KR100822421B1 - Film forming apparatus, film forming method, patterning method, optical device manufacturing method, and electronic device manufacturing method - Google Patents

Abstract

This invention makes it a subject to obtain the film forming apparatus which can improve the precision of formation of a fine pattern.

A first nozzle 102a for discharging the first chemical species on the substrate 160, a second nozzle 102b for discharging the second chemical species on the substrate 160, and a first chemical A material storage chamber 101a for storing the species, a reactive active species generator 103a for generating the reactive active species, a material storage chamber 101b for storing the second chemical species, and a reactive active species generator for generating the reactive active species ( 103b), the first nozzle 102a and the second nozzle 102b are installed so that the flow of the discharged first chemical species and the flow of the second chemical species cross each other.

Gas, material storage chamber, nozzle, reactive active species generator

Description

A film forming apparatus, a film forming method, a patterning method, a manufacturing method of an optical device, and a manufacturing method of an electronic device.

BRIEF DESCRIPTION OF THE DRAWINGS The figure which showed the structure of the film forming apparatus by this invention.

(A)-(d) is a figure which shows the example of the silicon compound used as a precursor of silylene.

3 (a) and 3 (b) are schematic diagrams showing the arrangement of the nozzles and the state of the free-jet discharged from the nozzle onto the base;

4 is a view for explaining a polymerization reaction of silylene and silane.

5 (a) to 5 (c) show a step of manufacturing a TFT.

6 (a) and 6 (b) are diagrams showing a configuration example in which the chemical species generating unit and the nozzle of the film forming apparatus according to the present invention are integrated.

Explanation of symbols for the main parts of the drawings

100: film forming apparatus 101a, 101b: material storage chamber

102a, 102b: nozzles 103a, 103b: reactive active species generating unit

104 chamber 105 carrier gas supply source

106: gas stage 108: piping

150: vacuum device 160: gas

The present invention relates to a film forming apparatus, a film forming method, a patterning method, a manufacturing method of an optical device, and a manufacturing method of an electronic device.

In the manufacture of electronic devices such as transistors, an inkjet method, a method by mask patterning, or the like is known as a method of forming a fine pattern. However, in the case of the inkjet method, it is necessary to miniaturize the ejected droplets in order to obtain high patterning accuracy, but the micronization of the droplets is limited in the phenomenon. Further, in the mask patterning method, since the warpage of the mask occurs due to the large area of the mask, patterning of the large area substrate is particularly difficult.

Patent Document 1 includes a vacuum chamber that is adjustable to a predetermined vacuum degree, a nozzle connected to a material supply source and attached to the vacuum chamber to supply material from a material supply source into the vacuum chamber, and installed in the vacuum chamber to hold gas. A film forming apparatus including a gas stage for fixing and a moving mechanism for moving at least one of the nozzle and the gas stage, and capable of controlling the relative positions of the nozzle and the gas by the moving mechanism is disclosed. This makes it possible to selectively form a film at a desired position of the gas. In addition, by controlling the distance between the nozzle and the gas, the area of the region for forming the film can be appropriately set.

[Patent Document 1] WO2003 / 026359 Publication

[Non-Patent Document 1] YUAN TSEH LEE, "MOLECULAR BEAM STUDIES OF ELEMENTARY CHEMICAL PROCESSES", Nobel lecture, 8 December, 1986, p.320-354

One embodiment of the present invention has an effect on formation of a finer pattern in a film forming apparatus, a film forming method, a patterning method, an optical device manufacturing method, and an electronic device manufacturing method.

The film forming apparatus of the present invention includes a first nozzle for discharging the first chemical species and a second nozzle for discharging the second chemical species.

This makes it possible to form a film made of different chemical species by discharging different chemical species from the plurality of nozzles.

In addition, when the first species and the second species cause a chemical reaction, it is possible to form a film of a product produced by the chemical reaction without being isolated from the first species or the second species. have. It is also possible to react the first chemical species and the second chemical species with the third chemical species, and the first chemical species and the second chemical species may be reacted with different chemical species, respectively. That is, by suitably combining the chemical species according to the desired film, it is possible to form a film having a different composition at the same time.

Also, preferably, the first nozzle and the first agent overlap at least a part of the flow of the first chemical species discharged from the first nozzle and at least a part of the flow of the second chemical species discharged from the second nozzle. Two nozzles are installed.

As a result, a reaction is caused at the overlapping portion of the flow of the first chemical species and the flow of the second chemical species, so that a film smaller than the cross-sectional area of the flow of each chemical species can be formed.

In addition, the first chemical species generating unit for generating the first chemical species, wherein the first chemical species generating unit generates the reactive active species as the first chemical species.

Here, the reactive active species is, for example, a chemical species that reacts with each other by polymerization or the like, or a chemical species that chemically reacts with another species, and specifically, for example, radicals, ionic radicals, ions, or low atoms (低 原子 價) chemical species.

As a means for generating reactive active species, there is a method of irradiating electromagnetic waves, for example. Examples of the electromagnetic waves include millimeter waves, submillimeter waves, microwaves, infrared light, visible light, ultraviolet light, vacuum ultraviolet light, electromagnetic waves having various wavelengths represented by so-called radio waves, light, and X-rays. It can use suitably according to the 1 species or the precursor of the said 1st species.

For example, the first chemical species may be generated using a plasma generated by irradiating a precursor of the first chemical species with microwaves, radio waves, or the like as the electromagnetic waves.

In addition, light may be used as the electromagnetic wave. For example, light may be introduced into the first chemical species generating unit using an optical window or an optical fiber, or a light source may be directly installed.

In addition, a heating unit may be provided in the first chemical species generating unit to generate reactive active species by heating.

Moreover, it is preferable that a chamber is provided, and the said 1st and 2nd nozzle are provided in the said chamber, and the pressure in the said chamber can be set to 1.3x10 <^-1> Pa or less. Thereby, the chemical species which is hard to be discharged can also be discharged easily.

In addition, the flow of the first and second species is preferably in a free-jet or supersonic molecular jet state. By generating the prejet, energy levels such as vibration and rotation of molecules can be made the lowest state, so that side reactions from chemical species or reactive active species can be suppressed.

In the film forming method of the present invention, the first chemical species and the above-mentioned species are overlapped by overlapping at least a portion of the flow of the first chemical species discharged from the first nozzle and at least a portion of the flow of the second chemical species discharged from the second nozzle. A chemical reaction of the second species is induced to form a film of the product resulting from the chemical reaction on the gas.

As a result, a reaction is caused at the overlapping portion of the flow of the first chemical species and the flow of the second chemical species, so that a film smaller than the cross-sectional area of the flow of each chemical species can be formed.

It is also preferable that at least one of the first and second chemical species is a reactive active species.

Here, the reactive active species is a chemical species that reacts with each other by polymerization or the like, or a chemical species that chemically reacts with another species, and is specifically, a radical, an ionic radical, an ion, or a low valence chemical species.

As a means for generating reactive active species, for example, there is a method of irradiating electromagnetic waves. Examples of the electromagnetic waves include millimeter waves, submillimeter waves, microwaves, infrared light, visible light, ultraviolet light, vacuum ultraviolet light, electromagnetic waves having various wavelengths represented by so-called radio waves, light, and X-rays. It can use suitably according to the 1 species or the precursor of the said 1st species.

For example, the first chemical species may be generated using a plasma generated by irradiating a precursor of the first chemical species with microwaves, radio waves, or the like as the electromagnetic waves.

In addition, light may be used as the electromagnetic wave. For example, light may be introduced into the first chemical species generating unit using an optical window or an optical fiber, or a light source may be directly installed.

The reactive active species may also be generated by applying heat.

In addition, it is preferable that the base includes a base film made of a material that does not react with any of the first and second chemical species on the outermost surface.

Thereby, chemical reaction in the area | region other than the overlapping part of the flow of a 1st chemical species and the flow of a 2nd chemical species can be suppressed.

In addition, the flow of the first and second species is preferably a prejet. Thereby, since energy levels, such as vibration and rotation of a molecule | numerator, can be made into the lowest state, side reactions from a chemical species or reactive active species can be suppressed.

Preferably, the discharge of the first species from the first nozzle and the discharge of the second species from the second nozzle are performed in a chamber adjusted to a pressure of 1.3 × 10 ⁻¹ Pa or less. Thereby, the chemical species which is hard to be discharged can also be discharged easily.

The film forming method of the present invention is also useful in the manufacture of optical devices and electronic devices including them, such as LED arrays, TFTs, sensors, and further, in a combination process. Here, the optical device is, for example, a device provided with a liquid crystal element, an electrophoretic element having a dispersion medium in which electrophoretic particles are dispersed, an EL element, or the like. Further, the electronic device may be, for example, an IC card, a mobile phone, a video camera, a personal computer, a head mounted display, a rear or front projector, a fax device having a display function, a finder of a digital camera, a portable TV, a DSP device, PDA, electronic notebook, electronic bulletin board, display for advertisement.

The patterning method of the present invention, by overlapping at least a portion of the flow of the first chemical species discharged from the first nozzle and at least a portion of the flow of the second chemical species discharged from the second nozzle, the first chemical species and the A chemical reaction of the second species is induced to form a film pattern of the product resulting from the chemical reaction.

As a result, a reaction is caused at the overlapping portion of the flow of the first chemical species and the flow of the second chemical species, so that a film smaller than the cross-sectional area of the flow of each chemical species can be formed.

It is also preferable that at least one of the first and second chemical species is a reactive active species.

Here, the reactive active species is, for example, a chemical species that reacts with each other by polymerization or the like, or a chemical species that chemically reacts with another chemical species. Specifically, for example, radicals, ionic radicals, ions, low-valent chemical species, etc. to be.

Best Mode for Carrying Out the Invention Embodiments of the present invention will be described below with reference to the drawings.

1 is a diagram illustrating a configuration of a film forming apparatus 100 according to the present invention.

As shown in FIG. 1, the film forming apparatus 100 includes the material storage chambers 101a and 101b, the nozzles 102a and 102b, the heating units (the first and second chemical species generating units) 103a and 103b, and the chamber 104. ), A carrier gas supply source 105, and a gas stage 106.

The nozzles 102a and 102b and the gas stage 106 are provided in the chamber 104. The chamber 104 is connected to the vacuum apparatus 150 via the piping 108, and can adjust the degree of vacuum in the chamber 104.

The chemical species discharged from the nozzles 102a and 102b or the precursors of the chemical species discharged from the nozzles 102a and 102b are stored in the material storage chambers 101a and 101b.

The heating parts 103a and 103b are provided between the material storage chambers 101a and 101b and the nozzles 102a and 102b, respectively, and are equipped with a heating mechanism. The heating unit 103 generates reactive active species by heating using the material supplied from the material storage chamber 101 as a precursor.

The reactive active species is a chemical species that reacts with the same species by polymerization or the like, or a chemical species that reacts with another species, for example, radicals, ionic radicals, ions, or low-atomic species.

The heating mechanism of the heating part 103 is a chemical species such as physical properties such as boiling point or melting point of the material used, chemical properties such as reaction mode, the kind of chemical species to be generated, etc. It is selected in consideration of the required amount and the like, for example, a nirvana heater, a radiant tube heater, a sheath (pipe) heater, a plug heater, a flange heater, a fin ( Fin heater, cartridge heater, micro heater, cast-in heater, band heater, plate heater, block heater, quartz tube heater, silicon louver heater, ribbon heater, carbon heater, Ni It is also possible to use a heating device such as a -Cr heating element, a Fe-Cr heating element, a SiC heating element, or a heating device having an electromagnetic wave generator such as high frequency or microwave. In addition, a reactive gas such as oxygen, chlorine or fluorine or an inert gas such as argon, helium or nitrogen may be appropriately introduced into the heating unit 103. In addition, a catalyst or the like may be provided in the heating section 103 to promote generation of chemical species or to adjust generation efficiency or reaction temperature.

In addition, instead of providing the heating units 103a and 103b, reactive active species may be generated using electromagnetic waves. When light is used as the electromagnetic wave, an optical window may be provided on the flow path connecting the material storage chambers 101a and 101b and the nozzles 102a and 102b to generate reactive active species by light. . Instead of providing an optical window, light may be introduced using a light source such as an optical fiber.

Alternatively, an electromagnetic wave irradiation mechanism such as a microwave or radio wave may be provided to generate reactive active species using the state of the plasma generated by the microwave or radio wave irradiation.

The nozzles 102a and 102b discharge the reactive active species supplied from the heating unit 103 to generate a prejet. The nozzle 102a and the nozzle 102b are arrange | positioned so that at least one part of the prejet which each may eject may overlap.

The discharge mechanism of the nozzles 102a and 102b is, for example, a mechanism by a mechanical shutter, furthermore, a mechanism by a continuous method such as a charge control type or a pressure vibration type, an electromechanical conversion type (so-called piezo type), an electric thermal conversion method, A mechanism by an on-demand method such as an electrostatic suction method can be employed.

The state in the chamber 104 of the reactive active species discharged from the nozzles 102a and 102b can be set by appropriately adjusting various conditions such as temperature, vacuum degree, discharge amount, time interval of discharge, and the like.

In order to suppress side reactions of the reactive active species, the reactive active species discharged into the chamber 104 become so-called supersonic molecular fractions or prejets, and the energy levels such as internal vibration and rotation of the reactive active species are set to the lowest state. Side reactions of reactive active species can be suppressed.

When activation energy is required for the chemical reaction of the reactive active species, it is possible to generate the chemical reaction when the energy level such as internal vibration or rotation of the reactive active species is higher than the level corresponding to the activation energy of the chemical reaction. Do.

Although the carrier gas supply source 105 mainly supplies inert gas, such as helium, argon, nitrogen, as a carrier gas, it can use suitably also as a supply source of reactive gas, such as oxygen and a halogen gas.

In addition, when storing the chemical species itself discharged from the nozzles 102a or 102b in the material storage chamber 101a or the material storage chamber 101b, the material storage chamber 101a or the material storage chamber 101b itself may be used as the chemical species generator. It may be.

In addition, by providing means such as the heating units 103a and 103b, vaporization of the chemical species having a high boiling point becomes easier.

Next, operation | movement of the film forming apparatus 100 is demonstrated.

Here, the film formation of the silicon semiconductor film on the glass substrate in TFT (Thin Film Transistor) manufacture is demonstrated as an example. In the material storage chamber 101a, a silylene (SiH ₂ ) precursor, which is a low-atomic chemical species of silicon, is stored. As a silylene precursor, the silicon compound shown to Fig.2 (a) and (b) is mentioned, for example. In addition, silane (SiH ₄ ) is stored in the material storage chamber 101b.

In addition, when using the silicon compound shown to Fig.2 (c) and (d), it is preferable to generate | occur | produce chemical species, such as reactive active species, by the light of wavelength about 200 nm.

The precursors in the material storage chambers 101a and 101b are conveyed by the carrier gas supplied from the carrier gas supply source 105 and supplied to the heating units 103a and 103b, respectively.

In the heating sections 103a and 103b, heat is applied to the precursor by the heating mechanism, and generates reactive active species from the precursor. Here, silylene (SiH ₂ ) is generated in the heating section 103a as the reactive active species. On the other hand, since the silane (SiH ₄ ) stored in the material storage chamber 101b can be used as it is, the heating in the heating part 103b is unnecessary.

Silylene and silane supplied from the heating parts 103a and 103b are conveyed by the carrier gas, and are discharged in the prejet state from the nozzle 102a and the nozzle 102b, respectively.

Here, the pressure in the chamber 104 is adjusted to a high vacuum atmosphere of 10 ⁻³ torr (1.33322 × 10 ⁻¹ Pa) or less, more preferably 10 ⁻⁵ torr (1.33322 × 10 ⁻³ Pa) or less. Do. When the vacuum atmosphere is set to 10 ⁻³ torr or less, materials that are difficult to be discharged can be easily discharged. In addition, when it is 10 ^-5 torr or less, it is possible to discharge more kinds of materials, and at the same time, the material to be discharged is easily vaporized to form a molecular line. Therefore, when the inside of the chamber 104 is made high vacuum, prejet will become easy to generate | occur | produce.

The discharged prejet is disposed on the gas 160 fixed on the gas stage 106.

The substrate 160 is a glass substrate, but a silicon nitride film SiN is formed in advance on the surface from which the silicon and the silane are discharged. This is for suppressing the occurrence of a chemical reaction in a region other than the portion where the silylene reacts with the OH group and overlaps with the OH group because the OH group is exposed on the outermost surface in a normal glass substrate.

The silicon nitride film can be formed by CVD. Specifically, silane (SiH ₄ ) and ammonia (NH ₃ ) are introduced into the hydrogen carrier gas in an appropriate ratio, and the sedimentary species such as radicals and ions generated by the catalytic reaction or pyrolysis reaction by the heating catalyst body are released. It forms into a film by depositing on a board | substrate.

Moreover, organic materials, such as polyethylene and a polystyrene, can also be used as what does not have reactivity with a silylene, and these can also be provided as a base layer on a glass substrate.

FIG. 3A is a schematic diagram showing the state of the prejet discharged onto the substrate 160 from the nozzles 102a and 102b. As shown in FIG. 3A, the cross sections of the prejets injected onto the substrate 160 from the nozzles 102a and 102b each occupy a predetermined area. The nozzles 102a and 102b are arranged such that the prejets discharged to each other overlap on the base 160.

The nozzles 102a and 102b can also be provided in an arrangement as shown in Fig. 3B.

Above the gas 160, the polymerization reaction of the silane and the silane as shown in FIG. 4 is caused in this overlapping region. As a result, a silicon semiconductor film is formed in and near the overlapping region on the substrate 160. Since the overlap region can be made smaller than the cross section of each prejet, a film smaller than the cross section of the prejet can be formed.

5 is a diagram illustrating a process of manufacturing a TFT. As shown in FIG. 5A, a silicon semiconductor film 52 is formed on the glass substrate 51 by the above method. In addition, as shown in Fig. 5B, the gate insulating film 53 is formed by depositing SiO ₂ on the silicon semiconductor film 52 by CVD with a predetermined silicon compound. As shown in FIG. 5C, the gate electrode 54 is formed on the gate insulating film 53. After that, a TFT can be obtained by performing a known transistor manufacturing step.

In addition, although the film forming of the silicon semiconductor film in TFT manufacture was mentioned here as an example, the film forming apparatus of this invention is applicable to formation of various films, such as an insulator, a semiconductor, a good conductor, or a superconductor.

Moreover, the film forming apparatus of the present invention is also effective in the combination process. That is, a plurality of films formed under different film forming conditions can be formed in a plurality of regions on the substrate. For example, a plurality of films having different film forming conditions can be formed at one time by adjusting conditions such as the pressure of the carrier gas or the reactive gas, the degree of decompression of the chamber, and the like.

In addition, examples of the combination of the precursor species or species used in the film-forming apparatus of the present invention suitable, a combination of the addition, for example zinc dialkyl (ZnR ₂₎ and oxygen (O _2). By combination of dialkyl zinc (ZnR ₂ ) and oxygen (O ₂ ), ZnO is formed in an overlapping region, and for example, a light emitting layer in an LED array can be formed.

In addition, when trimethylgallium (Me ₃ Ga) and ammonia (NH ₃ ) are used, gallium nitride (GaN) is formed in the overlapping region.

In addition, the material storage chambers 101a and 101b (or the heating parts 103a and 103b) and the nozzles 102a and 102b may be integrated into an apparatus as shown in FIG. FIG. 6A is a perspective view of the apparatus, and FIG. 6B is a view showing the arrangement of the nozzles and the state of the prejet discharged onto the gas from the nozzles.

As described above, according to the present invention, the film forming apparatus, the film forming method, the patterning method, the optical device manufacturing method, and the electronic device manufacturing method can exhibit an effect on the formation of finer patterns.

Claims (18)

A first chemical species generating unit for generating a first chemical species, A first nozzle for discharging the first chemical species, And a second nozzle for discharging a second chemical species chemically reacting with the first chemical species, The first nozzle and the second nozzle is installed so that a part of the flow of the first chemical species discharged from the first nozzle and a part of the flow of the second chemical species discharged from the second nozzle overlap. Filmmaking device. delete The method of claim 1, The first chemical species is a film forming apparatus, characterized in that the reactive active species. The method of claim 1, The film forming apparatus of claim 1, wherein the first chemical species generator is capable of irradiating electromagnetic waves. The method of claim 1, A film forming apparatus, wherein a heating unit is provided in the first chemical species generating unit. The method of claim 1, With a chamber, The first and second nozzles are installed in the chamber, The pressure in the said chamber can be set to 1.3x10 <^-1> Pa or less, The film forming apparatus characterized by the above-mentioned. The method of claim 1, And the flow of the first and second species is free-jet. By superimposing a part of the flow of the first species discharged from the first nozzle and a part of the flow of the second species discharged from the second nozzle, a chemical reaction of the first species and the second species is induced. A film forming method for forming a film of a product produced by the chemical reaction on a substrate. The method of claim 8, One or both of said 1st and 2nd chemical species are reactive active species, The film forming method characterized by the above-mentioned. The method of claim 9, The reactive active species is generated by electromagnetic wave irradiation. The method of claim 9, The reactive active species is generated by applying heat. The method according to any one of claims 8 to 11, The film forming method, characterized in that the base includes a base film made of a material which does not react with any of the first and second chemical species on the outermost surface. The method of claim 8, Wherein said flow of said first and second species is a prejet. The method of claim 8, Wherein the discharge of the first chemical species from the first nozzle and the discharge of the second chemical species from the second nozzle are performed in a chamber adjusted to a pressure of 1.3 × 10 ⁻¹ Pa or less. Way. By superimposing a part of the flow of the first species discharged from the first nozzle and a part of the flow of the second species discharged from the second nozzle, a chemical reaction of the first species and the second species is induced. A patterning method for forming a film pattern of a product produced by the chemical reaction. The method of claim 15, One or both of the first and second chemical species is a patterning method, characterized in that the reactive active species. The manufacturing method of the optical apparatus using the film forming method of Claim 8. The manufacturing method of the electronic device using the film forming method of Claim 8.

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