JP2008153438A - Method for measuring buffer layer film thickness - Google Patents

Method for measuring buffer layer film thickness Download PDF

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JP2008153438A
JP2008153438A JP2006339937A JP2006339937A JP2008153438A JP 2008153438 A JP2008153438 A JP 2008153438A JP 2006339937 A JP2006339937 A JP 2006339937A JP 2006339937 A JP2006339937 A JP 2006339937A JP 2008153438 A JP2008153438 A JP 2008153438A
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buffer layer
type buffer
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film thickness
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JP4734224B2 (en
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Satoshi Yonezawa
諭 米澤
Hajime Ito
元 伊藤
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Honda Motor Co Ltd
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Abstract

<P>PROBLEM TO BE SOLVED: To obtain the substantially correct film thickness of an n-type buffer layer which is one of the films constituting a chalcopyrite solar cell. <P>SOLUTION: XRF analysis is performed by fixing the incident angle θ of an X-ray with respect to a semifinished product 30 before arranging a transparent electrode layer 18. When an Mo electrode layer 12 is arranged, the incident angle θ of the X-ray is made to be within a range being over 0° to 1°. The film thickness of the n-type buffer layer 16 is obtained based on the strength of a fluorescent X-ray of S from the n-type buffer layer 16 (sulfide), which is obtained by the XRF analysis, and a previously generated analytical curve between the film thickness of the n-type buffer layer 16 and the strength of the fluorescent X-ray of S. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

本発明は、カルコパイライト型太陽電池中のｎ型バッファ層の膜厚を測定するバッファ層膜厚測定方法に関する。   The present invention relates to a buffer layer thickness measuring method for measuring the thickness of an n-type buffer layer in a chalcopyrite solar cell.

カルコパイライト型太陽電池は、例えば、図６に模式的に示すように、ガラス基板１０上にＭｏ電極層１２、Ｃｕ（Ｉｎ，Ｇａ）Ｓｅ等のカルコパイライト化合物からなりｐ型半導体である光吸収層１４、ＩｎＳからなるｎ型バッファ層１６、ＺｎＯ：Ａｌからなる透明電極層１８がこの順序で積層されることで構成される。また、Ｍｏ電極層１２及び透明電極層１８の上方には、それぞれ、集電電極２０、２２が設けられる。   A chalcopyrite solar cell is a p-type semiconductor composed of a chalcopyrite compound such as a Mo electrode layer 12 and Cu (In, Ga) Se on a glass substrate 10 as schematically shown in FIG. The layer 14, the n-type buffer layer 16 made of InS, and the transparent electrode layer 18 made of ZnO: Al are laminated in this order. In addition, current collecting electrodes 20 and 22 are provided above the Mo electrode layer 12 and the transparent electrode layer 18, respectively.

このような構成のカルコパイライト型太陽電池２４では、光吸収層１４とｎ型バッファ層１６とでｐｎ接合が形成される。すなわち、ｎ型バッファ層１６はカルコパイライト型太陽電池２４の発電性能に影響をもたらす層であり、従って、ｎ型バッファ層１６の膜厚を管理することが重要となる。   In the chalcopyrite solar cell 24 having such a configuration, a pn junction is formed by the light absorption layer 14 and the n-type buffer layer 16. That is, the n-type buffer layer 16 is a layer that affects the power generation performance of the chalcopyrite solar cell 24, and therefore it is important to manage the film thickness of the n-type buffer layer 16.

ここで、図７に示すように、実際の光吸収層１４の上端面は起伏及び陥没が大きく、且つｎ型バッファ層１６の膜厚は光吸収層１４に比して著しく小さい。このため、光吸収層１４上に形成されたｎ型バッファ層１６は、光吸収層１４の起伏及び陥没に対応して起伏及び陥没する。また、ｎ型バッファ層１６がいわゆるウェットプロセスで製膜された場合、該ｎ型バッファ層１６は、膜強度が小さいものとなる。このような理由から、透過型電子顕微鏡（ＴＥＭ）や、透過型電子顕微鏡−Ｘ線マイクロアナライザ（ＴＥＭ−ＥＰＭＡ）以外の手法でｎ型バッファ層１６の膜厚を測定することは、困難を窮める。   Here, as shown in FIG. 7, the actual upper end surface of the light absorption layer 14 is greatly undulated and depressed, and the thickness of the n-type buffer layer 16 is significantly smaller than that of the light absorption layer 14. For this reason, the n-type buffer layer 16 formed on the light absorption layer 14 is undulated and depressed corresponding to the undulation and depression of the light absorption layer 14. Further, when the n-type buffer layer 16 is formed by a so-called wet process, the n-type buffer layer 16 has a low film strength. For these reasons, it is difficult to measure the film thickness of the n-type buffer layer 16 by a method other than a transmission electron microscope (TEM) or a transmission electron microscope-X-ray microanalyzer (TEM-EPMA). .

例えば、エリプソメータを用いるエリプソ法（特許文献１参照）でのｎ型バッファ層１６の膜厚の測定値は、ＴＥＭによる測定値の１／２〜２倍となる。すなわち、ｎ型バッファ層１６の膜厚は略一定であるにも関わらず、測定値にバラツキが生じる。この理由は、エリプソ法ではｎ型バッファ層１６の光学定数ｎ、ｋの双方が一定であることを前提とするが、上記したようにｎ型バッファ層１６に起伏及び陥没が多数存在するため、この影響を受けてｋの値が変化するためであると推察される。   For example, the measured value of the film thickness of the n-type buffer layer 16 by an ellipsometer method using an ellipsometer (see Patent Document 1) is 1/2 to 2 times the measured value by TEM. That is, although the film thickness of the n-type buffer layer 16 is substantially constant, the measurement value varies. The reason is that, in the ellipso method, it is assumed that both the optical constants n and k of the n-type buffer layer 16 are constant. However, as described above, the n-type buffer layer 16 has many undulations and depressions. It is assumed that this is because the value of k changes under this influence.

また、特許文献２に記載されているように蛍光Ｘ線（ＸＲＦ）分析装置を用いてｎ型バッファ層１６の化学組成を定量し、その結果に基づいて膜厚を求めることも想起されるが、この場合、Ｍｏ電極層１２のＭｏからの蛍光Ｘ線エネルギ（Ｌα線＝２．２９３ｅＶ）とｎ型バッファ層１６（ＩｎＳ）のＳからの蛍光Ｘ線エネルギ（Ｋα線＝２．３０８ｅＶ）との値が極めて近い値であり、ＳとＭｏの両蛍光Ｘ線エネルギからＳの分のみを分離することもできないので、Ｓを定量すること、ひいてはｎ型バッファ層１６の膜厚を求めることができない。   It is also recalled that the chemical composition of the n-type buffer layer 16 is quantified using a fluorescent X-ray (XRF) analyzer as described in Patent Document 2, and the film thickness is obtained based on the result. In this case, the fluorescent X-ray energy from Mo of the Mo electrode layer 12 (Lα ray = 2.293 eV) and the fluorescent X-ray energy from S of the n-type buffer layer 16 (InS) (Kα ray = 2.308 eV) Since the value of S is very close and it is impossible to separate only the amount of S from both fluorescent X-ray energies of S and Mo, it is possible to quantify S and thus to determine the film thickness of the n-type buffer layer 16. Can not.

一方、Ｉｎで定量を試みる場合、光吸収層１４及びｎ型バッファ層１６の双方にＩｎが含まれているため、Ｉｎの蛍光Ｘ線の強度が光吸収層１４由来のものであるのか、ｎ型バッファ層１６由来のものであるのかが区別できない。   On the other hand, when quantification is attempted with In, since In is contained in both the light absorption layer 14 and the n-type buffer layer 16, whether the intensity of the fluorescent X-ray of In is derived from the light absorption layer 14, n It cannot be distinguished whether it is derived from the mold buffer layer 16.

結局、ｎ型バッファ層１６の略正確な膜厚を求めるには、ＴＥＭ、ＴＥＭ−ＥＰＭＡが好適ではあるが、これらの手法には、膜厚を１箇所のみ測定する場合でも比較的長時間を要し、さらに高額の費用が必要であるという不具合がある。すなわち、カルコパイライト型太陽電池２４を量産した場合等、１つのカルコパイライト型太陽電池２４につき膜厚を迅速に測定することが必要な場合、ＴＥＭ、ＴＥＭ−ＥＰＭＡでは対応することができない。   Eventually, TEM and TEM-EPMA are suitable for obtaining a substantially accurate film thickness of the n-type buffer layer 16, but these methods require a relatively long time even when measuring the film thickness at only one location. In other words, there is a problem that a higher cost is required. That is, when it is necessary to quickly measure the film thickness of one chalcopyrite solar cell 24, such as when the chalcopyrite solar cell 24 is mass-produced, TEM and TEM-EPMA cannot cope with it.

特開２００１−１１１０７０号公報JP 2001-1111070 A 特開２００６−１９６７９８号公報JP 2006-196798 A

本発明は上記した問題を解決するためになされたもので、カルコパイライト型太陽電池に含まれるｎ型バッファ層の略正確な膜厚を求めることが可能なバッファ層膜厚測定方法を提供することを目的とする。   The present invention has been made to solve the above-described problem, and provides a buffer layer thickness measurement method capable of obtaining a substantially accurate thickness of an n-type buffer layer included in a chalcopyrite solar cell. With the goal.

前記の目的を達成するために、本発明は、硫化物からなり、且つカルコパイライト型太陽電池に含まれるｎ型バッファ層の膜厚を測定するバッファ層膜厚測定方法であって、
基板の上方に金属電極層を設ける工程と、
前記金属電極層の上方にｐ型の光吸収層を設ける工程と、
前記光吸収層上に前記ｎ型バッファ層を設けて半製品を設ける工程と、
蛍光Ｘ線分析装置を用いて前記半製品にＸ線を入射する工程と、
を有し、
前記Ｘ線を、０°を超え、且つ前記金属電極層の材質である金属を検出した蛍光Ｘ線検出強度が前記ｎ型バッファ層の構成元素であるＳを検出した蛍光Ｘ線検出強度を下回る角度の範囲内の固定角度で前記半製品に入射して前記Ｓの蛍光Ｘ線検出強度を測定し、
前記固定角度における蛍光Ｘ線分析での前記Ｓの蛍光Ｘ線検出強度と前記ｎ型バッファ層の膜厚との関係式から、前記ｎ型バッファ層の膜厚を求めることを特徴とする。なお、前記関係式は、検量線であってもよい。すなわち、検量線は、関係式を関数としてグラフ上に表したものであるからである。 To achieve the above object, the present invention is a buffer layer thickness measuring method for measuring the thickness of an n-type buffer layer made of a sulfide and included in a chalcopyrite solar cell,
Providing a metal electrode layer above the substrate;
Providing a p-type light absorption layer above the metal electrode layer;
Providing the n-type buffer layer on the light absorption layer to provide a semi-finished product;
Injecting X-rays into the semi-finished product using a fluorescent X-ray analyzer;
Have
The X-ray fluorescence intensity detected by detecting the metal that is greater than 0 ° and detecting the metal that is the material of the metal electrode layer is lower than the X-ray fluorescence intensity detected by detecting S that is a constituent element of the n-type buffer layer. Measure the fluorescence X-ray detection intensity of the S incident on the semi-finished product at a fixed angle within the range of angles,
The film thickness of the n-type buffer layer is obtained from the relational expression between the fluorescent X-ray detection intensity of S in the fluorescent X-ray analysis at the fixed angle and the film thickness of the n-type buffer layer. The relational expression may be a calibration curve. That is, the calibration curve is a graph representing the relational expression as a function.

先ず、透明電極層を設ける前の半製品のｎ型バッファ層の膜厚を、ＴＥＭ、ＴＥＭ−ＥＰＭＡ等によって略正確に求める一方、該半製品に対してＸＲＦ分析を行う。このＸＲＦ分析は、Ｓの検出強度と、金属電極層からの金属の検出強度とを区別可能な角度で行う。以上によって得られたｎ型バッファ層の略正確な膜厚とＳの検出強度とから、ｎ型バッファ層の膜厚とＳの検出強度との関係式（検量線）を求めておく。   First, the thickness of the n-type buffer layer of the semi-finished product before providing the transparent electrode layer is determined approximately accurately by TEM, TEM-EPMA or the like, and XRF analysis is performed on the semi-finished product. This XRF analysis is performed at an angle at which the detection intensity of S and the detection intensity of metal from the metal electrode layer can be distinguished. The relational expression (calibration curve) between the film thickness of the n-type buffer layer and the S detection intensity is obtained from the substantially accurate film thickness of the n-type buffer layer and the S detection intensity obtained as described above.

次に、別途作製された半製品に対し、前記の角度でＸＲＦ分析を行ってＳの検出強度を求めれば、この検出強度と、前記の関係式（検量線）とから、該半製品におけるｎ型バッファ層の略正確な膜厚を求めることができる。なお、測定結果のドリフトを回避するべく、出力管電圧や出力管電流等をはじめとするＸＲＦの諸測定条件を同一とすることは勿論である。   Next, if the XRF analysis is performed on the separately manufactured semi-finished product at the above angle to obtain the detected intensity of S, the n in the semi-finished product is calculated from the detected intensity and the relational expression (calibration curve). A substantially accurate film thickness of the mold buffer layer can be obtained. Needless to say, various measurement conditions of XRF including the output tube voltage and the output tube current are made the same in order to avoid the drift of the measurement result.

ＸＲＦ分析は比較的短時間で実施可能であるので、本発明によれば、ｎ型バッファ層の略正確な膜厚を迅速に測定することが可能となる。従って、カルコパイライト型太陽電池を量産する場合に対応することもできる。   Since XRF analysis can be performed in a relatively short time, according to the present invention, it is possible to quickly measure a substantially accurate film thickness of the n-type buffer layer. Therefore, it is possible to deal with the case of mass-producing chalcopyrite solar cells.

しかも、ＸＲＦ分析は非破壊分析方法であるので、カルコパイライト型太陽電池を損傷する懸念もない。   Moreover, since the XRF analysis is a non-destructive analysis method, there is no fear of damaging the chalcopyrite solar cell.

なお、Ｓは、Ｘ線の入射角度が０°超〜５°の極低角度であっても十分な検出強度を示す。一方、この角度範囲内では、各種の金属の検出強度はＳに比して小さい。従って、Ｘ線の入射角度は、０°超〜５°とすることが好ましい。   In addition, S shows sufficient detection intensity even if the incident angle of X-rays is an extremely low angle of more than 0 ° to 5 °. On the other hand, the detected intensity of various metals is smaller than S within this angular range. Therefore, the incident angle of X-rays is preferably more than 0 ° to 5 °.

特に、金属電極層の材質がＭｏである場合、Ｘ線の入射角度を０°超〜１°とすることにより、Ｍｏの検出強度とＳの検出強度とを確実且つ容易に区別することができる。   In particular, when the material of the metal electrode layer is Mo, the detection intensity of Mo and the detection intensity of S can be reliably and easily distinguished by setting the incident angle of X-rays to more than 0 ° to 1 °. .

本発明においては、ｎ型バッファ層の略正確な膜厚と、所定角度でのＸＲＦ分析におけるＳの検出強度とからｎ型バッファ層の膜厚とＳの検出強度との関係式（検量線）を先ず求め、次に、別途作製された半製品に対してＸＲＦ分析を行ってＳの検出強度を求めるようにしている。前記の関係式（検量線）を予め求めておくことで、ＸＲＦ分析におけるＳの検出強度に基づいて、該半製品におけるｎ型バッファ層の略正確な膜厚を迅速に求めることができる。   In the present invention, the relational expression (calibration curve) between the thickness of the n-type buffer layer and the detected intensity of S from the substantially accurate thickness of the n-type buffer layer and the detected intensity of S in the XRF analysis at a predetermined angle. First, the XRF analysis is performed on a separately manufactured semi-finished product to determine the S detection intensity. By obtaining the relational expression (calibration curve) in advance, it is possible to quickly obtain a substantially accurate film thickness of the n-type buffer layer in the semi-finished product based on the detected intensity of S in the XRF analysis.

すなわち、本発明によれば、ｎ型バッファ層の膜厚を略正確且つ迅速に、しかも、カルコパイライト型太陽電池を損傷する懸念もなく測定することができる。従って、カルコパイライト型太陽電池を量産する場合にも対応可能である。   That is, according to the present invention, the film thickness of the n-type buffer layer can be measured substantially accurately and quickly, and without fear of damaging the chalcopyrite solar cell. Therefore, it is possible to cope with mass production of chalcopyrite solar cells.

以下、本発明に係るｎ型バッファ層膜厚測定方法につき好適な実施の形態を挙げ、添付の図面を参照して詳細に説明する。なお、本実施の形態では、図６に示すカルコパイライト型太陽電池２４を設ける場合を例示して説明する。また、図６中の構成要素と同一の構成要素には同一の参照符号を付し、その詳細な説明を省略する。   Preferred embodiments of the n-type buffer layer thickness measuring method according to the present invention will be described below in detail with reference to the accompanying drawings. In this embodiment, a case where the chalcopyrite solar cell 24 shown in FIG. 6 is provided will be described as an example. Also, the same components as those in FIG. 6 are denoted by the same reference numerals, and detailed description thereof is omitted.

本実施の形態では、先ず、図１に示す半製品３０を作製する。すなわち、ガラス基板１０上にＭｏ電極層１２、Ｃｕ（Ｉｎ，Ｇａ）Ｓｅ等からなる光吸収層１４、ＩｎＳからなるｎ型バッファ層１６をこの順序で製膜し、堆積させる。なお、各層１２、１４、１６は、スパッタ法や溶液成長法、Ｓｅ化法等の公知の手法によって製膜すればよい。   In the present embodiment, first, a semi-finished product 30 shown in FIG. 1 is manufactured. That is, the Mo electrode layer 12, the light absorption layer 14 made of Cu (In, Ga) Se, and the n-type buffer layer 16 made of InS are formed on the glass substrate 10 in this order and deposited. The layers 12, 14, and 16 may be formed by a known method such as sputtering, solution growth, or Se conversion.

次に、この半製品３０をＸＲＦ分析装置にて分析する。すなわち、半製品３０に対してＸ線を入射する。   Next, this semi-finished product 30 is analyzed with an XRF analyzer. That is, X-rays are incident on the semi-finished product 30.

ここで、ｎ型バッファ層１６を設ける前、すなわち、ガラス基板１０上にＭｏ電極層１２と光吸収層１４のみが設けられた半製品に対し、Ｘ線の入射角度θを０°超〜５°としたときの蛍光Ｘ線の強度を図２に示す。この図２から諒解されるように、入射角度が０°超〜１°の範囲内では、蛍光Ｘ線の強度はほとんど０であるが、入射角度が１°を超えると強度が急激に上昇する。この理由は、入射角度が０°超〜１°である場合には入射Ｘ線の進入の度合いが浅く光吸収層１４に留まるため、Ｍｏをはじめ、各種元素に由来する蛍光Ｘ線は検出されないのに対し、１°を超えると入射Ｘ線がＭｏ電極層１２に進入し、その結果、Ｍｏが検出されるようになるためである。   Here, before the n-type buffer layer 16 is provided, that is, with respect to a semi-finished product in which only the Mo electrode layer 12 and the light absorption layer 14 are provided on the glass substrate 10, the X-ray incident angle θ exceeds 0 ° to 5 °. FIG. 2 shows the intensity of the fluorescent X-ray when the angle is. As can be seen from FIG. 2, the intensity of the fluorescent X-ray is almost 0 when the incident angle is in the range of more than 0 ° to 1 °, but the intensity rapidly increases when the incident angle exceeds 1 °. . The reason for this is that when the incident angle is greater than 0 ° to 1 °, the degree of incident X-ray entry is shallow and remains in the light absorption layer 14, so that fluorescent X-rays derived from various elements including Mo are not detected. On the other hand, when the angle exceeds 1 °, incident X-rays enter the Mo electrode layer 12, and as a result, Mo is detected.

一方、半製品３０に対して０°超〜１°の入射角度でＸ線を入射した場合、図２に併せて示すように、蛍光Ｘ線の強度は３０を超え、０．４°〜０．９°では６０で略一定となる。ｎ型バッファ層１６（ＩｎＳ）が存在する半製品３０において蛍光Ｘ線が観察されたこと、及び、Ｃｕ（Ｉｎ，Ｇａ）Ｓｅ等からなる光吸収層１４が存在する半製品で蛍光Ｘ線が観察されなかったことから、この蛍光Ｘ線は、ｎ型バッファ層１６のＳに由来するものである。   On the other hand, when X-rays are incident on the semi-finished product 30 at an incident angle of more than 0 ° to 1 °, the intensity of fluorescent X-rays exceeds 30 and 0.4 ° to 0, as shown in FIG. .9 ° is substantially constant at 60 °. Fluorescence X-rays were observed in the semi-finished product 30 in which the n-type buffer layer 16 (InS) was present, and fluorescence X-rays were observed in the semi-finished product in which the light absorption layer 14 made of Cu (In, Ga) Se or the like was present. Since it was not observed, this fluorescent X-ray originates from S of the n-type buffer layer 16.

このように、Ｘ線の入射角度θを０°超〜１°の極低角度とした場合、Ｍｏの蛍光Ｘ線は検出されず、Ｓの蛍光Ｘ線のみが検出される。このため、Ｓの定量が可能となる。なお、極低角度でのＸＲＦ分析によってＳの蛍光Ｘ線のみが得られるようになる理由は、図３に示すように高角度でＸ線を入射すると、該Ｘ線がガラス基板１０まで到達する結果、Ｍｏ電極層１２の材質であるＭｏからの蛍光Ｘ線が検出されるようになるためであるのに対し、極低角度でＸ線を入射すると該Ｘ線が光吸収層１４の上層部までしか到達せず（図１参照）、このためにＭｏ電極層１２からの蛍光Ｘ線が検出されなくなるためであると推察される。   As described above, when the incident angle θ of X-rays is set to an extremely low angle of more than 0 ° to 1 °, Mo fluorescent X-rays are not detected, but only S fluorescent X-rays are detected. For this reason, it is possible to quantify S. The reason why only X fluorescent X-rays can be obtained by XRF analysis at an extremely low angle is that when X-rays are incident at a high angle as shown in FIG. 3, the X-rays reach the glass substrate 10. As a result, fluorescent X-rays from Mo which is the material of the Mo electrode layer 12 are detected, whereas when X-rays are incident at an extremely low angle, the X-rays are the upper layers of the light absorption layer 14. (See FIG. 1), it is assumed that this is because the fluorescent X-rays from the Mo electrode layer 12 are not detected.

なお、入射角度をさらに大きくすると、図２に併せて示すように、半製品３０において検出されたＳの強度と、ｎ型バッファ層１６が存在しない半製品において検出されたＭｏの強度とが略同等となる。このため、蛍光Ｘ線の強度がＳ由来のものであるのか又はＭｏ由来のものであるのかを判別することが容易でなくなる。   When the incident angle is further increased, the intensity of S detected in the semi-finished product 30 and the intensity of Mo detected in the semi-finished product in which the n-type buffer layer 16 does not exist are substantially as shown in FIG. It becomes equivalent. For this reason, it is not easy to determine whether the intensity of fluorescent X-rays is derived from S or Mo.

以上の結果に基づき、本実施の形態では、Ｘ線の入射角度θを０°超〜１°としてＸＲＦ分析を行う。   Based on the above results, in this embodiment, the XRF analysis is performed with the incident angle θ of X-rays set to more than 0 ° to 1 °.

図４に、ｎ型バッファ層１６の膜厚が１７０Å、３５０Å、５１０Åである半製品３０にＸ線を入射した際のＸ線の入射角度と、ｎ型バッファ層１６からのＳの蛍光Ｘ線の強度との関係をグラフにして示す。なお、膜厚は、ＴＥＭ、ＴＥＭ−ＥＰＭＡ等によって予め測定しておく。   FIG. 4 shows the incident angle of X-rays when X-rays are incident on the semi-finished product 30 whose n-type buffer layer 16 has a thickness of 170 mm, 350 mm, and 510 mm, and S fluorescent X-rays from the n-type buffer layer 16. The relationship with the intensity is shown as a graph. The film thickness is measured in advance by TEM, TEM-EPMA, or the like.

この図４から、Ｘ線の入射角度が同一であっても、膜厚が異なると蛍光Ｘ線の強度も異なること、換言すれば、Ｓの蛍光Ｘ線の強度に膜厚依存性があることが明らかである。なお、入射角度を０．６°としたときの測定再現性は１σ％で２％以下であり、再現性が良好であることが確認された。   From FIG. 4, even if the incident angle of X-rays is the same, the intensity of fluorescent X-rays differs when the film thickness is different, in other words, the intensity of S fluorescent X-rays is dependent on the film thickness. Is clear. The measurement reproducibility when the incident angle was 0.6 ° was 2% or less at 1σ%, and it was confirmed that the reproducibility was good.

このようにして、Ｘ線の入射角度を０°超〜１°の範囲内の所定角度で固定する一方、ｎ型バッファ層１６の膜厚を種々変更しながら、Ｓの蛍光Ｘ線の強度を測定する。任意の入射角度での測定が終了した後、入射角度を変更して同様の測定を行う。入射角度を０．１°、０．６°、１°としたときの各測定結果を、代表例として図５に併せて示す。   In this way, the X-ray incident angle is fixed at a predetermined angle in the range of more than 0 ° to 1 °, while the thickness of the n-type buffer layer 16 is changed variously, and the intensity of the fluorescent X-rays of S is increased. taking measurement. After the measurement at an arbitrary incident angle is completed, the incident angle is changed and the same measurement is performed. Each measurement result when the incident angle is 0.1 °, 0.6 °, and 1 ° is shown in FIG. 5 as a representative example.

ｎ型バッファ層１６の膜厚は、この測定結果に基づいて作成された図５の検量線に基づいて求めることができる。すなわち、例えば、半製品３０へのＸ線の入射角度を０．１°としたとき、Ｓの蛍光Ｘ線の強度が２００であれば、縦軸の２００から水平線ｌ１を引き、さらに、該水平線ｌ１と０．１°での直線との交点から横軸に向けて垂線ｍ１を引く。垂線ｍ１と横軸との交点のｘ座標の値（約３２０）が、ｎ型バッファ層１６の膜厚である。   The film thickness of the n-type buffer layer 16 can be determined based on the calibration curve of FIG. 5 created based on the measurement result. That is, for example, when the incident angle of X-rays to the semi-finished product 30 is 0.1 °, if the intensity of the fluorescent X-rays of S is 200, the horizontal line 11 is drawn from the vertical axis 200, and the horizontal line A perpendicular line m1 is drawn from the intersection of l1 and the straight line at 0.1 ° toward the horizontal axis. The value of the x coordinate (about 320) at the intersection of the vertical line m 1 and the horizontal axis is the film thickness of the n-type buffer layer 16.

また、半製品３０へのＸ線の入射角度を０．６°としたときにＳの蛍光Ｘ線の強度が３００であった場合も、上記と同様にすればよい。すなわち、縦軸の３００から水平線ｌ２を引き、さらに、該水平線ｌ２と０．６°での直線との交点から横軸に向けて垂線ｍ２を引いて、該垂線ｍ２と横軸との交点のｘ座標の値を求める。この場合、ｘ座標の値、すなわち、ｎ型バッファ層１６の膜厚は、約２７０Åとなる。   Further, when the incident angle of X-rays to the semi-finished product 30 is 0.6 °, the intensity of S fluorescent X-rays is 300. That is, a horizontal line l2 is drawn from 300 on the vertical axis, and a perpendicular line m2 is drawn toward the horizontal axis from the intersection of the horizontal line l2 and the straight line at 0.6 °, and the intersection of the vertical line m2 and the horizontal axis is calculated. Find the x-coordinate value. In this case, the value of the x coordinate, that is, the film thickness of the n-type buffer layer 16 is about 270 mm.

このようにして、Ｍｏの蛍光Ｘ線が検出されない極低角度側でＸＲＦ分析を行うことにより、ｎ型バッファ層１６の膜厚を略正確に測定することが可能となる。   In this way, by performing XRF analysis on the extremely low angle side where Mo fluorescent X-rays are not detected, the film thickness of the n-type buffer layer 16 can be measured substantially accurately.

ここで、検量線の傾きが大きいほど検出感度が高いことを意味している。すなわち、図５に示す０．１°、０．６°、１°の場合では、０．６°の方が傾きが大きく検出感度が高い、良好な分析条件であるといえる。   Here, the greater the slope of the calibration curve, the higher the detection sensitivity. That is, in the case of 0.1 °, 0.6 °, and 1 ° shown in FIG. 5, it can be said that 0.6 ° is a better analysis condition with a larger inclination and higher detection sensitivity.

ＸＲＦ分析は、出力管電圧を２０ｋＶ、出力管電流を５ｍＡとした場合、僅か約１００秒程度で測定が終了する。すなわち、ｎ型バッファ層１６からＳの蛍光Ｘ線を迅速に検出することができ、その結果に基づいて、膜厚を容易且つ即座に求めることが可能である。従って、カルコパイライト型太陽電池２４を量産する場合においても、各々を迅速に検査することができる。   The XRF analysis is completed in about 100 seconds when the output tube voltage is 20 kV and the output tube current is 5 mA. That is, S fluorescent X-rays can be quickly detected from the n-type buffer layer 16, and the film thickness can be easily and immediately determined based on the result. Therefore, even when the chalcopyrite solar cell 24 is mass-produced, each can be quickly inspected.

しかも、ＸＲＦ分析は非破壊検査であるので、カルコパイライト型太陽電池２４に損傷を与える懸念もない。   In addition, since the XRF analysis is a nondestructive inspection, there is no fear of damaging the chalcopyrite solar cell 24.

その上、この実施の形態では、光吸収層１４の材質であるＣｕ（Ｉｎ，Ｇａ）Ｓｅと、ｎ型バッファ層１６の材質であるＩｎＳの双方にＩｎが含まれているものの、ｎ型バッファ層１６のＳの蛍光Ｘ線のみを検出するようにしているので、光吸収層１４中のＩｎに影響されることなくｎ型バッファ層１６の膜厚を略正確に測定することができる。   In addition, in this embodiment, although both Cu (In, Ga) Se, which is the material of the light absorption layer 14, and InS, which is the material of the n-type buffer layer 16, contain In, the n-type buffer Since only the S fluorescent X-rays of the layer 16 are detected, the film thickness of the n-type buffer layer 16 can be measured almost accurately without being affected by In in the light absorption layer 14.

その後、ｎ型バッファ層１６の上方に透明電極層１８を設け、エッチングによって露呈したＭｏ電極層１２の上部と、透明電極層１８の上部に集電電極２０、２２を設けることにより、カルコパイライト型太陽電池２４が得られるに至る。   Thereafter, the transparent electrode layer 18 is provided above the n-type buffer layer 16, and the collector electrodes 20 and 22 are provided on the upper portion of the Mo electrode layer 12 exposed by etching and the upper portion of the transparent electrode layer 18. The solar cell 24 is obtained.

なお、上記した実施の形態では、ｎ型バッファ層１６としてＩｎＳを例示して説明したが、ｎ型バッファ層１６の材質は、ＣｄＳやＺｎＳ等の他の硫化物であってもよい。   In the above-described embodiment, InS has been described as an example of the n-type buffer layer 16, but the material of the n-type buffer layer 16 may be other sulfides such as CdS and ZnS.

また、Ｍｏ電極層１２に代替し、その他の金属からなる電極層を設けるようにしてもよい。この場合、Ｘ線の入射角度θを、他の前記金属の蛍光Ｘ線が検出され難くＳの蛍光Ｘ線と区別が容易な範囲内に設定すればよい。好適な入射角度は、０°超〜５°の範囲内である。   Further, instead of the Mo electrode layer 12, an electrode layer made of another metal may be provided. In this case, the incident angle θ of the X-ray may be set within a range in which it is difficult to detect the other fluorescent X-rays of the metal and can be easily distinguished from the S fluorescent X-ray. A suitable incident angle is in the range of more than 0 ° to 5 °.

さらに、例えば、ガラス基板１０とＭｏ電極層１２との間に他の層を介装するようにしてもよい。   Furthermore, for example, another layer may be interposed between the glass substrate 10 and the Mo electrode layer 12.

本実施の形態に係るＸＲＦ分析を行っている状態を模式的に示す要部概略構成説明図である。It is principal part schematic structure explanatory drawing which shows typically the state which is performing the XRF analysis which concerns on this Embodiment. ｎ型バッファ層（ＩｎＳ）が存在する半製品及び存在しない半製品に対し、Ｘ線の入射角度を０°超〜５°の範囲内で変更させたときの蛍光Ｘ線の強度を示すグラフである。It is a graph which shows the intensity | strength of fluorescent X-ray when changing the incident angle of X-rays within the range of more than 0 degree-5 degrees with respect to the semi-finished product which an n-type buffer layer (InS) exists, and a semi-finished product which does not exist. is there. 高角度側でＸＲＦ分析を行っている状態を模式的に示す要部概略構成説明図である。It is principal part schematic structure explanatory drawing which shows typically the state which is performing the XRF analysis on the high angle side. ｎ型バッファ層の膜厚が１７０Å、３５０Å、５１０Åである半製品にＸ線を入射した際のＸ線の入射角度と、ｎ型バッファ層からのＳの蛍光Ｘ線の強度との関係を示すグラフである。The relationship between the incident angle of X-rays when X-rays are incident on semi-finished products having an n-type buffer layer thickness of 170 mm, 350 mm, and 510 mm and the intensity of S fluorescent X-rays from the n-type buffer layer is shown. It is a graph. Ｘ線の入射角度を０．１°、０．６°、１°としたときのｎ型バッファ層の膜厚とＳの蛍光Ｘ線の強度との関係を示すグラフである。It is a graph which shows the relationship between the film thickness of an n-type buffer layer when the incident angle of X-ray is 0.1 °, 0.6 ° and 1 ° and the intensity of S fluorescent X-rays. 一般的なカルコパイライト型太陽電池の積層方向に沿う概略全体断面説明図である。It is a schematic whole cross-section explanatory drawing along the lamination direction of a general chalcopyrite solar cell. 図６の要部拡大説明図である。FIG. 7 is an enlarged explanatory diagram of a main part of FIG. 6.

符号の説明Explanation of symbols

１０…ガラス基板 １２…Ｍｏ電極層
１４…光吸収層 １６…ｎ型バッファ層
１８…透明電極層 ２０、２２…集電電極
３０…半製品 DESCRIPTION OF SYMBOLS 10 ... Glass substrate 12 ... Mo electrode layer 14 ... Light absorption layer 16 ... N-type buffer layer 18 ... Transparent electrode layer 20, 22 ... Current collecting electrode 30 ... Semi-finished product

Claims (3)

硫化物からなり、且つカルコパイライト型太陽電池に含まれるｎ型バッファ層の膜厚を測定するバッファ層膜厚測定方法であって、
基板の上方に金属電極層を設ける工程と、
前記金属電極層の上方にｐ型の光吸収層を設ける工程と、
前記光吸収層上に前記ｎ型バッファ層を設けて半製品を設ける工程と、
蛍光Ｘ線分析装置を用いて前記半製品にＸ線を入射する工程と、
を有し、
前記Ｘ線を、０°を超え、且つ前記金属電極層の材質である金属を検出した蛍光Ｘ線検出強度が前記ｎ型バッファ層の構成元素であるＳを検出した蛍光Ｘ線検出強度を下回る角度の範囲内の固定角度で前記半製品に入射して前記Ｓの蛍光Ｘ線検出強度を測定し、
前記固定角度における蛍光Ｘ線分析での前記Ｓの蛍光Ｘ線検出強度と前記ｎ型バッファ層の膜厚との関係式から、前記ｎ型バッファ層の膜厚を求めることを特徴とするバッファ層膜厚測定方法。 A buffer layer thickness measuring method for measuring the thickness of an n-type buffer layer made of sulfide and included in a chalcopyrite solar cell,
Providing a metal electrode layer above the substrate;
Providing a p-type light absorption layer above the metal electrode layer;
Providing the n-type buffer layer on the light absorption layer to provide a semi-finished product;
Injecting X-rays into the semi-finished product using a fluorescent X-ray analyzer;
Have
The X-ray fluorescence intensity detected by detecting the metal that is greater than 0 ° and detecting the metal that is the material of the metal electrode layer is lower than the X-ray fluorescence intensity detected by detecting S that is a constituent element of the n-type buffer layer. Measure the fluorescent X-ray detection intensity of the S incident on the semi-finished product at a fixed angle within the range of angles,
A buffer layer characterized in that the film thickness of the n-type buffer layer is obtained from a relational expression between the detected X-ray fluorescence intensity of S in the fluorescent X-ray analysis at the fixed angle and the film thickness of the n-type buffer layer. Film thickness measurement method. 請求項１記載の方法において、前記Ｘ線の入射角度を０°超〜５°とすることを特徴とするバッファ層膜厚測定方法。   2. The buffer layer thickness measuring method according to claim 1, wherein an incident angle of the X-ray is more than 0 ° to 5 °. 請求項１記載の方法において、前記金属電極層をＭｏで設け、且つ前記Ｘ線の入射角度を０°超〜１°とすることを特徴とするバッファ層膜厚測定方法。   2. The buffer layer thickness measuring method according to claim 1, wherein the metal electrode layer is made of Mo, and the incident angle of the X-ray is set to more than 0 [deg.] To 1 [deg.].
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