gas pressure of 0.27 Pa to form a gate electrode 1 having a width of 0.1 μm.
04 was formed.

Next, the diffusion layer 106 (a) of the transistor
Arsenic is ion-implanted into the portion to be (b),
After performing N ₂ annealing for 5 minutes, the gate electrode 10 is
After a SiO ₂ film 107 was formed on the side wall of No. 4 and electrically insulated, the surfaces of the diffusion layers 106 (a) and (b) of the transistor were exposed.

Hereinafter, phosphorus glass (PS)
G), an insulating film 108 is formed, a contact hole (not shown) is provided therein, an electrode wiring, an interlayer insulating film, and a second wiring (both not shown) are formed in the hole, and a passivation step is performed. Then, a semiconductor device was manufactured.

[0040]

According to the dry developing method of the present invention, a silicon-containing resist film having high resistance to oxygen-reactive ion etching can be patterned by a dry process, and an ultrafine pattern having high resolution can be formed at high throughput. Could be formed. Further, according to the method of manufacturing a semiconductor device of the present invention, an extremely fine pattern of a semiconductor element can be formed without shape deterioration.

[Brief description of the drawings]

FIG. 1 is an explanatory view showing a process of a conventional dry developing method.

FIG. 2 is an explanatory diagram illustrating a process of a dry developing method according to a first embodiment of the present invention.

FIG. 3 is a schematic diagram illustrating a configuration of a pattern forming apparatus used in a dry developing method according to a second embodiment of the present invention.

FIG. 4 is a sectional view of a semiconductor device according to a third embodiment of the present invention.

[Explanation of symbols]

1, 53: silicon substrate 2: lower resist film 3, 12, 20, 55: upper resist film 4: soft X-ray 5, 8, 9, 13, 16, 17: fragment 6, 14: pattern (for upper resist film) 7, 15 ... remaining resist film 10, 18, 56, 57 ... pattern 11, 19 ... pattern (pattern transferred to lower resist film) 21, 22, 23, 24, 25 ... gate valve 26 ... Vacuum chamber for plasma polymerization 27 ... Vacuum chamber for photoexcited chemical vapor deposition 28 ... Vacuum chamber for exposure 29 ... Vacuum chamber for reactive ion etching 30, 31, 32, 33 ... Turbo molecular pump 34, 35, 36, 37, 38 ... Vacuum Valves 39, 42: High-frequency voltage application electrode / substrate stage 40, 41: Substrate stage 43, 44: High-frequency voltage application device 4 5 ... Counter electrode 46 ... Ultraviolet irradiation device 47 ... Soft X-ray flux 48, 49 ... Methyl methacrylate gas 50 ... Trimethylsilylmethylstyrene gas 51 ... Sulfur hexafluoride 52 ... Oxygen 54 ... Polymethyl methacrylate film 101 ... Si single crystal substrate 102 ... Element isolation region 103: gate insulating film 104: gate electrode 105, 107: SiO ₂ film 106 (a) (b): diffusion layer 108: insulating film

──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Takashi Soga 1-280 Higashi Koikekubo, Kokubunji-shi, Tokyo Inside the Central Research Laboratory, Hitachi, Ltd. (72) Inventor Masaaki Ito 1-280 Higashi Koikebo, Kokubunji-shi, Tokyo Hitachi, Ltd. Inside the Central Research Laboratory (72) Inventor Takashi Matsuzaka 1-280 Higashi Koikekubo, Kokubunji-shi, Tokyo Inside the Central Research Laboratory, Hitachi, Ltd. (72) Inventor Hiroaki Tachibana 1-1-1-1 Higashi, Tsukuba-shi, Ibaraki Pref. (72) Inventor Mutsuru Matsumoto 1-1-1 Higashi, Tsukuba-shi, Ibaraki Pref. Tsutomu Iwamoto, Examiner, National Institute of Advanced Industrial Science and Technology, Institute of Materials Engineering (56) References JP-A-59-53841 (JP, A) JP-A-1- 154050 (JP, A) JP-A-7-92683 (JP, A) JP-A-2-23352 (JP, A) JP 62-73250 (JP, A) (58 ) investigated the field (Int.Cl. ^7, DB name) H01L 21/027 G03F 7/26

Claims (11)

(57) [Claims] 1. A first step of forming at least one lower resist film made of a resist material on a substrate, and a silicon-containing resist containing a copolymer of an acrylic monomer and a silylated olefin on the lower resist film. Chemical vapor deposition, plasma polymerization or vapor deposition of upper resist film made of material
A second step of forming by polymerization, a third step of irradiating a desired portion of the upper resist film with ionizing radiation to reduce the thickness of the exposed part, A fourth step of removing the upper resist film by a dry etching using a gas containing a compound to form a desired pattern of the upper resist film. 2. The dry developing method according to claim 1, wherein
After the fourth step, reactive ions using oxygen gas
Etching is performed, and the desired pattern is
A fifth step of transferring to a strike film.
Dry development method. 3. An acrylic resin on a substrate having a carbon surface.
Containing copolymers of terpolymer monomers and silylated olefins
A resist film made of a resist material containing silicon is chemically vapor-deposited.
First process formed by deposition, plasma polymerization or vapor deposition polymerization
By irradiating a desired portion of the resist film with ionizing radiation.
A second step of reducing the film thickness of the exposed portion and a registration of the exposed portion;
Gas containing halogen or halide
And remove the resist film by dry etching.
And a third step of forming a desired pattern.
Dry development method. 4. The dry developing method according to claim 3, wherein
After the third step, reactive ions using oxygen gas
Perform etching and apply the desired pattern to the substrate surface
Having a fourth step of transferring to carbon.
Dry development method. 5. The drive according to claim 1, wherein
B) In the developing method, the halogen or halide is contained.
Gases include chlorine, bromine, hydrogen bromide, sulfur hexafluoride,
With sulfur nitride, hydrocarbon trifluoride or carbon tetrafluoride
A dry development method, characterized in that: 6. The drive according to claim 1, wherein :
In the developing method, the acrylic monomer is
Group consisting of acrylate, methacrylate and ethacrylate
At least one monomer selected from
Dry development method as a feature. 7. The dry developing method according to claim 6, wherein
The acrylate is an alkyl acrylate,
Methacrylate is an alkyl methacrylate,
The ethacrylate is an alkyl ethacrylate.
And a dry development method. 8. The drive according to claim 1, wherein :
In the developing method, the silylated olefin is trimmed.
Tylsilyl group, trimethylsilylmethyl group, pentamethyl
Has a rudisilyl group or a pentamethyldisilylmethyl group
A dry developing method characterized by being an olefin. 9. Dora according to one any one of claims 1 to 7
In the developing method, the silylated olefin is
A dry development method, characterized by being styrene chloride. 10. The dry developing method according to claim 9, wherein
The silylated styrene is a trimethylsilyl group,
Tylsilylmethyl group, pentamethyldisilyl group or pen
Styrene having a tamethyldisilylmethyl group
A dry development method characterized by the above-mentioned. 11. according to any one of claims 1 10
The dry development method is at least one of the semiconductor element manufacturing methods.
A method for manufacturing a semiconductor device, wherein the method is used for a part.