JPH09166874A - Formation of pattern and production of semiconductor device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To make it possible to form patterns which have high resolution performance, high dry etching resistance and excellent dimensional controllability and have high throughput with a decreased number of stages at a low cost. SOLUTION: The surface of a ground surface substrate 201 is spin coated with a photosensitive material consisting esssentially of a polymer or oligomer contg. siloxane bonds and carbon double bonds. Far UV light is selectively exposed to this material, by which the chemical bonds in the photosensitive molecules are cut to form polar groups and the polarities of the exposed parts are changed. The photosensitive material is thereafter developed and the films of the exposed parts or unexposed parts are selectively removed, by which the patterns are formed.

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 in an optical lithography apparatus and a semiconductor device manufacturing method using the above technique.

[0002]

2. Description of the Related Art At present, in the manufacture of semiconductor devices, a technique for forming finer patterns is required in accordance with higher integration of circuits. Industrially, fine processing is performed by a thin film forming technique and photolithography. ing.

Hitherto, in photolithography, i-line and g-line of a high pressure mercury lamp have been used as an exposure light source. Since the resolution of this method is proportional to the exposure wavelength, a KrF excimer laser (λ = 245 nm) having a shorter wavelength than the i-line is being put into practical use in order to further improve the minimum processing size. Moreover, in recent years, an ArF excimer laser (λ = 193 nm) has been studied as a light source of a shorter wavelength.

In general, in exposure using a g-ray or i-ray as a light source, a single-layer organic resist in which an organic resist containing a novolac resin and an azide-based photosensitizer as a main component is spin-coated on a substrate to be processed, and exposed and developed. Method is used. On the other hand, K
In the exposure using the rF excimer laser, a chemically amplified resist that uses an acid-catalyzed reaction is used in order to improve the sensitivity and reduce the light absorption of the resist in the exposure wavelength region.

A silicon-containing resist is used as a method for improving the problems caused by an increase in the level difference of the underlayer caused by the three-dimensionalization of the device due to the high integration, a reduction in the depth of focus with the increase in resolution, and a dimensional variation due to substrate reflection. A two-layer resist method used for the upper layer has been proposed. As the silicon-containing resist, a chemically amplified resist obtained by adding an acid generator or a base generator to polysiloxane, a polysilane film containing a photosensitizer, a polysilene film formed by plasma CVD, and the like are known.

Further, when a pattern such as wiring or capacitance is processed, if the organic resist mask has insufficient dry etching resistance, a silicon oxide film is formed on the substrate to be processed,
A method (a hard mask method) is known in which a pattern is transferred to a base silicon oxide film by a single-layer organic resist method and then a base metal or the like is processed using the transfer pattern as an etching mask.

These various conventional pattern forming methods using resists are discussed in, for example, "Resist Material / Process Technology" published by Technical Information Association, Chapter 1, Sections 1 to 5.

[0008]

In the pattern formation method using a single-layer organic resist, in order to secure the resist film thickness necessary for anisotropic dry etching of the underlayer, the aspect ratio of the resist pattern (resist pattern Height / width) is increasing. For this reason,
Problems such as resist pattern collapse during development and microloading effect during etching occur. On the other hand, a phenol resin-based resist used for KrF excimer laser exposure has a high dry etch resistance, but pattern formation becomes difficult in ArF excimer laser exposure with a wavelength of 200 nm or less due to strong absorption of benzene rings. Therefore, it is necessary to use an acrylic resin, but since these materials lack dry etching resistance, the problem of increasing the aspect ratio becomes more serious. Further, in the single-layer organic resist method, generally, due to multiple interference in the resist film during exposure,
There is a problem that the dimension of the pattern varies with the variation of the resist film thickness.

Further, in the chemically amplified resist, there is generally a problem in stability such that a surface insoluble layer is formed after exposure due to a slight amount of contamination such as amine in the air and the resist sensitivity depends on the standing time in the air. It is said that.
Further, since the catalytic reaction by the heat treatment (PEB) after exposure is used, the sensitivity and the size greatly vary due to a slight change in the PEB condition. Further, since the acid catalyst generated in the exposed portion diffuses in the resist, there is a problem in pattern shape controllability and size controllability.

On the other hand, the pattern forming method using the multi-layer resist has a problem that the throughput is reduced due to the complicated process, and the cost is increased due to a reduction in yield. Similarly, the hard mask method has a problem in that the process is complicated and the cost is increased.

Since polysilane, polysilene and the like use a metal catalyst such as sodium for the synthesis, there is a problem of contamination of the semiconductor device. Further, when the polysilane film is formed by plasma CVD, an increase in cost due to a decrease in throughput is inevitable as compared with the conventional spin coating method.

An object of the present invention is to provide a novel pattern forming method which has high resolution performance and extremely high dry etch resistance, and therefore can solve various problems in the above single layer organic resist method. is there.

A second object of the present invention is to solve the problems of the chemically amplified resist, and to provide a pattern forming method having a large process latitude and excellent dimensional controllability.

A third object of the present invention is to solve the problems of the pattern forming method using a multi-layer resist and the pattern forming method using a hard mask, and to provide a pattern forming method having a small number of steps and a low cost and a high throughput. is there. Furthermore, this is to provide a semiconductor device manufacturing method that is simpler than in the past.

[0015]

Means for Solving the Problems The first to third problems described above include spin-coating a photosensitive material containing a polymer or oligomer containing a siloxane bond and a carbon double bond as a main component on a base substrate by spin coating. By selectively exposing to far-ultraviolet light, the chemical bond in the photosensitive molecule is broken to generate a hydroxyl group to change the polarity of the exposed area and then developed to selectively remove the film in the exposed or unexposed area. It is solved by forming a pattern.

For example, when a polymer having an aromatic functional group in the main chain and a side chain having a siloxane bond is irradiated with ArF excimer laser light, the chemical bond between the silicon atom in the photosensitive molecule and the aromatic functional group is broken, An OH group is generated at the Si atomic end of the cut portion, and a positive pattern can be formed by alkali development.

As the main component of the photosensitive material, it is desirable to use a Si-containing polymer or oligomer in which the ratio of the number of oxygen atoms to the number of silicon atoms is 1 or more.

For example, any of the compounds represented by the chemical formula 1, the chemical formula 2, or the general formula of the chemical formula 3, or a mixture thereof can be used.

[0019]

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[0020]

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[0021]

[Chemical 6]

However, the molecules of Chemical Formulas 1 to 3 have at least one functional group containing a carbon double bond in the side chain.

A metal complex, an organic metal, a metal oxide, or a compound capable of generating radicals by irradiation with far-ultraviolet light can be introduced and mixed into the photosensitive material.

Further, it is desirable to form the pattern so that the aspect ratio becomes 3 or less with respect to the desired minimum pattern dimension.

Incidentally, it is desirable that the exposure is performed in a humidity controlled environment. After the development, the substrate can be heated, or oxygen reactive ion etching, or irradiation with light of 300 nm or less, to remove organic substances from the pattern.

The fourth object is achieved by manufacturing a semiconductor device using a pattern forming method. For example,
Using the pattern after development as a mask, it is possible to etch the base of organic matter, metal, semiconductor, metal oxide or the like. In particular, it is suitable for processing gates, wirings, or capacitors in MOS transistor circuits. At this time Ar
It is desirable to expose using an F excimer laser stepper. The mask may be removed after etching, but if it is left in the device without removing it, the manufacturing process becomes simpler.

The operation of the present invention will be described with reference to FIG. 1 in the case of polymethylphenylsilsesquioxane 102 in which the ratio of side chain methyl groups to phenyl groups is 2: 1.

When a film formed on the substrate by spin coating or the like is irradiated with excimer laser light 101, the exposure energy is mainly absorbed by the benzene ring 103 of the side chain of the silsesquioxane molecule, and the bond between the main chain and the benzene ring is formed. Be disconnected.
The radical generated by the cleavage reacts with a water molecule or the like to form a hydroxyl group 104 at the cleavage site, and the polarity of the silsesquioxane molecule changes.

This reaction is supported by the following analytical results.

First, when the change in Fourier infrared absorption spectrum of polymethylphenylsilsesquioxane before and after ArF excimer laser exposure was examined, an increase in absorption due to hydroxyl groups was observed after ArF exposure.

Second, ArF excimer laser irradiation of polymethylphenylsilsesquioxane (about 100 mJ / cm 2
² ) According to the change of XPS before and after, the ratio of carbon atoms in the film was reduced by 10% after ArF exposure, and the oxygen atoms were 1%.
It increased by 0%. On the other hand, since there is no change in the number of silicon atoms, the number of benzene rings in the film of the exposed portion is decreased and the oxidation reaction such as the generation of hydroxyl groups is shown.

Thirdly, the polymethylphenylsilsesquioxane changes its polarity by exposing the exposed part to hydrophilicity by ArF exposure.

The exposed portion whose polarity has been changed by the short-wavelength exposure can be developed with an alkaline solution, so that a positive pattern without swelling can be obtained. Also, a negative pattern can be obtained by organic development. The difference in hydrophilicity and hydrophobicity between the exposed area and the unexposed area in this development not only increases the development contrast, but also helps prevent swelling. It is preferable to optimize the developer concentration in order to improve the development contrast.

Since the polarity change reaction is not a chemical amplification reaction, it is a chemical reaction which is excellent in size control and has environmental resistance.
Moreover, since the presence of water and oxygen molecules is important for the reaction, it is desirable to control humidity and oxygen partial pressure.

The benzene ring has a strong absorption centered at 190 nm, and has a wavelength of the ArF excimer laser (λ = 193
(nm), so that the exposure energy is absorbed efficiently. The photon energy of the ArF excimer laser is about 6.1 eV, and the probability of breaking the bond is small because it is smaller than the siloxane bond energy of 8.3 eV, but the bond between silicon and carbon (bond energy is 4.5 eV) or silicon and hydrogen.
The probability of breaking a weak bond such as (bonding energy is 3.24 eV) is high. Therefore, the main chain silicon and side chains are efficiently cut by ArF exposure.

In this description, the case of polymethylphenylsilsesquioxane was described, but any silicon-containing photosensitive material can be used within the range not changing the gist of the present invention. For example, a light-sensitive material in which a functional group containing a carbon double bond that strongly absorbs at an exposure wavelength is introduced into a main chain or a side chain of a polymer or oligomer having a siloxane structure at a desired ratio can also be used. Further, a light-sensitive material in which a benzene ring derivative is introduced into a side chain or a main chain of a polymer or an oligomer having a siloxane structure at a desired ratio can be mainly used. Alternatively, a photosensitive material in which a siloxane-based polymer containing an aromatic functional group and a siloxane-based polymer not containing an aromatic functional group are mixed in a desired ratio can be used. It is also effective to add a radical generator to improve the sensitivity. For a silicon-containing photosensitive material, a resist pattern having a good shape can be obtained by adjusting the transmittance by changing the ratio of introduction of a functional group having absorption at an exposure wavelength such as a benzene ring into a side chain or the like. .

In order to enhance the adhesion between the photosensitive material and the substrate, it is preferable to subject the underlying substrate to a surface treatment and to add a material that improves the adhesion to the photosensitive material.

Since the siloxane bond has a high etching resistance, a dry etching process of polysilicon or the like using the resist pattern as a mask provides a selectivity higher than that of the case of using a conventional resist made of an organic material as a mask. In particular, a material having a ratio of the number of oxygen atoms to the number of silicon atoms of 1 or more has a remarkable improvement in dry etching resistance. Further, various metal complexes may be added to the photosensitive material in order to further improve the dry etching resistance.

The pattern formed by the dry etching resistance strengthening method can be applied to a dry etching mask of a metal film. Further, it goes without saying that this material can be used as an upper layer resist in the past two-layer resist method.

The organic component remaining in the resist pattern portion can be removed by oxygen ashing, oxygen reactive ion etching, heat treatment, or the like.
It is possible to improve film properties such as dry etching resistance and hygroscopicity.

The pattern formed according to the present invention can be left in the semiconductor device after the base processing, and in this case, its dielectric constant is smaller than that of the CVD silicon oxide film or the like. However, to ensure reliability,
It is preferably used in combination with an ordinary CVD film.

On the other hand, the resist pattern can be removed by mechanical polishing or a wet process such as dilute hydrofluoric acid or dry etching using a fluorine gas system or the like after the base processing.

The conventional pattern forming process using an organic resist including the hard mask method can be replaced by the pattern forming method of the present invention. As a result, it is possible to form a pattern with a small number of steps and excellent dimensional control.

The pattern forming method of the present invention is applied to various semiconductor integrated circuits (LS) such as a memory or a microprocessor.
It can be applied to the production of I). In the case of a MOS semiconductor, pattern formation of a silicon nitride film used as a mask for LOCOS field oxidation, pattern formation of gate material such as amorphous silicon or metal, pattern formation of wiring material such as tungsten and copper, formation of contact holes, etc. The pattern forming method of the present invention can be used in various steps. According to the implementation of the present invention, there is an advantage that throughput and yield are good because the process is simple. In addition, since the dimensional controllability is good, it is possible to manufacture an LSI with high performance in which variations in the threshold voltage of the gate are suppressed.

[0045]

BEST MODE FOR CARRYING OUT THE INVENTION

Example 1 A 5% by weight solution of polymethylphenylsilsesquioxane (methyl group: phenyl group = 2: 1) in ethyl cellosolve was spin-coated on a silicon substrate at 4000 rpm for 60 seconds, and then at 80 ° C. A heat treatment was performed for 3 minutes to form a resist film having a film thickness of 60 nm. Polymethylphenylsilsesquioxane is an oligomer having a molecular weight of about 1000 and can be formed into a film having a thickness of 30 to 40 nm by spin coating. Excellent safety because alcoholic solvents can be used. ArF excimer laser exposure device (NA =
0.55) was used to expose various patterns having a size of 0.13 μm to 1 μm. Next, it was developed with a 2.38% aqueous solution of tetramethylammonium hydroxide for 30 seconds, washed with water, and heat-treated at 100 ° C. for 40 seconds. As a result of observing the pattern exposure portion with a scanning electron microscope, the laser irradiation amount was 4
It was confirmed that a pattern having a minimum dimension of 0.13 μm was formed for 0 mJ / cm ² . Further, when the periodic type phase shift mask was used, a pattern having a size of 80 nm could be formed.

In this example, polymethylphenylsilsesquioxane was used for the resist. However, if it is a material having a siloxane bond and having an appropriate absorption coefficient and sensitivity and its polarity changes by exposure, it is shown in this example. Not limited to things.

According to this example, a fine pattern having a high dry etch resistance could be formed by using ArF exposure with a practical sensitivity.

Example 2 A 4: 1 mixture of polymethylsilsesquioxane and polyphenylsilsesquioxane has a transmittance of 70% for an ArF excimer laser at a film thickness of 0.1 μm. A 10 wt% solution of the above mixture in ethyl cellosolve was spin-coated on the substrate at 2000 rpm for 60 seconds, and then heat-treated at 80 ° C. for 3 minutes to give a film thickness of 16
A 0 nm resist film was formed. An ArF excimer laser exposure device (NA = 0.55) was used to measure the above substrate to a size of 0.1.
Various patterns of 3 μm to 1 μm were exposed. Next, 2.38% of tetramethylammonium hydroxide
After developing with an aqueous solution for 30 seconds, it was washed with water and heat-treated at 100 ° C. for 40 seconds. As a result of observing the pattern exposed portion with a scanning electron microscope, it was confirmed that a pattern having a size of 0.13 μm was formed with respect to a laser irradiation amount of 60 mJ / cm ² .

According to this example, a resist pattern having a large film thickness which can be used for a dry etching mask for metal processing or the like could be formed by ArF exposure.

(Example 3) Polymethylphenylsilsesquioxane and trichlorophenol (radical generator) were mixed on a silicon substrate at a weight ratio of 3: 1 to prepare a 10% butanol solution, and the substrate was treated at 4000 rpm for 60 seconds. Was spin coated and then heat treated at 80 ° C. for 3 minutes to form a photosensitive film having a thickness of 60 nm. Using an ArF excimer laser exposure device (NA = 0.55), the above substrate was 0.13 μm.
A pattern with a size of m to 1 μm was exposed. After that, organic development is performed to form a negative pattern, followed by washing with water to 100
Heat treatment was performed at 40 ° C. for 40 seconds. As a result of observing the pattern exposed portion with a scanning electron microscope, it was confirmed that a pattern having a size of 0.13 μm was formed for a laser irradiation amount of 10 mJ / cm ² .

In this embodiment, trichlorophenol was used as a radical generator for higher sensitivity, but it is not limited to this embodiment as long as it can generate radicals by exposure. For example, chlorine compounds, bromine compounds, iodine compounds and the like are conceivable, but the mixing ratio with the silicon-containing polymer must be adjusted according to the absorption coefficient of the compound used.

According to this example, a resist pattern could be formed with high sensitivity by ArF exposure.

Example 4 Polymethylphenylsilsesquioxane and titanium alkoxide 4: on a silicon substrate:
A 5 wt% butanol solution of 1 was spin-coated on the substrate at 3000 rpm for 60 seconds, and then heat-treated at 80 ° C. for 3 minutes to form a resist film having a thickness of 40 nm. Ar on the substrate
A pattern having a size of 0.13 μm to 1 μm was exposed using an F excimer laser exposure device (NA = 0.55).
Tetramethylammonium hydroxide 2.38
% Aqueous solution for 30 seconds, then wash with water, 100 ℃ 4
Heat treatment was performed for 0 seconds. As a result of observing the pattern-exposed portion with a scanning electron microscope, it was confirmed that a pattern having a size of 0.13 μm was formed for a laser irradiation amount of 40 mJ / cm ² .

When a tungsten film was dry-etched using this pattern using a fluorine-based gas, C
The etching selectivity was improved with respect to the underlying tungsten film as compared with the silicon oxide film formed by the VD method.

In this example, a material in which titanium alkoxide was mixed with polymethylphenylsilsesquioxane was used. However, a material having a siloxane bond, which has an appropriate absorption coefficient and sensitivity and whose polarity changes by exposure, A mixture with a metal-containing material that improves dry etching resistance can be used regardless of the present embodiment.

(Embodiment 5) Next, a method of manufacturing a MOS semiconductor device using the present invention will be described with reference to FIG.

(1) LOCOS formation After lightly oxidizing the silicon substrate 201, a silicon nitride (SiN) film 202 having a film thickness of 0.1 μm is formed on the substrate.
Was formed. After that, a resist pattern 203 was formed using the method shown in Example 2 (FIG. 2A). Next, using this as a mask, dry etching was performed on the SiN film using tetrafluorocarbon (+ oxygen) as an etching gas to form a SiN pattern, and further field oxidation was performed to form LOCOS 204. After that, the SiN film and the silicon oxide film in the active region were removed (FIG. 2B).

(2) Gate formation Next, after performing gate oxidation 205 by dry oxidation,
A 0.2 μm-thick phosphorus-doped polysilicon film 206 was formed on the silicon oxide film by CVD, and a gate processing resist pattern 207 was formed on this substrate by the method shown in Example 1 (see FIG. 2 (c)). Using the pattern as a mask, ECR μ wave plasma etching was performed using chlorine (+ oxygen) as an etching gas to process the underlying polysilicon gate 209 (FIG. 2D).

Although chlorine gas was used as the etching gas, any gas known as an etching gas for polysilicon is not limited to this embodiment. For example, bromic acid (+
A bromine-based gas such as oxygen) or a fluorine-based gas may be used. Further, similarly to this embodiment, processing of an amorphous silicon gate, a metal gate, etc. can be performed.

(3) Formation of Contact Hole Normal LD without removing the resist pattern for gate processing
After forming the source / drain 208 according to the D formation process, an insulating film made of a silicon oxide film is formed and planarization 2
I did 10. A novolak resin film 211 having a thickness of 0.7 μm was formed on the substrate by spin coating and hard baking was performed. After that, a contact hole resist pattern 212 was formed using the method shown in Example 3 (FIG. 2).
(E)). Next, a pattern was transferred to the underlying novolak resin by oxygen reactive ion etching using this as a mask. Further, using this as a mask, the silicon oxide film was dry-etched using tetrachlorocarbon (+ oxygen) as an etching gas to form a contact hole 213 (FIG. 2F). After that, the resin was removed by ashing.

(4) Wiring formation After forming an aluminum film 214 having a film thickness of 0.5 μm on the layer to be wired by a sputtering method, a wiring resist pattern 215 was formed by the method shown in Example 4 (see FIG. 2 (g)). Next, using this as a mask, dry etching was performed using tetrachlorocarbon (+ chlorine) as an etching gas to form a wiring 216 (FIG. 2H).

The etching gas is not limited to the above, and can be changed appropriately. For example, an etching gas such as trichloroboron + chlorine (+ tetrachlorocarbon) may be used.

Wiring patterns of tungsten, titanium nitride, copper, etc. can be formed in the same manner as described above, but the etching methods must be optimized.

Although not shown here, the pattern forming method according to the present invention is not limited to the other components of the MOS semiconductor device.
For example, it can be used for processing a capacitor in a DRAM or a ferroelectric memory. Since the resist pattern according to the present invention has extremely excellent dry etching resistance, it is possible to collectively etch the capacitor film having the platinum-PZT-platinum structure by using the resist pattern as a mask.

A MOS integrated circuit was manufactured by using the above steps, and its operation was confirmed. According to this embodiment, the number of manufacturing steps can be reduced as compared with the conventional method.

The example in which the present invention is applied to the basic pattern of the MOS LSI has been described above. However, other steps of the LSI and other types of semiconductor devices such as bipolar L are used.
It can also be applied to SI, optical electronic IC, laser and the like.

The material to be processed, the type of the photosensitive material, the exposure method, the developing method, the etching method, the gas and the like can be freely changed without departing from the spirit of the present invention. In that case, it is desirable to change and optimize the resist film thickness, coating conditions, etching gas, and other conditions.

[0068]

According to the present invention, a silicon-containing resist film formed on a substrate having a material to be processed on its surface is selectively irradiated with light to directly generate a hydroxyl group in the resist molecule in the exposed portion. Then, by developing this and selectively removing the exposed or unexposed areas to form a resist pattern, it is possible to form a pattern with high resolution, large dry etch resistance, and excellent dimensional controllability. Is. Furthermore, by etching the device material using the pattern as a mask, it becomes possible to manufacture a low-cost semiconductor manufacturing apparatus with a small number of steps.

[Brief description of the drawings]

FIG. 1 is an explanatory view showing the principle of the present invention.

FIG. 2 is an explanatory view of a semiconductor device manufacturing process showing an embodiment of the present invention.

[Explanation of symbols]

201 ... Silicon substrate, 202 ... Silicon nitride film, 203 ... LOCOS resist pattern, 204 ... LOC
OS, 205 ... Gate oxide film, 206 ... Gate polysilicon, 207 ... Gate resist pattern, 208 ... Source / drain, 209 ... Gate, 210 ... Interlayer insulating film,
211 ... Novolac resin film, 212 ... Contact hole resist pattern, 213 ... Contact hole, 214
... Wiring material film, 215 ... Wiring resist pattern, 216
…wiring.

Claims (19)

[Claims] 1. A method for forming a pattern on a base substrate by selectively irradiating light, wherein a photosensitive material composed mainly of a polymer or oligomer containing a siloxane bond and a carbon double bond is formed on the substrate. A step of forming a thin film by a spin coating method, the photosensitive film is selectively exposed to far-ultraviolet light, and a chemical bond in the exposed portion of the photosensitive molecule is cut to generate a hydroxyl group at the cut portion to form the photosensitive molecule. And a step of developing the photosensitive film to selectively remove the exposed portion or a film other than the exposed portion to form a pattern. 2. A method of forming a pattern on an underlying substrate by selectively irradiating light, which comprises a main chain having a siloxane bond and a polymer or an oligomer having an aromatic functional group in a side chain as main components. Step of forming a thin film of a photosensitive material on the substrate by a spin coating method, selectively exposing the photosensitive film to ArF excimer laser light to break the chemical bonds between the main chain and side chains in the exposed molecule. Thereby forming a hydroxyl group in the cut portion of the main chain to change the polarity of the photosensitive molecule, and developing the photosensitive film with an alkali to selectively remove the exposed portion to form a pattern. The pattern forming method according to claim 1. 3. The pattern forming method according to claim 1, wherein the ratio of the number of oxygen atoms to the number of silicon atoms in the polymer or oligomer as the main component of the photosensitive material is 1 or more. 4. The polymer or oligomer as a main component of the photosensitive material is any of compounds represented by the general formulas of chemical formula 1, chemical formula 2, or chemical formula 3, or a mixture thereof. Pattern formation method. Embedded image Embedded image Embedded image The molecule represented by Chemical Formula 1, Chemical Formula 2 or Chemical Formula 3 has at least one functional group having a carbon double bond in the side chain.
R in each chemical formula is an alcohol group, an alkyl group, an aromatic group, an aromatic derivative group, or a hydroxyl group,
Or a functional group containing a carbon double bond. 5. The pattern forming method according to claim 1, wherein the photosensitive material contains at least one of a metal complex, an organic metal, and a metal oxide. 6. The pattern forming method according to claim 1, wherein the photosensitive material contains a compound that generates radicals by irradiation with far-ultraviolet light. 7. The pattern forming method according to claim 1, wherein the photosensitive material film having a film thickness having an aspect ratio of 3 or less with respect to a desired minimum pattern dimension is formed. 8. The pattern forming method according to claim 1, wherein the exposure is performed in a humidity-controlled environment. 9. The pattern forming method according to claim 1, further comprising a step of removing organic substances from the pattern after the development. 10. A pattern forming method comprising heating the substrate after the development. 11. The pattern forming method according to claim 1, further comprising a step of exposing the pattern to oxygen plasma or irradiating with light having a wavelength of 300 nm or less after the development. 12. The pattern forming method according to claim 1, wherein the substrate has a work material on its surface, and includes a step of etching the work material using the pattern as a mask. 13. The material to be processed is an organic material or a metal,
Or a semiconductor or an oxide.
2. The pattern forming method as described in 2. 14. The pattern forming method according to claim 12, wherein the material to be processed is any one of a gate, a wiring, and a capacitor in a MOS transistor circuit. 15. The pattern forming method according to claim 12, further comprising a step of removing the mask after the etching. 16. A method for forming a pattern by selectively irradiating the surface of the device for forming a pattern in a semiconductor device manufacturing method, the method comprising forming a polymer or oligomer containing a siloxane bond and a carbon double bond. A step of forming a thin film of a photosensitive material as a main component on the substrate by a spin coating method, selectively exposing the photosensitive film to far-ultraviolet light, and breaking the chemical bond of the polymer or oligomer to polarize. A step of generating a group to change the polarity of the exposed portion, a step of developing the photosensitive film to selectively remove the exposed portion or a film other than the exposed portion to form a pattern. Semiconductor device manufacturing method. 17. The method of manufacturing a semiconductor device according to claim 16, further comprising the step of etching the underlying device material using the pattern as a mask after the development. 18. The method of manufacturing a semiconductor device according to claim 16, wherein the mask is not removed after the etching. 19. The method of manufacturing a semiconductor device according to claim 16, further comprising the step of exposing using an ArF excimer laser stepper.