JP2005277181A - Method for manufacturing semiconductor device - Google Patents

Method for manufacturing semiconductor device Download PDF

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JP2005277181A
JP2005277181A JP2004089598A JP2004089598A JP2005277181A JP 2005277181 A JP2005277181 A JP 2005277181A JP 2004089598 A JP2004089598 A JP 2004089598A JP 2004089598 A JP2004089598 A JP 2004089598A JP 2005277181 A JP2005277181 A JP 2005277181A
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antireflection film
semiconductor device
light
manufacturing
refractive index
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Yoshiya Abiko
義哉 安彦
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Sharp Corp
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Abstract

<P>PROBLEM TO BE SOLVED: To provide a semiconductor device that enables the reception and emission of light in a wide light wavelength region and has an antireflection film for reducing the loss of light that can be received or emitted owing to light reflection. <P>SOLUTION: This semiconductor device manufacturing method is characterized by an antireflection film whose refractive index changes in the direction of film thickness, changing the composition ratio of raw material gas on a semiconductor device by the plasma CVD technique. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

本発明は、光の反射を低減させることを目的とした反射防止膜を有する半導体装置の製造方法に関する。   The present invention relates to a method for manufacturing a semiconductor device having an antireflection film for the purpose of reducing light reflection.

従来、太陽電池などの受光素子、ＬＥＤおよび半導体レーザーなどの発光素子ならびにレンズなどの光学部品では、表面での光の反射を抑えるために、光が入射または放射する面に防呟膜や反射防止膜を施すことがある。そして、該反射防止膜では、単層からなるもの以外に、二層以上の層を積層させて光の干渉作用を利用して光の反射率を低減させる技術が知られている。一般に、多層からなる反射防止膜は、ＣＶＤ法（化学気相成長法）、真空蒸着法、スパッタリング法などを用いて、屈性率の異なる層を積層させることにより、単層の場合よりも広い光波長領域での光の反射を低減させることができる。しかし、その場合、各層で材料の異なるものを使用するか、または各層で材料の混合比が異なるものを使用する。   Conventionally, in light receiving elements such as solar cells, light emitting elements such as LEDs and semiconductor lasers, and optical components such as lenses, in order to suppress reflection of light on the surface, an anti-reflection film or anti-reflection is provided on the surface on which light is incident or emitted A film may be applied. In addition to the single-layered anti-reflection film, a technique is known in which two or more layers are stacked to reduce the light reflectance by utilizing the light interference action. In general, a multilayer antireflection film is wider than a single layer by laminating layers having different reflectivities using CVD (chemical vapor deposition), vacuum deposition, sputtering, or the like. The reflection of light in the light wavelength region can be reduced. However, in that case, a material having a different material is used in each layer, or a material having a different material mixing ratio in each layer.

特許文献１では、プラズマＣＶＤ法を用いて、層毎で面方向および厚み方向に屈折率が一定な窒化ケイ素からなる層、酸窒化ケイ素からなる層および酸化ケイ素からなる層などの各層を積層させて形成した反射防止膜の製造方法が開示されている。該公報では、酸窒化ケイ素からなる層を製膜する際のＣＶＤ法の条件（成形方法および原料ガスのガス流量など）を調節して元素組成を制御することで、窒化ケイ素からなる層と酸化ケイ素からなる層の界面での屈折率を任意に制御する方法を開示している。しかし上記方法では、各層の界面および反射防止膜と基体の界面で屈折率に差があるため、それら界面で反射が起こり、入射光の反射が残留してしまうことがある。   In Patent Document 1, plasma CVD is used to stack each layer such as a layer made of silicon nitride, a layer made of silicon oxynitride, and a layer made of silicon oxide having a constant refractive index in the plane direction and thickness direction for each layer. A method of manufacturing an antireflection film formed in this manner is disclosed. In this publication, a silicon nitride layer and an oxide layer are oxidized by controlling the elemental composition by adjusting the conditions of the CVD method (molding method, gas flow rate of raw material gas, etc.) when forming the silicon oxynitride layer. A method for arbitrarily controlling the refractive index at the interface of a layer made of silicon is disclosed. However, in the above method, since there is a difference in refractive index between the interface of each layer and the interface between the antireflection film and the substrate, reflection may occur at those interfaces, and reflection of incident light may remain.

さらに、多層からなる反射防止膜では、各層の厚みが、数１０nm程度必要とするため、屈折率の高い反射防止膜を製膜する場合、自然と反射防止膜全体の厚みも厚くなる。そして、そのことは、膜内での光の吸収を伴うことが多い。さらに、該反射防止膜を連続的に製膜する場合、単一の層からなる反射防止膜を製造するときと比べて、製造時間や製造コストが余分に必要となる。そして、これらのことを考慮して反射防止膜を製造したとしても、ごく限られた波長領域の光でしか反射防止効果を得られないことが多かった。   Furthermore, since the multilayer antireflection film requires a thickness of several tens of nanometers, when an antireflection film having a high refractive index is formed, the thickness of the entire antireflection film naturally increases. And that often involves the absorption of light within the film. Further, when the antireflection film is continuously formed, extra manufacturing time and manufacturing cost are required as compared with the case of manufacturing an antireflection film composed of a single layer. Even when an antireflection film is manufactured in consideration of these matters, the antireflection effect is often obtained only with light in a very limited wavelength region.

特に、太陽電池の分野においては、半導体基板の表面で起こる光の反射を低減させ、半導体基板内に取り込まれる光の量を増大させることで、電気エネルギーへの変換効率を高めることを目的として、反射防止膜について盛んに研究がなされてきた。例えば、特許文献２では、ＴｉＯ2からなる層とＳｉＯＮからなる層などで形成される各層で、屈折率が異なる反射防止膜を、スパッタリング法を用いて製造する方法が開示されている。該公報では、ＴｉＯ2を製膜する際にＡｒとＯ2の混合ガスでのＯ2の分圧を変化させることで、層内での屈折率を３．３〜２．４まで変化させ、ＳｉＯＮ層を製膜する際に、ＡｒとＮ2の混合ガスを、ＡｒとＯ2の混合ガスへ連続的に移行させることによって層内での屈折率を２．３〜１．４まで変化させた反射防止膜を形成することで、各層内での屈折率の差を０．１、半導体層とＴｉＯ2の界面での屈折率の差を０．２、ＳｉＯＮ層と入射側の媒質である空気との界面での屈折率の差を０．４に抑えることを可能にし、広い波長域での光の反射を大幅に低減させ、光エネルギーへの変換効率を大幅に向上させることができたと開示している。 In particular, in the field of solar cells, by reducing the reflection of light that occurs on the surface of the semiconductor substrate and increasing the amount of light taken into the semiconductor substrate, the purpose is to increase the conversion efficiency into electrical energy, Active research has been conducted on antireflection films. For example, Patent Document 2 discloses a method of manufacturing an antireflection film having a different refractive index in each layer formed of a layer made of TiO 2 and a layer made of SiON by a sputtering method. In this publication, by changing the partial pressure of O 2 in a mixed gas of Ar and O 2 in the course of film production of the TiO 2, to change the refractive index in the layer to 3.3 to 2.4, When the SiON layer is formed, the refractive index in the layer is changed from 2.3 to 1.4 by continuously transferring the mixed gas of Ar and N 2 to the mixed gas of Ar and O 2. By forming an antireflection film, the refractive index difference within each layer is 0.1, the refractive index difference at the interface between the semiconductor layer and TiO 2 is 0.2, and the SiON layer and the incident side medium. It was possible to suppress the difference in refractive index at the interface with air to 0.4, greatly reduce the reflection of light in a wide wavelength range, and greatly improved the conversion efficiency to light energy. Disclosure.

また、レンズなどの光学部品では、反射防止膜を用いてレンズ表面で起こる光の反射を少なくして光の透過率を向上させることが重要な課題となっている。特に、太陽電池などの受光素子の場合、広範囲にわたる光波長域において受光素子の表面で起こる光の反射による損失を抑えることで、光の受光率を高め、光エネルギーを電気エネルギーに変換する光電変換効率を向上させることが重要な課題として挙げられている。   Further, in an optical component such as a lens, it is an important issue to improve the light transmittance by reducing the reflection of light that occurs on the lens surface using an antireflection film. In particular, in the case of light-receiving elements such as solar cells, photoelectric conversion that increases the light reception rate and converts light energy into electrical energy by suppressing loss due to light reflection occurring on the surface of the light-receiving element in a wide range of light wavelengths Improving efficiency is cited as an important issue.

特開平５−１２９２７７号公報JP-A-5-129277 特開平７−２３５６８４号公報JP-A-7-235684

しかし、前述のように屈折率の異なる層を積層させた反射防止膜では、最適設計時には85％以上の表面反射を低減させることができるものの、依然として、基板と反射防止膜、あるいは各層の界面、反射防止膜と入射側の媒質である空気などとの界面で光の反射が起こるため、利用可能な光の損失が生じる。   However, in the antireflection film in which layers having different refractive indexes are laminated as described above, surface reflection of 85% or more can be reduced at the time of optimum design, but still the substrate and the antireflection film, or the interface between each layer, Since light is reflected at the interface between the antireflection film and air, which is a medium on the incident side, a loss of usable light occurs.

そこで本発明は、広範囲の波長域の光を受光または発光でき、かつ光の反射によって起こる光の損失を低減させることを目的とした反射防止膜を有する半導体装置の製造方法を提供することを課題とする。   In view of the above, an object of the present invention is to provide a method of manufacturing a semiconductor device having an antireflection film that can receive or emit light in a wide wavelength range and reduce light loss caused by light reflection. And

本発明は、プラズマＣＶＤ法により、半導体素子上に、原料ガスの組成比を変化させながら、膜厚方向で屈折率が変化する反射防止膜を形成することを特徴とする半導体装置の製造方法を提供することで、上記課題を解決した。   The present invention provides a method for manufacturing a semiconductor device, characterized in that an antireflection film whose refractive index changes in the film thickness direction is formed on a semiconductor element by a plasma CVD method while changing the composition ratio of the source gas. By providing this, the above problems were solved.

本発明の半導体装置の製造方法に従って反射防止膜を有する半導体装置を製造することで、空気などの媒質と反射防止膜の界面、反射防止膜内部、および反射防止膜と半導体素子との界面で起こる反射による光の損失を低減させることができる半導体装置を提供することができた。
そして、このようにプラズマＣＶＤ法で反射防止膜を形成することで、水素パッシベーション効果を得ることができた。つまり、半導体基板が多結晶シリコンからなる場合、粒界中に多数存在するシリコンの未結合手を、成膜中に生じる水素ラジカルによって終端させることができ、他の形成法と比べて、本願発明の製造方法で得られた半導体装置の方が、半導体装置の特性を大きく向上させることができた。
また熱酸化膜のパッシベーションと比べて、低温で形成できるため、基板へのダメージを小さくすることができた。
そして、本製造方法を用いて太陽電池を製造した場合、太陽電池の短絡電流値の向上による変換効率を上昇させ、さらに受光素子の透過光増大による感度の上昇をもたらすことができた。さらに本発明の製造方法を用いてレーザーやＬＥＤなどを製造した場合、発光素子の輝度を向上させることができた。 By manufacturing a semiconductor device having an antireflection film according to the method for manufacturing a semiconductor device of the present invention, it occurs at the interface between a medium such as air and the antireflection film, inside the antireflection film, and at the interface between the antireflection film and the semiconductor element. It was possible to provide a semiconductor device capable of reducing light loss due to reflection.
And the hydrogen passivation effect was able to be acquired by forming an antireflection film by plasma CVD method in this way. That is, when the semiconductor substrate is made of polycrystalline silicon, a large number of silicon dangling bonds existing in the grain boundary can be terminated by hydrogen radicals generated during film formation. The semiconductor device obtained by this manufacturing method was able to greatly improve the characteristics of the semiconductor device.
Moreover, since it can be formed at a lower temperature than the thermal oxide film passivation, the damage to the substrate can be reduced.
And when the solar cell was manufactured using this manufacturing method, the conversion efficiency by the improvement of the short circuit current value of a solar cell could be raised, and also the raise of the sensitivity by the increase in the transmitted light of a light receiving element could be brought about. Furthermore, when a laser, LED, etc. were manufactured using the manufacturing method of this invention, the brightness | luminance of the light emitting element was able to be improved.

本名発明の製造方法で得られる半導体装置は、半導体素子上に、膜厚方向で屈折率が異なる反射防止膜が形成されている半導体装置である。
本発明の反射防止膜を有する半導体素子には、公知の太陽電池などの受光素子、レーザーおよびＬＥＤなどの発光素子が含まれる。中でも、太陽電池が好ましく、特にＰＮ接合型結晶シリコン太陽電池セルが好ましい。
また、本発明で述べる「膜厚方向」とは、半導体素子の表面から反射防止膜の受光面または発光面に向かう方向を意味している。
反射防止膜は、半導体素子の受光部または発光部の前面に渡って形成していてもよいし、光の反射半導体素子の性能に影響を与える部分にのみに形成していてもよい。
また、本発明の反射防止膜は形成する反射防止膜全体にわたって膜厚方向に屈折率が変化している必要はなく、少なくとも光の反射が半導体素子の性能に影響を与える部分が変化していればよい。
具体的な実施の形態として、以下に、ＰＮ接合型結晶シリコン太陽電池を１例として用い、本願発明の反射防止膜を有する半導体装置の製造方法によって得られる半導体装置について説明する。
図３（ｇ）は、本願発明の半導体装置の製造方法で得られる半導体装置の１例を示したものである。この半導体装置は、Ｐ型のドーパントが注入された半導体基板（２）の受光表面（４）にＮ型の不純物を熱拡散させて形成させたＰＮ接合層（３）を形成しており、該接合層の表面には表面電極（６）が配されている。さらにその上に反射防止膜（８）が配されている。さらに、受光面の反対側には、ほぼ全面にわたって裏面電極（７）が配された構造となっている。 The semiconductor device obtained by the manufacturing method of the present invention is a semiconductor device in which an antireflection film having a different refractive index in the film thickness direction is formed on a semiconductor element.
The semiconductor element having the antireflection film of the present invention includes a light receiving element such as a known solar cell, and a light emitting element such as a laser and an LED. Among these, a solar cell is preferable, and a PN junction type crystalline silicon solar cell is particularly preferable.
The “film thickness direction” described in the present invention means a direction from the surface of the semiconductor element toward the light receiving surface or light emitting surface of the antireflection film.
The antireflection film may be formed over the front surface of the light receiving portion or the light emitting portion of the semiconductor element, or may be formed only on a portion that affects the performance of the light reflecting semiconductor element.
Further, the antireflective film of the present invention does not have to change the refractive index in the film thickness direction over the entire antireflective film to be formed, and at least the part where the reflection of light affects the performance of the semiconductor element is changed. That's fine.
As a specific embodiment, a semiconductor device obtained by a method for manufacturing a semiconductor device having an antireflection film according to the present invention will be described below using a PN junction type crystalline silicon solar cell as an example.
FIG. 3G shows an example of a semiconductor device obtained by the method for manufacturing a semiconductor device of the present invention. This semiconductor device has a PN junction layer (3) formed by thermally diffusing N-type impurities on the light-receiving surface (4) of a semiconductor substrate (2) implanted with a P-type dopant, A surface electrode (6) is disposed on the surface of the bonding layer. Furthermore, an antireflection film (8) is disposed thereon. Further, on the opposite side of the light receiving surface, a back electrode (7) is arranged over almost the entire surface.

そして、本願発明の半導体装置の製造方法では、半導体素子上に、プラズマＣＶＤ法を用いて膜厚方向で屈折率が異なる反射防止膜を形成することに特徴がある。
そして図４は、プラズマＣＶＤ法を用いて窒化ケイ素からなる膜を形成する場合のシラン（ＳｉＨ4）ガスとアンモニア（ＮＨ3）ガスの流量比が、製膜される膜（窒化ケイ素）の屈折率の関係を調べたものである。その結果、製膜時に使用するガス（この場合、ＳｉＨ4／ＮＨ3）の流量比を段階的に変化させることで、製膜される膜の屈折率を段階的に変化させることができることが判明した。 The semiconductor device manufacturing method of the present invention is characterized in that an antireflection film having a different refractive index in the film thickness direction is formed on a semiconductor element using a plasma CVD method.
FIG. 4 shows that the flow rate ratio of silane (SiH 4 ) gas and ammonia (NH 3 ) gas when a film made of silicon nitride is formed using the plasma CVD method is the refraction of the film to be formed (silicon nitride). We investigated the relationship between rates. As a result, it was found that the refractive index of the film to be formed can be changed stepwise by changing the flow rate ratio of the gas used in the film formation (in this case, SiH 4 / NH 3 ) step by step. did.

そして、この特徴を利用して、半導体素子上に、膜を形成するための複数の原料のガス（以下、原料ガスと称する）の組成比を変化させながらプラズマＣＶＤ法を用いて、反射防止膜を形成することで、膜厚方向に屈折率が異なる反射防止膜を形成することができる。
組成比を変化させる方法としては、各々の原料ガスの流量比を変化させながらプラズマＣＶＤ法を用いることで行うことが挙げられる。
さらに好ましくは、原料ガスが少なくとも２成分系である場合には、一方の原料ガスの流量を固定して、他方の原料ガスの流量を変化させることで、原料ガスの組成比を変化させることである。
さらに反射防止膜の屈折率は、半導体素子の表面から反射防止膜の受光面または発光面に向かって低くなるよう製造することである。
用いる原料ガスは、製造する半導体装置の特性に応じて、所望の屈折率および形成する膜の組成に従って適宜選択すればよい。そのため、原料ガスの成分としては、具体的には窒化ケイ素、酸化ケイ素、酸窒化ケイ素、酸化チタン、酸化アルミニウム、フッ化マグネシウム、酸化タンタル、硫化亜鉛、酸化セリウムおよびフッ化セリウムなどが挙げられる。中でも、太陽電池の反射防止膜を形成する場合には、窒化ケイ素などを用いることが好ましい。 Then, by utilizing this feature, an antireflection film is formed using a plasma CVD method while changing the composition ratio of a plurality of source gases (hereinafter referred to as source gases) for forming a film on a semiconductor element. By forming, an antireflection film having a different refractive index in the film thickness direction can be formed.
As a method for changing the composition ratio, it is possible to use a plasma CVD method while changing the flow rate ratio of each source gas.
More preferably, when the source gas is at least a two-component system, the flow rate of one source gas is fixed and the flow rate of the other source gas is changed to change the composition ratio of the source gas. is there.
Furthermore, the refractive index of the antireflection film is manufactured so as to decrease from the surface of the semiconductor element toward the light receiving surface or the light emitting surface of the antireflection film.
The source gas to be used may be appropriately selected according to the desired refractive index and the composition of the film to be formed in accordance with the characteristics of the semiconductor device to be manufactured. Therefore, specific examples of the component of the source gas include silicon nitride, silicon oxide, silicon oxynitride, titanium oxide, aluminum oxide, magnesium fluoride, tantalum oxide, zinc sulfide, cerium oxide, and cerium fluoride. Among these, when forming an antireflection film for a solar cell, it is preferable to use silicon nitride or the like.

また、反射防止膜を形成する際に用いる原料ガスの流速は、所望する反射防止膜の特性に応じて適宜選択すれよい。   The flow rate of the source gas used when forming the antireflection film may be appropriately selected according to the desired characteristics of the antireflection film.

また、反射防止膜を形成する際の原料ガスの流量比を変化させる速度は、所望する屈折率に応じて適宜選択すればよい。
また、単層構造の反射防止膜の場合、ガラス基体表面の屈折率をｎｓとし、反射防止膜の屈折率をｎ１とし、光の入射または放射面に接する媒質の屈折率をｎ０とし、反射防止膜の厚みをｄ１とし、光の波長をλとした場合、ｎ１２＝ｎ０×ｎ２およびｎ１×ｄ１＝λ／４の関係が成り立つ際に、波長λの光に対する反射率が最小となるとされている。
そのため、膜厚（ｄ１）は、例えば最も必要とする光の波長などに応じて適宜選択すればよく、一般には50〜100、好ましくは上記最も必要とする光の波長（λ１）に対してλ／４[nm]に相当する厚みに設定することが好ましい。 Further, the speed for changing the flow rate ratio of the source gas when forming the antireflection film may be appropriately selected according to the desired refractive index.
In the case of an antireflection film having a single layer structure, the refractive index of the surface of the glass substrate is ns, the refractive index of the antireflection film is n1, and the refractive index of the medium that is in contact with the light incident or radiation surface is n0. When the thickness of the film is d1 and the wavelength of light is λ, the reflectance for light of wavelength λ is minimized when the relationship of n12 = n0 × n2 and n1 × d1 = λ / 4 holds. .
Therefore, the film thickness (d1) may be appropriately selected according to, for example, the most necessary light wavelength, and is generally 50 to 100, preferably λ with respect to the most necessary light wavelength (λ1). It is preferable to set the thickness corresponding to / 4 [nm].

また図５では、Applied Surface Science 113/4 1997 p610-613に記載されているＸ線分光分析（ＸＰＳ）を用いて、アンモニアプラズマ処理を施す時間が膜の表面の結合力と張力に与える影響について示したものである。このことは、分光強度がアンモニアプラズマ処理を施す時間に依存して高まることを示している。つまり、膜の表面付近のＳｉ−Ｈ結合濃度がプラズマ処理する時間に依存していることを示している。
そのため、反射防止膜、特に表面部分をアンモニアプラズマ処理して屈折率を制御させることも好ましい。
その際、アンモニアプラズマ処理する時間は、所望する屈折率に応じて適宜選択すればよい。 In addition, in FIG. 5, the effect of the time during which ammonia plasma treatment is applied on the binding force and tension of the membrane surface using X-ray spectroscopy (XPS) described in Applied Surface Science 113/4 1997 p610-613 It is shown. This indicates that the spectral intensity increases depending on the time for performing the ammonia plasma treatment. That is, it shows that the Si—H bond concentration near the surface of the film depends on the plasma processing time.
Therefore, it is also preferable to control the refractive index by treating the antireflection film, particularly the surface portion, with ammonia plasma.
At that time, the time for the ammonia plasma treatment may be appropriately selected according to the desired refractive index.

以下に、本発明の反射防止膜を有する半導体装置の製造方法にて、PN接合型結晶太陽電池を製造した場合の１例を示す。
その製造方法として、以下の主に４工程からなる製造方法を挙げることができる。
（Ｉ）P型のドーパントが注入された半導体基板上にN型の不純物拡散層を形成する工程
（II）不純物拡散層に電極を形成する工程
（III）受光面上に反射防止膜を形成する工程
（IV）ダイシング工程
具体的には、
（Ｉ）のP型のドーパントが注入された半導体基板上にN型の不純物拡散層を形成する工程とは、図３（ａ）および（ｂ）に示すように、P型基板（（ａ）２）の表面に、リンなどの不純物を熱拡散させてN型の不純物拡散層を形成し、（ａ）に示すようなP／N接合を形成する。そして、受光面（（ｂ）４）と逆面に存在する不純物拡散層をエッチングにより取り除く（ｂ）工程であり、公知の方法を利用して行うことができる。
半導体基板（２）としてはシリコンだけでなく、例えばゲルマニウム、GaAsやInGaAsなどの化合物等を用いることもでき、その厚さについては、特に限定されるものではない。
（II）の不純物拡散層に電極を形成する工程とは、図３（ｃ）、（ｄ）、（ｅ）および（ｆ）に示すように、上記不純物拡散層を形成した受光面（（ｃ）４）に、ネガ型フォトレジスト液を用いて電極パターンを有するマスクを形成し（ｃ）、電極材料（（ｃ）６）を受光面上に部分的に蒸着させる（ｄ）。そしてレジストマスクを剥離し、電極部分以外に蒸着した電極材料をはがし、受光面上に（ｅ）に示す電極パターンを形成する。そして、受光面とは逆面の全面に、電極材料を形成する（ｆ）からなる工程であり、公知の方法を利用して行うことができる。 An example in the case where a PN junction type crystal solar cell is manufactured by the method for manufacturing a semiconductor device having the antireflection film of the present invention is shown below.
Examples of the manufacturing method include the following mainly four manufacturing steps.
(I) Step of forming an N-type impurity diffusion layer on a semiconductor substrate implanted with P-type dopant (II) Step of forming an electrode on the impurity diffusion layer (III) Forming an antireflection film on the light receiving surface Process (IV) Dicing process Specifically,
The step of forming the N-type impurity diffusion layer on the semiconductor substrate into which the P-type dopant of (I) is implanted includes a P-type substrate ((a) as shown in FIGS. 3A and 3B). An impurity such as phosphorus is thermally diffused on the surface of 2) to form an N-type impurity diffusion layer, and a P / N junction as shown in (a) is formed. And it is the (b) process which removes the impurity diffusion layer which exists in a light-receiving surface ((b) 4) and an opposite surface by an etching, It can carry out using a well-known method.
As the semiconductor substrate (2), not only silicon but also compounds such as germanium, GaAs and InGaAs can be used, and the thickness is not particularly limited.
The step (II) of forming an electrode in the impurity diffusion layer is a light receiving surface ((c) formed with the impurity diffusion layer as shown in FIGS. 3 (c), (d), (e) and (f). 4) A negative photoresist solution is used to form a mask having an electrode pattern (c), and an electrode material ((c) 6) is partially deposited on the light receiving surface (d). Then, the resist mask is peeled off, the electrode material deposited other than the electrode portion is peeled off, and the electrode pattern shown in (e) is formed on the light receiving surface. And it is the process which consists of (f) which forms an electrode material in the whole surface on the opposite surface to a light-receiving surface, and it can carry out using a well-known method.

電極材料には、銀、アルミニウム、銅、金、亜鉛、スズ、チタン、タングステン、タンタルニウム、モリブデンといった金属、ZnO、SnO2、ITOなどの透明導電性酸化物、更にこれらを積層させたものが含まれる。
電極形成方法については、公知の方法、例えば蒸着法を始め、スクリーン印刷法、スパッタリング法、CVD法、レーザー堆積法などいずれの方法を用いても良い。
そして、裏面側にはほぼ全面に銀またはアルミニウムからなる電極を形成する方法は、具体的には、電極材料である銀を受光面4側に部分的に蒸着して厚さ約5μmの表面電極6を成膜し（図３（ｄ））、その後電極パタ−ン5を剥離し不要な電極材料を取り除く(図3（ｅ）)。次にパタ―ニングしたシリコン基板2の裏側に前面に電極材料である銀あるいはアルミニウムを約５μm成膜する
またパタ−ニング及び電極形成を同時に行うことができるスクリーン印刷法を用いることで電極を形成することもできる。電極材料の厚さについては特に限定されるものではない。 Electrode materials include metals such as silver, aluminum, copper, gold, zinc, tin, titanium, tungsten, tantalum, and molybdenum, transparent conductive oxides such as ZnO, SnO 2 , and ITO, and a laminate of these. included.
As the electrode formation method, any known method such as a vapor deposition method, a screen printing method, a sputtering method, a CVD method, or a laser deposition method may be used.
The method of forming an electrode made of silver or aluminum almost entirely on the back side is specifically a surface electrode having a thickness of about 5 μm by partially depositing silver as an electrode material on the light receiving surface 4 side. 6 is formed (FIG. 3D), and then the electrode pattern 5 is peeled off to remove unnecessary electrode material (FIG. 3E). Next, about 5 μm of silver or aluminum as an electrode material is formed on the front side of the patterned silicon substrate 2 on the front side. Also, an electrode is formed by using a screen printing method capable of simultaneously performing patterning and electrode formation. You can also The thickness of the electrode material is not particularly limited.

（III）受光面上に反射防止膜を形成する工程は、上記で示したような工程である。
その一例として、原料ガスとしてＳｉＨ4（シラン）ガスとＮＨ3(アンモニア)ガスを用い、大きさ１０００×１５００ｍｍの基板間距離１０ｃｍの対向型平行平板電極に、周波数２５０ｋＨｚのＲＦ交流電圧を印加させてグロー放電を発生させ、ＮＨ3の流量を１０００[ｓｃｃｍ]としたままで、ＳｉＨ4の初期流量を順次下げていくことにより、屈折率が半導体素子の表面から反射防止膜の受光面に向かって低くなる反射防止膜を半導体素子上に形成することができる。
具体的には、基板温度が４００℃の場合に、ＮＨ3の流量を１０００[sccm]としたままで、ＳｉＨ4の初期流量を４２０[ｓｃｃｍ]とし、ＳｉＨ4の流量だけを順次３６０、３２０、２４０[ｓｃｃｍ]と下げていくことにより、屈折率が半導体素子の表面から反射防止膜の受光面に向かって２．３、２．２、２．１、２．０へと低くなる窒化ケイ素からなる反射防止膜を半導体素子上に形成することができる。 (III) The step of forming the antireflection film on the light receiving surface is a step as described above.
As an example, SiH 4 (silane) gas and NH 3 (ammonia) gas are used as source gases, and an RF AC voltage with a frequency of 250 kHz is applied to an opposing parallel plate electrode having a size of 1000 × 1500 mm and a substrate distance of 10 cm. Glow discharge is generated, and the initial flow rate of SiH 4 is sequentially decreased while keeping the NH 3 flow rate at 1000 [sccm], so that the refractive index is directed from the surface of the semiconductor element to the light receiving surface of the antireflection film. Thus, an antireflection film can be formed on the semiconductor element.
Specifically, when the substrate temperature is 400 ° C., the flow rate of NH 3 is kept at 1000 [sccm], the initial flow rate of SiH 4 is set to 420 [sccm], and only the flow rate of SiH 4 is sequentially transferred to 360, 320. , 240 [sccm], the refractive index decreases to 2.3, 2.2, 2.1, 2.0 from the surface of the semiconductor element toward the light receiving surface of the antireflection film. An antireflective film made of can be formed on the semiconductor element.

そして、個々の太陽電池を切り出す（IV）のダイシング工程を行い太陽電池を製造する。   Then, a solar cell is manufactured by performing the dicing step (IV) of cutting out each individual solar cell.

本製造方法を用いて太陽電池を製造した場合、太陽電池の短絡電流値の向上による変換効率を上昇させ、さらに受光素子の透過光増大による感度の上昇をもたらすことができた。さらに本発明の製造方法を用いてレーザーやＬＥＤなどを製造した場合、発光素子の輝度を向上させることができる。   When a solar cell was manufactured using this manufacturing method, the conversion efficiency due to the improvement of the short-circuit current value of the solar cell was increased, and the sensitivity was increased due to an increase in the transmitted light of the light receiving element. Furthermore, when a laser, LED, or the like is manufactured using the manufacturing method of the present invention, the luminance of the light emitting element can be improved.

本願発明の製造方法で得られる半導体層地の断面図の概略図。Schematic of sectional drawing of the semiconductor layer ground obtained with the manufacturing method of this invention. 多層反射防止膜を有する従来の半導体装置の概略図。Schematic of the conventional semiconductor device which has a multilayer antireflection film. 本願発明の製造方法を用いたＰＮ接合型結晶シリコン太陽電池セルの製造工程。The manufacturing process of the PN junction type crystalline silicon solar cell using the manufacturing method of this invention. プラズマＣＶＤ法を用いた窒化ケイ素膜の屈折率と、原料ガス（ＮＨ3／ＳｉＨ4）流量比との関係を示した図。Shows a refractive index of the silicon nitride film using the plasma CVD method, the relationship between the raw material gas (NH 3 / SiH 4) flow rate ratio. Applied Surface Science 113/4 1997 p610-613に記載されているアンモニアプラズマ処理によるＸＰＳ（Ｘ線分光分析）の測定結果を示した図。The figure which showed the measurement result of XPS (X-ray spectroscopic analysis) by the ammonia plasma process described in Applied Surface Science 113/4 1997 p610-613.

符号の説明Explanation of symbols

１：太陽電池セル本体
２：半導体基板
３：不純物拡散層
４：受光面
５：電極パターン
６：表面電極
７：裏面電極
８：反射防止膜 1: Solar cell body 2: Semiconductor substrate 3: Impurity diffusion layer 4: Light receiving surface 5: Electrode pattern 6: Front electrode 7: Back electrode 8: Antireflection film

Claims (7)

プラズマＣＶＤ法により、半導体素子上に、原料ガスの組成比を変化させながら、膜厚方向で屈折率が変化する反射防止膜を形成することを特徴とする半導体装置の製造方法。 A method of manufacturing a semiconductor device, comprising: forming an antireflection film having a refractive index changing in a film thickness direction while changing a composition ratio of a source gas on a semiconductor element by a plasma CVD method. 原料ガスが少なくとも２成分系であり、一方の原料ガスの流量を固定して、他方の原料ガスの流量を変化させることで、原料ガスの組成比を変化させる請求項１に記載の半導体装置の製造方法。 2. The semiconductor device according to claim 1, wherein the source gas is at least a two-component system, and the composition ratio of the source gas is changed by fixing the flow rate of one source gas and changing the flow rate of the other source gas. Production method. 反射防止膜の屈折率が、半導体素子の表面から反射防止膜の受光面または発光面に向かって低くなるように製造する請求項1または２に記載の半導体素子の製造方法。 3. The method of manufacturing a semiconductor device according to claim 1, wherein the refractive index of the antireflection film is manufactured so as to decrease from the surface of the semiconductor element toward the light receiving surface or the light emitting surface of the antireflection film. 反射防止膜の膜厚が、光の入射または放射設計波長λに対し、λ／４[nm]に相当するように製造する請求項1〜３のいずれか１つに記載の半導体装置の製造方法。 4. The method of manufacturing a semiconductor device according to claim 1, wherein the antireflection film is manufactured so that a film thickness corresponds to λ / 4 [nm] with respect to a light incident or radiation design wavelength λ. . 反射防止膜が、窒化ケイ素化合物、酸化ケイ素化合物、酸窒化ケイ素化合物、酸化チタン化合物、酸化アルミニウム化合物、フッ化マグネシウム、酸化タンタル、硫化亜鉛、酸化セリウムおよびフッ化セリウムの少なくとも1つを含む請求項１〜４のいずれか１つに記載の半導体素子の製造方法。 The antireflection film contains at least one of a silicon nitride compound, a silicon oxide compound, a silicon oxynitride compound, a titanium oxide compound, an aluminum oxide compound, magnesium fluoride, tantalum oxide, zinc sulfide, cerium oxide, and cerium fluoride. The manufacturing method of the semiconductor element as described in any one of 1-4. 反射防止膜の表面をプラズマ処理することを特徴とする請求項１〜５のいずれか１つに記載の半導体装置の製造方法。 6. The method for manufacturing a semiconductor device according to claim 1, wherein the surface of the antireflection film is subjected to plasma treatment. 半導体装置が太陽電池である請求項１〜６のいずれか１つに記載の半導体装置の製造方法。 The method for manufacturing a semiconductor device according to claim 1, wherein the semiconductor device is a solar battery.
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