JP3668292B2 - Pattern forming method and pattern forming apparatus - Google Patents

Description

【００５５】
【表２】

表１に示されるように、紫外光照射時間が長いほど透明性が向上することが確認された。また、表２に示されるように、紫外光照射時間が長いほど表面抵抗が低下することが確認された。しかしながら、透明性の向上および表面抵抗の低下とも、ある程度の照射時間が経過すると、それ以上照射時間を長くしてもほとんど変化しないものであった。
（実施例２）
クロム層の厚みを０Å、１０Å、１５Å、２０Å、２５Å、３０Å、３５Åの７種とし、紫外光照射時間を５分とした他は、実施例１と同様にしてガラス基板上にＩＴＯ膜とクロム−フッ素化合物膜の積層体からなる微細パターンを得た。
【００５６】
このようにして作成した各試料について、パターン精度を測定しパターニング性を評価して下記の表３に示した。また、実施例１と同様にパターン部分の透明性、表面抵抗を測定して下記の表３に示した。
【００５７】
【表３】

表３に示されるように、クロム層の厚みが１０Åでは、クロム−フッ素化合物膜の耐性が不十分なためパターニング性が低いものであった。一方、クロム層の厚みが３５Åであると、パターニング性は良好であるが透明性が低く実用に供し得ないものであった。
【００５８】
【発明の効果】
以上詳述したように、本発明によれば、チャンバー内に反応性層を形成した基板を載置し、このチャンバー内で反応性層に反応性ガスを接触させた状態で、マスクを介して照射された紫外光により反応性ガスを活性化して反応性層と反応させ、所定のパターンで化合物膜を反応性層上に形成し、この化合物膜をマスキングとしてエッチングを行うことにより、パターン形成が可能となるので、▲１▼反応性層の形成、▲２▼化合物膜の形成、▲３▼エッチングという３段階の処理により材料層の微細パターン形成を行うことができ、工程の大幅な簡略化が可能であり、シャドーマスクやメタルマスク等の製造、半導体プロセスでの配線や回路パターンの形成、あるいは薄膜の微細パターン形成等の微細加工工程における製造コストの低減が可能となり、また、パターン形成装置ではチャンバー内に薄膜形成手段と紫外光照射装置とが配設されていることによって、雰囲気ガスを入れ替えることのみで反応性層の形成と上記の化合物膜の形成（上記の▲１▼と▲２▼の２段階の処理）を同一チャンバー内で連続して行うことができ、チャンバーの減圧時間の短縮、ゴミの混入防止が可能となり、さらに、このパターン形成装置から取り出した基板は、エッチング処理を行うだけで微細なパターンの形成が可能となり、工程の大幅な簡略化が可能である。また、反応性層をクロム層とし化合物膜をクロム−フッ素化合物膜とすることにより、化合物膜は透明となるので、材料層が透明導電膜である場合、透明導電膜と透明なクロム−フッ素化合物膜の積層体からなる微細な透明導電膜パターンを備えた基板が可能となり、この透明導電膜パターンは表面にクロム−フッ素化合物膜が存在するため耐久性が高いものとなる。また、材料層を介することなく基板上に直接反応性層を形成した場合、基板上に透明なクロム−フッ素化合物膜からなる微細パターンの形成が可能となる。
【図面の簡単な説明】
【図１】本発明のパターン形成方法の一例を説明するための工程図である。
【図２】本発明のパターン形成方法の他の例を説明するための工程図である。
【図３】本発明のパターン形成装置の一例を示す概略構成図である。
【図４】本発明のパターン形成装置の動作およびパターン形成方法を説明するための図である。
【符号の説明】
２，１２，４２…基板
３，１３…材料層
４，１４，４４…反応性層
５，１５，４５…化合物膜
２１…パターン形成装置
２２（２２ａ，２２ｂ）…真空チャンバー
２３…隔壁
２３ａ…開口部
２４ａ，２４ｂ…ガス供給管
２５ａ，２５ｂ…排気管
２６…薄膜形成手段（スパッタリング装置）
２７…ターゲット
２８…基板ホルダ
２９…紫外光照射装置
３０…照射光源
３１…マスク板[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a pattern forming method and a pattern forming apparatus for forming a fine pattern, and more particularly to pattern formation capable of forming a fine pattern efficiently and with high accuracy on a pattern forming object in a fine processing step such as a semiconductor process. The present invention relates to a method and a pattern forming apparatus useful for the pattern formation.
[0002]
[Prior art]
Conventionally, the photolithography method has been most commonly used for the formation of printed wiring and circuit patterns in a semiconductor process, or the formation of a fine pattern of a thin film.
[0003]
In this photolithography method, a resist layer is formed on a material layer on which a fine pattern is to be formed, and exposure is performed with a mask on which a predetermined pattern is drawn placed on the resist layer, and the resist layer is developed. Then, the exposed portion or the non-exposed portion is removed, the remaining resist layer is used as an etching resist, the material layer is etched, and then the resist layer is removed.
[0004]
[Problems to be solved by the invention]
However, photolithography requires five steps: (1) formation of a resist layer, (2) exposure using a mask, (3) development of the resist layer, (4) etching, and (5) removal of the resist layer. Therefore, there are problems that the process is complicated, and that a dedicated apparatus including a large exposure apparatus is required as the workpiece is enlarged, and the cost required for the apparatus becomes enormous.
[0005]
In addition, for example, in the manufacturing process of a thin film transistor (TFT) type liquid crystal display, a fine pattern of a transparent conductive film is formed as a transparent electrode. However, the conventional transparent conductive film has a problem that its durability is insufficient. there were.
[0006]
The present invention has been made in view of the circumstances as described above, and provides a pattern forming method capable of efficiently forming a fine pattern by a simple process, and a pattern forming apparatus that can easily carry out this pattern forming method. The purpose is to provide.
[0007]
[Means for Solving the Problems]
  In order to achieve such an object, the pattern forming method of the present invention comprises:Chrome layerThe substrate formed with is placed in a chamber,Fluorine-containing gasAnd the ultraviolet light through a mask having a predetermined patternChrome layerIrradiateFluorine-containing gasActivate the aboveChrome layerReact with theChrome layerIn the pattern corresponding to the pattern aboveChromium-fluorine compound filmForming the saidChromium-fluorine compound filmThe masking as aboveChrome layerTheUsing etchantThe pattern was formed by etching.
[0008]
  Moreover, the pattern forming method of the present invention includes:Chrome layerThe substrate formed with is placed in a chamber,Fluorine-containing gasAnd supplying the ultraviolet lightChrome layerIrradiateFluorine-containing gasActivate the aboveChrome layerReact with theChrome layeraboveChromium-fluorine compound filmForming the saidChromium-fluorine compound filmSo that only a predetermined pattern area remains.Chromium-fluorine compound filmDisassembled and left in a predetermined patternChromium-fluorine compound filmThe masking as aboveChrome layerThe pattern is formed by etching.
[0009]
  Furthermore, the pattern forming method of the present invention is configured such that the ultraviolet light is ultraviolet light having a wavelength of 200 nm or less,Chromium-fluorine compound filmIsVisible light transmittance of 70% or moreA configuration such that the substrate and theChrome layerBetweenTransparent conductive filmProvidedChromium-fluorine compound filmThe masking as aboveChrome layerAnd saidTransparent conductive filmThe pattern is formed by etching.
[0010]
  The pattern forming apparatus according to the present invention is provided with a vacuum chamber, a gas supply unit and an exhaust unit connected to the vacuum chamber, and the vacuum chamber.Sputtering equipment, An ultraviolet light irradiation device and a substrate holder, the substrate placed on the substrate holderSputtering equipmentByChrome layerCan be formed, andA fluorine-containing gas is introduced from the gas supply means into the vacuum chamber.The substrate placed on the substrate holder can be irradiated with ultraviolet light by the ultraviolet light irradiation device.
[0011]
  Further, the pattern forming apparatus of the present invention is the above-mentionedSputtering equipmentAnd a structure including a partition wall between the ultraviolet light irradiation device and the substrate holder.Sputtering equipmentAnd a configuration in which the partition wall includes an opening for passing through the substrate holder.
[0012]
In the present invention as described above, the reactive layer provided on the material layer is in contact with the reactive gas in the chamber. Of this reactive gas, the reactive layer is activated by the ultraviolet light irradiated through the mask. As a result, the compound layer reacts with the reactive layer, and a compound film is formed on the reactive layer in a predetermined pattern, so that the etching rate of the material layer and the reactive layer is larger than the etching rate of the compound film. By performing etching using the compound film as a mask under various conditions, the pattern of the material layer can be formed. In addition, by forming a reactive layer directly on the substrate without using a material layer and etching the reactive layer on which the compound film is formed as described above, it is possible to form a pattern made of the compound film on the substrate. Become. In particular, when the reactive layer is a chromium layer with a thickness in the range of 15 to 30 mm and the compound film is a chromium-fluorine compound film, the compound film becomes transparent, and the material layer is a transparent conductive film. And a fine pattern made of a transparent chromium-fluorine compound film can be formed. In addition, since the thin film forming means and the ultraviolet light irradiation device are disposed in the chamber, the reactive layer formation and the compound film formation can be continuously performed in the same chamber only by changing the atmospheric gas. The substrate taken out from the pattern forming apparatus of the present invention can form a fine pattern only by performing an etching process.
[0013]
DETAILED DESCRIPTION OF THE INVENTION
The present invention will be described below with reference to the drawings.
[0014]
FIG. 1 is a process diagram for explaining an example of the 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 provided on a substrate 2 (FIG. 1A).
[0015]
The substrate 2 is not particularly limited, 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. It can be selected as appropriate from the relationship, purpose of use, etc.
[0016]
The material layer 3 includes a metal layer such as Al, Si, Ti, Cr, Fe, Co, Ni, Cu, Zn, Mo, Ag, In, Sn, Te, Ta, W, Pt, Au, transparent conductive Film ITO, SnO₂ ZnO or a layer of a compound obtained by doping such transparent conductive film with Sb, F, Al, Cd, Si, etc., polyimide, polyimide, SiN_x , SiO₂ Any insulating layer such as SiO can be applied.
[0017]
Further, the reactive layer 4 is a metal layer such as Al, Si, Ti, Cr, Fe, Co, Ni, Cu, Zn, Mo, Ag, In, Sn, Te, Ta, W, Pt, Au, and the like. Can do. For example, in the case of a metal layer, the reactive layer 4 can be formed by a general film forming method such as a vacuum deposition method, a sputtering method, a CVD method, or a plating method. The thickness of the reactive layer 4 can be set from the thickness of the compound film generated by the reaction with the reactive gas described later, the etching rate of the compound film, the etching rate of the reactive layer and the material layer, and the like. it can. However, if the thickness of the reactive layer 4 is too small, the resulting compound film has insufficient resistance and the etching characteristics are deteriorated. Therefore, the thickness of the reactive layer 4 is preferably 15 mm or more. In order to allow reactive gas to exist between the surface of the reactive layer 4 and the lower surface of the mask plate 6 when the mask plate 6 is placed on the reactive layer 4 as described later, The lower surface of the mask plate 6 is preferably slightly rough.
[0018]
Next, in a chamber (not shown), a mask plate 6 having a predetermined translucent portion 6a is placed on the reactive layer 4, and then a reactive gas is introduced into the chamber (FIG. 1B). ). Any reactive gas may be used as long as it is decomposed by being given activation energy by ultraviolet light and causes a chemical reaction with at least the surface of the reactive layer 4 to produce a compound different from the reactive layer. Other gases can also be used. For example, when a chromium layer is used as the reactive layer 4, as an example of the reactive gas, a gas containing fluorine (SF₆ , CF_Four , CHF_Three , F₂ Etc.) can be used.
[0019]
Thereafter, ultraviolet light is irradiated from the mask plate 6 side (FIG. 1C). Thereby, the reactive gas existing between the translucent part 6a and the reactive layer 4 is activated and decomposed by the ultraviolet light transmitted through the translucent part 6a to cause a chemical reaction with the reactive layer 4, A compound film 5 is formed on the surface (FIG. 1D). The ultraviolet light to be used is not particularly limited, and a low pressure mercury lamp, excimer laser, argon laser, nitrogen laser or the like can be used as a light source. In particular, when ultraviolet light irradiation is performed in a vacuum chamber, absorption of short-wavelength ultraviolet light by the atmosphere does not cause a problem. Therefore, it is preferable to use ultraviolet light having a wavelength of 200 nm or less that is high in energy. The mask plate 6 is a glass plate, a metal plate, or the like provided with openings in a predetermined pattern to form a light transmitting portion 6a, or a predetermined shape so that the light transmitting portion 6a is left on the surface of the glass plate. There are no particular restrictions on the light-shielding layer formed in a pattern, but when using ultraviolet light having a wavelength of 200 nm or less as described above, it is preferable to use quartz glass having good ultraviolet light transmittance.
[0020]
Depending on the conditions, a coating film made of a component of the reactive gas to be used may be formed. In the present invention, such a coating film is also included in the compound film.
[0021]
After the compound film 5 is formed in a predetermined pattern as shown in FIG. 1D, the reactive layer 4 and the material layer 3 are selectively etched using the compound film 5 as a mask. That is, the etching is performed under such a condition that the etching rate of the material layer 3 and the reactive layer 4 is 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 other regions are removed to form a desired fine pattern. (FIG. 1E).
[0022]
In the above-described embodiment, irradiation with ultraviolet light is performed in a state where the mask plate 6 is in contact with the reactive layer 4. However, in the pattern forming method of the present invention, the reactive layer 4 and the mask plate 6 are exposed. A gap may be provided.
[0023]
FIG. 2 is a process diagram for explaining another example of the pattern forming method of the present invention. In FIG. 2, first, the reactive layer 14 is formed on the material layer 13 which is a pattern formation target provided on the substrate 12 (FIG. 2A). The substrate 12, the material layer 13 and the reactive layer 14 can be the same as the substrate 2, the material layer 3 and the reactive layer 4 in the pattern forming method described above, and the description thereof is omitted here.
[0024]
Next, after the substrate 12 is placed in a chamber (not shown), a reactive gas is introduced into the chamber, and ultraviolet light is irradiated from the reactive layer 14 side. Thus, the reactive gas is decomposed by being given activation energy by ultraviolet light, and causes a chemical reaction with the reactive layer 14 to form a compound film 15 different from the reactive layer 14 (FIG. 2B). )). The reactive gas and ultraviolet light to be used can be the same as those in the above-described embodiment, and thus description thereof is omitted here.
[0025]
Next, after placing a mask plate 16 having a predetermined opening 16a on the compound film 15, it is placed in an atmosphere of decomposable gas (FIG. 2C). Thereby, the compound film 15 exposed from the opening 16a is decomposed by the decomposable gas, and only the non-exposed region of the compound film 15 remains (FIG. 2D). For example, a gas containing fluorine as a reactive gas (SF₆ , CF_Four , CHF_Three , F₂ Etc.), the fluorine compound film 15 can be removed by sputtering the fluorine compound film 15 using argon gas. 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.
[0026]
After the compound film 15 is formed in a predetermined pattern in this way, the reactive layer 14 and the material layer 13 are selectively etched using the compound film 15 as a mask in the same manner as described above. By leaving only the reactive layer 14 and the material layer 13 in the region where the film 15 is formed, the reactive layer 14 and the material layer 13 in other regions can be removed to form a desired fine pattern (FIG. 2). (E)).
[0027]
In the pattern forming method of the present invention described above, when the material layer is an opaque conductive film such as Ag, Cu, Al or the like, there is no upper limit to the thickness of the reactive layer, but the material layer is ITO or the like. When the compound film is required to be transparent, the thickness of the reactive layer (for example, the thickness of 15 to 15) is set so that the visible light transmittance of the formed compound film is 70% or more. 30Å) must be set.
[0028]
In any of the above-described pattern forming methods of the present invention, first, the material layers 3 and 13 are formed on the substrates 2 and 12, and the reactive layers 4 and 14 are formed on the material layers. In the pattern forming method of the present invention, a reactive layer is provided directly on the substrate without forming the material layers 3 and 13, and the reactive layer is formed on the reactive layer. After forming the compound film, the reactive layer may be etched. This is because, as described above, 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 compound film decomposing region. This is because only the pattern made of the compound film can be left by etching. In this case, the thickness of the reactive layer is not particularly limited, but when the reactive layer is transparent and the compound film is also required to have transparency, the visible light transmittance of the formed compound film is 70%. It is necessary to set so that it becomes the above, and usually the range of 15-30cm is preferable.
[0029]
Next, the pattern forming apparatus of the present invention will be described. FIG. 3 is a schematic configuration diagram showing an example of the pattern forming apparatus of the present invention. In FIG. 3, the pattern forming apparatus 21 includes a vacuum chamber 22, thin film forming means 26 and an ultraviolet light irradiation device 29 provided in the vacuum chamber 22.
[0030]
The vacuum chamber 22 is divided into two chambers 22a and 22b by a partition wall 23 having an opening 23a. The vacuum chambers 22a and 22b are provided with gas supply pipes 24a and 24b and exhaust pipes 25a and 25b, respectively, and are connected to an external gas supply device (not shown) and an exhaust device (not shown). . The thin film forming means 26 is disposed in one vacuum chamber 22a, and in the illustrated example, is a sputtering apparatus provided with a target 27 and a substrate holder 28 at a position facing the target 27. Further, the ultraviolet light irradiation device is disposed in the other vacuum chamber 22b and includes an irradiation light source 30 and a mask plate 31 having a light transmitting portion 31a. The substrate holder 28 can be reciprocated between the vacuum chamber 22a and the vacuum chamber 22b through the opening 23a of the partition wall 23, and the substrate holder 28 moved from the vacuum chamber 22a to the vacuum chamber 22b is masked. Positioned below the plate 31, the ultraviolet light from the irradiation light source 30 can be irradiated through the mask plate 31. The substrate holder 28 is preferably provided with a heating means for heating the substrate to a predetermined temperature.
[0031]
Next, the operation of the pattern forming apparatus of the present invention will be described together with the pattern forming method of the present invention. First, a desired substrate 42 is placed on the substrate holder 28 located in the vacuum chamber 22a, the inside of the vacuum chamber 22 is reduced to a predetermined pressure by the exhaust pipes 25a and 25b, and then argon gas or the like is supplied from the gas supply pipe 24a. The atmospheric gas is supplied into the vacuum chamber 22 until a predetermined pressure is reached. And the reactive layer 44 is formed on the board | substrate 42 with the sputtering device 26 which is a thin film formation means (FIG. 4 (A)).
[0032]
Next, the inside of the vacuum chamber 22 is depressurized to a predetermined pressure by the exhaust pipes 25a and 25b to remove atmospheric gas such as argon gas, and then the reactive gas is supplied from the gas supply pipe 24b to the predetermined pressure until the predetermined pressure is reached. To do. On the other hand, the substrate holder 28 on which the substrate 42 on which the reactive layer 44 is formed is placed is moved from the vacuum chamber 22a to the vacuum chamber 22b and fixed at a predetermined position below the mask plate 31. In this state, the reactive layer 44 is in contact with the reactive gas, but since the reactive gas is not yet in an active state, the reaction between the reactive gas and the reactive layer 44 does not occur.
[0033]
Next, ultraviolet light is irradiated on the reactive layer 44 from the irradiation light source 30 through the mask plate 31 in a predetermined pattern. By this ultraviolet light irradiation, among the reactive gases in contact with the reactive layer 44, only the reactive gas in the region irradiated with the ultraviolet light is activated and decomposed to cause a chemical reaction with the reactive layer 44, A compound film 45 is formed on the surface (FIG. 4B).
[0034]
As described above, in the pattern forming apparatus 21 of the present invention, the formation of the reactive layer 44 on the substrate 42 and the formation of the compound film 45 having a predetermined pattern on the reactive layer 44 are performed using the gas in the vacuum chamber 22. Can be performed easily and continuously. Therefore, it is not necessary to transfer the substrate 42 between the vacuum chambers, and it is possible to prevent the occurrence of an accident such as adhesion of impurities on the substrate 42 (reactive layer 44). It is possible to reduce the manufacturing time and the manufacturing cost.
[0035]
After the substrate 42 having the compound film 45 formed on the reactive layer 44 as described above is taken out from the pattern forming apparatus 21, it is fine to perform selective etching of the reactive layer 44 using the compound film 45 as a mask. A pattern can be formed (FIG. 4C).
[0036]
In the above-described example, only the reactive layer 44 is formed on the substrate 42 by the sputtering apparatus 26, but a material layer and a reactive layer can be formed on the substrate 42.
[0037]
The sputtering apparatus 26 as a thin film forming means used in the pattern forming apparatus 21 of the present invention can be a conventionally known sputtering apparatus. The ultraviolet light irradiation device 30 can be a low-pressure mercury lamp, excimer laser, argon laser, nitrogen laser, or the like. And in the vacuum chamber 22, since absorption of the short wavelength ultraviolet light by air | atmosphere does not arise, it is preferable to use the ultraviolet light with a wavelength of 200 nm or less with high energy. In addition, the mask plate 31 is a glass plate, a metal plate or the like provided with openings in a predetermined pattern to form a light transmitting portion 31a, or is shielded so as to leave a light transmitting portion 31a having a predetermined pattern on the surface of the glass plate There is no particular limitation on the layer formed, but when using ultraviolet light having a wavelength of 200 nm or less as described above, it is preferable to use quartz glass having good ultraviolet light transmittance.
[0038]
The pattern forming apparatus of the present invention is not limited to the above-described embodiment. For example, in the pattern forming apparatus 21, the partition wall 23 is provided, but an embodiment in which the partition wall 23 is not provided is also possible. Further, although the substrate holder 28 can be moved between the sputtering apparatus 26 and the ultraviolet light irradiation apparatus 29, the substrate holder 28 is fixed, and the sputtering apparatus 26 and the ultraviolet light irradiation apparatus 29 are moved with respect to the substrate holder 28. It may be possible. In the pattern forming apparatus 21, a sputtering apparatus is provided as the thin film forming means. However, other conventionally known means such as a vacuum vapor deposition apparatus may be provided as the thin film forming means.
[0039]
Next, formation of the transparent conductive film pattern by the pattern forming method of the present invention will be described using the pattern forming apparatus 21 of the present invention.
[0040]
First, a substrate is placed on a substrate holder 28 located in the vacuum chamber 22a, and a transparent conductive film as a material layer is formed on the substrate by a sputtering apparatus 26 which is a thin film forming means. The substrate constituting the transparent conductive film pattern forming substrate is any one of 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. Although it may be a substrate, its thickness can be appropriately set according to the purpose of use, and can be, for example, about 0.01 to 10 mm. The transparent conductive film can be formed of indium tin oxide (ITO), zinc oxide (ZnO), tin oxide (SnO), or an alloy thereof. The thickness of the transparent conductive film at this stage is about 1 to 1000 nm.
[0041]
Next, a chromium layer is formed as a reactive layer on the transparent conductive film by the sputtering apparatus 26 which is a thin film forming means in the vacuum chamber 22a. The thickness of the chromium is 30 mm or less, preferably 15 to 30 mm, and more preferably 20 to 25 mm. When the chromium layer is 10 mm or less, the resistance of the chromium-fluorine compound film formed as described later becomes insufficient, and the etching characteristics deteriorate, which is not preferable. On the other hand, if it exceeds 30%, the transparency of the chromium-fluorine compound film becomes insufficient, which is not preferable.
[0042]
Next, the substrate holder 28 on which the substrate is placed is moved from the vacuum chamber 22 a to the vacuum chamber 22 b and fixed at a predetermined position below the mask plate 31. In addition, a reactive gas is introduced into the vacuum chamber 22 to create a reactive gas atmosphere. As the reactive gas, any gas can be used as long as it is activated and decomposed by irradiation with ultraviolet light to cause a chemical reaction with the chromium layer to form a transparent chromium-fluorine compound film. , Fluorine-containing gas (SF₆ , CF_Four , CHF_Three , F₂ Etc.) can be used.
[0043]
Next, ultraviolet light is irradiated on the chromium layer from the irradiation light source 30 through the mask plate 31 in a predetermined pattern. By this ultraviolet light irradiation, only the reactive gas in the region irradiated with ultraviolet light is activated and decomposed among the reactive gases in contact with the chromium layer, causing a chemical reaction with the chromium layer, and a transparent chromium-fluorine compound Become a film.
[0044]
Thereafter, the substrate is taken out from the pattern forming apparatus, and the chromium layer and the transparent conductive film are selectively etched using the transparent chromium-fluorine compound film as a mask. As this etching, there is a two-stage etching method in which the etching of the chromium layer as the reactive layer and the etching of the transparent conductive film as the material layer are performed with different etching solutions.
[0045]
In this two-step etching method, first, a chromium layer is etched with a ceric ammonium nitrate solution (the etching rate of the chromium layer is 10 times the etching rate of the chromium-fluorine compound film), and then HCl: H₂ O: HNO_Three = 1: 1: 0.08 The transparent conductive film can be etched (the etching rate of the transparent conductive film is 10 times the etching rate of the chromium-fluorine compound film).
[0046]
By such etching, leaving only the chromium layer and the transparent conductive film in the region where the chromium-fluorine compound film is formed, and removing the chromium layer and the transparent conductive film in other regions, the transparent conductive film and the transparent conductive film are removed. A fine pattern made of a chromium-fluorine compound film can be formed.
[0047]
In the formation of the transparent conductive film pattern described above, only the chromium layer was formed on the substrate without forming the transparent conductive film as the material layer, and after forming the transparent chromium-fluorine compound film in the same manner as described above, Etching the chromium layer with ceric ammonium nitrate solution using this chromium-fluorine compound film as a mask leaves the region where the chromium-fluorine compound film is formed, and the chromium layer in other regions is removed and transparent. A fine pattern made of a chromium-fluorine compound film can be formed.
[0048]
【Example】
Next, an Example is shown and this invention is demonstrated further in detail.
Example 1
A 1.1 mm thick Corning 7059 glass substrate is placed on the substrate holder of the pattern forming apparatus of the present invention as shown in FIG. 3, and indium tin oxide (ITO) is transparent by sputtering under the following film forming conditions. A conductive film (thickness 0.2 μm) was formed, and subsequently a chromium layer (chrome layer thickness = 20 mm, 25 mm, 30 mm) was formed on this ITO film by sputtering under the following film forming conditions. For each of these samples, the substrate holder is moved below the mask plate made of quartz glass having a translucent pattern with a minimum of 5 μm line & space (interval between the chromium layer and the mask plate = 1 μm), The chromium layer was irradiated with ultraviolet light from a low-pressure mercury lamp through a mask plate under the following irradiation conditions.
[0049]
ITO deposition conditions
Atmospheric gas: Ar = 100 sccm, O₂ = 3sccm
・ Atmospheric pressure: 0.3 Torr
・ RF power: 2.5kW
・ Deposition rate: 2.2 Å / sec
Chromium layer deposition conditions
・ Atmosphere gas: Ar = 30sccm
・ Atmospheric pressure: 0.3 Torr
・ RF power: 100W
・ Deposition rate: 0.48mm / sec
Ultraviolet light irradiation conditions
・ Reactive gas: SF₆
・ Atmospheric pressure: 1 Torr
・ Irradiation power: 10 mW / cm²
・ Irradiation time: 4 types of 0 min, 5 min, 10 min, 20 min
Each sample irradiated with ultraviolet light in a reactive gas atmosphere in this manner was taken out of the pattern forming apparatus and subjected to composition analysis using XPS. As a result, a fluorine peak was confirmed at the ultraviolet light irradiated portion of the chromium layer. As a result, formation of a chromium-fluorine compound film was confirmed.
[0050]
Next, for each sample, ceric ammonium nitrate solution and HCl: H₂ O: HNO_Three = 1: 1: Etching is performed by a two-step etching method using an etching solution of 0.08 to remove the chromium layer and the ITO film other than the chromium-fluorine compound film forming region, and the ITO film and the chromium are formed on the glass substrate. -A fine pattern composed of a laminate of fluorine compound films was obtained.
[0051]
For each sample thus prepared, the transparency, surface resistance and pattern accuracy of the pattern portion were measured and shown in Tables 1 and 2 below.
[0052]
Transparency measurement method
With respect to light having a wavelength of 550 nm, the transmittance of the pattern portion was measured with a transmittance of 100% obtained by forming an ITO film (0.2 μm) on a Corning 7059 glass substrate.
[0053]
Measuring method of surface resistance
It measured using the 4-terminal measuring device (Loresta (type MCP-TESTER)) made from Mitsubishi Oil Chemical Co., Ltd.
[0054]
[Table 1]

[0055]
[Table 2]

As shown in Table 1, it was confirmed that the longer the ultraviolet light irradiation time, the higher the transparency. Moreover, as Table 2 showed, it was confirmed that surface resistance falls, so that ultraviolet light irradiation time is long. However, both the improvement in transparency and the decrease in surface resistance are such that after a certain irradiation time has passed, even if the irradiation time is further increased, there is almost no change.
(Example 2)
The ITO film and chromium were formed on the glass substrate in the same manner as in Example 1 except that the thickness of the chromium layer was 7 types of 0 mm, 10 mm, 15 mm, 20 mm, 25 mm, 30 mm, and 35 mm, and the ultraviolet light irradiation time was 5 minutes. -A fine pattern composed of a laminate of fluorine compound films was obtained.
[0056]
For each sample thus prepared, the pattern accuracy was measured and the patterning property was evaluated, and the results are shown in Table 3 below. Further, the transparency and surface resistance of the pattern portion were measured in the same manner as in Example 1 and are shown in Table 3 below.
[0057]
[Table 3]

As shown in Table 3, when the thickness of the chromium layer was 10 mm, the patterning property was low because the resistance of the chromium-fluorine compound film was insufficient. On the other hand, when the thickness of the chromium layer was 35 mm, the patterning property was good, but the transparency was low and it could not be put to practical use.
[0058]
【The invention's effect】
As described above in detail, according to the present invention, a substrate on which a reactive layer is formed is placed in a chamber, and a reactive gas is brought into contact with the reactive layer in the chamber through a mask. The reactive gas is activated by the irradiated ultraviolet light to react with the reactive layer, a compound film is formed on the reactive layer in a predetermined pattern, and etching is performed using this compound film as a mask, thereby forming a pattern. Therefore, it is possible to form a fine pattern of the material layer by three steps of (1) reactive layer formation, (2) compound film formation, and (3) etching, which greatly simplifies the process. It is possible to reduce manufacturing costs in microfabrication processes such as manufacturing shadow masks and metal masks, forming wiring and circuit patterns in semiconductor processes, and forming fine patterns in thin films. In the pattern forming apparatus, since the thin film forming means and the ultraviolet light irradiation device are disposed in the chamber, the reactive layer can be formed and the compound film can be formed only by replacing the atmospheric gas (described above). (1) and (2) in 2 steps) can be performed continuously in the same chamber, the pressure reduction time of the chamber can be shortened and dust can be prevented from being mixed. In addition, the substrate can be formed with a fine pattern only by performing an etching process, and the process can be greatly simplified. Further, since the reactive layer is a chromium layer and the compound film is a chromium-fluorine compound film, the compound film becomes transparent. Therefore, when the material layer is a transparent conductive film, the transparent conductive film and the transparent chromium-fluorine compound are used. A substrate having a fine transparent conductive film pattern made of a laminate of films can be obtained, and this transparent conductive film pattern has high durability since a chromium-fluorine compound film is present on the surface. Further, when the reactive layer is formed directly on the substrate without passing through the material layer, it is possible to form a fine pattern made of a transparent chromium-fluorine compound film on the substrate.
[Brief description of the drawings]
FIG. 1 is a process diagram for explaining an example of a pattern forming method of the present invention.
FIG. 2 is a process diagram for explaining another example of the pattern forming method of the present invention.
FIG. 3 is a schematic configuration diagram showing an example of a pattern forming apparatus of the present invention.
FIG. 4 is a diagram for explaining the operation of the pattern forming apparatus and the pattern forming method of the present invention.
[Explanation of symbols]
2, 12, 42 ... substrate
3, 13 ... Material layer
4, 14, 44 ... reactive layer
5, 15, 45 ... Compound membrane
21 ... Pattern forming apparatus
22 (22a, 22b) ... Vacuum chamber
23 ... Bulkhead
23a ... opening
24a, 24b ... gas supply pipes
25a, 25b ... exhaust pipe
26. Thin film forming means (sputtering apparatus)
27 ... Target
28 ... Board holder
29 ... Ultraviolet light irradiation device
30 ... Irradiation light source
31 ... Mask plate

Claims (9)

A substrate on which a chromium layer is formed is placed in a chamber, fluorine-containing gas is supplied into the chamber, and ultraviolet light is irradiated to the chromium layer through a mask having a predetermined pattern to activate the fluorine-containing gas . chromium in a pattern corresponding to the pattern on the chromium layer is reacted with the chromium layer turned into - fluorine compound film is formed,
A pattern forming method comprising forming a pattern by etching the chromium layer with an etchant using the chromium-fluorine compound film as a mask. A substrate on which a chromium layer is formed is placed in a chamber, a fluorine-containing gas is supplied into the chamber, and ultraviolet light is irradiated to the chromium layer to activate the fluorine-containing gas to react with the chromium layer. Forming a chromium-fluorine compound film on the chromium layer ;
The chromium - the chromium so that only a predetermined pattern area remains out of the fluorine compound film - fluorine compound film to decompose,
A pattern forming method comprising: forming a pattern by etching the chromium layer using the chromium-fluorine compound film remaining in a predetermined pattern as a mask.   The pattern forming method according to claim 1, wherein the ultraviolet light is ultraviolet light having a wavelength of 200 nm or less. The pattern forming method according to any one of claims 1 to 3, wherein the chromium-fluorine compound film has a visible light transmittance of 70% or more . A transparent conductive film is provided between the substrate and the chromium layer, and the chromium layer and the transparent conductive film are etched using the chromium-fluorine compound film as a mask to form a pattern. The pattern formation method according to claim 4. A vacuum chamber, a gas supply unit and an exhaust unit connected to the vacuum chamber, and a sputtering device , an ultraviolet light irradiation device, and a substrate holder disposed in the vacuum chamber are mounted on the substrate holder. A chromium layer can be formed on the substrate by the sputtering apparatus , and a fluorine-containing gas is introduced from the gas supply means into the vacuum chamber and placed on the substrate holder. A pattern forming apparatus capable of irradiating with light. The pattern forming apparatus according to claim 6, further comprising a partition wall between the sputtering apparatus and the ultraviolet light irradiation apparatus. The pattern forming apparatus according to claim 6, wherein the substrate holder is movable between the sputtering apparatus and the ultraviolet light irradiation apparatus.   The pattern forming apparatus according to claim 8, wherein the partition wall includes an opening for passing through the substrate holder.

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