JP2000114562A - Photoelectric conversion element and manufacture thereof - Google Patents
Photoelectric conversion element and manufacture thereofInfo
- Publication number
- JP2000114562A JP2000114562A JP10287872A JP28787298A JP2000114562A JP 2000114562 A JP2000114562 A JP 2000114562A JP 10287872 A JP10287872 A JP 10287872A JP 28787298 A JP28787298 A JP 28787298A JP 2000114562 A JP2000114562 A JP 2000114562A
- Authority
- JP
- Japan
- Prior art keywords
- photoelectric conversion
- transparent conductive
- conductive film
- film
- fine particles
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
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- Photovoltaic Devices (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、特に太陽電池や受
光器等に使用される光電変換素子及びその製造方法に関
する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photoelectric conversion element used particularly for a solar cell, a photodetector, and the like, and a method for manufacturing the same.
【０００２】[0002]
【従来の技術】従来、光電変換材料に非晶質Ｓｉなどの
薄膜を用いた光電変換装置では、図２に示すような光電
変換素子（特公昭６０−３４０７６）が用いられてい
る。2. Description of the Related Art Conventionally, in a photoelectric conversion device using a thin film of amorphous Si or the like as a photoelectric conversion material, a photoelectric conversion element as shown in FIG. 2 (JP-B-60-34076) is used.
【０００３】図中の符番１はガラス基板を示す。このガ
ラス基板１の片面には、透明導電膜２、非晶質シリコン
などの光電変換膜３を介して裏面電極４が形成されてい
る。前記非晶質シリコンは、例えばプラズマ化学蒸着法
により形成される。前記透明導電膜２の裏面側は、平均
粒径０．２〜０．９μｍの凹凸面となっている。また、
前記裏面電極として第２の透明導電膜を用いることによ
り短絡電流が向上できる。[0003] Reference numeral 1 in the figure denotes a glass substrate. On one surface of the glass substrate 1, a back electrode 4 is formed via a transparent conductive film 2 and a photoelectric conversion film 3 such as amorphous silicon. The amorphous silicon is formed by, for example, a plasma chemical vapor deposition method. The rear surface side of the transparent conductive film 2 is an uneven surface having an average particle size of 0.2 to 0.9 μm. Also,
The short-circuit current can be improved by using the second transparent conductive film as the back electrode.
【０００４】こうした従来技術では、裏面電極として第
２の透明導電膜を用いることで短絡電流が増加すること
を示しているが、これは透明導電膜２の裏面が平均粒径
０．２〜０．９μｍの凹凸面であることから、ガラス基
板１を通して入射した光が散乱することが必要であり、
これがなくては上述のような短絡電流の向上は得られな
い。In such prior art, it has been shown that the use of the second transparent conductive film as the back surface electrode increases the short-circuit current. This is because the back surface of the transparent conductive film 2 has an average particle size of 0.2 to 0. Because of the irregular surface of 0.9 μm, it is necessary that light incident through the glass substrate 1 be scattered,
Without this, the improvement in short-circuit current as described above cannot be obtained.
【０００５】また、凹凸表面形状を有する基板上にプラ
ズマＣＶＤ法等により成長する非晶質シリコン膜が、下
地の形状の影響を受けて凹凸のある成長最表面の形状を
有するために、非晶質シリコン膜と裏面電極４の境界に
凹凸を形成することになる。この裏面電極４の凹凸によ
りガラス基板１を通して入射し発電膜である非晶質シリ
コンにより吸収されずにその一部分が透過した光を乱反
射させることで発電膜である非晶質シリコン層での光の
吸収確率を高くすることができる。この効果により短絡
電流が向上する。In addition, since an amorphous silicon film grown on a substrate having an uneven surface shape by a plasma CVD method or the like has an uneven uppermost surface shape under the influence of the shape of an underlayer, the amorphous silicon film is amorphous. As a result, irregularities are formed at the boundary between the porous silicon film and the back electrode 4. Due to the irregularities of the back electrode 4, light incident on the glass substrate 1 and not partially absorbed by the amorphous silicon serving as the power generation film but partially transmitted therethrough is irregularly reflected, whereby light in the amorphous silicon layer serving as the power generation film is reflected. The absorption probability can be increased. This effect improves the short-circuit current.
【０００６】一方、非晶質シリコンなどの光電変換膜で
は、凹凸面の基板を用いた場合には場所による膜厚の不
均一が原因となって光電変換膜３内部での電界が不均一
になるため、開放電圧が低下する欠点がある。また、基
板の凹凸に起因する光電変換膜３の膜質の低下により光
電変換性能の形状因子や短絡電流が低下する欠点もあ
る。On the other hand, in the case of a photoelectric conversion film made of amorphous silicon or the like, when a substrate having an uneven surface is used, the electric field inside the photoelectric conversion film 3 becomes uneven due to uneven film thickness depending on the location. Therefore, there is a disadvantage that the open-circuit voltage is reduced. In addition, there is a disadvantage that the shape factor of the photoelectric conversion performance and the short-circuit current are reduced due to the deterioration of the quality of the photoelectric conversion film 3 due to the unevenness of the substrate.
【０００７】[0007]
【発明が解決しようとする課題】本発明はこうした事情
を考慮してなされたもので、透光性基板の片面側に、第
１の透明導電膜、光電変換膜、核となる複数の微粒子を
順次形成し、更にれら微粒子により凹凸面となった前記
光電変換膜の片面に微粒子を被覆するように形成された
第２の透明導電膜、裏面金属電極を順次形成した構成と
することにより、開放電圧や形状因子の低下を起こすこ
となく短絡電流を向上できる光電変換素子を提供するこ
とを目的とする。SUMMARY OF THE INVENTION The present invention has been made in view of such circumstances, and a first transparent conductive film, a photoelectric conversion film, and a plurality of fine particles serving as nuclei are provided on one side of a light-transmitting substrate. By sequentially forming, a second transparent conductive film formed so as to cover the fine particles on one side of the photoelectric conversion film which has been made uneven by the fine particles, and a structure in which a back metal electrode is sequentially formed, It is an object of the present invention to provide a photoelectric conversion element capable of improving short-circuit current without lowering open-circuit voltage and form factor.
【０００８】また、本発明は、複数の微粒子の形成と記
第２の透明導電膜の形成を蒸発源の加熱温度及び雰囲気
の酸素圧力を変えることにより制御して、連続的に形成
することにより、開放電圧や形状因子の低下を起こすこ
となく短絡電流を向上できる光電変換素子の製造方法を
提供することを目的とする。Further, the present invention provides a method of controlling the formation of a plurality of fine particles and the formation of the second transparent conductive film by changing the heating temperature of the evaporation source and the oxygen pressure of the atmosphere to form the second transparent conductive film continuously. It is another object of the present invention to provide a method for manufacturing a photoelectric conversion element capable of improving a short-circuit current without lowering an open voltage or a form factor.
【０００９】[0009]
【課題を解決するための手段】本願第１の発明は、透光
性基板と、この透光性基板の片面に形成された第１の透
明導電膜と、この第１の透明導電膜の片面に形成された
光電変換膜と、この光電変換膜の片面に形成された核と
なる複数の微粒子と、これらの微粒子により凹凸面とな
った前記光電変換膜の片面に微粒子を被覆するように形
成された第２の透明導電膜と、この第２の透明導電膜の
片面に形成された裏面金属電極とを具備することを特徴
とする光電変換素子である。Means for Solving the Problems A first invention of the present application is directed to a light-transmitting substrate, a first transparent conductive film formed on one surface of the light-transmitting substrate, and one surface of the first transparent conductive film. Formed on the photoelectric conversion film, a plurality of fine particles serving as nuclei formed on one surface of the photoelectric conversion film, and formed so as to cover the fine particles on one surface of the photoelectric conversion film formed into an uneven surface by these fine particles. And a back metal electrode formed on one surface of the second transparent conductive film.
【００１０】本願第２の発明は、透光性基板の片面に第
１の透明導電膜、光電変換膜、核となる複数の微粒子、
第２の透明導電膜及び裏面金属電極を順次形成してなる
光電変換素子を製造する方法において、前記微粒子の形
成と前記第２の透明導電膜の形成を蒸発源の加熱温度及
び雰囲気の酸素圧力を変えることにより制御し、連続的
に形成することを特徴とする光電変換素子の製造方法で
ある。According to a second aspect of the present invention, a first transparent conductive film, a photoelectric conversion film, a plurality of fine particles serving as nuclei,
In a method for manufacturing a photoelectric conversion element in which a second transparent conductive film and a back metal electrode are sequentially formed, the formation of the fine particles and the formation of the second transparent conductive film are performed by heating a heating source of an evaporation source and an oxygen pressure of an atmosphere. This is a method for manufacturing a photoelectric conversion element, characterized in that the photoelectric conversion element is formed continuously by controlling by changing the thickness.
【００１１】本発明において、前記微粒子の平均直径は
０．０５〜１μｍであり、表面被覆率が０．０１〜１で
あることが好ましい。ここで、微粒子の平均直径が０．
０５μｍ未満であると光電変換装置の変換効率が低くな
り、平均直径が１μｍを越えると光電変換膜と第２の透
明導電膜との接触が技術的に困難になる。また、表面被
覆率を０．０１〜１としたのも同様な理由からである。In the present invention, the fine particles preferably have an average diameter of 0.05 to 1 μm and a surface coverage of 0.01 to 1. Here, the average diameter of the fine particles is 0.
If it is less than 05 μm, the conversion efficiency of the photoelectric conversion device will be low, and if the average diameter exceeds 1 μm, it will be technically difficult to make contact between the photoelectric conversion film and the second transparent conductive film. Further, the surface coverage was set to 0.01 to 1 for the same reason.
【００１２】本発明において、前記微粒子の材料として
は、例えばＳｎＯ2 又はＺｎＯ又はＩｎ2 Ｏ3 を主とし
た材料である透明導電性酸化膜、もしくはＡｌなどの金
属が挙げられる。In the present invention, examples of the material of the fine particles include a transparent conductive oxide film mainly composed of SnO 2, ZnO or In 2 O 3 , or a metal such as Al.
【００１３】本発明において、第２の透明導電膜の膜厚
は、微粒子の平均直径の０．５倍以上であることが好ま
しい。これは、第２の透明導電膜の膜厚が微粒子の平均
直径の０．５倍未満であると、微粒子が形成された光電
変換膜の片面での反射率が低くなるからである。In the present invention, the thickness of the second transparent conductive film is preferably at least 0.5 times the average diameter of the fine particles. This is because if the thickness of the second transparent conductive film is less than 0.5 times the average diameter of the fine particles, the reflectance on one side of the photoelectric conversion film on which the fine particles are formed becomes low.
【００１４】[0014]
【発明の実施の形態】以下、本発明の一実施例に係る光
電変換素子について説明する。まず、その構成について
図１を参照して説明する。DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, a photoelectric conversion device according to one embodiment of the present invention will be described. First, the configuration will be described with reference to FIG.
【００１５】図中の符番11は、厚さ１．１ｍｍのガラス
基板（透光性基板）を示す。このガラス基板11の裏面に
は、酸化スズからなる厚さ８００ｎｍの第１の透明導電
膜12が被着されている。この透明導電膜12の裏面には、
ｐ型，ｉ型，ｎ型の非晶質シリコン半導体からなる光電
変換膜13が形成されている。この光電変換膜13の裏面に
は、核となる微粒子14が被着されている。これらの微粒
子14を含む前記光電変換膜13の裏面には、酸化スズから
なる厚さ２００ｎｍの第２の透明導電膜15が形成されて
いる。この第２の透明導電膜15の裏面には、Ａｌからな
る裏面金属電極16が形成されている。Reference numeral 11 in the figure denotes a glass substrate (light-transmitting substrate) having a thickness of 1.1 mm. On the back surface of the glass substrate 11, a first transparent conductive film 12 made of tin oxide and having a thickness of 800 nm is applied. On the back surface of this transparent conductive film 12,
A photoelectric conversion film 13 made of a p-type, i-type, or n-type amorphous silicon semiconductor is formed. On the back surface of the photoelectric conversion film 13, fine particles 14 serving as nuclei are adhered. On the back surface of the photoelectric conversion film 13 including these fine particles 14, a 200 nm-thick second transparent conductive film 15 made of tin oxide is formed. On the back surface of the second transparent conductive film 15, a back surface metal electrode 16 made of Al is formed.
【００１６】次に、こうした構成の光電変換素子の製造
方法について説明する。但し、この製造に際しては図３
に示す製造装置を用いた。図３において、符番21は真空
容器であり、この真空容器21内の底部側には加熱ヒータ
22を埋めこんだるつぼ23が配置されている。このるつぼ
22には酸素ガス導入管24が接続されている。前記るつぼ
22の真上には、開閉可能な蒸着用シャッター25、前記基
板11を支持する基板加熱ヒータ26が配置されている。更
に、前記るつぼ22と蒸着用シャッター25間には、高周波
放電を起こすためのＲＦアンテナ27が配置されている。Next, a method for manufacturing a photoelectric conversion element having such a configuration will be described. However, in this production, FIG.
Was used. In FIG. 3, reference numeral 21 denotes a vacuum vessel.
A crucible 23 in which 22 is embedded is arranged. This crucible
An oxygen gas introduction pipe 24 is connected to 22. The crucible
Immediately above the substrate 22, an opening / closing evaporation shutter 25 and a substrate heater 26 supporting the substrate 11 are arranged. Further, between the crucible 22 and the vapor deposition shutter 25, an RF antenna 27 for generating a high-frequency discharge is disposed.
【００１７】まず、前記ガラス基板11を５００℃に加熱
したところに、Ｓｉ2 Ｈ6 とＯ2 を別々なノズルから基
板11上に噴射する熱ＣＶＤ法により１００ｎｍ堆積させ
た。つづいて、基板温度を４５０℃に加熱し、ＳｎＣｌ
4 、Ｈ2 Ｏ、ＨＦを別々なノズルから基板11上に噴射す
る熱ＣＶＤ法により基板11上に約８００ｎｍ堆積させ
た。これにより、凹凸の小さい透明導電性基板を得た。[0017] First, were heating the glass substrate 11 at 500 ° C., was 100nm deposited by a thermal CVD method for injecting Si 2 H 6 and O 2 from separate nozzles onto the substrate 11. Subsequently, the substrate temperature was increased to 450 ° C.
4 , H 2 O and HF were deposited on the substrate 11 by a thermal CVD method of spraying them onto the substrate 11 from separate nozzles to a thickness of about 800 nm. Thus, a transparent conductive substrate having small irregularities was obtained.
【００１８】次に、ＲＦアンテナ27を用いた周波数１
３．５６ＭＨｚの高周波放電による気相成長法により、
ｐ型層，ｉ型層，ｎ型層よりなる非晶質シリコン半導体
層を形成した。ここで、ｐ型層を形成するには、ＳｉＨ
4 とＢ2 Ｈ6 、Ｈ2 を原料として用いた。さらに必要で
あればＣＨ4 を加えて用いる。ｎ型層を形成するには、
ＳｉＨ4 とＰＨ3 ，Ｈ2 を原料に用いた。ｉ型層を形成
するには、ＳｉＨ4 を原料に用い、さらに必要であれば
Ｈ2 を追加して用いる。Next, the frequency 1 using the RF antenna 27
By the vapor phase growth method using 3.56 MHz high frequency discharge,
An amorphous silicon semiconductor layer including a p-type layer, an i-type layer, and an n-type layer was formed. Here, to form the p-type layer, SiH
4 , B 2 H 6 , and H 2 were used as raw materials. Further, if necessary, CH 4 is used. To form an n-type layer,
SiH 4 , PH 3 and H 2 were used as raw materials. To form an i-type layer, SiH 4 is used as a raw material, and H 2 is additionally used if necessary.
【００１９】次に、真空容器21内に非晶質シリコン層ま
で積層した基板11をるつぼ23の上方４００ｍｍにセット
し真空に排気し、基板を基板加熱用ヒータ26により１５
０℃に加熱した。そして、加熱ヒータ22によりるつぼ23
内のＳｎＯ原料を１５００℃に加熱した。蒸着用シャッ
ター25を開ける前に酸素ガス導入管26から酸素ガスを１
０ｍＴｏｒｒの圧力に制御して導入し、さらに１３．５
６ＭＨｚの高周波によりプラズマを励起した。これによ
り、平均粒径１００ｎｍの粒子状のＳｎＯ2 が発電膜上
に堆積した。Next, the substrate 11 laminated up to the amorphous silicon layer in the vacuum vessel 21 is set at 400 mm above the crucible 23 and evacuated to a vacuum.
Heated to 0 ° C. Then, the crucible 23 is heated by the heater 22.
The SnO material inside was heated to 1500 ° C. Before opening the vapor deposition shutter 25, supply 1 oxygen gas from the oxygen gas introduction pipe 26.
The pressure was controlled at 0 mTorr and introduced.
The plasma was excited by a high frequency of 6 MHz. As a result, particulate SnO 2 having an average particle diameter of 100 nm was deposited on the power generation film.
【００２０】次に、蒸着用シャッター25を開いた２０秒
後にるつぼ23の温度を６００℃に下げると共に酸素圧力
を０．１ｍＴｏｒｒに調整した。これにより均一な膜を
成膜できるようになった。そして、連続的な膜が２００
ｎｍになったところで蒸着用シャッター25を閉じた。本
手順により非晶質シリコン膜の上には、ヘイズ率４３％
の凹凸を有する第２の透明導電膜15が形成された。つづ
いて、蒸着装置よりＡｌを５００ｎｍ蒸着して裏面金属
電極16を形成し、光電変換素子を製造した。Next, 20 seconds after the shutter 25 was opened, the temperature of the crucible 23 was lowered to 600 ° C. and the oxygen pressure was adjusted to 0.1 mTorr. As a result, a uniform film can be formed. And a continuous film is 200
When the thickness reached nm, the vapor deposition shutter 25 was closed. According to this procedure, the haze ratio is 43% on the amorphous silicon film.
The second transparent conductive film 15 having the unevenness was formed. Subsequently, Al was vapor-deposited to a thickness of 500 nm from a vapor deposition apparatus to form a back metal electrode 16, thereby producing a photoelectric conversion element.
【００２１】図１の構成の光電変換素子において、ガラ
ス基板11（図面の上方）から入射した光は光電変換膜13
により電気に変換され、第１の透明導電膜12と，微粒子
14及び第２の透明導電膜15からなる第２の透明導電膜及
び裏面金属電極16を通じて、図示されていない電力出力
端子より電力を出力する。入射した光電変換膜で吸収さ
れなかった光の一部は、主に光電変換膜13と第２の透明
導電膜15の界面及び第２の透明導電膜15と裏面金属電極
16の界面で反射され、再び光電変換膜により電気に変換
される。In the photoelectric conversion device having the structure shown in FIG. 1, light incident from the glass substrate 11 (upper part of the drawing)
Is converted into electricity by the first transparent conductive film 12 and the fine particles.
Power is output from a power output terminal (not shown) through the second transparent conductive film composed of 14 and the second transparent conductive film 15 and the back metal electrode 16. Part of the light that has not been absorbed by the photoelectric conversion film is mainly emitted at the interface between the photoelectric conversion film 13 and the second transparent conductive film 15 and between the second transparent conductive film 15 and the back metal electrode.
The light is reflected at the interface of No. 16 and converted again into electricity by the photoelectric conversion film.
【００２２】従来の光電変換素子ではその変換効率を向
上させるために、裏面凹凸形状を有するところに光電変
換膜を形成する方法であったが、本発明では表面凹凸形
状が小さい基板を用いることで従来の方法における課題
であった光電変換膜の膜質低下による光電変換効率の低
下及び膜質の不均一による開放電圧、形状因子の低下に
よる光電変換効率の低下を解決できる。In a conventional photoelectric conversion element, a method of forming a photoelectric conversion film in a place having a concave and convex shape on the back side is used in order to improve the conversion efficiency. However, in the present invention, a substrate having a small concave and convex shape on the surface is used. It is possible to solve the problems of the conventional method, that is, the decrease in photoelectric conversion efficiency due to the deterioration of the film quality of the photoelectric conversion film, and the decrease in the photoelectric conversion efficiency due to the decrease in the open voltage and the form factor due to the unevenness of the film quality.
【００２３】一方、光電変換膜では波長特性として長波
長の光は吸収係数が低く、光電変換効率が小さいため
に、吸収されずに第２の透明導電膜15側に透過する。透
過した光は光電変換膜13と第２の透明導電膜15又は微粒
子の界面において屈折率の違いから一部が反射するが、
多くは界面を透過して微粒子14を含む第２の透明導電膜
15に透過する。第２の透明導電膜15は透明な材料から構
成されているから、透過した光は第２の透明導電膜15と
裏面金属電極16の界面で反射される。このとき、第２の
透明導電膜15は膜中に微粒子14を含有するため、その表
面形状は微粒子の直径程度の凹凸を有する。そのため、
第２の透明導電膜15と裏面金属電極16の界面で反射され
た光は高い確率で入射光とは異なる方向に反射される。On the other hand, in the photoelectric conversion film, light having a long wavelength as a wavelength characteristic has a low absorption coefficient and a small photoelectric conversion efficiency, so that it is transmitted through the second transparent conductive film 15 without being absorbed. The transmitted light is partially reflected at the interface between the photoelectric conversion film 13 and the second transparent conductive film 15 or the fine particles due to a difference in refractive index.
A second transparent conductive film, often containing fine particles 14, passing through the interface
Transmit to 15 Since the second transparent conductive film 15 is made of a transparent material, the transmitted light is reflected at the interface between the second transparent conductive film 15 and the back metal electrode 16. At this time, since the second transparent conductive film 15 contains the fine particles 14 in the film, the surface shape has irregularities about the diameter of the fine particles. for that reason,
The light reflected at the interface between the second transparent conductive film 15 and the back metal electrode 16 is reflected in a direction different from the incident light with a high probability.
【００２４】従って、例えば垂直に入射した光は裏面の
第２の透明導電膜15と微粒子14の界面で斜めに反射さ
れ、光電変換膜13に再度入射することになる。そのた
め、光路長が長くなるとともに、特定の角度以上に斜め
に反射された光は、光電変換膜13と第１の透明導電膜12
の界面で光電変換膜13の光電変換膜側から入射した光に
対する全反射条件となり、再度光電変換膜中に反射され
る。従って、さらに光路が長くなり光電変換膜に吸収さ
れ電力に変換される確率が高くなり、短絡電流を向上す
る。Therefore, for example, the vertically incident light is obliquely reflected at the interface between the second transparent conductive film 15 and the fine particles 14 on the back surface, and reenters the photoelectric conversion film 13. Therefore, the light path length becomes longer and the light obliquely reflected at a certain angle or more is reflected by the photoelectric conversion film 13 and the first transparent conductive film 12.
At the interface, the condition for total reflection of light incident from the photoelectric conversion film side of the photoelectric conversion film 13 is satisfied, and the light is reflected back into the photoelectric conversion film. Therefore, the optical path is further lengthened, the probability of being absorbed by the photoelectric conversion film and being converted into electric power is increased, and the short-circuit current is improved.
【００２５】このとき、裏面の凹凸の大きさは波長に対
して適当に大きくなければ斜めの反射率が低くなるた
め、微粒子の直径としては非晶質シリコンを用いた光電
変換装置の変換効率が高くなる波長である５００ｎｍの
光学膜厚として０．５倍以上である１２５ｎｍ以上ある
ことが最も望ましいが、５０ｎｍ以上であればよい。そ
の一方で、微粒子の直径が大きくなり過ぎると、光電変
換膜と微粒子を含有する第２の透明導電膜15との接触が
技術的に困難となるため、１μｍ以下が適当である。ま
た、同様な理由により、微粒子の表面被覆率は０．０１
〜１の範囲が望ましい。At this time, if the size of the irregularities on the back surface is not appropriately large with respect to the wavelength, the oblique reflectance will be low, and the conversion efficiency of the photoelectric conversion device using amorphous silicon will be small as the diameter of the fine particles. Most preferably, the optical film thickness of 500 nm, which is a higher wavelength, is 125 nm or more, which is 0.5 times or more, but may be 50 nm or more. On the other hand, if the diameter of the fine particles is too large, it becomes technically difficult to make contact between the photoelectric conversion film and the second transparent conductive film 15 containing the fine particles. For the same reason, the surface coverage of the fine particles is 0.01%.
The range of ~ 1 is desirable.
【００２６】なお、上記光学膜厚「１２５ｎｍ」は、次
のようにして求めた。即ち、微粒子の直径をＤとする
と、Ｄ＝λ／２ｎとなる。但し、λ：波長、ｎ：屈折
率。ここで、λ＝５００ｎｍ、ｎ＝２とすると、Ｄ＝５
００／２×２＝１２５ｎｍとなる。The optical thickness "125 nm" was obtained as follows. That is, assuming that the diameter of the fine particles is D, D = λ / 2n. Here, λ: wavelength, n: refractive index. Here, if λ = 500 nm and n = 2, D = 5
00/2 × 2 = 125 nm.
【００２７】従って、微粒子を成膜するときのＳｎＯの
加熱温度としては７００℃から２０００℃の範囲であれ
ばよいが、望ましくは１０００℃から１２００℃の範囲
が良い。酸素の圧力は１ｍＴｏｒｒから１０Ｔｏｒｒの
範囲であればよいが、望ましくは５ｍＴｏｒｒから１０
０ｍＴｏｒｒの範囲である。また、高周波電力は１Ｗ以
上であればよいが、１０Ｗから２００Ｗの範囲が望まし
い。更に、成膜時間は微粒子の表面被覆率により適当に
定める。Accordingly, the heating temperature of SnO for forming fine particles may be in the range of 700 ° C. to 2000 ° C., and preferably in the range of 1000 ° C. to 1200 ° C. The pressure of oxygen may be in the range of 1 mTorr to 10 Torr, but is preferably 5 mTorr to 10 Torr.
The range is 0 mTorr. The high-frequency power may be 1 W or more, but is preferably in the range of 10 W to 200 W. Further, the film formation time is appropriately determined depending on the surface coverage of the fine particles.
【００２８】微粒子形成後のＳｎＯの加熱温度は５００
℃から１０００℃の範囲であればよいが、５７０℃から
６８０℃の範囲が望ましい。その時の酸素圧力は１Ｔｏ
ｒｒ以下であればよいが、５０Ｗから４００Ｗの範囲が
望ましい。また、微粒子に入射した光は、微粒子14を包
含する第２の透明導電膜15との界面において反射され
る。このとき、微粒子14と第２の透明導電膜15の組成が
異なればそれらの界面での反射が起こり、上記と同様に
斜めの反射率が高くなる。その結果、短絡電流に向上が
得られる。The heating temperature of SnO after the formation of fine particles is 500
The temperature may be in the range of ℃ to 1000 ° C, but preferably in the range of 570 ° C to 680 ° C. The oxygen pressure at that time is 1 To
rr or less, but preferably in the range of 50W to 400W. Light incident on the fine particles is reflected at the interface with the second transparent conductive film 15 including the fine particles 14. At this time, if the compositions of the fine particles 14 and the second transparent conductive film 15 are different, reflection occurs at the interface between them, and the oblique reflectance increases as described above. As a result, the short-circuit current is improved.
【００２９】なお、上記実施例では、微粒子としてＳｎ
Ｏ2 、ＺｎＯ、Ｉｎ2 Ｏ3 が主とした構成材料である透
明導電性酸化物を用いた場合について述べたが、これに
限らず、ＡｌやＡｇ、Ａｕなどの金属を用いても良い。
また、この場合にも微粒子の粒径は上記と同様に光の散
乱性能のために５０ｎｍ以上が望ましい。In the above embodiment, Sn was used as the fine particles.
Although a case has been described where a transparent conductive oxide mainly composed of O 2 , ZnO, and In 2 O 3 is used, the invention is not limited to this, and a metal such as Al, Ag, or Au may be used.
Also in this case, the particle diameter of the fine particles is desirably 50 nm or more for the light scattering performance in the same manner as described above.
【００３０】また、上記実施例では微粒子を光電変換膜
に付着させた後、第２の透明導電膜を連続的に被着する
手順を示したが、別々の手順として実施してもよい。ま
た、第２の透明導電膜を形成した後に微粒子を形成して
もよく、一部の第２の透明導電膜を形成した後に微粒子
を形成し、再び残りの第２の透明導電膜を形成してもよ
く、更に第２の透明導電膜と微粒子を同時に形成しても
良く、さらにはこれらを組合わせても繰り返し形成して
も良い。このうち、第２の透明導電膜を形成した後に、
第２の透明導電膜と微粒子を同時に形成し、その後第２
の透明導電膜を形成する手順が最も望ましい。本手順に
より、微粒子を含有する第２の透明導電膜と光電変換膜
及び裏面金属電極との密着性が高くなり、電気的な抵抗
を小さくできる。このとき、第２の透明導電膜の膜厚
は、内部に含有する微粒子の直径の１倍以上であること
が望ましい。Further, in the above-described embodiment, the procedure in which fine particles are adhered to the photoelectric conversion film and then the second transparent conductive film is continuously applied is described. Alternatively, the fine particles may be formed after forming the second transparent conductive film. The fine particles may be formed after forming a part of the second transparent conductive film, and the remaining second transparent conductive film may be formed again. Alternatively, the second transparent conductive film and the fine particles may be simultaneously formed, or these may be combined or repeatedly formed. After forming the second transparent conductive film,
The second transparent conductive film and the fine particles are formed at the same time.
Is most desirable. According to this procedure, the adhesion between the second transparent conductive film containing fine particles, the photoelectric conversion film, and the back metal electrode is increased, and the electrical resistance can be reduced. At this time, the thickness of the second transparent conductive film is desirably at least one time the diameter of the fine particles contained therein.
【００３１】[0031]
【発明の効果】以上詳述したように本発明によれば、透
明導電膜として凹凸のない表面のものを用いて開放電圧
や形状因子の低下を起こすことなく短絡電流を向上でき
る光電変換素子及びその製造方法を提供できる。As described above in detail, according to the present invention, a photoelectric conversion element capable of improving a short-circuit current without lowering the open-circuit voltage and the form factor by using a transparent conductive film having a surface without unevenness is provided. The manufacturing method can be provided.
【図１】本発明の一実施例に係る光電変換素子の断面
図。FIG. 1 is a sectional view of a photoelectric conversion element according to one embodiment of the present invention.
【図２】従来の光電変換素子の断面図。FIG. 2 is a cross-sectional view of a conventional photoelectric conversion element.
【図３】光電変換素子を製造するための装置の説明図。FIG. 3 is an explanatory view of an apparatus for manufacturing a photoelectric conversion element.
11…ガラス基板、 12…第１の透明導電膜、 13…光電変換膜、 14…微粒子、 15…第２の透明導電膜、 16…裏面金属電極、 21…真空容器、 23…るつぼ、 25…蒸着用シャッター、 26…基板加熱用ヒータ、 27…ＲＦアンテナ。 11: glass substrate, 12: first transparent conductive film, 13: photoelectric conversion film, 14: fine particles, 15: second transparent conductive film, 16: back metal electrode, 21: vacuum vessel, 23: crucible, 25 ... Shutter for evaporation, 26: heater for substrate heating, 27: RF antenna.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 森田 章二 長崎県長崎市深堀町五丁目717番１号 三 菱重工業株式会社長崎研究所内 (72)発明者 竹内 良昭 長崎県長崎市深堀町五丁目717番１号 三 菱重工業株式会社長崎研究所内 (72)発明者 西宮 立享 長崎県長崎市深堀町五丁目717番１号 三 菱重工業株式会社長崎研究所内 Ｆターム(参考） 5F051 DA20 FA02 FA06 FA15 FA18 FA19 FA23 FA30 GA03 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Shoji Morita 5-717-1, Fukahori-cho, Nagasaki-shi, Nagasaki Sansei Heavy Industries Co., Ltd. Nagasaki Research Institute (72) Inventor Yoshiaki Takeuchi 5-chome, Fukahori-cho, Nagasaki-shi, Nagasaki No. 717 No. 1 in Nagasaki Laboratory, Mitsubishi Heavy Industries, Ltd. (72) Inventor Tatsuyoshi Nishimiya 5-717-1, Fukahori-cho, Nagasaki-shi, Nagasaki F-term in Nagasaki Research Laboratory, Mitsubishi Heavy Industries, Ltd. 5F051 DA20 FA02 FA06 FA06 FA15 FA18 FA19 FA23 FA30 GA03
Claims (4)
形成された第１の透明導電膜と、この第１の透明導電膜
の片面に形成された光電変換膜と、この光電変換膜の片
面に形成された核となる複数の微粒子と、これらの微粒
子により凹凸面となった前記光電変換膜の片面に微粒子
を被覆するように形成された第２の透明導電膜と、この
第２の透明導電膜の片面に形成された裏面金属電極とを
具備することを特徴とする光電変換素子。A light-transmitting substrate; a first transparent conductive film formed on one surface of the light-transmitting substrate; a photoelectric conversion film formed on one surface of the first transparent conductive film; A plurality of fine particles serving as nuclei formed on one surface of the conversion film, and a second transparent conductive film formed so as to cover the fine particles on one surface of the photoelectric conversion film formed into an uneven surface by these fine particles; And a back metal electrode formed on one surface of the second transparent conductive film.
ｍであり、表面被覆率が０．０１〜１であることを特徴
とする請求項１記載の光電変換素子。2. The fine particles have an average diameter of 0.05 to 1 μm.
The photoelectric conversion element according to claim 1, wherein m is 1 and the surface coverage is 0.01 to 1.
均直径の０．５倍以上であることを特徴とする請求項１
記載の光電変換素子。3. The film thickness of the second transparent conductive film is at least 0.5 times the average diameter of the fine particles.
The photoelectric conversion device according to any one of the preceding claims.
光電変換膜、核となる複数の微粒子、第２の透明導電膜
及び裏面金属電極を順次形成してなる光電変換素子を製
造する方法において、 前記微粒子の形成と前記第２の透明導電膜の形成を蒸発
源の加熱温度及び雰囲気の酸素圧力を変えることにより
制御し、連続的に形成することを特徴とする光電変換素
子の製造方法。4. A first transparent conductive film on one side of a translucent substrate,
In a method of manufacturing a photoelectric conversion element in which a photoelectric conversion film, a plurality of fine particles serving as a nucleus, a second transparent conductive film, and a back metal electrode are sequentially formed, the formation of the fine particles and the formation of the second transparent conductive film And controlling the temperature by changing the heating temperature of the evaporation source and the oxygen pressure of the atmosphere to form the photoelectric conversion element continuously.
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|---|---|---|---|
| JP10287872A JP2000114562A (en) | 1998-10-09 | 1998-10-09 | Photoelectric conversion element and manufacture thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10287872A JP2000114562A (en) | 1998-10-09 | 1998-10-09 | Photoelectric conversion element and manufacture thereof |
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| Publication Number | Publication Date |
|---|---|
| JP2000114562A true JP2000114562A (en) | 2000-04-21 |
Family
ID=17722843
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10287872A Pending JP2000114562A (en) | 1998-10-09 | 1998-10-09 | Photoelectric conversion element and manufacture thereof |
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| Country | Link |
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| JP (1) | JP2000114562A (en) |
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| JP2008506249A (en) * | 2004-07-07 | 2008-02-28 | サン−ゴバン グラス フランス | Solar cell and solar module |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008506249A (en) * | 2004-07-07 | 2008-02-28 | サン−ゴバン グラス フランス | Solar cell and solar module |
| JP2006128478A (en) * | 2004-10-29 | 2006-05-18 | Mitsubishi Heavy Ind Ltd | Photoelectric converter |
| US8129611B2 (en) | 2004-12-10 | 2012-03-06 | Mitsubishi Heavy Industries, Ltd. | Light-scattering film and optical device using the same |
| JP2008270562A (en) * | 2007-04-20 | 2008-11-06 | Sanyo Electric Co Ltd | Multi-junction type solar cell |
| JP2009099643A (en) * | 2007-10-15 | 2009-05-07 | Mitsubishi Electric Corp | Thin-film solar cell element, and its manufacturing method |
| JP4619388B2 (en) * | 2007-10-15 | 2011-01-26 | 三菱電機株式会社 | Thin film solar cell element and manufacturing method thereof |
| WO2010004811A1 (en) * | 2008-07-07 | 2010-01-14 | 三菱電機株式会社 | Thin film solar cell and manufacturing method thereof |
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