JPS61244025A - Manufacture of thin film - Google Patents
Manufacture of thin filmInfo
- Publication number
- JPS61244025A JPS61244025A JP60086116A JP8611685A JPS61244025A JP S61244025 A JPS61244025 A JP S61244025A JP 60086116 A JP60086116 A JP 60086116A JP 8611685 A JP8611685 A JP 8611685A JP S61244025 A JPS61244025 A JP S61244025A
- Authority
- JP
- Japan
- Prior art keywords
- substrate
- ultrasonic
- thin film
- raw material
- vibrator
- 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
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02518—Deposited layers
- H01L21/02521—Materials
- H01L21/02524—Group 14 semiconducting materials
- H01L21/02532—Silicon, silicon germanium, germanium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02367—Substrates
- H01L21/0237—Materials
- H01L21/02422—Non-crystalline insulating materials, e.g. glass, polymers
Abstract
Description
【発明の詳細な説明】
本発明は、薄膜の製造方法に関するものであり、特に超
音波技術及び熱分解反応を利用した薄膜製造方法に関す
るものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for manufacturing a thin film, and particularly to a method for manufacturing a thin film using ultrasonic technology and a thermal decomposition reaction.
び。Beauty.
近年、半導体装置、液晶ディスプレー装置、反射鏡、そ
の他の用途において、ガラス等のような基板上に酸化す
ず、酸化インジウム等の金属酸化物の薄膜を形成する必
要性が増大している。In recent years, there has been an increasing need to form thin films of metal oxides such as tin oxide and indium oxide on substrates such as glass in semiconductor devices, liquid crystal display devices, reflective mirrors, and other applications.
第６図に図示するように１例えばアモルファスシリコン
太陽電池１は、透明電極？、α−３ｉｌ１４及び裏面金
属６が積層されて形成されている。As shown in FIG. 6, for example, an amorphous silicon solar cell 1 has a transparent electrode. , α-3il 14 and back metal 6 are laminated.
従って、その製造工程は、
（１）ガラス基板２ａ上に０．２〜１．０＃Ｌｍ程度の
厚さにて透明導電１１２ｂを製膜し透明電極２を形成す
る工程、
（２）プラズマＣＶＤ法にて上記透明電極２上にアモル
ファスシリコンを製膜しα−３ｉ膜４を形成する工程、
（３）スパッタ法又は真空蒸着法を利用しＡＩｉを０．
２ｐｍ程度の厚さにて上記α−３ｉ膜４上に製膜し裏面
金属６を形成する工程、
から成る。Therefore, the manufacturing process is as follows: (1) forming a transparent conductive film 112b with a thickness of about 0.2 to 1.0 #Lm on a glass substrate 2a to form a transparent electrode 2; (2) plasma CVD (3) forming an α-3i film 4 by depositing amorphous silicon on the transparent electrode 2 using a sputtering method or a vacuum evaporation method;
It consists of a step of forming a film on the α-3i film 4 to a thickness of about 2 pm to form a back metal 6.
上記透明電極形成工程（１）は、従来ガラス基板２ａ上
に化学気相蒸着（ＣＶＤ）法又はスプレー熱分解法にて
酸化すず（Ｓ ｎｏｚ ）！Ｉを製膜するのが一般的で
あった。In the transparent electrode forming step (1), tin oxide (S noz ) is conventionally deposited on the glass substrate 2a by a chemical vapor deposition (CVD) method or a spray pyrolysis method. It was common to form a film using I.
化学気相蒸着（ＣＶＤ）法は、常圧での反応であり、又
コンベア炉を用いた連続プロセスが可能であり、多量生
産が容易であり、且つ大面積に均一な製膜が容易に行な
い得るといった利点を有しており、現在主流をなしてい
る。The chemical vapor deposition (CVD) method is a reaction at normal pressure, and a continuous process using a conveyor furnace is possible, making it easy to mass produce and uniformly forming a film over a large area. It has the advantage that it can be obtained easily, and is currently the mainstream.
一方、上記スプレー熱分解法は、ＣＶＤ法と同様に常圧
化でのプロセスであるために多量生産は可能であるが、
大面積への均一な製膜が困難であること、原料の利用率
が一般にひくいことにより、現在工業的にはあまり利用
されてはいない。On the other hand, the above-mentioned spray pyrolysis method is a process under normal pressure like the CVD method, so it is possible to produce in large quantities.
Currently, it is not used industrially much because it is difficult to uniformly form a film over a large area and the utilization rate of raw materials is generally low.
しかしながら１例えばアモルファス太陽電池を作製した
場合等には、該方法にて製造した基板を利用した方が高
い変換効率を達成し得ることが分かった。However, it has been found that, for example, in the case of manufacturing an amorphous solar cell, higher conversion efficiency can be achieved by using a substrate manufactured by this method.
髪」Ｊと１缶
従って、本発明の目的は、原料液を粒径がそろった微粒
子にて霧化し、大面積への均一な製膜を可能とするスプ
レー熱分解法による薄膜の製造方法を提供することであ
る。Therefore, the purpose of the present invention is to provide a method for producing a thin film using a spray pyrolysis method that atomizes a raw material liquid into fine particles with uniform particle sizes and enables uniform film formation over a large area. It is to provide.
本発明の他の目的は、膜圧分布を均一にし、又原料の歩
留りを向上せしめることのできるスプレー熱分解法によ
る薄膜の製造方法を提供することである。Another object of the present invention is to provide a method for producing a thin film by spray pyrolysis, which can make the film pressure distribution uniform and improve the yield of raw materials.
一
上記目的は本発明によって達成される。＊約すれば本発
明は、原料液を超音波振動手段を用いて霧化し、該霧化
物を加熱基板上に導き、熱分解反応により該基板に薄膜
を形成することを特徴とする薄膜製造方法である０本発
明の好ましい実施態様によると、超音波振動手段は超音
波発生手段によって振動する振動子を有し、該振動子は
先端部にエツジ部を形成し、該エツジ部に原料液が供給
される。One of the above objects is achieved by the present invention. *In short, the present invention is a thin film manufacturing method characterized by atomizing a raw material liquid using an ultrasonic vibration means, guiding the atomized product onto a heated substrate, and forming a thin film on the substrate by a thermal decomposition reaction. According to a preferred embodiment of the present invention, the ultrasonic vibrating means has a vibrator that is vibrated by the ultrasonic generating means, and the vibrator has an edge portion at its tip, and the raw material liquid is in the edge portion. Supplied.
次に、本発明に係る薄膜製造方法を更に詳細に説明する
。Next, the thin film manufacturing method according to the present invention will be explained in more detail.
第１図を参照すると、本発明に係る薄膜製造方法を実施
する一つの製造装置が例示される０本実施例装置１０に
よると熱源１２によって加熱されるホットプレート１４
が設けられ、該ホットプレート１４上に、例えばガラス
板のような基板２ａが載置される。Referring to FIG. 1, one manufacturing apparatus for implementing the thin film manufacturing method according to the present invention is illustrated.According to the present embodiment apparatus 10, a hot plate 14 heated by a heat source 12 is shown.
A substrate 2a, such as a glass plate, is placed on the hot plate 14.
一方、前記基板２ａ上に製膜される材料２ｂを含んだ原
料液１６は、送液定量ポンプ１８によって超音波噴射手
段２０に送給され、微粒化即ち霧化される。該原料液の
微粒子は導管手段２２によって前記基板２ａへと導かれ
る。前記導管手段２２には、超音波噴射手段２０によっ
て霧化された原料液の微粒子を効率よく基板？ｂの方へ
と送給するためにファン２４を設けることが好ましい。On the other hand, the raw material liquid 16 containing the material 2b to be formed into a film on the substrate 2a is fed to the ultrasonic spraying means 20 by the liquid feeding metering pump 18, and is atomized, that is, atomized. The fine particles of the raw material liquid are guided to the substrate 2a by conduit means 22. The conduit means 22 efficiently transfers fine particles of the raw material liquid atomized by the ultrasonic jetting means 20 to the substrate. Preferably, a fan 24 is provided for feeding towards b.
他の実施例として、超音波噴射手段２０を前記基板２ｂ
に近接して配置し、該超音波噴射手段２０によって霧化
された原料液の微粒子を直接加熱基板２ｂに吹付けるこ
とも可能であるが、上述のように、超音波噴射手段２０
によって霧化された原料液の微粒子は、例えば空気のよ
うなキャリアガスと共に基板ｚｂ上へと導管手段２２に
よって輸送し該基板２ｂに吹付ける方が均一な製膜が達
成される。As another embodiment, the ultrasonic jetting means 20 is connected to the substrate 2b.
Although it is also possible to arrange the ultrasonic spraying means 20 close to the heating substrate 2b and directly spray the fine particles of the raw material liquid atomized by the ultrasonic spraying means 20 onto the heating substrate 2b, as described above, the ultrasonic spraying means 20
A more uniform film formation can be achieved by transporting the fine particles of the raw material liquid atomized by, for example, a carrier gas such as air onto the substrate zb by the conduit means 22 and spraying them onto the substrate 2b.
第２図は、本発明に使用し得る超音波噴射手段２０の好
ましい実施例を示す。FIG. 2 shows a preferred embodiment of an ultrasonic jetting means 20 that can be used in the present invention.
本出願人は、大容量の液体の微粒化を達成するべく、超
音波による液体微粒化メカニズム及び超音波振動子の形
状の研究及び実験を数多く行なった結果、超音波振動子
の端部にエツジ部を設け。In order to achieve atomization of a large volume of liquid, the applicant has conducted numerous studies and experiments on the liquid atomization mechanism using ultrasonic waves and the shape of the ultrasonic vibrator, and as a result, the applicant has found that an edge is added to the end of the ultrasonic vibrator. Establishment of a department.
該エツジ部に液体を薄膜状で供給することによって、該
エツジ部より液体が大量に微粒化されることを見出し、
超音波噴射方法及び噴射ノズルを提案した（特願昭５９
−７７５７２を参照せよ）。It has been discovered that a large amount of liquid can be atomized from the edge portion by supplying the liquid in the form of a thin film to the edge portion,
Proposed an ultrasonic injection method and an injection nozzle (patent application 1983)
-77572).
本発明者等の研究の結果、該超音波噴射ノズルは、本発
明にて使用する超音波噴射手段２０として極めて好適に
使用し得ることが分かった。As a result of research conducted by the present inventors, it has been found that the ultrasonic jet nozzle can be used very suitably as the ultrasonic jet means 20 used in the present invention.
第２図を参照すると、超音波噴射手段、即ち、超音波噴
射ノズル２０は、中心に中心孔２６を有した細長の概略
円筒形状の弁箱２８を具備する。Referring to FIG. 2, the ultrasonic injection means, ie, the ultrasonic injection nozzle 20, includes an elongated, generally cylindrical valve body 28 having a central hole 26 in the center.
該弁箱２８の下端には、弁箱２Ｂの中心孔２６と同軸に
て整列した貫通孔３０が形成された液体供給手段、即ち
、原料液供給手段３２がリテイナー３４によって通常の
方法で一体的に設けられる。At the lower end of the valve box 28, a liquid supply means, ie, a raw material liquid supply means 32, in which a through hole 30 is formed coaxially with the center hole 26 of the valve case 2B, is integrally connected by a retainer 34 in a normal manner. established in
前記弁箱２８の中心孔２６及び原料液供給手段３２の貫
通孔３０とを貫いて振動子３６が配置される。該振動子
３６は、上部の本体部３８、該本体部３８より小径の細
長円柱状の振動子軸部４０及び本体部３８と軸部４０と
を連結する遷移部４２を有する０本体部３８にはより大
径とされた鍔４４が設けられており、該鍔４４が弁箱２
８の上端に形成された肩部４６と、該弁箱２８の上端面
にボルト（図示せず）によって取付られた環状の振動子
押え４８とによって弁箱２８に取付ちれる。A vibrator 36 is disposed passing through the center hole 26 of the valve box 28 and the through hole 30 of the raw material liquid supply means 32. The vibrator 36 includes an upper main body part 38, an elongated cylindrical transducer shaft part 40 having a smaller diameter than the main body part 38, and a transition part 42 connecting the main body part 38 and the shaft part 40. is provided with a flange 44 having a larger diameter, and the flange 44 is connected to the valve box 2.
It is attached to the valve case 28 by a shoulder 46 formed at the upper end of the valve case 8 and an annular vibrator retainer 48 attached to the upper end surface of the valve case 28 with bolts (not shown).
振動子３６の軸部４０は弁箱２８及び液体供給手段３２
より下方に、つまり外方へと更に突出している。振動子
３６の先端、つまり軸部４０の先端にはエツジ部５０が
形成される。The shaft portion 40 of the vibrator 36 is connected to the valve box 28 and the liquid supply means 32.
It protrudes further downward, that is, outward. An edge portion 50 is formed at the tip of the vibrator 36, that is, the tip of the shaft portion 40.
前記振動子３６のエツジ部５０は、第１図によると、漸
次径が小さくされた５段から成る環状の階段状とされる
が、２段、３段又は４段の階段状とすることもでき、又
漸次径が増大したり、又漸次径が小さくなり次で大きく
なるような形状とすることもでき、更には全ての段が同
径となるように形成することもできる０重要なことは振
動子先端部にエツジが形成されることである。According to FIG. 1, the edge portion 50 of the vibrator 36 has an annular step shape consisting of five steps whose diameter is gradually reduced, but it may also have a step shape of two steps, three steps, or four steps. It can also be shaped so that the diameter increases gradually, or the diameter gradually decreases and then increases, or even can be formed so that all stages have the same diameter. This means that an edge is formed at the tip of the vibrator.
又、第３図に図示されるように、エツジ部５０のエツジ
の暢（Ｗ）及び高さくｈ）は、液体原料液の薄膜化が行
ない得るような且つ又液体の流れを堰止めるような寸法
形状とされる。Further, as shown in FIG. 3, the edge width (W) and height h) of the edge portion 50 are such that the liquid raw material liquid can be made into a thin film and that the flow of the liquid can be dammed. Dimensions and shape.
前記原料液供給手段３２には、振動子３Ｂの前記エツジ
部５０に原料液を供給するための供給通路５２が１つ又
は複数個環状に配列して形成される。該供給通路５２の
原料液供給口５４は概略前記エツジ部５０の上端に隣接
して開口し、Ｊ［料液供給口５４の他端５６は互に連結
され且つ弁箱２８に形成された原料液導通孔５８に連結
される。The raw material liquid supply means 32 is formed with one or more supply passages 52 arranged in an annular shape for supplying the raw material liquid to the edge portion 50 of the vibrator 3B. The raw material liquid supply port 54 of the supply passage 52 opens approximately adjacent to the upper end of the edge portion 50, and the other ends 56 of the raw material liquid supply ports 54 are connected to each other and are formed in the valve box 28. It is connected to the liquid passage hole 58.
原料液導通孔５８には原料液１６が送液定量ポンプ１８
を介して供給される。The raw material liquid 16 is supplied to the raw material liquid communication hole 58 through the liquid feeding metering pump 18.
Supplied via.
上記構成において、振動子３６は、本体部３８に作動的
に接続された超音波撮動発生手段１００により連続的に
又は間欠的に振動される。従って、液体原料液１６が供
給弁１８、導通孔５Ｂ及び供給通路５２を介してエツジ
部５０に供給されると、液体原料液は微粒化され導管手
段２２内へと噴射される。In the above configuration, the vibrator 36 is vibrated continuously or intermittently by the ultrasonic imaging generating means 100 operatively connected to the main body 38 . Therefore, when the liquid raw material liquid 16 is supplied to the edge part 50 through the supply valve 18, the through hole 5B, and the supply passage 52, the liquid raw material liquid is atomized and injected into the conduit means 22.
第４図は、超音波噴射手段２０の他の実施例を示す、該
実施例の噴射ノズル２０ａは、上述の噴射ノズル２とそ
の作動メカニズムは同じであるが、振動子の形状及び原
料液の供給態様において相違している。つまり、本実施
例において、振動子３６ａはエツジ部５０ａが先端内周
部に形成され、原料液は該振動子３６ａの内部を貫通し
て形成された供給通路５２ａを介して行なわれる。FIG. 4 shows another embodiment of the ultrasonic injection means 20. The injection nozzle 20a of this embodiment has the same operating mechanism as the injection nozzle 2 described above, but the shape of the vibrator and the flow rate of the raw material liquid are the same. They differ in the way they are supplied. That is, in this embodiment, the vibrator 36a has an edge portion 50a formed at the inner circumferential portion of the tip, and the raw material liquid is supplied through a supply passage 52a formed through the inside of the vibrator 36a.
第５図は、上記構成の超音波噴射ノズル２０（又は２０
ａ）と従来の圧力噴霧器の霧化の粒径分布を示すもので
ある。該図面より、上記構成のノズル２０（又は２０ａ
）によると、霧化物の粒径分布は従来ノズルによる粒径
分布よりも狭く、均一な製膜が可能とされことが理解さ
れるであろう。FIG. 5 shows an ultrasonic jet nozzle 20 (or 20
a) and the particle size distribution of the atomization of a conventional pressure atomizer. From the drawing, the nozzle 20 (or 20a
), it will be understood that the particle size distribution of the atomized product is narrower than that of conventional nozzles, making it possible to form a uniform film.
実施例
次に、本発明に係る方法を、半導体装置に使用される酸
化すず膜基板の作製に適用した一実施例について説明す
る。Example Next, an example will be described in which the method according to the present invention is applied to the production of a tin oxide film substrate used in a semiconductor device.
製造装置は概略第１図に図示されるような構成とされた
。基板２ａとしては表面に５ｉＯｚアンダーコートを施
した１０ｃｍ角の並ガラスを用い、ホットプレート１４
上に載置し、表面温度４５０℃にまで加熱された。The manufacturing apparatus had a configuration as schematically shown in FIG. As the substrate 2a, a 10 cm square ordinary glass with a 5iOz undercoat on the surface is used, and a hot plate 14 is used.
It was placed on top and heated to a surface temperature of 450°C.
原料液はエタノール中に５ｎＣＪｌ＋ ・５Ｈ２Ｏを０
．０２モル／ｉ、ＮＨ４Ｆを０．０２モル／文、塩酸を
０．５重量パーセントそれぞれ溶解させたものを用いた
。The raw material solution contains 5nCJl+ ・5H2O in ethanol.
．． 0.02 mol/i of NH4F, 0.02 mol/liter of NH4F, and 0.5 weight percent of hydrochloric acid were used.
超音波噴射手段としては第２図に図示される超音波噴射
ノズル２０を使用した。この時、超音波噴射ノズル２０
の諸寸法は次の如くであった。As the ultrasonic injection means, an ultrasonic injection nozzle 20 shown in FIG. 2 was used. At this time, the ultrasonic jet nozzle 20
The dimensions were as follows.
超音波発生手段の出カニ １０ｗ
振動子の振幅 ３０終ｍ
振動数 ３８ＫＨｚ
振動子の形状寸法
１段 ：直径 ７ｍｍ
２段 ：直径 ６ｍｍ
３段 ：直径 ５ｍｍ
４段 ：直径 ４ｍｍ
５段 ：直径 ３ｍｍ
各段の高さくｈ）： １．５ｍｍ
振動子の材料 ：直径７ｍｍチタン丸棒加工品
導管手段２２はステンレスで作製し、基板２ａが載った
ホットプレート１４上を、ステンレス製のケースでおお
い、このケース内に超音波噴射弁で霧化した原料液を乾
燥空気とともに送りこんだ、 超音波噴射弁への原料液
送液量は０．１５ｃｃ／秒とし、１ｏｏｃｃの原料液を
連続噴霧した。又、キャリアガスとして用いた乾燥空気
の液量は５１／分であった。Output of ultrasonic generating means 10w Vibrator amplitude 30m Frequency 38KHz Transducer shape and dimensions 1 stage: Diameter 7 mm 2 stages: Diameter 6 mm 3 stages: Diameter 5 mm 4 stages: Diameter 4 mm 5 stages: Diameter 3 mm Each stage Height (h): 1.5 mm Vibrator material: 7 mm diameter titanium round bar product The conduit means 22 is made of stainless steel, and the hot plate 14 on which the substrate 2a is placed is covered with a stainless steel case. The raw material liquid atomized by an ultrasonic injection valve was sent into the chamber together with dry air.The raw material liquid feed rate to the ultrasonic injection valve was 0.15 cc/sec, and 10cc of the raw material liquid was continuously sprayed. Further, the liquid volume of dry air used as a carrier gas was 51/min.
このようにして作製した酸化すず膜の特性を第１表に示
す、膜厚はエツチングしてから触針式膜厚計で、粒径分
布は走査型電子ｍ＊鏡で、シート抵抗は４端子法により
測定した。The properties of the tin oxide film produced in this way are shown in Table 1.The film thickness was measured using a stylus thickness meter after etching, the particle size distribution was measured using a scanning electronic m* mirror, and the sheet resistance was measured using a 4-terminal It was measured by the method.
比較例
従来のスプレー熱分解法にて、上記実施例と同様に酸化
すず膜基板を製造した。Comparative Example A tin oxide film substrate was manufactured in the same manner as in the above example using the conventional spray pyrolysis method.
該方法において、基板とスプレーヘッドの距離を４０ｃ
ｍとし、キャリアガスには圧力２Ｃｇ／ｃｒｎ’の乾燥
空気を用い、１０秒間噴霧、１０秒間待機、のくり返し
で噴霧を行なった。噴霧中の平均噴霧量は０．３ｃｃ／
秒であり、１００ｃｃの原料液を噴霧した。尚、連続噴
霧を行なわず間欠噴霧としたのは、ガラス表面温度の低
下を避けるためである。In this method, the distance between the substrate and the spray head is 40c.
m, dry air at a pressure of 2 Cg/crn' was used as the carrier gas, and spraying was performed by repeating the following steps: spraying for 10 seconds, waiting for 10 seconds. Average spray amount during spraying is 0.3cc/
100 cc of raw material liquid was sprayed. The reason why the spraying was not continuous but was sprayed intermittently was to avoid a drop in the glass surface temperature.
このようにして作製した酸化すず膜の特性を第１表に示
す、膜厚は、上記実施例と同様に、エツチングしてから
触針式膜厚計で１粒径分布は走査型電子顕微鏡で、シー
ト抵抗は４端子法により測定した。The properties of the tin oxide film produced in this way are shown in Table 1.The film thickness was determined by a stylus thickness meter after etching, as in the above example, and the grain size distribution was determined by a scanning electron microscope. The sheet resistance was measured by a four-terminal method.
表 １
皇−一察
第１表から分かるように、従来のスプレー法においては
、噴霧の不均一が避けられず、周辺部では膜厚が薄く、
シート抵抗も高くなっている。Table 1 As can be seen from Table 1, in the conventional spray method, non-uniformity of the spray is unavoidable, and the film thickness is thinner in the peripheral areas.
Sheet resistance is also high.
一方、本発明に係る超音波噴射を利用した方法において
は、キャリアガス導入部に近い側の周辺部Ａが最も厚く
、キャリアガス出口側に近い周辺部Ｂが幾分薄くなって
いるが、従来のスプレー法に比較すると均一性がはるか
に向上している。On the other hand, in the method using ultrasonic jetting according to the present invention, the peripheral part A near the carrier gas introduction part is thickest, and the peripheral part B near the carrier gas outlet side is somewhat thinner. The uniformity is much improved compared to the spray method.
又、本発明の上記実施例における斯る小さな不均一性も
、導管手段２２、特に基板２ａを覆ったステンレスカバ
ーの形状、キャリアガスの流量等を最適化することによ
り、より均一な製膜が可能であることがその後の実験に
より確認されている。Further, such small non-uniformity in the above embodiments of the present invention can be solved by optimizing the shape of the conduit means 22, especially the stainless steel cover covering the substrate 2a, the flow rate of the carrier gas, etc., to achieve more uniform film formation. Subsequent experiments have confirmed that this is possible.
更に１本発明により製造された酸化すず膜においては粒
径の分布が狭くなっており、均質な膜が作製されている
ことが分かる。又１本発明の方法は、上述より原料液の
歩留まりが向上しているが理解されるであろう。Furthermore, it can be seen that in the tin oxide film produced according to the present invention, the particle size distribution is narrow, and a homogeneous film is produced. Furthermore, it will be understood that the method of the present invention improves the yield of the raw material liquid as compared to the above.
兄」Ｊと１１
以上説明したように、本発明に係る薄膜製造方法による
と、原料液を粒径がそろった微粒子にて霧化することが
でき、大面積への均一な製膜が可能となり、且つ膜厚分
布を均一にし、更には原料の歩留りを向上せしめること
ができる。As explained above, according to the thin film manufacturing method of the present invention, the raw material liquid can be atomized into fine particles with uniform particle sizes, making it possible to form a uniform film over a large area. In addition, it is possible to make the film thickness distribution uniform and further improve the yield of raw materials.
又、本発明に係る方法は、従来使用されている連続コン
ベア炉を使用した薄膜製造装置にて容易に実現すること
ができ、種々の薄膜を多量に生産することができる。Further, the method according to the present invention can be easily realized with a thin film production apparatus using a conventionally used continuous conveyor furnace, and various thin films can be produced in large quantities.
第１図は、本発明に係る薄膜製造方法を実施するための
装置の一実施例を説明する概略断面図である。
第２図は、超音波噴射ノズルの一実施例の断面図である
。
第３図は、超音波噴射ノズル振動子のエツジ部の部分拡
大図である。
第４図は、超音波噴射ノズルの他の実施例の断面図であ
る。
第５図は、従来のスプレーヘッドと超音波噴射ノズルの
粒径分布を示すグラフであり、従来の圧力噴射式の場合
の縦座標（頻度％）は４倍に拡大して示される。
第６図は、アモルファスシリコン太陽電池の断面図であ
る。
２ａ：基板
２ｂ＝薄膜
１４：ホットプレート
１６：Ｊ［料液
２０．２０ａ：超音波噴射手段
３６．３６ａ：振動子
５０．５０ａ：エツジ部
１００：超音波振動発生手段
図面の浄書（内容に変更なし）
０ａ
第５図
オ％今青、Ｊ、１ｍ
第６図
手続補正書（方丈）
昭和６０年８月２９日FIG. 1 is a schematic cross-sectional view illustrating an embodiment of an apparatus for carrying out the thin film manufacturing method according to the present invention. FIG. 2 is a cross-sectional view of one embodiment of an ultrasonic jet nozzle. FIG. 3 is a partially enlarged view of the edge portion of the ultrasonic jet nozzle vibrator. FIG. 4 is a sectional view of another embodiment of the ultrasonic jet nozzle. FIG. 5 is a graph showing the particle size distribution of a conventional spray head and an ultrasonic jet nozzle, and the ordinate (frequency %) for the conventional pressure jet type is shown enlarged four times. FIG. 6 is a cross-sectional view of an amorphous silicon solar cell. 2a: substrate 2b = thin film 14: hot plate 16: J [liquid 20.20a: ultrasonic injection means 36.36a: vibrator 50.50a: edge portion 100: ultrasonic vibration generation means Engraving of drawing (changed in content) None) 0a Figure 5 O% Imao, J, 1m Figure 6 Procedural Amendment (Hojo) August 29, 1985
Claims (1)
を加熱基板上に導き、熱分解反応により該基板に薄膜を
形成することを特徴とする薄膜製造方法。 ２）超音波振動手段は超音波発生手段によつて振動する
振動子を有し、該振動子は先端部にエッジ部を形成し、
該エッジ部に原料液が供給されて成る特許請求の範囲第
１項記載の方法。 ３）エッジ部は階段状に形成されて成る特許請求の範囲
第２項記載の方法。 ４）エッジ部は振動子の外周部に形成されて成る特許請
求の範囲第３項記載の方法。 ５）エッジ部は振動子の内周部に形成されて成る特許請
求の範囲第３項記載の方法。 ６）薄膜は酸化すずを主成分とする薄膜である特許請求
の範囲第１項〜第５項のいずれかの項に記載の方法。[Claims] 1) A method for producing a thin film, which comprises: atomizing a raw material liquid using ultrasonic vibration means, guiding the atomized product onto a heated substrate, and forming a thin film on the substrate through a thermal decomposition reaction. . 2) The ultrasonic vibration means has a vibrator that is vibrated by the ultrasonic generation means, and the vibrator has an edge portion at its tip,
2. The method according to claim 1, wherein the raw material liquid is supplied to the edge portion. 3) The method according to claim 2, wherein the edge portion is formed in a stepped shape. 4) The method according to claim 3, wherein the edge portion is formed on the outer periphery of the vibrator. 5) The method according to claim 3, wherein the edge portion is formed on the inner peripheral portion of the vibrator. 6) The method according to any one of claims 1 to 5, wherein the thin film is a thin film containing tin oxide as a main component.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60086116A JPS61244025A (en) | 1985-04-22 | 1985-04-22 | Manufacture of thin film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60086116A JPS61244025A (en) | 1985-04-22 | 1985-04-22 | Manufacture of thin film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS61244025A true JPS61244025A (en) | 1986-10-30 |
Family
ID=13877723
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60086116A Pending JPS61244025A (en) | 1985-04-22 | 1985-04-22 | Manufacture of thin film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61244025A (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6417873A (en) * | 1987-07-13 | 1989-01-20 | Matsumoto Seiyaku Kogyo Kk | Formation of thin film of metal compound decomposition product |
| JPH0371619A (en) * | 1989-08-11 | 1991-03-27 | Sanyo Electric Co Ltd | Method of formation of semiconductor thin film |
| JPH0373519A (en) * | 1989-08-14 | 1991-03-28 | Hoxan Corp | Formation of polycrystalline silicon film on semiconductor substrate |
| FR2669246A1 (en) * | 1990-11-16 | 1992-05-22 | Centre Nat Rech Scient | SOL-GEL PROCESS FOR THE DEPOSITION OF THIN FILMS BY ULTRASONIC SPRAYING. |
| JP2006015332A (en) * | 2004-06-03 | 2006-01-19 | Canon Inc | Film forming method and production method for spacer and thin type flat panel display using the same |
| US7819081B2 (en) | 2002-10-07 | 2010-10-26 | Sekisui Chemical Co., Ltd. | Plasma film forming system |
| EP2484805A1 (en) * | 2011-02-03 | 2012-08-08 | Mott Corporation | Sinter bonded porous metallic coatings |
| WO2013022032A1 (en) * | 2011-08-10 | 2013-02-14 | 日本曹達株式会社 | Laminate and manufacturing process therefor |
| US9149750B2 (en) | 2006-09-29 | 2015-10-06 | Mott Corporation | Sinter bonded porous metallic coatings |
-
1985
- 1985-04-22 JP JP60086116A patent/JPS61244025A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6417873A (en) * | 1987-07-13 | 1989-01-20 | Matsumoto Seiyaku Kogyo Kk | Formation of thin film of metal compound decomposition product |
| JPH0371619A (en) * | 1989-08-11 | 1991-03-27 | Sanyo Electric Co Ltd | Method of formation of semiconductor thin film |
| JPH0373519A (en) * | 1989-08-14 | 1991-03-28 | Hoxan Corp | Formation of polycrystalline silicon film on semiconductor substrate |
| FR2669246A1 (en) * | 1990-11-16 | 1992-05-22 | Centre Nat Rech Scient | SOL-GEL PROCESS FOR THE DEPOSITION OF THIN FILMS BY ULTRASONIC SPRAYING. |
| US7819081B2 (en) | 2002-10-07 | 2010-10-26 | Sekisui Chemical Co., Ltd. | Plasma film forming system |
| JP2006015332A (en) * | 2004-06-03 | 2006-01-19 | Canon Inc | Film forming method and production method for spacer and thin type flat panel display using the same |
| US9149750B2 (en) | 2006-09-29 | 2015-10-06 | Mott Corporation | Sinter bonded porous metallic coatings |
| EP2484805A1 (en) * | 2011-02-03 | 2012-08-08 | Mott Corporation | Sinter bonded porous metallic coatings |
| WO2013022032A1 (en) * | 2011-08-10 | 2013-02-14 | 日本曹達株式会社 | Laminate and manufacturing process therefor |
| US9338884B2 (en) | 2011-08-10 | 2016-05-10 | Nippon Soda Co., Ltd. | Laminated body and manufacturing process therefor |
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