JPH07254556A - Pattern forming method and equipment therefor - Google Patents

Abstract

PURPOSE:To make it possible to perform pattern formation by a full dry integrated process by producing Si radical in non-oxidizing atmosphere under a reduced pressure, by forming a photoresist by recombination and by radiating electromagnetic wave to the photoresist through a mask. CONSTITUTION:Gases are exhausted by vacuum from a reaction chamber 6-3 and a decomposition chamber 6-2, a substrate holder 10 is carried to the reaction chamber 6-3, N2 gas is introduced to a gasification chamber 6-1, a sample boat 11 is filled with a sample 12 containing Si and it is exhausted by vacuum, the sample 12 is heated and gasified in a gasification chamber 6-1, Si-Si bonding is cleavaged by the temperature inside a quartz tube 17 in the decomposition chamber 6-2, it is then recombined in the reaction chamber 6-3 and the photoresist is formed on the substrate. Next, the substrate holder 10 is carried to an exposure and developing chamber, laser light is radiated to a photomask having a predetermined pattern by means of illuminating optical system, and the pattern image of the photomask is transferred to the photoresist.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a pattern forming method and its forming apparatus, and more particularly to a pattern forming method and its forming apparatus suitable for forming a fine pattern in the fields of semiconductor devices and electronics.

[0002]

2. Description of the Related Art Recently, as represented by the semiconductor field,
With the rapid increase in the capacity and functionality of devices, the circuit patterns have become finer and the circuit structures have become more complicated. A photo-etching technique is used for forming this fine pattern. The general process consists of the following steps.

(1) A film to be processed is formed on the entire surface of a substrate. (2) A photoresist is applied, exposed and developed to form a photoresist mask having a predetermined pattern. (3) Etching the processed film in the portion of the photoresist not covered by the mask. (4) Remove the photoresist.

The above-mentioned steps are mixed with various steps from those performed in vacuum such as sputtering to those performed in the atmosphere or solution such as exposure and development. for that reason,
There were many factors that hindered reduction of manufacturing time and cleanliness, such as increase in the number of steps, complication, movement of substrate, and increase in time.

On the other hand, as a method for solving these problems, there has been proposed a method in which the above-described series of steps are carried out consistently in a state in which the atmosphere is shut off and the pressure is reduced. Here, such an integrated process is defined as an all dry integrated process. The biggest problem in making the photoetching process an all-dry integrated process is to perform all the steps of film formation, exposure, development, and removal of the photoresist by a dry process.

Therefore, recently, for example, Japanese Unexamined Patent Application Publication No. 4-6.
As seen in Japanese Patent No. 3414, a method using no photoresist has been proposed. That is, this method
By irradiating the Si film (or Al film) with an excimer laser through a predetermined mask in the presence of O ₂ gas, the surface is selectively oxidized, for example, SiOx (AlOx) having a thickness of about 2 nm. A film is formed, and using this as an etching mask, the surface region that is not oxidized is selectively etched by dry etching to form a predetermined pattern. However, this method is limited to the case where the film to be processed is at least a metal that is photooxidized. Also,
Since photooxidation using NO ₂ is a reaction on the outermost surface having a depth of several nm, there is a problem that it is difficult to obtain an etching mask having a sufficient thickness.

Also, Applied Physics Letters, 62 (4), page 372 (1993) [App.
l. Phis. Lett. , 62 (4), 372 (19
93)], a plasma-polymerized film, which is a photoresist formed from a monoalkylsilane as a raw material, is treated with O ₂
By irradiating and exposing the excimer laser light through a predetermined mask in the presence of Si-O-Si
It has been reported that it is possible to form a pattern having a structure, generate an etching selection ratio with respect to an unexposed portion, and form a photoresist pattern in a developing process using a Cl ₂ etching gas. However, this method requires the use of a monoalkylsilane compound that is difficult to handle for safety (generally, a gas that is ignitable in the air at room temperature), and the removal of the photoresist has not been considered.

[0008]

SUMMARY OF THE INVENTION It is therefore an object of the present invention to overcome the above-mentioned problems of the prior art, the first of which is an improved pattern forming pattern by an all dry integrated process. A forming method and a second purpose thereof are to provide the forming apparatus, respectively.

[0009]

The above-mentioned first object of the present invention is to provide a first step of depositing a film to be processed on a substrate and a second step of forming a photoresist on the film to be processed. Obtained by the third step of exposing the photoresist through a photomask having a predetermined pattern, the fourth step of developing the exposed photoresist, and the third and fourth steps. In the pattern forming method, the photo-etching process including at least a fifth step of etching the film to be processed using the photoresist pattern as a mask and a sixth step of removing the photoresist pattern is an all-dry integrated process. The second step is a step of vaporizing a solid or liquid organic compound containing Si in a non-oxidizing atmosphere under reduced pressure, and a step of decomposing the vaporized organic compound to produce a Si radical. And a step of forming a photoresist made of an organic compound having a Si—Si bond on the film to be processed by reacting and recombining the decomposed and generated Si radicals, In the third step and the fourth step, Si-
A pattern forming method comprising a photoresist mask pattern forming step including a step of advancing development with exposure by irradiating the photoresist with an electromagnetic wave having sufficient energy to break Si bonds. It

In the second step, in order to decompose the vaporized organic compound to generate Si radicals, the organic compound is decomposed by heating, for example, with a heater or an infrared lamp, or is decomposed by electromagnetic wave irradiation (for example, wavelength). Ultraviolet irradiation of 350 nm or less, preferably about 190 nm for practical use) or decomposition by low-temperature plasma irradiation (afterglow part is used as preferable plasma irradiation area)
It is desirable to carry out by any one of the above decomposition methods. It should be noted that all of the above steps may be performed consistently in a state in which the atmosphere is shut off and the pressure is reduced.

Here, the starting material for forming the photoresist film is an organic compound containing Si and having 2 or less H bonded to Si, and is represented by, for example, the following chemical structural formula (1). A cyclic dialkylsilane compound,
One or more of the fluorosilane compound represented by (2) or the chain-like dialkylsilane compound or polysilane compound represented by (3) is used. However, R ₁ and R ₂ in the formula represent an organic group selected from an alkyl group and an aryl group, and R ₃ and R ₄ represent a fluoro group, a perfluoroalkyl group, a phenyl group, a perfluorophenyl group, a perfluoroalkyl group. It represents different organic groups selected from substituted phenyl groups, and n ₁ and n ₂ are both positive integers. Practically preferably, n ₁ = 1 to 1
5, n ₂ = 1 to 1,000, especially 600 to
1,000 is preferred.

[0012]

[Chemical 4]

[0013]

[Chemical 5]

[0014]

[Chemical 6]

As a specific starting material, preferably,
Hexamesitylcyclopropasilane, octaphenylcyclobutasilane, decamethylcyclopentasilane, dodecamethylcyclohexasilane, tetradecamethylcycloheptasilane, phenylfluorosilane, perfluorophenylfluorosilane and the following chemical structural formula (4) And (5).

[0016]

[Chemical 7]

[0017]

[Chemical 8]

The photoresist formed in the second step is an organic compound having at least two Si-Si bonds in which the once decomposed organic compound is recombined.

The third step of exposing the photoresist and the fourth step of developing the exposed photoresist are integrated and performed in the same step. That is, the exposure is performed by irradiating the photoresist having the Si-Si bond with an electromagnetic wave having a wavelength and energy sufficient to break the Si-Si bond through a predetermined mask pattern. As the electromagnetic wave to be applied, ultraviolet rays having a wavelength of 350 nm or less in the vacuum ultraviolet region are effective, and at present, a light source up to about 190 nm can be used as a practically preferable one. Needless to say, if a light source with a shorter wavelength is developed in the future, it can be used as an effective light source. The irradiation dose depends on the composition of the photoresist used (organic compound having a Si—Si bond), but at least 500 mJ / cm ² is required for practical use.

Here, the organic compound having a Si--Si bond in the exposed region of the photoresist is selectively decomposed, and the decomposition product containing Si is removed as a gaseous substance outside the system under vacuum exhaust, Development proceeds with exposure. In this exposure-development process under vacuum exhaust, it is also effective to introduce a carrier gas into the exposure atmosphere and perform exposure-development under a gas flow in order to efficiently exhaust and remove decomposition products out of the system. The carrier gas is, for example, Ar or N so as not to deteriorate the photoresist forming the mask.
An inert gas such as _{2 and} , depending on the case, a reducing gas such as hydrogen is used.

The sixth step of removing the photoresist pattern (resist mask) is the same as the third and fourth exposure-development steps of forming the photoresist pattern.
By irradiating the entire surface of the photoresist with an electromagnetic wave having a wavelength and energy sufficient to break the i-Si bond,
This is a step of decomposing the organic compound having a Si—Si bond constituting the photoresist, and exhausting and removing the decomposition product as a gaseous substance out of the system.

In the case of a substrate having a step, among polymer compounds capable of forming a film in a vapor phase, represented by, for example, di-p-xylylene, polyamic acid, polyimide, polyurea, etc., on the entire surface of the substrate. A step of forming an organic planarizing film is provided by using an organic compound having a relatively small molecular weight and having a property of softening and deforming when heated, and a step of forming the photoresist on the organic planarizing film. It may be provided.

Further, a step of forming an etching mask having a sufficient etching selectivity with respect to the film to be processed, which is represented by, for example, phenol novolac resin, polyimide resin, carbon film, etc., on the film to be processed of the substrate. A step of forming the photoresist may be provided on the etching mask. As a result, it is possible to form a two-layer resist having a double layer of the etching mask and the photoresist.

A second object of the present invention is to provide at least a first chamber for forming a photoresist on the substrate, a second chamber for exposing the photoresist, and a third chamber for transferring the substrate. A pattern forming apparatus including at least: each of the chambers is configured to be vacuum-sealable, and the first chamber and the second chamber each have a third chamber through a gate valve provided individually. The first chamber, which is connected to the chamber for forming the photoresist, has a non-oxidizing atmosphere,
The photoresist includes a vaporization chamber that vaporizes a solid or liquid organic compound containing Si, a decomposition chamber that decomposes the vaporized organic compound to generate Si radicals, and a reaction chamber that recombines the decomposed organic compound. Exposure to the second
Is an exposure chamber provided with means for irradiating the photoresist with electromagnetic waves having energy sufficient to break the recombination (for example, electromagnetic wave irradiating means for irradiating ultraviolet rays having a wavelength of 350 nm or less in the vacuum ultraviolet region). It is achieved by configuring.

As means for decomposing the organic compound vaporized in the decomposition chamber to generate Si radicals, for example, heating means by a heater or an infrared lamp, electromagnetic wave irradiating means by ultraviolet irradiation with a wavelength of 350 nm or less in the vacuum ultraviolet region, micro A decomposition means such as a low temperature plasma irradiation means by wave discharge is used.

Further, since the first chamber is for forming a thin film using an organic compound as a raw material, not only is a photoresist formed, but also an organic planarizing film and an etching mask to be a base film for forming a photoresist are formed. Alternatively, it may be configured to be formed.

[0027]

The function of the pattern forming method will be described.
In the film forming step, the step of vaporizing is performed by using an organic compound, such as Si, which is a raw material of a photoresist that is solid or liquid at room temperature, as a safe and easy-to-handle organic compound under vacuum evacuation for dry process by Si--O-- It is vaporized in a non-oxidizing atmosphere so that no Si structure is generated.

In the step of decomposing the organic compound, the Si-Si bond of the vaporized organic Si compound is thermally decomposed under vacuum exhaust (for example, under a temperature condition of 400 ° C. or higher) or is decomposed by electromagnetic waves (for example, Or with ultraviolet light having a wavelength of 350 nm or less) or by using low temperature plasma (for example, using an afterglow part of low temperature plasma of Ar gas) to generate Si radicals in which the Si—Si bond is cleaved.

Further, in the reacting step, the Si radicals are cooled under evacuation, and at least two or more S radicals are added.
Recombines to i-Si bond. That is, Si-on the substrate
A Si-bonded film is deposited to form a photoresist thin film. As described above, since the step of decomposing the organic compound by using the organic compound which is easy to handle for safety is the step of supplying the material of the thin film and the step of reacting is the step of depositing the film, the organic planarizing film A photoresist having a desired thickness can be safely and easily formed even on a substrate or film other than metal such as (including an etching mask such as a carbon film).

Since the thin film of the organic compound can be formed in this film forming step, not only the film forming of the photoresist but also the film forming of the etching mask such as the organic flattening film or the carbon film is possible.

In the exposure step and the development step, an electromagnetic wave (ultraviolet ray having a wavelength of 350 nm or less, for example, KrF excimer laser having a wavelength of 248 nm, irradiation amount of 500 mJ / (irradiation at cm ² or more) is selectively applied to the photoresist through a mask on which a desired pattern is formed. Therefore, in the exposed region of the photoresist, many Si-Si bond cleavages occur, and Can be decomposed into gaseous Si radicals of sufficient size to be exhausted out of the system. That is, when exposure is performed under vacuum exhaustion, the exposed portion is decomposed into a low molecular weight gaseous substance, which is removed and developed (development proceeds with exposure).

By introducing a carrier gas such as an inert gas onto the exposed surface during the exposure under the vacuum evacuation, the decomposition products of the photoresist produced by the exposure are efficiently transferred out of the system together with the carrier gas. There is an effect that exhaust gas can be removed well.

In such a process in which the exposure process and the development process are integrated, the photoresist is selectively etched to obtain a resist mask on which a positive image pattern is formed. Therefore, the number of processes can be reduced and the substrate can be simplified. By reducing the amount of movement, the pattern formation time can be shortened and the yield can be improved.

The etching of the film to be processed using the photoresist pattern as a mask can be carried out by a known dry etching method.

The photoresist pattern removing step is performed in the same manner as the above-mentioned step in which the exposure step and the developing step are integrated. That is, by irradiating the entire surface of the substrate with electromagnetic waves, S
By cleaving the i-Si bond, the photoresist pattern is decomposed into gaseous Si radicals and removed. As a result, it is possible to provide a dry integrated process in which the number of steps is reduced and simplified, the substrate movement amount is further reduced, and the pattern formation time is shortened and the yield is further improved. In addition,
When exposure is carried out under a flow of a carrier gas such as an inert gas, it is effective that the film-forming substance which is hard to volatilize can be easily removed by the action of the carrier gas.

Next, the invention of the pattern forming apparatus will be described. The first chamber for depositing a photoresist is composed of a vaporization chamber, a decomposition chamber and a reaction chamber, and the vaporization chamber is provided with heating means, gas introduction and exhaust. And an organic compound that is solid or liquid at room temperature and is easy to handle for safety, including Si, which is a raw material for photoresist, is introduced into the chamber at atmospheric pressure, and then heated under vacuum exhaust for dry process to oxidize it. The structure is such that vaporization is performed in a non-oxidizing atmosphere so that a Si-O-Si structure is not generated due to a reaction or the like.

The decomposition chamber has a decomposition means such as a heating means such as a heater, an electromagnetic wave irradiation means, or a plasma irradiation means (low temperature plasma), and is a vaporized organic Si compound of Si--Si.
The bond is decomposed by the above-described means under vacuum evacuation to obtain Si
-Si bonds are cleaved to generate Si radicals.

The reaction chamber has at least a substrate support and an evacuation means, and the Si radicals generated in the decomposition chamber are
Cooled under vacuum exhaust and at least two or more Si-Si
Rejoin to join. That is, a recombination film having a Si—Si bond is deposited on the surface of a substrate placed on a substrate support table equipped with a cooling unit to form a photoresist thin film.

As described above, in the vaporization chamber, a vaporized compound for dry process which is easy to handle for safety is prepared and decomposed in the decomposition chamber to generate low molecular Si radicals.
It is recovered by recombining in the reaction chamber and forming a thin film on the substrate surface. That is, since a solid or liquid organic compound that is easy to handle for safety is handled outside the pattern forming apparatus, it is possible to realize a highly safe pattern forming apparatus that has few restrictions on the installation location and is easy to handle.

Further, since the vaporization chamber, the decomposition chamber, the reaction chamber, and the detailed process are divided and connected through a gate valve so that each chamber can be separated, the process control is easy and simple control is possible. A photoresist having a desired thickness can be easily formed on a substrate or film other than metal, such as an organic flattening film or an etching mask. Since the substrate on which the photoresist is formed may be installed in the reaction chamber adjacent to the transfer chamber, the number of steps can be reduced and simplified, and the amount of substrate movement can be reduced to shorten the pattern formation time and improve the yield. A pattern forming device can be realized.

Further, the second chamber contains Si of an organic Si compound.
An exposure chamber provided with an irradiation unit (ultraviolet radiation source) of electromagnetic waves (ultraviolet rays having a wavelength of 350 nm or less) having a wavelength and energy sufficient to cleave —Si bonds and an exhaust unit. All the steps of exposure and development at the time of forming the photoresist pattern in the process and removal of the photoresist after using the resist pattern as a mask are performed.

That is, at the time of forming the resist pattern, the light from the light source is irradiated onto the photoresist through a mask having a predetermined pattern and exposed, or in the step of removing the photoresist, the entire surface of the photoresist is irradiated. Then, the photoresist pattern is decomposed into gaseous Si radicals and removed by cleavage of the Si—Si bond in the exposed portion. Therefore, by the second chamber, the number of steps can be reduced and simplified, and the amount of substrate movement for each step can be reduced to shorten the pattern formation time and improve the yield.
Moreover, it is possible to realize a common, compact and economical pattern forming apparatus in which only one light source is provided without providing a chamber for each process.

Since this second chamber is an exposure chamber for carrying out the step of exposing and patterning the photoresist, it does not vibrate because it includes an exposure optical system, so that another processing chamber, for example, a substrate, can be removed. It is desirable to provide an anti-vibration structure in the connecting portion with the third chamber for carrying, so that the exposure chamber can perform precise exposure.

[0044]

An embodiment of the present invention will be described in detail below with reference to the drawings. <Embodiment 1> A configuration example of a pattern forming apparatus for carrying out a pattern forming method according to the present invention will be described with reference to FIGS. 1, 2, and 4.

FIG. 1 is a top view showing the main part of the pattern forming apparatus. The pattern forming apparatus includes a load lock chamber 1 for loading and unloading a substrate holder 10 that holds and transports a substrate (not shown), a substrate pretreatment chamber 2 for cleaning the substrate, and a deposition chamber 3 for a film to be processed. A photoresist film forming chamber 6 including an etching mask film forming chamber 4, an organic planarizing film film forming chamber 5, and a vaporization chamber 6-1, a decomposition chamber 6-2, and a reaction chamber 6-3. Corresponding to the first chamber of the present invention),
Exposure and development chamber 7 (corresponding to the second chamber of the present invention)
And an etching chamber 8 and a transfer chamber 9 having a transfer mechanism (not shown) for transferring the substrate holder 10 between the chambers (corresponding to the third chamber of the present invention). However, the transfer of the substrate to the film forming chamber 6 of the photoresist is performed only in the reaction chamber 6-3.

In this structure, the load lock chamber 1, the substrate pretreatment chamber 2, the film formation chamber 3 for the film to be processed, the film formation chamber 4 for the etching mask, the film formation chamber 5 for the organic planarization film, and the film formation for the photoresist. Chamber 6, Vaporization Chamber 6-1, Decomposition Chamber 6-2, Reaction Chamber 6-
3, all of the exposure and development chamber 7, the etching chamber 8 and the transfer chamber 9 are configured to be vacuum-tight, and a vacuum exhaust device (not shown) for exhausting the interior of the chamber is provided with a decomposition chamber 6-.
Each is equipped with the exception of 2.

A load lock chamber 1, a substrate pretreatment chamber 2, a film forming chamber 3 for a film to be processed, an etching mask film forming chamber 4, an organic planarizing film forming chamber 5, and a photoresist film forming chamber 6. The (reaction chamber 6-3), the exposure and development chamber 7, and the etching chamber 8 are arranged around the transport chamber 9 and transported through the gate valves 9a, 9b, 9c, 9d, 9e, 9f, 9g, and 9h, respectively. Connected to chamber 9.

In addition to the gate valve 9a connected to the transfer chamber 9, the load lock chamber 1 is provided with a door 1a for loading and unloading the substrate holder 10, and a reaction chamber 6-
3 and the decomposition chamber 6-2 are connected via a valve 6c, and further, the vacuum of the decomposition chamber 6-2 and the reaction chamber 6-3 is kept and vaporized (a raw material for forming a photoresist film and In order to install the Si-containing organic compound), a valve 6b is provided between the vaporization chamber 6-1 and the decomposition chamber 6-2, and a door 6a is provided for taking the sample boat (or the sample cylinder) in and out. It was

The substrate pretreatment chamber 2 has a function capable of being cleaned by sputter etching, and in this embodiment, it is carried out by RF sputter etching.
If equipped with an ion gun, cleaning can be performed by ion beam etching instead of sputter etching.

Although the film forming chamber 3 for the film to be processed is a normal sputtering chamber, it may be a known film forming chamber by vacuum vapor deposition or plasma CVD instead. Further, the etching mask film forming chamber 4 used when forming the two-layer resist film was a film forming chamber by sputtering or plasma CVD.

When there is a step on the substrate, a plurality of film forming chambers 4 for forming an organic planarizing film for eliminating the step are usually required depending on the film forming material. In this example, two evaporation sources are used. It was a vacuum evaporation system having.

FIG. 2 is an example of a sectional view showing the detailed structure of the photoresist film forming chamber 6. The vaporization chamber 6-1 includes a boat 11 for containing a sample 12 of an organic compound, a support 13 for holding the boat 11, and a heating means for vaporizing the sample 12 (in this embodiment, an infrared lamp is used, but an ultraviolet lamp may also be used. 14), and when the sample 12 is put into the vaporization chamber 6-1, it is composed of a gas introduction port 15 and an exhaust port 16 for making the vaporization chamber atmospheric pressure by N ₂ gas or the like. Two
Is a cylindrical tube (a quartz tube is used in this embodiment) 17 suitable for uniformly transmitting the heat that decomposes the vaporized sample, a heating means (an infrared lamp is used in this embodiment) 18, and a decomposition chamber by heating. A water cooling mechanism 1 which is a cooling mechanism of the decomposition chamber 6-2 for preventing the degree of vacuum from deteriorating due to the deformation of 6-2.
9 and 9. Further, the reaction chamber 6-3 is the substrate holder 1
It is composed of a support base 20 (not shown) in which a temperature control means such as cooling is built in, a film thickness monitor 21 for measuring the film thickness, and an exhaust port 22.

Since this photoresist film forming chamber 6 can form a thin film of an organic compound as a raw material, it can also be used for forming a thin film of an organic compound other than the photoresist as shown in Examples described later. In addition, in order to form an organic flattening film as shown in Examples described later on the support 20,
A heating means was provided so that an organic compound having a property of softening and deforming when heated could be processed.

FIG. 3 is a sectional view showing the structure of the exposure and development chamber 7. The exposure and development chamber 7 has a light source 27 that emits a KrF excimer laser, an illumination optical system 28, a photomask 29 having a predetermined pattern, and a projection optical system 30 arranged outside the exposure and development chamber 7. , A window 31 for introducing light into the exposure and development chamber 7, a sample holder 32 for mounting the substrate holder 10, and a gas inlet 3
3 and the exhaust port 34 are provided.

The exposure and development chamber 7 includes a step of forming a resist pattern by exposing and developing a photoresist.
It is possible to carry out a subsequent step of removing the photoresist. In the present embodiment, the carrier gas inlet 33 is provided on the upstream side of the exhaust system, and in addition to the processing of a thin film that is usually performed under vacuum exhaust, an inert gas such as Ar gas is used as a raw material for a photoresist thin film. The thin film can be processed by exposure while flowing a carrier gas of a type corresponding to the above, and the decomposition products of the photoresist decomposed by exposure can be efficiently exhausted and removed to the outside by this carrier gas. The raw material with low volatility can be used.

In the etching chamber 8 for the film to be processed, RF is applied.
The configuration is such that reactive ion etching using plasma is possible. Alternatively, a method of generating plasma with microwaves can be used.

<Embodiment 2> FIG. 4 is a sectional view showing another structural example corresponding to the photoresist film forming chamber 6 shown in FIG. As shown in the figure, the point different from FIG. 2 of Example 1 is the configuration of the vaporization chamber 6-1 of the sample 12 and the decomposition chamber 6-2. The decomposition chamber 6-2 is composed of a cylinder 23, heating means for vaporizing a sample (heating wire is used in this embodiment) 24, and a temperature controller (not shown). Instead, a plasma irradiation means for irradiating the vaporized sample with plasma to decompose it was provided.

That is, 25 in the decomposition chamber 6-2 is a plasma generator (in this embodiment, a microwave power source is used), and Ar gas, which is a raw material gas for generating plasma, is introduced from the gas inlet 26. Low-temperature plasma is generated when the plasma is supplied to the plasma generation unit 25 via the flow rate control valve 6d. When the gas of the organic compound sent from the vaporization chamber 6-1 is exposed to this plasma, decomposition occurs and Si radicals are generated. The position exposed to this plasma is set to be the afterglow part of the low-temperature plasma, and the conditions are such that an organic compound is easily decomposed and Si radicals are easily generated.

The sample cylinder 23 in the vaporization chamber 6-1
And a valve 6e for connecting the quartz gas supply pipe 17a
Is a solenoid valve, and is a quartz tube 17b in the decomposition chamber 6-2.
The valve 6b that connects the gas supply pipe 17a of the vaporization chamber 6-1 with the valve 6b is a flow rate control valve.

Since this photoresist film forming chamber 6 can form a thin film of an organic compound as a raw material, it can also be used for forming a thin film of an organic compound other than the photoresist as shown in Examples described later.

<Embodiment 3> FIG. 5 is a cross-sectional view showing a modification in which a decomposition means by electromagnetic wave irradiation is provided in place of the decomposition means by plasma irradiation in the photoresist film forming chamber 6 shown in FIG. . The structure is basically the same as that of the second embodiment, but only the structure of the decomposition chamber 6-2 is different. That is, electromagnetic waves are emitted from the light source 27 disposed outside the quartz tube 17b in the decomposition chamber 6-2 by the illumination optical system 28 to the quartz tube 17b.
The vaporized organic compound in the interior is irradiated and produces Si radicals. The light source 27 may be any one that emits ultraviolet rays having a wavelength of 350 nm or less, such as a mercury lamp,
Alternatively, the KrF excimer laser used in the exposure-developing chamber of FIG. 3 is used.

<Embodiment 4> FIG. 6 is a top view showing another embodiment of the pattern forming apparatus. The device configuration is basically the same as the configuration shown in FIG. 1 of the first embodiment. However, the difference is that the etching mask film forming chamber 4 and the organic planarizing film forming chamber 5 are removed from FIG. 1 in order to downsize the device configuration. Other device configurations and device functions are the same as those described in the first embodiment with reference to FIG. For the photoresist film forming chamber 6, any of the structure shown in FIG. 2 of the first embodiment, the structure shown in FIG. 4 of the second embodiment, and the structure shown in FIG. 5 of the third embodiment can be used. .

<Embodiment 5> Next, one embodiment in which a pattern is actually formed by using the pattern forming apparatus of the present invention shown in Embodiment 1 will be described with reference to FIGS. 1 to 3 and 7. To do. 7A to 7C are process diagrams showing the process of pattern formation according to this embodiment in a sectional view of the substrate.

Prior to the description of the process chart of FIG. 7, the substrate was pretreated in the following steps. First, the Si substrate 35 is set on the substrate holder 10 of the pattern forming apparatus shown in FIG. 1 and put into the load lock chamber 1 through the door 1a, and the inside of the load lock chamber 1 is evacuated by a vacuum exhaust device (not shown). Three
Evacuate to × 10 to ³ Pa or less. The transfer chamber 9 was constantly evacuated by a vacuum exhaust device (not shown) so that the degree of vacuum was maintained at a pressure of 1.3 × 10 ³ or less. Here, the gate valve 9a is opened, and the substrate holder 10 is moved to the transfer chamber 9
And the gate valve 9a is closed.

Next, the substrate pretreatment chamber 2 is evacuated to a vacuum degree of 5 × 10 ⁵ Pa or less. The gate valve 9b is opened, the substrate holder 10 is transported to the substrate pretreatment chamber 2, and the gate valve 9b is closed. The substrate holder 10 is installed on the RF application side electrode (not shown) of the substrate pretreatment chamber 2. Here, Ar gas of 80 sccm is flown into the substrate pretreatment chamber 2, the pressure in the system is adjusted to 3 Pa, and the RF power of 300 W is set to 1
It was applied for a minute. After the pretreatment is completed, the introduction of Ar gas is stopped, the vacuum is evacuated to a vacuum degree of 1.3 × 10 ³ Pa or less, the gate valve 9 b is opened, and the substrate holder 10 is transferred to the transfer chamber 9. The substrate pretreatment chamber 2 is evacuated to a vacuum degree of 5 × 10 ⁵ Pa or less.

The steps will be sequentially described below with reference to the process chart of FIG. The process of forming the film to be processed 36 shown in FIG. 7A was performed as follows. The film forming chamber 3 (sputtering chamber in this embodiment) of the film to be processed of the apparatus shown in FIG. 1 is evacuated to a vacuum degree of 5 × 10 ⁵ Pa or less, the gate valve 9c is opened, and the substrate holder 10 is opened. The film is transferred to the film forming chamber 3 for the film to be processed, and the gate valve 9c is closed. Here, Ar gas of 80 sccm is flown into the film forming chamber 3 for the film to be processed, and the pressure in the chamber is set to 0.
The pressure was adjusted to 5 Pa, RF power of 500 W was applied, and a SiO ₂ film 36 as a film to be processed was formed to a thickness of 200 nm. After forming the film to be processed, the introduction of Ar gas is stopped and the chamber is evacuated to a vacuum degree of 5 × 10 ⁵ Pa or less. Next, the gate valve 9c is opened, the substrate holder 10 is moved to the transfer chamber 9, and the gate valve 9c is closed. The film forming chamber 3 for the film to be processed is evacuated to a vacuum degree of 5 × 10 ⁵ Pa or less.

The step of forming the photoresist film 37 shown in FIG. 7B was carried out as follows. As shown in FIGS. 1 and 2, the valve 6b between the vaporization chamber 6-1 and the decomposition chamber 6-2 of the photoresist film forming chamber 6 is closed. The valve 6c between the decomposition chamber 6-2 and the reaction chamber 6-3 is opened. The reaction chamber 6-3 and the decomposition chamber 6-2 are evacuated to a vacuum degree of 5 × 10 to ⁵ P.
a, the gate valve 9f is opened, and the substrate holder 1
0 is conveyed to the reaction chamber 6-3, and the gate valve 9f is closed. In addition, after introducing N ₂ gas into the vaporization chamber 6-1 and returning the degree of vacuum to atmospheric pressure, the door 6a is opened, and dodecamethylcyclohexahexa which is an organic compound containing Si serving as a raw material for forming a photoresist film. The sample boat 11 is filled with orchid as the sample 12, the door 6a is closed, and the chamber is evacuated to a vacuum degree of 5 × 10 ⁵ Pa or less. Next, the infrared lamp 18 in the decomposition chamber 6-2 was used to increase the internal temperature of the quartz tube 17 to 600
Adjust to ℃.

Next, the valve 6b is opened and the sample 12 is heated by the infrared lamp 14 and kept at 150.degree. Dodecamethylcyclohexasilane is heated to 150 ° C. in the vaporization chamber 6-1 and vaporized, and further, the temperature inside the quartz tube 17 (600 ° C.) in the decomposition chamber 6-2 causes the Si—Si bond to be broken, A species containing the species Si is generated. The chemical species are recombined in the reaction chamber 6-3 to form Si-Si on the substrate.
Deposited in the form of a bond. The support 20 in the reaction chamber 6-3 is provided with temperature control means (not shown in FIG. 2) capable of setting the substrate temperature at room temperature or lower. It was set at room temperature and deposited. As a result, the photoresist 37 having a thickness of 500 nm could be formed on the substrate in the reaction chamber 6-3. In addition,
The film thickness is controlled by closing the valve 6c when the film thickness monitor 21 reaches a desired film thickness.

After forming the photoresist film, the infrared lamps 14 and 18 in the vaporization chamber 6-1 and the decomposition chamber 6-2 are turned off, the gate valve 9f is opened, the substrate holder 10 is transferred to the transfer chamber 9, and the gate valve is opened. Close 9f. The valve 6b is also closed.

The exposure and development process shown in FIG.
It was carried out as follows. Exposure and development chamber 7 shown in FIG.
Is evacuated to a vacuum degree of 5 × 10 to ⁵ Pa or less, the gate valve 9g is opened, the substrate holder 10 is transported to the exposure and development chamber 7, and the gate valve 9g is closed. Then, a laser beam having a wavelength of 248 nm oscillated by the KrF excimer laser of the light source 27 is uniformly irradiated on the photomask 29 having a predetermined pattern (1 μm line and space pattern in this embodiment) by the illumination optical system 28,
The pattern image of the photomask 29 is formed by the projection optical system 30 on the surface of the photoresist 37 on the substrate 35 through the window 31 made of quartz. In the portion irradiated with light, the Si—Si bond of the photoresist molecule is cleaved, and the chemical species whose molecular weight has been lowered becomes a gaseous substance and is exhausted to the outside through the exhaust port 34. Therefore, the photoresist 37 gives a positive image to the pattern image of the photomask. In this way, the pattern image of the photomask 29 was transferred to the photoresist 37.

As another method of exposure using FIG. 3, Ar, N ₂ as a carrier gas from the gas inlet 33 is used.
It is also possible to perform exposure while supplying an inert gas such as. According to this method, the chemical species (gaseous substance) whose molecular weight has been lowered due to the cleavage of the Si-Si bond of the photoresist molecule by exposure can be more efficiently exhausted and removed to the outside of the room.

Processed film (SiO ₂ ) 3 shown in FIG. 7D
The etching process of No. 6 was performed as follows. The degree of vacuum in the etching chamber 8 for the film to be processed shown in FIG. 1 is set to 5 × 10 to ⁵ P
a, the gate valve 9h is opened, the substrate holder 1
0 is transferred to the etching chamber 8 and the gate valve 9h is closed. CH ₂ F ₂ gas as the etching gas is 20 sccm
At a flow rate of, and the degree of vacuum in the room is adjusted to 7 Pa. Three
The RF power of 00 W was applied to etch the SiO ₂ film 36 as the film to be processed. Next, gate valve 9h
Open, the substrate holder 10 is transferred to the transfer chamber 9, and the gate valve 9h is closed.

Finally, the step of removing the photoresist 37 shown in FIG. 7E was carried out as follows. The exposure and development chamber 7 shown in FIGS. 1 and 3 is evacuated to a vacuum degree of 5 ×.
The pressure is set to 10 to ⁵ Pa or less, the gate valve 9g is opened, the substrate holder 10 is conveyed to the exposure and development chamber 7, and the gate valve 9g is closed. Next, a laser beam having a wavelength of 248 nm oscillated by the KrF excimer laser of the light source 27 is focused on the outermost surface of the photoresist 37 remaining on the substrate 35 by the illumination optical system 28, and the entire surface is irradiated and exposed. As a result, the photoresist 37 can be decomposed and exhausted to the outside of the room. After the removal of the photoresist 37 is completed, the gate valve 9g is opened, the substrate holder 10 is transferred to the transfer chamber 9, and the gate valve 9g is closed.

As described above, the film to be processed SiO ₂
A 1 μm line and space pattern of the film 36 could be formed. The steps of forming the film to be processed 36, forming the photoresist 37, exposing, developing, etching the film to be processed, and removing the photoresist can be performed consistently in a state where the atmosphere is shielded and the pressure is reduced. It was

<Embodiment 6> Next, with reference to FIGS. 1 and 3 and FIGS. 4 and 7, another embodiment in which a pattern is actually formed by using the apparatus shown in Embodiments 1 and 2 will be described. explain. In this embodiment, when a photoresist is formed, a solid or liquid organic compound containing Si is decomposed by using low temperature plasma. 7A to 7C are process diagrams showing the process of pattern formation according to this embodiment in a sectional view of the substrate. In this example, except for the step of FIG. 7B, the steps of FIG. 7A and FIGS. 5C to 5E were performed in the same manner as in Example 4, and therefore, here, these steps are omitted. Description will be omitted, and the description will focus on the process of FIG.

The step of forming the photoresist film 37 shown in FIG. 7B was carried out as follows. Film forming chamber 6 shown in FIG.
The valve 6c between the decomposition chamber 6-2 and the reaction chamber 6-3 is opened. The reaction chamber 6-3 and the decomposition chamber 6-2 are evacuated to a vacuum degree of 5 × 10 to ⁵ Pa or less, the gate valve 9f is opened, the substrate holder 10 is transferred to the reaction chamber 6-3, and the gate valve 9f is opened. Close. Phenylfluorosilane, which is an organic compound containing Si, which is a raw material for forming a photoresist film, is preliminarily filled as a sample 12 in a sample cylinder 23 which is a vaporization chamber 6-1. The sample cylinder 23 is partitioned by a vaporization chamber 6-1 and a flow rate adjusting valve 6b via an electromagnetic valve 6e, and an electric heater 24 keeps the temperature constant at all times.
The temperature is controlled by a temperature controller (not shown).

While evacuating the reaction chamber 6-3 and the decomposition chamber 6-2, the quartz tube 17b connected to the decomposition chamber 6-2 was
2 Ar gas per minute through the gas inlet 26 and the valve 6d
0 ml was supplied and the degree of vacuum was maintained at 10 Pa. Quartz tube 17
In step b, a microwave is guided from a microwave power source (not shown) to the plasma generation unit 25 to generate Ar plasma.

Next, the decomposition chamber 6-2 is evacuated to a vacuum degree of 5 × 10 to ⁵ Pa or less. Next, the raw material Si
10 ml / min of an organic compound containing phenylfluorosilane was supplied and brought into contact with Ar plasma. As a result, in the phenylfluorosilane, two Si—H bonds are exploded to generate Si radicals, which are cooled in the reaction chamber 6-3 and recombined to generate Si—Si bonds. A film is deposited on top. Thus, the photoresist 37 having a thickness of 300 nm can be formed on the substrate 35 in the reaction chamber 6-3. The film thickness can be controlled by
When the film thickness monitor 21 reaches a desired film thickness, the supply of the raw material gas is stopped.

After the photoresist is formed, the supply of microwave and Ar is stopped. Reaction chamber 6-3 and decomposition chamber 6-
2 is evacuated to a vacuum degree of 5 × 10 to ⁵ Pa or less,
The gate valve 9f is opened, and the substrate holder 10 is placed in the transfer chamber 9
And the gate valve 9f is closed. The valve 6b is also closed.

By the above method, a 1 μm line-and-space pattern of the SiO ₂ film 36 could be finally formed in the same manner as in Example 4. Formation of the film to be processed 36,
The steps of forming the photoresist 37, exposing, developing, etching the film to be processed, and removing the photoresist could be consistently performed under a reduced pressure while being shielded from the atmosphere.

<Embodiment 7> Next, another embodiment in which a pattern is actually formed by using the pattern forming apparatus shown in Embodiment 1 will be described with reference to FIGS. 1 to 3 and 8. In this embodiment, in order to maintain the pattern forming accuracy of the all dry consistent process on a substrate having a step, an organic planarizing film is formed to planarize the substrate, and a photoresist is formed on this. Is. FIG. 8 is a process drawing showing a cross-sectional view of a substrate for the process of pattern formation according to this embodiment, and the process will be sequentially described below with reference to this drawing.

First, the pretreatment of the substrate 38 and the process of forming the film to be processed 39 shown in FIG. 8F were carried out as follows. Pretreatment of the substrate 38 was performed on the substrate 38 having steps by using the substrate pretreatment chamber 2 of the apparatus shown in FIG. 1 in the same manner as in Example 5. Next, in the process of forming the processed film 39,
It was carried out as follows. The film forming chamber 3 for the film to be processed (sputtering chamber in this embodiment) is evacuated to a vacuum degree of 5 × 10 5.
The pressure is set to ⁵ Pa or less, the gate valve 9c is opened, and the substrate holder 10 is transferred to the film forming chamber 3 for the film to be processed.
Close c. Here, Ar gas is supplied to the film forming chamber 3 for the film to be processed in an amount of 5
Flow at 0 sccm, adjust the pressure in the room to 0.5 Pa, and
Al film 3 which is a film to be processed by applying RF power of 00W
9 was deposited to a thickness of 500 nm.

After forming the film to be processed, the introduction of Ar gas is stopped and the chamber is evacuated to a vacuum degree of 5 × 10 ⁵ Pa or less. Next, the gate valve 9c is opened, the substrate holder 10 is moved to the transfer chamber 9, and the gate valve 9c is closed.
The film forming chamber 3 for the film to be processed is evacuated to a vacuum degree of 5 × 10 to ⁵
Keep at Pa or less.

In the step of forming the organic planarizing film 40 for planarizing the substrate 38 having the step shown in FIG. 8G, the organic planarizing film forming chamber (vapor deposition apparatus in this embodiment) 5 of FIG. 1 is used. It was carried out as follows. After closing the gate valve 9e, N ₂ gas was introduced into the film forming chamber 5 for the organic planarizing film, the vacuum degree was returned to atmospheric pressure, the door 5a was opened, and pyromellitic acid was placed in each of the two vapor deposition boats. Dianhydride and 4,4'-
Install equimolar amounts of diaminodiphenyl ether. The door 5a is closed and evacuated to a vacuum degree of 5 × 10 ⁵ Pa or less. Open the gate valve 9e and open the substrate holder 10.
Is transferred to the organic flattening film forming chamber 5, where the gate valve 9e
Close. Next, add pyromellitic dianhydride to 100 ° C.
Then, add 4,4'-diaminodiphenyl ether to 150 ° C.
Heated to. In this way, a polyamic acid film was deposited on the substrate. The substrate is heated under vacuum exhaust to
The temperature was maintained at 00 ° C. and changed to polyimide to form the organic flattening film 40.

The step of forming the photoresist 41 shown in FIG. 8H was carried out as follows. As in Example 5, the photoresist film forming chamber 6 was used to form the photoresist 41 on the planarized organic flattening film 40 using dodecamethylcyclohexasilane as a raw material.

The exposure and development steps shown in FIG.
It was carried out as follows. In the exposure and development chamber 7 of FIG. 1, the pattern of the photoresist 41 is obtained in the same manner as in the fifth embodiment.

The etching process of the organic flattening film 40 shown in FIG. 8 (j) was carried out as follows. The etching chamber 8 for the film to be processed in FIG. 1 is evacuated to 5 × 10 to ⁵ Pa or less, the gate valve 9h is opened, the substrate holder 10 is transferred to the etching chamber 8 for the film to be processed, and the gate valve 9h is closed. O ₂ gas was introduced as an etching gas at a flow rate of 80 sccm to adjust the degree of vacuum in the chamber to 10 Pa. 300W R
The organic flattening film 40 was etched by applying F power. This etching process is performed by a well-known plasma asher which burns and removes the exposed organic planarizing film 40 with oxygen plasma.

The etching process of the processed film 39 shown in FIG. 8 (k) was carried out as follows. After the organic flattening film 40 is etched, the same chamber (etching chamber 8) is kept as it is.
Then, stop the supply of O ₂ gas, evacuate it, and adjust the vacuum to 5
× not exceed 10 ~ ⁵ Pa, it was etched Al film 39 steps and a film to be processed in the same manner in FIG. 7 of Example 5 (d).

Finally, after the etching is completed, the step of removing the photoresist 41 shown in FIG. 8L is carried out as follows. Similar to the process of FIG. 7E of Example 5, the photoresist 41 was removed in the exposure and development chamber 7.

In this way, even when the organic flattening layer 40 is provided and the patterning of the film to be processed 39 is performed, the dry consistent process can be performed over the whole process.

<Embodiment 8> Next, another embodiment in which a pattern is formed by using the pattern forming apparatus of Embodiment 1 will be described with reference to FIGS. 1, 2 and 9. This example shows a method of forming a carbon film as a second resist film on a base of a photoresist film to form a two-layer resist film and etching a film to be processed. The manufacturing process is based on the all dry integrated process as in the previous examples. Hereinafter, description will be sequentially made according to the cross-sectional process diagram shown in FIG.

The pretreatment of the substrate and the process of forming the film 43 to be processed shown in FIG. 9 (m) were carried out as follows. Board 42
Using the substrate pretreatment chamber 2 and the film formation chamber 3 for the film to be processed shown in FIG. 1, the Al film 43 having a thickness of 500 nm is formed as the film to be processed after the substrate pretreatment is performed in the same manner as in Example 7. Formed.

The step of forming the etching mask 44 shown in FIG. 9N was performed as follows. The etching mask film forming chamber 4 (sputtering chamber in this embodiment) in FIG. 1 is evacuated to a vacuum degree of 5 × 10 ⁵ Pa or less, the gate valve 9d is opened, and the substrate holder 10 is used as an etching mask film. It is conveyed to the chamber 4 and the gate valve 9d is closed. Here, Ar gas of 50 scc is applied to the film forming chamber 4 of the etching mask.
m flow, the pressure inside the chamber was adjusted to 0.5 Pa, RF power of 600 W was applied, and a carbon film 44 as an etching mask was formed to a thickness of 400 nm. Carbon film 44
After film formation, the introduction of Ar gas is stopped and the chamber is evacuated to a vacuum degree of 5 × 10 ⁵ Pa or less. Next, the gate valve 9d is opened, the substrate holder 10 is moved to the transfer chamber 9, and the gate valve 9d is closed. The film forming chamber 4 for the etching mask is evacuated to a vacuum degree of 5 × 10 ⁵ Pa or less.

The step of forming the photoresist film 45 shown in FIG. 9 (o) was performed as follows. FIG. 7 of Example 5
In the same manner as the photoresist film forming step shown in (b), the photoresist film forming chamber 6 is used, and the photoresist 45 is formed using dodecamethylcyclohexasilane as a raw material.
Was formed on the carbon film 44.

The exposure and development steps shown in FIG.
It was carried out as follows. Using the exposure and development chamber 7, a positive pattern is obtained in the same manner as in the step shown in FIG.

The etching process of the etching mask 44 shown in FIG. 9 (q) was carried out as follows. The degree of vacuum in the etching chamber 8 for the film to be processed in FIG. 1 is set to 5 × 10 to ⁵ Pa or less, the gate valve 9h is opened, the substrate holder 10 is transferred to the etching chamber 8 for the film to be processed, and the gate valve 9h is closed. O ₂ gas was introduced as an etching gas at a flow rate of 50 sccm to adjust the degree of vacuum in the chamber to 10 Pa. Thirty
The carbon film 44 was etched by applying RF power of 0 W.

The etching process of the processed film 43 shown in FIG. 9 (r) was performed as follows. Etching mask 44
After the etching was performed, the supply of O ₂ gas was stopped in the same chamber (etching chamber 8) as it was, and the chamber was evacuated to a degree of vacuum of 5 × 10 to ⁵ Pa. The Al film 43 which is the film to be processed was etched in the same manner as in the process.

After the etching, the step of removing the photoresist 45 shown in FIG. 9 (s) was carried out as follows. As in Example 5, the photoresist 45 was removed in the exposure and development chamber 7 shown in FIG.

Finally, the step of removing the etching mask 44 shown in FIG. 9 (t) was performed as follows. The degree of vacuum in the etching chamber 8 for the film to be processed in FIG. 1 is set to 5 × 10 to ⁵ Pa or less, the gate valve 9h is opened, the substrate holder 10 is transferred to the etching chamber 8 for the film to be processed, and the gate valve 9h is closed. O ₂ gas was introduced as an etching gas at a flow rate of 50 sccm to adjust the degree of vacuum in the chamber to 10 Pa. Thirty
The carbon film 44 was removed by applying RF power of 0 W.

In this way, even when the patterning of the film 43 to be processed is performed using the two-layer resist film of the etching mask 44 and the photoresist 45, it is possible to perform the whole process in the same manner as in the above-described embodiments. It could be done in a dry integrated process.

[0101]

As described above in detail, according to the present invention, the intended purpose can be achieved. That is, the steps of forming a film to be processed, forming a photoresist, exposing, developing, etching a film to be processed, and removing a photoresist can be performed consistently in a state where the atmosphere is shielded and the pressure is reduced. It was As a result, it is possible to eliminate the steps that are conventionally required, such as the step of performing vacuum evacuation from the atmospheric pressure between the steps, and the steps such as cleaning and drying steps after the solution treatment, and shortening the manufacturing time and improving productivity. Can be improved.

Further, the number of steps and the amount of movement of the substrate between steps are reduced, the chances of dust adhesion are reduced, and the manufacturing yield is improved. Furthermore, since we were able to realize an all-dry integrated process that uses an organic compound containing Si as a photoresist material that is safe and easy to handle, there are fewer restrictions on pattern formation work and equipment installation, and economical and safe photo etching. The process becomes feasible.

[Brief description of drawings]

FIG. 1 is a top view showing a configuration example of a pattern forming apparatus of the present invention.

FIG. 2 is a sectional view of a photoresist film forming chamber.

FIG. 3 is a sectional view of the exposure and development chamber.

FIG. 4 is a sectional view showing another example of the structure of a photoresist film forming chamber.

FIG. 5 is a cross-sectional view showing still another example of the structure of the photoresist film forming chamber.

FIG. 6 is a top view showing another configuration example of the pattern forming apparatus.

FIG. 7 is a process drawing that similarly shows an embodiment of a pattern forming method.

FIG. 8 is a process drawing showing another embodiment of the pattern forming method.

FIG. 9 is a process drawing showing another embodiment of the same pattern forming method.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 ... Load lock chamber, 1a, 5a, 6a ... Door, 2 ... Substrate pretreatment chamber, 3 ... Processed film forming chamber, 4 ... Etching mask forming chamber, 5 ... Organic planarization film forming chamber , 6 ... Photoresist film forming chamber, 6-1 ... Vaporization chamber, 6-2 ... Decomposition chamber, 6-3 ... Reaction chamber, 6b to 6d ... Valve (flow control valve) 6e ... Electromagnetic valve, 7 ... Exposure and Developing chamber, 8 ... Etching chamber, 9 ... Transfer chamber, 9a to 9h ... Gate valve, 10 ... Substrate holder, 11 ... Sample boat (or sample cylinder), 12 ... Sample, 13, 20, 32 ... Support base, 14 ... infrared lamp, 15, 26, 33 ... gas inlet, 16, 22, 34 ... exhaust port, 17 ... quartz tube, 18 ... infrared lamp (or ultraviolet lamp), 19 ... cooling mechanism, 21 ... film thickness monitor, 25 ... Plasma generator, 27 ... Light source, 28 ... Meiko science system, 29 ... photomask, 30 ... projection optical system, 31 ... window, 35,38,42 ... substrate, 36 ... SiO ₂ film, 37,41,45 ... photoresist, 39, 43 ... Al film, 40 ... organic flattening layer, 44 ... carbon film.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location H01L 21/30 515 B 567 21/302 H (72) Inventor Yoshitada Oshida Yoshida Totsuka-ku, Yokohama, Kanagawa Prefecture 292, Machi Incorporated company Hitachi, Ltd.

Claims (17)

[Claims] 1. A first step of depositing a film to be processed on a substrate, a second step of forming a photoresist on the film to be processed, and exposure through a photomask having a predetermined pattern on the photoresist. And a fourth step of developing the exposed photoresist, and a fifth step of etching the film to be processed by using the photoresist patterns obtained in the third and fourth steps as a mask. And a sixth step of removing the photoresist pattern, a pattern forming method in which the photoetching process is an all-dry integrated process, wherein the second step is a non-oxidizing atmosphere under reduced pressure, and a solid or A step of vaporizing a liquid organic compound containing Si, a step of decomposing the vaporized organic compound to generate a Si radical, and a decomposed Si radical Reacting and recombining to form a photoresist made of an organic compound having a Si—Si bond on the film to be processed. The third step and the fourth step include: A photoresist mask pattern forming process including a step of advancing development together with exposure by irradiating the photoresist with an electromagnetic wave having sufficient energy for breaking Si-Si bonds of the organic compound through the mask. Pattern formation method. 2. A sixth step of removing the photoresist pattern is to expose the entire surface of the photoresist mask pattern by the same exposure step as the third step, and decompose and remove the photoresist mask by the exposure. The pattern forming method according to claim 1, wherein the pattern forming method comprises the step of: 3. The organic compound is decomposed in the second step to obtain S.
2. The pattern forming method according to claim 1, wherein the step of generating i radicals is performed by any one of decomposition methods such as thermal decomposition of the organic compound, decomposition by electromagnetic wave irradiation, or decomposition by low temperature plasma irradiation. 4. The solid or liquid organic compound containing Si is constituted by at least one of compounds represented by the following chemical structural formulas (1), (2) and (3). The described pattern forming method. [Chemical 1] [Chemical 2] [Chemical 3] However, R ₁ and R ₂ in the formula represent an organic group selected from an alkyl group and an aryl group, and R ₃ and R ₄ represent a fluoro group, a perfluoroalkyl group, a phenyl group, a perfluorophenyl group, a perfluoroalkyl group. It represents a different organic group selected from substituted phenyl groups, and n ₁ and n ₂ represent positive integers. 5. The pattern forming method according to claim 1, wherein the first to sixth steps are carried out in a state of being shielded from the atmosphere and under a reduced pressure. 6. A first step of depositing a film to be processed on a substrate having a step, a second step of forming an organic planarizing film on the film to be processed, and a photoresist on the organic planarizing film. Forming step, a fourth step of exposing the photoresist through a mask having a predetermined pattern, a fifth step of developing the exposed photoresist, a fourth step and a fourth step A sixth step of etching the organic planarizing film using the photoresist pattern obtained in the step 5 as a mask, and a seventh step of etching the film to be processed using the obtained organic planarizing film pattern as a mask. And a photoetching process including at least an eighth step of removing the photoresist pattern as an all dry integrated process, wherein the third step is a non-oxidizing atmosphere under reduced pressure. A film to be processed by vaporizing a solid or liquid organic compound containing Si, decomposing the vaporized organic compound to generate Si radicals, and reacting the decomposed Si radicals to recombine And a step of depositing a photoresist made of an organic compound having a Si-Si bond thereon, wherein the third step and the fourth step are Si- of the organic compound.
A pattern forming method comprising a photoresist mask pattern forming step including a step of irradiating an electromagnetic wave having sufficient energy for breaking Si bonds to the photoresist through the mask to proceed with development along with exposure. 7. A first step of depositing a film to be processed on a substrate, a second step of forming an etching mask having a sufficient etching selection ratio with the film to be processed on the film to be processed, and an etching mask. A third step of forming a photoresist, a fourth step of exposing the photoresist through a photomask having a predetermined pattern, a fifth step of developing the exposed photoresist, and A sixth step of etching the etching mask using the photoresist pattern obtained in the steps 4 and 5 as a mask, and a step of etching the film to be processed using the etching mask obtained in the sixth step. And a photoetching process including at least an eighth step of removing the photoresist pattern and a ninth step of removing the etching mask. In the pattern forming method which is a dry integrated process, the third step is a step of vaporizing a solid or liquid organic compound containing Si in a non-oxidizing atmosphere under reduced pressure, and a step of decomposing the vaporized organic compound to produce Si. And a step of forming a photoresist made of an organic compound having a Si—Si bond on the film to be processed by reacting and recombining the decomposed and generated Si radicals. In the third step and the fourth step, the photoresist is irradiated with an electromagnetic wave having sufficient energy to cleave the Si-Si bond of the organic compound, and the photoresist is exposed and developed together. A pattern forming method comprising a photoresist mask pattern forming step having a step of advancing. 8. The organic compound is decomposed in the third step to obtain S.
The pattern forming method according to claim 6 or 7, wherein the step of generating i radicals is performed by a decomposition method such as thermal decomposition of the organic compound, decomposition by electromagnetic wave irradiation, or decomposition by low temperature plasma irradiation. 9. In an eighth step of removing the photoresist pattern, the entire surface of the photoresist mask pattern is exposed by the same exposure step as in the fourth step, and the photoresist mask is decomposed and removed by the exposure. 8. The pattern forming method according to claim 6 or 7, which comprises the step of: 10. The second step of forming the organic planarizing film comprises the steps of vaporizing a solid or liquid organic compound in a non-oxidizing atmosphere under reduced pressure, and thermally decomposing the vaporized organic compound to generate radicals. 7. The pattern forming method according to claim 6, comprising: a step of generating the radicals, and a step of reacting the generated radicals to recombine to form an organic planarizing film on the film to be processed. 11. The second step of forming the organic planarizing film comprises the steps of vaporizing at least two kinds of solid or liquid organic compounds under reduced pressure and reacting the vaporized organic compounds on the film to be processed. 7. The pattern forming method according to claim 6, comprising the steps of: forming a thin film on the substrate; and heating the formed thin film to form an organic planarization film. 12. The second step of forming the etching mask comprises the steps of vaporizing at least two kinds of solid or liquid organic compounds under reduced pressure and reacting the vaporized organic compounds to form a thin film on the film to be processed. 8. The pattern forming method according to claim 7, further comprising the steps of: forming a film, and heating the formed thin film to form an etching mask. 13. In the second step of forming the etching mask, an organic compound or carbon is used as a target to form an etching mask on the film to be processed by a sputtering method, or plasma using an organic compound is used. C
The pattern forming method according to claim 7, further comprising the step of forming an etching mask on the film to be processed by the VD method. 14. A first method for forming a photoresist on a substrate.
And a second chamber for exposing the photoresist, and a third chamber for transferring the substrate, each of which is configured to be vacuum-sealable. The first chamber and the second chamber are connected to the third chamber via gate valves individually provided,
The first chamber for forming the photoresist is a non-oxidizing atmosphere, a vaporizing chamber for vaporizing a solid or liquid organic compound containing Si, and a vaporizing organic compound for decomposing the vaporized organic compound to produce Si.
The second chamber, which includes a decomposition chamber for generating radicals and a reaction chamber for recombining decomposed organic compounds, and which exposes the photoresist has at least an electromagnetic wave having sufficient energy to break the recombination. Forming apparatus comprising an exposure chamber equipped with means for irradiating the photoresist. 15. The vaporization chamber, the decomposition chamber, and the reaction chamber of the first chamber are all vacuum-sealable, and the vaporization chamber and the decomposition chamber, the decomposition chamber and the reaction chamber, and the reaction chamber. The third room is
Each of them is connected through a gate valve provided individually, and a gate valve for inserting at least a solid or liquid organic compound into the vaporization chamber, and a gas introduction means for returning the vaporization chamber to atmospheric pressure, and an organic compound. The decomposition chamber is equipped with a heating means, an electromagnetic wave irradiation means, or a low-temperature plasma irradiation means as a means for decomposing at least an organic compound, and the reaction chamber is loaded from at least the third chamber. 15. The pattern forming apparatus according to claim 14, further comprising: a holding unit that holds the substrate, an exhaust unit, and a unit that reacts radicals generated in the decomposition chamber to recombine to form a film. 16. The second chamber holds at least exposure means for irradiating the photoresist with electromagnetic waves having sufficient energy to break the recombination, and a substrate carried in from the third chamber. 15. The pattern forming apparatus according to claim 14, further comprising: a holding unit for removing the decomposition product of the photoresist decomposed by exposure by exhaustion. 17. The second chamber irradiates the photoresist with gas introducing means for introducing a carrier gas into the chamber and an electromagnetic wave having sufficient energy to break the recombination under a flow of the introduced gas. 15. The pattern forming apparatus according to claim 14, further comprising: an exposure unit, a holding unit for holding the substrate carried in from the third chamber, and an exhaust unit for exhausting and removing the decomposition product of the photoresist cleaved by the exposure. .