JP4034976B2 - Resistor - Google Patents

Description

【００３２】
かくして得られた本発明の抵抗体について、その内部応力をソリ量から測定したところ、そのようなソリもなかった。さらに抵抗体の上に１ｍｍ幅の電極を十字方向に蒸着し、発熱の有無を評価したところ、十分なる発熱を確認することができた。
【００３３】
また、抵抗の測定用として＃７０５９ガラスからなる基板１（４０ｍｍ×１０ｍｍ×厚み１ｍｍ）上に発熱層３を触媒ＣＶＤ法（触媒体：Ｔａ）により形成し、発熱抵抗体用にする。この層は表１に示す成膜条件により２００００Åの厚みでアモルファスシリコン層を成膜形成した。この試料によれば、基板上に直接発熱層を形成し、その上に櫛形電極を蒸着し、測定を行った。その結果、比抵抗は１０¹ Ω・ｃｍとなり、良好な結果が得られた。
【００３４】
（例２）
つぎに（例１）に示す抵抗体を作製するに当たり、発熱層の成膜において、触媒体を１５００〜２５００℃の範囲で変え、その他の成膜条件を（例１）の抵抗体と同じにて設定し、各種抵抗体を作製した。
【００３５】
このように触媒体温度を増減させることにより、触媒元素Ｔａの含有量を０．０５ｐｐｍ以上に幾とおりにも変えた各種抵抗体を作製した。そして、これら抵抗体の比抵抗、発熱および内部応力と密着性を測定したところ、表２に示すような結果が得られた。
【００３６】
発熱の評価は、○、△、×の３とおりに区分し、○印は規格の発熱量を満足している場合、△印は一部のみ規格の発熱量を満足している場合、×印は全面が規格の発熱量を満足していない場合を示す。
【００３７】
また、密着性の評価は、○、△、×の３とおりに区分し、○印は膜ハガレの全くない状態の場合、△印は一部のみ膜ハガレがある状態の場合、×印は全面に膜ハガレがある状態の場合を示す。
【００３８】
【表２】

【００３９】
この表から明らかなとおり、触媒体温度が増大することで触媒体元素の含有量が多くなり、比抵抗が小さくなることがわかる。これは、触媒体温度が上昇することで、触媒元素が蒸発し、膜中に元素が入るためである。そして、触媒元素が膜中に入っていくことで、比抵抗が小さくなり、発熱性が向上したことがわかる。
【００４０】
Ｔａの場合、触媒体温度が２１００℃〜２３００℃では、発熱・密着性ともに良好な結果が得られた。触媒体温度が２４００℃では、膜中に触媒元素が入りすぎ、粗な膜となりボロボロと剥がれてしまう結果となった。また、温度が高すぎて触媒体が切れてしまうこともあった。さらに、２５００℃以上では、触媒体が成膜中に常時切れてしまい、膜が付着しない結果となった。
【００４１】
内部応力については、一般的なプラズマＣＶＤ法で作製されたアモルファスシリコン膜であれば、１.０×１０⁸〜７.５×１０⁸（Ｎ／ｍ²）であるが、本例にて作製された抵抗体については、相当に小さい値（一桁小さい）であり、密着性等に顕著な効果を奏する。
【００４２】
（例３）
つぎに（例１）に示す抵抗体を作製するに当たり、薄膜層（発熱層１３）の成膜において、ＰＨ₃ガスの流量（４０ｐｐｍと０．２％にて水素希釈したボンベを使用）を０〜３００ｓｃｃｍの範囲にて変え、そして、ＳｉＨ₄ガスは２０ｓｃｃｍの流量にて、その他の成膜条件を（例１）の抵抗体と同じにて設定し、各種抵抗体を作製した。
【００４３】
すなわち、薄膜層を成膜形成するに際し、ＳｉＨ₄ガスに対するＰＨ₃ガス流量を変えることで、Ｐ（リン）の含有量を０〜１．５％にまで幾とおりにも変えた各種抵抗体を作製した。
【００４４】
そして、これら抵抗体の比抵抗、発熱、内部応力および密着性を測定したところ、表３に示すような結果が得られた。
【００４５】
【表３】

【００４６】
同表から明らかなとおり、ＰＨ₃ガス流量が増大することで、リン元素の含有量が多くなり、比抵抗が小さくなることがわかる。これは、ＰＨ₃ガス流量が増大することで、ＳｉＨ₄ガスに対する流量比が高くなり、リン元素がシリコンの膜中に多く入っていくからである。そして、リン元素が膜中に入っていくことで、比抵抗が小さくなり、発熱性が向上したことがわかる。
【００４７】
また、リン含有量が１.０ｐｐｍ〜０．５％の原子比率にて含有させたことで、発熱・密着性ともに、良好な結果が得られた。
【００４８】
リン含有量が１．０ｐｐｍ未満では、比抵抗が大きくなり、発熱しない結果となった。一方、リン含有量が０．５２％以上になると、膜中にリン元素が入りすぎて、内部応力が大きくなり、これにより、基板のソリが大きくなり、膜が剥がれ、さらに粗な膜となり、ボロボロと剥がれてしまう結果となった。
【００４９】
さらに、リン元素の含有量を０．８０％以上に多くすると、成膜速度が極端に遅くする必要があり、量産には不向きであると考えられる。成膜速度が大きくなると、ボロンの分解効率が低下し、粗な膜質となるためである。
【００５０】
（例４）
つぎに（例２）に示す抵抗体を作製するに当たり、触媒元素をＴａに代えて、Ｗにして、触媒体を１５００〜３０００℃の範囲で変え、その他の成膜条件を（例１）の抵抗体と同じにて設定し、各種抵抗体を作製した。
【００５１】
このように触媒体温度を増減させることにより、触媒元素Ｗの含有量を０．０４ｐｐｍ以上に幾とおりにも変えた各種抵抗体を作製した。そして、これら抵抗体の比抵抗、発熱および内部応力と密着性を測定したところ、表４に示すような結果が得られた。
【００５２】
【表４】

【００５３】
この表から明らかなとおり、触媒体温度が増大することで触媒体元素の含有量が多くなり、比抵抗が小さくなることがわかる。これは、触媒体温度が上昇することで、触媒元素が蒸発し、膜中に元素が入るためである。そして、触媒元素が膜中に入っていくことで、比抵抗が小さくなり、発熱性が向上したことがわかる。
【００５４】
Ｗの場合、触媒体温度が２０００℃〜２５００℃では、発熱・密着性ともに良好な結果が得られた。触媒体温度が２７００℃では、膜中に触媒元素が入りすぎ、粗な膜となりボロボロと剥がれてしまう結果となった。また、温度が高すぎて触媒体が切れてしまうこともあった。さらに、３０００℃以上では、触媒体が成膜中に常時切れてしまい、膜が付着しない結果となった。
【００５５】
内部応力については、一般的なプラズマＣＶＤ法で作製されたアモルファスシリコン膜であれば、１.０×１０⁸〜７.５×１０⁸（Ｎ／ｍ²）であるが、本例にて作製された抵抗体については、相当に小さい値（一桁小さい）であり、密着性等に顕著な効果を奏する。
【００５６】
（例５）
つぎに（例４）に示す抵抗体を作製するに当たり、薄膜層（発熱層１３）の成膜において、ＰＨ₃ガスの流量（４０ｐｐｍと０．２％にて水素希釈したボンベを使用）を０〜３００ｓｃｃｍの範囲にて変え、そして、ＳｉＨ₄ガスは２０ｓｃｃｍの流量にて、その他の成膜条件を（例１）の抵抗体と同じにて設定し、各種抵抗体を作製した。
【００５７】
すなわち、薄膜層を成膜形成するに際し、ＳｉＨ₄ガスに対するＰＨ₃ガス流量を変えることで、Ｐ（リン）の含有量を０〜１．４２％にまで幾とおりにも変えた各種抵抗体を作製した。
【００５８】
そして、これら抵抗体の比抵抗、発熱、内部応力および密着性を測定したところ、表５に示すような結果が得られた。
【００５９】
【表５】

【００６０】
同表から明らかなとおり、ＰＨ₃ガス流量が増大することで、リン元素の含有量が多くなり、比抵抗が小さくなることがわかる。これは、ＰＨ₃ガス流量が増大することで、ＳｉＨ₄ガスに対する流量比が高くなり、リン元素がシリコンの膜中に多く入っていくからである。そして、リン元素が膜中に入っていくことで、比抵抗が小さくなり、発熱性が向上したことがわかる。
【００６１】
また、リン含有量が１.０ｐｐｍ〜０．５％の原子比率にて含有させたことで、発熱・密着性ともに、良好な結果が得られた。
【００６２】
リン含有量が１．０ｐｐｍ未満では、比抵抗が大きくなり、発熱しない結果となった。一方、リン含有量が０．７５％以上になると、膜中にリン元素が入りすぎて、内部応力が大きくなり、これにより、基板のソリが大きくなり、膜が剥がれ、さらに粗な膜となり、ボロボロと剥がれてしまう結果となった。
【００６３】
さらに、リン元素の含有量を０．７５％以上に多くすると、成膜速度が極端に遅くする必要があり、量産には不向きであると考えられる。成膜速度が大きくなると、ボロンの分解効率が低下し、粗な膜質となるためである。
【００６４】
（例６）
つぎに（例２）に示す抵抗体を作製するに当たり、触媒元素をＴａに代えて、Ｍｏにして、触媒体を１５００〜３０００℃の範囲で変え、その他の成膜条件を（例１）の抵抗体と同じにて設定し、各種抵抗体を作製した。
【００６５】
このように触媒体温度を増減させることにより、触媒元素Ｍｏの含有量を０．０４ｐｐｍ以上に幾とおりにも変えた各種抵抗体を作製した。そして、これら抵抗体の比抵抗、発熱および内部応力と密着性を測定したところ、表６に示すような結果が得られた。
【００６６】
【表６】

【００６７】
この表から明らかなとおり、触媒体温度が増大することで触媒体元素の含有量が多くなり、比抵抗が小さくなることがわかる。これは、触媒体温度が上昇することで、触媒元素が蒸発し、膜中に元素が入るためである。そして、触媒元素が膜中に入っていくことで、比抵抗が小さくなり、発熱性が向上したことがわかる。
【００６８】
Ｍｏの場合、触媒体温度が２０００℃〜２７００℃では、発熱・密着性ともに良好な結果が得られた。触媒体温度が２８００℃では、膜中に触媒元素が入りすぎ、粗な膜となりボロボロと剥がれてしまう結果となった。また、温度が高すぎて触媒体が切れてしまうこともあった。さらに、３０００℃以上では、触媒体が成膜中に常時切れてしまい、膜が付着しない結果となった。
【００６９】
内部応力については、一般的なプラズマＣＶＤ法で作製されたアモルファスシリコン膜であれば、１.０×１０⁸〜７.５×１０⁸（Ｎ／ｍ²）であるが、本例にて作製された抵抗体については、相当に小さい値（一桁小さい）であり、密着性等に顕著な効果を奏する。
【００７０】
（例７）
つぎに（例６）に示す抵抗体を作製するに当たり、薄膜層（発熱層１３）の成膜において、ＰＨ₃ガスの流量（４０ｐｐｍと０．２％にて水素希釈したボンベを使用）を０〜３００ｓｃｃｍの範囲にて変え、そして、ＳｉＨ₄ガスは２０ｓｃｃｍの流量にて、その他の成膜条件を（例１）の抵抗体と同じにて設定し、各種抵抗体を作製した。
【００７１】
すなわち、薄膜層を成膜形成するに際し、ＳｉＨ₄ガスに対するＰＨ₃ガス流量を変えることで、Ｐ（リン）の含有量を０〜１．５７％にまで幾とおりにも変えた各種抵抗体を作製した。
【００７２】
そして、これら抵抗体の比抵抗、発熱、内部応力および密着性を測定したところ、表７に示すような結果が得られた。
【００７３】
【表７】

【００７４】
同表から明らかなとおり、ＰＨ₃ガス流量が増大することで、リン元素の含有量が多くなり、比抵抗が小さくなることがわかる。これは、ＰＨ₃ガス流量が増大することで、ＳｉＨ₄ガスに対する流量比が高くなり、リン元素がシリコンの膜中に多く入っていくからである。そして、リン元素が膜中に入っていくことで、比抵抗が小さくなり、発熱性が向上したことがわかる。
【００７５】
また、リン含有量が１.０ｐｐｍ〜０．５％の原子比率にて含有させたことで、発熱・密着性ともに、良好な結果が得られた。
【００７６】
リン含有量が１．０ｐｐｍ未満では、比抵抗が大きくなり、発熱しない結果となった。一方、リン含有量が０．５２％以上になると、膜中にリン元素が入りすぎて、内部応力が大きくなり、これにより、基板のソリが大きくなり、膜が剥がれ、さらに粗な膜となり、ボロボロと剥がれてしまう結果となった。
【００７７】
さらに、リン元素の含有量を０．５２％以上に多くすると、成膜速度が極端に遅くする必要があり、量産には不向きであると考えられる。成膜速度が大きくなると、ボロンの分解効率が低下し、粗な膜質となるためである。
【００７８】
なお、本発明は上記の実施形態例に限定されるものではなく、本発明の要旨を逸脱しない範囲内で種々の変更や改良等はなんら差し支えない。たとえば、本発明によれば、触媒体には、Ｔａ、Ｗ、Ｍｏを単独にて用いたが、これに代えて、これらを組合せた複合材にて、そして、複数の触媒元素を発熱層に添加してもよい。
【００７９】
以上のとおり、本発明によれば、基板支持体上にアモルファスシリコン層を触媒ＣＶＤ法により成膜した抵抗体において、Ｔａ、Ｗ、Ｍｏから選択される触媒元素を０．５ｐｐｍ〜１５％の範囲で含有させ、かつ周期律表第Ｖ族元素を１．０ｐｐｍ〜０．５％の原子比率にて含有させたことで、すぐれた発熱性が得られ、さらに、安価で品質が安定し（密着性等）量産性に優れた抵抗体が提供できた。
【００８０】
また、本発明の抵抗体によれば、サーマルヘッド用発熱部、インクジェット用発熱部に、また、半導体露光装置の電子ビーム機構部の帯電防止コートとして、エッチング部材用(反応炉)の保護コ−トとしても適用できる。たとえば、インクジェット用発熱部ならびに半導体露光装置の帯電防止コートとして、比抵抗１０³〜１０⁰ (Ω・ｃｍ)の膜が形成できる。
【図面の簡単な説明】
【図１】本発明の抵抗体の断面図である。
【図２】本発明に係る触媒ＣＶＤ法の概略構成を示す図である。
【図３】抵抗体のソリ量の測定方法を示す説明図である。
【符号の説明】
１・・・基板
２、４・・・電極
５・・・真空容器
６・・・支持体
７・・・被成膜用基板
８・・・ガス導入部
９・・・フィラメント[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a resistor formed with an amorphous silicon layer.
[0002]
[Prior art]
Conventionally, when the heating layer of the resistor is formed by a thin film forming method, a vacuum deposition method, a plasma CVD method, a photo CVD method, a thermal CVD method, a reactive sputtering method, an ion plating method, or the like is used.
[0003]
For example, when the heat generating layer is formed of an amorphous silicon layer, a film-formed body is formed particularly by the plasma CVD method for the amorphous silicon layer.
[0004]
According to Japanese Patent Laid-Open No. 9-120907, a technique for producing a resistor made of Ta, Si, C, and O by high-frequency sputtering has been reported.
[0005]
Japanese Patent Application Laid-Open No. 11-10879 reports a heating resistor in which a metal is added to C and SiO by a plasma CVD method or the like.
[0006]
[Problems to be solved by the invention]
However, when the resistor is formed by plasma CVD or sputtering as described above, in order to form a low resistance film, particularly a film having a specific resistance of 10 ³ to 10 ⁰ (Ω · cm). Boron, phosphorus, and the like need to be doped in large quantities, which slows the film formation rate, increases production costs, and is not suitable for mass production.
[0007]
In addition, with such a heat generating layer, the film stress increases, thereby reducing the adhesion, and as a result, a large number of defects such as peeling occur.
[0008]
The present inventor made extensive studies in view of the above circumstances, and as a result, the catalytic CVD method was used to further form the catalyst body with a catalytic element selected from Ta, W, and Mo. It has been found that such a problem can be solved by containing a group element at an atomic ratio of 1.0 ppm to 0.5%.
[0009]
Accordingly, the present invention has been completed based on the above findings, and an object thereof is to provide a resistor in which an amorphous silicon layer having low resistance and low stress is stably formed at a high film formation rate.
[0010]
[Means for Solving the Problems]
The resistor according to the first aspect of the present invention is formed by forming a thin film layer containing amorphous silicon, Ta, and a group V element of the periodic table on a substrate by catalytic CVD, and Ta atoms in the thin film layer. The ratio is 0.55 ppm to 1.20%, and the atomic ratio of Group V elements in the periodic table in the thin film layer is 1.0 ppm to 0.5% . In the resistor according to the second aspect of the present invention, a thin film layer containing amorphous silicon, W, and a group V element of the periodic table is formed on a substrate by catalytic CVD, and W atoms in the thin film layer are formed. The ratio is 0.50 ppm to 1.15%, and the atomic ratio of Group V elements in the periodic table in the thin film layer is 1.0 ppm to 0.48%. The resistor according to the third aspect of the present invention is formed by forming a thin film layer containing amorphous silicon, Mo, and a group V element of the periodic table on a substrate by catalytic CVD, and the atoms of Mo in the thin film layer. The resistor is characterized in that the ratio is 0.53 ppm to 15.0%, and the atomic ratio of Group V elements in the periodic table in the thin film layer is 1.0 ppm to 0.09%. In the resistor according to the first to third aspects of the present invention, the internal stress of the thin film layer is preferably set to 1.7 × 10 ^{7 to} 4.6 × 10 ⁷ N / m ² . In the resistor according to the first to third aspects of the present invention, the thin film layer is preferably any one of a heat generating layer , an antistatic layer, and a protective layer . In the resistor according to the first to third aspects of the present invention, the amorphous silicon is preferably doped with carbon, nitrogen, or oxygen .
[0011]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the resistor of the present invention will be described with reference to the drawings, taking an ink-jet heat generating portion as an example.
[0012]
FIG. 1 is a cross-sectional view of a principal part of an ink-jet heat generating portion which is a resistor according to the present invention. FIG. 2 is a diagram showing a schematic configuration of the catalytic CVD method according to the present invention.
[0013]
According to the resistor shown in FIG. 1, an electrode 2 made of a metal such as aluminum or chromium is formed on an insulating substrate 1 such as glass or ceramic as the base, and the amorphous silicon is formed on the electrode 2. The heat generating layer 3 as a layer is formed by catalytic CVD, and another electrode 4 made of a metal such as aluminum or chromium is formed on the heat generating layer 3.
[0014]
The electrodes 2 and 4 may be formed by a vacuum vapor deposition method or a sputtering method.
[0015]
The heat generating layer 3 is made of amorphous silicon. For amorphous silicon, carbon or nitrogen may be further doped with oxygen.
[0016]
In the present invention, a group V element of the periodic table is contained at an atomic ratio of 1.0 ppm to 0.5% for adjusting the resistance value of the heat generating layer 3, thereby the specific resistance of the heat generating layer 3. The value can be in the range of 4.1 × 10 ^{3 to} 7.8 × 10 ⁰ Ω · cm. As the V group element of the periodic table, there are N, P, As, Sb, and Bi, and any element may be used.
[0017]
The heat generating layer 3 is formed by a catalytic CVD method. For reference, the technique described in JP-A-6-338491 may be used.
[0018]
Hereinafter, the case where phosphorus (P) is used as a group V element of the periodic table is shown.
[0019]
FIG. 2 shows the configuration of the catalytic CVD apparatus.
[0020]
In the figure, reference numeral 5 denotes a vacuum container, and a support 6 is disposed inside the vacuum container 5, and a film formation substrate 7 is disposed on the support 6. Reference numeral 8 denotes a gas introduction part, and a filament 9 which is the catalyst body is disposed between the gas introduction part 8 and the deposition target substrate 7.
[0021]
Then, when the semiconductor gas is introduced, it is ejected from the gas introduction part 8 and is formed on the film formation substrate 7 through the filament 9.
[0022]
The film forming conditions are, for example, a degree of vacuum of 13.3 Pa, a substrate temperature of 250 ° C., and a temperature of the catalyst body (filament 9) of 2200 ° C.
[0023]
As the raw material gas, silicon hydride gas (monosilane, disilane) or the like is used. As the carrier gas, hydrogen gas or argon gas which is generally used is used. Further, a slight doping gas may be added to adjust the resistance value, and a gas such as PH ₃ may be used as the gas for that purpose.
[0024]
According to the present invention, the catalyst body is made of a catalyst element selected from Ta, W, and Mo, and the catalyst body is evaporated by increasing the catalyst body temperature to, for example, 2200 ° C. The catalyst element is incorporated in the layer.
[0025]
Thus, according to the present invention, a film having a desired specific resistance can be obtained at low cost only by adding a small doping gas (a gas such as PH ₃ ) by the catalytic CVD method.
[0026]
According to experiments repeatedly conducted by the present inventor, when such a catalytic element is not contained, the P content is required to be 5000 ppm (0.5%) or more. For example, when the P content was 1.0 ppm or more, a film having a specific resistance of 4.1 × 10 ³ Ω · cm or less was obtained.
[0027]
In the present invention, since the film was formed by the catalytic CVD method, the plasma was not damaged, thereby reducing the internal stress of the film and forming a film that was not easily peeled off.
[0028]
【Example】
(Example 1)
As shown in FIG. 3, a heat generating layer 13 is formed on a substrate 11 (40 mm × 10 mm × thickness 0.1 mm) made of AF45 glass by a catalytic CVD method (catalyst body: Ta). This layer was formed by depositing an amorphous silicon layer with a thickness of 20000 mm according to the deposition conditions shown in Table 1. And it measured from the amount of warping.
[0029]
According to the figure, the end of the substrate 11 was fixed to the substrate support 10, and a thin film layer (heat generation layer) 13 was formed on the substrate 11, and the amount of warpage δ was measured.
[0030]
On the other hand, in order to measure other characteristics, an aluminum electrode 2 having a width of 1 mm is vapor-deposited on a substrate 1 (40 mm × 10 mm × thickness 1 mm) made of # 7059 glass, and a heating layer 3 is formed thereon by catalytic CVD ( A catalyst body: Ta) is used for a heating resistor. This layer was formed by depositing an amorphous silicon layer with a thickness of 20000 mm according to the deposition conditions shown in Table 1.
[0031]
[Table 1]

[0032]
With respect to the resistor of the present invention thus obtained, the internal stress was measured from the amount of warp, and there was no such warp. Furthermore, when a 1 mm wide electrode was vapor-deposited in the cross direction on the resistor and the presence or absence of heat generation was evaluated, sufficient heat generation could be confirmed.
[0033]
Further, for resistance measurement, the heat generating layer 3 is formed on the substrate 1 (40 mm × 10 mm × thickness 1 mm) made of # 7059 glass by the catalytic CVD method (catalyst body: Ta) to be used for the heat generating resistor. This layer was formed by depositing an amorphous silicon layer with a thickness of 20000 mm according to the deposition conditions shown in Table 1. According to this sample, a heat generating layer was directly formed on a substrate, and a comb-shaped electrode was deposited thereon for measurement. As a result, the specific resistance was 10 ¹ Ω · cm, and good results were obtained.
[0034]
(Example 2)
Next, in producing the resistor shown in (Example 1), in forming the heat generating layer, the catalyst body is changed in the range of 1500 to 2500 ° C., and other film forming conditions are the same as those of the resistor in (Example 1). Various resistors were prepared.
[0035]
In this way, by varying the catalyst body temperature, various resistors having various contents of the catalyst element Ta changed to 0.05 ppm or more were prepared. When the specific resistance, heat generation, internal stress and adhesion of these resistors were measured, the results shown in Table 2 were obtained.
[0036]
The evaluation of heat generation is divided into three categories: ○, △, and ×. ○ indicates that the standard heating value is satisfied, and Δ indicates that only a portion of the standard heating value is satisfied. Indicates the case where the entire surface does not satisfy the standard heating value.
[0037]
In addition, the evaluation of adhesion is classified into three categories, ○, Δ, and ×, where ○ indicates that there is no film peeling, Δ indicates that there is only part of film peeling, and × indicates the entire surface The case where there is a film peeling is shown.
[0038]
[Table 2]

[0039]
As is apparent from this table, it can be seen that as the catalyst body temperature increases, the content of the catalyst element increases and the specific resistance decreases. This is because the catalyst element evaporates and the element enters the film as the temperature of the catalyst body rises. And it turns out that specific resistance became small and heat_generation | fever improved because the catalyst element entered in the film | membrane.
[0040]
In the case of Ta, when the catalyst body temperature was 2100 ° C. to 2300 ° C., good results were obtained in both heat generation and adhesion. When the catalyst body temperature was 2400 ° C., the catalyst element was excessively contained in the film, resulting in a rough film and peeling off. In addition, the catalyst body may be cut off due to the temperature being too high. Furthermore, at 2500 ° C. or higher, the catalyst body was always cut during film formation, and the film did not adhere.
[0041]
The internal stress is 1.0 × 10 ^{8 to} 7.5 × 10 ⁸ (N / m ² ) in the case of an amorphous silicon film manufactured by a general plasma CVD method. About the resistor which was made, it is a considerably small value (one digit smaller), and there exists a remarkable effect on adhesiveness etc.
[0042]
(Example 3)
Next, in producing the resistor shown in (Example 1), the flow rate of PH ₃ gas (using a cylinder diluted with hydrogen at 40 ppm and 0.2%) was set to 0 in forming the thin film layer (heat generation layer 13). Various resistors were prepared by changing the range of ˜300 sccm, setting the other film forming conditions to the same as the resistor of Example 1 at a flow rate of 20 sccm for the SiH ₄ gas.
[0043]
That is, when the thin film layer is formed, various resistors whose content of P (phosphorus) is changed in various ways from 0 to 1.5% by changing the flow rate of PH ₃ gas with respect to SiH ₄ gas. Produced.
[0044]
When the specific resistance, heat generation, internal stress and adhesion of these resistors were measured, the results shown in Table 3 were obtained.
[0045]
[Table 3]

[0046]
As is apparent from the table, it can be seen that when the PH ₃ gas flow rate is increased, the phosphorus element content is increased and the specific resistance is decreased. This is because the flow rate ratio with respect to the SiH ₄ gas increases as the PH ₃ gas flow rate increases, and a large amount of phosphorus element enters the silicon film. And it turns out that a specific resistance becomes small and heat_generation | fever improves because phosphorus element enters in a film | membrane.
[0047]
Moreover, when the phosphorus content was included at an atomic ratio of 1.0 ppm to 0.5%, good results were obtained for both heat generation and adhesion.
[0048]
When the phosphorus content was less than 1.0 ppm, the specific resistance increased and no heat was generated. On the other hand, when the phosphorus content is 0.52% or more, phosphorus element is excessively contained in the film, and the internal stress increases, thereby increasing the warpage of the substrate, peeling off the film, and forming a rougher film. As a result, it was tattered.
[0049]
Furthermore, if the phosphorus element content is increased to 0.80% or more, the film forming speed needs to be extremely slow, which is considered unsuitable for mass production. This is because when the film formation rate is increased, the decomposition efficiency of boron is reduced, resulting in a rough film quality.
[0050]
(Example 4)
Next, in producing the resistor shown in (Example 2), the catalyst element was changed to W instead of Ta, the catalyst body was changed in the range of 1500 to 3000 ° C., and other film forming conditions were changed to those in (Example 1). Various resistors were prepared by setting the same as the resistors.
[0051]
In this way, by varying the catalyst body temperature, various resistors having various contents of the catalyst element W changed to 0.04 ppm or more were produced. When the specific resistance, heat generation, internal stress and adhesion of these resistors were measured, the results shown in Table 4 were obtained.
[0052]
[Table 4]

[0053]
As is apparent from this table, it can be seen that as the catalyst body temperature increases, the content of the catalyst element increases and the specific resistance decreases. This is because the catalyst element evaporates and the element enters the film as the temperature of the catalyst body rises. And it turns out that specific resistance became small and heat_generation | fever improved because the catalyst element entered in the film | membrane.
[0054]
In the case of W, when the catalyst body temperature was 2000 ° C. to 2500 ° C., good results were obtained for both heat generation and adhesion. When the catalyst body temperature was 2700 ° C., the catalyst element was excessively contained in the film, resulting in a rough film and peeling off. In addition, the catalyst body may be cut off due to the temperature being too high. Furthermore, at 3000 ° C. or higher, the catalyst body was always cut during film formation, and the film did not adhere.
[0055]
The internal stress is 1.0 × 10 ^{8 to} 7.5 × 10 ⁸ (N / m ² ) in the case of an amorphous silicon film manufactured by a general plasma CVD method. About the resistor which was made, it is a considerably small value (one digit smaller), and there exists a remarkable effect on adhesiveness etc.
[0056]
(Example 5)
Next, in producing the resistor shown in (Example 4), the flow rate of PH ₃ gas (using a cylinder diluted with hydrogen at 40 ppm and 0.2%) was set to 0 in forming the thin film layer (heating layer 13). Various resistors were prepared by changing the range of ˜300 sccm, setting the other film forming conditions to the same as the resistor of Example 1 at a flow rate of 20 sccm for the SiH ₄ gas.
[0057]
That is, when the thin film layer is formed, various resistors having various contents of P (phosphorus) changed from 0 to 1.42% by changing the flow rate of PH ₃ gas with respect to SiH ₄ gas. Produced.
[0058]
When the specific resistance, heat generation, internal stress and adhesion of these resistors were measured, the results shown in Table 5 were obtained.
[0059]
[Table 5]

[0060]
As is apparent from the table, it can be seen that when the PH ₃ gas flow rate is increased, the phosphorus element content is increased and the specific resistance is decreased. This is because the flow rate ratio with respect to the SiH ₄ gas increases as the PH ₃ gas flow rate increases, and a large amount of phosphorus element enters the silicon film. And it turns out that a specific resistance becomes small and heat_generation | fever improves because phosphorus element enters in a film | membrane.
[0061]
Moreover, when the phosphorus content was included at an atomic ratio of 1.0 ppm to 0.5%, good results were obtained for both heat generation and adhesion.
[0062]
When the phosphorus content was less than 1.0 ppm, the specific resistance increased and no heat was generated. On the other hand, when the phosphorus content is 0.75% or more, the phosphorus element is excessively contained in the film, and the internal stress increases, thereby increasing the warpage of the substrate, peeling off the film, and further forming a rough film. As a result, it was tattered.
[0063]
Furthermore, if the content of the phosphorus element is increased to 0.75% or more, the film forming speed needs to be extremely slow, which is not suitable for mass production. This is because when the film formation rate is increased, the decomposition efficiency of boron is reduced, resulting in a rough film quality.
[0064]
(Example 6)
Next, in producing the resistor shown in (Example 2), the catalyst element is changed to Mo instead of Ta, and the catalyst body is changed in the range of 1500 to 3000 ° C., and other film forming conditions are set as in (Example 1). Various resistors were prepared by setting the same as the resistors.
[0065]
Thus, by varying the catalyst body temperature, various resistors having various contents of the catalyst element Mo changed to 0.04 ppm or more were produced. When the specific resistance, heat generation, internal stress and adhesion of these resistors were measured, the results shown in Table 6 were obtained.
[0066]
[Table 6]

[0067]
As is apparent from this table, it can be seen that as the catalyst body temperature increases, the content of the catalyst element increases and the specific resistance decreases. This is because the catalyst element evaporates and the element enters the film as the temperature of the catalyst body rises. And it turns out that specific resistance became small and heat_generation | fever improved because the catalyst element entered in the film | membrane.
[0068]
In the case of Mo, when the catalyst body temperature was 2000 ° C. to 2700 ° C., good results were obtained for both heat generation and adhesion. When the catalyst body temperature was 2800 ° C., the catalyst element was excessively contained in the film, resulting in a rough film and peeling off. In addition, the catalyst body may be cut off due to the temperature being too high. Furthermore, at 3000 ° C. or higher, the catalyst body was always cut during film formation, and the film did not adhere.
[0069]
The internal stress is 1.0 × 10 ^{8 to} 7.5 × 10 ⁸ (N / m ² ) in the case of an amorphous silicon film manufactured by a general plasma CVD method. About the resistor which was made, it is a considerably small value (one digit smaller), and there exists a remarkable effect on adhesiveness etc.
[0070]
(Example 7)
Next, in producing the resistor shown in (Example 6), the flow rate of PH ₃ gas (using a cylinder diluted with hydrogen at 40 ppm and 0.2%) was set to 0 in forming the thin film layer (heat generation layer 13). Various resistors were prepared by changing the range of ˜300 sccm, setting the other film forming conditions to the same as the resistor of Example 1 at a flow rate of 20 sccm for the SiH ₄ gas.
[0071]
That is, when the thin film layer is formed, various resistors having various contents of P (phosphorus) changed from 0 to 1.57% by changing the flow rate of PH ₃ gas with respect to SiH ₄ gas. Produced.
[0072]
When the specific resistance, heat generation, internal stress and adhesion of these resistors were measured, the results shown in Table 7 were obtained.
[0073]
[Table 7]

[0074]
As is apparent from the table, it can be seen that when the PH ₃ gas flow rate is increased, the phosphorus element content is increased and the specific resistance is decreased. This is because the flow rate ratio with respect to the SiH ₄ gas increases as the PH ₃ gas flow rate increases, and a large amount of phosphorus element enters the silicon film. And it turns out that a specific resistance becomes small and heat_generation | fever improves because phosphorus element enters in a film | membrane.
[0075]
Moreover, when the phosphorus content was included at an atomic ratio of 1.0 ppm to 0.5%, good results were obtained for both heat generation and adhesion.
[0076]
When the phosphorus content was less than 1.0 ppm, the specific resistance increased and no heat was generated. On the other hand, when the phosphorus content is 0.52% or more, phosphorus element is excessively contained in the film, and the internal stress increases, thereby increasing the warpage of the substrate, peeling off the film, and forming a rougher film. As a result, it was tattered.
[0077]
Furthermore, if the phosphorus element content is increased to 0.52% or more, the film formation rate needs to be extremely slow, which is considered unsuitable for mass production. This is because when the film formation rate is increased, the decomposition efficiency of boron is reduced, resulting in a rough film quality.
[0078]
It should be noted that the present invention is not limited to the above-described embodiments, and various changes and improvements can be made without departing from the scope of the present invention. For example, according to the present invention, Ta, W, and Mo are used alone for the catalyst body, but instead of this, a composite material that combines these, and a plurality of catalyst elements in the heat generating layer. It may be added.
[0079]
As described above, according to the present invention, in the resistor in which the amorphous silicon layer is formed on the substrate support by the catalytic CVD method, the catalytic element selected from Ta, W, and Mo is in the range of 0.5 ppm to 15%. In addition, the Group V element of the periodic table is contained in an atomic ratio of 1.0 ppm to 0.5%, so that excellent exothermic property is obtained, and the quality is stable at low cost (adhesion) Resistors with excellent mass productivity could be provided .
[0080]
Further, according to the resistor of the present invention, a protective coating for an etching member (reactor) is used as a heat generating part for a thermal head, a heat generating part for an ink jet, and as an antistatic coating for an electron beam mechanism part of a semiconductor exposure apparatus. It can also be applied as a For example, a film having a specific resistance of 10 ³ to 10 ⁰ (Ω · cm) can be formed as a heat generating part for an ink jet and an antistatic coating for a semiconductor exposure apparatus.
[Brief description of the drawings]
FIG. 1 is a cross-sectional view of a resistor according to the present invention.
FIG. 2 is a diagram showing a schematic configuration of a catalytic CVD method according to the present invention.
FIG. 3 is an explanatory diagram showing a method for measuring the amount of warping of a resistor.
[Explanation of symbols]
DESCRIPTION OF SYMBOLS 1 ... Substrate 2, 4 ... Electrode 5 ... Vacuum container 6 ... Support body 7 ... Film-forming substrate 8 ... Gas introduction part 9 ... Filament

Claims (6)

A thin film layer containing amorphous silicon, Ta, and a group V element of the periodic table is formed on a substrate by catalytic CVD, and the atomic ratio of Ta in the thin film layer is 0.55 ppm to 1.20%. The atomic ratio of the group V element of the periodic table in the thin film layer is 1.0 ppm to 0.5% . A thin film layer containing amorphous silicon, W, and a group V element of the periodic table is formed on a substrate by catalytic CVD, and the atomic ratio of W in the thin film layer is 0.50 ppm to 1.15%, The atomic ratio of the group V element of the periodic table in the thin film layer is 1.0 ppm to 0.48%. A thin film layer containing amorphous silicon, Mo, and a group V element of the periodic table is formed on a substrate by catalytic CVD, and the atomic ratio of Mo in the thin film layer is 0.53 ppm to 15.0%, The atomic ratio of the group V element of the periodic table in the thin film layer is 1.0 ppm to 0.09%. Resistor according to any one of claims 1 to 3, characterized in that the internal stress of the thin film layer is set to ^{1.7 × 10 7 ~4.6 × 10 7} N / m 2. The resistor according to any one of claims 1 to 4, wherein the thin film layer is any one of a heat generating layer , an antistatic layer, and a protective layer . 6. The resistor according to claim 1, wherein the amorphous silicon is doped with any one of carbon, nitrogen, and oxygen .

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