JPH0714073B2 - Photoelectric conversion element manufacturing method and manufacturing apparatus thereof - Google Patents
Photoelectric conversion element manufacturing method and manufacturing apparatus thereofInfo
- Publication number
- JPH0714073B2 JPH0714073B2 JP60284381A JP28438185A JPH0714073B2 JP H0714073 B2 JPH0714073 B2 JP H0714073B2 JP 60284381 A JP60284381 A JP 60284381A JP 28438185 A JP28438185 A JP 28438185A JP H0714073 B2 JPH0714073 B2 JP H0714073B2
- Authority
- JP
- Japan
- Prior art keywords
- electrode
- substrate
- conductive layer
- photoactive layer
- formation
- 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.)
- Expired - Fee Related
Links
- 238000006243 chemical reaction Methods 0.000 title claims description 24
- 238000004519 manufacturing process Methods 0.000 title claims description 20
- 239000000758 substrate Substances 0.000 claims description 43
- 230000015572 biosynthetic process Effects 0.000 claims description 42
- PZPGRFITIJYNEJ-UHFFFAOYSA-N disilane Chemical compound [SiH3][SiH3] PZPGRFITIJYNEJ-UHFFFAOYSA-N 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 15
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 9
- 238000000354 decomposition reaction Methods 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 4
- 229910052990 silicon hydride Inorganic materials 0.000 claims description 4
- 239000010409 thin film Substances 0.000 claims description 4
- 230000001419 dependent effect Effects 0.000 claims description 3
- 238000010924 continuous production Methods 0.000 claims 1
- 238000002360 preparation method Methods 0.000 claims 1
- 239000010408 film Substances 0.000 description 22
- 239000007789 gas Substances 0.000 description 13
- 229910021417 amorphous silicon Inorganic materials 0.000 description 9
- 230000007423 decrease Effects 0.000 description 6
- 229910052734 helium Inorganic materials 0.000 description 5
- 239000001307 helium Substances 0.000 description 5
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000011521 glass Substances 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000003085 diluting agent Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 238000003780 insertion Methods 0.000 description 3
- 230000037431 insertion Effects 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- 230000002542 deteriorative effect Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000011810 insulating material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 150000001343 alkyl silanes Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- ZOCHARZZJNPSEU-UHFFFAOYSA-N diboron Chemical compound B#B ZOCHARZZJNPSEU-UHFFFAOYSA-N 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910001120 nichrome Inorganic materials 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 150000003376 silicon Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/20—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof such devices or parts thereof comprising amorphous semiconductor materials
- H01L31/202—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof such devices or parts thereof comprising amorphous semiconductor materials including only elements of Group IV of the Periodic System
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Description
【発明の詳細な説明】 〔技術分野〕 本発明は非晶質シリコン（以下ａ−Si:Hと略称する）光
電変換素子の製法及びその製造装置に関し、特にその高
効率化、高速製造およびその製造装置に関する。TECHNICAL FIELD The present invention relates to a method for manufacturing an amorphous silicon (hereinafter abbreviated as a-Si: H) photoelectric conversion element and an apparatus for manufacturing the same, and more particularly, to high efficiency, high speed manufacturing and the same. Manufacturing equipment
光電変換素子特に非晶質シリコン太陽電池の高効率化が
検討されて通常の成膜速度においては或る程度の成果を
あげつつあるが、高速成膜条件においては、未だ効率の
向上は緒についたばかりである。すなわち、光活性層の
形成速度が20Å/S程度もしくはこれを越えるような高速
成膜条件においては、所望の高効率化は達成されていな
い。Higher efficiency of photoelectric conversion elements, especially amorphous silicon solar cells, has been studied and some results have been achieved at normal film forming speeds, but under high-speed film forming conditions, the improvement of efficiency is still in progress. I just started. That is, the desired high efficiency has not been achieved under the high-speed film forming conditions in which the formation rate of the photoactive layer is about 20 Å / S or more.
本発明者らは先に、高速でかつ高効率を達成するために
ジシラン（Si2H6）を原料とする非晶質シリコン太陽電
池の製造方法を開示した。これはジシランを原料とした
場合、或る閾値を越えるエネルギーが供給される条件下
でジシランを分解することが原理的に不可欠であること
を開示したものである。The present inventors have previously disclosed a method for producing an amorphous silicon solar cell using disilane (Si 2 H 6 ) as a raw material in order to achieve high speed and high efficiency. This discloses that when disilane is used as a raw material, it is in principle essential to decompose the disilane under the condition that energy exceeding a certain threshold is supplied.
しかしながら、ジシランは、本発明者が見出したように
本質的に高速成膜性であるが故に、素子の半導体接合界
面の制御が困難であった。なんとなれば、この界面領域
は高々1000Å以下の厚みであり、20Å/Sの如き高速で成
膜を行う場合、僅か50秒以下の短い時間で該界面領域を
制御しなければならないからである。本発明者らは、こ
の領域をモノシランで形成したり、放電電力を低下させ
て膜形成速度（以下単に形成速度と称する）を遅くした
りして該領域を制御しながら形成することを試みたが未
だ充分な成果は得ていない。However, since disilane has an essentially high-speed film-forming property as found by the present inventor, it was difficult to control the semiconductor junction interface of the device. This is because this interface region has a thickness of 1000 Å or less at most, and when the film is formed at a high speed of 20 Å / S, the interface region must be controlled in a short time of only 50 seconds or less. The present inventors attempted to form this region with monosilane, or to reduce the discharge power to slow the film formation rate (hereinafter simply referred to as the formation rate) to form the region while controlling it. However, we have not yet obtained sufficient results.
本発明者らは、モノシランで界面領域を作成してジシラ
ンへ移行することや、ジシランを用いかつ放電電力を低
下させて形成速度を遅くすることは、たとえ数100Åの
微小領域と雖も好ましくないことを見出した。けだし、
これらの場合は、曲線因子（F.F.）および短絡電流（J
SC）の著しい低下が生ずるからである。The present inventors have found that it is not preferable to create an interface region with monosilane and transfer it to disilane, or to use disilane and reduce the discharge power to slow the formation rate, even if it is a minute region of several hundred Å and a drop. I found that. Kashi,
In these cases, fill factor (FF) and short-circuit current (J
This is because a significant decrease in SC ) occurs.
本発明の目的は高速成膜条件においても短絡電流の低下
や曲線因子の低下を起すことがない、高光電変換効率の
光電変換素子を製造する方法およびかかる方法に使用さ
れる製造装置を提供することである。An object of the present invention is to provide a method for manufacturing a photoelectric conversion element having high photoelectric conversion efficiency and a manufacturing apparatus used for such a method, which does not cause a decrease in short-circuit current or a decrease in fill factor even under high-speed film forming conditions. That is.
本発明者らはジシランとモノシランの併用は好ましくな
いので、ジシランのみで光活性層を製造する技術につい
て検討し、必要エネルギーを与えつつ、形成速度を制御
することにより、膜質を劣化させることなく界面を形成
しうることに着目し、本発明を完成するに到ったもので
ある。Since the present inventors do not prefer the combined use of disilane and monosilane, we examined a technique for producing a photoactive layer using only disilane, and by controlling the formation rate while giving necessary energy, the interface without deteriorating the film quality. The present invention has been completed, paying attention to the fact that the above can be formed.
すなわち、本発明は、 第１の電極を有する基板上に、シリコン水素化物のグロ
ー放電分解により、第１の導電層、光活性層および第２
の導電層を順次形成し、第２の電極を設ける光電変換素
子の製法において、少なくとも該光活性層の形成をジシ
ランにより行い、かつ、該ジシラン単位質量当たり、活
性層薄膜の形成速度が主としてジシラン流量に依存し印
加エネルギー量によっては実質的に影響されることのな
い最低のエネルギー量（以下閾値と言う）以上のエネル
ギーを印加すると共に、該光活性層形成の少なくとも初
期領域は、該基板と該基板の光活性層形成主面に対向す
る放電電極との間に斜向して設けた第３の電極のバイア
ス電圧を印加して行うことを特徴とする光電変換素子の
製法、および、 第１の電極を有する基板上に、シリコン水素化物のグロ
ー放電分解により、第１の導電層、光活性層および第２
の導電層を順次形成しうる形成室を少なくとも備えた光
電変換素子の連続製造装置であって、該光活性層の形成
室は対向して設備されたグロー放電電極間にバイアス電
圧を印加出来る第３の電極が斜向して設けられているこ
とを特徴とする光電変換素子の連続製造装置を要旨とす
るものである。That is, the present invention provides a first conductive layer, a photoactive layer, and a second active layer on a substrate having a first electrode by glow discharge decomposition of silicon hydride.
In the method for producing a photoelectric conversion element in which conductive layers are sequentially formed and a second electrode is provided, at least the photoactive layer is formed by disilane, and the formation rate of the active layer thin film is mainly disilane per unit mass of the disilane. An energy of a minimum energy amount (hereinafter referred to as a threshold value) or more that is dependent on the flow rate and is not substantially affected by the applied energy amount is applied, and at least the initial region of the photoactive layer formation is applied to the substrate. A method for manufacturing a photoelectric conversion element, characterized in that a bias voltage is applied to a third electrode obliquely provided between the substrate and a discharge electrode facing the photoactive layer forming main surface, and The first conductive layer, the photoactive layer and the second layer are formed on the substrate having the first electrode by glow discharge decomposition of silicon hydride.
An apparatus for continuously manufacturing a photoelectric conversion element, which is provided with at least a forming chamber capable of sequentially forming a conductive layer, wherein the forming chamber of the photoactive layer is capable of applying a bias voltage between glow discharge electrodes provided facing each other. The gist of the present invention is a continuous manufacturing apparatus for photoelectric conversion elements, characterized in that three electrodes are provided obliquely.
以下、本発明を詳細に説明する。Hereinafter, the present invention will be described in detail.
本発明において使用するジシランとは、モノシラン含量
が10vol％未満、より好ましくは５％未満より好ましく
は1vol％未満、さらに好ましくは0.1％未満、最も好ま
しくはほぼ０％のものである。モノシランの含量がこれ
より大になると、太陽電池の曲線因子（F.F.）が急激に
悪化するからである。The disilane used in the present invention has a monosilane content of less than 10 vol%, more preferably less than 5%, more preferably less than 1 vol%, further preferably less than 0.1%, most preferably almost 0%. When the content of monosilane is higher than this, the fill factor (FF) of the solar cell deteriorates rapidly.
本発明において閾値とは、活性層薄膜の形成速度が主と
してジシラン流量にのみ依存して変化し、印加エネルギ
ー量によっては実質的に影響されることのないような、
ジシラン単位質量当たりの最低のエネルギー量として定
義される。該閾値について、より具体的には、本発明者
らが特開昭58−1726号公報に開示してように、ａ−Si:H
膜の形成速度がグロー放電に用いる高周波電力に依存し
て変化しなくなるところのグロー放電電力の値である。In the present invention, the threshold is such that the formation rate of the active layer thin film changes mainly depending only on the disilane flow rate and is not substantially affected by the applied energy amount,
It is defined as the lowest amount of energy per unit mass of disilane. Regarding the threshold value, more specifically, as disclosed by the present inventors in Japanese Patent Laid-Open No. 58-1726, a-Si: H
It is the value of glow discharge power at which the film formation rate does not change depending on the high frequency power used for glow discharge.
本発明においては、該閾値、つまり最低限度の必要エネ
ルギーを与えつつ、形成速度を変更・制御することが最
も重要な点であるが、かかる目的を達成するために、光
電変換素子が形成される基板と該基板の光活性層形成主
面に対向する放電電極との間に斜向して設けた第３の電
極にバイアス電圧を印加するものである。In the present invention, it is the most important point to change and control the formation speed while giving the threshold value, that is, the minimum required energy, but in order to achieve such an object, a photoelectric conversion element is formed. A bias voltage is applied to a third electrode obliquely provided between the substrate and the discharge electrode facing the main surface of the substrate on which the photoactive layer is formed.
かかる方法を用いることにより、ジシランによりａ−S
i:H膜を形成するにあたっても、その膜質を低下させる
ことなく、肝心の界面領域の形成速度を充分な制御下に
行いうるので、界面における不純物の分布を好適に制御
しかつ膜質の異なる界面の形成を実質的に回避すること
が出来ると考えられる。これに対し、SiH4を用いる方法
や、Si2H6を用いてもその流量を変化させる従来の方法
においては、前記の問題点は実質的に解決出来ないので
ある。By using such a method, a
Even when forming an i: H film, it is possible to perform the formation of the interfacial region of the core under sufficient control without deteriorating the film quality. It is believed that the formation of On the other hand, in the method using SiH 4 and the conventional method in which the flow rate is changed even if Si 2 H 6 is used, the above problems cannot be substantially solved.
本発明においてかかる閾値は供給エネルギー（Supplied
Energy）として表すのが便利である。In the present invention, the threshold value is the supplied energy (Supplied
Energy) is convenient.
供給エネルギーの算出は次式による。The supply energy is calculated by the following formula.
〔Ｉ〕式に用いる成膜条件の単位はRF電力（Ｗ）、原料
ガス流量（標準状態毎分当たりの流量＝SCCM）、であ
り、1344＝60（分）×22.4（/mol）で表される係数で
ある。たとえば、ジシラン30SCCM、希釈のためのヘリウ
ムガス270SCCMのときは、平均分子量＝（30×62.2＋270
×4/300＝98.2、ジシラン重量分率＝（30×62.2）／（3
00×9.82）＝0.633であり、RF電力（グロー放電電力）
＝100Wのときには、〔Ｉ〕式に代入して、 を得る。 The unit of the film forming conditions used in the formula [I] is RF power (W), raw material gas flow rate (standard state flow rate per minute = SCCM), and is represented by 1344 = 60 (min) × 22.4 (/ mol) Is a coefficient that is For example, in the case of disilane 30SCCM and helium gas 270SCCM for dilution, the average molecular weight = (30 x 62.2 + 270
X4 / 300 = 98.2, disilane weight fraction = (30 x 62.2) / (3
00 x 9.82) = 0.633, RF power (glow discharge power)
= 100W, substitute in the formula [I], To get
なお、閾値の値は先に定義した通りであるが、該閾値は
使用する反応装置や反応条件によって異なることは言う
までもない。かかる閾値についてたとえば平行平板型プ
ラズマCVD装置について本発明者らの検討結果による実
際の具体的な数値を例示すると、ジシラン単独では40
（KJ/g−Si2H6）、ヘリウム希釈10％ジシランの場合は1
0（KJ/g−Si2H6）、水素希釈10％ジシランの場合は30
（KJ/g−Si2H6）の如くであり、希釈されたジシランの
方が低い閾値を示す。The threshold value is as defined above, but it goes without saying that the threshold value varies depending on the reaction apparatus and reaction conditions used. With respect to such a threshold value, for example, when an actual specific numerical value based on the result of the study conducted by the present inventors for a parallel plate type plasma CVD apparatus is illustrated, disilane alone is 40
(KJ / g-Si 2 H 6 ), 1 for helium diluted 10% disilane
0 (KJ / g-Si 2 H 6 ), 30 for hydrogen diluted 10% disilane
(KJ / g-Si 2 H 6 ), with diluted disilane showing a lower threshold.
本発明の方法は光活性層の形成をジシランにより行い、
かつジシランにかかる閾値以上の供給エネルギーを常に
印加するとともに、特に光活性層の少なくとも初期領域
（界面領域）を充分な形成速度の制御下に形成すること
を基本的の特徴とするものであるが、そのための具体的
手段としてその形成速度を第３の電極に印加するバイア
ス電流により変更制御するものである。In the method of the present invention, the photoactive layer is formed by disilane,
In addition, the basic feature is to constantly apply a supply energy equal to or more than the threshold value for disilane and to form at least the initial region (interface region) of the photoactive layer under sufficient control of the formation rate. As a specific means therefor, the formation rate is changed and controlled by a bias current applied to the third electrode.
光活性層の形成はまず界面領域から行われる。本発明に
おける界面領域とは、光活性層の形成開始もしくは形成
終了点から約1000Åの膜厚部分、より好ましくは、50〜
500Åの膜厚部分を意味する。The photoactive layer is first formed from the interface region. The interface region in the present invention is a film thickness portion of about 1000 Å from the formation start or formation end point of the photoactive layer, more preferably 50 to
It means the film thickness part of 500Å.
界面領域の形成、特に第１導電層に接する界面領域の形
成は、該基板と該基板の光活性層形成主面に対向する放
電電極との間に斜向して設けた第３の電極にバイアス電
圧を印加し、該第３の電極の電位が接地電位に対してよ
り負電位になるように保持して行われる。負電位の値は
−500Vから0V未満であり、好ましくは−300Vから−1Vで
ある。さらに好ましくは−150Vから−10Vである。負電
位を大きくすると該形成速度は小さくなり、接地電位に
近づくにつれて大きくなる。このために該電位を変更す
ることにより、他の形成条件を変更することなく形成速
度のみを任意の制御することができるのである。しかも
本発明においては、斜向して設備した第３の電極によ
り、形成速度を連続的に変更出来るという作用効果をも
奏するのである。すなわち、第３の電極と基板との距離
が大になる程形成速度は逆に小になるところ、本発明に
おいては該第３の電極は第１導電層形成室側から第２導
電層形成室側に向かって、基板との距離が小さくなるよ
うに斜向して設備されているので、この形成室内を輸送
される基板は、上記した如き最も重要な光活性層形成初
期において低速から連続的に形成速度を増加するという
態様で形成速度を連続的に変更しつつ光活性層を形成す
ることが出来るのである。かかる意味において、該第３
の電極は光活性層を形成する光活性層形成室全体に渡っ
て設備されているのが最も望ましいが、少なくとも、光
活性層形成初期領域に対応する部分、言い換えれば第１
導電層形成室側には設備されていることが望ましい。該
形成速度は界面領域の形成開始から50〜500Å以内にお
いては10Å/s以下であることが好ましく、この形成速度
になるように該第３の電極および該バイアス電圧を調節
制御する。The formation of the interface region, in particular, the formation of the interface region in contact with the first conductive layer is performed on the third electrode obliquely provided between the substrate and the discharge electrode facing the photoactive layer formation main surface of the substrate. A bias voltage is applied, and the third electrode is held so that the potential of the third electrode becomes more negative with respect to the ground potential. The value of the negative potential is -500V to less than 0V, preferably -300V to -1V. More preferably, it is −150V to −10V. When the negative potential is increased, the formation rate is decreased, and it is increased as the potential approaches the ground potential. Therefore, by changing the potential, only the forming speed can be arbitrarily controlled without changing other forming conditions. Moreover, in the present invention, the third electrode, which is obliquely installed, has the effect that the forming rate can be continuously changed. That is, as the distance between the third electrode and the substrate increases, the forming speed decreases. Conversely, in the present invention, the third electrode moves from the first conductive layer forming chamber side to the second conductive layer forming chamber side. Since the equipment is installed so as to be inclined toward the side so that the distance to the substrate becomes small, the substrate transported in this formation chamber is continuous from a low speed at the initial stage of the most important photoactive layer formation as described above. It is possible to form the photoactive layer while continuously changing the formation rate in the manner of increasing the formation rate. In this sense, the third
It is most preferable that the electrode of (1) is installed over the entire photoactive layer forming chamber for forming the photoactive layer, but at least a portion corresponding to the photoactive layer forming initial region, that is, the first
It is desirable to be installed on the side of the conductive layer forming chamber. The formation rate is preferably 10 Å / s or less within 50 to 500 Å from the start of the formation of the interface region, and the third electrode and the bias voltage are adjusted and controlled so as to achieve this formation rate.
以下本発明の方法を実施するための好ましい形態をガラ
ス基板を用いる例について示す。グロー放電反応室に透
明導電膜が形成されたガラス基板を挿入する。ついで減
圧下100〜400℃の温度に加熱維持する。ジシランとｐ型
ドーピングガス、さらに必要に応じてアルキルシランの
如き炭素含有化合物、水素やヘリウムの希釈ガス等から
なる混合ガスをグロー放電分解や光分解により、ｐ型ａ
−Si:H膜やｐ型ａ−Si1-xCx:H膜を形成する。ついでジ
シランをａ−Si:H膜の形成速度がグロー放電に用いる高
周波電力に依存しては変化しない領域、即ち閾値以上の
領域において分解し光活性層を形成する。なお、光活性
層は我々がすでに提案しているようにジシランに対し1v
ppm以下の微量のジボランを添加して形成されることも
ありうる。Hereinafter, preferred embodiments for carrying out the method of the present invention will be described with respect to an example using a glass substrate. A glass substrate on which a transparent conductive film is formed is inserted into the glow discharge reaction chamber. Then, it is heated and maintained at a temperature of 100 to 400 ° C. under reduced pressure. A gas mixture containing disilane and a p-type doping gas, and optionally a carbon-containing compound such as an alkylsilane, and a diluting gas of hydrogen or helium, is subjected to glow discharge decomposition or photolysis to obtain a p-type a gas.
A -Si: H film or a p-type a-Si 1-x C x : H film is formed. Then, disilane is decomposed in a region where the formation rate of the a-Si: H film does not change depending on the high frequency power used for glow discharge, that is, a region equal to or more than a threshold value to form a photoactive layer. It should be noted that the photoactive layer should be 1v vs. disilane as we have already proposed.
It may be formed by adding a trace amount of diborane below ppm.
該光活性層の形成に際してその初期に基板と該基板の光
活性層形成主面に対向する放電電極との間に斜向して設
けた第３の電極にバイアス電圧を印加して、該電極が接
地電位に対して負電位になるようにし、形成速度を低速
より高速へと連続的に変化させつつ、1000Å以下の、好
ましくは50〜500Åの光活性層を形成する。When the photoactive layer is formed, a bias voltage is applied to the third electrode obliquely provided between the substrate and the discharge electrode facing the photoactive layer-forming main surface of the substrate at the initial stage to apply the bias voltage to the electrode. Is a negative potential with respect to the ground potential, and while continuously changing the formation speed from a low speed to a high speed, a photoactive layer of 1000 Å or less, preferably 50 to 500 Å is formed.
ついでジシランとｎ型ドーピングガスによりｎ型ａ−S
i:H膜又はｎ型微結晶化水素化シリコン膜を形成する。
さらに第２の電極を形成して本発明の光電変換素子を完
成する。Then, using disilane and n-type doping gas, n-type aS
An i: H film or an n-type microcrystallized hydrogenated silicon film is formed.
Further, the second electrode is formed to complete the photoelectric conversion element of the present invention.
光活性層の形成条件は形成温度100〜400℃、圧力0.05〜
2Torrである。このとき希釈ガスとして水素やヘリウム
を用いることができる。希釈ガスを用いることにより光
活性層の光導電度を希釈ガスを用いない場合に比べ２〜
10倍増加させることができる。The conditions for forming the photoactive layer are a forming temperature of 100 to 400 ° C. and a pressure of 0.05 to
2 Torr. At this time, hydrogen or helium can be used as the diluent gas. By using a diluent gas, the photoconductivity of the photoactive layer is 2 to 2 times as compared with the case where the diluent gas is not used.
It can be increased 10 times.
ｐ型又はｎ型のドーピングガスとしてはそれぞれジボラ
ン（B2H6）およびホスフィン（PH3）を水素又はヘリウ
ムで希釈して用いられる。As a p-type or n-type doping gas, diborane (B 2 H 6 ) and phosphine (PH 3 ) are diluted with hydrogen or helium, respectively.
本発明における第３の電極としては、プラズマの拡がり
を妨げない形状を有する導電性材料が好ましく、特に好
ましくは10〜100メッシュの網状物や直径0.5〜2mmの多
数の小孔を有する多孔板を用いることが出来る。かかる
第３の電極は、すでに述べたように基板と該基板の光活
性層形成主面に対向する放電電極との間に斜向して設け
られるが、直流バイアス電圧が印加されるべく、反応器
壁および接地電極（基板側電極）とは絶縁物質で電気的
に絶縁されている。もちろんかかる第３の電極は光活性
層形成室のみでなく、ｐ層やｎ層形成室にも設置するこ
とが出来る。The third electrode in the present invention is preferably a conductive material having a shape that does not hinder the spread of plasma, particularly preferably a mesh of 10 to 100 mesh or a porous plate having a large number of small holes of 0.5 to 2 mm in diameter. Can be used. As described above, the third electrode is provided obliquely between the substrate and the discharge electrode facing the photoactive layer-forming main surface of the substrate, but the third electrode does not react so that a DC bias voltage is applied. The container wall and the ground electrode (electrode on the substrate side) are electrically insulated by an insulating material. Of course, such a third electrode can be installed not only in the photoactive layer forming chamber but also in the p layer or n layer forming chamber.
本発明において太陽電池の形成方法は、上記の態様の外
にも（ｉ）基板側からｎ型−ｉ型−ｐ型と積層する方法
（ii）電極を分割しておいて、複数の太陽電池を形成し
これらを直列接続した型で得る集積型太陽電池を製造す
る方法、（iii）電極およびａ−Si:H膜を一様に形成し
た後、レーザー光のような加熱手段で分割し、ついで集
積化する方法等いろいろあるが、これらのいずれの方法
をも用いることができる。またｐ、ｉ、ｎ型のａ−Si:H
膜を単一の反応室で形成する方法や別々の反応室で作成
することもできる。In the present invention, the method for forming a solar cell includes, in addition to the above-mentioned aspects, (i) a method of stacking n-type-i-type-p-type from the substrate side (ii) dividing an electrode into a plurality of solar cells And a method for producing an integrated solar cell in which these are connected in series, (iii) after uniformly forming an electrode and an a-Si: H film, dividing by a heating means such as laser light, Then, there are various methods such as integration, and any of these methods can be used. In addition, p, i, n type a-Si: H
It is also possible to form the membrane in a single reaction chamber or to make it in separate reaction chambers.
なお、本発明においてｐ型、ｉ型、もしくはｎ型ａ−S
i:H層の膜厚はそれぞれ50〜500Å、2000〜10000Å、50
〜500Å程度である。In the present invention, p-type, i-type, or n-type aS
i: H layer thickness is 50-500Å, 2000-10000Å, 50 respectively
It is about 500Å.
本発明で用いる基板や電極の材料については特に制限さ
れず、従来用いられている物質が有効に用いられる。The materials of the substrate and electrodes used in the present invention are not particularly limited, and conventionally used substances are effectively used.
たとえば、基板としては絶縁性又は導電性、透明又は不
透明のいずれかの性質を有するものでもよい。基本的に
はガラス、アルミナ、シリコン、ステンレススティー
ル、アルミニウム、モリブデン、耐熱性高分子等の物質
で形成されるフィルムあるいは板状の材料を基板として
有効に用いることができる。電極材料としては、光入射
側にはもちろん透明あるいは透明性の材料を用いなけれ
ばならないが、これ以外の実質的な制限はない。アルミ
ニウム、モリブデン、ニクロム、ITO、酸化錫、ステン
レススティール等の薄膜又は薄板が電極材料として有効
に用いられる。For example, the substrate may be one having an insulating property, a conductive property, a transparent property, or an opaque property. Basically, a film or plate-like material formed of a substance such as glass, alumina, silicon, stainless steel, aluminum, molybdenum, and heat resistant polymer can be effectively used as the substrate. As the electrode material, of course, a transparent or transparent material must be used on the light incident side, but there is no other practical limitation. Thin films or thin plates of aluminum, molybdenum, nichrome, ITO, tin oxide, stainless steel, etc. are effectively used as the electrode material.
以下、実施例により本発明を説明する。 Hereinafter, the present invention will be described with reference to examples.
基板挿入室、ｐ層、光活性層、ｎ層の各層形成室、電極
形成室、基板取出し室からなるプラズマCVD装置におい
て、本発明を実施した。The present invention was carried out in a plasma CVD apparatus including a substrate insertion chamber, a p-layer, a photoactive layer, an n-layer formation chamber, an electrode formation chamber, and a substrate extraction chamber.
光活性層形成室には金属メッシュから成る第３電極が二
枚の放電電極の間に該放電電極に対し斜向して設備され
ている装置をもちいた。In the photoactive layer forming chamber, there was used a device in which a third electrode made of a metal mesh was installed between two discharge electrodes in a direction oblique to the discharge electrodes.
透明電極付ガラス基板が、基板挿入室に入れられ真空排
気下加熱された。ついでｐ層形成室へ移送された。ｐ層
は原料ガスの流量比B2H6＝1/100、(CH3)2SiH2/Si2H6＝1
/2、Si2H6＝1/20で、基板温度100〜300℃、圧力0.1〜1T
orr、放電電力４〜40mW/cm2の条件ででグロー放電によ
り形成された。つぎに基板は光活性層形成室に移送さ
れ、ｐ層の上に光活性層（ｉ層）が形成された。光活性
層は形成温度100〜400℃、圧力0.05〜2Torrで閾値以上
の供給エネルギーでグロー放電を行うことにより形成さ
れた。該光活性層の形成開始から1000Åの厚みの形成に
相当する間、基板と該基板の光活性層形成主面に対向す
る放電電極との間に斜向して設けた第３の電極にバイア
ス電圧を印加して該第３の電極の電位が接地電位より負
電位になるよう保持してグロー放電が行われた。該負電
位は−200Vから0Vの範囲で印加した。形成速度は約0.5
Å/Sから25Å/Sまで連続的に変化させることが出来た。
光活性層を6000Åの厚みで形成したが、平均形成速度は
20Å/Sが確保された。ついでさらに基板はｎ層形成室に
移送されｎ層が形成された。ｎ層は微結晶化膜であり、
PH3/Si2H6＝1/100、Si2H6/H2＝1/50の原料流量比で形成
された。ついで基板はさらに電極形成室へ移送され、真
空蒸着によりアルミニウム電極が形成された。こうして
得た光電変換素子の特性をAMI、100mW/cm2の光を照射し
つつ調べた。この結果として、本発明の光電変換素子の
製造方法によれば、光活性層の平均形成速度が20Å/Sを
越す高速製造条件においても、JSC＝16〜17mA/cm2およ
びF.F.＝0.68〜0.73を維持して従来のごとく光電変換効
率の低下は実質的に生じていないことが明らかになっ
た。A glass substrate with a transparent electrode was placed in a substrate insertion chamber and heated under vacuum exhaust. Then, it was transferred to the p-layer forming chamber. The p layer has a flow rate ratio of source gas B 2 H 6 = 1/100, (CH 3 ) 2 SiH 2 / Si 2 H 6 = 1
/ 2, Si 2 H 6 = 1/20, substrate temperature 100-300 ℃, pressure 0.1-1T
It was formed by glow discharge under the conditions of orr and discharge power of 4 to 40 mW / cm 2 . Next, the substrate was transferred to the photoactive layer forming chamber, and the photoactive layer (i layer) was formed on the p layer. The photoactive layer was formed by performing glow discharge at a forming temperature of 100 to 400 ℃ and a pressure of 0.05 to 2 Torr with the supplied energy above the threshold value. A bias is applied to the third electrode obliquely provided between the substrate and the discharge electrode facing the photoactive layer-forming main surface of the substrate for a period corresponding to the formation of a thickness of 1000 Å from the start of the formation of the photoactive layer. A glow discharge was performed by applying a voltage and holding the potential of the third electrode to be a negative potential than the ground potential. The negative potential was applied in the range of -200V to 0V. Formation speed is about 0.5
It was possible to change continuously from Å / S to 25 Å / S.
The photoactive layer was formed with a thickness of 6000Å, but the average formation rate was
20Å / S was secured. Then, the substrate was transferred to the n-layer forming chamber to form the n-layer. The n layer is a microcrystallized film,
It was formed at a raw material flow rate ratio of PH 3 / Si 2 H 6 = 1/100 and Si 2 H 6 / H 2 = 1/50. Then, the substrate was further transferred to an electrode forming chamber and an aluminum electrode was formed by vacuum vapor deposition. The characteristics of the photoelectric conversion element thus obtained were examined while irradiating with AMI and light of 100 mW / cm 2 . As a result, according to the method for producing a photoelectric conversion element of the present invention, J SC = 16 to 17 mA / cm 2 and FF = 0.68 to even under high-speed production conditions in which the average formation rate of the photoactive layer exceeds 20 Å / S. Maintaining 0.73, it became clear that the photoelectric conversion efficiency did not substantially drop as in the conventional case.
以上のごとく、本発明の方法によれば、たとえば上記実
施例に示すように、20Å/Sを越すような高速製造条件に
おいてさえも短絡電流の低下や曲線因子の低下等の太陽
電池の低下を生じさせることなく光電変換効率の高効率
化を達成できる、という従来技術では予想しえない優れ
た作用効果を奏することが出来るものであり、その産業
上の利用可能性は極めて大きいと云わねばならない。As described above, according to the method of the present invention, for example, as shown in the above-mentioned embodiment, the deterioration of the solar cell such as the decrease of the short-circuit current and the decrease of the fill factor is suppressed even under the high-speed manufacturing conditions of exceeding 20Å / S. It is possible to achieve a high effect of photoelectric conversion that can be achieved without causing it, which is unexpected in the prior art, and it must be said that its industrial applicability is extremely high. .
第１図は本発明に有効に用いることのできる製造装置の
断面模式図である。この図において斜向して設備された
第３の電極が第１導電層側に設けられている。図におい
て１……基板挿入室、２……第１導電層形成室、３……
光活性層形成室、４……第２導電層形成室、５……電極
形成室を兼ねた基板取り出し室、６……基板、７……第
３電極、８……バイアス電源、９……放電電力印加電
極、10……接地電極、11……基板加熱ヒーター、12……
電極物質蒸発用ヒーター、13……金属マスク、14……真
空排気ライン、15……原料ガス導入ライン、16……基板
輸送手段、17……絶縁性物質、18……放電電力印加電
源、19……ゲート弁FIG. 1 is a schematic sectional view of a manufacturing apparatus that can be effectively used in the present invention. In this figure, a third electrode obliquely installed is provided on the first conductive layer side. In the figure, 1 ... Substrate insertion chamber, 2 ... First conductive layer forming chamber, 3 ...
Photoactive layer forming chamber, 4 ... Second conductive layer forming chamber, 5 ... Substrate takeout chamber that also serves as electrode forming chamber, 6 ... Substrate, 7 ... Third electrode, 8 ... Bias power supply, 9 ... Discharge power application electrode, 10 ... ground electrode, 11 ... substrate heating heater, 12 ...
Electrode material evaporation heater, 13 ... Metal mask, 14 ... Vacuum exhaust line, 15 ... Raw material gas introduction line, 16 ... Substrate transportation means, 17 ... Insulating material, 18 ... Discharge power application power supply, 19 ...... Gate valve
Claims (2)
素化物のグロー放電分解により、第１の導電層、光活性
層および第２の導電層を順次形成し、第２の電極を設け
る光電変換素子の連続的製法において、少なくとも該光
活性層の形成をジシランにより行い、かつ、該ジシラン
単位質量当たり、活性層薄膜の形成速度が主としてジシ
ラン流量に依存し印加エネルギー量によっては実質的に
影響されることのない最低のエネルギー量（以下閾値と
言う）以上のエネルギーを印加すると共に、該光活性層
形成の少なくとも初期領域は、該基板と該基板の光活性
層形成主面に対向する放電電極との間に第１の導電層形
成側から第２の導電層形成側に向かって基板との距離が
短くなるように斜向して設けた網状物もしくは多孔板で
構成される第３の電極に接地電位よりも負電位になるよ
うにバイアス電圧を印加して行うことを特徴とする光電
変換素子の連続的製法。1. A first conductive layer, a photoactive layer and a second conductive layer are sequentially formed on a substrate having a first electrode by glow discharge decomposition of silicon hydride, and a second electrode is provided. In a continuous production method of a photoelectric conversion element, at least the photoactive layer is formed by disilane, and the formation rate of the active layer thin film per unit mass of the disilane is mainly dependent on the disilane flow rate and may be substantially dependent on the applied energy amount. An energy of not less than a minimum energy amount (hereinafter referred to as a threshold value) that is not affected is applied, and at least an initial region of the photoactive layer formation faces the substrate and the photoactive layer formation main surface of the substrate. A third structure composed of a mesh-like material or a perforated plate obliquely provided between the discharge electrode and the first conductive layer formation side toward the second conductive layer formation side so that the distance from the substrate becomes shorter. of Continuous preparation of photoelectric conversion element, which comprises carrying out by applying a bias voltage to a negative potential than the ground potential electrode.
素化物のグロー放電分解により、第１の導電層、光活性
層および第２の導電層を順次形成しうる形成室を少なく
とも備えた光電変換素子の連続製造装置であって、該光
活性層の形成室は、対向して設備されたグロー放電電極
間の少なくとも第１の導電層形成室側端部を含む領域に
バイアス電圧を印加出来る網状物もしくは多孔板で構成
される第３の電極が第１の導電層形成室側から第２の導
電層形成室側に向かって基板との距離が短くなるように
斜向して設けられていることを特徴とする光電変換素子
の連続製造装置。2. A formation chamber capable of sequentially forming a first conductive layer, a photoactive layer and a second conductive layer by glow discharge decomposition of silicon hydride on a substrate having a first electrode. A photoelectric conversion element continuous manufacturing apparatus, wherein a photoactive layer forming chamber applies a bias voltage to a region including at least a first conductive layer forming chamber side end portion between glow discharge electrodes provided opposite to each other. A third electrode composed of a mesh-like material or a perforated plate that can be formed is obliquely provided from the first conductive layer forming chamber side toward the second conductive layer forming chamber side so that the distance from the substrate becomes shorter. A continuous manufacturing apparatus for photoelectric conversion elements.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60284381A JPH0714073B2 (en) | 1985-12-19 | 1985-12-19 | Photoelectric conversion element manufacturing method and manufacturing apparatus thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60284381A JPH0714073B2 (en) | 1985-12-19 | 1985-12-19 | Photoelectric conversion element manufacturing method and manufacturing apparatus thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62144371A JPS62144371A (en) | 1987-06-27 |
| JPH0714073B2 true JPH0714073B2 (en) | 1995-02-15 |
Family
ID=17677848
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60284381A Expired - Fee Related JPH0714073B2 (en) | 1985-12-19 | 1985-12-19 | Photoelectric conversion element manufacturing method and manufacturing apparatus thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0714073B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010116721A1 (en) * | 2009-04-06 | 2010-10-14 | 株式会社アルバック | Production system for photovoltaic device, and production method for photovoltaic device |
-
1985
- 1985-12-19 JP JP60284381A patent/JPH0714073B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62144371A (en) | 1987-06-27 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |