JP2013149644A - Transparent conductive film composition for solar cell and transparent conductive film - Google Patents
Transparent conductive film composition for solar cell and transparent conductive film Download PDFInfo
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Abstract
Description
本発明は、透明導電膜用組成物、および透明導電膜に関する。より詳しくは、太陽電池の透明導電膜用組成物、および透明導電膜に関する。 The present invention relates to a transparent conductive film composition and a transparent conductive film. In more detail, it is related with the composition for transparent conductive films of a solar cell, and a transparent conductive film.
現在、環境保護の立場から、クリーンエネルギーの研究開発、実用化が進められており、太陽電池は、エネルギー源である太陽光が無尽蔵であり、無公害であること等から注目されている。従来、太陽電池には、単結晶シリコンや多結晶シリコンのバルク太陽電池が用いられてきたが、バルク太陽電池は、製造コストが高く、生産性も低いことから、なるべくシリコン量を節約した太陽電池の開発が急がれている。 Currently, clean energy is being researched, developed and put into practical use from the standpoint of environmental protection, and solar cells are attracting attention because of the inexhaustible and non-polluting nature of sunlight as an energy source. Conventionally, single-crystal silicon or polycrystalline silicon bulk solar cells have been used for solar cells. However, since the bulk solar cells are high in production cost and low in productivity, the solar cells save as much silicon as possible. The development of is urgent.
そこで、厚さが、例えば、０．３〜２μｍのアモルファスシリコン等の半導体を用いた薄膜太陽電池の開発が、精力的に行われている。この薄膜太陽電池は、ガラス基板や耐熱性プラスチック基板上に、光電変換に必要な量の半導体層を形成する構造のため、薄型で軽量、低コスト、大面積化が容易である等の利点がある。 Therefore, development of a thin film solar cell using a semiconductor such as amorphous silicon having a thickness of, for example, 0.3 to 2 μm has been vigorously performed. This thin-film solar cell has the advantage that it is thin, lightweight, low-cost, and easy to increase in area because it has a structure in which a semiconductor layer of an amount necessary for photoelectric conversion is formed on a glass substrate or a heat-resistant plastic substrate. is there.
薄膜太陽電池には、スーパーストレート構造とサブストレート構造があり、スーパーストレート型構造は、透光性基板側から太陽光を入射させるため、通常、基板−透明電極−光電変換層−裏面電極の順に形成される構造をとる。一方、サブストレート構造は、透明電極側から太陽光を入射させるため、通常、基板−裏面電極−光電変換層−透明電極の順に形成される構造をとる。 A thin film solar cell has a superstrate structure and a substrate structure, and the superstrate type structure allows sunlight to enter from the translucent substrate side. Therefore, the substrate-transparent electrode-photoelectric conversion layer-rear electrode is usually used in this order. Take the structure to be formed. On the other hand, the substrate structure usually has a structure in which a substrate, a back electrode, a photoelectric conversion layer, and a transparent electrode are formed in order in order to allow sunlight to enter from the transparent electrode side.
この薄膜太陽電池では、従来、透明電極や反射膜は、スパッタ等の真空成膜法で形成されていたが、一般に、真空成膜法では、大型の真空成膜装置の導入、維持、運転に、多大なコストが必要である。この点を改良するため、裏面電極を構成する透明導電膜と導電性反射膜を、透明導電膜用組成物と導電性反射膜用組成物を用いて、より安価な製造方法である湿式塗工法で形成する技術が、開示されている（特許文献１）。 Conventionally, in this thin film solar cell, the transparent electrode and the reflective film are formed by a vacuum film formation method such as sputtering, but in general, the vacuum film formation method is used for introduction, maintenance, and operation of a large-scale vacuum film formation apparatus. Enormous costs are required. In order to improve this point, a wet coating method that is a cheaper manufacturing method using a transparent conductive film composition and a conductive reflective film, and a transparent conductive film and a conductive reflective film constituting the back electrode. A technique for forming the film is disclosed (Patent Document 1).
上記の湿式塗工法により製造される透明導電膜は、低屈折率であり、透明導電膜として十分な特性を有していたが、なお、一層改良される余地が残されていた。したがって、本発明は、上記の湿式塗工法により製造される透明導電膜を、さらに改良することを目的とする。本発明者らは、透明導電膜用組成物を改良し、湿式塗工法で用いられる透明導電膜を、上記の湿式塗工法により製造される透明導電膜より低屈折率化し、光電変換層の屈折率との差を大きくすることにより、透明導電膜−光電変換層界面での反射光が増加し、この増加した光電変換層への戻り光により、薄膜太陽電池の発電効率を向上させることができることを見出した。同様の手法は、サブストレート型太陽電池やバルクシリコン太陽電池にも適用可能である。 The transparent conductive film produced by the above wet coating method has a low refractive index and has sufficient characteristics as a transparent conductive film, but there is still room for further improvement. Therefore, an object of this invention is to further improve the transparent conductive film manufactured by said wet coating method. The present inventors improved the composition for transparent conductive film, and made the transparent conductive film used in the wet coating method have a lower refractive index than that of the transparent conductive film produced by the above wet coating method, and refracted the photoelectric conversion layer. By increasing the difference from the rate, the reflected light at the transparent conductive film-photoelectric conversion layer interface increases, and the increased return light to the photoelectric conversion layer can improve the power generation efficiency of the thin-film solar cell. I found. A similar technique can be applied to a substrate type solar cell and a bulk silicon solar cell.
本発明は、以下に示す構成によって上記課題を解決した太陽電池の透明導電膜用組成物、および透明導電膜に関する。
〔１〕導電性酸化物粒子と、リン酸と、シリコンアルコキシドまたはシリコンアルコキシドの加水分解物もしくは脱水物と、を含み、
リンを、シリコン：１００質量部に対して、０．８０〜１１．７２質量部含むことを特徴とする、太陽電池の透明導電膜用組成物。
〔２〕上記〔１〕記載の透明導電膜用組成物を用いる、太陽電池の透明導電膜の製造方法。
〔３〕上記〔２〕記載の透明導電膜の製造方法で製造される、太陽電池の透明導電膜。
〔４〕上記〔３〕記載の透明導電膜を含む、太陽電池。
The present invention relates to a composition for a transparent conductive film of a solar cell and the transparent conductive film, which have solved the above problems with the following configuration.
[1] conductive oxide particles, phosphoric acid, and silicon alkoxide or hydrolyzate or dehydration product of silicon alkoxide,
A composition for a transparent conductive film of a solar cell, comprising 0.80 to 11.72 parts by mass of phosphorus with respect to 100 parts by mass of silicon.
[2] A method for producing a transparent conductive film for a solar cell, using the composition for transparent conductive film according to [1].
[3] A transparent conductive film for a solar cell, produced by the method for producing a transparent conductive film according to [2].
[4] A solar cell comprising the transparent conductive film according to [3].
本発明〔１〕の透明導電膜用組成物は、湿式塗工法で光電変換層上に塗布、焼成することが可能であり、透明導電膜用組成物に含まれるリン酸は、透明導電膜用組成物から形成される透明導電膜の屈折率を低下させることができる。すなわち、透明導電膜の屈折率と、光電変換層の屈折率の差が大きくなり、透明導電膜−光電変換層界面での反射光が増加し、この増加した光電変換層への戻り光で、太陽電池の発電効率を向上させることが可能な透明導電膜を簡便に得ることができる。さらに、リン酸は、シリコンアルコキシドの加水分解反応の触媒としても作用し、従来、シリコンアルコキシドの加水分解反応の触媒として使用されている塩酸等の強酸とは異なり、湿式塗工法により塗布される層へのダメージを抑制することができる。 The composition for transparent conductive film of the present invention [1] can be applied and baked on the photoelectric conversion layer by a wet coating method, and the phosphoric acid contained in the composition for transparent conductive film is used for the transparent conductive film. The refractive index of the transparent conductive film formed from the composition can be lowered. That is, the difference between the refractive index of the transparent conductive film and the refractive index of the photoelectric conversion layer increases, the reflected light at the transparent conductive film-photoelectric conversion layer interface increases, and the increased return light to the photoelectric conversion layer, A transparent conductive film capable of improving the power generation efficiency of the solar cell can be easily obtained. Furthermore, phosphoric acid also acts as a catalyst for the hydrolysis reaction of silicon alkoxide, and is different from a strong acid such as hydrochloric acid conventionally used as a catalyst for the hydrolysis reaction of silicon alkoxide, and is a layer applied by a wet coating method. Damage to the can be suppressed.
本発明〔２〕によれば、高額な真空設備を用いずに、低屈折率の透明導電膜の形成が可能であるので、発電効率の高い薄膜太陽電池を簡便に、低コストで製造することができる。 According to the present invention [2], it is possible to form a transparent conductive film having a low refractive index without using expensive vacuum equipment, so that a thin-film solar cell having high power generation efficiency can be manufactured simply and at low cost. Can do.
本発明〔３〕によれば、低屈折率の透明導電膜を提供することができるので、透明導電膜−光電変換層界面での反射光が増加し、この増加した光電変換層への戻り光により、発電効率が向上した太陽電池を簡便に得ることができる。また、本発明〔４〕によれば、発電効率が向上した太陽電池を提供することができる。 According to the present invention [3], since a transparent conductive film having a low refractive index can be provided, the reflected light at the transparent conductive film-photoelectric conversion layer interface increases, and the increased return light to the photoelectric conversion layer. Thus, a solar cell with improved power generation efficiency can be easily obtained. Moreover, according to the present invention [4], a solar cell with improved power generation efficiency can be provided.
以下、本発明を実施形態に基づいて具体的に説明する。なお、％は特に示さない限り、また数値固有の場合を除いて質量％である。 Hereinafter, the present invention will be specifically described based on embodiments. Unless otherwise indicated, “%” means “% by mass” unless otherwise specified.
〔太陽電池の透明導電膜用組成物〕
本発明の太陽電池の透明導電膜用組成物（以下、「透明導電膜用組成物」という）は、導電性酸化物粒子と、リン酸と、シリコンアルコキシドと、を含み、
リンを、シリコン：１００質量部に対して、０．８０〜１１．７２質量部含むことを特徴とする。この透明導電膜用組成物は、薄膜太陽電池に適しており、特にスーパーストレート型薄膜太陽電池に適している。
[Composition for transparent conductive film of solar cell]
The composition for transparent conductive film of the solar cell of the present invention (hereinafter referred to as “transparent conductive film composition”) includes conductive oxide particles, phosphoric acid, and silicon alkoxide,
It is characterized by containing 0.80 to 11.72 parts by mass of phosphorus with respect to 100 parts by mass of silicon. This composition for transparent conductive films is suitable for thin film solar cells, and particularly suitable for super straight type thin film solar cells.
リン酸は、透明導電膜用組成物から形成される透明導電膜の屈折率を低下させることができる。すなわち、透明導電膜の屈折率と、光電変換層の屈折率の差が大きくなり、透明導電膜−光電変換層界面での反射光が増加し、この増加した光電変換層への戻り光で、太陽電池の発電効率を向上させることが可能な透明導電膜を簡便に得ることができる。さらに、リン酸は、シリコンアルコキシドの加水分解反応の触媒としても作用し、従来、シリコンアルコキシドの加水分解反応の触媒として使用されている塩酸等の強酸とは異なり、湿式塗工法により塗布される層へのダメージを抑制することができる。また、リン酸は、仮にＰが、下地の光電変換層（ｎ型）に拡散してもドナーとして働くため、光電変換層の変換効率が低くならず、むしろ変換効率が高くなり得る。 Phosphoric acid can reduce the refractive index of the transparent conductive film formed from the composition for transparent conductive film. That is, the difference between the refractive index of the transparent conductive film and the refractive index of the photoelectric conversion layer increases, the reflected light at the transparent conductive film-photoelectric conversion layer interface increases, and the increased return light to the photoelectric conversion layer, A transparent conductive film capable of improving the power generation efficiency of the solar cell can be easily obtained. Furthermore, phosphoric acid also acts as a catalyst for the hydrolysis reaction of silicon alkoxide, and is different from a strong acid such as hydrochloric acid conventionally used as a catalyst for the hydrolysis reaction of silicon alkoxide, and is a layer applied by a wet coating method. Damage to the can be suppressed. In addition, phosphoric acid acts as a donor even if P diffuses into the underlying photoelectric conversion layer (n-type), so that the conversion efficiency of the photoelectric conversion layer is not lowered, but rather the conversion efficiency can be increased.
リン酸としては、オルトリン酸（Ｈ３ＰＯ４）、ピロリン酸（Ｈ４Ｐ２Ｏ７）等が挙げられ、加水分解反応の反応速度、入手し易さの観点から、オルトリン酸が好ましい。リンの含有量は、シリコン：１００質量部に対して、０．８０〜１１．７２質量部であり、リンの含有量が、０．８０質量部未満では、透明導電膜の屈折率が十分に低下せず、また、シリコンアルコキシドの加水分解反応速度が遅くなってしまう。一方、リンの含有量が、１１．７２質量部を超えると、ゲル化してしまう。ここで、リン酸としてオルトリン酸を用いる場合には、リンの含有量は、シリコン：１００質量部に対して、２．３４〜１１．７２質量部であると好ましい。なお、リン酸として、市販されている８５％リン酸を用い、シリコンアルコキシドとしてテトラエトキシシランを用いる場合には、８５％リン酸の含有量は、テトラエトキシシラン：１００質量部に対して、０．４〜５．９質量部である。ここで、リンとシリコンの定量分析は、吸光光度法により行う。 Examples of phosphoric acid include orthophosphoric acid (H 3 PO 4 ) and pyrophosphoric acid (H 4 P 2 O 7 ). Orthophosphoric acid is preferred from the viewpoint of the reaction rate of the hydrolysis reaction and availability. The phosphorus content is 0.80 to 11.72 parts by mass with respect to 100 parts by mass of silicon. When the phosphorus content is less than 0.80 parts by mass, the refractive index of the transparent conductive film is sufficiently high. It does not decrease, and the hydrolysis reaction rate of silicon alkoxide becomes slow. On the other hand, if the phosphorus content exceeds 11.72 parts by mass, gelation occurs. Here, when orthophosphoric acid is used as phosphoric acid, the content of phosphorus is preferably 2.34 to 11.72 parts by mass with respect to 100 parts by mass of silicon. In addition, when using 85% phosphoric acid marketed as phosphoric acid and using tetraethoxysilane as silicon alkoxide, the content of 85% phosphoric acid is 0 with respect to 100 parts by mass of tetraethoxysilane. .4 to 5.9 parts by mass. Here, quantitative analysis of phosphorus and silicon is performed by absorptiometry.
シリコンアルコキシドまたはシリコンアルコキシドの加水分解物もしくは脱水物は、透明導電膜中でバインダーとして作用する。ここで、シリコンアルコキシドの加水分解物と脱水物について、シリコンアルコキシドがテトラエトキシシランの場合について説明する。テトラエトキシシランの加水分解物は、例えば、反応式（１）：
Ｓｉ（ＯＣ２Ｈ５）４＋４Ｈ２Ｏ →Ｓｉ（ＯＨ）４＋４Ｃ２Ｈ５ＯＨ （１）
により生成するＳｉ（ＯＨ）４等である。また、テトラエトキシシランの脱水物は、上記加水分解物の脱水物で、例えば、反応式（２）：
Ｓｉ（ＯＨ）４ → ＳｉＯ（ＯＨ）２＋Ｈ２Ｏ （２）
により生成するＳｉＯ（ＯＨ）２等であり、この脱水物は、焼成後には、例えば、反応式（３）：
ＳｉＯ（ＯＨ）２ → ＳｉＯ２＋Ｈ２Ｏ （３）
のような反応により、ＳｉＯ２となる。このようにして形成されたＳｉＯ２は低屈折率であり、透明導電膜を低屈折率にする。
Silicon alkoxide or a hydrolyzate or dehydrated product of silicon alkoxide acts as a binder in the transparent conductive film. Here, the hydrolyzate and dehydrated product of silicon alkoxide will be described in the case where the silicon alkoxide is tetraethoxysilane. Examples of the hydrolyzate of tetraethoxysilane include reaction formula (1):
Si (OC 2 H 5 ) 4 + 4H 2 O → Si (OH) 4 + 4C 2 H 5 OH (1)
Si (OH) 4 produced by the above. Further, the dehydrated product of tetraethoxysilane is a dehydrated product of the above hydrolyzate, for example, reaction formula (2):
Si (OH) 4 → SiO (OH) 2 + H 2 O (2)
SiO (OH) 2 or the like produced by the above, and this dehydrated product is, for example, reaction formula (3) after firing:
SiO (OH) 2 → SiO 2 + H 2 O (3)
By such a reaction, the SiO 2. The SiO 2 formed in this way has a low refractive index, and makes the transparent conductive film have a low refractive index.
シリコンアルコキシドとしては、テトラメトキシシラン、テトラエトキシシラン、テトラプロポキシシラン等が挙げられ、加水分解反応速度の観点からテトラエトキシシランが好ましい。シリコンアルコキシドの含有量は、導電性酸化物粒子、リン酸およびシリコンアルコキシドの合計：１００質量部に対して、５〜５０質量部であると好ましく、１０〜３０質量部であると、より好ましい。なお、シリコンアルコキシドの加水分解反応には、水が必要であり、水の含有量は、透明導電膜用組成物の焼成による硬化時に、重合度が高い網目構造をとったシリコンアルコキシドの加水分解溶液であると、収縮する際にかかる応力が導電性酸化物粒子同士のコンタクトを補助する形になる、と考えられるため、シリコンアルコキシド：１００質量部に対して、水が１０〜１２０質量部であると好ましい。 Examples of the silicon alkoxide include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and the like, and tetraethoxysilane is preferable from the viewpoint of the hydrolysis reaction rate. The content of silicon alkoxide is preferably 5 to 50 parts by mass and more preferably 10 to 30 parts by mass with respect to 100 parts by mass of the total of conductive oxide particles, phosphoric acid and silicon alkoxide. In addition, water is required for the hydrolysis reaction of silicon alkoxide, and the content of water is a hydrolyzed solution of silicon alkoxide having a network structure with a high degree of polymerization when the composition for transparent conductive film is cured by firing. In this case, since it is considered that the stress applied when shrinking assists the contact between the conductive oxide particles, the amount of water is 10 to 120 parts by mass with respect to 100 parts by mass of silicon alkoxide. And preferred.
導電性酸化物粒子としては、インジウム錫酸化物（ＩＴＯ）、アンチモンドープ酸化物（ＡＴＯ）や、Ａｌ、Ｉｎ、Ｇａ、Ｓｎ等をドープした酸化亜鉛等の粒子が挙げられ、インジウム錫酸化物、アンチモンドープ酸化物、ＡｌまたはＳｎをドープした酸化亜鉛（ＡＺＯまたはＴＺＯ）が好ましい。また、導電性酸化物微粒子の平均粒径は、分散媒中で安定性を保つため、１０〜１００ｎｍの範囲内であることが好ましく、２５〜５０ｎｍの範囲内であると、より好ましい。ここで、平均粒径は、ＱＵＡＮＴＡＣＨＲＯＭＥ ＡＵＴＯＳＯＲＢ−１による比表面測定によるＢＥＴ法を用いて測定する。 Examples of the conductive oxide particles include particles of indium tin oxide (ITO), antimony-doped oxide (ATO), zinc oxide doped with Al, In, Ga, Sn, etc., indium tin oxide, Antimony-doped oxide, zinc oxide doped with Al or Sn (AZO or TZO) is preferred. Moreover, in order to maintain stability in a dispersion medium, the average particle diameter of the conductive oxide fine particles is preferably within a range of 10 to 100 nm, and more preferably within a range of 25 to 50 nm. Here, an average particle diameter is measured using the BET method by the specific surface measurement by QUANTACHROME AUTOSORB-1.
透明導電膜用組成物は、成膜を良好にするために、分散媒を含むと好ましい。分散媒としては、水；メタノール、エタノール、イソプロピルアルコール、ブタノール等のアルコール類；アセトン、メチルエチルケトン、シクロヘキサノン、イソホロン等のケトン類；トルエン、キシレン、ヘキサン、シクロヘキサン等の炭化水素類；Ｎ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミド等のアミド類；ジメチルスルホキシド等のスルホキシド類やエチレングリコール等のグリコール類；エチルセロソルブ等のグリコールエーテル類等が挙げられる。分散媒の含有量は、良好な成膜性を得るために、透明導電膜用組成物：１００質量部に対して、６５〜９９質量部であると好ましい。 The composition for transparent conductive film preferably contains a dispersion medium in order to improve film formation. As a dispersion medium, water; alcohols such as methanol, ethanol, isopropyl alcohol and butanol; ketones such as acetone, methyl ethyl ketone, cyclohexanone and isophorone; hydrocarbons such as toluene, xylene, hexane and cyclohexane; N, N-dimethyl Examples include amides such as formamide and N, N-dimethylacetamide; sulfoxides such as dimethyl sulfoxide; glycols such as ethylene glycol; glycol ethers such as ethyl cellosolve and the like. In order to obtain good film formability, the content of the dispersion medium is preferably 65 to 99 parts by mass with respect to 100 parts by mass of the transparent conductive film composition.
透明導電膜用組成物は、本発明の本発明の目的を損なわない範囲で、さらに必要に応じ、カップリング剤、低抵抗化剤、水溶性セルロース誘導体、酸化防止剤、レベリング剤、揺変剤、フィラー、応力緩和剤、導電性ポリマー、その他の添加剤等を配合することができる。 The composition for transparent conductive film is a coupling agent, a low resistance agent, a water-soluble cellulose derivative, an antioxidant, a leveling agent, a thixotropic agent as necessary, as long as the object of the present invention is not impaired. , Fillers, stress relaxation agents, conductive polymers, other additives, and the like can be blended.
透明導電膜用組成物は、所望の成分を、常法により、ペイントシェーカー、ボールミル、サンドミル、セントリミル、三本ロール等によって混合し、導電性酸化物粒子、球状コロイダルシリカ粒子等を分散させ、製造することができる。無論、通常の攪拌操作によって製造することもできる。 A composition for transparent conductive film is produced by mixing desired components with a paint shaker, a ball mill, a sand mill, a centrimill, a triple roll, etc., and dispersing conductive oxide particles, spherical colloidal silica particles, etc., in a conventional manner. can do. Of course, it can also be produced by a normal stirring operation.
〔太陽電池の透明導電膜〕
本発明の太陽電池の透明導電膜（以下、透明導電膜という）は、上述の透明導電膜用組成物から製造される。この透明導電膜は、薄膜太陽電池に適しており、特に、スーパーストレート型薄膜太陽電池に適している。
[Transparent conductive film of solar cell]
The transparent conductive film (hereinafter referred to as transparent conductive film) of the solar cell of the present invention is produced from the above-described composition for transparent conductive film. This transparent conductive film is suitable for a thin film solar cell, and particularly suitable for a super straight type thin film solar cell.
図１に、本発明の透明導電膜を用いるスーパーストレート型薄膜太陽電池の断面の模式図を示す。スーパーストレート型薄膜電池１は、基材１０、透明電極層１３、光電変換層１２、透明導電膜１１、導電性反射膜１４の順に備えており、基板１０側から太陽光が入射する。入射した太陽光の多くは、導電性反射膜１４で反射され、光電変換層１２に戻り、変換効率を向上させている。ここで、透明導電膜１１と光電変換層１２の界面でも太陽光の反射は起きており、本発明の透明導電膜用組成物を用いた透明導電膜１１は、屈折率が低いため、透明導電膜１１と光電変換層１２の界面での反射光を増加させ、薄膜太陽電池の発電効率を向上させることができる。また、図２に、本発明の透明導電膜を用いるサブストレート型薄膜太陽電池の断面の模式図を示す。サブストレート型薄膜電池２は、基材２０、導電性反射膜２４、透明導電膜２１、光電変換層２２、透明電極層２３の順に備えており、透明電極層２３側から太陽光が入射する。入射した太陽光の多くは、導電性反射膜２４で反射され、光電変換層２２に戻り、変換効率を向上させている。サブストレート型薄膜電池の場合も、光電変換層２２と透明導電膜２１の界面でも太陽光の反射が起きており、本発明の透明導電膜用組成物を用いた透明導電膜２１は、屈折率が低いため、光電変換層２２と透明導電膜２１の界面での反射光を増加させ、薄膜太陽電池の発電効率を向上させることができる。なお、基板２０にスルーホール２５を形成し、導電性反射膜２４と集電極層２６を電気的に接続すると、薄膜太陽電池から発生した電力を取り出し易く、好ましい。 In FIG. 1, the schematic diagram of the cross section of the super straight type thin film solar cell using the transparent conductive film of this invention is shown. The super straight type thin film battery 1 includes a base material 10, a transparent electrode layer 13, a photoelectric conversion layer 12, a transparent conductive film 11, and a conductive reflective film 14, and sunlight enters from the substrate 10 side. Most of the incident sunlight is reflected by the conductive reflective film 14 and returns to the photoelectric conversion layer 12 to improve the conversion efficiency. Here, sunlight is also reflected at the interface between the transparent conductive film 11 and the photoelectric conversion layer 12, and the transparent conductive film 11 using the composition for transparent conductive film of the present invention has a low refractive index. The reflected light at the interface between the film 11 and the photoelectric conversion layer 12 can be increased, and the power generation efficiency of the thin film solar cell can be improved. Moreover, the schematic diagram of the cross section of the substrate type thin film solar cell using the transparent conductive film of this invention is shown in FIG. The substrate type thin film battery 2 includes a base material 20, a conductive reflective film 24, a transparent conductive film 21, a photoelectric conversion layer 22, and a transparent electrode layer 23 in this order, and sunlight enters from the transparent electrode layer 23 side. Most of the incident sunlight is reflected by the conductive reflective film 24 and returns to the photoelectric conversion layer 22 to improve the conversion efficiency. Also in the case of a substrate type thin film battery, sunlight is reflected also at the interface between the photoelectric conversion layer 22 and the transparent conductive film 21, and the transparent conductive film 21 using the composition for transparent conductive film of the present invention has a refractive index. Therefore, the reflected light at the interface between the photoelectric conversion layer 22 and the transparent conductive film 21 can be increased, and the power generation efficiency of the thin film solar cell can be improved. Note that it is preferable to form a through hole 25 in the substrate 20 and to electrically connect the conductive reflective film 24 and the collector electrode layer 26 because it is easy to extract electric power generated from the thin film solar cell.
〔薄膜太陽電池の透明導電膜の製造方法〕
薄膜太陽電池が、基材、透明電極層、光電変換層、透明導電膜、および導電性反射膜を、この順に備えるスーパーストレート型薄膜太陽電池の場合には、透明導電膜は、基材上の透明電極層に形成された光電変換層上に、上記透明導電膜用組成物を、湿式塗工法により塗布して透明導電塗膜を形成した後、透明導電塗膜を有する基材を焼成して、製造することができる。
[Method for producing transparent conductive film of thin film solar cell]
In the case where the thin film solar cell is a super straight type thin film solar cell including a base material, a transparent electrode layer, a photoelectric conversion layer, a transparent conductive film, and a conductive reflective film in this order, the transparent conductive film is on the base material. On the photoelectric conversion layer formed in the transparent electrode layer, the transparent conductive film composition is applied by a wet coating method to form a transparent conductive film, and then the substrate having the transparent conductive film is baked. Can be manufactured.
まず、基材、透明電極層、光電変換層、透明導電膜、および導電性反射膜、この順に備えるスーパーストレート型薄膜太陽電池の光電変換層上に、上記透明導電膜用組成物を、湿式塗工法により塗布する。ここでの塗布は、焼成後の透明導電膜の厚さが、好ましくは０．０３〜０．５μｍ、より好ましくは０．０５〜０．２μｍの厚さとなるようにする。続いて、この塗膜を、好ましくは温度２０〜１２０℃で、好ましくは１〜３０分間乾燥する。このようにして透明導電塗膜を形成する。ここで、焼成後の透明導電膜の厚さが０．０３〜０．５μｍの範囲となるように透明導電膜用組成物を塗布すると好ましい理由は、焼成後の厚さが０．０３μｍ未満、又は０．５μｍを越えると、透明導電膜−光電変換層界面での増反射効果が十分に得られにくいからである。 First, the composition for transparent conductive film is wet-coated on the photoelectric conversion layer of a superstrate thin-film solar cell provided in this order with a base material, a transparent electrode layer, a photoelectric conversion layer, a transparent conductive film, and a conductive reflective film. Apply by construction method. Application | coating here makes it the thickness of the transparent conductive film after baking become like this. Preferably it is 0.03-0.5 micrometer, More preferably, it is 0.05-0.2 micrometer. Subsequently, this coating film is preferably dried at a temperature of 20 to 120 ° C., preferably for 1 to 30 minutes. In this way, a transparent conductive coating film is formed. Here, the reason why the transparent conductive film composition is preferably applied so that the thickness of the transparent conductive film after firing is in the range of 0.03 to 0.5 μm is that the thickness after firing is less than 0.03 μm, Alternatively, if it exceeds 0.5 μm, it is difficult to sufficiently obtain the effect of increasing reflection at the transparent conductive film-photoelectric conversion layer interface.
上記湿式塗工法は、スプレーコーティング法、ディスペンサーコーティング法、スピンコーティング法、ナイフコーティング法、スリットコーティング法、インクジェットコーティング法、スクリーン印刷法、オフセット印刷法、またはダイコーティング法のいずれかであることが好ましいが、これに限られるものではなく、あらゆる方法を利用できる。 The wet coating method is preferably any one of a spray coating method, a dispenser coating method, a spin coating method, a knife coating method, a slit coating method, an inkjet coating method, a screen printing method, an offset printing method, or a die coating method. However, the present invention is not limited to this, and any method can be used.
最後に、透明導電塗膜を有する基材を、大気中または窒素やアルゴンなどの不活性ガス雰囲気中で、好ましくは、１３０〜４００℃の温度で、好ましくは５〜６０分間保持して焼成する。 Finally, the base material having the transparent conductive coating film is fired in the atmosphere or in an inert gas atmosphere such as nitrogen or argon, preferably at a temperature of 130 to 400 ° C., preferably for 5 to 60 minutes. .
上記基材には、ガラス、セラミックス、もしくはポリエチレン樹脂、ポリエチレンテレフタレート樹脂、エポキシ樹脂等の高分子材料からなる透光性基板のいずれか、またはガラス、セラミックス、高分子材料、およびシリコンからなる群より選ばれた２種類以上の透光性積層体を使用することができる。光電変換層としては、結晶系の単結晶型もしくは多結晶型、アモルファス型、化合物型、または単結晶型もしくは多結晶型とアモルファス型とを組合せたハイブリッド型等が挙げられる。透明電極層には、ＩＴＯ、酸化錫等を使用することができる。導電性反射膜には、Ａｇ等を使用することができる。基材上に、透明電極層、光電変換層を形成する方法は、特に限定されず、真空成膜法等の公知の用法でよい。導電性反射膜は、Ａｇナノ粒子焼結体であると、Ａｇナノ粒子を含む導電性反射膜用組成物を湿式塗工法で塗布した後、焼成することにより形成されることができ、好ましいが、真空成膜法等で形成してもよい。 From the group consisting of glass, ceramics, or a transparent substrate made of a polymer material such as polyethylene resin, polyethylene terephthalate resin, epoxy resin, or the group consisting of glass, ceramics, polymer material, and silicon. Two or more selected light-transmitting laminates can be used. Examples of the photoelectric conversion layer include a crystalline single crystal type or a polycrystalline type, an amorphous type, a compound type, or a hybrid type in which a single crystal type or a combination of a polycrystalline type and an amorphous type is used. ITO, tin oxide or the like can be used for the transparent electrode layer. Ag or the like can be used for the conductive reflective film. The method for forming the transparent electrode layer and the photoelectric conversion layer on the substrate is not particularly limited, and may be a known method such as a vacuum film forming method. The conductive reflective film is preferably an Ag nanoparticle sintered body, which can be formed by applying a composition for a conductive reflective film containing Ag nanoparticles by a wet coating method and then baking the composition. Alternatively, it may be formed by a vacuum film formation method or the like.
次に、薄膜太陽電池が、基材、導電性反射膜、透明導電膜、光電変換層、および透明電極層を、この順に備えるサブストレート型薄膜太陽電池の場合には、透明導電膜は、基材上に、上述の透明導電膜用組成物を、湿式塗工法により塗布して透明導電塗膜を形成した後、透明導電塗膜を有する基材を焼成して、製造することができる。 Next, in the case where the thin film solar cell is a substrate type thin film solar cell including a base material, a conductive reflective film, a transparent conductive film, a photoelectric conversion layer, and a transparent electrode layer in this order, the transparent conductive film On the material, the above-mentioned composition for transparent conductive film is applied by a wet coating method to form a transparent conductive coating film, and then a substrate having the transparent conductive coating film is baked for manufacturing.
基材、導電性反射膜、光電変換層、透明電極層は、スーパーストレート型薄膜太陽電池の場合と同様である。 The substrate, the conductive reflective film, the photoelectric conversion layer, and the transparent electrode layer are the same as in the case of the super straight type thin film solar cell.
以上により、本発明の透明導電膜を形成することができる。このように、透明導電膜の製造に、湿式塗工法を使用することにより、真空蒸着法やスパッタ法などの真空成膜法を用いるプロセスを可能な限り排除できるため、より安価に透明導電膜を製造できる。 As described above, the transparent conductive film of the present invention can be formed. In this way, by using a wet coating method for the production of a transparent conductive film, a process using a vacuum film formation method such as a vacuum deposition method or a sputtering method can be eliminated as much as possible. Can be manufactured.
以下に、実施例により、本発明を詳細に説明するが、本発明はこれらに限定されるものではない。 Hereinafter, the present invention will be described in detail by way of examples, but the present invention is not limited thereto.
〔実施例１〕
まず、ＳｉＯ２結合剤を作製した。５００ｃｍ３のガラス製の４つ口フラスコを用い、１４０ｇのテトラエトキシシラン（シリコン含有量：１８．８７ｇ）と、１４０ｇのエチルアルコールを加え、攪拌しながら、０．５６ｇの８５％リン酸（リン含有量：０．１５ｇ）を、１２０ｇの純水に溶解した溶液を一度に加え、その後５０℃で３時間反応させることにより、ＳｉＯ２結合剤を製造した。
[Example 1]
First, a SiO 2 binder was prepared. Using a 4-cm flask made of glass of 500 cm 3 , 140 g of tetraethoxysilane (silicon content: 18.87 g) and 140 g of ethyl alcohol were added, and 0.56 g of 85% phosphoric acid (phosphorus) was added while stirring. A content of 0.15 g) dissolved in 120 g of pure water was added all at once, and then reacted at 50 ° C. for 3 hours to produce a SiO 2 binder.
次に、表１に示すように、分散媒となるエタノール中に、導電性酸化物粉末として平均粒径：３０ｎｍのＩＴＯ粉末を、導電性酸化物粒子とリン酸とシリコンアルコキシドとを合わせた固形物粒子：１００質量％に対して、７８質量％の比率で、また、バインダーとしてＳｉＯ２結合剤を、シリコンアルコキシドが、導電性酸化物粒子とリン酸とシリコンアルコ+キシドとを合わせた固形物粒子：１００質量％に対して、２１．９３質量％の比率になるように、合計が６０ｇで、混合した。１００ｃｍ３のガラス瓶中に入れ、直径：０．３ｍｍのジルコニアビーズ（ミクロハイカ、昭和シェル石油製）：１００ｇを用いて、ペイントシェーカーで６時間分散することにより、実施例１の透明導電膜用組成物を作製した。 Next, as shown in Table 1, in ethanol as a dispersion medium, an ITO powder having an average particle size of 30 nm as a conductive oxide powder is combined with conductive oxide particles, phosphoric acid, and silicon alkoxide. Solid particles: in a ratio of 78% by mass with respect to 100% by mass, a SiO 2 binder as a binder, a silicon alkoxide, a solid material in which conductive oxide particles, phosphoric acid, and silicon alkoxide are combined. Particles: A total of 60 g was mixed so that the ratio was 21.93% by mass with respect to 100% by mass. The composition for a transparent conductive film of Example 1 was put in a 100 cm 3 glass bottle and dispersed with a paint shaker for 6 hours using 100 g of zirconia beads having a diameter of 0.3 mm (Microhaika, Showa Shell Sekiyu KK). Was made.
〔実施例２〜１２、比較例１〜３〕
表１、表２に示す組成（数値は、質量部を示す）になるようにしたこと以外は、実施例１と同様にして、実施例２〜１２、比較例１〜３の透明導電膜用組成物を作製した。なお、表１、表２の「ＴＥＯＳ」はテトラエトキシシラン、「ＴＭＯＳ」はテトラメトキシシランを表し、比率欄の「導」は導電性酸化物粒子を、「アルコキシド」はシリコンアルコキシドを表す。
[Examples 2 to 12, Comparative Examples 1 to 3]
For transparent conductive films of Examples 2 to 12 and Comparative Examples 1 to 3, in the same manner as in Example 1, except that the compositions shown in Tables 1 and 2 (numerical values indicate parts by mass) were used. A composition was prepared. In Tables 1 and 2, “TEOS” represents tetraethoxysilane, “TMOS” represents tetramethoxysilane, “conduction” in the ratio column represents conductive oxide particles, and “alkoxide” represents silicon alkoxide.
〔透明導電膜用組成物の屈折率評価〕
屈折率評価については、実施例１〜１２、比較例１〜３に示す透明導電膜用組成物について、光学定数が既知のガラス基板に対して、湿式塗工法（ダイコーティング法）により透明電極膜を成膜後、１６０〜２２０℃で２０〜６０分焼成することにより、厚さ：７０〜９５ｎｍの透明導電膜を形成した。その膜に対して、分光エリプソメトリー装置（Ｊ．Ａ．Ｗｏｏｌｌａｍ Ｊａｐａｎ（株）製 Ｍ−２０００）を用いて測定し、透明電極膜部分についてデータを解析し、光学定数を求めた。解析した光学定数から、６３３ｎｍの値を屈折率とした。表１、表２に、これらの結果を示す。
[Evaluation of refractive index of composition for transparent conductive film]
About refractive index evaluation, it is a transparent electrode film by the wet coating method (die coating method) with respect to the glass substrate whose optical constant is known about the composition for transparent conductive films shown in Examples 1-12 and Comparative Examples 1-3. After the film was formed, the transparent conductive film having a thickness of 70 to 95 nm was formed by baking at 160 to 220 ° C. for 20 to 60 minutes. The film was measured using a spectroscopic ellipsometry apparatus (JA Woollam Japan Co., Ltd. M-2000), data was analyzed for the transparent electrode film portion, and the optical constant was determined. From the analyzed optical constant, a value of 633 nm was taken as the refractive index. Tables 1 and 2 show these results.
〔透明導電膜用組成物のスーパーストレート型薄膜太陽電池での評価〕
図１に示すように、まず、一方の主面に厚さ：５０ｎｍのＳｉＯ2層（図示せず）が形成されたガラス基板を基板１０として準備し、このＳｉＯ2層上に表面に凹凸テクスチャを有しかつＦ（フッ素）ドープされた厚さ：８００ｎｍの表面電極層（ＳｎＯ２膜）を、透明電極層１３として形成した。この透明電極層１３にはレーザー加工法を用いてパターニングすることによりアレイ状とするとともに、それらを電気的に相互接続する配線を形成した。次に、透明電極層１３上にプラズマＣＶＤ法を用いて、光電変換層１２を形成した。この光電変換層１２は、この実施例では、基板１０側から順に、ｐ型ａ−Ｓｉ：Ｈ（アモルファスシリコン）、ｉ型ａ−Ｓｉ（アモルファスシリコン）及びｎ型μｃ−Ｓｉ（微結晶シリコン）、からなる膜を積層して得た。上記光電変換層１２を、レーザー加工法を用いてパターニングした。こちらを既に成膜が進んでいるスーパーストレート型薄膜太陽電池セルとして実施例にて示した透明導電膜用組成物評価に利用した。
[Evaluation of composition for transparent conductive film in super straight type thin film solar cell]
As shown in FIG. 1, first, a glass substrate having a SiO 2 layer (not shown) having a thickness of 50 nm formed on one main surface is prepared as a substrate 10, and an uneven texture is formed on the surface of this SiO 2 layer. A surface electrode layer (SnO 2 film) having a thickness of 800 nm and doped with F (fluorine) was formed as the transparent electrode layer 13. The transparent electrode layer 13 was patterned using a laser processing method to form an array, and wirings for electrically connecting them were formed. Next, the photoelectric conversion layer 12 was formed on the transparent electrode layer 13 using a plasma CVD method. In this embodiment, the photoelectric conversion layer 12 is made of p-type a-Si: H (amorphous silicon), i-type a-Si (amorphous silicon) and n-type μc-Si (microcrystalline silicon) in this order from the substrate 10 side. A film made of The photoelectric conversion layer 12 was patterned using a laser processing method. This was utilized for the evaluation of the composition for transparent conductive films shown in Examples as a super straight type thin-film solar cell in which film formation had already progressed.
実施例１〜１２、比較例１〜３に示す透明導電膜用組成物について、既に成膜が進んでいるスーパーストレート型薄膜太陽電池セルに対して、焼成後の厚さが７０〜９５ｎｍとなるように湿式塗工法（ダイコーティング法）で、塗布した後、温度２５〜６０℃の低温で５分間乾燥して、透明導電膜１を形成した。また、表１、表２に、透明導電膜１１の焼成後膜厚を示す。ここで、膜厚は、日立ハイテクノロジーズ製走査型電子顕微鏡（ＳＥＭ、装置名：Ｓ−４３００、ＳＵ−８０００）による断面観察により測定した。 About the composition for transparent conductive films shown in Examples 1-12 and Comparative Examples 1-3, the thickness after baking will be 70-95 nm with respect to the super straight type thin film photovoltaic cell in which film-forming has already progressed. Thus, after apply | coating with the wet coating method (die coating method), it dried for 5 minutes at the low temperature of 25-60 degreeC, and the transparent conductive film 1 was formed. Tables 1 and 2 show the post-baking film thickness of the transparent conductive film 11. Here, the film thickness was measured by cross-sectional observation using a scanning electron microscope (SEM, apparatus names: S-4300, SU-8000) manufactured by Hitachi High-Technologies.
次いで、この透明導電膜１１上に次の方法で調製した導電性反射膜用組成物を、焼成後の厚さが０．０５〜２．０μｍとなるように湿式塗工法で塗布した後、２５〜６０℃の低温で５分間乾燥して、導電性反射膜１４を形成した。次いで、１６０〜２２０℃で２０〜６０分焼成することにより、太陽電池セル上に複合膜を形成した。なお、導電性反射膜用組成物の調製方法は以下のようにした。 Next, the conductive reflective film composition prepared by the following method was applied on the transparent conductive film 11 by a wet coating method so that the thickness after firing was 0.05 to 2.0 μm, and then 25 The conductive reflective film 14 was formed by drying at a low temperature of ˜60 ° C. for 5 minutes. Subsequently, the composite film was formed on the photovoltaic cell by baking at 160-220 degreeC for 20-60 minutes. In addition, the preparation method of the composition for electroconductive reflective films was as follows.
まず、硝酸銀を脱イオン水に溶解して、金属イオン水溶液を調製した。また、クエン酸ナトリウムを脱イオン水に溶解して、濃度が２６重量％のクエン酸ナトリウム水溶液を調製した。このクエン酸ナトリウム水溶液に、３５℃に保持された窒素ガス気流中に粒状の硫酸第１鉄を直接加えて溶解させ、クエン酸イオンと第１鉄イオンを３：２のモル比で含有する還元剤水溶液を調製した。次いで、上記窒素ガス気流を３５℃に保持した状態で、マグネチックスターラー上に置いた還元剤水溶液中に攪拌子を入れ、攪拌子を１００ｒｐｍの回転速度で回転させて、上記還元剤水溶液を攪拌しながら、この還元剤水溶液に上記金属塩水溶液を滴下して合成した。ここで、還元剤水溶液への金属塩水溶液の添加量は、還元剤水溶液の量の１／１０以下になるように、各溶液の濃度を調整することで、室温の金属塩水溶液を滴下しても反応温度が４０℃に保持されるようにした。また、上記還元剤水溶液と金属塩水溶液との混合比は、還元剤として加えられる第１鉄イオンの当量が、金属イオンの当量の３倍となるように調整した。還元剤水溶液への金属塩水溶液の滴下が終了した後、混合液の攪拌をさらに１５分間続けることにより、混合液内部に金属粒子を生じさせ、金属粒子が分散した金属粒子分散液を得た。金属粒子分散液のｐＨは５．５であり、分散液中の金属粒子の化学量論的生成量は、５ｇ／リットルであった。得られた分散液は、室温で放置することにより、分散液中の金属粒子を沈殿させ、沈殿した金属粒子の凝集物をデカンテーションにより分離した。分離した金属凝集物に脱イオン水を加えて分散体とし、限外濾過により脱塩処理した後、さらにメタノールで置換洗浄することにより、金属（銀）の含有量を５０質量％とした。その後、遠心分離機を用い、この遠心分離機の遠心力を調整して、粒径が１００ｎｍを超える比較的大きな銀粒子を分離し、銀ナノ粒子分散液を得た。銀ナノ粒子の平均粒径を、堀場製作所製ＬＢ−５５０による動的光散乱法を用いて測定した結果、平均粒径は、３５ｎｍであった。得られた銀ナノ粒子は、クエン酸ナトリウムの保護剤が化学修飾されていた。 First, silver nitrate was dissolved in deionized water to prepare a metal ion aqueous solution. In addition, sodium citrate was dissolved in deionized water to prepare a sodium citrate aqueous solution having a concentration of 26% by weight. Reduction in which aqueous ferric sulfate is directly added and dissolved in this sodium citrate aqueous solution in a nitrogen gas stream maintained at 35 ° C. to contain citrate ions and ferrous ions in a molar ratio of 3: 2. An aqueous agent solution was prepared. Next, with the nitrogen gas stream maintained at 35 ° C., a stirrer is placed in the reducing agent aqueous solution placed on the magnetic stirrer, and the stirrer is rotated at a rotational speed of 100 rpm to stir the reducing agent aqueous solution. The metal salt aqueous solution was dropped into this reducing agent aqueous solution and synthesized. Here, the amount of the metal salt aqueous solution added to the reducing agent aqueous solution is adjusted so that the concentration of each solution is adjusted to 1/10 or less of the amount of the reducing agent aqueous solution. The reaction temperature was maintained at 40 ° C. The mixing ratio of the reducing agent aqueous solution and the metal salt aqueous solution was adjusted so that the equivalent of ferrous ions added as a reducing agent was three times the equivalent of metal ions. After the addition of the aqueous metal salt solution to the reducing agent aqueous solution was completed, stirring of the mixed solution was continued for an additional 15 minutes to generate metal particles inside the mixed solution to obtain a metal particle dispersion in which the metal particles were dispersed. The pH of the metal particle dispersion was 5.5, and the stoichiometric amount of metal particles in the dispersion was 5 g / liter. The obtained dispersion was allowed to stand at room temperature to precipitate the metal particles in the dispersion, and the aggregates of the precipitated metal particles were separated by decantation. Deionized water was added to the separated metal agglomerated to form a dispersion, subjected to desalting treatment by ultrafiltration, and further subjected to substitution washing with methanol, whereby the metal (silver) content was set to 50% by mass. Thereafter, using a centrifuge, the centrifugal force of the centrifuge was adjusted to separate relatively large silver particles having a particle size exceeding 100 nm, thereby obtaining a silver nanoparticle dispersion. As a result of measuring the average particle diameter of the silver nanoparticles using a dynamic light scattering method using LB-550 manufactured by Horiba, the average particle diameter was 35 nm. The obtained silver nanoparticles were chemically modified with a protective agent for sodium citrate.
次に、得られた金属ナノ粒子１０質量部を、水、エタノールおよびメタノールを含む混合溶液９０質量部に添加混合することにより分散させた。さらに、この分散液に添加物としてポリビニルピロリドンを４質量％と、クエン酸銀を１質量％と、金属ナノ粒子の比率が９５質量％となるように加えることで、導電性反射膜用組成物を得た。 Next, 10 parts by mass of the obtained metal nanoparticles were dispersed by adding to 90 parts by mass of a mixed solution containing water, ethanol and methanol. Further, 4% by mass of polyvinylpyrrolidone, 1% by mass of silver citrate, and 95% by mass of the metal nanoparticles are added to the dispersion as additives, so that the composition for conductive reflective film is added. Got.
次いで、太陽電池セルとして発電効率を評価するにあたり、導電性反射膜１４上に補強膜として、補強膜用組成物をダイコーティング装置により、既に導電性反射膜まで成膜が進んでいる太陽電池セル上に塗布して、補強膜用組成物を焼成後の厚さが３５０ｎｍになるように、真空乾燥により補強膜用塗布膜から溶媒を離脱させた後に、太陽電池セルを熱風乾燥炉内で１８０℃に２０分間保持して、補強膜用塗布膜を熱硬化させ、導電性反射膜用補強膜を得た。なお、補強膜用組成物の調製方法は以下のようにした。 Next, in evaluating the power generation efficiency as a solar battery cell, the solar battery cell in which the composition for the reinforcing film is already formed as a reinforcing film on the conductive reflective film 14 to the conductive reflective film by the die coating apparatus. After the solvent was removed from the coating film for reinforcing film by vacuum drying so that the thickness after baking of the composition for reinforcing film was 350 nm, the solar battery cell was placed in a hot air drying furnace. Holding at 20 ° C. for 20 minutes, the coating film for reinforcing film was thermally cured to obtain a reinforcing film for conductive reflective film. In addition, the preparation method of the composition for reinforcing films was as follows.
まず、導電性酸化物微粒子として平均粒径：２５ｎｍのＩＴＯ粒子を８質量％と、カップリング剤としてジアルキルパイロホスファイト基を有するチタンカップリング剤を２質量％と、分散媒としてエタノール及びブタノールの混合液（質量比９８：２）を９０質量％とを混合し、室温にて８００ｒｐｍの回転速度で１時間攪拌した。次に、この混合物６０ｇを１００ｃｃのガラス瓶中に入れ、直径０．３ｍｍのジルコニアビーズ（昭和シェル石油製：ミクロハイカ）１００ｇを用いてペイントシェーカーで６時間分散することにより、ＩＴＯ粒子の分散液を調製した。ここで、ジアルキルパイロホスファイト基を有するチタンカップリング剤は、化学式（１）： First, 8% by mass of ITO particles having an average particle diameter of 25 nm as conductive oxide fine particles, 2% by mass of titanium coupling agent having a dialkylpyrophosphite group as a coupling agent, and ethanol and butanol as dispersion media. 90% by mass of the mixed liquid (mass ratio 98: 2) was mixed and stirred at room temperature at a rotation speed of 800 rpm for 1 hour. Next, 60 g of this mixture is placed in a 100 cc glass bottle and dispersed in a paint shaker for 6 hours using 100 g of zirconia beads having a diameter of 0.3 mm (manufactured by Showa Shell Sekiyu KK: Microhaika) to prepare a dispersion of ITO particles. did. Here, the titanium coupling agent having a dialkyl pyrophosphite group has the chemical formula (1):
で示される。 Indicated by
また、ＳｉＯ２結合剤１を、５００ｃｍ３のガラス製の４つ口フラスコを用い、１４０ｇのテトラエトキシシランと、１４０ｇのエチルアルコールを加え、攪拌しながら、１．７ｇの６０％硝酸を１２０ｇの純水に溶解した溶液を一度に加え、その後５０℃で３時間反応させることにより、調製した。 In addition, using a 500 cm 3 glass four-necked flask, 140 g of tetraethoxysilane and 140 g of ethyl alcohol were added to the SiO 2 binder 1, and while stirring, 1.7 g of 60% nitric acid was added to 120 g. It prepared by adding the solution melt | dissolved in the pure water at once, and making it react at 50 degreeC after that for 3 hours.
次に、ＩＴＯ粒子の分散液４質量％を、分散媒であるエタノール８６質量％と混合した後、ＳｉＯ２結合剤１を１０質量％でさらに混合し、補強膜用組成物のベース液を得た後、このベース液９５質量％と、添加剤としてフュームドシリカ分散液５質量％とを混合し、超音波振動器により室温にて１０分間分散混合して混合物を全体になじませ、補強膜用組成物である塗液を調製した。 Next, 4% by mass of the dispersion liquid of ITO particles was mixed with 86% by mass of ethanol as a dispersion medium, and then the SiO 2 binder 1 was further mixed at 10% by mass to obtain a base liquid of the composition for reinforcing film. After that, 95% by mass of this base solution and 5% by mass of fumed silica dispersion as an additive are mixed, and dispersed and mixed at room temperature for 10 minutes by an ultrasonic vibrator, and the mixture is thoroughly blended to form a reinforcing membrane. A coating liquid, which is a composition for use, was prepared.
導電性反射膜用補強膜まで形成された太陽電池セルは、光電変換層１２および、その上に成膜した透明導電膜１１、導電性反射膜１４、および導電性反射膜用補強膜を、レーザー加工法を用いてパターニングを実施した。 The solar battery cell formed up to the reinforcing film for the conductive reflective film is obtained by lasering the photoelectric conversion layer 12, the transparent conductive film 11 formed thereon, the conductive reflective film 14, and the conductive reflective film reinforcing film. Patterning was performed using a processing method.
太陽電池セルの評価方法としては、レーザー加工法を用いてパターンニングを実施した加工後の基板にリード線配線を実施し、ＩＶ特性カーブを確認した際の出力特性及び短絡電流である（Ｊｓｃ）の値を、実施例と同様の製造方法にて得た光電変換層を用い、透明導電膜、導電性反射膜、補強膜が全てスパッタ法により形成されたスーパーストレート型太陽電池セルを１００とした際の相対出力評価を行った。表１、表２に、これらの結果を示す。 Solar cell evaluation methods include output characteristics and short-circuit current when lead wiring is performed on a processed substrate that has been patterned using a laser processing method and an IV characteristic curve is confirmed (Jsc) Using a photoelectric conversion layer obtained by the same production method as in the examples, a super straight type solar cell in which a transparent conductive film, a conductive reflective film, and a reinforcing film were all formed by a sputtering method was defined as 100. Relative output evaluation was performed. Tables 1 and 2 show these results.
ここで、全てスパッタ法により形成されたスーパーストレート型太陽電池セルとは、図１に示すように、先ず、一方の主面に厚さ：５０ｎｍのＳｉＯ2層（図示せず）が形成されたガラス基板を基板１０として準備し、このＳｉＯ2層上に表面に凹凸テクスチャを有しかつＦ（フッ素）ドープされた厚さ：８００ｎｍの表面電極層（ＳｎＯ２膜）１３を形成した。この透明電極層１３にはレーザー加工法を用いてパターニングすることによりアレイ状とするとともに、それらを電気的に相互接続する配線を形成した。次に、透明電極層１３上にプラズマＣＶＤ法を用いて、光電変換層１２を形成した。この光電変換層１２は、この実施例では、基板１０側から順に、ｐ型ａ−Ｓｉ：Ｈ（アモルファスシリコン、厚さ：４０ｎｍ）、ｉ型ａ−Ｓｉ（アモルファスシリコン、厚さ：２００ｎｍ）及びｎ型μｃ−Ｓｉ（微結晶シリコン、厚さ：４０ｎｍ）、からなる膜を積層して得た。上記光電変換層１２を、レーザー加工法を用いてパターニングした後、マグネトロンインライン式スパッタリング装置を用いて、光電変換層１２上に、厚さ：８０ｎｍの透明導電膜（ＺｎＯ層）１１及び厚さ：２００ｎｍの導電性反射膜（銀電極層）１４を順次形成したものである。 Here, as shown in FIG. 1, a super straight type solar battery cell formed entirely by sputtering is first formed with a SiO 2 layer (not shown) having a thickness of 50 nm on one main surface. A glass substrate was prepared as the substrate 10, and a surface electrode layer (SnO 2 film) 13 having an uneven texture on the surface and F (fluorine) -doped thickness: 800 nm was formed on this SiO 2 layer. The transparent electrode layer 13 was patterned using a laser processing method to form an array, and wirings for electrically connecting them were formed. Next, the photoelectric conversion layer 12 was formed on the transparent electrode layer 13 using a plasma CVD method. In this embodiment, the photoelectric conversion layer 12 includes p-type a-Si: H (amorphous silicon, thickness: 40 nm), i-type a-Si (amorphous silicon, thickness: 200 nm), and in order from the substrate 10 side. A film made of n-type μc-Si (microcrystalline silicon, thickness: 40 nm) was obtained by stacking. After patterning the photoelectric conversion layer 12 using a laser processing method, the transparent conductive film (ZnO layer) 11 having a thickness of 80 nm and the thickness are formed on the photoelectric conversion layer 12 using a magnetron in-line sputtering apparatus. A 200 nm conductive reflective film (silver electrode layer) 14 is sequentially formed.
表１、表２から明らかなように、実施例１〜１２の全てで、屈折率が低く、相対発電効率は１０５〜１２０％と著しく高く、相対短絡電流密度も１０３〜１１２％と高かった。また、実施例１〜１２の全てで、透明導電層を形成した光電変換層に、ダメージは観察されなかった。これに対して、リン酸を含まない比較例１、リン酸を含むがリンを０．４７質量部しか含まない比較例２では、屈折率が高く、相対発電効率、相対短絡電流密度ともに、略１００％であった。リン酸を含むがリンを１２．８９質量部含む比較例３では、透明導電膜用組成物がゲル化したため、湿式塗工できなかった。 As is clear from Tables 1 and 2, in all of Examples 1 to 12, the refractive index was low, the relative power generation efficiency was remarkably high at 105 to 120%, and the relative short-circuit current density was also high at 103 to 112%. In all of Examples 1 to 12, no damage was observed in the photoelectric conversion layer on which the transparent conductive layer was formed. On the other hand, Comparative Example 1 containing no phosphoric acid and Comparative Example 2 containing phosphoric acid but containing only 0.47 parts by mass of phosphorus have a high refractive index, and both the relative power generation efficiency and the relative short-circuit current density are substantially the same. 100%. In Comparative Example 3 containing phosphoric acid but containing 12.89 parts by mass of phosphorus, wet coating could not be performed because the transparent conductive film composition gelled.
〔実施例１３、１４〕
実施例１３では、実施例１の透明導電膜用組成物を使用した。また、実施例１４では、実施 例５の透明導電膜用組成物を使用した。
[Examples 13 and 14]
In Example 13, the composition for transparent conductive film of Example 1 was used. In Example 14, the composition for transparent conductive film of Example 5 was used.
＜比較例４＞
比較例４では、比較例１の透明導電膜用組成物を使用した。
<Comparative example 4>
In Comparative Example 4, the composition for transparent conductive film of Comparative Example 1 was used.
〔透明導電膜用組成物のサブストレート型薄膜太陽電池での評価〕
図２に示すように、基材２０として、縦：１００ｍｍ、横：１００ｍｍ、厚さ：５０μｍのポリイミド樹脂製のフィルム基板を用意し、このフィルム基板２０に直径：１００μｍのスルーホール２５を形成した。先ず、フィルム基板の下面にスパッタ法により、Ａｇからなる集電極層２６（厚さ：２００ｎｍ）を形成した。このときスルーホール２５にもＡｇからなる通電部材が充填された。次に、基材２０の上面に、導電性反射膜用組成物を、湿式塗工法（スクリーン印刷法）により塗布した後に、フィルム基板を熱風循環炉に投入し、２００℃の温度で３０分間保持して導電性反射膜２４を焼成し、既に成膜が進んでいるサブストレート型薄膜太陽電池セルとした。なお、焼成後の導電性反射膜２４の厚さは２００ｎｍであった。
[Evaluation of composition for transparent conductive film in substrate type thin film solar cell]
As shown in FIG. 2, a polyimide resin film substrate having a length of 100 mm, a width of 100 mm, and a thickness of 50 μm was prepared as the base material 20, and a through hole 25 having a diameter of 100 μm was formed in the film substrate 20. . First, the collector electrode layer 26 (thickness: 200 nm) made of Ag was formed on the lower surface of the film substrate by sputtering. At this time, the through hole 25 was also filled with an energizing member made of Ag. Next, after applying the conductive reflective film composition on the upper surface of the base material 20 by a wet coating method (screen printing method), the film substrate is put into a hot air circulating furnace and held at a temperature of 200 ° C. for 30 minutes. Then, the conductive reflective film 24 was baked to obtain a substrate-type thin film solar cell in which film formation had already progressed. Note that the thickness of the conductive reflective film 24 after firing was 200 nm.
次に、導電性反射膜２４上に、実施例１２と１３、比較例４の透明導電膜用組成物を、既に成膜が進んでいるサブストレート型薄膜太陽電池セルに対して、スピンコーティング法で塗布した後、温度：５０℃で５分間乾燥し、次いで、１８０℃で３０分焼成することにより、太陽電池セル上に透明導電膜２１を形成した。透明導電膜２１の焼成後膜厚は、実施例１３：８０ｎｍ、実施例１４：８０ｎｍ、比較例４：８０ｎｍであった。 Next, on the conductive reflective film 24, spin-coating method is applied to the substrate-type thin-film solar cells in which the transparent conductive film compositions of Examples 12 and 13 and Comparative Example 4 have already been formed. After coating, the transparent conductive film 21 was formed on the solar cell by drying at a temperature of 50 ° C. for 5 minutes and then baking at 180 ° C. for 30 minutes. The film thickness after baking of the transparent conductive film 21 was Example 13: 80 nm, Example 14: 80 nm, and Comparative Example 4: 80 nm.
形成した透明導電膜２１と導電性反射膜２４には、レーザー加工法を用いてパターニングすることによりアレイ状とするとともに、それらを電気的に相互接続可能にする配線を形成した。次に透明電極層２１上にプラズマＣＶＤ法を用いて、光電変換層２２を形成した。この光電変換層２２は、基材２０側から順に、ｎ型μｃ−Ｓｉ（微結晶シリコン）、ｉ型ａ−Ｓｉ（アモルファスシリコン）及びｐ型ａ−Ｓｉ：Ｈ（アモルファスシリコン）からなる膜を積層して得た。上記光電変換層２２を、レーザー加工法を用いてパターニングした。 The formed transparent conductive film 21 and conductive reflective film 24 were formed into an array by patterning using a laser processing method, and wirings were formed so that they could be electrically interconnected. Next, the photoelectric conversion layer 22 was formed on the transparent electrode layer 21 using a plasma CVD method. The photoelectric conversion layer 22 is a film composed of n-type μc-Si (microcrystalline silicon), i-type a-Si (amorphous silicon), and p-type a-Si: H (amorphous silicon) in this order from the substrate 20 side. Obtained by laminating. The photoelectric conversion layer 22 was patterned using a laser processing method.
さらに、光電変換層２２上に、表面に凹凸テクスチャを有しかつＦ（フッ素）ドープされた厚さ８００ｎｍの表面電極層（ＳｎＯ２膜）を、透明電極層２３として形成した。この透明電極層２３にはレーザー加工法を用いてパターニングすることによりアレイ状とするとともに、それらを電気的に相互接続する配線を形成し、サブストレート型薄膜太陽電池を得た。 Further, on the photoelectric conversion layer 22, a surface electrode layer (SnO 2 film) having a thickness of 800 nm and having an uneven texture on the surface and doped with F (fluorine) was formed as the transparent electrode layer 23. The transparent electrode layer 23 was patterned using a laser processing method to form an array, and wirings for electrically connecting them were formed to obtain a substrate type thin film solar cell.
得られたサブストレート型薄膜太陽電池の相対発電効率及び短絡電流（Ｊｓｃ）を、スーパーストレート型太陽電池と同様にして、評価した。ここで、基材２０、導電性反射膜２４、透明導電膜２１、光電変換層２２、透明電極層２３の全てをスパッタ法で作製したサブストレート型薄膜太陽電池セルを１００として、相対出力評価を行った。 The relative power generation efficiency and short circuit current (Jsc) of the obtained substrate type thin film solar cell were evaluated in the same manner as the super straight type solar cell. Here, relative output evaluation is performed with a substrate-type thin film solar cell in which all of the base material 20, the conductive reflective film 24, the transparent conductive film 21, the photoelectric conversion layer 22, and the transparent electrode layer 23 are produced by sputtering as 100. went.
実施例１３では、相対発電効率が１０６％、相対短絡電流密度が１０４％といずれも向上した。実施例１４では、相対発電効率が１０８％、相対短絡電流密度が１１１％といずれも向上した。一方、リン酸を含まない比較例４では、相対発電効率が９７％、相対短絡電流密度が９８％と実施例１３及び１４と比べて低い結果となった。 In Example 13, the relative power generation efficiency was improved by 106% and the relative short-circuit current density by 104%. In Example 14, the relative power generation efficiency was improved by 108% and the relative short-circuit current density by 111%. On the other hand, in Comparative Example 4 containing no phosphoric acid, the relative power generation efficiency was 97%, and the relative short-circuit current density was 98%, which was lower than in Examples 13 and 14.
以上のように、本発明の透明導電膜用組成物は、湿式塗工法で光電変換層上に塗布、焼成することができ、リン酸の含有量によって、得られた透明導電膜の屈折率を調整することができた。したがって、薄膜太陽電池の発電効率を向上させることが可能な透明導電膜を簡便に得ることができる。 As described above, the composition for transparent conductive film of the present invention can be applied and baked on the photoelectric conversion layer by a wet coating method, and the refractive index of the obtained transparent conductive film can be changed depending on the phosphoric acid content. I was able to adjust. Therefore, a transparent conductive film capable of improving the power generation efficiency of the thin film solar cell can be easily obtained.
１ スーパーストレート型薄膜太陽電池
２ サブストレート型薄膜太陽電池
１０、２０ 基材
１１、２１ 透明導電膜
１２、２２ 光電変換層
１３、２３ 透明電極層
１４、２４ 導電性反射膜
２５ スルーホール
２６ 集電極層
DESCRIPTION OF SYMBOLS 1 Super straight type thin film solar cell 2 Substrate type thin film solar cell 10, 20 Base material 11, 21 Transparent conductive film 12, 22 Photoelectric conversion layer 13, 23 Transparent electrode layer 14, 24 Conductive reflective film 25 Through hole 26 Collector electrode layer
Claims (4)
リンを、シリコン：１００質量部に対して、０．８０〜１１．７２質量部含むことを特徴とする、太陽電池の透明導電膜用組成物。 Conductive oxide particles, phosphoric acid, silicon alkoxide or hydrolyzate or dehydration product of silicon alkoxide,
A composition for a transparent conductive film of a solar cell, comprising 0.80 to 11.72 parts by mass of phosphorus with respect to 100 parts by mass of silicon.
A solar cell comprising the transparent conductive film according to claim 3.
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|---|---|---|---|---|
| JPH07242842A (en) * | 1994-03-04 | 1995-09-19 | Mitsubishi Materials Corp | Composition for forming transparent electrically-conductive film and transparent electrically-conductive film |
| JP2009059506A (en) * | 2007-08-30 | 2009-03-19 | Jgc Catalysts & Chemicals Ltd | Substrate with transparent conductive film, and coating liquid for transparent conductive film formation |
| JP2009088489A (en) * | 2007-09-12 | 2009-04-23 | Mitsubishi Materials Corp | Composite film for super straight type thin film solar battery and method of manufacturing the same |
| JP2011063478A (en) * | 2009-09-17 | 2011-03-31 | Jgc Catalysts & Chemicals Ltd | Phosphorus-containing antimony pentoxide microparticle, coating liquid for forming transparent conductive film containing the microparticle, and base material with transparent conductive film |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07242842A (en) * | 1994-03-04 | 1995-09-19 | Mitsubishi Materials Corp | Composition for forming transparent electrically-conductive film and transparent electrically-conductive film |
| JP2009059506A (en) * | 2007-08-30 | 2009-03-19 | Jgc Catalysts & Chemicals Ltd | Substrate with transparent conductive film, and coating liquid for transparent conductive film formation |
| JP2009088489A (en) * | 2007-09-12 | 2009-04-23 | Mitsubishi Materials Corp | Composite film for super straight type thin film solar battery and method of manufacturing the same |
| JP2011063478A (en) * | 2009-09-17 | 2011-03-31 | Jgc Catalysts & Chemicals Ltd | Phosphorus-containing antimony pentoxide microparticle, coating liquid for forming transparent conductive film containing the microparticle, and base material with transparent conductive film |
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