JPH0869959A - Dry-developing method and manufacturing method of semiconductor device - Google Patents

Abstract

PURPOSE: To provide the method capable of avoiding the deterioration in shape when the residual resist film of a resist pattern formed by self-development is removed in the dry developing process. CONSTITUTION: A lower layer resist film 2 is formed on a silicon substrate 1 and then an upper layer resist film 12 comprising silicon containing resist material containing copolymer of acrylic monomer and silylated olefin or another copolymer of sulfon and silane is formed on this lower layer resist film 2. Next, specific part of the upper layer resist film 12 is irradiated with electrolytic radiation to reduce the film thickness of the exposed part furthermore, the residual resist film 15 in the exposed part is removed by the dryetching step using halogen or halogenate so as to obtain a specific pattern 18.

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 lithographic process or the like in manufacturing a semiconductor element or the like and a semiconductor device manufacturing method using the dry developing method.

[0002]

2. Description of the Related Art Lithography for forming an etching mask on a substrate when manufacturing a semiconductor element is an important pattern forming process which is performed not only when processing a semiconductor, but also when processing a dielectric, metal or the like. Conventionally, in lithography, a wet development method is widely used in which a substrate on which a resist film has been deposited is immersed in a developing solution after exposure to dissolve exposed or unexposed portions to form positive or negative resist patterns, respectively. There is. However, as the processing size becomes finer, it is becoming an important problem to reduce the deterioration of the shape of the resist pattern due to the penetration of the developing solution. Further, as the number of resist layers increases, the number of steps increases, which is becoming a problem.

One of the solutions to this is to dry the resist developing process. Dry development uses energy of exposure light itself, heat, plasma, etc. to remove the resist film. Since it does not use a developing solution, it has the potential to improve resolution. It has the potential to improve throughput and reduce process and equipment costs.

As a resist material for dry development, International Conference Polymers for Microelectronics (1993) Proceedings, pp. 302-305.
(The International Symposium on Polymers for Micro
electronics, pp302-305 (1993)). Among them, polymethacrylate containing silicon in the side chain has high self-developing property 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 for a multilayer resist film used in a normal wet development system. In particular, polysilane, silicon-containing polymethacrylate, and polyolefin have photosensitivity and oxygen-reactive ion etching resistance, and thus have been actively studied as positive resist materials. For details, see Chemical Reviews, Vol. 89, (1989) pp. 1359 to 14.
Page 10 (Chemical Reviews, 198
9, vol. 89, pp 1359-1410), 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 conventional resist made of polymethacrylate containing silicon in the side chain, the residue after exposure is removed by dry etching using a halide gas. There is a problem that the pattern shape is deteriorated because the etching rate of the residual resist film in the exposed area is smaller than that of the unexposed area. This state will be described with reference to FIG. In FIG. 1, 1 is a silicon substrate, 2 is a lower-layer resist film having a thickness of 1 μm and made of novolac resin formed by spin coating, and 3 is an upper-layer resist film having a thickness of 0.2 μm. -Containing resist film composed of a copolymer of methacrylic acid and methyl methacrylate, 5 is a fragment of a silicon-containing resist material decomposed and evaporated by soft X-ray exposure, and 8 is a resist of an unexposed portion during reactive ion etching using SF _6. A fragment generated by etching the film, and 9 is a fragment generated by etching the residual resist film in the exposed portion during reactive ion etching using SF ₆ .

[0007]

Embedded image

The two-layer resist shown in FIG. 1A is irradiated with 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 resist film surface for 5 seconds. . Then, as shown in FIG. 1 (b), the polymer is decomposed and evaporated in the exposed part, and 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. 1D, when reactive ion etching is performed using SF ₆ gas, the residual resist film in the exposed area is removed, but the etching rate is 0% of the etching rate in the unexposed area. Since the residual resist film 7 in the exposed portion is completely removed, the height of the pattern 10 of the unexposed portion, that is, the upper resist film is reduced to about 0.03 μm (FIG. 1 ( e)).

The cause is considered as follows. Upon irradiation with ionizing radiation, the ester bond in the acrylate portion is cleaved to form CO or CO _2, and the end portion of the side chain bonded to the ester portion is also evaporated. As a result, the silicon content of the exposed area is reduced, and during reactive ion etching using SF ₆ gas, it is more difficult to etch than the unexposed area where the silicon content is relatively high. Therefore, the height of the pattern formed on the silicon-containing resist film decreases when the residual resist film in the exposed portion is removed.

When oxygen-reactive ion etching is performed using the pattern 10 of the upper layer resist film containing silicon thus obtained as a mask, the thickness of the silicon-containing resist film becomes smaller than that of the lower layer resist film 2. Since it is insufficient, 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-developing. A second object of the present invention is to provide a method of manufacturing a semiconductor device using such a dry development method.

[0012]

In order to achieve the above first object, the dry developing method of the present invention comprises forming at least one lower layer resist film made of a resist material on a substrate, and forming a lower layer resist film on the substrate. To form an upper resist film made of a silicon-containing resist material containing a copolymer of an acrylic monomer and a silylated olefin or a copolymer of a sulfone and a silane, and irradiating a desired portion of the upper resist film with ionizing radiation. Then, the film thickness of the exposed portion is reduced, and the remaining film of the upper resist film of 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. It is a thing. Further, after these steps, it is preferable to carry out reactive ion etching using oxygen gas to transfer the desired pattern to the lower resist film.

Further, in order to achieve the first object,
The dry development method of the present invention forms a resist film made of a silicon-containing resist material containing a copolymer of an acrylic monomer and a silylated olefin or a copolymer of sulfone and silane on a substrate whose surface is carbon. Then, the desired portion of the resist film is irradiated with ionizing radiation to reduce the film thickness of the exposed portion, and the residual film of the resist film in the exposed portion is removed by dry etching using a gas containing halogen or a halide, The resist film has a desired pattern. Also in this case, it is preferable to further perform reactive ion etching using oxygen gas after these steps to transfer the desired pattern to carbon on the substrate surface.

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

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 is preferable, and 0.5 ≦ k ≦ 0.9.
The range is more preferably. When k is 0.5 or more, good self-developing property can be secured, and k
Has a high etching resistance when k is 3 or less, and k is 0.
This is because if it is 9 or less, the etching resistance is higher.

As the acrylic monomer, at least one kind of monomer selected from the group consisting of acrylate, methacrylate and ethacrylate can be used, but the use of methacrylate or ethacrylate produces a resist film having a uniform film thickness. Therefore, it is preferable.
Furthermore, 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 shows high self-developing property.

Further, the silylated olefin is preferably an olefin having a trimethylsilyl group, a trimethylsilylmethyl group, a pentamethyldisilyl group or a pentamethyldisilylmethyl group because of high self-developing property. Furthermore, when the silylated olefin is silylated styrene, the silicon content in the exposed area becomes high, which is preferable. As such a copolymer, for example, a copolymer of methyl methacrylate and trimethylsilylmethylstyrene represented by the following formula 2 can be mentioned.

[0018]

Embedded image

As the copolymer of sulfone and silane,
It is preferable to use a copolymer of styrene with a trimethylsilyl group, a trimethylsilylmethyl group, a pentamethyldisilyl group or a pentamethyldisilylmethyl group, and a sulfone. As such a copolymer, for example, polytrimethylsilylstyrene / sulfone represented by the following formula 3 can be mentioned.

[0020]

[Chemical 3]

Further, in order to achieve the above-mentioned second object, in the method for manufacturing a semiconductor device of the present invention, any one of the above dry developing methods is used for at least part of the method for manufacturing a semiconductor element. Is.

[0022]

When a resist film containing, for example, a copolymer of acrylate and silylated olefin is formed directly on the substrate or through a lower resist film made of an arbitrary resist material laminated on one or more layers and irradiated with ionizing radiation, Cleavage of the polymer backbone and side chains occurs. The CO-O bond in the acrylate portion becomes carbon monoxide or carbon dioxide and evaporates, so that the end portion of the side chain of the acrylate portion also evaporates, which contributes to reduction of the resist film thickness, that is, self-development. However, since the atom forming the olefin part or the bonded atom is less likely to scatter, the silyl group existing at the end of the side chain of the olefin part does not evaporate and remains in the resist film. For this reason, after self-developing, the silicon content in the residual resist film in the exposed area becomes higher than that in the unexposed area.

When dry etching is subsequently carried out using halogen or a halide, radicals and ions generated from the halogen or halide react with silicon atoms to form volatile substances. Therefore, the residual resist film in the exposed portion having a high silicon content is etched faster than in the unexposed portion. As a result, it is possible to prevent deterioration of the pattern shape when the residual 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, irradiation with ionizing radiation causes the sulfonyl group to decompose and evaporate. Therefore, the silicon content in the residual resist film is higher than that in the unexposed area.

[0024]

【Example】

<Embodiment 1> Hereinafter, a first embodiment of the present invention will be described in more detail with reference to the drawings. FIG. 2 is an explanatory view showing the steps of the dry developing method of this embodiment. In FIG.
Reference numeral 1 is a silicon substrate, 2 is a lower resist film having a thickness of 1 μm and made of a novolac resin formed by spin coating, and 4 is a resist film having a 0.1 μm line-and-space pattern with a wavelength of 13 nm and an intensity of 20 mW / cm.
² is soft X-ray, 12 is polytrimethylsilylstyrene sulfone represented by the structural formula 3 and has a thickness of 0.2 μm
Upper resist film, 13 is a fragment of the silicon-containing resist material decomposed and evaporated by soft X-ray exposure, 14 is a pattern formed on the upper resist film by self-developing,
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 A fragment generated by etching the remaining resist film, 18 is a pattern of the formed upper layer resist film, 19 is a pattern transferred to the lower layer resist film, and 20 is a remaining upper layer resist film.

First, a lower layer 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. 2 (a) was formed. Next, in the vacuum chamber evacuated to a pressure of 1 × 10 ^-2 Pa or less, the soft X-ray 4 is used to perform exposure for 5 seconds (FIG. 2B), and the resist film thickness in the exposed portion is reduced to 0.1 μm. Let As a result, as shown in FIG. 2C, a pattern 14 having a height of 0.1 μm was formed.

Then, SF ₆ gas was introduced to give 0.27P.
Reactive ion etching was performed for 1 minute while maintaining the gas pressure of a. Both exposed and unexposed areas generate volatile substances by reaction with plasma and ions, and fragments 16, 1
However, the etching rate of the exposed portion is higher than that of the exposed portion of FIG.
As shown in (e), while the residual resist film 15 in the exposed portion was removed, the difference in resist film thickness between the exposed portion and the unexposed portion was increased, and a pattern 18 having a height of 0.15 μm was formed.

Subsequently, the vacuum chamber was evacuated to a pressure of 1 × 10 ^-2 Pa or less, and then oxygen gas was introduced to obtain 1.3 Pa.
When the oxygen-reactive ion etching was carried out while maintaining the gas pressure of 1, the pattern 18 of the upper resist film had a height sufficient to process the novolac 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 formed.
was gotten.

The upper resist film was changed to polytrimethylsilylstyrene / sulfone, and (1) a copolymer of methyl acrylate and trimethylsilylstyrene,
(2) Copolymer of ethyl acrylate and trimethylsilylstyrene, (3) Copolymer of methyl acrylate and trimethylsilylmethylstyrene, (4) Copolymer of methyl acrylate and pentamethyldisilylstyrene,
(5) Copolymer of methyl acrylate and pentamethyldisilylmethyl styrene, (6) Copolymer of methyl methacrylate and trimethylsilyl styrene, (7) Copolymer of methyl methacrylate and trimethylsilyl methyl styrene, (8) Methyl methacrylate Copolymer of pentamethyldisilylstyrene, (9) Copolymer of methylmethacrylate and pentamethyldisilylmethylstyrene,
(10) Copolymer of ethylmethacrylate and pentamethyldisilylstyrene, (11) Copolymer of methylethacrylate and trimethylsilylstyrene, (12) Copolymer of ethylethacrylate and trimethylsilylmethylstyrene, (13) Copolymer of ethylethacrylate and pentamethyldisilylmethylstyrene, (14) Copolymer of ethylethacrylate and pentamethyldisilylstyrene, (15) Copolymer of trimethylsilylmethylstyrene and sulfone, (16) A pattern was formed in the same manner using a copolymer of pentamethyldisilylstyrene and sulfone and a copolymer of (17) pentamethyldisilylmethylstyrene and sulfone. In either case,
A pattern of the lower resist film without shape deterioration similar to the above was obtained. Further, as the gas used for the reactive ion etching, instead of SF ₆ , Cl ₂ , Br ₂ , HB
Similar results were obtained using r, SF ₄ , CHF ₃ , and CF ₄ .

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

<Second Embodiment> 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 this embodiment.
In FIG. 3, reference numerals 21, 22, 23, 24 and 25 are gate valves, 26 is a vacuum chamber for plasma polymerization, 27 is a vacuum chamber for photo-excited chemical vapor deposition, 28 is a vacuum chamber for exposure, and 29 is a vacuum chamber for reactive ion etching. Three
0, 31, 32, 33 are turbo molecular pumps, 34, 3
5, 36, 37 and 38 are vacuum valves, 39 is a high frequency voltage applying electrode / substrate stage, 40 and 41 are substrate stages, 42 is a high frequency voltage applying electrode / substrate stage, 4
3, 44 are high-frequency voltage applying devices, 45 is a counter electrode, 46
Is an ultraviolet irradiator, and 47 has an intensity of 2 on the resist film surface.
0.1 μm line and space soft X-ray flux of 0 mW / cm ² , 48 and 49 methyl methacrylate gas, 50 trimethylsilylmethylstyrene gas, 51
Is sulfur hexafluoride, 52 is oxygen, 53 is a silicon substrate, 5
4 is a polymethylmethacrylate film deposited on a silicon substrate, 55 is an upper resist film made of a copolymer of methylmethacrylate and trimethylsilylmethylstyrene deposited on a polymethylmethacrylate film, and 56 is an upper resist film. 0.1 μm line and
A space pattern, 57 is a 0.1 μm line-and-space pattern transferred to the polymethylmethacrylate film.

First, the gate valve 21 was opened, and the silicon substrate 53 was mounted on the high frequency voltage applying electrode / substrate stage 39. The gate valve 21 is closed, and the turbo polymerization pump 30 is used to set the vacuum chamber 26 for plasma polymerization to 1 × 1.
After evacuating to a pressure of 0 ^-4 Pa or less, the vacuum valve 34 is opened and the methyl methacrylate gas 48 is introduced to make 1.3P.
While maintaining the pressure of a, the high frequency voltage applying device 43 was set to 13.
Substrate 5 when operated at 56 MHz and 10 W
A polymethylmethacrylate film 54 was deposited on the No. 3 film.

Next, after the vacuum chamber 26 for plasma polymerization and the vacuum chamber 27 for photoexcited chemical vapor deposition are evacuated to a pressure of 1 × 10 ^-2 Pa or less by the turbo molecular pumps 30 and 31, the gate valve 22 is opened and the silicon is removed. Board 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, the methyl methacrylate gas 49 and the trimethylsilylmethylstyrene gas 50 are introduced, and the ultraviolet irradiation device 4
6 to activate vacuum ultraviolet light with a wavelength of 200 nm or less.
The entire surface of the substrate was irradiated with the 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 polymethylmethacrylate film 54.

Next, after the photoexcitation chemical vapor deposition vacuum chamber 27 and the exposure vacuum chamber 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. 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 with the soft X-ray flux 47 for 5 seconds, the upper-layer resist film 55 of the exposed portion was decomposed and evaporated, resulting in an exposure of 0.
A 1 μm line and space pattern 56 was formed.

Next, after the exposure vacuum chamber 28 and the reactive ion etching vacuum chamber 29 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 is removed. Board 5
3 was transferred into the reactive ion etching vacuum chamber 29, the gate valve 24 was closed, and the silicon substrate 53 was mounted on the high frequency voltage applying electrode / substrate stage 42. Then, 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. The residual material in the exposed portion of 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, and then the vacuum valve 38 is opened to introduce oxygen 52 to adjust the pressure. When the high frequency voltage applying device 44 was operated while keeping the pressure at 1.3 Pa and oxygen reactive ion etching was performed, the pattern 56 was transferred to the polymethylmethacrylate film, and a pattern with a high aspect ratio of 0.1 μm line and space. 57 was formed. In this embodiment, the first embodiment
Throughput was further improved than in the above case.

Also in this embodiment, as in the first embodiment, a substrate having a carbon surface is used, an upper layer resist film is directly formed on the substrate without forming a lower layer resist film, and self-development by exposure, The residual resist film was removed, and the substrate could be processed by performing oxygen reactive ion etching using the formed resist film pattern containing silicon as an etching mask. Although the upper resist film was formed by chemical vapor deposition, substantially the same effect was obtained even if it was formed by plasma polymerization or vapor deposition polymerization.

<Third Embodiment> FIG. 4 is a sectional view of a semiconductor device for explaining a third embodiment of the present invention. A method of manufacturing this semiconductor device will be described. First, after forming the element isolation region 102 on the P-type Si single crystal substrate 101 by the LOCOS method (silicon selective oxidation method), 850 ° C.
The SiO ₂ film 103 having a thickness of 8 nm to be the 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) method 200.
A phosphorus-doped polycrystalline Si film having a thickness of 1 nm and a SiO ₂ film 105 are sequentially formed. The formation of the phosphorus-doped polycrystalline Si film is made of Si
It was carried out at a temperature of 580 ° C. using H ₄ gas and PH ₃ gas.

Next, a lower resist film having a thickness of 1 μm made of a novolac resin is formed on the SiO ₂ film 105 by a spin coating method, and further, a thickness made of a copolymer of trimethylsilylmethylstyrene and methylmethacrylate is formed thereon. An upper resist film having a thickness of 0.2 μm was formed by spin coating. Then, a soft X-ray having a wavelength of 13 nm and an intensity of 500 mJ / cm ² is irradiated through a mask, and then reactive ion etching using SF ₆ gas is performed at a gas pressure of 0.27 Pa to form a pattern on the upper resist film. did. Further, using this as a mask, the gas pressure is 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 using CHF ₃ gas was performed under a gas pressure of 0.27 Pa to obtain 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), and the temperature is 850 ° C. for 1
N ₂ annealing is performed for 5 minutes, and the gate electrode 10 is formed by the CVD method.
A SiO ₂ film 107 was formed on the side wall of No. 4 and electrically insulated, and then the surfaces of the diffusion layers 106 (a) and (b) of the transistor were exposed.

Thereafter, phosphorus glass (PS
G), the insulating film 108 is formed, a contact hole (not shown) is formed in the insulating film 108, an electrode wiring, an interlayer insulating film, and a second wiring (neither is shown) are formed in the hole, and a passivation process is performed. Then, a semiconductor device was manufactured.

[0040]

According to the dry development method of the present invention, a silicon-containing resist film having high oxygen reactive ion etching resistance can be patterned by a dry process, and an extremely fine pattern with high resolution can be obtained with high throughput. Could be formed. Further, according to the method of manufacturing a semiconductor device of the present invention, it is possible to form an extremely fine pattern of a semiconductor element without deteriorating the shape.

[Brief description of drawings]

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

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

FIG. 3 is a schematic diagram showing 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 shown in a third embodiment of the present invention.

[Explanation of symbols]

1, 53 ... Silicon substrate 2 ... Lower layer resist film 3, 12, 20, 55 ... Upper layer resist film 4 ... Soft X-ray 5, 8, 9, 13, 16, 17 ... Fragment 6, 14 ... Pattern (on upper layer resist film Formed pattern) 7, 15 ... Residual 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 ... Electrode for high-frequency voltage application and substrate stage 40, 41 ... Substrate stage 43, 44 ... High-frequency voltage applying 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 ... Polymethylmethacrylate film 101 ... Si single crystal substrate 102 ... Element isolation region 103 ... Gate insulating film 104 ... Gate electrodes 105, 107 ... SiO ₂ film 106 (a) (b) ... Diffusion layer 108 ... Insulating film

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Taro Ogawa 1-280 Higashi Koikekubo, Kokubunji, Tokyo Inside Hitachi Central Research Laboratory (72) Inventor Takashi Soga 1-280 Higashi Koikeku, Kokubunji, Tokyo Hitachi, Ltd. Central Research Laboratory (72) Inventor Masaaki Ito 1-280 Higashi Koikekubo, Kokubunji, Tokyo Hitachi Central Research Institute (72) Inventor Takashi Matsuzaka 1-280 Higashi Koikeku, Kokubunji, Tokyo Hitachi Central Research Center ( 72) Inventor Hiroaki Tachibana, 1-1, Higashi, Tsukuba-shi, Ibaraki Institute of Industrial Science and Technology, Institute of Materials Engineering (72) Inventor Mutsuyoshi Matsumoto, 1-1, Higashi, Tsukuba-shi, Ibaraki Institute of Industrial Technology

Claims (14)

[Claims] 1. A first step of forming at least one lower resist film made of a resist material on a substrate, and a copolymer of an acrylic monomer and a silylated olefin or sulfone and silane on the lower resist film. Second step of forming an upper resist film made of a silicon-containing resist material containing the above copolymer, and third step of irradiating a desired portion of the upper resist film with ionizing radiation to reduce the film thickness of the exposed portion. And a fourth step of removing the remaining film of the upper resist film in the exposed portion by dry etching using a gas containing halogen or a halide to form the upper resist film into a desired pattern. . 2. The dry developing method according to claim 1, wherein the upper resist film is formed by chemical vapor deposition, plasma polymerization or vapor deposition polymerization. 3. The dry developing method according to claim 1, wherein after the fourth step, reactive ion etching using oxygen gas is performed to transfer the desired pattern to the lower resist film. A dry development method comprising the steps of 5. 4. A resist film comprising a silicon-containing resist material containing a copolymer of an acrylic monomer and a silylated olefin or a copolymer of sulfone and silane is formed on a substrate whose surface is carbon. The second step of irradiating a desired portion of the resist film with ionizing radiation to reduce the film thickness of the exposed portion, and the remaining film of the resist film of the exposed portion is dried using a gas containing halogen or a halide. A dry development method comprising a third step of removing by etching to form a resist film into a desired pattern. 5. The dry development method according to claim 4, wherein the resist film is formed by chemical vapor deposition, plasma polymerization or vapor deposition polymerization. 6. The dry development method according to claim 4, wherein after the third step, reactive ion etching using oxygen gas is performed to transfer the desired pattern to carbon on the surface of the substrate. A dry development method comprising a fourth step. 7. The dry developing method according to claim 1, wherein the gas containing halogen or halide is chlorine, bromine, hydrogen bromide, sulfur hexafluoride, sulfur tetrafluoride. A dry developing method, wherein the gas is a trifluorohydrocarbon or a carbon tetrafluoride gas. 8. The dry development method according to claim 1, wherein the acrylic monomer is at least one monomer selected from the group consisting of acrylate, methacrylate and ethacrylate. And dry development method. 9. The dry developing method according to claim 8, wherein the acrylate is an alkyl acrylate, the methacrylate is an alkyl methacrylate, and the ethacrylate is an alkyl ethacrylate. Development method. 10. The dry development method according to claim 1, wherein the silylated olefin has a trimethylsilyl group, a trimethylsilylmethyl group, a pentamethyldisilyl group or a pentamethyldisilylmethyl group. A dry development method characterized by being an olefin. 11. The dry developing method according to claim 1, wherein the silylated olefin is silylated styrene. 12. The dry developing method according to claim 11, wherein the silylated styrene is styrene having a trimethylsilyl group, a trimethylsilylmethyl group, a pentamethyldisilyl group or a pentamethyldisilylmethyl group. Dry developing method. 13. The dry developing method according to claim 1, wherein the copolymer of sulfone and silane is a trimethylsilyl group, a trimethylsilylmethyl group, a pentamethyldisilyl group or a pentamethyldigroup. A dry developing method, which is a copolymer of styrene having a silylmethyl group and sulfone. 14. The method according to claim 1, wherein the dry development method is at least one of semiconductor device manufacturing methods.
A method for manufacturing a semiconductor device, which is used for a semiconductor device.