JPH0883763A - Fine pattern forming method and transparent conductive film pattern forming substrate - Google Patents

Abstract

(57) [Abstract] [Purpose] A fine pattern forming method capable of efficiently forming a fine pattern by a simple process, and a transparent conductive film pattern forming substrate on which a transparent conductive film pattern having high durability is formed. provide. [Structure] A reactive layer is provided on a material layer to be patterned, and the reactive layer is provided with a predetermined gas by using any one of reactive gas, reactive particles, and ion beam that cause a chemical reaction with the reactive layer. Form a compound film in a pattern, then
The reactive layer and the material layer are etched using the compound film as a mask to form a fine pattern.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fine pattern forming method and a transparent conductive film pattern forming substrate, and in particular, it is capable of forming a fine pattern with high accuracy and efficiency on a pattern forming object in a fine processing step such as a semiconductor process. The present invention relates to a fine pattern forming method that can be performed and a transparent conductive film pattern forming substrate that is useful for manufacturing thin film transistors and the like.

[0002]

2. Description of the Related Art Conventionally, photolithography has been most commonly used for forming printed wirings and circuit patterns, or for forming fine patterns of thin films.

According to this photolithography method, a resist layer is formed on a material layer on which a fine pattern is to be formed, and a resist having a predetermined pattern is placed on the resist layer for exposure to expose the resist. The layer is developed to remove the exposed or unexposed portion, the remaining resist layer is used as an etching resist to etch the material layer, and then the resist layer is removed.

[0004]

However, the photolithography method requires five steps of forming a resist layer, exposing with a mask, developing the resist layer, etching, and removing the resist layer, and therefore the process is complicated. There is also a problem that a dedicated device including a large-scale exposure device is required as the size of the workpiece increases, and the cost required for the device becomes enormous.

Further, for example, a thin film transistor (TF)
Although a fine pattern of a transparent conductive film is formed as a transparent electrode in a T) type liquid crystal display, there is also a problem that the durability of the transparent conductive film formed on the substrate is insufficient.

The present invention has been made in view of the above circumstances, and a fine pattern forming method capable of efficiently forming a fine pattern by a simple process, and a transparent conductive film pattern having high durability. It is an object of the present invention to provide a transparent conductive film pattern forming substrate on which is formed.

[0007]

In order to achieve such an object, the method for forming a fine pattern of the present invention is a reactive gas which forms a reactive layer on a substrate and causes a chemical reaction with the reactive layer. A transparent compound film is formed on the reactive layer in a predetermined pattern by using either reactive particles or an ion beam, and the reactive layer is etched to form a fine pattern including the compound film forming region. It was configured like this.

The fine pattern forming method of the present invention is
Forming a reactive layer on a substrate, forming a transparent compound film on the reactive layer using any of reactive gas, reactive particles and ion beam that causes a chemical reaction with the reactive layer, The compound film is decomposed so that only a predetermined pattern region of the compound film remains, and the reactive layer is etched to form a fine pattern composed of the compound film region remaining in a predetermined pattern. .

The fine pattern forming method of the present invention is
A reactive layer is formed on a material layer on a substrate, and a compound is formed in a predetermined pattern on the reactive layer by using any one of a reactive gas, a reactive particle and an ion beam which causes a chemical reaction with the reactive layer. A film was formed, and the reactive layer and the material layer were etched using the compound film as a mask to form a fine pattern.

Further, in the fine pattern forming method of the present invention, a reactive layer is formed on a material layer on a substrate, and any one of reactive gas, reactive particles and ion beam which causes a chemical reaction with the reactive layer. A compound film is formed on the reactive layer by using the above, and the compound film is decomposed so that only a predetermined pattern region of the compound film remains, and the compound film remaining in a predetermined pattern is used as masking. The material layer and the reactive layer were etched to form a fine pattern.

Further, the transparent conductive film pattern forming substrate of the present invention comprises a substrate and a transparent chrome-fluorine compound film laminated on the substrate in a predetermined pattern.

Further, the transparent conductive film pattern forming substrate of the present invention includes a substrate, a transparent conductive film laminated on the substrate in a predetermined pattern, and a transparent chromium-fluorine compound formed on the transparent conductive film. And a physical film.

[0013]

[Function] The reactive layer provided on the material layer forms a compound film in a predetermined pattern by any one of the reactive gas, the reactive particles and the ion beam. The etching rate of the compound film By performing etching with the compound film as a masking under the condition that the etching rate of the material layer and the reactive layer is larger than that,
It becomes possible to form a pattern of the material layer. Further, by forming the reactive layer directly on the substrate without interposing the material layer and etching the reactive layer on which the transparent compound film is formed as described above, the pattern formation of the compound film on the substrate can be performed. It will be possible. In particular, the reactive layer has a thickness of 10 to 30.
By making the compound layer a chromium-fluorine compound film in the chrome layer in the range of Å, the compound film becomes transparent, and by making the material layer a transparent conductive film, it is composed of a transparent conductive film and a transparent chromium-fluorine compound film. A transparent conductive film pattern-formed substrate having a fine pattern can be provided, and a transparent conductive film pattern-formed substrate having a fine pattern made of a transparent chromium-fluorine compound film can be provided on the substrate.

[0014]

Embodiments of the present invention will be described below with reference to the drawings.

FIG. 1 is a process chart for explaining an example of the fine pattern forming method of the present invention. In FIG. 1, first, a reactive layer 4 is formed on a material layer 3 which is a pattern formation target and is provided on a substrate 2 (FIG. 1A).

The substrate 2 is not particularly limited and may be a glass substrate, a ceramics substrate, a silicon substrate, a polycarbonate resin, a polyethylene terephthalate resin, a polyester resin, an epoxy resin, an acrylic resin, a polystyrene resin or a resin substrate or a metal substrate. It can be appropriately selected depending on the relationship with the layer 3 and the purpose of use.

The material layer 3 is made of Al, Si, T.
i, Cr, Fe, Co, Ni, Cu, Zn, Mo, A
g, In, Sn, Te, Ta, W, Pt, Au and other metal layers, transparent conductive films ITO, SnO ₂ , ZnO and such transparent conductive films are doped with Sb, F, Al, Cd, Si and the like. Compound layer, polyimide, polyimide, SiN _x ,
Any insulating layer such as SiO ₂ or SiO can be applied.

Further, the reactive layer 4 is made of Al, Si, T.
i, Cr, Fe, Co, Ni, Cu, Zn, Mo, A
It may be a metal layer of g, In, Sn, Te, Ta, W, Pt, Au or the like. The reactive layer 4 is formed, for example, by
For metal layers, vacuum evaporation, sputtering, CVD
The film can be formed by a general film forming method such as a plating method or a plating method. The thickness of the reactive layer 4 is the thickness of the compound film generated by the reaction with the reactive gas, the reactive particles or the ion beam described later, the etching rate of the compound film and the etching of the reactive layer and the material layer. It can be set from the rate etc. However, if the thickness of the reactive layer 4 is too small, the resistance of the produced compound film becomes insufficient and the etching characteristics deteriorate. Therefore, the thickness of the reactive layer 4 is preferably 10 Å or more. As will be described later, when the mask plate 6 is placed on the reactive layer 4, in order to enhance the adhesion between the surface of the reactive layer 4 and the lower surface of the mask plate 6, the reactive layer 4 is smoothed. The higher the degree, the better.

Next, a mask plate 6 having a predetermined opening 6a is placed on the reactive layer 4 and then placed in an atmosphere of a reactive gas which causes a chemical reaction with the reactive layer 4 (FIG. 1).
(B)). As a result, the exposed surface of the reactive layer 4 exposed from the opening 6a causes a chemical reaction with the reactive gas, and the compound film 5 is formed on the surface (FIG. 1C). still,
Depending on the conditions, a coating film composed of the constituent components of the reactive gas used may be formed, but the present invention also includes such a coating film in the compound film. As the reactive gas, any gas can be used as long as it is a gas that causes a chemical reaction with at least the surface of the reactive layer 4 to generate a compound different from the reactive layer, and further, any desired gas can be used. It is also possible to use the reactive gas in the form of plasma. For example, when a chromium layer is used as the reactive layer 4, as an example of the reactive gas, a gas containing fluorine (CF ₄ , SF _6, etc.) or a gas obtained by converting this into plasma can be used. .

What is important in carrying out the chemical reaction in the above-mentioned reactive gas atmosphere is to prevent the reaction from occurring on the exposed surface of the reactive layer 4 and not on the non-exposed surface. For that purpose, it is necessary to supply the reactive gas only to the exposed surface of the reactive layer 4 and not to contact the non-exposed surface. This is possible by improving the physical adhesion between the upper surface of the reactive layer 4 and the lower surface of the mask plate 6, and as described above, smoothing the surface of the reactive layer 4 and the lower surface of the mask plate 6. It is enough to set the degree to be fairly high. Further, when using the gas converted into plasma as described above, as shown in FIG. 1 (B), directivity is provided by applying an electric field E perpendicular to the exposed surface of the reactive layer 4. Chemical reactions can be performed. That is, by applying the electric field E, the reaction direction of the plasma gas is biased in the vertical direction in the figure, and the reaction on the non-exposed surface due to the wraparound of the plasma gas can be prevented. After the compound film 5 is formed in a predetermined pattern as shown in FIG. 1C, the reactive layer 4 and the material layer 3 are selectively etched by using the compound film 5 as a mask. That is, the etching is performed under the condition that the etching rates of the material layer 3 and the reactive layer 4 are higher than the etching rate of the compound film 5.
By such etching, only the reactive layer 4 and the material layer 3 in the region where the compound film 5 is formed are left, and the reactive layer 4 and the material layer 3 in the other region are removed to form a desired fine pattern. This can be done (FIG. 1 (D)).

The method for forming a fine pattern of the present invention is not limited to the method using a reactive gas for forming a compound film, and reactive particles or an ion beam which causes a chemical reaction with the reactive layer may be used. it can.

First, when reactive particles are used, a mask plate 6 having a predetermined opening 6a is placed above the reactive layer 4 in a chamber (not shown) as shown in FIG. 2 (A). In this state, the reactive particles are irradiated from the reactive particle generator (not shown) arranged above the mask plate 6 as parallel fluxes substantially perpendicularly to the layer surface of the reactive layer 4. As a result, the reactive particles irradiated on the openings 6a of the mask plate 6 reach the surface of the reactive layer 4 through the mask plate 6, but the reaction particles other than the openings 6a of the mask plate 6 are irradiated. The flux of the reactive particles is blocked by the mask plate 6 and cannot reach the surface of the reactive layer 4. Moreover,
Since the flux of the reactive particles has such a linearity that it is incident in a direction substantially perpendicular to the surface of the reactive layer 4, the opening pattern of the mask plate 6 is projected on the surface of the reactive layer 4. It will be in the state of being. In this way, the chemical reaction between the reactive particles colliding with the reactive layer 4 and the reactive layer 4 forms the compound film 5 (FIG. 2B). Also in this case, a coating film composed of the constituent components of the reactive particles to be used may be formed depending on the conditions, but the present invention also includes such a coating film in the compound film.

The reactive particles include ions, neutral particles,
Ion beams, fast neutral particles, etc. can be used. When ions are used as the reactive particles, for example, when a chromium layer is used as the reactive layer 4, fluorine ions F ⁺ or fluorine compound gas ions can be used as the ions. Examples of the fluorine compound gas ions include CF ₃ ⁺ and CF when CF ₄ gas is used.
^Examples include SF ₅ ⁺ and SF ₄ ²⁺ when ₂ ²⁺ or SF ₆ gas is used. As a reactive particle generator,
A known Kauffman type ion gun can be used. Furthermore, the ions generated by the Kauffman type ion gun can be converted into radicals and used as reactive particles. In this case, for example, the above-mentioned fluorine ions or fluorine compound gas ions are generated by a Kauffman type ion gun, and then passed through a chamber in which a helium atmosphere is formed to collide with helium molecules to cause fluorine ions or fluorine compounds. The gas ions may be fluorine radicals or fluorine compound gas radicals. When neutral particles are used as the reactive particles, a known high speed neutral particle gun can be used as the reactive particle generator.

When an ion beam is used in the fine pattern forming method of the present invention, an ion gun 8 is arranged above the reactive layer 4 in a chamber (not shown) as shown in FIG. 3 (A). The ion gun 8 irradiates an ion beam. Then, the scanning stage 9 on which the substrate 2 on which the material layer 3 and the reactive layer 4 are formed is vertically and horizontally moved in a plane perpendicular to the irradiation direction of the ion beam, thereby reacting the ion beam. The reactive layer 4 can be scanned, and an arbitrary pattern can be drawn on the reactive layer 4 by the ion beam. As a result, the compound film 5 is formed by the chemical reaction between the ions and the reactive layer 4 only in the region of the reactive layer 4 which is drawn by the ion beam (FIG. 3 (B)). The ion beam scanning on the reactive layer 4 is not limited to the above method, and the scanning stage side may be fixed and the ion gun 8 or the ion beam itself may be moved for scanning.

FIG. 4 is a process chart for explaining another example of the fine pattern forming method of the present invention. In FIG. 4, first, the reactive layer 14 is formed on the material layer 13 which is the pattern formation target and is provided on the substrate 12 (FIG. 4).
(A)). This substrate 12, material layer 13 and reactive layer 1
4 can be the same as the substrate 2, the material layer 3, and the reactive layer 4 in the above-described fine pattern forming method, and the description thereof is omitted here.

Next, a compound film 15 is formed on the entire surface of the reactive layer 14 by using any one of a reactive gas, a reactive particle and an ion beam which cause a chemical reaction with the reactive layer 14 (FIG. 4 ( B)). Such formation of the compound film 15 on the entire surface of the reactive layer 14 can be performed by not using the mask plate 6 in the above-described embodiment when using the reactive gas or the reactive particles. Therefore, in this embodiment, the substrate 12 having the material layer 13 and the reactive layer 14 is provided.
The compound film 15 is formed simply by exposing the substrate to a plasma (fluorine compound gas) atmosphere. When an ion beam is used, it can be performed by drawing the entire surface of the reactive layer 14 with an ion beam. The reactive gas, the reactive particles and the ion beam used can be the same as those in the above-mentioned embodiment, and therefore the description thereof will be omitted.

Next, a predetermined opening 16 is formed on the compound film 15.
After mounting the mask plate 16 having a, it is placed in an atmosphere of decomposable gas (FIG. 4C). Thereby, the opening 1
The compound film 15 exposed from 6a is decomposed by the decomposable gas, and only the non-exposed region of the compound film 15 is left (FIG. 4D). For example, when the fluorine compound film 15 is formed using a gas containing fluorine (CF ₄ , SF _6, etc.) as a reactive gas, the fluorine compound film 15 is sputtered using argon gas to expel the fluorine. The fluorine compound film 15 can be decomposed. Alternatively, the fluorine compound film 15 can be decomposed by expelling fluorine by utilizing the difference in reactivity between oxygen and fluorine in an oxygen atmosphere.

After the compound film 15 is formed in a predetermined pattern in this manner, the reactive layer 14 and the material layer 1 are masked with the compound film 15 as in the above-described embodiment.
By performing selective etching of No. 3, the compound film 1
It is possible to form the desired fine pattern by removing the reactive layer 14 and the material layer 13 in other regions, while leaving only the reactive layer 14 and the material layer 13 in the region in which 5 is formed (see FIG. 4 ( E)).

In the above fine pattern forming method of the present invention, when the material layer is an opaque conductive film such as Ag, Cu or Al, there is no upper limit to the thickness of the reactive layer,
When the material layer is a transparent conductive film such as ITO and the compound film is also required to be transparent, the thickness of the reactive layer so that the visible light transmittance of the formed compound film is 80% or more ( For example, it is necessary to set the thickness 10 to 30Å).

The fine pattern forming method of the present invention described above is
In both cases, first, the material layers 3 and 13 are formed on the substrates 2 and 12, the reactive layers 4 and 14 are formed on the material layers, and then the compound films 5 and 15 are formed on the reactive layers. However, according to the method for forming a fine pattern of the present invention, the reactive layer is directly provided on the substrate without forming the material layers 3 and 13, and a transparent compound film is formed on the reactive layer. The reactive layer may be etched. This is because there is a large difference in the etching rate between the reactive layer and the compound film or the etching rate between the compound film and the decomposition region of the compound film as described above. This is because by etching, only a fine pattern made of a transparent compound film can be left. In this case, the thickness of the reactive layer needs to be set so that the transmittance of the formed compound film in visible light is 80% or more, and usually, the range of 10 to 30 Å is preferable.

FIG. 5 is a schematic sectional view showing an example of the transparent conductive film pattern forming substrate of the present invention. In FIG. 5, the transparent conductive film pattern forming substrate 21 includes a transparent conductive film 23 laminated on the substrate 22 in a predetermined pattern, and a transparent chromium-fluorine compound film 25 formed on the transparent conductive film 23.
It has and.

FIG. 6 is a schematic sectional view showing another example of the transparent conductive film pattern forming substrate of the present invention. In FIG. 6, the transparent conductive film pattern forming substrate 31 includes a transparent chromium-fluorine compound film 35 formed on the substrate 32 in a predetermined pattern.

Such a transparent conductive film pattern forming substrate 2
1 can be manufactured according to any of the embodiments of the fine pattern forming method of the present invention shown in FIGS.
In addition, the transparent conductive film pattern forming substrate 31 is also subjected to any one of the embodiments of the above-described fine pattern forming method of the present invention to form a transparent compound film without forming a transparent conductive film which is a material layer. Can be manufactured by. Here, for the sake of convenience, a method of forming the transparent conductive film pattern forming substrate 21 will be described according to the aspect of the fine pattern forming method shown in FIG.

First, the transparent conductive film 23 as a material layer is formed on the substrate 21 (FIG. 7A). The substrate 22 constituting the transparent conductive film pattern forming substrate 21 is a resin substrate such as a glass substrate, a ceramic substrate, a silicon substrate, a polycarbonate resin, a polyethylene terephthalate resin, a polyester resin, an epoxy resin, an acrylic resin, a polystyrene resin, or a metal substrate. Any substrate may be used, and the thickness thereof may be appropriately set depending on the purpose of use, but may be, for example, about 0.01 to 10 mm. The transparent conductive film 23 is made of indium tin oxide (ITO), zinc oxide (ZnO), tin oxide (S).
nO) and the like, and alloys thereof. The transparent conductive film 23 can be formed by a known method such as a sputtering method, a spray method, a vacuum vapor deposition method, or a CVD method. The thickness of the transparent conductive film 23 at this stage is 1 to 1000.
It can be about nm. In forming the transparent conductive film pattern forming substrate 31, it is not necessary to form such a transparent conductive film, and a chromium layer as described below is directly formed on the substrate.

Next, a chromium layer 24 is formed as a reactive layer on the transparent conductive film 23 (FIG. 7 (B)). The chromium layer 24 is formed by vacuum vapor deposition, sputtering, CVD.
The film can be formed by a general film forming method such as a plating method or a plating method. The thickness of the chrome 24 is preferably in the range of 10 to 30Å. When the chrome layer 24 is less than 10Å,
Sputtering that occurs during the reaction of forming the chromium-fluorine compound film with an ion beam or the like causes the resistance of the formed chromium-fluorine compound film 25 to become insufficient, which undesirably lowers the etching characteristics. On the other hand, if it exceeds 30 Å, the transparency of the chromium-fluorine compound film 25 becomes insufficient, which is not preferable.

Next, after the mask plate 26 having a predetermined opening 26a is placed on the chromium layer 24, the chromium layer 2 is formed.
It is placed in an atmosphere of a reactive gas that causes a chemical reaction with 4 (FIG. 7C). As the reactive gas, any gas can be used as long as it reacts with the chromium layer 24 to form a transparent chromium-fluorine compound film, and for example, a gas containing fluorine (CF ₄ , SF ₆ or the like), or a gas obtained by converting this into plasma can be used. As a result, the chromium layer 24 exposed from the opening 26a chemically reacts with the reactive gas to become the transparent chromium-fluorine compound film 25 (FIG. 7D).

After that, the chromium layer 24 and the transparent conductive film 23 are selectively etched by using the transparent chromium-fluorine compound film 25 as a mask. For this etching, the two-step etching method in which the etching of the chrome layer 24 which is the reactive layer and the etching of the transparent conductive film 23 which is the material layer are performed with different etching solutions, and the chrome layer 24 and the transparent copper conductive film 23 are the same. There is a one-step etching method which is performed by using the above etching solution.

As the two-step etching method, first, the chromium layer 24 is etched with a ceric ammonium nitrate solution (the etching rate of the chromium layer 24 is 10 times the etching rate of the chromium-fluorine compound film 5), and then, , HCl: H ₂ O: HNO ₃ = 1: 1: 0.08 is used to etch the transparent conductive film 23 (the etching rate of the transparent conductive film 23 is 10 times the etching rate of the chromium-fluorine compound film 5). be able to.

As the one-step etching method, a ceric nitrate ammonium solution: (HCl: H ₂ O: HNO _{3) is used.}
= 1: 1: 0.08 solution) = 1: 4 is used to etch the chromium layer 24 and the transparent conductive film 23 (the etching rates of the chromium layer 24 and the transparent conductive film 23 are the chromium-fluorine compound film 5). Etching rate of 10
Double). Alternatively, etching of the chromium layer 24 and the transparent conductive film 23 with a solution of HCl: H ₂ O = 1: 1 (the etching rate of the chromium layer 24 and the transparent conductive film 23 is 8 times the etching rate of the chromium-fluorine compound film 5). )It can be performed.

By such etching, chromium-
Only the chromium layer 24 and the transparent conductive film 23 in the region where the fluorine compound film 25 is formed are left, and the chromium layer 24 and the transparent conductive film 23 in the other regions are removed, and the transparent conductive film 23 and the transparent chromium-fluorine compound are removed. It is possible to form the transparent conductive film pattern formation substrate 21 having a fine pattern made of the film 25 (FIG. 7E).

In forming the transparent conductive film pattern forming substrate 31, the chrome layer is etched with a cerium nitrate ammonium nitrate solution to leave only the chrome layer in the region where the chrome-fluorine compound film is formed. By removing the chromium layer in the other regions, the transparent conductive film pattern forming substrate 31 having the fine pattern made of the transparent chromium-fluorine compound film 35 can be formed.

Next, the present invention will be described in more detail with reference to specific examples. Example 1 A transparent conductive film of indium tin oxide (ITO) (thickness: 0.2) was formed on a 1.1 mm-thick Corning 7059 glass substrate by the sputtering method under the following film forming conditions.
μm). Next, a chromium layer was formed on this ITO film by a sputtering method under the following film forming conditions to prepare samples 1 to 24 shown in Table 1 below.

ITO film forming conditions / atmosphere gas: Ar = 100 sccm, O ₂ = 3 s
ccm-Atmospheric pressure: 0.3 Torr-RF power: 2.5 kW-Film forming rate: 2.2 Å / sec Chromium layer film forming conditions -Atmospheric gas: Ar = 30 sccm-Atmospheric pressure: 0.3 Torr-RF power: 100 W ・ Film forming rate: 0.48 Å / sec. Next, for samples 1 to 18, a minimum of 5 μm on the chromium layer
A metal mask plate having an opening pattern with line and space accuracy was placed, a permanent magnet was installed on the lower surface side of the substrate, and this mask plate was suction-fixed onto the chrome layer. This is housed in the chamber of a plasma etching apparatus that has been generally used in the past, and CF ₄ and O ₂ are mixed at a mixing ratio of 95:
100 sccm (standard c
The pressure in the chamber was kept at 50 Pa while introducing into the chamber at a rate of (c per minute: standard introduction amount per minute). Then, 500 W of RF AC power was supplied into the chamber to cause an electric discharge, and the plasma was maintained for 5 minutes, 10 minutes, and 20 minutes in a state where the plasma was generated with the reactive gas, and each sample was treated with the reactive gas. did.

As a result of the composition analysis using XPS of the samples 1 to 18 thus treated with the reactive gas, a peak of fluorine was confirmed in the exposed portion of the chromium layer, and the chromium-fluorine compound film. Formation was confirmed.

Next, with respect to Samples 1 to 18, cerium ammonium nitrate liquid and HCl: H ₂ O: HNO ₃ = 1:
Etching is performed by a two-step etching method using an etching solution of 1: 0.08 to remove the chromium layer and the ITO film other than the region where the chromium-fluorine compound film is formed, and the ITO film and the chromium-fluorine compound are formed on the glass substrate. A fine pattern consisting of a stack of films was obtained.

With respect to Samples 1 to 24 thus prepared, the transparency, surface resistance and pattern accuracy of the pattern portion were measured and shown in Table 1 below.

Transparency Measuring Method With respect to light having a wavelength of 550 nm, the transmittance after forming the chromium layer is defined as 100% of the transmittance obtained by forming an ITO film (0.2 μm) on a Corning 7059 glass substrate. (Samples 19 to 23) and the transmittance (Samples 1 to 18) after the treatment with the reactive gas were measured.

Measuring Method of Surface Resistance The surface resistance was measured using a four-terminal measuring instrument (Loresta (type MCP-TESTER)) manufactured by Mitsubishi Petrochemical Co., Ltd.

For comparison, after forming the ITO film on the Corning 7059 glass substrate as described above,
Samples 25 to 28 were prepared by directly treating the ITO film with a reactive gas (processing time: 0 minutes, 3 minutes, 5 minutes, 8 minutes, other conditions are the same as above) without forming a chromium layer. Got As a result of a composition analysis using XPS for these samples 24 to 28, a fluorine peak was confirmed in the exposed portion of the ITO film, but the etching rate was the same in the exposed portion and the non-exposed portion of the ITO film. , Patterning was impossible. The transparency and surface resistance of Samples 24 to 28 were measured and shown in Table 1 below.

[0050]

[Table 1] As shown in Table 1, the thickness of the chrome layer is 10-30Å
Samples 2 to 5, 8 to 11, and 14 to 17 in the range of No. 3 have good transparency of approximately 80% or more in the pattern portion and low surface resistance.

However, Samples 1, 7, and 13 in which the thickness of the chrome layer was less than 10Å had insufficient patterning characteristics.
In addition, the samples 6, 12, whose chrome layer thickness exceeds 30Å
No. 18 had insufficient transparency, and it was confirmed that the transparent chromium-fluorine compound film formation by the reactive gas treatment had a limit of 30Å in the thickness direction even if the treatment time was lengthened. (Example 2) As in Example 1, Corning 7059
Samples 1 to 24 were prepared by forming an ITO film and a chrome layer on a glass substrate.

Next, the samples 1 to 18 were placed in a chamber equipped with an ion gun, and CF ₄ and O ₂ were mixed at a mixing ratio of 95:
The reactive gas mixed in 5 was introduced into the chamber at a rate of 30 sccm, and the chamber was evacuated to maintain the pressure in the chamber at 2.0 × 10 ^-2 Pa. Also, a minimum of 5 μm
A metal mask plate having an opening pattern having line and space accuracy was placed so as to be in close contact with the sample, and an ion gun was arranged at a distance of 30 cm from the metal mask plate. Then, the chromium layer was surface-treated by irradiating the sample with an ion flow of the fluorine compound gas ions CF ₃ ⁺ from the ion gun under the following conditions.

Fluorine ion F ⁺ generation conditions・ Beam voltage: 700 V ・ Acceleration voltage: 300 V ・ Ionization voltage: 60 V ・ Filament current: 10 A ・ Nutrizer current: 14 A ・ Treatment time: 1 minute, 3 minutes, 5 minutes As a result of performing a composition analysis using XPS on Samples 1 to 18 which had been surface-treated with a surface treatment, a peak of fluorine was confirmed in the exposed portion of the chromium layer.
Formation of a fluorine compound film was confirmed.

Then, the samples 1 to 18 were etched in the same manner as in Example 1 to remove the chromium layer and the ITO film other than the chromium-fluorine compound film forming region, and the ITO film was formed on the glass substrate. A fine pattern composed of a laminate of a chromium-fluorine compound film was obtained.

With respect to Samples 1 to 24 thus prepared, the transparency, surface resistance, resistivity and pattern accuracy of the pattern portion were measured and shown in Table 2 below.

Low-efficiency measuring method From the sheet resistance R (Ω / □) and the film thickness d (nm), the resistivity ρ (Ω · cm) was calculated by the following formula.

Ρ = R · d × 10 ⁻⁷

[0058]

[Table 2] As a condition of the transparent conductive film, it is required that the transmittance is 80% or more and the resistivity is 1 × 10 ⁻³ Ω · cm or less.
From the results of Table 2, although the resistivity of all the samples is sufficiently low, the samples 22 to 24 have low transmittance, and in this respect, they are unsuitable as transparent conductive films. (Embodiment 3) Corning 7059 in the same manner as in Embodiment 1.
Samples 1 to 12 were prepared by forming an ITO film and a chrome layer on a glass substrate.

Next, the samples 1 to 12 are placed in a chamber of a plasma etching apparatus generally used in the past, and C
Evacuation was carried out while introducing a reactive gas, which was a mixture of F ₄ and O ₂ , at a mixing ratio of 95: 5 into the chamber at a rate of 100 sccm, and the pressure in the chamber was maintained at 50 Pa. Then, 500 W of RF AC power was supplied into the chamber to cause an electric discharge, and the plasma was maintained for 5 minutes, 10 minutes, and 20 minutes in a state where the plasma was generated with the reactive gas, and each sample was treated with the reactive gas. did.

As a result of the composition analysis using XPS of the samples 1 to 12 thus treated with fluorine by the reactive gas, a peak of fluorine was confirmed in the exposed portion of the chromium layer, and the chromium-fluorine compound was obtained. Formation of a film was confirmed.

Next, a minimum of 5 is formed on the chromium-fluorine compound film.
A metal mask plate provided with an opening pattern having an accuracy of μm line & space was placed, a permanent magnet was installed on the lower surface side of the substrate, and this mask plate was suction-fixed on the chromium-fluorine compound film. This was housed in a chamber, and the exposed surface of the chromium-fluorine compound film was subjected to oxygen ion beam treatment under the following conditions to decompose the chromium-fluorine compound film.

Oxygen ion beam treatment conditions Reactive gas: O ₂ = 30 sccm Vacuum degree: 2.0 × 10 ^-2 Pa Beam voltage: 500 V Acceleration voltage: 300 V Ionization voltage: 60 V Filament current: 10 A Neutralizer current: 14 A ・ Treatment time: 1 minute, 3 minutes, 5 minutes As a result of composition analysis using XPS, no fluorine peak was observed in the exposed portion subjected to the oxygen ion beam treatment, and oxidation was observed. Was confirmed to be progressing. That is, by performing this oxygen ion beam treatment, the chromium-fluorine compound changed to chromium oxide. This chromium oxide has an etching rate about twice that of chromium.

Next, the samples 1 to 12 were etched with a 50% by weight aqueous solution of hydrochloric acid to remove the chromium layer and the ITO film in the region where the chromium-fluorine compound film was decomposed and removed, and the ITO was formed on the glass substrate. A fine pattern composed of a laminate of the film and the chromium-fluorine compound film was obtained.

With respect to Samples 1 to 12 thus prepared, the transparency, surface resistance and pattern accuracy of the pattern portion were measured and shown in Table 3 below.

[0065]

[Table 3] (Example 4) ITO on a Corning 7059 glass substrate
Samples 1 to 24 were prepared by directly forming a chrome layer under the same conditions as in Example 1 without forming a film.

Next, samples 1 to 18 were subjected to fluorine treatment (5 minutes, 10 minutes, 20 minutes) with a reactive gas in the same manner as in Example 1.

Next, the samples 1 to 18 were subjected to etching using a cerium ammonium nitrate solution to remove chromium.
The chromium layer other than the fluorine compound film forming region was removed to obtain a fine pattern made of a chromium-fluorine compound film on the glass substrate.

With respect to Samples 1 to 24 thus prepared, the transparency, surface resistance and pattern accuracy of the pattern portion were measured in the same manner as in Example 1 and shown in Table 4 below.

[0069]

[Table 4]

[0070]

As described in detail above, according to the present invention,
The fine pattern formation of the material layer can be performed by the three-step processing of forming the reactive layer, forming the compound film, and etching, and the process can be significantly simplified, and a shadow mask, a metal mask, or the like can be manufactured. It is possible to reduce the manufacturing cost in fine processing steps such as forming wiring and circuit patterns in the semiconductor process, or forming fine patterns of thin films. Also, the reactive layer is a chromium layer and the compound film is a chromium-fluorine compound film. As a result, the compound film becomes transparent, so that when the material layer is a transparent conductive film, a substrate having a fine transparent conductive film pattern made of a laminate of a transparent conductive film and a transparent chromium-fluorine compound film becomes possible. Since the transparent conductive film pattern has a chromium-fluorine compound film on its surface, it has high durability. Also,
When the reactive layer is directly formed on the substrate without interposing the material layer, a transparent conductive film pattern forming substrate having a fine pattern made of a transparent chromium-fluorine compound film on the substrate becomes possible.

[Brief description of drawings]

FIG. 1 is a process drawing for explaining an example of a fine pattern forming method of the present invention.

FIG. 2 is a diagram for explaining an example of a fine pattern forming method of the present invention using reactive particles.

FIG. 3 is a diagram for explaining an example of a fine pattern forming method of the present invention using an ion beam.

FIG. 4 is a process chart for explaining another example of the fine pattern forming method of the present invention.

FIG. 5 is a schematic cross-sectional view showing an example of a transparent conductive film pattern forming substrate of the present invention.

FIG. 6 is a schematic cross-sectional view showing another example of the transparent conductive film pattern forming substrate of the present invention.

FIG. 7 is a process chart for explaining an example of manufacturing the transparent conductive film pattern-formed substrate of the present invention.

[Explanation of symbols]

 2, 12 ... Substrate 3, 13 ... Material layer 4, 14 ... Reactive layer 5, 15 ... Compound film 21, 31 ... Transparent conductive film pattern forming substrate 22, 32 ... Substrate 23 ... Transparent conductive film 24 ... Chrome layer 25, 35 ... Chromium-fluorine compound film

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] May 25, 1995

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0038

[Correction method] Change

[Correction content]

As the two-step etching method, first, the chromium layer 24 is etched with a ceric ammonium nitrate solution (the etching rate of the chromium layer 24 is 10 times the etching rate of the chromium-fluorine compound film 25 ),
_{Next, HCl: H 2 O: HNO} 3 = 1: 1: 0.08 in the etching solution in the transparent conductive film 23 (etching rate of the transparent conductive film 23 chromium - 10 times the etching rate of the fluorine compound film 25) It can be performed.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0039

[Correction method] Change

[Correction content]

Further, as the one-step etching method, a cerium ammonium nitrate solution: (HCl: H ₂ O: HNO)
₃ = 1: 1: 0.08 solution) = 1: 4 etching of the chromium layer 24 and the transparent conductive film 23 (the etching rates of the chromium layer 24 and the transparent conductive film 23 are chromium-fluorine compound film). 25 etching rate of 10
Double). Alternatively, etching of the chromium layer 24 and the transparent conductive film 23 with a solution of HCl: H ₂ O = 1: 1 (the etching rate of the chromium layer 24 and the transparent conductive film 23 is 8 times the etching rate of the chromium-fluorine compound film 25 ). )It can be performed.

[Procedure 3]

[Document name to be corrected] Drawing

[Name of item to be corrected] Fig. 4

[Correction method] Change

[Correction content]

[Figure 4]

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location G03F 7/20 506 7/40 521 H01L 21/3065

Claims (9)

[Claims] 1. A reactive layer is formed on a substrate, and the reactive layer is transparent in a predetermined pattern by using any one of a reactive gas, a reactive particle and an ion beam which causes a chemical reaction with the reactive layer. Forming a fine compound film, and etching the reactive layer to form a fine pattern including the compound film forming region. 2. A transparent compound film formed on a reactive layer by forming a reactive layer on a substrate and using any one of a reactive gas, a reactive particle and an ion beam which causes a chemical reaction with the reactive layer. Is formed, the compound film is decomposed so that only a predetermined pattern region of the compound film remains, and the reactive layer is etched to form a fine pattern composed of the compound film region remaining in a predetermined pattern. A method for forming a fine pattern characterized by the above. 3. A reactive layer is formed on a material layer on a substrate, and the reactive layer is formed by using any one of a reactive gas, a reactive particle and an ion beam which causes a chemical reaction with the reactive layer. A fine pattern forming method, comprising forming a compound film in a predetermined pattern, and etching the reactive layer and the material layer using the compound film as a mask to form a fine pattern. 4. A reactive layer is formed on a material layer on a substrate, and the reactive layer is formed by using any one of a reactive gas, a reactive particle and an ion beam which causes a chemical reaction with the reactive layer. To form a compound film, decompose the compound film so that only a predetermined pattern region of the compound film remains, and etch the material layer and the reactive layer using the compound film remaining in a predetermined pattern as a mask A fine pattern forming method, characterized in that a fine pattern is formed. 5. The reactive layer is a chromium layer, the reactive gas is a fluorine compound gas, and the reactive particles are any one of a fluorine ion, a fluorine radical, a fluorine compound gas ion and a fluorine compound gas radical, and the ion. 5. The fine pattern forming method according to claim 1, wherein the beam is a fluorine ion beam or a fluorine compound ion beam. 6. The fine pattern forming method according to claim 5, wherein the chromium layer has a thickness within a range of 10 to 30 Å. 7. The fine pattern forming method according to claim 3, wherein the material layer is a transparent conductive film. 8. A transparent conductive film pattern forming substrate comprising: a substrate; and a transparent chromium-fluorine compound film laminated on the substrate in a predetermined pattern. 9. A transparent conductive film comprising a substrate, a transparent conductive film laminated on the substrate in a predetermined pattern, and a transparent chromium-fluorine compound film formed on the transparent conductive film. A film pattern forming substrate.