JPH0375967B2 - - Google Patents
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- Publication number
- JPH0375967B2 JPH0375967B2 JP56193289A JP19328981A JPH0375967B2 JP H0375967 B2 JPH0375967 B2 JP H0375967B2 JP 56193289 A JP56193289 A JP 56193289A JP 19328981 A JP19328981 A JP 19328981A JP H0375967 B2 JPH0375967 B2 JP H0375967B2
- Authority
- JP
- Japan
- Prior art keywords
- transparent electrode
- gas
- flow rate
- sputtering
- gas flow
- 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 - Lifetime
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- Physical Vapour Deposition (AREA)
- Electrodes Of Semiconductors (AREA)
- Non-Insulated Conductors (AREA)
- Manufacturing Of Electric Cables (AREA)
Description
【発明の詳細な説明】
本発明は、透明電極の製造方法およびその製造
装置に関するもので、低抵抗で高透過率の透明電
極を安定にかつ迅速に製造することを目的とす
る。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for manufacturing a transparent electrode and an apparatus for manufacturing the same, and an object thereof is to stably and quickly manufacture a transparent electrode with low resistance and high transmittance.
透明電極の製造方法は種々あり、例えば電子ビ
ーム法、抵抗加熱法、化学スプレー法、スパツタ
リング法がある。この中でも、スパツタリング法
は、基板温度が室温においても低抵抗で透過率の
すぐれた透明電極が得られるので、その使用範囲
は広い。一般に、スパツタリング法を用いた透明
電極の製造方法は、InあるいはSnおよびその合
金、またはIn2O3あるいはSnO2およびその混晶を
ターゲツトとし、スパツタ装置内に酸素ガスを含
む不活性ガスを導入してプラズマを発生せしめ、
ターゲツトをスパツタリングすることにより透明
電極を形成する。その場合の透明電極の抵抗値や
透過率は、スパツタリング条件即ちスパツタリン
グ時の電力、基板温度、ターゲツト組成、導入ガ
ス圧力等に依存するが、特に導入ガスにおける不
活性ガス中の酸素ガスはその影響が大きく、精度
のよい制御が必要である。 There are various methods for producing transparent electrodes, such as an electron beam method, a resistance heating method, a chemical spray method, and a sputtering method. Among these methods, the sputtering method can be used in a wide range of applications because it can produce transparent electrodes with low resistance and excellent transmittance even when the substrate temperature is room temperature. In general, the method for producing transparent electrodes using the sputtering method targets In or Sn and its alloys, or In 2 O 3 or SnO 2 and its mixed crystals, and introduces an inert gas containing oxygen gas into the sputtering equipment. to generate plasma,
A transparent electrode is formed by sputtering the target. In that case, the resistance value and transmittance of the transparent electrode depend on the sputtering conditions, that is, the electric power during sputtering, the substrate temperature, the target composition, the introduced gas pressure, etc., but in particular the oxygen gas in the inert gas introduced has an effect. is large and requires precise control.
従来、このガスの導入法としてはガスの流量制
御計を用いて一定量のガスをスパツタリング装置
内に導入し、プラズマを発生せしめてスパツタリ
ングを行ない透明電極を形成していたが、このよ
うな従来の方法で透明電極を形成した場合には導
入ガス流量および不活性ガスと酸素ガスの混合比
率を一定にしているにもかかわらず、スパツタリ
ング初期と後期において大幅に抵抗値や透過率が
変化したり、また蒸着ロツト毎のばらつきも極め
て大きかつた。これは、導入ガス量を一定にして
いるにもかかわらず、スパツタリング装置内のタ
ーゲツトや基板あるいは器壁等からH2OやCOや
O2が放出されこれらの分子がプラズマにより分
解されて酸素ラジカルや酸素原子となるため実効
的な酸素ガス量の変化なり、スパツタリング蒸着
における初期と後期のばらつきあるいは蒸着ロツ
ト毎のバラツキとなつていた。このような影響を
避けるため、従来は予備スパツタリング時間を長
くしたり、ベルジヤーを加熱したりスパツタリン
グ前の排気時間を長くしたりする方法がとられて
いたが、これらの方法でもその効果は充分でなか
つた。さらにこれらの方法では透明電極の製造時
間が長くなるため、再現性がすぐれかつ生産性に
おいても良好な製造方法が望まれていた。本発明
は上記のような欠点を克服すべく開発された透明
電極の製造方法およびその製造装置を提供するも
ので、本発明を用いるなら安定で迅速に、低抵抗
で高透過率の透明電極を形成することが出来る。 Conventionally, the method of introducing this gas was to introduce a fixed amount of gas into a sputtering device using a gas flow rate controller, generate plasma, and perform sputtering to form a transparent electrode. When a transparent electrode is formed using the above method, the resistance value and transmittance change significantly between the early and late stages of sputtering, even though the introduced gas flow rate and the mixing ratio of inert gas and oxygen gas are kept constant. , and the variation among vapor deposition lots was also extremely large. This is due to the fact that even though the amount of gas introduced is constant, H 2 O, CO, etc.
O 2 is released and these molecules are decomposed by the plasma to become oxygen radicals and oxygen atoms, resulting in a change in the effective amount of oxygen gas, leading to variations between the early and late stages of sputtering deposition or variations between deposition lots. . In order to avoid such effects, conventional methods have been taken such as increasing the preliminary sputtering time, heating the bell gear, and increasing the exhaust time before sputtering, but even these methods are insufficiently effective. Nakatsuta. Furthermore, since these methods require a long time to manufacture transparent electrodes, a manufacturing method with excellent reproducibility and good productivity has been desired. The present invention provides a transparent electrode manufacturing method and its manufacturing apparatus developed to overcome the above-mentioned drawbacks.Using the present invention, it is possible to stably and quickly produce a transparent electrode with low resistance and high transmittance. can be formed.
第１図は本発明の一実施例における透明電極の
製造装置であるスパツタリング装置の概略構成を
示したものである。同図において１はベルジヤ
ー、２は排気系である。３は基板４とInおよび
Snあるいはその合金とよりなるターゲツト５間
にプラズマを発生させるための、例えば発振周波
数が13.56MHzの高周波電源であるが、これは直
流高圧電源であつても構わない。６は蒸着速度の
測定子で水晶振動子を用いたものが適している。
７は測定子６を駆動するための電源で、蒸着速度
に比例した信号が出力される。この動作原理は、
“薄膜作成の基礎”181〜182頁（麻蒔立男著、日
刊工業新聞社）に記載のように、水晶振動板の固
有振動数は、その片面につく蒸着物質の量により
変化する。蒸着中の水晶振動板の固有振動数の変
化を測定することにより、蒸着中の蒸着厚の変化
を計測することができる。８は不活性ガスボンベ
でAr等の供給源であり、９は酸素ガスボンベで
ある。１０および１０′は酸素ガスあるいは不活
性ガスの流量制御計で、電気的信号により流量制
御が可能なマスフローコントローラーが好まし
い。１１はフイードバツク回路で、測定子６で得
られる出力信号が常に一定値に保たれるように、
流量制御計１０および１０′をコントロール可能
とする設定がなされている。 FIG. 1 shows a schematic configuration of a sputtering apparatus which is a transparent electrode manufacturing apparatus in one embodiment of the present invention. In the figure, 1 is a bell gear, and 2 is an exhaust system. 3 is the substrate 4 and In and
A high frequency power source with an oscillation frequency of 13.56 MHz, for example, is used to generate plasma between the targets 5 made of Sn or its alloy, but it may also be a DC high voltage power source. Reference numeral 6 indicates a measuring element for measuring the deposition rate, and one using a crystal oscillator is suitable.
Reference numeral 7 denotes a power source for driving the probe 6, which outputs a signal proportional to the deposition rate. This operating principle is
As described in "Fundamentals of Thin Film Creation", pages 181-182 (written by Tatsuo Asamaki, published by Nikkan Kogyo Shimbun), the natural frequency of a crystal diaphragm changes depending on the amount of deposited material on one side of the plate. By measuring the change in the natural frequency of the crystal diaphragm during vapor deposition, it is possible to measure the change in the deposition thickness during vapor deposition. 8 is an inert gas cylinder which is a supply source of Ar, etc., and 9 is an oxygen gas cylinder. Reference numerals 10 and 10' denote flow rate controllers for oxygen gas or inert gas, preferably mass flow controllers capable of controlling the flow rate by electrical signals. 11 is a feedback circuit, so that the output signal obtained from the probe 6 is always kept at a constant value.
Settings are made to enable control of the flow rate controllers 10 and 10'.
以下に、前記構成の製造装置を用いた透明電極
の製造方法を実施例として第１図をもとに説明
し、その効果を第２図、第３図を用いて説明す
る。まずベルジヤー１を排気系２により排気す
る。この時、従来はベルジヤ内の真空度を
10-6Torr台まで排気した後、ガス導入をはかつ
ていたが、本実施例の方法では10-5Torr台でガ
ス導入を行なつても透明電極は充分に低い抵抗値
及びその製造法の再現性を示した。排気時間は装
置によつても異なるが、通常のスパツタリング装
置では10-6Torr台に到達するには約30分を要す
るが、10-5Torr台には10分以内で可能であり、
時間短縮が可能である。このように排気した後、
例えばArガスおよび酸素ガスを流量制御計１
０′および１０によりそれぞれ20c.c.／min、５
c.c.／minをスパツタリング装置内に導入する。装
置内のガス圧は10-2〜10-3Torrとなり放電可能
なガス圧となる。しかる後、電源３により100〜
300Wを投入すると、基板４とターゲツト５間で
放電が開始されスパツタリングがはじまる。 Below, a method for manufacturing a transparent electrode using the manufacturing apparatus having the above configuration will be described as an example with reference to FIG. 1, and its effects will be described using FIGS. 2 and 3. First, the bell gear 1 is exhausted by the exhaust system 2. At this time, conventionally the degree of vacuum inside the bell gear was
In the past, gas was introduced after exhausting to the 10 -6 Torr level, but in the method of this example, even if gas is introduced at the 10 -5 Torr level, the transparent electrode has a sufficiently low resistance value and its manufacturing method. Reproducibility was demonstrated. The evacuation time varies depending on the equipment, but with normal sputtering equipment, it takes about 30 minutes to reach the 10 -6 Torr level, but it is possible to reach the 10 -5 Torr level within 10 minutes.
It is possible to save time. After exhausting like this,
For example, flow rate controller 1 for Ar gas and oxygen gas.
0' and 10 respectively 20c.c./min, 5
cc/min into the sputtering equipment. The gas pressure inside the device is 10 -2 to 10 -3 Torr, which is the gas pressure that allows discharge. After that, 100~ by power supply 3
When 300W is applied, discharge starts between the substrate 4 and the target 5, and sputtering begins.
第２図は、前記方法によつて製造される透明電
極のシート抵抗と蒸着速度の時間変化をそれぞれ
示している。第２図において従来例を示す特性曲
線２１，２２（２１：シート抵抗、２２：蒸着速
度）はArガス流量を20c.c.／min、O2ガス流量を
５c.c.／minと一定にした時の測定結果を示してい
る。従来例の場合は特性曲線２２に示すように時
間と共に蒸着速度が低下し、それにつれて特性曲
線２１に示すようにシート抵抗の上昇もみられ
る。それに対して本発明の実施例の場合、Arガ
ス流量は特性曲線２３に示すように20c.c.／minと
一定であるが、これは蒸着速度の変化に対応させ
てO2ガス流量を減少させ蒸着速度を一定となる
よう制御したことによるものであり、この場合、
シート抵抗は特性曲線２４に示すように時間に関
係なく一定値をとつていることがわかる。透明電
極の蒸着速度を一定とする方法はO2ガス流量制
御ばかりでなくArガス流量制御によつても可能
であるが、その範囲は、放電が継続し得ることと
良好な特性値が得られる範囲に限られる。傾向的
には、抵抗値を低く保つために時間と共にO2ガ
ス流量を減少させること、あるいはArガス流量
を増大させることおよびそれらを複合させる方法
が有効である。 FIG. 2 shows the changes over time in the sheet resistance and deposition rate of the transparent electrode manufactured by the method described above. In FIG. 2, characteristic curves 21 and 22 (21: sheet resistance, 22: evaporation rate) showing the conventional example are obtained when the Ar gas flow rate is constant at 20 c.c./min and the O 2 gas flow rate is constant at 5 c.c./min. The results are shown below. In the case of the conventional example, as shown in characteristic curve 22, the deposition rate decreases with time, and as a result, as shown in characteristic curve 21, sheet resistance increases. On the other hand, in the case of the embodiment of the present invention, the Ar gas flow rate is constant at 20 c.c./min as shown in characteristic curve 23, but this means that the O 2 gas flow rate is decreased in response to changes in the deposition rate. This is because the deposition rate is controlled to be constant.
It can be seen that the sheet resistance takes a constant value regardless of time, as shown in the characteristic curve 24. It is possible to keep the deposition rate of the transparent electrode constant not only by O 2 gas flow control but also by Ar gas flow control, but the range is limited to the extent that discharge can continue and good characteristic values can be obtained. limited to a range. In order to keep the resistance value low, it tends to be effective to reduce the O 2 gas flow rate over time, increase the Ar gas flow rate, and combine these methods.
第３図は従来および、本発明の実施例の各場合
における蒸着回数毎のシート抵抗のばらつきを示
したものである。従来例に関する特性曲線３１は
ガス流量を一定とした時のシート抵抗変化を示し
ており、本発明の実施例に関する特性曲線３２は
蒸着速度を一定となるよう制御して得られた透明
電極のシート抵抗変化を示しており、同図より明
らかに本発明による製造方法の方がすぐれている
ことがわかる。ガス流量を一定にしているにもか
かわらず、蒸着回毎にシート抵抗がばらつくのは
器壁等に吸着するガス量が１回毎に変化するため
一定時間の排気にもかかわらずスパツタリング時
の放出ガス量が変化するためと考えられる。 FIG. 3 shows variations in sheet resistance for each number of depositions in the conventional case and in the embodiment of the present invention. A characteristic curve 31 related to the conventional example shows the change in sheet resistance when the gas flow rate is constant, and a characteristic curve 32 related to the example of the present invention shows a transparent electrode sheet obtained by controlling the vapor deposition rate to be constant. The figure shows the resistance change, and it is clear from the figure that the manufacturing method according to the present invention is superior. Even though the gas flow rate is kept constant, the sheet resistance varies from deposition to deposition because the amount of gas adsorbed to the vessel wall changes from deposition to deposition. This is thought to be due to changes in the amount of gas.
以上のように本発明の蒸着速度を一定となるよ
う制御する透明電極の製造方法は、蒸着中の透明
電極の抵抗変化や蒸着回数毎の透明電極の抵抗変
化が少ない。これはターゲツトや基板および器壁
からの放出ガス量がスパツタリング中に変化した
り、あるいは蒸着回毎に変化したりするのを補償
し、実効的に不活性ガス中の酸素ガス混合比を同
一としているためと考えられる。 As described above, the method of manufacturing a transparent electrode in which the vapor deposition rate is controlled to be constant according to the present invention has a small resistance change in the transparent electrode during vapor deposition and a small change in resistance of the transparent electrode depending on the number of vapor depositions. This compensates for the fact that the amount of gas emitted from the target, substrate, and vessel wall changes during sputtering, or from one deposition cycle to another, and effectively maintains the same oxygen gas mixture ratio in the inert gas. This is thought to be due to the presence of
以上述べてきたように、本発明による透明電極
の製造方法およびその製造装置によれば、低抵抗
で高透過率の透明電極を迅速にかつ再現性よく得
ることが出来るので、その産業上の利用価値は極
めて大きいと言える。 As described above, according to the method and apparatus for manufacturing a transparent electrode according to the present invention, a transparent electrode with low resistance and high transmittance can be obtained quickly and with good reproducibility, so that it can be used for industrial purposes. It can be said that the value is extremely large.
第１図は本発明の一実施例における透明電極の
製造装置の概略断面正面図、第２図は同装置を用
いたスパツタリング中におけるシート抵抗と蒸着
速度の時間変化特性図、第３図は同装置を用いた
スパツタリングにおける蒸着回数毎のシート抵抗
のばらつきを示した特性図である。
１……ベルジヤー、２……排気系、３……高周
波電源、４……基板、５……ターゲツト、６……
蒸着速度の測定子、７……電源、８，９……ガス
ボンベ、１０，１０′……流量制御計、１１……
フイードバツク回路。
Fig. 1 is a schematic cross-sectional front view of a transparent electrode manufacturing apparatus according to an embodiment of the present invention, Fig. 2 is a temporal change characteristic diagram of sheet resistance and vapor deposition rate during sputtering using the same apparatus, and Fig. 3 is the same. FIG. 2 is a characteristic diagram showing variations in sheet resistance for each number of times of vapor deposition in sputtering using the apparatus. 1... Bell gear, 2... Exhaust system, 3... High frequency power supply, 4... Board, 5... Target, 6...
Vapor deposition rate measuring element, 7...Power supply, 8,9...Gas cylinder, 10,10'...Flow rate controller, 11...
Feedback circuit.
Claims (1)
において、スパツタリング中の蒸着速度を検出す
る検出手段を備え、前記検出手段の検出値を所定
値になるように酸素ガス流量と不活性ガス流量の
時間変化を制御し、前記検出値を一定に保つこと
を特徴とする透明電極の製造方法。 ２ 透明電極形成用のスパツタ装置と、前記スパ
ツタ装置に酸素ガスおよび不活性ガスをそれぞれ
供給するガス供給手段と、前記スパツタ装置に設
けられ前記透明電極の蒸着速度を測定する蒸着速
度計と、前記ガス供給手段から前記スパツタ装置
に供給される酸素ガスおよび不活性ガスの流量の
時間変化を制御するガス流量制御計と、前記蒸着
速度計の測定値が所定値になるようにガス流量を
制御する信号を前記ガス供給手段に供給する制御
手段とを具備することを特徴とする透明電極の製
造装置。[Scope of Claims] 1. A method of forming a transparent electrode using a sputtering device, comprising a detection means for detecting a vapor deposition rate during sputtering, and adjusting the oxygen gas flow rate and inertness so that the detected value of the detection means becomes a predetermined value. A method for manufacturing a transparent electrode, characterized in that the detected value is kept constant by controlling a change in gas flow rate over time. 2. A sputtering device for forming a transparent electrode, a gas supply means for supplying oxygen gas and an inert gas to the sputtering device, respectively, a vapor deposition rate meter provided in the sputtering device to measure the vapor deposition rate of the transparent electrode, and a gas flow rate controller that controls time changes in the flow rates of oxygen gas and inert gas supplied from the gas supply means to the sputtering device; and a gas flow rate controller that controls the gas flow rate so that the measured value of the vapor deposition rate meter becomes a predetermined value. A transparent electrode manufacturing apparatus comprising: a control means for supplying a signal to the gas supply means.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56193289A JPS5894703A (en) | 1981-11-30 | 1981-11-30 | Method of producing transparent electrode and device for producing same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56193289A JPS5894703A (en) | 1981-11-30 | 1981-11-30 | Method of producing transparent electrode and device for producing same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5894703A JPS5894703A (en) | 1983-06-06 |
| JPH0375967B2 true JPH0375967B2 (en) | 1991-12-04 |
Family
ID=16305435
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP56193289A Granted JPS5894703A (en) | 1981-11-30 | 1981-11-30 | Method of producing transparent electrode and device for producing same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5894703A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0751746B2 (en) * | 1988-08-05 | 1995-06-05 | 松下電器産業株式会社 | Oxide thin film manufacturing method |
| US20140083841A1 (en) * | 2011-05-13 | 2014-03-27 | Sharp Kabushiki Kaisha | Thin film-forming method |
| JP6775972B2 (en) | 2016-03-17 | 2020-10-28 | 芝浦メカトロニクス株式会社 | Film formation equipment and film formation method |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS51116999A (en) * | 1975-04-08 | 1976-10-14 | Toppan Printing Co Ltd | Process for manufacturing transparent conductive plastic |
| JPS53118417A (en) * | 1977-03-25 | 1978-10-16 | Asahi Glass Co Ltd | Production of glass with transparent* electrically conductive coat of sno2 |
| JPS56130009A (en) * | 1980-03-17 | 1981-10-12 | Sharp Kk | Method of producing transparent conductive film |
-
1981
- 1981-11-30 JP JP56193289A patent/JPS5894703A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5894703A (en) | 1983-06-06 |
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